JP6520495B2 - Process for producing aromatic polyketone - Google Patents

Description

The present invention relates to the production how aromatic polyketones.

  Aromatic polyimides have excellent heat resistance and mechanical properties, and are attracting attention as engineering plastics (see, for example, Non-Patent Document 1). Further, as with aromatic polyimides, aromatic polyketones having an aromatic ring and a carbonyl group in the main chain also have excellent heat resistance and chemical resistance, and are attracting attention as engineering plastics (for example, Patent Document 1 and See Non-Patent Document 2). Furthermore, it is known that an aromatic polyketone having excellent heat resistance and transparency can be obtained by introducing an alicyclic structure into the aromatic polyketone (see, for example, Patent Document 2), an optical element etc. It is expected to be used.

  Further, in recent years, the demand for a portable image display device (mobile display) represented by a mobile phone is increasing, and weight reduction of optical elements such as the image display device is required. In order to meet such requirements, it has been proposed to apply a lightweight, high-transparent, lightweight polymeric material (glass substitute) to replace glass.

  On the other hand, with the increase of the calorific value due to the miniaturization of optical parts, yellowing due to the heat of the resin, cracks and the like have become problems (for example, see Patent Document 3). In order to replace glass with resin, heat resistance is required along with high transparency and strength.

JP, 2005-272728, A JP, 2013-53194, A JP, 2009-280768, A

Japan Polyimide Research Group, "Latest Polyimide-Basics and Applications" (2002) Future Materials, 2008, Vol. 8, No. 8, pages 42-47

In patent document 1, after immersing the cast film of aromatic polyketone in water, the film heated and dried at 60 degreeC is applied as a separator for electric double layer capacitors. However, since the membrane is microporous, it has low strength and is difficult to apply to glass substitutes.
Since the aromatic polyketone described in Patent Document 2 is transparent, application to a glass substitute can be expected. However, in the production method described in Patent Document 2, the molecular weight of the obtained polyketone is low, and sufficient strength and heat resistance can not be exhibited.

  The present invention has been made in view of such circumstances, and is excellent in transparency and heat resistance, a method for producing an aromatic polyketone for obtaining an aromatic polyketone having a high molecular weight, and excellent in transparency, heat resistance and strength. Provided are an aromatic polyketone, an aromatic polyketone film, a substrate with an aromatic polyketone film, an optical element, and an image display.

As a result of intensive studies to solve the above problems, the present inventors devise the preparation ratio of monomers when polymerizing in the state of a solution or a slurry in which the monomers to be structural units of aromatic polyketone are dissolved. It has been found that an aromatic polyketone having a high average molecular weight (especially weight average molecular weight (Mw)) can be obtained. Furthermore, the reaction liquid of aromatic polyketone or the solution of aromatic polyketone is introduced into a poor solvent for aromatic polyketone to precipitate aromatic polyketone, followed by filtration, and the deposited aromatic polyketone is washed with a solvent to remove low molecular weight impurities. It has been found that, by devising the step of removing C, it is possible to effectively purify and to obtain an aromatic polyketone having a high average molecular weight (in particular, a number average molecular weight (Mn)).
As mentioned above, in order to solve the above-mentioned subject, the present invention contains the following modes.

<1> 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 at least one represented by the following general formula (5) An aromatic polyketone which causes a condensation reaction with one kind of dicarboxylic acid monomer in an acidic medium at a molar ratio of aromatic monomer to dicarboxylic acid monomer (aromatic monomer / dicarboxylic acid monomer) in the range of 0.5 or more and less than 1. Manufacturing method.

In the 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 It shows the C1-C30 hydrocarbon group which may have.

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

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

In the general formula (4), each R ⁵ is independently a hydrogen atom or a hydrocarbon group having a substituent 1 to 30 carbon atoms which may have a.

  In general formula (5), Y shows a C1-C30 bivalent hydrocarbon group.

The manufacturing method of the aromatic polyketone as described in said <1> whose Y is a bivalent saturated hydrocarbon group in <2> said General formula (5).

<3> The fragrance according to the above <1> or <2>, wherein in the general formula (5), Y is a divalent hydrocarbon group having 6 to 30 carbon atoms including a saturated alicyclic hydrocarbon group. Of making polynuclear polyketones.

<4> Any of the above <1> to <3>, wherein a solution containing an aromatic polyketone obtained after the condensation reaction is brought into contact with a solution containing a good solvent of an aromatic polyketone and a poor solvent of an aromatic polyketone The manufacturing method of the aromatic polyketone as described in any one of-.

<5> An aromatic polyketone obtainable by the method according to any one of <1> to <4>.

<6> An aromatic polyketone film containing the aromatic polyketone as described in <5>.

