JP2017132917A - Aromatic polyketone having alkylene group in main chain, aromatic polyketone varnish, aromatic polyketone film, and method for producing aromatic polyketone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polyketone that has excellent heat resistance and transparency and can form a flexible film, an aromatic polyketone varnish and a method for producing an aromatic polyketone, and an aromatic polyketone film that has excellent heat resistance and transparency as well as flexibility.SOLUTION: An aromatic polyketone has a structural unit represented by formula (5-1) and a structural unit represented by general formula (5-2), and also has a structural unit selected from a specific biphenyl structure, a specific biphenyl ether structure, and a specific biphenyl alkylene structure.SELECTED DRAWING: None

Description

  The present invention relates to an aromatic polyketone, an aromatic polyketone varnish, an aromatic polyketone film, and a method for producing an aromatic polyketone.

  An aromatic polyketone having an aromatic ring and a carbonyl group in the main chain has excellent heat resistance and mechanical properties, and is used as an engineering plastic. Most of the polymers belonging to the aromatic polyketone are aromatic polyether ketones polymerized using a nucleophilic aromatic substitution reaction, and have an ether bond in the main chain. On the other hand, an aromatic polyketone that does not have an ether bond in the main chain can exhibit better heat resistance and chemical resistance than aromatic polyether ketone (see, for example, Patent Document 1 and Patent Document 2). ).

  In recent years, it has been reported that an aromatic polyketone having both high transparency and heat resistance can be obtained by directly polymerizing an alicyclic dicarboxylic acid and a 2,2′-dialkoxybiphenyl compound by Friedel-Crafts acylation. Therefore, application to optical components is expected (see, for example, Patent Document 3).

  When a resin material is applied to an optical component, properties that cannot be obtained with an inorganic material are expected. Examples of such properties include lightness and flexibility. Examples of applications that take advantage of lightness include glass substitutes and coating materials for portable devices, and examples of applications that take advantage of flexibility include flexible displays. Among these, application of resin materials to flexible displays has attracted particular attention in recent years.

JP-A-62-273030 JP 2005-272728 A JP 2013-53194 A

  However, the aromatic polyketone polymerized from the alicyclic dicarboxylic acid and the 2,2′-dialkoxybiphenyl compound described in Patent Document 3 has excellent heat resistance and transparency, but the molded product tends to be hard. . This makes it difficult to obtain a flexible film that can be bent.

  The present invention has been made in view of the above circumstances, and has an excellent heat resistance and transparency, and an aromatic polyketone capable of forming a flexible film, an aromatic polyketone varnish, a method for producing an aromatic polyketone, and an excellent An aromatic polyketone film having heat resistance, transparency and flexibility is provided.

  The present invention includes the following aspects <1> to <7>.

<1> Represented by the following general formula (5-1), at least one structural unit selected from the group consisting of the following general formula (1), the following general formula (2), and the following general formula (4) An aromatic polyketone having at least one structural unit and at least one structural unit represented by the following general formula (5-2).

In general formula (1), each R ₁ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ₂ each independently represents a hydrogen atom or a substituent. The C1-C30 hydrocarbon group which may have is shown.

In General Formula (2), each R ₁ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and X represents an oxygen atom or the following General Formula (3) The divalent group represented is shown.

In General Formula (3), R ₃ and R ₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.

In General Formula (4), each R ₅ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.

In General Formula (5-1), Y ₁ represents a C 3-30 divalent alicyclic hydrocarbon group which may have a substituent. In General Formula (5-2), Y ₂ represents a linear or branched alkylene group having 1 to 30 carbon atoms which may have a substituent.

<2> At least one aromatic monomer selected from the group consisting of the following general formula (1 ′), the following general formula (2 ′) and the following general formula (4 ′), and the following general formula (5-1 ′) ) And an aromatic obtained by subjecting at least one dicarboxylic acid monomer represented by the following general formula (5-2 ′) to a condensation reaction in an acidic medium. Polyketone.

In General Formula (1 ′), each R ₁ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and each R ₂ independently represents a hydrogen atom or a substituent. The C1-C30 hydrocarbon group which may have a group is shown.

In General Formula (2 ′), each R ₁ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and X represents an oxygen atom or the following General Formula (3 ′) ) Is a divalent group represented by:

In General Formula (3 ′), R ₃ and R ₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.

In General Formula (4 ′), each R ₅ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.

In General Formula (5-1 ′), Y ₁ represents a C 3-30 divalent alicyclic hydrocarbon group which may have a substituent. In General Formula (5-2 ′), Y ₂ represents a linear or branched alkylene group having 1 to 30 carbon atoms which may have a substituent.

