TW201837118A - Flexible substrate composition and flexible substrate - Google Patents

Abstract

A flexible substrate composition capable of forming a flexible substrate with excellent phase difference, and the flexible substrate are provided. The flexible substrate composition includes a polymer (A), and a solvent (B). Polymer (A) is obtained by reacting a mixture. The mixture includes a tetracarboxylic dianhydride component (a) and a diamine component (b). The tetracarboxylic dianhydride component (a) includes a compound (a1) represented by formula (a-1), and a compound (a2) represented by formula (a-2). formula (a-1) formula (a-2).

Description

Composition for flexible substrate and flexible substrate

The present invention relates to a composition for a flexible substrate and a flexible substrate, and more particularly to a composition for a flexible substrate to produce a flexible substrate with a good phase difference.

In recent years, organic polymer materials have been widely used in various electronic components or devices to improve various characteristics (such as electrical insulation, heat resistance, or mechanical properties) of electronic components or devices. Among them, polyimide polymer is the most widely used. Because of its excellent mechanical properties and good electrical properties, it is favored by related industries.

WO 2009/107429 discloses a polyimide precursor composition for a transparent flexible substrate. The polyfluorene imide precursor is prepared by reacting diamine (including fluorinated benzidine and 1,4-cyclohexanediamine) with tetracarboxylic dianhydride, and the composition can form a flexible substrate with high transparency . However, when the above polyfluorene imide precursor is heated and hardened to form a polyfluorene, it is easy to cause the problem of poor phase difference, which cannot meet the needs of the industry.

Therefore, it is urgent to provide a composition for a flexible substrate and a flexible substrate to improve the defects of the conventional composition for a flexible substrate and the flexible substrate. [Patent Literature]

[Patent Document 1] WO 2009/107429 A1

In view of this, the present invention provides a composition for a flexible substrate, and the use of the composition for a flexible substrate can improve the problem of poor phase difference of the flexible substrate.

The present invention provides a composition for a flexible substrate, which includes a polymer (A) and a solvent (B). The polymer (A) is obtained by reacting a mixture, and the mixture includes a tetracarboxylic dianhydride component (a) and a diamine component (b). The tetracarboxylic dianhydride component (a) includes a compound (a1) represented by the formula (a-1) and a compound (a2) represented by the formula (a-2): Formula (a-1) In formula (a-1), R each independently represents an alkylene group having 1 to 6 carbon atoms; R _X represents a divalent aliphatic cyclic hydrocarbon group, and the divalent aliphatic cyclic hydrocarbon group is A divalent group substituted or substituted with a halogen atom, a linear hydrocarbon group, or a branched hydrocarbon group. Formula (a-2) In formula (a-2), R ₁ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and R ₂ each independently represents a hydrogen atom, a methyl group, or an ethane group.

In an embodiment of the present invention, in the above formula (a-1), R _x has a structure represented by the formula (a-1-x): Formula (a-1-x) In formula (a-1-x), m represents an integer of 0 to 4; R and _Z each independently represent a halogen atom, a linear hydrocarbon group having 1 to 4 carbon atoms, and 1 carbon number A branched hydrocarbon group of 4 or a plurality of R _Z are connected to each other to form a cyclic structure.

In an embodiment of the present invention, in the formula (a-1), each R independently represents an alkylene group having 1 to 3 carbon atoms.

In one embodiment of the present invention, the total mole number based on the tetracarboxylic dianhydride component (a) is 100 moles, and the amount of the compound (a1) represented by the formula (a-1) is 15 to 85. Mol, the compound (a2) represented by the formula (a-2) is used in an amount of 15 to 85 moles.

In an embodiment of the present invention, the total amount of the polymer (A) is 100 parts by weight, and the amount of the solvent (B) is 200 to 2000 parts by weight.

In one embodiment of the present invention, the viscosity of the composition for a flexible substrate is from 100 cps to 20,000 cps at 25 ° C.

The present invention further provides a flexible substrate including the composition for a flexible substrate as described above.

Based on the above, since the composition for a flexible substrate of the present invention contains a specific polymer (A), the problem of poor phase difference of the flexible substrate can be improved.

In order to make the above features and advantages of the present invention more comprehensible, the following specific embodiments are described in detail below.

< Composition for a Flexible Substrate > The present invention provides a composition for a flexible substrate, which includes a polymer (A) and a solvent (B). In addition, if necessary, the composition for a flexible substrate may further include an additive (C).

Hereinafter, each component of the composition for a flexible substrate used in the present invention will be described in detail. Polymer ( A )

The polymer (A) is selected from a polyamic acid resin, a polyimide resin, or any combination thereof. And the polymer (A) can be prepared by reacting a mixture including a tetracarboxylic dianhydride component (a) and a diamine component (b), wherein the tetracarboxylic dianhydride component (a) and the diamine component ( b) and the method for preparing the polymer (A) are as follows. Tetracarboxylic dianhydride component ( a )

The tetracarboxylic dianhydride component (a) includes the compound (a1) represented by the formula (a-1), the compound (a2) represented by the formula (a-2), and other tetracarboxylic dianhydride compounds (a3). Compound ( a1 ) represented by formula (a-1 )

The compound (a1) represented by the formula (a-1) is shown below: Formula (a-1) In formula (a-1), R each independently represents an alkylene group having 1 to 6 carbon atoms; R _X represents a divalent aliphatic cyclic hydrocarbon group, and the divalent aliphatic cyclic hydrocarbon group is A divalent group substituted or substituted with a halogen atom, a linear hydrocarbon group, or a branched hydrocarbon group.

The linear hydrocarbon group or branched hydrocarbon group substituted on the divalent aliphatic cyclic hydrocarbon group is preferably a saturated hydrocarbon group. The divalent aliphatic cyclic hydrocarbon group may be a monocyclic ring, a condensed ring composed of two or more rings, a polycyclic ring, a spiro compound, or a cyclic hydrocarbon group. Preferably, the carbon number of R _X may be 3 to 15.

Specifically, R _X may preferably be cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornene, dicyclopenta diene, and Adamantane. ), Or a divalent aliphatic cyclic hydrocarbon group formed by removing a hydrogen atom from an aliphatic cyclic hydrocarbon selected from a hydrogenated naphthalene ring and a hydrogenated bisphenol. The divalent aliphatic cyclic hydrocarbon group may be substituted with a halogen atom, a linear hydrocarbon group, or a branched hydrocarbon group (preferably a saturated hydrocarbon group).