<7> base material,
The aromatic polyketone film according to <6>, provided on at least a part of the surface of the substrate;
A substrate with an aromatic polyketone film having

<8> An optical element having the aromatic polyketone film as set forth in <6> or the base material with an aromatic polyketone film as set forth in <7>.

<9> An image display device having the aromatic polyketone film according to <6> or the substrate with an aromatic polyketone film according to <7>.

  According to the present invention, a method for producing an aromatic polyketone which is excellent in transparency and heat resistance and obtains a high molecular weight aromatic polyketone, and an aromatic polyketone excellent in transparency, heat resistance and strength, an aromatic polyketone film, an aroma It is possible to provide a substrate having a group polyketone film, an optical element and an image display device.

Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including the element steps and the like) are not essential unless clearly indicated otherwise in principle, in the case where it is clearly indicated in principle. The same applies to numerical values and ranges thereof, and does not limit the present invention.
In the present specification, “step” is not limited to an independent step, and can be included in the term if the intended function of the step is achieved even if it can not be clearly distinguished from other steps.

The numerical range shown using "-" in this specification shows the range which includes the numerical value described before and after "-" as minimum value and the maximum value, respectively.
In the present specification, the “film” includes the configuration of a shape formed in part, in addition to the configuration of the shape formed on the entire surface when observed as a plan view. In the present specification, the term “layer” includes the configuration of a shape formed in part, in addition to the configuration of a shape formed on the entire surface when observed as a plan view. The term "stacking" refers to stacking layers, two or more layers may be combined, and two or more layers may be removable.

In the present specification, “transparency” means that the visible light transmittance and the visible light transmittance of at least 400 nm are at least 80% (film thickness is 1 μm).
In the present specification, “heat resistance” means that generation of yellowing and cracking due to heating is suppressed in a member containing an aromatic polyketone.

  Moreover, in the present specification, "poor solvent" means being a poor solvent for aromatic polyketones, specifically, a solvent in which only 0.01 g or less of aromatic polyketone is dissolved in 100 g of solvent is used. means. And a "good solvent" means being a good solvent to aromatic polyketone, and specifically means a solvent in which 1 g or more of aromatic polyketone is dissolved in 100 g of solvent.

<Method of producing aromatic polyketone>
The method for producing an aromatic polyketone comprises 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) Condensation reaction in an acidic medium with a molar ratio of aromatic monomer to dicarboxylic acid monomer (aromatic monomer / dicarboxylic acid monomer) in a range of 0.5 or more and less than 1 with at least one dicarboxylic acid monomer represented by Let The aromatic polyketone obtained by this production method is hereinafter also referred to as "specific aromatic polyketone".

  Generally, a polymer is polymerized using a monomer A ′ having two or more identical functional groups A in the molecule and a monomer B ′ having two or more functional groups B capable of reacting with A ′ in the molecule. In the case where the monomer A ′ and the monomer B ′ are charged in equal amounts, the molecular weight tends to be the highest.

  However, as a result of intensive studies, the present inventors have found that, in the condensation reaction of a specific aromatic polyketone, the molecular weight tends to be high by charging a dicarboxylic acid monomer to the aromatic monomer in a larger amount than the equivalent amount. . The higher the molecular weight, the better the heat resistance and the strength.

  On the other hand, as the preparation amount of the dicarboxylic acid monomer to the aromatic monomer increases, the aromatic polyketone which is the reaction product is colored in red or yellow. The coloring of the aromatic polyketone can be removed by bringing a solution of the aromatic polyketone in a good solvent into contact with a poor solvent to wash the aromatic polyketone. However, when the coloring of the aromatic polyketone is strong, a plurality of washing steps are required to remove the color before it can be used as a transparent resin, and the productivity is inferior.

  As a result of intensive studies, the inventors of the present invention have found that, in the condensation reaction of a specific aromatic polyketone, the molar ratio of aromatic monomer to dicarboxylic acid monomer (aromatic monomer / dicarboxylic acid monomer) (hereinafter referred to as “molar ratio (A / C) It can be removed by washing by reprecipitation within 3 times by setting the range of 0.5 or more and less than 1) and setting the number of moles of dicarboxylic acid monomer to be larger than the number of moles of aromatic monomer. It has been found that specific aromatic polyketones with high molecular weight can be obtained while suppressing the coloration to some extent.

From the viewpoint of suppressing coloring and simplifying the washing step and improving the transparency of the specific aromatic polyketone to be obtained, the range of the molar ratio (A / C) is preferably 3/5 or more and less than 1, more preferably 3/4 or more Less than 1 is more preferred.
Further, from the viewpoint of the heat resistance of the specific aromatic polyketone and the strength of the member using the specific aromatic polyketone, the range of the molar ratio (A / C) is more preferably 3/5 or more and 95/105 or less.