<3> The aromatic polyketone according to <1> or <2>, wherein the molar ratio of Y ₁ and Y ₂ (Y ₁ : Y ₂ ) is 9: 1 to 3: 7.

<4> An aromatic polyketone varnish containing the aromatic polyketone according to any one of <1> to <3> and a solvent.

<5> An aromatic polyketone film containing the aromatic polyketone according to any one of <1> to <3>.

<6> A display element having the aromatic polyketone film according to <5>.

<7> At least one aromatic monomer selected from the group consisting of the following general formula (1 ′), the following general formula (2 ′) and the following general formula (4 ′), and the following general formula (5-1 ′) ) And at least one dicarboxylic acid monomer represented by the following general formula (5-2) are subjected to a condensation reaction in an acidic medium. .

In General Formula (1 ′), each R ₁ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and each R ₂ independently represents a hydrogen atom or a substituent. The C1-C30 hydrocarbon group which may have a group is shown.

In General Formula (2 ′), each R ₁ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and X represents an oxygen atom or the following General Formula (3 ′) ) Is a divalent group represented by:

In General Formula (3 ′), R ₃ and R ₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.

In General Formula (4 ′), each R ₅ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.

In General Formula (5-1 ′), Y ₁ represents a C 3-30 divalent alicyclic hydrocarbon group which may have a substituent. In General Formula (5-2 ′), Y ₂ represents a linear or branched alkylene group having 1 to 30 carbon atoms which may have a substituent.

  According to the present invention, the aromatic polyketone, the aromatic polyketone varnish and the aromatic polyketone, which have excellent heat resistance and transparency and capable of forming a flexible film, and excellent heat resistance, transparency and flexibility An aromatic polyketone film having properties can be provided.

2 is a ¹³ C-NMR spectrum of polyketone PK1 obtained in Example 1. FIG. 3 is a ¹³ C-NMR spectrum of polyketone PK2 obtained in Example 2. 3 is a ¹³ C-NMR spectrum of polyketone PK3 obtained in Example 3.

Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
In the present specification, a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In the present specification, the “film” includes a configuration formed in a part in addition to a configuration formed over the entire surface when observed as a plan view.
In this specification, the “step” is not limited to an independent step, and is included in the term if the intended action of the step is achieved even when it cannot be clearly distinguished from other steps.
In the present specification, “transparency” means that the transmittance of visible light and the transmittance of visible light having a wavelength of at least 400 nm are 80% or more (in terms of film thickness 1 μm).
In the present specification, “heat resistance” means that the occurrence of cracks due to heating is suppressed in a member containing an aromatic polyketone.
In this specification, “flexibility” means that the occurrence of cracks is suppressed when the mandrel test is performed on the aromatic polyketone film and the diameter of the mandrel is reduced.

<Aromatic polyketone>
The aromatic polyketone is represented by the following general formula (5-1), at least one structural unit selected from the group consisting of the following general formula (1), the following general formula (2), and the following general formula (4). And at least one structural unit represented by the following general formula (5-2). This aromatic polyketone is also referred to as “specific aromatic polyketone”.

  The specific aromatic polyketone has at least one structural unit selected from the group consisting of the general formulas (1), (2) and (4) as a structural unit derived from an aromatic monomer, and a dicarboxylic acid monomer Having at least one structural unit represented by the general formula (5-1) and at least one structural unit represented by the following general formula (5-2) as a structural unit derived from An aromatic polyketone film having excellent properties, transparency and flexibility can be formed. The reason for this is not clear, but can be considered as follows.

By having an alicyclic hydrocarbon group that certain aromatic polyketones represented by Y _1, are exhibited excellent heat resistance and transparency. Moreover, when the specific aromatic polyketone has an alkylene group represented by Y ₂ , excellent flexibility is obtained when a film is formed.

In general formula (1), each R ₁ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ₂ each independently represents a hydrogen atom or a substituent. The C1-C30 hydrocarbon group which may have is shown. In addition, the part which attached | subjected the wavy line means a joint. Hereinafter, the same applies to the wavy line in the chemical formula.

From the viewpoint of heat resistance, each R ₁ is preferably independently a hydrocarbon group having 1 to 10 carbon atoms, and more preferably a hydrocarbon group having 1 to 5 carbon atoms from the viewpoint of reaction control.

Examples of the substituent for R ₁ include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. When the hydrocarbon group has a substituent, the carbon number of the hydrocarbon group does not include the carbon number of the substituent. The same applies thereafter.