In an embodiment, R _{x is} preferably a divalent group having a structure represented by formula (a-1-x): Formula (a-1-x) In formula (a-1-x), m represents an integer of 0 to 4; R and _Z each independently represent a halogen atom, a linear hydrocarbon group having 1 to 4 carbon atoms, and 1 carbon number A branched hydrocarbon group of 4 or a plurality of R _Z are connected to each other to form a cyclic structure. If R _x in the above formula (a-1) has a structure like the formula (a-1-x), the phase difference of the formed flexible substrate is more favorable.

In a preferred example, R represents an alkylene group having 1 to 3 carbon atoms. When R in the above formula (a-1) represents an alkylene group having 1 to 3 carbon atoms, the phase difference of the formed flexible substrate is better.

A method for synthesizing the compound (a1) represented by the formula (a-1) will be described below. In one embodiment, the compound (a1) represented by the formula (a-1) is prepared by reacting trimellitic anhydride chloride with an aliphatic dihydroxy compound. Acetonitrile, propionitrile (Propanenitrile) and other organic nitriles as the reaction solvent.

Specific examples of the aliphatic dihydroxy compound may include cyclohexane-1,4-diyldimethanol, 2- (4- (hydroxymethyl) cyclohexyl) propanol (2 -(4- (hydroxymethyl) cyclohexyl) propan-1-ol), cyclohexane-1,3-diyldimethanol, 1,1 '-(cyclohexane-1, 4-Diyl) diethanol (1,1 '-(cyclohexane-1,4-diyl) diethanol), (2-methylcyclohexane-1,4-diyl) dimethanol ((2-methylcyclohexane-1 , 4-diyl) dimethanol), (2-chlorocyclohexane-1,4-diyl) dimethanol, (2-chlorocyclohexane-1,4-diyl) dimethanol, 2- (3- (hydroxymethyl) Cyclohexyl) propanol (2- (3- (hydroxymethyl) cyclohexyl) propan-1-ol), 3- (4- (hydroxymethyl) cyclohexyl) propan (3- (4- (hydroxylmethyl) cyclohexyl) propan -1-ol), 5-tert-butyl-1,3-cyclohexanedimethanol, 3- (2- (hydroxymethyl) cyclohexyl) propane Alcohol (3- (2- (hydroxymethyl) cyclohexyl) propan-1-ol), 1,4-cyclohexanedibutanol, 1,4-cyclohexanedihexanol (1, 4-cyclohexanedihexanol), 2- (5- (hydroxymethyl) bicyclo [2.2.1] heptane-2-yl) propanol (2- (5 -(hydroxymethyl) bicyclo [2.2.1] heptan-2-yl) propan-1-ol), bicyclo [2.2.1] heptane-1,4-diyldimethanol (bicyclo [2.2.1] heptane-1 , 4-diyldimethanol), 1,1 '-(bicyclo [2.2.2] octane-1,4-diyl) diethanol (1,1'- (bicycle [2.2.2] octane-1,4-diyl ) bis (ethan-1-ol)), 3- (6- (hydroxymethyl) bicyclo [2.2.1] heptane-2-yl) propanol (3- (6- (hydroxymethyl) bicyclo [2.2.1 ] heptan-2-yl) propan-1-ol), (decahydro naphthalene-1,4-diyl) dimethanol, (decahydronaphthalene-1,4-diyl) dimethanol, -(Dica) diethanol ((decahydronaphthalene-2,3-diyl) dimethanol), 2- (4- (hydroxymethyl) octahydro-1H-inden-5-yl) ethanol (2- (4- (hydroxymethyl) octahydro-1H-inden-5-yl) ethanol), 2- (3- (hydroxymethyl) adamantan-1-yl) ethanol), (2- (3- (hydroxyl methyl) adamantan-1-yl) ethanol), 2,2 '-(adamantane-1,3-diyl) diethanol (2,2'-(adamantane-1,3-diyl) diethanol), (decahydronaphthalene-2,6-diyl) dimethanol ((decahydronaphthalene-2,6-diyl) dimethanol), octahydro-4,7-methylene-1H-indene-2,5-dimethanol (octahydro-4,7-methano-1H-indene-2,5 -dimethanol) or 1,3-cyclopentanedibutanol anedibutanol), etc.

In one example, the amount of the organic nitrile used is preferably an amount capable of dissolving the chlorotrimellitic anhydride and the aliphatic dihydroxy compound. The amount of the organic nitrile that can dissolve the chlorinated trimellitic anhydride is usually 1 to 3 times, preferably 1.5 to 2 times, the weight of the chlorinated trimellitic anhydride. In addition, the amount of the organic nitrile that can dissolve the aliphatic dihydroxy compound is usually 7 to 12 times, preferably 9 to 10 times, the weight of the aliphatic dihydroxy compound.

Because in the reaction process, by-products of insoluble hydrochloride are produced, which further reduces the quality of the finished product. If the above-mentioned by-products are too much, it is not conducive to economic considerations. Therefore, in the above-mentioned reaction process, a hydrochloric acid scavenger can be used. The above-mentioned hydrochloric acid trapping agent may be any conventional salt soluble in organic nitriles, among which pyridine is preferred. These salts may be mixed in an organic nitrile containing an aliphatic dihydroxy compound.

In addition, the molar content of trimellitic acid chloride and aliphatic dihydroxy compound is preferably 2.1 to 2.4. The salt of the aforementioned hydrochloric acid scavenger is preferably 1.0 to 1.2 as compared with the molar content of trimellitic acid chloride.

In one example, the organic nitrile solution of the above-mentioned aliphatic dihydroxy compound is dropped into the organic nitrile solution of trimellitic acid chloride to start the reaction. At this time, a pyridine system as a hydrochloric acid trapping agent was dissolved in an organic nitrile solution of an aliphatic dihydroxy compound. In addition, if the organic nitrile solution of chlorotrimellitic anhydride is dropped into the organic nitrile solution of an aliphatic dihydroxy compound, contrary to the above, it is easier to generate a by-product. Therefore, it is suitable to drip the organic nitrile solution of an aliphatic dihydroxy compound into the organic nitrile solution of trimellitic acid chloride.

The step of dropping is performed at a temperature of 0 ° C to 40 ° C, preferably 5 ° C to 25 ° C. There is no time limit for the step of dropping, and it is only appropriate that the dropping rate can be timed at a predetermined temperature. After the step of dropping is completed, the reaction is performed at 15 ° C to 40 ° C for 1 to 10 hours, and the above temperature is preferably 20 ° C to 30 ° C.

After completion of the reaction, the solid of the produced compound (a1) was filtered and recovered. The preferred form of the hydrochloride by-product is pyridine hydrochloride, which is dissolved in an organic nitrile. Therefore, the compound (a1) and the by-product can be separated by filtering off the above reaction solution.

