JP2020105287A - Polyketone composition containing hydrazide compound, polyketone cured product, optical element and image display device - Google Patents

Abstract

To provide a polyketone composition that can be cured to give a cured product having excellent heat resistance and low linear expansion coefficients, and a cured product thereof, and an optical element and an image display device having the polyketone cured product.SOLUTION: This polyketone composition contains a hydrazide compound and a polyketone that contains a structural unit represented by general formula (I). In general formula (I), each X independently represents a C6-50 divalent group having an aromatic ring; each Y independently represents a C6-50 divalent group having an aromatic ring; and n represents a number of structural units.SELECTED DRAWING: None

Description

The present disclosure relates to a polyketone composition, a polyketone cured product, an optical element, and an image display device.

Aromatic polyketones having an aromatic ring and a carbonyl group in the main chain have excellent heat resistance and mechanical properties and are used as engineering plastics. Most of polymers belonging to aromatic polyketones are aromatic polyether ketones polymerized by utilizing a nucleophilic aromatic substitution reaction (for example, Patent Document 1).

Further, it has been reported that an aromatic polyketone excellent in mechanical strength, electrical characteristics and the like can be obtained by directly polymerizing an aromatic dicarboxylic acid and a diaryl compound by Friedel-Crafts acylation (for example, Patent Document 2). reference).

Further, in recent years, it has been reported that an aromatic polyketone having high transparency and heat resistance can be obtained by directly polymerizing an aromatic compound such as 2,2′-dialkoxybiphenyl and an alicyclic dicarboxylic acid. (For example, refer to Patent Document 3). Such a material having both transparency and heat resistance can be expected to be applied to an optical member such as a flexible display substrate.

JP 62-7730 A JP-A-59-135224 JP, 2013-53194, A

In addition to high transparency, an optical member may be required to have a high glass transition point (Tg) and a low linear expansion coefficient (CTE). However, the conventional aromatic polyketone has room for improvement in the glass transition point and the linear expansion coefficient.

In view of the above situation, the present disclosure provides a polyketone composition capable of producing a cured product having excellent heat resistance and a low linear expansion coefficient, and a cured product thereof, and an optical element having the polyketone cured product. Another object of the present invention is to provide an image display device.

Means for solving the above problems include the following embodiments.

<1> A polyketone composition containing a polyketone containing a structural unit represented by the following general formula (I) and a hydrazide compound.

[In the general formula (I), X's each independently represent a divalent group having 6 to 50 carbon atoms containing an aromatic ring, and Y's each independently represent 2 having 2 to 6 carbon atoms containing an aromatic ring. Represents a valent group, and n represents the number of structural units. ]
<2> In the general formula (I), each X independently represents a divalent group represented by at least one selected from the group consisting of the following general formulas (II-1) to (II-3). The polyketone composition according to <1>, which comprises:

[In the general formula ^{(II-1), R} 1 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, ^{R 2} each independently represents a substituent, m, respectively It independently represents an integer of 0 to 3. ]

[In the general formula (II-2), ^{R 1} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, ^{R 2} each independently represents a substituent, m, respectively Independently, it represents the integer of 0-3 and Z represents the divalent group selected from an oxygen atom or the following general formula (III-1)-(III-7). ]

[In general formulas (III-1) to (III-7), R ^1's each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and R ^2's each independently represent a substituent. R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. m represents the integer of 0-3 each independently, n represents the integer of 0-4 each independently, p represents the integer of 0-2 each independently. ]

[In the general formula (II-3), ^{R 5} each independently represent a substituent, n is independently an integer of 0-4. ]
<3> In the general formula (I), Y contains at least one divalent group selected from the group consisting of the following general formulas (IV-1) to (IV-5), <1> or < The polyketone composition according to 2>.

[In general formulas (IV-1) to (IV-5), each R ⁶ independently represents a substituent. In formula (IV-5), R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. n represents the integer of 0-4 each independently. m independently represents an integer of 0 to 3. ]
<4> The polyketone composition according to any one of <1> to <3>, wherein the hydrazide compound has two or more hydrazide groups in the molecule.
<5> The polyketone composition according to any one of <1> to <4>, wherein the hydrazide compound is an aromatic hydrazide compound.
<6> The polyketone composition according to any one of <1> to <5>, which further contains a solvent.
<7> A polyketone cured product, which is a cured product of the polyketone composition according to any one of <1> to <6>.
<8> An optical element having the polyketone cured product according to <7>.
<9> An image display device having the polyketone cured product according to <7>.

According to the present disclosure, when a cured product is obtained, a polyketone composition capable of producing a cured product having excellent heat resistance and a low linear expansion coefficient, the cured product thereof, and an optical element and an image display having the polyketone cured product are provided. A device can be provided.

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 element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and does not limit the present invention.

In the present disclosure, the numerical range indicated by using "to" indicates the range including the numerical values before and after "to" as the minimum value and the maximum value, respectively.
In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other stages. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, each component may include a plurality of types of corresponding substances. When there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, the term “layer” or “film” means that when the region in which the layer or film is present is observed, in addition to being formed over the entire region, only in a part of the region. The case of being formed is also included.
In the present disclosure, the term “laminate” refers to stacking layers, two or more layers may be combined and two or more layers may be removable.

