TWI690544B - Flexible substrate composition, method of producing the same and flexible substrate - Google Patents

Abstract

The present invention provides a flexible substrate composition, a method of producing the same and a flexible substrate. The flexible substrate composition is produced by mixing a mixture of a polymer (A) and a solvent (B), in which the polymer (A) is obtained by reacting a mixture of tetracarboxylic dianhydride component (a) and diamine component (b), and the diamine component (b) includes a diamine compound (b-1). The flexible substrate composition has a specific viscosity, thereby producing the flexible substrate having sufficient toughness.

Description

Composition for flexible substrate, its manufacturing method and flexible substrate

The present invention relates to a composition for a flexible substrate, a method for manufacturing the same, and a flexible substrate, and particularly relates to a composition for a flexible substrate having a specific viscosity and a method for manufacturing the same, to obtain a flexible substrate with good toughness.

In recent years, organic polymer materials have been widely used in various electronic components or devices to improve various characteristics of electronic components or devices (eg, electrical insulation, heat resistance, mechanical properties, etc.). 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 transparent flexible substrates. The polyimide precursor is prepared by reacting diamine (including fluorine-containing benzidine and 1,4-cyclohexanediamine) with tetracarboxylic dianhydride, and the above composition can form a highly transparent flexible substrate . However, when the above-mentioned polyimide precursor is heated and hardened to form polyimide, the problem of poor toughness tends to occur, which cannot meet the needs of the industry.

Therefore, there is an urgent need 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.

One aspect of the present invention is to provide a composition for a flexible substrate, which contains a polymer (A) and a solvent (B) and has a viscosity within a specific range.

Another aspect of the present invention is to provide a flexible substrate including the above-mentioned composition for a flexible substrate.

Another aspect of the present invention is to provide a method for manufacturing a composition for a flexible substrate, which includes a mixed polymer (A) and a solvent (B), wherein the polymer (A) can utilize the tetracarboxylic dianhydride component (a ) And the diamine component (b) are prepared by reaction.

Another aspect of the present invention is to provide a flexible substrate, which may include a composition for a flexible substrate formed by the above-described manufacturing method.

According to the above aspect of the present invention, first, a composition for a flexible substrate is proposed. In one embodiment, the composition for a flexible substrate may include a polymer (A) and a solvent (B), and at 25° C., the viscosity of the composition for a flexible substrate may be 100 cps to 20,000 cps. In a preferred example, the viscosity of the flexible substrate composition may be 120 cps to 18,000 cps. In a more preferred example, the viscosity of the flexible substrate composition may be 150 cps to 15,000 cps. Hereinafter, the polymer (A) and the solvent (B) contained in the composition for a flexible substrate will be described separately.

Polymer (A)

The polymer (A) is selected from the group consisting of polyamide resins, polyimide resins, or any combination of the above resins, and the polymer (A) may include a tetracarboxylic dianhydride component (a) and a diamine component (b) A mixture is prepared by reaction.

The polymer (A) of the present invention may include a structure represented by the following formula (I):

In formula (I), Z _{1 is} each and independently an ether bond or an ester bond; R _{1 is} each and independently a single bond, methylene or an alkylene group having 2 to 6 carbon atoms; R _{2 is} each and independently Is a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; R ₃ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 9 carbon atoms, and 1 to 9 carbon atoms Alkoxy, cycloalkyl having 3 to 12 carbons, aryl having 6 to 12 carbons; m is an integer from 0 to 4; and, * ^a represents a bond.

In one embodiment, the polymer (A) further includes a structure represented by the following formula (II):

In formula (II), * ^b represents the bond, and X represents the structure of the following formula (II-1):

In formula (II-1), Y represents a single bond, -O-, -CH ₂ -, -SO ₂ -, -C(CH ₃ ) ₂ -or -C(CF ₃ ) ₂ -, and * ^c Represents the bond between the structure of formula (II-1) and X of formula (II).

Tetracarboxylic dianhydride component (a)

The tetracarboxylic dianhydride component can be selected from aliphatic tetracarboxylic dianhydride compounds, alicyclic tetracarboxylic dianhydride compounds, aromatic tetracarboxylic dianhydride compounds, and the following formula (IV-1) to formula (IV -6) The tetracarboxylic dianhydride compound and the fluorine-containing tetracarboxylic dianhydride compound shown in FIG.

Specific examples of the aliphatic tetracarboxylic dianhydride compound may include, but are not limited to, aliphatic tetracarboxylic dianhydride components such as ethane tetracarboxylic dianhydride or butane tetracarboxylic dianhydride.

Specific examples of the alicyclic tetracarboxylic dianhydride compound may include, but are not limited to, 1,2,3,4-cyclobutane tetracarboxylic 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-ring 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 ring An alicyclic tetracarboxylic dianhydride compound such as heptyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride or 2,3,5-tricarboxycyclopentylacetic acid dianhydride.

The alicyclic tetracarboxylic dianhydride compound may also include a bicyclic alicyclic tetracarboxylic dianhydride compound. Preferably, the bicyclic alicyclic tetracarboxylic dianhydride compound has a tetravalent bridged hydrocarbon group with a total number of atoms of 7 to 9, and one of the bridges of the tetravalent bridged hydrocarbon group 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, bicyclic [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, bicyclic[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 dianhydride, 7-thia Bicyclo[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 dianhydride, bicyclic[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-tetracarboxy Acid dianhydride, 8-oxabicyclo[3.2.2]nonane-2,3,6,7-tetracarboxylic dianhydride, 8-oxabicyclo[3.2.2]nonane-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, etc.