The solid of the compound (a1) is washed with an organic solvent, and a compound (a1) with high purity can be obtained. Furthermore, the compound (a1) can be warmed and dissolved in an organic solvent. The organic solvent is not particularly limited, and it is preferable to use only the soluble compound (a1). Specifically, the organic solvent may be N, N-dimethylformamide (DMF), N, N-dimethylacetamide, or any combination thereof. The amount of the organic solvent used may be 2.5 to 5 times, and preferably 3 to 4 times, the solid weight of the compound (a1).

In particular, in general, if the organic solvents referred to herein in the present invention use industrial-grade organic solvents, they may contain a small amount of moisture. The water may generate a hydrolyzed product of the compound (a1). However, a small amount of hydrolysate can be removed when the filtrate is recrystallized to remove the filtrate without affecting the quality of the product. In other words, if a water-removing solvent is used to improve the yield, it is not conducive to cost considerations. Therefore, it is preferable to use an industrial-grade organic solvent and to add 1% by mass of anhydrous acetic acid as a dehydrating agent. According to this, the compound (a1) represented by the formula (a-1) can be produced, and even if a by-product is generated, the purity of the compound (a1) has only a small influence, and therefore, it can have both yield and purity.

The organic solvent dissolves the compound (a1) at a temperature of 60 ° C to 110 ° C, preferably 70 ° C to 85 ° C. If the above temperature is too high, the prepared liquid crystal alignment film may be discolored. On the other hand, if the temperature is too low, a good refining effect cannot be achieved.

After the compound (a1) is dissolved in an organic solvent, the solution is cooled to recrystallize and precipitate the compound (a1). The cooling temperature may be -10 ° C to 30 ° C, and preferably 5 ° C to 25 ° C. If the temperature is too low, it is difficult to move the precipitated crystals, which further increases the difficulty of processing. If the above-mentioned temperature is too high, the yield of the product decreases and it does not meet economic considerations.

The precipitated crystalline solid was filtered to isolate the compound (a1). The isolated compound (a1) was then washed with an organic solvent. Examples of the organic solvent include aliphatic ketones, ethers, and aromatic hydrocarbons. For example, the aliphatic ketone may be acetone, methyl ethyl ketone, methyl isobutyl ketone, or the like. Examples of the ethers include tetrahydrofuran, methyl isobutyl ether, and methyl isopropyl ether. Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and ethylbenzene.

The tetracarboxylic dianhydride compound after washing was dried under reduced pressure at 80 ° C. for 24 hours to obtain a compound (a1) with high purity.

Examples of the compound (a1) represented by the formula (a-1) include compounds represented by the following formulae (a-1-1) to (a-1-24): (A-1-1) (A-1-2) (A-1-3) (A-1-4) (A-1-5) (A-1-6) Formula (a-1-7) Formula (a-1-8) (A-1-9) Formula (a-1-10) (A-1-11) Formula (a-1-12) Formula (a-1-13) Formula (a-1-14) Formula (a-1-15) Formula (a-1-16) (A-1-17) Formula (a-1-18) (A-1-19) Formula (a-1-20) Formula (a-1-21) (A-1-22) Formula (a-1-23) Formula (a-1-24)

The total mole number based on the tetracarboxylic dianhydride component (a) is 100 moles, and the amount of the compound (a1) represented by the formula (a-1) is 15 to 85 moles, preferably 20 to 80 Mohr, more preferably 25 to 75 moles.

If the compound (a1) represented by the formula (a-1) is not used in the composition for a flexible substrate, the phase difference of the formed flexible substrate is not good. Compound ( a2 ) represented by formula (a-2 )

The compound (a2) represented by the formula (a-2) is shown below: Formula (a-2) In formula (a-2), R ₁ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and R ₂ each independently represents a hydrogen atom, a methyl group, or an ethane group.

Examples of the compound (a2) represented by the formula (a-2) include compounds represented by the following formulae (a-2-1) to (a-2-14): (A-2-1) Formula (a-2-2) (A-2-3) (A-2-4) Formula (a-2-5) Formula (a-2-6) Formula (a-2-7) Formula (a-2-8) Formula (a-2-9) Formula (a-2-10) Formula (a-2-11) Formula (a-2-12) Formula (a-2-13) Formula (a-2-14)

The total mole number based on the tetracarboxylic dianhydride component (a) is 100 moles, and the amount of the compound (a2) represented by the formula (a-2) is 15 to 85 moles, preferably 20 to 80 Mohr, more preferably 25 to 75 moles.

If the compound (a1) represented by the formula (a-2) is not used for the composition for a flexible substrate, the phase difference of the formed flexible substrate is not good. Other tetracarboxylic dianhydride compounds ( a3 )

Other tetracarboxylic dianhydride compounds (a3) include aliphatic tetracarboxylic dianhydride compounds, alicyclic tetracarboxylic dianhydride compounds, aromatic tetracarboxylic dianhydride compounds, from formula (a-3-1) to formula A tetracarboxylic dianhydride compound represented by (a-3-6), a fluorine-containing tetracarboxylic dianhydride compound, and the like.

Specific examples of the aliphatic tetracarboxylic dianhydride compound may include, but are not limited to, ethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, or a combination thereof.

Specific examples of the alicyclic tetracarboxylic dianhydride compound may include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclo Butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl Cyclopeptyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, or a combination of the foregoing compounds.

The alicyclic tetracarboxylic dianhydride compound may include a bicyclic alicyclic tetracarboxylic dianhydride compound. Preferably, the bicyclic alicyclic tetracarboxylic dianhydride compound has a tetravalent bridged hydrocarbon group having a total number of atoms of 7 to 9, and one of the bridges of the tetravalent bridge hydrocarbon group is The number of bridge atoms is 1 or 2.