In the present disclosure, when the hydrocarbon group has a substituent, the carbon number of the hydrocarbon group does not include the carbon number of the substituent. When the chain hydrocarbon group has a branched chain, the branched chain is not included in the substituents of the chain hydrocarbon group.

In the present disclosure, “excellent in transparency” means that the transmittance of visible light (at least the transmittance of visible light having a wavelength of 500 nm) is 80% or more (converted to a film thickness of 10 μm).

In the present disclosure, “heat resistance” means that the glass transition point (Tg) of the member containing polyketone is 270° C. or higher.

In the present disclosure, “low CTE” means that the CTE of the member containing polyketone is 60 ppm/° C. or less.

In the present disclosure, “excellent flexibility” means that even if the cured film is subjected to a mandrel test using a core rod having a diameter of 2 mm by the method of the example, the film does not crack.

<Polyketone composition>
The polyketone composition of the present disclosure contains a polyketone including a structural unit represented by the following general formula (I) (hereinafter, also referred to as “specific polyketone”) and a hydrazide compound.

In the general formula (I), X's each independently represent a divalent group having 6 to 50 carbon atoms containing an aromatic ring, and Y's each independently represent a divalent group containing 6 to 50 carbon atoms containing an aromatic ring. Represents the group, and n represents the number of structural units.

With the above configuration, the polyketone composition of the present disclosure can achieve excellent heat resistance and a low linear expansion coefficient when made into a cured product. The reason is not clear, but it is considered as follows.
The specific polyketone has excellent heat resistance. Furthermore, when the polyketone composition contains a hydrazide compound, the hydrazide compound can act on the specific polyketone to form a crosslinked structure. Therefore, it is considered that when the polyketone composition is used as a cured product, it exhibits a high Tg and a low CTE.
Further, the cured product produced using the polyketone composition of the present disclosure tends not to have cracks even when bent, that is, it tends to have good flexibility. It is presumed that this is because the cured product forms a crosslinked structure, and therefore the toughness is improved.
Furthermore, since the specific polyketone has excellent transparency, the cured product produced using the polyketone composition of the present disclosure tends to have excellent transparency.
Hereinafter, each component contained in the polyketone composition of the present disclosure will be described.

(A) Specific Polyketone The polyketone composition contains a specific polyketone. The specific polyketone includes a structural unit represented by the following general formula (I).

In the general formula (I), X's each independently represent a divalent group having 6 to 50 carbon atoms containing an aromatic ring, and Y's each independently represent a divalent group containing 6 to 50 carbon atoms containing an aromatic ring. Represents the group, and n represents the number of structural units.

The specific polyketone may include the structural unit represented by the general formula (I) in the main chain or in the side chain, and it is preferable to include it in the main chain.

In general formula (I), n represents the number of structural units. n is preferably an integer of 1 to 1500, and more preferably an integer of 2 to 1000.

X's each independently represent a divalent group having 6 to 50 carbon atoms and containing an aromatic ring. The divalent group represented by X has 6 to 50 carbon atoms, preferably 6 to 30 carbon atoms, and more preferably 6 to 24 carbon atoms.

The divalent group represented by X may have a substituent. The substituent that X may have is not particularly limited, and specific examples thereof include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, and the like.

Examples of the aromatic ring contained in X include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a naphthacene ring, a chrysene ring, a pyrene ring, a triphenylene ring, a pentacene ring, and a benzopyrene ring. The aromatic ring contained in X is preferably present on the main chain of the specific polyketone, that is, one linked to the main chain.

Furthermore, the divalent group represented by X preferably contains a plurality of aromatic rings, and the plurality of aromatic rings are non-conjugated to each other or have a weak conjugation relationship with each other (hereinafter, It is more preferably a “specific aromatic ring group”). Thereby, when synthesizing a polyketone, good diacylation can be realized at a low reaction temperature, and a polyketone having a high molecular weight and excellent heat resistance tends to be obtained. The specific aromatic ring group preferably has 12 to 50 carbon atoms.

Here, "a plurality of aromatic rings are non-conjugated to each other or weak mutual conjugation relation" means that a plurality of aromatic rings are bonded via an ether bond or a methylene bond, or It means that conjugation between aromatic rings is suppressed by steric hindrance due to a substituent such as 2′-substituted biphenyl.

X is preferably a divalent group represented by at least one selected from the group consisting of the following general formulas (II-1) to (II-3).

In formula (II-1), R ^1's each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, R ^2's each independently represent a substituent, and m's are each independently. Represents an integer of 0 to 3.
The wavy line portion means a bond. The same applies thereafter.

In formula (II-1), R ^1's each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. When R ¹ is a hydrocarbon group having 1 to 30 carbon atoms, the hydrocarbon group represented by R ¹ preferably has 1 to 10 carbon atoms, and preferably 1 to 6 from the viewpoint of heat resistance. Is more preferable.

The hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ may be a chain hydrocarbon group or a cyclic hydrocarbon group. In the present disclosure, the cyclic hydrocarbon group means a hydrocarbon group having at least one cyclic hydrocarbon. When R ¹ is a chain hydrocarbon group, the chain hydrocarbon group may be linear or branched.
The hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ may or may not have an unsaturated bond.
The hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ may or may not have a substituent. The substituent that the hydrocarbon group represented by R ¹ may have is not particularly limited, and examples thereof include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms.

Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ include a chain saturated aliphatic hydrocarbon group, a chain unsaturated aliphatic hydrocarbon group, and an alicyclic hydrocarbon group.

Examples of the chain saturated aliphatic hydrocarbon group include 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-triaconta group Examples thereof include a nyl group.

Examples of the chain unsaturated aliphatic hydrocarbon group include a vinyl group, an alkenyl group such as an allyl group, and an alkynyl group such as an ethynyl group.

Examples of the alicyclic structure contained in the alicyclic hydrocarbon group include cycloalkyl groups such as cyclohexyl group, cycloheptyl group, cyclooctyl group and norbornyl group; cycloalkenyl groups such as cyclohexenyl group. The alicyclic hydrocarbon group may or may not have an unsaturated bond.

The hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ may be, for example, a combination of a chain saturated aliphatic hydrocarbon group and a chain unsaturated aliphatic hydrocarbon group (in this case, R ^{1 as a} whole may be a chain unsaturated aliphatic hydrocarbon group) or a combination of a chain saturated aliphatic hydrocarbon group and an alicyclic hydrocarbon group (in this case, R ¹ It may be classified as an alicyclic hydrocarbon group as a whole), or may be a combination of a chain unsaturated aliphatic hydrocarbon group and an alicyclic hydrocarbon group (in this case, R ^{1 as a} whole is an alicyclic group). Formula hydrocarbon group), a combination of a chain saturated aliphatic hydrocarbon group, a chain unsaturated aliphatic hydrocarbon group and an alicyclic hydrocarbon group (in this case, R ^{1 as a} whole) As classified as alicyclic hydrocarbon groups).

In formula (II-1), R ^2's each independently represent a substituent. Examples of the substituent represented by R ² include a hydrocarbon group having 1 to 30 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, and the like. It is preferably 30 hydrocarbon groups.

When R ² is a hydrocarbon group having 1 to 30 carbon atoms, the hydrocarbon group represented by R ² preferably has 1 to 10 carbon atoms, and preferably 1 to 5 from the viewpoint of heat resistance. Is more preferable. The details of the hydrocarbon group having 1 to 30 carbon atoms represented by R ² can be the details of the hydrocarbon group having 1 to 30 carbon atoms exemplified for R ¹ .

In the general formula (II-1), m independently represents an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1.

In formula (II-2), R ^1's each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, R ^2's each independently represent a substituent, and m's are each independently. Represents an integer of 0 to 3, Z represents an oxygen atom or a divalent group selected from the following general formulas (III-1) to (III-7).

In formulas (III-1) to (III-7), R ^1's each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and R ^2's each independently represent a substituent. , R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. m represents the integer of 0-3 each independently, n represents the integer of 0-4 each independently, p represents the integer of 0-2 each independently.

Each of the details of the ^R 1, ^{R 2,} and m in formula (II-2), is the same as ^R 1, ^{R 2,} and m in Formula (II-1).

In General Formula (III-1), R ³ and R ⁴ represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and from the viewpoint of heat resistance, a hydrocarbon group having 1 to 5 carbon atoms. Is preferred. Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ³ and R ⁴ are exemplified as “hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ ” in the general formula (II-1). The same thing as a hydrocarbon group is mentioned.

In formulas (III-1) to (III-7), n independently represents an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1. ..

In general formulas (III-1) to (III-7), p's each independently represent an integer of 0 to 2, and preferably 0 or 1.

In formula (II-3), R ^5's each independently represent a substituent, and n's each independently represent an integer of 0 to 4.

From the viewpoint of heat resistance, examples of the substituent represented by R ⁵ include a hydrocarbon group having 1 to 30 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, and the like. It is preferably a hydrocarbon group having 1 to 30 carbon atoms.

When R ⁵ is a hydrocarbon group having 1 to 30 carbon atoms, the hydrocarbon group represented by R ⁵ preferably has 1 to 10 carbon atoms and has 1 to ⁵ carbon atoms in terms of heat resistance. Is more preferable. The details of the hydrocarbon group having 1 to 30 carbon atoms represented by R ⁵ can be the details of the hydrocarbon group having 1 to 30 carbon atoms exemplified for R ¹ in formula (II-1).

In general formula (II-3), n each independently represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and 0 or 1 Is more preferable.