Examples of the hydrocarbon group represented by R ₁ include a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, and an alicyclic hydrocarbon group. Moreover, what combined these hydrocarbon groups may be used.

Examples of the saturated aliphatic hydrocarbon group represented by R ₁ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, and n-pentyl group. , Isopentyl group, sec-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-icosanyl group, n -A triacontanyl group etc. are mentioned.

Examples of the unsaturated aliphatic hydrocarbon group represented by R ₁ include alkenyl groups such as vinyl groups and allyl groups, and alkynyl groups such as ethynyl groups.

Examples of the alicyclic hydrocarbon group represented by R ₁ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cycloalkyl group such as a norbornyl group, and a cycloalkenyl group such as a cyclohexenyl group. Group and the like.

In General Formula (1), each R ₂ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. From the viewpoint of heat resistance, R ² is preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Examples of such a hydrocarbon group include the same groups as those exemplified for R ₁ . Moreover, as a substituent, a halogen atom, a C1-C5 alkoxy group, a C2-C5 acyl group, etc. are mentioned.

In General Formula (2), each R ₁ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. The general formula (2) ^{R 1} in detail, is the same as ^{R 1} in general formula (1).

  In the general formula (2), X represents an oxygen atom or a divalent group represented by the following general formula (3).

In General Formula (3), R ₃ and R ₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. From the viewpoint of heat resistance, R ³ and R ⁴ are each independently preferably a hydrocarbon group having 1 to 10 carbon atoms, and more preferably a hydrocarbon group having 1 to 5 carbon atoms. As such a hydrocarbon group, the thing similar to what was illustrated by R < ₁ > in General formula (1) is mentioned. Moreover, as a substituent, a halogen atom, a C1-C5 alkoxy group, a C2-C5 acyl group, etc. are mentioned.

In General Formula (4), each R ₅ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. From the viewpoint of heat resistance, R ⁵ is preferably each independently a hydrocarbon group having 1 to 10 carbon atoms, and more preferably a hydrocarbon group having 1 to 5 carbon atoms. As such a hydrocarbon group, the thing similar to what was illustrated by R < ₁ > in General formula (1) is mentioned. Moreover, as a substituent, a halogen atom, a C1-C5 alkoxy group, a C2-C5 acyl group, etc. are mentioned.

In General Formula (5-1), Y ₁ represents a C 3-30 divalent alicyclic hydrocarbon group which may have a substituent. In General Formula (5-2), Y ₂ represents a linear or branched alkylene group having 1 to 30 carbon atoms which may have a substituent.

Y carbon atoms in the alicyclic hydrocarbon group represented by _1, 3 to 30, from the viewpoint of heat resistance, it is preferably from 5 to 20.

Examples of the alicyclic hydrocarbon group represented by Y ₁ include a cyclopropane skeleton, a cyclobutane skeleton, a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cubane skeleton, a norbornane skeleton, and tricyclo [5.2.1. 0] a divalent group having a decane skeleton, an adamantane skeleton, a diadamantane skeleton, a bicyclo [2.2.2] octane skeleton, or the like. From the viewpoint of solubility, a divalent group having an adamantane skeleton is preferable.

The alkylene group represented by Y ₂ is 1 to 30, in view of heat resistance and transparency, is preferably 3 to 30.

Examples of the alkylene group represented by Y ₂ include methylene group, ethylene group, trimethylene group, methylethylene group, tetramethylene group, n-methyltrimethylene group, ethylethylene group, dimethylethylene group, pentylene group, and n-methyltetramethylene. Group, n-ethyltrimethylene group, n, n-dimethyltrimethylene group, propylethylene group, ethylmethylethylene group, hexylene group, n-methylpentylene group, n-ethyltetramethylene group, n-propyltrimethylene group Butylethylene group, n, n-dimethyltetramethylene group, trimethyltrimethylene group, n, n-ethylmethyltrimethylene group, heptylene group, octylene group, nonylene group, decylene group, icosanylene group, triacontanilene group, etc. Can be mentioned.

The molar ratio of Y ₁ and Y ₂ can be adjusted according to the desired physical properties. From the viewpoint of heat resistance and flexibility, the molar ratio of Y ₁ and Y ₂ is preferably Y ₁ : Y ₂ = 9: 1 to 3: 7, and Y ₁ : Y ₂ = 8: 2 to 3: 7 is more preferable.