Specific examples of the aromatic tetracarboxylic dianhydride compound may include but are not limited to 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'- Biphenyl tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3'-4,4'-di Phenylethanetetracarboxylic 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) diphenyl sulfide dianhydride, 2,3,3',4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl dianhydride, 4,4'-bis( 3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 2,3,3',4'-diphenyltetracarboxylic acid Acid dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) ) Dianhydride, m-phenylene-bis (triphenyl phthalic acid) dianhydride, bis (triphenyl phthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylbenzene Diacid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis (dehydrated trimellitate), propylene glycol-bis (dehydrated trimellitate), 1,4-butanediol- Bis(dehydrated trimellitate), 1,6-hexanediol-bis(dehydrated trimellitate), 1,8-octanediol-bis(dehydrated trimellitate), 2,2- Bis(4-hydroxyphenyl)propane-bis(anhydrotrimellitic acid ester), 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro- 5-(tetrahydro-2,5-bi- pendant-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5, 9b-Hexahydro-5-methyl-5-(tetrahydro-2,5-bi- pendant-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2,5-bi- pendant-3-furanyl)-naphtho[1,2-c] -Furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-bi- pendant-3-enyl) )-Naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5 -Bi- pendant-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl Yl-5-(tetrahydro-2,5-bi- pendant-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4, 5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-bi- pendant-3-furanyl)-naphtho[1,2-c]-furan-1,3-di Ketone, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-bi- pendant-3-furanyl)-naphtho[1 ,2-c]-furan-1,3-dione, 5-(2,5-bi- pendant tetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride Wait.

The components of tetracarboxylic dianhydride represented by formula (IV-1) to formula (IV-6) are as follows:

In formula (IV-5), A ₁ represents a divalent group containing an aromatic ring; a represents an integer of 1 to 2; A ₂ and A ₃ may be the same or different, and may represent a hydrogen atom or an alkyl group, respectively. Preferably, the tetracarboxylic dianhydride component represented by formula (IV-5) can be selected from the compounds represented by the following formula (IV-5-1) to formula (IV-5-3).

In formula (IV-6), A ₄ represents a divalent group containing an aromatic ring; A ₅ and A ₆ may be the same or different, and each represents a hydrogen atom or an alkyl group. Preferably, the tetracarboxylic dianhydride component represented by formula (IV-6) can be selected from compounds represented by the following formula (IV-6-1).

Specific examples of fluorine-containing tetracarboxylic dianhydride compounds may include, but are not limited to 9,9-bis(trifluoromethyl)-9H-dibenzopyran-2,3,6,7-tetracarboxylic dianhydride, The tetracarboxylic dianhydride compound represented by the following formula (IV-7) to formula (IV-13) or any combination of the above compounds:

In formula (IV-7), at least one of A ₇ and A ₈ is a fluorine atom or a trifluoromethyl group.

The above tetracarboxylic dianhydride components can be used alone or in combination. The tetracarboxylic dianhydride component preferably includes but is not limited to 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2, 3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, bicyclic [2.2.1]Heptane-2,3,5,6-tetracarboxylic dianhydride, 7-oxabicyclo[2.2.1]Heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclic [2.2.2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 8-thiabicyclo[3.2.2]nonane-2,3,6,7-tetracarboxylic dicarboxylic acid Anhydride, 3,4-dicarboxy-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'-biphenyl tetracarboxylic dianhydride, 9,9-bis( Trifluoromethyl)-9H-dibenzofuran-2,3,6,7-tetracarboxylic dianhydride, or a tetracarboxylic dianhydride compound represented by formula (IV-8) or formula (IV-10) Wait.

Based on the total mole number of the diamine component (b) being 100 moles, the usage amount of the tetracarboxylic dianhydride component is preferably 20 moles to 200 moles, more preferably 30 moles to 120 moles.

Diamine component (b)

The diamine component (b) of the present invention contains at least one diamine compound (b-1). In a preferred example, the diamine component (b) may further include a diamine compound (b-2). In addition, the diamine component (b) may optionally add other diamine compounds (b-3). It is described below.

Diamine compound (b-1)

The diamine compound (b-1) referred to herein may include the structure represented by the following formula (I'):

In formula (I'), Z _{1 is} each and independently an ether bond or an ester bond; R _{1 is} each and independently a single bond, methylene or an alkylene group having 2 to 6 carbon atoms; R _{2 is} each and independently Ground is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms; R ₃ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 9 carbon atoms, and a carbon number is 1 to An alkoxy group of 9, a cycloalkyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms; and, m is an integer of 0 to 4.

Specifically, specific examples of the above-mentioned diamine compound (b-1) may include compounds represented by the following formula (I'-1) to formula (I'-26).

The above-mentioned diamine compound (b-1) is synthesized by a combination of appropriate organic chemical standard methods. The following uses some examples to illustrate the synthesis of the diamine compound (b-1) of the present invention. However, it should be particularly noted that the diol compound and diacid compound used in the following, nitrobenzoyl chloride and fluoronitrobenzene can be arbitrarily combined, and the present invention is not limited to the examples given.

In one embodiment, the synthesis method of the diamine compound (b-1) of the above formula (I'-1) to formula (I'-16) is as follows. First, 1 equivalent of a diol compound is reacted with 2 equivalents of 4-fluoronitrobenzene (4-fluoronitrobenzene) to form a dinitro compound. Next, the aforementioned nitro group is reduced to an amine group with an appropriate reducing agent to synthesize the diamine compound (b-1) of the aforementioned formula (I'-1) to formula (I'-16). For example, by using 1,3-dioxane-5,5-dimethanol as the diol compound, the diamine compound represented by the formula (I'-1) can be prepared. If 1,3-dioxane-5,5-dimethanol is replaced with 2-methyl-1,3-dioxane-5,5-dimethanol, it can be prepared as formula (I'-2) The diamine compound shown. In another example, if 2-butyl-1,3-dioxane-5,5-dimethanol is used as the diol compound, and the aforementioned 4-fluoronitrobenzene is replaced with 3-fluoronitrobenzene , The diamine compound with the amine group in the meta position as shown in formula (I'-4) can be prepared.