The specific polyketone contains two or more kinds of structural units having a divalent group represented by at least one selected from the group consisting of the general formulas (II-1) to (II-3) at the X position. May be

In formula (I), Y's each independently represent a divalent group having 6 to 50 carbon atoms and containing an aromatic ring. The divalent group represented by Y has 6 to 50 carbon atoms, and preferably 6 to 30 carbon atoms. When Y has an aromatic ring, the cured product produced using the polyketone composition of the present disclosure tends to achieve higher heat resistance.
The aromatic ring contained in Y is preferably present on the main chain of the specific polyketone, that is, one which is linked to the main chain.

The divalent group represented by Y may or may not have a substituent. The substituent that Y may have is not particularly limited, and specific examples thereof include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, and the like.

Y is preferably a group containing a divalent group represented by at least one selected from the group consisting of the following general formulas (IV-1) to (IV-5), and from the viewpoint of low CTE: Is preferably a divalent group represented by at least one selected from the group consisting of the following general formulas (IV-1) to (IV-5). Y may be a divalent group represented by at least one selected from the group consisting of general formulas (IV-1) to (IV-5) in which an alkylene group or the like is linked to a bond. ..

In formulas (IV-1) to (IV-5), R ^6's each independently represent a substituent. In formula (IV-5), R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. n represents the integer of 0-4 each independently. m independently represents an integer of 0 to 3.

R ^6's each independently represent a substituent. As the details of R ^6, the details of R ² of the general formula (II-1) can be applied.

R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and preferably a hydrocarbon group having 1 to 5 carbon atoms. Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ³ and R ⁴ include those similar to the hydrocarbon group having 1 to 30 carbon atoms exemplified for R ¹ in the general formula (II-1). To be

The specific polyketone contains two or more kinds of structural units having a divalent group represented by at least one selected from the group consisting of the above general formulas (IV-1) to (IV-5) at the Y position. May be

Specific examples of preferred embodiments of the specific polyketone include X represented by at least one selected from the group consisting of the formulas (II-1) to (II-3) and the formulas (IV-1) to ( And IV represented by at least one selected from the group consisting of IV-5). More specifically, a combination of at least one selected from the group consisting of X1 to X4 below and at least one selected from the group consisting of Y1 to Y5 below can be mentioned.

The weight average molecular weight (Mw) of the specific polyketone is preferably 500 or more in terms of polystyrene standard GPC (gel permeation chromatography, gel permeation chromatography) from the viewpoint of maintaining heat resistance, and higher heat resistance and solvent. From the standpoint of solubility in, it is more preferably 1,000 to 1,000,000, and even more preferably 4,000 to 500,000. The weight average molecular weight (Mw) of the specific polyketone is a value measured by the method described in Examples.

The number average molecular weight (Mn) of the specific polyketone is preferably 500 or more in terms of standard GPC in terms of polystyrene from the viewpoint of maintaining heat resistance, and is 1,000 to 100,000 from the viewpoint of higher thermal decomposition resistance. It is more preferable to be present, and it is further preferable to be 1,500 to 50,000. The number average molecular weight of the polyketone is a value measured by the method described in Examples.

The specific polyketone may be used alone or in combination of two or more. In addition, the polyketone composition may contain a polyketone other than the specific polyketone. Hereinafter, the specific polyketone and other polyketones may be collectively referred to as “polyketone”.
From the viewpoint of heat resistance and low coefficient of thermal expansion when it is a cured product, the content of the specific polyketone with respect to the total amount of polyketone is preferably 50 mass% or more, more preferably 60 mass% or more, It is more preferably 70% by mass or more.

From the viewpoint of heat resistance, transparency, and flexibility when it is a cured product, the total content of the polyketone is 50 parts by mass to 99 parts by mass with respect to 100 parts by mass of the total amount of the polyketone and the hydrazide compound. It is more preferably 50 parts by mass to 95 parts by mass.

[Method for producing polyketone]
The method for producing the polyketone of the present disclosure is not particularly limited, and for example, it has a monomer having a divalent group having 6 to 50 carbon atoms containing an aromatic ring and a divalent group having 6 to 50 carbon atoms containing an aromatic ring. A method in which a dicarboxylic acid is subjected to a condensation reaction in an acidic medium can be used.

The details of the “divalent group having 6 to 50 carbon atoms containing an aromatic ring” in the “monomer having a divalent group containing 6 to 50 carbon atoms containing an aromatic ring” are described in the above formula (I). Is the same as the details. As the "monomer having a divalent group having 6 to 50 carbon atoms containing an aromatic ring", for example, the bond in each of the above general formulas (II-1) to (II-3) is replaced with a hydrogen atom. Monomers are examples. The "monomer containing a divalent group having 6 to 50 carbon atoms containing an aromatic ring" may be used alone or in combination of two or more.

The details of the "divalent group having 6 to 50 carbon atoms and containing an aromatic ring" in the "dicarboxylic acid having a divalent group having 6 to 50 carbon atoms and containing an aromatic ring" are described in the above general formula (I). The details of Y are the same. In the present disclosure, the carbon number of the dicarboxylic acid does not include the carbon of the carboxy group. Examples of the "dicarboxylic acid having a divalent group having 6 to 50 carbon atoms containing an aromatic ring" include dicarboxylic acids in which the bonds in the general formulas (IV-1) to (IV-5) are each replaced by a carboxyl group. An acid is mentioned. The "dicarboxylic acid having an aromatic ring-containing divalent group having 6 to 50 carbon atoms" may be used alone or in combination of two or more.