Specific examples of the bicyclic alicyclic tetracarboxylic dianhydride compound may include, but are not limited to, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 7-azabicyclo [2.2. 1] heptane-2,3,5,6-tetracarboxylic dianhydride, 7-oxabicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 7-thia Bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 6- (carboxymethyl) bicyclo [2.2.1] heptane-2,3,5-tricarboxylic acid-2 , 3,5,6-dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5 , 6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-5-ene-1,2,7,8-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-2-ene-2,3 , 5,6-tetracarboxylic dianhydride, 7-azabicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, 7-oxabicyclo [2.2.2] octane -2,3,5,6-tetracarboxylic dianhydride, 7-thiabicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [3.2.1] octane -2,3,5,6-tetracarboxylic dianhydride, bicyclo [3.2.1] octane-2,4,5,6-tetracarboxylic dianhydride, 7-azabicyclo [3.2.1] octane -2,3,5,6-tetracarboxylic dianhydride, 7-azabicyclo [3.2.1] octane-2,4,5,6-tetracarboxylic dianhydride, 7-oxabicyclo [3.2. 1] octane-2,3,5,6-tetracarboxylic dianhydride, 7-oxabicyclo [3.2.1] octane-2,4,5,6-tetracarboxylic Acid dianhydride, 7-thiabicyclo [3.2.1] octane-2,3,5,6-tetracarboxylic dianhydride, 7-thiabicyclo [3.2.1] octane-2,4,5, 6-tetracarboxylic dianhydride, bicyclo [3.2.2] nonane-2,3,6,7-tetracarboxylic dianhydride, bicyclo [3.2.2] nonane-2,4,6,7-tetracarboxylic acid Acid dianhydride, bicyclo [3.2.2] non-8-alkenyl-2,3,6,7-tetracarboxylic dianhydride, bicyclo [3.2.2] non-8-alkenyl-2,4,6, 7-tetracarboxylic dianhydride, 8-azabicyclo [3.2.2] nonane-2,3,6,7-tetracarboxylic dianhydride, 8-azabicyclo [3.2.2] nonane-2, 4,6,7-tetracarboxylic dianhydride, 8-oxabicyclo [3.2.2] nonane-2,3,6,7-tetracarboxylic dianhydride, 8-oxabicyclo [3.2.2] nonane Ethane-2,4,6,7-tetracarboxylic dianhydride, 8-thiabicyclo [3.2.2] nonane-2,3,6,7-tetracarboxylic dianhydride or 8-thiabicyclo [3.2 .2] nonane-2,4,6,7-tetracarboxylic dianhydride and the like.

Specific examples of the aromatic tetracarboxylic dianhydride compound may include, but are not limited to, 3,4-dicarboxyl-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'- Biphenylphosphonium tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'-4,4'-di Phenylethane tetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic acid Dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 2,3,3 ', 4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether Tetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 2,3,3 ', 4'-diphenylsulfide tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfide tetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylarsine dianhydride, 4,4'-bis ( 3,4-dicarboxyphenoxy) diphenylpropane dianhydride (4,4'-bis (3,4-dicarboxy phenoxy) diphenylpropane dianhydride), 3,3 ', 4,4'-perfluoroisopropylidene Diphthalic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, bis Phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (tris Phenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrodehydrobenzene Triester), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydromellitate Esters), 1,8-octanediol-bis (anhydrotrimellitic acid esters), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitic acid esters), 2,3,4 , 5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1 , 2-c] -furan-1,3-dione {(1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo- 3-furanyl) naphtho [1,2 -c] furan-1,3-dione)}, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3- Furyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro-2 , 5-dioxo-3-furyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3, 3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1 , 3-diketone, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo -3-furyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetra Hydrogen-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro -5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5 -An aromatic tetracarboxylic dianhydride compound such as (2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride or a combination thereof.

The tetracarboxylic dianhydride compounds represented by the formula (a-3-1) to the formula (a-3-6) are shown below. (A-3-1) Formula (a-3-2) Formula (a-3-3) (A-3-4) Formula (a-3-5) In formula (a-3-5), A ₁ represents a divalent group containing an aromatic ring; r represents an integer of 1 to 2; A ₂ and A ₃ may be the same or different, and Each may independently represent -H or alkyl. Specific examples of the tetracarboxylic dianhydride compound represented by the formula (a-3-5) include at least one of compounds represented by the formula (a-3-5-1) to the formula (a-3-5-3) . Formula (a-3-5-1) (A-3-5-2) (A-3-5-3) Formula (a-3-6) In formula (a-3-6), A ₄ represents a divalent group containing an aromatic ring; A ₅ and A ₆ may be the same or different, and each independently represents -H or an alkyl group. . The tetracarboxylic dianhydride compound represented by the formula (a-3-6) is preferably a compound represented by the formula (a-3-6-1). Formula (a-3-6-1)

Specific examples of the fluorine-containing tetracarboxylic dianhydride compound may include, but are not limited to, 9,9-bis (trifluoromethyl) -9H-dibenzoran-2,3,6,7-tetracarboxylic dianhydride, A tetracarboxylic dianhydride compound represented by the following formula (a-3-7) to formula (a-3-13) or any combination of the above compounds: Formula (a-3-7) Formula (a-3-8) Formula (a-3-9) Formula (a-3-10) Formula (a-3-11) Formula (a-3-12) Formula (a-3-13) In formula (a-3-7), A ₇ and A ₈ may be the same or different, and each represents a hydrogen atom, an alkyl group, a fluorine atom, or a trifluoromethyl group, wherein, At least one of A ₇ and A ₈ is a fluorine atom or a trifluoromethyl group.

Preferably, the other tetracarboxylic dianhydride compounds (a3) include, but are not limited to, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride Anhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic acid Dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 7-oxabicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid Dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 8-thiabicyclo [3.2.2] nonane-2,3,6,7- Tetracarboxylic dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'- Benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 3,3', 4,4'-biphenylfluorenetetracarboxylic dianhydride, 9, 9-bis (trifluoromethyl) -9H-dibenzofuran-2,3,6,7-tetracarboxylic dianhydride, or the formula (a-3-8) or (a-3-10) Shown tetracarboxylic dianhydride compounds and the like. The other tetracarboxylic dianhydride compounds (a3) may be used alone or in combination.

Based on the total mole number of the diamine component (b) is 100 moles, the amount of the tetracarboxylic dianhydride component (a) used is preferably from 20 moles to 200 moles; more preferably from 30 moles to 120 mol. Diamine component ( b )

The diamine component (b) may be selected from an aliphatic diamine compound, an alicyclic diamine compound, and an aromatic diamine compound, such as the diamine compounds represented by the following formulae (b-1) to (b-15) or Fluorine-containing diamine compounds and the like.

Aliphatic diamine compounds include, but are not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1, 6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 4, 4'-diaminoheptane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamine -2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-di Amino-5-methylnonane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis (3-aminopropoxy) ethane, and the like.

The alicyclic diamine compound includes, but is not limited to, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, 1,3-di Aminocyclohexane, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienediamine, tricyclo [6.2.1.0 ^2,7 ] -undecenediene Methyldiamine, 4,4'-methylenebis (cyclohexylamine) and the like.

Aromatic diamine compounds include, but are not limited to, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylphosphonium, 4 4,4'-diaminobenzidine aniline, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amine 1-1- (4'-aminophenyl) -1,3,3-trimethylhydroindene, 6-amino-1- (4'-aminophenyl) -1,3,3-tri Methylindene, hexahydro-4,7-methyl bridged indenyldimethylene diamine, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone , 4,4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3- Bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 9,10-bis (4-aminophenyl) anthracene [9,10- bis (4-aminophenyl) anthracene], 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 4,4 '-(p-phenylene isopropylidene) bisaniline, 4,4'-(m-phenylene isopropylidene) bisaniline, 5- [4- (4-n-pentylalkyl) Cyclohexyl) cyclohexyl] phenyl-methylene-1,3-diaminobenzene {5- [4- (4-n-pentylcyclohexyl) cyclohexyl] pheny lmethylene-1,3-diamino benzene}, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane {1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane} and the like.