In one embodiment, the synthesis method of the diamine compound (b-1) of the above formula (I'-17) to formula (I'-23) is as follows. First, 1 equivalent of a diol compound is reacted with 2 equivalents of 4-nitrobenzoyl chloride to form a dinitro compound. Next, the aforementioned nitro group is reduced to an amine group with an appropriate reducing agent to synthesize the diamine compound (b-1) of the aforementioned formula (I'-17) to formula (I'-23). For example, if 2,2-dimethyl-1,3-dioxane-5,5-dimethanol is used as the diol compound, the diamine represented by formula (I'-17) can be prepared Compound. If 2,2-dimethyl-1,3-dioxane-5,5-dimethanol is replaced with 2-ethyl-1,3-dioxane-5,5-dimethanol, it can be obtained The diamine compound represented by the formula (I'-18). On the other hand, if 2-benzyl-1,3-dioxane-5,5-dimethanol is used as the diol compound, and 4-nitrobenzyl chloride is replaced by 3-nitrobenzyl chloride Chlorine can produce a diamine compound with the amine group in the meta position as formula (I'-22).

In one embodiment, the synthesis method of the diamine compound (b-1) of the above formula (I'-24) to formula (I'-26) is as follows. First, 1 equivalent of the diacid compound is reacted with 2 equivalents of 4-fluoronitrobenzene to form a dinitro compound. Next, by reducing the aforementioned nitro group to an amine group, the diamine compound (b-1) according to the aforementioned formula (I'-24) to formula (I'-26) can be synthesized. For example, with 2,2'-(1,3-dioxane-5,5-diyl)diacetic acid as the diacid compound, the diamine represented by formula (I'-24) can be prepared Compound. If 2,2'-(1,3-dioxane-5,5-diyl)diacetic acid is replaced by 2-heptyl-1,3-dioxane-5,5-dicarboxylic acid, then The diamine compound represented by the formula (I'-25) is prepared. On the other hand, if 2-methyl-1,3-dioxane-5,5-dicarboxylic acid is used as the diacid compound, and 4-fluoronitrobenzene is replaced with 3-fluoronitrobenzene, then A diamine compound having the meta position in the amine group as shown in formula (I'-26) is prepared.

In one example, the aforementioned diol compounds may include, but are not limited to, 1,3-dioxane-5,5-dimethanol, 2-methyl-1,3-dioxane-5,5-dioxane Methanol, 2-propyl-1,3-dioxane-5,5-dimethanol, 2-butyl-1,3-dioxane-5,5-dimethanol, 2-hexyl-1,3- Dioxane-5,5-dimethanol, 2-isopropyl-1,3-dioxane-5,5-dimethanol, 2-nonyl-1,3-dioxane-5,5-dioxane Methanol, 1,3-dioxane-5-methanol-5-n-propanol, 2-ethoxy-1,3-dioxane-5,5 dimethanol, 2-(chloromethyl)-1, 3-dioxane-5,5-dimethanol, 2-phenyl-1,3-dioxane-5,5-dimethanol, 2-phenethyl-1,3-dioxane-5,5 -Dimethanol, 2-(naphthalen-2-yl)-1,3-dioxane-5,5-dimethanol, 2-([1,1'-bis(cyclohexyl)]-4-yl)- 1,3-dioxane-5,5-dimethanol, 2-phenyl-1,3-dioxane-5,5-diol, 2-([1,1'-diphenyl]-4 -Yl)-1,3-dioxane-5,5-dimethanol, 2,2-dimethyl-1,3-dioxane-5,5-dimethanol, 2-ethyl-1,3 -Dioxane-5,5-dimethanol, 2-pentyl-1,3-dioxane-5,5-dimethanol, 2-methyl-1,3-dioxane-5,5-dioxane Ethanol, 2-propoxy-1,3-dioxane-5,5-dimethanol, 2-benzyl-1,3-dioxane-5,5-dimethanol or 2-(p-toluene )-1,3-dioxane-5,5-dimethanol.

In one example, the aforementioned diacid compound may include, but is not limited to 2,2'-(1,3-dioxane-5,5-diyl)diacetic acid, 2-heptyl-1,3- Dioxane-5,5-dicarboxylic acid or 2-methyl-1,3-dioxane-5,5-dicarboxylic acid.

In one example, the aforementioned reducing agents include but are not limited to zinc, hydrazine, hydrazine hydrate, hydrazine sulfate, hydrazine carbonate, and hydrazine hydrochloride.

The diamine compound (b-1) can be used alone or in combination.

The use amount of the diamine component (b) is 100 mol, and the use amount of the diamine compound (b-1) is 5 mol to 60 mol, preferably 8 mol to 55 mol, and then 10 Molar to 50 molar is better.

If the diamine compound (b-1) is not used, the toughness of the resulting flexible substrate is not good.

Diamine compound (b-2)

The diamine compound (b-2) of the present invention may include the structure of the following formula (II'):

In formula (II), X represents the structure of the following formula (II-1):

In formula (II-1), Y represents a single bond, -O-, -CH ₂ -, -SO ₂ -, -C(CH ₃ ) ₂ -or -C(CF ₃ ) ₂ -, and * ^c Represents the bond between X of formula (II-1) and formula (II').

Specifically, the diamine compound (b-2) including the structure represented by the formula (II′) may include, but not limited to, 2,2-bis(4-aminophenoxy(4-phenyl))propane , 2,2-bis(4-aminophenoxy(4-phenyl))hexafluoropropane, 4,4'-bis(4-aminophenoxy)diphenyl(4,4'-Bis (4-aminophenoxy)biphenyl), bis[4-(4-aminophenoxy)phenyl] phenanthrene or bis[4-(3-aminophenoxy)phenyl] phenanthrene.

In the above example, the diamine compound (b-2) is preferably 2,2-bis(4-aminophenoxy(4-phenyl))propane, 4,4'-bis(4-amino Phenoxy) diphenyl or bis[4-(4-aminophenoxy)phenyl] benzene.

The use amount of the diamine component (b) is 100 mol, and the use amount of the diamine compound (b-2) is 10 mol to 95 mol, preferably 15 mol to 92 mol, and then 20 Mole to 90 mole is better.