From the viewpoint of heat resistance, the aromatic polyketone preferably has a weight average molecular weight (Mw) of 10,000 or more, more preferably 20,000 or more. Further, the number average molecular weight (Mn) is preferably 1000 or more, and more preferably 2000 or more.
From the viewpoint of solubility, the weight average molecular weight (Mw) of the aromatic polyketone is preferably 350,000 or less, and more preferably 300,000 or less. The number average molecular weight (Mn) is preferably 200000 or less, and more preferably 100000 or less.

<Method for producing aromatic polyketone>
The specific aromatic polyketone is at least one structural unit selected from the group consisting of the general formulas (1), (2) and (4), and at least one kind represented by the general formula (5-1). As long as it has at least one kind of structural unit represented by the general formula (5-2), the production method is not particularly limited. For example, at least one aromatic monomer selected from the group consisting of the following general formulas (1 ′), (2 ′) and (4 ′), and at least 1 represented by the following general formula (5-1 ′) A dicarboxylic acid monomer of a kind and at least one dicarboxylic acid monomer represented by the following general formula (5-2 ′) can be obtained by a condensation reaction in an acidic medium.

In General Formula (1 ′), each R ₁ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and each R ₂ independently represents a hydrogen atom or a substituent. The C1-C30 hydrocarbon group which may have a group is shown. The general formula (1 ') of _{R 1} and _{R 2} in detail, is the general formula (1) and _{R 1} and _{R 2} in the same respectively.

In General Formula (2 ′), each R ₁ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and X represents an oxygen atom or the following General Formula (3 ′) ) Is a divalent group represented by: The general formula (2 ') of _{R 1} in detail, the same as _{R 1} in the general formula (2).

In General Formula (3 ′), R ₃ and R ₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. The more general formula (3 ') in _{R 3} or _{R 4,} are each similar to the general formula (3) _{R 3} or _{R 4} in.

In General Formula (4 ′), each R ₅ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. Details of the general formula (4 ') in _{R 5,} is the same as _{R 5} in the general formula (4).

In General Formula (5-1 ′), Y ₁ represents a C 3-30 divalent alicyclic hydrocarbon group which may have a substituent. In General Formula (5-2 ′), Y ₂ represents a linear or branched alkylene group having 1 to 30 carbon atoms which may have a substituent. The general formula (5-1 ') of _{Y 1} in detail, the same as _{Y 1} in the general formula (5-1). The general formula (5-2 ') of _{Y 2} in detail, the same as _{Y 2} in the general formula (5-2) in.

Examples of the dicarboxylic acid monomer represented by the general formula (5-1 ′) include 1,3-adamantane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, and 2,3-cyclohexane dicarboxylic acid. Examples include acid, 1,3-norbornane dicarboxylic acid, 1,4-norbornane dicarboxylic acid, 2,3-norbornane dicarboxylic acid, 1,4-decahydronaphthalenedicarboxylic acid, 2,3-decahydronaphthalenedicarboxylic acid, and the like. From the viewpoint of reactivity, an alicyclic carboxylic acid bonded to a carboxyl group at the 1,3-position or the 2,3-position is preferable.
Examples of the dicarboxylic acid monomer represented by the general formula (5-2 ′) include dodecanedioic acid, undecanedioic acid, decanedioic acid, nonanedioic acid, octanedioic acid, heptanedioic acid, nonanedioic acid, adipic acid, and glutar. An acid, a succinic acid, malonic acid, etc. are mentioned.

By changing the proportion of the dicarboxylic acid monomer represented by the general formula (5-1 ′) and the dicarboxylic acid monomer represented by the general formula (5-2 ′), in the specific aromatic polyketone obtained by the condensation reaction it is possible to adjust the ratio of Y ₁ and _{Y 2.}

  The condensation reaction is carried out in an acidic medium. The acidic medium is not particularly limited, and an organic solvent solution of aluminum chloride, an organic solvent solution of trifluoroalkanesulfonic acid, polyphosphoric acid, a mixture of diphosphorus pentoxide and organic sulfonic acid, or the like can be used. From the viewpoint of reactivity and handling, it is preferable to use a mixture of diphosphorus pentoxide and organic sulfonic acid as the acidic medium, and methanesulfonic acid is preferable as the organic sulfonic acid.

  In the mixture of diphosphorus pentoxide and organic sulfonic acid, if the amount of diphosphorus pentoxide is too small, the reactivity tends to be poor. The mixing ratio of diphosphorus pentoxide and organic sulfonic acid is preferably diphosphorus pentoxide: organic sulfonic acid = 1: 5 to 1:20 in terms of mass ratio from the viewpoint of controllability and acceleration of the reaction. It is more preferable that it is 1: 5 to 1:10.