The diamine compounds represented by formula (b-1) to formula (b-15) are as follows: Formula (b-1) In formula (b-1), B ¹ represents , , , , ,or ; B ² represents a group having a steroid (cholesterol) skeleton, an alkyl group having 2 to 30 carbon atoms, or one derived from a nitrogen atom-containing cyclic structure such as pyridine, pyrimidine, triazine, piperidine, or piperazine Valence group.

Specific examples of the compound represented by the formula (b-1) include, but are not limited to, 2,4-diaminophenyl ethyl formate, 3,5-diaminophenyl ethyl formate Ester (3,5-diaminophenyl ethyl formate), 2,4-diaminophenyl propyl formate, 3,5-diaminophenyl propyl formate (3,5- diaminophenyl propyl formate), 1-dodecoxy-2,4-diaminobenzene, 1-dodecoxy-2,4-diaminobenzene, 1-dodecoxy-2,4-diaminobenzene ( 1-hexadecoxy-2,4-diaminobenzene), 1-octadecoxy-2,4-diaminobenzene, from formula (b-1-1) to formula At least one of the compounds represented by (b-1-4), or a combination thereof.

The compounds represented by the formula (b-1-1) to the formula (b-1-4) are as follows: Formula (b-1-1) (B-1-2) Formula (b-1-3) Formula (b-1-4)

In the formula (b-2) of formula (b-2), (b -1) ^{. 1} and B in the same formula B ^1, B ³ and B ⁴ each independently represents a divalent aliphatic ring, aromatic ring or two divalent A valent heterocyclic group; B ⁵ represents an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, a cyano group, or a halogen atom.

Specific examples of the compound represented by the formula (b-2) include at least one of compounds represented by the following formulae (b-2-1) to (b-2-8): Formula (b-2-1) Formula (b-2-2) (B-2-3) Formula (b-2-4) Formula (b-2-5) Formula (b-2-6) Formula (b-2-7) Formula (b-2-8) In formula (b-2-5) to formula (b-2-8), s represents an integer of 3 to 12.

Formula (b-3-3) In formula (b-3), B ⁶ each independently represents a hydrogen atom, a fluorenyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. Alkoxy or halogen atom, and B ⁶ in each repeating unit may be the same or different; u represents an integer of 1 to 3.

Specific examples of the compound represented by the formula (b-3) include when u is 1: p-diaminebenzene, m-diaminebenzene, o-diaminebenzene, 2,5-diaminotoluene, and the like; when u When 2: 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-di Aminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'- Dichloro-4,4'-diaminobiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4' -Diamino-5,5'-dimethoxybiphenyl or 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, etc .; or when u is 3: 1 , 4-bis (4'-aminophenyl) benzene and the like.

Specific examples of the compound represented by the formula (b-3) preferably include p-diaminobenzene, 2,5-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-dimethyl Oxy-4,4'-diaminobiphenyl, 1,4-bis (4'-aminophenyl) benzene or a combination thereof.

Formula (b-4) In Formula (b-4), k is an integer of 2-12.

Formula (b-5) In Formula (b-5), w represents an integer of 1 to 5. The compound represented by the formula (b-5) is preferably 4,4'-diamino-diphenylsulfide.

Formula (b-6) In formula (b-6), B ⁷ and B ⁹ each independently represent a divalent organic group, and B ⁷ and B ⁹ may be the same or different; B ⁸ represents a derivative derived from pyridine, pyrimidine, tris Divalent group of a cyclic structure containing a nitrogen atom such as azine, piperidine, or piperazine.

Formula (b-7) In formula (b-7), B ¹⁴ represents an oxygen atom or a cyclohexane group; B ¹⁵ represents a methylene group; B ¹⁶ represents a phenyl group or a cyclohexane group; B ¹⁷ represents hydrogen Atom or heptyl.

Specific examples of the compound represented by the formula (b-7) include a compound represented by the formula (b-7-1), a compound represented by the formula (b-7-2), or a combination thereof: (B-7-1) Formula (b-7-2)

The compounds represented by the formula (b-8) to the formula (b-15) are shown below. (B-8) (B-9) Formula (b-10) (B-11) (B-12) Formula (b-13) (B-14) (B-15)

The fluorine-containing diamine compound is preferably selected from 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2 , 2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (4-aminobenzene (Oxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1, 3,3,3-hexafluoropropane, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-amine (Phenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3- Hexafluoropropane, bis (2,3,5,6-tetrafluoro-4-aminophenyl) ether, bis (2,3,5,6-tetrafluoro-4-aminophenyl) sulfide, 2 , 2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, formula (b -16) to a diamine compound represented by the formula (b-43) or any combination thereof. (B-16) (B-17) (B-18) (B-19) Formula (b-20) (B-21) (B-22) (B-23) (B-24) (B-25) (B-26) (B-27) (B-28) (B-29) Formula (b-30) (B-31) (B-32) (B-33) (B-34) (B-35) (B-36) (B-37) (B-38) (B-39) Formula (b-40) (B-41) (B-42) (B-43)

These diamine components can be used singly or in combination. The diamine component preferably includes, but is not limited to, 1,2-diaminoethane, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 4,4'-di Aminodiphenylmethane, 4,4'-diaminodiphenyl ether, 5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diamine Phenylbenzene, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane, ethyl 2,4-diaminophenylcarboxylate , P-diaminobenzene, m-diaminebenzene, o-diaminebenzene, 4,4'-diaminobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, bis (2 , 3,5,6-tetrafluoro-4-aminophenyl) ether, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, or formula (b-1- 1), formula (b-1-2), formula (b-2-1), formula (b-2-6), formula (b-7-1), formula (b-23), formula (III- 25), a diamine compound represented by formula (b-26), formula (b-27) or formula (b-33). Method for preparing polymer ( A ) for preparing polyamino acid resin

The method for preparing polyamic acid resin comprises the following steps: firstly dissolving the mixture in a solvent, wherein the mixture comprises a tetracarboxylic dianhydride component (a) and a diamine component (b), and the temperature is from 0 ° C to 100 ° C; The polymerization is carried out at a temperature of from 1 hour to 24 hours. Next, the above reaction solution is distilled under reduced pressure by an evaporator to obtain a polyamic acid resin, or the above reaction solution is poured into a large amount of a lean solvent to obtain a precipitate. Then, the precipitate is dried and processed under reduced pressure to obtain a polyamino acid resin.