If the diamine component (b) of the present invention contains a diamine compound (b-2), the toughness of the obtained flexible substrate can be further improved.

In particular, the structure represented by the formula (I) included in the polymer (A) of the present invention can be referred to the content of the above-mentioned diamine compound (b-1); and, the polymer (A) of the present invention For the structure represented by the formula (II), please refer to the content of the above diamine compound (b-2). The difference is that the structures of the above formula (I) and formula (II) make the diamine compound (b-1) of the aforementioned formula (I′) and the diamine compound (b-2) of the formula (II′) respectively Dehydration condensation with tetracarboxylic dianhydride component (a) to form an amide bond (that is, the bond represented by * ^a and * ^b ).

Other diamine compounds (b-3)

The diamine component (b) of the present invention can optionally contain other diamine compounds (b-3), which can be selected from aliphatic diamine compounds, alicyclic diamine compounds, and aromatic diamine compounds, as follows The diamine compounds represented by formulae (III-1) to (III-15) or fluorine-containing diamine compounds, etc., and the other diamine compounds (b-3) described above may be used singly or in combination.

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 Yl-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, etc.

Alicyclic diamine compounds include, but are not limited to 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, 1,3-di Aminocyclohexane, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, tricyclo[6.2.1.02,7]-eleven Carbene dimethyl diamine, 4,4'-methylene bis (cyclohexylamine), etc.

Aromatic diamine compounds include, but are not limited to 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylbenzene, 4 ,4'-diaminobenzylaniline, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amine Yl-1-(4'-aminophenyl)-1,3,3-trimethylhydroindene, 6-amino-1-(4'-aminophenyl)-1,3,3-tri Methylhydroindene, hexahydro-4,7-methyl bridged indanyl dimethylene 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-diamino stilbene, 9,9-bis(4-aminophenyl) stilbene, 4,4'-methylene-bis(2-chloroaniline), 4,4'-(p-phenylene isopropylidene) bisaniline, 4,4'-(m-phenylene isopropylidene) bisaniline, 5-[4-(4-n-pentyl (Cyclohexyl)cyclohexyl]phenyl-methylene-1,3-diaminobenzene{5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenyl methylene-1,3-diaminobenzene}, 1,1- Bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane{1,1-bis[4-(4-amino phenoxy)phenyl]-4- (4-ethylphenyl)cyclohexane} etc.

The diamine compounds represented by formulae (III-1) to (III-15) are as follows:

In formula (III-1), B ₁ represents -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -CO-; B ₂ represents a steroid (steroid) skeleton and the carbon number is The alkyl group of 2 to 30 or a monovalent group derived from a nitrogen atom-containing cyclic structure such as pyridine, pyrimidine, triazine, piperidine, and piperazine.

The diamine compound represented by formula (III-1) is preferably selected from 2,4-diaminophenyl ethyl formate and 3,5-diaminophenyl formic acid Ethyl (3,5-diaminophenyl ethyl formate), 2,4-diaminophenyl propyl formate (2,4-diaminophenyl propyl formate), 3,5-diaminophenyl propyl formate (3,5 -diaminophenyl propyl formate), 1-dodecoxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene (1-hexadecoxy-2,4-diaminobenzene), 1-octadecyloxy-2,4-diaminobenzene (1-octadecoxy-2,4-diaminobenzene) or the following formula (III-1-1) to The diamine compound represented by the formula (III-1-4).

In formula (III-2), B ₃ represents -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -CO-; B ₄ and B ₅ represent aliphatic ring, aromatic ring A bivalent group of a ring or a heterocyclic ring; B ₆ represents an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, a cyano group or a chlorine atom. Preferably, the diamine compound represented by the formula (III-2) is selected from diamine compounds represented by the following formula (III-2-1) to formula (III-2-8):

In formula (III-2-5) to formula (III-2-8), b may represent an integer of 3 to 12.

In formula (III-3), B ₇ represents hydrogen, an acetyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an alkoxy group or a chlorine atom having 1 to 5 carbon atoms, and each B ₇ in the repeating units may be the same or different; B ₈ is an integer from 1 to 3.

The diamine compound represented by formula (III-3) is preferably selected from (1) B ₈ is 1: p-diamine benzene, m-diamine benzene, o-diamine benzene or 2,5-diamine Toluene, etc.; (2) B ₈ is 2: 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl -4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl Benzene, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl or 2,2'- Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, etc.; (3) B ₈ is 3:1,4-bis(4'-aminophenyl)benzene, etc., More preferably, it is selected from p-diaminebenzene, 2,5-diaminetoluene, 4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl Benzene or 1,4-bis(4'-aminophenyl)benzene.

In formula (III-4), B ₉ is an integer of 2 to 12.

In formula (III-5), B ₁₀ represents an integer of 1 to 5. The formula (III-5) is preferably selected from 4,4′-diaminodiphenyl sulfide.

In formula (III-6), B ₁₁ and B ₁₂ may be the same or different, and each represents a divalent organic group, and B ₁₃ represents a nitrogen-containing atom derived from pyridine, pyrimidine, triazine, piperidine, and piperazine. Bivalent group of ring structure.

In formula (III-7), B ₁₄ represents -O- or cyclohexane, B ₁₅ represents -CH ₂ -, B ₁₆ represents phenyl or cyclohexane, and B ₁₇ represents hydrogen or heptyl .

The diamine compound represented by the formula (III-7) is preferably selected from the diamine compounds represented by the following formula (III-7-1) to formula (III-7-2).

The other diamine compounds (b-3) represented by formula (III-8) to formula (III-15) are shown below.

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-amino 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, the following formula ( III-16) to the diamine compound represented by the formula (III-43) or any combination of the above compounds.