  The amount of diphosphorus pentoxide and organic sulfonic acid used in the condensation reaction is not particularly limited as long as it is an amount capable of dissolving the aromatic monomer and the dicarboxylic acid monomer, and may be used in a range from a so-called catalyst amount to a solvent amount. it can. From the viewpoint of reactivity and ease of handling, it is preferable to use a mixture of diphosphorus pentoxide and organic sulfonic acid in a range of 50 to 100 parts by mass with respect to 1 part by mass of the dicarboxylic acid monomer.

  The temperature of the condensation reaction is preferably set to 10 ° C. to 100 ° C. from the viewpoint of preventing coloration and side reaction of the reaction product, and from the viewpoint of increasing the reaction rate and improving the productivity, 20 ° C. to 100 ° C. It is more preferable to set to ° C.

  The atmosphere of the condensation reaction is not particularly limited, and can be performed in an open system. However, since the reactivity of the acidic medium is reduced due to the presence of moisture, it is preferably carried out in an atmosphere of dry air, nitrogen, argon or the like. From the viewpoint of preventing an unexpected side reaction, it is more preferable to carry out in an atmosphere of nitrogen or argon.

  The condensation reaction can be promoted by stirring the reaction solution. The stirring method is not particularly limited, and a magnetic stirrer, a mechanical stirrer, or the like can be used.

  The reaction time of the condensation reaction is preferably set as appropriate depending on the reaction temperature, the molecular weight of the target specific aromatic polyketone, the type of monomer used in the reaction, and the like. From the viewpoint of obtaining a polyketone having a sufficiently high molecular weight, the reaction time is preferably 1 hour to 120 hours, and more preferably 1 hour to 72 hours from the viewpoint of productivity.

  The pressure of the reaction system in the condensation reaction is not particularly limited, and the reaction may be performed under normal pressure, increased pressure, or reduced pressure. From the viewpoint of cost, it is preferable to perform the condensation reaction under normal pressure.

  After the condensation reaction between the aromatic monomer and the dicarboxylic acid monomer is completed, the liquid containing the specific aromatic polyketone (for example, the condensation reaction liquid or the solution in which the specific aromatic polyketone is dissolved) is contacted with the poor solvent and specified. Aromatic polyketone is precipitated, impurities are extracted into the poor solvent layer, and the deposited specific aromatic polyketone is separated from the liquid by a method such as filtration, decantation, and centrifugation. Thereafter, the separated specific aromatic polyketone is dissolved again in a good solvent, and again contacted with a poor solvent to precipitate the specific aromatic polyketone, and impurities are extracted into the poor solvent layer. You may isolate | separate from a liquid by methods, such as filtration, a decantation, and centrifugation. By repeating this operation, impurities can be more sufficiently removed from the specific aromatic polyketone.

  In the present specification, the “poor solvent” means a poor solvent for the aromatic polyketone, and specifically means a solvent in which the aromatic polyketone dissolves in an amount of 0.01 g or less in 100 g of the solvent. . The “good solvent” means that it is a good solvent for the aromatic polyketone, and specifically means a solvent in which 1 g or more of the aromatic polyketone is dissolved in 100 g of the solvent.

  The specific aromatic polyketone can obtain an aromatic polyketone film excellent in transparency, heat resistance and flexibility, and can be used as a flexible transparent heat-resistant material.

<Aromatic polyketone varnish>
The aromatic polyketone varnish contains a specific aromatic polyketone and a solvent. The aromatic polyketone varnish can be obtained by dissolving a specific aromatic polyketone in a solvent. A method for dissolving the specific aromatic polyketone in the solvent is not particularly limited, and a method known in the art can be used. Moreover, you may filter an insoluble component after melt | dissolution as needed.

  The solvent contained in the varnish is not particularly limited as long as it dissolves the specific aromatic polyketone. Examples of solvents include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, butyl acetate, benzyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N-cyclohexyl -2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, xylene, mesitylene, ethylbenzene, Ropirubenzen, cumene, diisopropylbenzene, hexyl benzene, anisole, diglyme, dimethyl sulfoxide, chloroform, dichloromethane, dichloroethane, chlorobenzene and tetrahydrofuran. These solvents can be used alone or in combination of two or more.

  The aromatic polyketone varnish may further contain additives and the like in addition to the specific aromatic polyketone and the solvent. Examples of the additive include an adhesion assistant, a surfactant, a leveling agent, an antioxidant, and an ultraviolet deterioration preventing agent.