In general formula (1), R ¹ each 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 ¹ is preferably a hydrocarbon group having 1 to 10 carbon atoms, and from the viewpoint of reaction control, a hydrocarbon group having 1 to 5 carbon atoms is more preferable.
As the substituent in R ^1, 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 saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, alicyclic hydrocarbon groups and the like. Moreover, what combined these hydrocarbon groups may be used.

As a saturated aliphatic hydrocarbon group shown by R ¹ , methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, 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 -Triacontanyl group etc. are mentioned.

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

Examples of the alicyclic hydrocarbon group represented by R ¹ include cycloalkyl groups such as cyclohexyl, cycloheptyl, cyclooctyl and norbornyl, and cycloalkenyl groups such as cyclohexenyl.

In the general formula (1), R ² each independently represents a hydrocarbon group having a hydrogen atom or a substituent 1 to 30 carbon atoms which may have a. From the viewpoint of heat resistance, R ² is preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. As such a hydrocarbon group, those similar to those exemplified for R ¹ in the general formula (1) can be mentioned. Moreover, a halogen atom, a C1-C5 alkoxy group, a C2-C5 acyl group etc. are mentioned as a substituent.

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

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

In the general formula (3), R ³ and R ⁴ each independently represents a hydrocarbon group having a hydrogen atom or a substituent 1 to 30 carbon atoms which may have a. In addition, the part which attached the wavy line means a bond. Hereinafter, the same applies to the wavy line in the chemical formula. From the viewpoint of heat resistance, R ³ and R ⁴ are preferably each independently a hydrocarbon group having 1 to 5 carbon atoms. As such a hydrocarbon group, those similar to those exemplified for R ¹ in the general formula (1) can be mentioned. Moreover, a halogen atom, a C1-C5 alkoxy group, a C2-C5 acyl group etc. are mentioned as a substituent.

In the general formula (4), each R ⁵ is independently a hydrogen atom or a hydrocarbon group having a substituent 1 to 30 carbon atoms which may have a. From the viewpoint of heat resistance, R ⁵ is preferably independently a hydrocarbon group having 1 to 5 carbon atoms. As such a hydrocarbon group, those similar to those exemplified for R ¹ in the general formula (1) can be mentioned. Moreover, a halogen atom, a C1-C5 alkoxy group, a C2-C5 acyl group etc. are mentioned as a substituent.

  In general formula (5), Y shows a C1-C30 bivalent hydrocarbon group. The divalent group represented by Y preferably has 6 to 30 carbon atoms from the viewpoint of heat resistance.

  The divalent group represented by Y is a hydrocarbon group, and preferably contains a saturated hydrocarbon group from the viewpoint of transparency. The saturated hydrocarbon group may be a saturated aliphatic hydrocarbon group or a saturated alicyclic hydrocarbon group. From the viewpoint of achieving both higher heat resistance and transparency, the divalent group represented by Y preferably contains a saturated alicyclic hydrocarbon group. Moreover, when it contains bulky alicyclic hydrocarbon group, it exists in the tendency which can make high the solubility to a solvent, maintaining high heat resistance and transparency. In addition, the divalent group represented by Y may be a plurality of aliphatic hydrocarbon groups, a plurality of alicyclic hydrocarbon groups, or a combination thereof.

  Examples of saturated aliphatic hydrocarbon groups include methylene, ethylene, trimethylene, methylethylene, tetramethylene, 1-methyltrimethylene, ethylethylene, dimethylethylene, pentylene and n-methyltetramethylene 1-ethyltrimethylene group, 1,1-dimethyltrimethylene group, propyl ethylene group, ethyl methyl ethylene group, hexylene group, 1-methyl pentylene group, 1-ethyl tetramethylene group, 1-propyl trimethylene group, Butyl ethylene, 1,1-dimethyltetramethylene, trimethyltrimethylene, 1,1-ethylmethyltrimethylene, heptylene, octylene, nonylene, nonylene, decylene, icosanylene, triacontanylene etc. Be

  From the viewpoint of heat resistance, as a saturated aliphatic hydrocarbon group, a hexylene group, 1-methyl pentylene group, 1-ethyl tetramethylene group, 1-propyl trimethylene group, butyl ethylene group, 1,1-dimethyl tetramethylene Groups, trimethyltrimethylene group, 1,1-ethylmethyltrimethylene group, heptylene group, octylene group, nonylene group, decylene group, decylene group, icosanylene group, triacontanylene group and the like are preferable.