Specific examples of the monomer having an aromatic ring-containing divalent group having 6 to 50 carbon atoms include 2,2′-dimethoxybiphenyl, 2,2′-bis(2-methoxyphenyl)propane, biphenyl ether, and the following formulas. The compound etc. which are represented by (VII) are mentioned.

Specific examples of the dicarboxylic acid having a divalent group having 6 to 50 carbon atoms including an aromatic ring include 4,4′-dicarboxybiphenyl ether, terephthalic acid, isophthalic acid, diphenic acid and 2,6-naphthalenedicarboxylic acid. Etc.

The acidic medium used for the condensation reaction is not particularly limited and, for example, an organic solvent solution of aluminum chloride, an organic solvent solution of trifluoroalkanesulfonic acid, polyphosphoric acid, and a mixture of diphosphorus pentoxide and organic sulfonic acid may be used. it can. From the viewpoint of reactivity and handleability, it is preferable to use a mixture of diphosphorus pentoxide and organic sulfonic acid as the acidic medium, and more preferably methanesulfonic acid as the organic sulfonic acid.

The mixing ratio of diphosphorus pentoxide and organic sulfonic acid is preferably phosphorus pentoxide:organosulfonic acid=1:5 to 1:20 in terms of mass ratio from the viewpoint of control of the mixing ratio and reactivity. It is more preferably 1:5 to 1:10. When the mixing ratio of diphosphorus pentoxide and organic sulfonic acid is within the above range, the reactivity tends to be excellent.

The amount of the acidic medium to be mixed with the raw material is not particularly limited, and the acidic medium can be used in the range from the catalytic amount to the solvent amount. From the viewpoint of reactivity and ease of handling, the amount of the acidic medium is preferably in the range of 5 parts by mass to 100 parts by mass with respect to 1 part by mass of the total amount of the dicarboxylic acid.

The reaction temperature is preferably 10°C to 100°C from the viewpoint of preventing coloration of reaction products and side reactions, and is 20°C to 100°C from the viewpoint of increasing the reaction rate and improving productivity. More preferably.

The reaction atmosphere is not particularly limited, and the reaction can be performed in an open system. If the water content is low, the reactivity of the acidic medium tends to be improved, so that it is preferable to use dry air, nitrogen, argon or the like. From the viewpoint of preventing an unexpected side reaction, it is more preferable to use nitrogen or argon.

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

The reaction time is not particularly limited, and can be appropriately adjusted depending on the reaction temperature, the target molecular weight of the polyketone, the type of raw material used in the reaction, and the like. The reaction time is preferably about 1 to 120 hours from the viewpoint of obtaining a polyketone having a sufficiently high molecular weight, and more preferably 1 to 72 hours from the viewpoint of productivity.

The reaction pressure is not particularly limited, and the reaction may be carried out under normal pressure, increased pressure, or reduced pressure.
From the viewpoint of cost, it is preferable to carry out the reaction under normal pressure.

After completion of the reaction, the reaction solution may be contacted with a poor solvent to precipitate polyketone, impurities may be extracted into the poor solvent phase, and the precipitated polyketone may be separated from the liquid by a method such as filtration, decantation, or centrifugation. it can. Further after this, the separated polyketone is again dissolved in a good solvent, and again brought into contact with a poor solvent to precipitate the polyketone, impurities are extracted into the poor solvent phase, and the precipitated polyketone is filtered, decanted, centrifuged or the like. The step of separating from the liquid with may be repeated.

<Hydrazide compound>
The polyketone composition of the present disclosure contains a hydrazide compound. When the polyketone composition of the present disclosure contains a hydrazide compound in combination with the above polyketone, a cured product having excellent heat resistance and a low linear expansion coefficient can be obtained. Although the detailed reason is not clear, it is considered that the use of the hydrazide compound as the curing agent stabilizes the crosslinked structure, and exhibits excellent Tg and a low linear expansion coefficient. The above-mentioned effect tends to be excellently exhibited, for example, as compared with the case where an amine compound is used as a curing agent.

The hydrazide compound preferably has two or more hydrazide groups in the molecule. Among them, the hydrazide compound preferably has 2 to 6 hydrazide groups in the molecule, more preferably 2 to 4 hydrazide groups, and more preferably 2 or 3 hydrazide groups. Is particularly preferable. The hydrazide group represents a group represented by the following formula (VII).

As the hydrazide compound, a chain aliphatic hydrazide compound may be used, an alicyclic hydrazide compound may be used, or an aromatic hydrazide compound may be used. From the viewpoint of heat resistance, it is preferable to use an aromatic hydrazide compound.