<Aromatic polyketone membrane>
The aromatic polyketone film contains a specific aromatic polyketone. The aromatic polyketone film can be formed using an aromatic polyketone varnish. Aromatic polyketone membranes are more flexible than aromatic polyketone membranes containing conventional aromatic polyketones that are polymerized without using anything other than alicyclic dicarboxylic acids and 2,2′-dialkoxybiphenyl compounds as raw materials .

The method for producing the specific aromatic polyketone film is not particularly limited. For example, it can be obtained by the following method.
The aromatic polyketone varnish of this embodiment is applied to at least a part of the surface of the substrate to form a varnish layer. The method for applying the varnish is not particularly limited as long as the varnish layer can be formed in an arbitrary shape on an arbitrary place on the substrate. For example, as the application method, a dip coating method, a spray coating method, a screen printing method, a spin coating method or the like is preferably used.

  The base material to which the aromatic polyketone varnish is applied is not particularly limited, and a glass base material, a semiconductor base material, a metal oxide insulator base material (for example, a titanium oxide base material and a silicon oxide base material), a silicon nitride base material, Examples thereof include transparent resin base materials such as acetyl cellulose, transparent polyimide, polycarbonate, acrylic polymer, and cycloolefin resin. The shape of the substrate is not particularly limited, and may be a plate shape or a film shape.

  After forming the varnish layer, the varnish layer is dried in a drying step. The drying method is not particularly limited, and for example, the drying can be performed by heating using a hot plate, an oven, or the like. If necessary, the dried aromatic polyketone film can be peeled off from the substrate.

  Moreover, you may heat-process the dried aromatic polyketone film | membrane further as needed. The heat treatment method is not particularly limited. For example, ovens such as box dryers, hot air conveyor dryers, quartz tube furnaces, hot plates, rapid thermal annealing, vertical diffusion furnaces, infrared curing furnaces, microwave curing furnaces, etc. Can be used. Moreover, as atmospheric conditions in a heat treatment process, either air | atmosphere or inert gas, such as nitrogen, may be sufficient.

<Display element>
The display element has the aromatic polyketone film of this embodiment.
The display device can be obtained, for example, by attaching an aromatic polyketone film to a constituent member such as an LCD (liquid crystal display) or an ELD (electroluminescence display) via an adhesive, an adhesive, or the like. Examples of the constituent member to which the aromatic polyketone film is attached include various optical elements such as a polarizing plate.

  The display device of this embodiment may have the same configuration as that of a conventional display device except that the display device has an aromatic polyketone film. For example, when the display device is a liquid crystal display device, a liquid crystal cell, an optical element such as a polarizing plate, and various components such as a lighting system (backlight etc.) are assembled by a conventional method and a drive circuit is incorporated. It can manufacture by. The liquid crystal cell is not particularly limited, and various types such as a TN type, an STN type, and a π type can be used.

  The display device is used for any suitable application. Applications include, for example, OA equipment such as desktop personal computers, notebook personal computers, and copiers, mobile phones, watches, digital cameras, personal digital assistants (PDAs), portable devices such as portable game machines, video cameras, televisions, microwave ovens, etc. Household electrical equipment, back monitors, car navigation system monitors, in-car equipment such as car audio, display equipment such as information monitors for commercial stores, security equipment such as monitoring monitors, nursing equipment such as nursing monitors, Examples thereof include medical equipment such as a medical monitor.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples without departing from the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

(Example 1) Synthesis of polyketone PK1 As a monomer, a mixture of 2,2'-dimethoxybiphenyl 10 mmol, 1,3-adamantane dicarboxylic acid 5 mmol and dodecanedioic acid 5 mmol was mixed with diphosphorus pentoxide and methanesulfonic acid. 30 ml of a liquid (mass ratio 1:10) was added, and a nitrogen balloon was attached, followed by stirring at 60 ° C. for 40 hours. After the reaction, the reaction solution was poured into 500 ml of methanol, and the produced precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain polyketone PK1. A ¹³ C-NMR spectrum of the resulting polyketone PK1 is shown in FIG. Moreover, the weight average molecular weight was 30,000 and the number average molecular weight was 5,000.

(Example 2) Synthesis of polyketone PK2 As Example 1, except that 10 mmol of 2,2'-dimethoxybiphenyl, 7.5 mmol of 1,3-adamantane dicarboxylic acid and 2.5 mmol of dodecanedioic acid were used as monomers. Polyketone PK2 was obtained. The ¹³ C-NMR of the resulting polyketone PK2 is shown in FIG. Moreover, the weight average molecular weight was 180,000 and the number average molecular weight was 3,000.