  As a saturated alicyclic hydrocarbon group, cyclopropane skeleton, cyclobutane skeleton, cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cycloheptane skeleton, cyclooctane skeleton, cubane skeleton, norbornane skeleton, tricyclo [5.2.1.0] decane skeleton And bivalent groups such as adamantane skeleton, diadamantane skeleton and bicyclo [2.2.2] octane skeleton.

  From the viewpoint of heat resistance, examples of the saturated alicyclic hydrocarbon group include a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cubane skeleton, a norbornane skeleton, a tricyclo [5.2.1.0] decane skeleton, an adamantane skeleton, and di Preferred are divalent groups such as adamantane skeleton and bicyclo [2.2.2] octane skeleton.

The aromatic monomer and the dicarboxylic acid monomer may each be used alone or in combination of two or more.
From the viewpoint of reactivity, the total amount of aromatic monomers desirably contains 30% by mass or more of the aromatic compound represented by the general formula (1), the general formula (2) and the general formula (4), 50% by mass It is more desirable to include% or more. From the viewpoint of reactivity, the total amount of dicarboxylic acid monomers preferably contains 30% by mass or more, and more preferably 50% by mass or more of the dicarboxylic acid compound represented by General Formula (5).

  The condensation reaction is carried out in an acidic medium. The acidic medium to be used is not particularly limited, and, for example, a mixture of diphosphorus pentaoxide and an organic sulfonic acid having a pKa of -3.0 or more (aqueous solution) (hereinafter, also referred to as "specified organic sulfonic acid") can be used. .

  In the method using a mixture of phosphorus pentoxide and a specific organic sulfonic acid, for example, an alkanesulfonic acid having 1 to 5 carbon atoms can be used as the specific organic sulfonic acid, and from the viewpoint of the transparency of the resulting polyketone, And methanesulfonic acid are preferred.

  The compounding ratio of diphosphorus pentoxide to the specific organic sulfonic acid is 1: 3 to 1:30 by mass ratio of diphosphorus pentoxide: specific organic sulfonic acid in consideration of the viscosity and the function as a condensing agent. Is preferable, and 1:10 to 1:20 is more preferable.

  The use amount of diphosphorus pentoxide and the specific organic sulfonic acid in the condensation reaction is not particularly limited as long as it can dissolve the aromatic monomer and the dicarboxylic acid monomer, and it can be used in a range from a so-called catalytic amount to a solvent amount it can. From the viewpoint of reactivity and handleability, it is preferable to use a mixture of phosphorus pentoxide and a specific organic sulfonic acid in an amount of 5 parts by mass to 100 parts by mass with respect to 1 part by mass of the dicarboxylic acid monomer.

  After completion of the condensation reaction of the aromatic monomer and the dicarboxylic acid monomer, a solution containing the aromatic polyketone (for example, a reaction solution after the condensation reaction or a solution in which the aromatic polyketone is dissolved) is brought into contact with the poor solvent The aromatic polyketone is precipitated, impurities are extracted into a poor solvent layer, and the precipitated aromatic polyketone is separated from the liquid by filtration, decantation, centrifugation or the like. After this, the separated aromatic polyketone is again dissolved in a good solvent and brought into contact with a poor solvent again to precipitate an aromatic polyketone, the impurities are extracted into a poor solvent layer, and the precipitated aromatic polyketone is filtered, decane It may be separated from the liquid by a method such as filtration or centrifugation. By repeating this operation, impurities can be more sufficiently removed from the resin.

  In the step of contacting the liquid containing the aromatic polyketone with the poor solvent to precipitate the aromatic polyketone, it is preferable to bring the liquid containing the aromatic polyketone into contact with a solution containing the poor solvent and the good solvent. It is more preferable to mix and use a good solvent. By mixing and using a poor solvent and a good solvent, low molecular weight components can be effectively removed, and a specific aromatic polyketone having a high molecular weight can be obtained.

  When the poor solvent and the good solvent are mixed and used, the blending ratio of the poor solvent and the good solvent is not particularly limited, and can be appropriately set according to the structure of the specific aromatic polyketone and the desired molecular weight. From the viewpoint of yield, the compounding ratio of the poor solvent to the good solvent (poor solvent / good solvent) is preferably more than 1/4 on a volume basis. Furthermore, from the viewpoint of the heat resistance of the specific aromatic polyketone and the strength of the member using the specific aromatic polyketone, the compounding ratio of the poor solvent to the good solvent (poor solvent / good solvent) exceeds 1/4 on a volume basis 1 / 1 or less is more preferable, and more than 1/4 and 2/3 or less is more preferable.

  In the present invention, the good solvent is not particularly limited as long as it dissolves the specific aromatic polyketone, and any solvent used in the art can be used. Examples of good solvents include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, butyl acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methyl methoxy propionate, 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, Ren, ethylbenzene, propylbenzene, cumene, diisopropylbenzene, hexyl benzene, anisole, diglyme, dimethyl sulfoxide, chloroform, dichloromethane, dichloroethane, chlorobenzene and tetrahydrofuran. These good solvents can be used singly or in combination of two or more.