The above-mentioned diamine components can be used alone 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 Benzene, 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 (III-1- 1), formula (III-1-2), formula (III-2-1), formula (III-2-6), or formula (III-7-1), formula (III-23), formula (III -25), the diamine compound represented by formula (III-26), formula (III-27) or formula (III-33). The use amount of the diamine component (b) is 100 moles, and the use amount of the other diamine compounds (b-3) is 0 moles to 85 moles, preferably 0 moles to 77 moles, and then 0 mole to 70 mole is better.

Manufacturing method of polymer (A)

Method for preparing polyamide resin

The preparation method of the polyamic acid resin includes the following steps: dissolving a mixture including the tetracarboxylic dianhydride component and the diamine component in a solvent, and carrying out the polymerization reaction at a temperature of 0°C to 100°C for 1 hour To 24 hours. Next, the above reaction solution is distilled under reduced pressure in an evaporator to obtain a polyamide resin, or the above reaction solution is poured into a large amount of lean solvent to obtain a precipitate. Then, the precipitate is dried by vacuum drying to obtain a polyamic 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) Aprotic polar solvents: N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, di Methyl sulfoxide, γ-butyrolactone, tetramethylurea or hexamethylphosphate triamine, etc.; (2) Phenolic solvents: m-cresol, xylenol, phenol or halogenated phenols, etc. Preferably, based on the total amount of the mixture used is 100 parts by weight, the amount of solvent used in the polymerization reaction ranges from 200 parts by weight to 2,000 parts by weight; more preferably, the amount of solvent used in the polymerization reaction ranges From 300 parts by weight to 1,800 parts by weight.

In particular, in the above-mentioned polymerization reaction, an appropriate amount of a poor solvent may be used in combination as long as the polyacrylic acid resin is not precipitated. The lean solvent can be used alone or in combination, and the lean solvent includes but is 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 Ester, 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 of the above. Preferably, based on the total use amount of the diamine component is 100 parts by weight, the use amount of the poor solvent ranges from 0 parts by weight to 60 parts by weight; more preferably, the use amount of the poor solvent ranges from 0 parts by weight to 50 parts by weight Copies.

Method for preparing polyimide resin

The preparation method of the polyimide resin includes the following steps: dissolving the mixture including the tetracarboxylic dianhydride component and the diamine component in a solvent, and performing a polymerization reaction to form a polyamic acid resin, and in a dehydrating agent and a catalyst In the presence of, further heating and dehydration ring-closing reaction, so that the amide acid functional group generated during the polymerization reaction is converted into an amide imine functional group (ie, imidate).

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

The solvent used in the dehydration ring-closure reaction may be the same as the solvent in the composition for the flexible substrate, so it will not be described in detail. Preferably, the amount of use based on the polyamide resin is 100 parts by weight, and the amount of solvent used in the dehydration ring-closure reaction ranges from 200 parts by weight to 2,000 parts by weight, more preferably, the amount used in the dehydration ring-closure reaction The amount of solvent used ranges from 300 parts by weight to 1,800 parts by weight.

The dehydrating agent used in the dehydration ring-closure reaction is selected from (1) acid anhydride compounds: acetic anhydride, propionic anhydride or trifluoroacetic anhydride. Based on 1 mol of polyamide resin, the amount of dehydrating agent used ranges from 0.01 mol to 20 mol. The catalyst used in the dehydration ring-closure reaction is selected from (1) pyridine compounds: pyridine, trimethylpyridine or lutidine; (2) tertiary amine compounds: triethylamine and the like. Based on the dehydrating agent being 1 mol, the amount of catalyst used ranges from 0.5 mol to 10 mol.

The polymer (A) of the present invention has a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of 10,000 to 90,000, preferably 12,000 to 75,000, and more preferably 15,000 to 60,000.

Solvent (B)

Preferably, the solvent (B) used in the composition for flexible substrates is selected from N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, 4-hydroxy-4-methyl 2-pentanone, 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, N, N -Dimethylformamide, N,N-dimethylacetamide, or a combination of these.

The use amount of the polymer (A) is 100 parts by weight, and the use amount of the solvent (B) is 200 to 2,000 parts by weight, preferably 250 to 1,800 parts by weight, more preferably 300 to 1,500 parts by weight Copies.

Additive (C)

To the extent that it does not affect the efficacy of the present invention, the composition for flexible substrates may optionally add additives (C), where the additives (C) include but are not limited to fillers, plasticizers, weathering agents, viscosity modifiers, surfaces Treatment agent, antioxidant, defoamer, colorant, heat stabilizer, adhesion aid, release agent, etc. The additives may be those used in the field.

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

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

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

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

The amount of use of the polymer (A) is 100 parts by weight, and the amount of use of the additive (C) may be 0.1 to 40 parts by weight, and preferably 1 to 30 parts by weight.

Method for preparing composition for flexible substrate

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

At 25°C, the viscosity of the composition for flexible substrates of the present invention can be adjusted according to the proportion of each component of the composition, and the viscosity ranges from 100 cps to 20,000 cps. In a preferred example, the viscosity of the composition for flexible substrates It may be 120 cps to 18,000 cps. In a more preferred example, the viscosity of the composition for flexible substrates may be 150 cps to 15,000 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, for the formation method of the flexible substrate, the composition for a flexible substrate of the present invention may be coated on a base material, and after drying and curing treatment, it may be detached from the base material.

The coating method can be a known method, such as a coating method such as spin coating, cast coating, or roll coating, which will not be repeated here. The drying process can be carried out in a known manner in order 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 curing process can be performed in a known manner, with the purpose of completely removing the residual solvent and forming a dense structure of the flexible substrate. The operating temperature range of the curing process is preferably 150°C to 500°C, and the time is 10 minutes to 2 hours.

The method of detachment may be a known method, for example, directly tearing off the flexible substrate from the substrate, using dry etching to remove the substrate, or using wet etching to remove the substrate, etc.

Substrates include, but are not limited to, alkali-free glass, soda lime glass, hard glass (Pales glass), quartz glass, or silicon wafers used in liquid crystal display devices.

The flexible substrate of the present invention can be applied to flexible liquid crystal displays or electronic books.