In the present disclosure, the alicyclic hydrazide compound refers to a hydrazide compound having an alicyclic structure in the molecule. The aromatic hydrazide compound means a hydrazide compound having an aromatic ring in the molecule. The chain aliphatic hydrazide compound means a chain aliphatic hydrazide compound having neither an alicyclic ring nor an aromatic ring in the molecule. The hydrazide compound may be a compound having both an alicyclic ring and an aromatic ring in the molecule. That is, the hydrazide compound may be a compound corresponding to both an alicyclic hydrazide compound and an aromatic hydrazide compound.

When the hydrazide compound is a chain aliphatic hydrazide compound, it is preferable that the portion excluding the hydrazide group of the hydrazide compound (hereinafter, also referred to as a skeleton portion) is a chain aliphatic hydrocarbon group having 1 to 30 carbon atoms. It is more preferably a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms, and further preferably a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms. Further, the aliphatic hydrazide compound may be a hydrazide compound having no aliphatic skeleton portion (that is, a hydrazide group is directly linked) such as oxalic acid dihydrazide.
The chain aliphatic hydrocarbon group may be linear or branched, and is preferably linear.
The chain aliphatic hydrocarbon group may or may not have a substituent. When the chain aliphatic hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include a halogen atom, an alkoxy group having 1 to 5 carbon atoms and an acyl group having 2 to 5 carbon atoms.
The chain aliphatic hydrocarbon group may or may not have an unsaturated bond, and preferably has no unsaturated bond.

When the hydrazide compound is an alicyclic hydrazide compound, the skeleton part of the hydrazide compound is, for example, preferably an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an alicyclic hydrocarbon having 3 to 8 carbon atoms. A group is more preferable, and an alicyclic hydrocarbon group having 3 to 6 carbon atoms is further preferable. The alicyclic hydrocarbon group is a hydrocarbon group having an alicyclic structure in at least a part thereof, and may have a chain aliphatic hydrocarbon group in addition to the alicyclic structure.
The alicyclic hydrocarbon group may or may not have a substituent. When the alicyclic hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include an alkyl group, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, and the like.
The alicyclic hydrocarbon group may or may not have an unsaturated bond.

When the hydrazide compound is an aromatic hydrazide compound, the skeleton portion of the hydrazide compound is, for example, preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms. Is more preferable, and an aromatic hydrocarbon group having 6 to 10 carbon atoms is further preferable. The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring in at least a part thereof, and has a chain aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a combination thereof in addition to the aromatic ring. You may have.
The aromatic hydrocarbon group may or may not have a substituent. When the aromatic hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include an alkyl group, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms.

The hydrazide compound is preferably a compound represented by the following general formula (VI).

In formula (VI), W represents a hydrocarbon group and n represents an integer of 2 to 6.
The hydrocarbon group represented by W is the above-mentioned chain aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group, and n is preferably an integer of 2 to 4, and 2 or 3 Is more preferable.

Specific examples of the hydrazide compound include, for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, sebacic acid dihydrazide, and Examples include fumaric acid dihydrazide, itaconic acid dihydrazide and citric acid trihydrazide. From the viewpoint of heat resistance, adipic acid dihydrazide and isophthalic acid dihydrazide are preferable, and isophthalic acid dihydrazide is more preferable. The hydrazide compound may be a commercially available product or may be one synthesized by a known method.

The hydrazide compounds may be used alone or in combination of two or more. The content of the hydrazide compound is 1 part by mass to 50 parts by mass with respect to 100 parts by mass of all polyketones contained in the polyketone composition, from the viewpoint of heat resistance, transparency, and flexibility of the cured product. It is preferably 5 parts by mass to 50 parts by mass, more preferably 5 parts by mass to 30 parts by mass.

<Solvent>
The polyketone composition may further contain a solvent. The solvent is not particularly limited as long as it dissolves or disperses each component. Examples of the solvent include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, butyl acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, propylene glycol monomethyl Ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, xylene, mesitylene, ethylbenzene, propylbenzene, cumene, diisopropylbenzene, hexylbenzene, anisole, diglyme, dimethylsulfoxide, chloroform, dichloromethane, dichloroethane, chlorobenzene Etc. The solvent may be used alone or in combination of two or more kinds.

When the polyketone composition contains a solvent, the content of the solvent is preferably 5 parts by mass to 95 parts by mass, and preferably 10 parts by mass to 100 parts by mass of the total amount of the polyketone, the hydrazide compound, and the solvent. It is more preferably 90 parts by mass.

<Other additives>
The polyketone composition may further contain other additives. Other additives include adhesion promoters, surfactants, leveling agents, antioxidants, ultraviolet deterioration inhibitors, sliding agents (polytetrafluoroethylene particles, etc.), light diffusing agents (acrylic crosslinked particles, silicone crosslinked particles). , Ultra-thin glass flakes, calcium carbonate particles, etc.), fluorescent dyes, inorganic phosphors (such as phosphors with aluminate as a mother crystal), antistatic agents, crystal nucleating agents, inorganic antibacterial agents, organic antibacterial agents, photocatalysts Examples of the antifouling agent (titanium oxide particles, zinc oxide particles, etc.), crosslinking agents, curing agents, reaction accelerators, infrared absorbers (heat ray absorbers), photochromic agents and the like.