  In the present invention, the poor solvent is not particularly limited as long as it precipitates the specific aromatic polyketone, and any solvent used in the art can be used. Examples of poor solvents include water, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, n-hexane, n-heptane and the like. These solvents may be used alone or in combination of two or more.

<Specific aromatic polyketone>
The specific aromatic polyketone is obtained by the above-mentioned production method. Specifically, the specific aromatic polyketone is 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 And at least one structural unit represented by the general formula (5 '). The specific aromatic polyketone has high molecular weight while the coloration is suppressed.

In general formula (1 ′), R ¹ each 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 a group is shown. Of each of the detailed general formula (1 ') ^{R 1} and ^{R 2} in, which is the general formula (1) and ^{R 1} and ^{R 2} in the same respectively.

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

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. Of each of the detailed general formula (3 ') in ^{R 3} and ^{R 4,} are each similar to the general formula (3) ^{R 3} and ^{R 4} in.

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

  In general formula (5 '), Y shows a C1-C30 bivalent group. The details of Y in the general formula (5 ') are the same as Y in the general formula (5).

<Specific aromatic polyketone membrane>
The aromatic polyketone film (hereinafter also referred to as "specific aromatic polyketone film") contains the above-mentioned aromatic polyketone. The aromatic polyketone film is excellent in strength, transparency and heat resistance.

  The method for producing the specific aromatic polyketone film is not particularly limited. For example, it can be obtained using a coating solution containing a specific aromatic polyketone. There are no particular limitations on the components of the coating solution other than the specific aromatic polyketone such as the solvent and the additives contained in the coating solution and the film forming method of the coating solution. The specific aromatic polyketone film containing the specific aromatic polyketone is superior in strength, transparency and heat resistance to an aromatic polyketone film obtained by the production method having a molar ratio (A / C) of 1 or more.

  Examples of the solvent which can be contained in the coating solution include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, butyl acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methyl methoxy pro Peonate, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 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 monomer Ether, xylene, mesitylene, ethylbenzene, propylbenzene, cumene, diisopropylbenzene, hexyl benzene, anisole, diglyme, dimethyl sulfoxide, chloroform, dichloromethane, dichloroethane, chlorobenzene and the like. These solvents may be used alone or in combination of two or more.

  The coating solution may further contain additives and the like in addition to the aromatic polyketone and the solvent. Examples of additives that can be contained in the coating solution include adhesion assistants, surfactants, leveling agents, antioxidants, and ultraviolet light deterioration inhibitors.

  From the viewpoint of enhancing the strength of the specific aromatic polyketone film and improving the reliability of the substrate, optical element and image display device using the specific aromatic polyketone film, the specific aromatic polyketone film was measured by the nanoindentation method. In this case, the elastic modulus is preferably 5.0 GPa to 15 GPa and the hardness is preferably 0.35 GPa to 1.0 GPa, and the elastic modulus is 6.0 GPa to 15 GPa and the hardness is 0.40 GPa to 1.G. More preferably, it is 0 GPa.

A nanoindentation method can apply a well-known method using a commercially available nanoindenter. In the measurement in the nanoindentation method, a substrate having a specific aromatic polyketone film (hereinafter, also referred to as a “specific aromatic polyketone film-coated substrate”) is used.
For example, using a nano indenter (Agilent Technologies Inc., Nano Indenter SA2 / DCM), triangular pyramid diamond is used as a terminal, under conditions of measurement frequency 60 MHz, indentation depth 0 nm to 500 nm, and measurement temperature 23 ° C. The elastic modulus and hardness of the specific aromatic polyketone film of the specific aromatic polyketone film-coated substrate can be measured.

<Base material with specified aromatic polyketone film>
The specific aromatic polyketone film-coated substrate has a substrate and a specific aromatic polyketone film provided on at least a part of the surface of the substrate.
In the specific aromatic polyketone film-coated substrate, the substrate is not particularly limited, and a glass substrate, a semiconductor substrate, a metal oxide insulator substrate (for example, a titanium oxide substrate and a silicon oxide substrate), a silicon nitride group And transparent resin base materials such as triacetyl cellulose, transparent polyimide, polycarbonate, acrylic resin, cycloolefin resin and the like. The shape of the substrate is not particularly limited, and may be plate-like or film-like.

  In the substrate with a specific aromatic polyketone film, the specific aromatic polyketone film may be provided on at least one surface of the substrate, and may be provided on both sides of the substrate. In the specific aromatic polyketone film-attached base material, the specific aromatic polyketone film may have a single-layer structure of one layer or a multi-layer structure in which two or more layers are laminated.