(Example 3) Synthesis of polyketone PK3 As Example 1, except that 10 mmol of 2,2'-dimethoxybiphenyl, 9.0 mmol of 1,3-adamantane dicarboxylic acid and 1.0 mmol of dodecanedioic acid were used as monomers. Polyketone PK3 was obtained. The ¹³ C-NMR of the resulting polyketone PK3 is shown in FIG. Moreover, the weight average molecular weight was 250,000 and the number average molecular weight was 5,000.

(Example 4) Varnish containing polyketone PK1 The polyketone PK1 obtained in Example 1 was dissolved in N-methyl-2-pyrrolidone (NMP) to a concentration of 20%, and a membrane made of polytetrafluoroethylene Filtration through a filter (pore size: 5 μm) gave a varnish of polyketone PK1.

(Example 5) Varnish containing polyketone PK2 A varnish of polyketone PK2 was obtained in the same manner as in Example 4 except that polyketone PK2 was used instead of polyketone PK1.

(Example 6) Varnish containing polyketone PK3 A varnish of polyketone PK3 was obtained in the same manner as in Example 4 except that polyketone PK3 was used instead of polyketone PK1.

(Example 7) Film containing polyketone PK1 The varnish of polyketone PK1 obtained in Example 4 was applied on a glass substrate and a Kapton film by a bar coating method, and heated on a hot plate heated to 120 ° C. After drying for a minute, a glass substrate with a film of polyketone PK1 and a Kapton film with a film of polyketone PK1 (hereinafter collectively referred to as “substrate with film”) were obtained. About the obtained board | substrate with a film | membrane, transparency, heat resistance, and a softness | flexibility (flexibility) were evaluated by the below-mentioned method.

(Example 8) Film containing polyketone PK2 A substrate with a film of polyketone PK2 was prepared in the same manner as in Example 7 except that the varnish of polyketone PK2 obtained in Example 5 was used instead of the varnish of polyketone PK1. Obtained and evaluated.

(Example 9) Film containing polyketone PK3 A substrate with a film of polyketone PK3 was prepared in the same manner as in Example 7 except that the varnish of polyketone PK3 obtained in Example 6 was used instead of the varnish of polyketone PK1. Obtained and evaluated.

(Comparative Synthesis Example) Synthesis of Polyketone PK4 Polyketone PK4 was obtained in the same manner as in Example 1 except that 10 mmol of 2,2′-dimethoxybiphenyl and 10 mmol of 1,3-adamantanedicarboxylic acid were used as monomers. . The resulting polyketone PK4 had a weight average molecular weight of 60,000 and a number average molecular weight of 4,000.

(Comparative Production Example) Varnish Using Polyketone PK4 A varnish containing polyketone PK4 was obtained in the same manner as in Example 4 except that polyketone PK4 was used instead of polyketone PK1.

(Comparative Example) Film Using Polyketone PK4 Varnish A polyketone PK4 film-coated substrate was obtained and evaluated in the same manner as in Example 7 except that the polyketone PK4 varnish was used instead of the polyketone PK1 varnish. .

(Measurement of molecular weight)
The molecular weight was measured by gas permeation chromatography (GPC) method using tetrahydrofuran (THF) in which 0.1% of tetrabutylammonium nitrate (TBA · NO ₃ ) was dissolved as an eluent, and converted to standard polystyrene. Asked. Details are as follows.

-Device names: RI-8020 (detector), DP-8020 (pump), SD-8022 (degasser) (Tosoh Corporation)
Column: Gelpack GL-A150, GL-A160, GL-A170 (product name, Hitachi Chemical Co., Ltd.)
Detector: RI detector Eluent: Tetrabutylammonium nitrate (TBA / NO ₃ ) 0.1% by mass tetrahydrofuran (THF)
・ Flow rate: 1 ml / min

(Evaluation of transparency)
The ultraviolet light transmittance at 400 nm of the glass substrate with the polyketone film obtained in Examples 7 to 9 or Comparative Example was measured by an ultraviolet-visible absorption spectrum method. An ultraviolet-visible spectrophotometer (“U-3310 Spectrophotometer”, Hitachi High-Tech Co., Ltd.) was used for the measurement. Table 1 shows the transmittance in terms of a film thickness of 1 μm, using a glass substrate without a polyketone film as a reference.