<Polyketone cured product>
The polyketone cured product of the present disclosure is a cured product of the polyketone composition of the present disclosure.
The polyketone cured product can be produced, for example, by the following method. First, a polyketone composition is applied to at least a part of the surface of a substrate to form a composition layer, and the composition is dried to remove the solvent from the composition layer, or after curing with the removal of the solvent, the composition of the present disclosure is disclosed. A polyketone cured product can be produced. The method for applying the polyketone composition to the substrate is not particularly limited as long as it is a method capable of forming the composition layer in an arbitrary shape on the substrate at an arbitrary position. Examples of the method of applying the polyketone composition to the substrate include a dipping method, a spray method, a screen printing method, a spin coating method, a spin coating method, and a bar coating method.

The substrate to which the polyketone composition is applied is not particularly limited, and includes glass, semiconductors, metal oxide insulators (titanium oxide, silicon oxide, etc.), inorganic materials such as silicon nitride, triacetyl cellulose, polyimide, polycarbonate, acrylic. Examples of the base material include resins such as a base polymer and a cycloolefin resin. The shape of the base material is not particularly limited and may be a plate shape or a film shape.

When the polyketone composition contains a solvent, it may be dried before and after curing. The drying method is not particularly limited, and examples thereof include a method of heat treatment using a device such as a hot plate and an oven, and a method of natural drying. The conditions for drying by heat treatment are not particularly limited as long as the solvent in the polyketone composition is sufficiently volatilized, and may be 50° C. to 250° C. for 1 minute to 180 minutes.

The method for curing the polyketone is not particularly limited, and the polyketone can be cured by heat treatment or the like.
Curing by heat treatment uses a box dryer, a hot air conveyor dryer, a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace, etc. Can be done.

The atmosphere for curing may be selected from the atmosphere, an inert atmosphere such as nitrogen, and the like, and is preferably performed under a nitrogen atmosphere from the viewpoint of preventing oxidation of the polyketone composition.
The temperature and time of the heat treatment for curing can be arbitrarily set in view of composition conditions, work efficiency, etc., and may be about 1 minute to 180 minutes at 50°C to 250°C.

If desired, the dried polyketone cured product of the present disclosure may be further heat treated to remove residual solvent. The method of heat treatment is not particularly limited, and is a box dryer, a hot air conveyor dryer, a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace. , A vacuum dryer or the like. Moreover, the atmosphere in the heat treatment step is not particularly limited, and examples thereof include the atmosphere and an inert atmosphere such as nitrogen. The conditions for heat treatment are not particularly limited and may be 50° C. to 250° C. for 1 minute to 180 minutes.

The haze when the polyketone cured product has a thickness of 10 μm is preferably less than 1%.
The transmittance of the polyketone cured product at the wavelength of 400 nm is preferably 80% or more in terms of the film thickness of 1 μm.

The obtained polyketone cured product can be used as a substrate with a polyketone cured product while the substrate is still attached, or can be peeled off from the substrate and used as necessary.
In the base material with a polyketone cured product, the polyketone cured product may be provided on at least a part of the surface of the base material, and may be provided on only one surface of the base material or on both surfaces. The polyketone cured product may have a single-layer structure 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 device of the present disclosure each include the polyketone cured product of the present disclosure.
The polyketone cured product applied to the optical element and the image display device may be applied as a substrate with a polyketone cured product with the substrate attached as described above. Moreover, if the base material is a transparent base material, it can be suitably used for an optical element. Examples of the transparent base material include base materials composed of resins such as triacetyl cellulose, transparent polyimide, polycarbonate, acrylic polymer, and cycloolefin resin.

The optical element and the image display device are applied to, for example, an LCD (liquid crystal display), an ELD (electroluminescence display), an organic EL display, or the like on the base material side of the base material with a polyketone cured product via an adhesive, an adhesive, or the like. You can get it by pasting it on the spot.

A cured product of polyketone and various optical elements such as a polarizing plate using the same can be preferably used in various image display devices such as liquid crystal display devices. The image display device is not particularly limited except that the polyketone cured product of the present disclosure is used, and may have the same configuration as a conventional image display device. When the image display device is a liquid crystal display device, by appropriately assembling each component such as a liquid crystal cell, an optical element such as a polarizing plate, and an illumination system (backlight, etc.) and the like, a drive circuit is incorporated. Can be manufactured. The liquid crystal cell is not particularly limited, and various types such as TN (twisted nematic) type, STN (super twisted nematic) type, and π type can be used.

Applications of image display devices include desktop personal computers, notebook computers, copiers and other OA devices, mobile phones, watches, digital cameras, personal digital assistants (PDAs), portable game devices and other portable devices, video cameras, televisions, electronic devices. Home appliances such as microwave ovens, back monitors, car navigation system monitors, car audio and other in-vehicle equipment, commercial store information monitors and other display equipment, monitoring monitors and other security equipment, nursing monitors and other nursing care Examples of the device include medical devices such as devices and medical monitors.