<Optical element and image display device>
The optical element and the image display apparatus have a specific aromatic polyketone film or a specific aromatic polyketone film-coated substrate. The optical element and the image display apparatus may be, for example, a liquid crystal display (LCD) or an ELD (electroluminescence) through a pressure-sensitive adhesive, an adhesive, or the like on the substrate side such as a transparent resin film constituting the substrate with the specific aromatic polyketone film. It can obtain by pasting to the member used for displays etc.).

  Various optical elements such as a polarizing plate using a specific aromatic polyketone film or a specific aromatic polyketone film-attached substrate can be preferably used for various image display devices such as liquid crystal display devices. The image display device of the present embodiment may have the same configuration as that of the conventional image display device except that a specific aromatic polyketone film or a specific aromatic polyketone film-attached substrate is used. When the image display device is a liquid crystal display device, assemble a component such as a liquid crystal cell, an optical element such as a polarizing plate, and an illumination system (backlight or the like) if necessary, and incorporate a drive circuit. It can be manufactured by The liquid crystal cell is not particularly limited, and various types such as TN type, STN type, and π type can be used, for example.

  The image display is used for any suitable application. The applications are, for example, desktop computers, notebook computers, office automation equipment such as copiers, mobile phones, watches, digital cameras, portable information terminals (PDAs), portable devices such as portable game machines, video cameras, televisions, microwave ovens, etc. Home electric appliances, back monitors, monitors for car navigation systems, in-car devices such as car audio, display devices such as information monitors for commercial stores, security devices such as monitoring monitors, care devices such as nursing care monitors, Medical devices, such as a medical monitor, etc. are mentioned.

  Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to these examples unless it deviates from the gist thereof. In addition, unless there is particular notice, "part" and "%" are mass references.

Synthesis Example 1
The polyketones PK1-1 to PK1-4 were obtained by the following synthesis method in common except changing the preparation amounts of the aromatic monomer and the dicarboxylic acid monomer as shown in Table 1.
To a flask containing a total of 8.0 mmol of 2,2'-dimethoxybiphenyl and 3-hexenoic acid, 12 ml of a mixed solution of phosphorus pentoxide and methanesulfonic acid (mass ratio 1:10) was added and stirred at 60 ° C. It was made to react. After the reaction, the contents were poured into 200 ml of methanol, and the formed precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain a polyketone.
At this time, when the obtained polyketone is visually colored, the polyketone is dissolved in 5 g of N-methyl-2-pyrrolidone (NMP), the solution is poured into 200 ml of distilled water, and the formed precipitate is The steps of filtration, washing and drying were repeated until the polyketone color disappeared visually.
Table 1 shows the ratio of charged monomers, the reaction time, the number of washings, and the molecular weight of the obtained polyketone.

(Composition example 2)
Polyketones PK2-1 to PK2-4 were obtained in the same manner as in Synthesis Example 1 except that dodecanedioic acid was used instead of 3-hexenedioic acid. Table 1 shows the ratio of charged monomers, the reaction time, the number of washings, and the molecular weight of the obtained polyketone.

(Composition example 3)
Polyketones PK3-1 to PK3-4 were obtained in the same manner as in Synthesis Example 1 except that cyclohexane-1,3-dicarboxylic acid was used instead of 3-hexenedioic acid. Table 1 shows the ratio of charged monomers, the reaction time, the number of washings, and the molecular weight of the obtained polyketone.

(Composition example 4)
Polyketones PK4-1 to PK4-4 were obtained in the same manner as in Synthesis Example 1 except that adamantane-1,3-dicarboxylic acid was used instead of 3-hexenedioic acid. Table 1 shows the ratio of charged monomers, the reaction time, the number of washings, and the molecular weight of the obtained polyketone.

(Measurement of molecular weight)
The molecular weight of the above polyketone is gelated using tetrahydrofuran (THF) or 1-methyl-2-pyrrolidone (NMP) dissolved so that tetrabutylammonium nitrate (TBA · NO ₃ ) is 0.1% as an eluent. It measured by the permeation chromatography (GPC) method, and calculated | required by standard polystyrene conversion. The details are as follows.