The solvent used in the polymerization reaction may be the same as or different from the solvent in the composition for a flexible substrate, and the solvent used in the polymerization reaction is not particularly limited as long as it can dissolve the reactant and the product. Preferably, the solvent includes, but is not limited to (1) an aprotic polar solvent: N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, diamine Methyl sulfene, γ-butyrolactone, tetramethyl urea, hexamethyl phosphate triamine, etc .; (2) Phenolic solvents: m-cresol, xylenol, phenol or halogenated phenols. Preferably, the used amount of the solvent used in the polymerization reaction ranges from 200 parts by weight to 2,000 parts by weight based on the total used amount of the mixture; more preferably, 300 to 1,800 parts by weight.

In particular, in the above-mentioned polymerization reaction, an appropriate amount of a lean solvent may be used in combination with the solvent, as long as the polyamic acid resin is not allowed to precipitate. The lean solvents can be used singly or in combination. The lean solvents include but are not limited to: (1) alcohols: methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butane Alcohol or triethylene glycol, etc .; (2) ketones: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc .; (3) esters: methyl acetate, ethyl acetate, butyl acetate Esters, diethyl oxalate, diethyl malonate, or ethylene glycol ethyl ether acetate; (4) ethers: diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethyl ether Glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether or diethylene glycol dimethyl ether, etc .; (5) halogenated hydrocarbons: methylene chloride, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene or o-dichlorobenzene, etc .; (6) hydrocarbons: tetrahydrofuran, hexane, heptane, octane, Benzene, toluene, xylene, etc .; or (7) any combination thereof. Preferably, the total amount of the diamine component is 100 parts by weight, and the amount of the lean solvent ranges from 0 to 60 parts by weight; more preferably, the amount of the lean solvent ranges from 0 to 50 parts by weight. Serving. Method for preparing polyfluorene imine resin

The method for preparing polyfluorene imine resin includes the following steps: dissolving the mixture in a solvent, wherein the mixture includes a tetracarboxylic dianhydride component (a) and a diamine component (b), and polymerizing to form a polyfluorinated resin In the presence of a dehydrating agent and a catalyst, further heating and dehydration ring-closing reaction are performed, so that the amido acid functional group generated during the polymerization reaction is converted into the amidine imine function (that is, amidine imidization).

The polymerization reaction and the dehydration ring-closing reaction can be carried out using the reaction temperature and reaction time of conventional operations in the field. Preferably, the operating temperature of the polymerization reaction ranges from 0 ° C to 100 ° C. Preferably, the operation time of the polymerization reaction ranges from 1 hour to 24 hours. Preferably, the operating temperature range of the dehydration ring-closing reaction is from 30 ° C to 200 ° C, and the operating time range of the dehydration ring-closing reaction is from 0.5 hours to 50 hours.

The solvent used in the dehydration ring-closing reaction may be the same as the solvent in the composition for a flexible substrate, and will not be described again. Preferably, the polyamine resin is used in an amount of 100 parts by weight, and the amount of the solvent used in the dehydration ring-closing reaction ranges from 200 parts by weight to 2,000 parts by weight. The solvent is used in an amount ranging from 300 parts by weight to 1,800 parts by weight.

The dehydrating agent used in the dehydration ring-closing reaction is selected from (1) acid anhydride compounds: acetic anhydride, propionic anhydride, or trifluoroacetic anhydride. Based on 1 mole of polyamic acid resin, the amount of dehydrating agent used ranges from 0.01 to 20 moles. The catalyst used in the dehydration ring-closing reaction is selected from (1) pyridine compounds: pyridine, trimethylpyridine or dimethylpyridine, etc .; (2) tertiary amine compounds: triethylamine, etc. Based on 1 mole of dehydrating agent, the amount of catalyst used ranges from 0.5 to 10 moles.

The polymer (A) of the present invention has a polystyrene-equivalent weight average molecular weight as measured by Gel Permeation Chromatography (GPC) of 10,000 to 90,000, preferably 12,000 to 75,000, and more preferably 15,000 to 60,000. Solvent ( B )

Specific examples of the solvent (B) include, but are not limited to, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, 4-hydroxy-4-methyl-2-pentanone, and ethylene glycol Monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, Ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Or N, N-dimethylformamide or N, N-dimethyl acetamide, etc. The solvent (B) may be used alone or in combination.

Based on 100 parts by weight of the polymer (A), 200 to 2000 parts by weight of the solvent (B), preferably 250 to 1800 parts by weight, and more preferably 300 to 1500 parts by weight. Additive ( C )

To the extent that the efficacy of the present invention is not affected, the composition for a flexible substrate may optionally include additives (C), where the additives (C) include, but are not limited to, fillers, plasticizers, weathering agents, viscosity modifiers, and surfaces. Treatment agents, antioxidants, defoamers, colorants, heat stabilizers, adhesion promoters, and release agents. The additives may be those used in the art.

Fillers include, but are not limited to, silicon dioxide (trade names such as IPA-ST (particle diameter 12nm), EG-ST (particle diameter 12nm), IPA-ST-L (particle diameter 45nm), IPA-ST-ZL (particle diameter 100nm), manufactured by Nissan Chemical Corporation), aluminum oxide, talc, calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, or a combination thereof.

Antioxidants include, but are not limited to, dibutylhydroxytoluene (trade names such as BHT, manufactured by Tokyo Chemical Industry (TCI) Co., Ltd.), 2,6-di-tert-butylphenol , Or a combination thereof.

Defoaming agents include, but are not limited to, silicon-based defoamers (trade names such as SH-203, manufactured by Toray-Dow corning Co., Ltd.), acetylene glycol-based defoamers (trade name such as Surfynol DF-100D , Surfynol DF-37, manufactured by Nissin Chemical Co., Ltd.), a silicon-based defoamer containing a fluorine atom (trade name such as FA-630, manufactured by Shin-Etsu Chemical Co., Ltd.), or a combination thereof.

The additive (C) may be used alone or in combination.

Based on the use amount of the polymer (A) being 100 parts by weight, the use amount of the additive (C) may be 0.1 to 40 parts by weight, and preferably 1 to 30 parts by weight. < Manufacturing method of composition for flexible substrates >

The method for producing the composition for a flexible substrate of the present invention is not particularly limited, and it can be prepared by a general mixing method. For example, the polymer (A) and the solvent (B) prepared in the above manner are first mixed uniformly to form a mixture. Next, the additive (C) is selectively added, and finally, stirring can be continued with a stirring device until it is dissolved.