The present invention will be further described with respect to the following embodiments, but it should be understood that these embodiments are merely illustrative and should not be construed as limitations of the implementation of the present invention.

Synthesis of diamine compound (b-1) Synthesis Example b-1-1

0.30 mol (44.45 g) of 1,3-dioxane-5,5-dimethanol, 0.66 mol (31.68 g suspension) of sodium hydride (NaH; 50% by weight oily suspension), 540 Milliliters of toluene and 360 milliliters of N,N-dimethylformamide were mixed, stirred and stirred at 80°C for 1 hour. Next, after cooling the above reaction mixture to 20°C, 0.63 mol (88.89 g) of 4-fluoronitrobenzene dissolved in 180 ml of N,N-dimethylformamide was added dropwise in 1 hour In the above reaction mixture. After completion of the dropping, the mixture was stirred and reacted at 110°C for 64 hours. After cooling the reaction mixture, distilled water was added and extraction was performed with dichloromethane. The dichloromethane layer was washed with distilled water and dried by adding magnesium sulfate, and the solvent was removed under reduced pressure. The obtained solid was recrystallized with ethanol to obtain Compound 1. Under a nitrogen atmosphere, 0.19 mol of compound 1, 3.35 g of palladium-carbon catalyst (Pd/C), 300 ml of tetrahydrofuran, and 300 ml of ethanol were mixed and stirred at 60°C. Next, after dropping 47.6 ml of hydrazine hydrate over 1 hour, the mixture was stirred and reacted at 60°C for 4 hours. After the reaction was completed, palladium-carbon catalyst was removed from the above reaction mixture by suction filtration. By recrystallizing the obtained solid with ethanol, the compound represented by formula (I'-1) can be obtained.

Synthesis Example b-1-2

Synthesis Example b-1-2 was prepared separately in the same procedure as Synthesis Example b-1-1, and the difference was that: 0.30 mole of 1,3-dioxane-5,5-dimethanol was replaced 0.30 mol of 2-butyl-1,3-dioxane-5,5-dimethanol (molecular weight: 204.26), and replacing 4-fluoronitrobenzene with 3-fluoronitrobenzene to obtain The compound represented by formula (I'-4).

Synthesis Example b-1-3

Synthesis Example b-1-3 was prepared separately in the same procedure as Synthesis Example b-1-1, and the difference was that: 0.30 mole of 1,3-dioxane-5,5-dimethanol was replaced 1,3-dioxane-5-methanol-5-n-propanol (molecular weight: 176.21), which is 0.30 mol, to obtain the compound represented by formula (I′-8).

Synthesis Example b-1-4

Synthesis Example b-1-4 was prepared separately in the same procedure as Synthesis Example b-1-1, and the difference was that: 0.30 mole of 1,3-dioxane-5,5-dimethanol was replaced It is 0.30 mol of 2-(chloromethyl)-1,3-dioxane-5,5-dimethanol (molecular weight: 196.63) to obtain the compound represented by formula (I′-10).

Synthesis Example b-1-5

Synthesis Example b-1-5 was prepared separately in the same procedure as Synthesis Example b-1-1, and the difference was that: 0.30 mole of 1,3-dioxane-5,5-dimethanol was replaced 0.30 mol of 2-([1,1'-bis(cyclohexyl)]-4-yl)-1,3-dioxane-5,5-dimethanol (molecular weight: 312.44) to obtain the formula The compound shown by (I'-14).

Synthesis Example b-1-6

Synthesis Example b-1-5 was prepared separately in the same procedure as Synthesis Example b-1-1, and the difference was that: 0.30 mole of 1,3-dioxane-5,5-dimethanol was replaced 2-phenyl-1,3-dioxane-5,5-diol (molecular weight: 196.20), which is 0.30 mol, to obtain the compound represented by formula (I′-15).

Synthesis Example b-1-7

Mix 0.5 mol (103.12 g) of 2-propoxy-1,3-dioxane-5,5-dimethanol, 1.50 mol (207.9 ml) of triethylamine, and 1200 ml of tetrahydrofuran in ice. Stir under the bath. After 1.05 mol (194.84 g) of 4-nitrobenzoyl chloride dissolved in 600 ml of tetrahydrofuran was dropped into the aforementioned solution over 2 hours, it was stirred and reacted at 25°C for 4 hours. Next, ethyl acetate was added to the reaction mixture and washed with distilled water, and then the solvent was removed under reduced pressure. The obtained solid was recrystallized with ethanol to obtain compound 2. Under a nitrogen atmosphere, 0.39 mol of Compound 2, 6.87 g of palladium-carbon catalyst (Pd/C), 600 ml of tetrahydrofuran, and 600 ml of ethanol were mixed and stirred at 60°C. After 97.6 ml of hydrazine hydrate was dropped into the aforementioned solution in 1 hour, it was stirred and reacted at 60°C for 4 hours. After the reaction was completed, the palladium-carbon catalyst was removed from the above reaction mixture by suction filtration, and the solvent was removed under reduced pressure. By recrystallizing the obtained solid with ethanol, the compound represented by formula (I'-21) can be obtained.