(Evaluation of heat resistance)
The glass substrate with a polyketone film obtained in Examples 7 to 9 or Comparative Example was left standing in an oven at 200 ° C. for 24 hours and heated, and the transmittance of ultraviolet light at 400 nm was measured by an ultraviolet-visible absorption spectrum method. An ultraviolet-visible spectrophotometer (“U-3310 Spectrophotometer”, Hitachi High-Tech Co., Ltd.) was used for the measurement. Moreover, the presence or absence of the crack of the polyketone film | membrane after a heating was confirmed visually. Table 1 shows the transmittance converted to a film thickness of 1 μm and the presence or absence of cracks in the film, using a glass substrate without a polyketone film as a reference.

(Evaluation of flexibility)
The Kapton film with a polyketone film obtained in Examples 7 to 9 or Comparative Example was evaluated by a mandrel test (cylindrical mandrel method). The test was conducted according to JIS K5600-5-1: 1999. The mandrel diameter was changed from 25 mm to 3 mm, and the presence or absence of cracks was confirmed visually. Table 1 shows the minimum diameter of the mandrel that does not crack.

  As shown in Table 1, the specific aromatic polyketone exhibits the same transmittance and heat resistance as the conventional aromatic polyketone, and is further excellent in bending resistance.

Claims (7)

At least one structural unit selected from the group consisting of the following general formula (1), the following general formula (2) and the following general formula (4), and at least one type represented by the following general formula (5-1) An aromatic polyketone having the following structural unit and at least one structural unit represented by the following general formula (5-2).

(In General Formula (1), each R ₁ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and each R ₂ independently represents a hydrogen atom or a substituent. (The C1-C30 hydrocarbon group which may have a group is shown.)

(In General Formula (2), each R ₁ independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and X represents an oxygen atom or the following General Formula (3). A divalent group represented by:

(In General Formula (3), R ₃ and R ₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.)

(In General Formula (4), each R ₅ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.)

(In General Formula (5-1), Y ₁ represents a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent. In General Formula (5-2), Y ₂ represents a linear or branched alkylene group having 1 to 30 carbon atoms which may have a substituent. The following general formula (1 ′), at least one aromatic monomer selected from the group consisting of the following general formula (2 ′) and the following general formula (4 ′), and the following general formula (5-1 ′) An aromatic polyketone obtained by subjecting at least one dicarboxylic acid monomer to be condensed with at least one dicarboxylic acid monomer represented by the following general formula (5-2 ′) in an acidic medium.

(In General Formula (1 ′), each R ₁ independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R ₂ independently represents a hydrogen atom or (The C1-C30 hydrocarbon group which may have a substituent is shown.)

(In the general formula (2 ′), each R ₁ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and X represents an oxygen atom or the following general formula (3 ') Represents a divalent group represented by

(In general formula (3 ′), R ₃ and R ₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.)

(In General Formula (4 ′), each R ₅ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.)

(In General Formula (5-1 ′), Y ₁ represents an optionally substituted divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms. General Formula (5-2 ′) Y ₂ represents a linear or branched alkylene group having 1 to 30 carbon atoms which may have a substituent. The aromatic polyketone according to claim 1 or 2, wherein the molar ratio of Y ₁ to Y ₂ (Y ₁ : Y ₂ ) is 9: 1 to 3: 7.   An aromatic polyketone varnish containing the aromatic polyketone according to any one of claims 1 to 3 and a solvent.   The aromatic polyketone film | membrane containing the aromatic polyketone of any one of Claims 1-3.   A display element comprising the aromatic polyketone film according to claim 5. The following general formula (1 ′), at least one aromatic monomer selected from the group consisting of the following general formula (2 ′) and the following general formula (4 ′), and the following general formula (5-1 ′) A method for producing an aromatic polyketone, comprising subjecting at least one dicarboxylic acid monomer to be condensed with at least one dicarboxylic acid monomer represented by the following general formula (5-2) in an acidic medium.

(In General Formula (1 ′), each R ₁ independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R ₂ independently represents a hydrogen atom or (The C1-C30 hydrocarbon group which may have a substituent is shown.)

(In the general formula (2 ′), each R ₁ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and X represents an oxygen atom or the following general formula (3 ') Represents a divalent group represented by

(In general formula (3 ′), R ₃ and R ₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.)

(In General Formula (4 ′), each R ₅ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.)

(In General Formula (5-1 ′), Y ₁ represents an optionally substituted divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms. General Formula (5-2 ′) Y ₂ represents a linear or branched alkylene group having 1 to 30 carbon atoms which may have a substituent.