At 25 ° C, the viscosity of the composition for a flexible substrate of the present invention can be adjusted according to the proportion of each component of the composition. The viscosity ranges from 100 cps to 20000 cps. In a preferred example, the viscosity of the composition for a flexible substrate The viscosity may be 120 cps to 18000 cps. In a more preferred example, the viscosity of the composition for a flexible substrate may be 150 cps to 15000 cps. < Method for forming flexible substrate >

The flexible substrate of the present invention is formed from the above-mentioned composition for a flexible substrate.

Specifically, the flexible substrate may be formed by applying the composition for a flexible substrate of the present invention to a substrate, drying it and hardening it, and then removing it from the substrate.

The coating method may adopt a known method, such as by a coating method such as spin coating, cast coating, or roll coating, and the details are not described again. The drying process can be performed in a known manner, and the purpose is to remove the solvent. The operating temperature range of the drying treatment is preferably 50 ° C to 200 ° C, and the time is 1 minute to 1 hour. The hardening process can adopt a known method, the purpose of which is to completely remove the residual solvent and to make the flexible substrate into a denser structure. The operating temperature range of the hardening process is preferably 150 ° C to 500 ° C, and the time is 10 minutes to 2 hours.

The detachment method can be a known method, such as tearing the flexible substrate directly from the substrate, removing the substrate using dry etching, or removing the substrate using wet etching.

The substrate includes, but is not limited to, alkali-free glass, soda-lime glass, rigid glass (Pales glass), quartz glass, or silicon wafer for a liquid crystal display device.

The flexible substrate of the present invention can be applied to a flexible liquid crystal display or an electronic book.

The present invention will be further described with reference to the following examples, but it should be understood that these examples are merely illustrative and should not be construed as limitations of the implementation of the present invention. < Example > Synthesis example of compound ( a1 ) represented by formula (a-1)

Synthesis Examples 1 to 8 of Compound (a1) represented by Formula (a-1) will be described below: Synthesis Example 1

A thermometer, a reflux tube, and a magnetic stirrer were placed on a 200-ml glass reaction vessel. Under a nitrogen environment, 22.11 g of trimellitic acid chloride (105 mmol) were dissolved in 25 g of acetonitrile in the reaction vessel, and then the reaction vessel was placed. The temperature was cooled to 5 ° C. Thereafter, 7.47 g of cyclohexane-1,4-diyldimethanol (50 millimoles, abbreviated as a-1) was dissolved in 30 g of acetonitrile, and 8.3 g of pyridine (hydrochloric acid trapping agent) was added ( 105 millimoles). The above solution was dropped into the aforementioned trimellitic acid chloride solution at 5 ° C within one hour. After the dropping was completed, the temperature was maintained at 35 ° C. and stirring was continued for 5 hours to obtain a product. After the above product was filtered, the above product was washed with acetonitrile to obtain white crystals. The white crystals were dried in a reduced-pressure environment of 5 mmHg and at 50 ° C. for 24 hours to obtain a tetracarboxylic dianhydride compound (a1-1) (that is, a compound represented by the formula (a-1-1)). Synthesis Examples 2 to 8

Synthetic Examples 2 to 8 were prepared by the same steps as Synthetic Example 1, except that the types, amounts, or reaction conditions of the compounds used were changed (as shown in Table 1).

The compounds corresponding to the numbers in Table 1 are shown below.

[Table 1] Synthesis example of polymer ( A )

Synthesis Examples A-1-1 to A-1-7, Synthesis Examples A-2-1 to A-2-7, and Comparative Synthesis Examples A'-1-1 to A'-1 are described below. -2, A'-2-1 to A'-2-2: Synthesis Example A-1-1

A 500-ml four-necked conical flask was provided with a nitrogen inlet, a stirrer, a condenser tube, and a thermometer, and nitrogen was introduced. Then, 5.41 g (0.05 mol) of p-diaminebenzene (abbreviated as b-1) and 70 g of N-methyl-2-pyrrolidone (abbreviated as NMP) were added and stirred at room temperature until dissolved. Next, 3.69 g (0.0075 mole) of the compound (a1) (abbreviated as a1-1) represented by the formula (a-1-1) and 12.0 g (0.04 mole) of the formula (a-2-1) were added. ) Compound (a2) (abbreviated a2-1), 0.89 g (0.0025 moles) of compound (a2) (abbreviated a2-4) represented by formula (a-2-12), and 30 g of NMP , And reacted at room temperature for 2 hours. After the reaction, the reaction solution was poured into 1500 ml of water to precipitate a polymer, the obtained polymer was filtered, and the steps of washing and filtering with methanol were repeated three times. After that, the product is placed in a vacuum oven and dried at a temperature of 60 ° C. to obtain a polymer (A-1-1). Synthesis Examples A-1-2 to A-1-7 and Comparative Synthesis Examples A-1'-1 to A-1'-2

Synthesis Examples A-1-2 to A-1-7 and Comparative Synthesis Examples A'-1-1 to A'-1-2 were prepared by the same procedures as in Synthesis Example A-1-1, respectively (A -1-2) to (A-1-7) and (A'-1-1) to (A'-1-2), and the difference is that: the type of monomer and its amount of use (as shown in the table 2). Synthesis Example A-2-1

A 500-ml four-necked conical flask was provided with a nitrogen inlet, a stirrer, a heater, a condenser tube, and a thermometer, and nitrogen was introduced. Then, 0.50 g (0.025 mole) of 4,4'-diaminodiphenylmethane (abbreviated as b-2) and 1.05 g (0.025 mole) of the formula (b-7-2) were added. The compound (b-3 for short) and 70 g of NMP were stirred at room temperature until dissolved. Next, 4.22 grams (0.0075 moles) of the compound (a1) (abbreviated as a1-8) represented by the formula (a-1-24) and 0.89 grams (0.04 moles) of the formula (a-2-12) were added. ) Compound (a2) (abbreviated a2-4) and 30 g of NMP. After 6 hours of reaction at room temperature. After the reaction, 97 g of NMP, 5.61 g of acetic anhydride, and 19.35 g of pyridine were added to the aforementioned reaction solution, the temperature was raised to 55 ° C., and stirring was continued for 2 hours to perform a dehydration ring-closing reaction. After the reaction, the reaction solution was poured into 1500 ml of water to precipitate a polymer, the obtained polymer was filtered, and the steps of washing and filtering with methanol were repeated three times. After that, the product was placed in a vacuum oven and dried at a temperature of 60 ° C. to obtain a polymer (A-2-1). Synthesis Examples A-2-2 to A-2-7 and Comparative Synthesis Examples A-2'-1 to A-2'-2

Synthesis Examples A-2-2 to A-2-7 and Comparative Synthesis Examples A'-2-1 to A'-2-2 were prepared by the same procedures as in Synthesis Example A-2-1, respectively (A -2-2) to (A-2-7) and (A'-2-1) to (A'-2-2), and they are different in that: the type of the monomer and its use amount, and dehydration The reaction temperature and reaction time of the ring-closing reaction (as shown in Table 3).