Synthesis Example b-1-8

Mix 0.5 mol (95.08 g) of 2-methyl-1,3-dioxane-5,5-dicarboxylic acid, 400 ml of sulfonium chloride and a small amount of dimethylformamide at 80 Stir and react at 1°C for 1 hour. Vacuum suction filtration is performed using water-flow suction to remove unreacted sulfite chloride from the reaction mixture. After that, 680 ml of methylene chloride was added to form a solution. After passing 150 ml of distilled water into the above solution in three times, the water was removed with magnesium sulfate and the solvent was removed under reduced pressure to obtain a solid. The above solid was dissolved with 450 ml of tetrahydrofuran to form a solution (1). 1.05 mol (146.07 g) of 3-nitrophenol, 800 ml of tetrahydrofuran, and 1.50 mol (207.9 ml) of triethylamine were mixed and stirred in an ice bath. Next, the above solution (1) was added dropwise to a mixed solution of 3-nitrophenol, tetrahydrofuran, and triethylamine over 1 hour, followed by stirring and reaction at 25°C for 4 hours. Next, ethyl acetate was added to the reaction mixture and washed with distilled water, and then the solvent was removed under reduced pressure to obtain a solid. Recrystallization of the resulting solid with ethanol yielded 0.41 moles of compound 3. Under a nitrogen atmosphere, mix 0.41 mol of Compound 3, 8.20 mol (536.20 g) of zinc, 1.64 mol (87.72 g) of ammonium chloride, 1500 ml of ethanol, and 1500 ml of tetrahydrofuran at 0°C Stir. Thereafter, 200 ml of distilled water was added, stirred and reacted at 25°C for 8 hours. The reaction mixture was suction filtered to remove insoluble catalyst, and the solution obtained by adding ethyl acetate was washed with distilled water. The solution after washing removes the solvent under reduced pressure, and a solid can be obtained. The obtained solid is recrystallized with ethanol to obtain the compound represented by formula (I'-26).

Synthetic polymer (A) Synthesis Example A-1-1

A nitrogen inlet, stirrer, condenser and thermometer are installed on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, 0.83 g (0.0025 mol) of the diamine compound (b-1-1) represented by the formula (I'-1) and 18.47 g (0.045 mol) of 2,2-bis(4-amine) are added Phenoxy (4-phenyl)) propane (b-2-1) and 70 grams of N-methyl-2-pyrrolidone (hereinafter referred to as NMP), and stirred at room temperature until dissolved. Next, 10.91 g (0.05 mol) of pyromellitic dianhydride (a-1) and 30 g of NMP were added and reacted at room temperature for 2 hours. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate the polymer, the obtained polymer was filtered, and the steps of washing and filtering were repeated three times with methanol. After that, the product was placed in a vacuum oven and dried at a temperature of 60°C to obtain a polymer (A-1-1). The results are shown in Table 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 used the same preparation method as the preparation method of the polymer (A-1-1) of Synthesis Example A-1-1, except for Synthesis Example A-1- 2 to A-1-7 change the type and amount of raw materials used in the polymer. The formula is shown in Table 1, which is not repeated here.

Synthesis Example A-2-1

Install a nitrogen inlet, stirrer, heater, condenser, and thermometer on a four-necked conical flask with a volume of 500 ml, and introduce nitrogen. Then, 0.83 g (0.0025 mol) of the diamine compound (b-1-1) represented by the formula (I′-1) and 16.58 g (0.045 mol) of 4,4-bis(4-amine Phenoxy) diphenyl (b-2-2) and 70 grams of NMP, and stirred at room temperature until dissolved. Next, 10.91 g (0.05 mol) of pyromellitic dianhydride (a-1) and 30 g of NMP were added. After 6 hours of reaction at room temperature. After the reaction was completed, 97 g of NMP, 5.61 g of acetic anhydride, and 19.35 g of pyridine were added to the aforementioned reaction liquid, and the temperature was raised to 55° C., and stirring was continued for 2 hours to perform a dehydration ring-closing reaction. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate the polymer, the obtained polymer was filtered, and the steps of washing and filtering were repeated three times with methanol. 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). The formula is shown in Table 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 use the same preparation method as the polymer (A-1-1) composition of Synthesis Example A-2-1, except for Synthesis Example A-2-2 From A-2-7, the type and amount of raw materials in the polymer and the reaction temperature and reaction time of the dehydration ring-closing reaction are changed.

Preparation of composition for flexible substrate Example 1

Weighing 100 parts by weight of the polymer (A-1-1) of Synthesis Example A-1-1 and 200 parts by weight of NMP, and stirring and mixing at room temperature, the composition for the flexible substrate of Example 1 can be obtained Thing. The obtained composition for flexible substrates was evaluated by the following evaluation method, and the results are shown in Table 2.

Examples 2 to 15 and Comparative Examples 1 to 4

Examples 2 to 15 and Comparative Examples 1 to 4 used the same preparation method as the composition for the flexible substrate of Example 1, except that Examples 2 to 15 and Comparative Examples 1 to 4 changed the raw materials in the composition for the flexible substrate The types and amounts of the formulations, their formulations and evaluation results are shown in Table 2 and Table 3 respectively, and will not be repeated here.

Evaluation method

1. Viscosity

The viscosity referred to in the present invention herein is measured at 25°C using a rotary viscometer (model DV-E, manufactured by BROOKFIELD) at 100 rpm to measure the viscosity of the composition for flexible substrates (unit is cps).

2. Resilience

The compositions for flexible substrates of Examples 1 to 15 and Comparative Examples 1 to 4 described above were applied on a glass substrate having a size of 100 mm×100 mm by spin coating. Then, after pre-baking at 80°C for 20 minutes, a pre-baking coating film with a thickness of 30 μm can be formed. Next, post-baking is performed at 300° C. to obtain a laminate including a glass substrate and a flexible substrate. After that, the obtained laminate was cut into test pieces having a width of 10 mm and a length of 100 mm. Next, using a tensile tester (manufactured by Shimadzu; AGS-X STD), under the conditions of 25° C. and humidity of 50% RH, under the conditions of a tensile speed of 50 mm/min and a distance between the chucks of 50 mm, the The above test piece was subjected to a tensile test, and the tensile breaking strength σ(GPa) when the test piece was broken was recorded. Repeat the above test 3 times, and evaluate the average value of the test according to the following criteria: ◎: 0.20<σ; ○: 0.15<σ≦0.20; △: 0.1<σ≦0.15; X: σ≦0.1.

According to the evaluation results of Table 1 and Table 2, when the polymer (A) of the composition for a flexible substrate of the present invention contains a specific structure represented by the formula (I′) (which is provided by the diamine compound (b-1) ), the produced flexible substrate has good toughness. In addition, when the polymer (A) of the composition for a flexible substrate of the present invention further includes a specific structure represented by the formula (II′) (which is provided by the diamine compound (b-2)), the flexibility can be further improved The toughness of the substrate.