-Device name: RI-8020 (detector), DP-8020 (pump), SD-8022 (Degassa) (Tosoh Corporation)
Column: Gelpack GL-A150, GL-A160, GL-A170 (product name, Hitachi Chemical Co., Ltd.)
-Detector: RI detector-Flow rate: 1 ml / min

(Composition example 1 ')
The polyketones PK1-5 to PK1-8 were commonly obtained by the following synthesis method except that the amounts of methanol and tetrahydrofuran in the mixture of methanol and tetrahydrofuran to which the reaction solution after reaction was charged were changed.
In a flask containing 3.5 mmol of 2,2'-dimethoxybiphenyl and 4.5 mmol of 3-hexenedioate, 12 ml of a mixed solution of phosphorus pentoxide and methanesulfonic acid (mass ratio 1:10) is added, and the solution is heated to 60 ° C. It stirred. After the reaction, the contents were poured into 200 ml of a mixture of methanol and tetrahydrofuran, and the formed precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain a polyketone.
At this time, if the obtained polyketone is visually colored, the polyketone is dissolved in 5 g of NMP, the solution is poured into 200 ml of distilled water, and the formed precipitate is collected by filtration, washed and dried. The process was repeated until the polyketone color disappeared visually.
Table 2 shows the amounts of methanol and tetrahydrofuran in a mixture of methanol and tetrahydrofuran into which the reaction liquid after reaction is charged, and the molecular weight of the obtained polyketone.

(Composition example 2 ')
Polyketones PK2-5 to PK2-8 were obtained in the same manner as in Synthesis Example 1 'except that dodecanedioic acid was used instead of 3-hexenedioic acid. Table 2 shows the amounts of methanol and tetrahydrofuran in a mixture of methanol and tetrahydrofuran into which the reaction liquid after reaction is charged, and the molecular weight of the obtained polyketone.

(Synthesis example 3 ')
Polyketones PK3-5 to PK3-8 were obtained in the same manner as in Synthesis Example 1 except that cyclohexane-1,3-dicarboxylic acid was used instead of 3-hexene diacid. Table 2 shows the amounts of methanol and tetrahydrofuran in a mixture of methanol and tetrahydrofuran into which the reaction liquid after reaction is charged, and the molecular weight of the obtained polyketone.

(Composition example 4 ')
Polyketones PK4-5 to PK4-8 were obtained in the same manner as in Synthesis Example 1 except that adamantane-1,3-dicarboxylic acid was used instead of 3-hexene diacid. Table 2 shows the amounts of methanol and tetrahydrofuran in a mixture of methanol and tetrahydrofuran into which the reaction liquid after reaction is charged, and the molecular weight of the obtained polyketone.

(Comparative Synthesis Example: Synthesis of Polyimide Precursor PI)
4.0 g of 4,4'-diaminodiphenyl ether was dissolved in 34 g of fully dehydrated N, N-dimethylacetamide (DMAc). Then, to this solution, 3.2 g of 4,4'-carbonylbis (benzene-1,2-dicarboxylic acid) 1,2: 1 ', 2'-dianhydride and benzene-1,2,4,5- A mixture of 2.2 g of tetracarboxylic acid 1,2: 4,5-dianhydride was slowly added. Then, the obtained solution was stirred at room temperature (25 ° C.) for 24 hours to obtain a DMAc solution of polyamic acid (polyimide precursor) PI.
The weight average molecular weight calculated | required by standard polystyrene conversion of the GPC method of polyimide precursor PI was 50,000.

(Measurement of thermal decomposition temperature)
The powder of the polyketone obtained in the synthesis example or the powder of the polyimide precursor obtained in the comparative synthesis example was weighed in an aluminum cup, and the weight loss was measured using a thermogravimetric balance (Hitachi High-Tech Science Co., Ltd., TG-DTA6300). The point of intersection of the tangents of the curve whose weight is greatly reduced by heating is defined as the thermal decomposition temperature. The thermal decomposition temperature of each polyketone is shown in Table 3.

(Film formation)
A solution of the polyketone obtained in the synthesis example in NMP or an N, N-dimethylacetamide (DMAc) solution of the polyimide precursor obtained in the comparative synthesis example is filtered with a membrane filter (pore diameter 5 μm) made of polytetrafluoroethylene The coating solution was obtained.
The resulting coating solution is coated on a silicon substrate or glass substrate using a spin coater (Mikasa Co., Ltd., MS-A) to a uniform thickness, and heated for 3 minutes on a hot plate at 120 ° C. Heated. This is put in a high-temperature clean oven (Koyo Thermo System Co., Ltd., CLH-21CD (III)) purged with nitrogen, heated from 25 ° C to 200 ° C in 1 hour, and further heated at 200 ° C for 1 hour to cure The temperature was lowered from 200.degree. C. to 80.degree. C. for 1 hour to obtain test substrates used in Examples and Comparative Examples. The thickness of the aromatic polyketone film or polyimide film in the obtained test substrate was 1 μm to 3 μm.