The compounds corresponding to the reference numerals in Tables 2 and 3 are shown below.

[Table 2]

[table 3] Examples of Compositions for Flexible Substrates Example 1

100 parts by weight of the polymer (A-1-1) of Synthesis Example A-1-1 and 200 parts by weight of NMP were weighed and stirred at room temperature to prepare the composition for the flexible substrate of Example 1 Thing.

The obtained composition for a flexible substrate was evaluated by the following evaluation method. The results are shown in Table 4. Examples 2 to 14 and Comparative Examples 1 to 4

Examples 2 to 14 and Comparative Examples 1 to 4 use the same preparation method as the composition for a flexible substrate of Example 1, except that Examples 2 to 14 and Comparative Examples 1 to 4 change the raw materials in the composition for a flexible substrate Table 4 and Table 5 show the types and usage amounts, their formulations and evaluation results, respectively.

The compounds corresponding to the abbreviations in Tables 4 and 5 are shown below.

[Table 4]

[table 5] ＜ Evaluation method ＞ Phase difference

The compositions for flexible substrates of Examples 1 to 14 and Comparative Examples 1 to 4 were applied to a glass substrate having a size of 100 mm × 100 mm by spin coating. Then, a pre-bake coating film having a thickness of 10 μm can be formed after pre-baking at 80 ° C. for 20 minutes. Then, post-baking is performed at 260 ° C. After 30 minutes, a laminated body including a glass substrate and a flexible substrate can be obtained. Refractive index in the X-axis direction of a flexible substrate on a laminated body was measured with an optical material inspection device (model RTS-100) manufactured by Otsuka Electronics Co., Ltd. at room temperature (20 ° C) with light having a wavelength of 550 nm. The refractive index ny in the nx, Y-axis directions, and the refractive index nz in the Z-axis direction. Then, based on the refractive index nx in the X-axis direction, the refractive index ny in the Y-axis direction, the refractive index nz in the Z-axis direction, and the thickness (d) of the film, a phase difference (Rth) in the thickness direction is calculated according to the following formula. Rth (nm) = [nz- (nx + ny) / 2] × d, and the obtained value is converted into a value when the thickness (d) is 10 μm, and evaluated based on the following criteria: ：: Rth <10 nm ○: 10 nm ≦ Rth <50 nm △: 50 nm ≦ Rth <200 nm ╳: 200 nm ≦ Rth ＜ Evaluation result ＞

As can be seen from Tables 4 and 5, when the tetracarboxylic dianhydride component (a) of the polymer (A) in the composition for a flexible substrate is different, the compound (a1) represented by the formula (a-1) and In the compound (a2) (Comparative Examples 1 to 4) represented by the formula (a-2), the phase difference of the formed flexible substrate is not good.

In addition, when the tetracarboxylic dianhydride component (a) of the polymer (A) in the composition for a flexible substrate includes a compound having a structure represented by the formula (a-1-x) as the compound (a1) ( In Examples 1 to 3, 5, 9 to 13), the phase difference of the formed flexible substrate is better.

In addition, when the tetracarboxylic dianhydride component (a) of the polymer (A) in the composition for a flexible substrate includes a compound in which R in the formula (a-1) represents an alkylene group having 1 to 3 carbon atoms, When it is the compound (a1) (Examples 1, 5 to 7, 9, 12 to 14), the phase difference of the formed flexible substrate is also better.

In summary, in the composition for a flexible substrate of the present invention, the tetracarboxylic dianhydride component (a) in the mixture forming the polymer (A) includes the compound (a1) represented by the formula (a-1) Since the compound (a2) represented by the formula (a-2) is used, the problem of poor phase difference can be improved in a flexible substrate obtained by using the composition for a flexible substrate.

On the other hand, in the composition for a flexible substrate of the present invention, the tetracarboxylic dianhydride component (a) in the mixture forming the polymer (A) includes a structure represented by the formula (a-1-x) Compound or R in the formula (a-1) represents a compound having an alkylene group having 1 to 3 carbons as the compound (a1), which makes the retardation of the flexible substrate better, and is therefore suitable for manufacturing a flexible liquid crystal display or EBook.

Although the present invention has been disclosed as above with the examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouching without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the attached patent application.

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Claims (7)

A composition for a flexible substrate includes: a polymer (A); and a solvent (B), wherein the polymer (A) is obtained by reacting a mixture including a tetracarboxylic dianhydride component (a ) And a diamine component (b), the tetracarboxylic dianhydride component (a) includes a compound (a1) represented by the formula (a-1) and a compound (a-2) a2): Formula (a-1) In formula (a-1), R each independently represents an alkylene group having 1 to 6 carbon atoms; R _X represents a divalent aliphatic cyclic hydrocarbon group, and the divalent aliphatic cyclic hydrocarbon group is A divalent group substituted or substituted with a halogen atom, a linear hydrocarbon group, or a branched hydrocarbon group, Formula (a-2) In formula (a-2), R ₁ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and R ₂ each independently represents a hydrogen atom, a methyl group, or an ethane group. The composition for a flexible substrate according to item 1 of the scope of patent application, wherein in the formula (a-1), the R _x has a structure represented by the formula (a-1-x): Formula (a-1-x) In formula (a-1-x), m represents an integer of 0 to 4; R and _Z each independently represent a halogen atom, a linear hydrocarbon group having 1 to 4 carbon atoms, and 1 carbon number A branched hydrocarbon group of 4 or a plurality of R _Z are connected to each other to form a cyclic structure. The composition for a flexible substrate according to item 1 of the scope of the patent application, wherein in the formula (a-1), each of R independently represents an alkylene group having 1 to 3 carbon atoms. The composition for a flexible substrate according to item 1 of the scope of patent application, wherein the total mole number based on the tetracarboxylic dianhydride component (a) is 100 moles, and the formula is represented by formula (a-1) The used amount of the compound (a1) is 15 to 85 mol, and the used amount of the compound (a2) represented by the formula (a-2) is 15 to 85 mol. The composition for a flexible substrate according to item 1 of the scope of the patent application, wherein the total amount of the polymer (A) used is 100 parts by weight, and the amount of the solvent (B) is 200 to 2000 parts by weight. The composition for a flexible substrate according to item 1 of the scope of the patent application, wherein the viscosity of the composition for a flexible substrate is from 100 cps to 20,000 cps at 25 ° C. A flexible substrate includes the composition for a flexible substrate according to any one of claims 1 to 6 of the scope of patent application.