On the other hand, according to the evaluation results in Tables 1 and 3, it is known that if the polymer (A) in the composition for flexible substrates is formed without the reaction of the diamine compound (b-1), the composition The toughness of the flexible substrate is not good. Furthermore, even if the polymer (A) is obtained by reacting with the diamine compound (b-2), but the diamine compound (b-1) is not included, a flexible substrate having sufficient toughness cannot be obtained.

Therefore, by applying the composition for a flexible substrate of the present invention, a method for producing the same, and a flexible substrate, the diamine compound (b-1) or the diamine compound (b-2) is further added to polymerize the composition for the flexible substrate The object (A) may have a specific structure. In this way, the produced flexible substrate can have good toughness.

Although the present invention has been disclosed in several embodiments as above, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field to which the present invention belongs can be regarded as various without departing from the spirit and scope of the present invention. Changes and retouching, therefore, the scope of protection of the present invention shall be subject to the scope defined in the appended patent application.

B-1 N-methyl-2-pyrrolidone

B-2 Ethylene glycol n-butyl ether

B-3 N,N-dimethylacetamide

C-1 Silicon dioxide (trade name IPA-ST (particle size 12nm), manufactured by Nissan Chemical)

C-2 Dibutylhydroxytoluene (trade name BHT, manufactured by Tokyo Chemical Industry (TCI))

Claims (14)

A composition for a flexible substrate, comprising: a polymer (A) selected from the group consisting of polyamide resin, polyimide resin and any combination of the above, wherein the polymer (A) contains The structure shown in the following formula (I):

In the formula (I), each Z ₁ is independently and independently an ether bond or an ester bond; each R ₁ is independently and independently a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms; the R ₂ Each and independently is a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; the R ₃ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 9 carbon atoms, carbon An alkoxy group having a number of 1 to 9, a cycloalkyl group having a carbon number of 3 to 12, and an aryl group having a carbon number of 6 to 12; the m is an integer of 0 to 4; and, the * ^a represents a bond; And a solvent (B), wherein, at 25°C, the viscosity of the composition for a flexible substrate is 100 cps to 20,000 cps. The composition for a flexible substrate as described in item 1 of the patent application range, wherein the viscosity of the composition for a flexible substrate is 120 cps to 18,000 cps. The composition for a flexible substrate as described in item 1 of the patent application range, wherein the viscosity of the composition for a flexible substrate is 150 cps to 15,000 cps. The composition for a flexible substrate as described in item 1 of the patent application scope, wherein the polymer (A) further includes a structure represented by the following formula (II):

In the formula (II), the * ^b represents the bond, and the X represents the structure of the following formula (II-1):

In the formula (II-1), the Y represents a single bond, -O-, -CH ₂ -, -SO ₂ -, -C(CH ₃ ) ₂ -or -C(CF ₃ ) ₂ -, and The * ^c represents the junction between the structure of formula (II-1) and the X of formula (II). The composition for a flexible substrate as described in item 1 of the patent application, wherein the amount of the polymer (A) used is 100 parts by weight, and the amount of the solvent (B) used is 200 parts by weight to 2,000 parts by weight. A flexible substrate comprising the composition for a flexible substrate according to any one of items 1 to 5 of the patent application. A method for manufacturing a composition for a flexible substrate, comprising mixing the following components: a polymer (A), wherein the polymer (A) is composed of a tetracarboxylic dianhydride component (a) and a diamine component (b ) A mixture prepared by reaction, wherein the diamine component (b) contains a diamine compound (b-1) having the structure represented by the following formula (I′):

In the formula (I'), each Z ₁ is independently and independently an ether bond or an ester bond; each R ₁ is independently and independently a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms; the R ₂ are each and independently a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; the R ₃ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 9 carbon atoms, Alkoxy group having 1 to 9 carbon atoms, cycloalkyl group having 3 to 12 carbon atoms, aryl group having 6 to 12 carbon atoms; and, m is an integer of 0 to 4; and a solvent (B), Wherein, at 25° C., the viscosity of the flexible substrate composition is 100 cps to 20,000 cps. The method for manufacturing a composition for a flexible substrate as described in item 7 of the patent application range, wherein the viscosity of the composition for a flexible substrate is 120 cps to 18,000 cps. The method for manufacturing a composition for a flexible substrate as described in item 7 of the patent application range, wherein the viscosity of the composition for a flexible substrate is 150 cps to 15,000 cps. The method for manufacturing a composition for a flexible substrate as described in item 7 of the patent application scope, wherein the usage amount based on the diamine component (b) is 100 moles, and the usage amount of the diamine compound (b-1) is 5 mol to 60 mol. The method for manufacturing a composition for a flexible substrate as described in item 7 of the patent application scope, wherein the diamine component (b) further includes a diamine compound (b-2) having a structure represented by the following formula (II′):

In the formula (II'), the X represents the structure of the following formula (II-1):

In the formula (II-1), the Y represents a single bond, -O-, -CH ₂ -, -SO ₂ -, -C(CH ₃ ) ₂ -or -C(CF ₃ ) ₂ -, and The * ^c represents the junction between the structure of formula (II-1) and the X of formula (II'). The method for manufacturing a composition for a flexible substrate as described in item 11 of the patent application scope, wherein the usage amount based on the diamine component (b) is 100 moles, and the usage amount of the diamine compound (b-2) is 10 mol to 95 mol. The method for manufacturing a composition for a flexible substrate as described in item 7 of the patent application, wherein the amount of the polymer (A) used is 100 parts by weight, and the amount of the solvent (B) used is 200 parts by weight to 2,000 parts by weight Copies. A flexible substrate comprising the composition for a flexible substrate formed by the method for manufacturing a composition for a flexible substrate as described in any one of claims 7 to 13.