(Measurement of elastic modulus and hardness)
The elastic modulus and hardness were measured using a nano indenter Nano Indenter SA2 / DCM (Agilent Technologies, Inc.) using the silicon substrate with aromatic polyketone film and the silicon substrate with polyimide film of Examples and Comparative Examples. A triangular pyramid diamond was used as a terminal, and measurement was performed under the conditions of measurement frequency 60 MHz, indentation depth 0 nm to 500 nm, and measurement temperature 23 ° C. The results are shown in Table 3.

(Measurement of transmittance)
The transmittance of ultraviolet light at 400 nm of the glass substrate with an aromatic polyketone film and the glass substrate with a polyimide film of Examples and Comparative Examples was measured using an ultraviolet-visible spectrophotometer (U-3310 Spectrophotometer, manufactured by Hitachi High-Technologies Corporation). It was measured by the UV-visible absorption spectrum method used. The transmittance of the film converted to a film thickness of 1 μm is shown in Table 3 with the glass substrate without the film as a reference.

(Heating test)
The transmittance of ultraviolet light at 400 nm of the glass substrate with an aromatic polyketone film or the glass substrate with a polyimide film of Example or Comparative Example was measured using an ultraviolet-visible spectrophotometer (U-3310 Spectrophotometer, manufactured by Hitachi High-Technologies Corporation). It was measured by the UV-visible absorption spectrum method used. Further, after the aromatic polyketone film-coated glass substrate or the polyimide film-coated glass substrate was allowed to stand in an oven at 200 ° C. for 72 hours, the transmittance of ultraviolet light at 400 nm was measured by the same method. The post-heating transmittance of the film converted to a film thickness of 1 μm is shown in Table 3 using the glass substrate without the film as a reference.

  As shown in Table 1, the aromatic polyketone obtained by the production method of the present invention is an aroma obtained by the production method of the comparative example in which the molar ratio (A / C) of the aromatic monomer to the dicarboxylic acid monomer is 1 or more. The weight average molecular weight and the number average molecular weight are higher than those of group

  Also, although the purification step after the condensation reaction is optional, as shown in Table 2, the solution containing the aromatic polyketone obtained after the condensation reaction is brought into contact with a solution containing a good solvent and a poor solvent, Aromatic polyketones having higher weight average molecular weight and number average molecular weight can be efficiently obtained. When the volume ratio of methanol to tetrahydrofuran (methanol: tetrahydrofuran) was 40: 160, recovery of the polyketones PK1-8, PK2-8, PK3-8 and PK4-8 was difficult. However, since it is shown in Table 2 that the molecular weight tends to increase as the ratio of tetrahydrofuran increases, the molecular weights of PK1-8, PK2-8, PK3-8 and PK4-8 are the same as PK1-4 of the comparative example. It can be seen that the molecular weight of PK2-4, PK3-4 and PK4-4 is higher than that of

As can be seen by comparing Examples 1 to 6 of Table 3 and Comparative Examples 1 to 4, the aromatic polyketone obtained by the production method of the present invention has a heat compared to the aromatic polyketone obtained by the production method of the Comparative Example. Decomposition temperature is high. Moreover, the aromatic polyketone film containing the aromatic polyketone obtained by the manufacturing method of the present invention is higher in strength than the polyketone film containing the aromatic polyketone obtained by the manufacturing method of the comparative example, and the transmittance decreases due to heating. Less is.
Further, as shown in Comparative Example 5, the aromatic polyketone film containing the aromatic polyketone obtained by the production method of the present invention is stronger and more transparent than the polyimide film containing the polyimide which is a thermosetting resin having high heat resistance. Excellent in quality.

Claims (4)

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 at least one kind of one represented by the following general formula (5) A method for producing an aromatic polyketone, in which a dicarboxylic acid monomer is condensation-reacted in an acidic medium at a molar ratio of aromatic monomer to dicarboxylic acid monomer (aromatic monomer / dicarboxylic acid monomer) in the range of 0.5 or more and less than 1. .


[In general formula (1), R ¹ each 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 a group is shown. ]


[In general formula (2), R ¹ each 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) And a divalent group represented by ]


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


[In general formula (4), R < ⁵ > shows a hydrogen atom or a C1-C30 hydrocarbon group which may have a substituent each independently. ]


[In general formula (5), Y shows a C1-C30 bivalent hydrocarbon group. ]   The method for producing an aromatic polyketone according to claim 1, wherein Y in the general formula (5) is a divalent saturated hydrocarbon group.   The aromatic polyketone according to claim 1 or 2, wherein in the general formula (5), Y is a C6-C30 divalent hydrocarbon group containing a saturated alicyclic hydrocarbon group. Method. The liquid containing the aromatic polyketone obtained after the said condensation reaction is made to contact with the solution containing the good solvent of aromatic polyketone and the poor solvent of aromatic polyketone to any one of Claims 1-3. producing how aromatic polyketone according.