Hereinafter, the embodiments of the present disclosure will be specifically described by way of examples, but the embodiments of the present disclosure are not limited to these examples.

<Polyketone composition>
The following components (A) to (C) are blended in the proportions shown in Table 3, filtered through a 5 μm pore PTFE (polytetrafluoroethylene) filter, and the polyketone compositions of Examples and Comparative Examples are obtained. Obtained. The numerical value in the parenthesis represents the compounding ratio (parts by mass). "-" represents that the component is not contained. Each component in Table 3 is shown below.

Component (A): Polyketone (Synthesis Example 1) Synthesis of Polyketone PK-1 A flask containing 10 mmol of 2,2'-dimethoxybiphenyl and 10 mmol of 4,4'-dicarboxybiphenyl ether as monomers was charged with diphosphorus pentoxide and 30 ml of a mixed solution of methanesulfonic acid (mass ratio 1:10) was added, and the mixture was stirred at 60°C. After the reaction, the content was thrown 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 PK-1.
The obtained polyketone PK-1 had a weight average molecular weight of 16,000 and a number average molecular weight of 8,000. The weight average molecular weight and number average molecular weight are measured and calculated by the methods described below. The weight average molecular weight (Mw) and number average molecular weight (Mn) of polyketone PK-2 to polyketone PK-16 described later were also measured by the same method.

(Synthesis Example 2) Synthesis of polyketone PK-2 Polyketone PK-2 was obtained in the same manner as in Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl and 10 mmol of terephthalic acid were used as monomers. The obtained polyketone PK-2 had a weight average molecular weight of 5,000 and a number average molecular weight of 2,000.

(Synthesis Example 3) Synthesis of Polyketone PK-3 Polyketone PK-3 was obtained in the same manner as in Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl and 10 mmol of isophthalic acid were used as monomers. The obtained polyketone PK-3 had a weight average molecular weight of 17,000 and a number average molecular weight of 8,000.

(Synthesis example 4) Synthesis of polyketone PK-4 Polyketone PK-4 was obtained in the same manner as in Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl and 10 mmol of diphenic acid were used as monomers. The obtained polyketone PK-4 had a weight average molecular weight of 20,000 and a number average molecular weight of 10,000.

(Synthesis example 5) Synthesis of polyketone PK-5 Polyketone PK-5 was obtained in the same manner as in Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl and 10 mmol of 2,6-naphthalenedicarboxylic acid were used as monomers. It was The obtained polyketone PK-5 had a weight average molecular weight of 5,000 and a number average molecular weight of 3,000.

(Synthesis Example 6) Synthesis of polyketone PK-6 In the same manner as in Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of 4,4'-dicarboxybiphenyl ether and 5 mmol of terephthalic acid were used as monomers. Polyketone PK-6 was obtained. The obtained polyketone PK-6 had a weight average molecular weight of 8,000 and a number average molecular weight of 4,000.

(Synthesis Example 7) Synthesis of Polyketone PK-7 In the same manner as in Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of 4,4'-dicarboxybiphenyl ether and 5 mmol of isophthalic acid were used as monomers, Polyketone PK-7 was obtained. The obtained polyketone PK-7 had a weight average molecular weight of 18,000 and a number average molecular weight of 9,000.

(Synthesis Example 8) Synthesis of Polyketone PK-8 In the same manner as in Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of 4,4'-dicarboxybiphenyl ether and 5 mmol of diphenic acid were used as monomers, Polyketone PK-8 was obtained. The obtained polyketone PK-8 had a weight average molecular weight of 17,000 and a number average molecular weight of 8,000.

(Synthesis Example 9) Synthesis of polyketone PK-9 Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of 4,4'-dicarboxybiphenyl ether and 5 mmol of 2,6-naphthalenedicarboxylic acid were used as monomers. Similarly, Polyketone PK-9 was obtained. The obtained polyketone PK-9 had a weight average molecular weight of 5,000 and a number average molecular weight of 3,000.

(Synthesis Example 10) Synthesis of Polyketone PK-10 Polyketone PK-10 was obtained in the same manner as in Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of terephthalic acid and 5 mmol of diphenic acid were used as monomers. The obtained polyketone PK-10 had a weight average molecular weight of 5,000 and a number average molecular weight of 3,000.

(Synthesis Example 11) Synthesis of Polyketone PK-11 Polyketone PK-11 was obtained in the same manner as in Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of isophthalic acid and 5 mmol of diphenic acid were used as monomers. .. The obtained polyketone PK-11 had a weight average molecular weight of 17,000 and a number average molecular weight of 9,000.

(Synthesis example 12) Synthesis of polyketone PK-12 Polyketone PK was carried out in the same manner as in Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of diphenic acid and 5 mmol of 2,6-naphthalenedicarboxylic acid were used as monomers. -12 was obtained. The obtained polyketone PK-12 had a weight average molecular weight of 5,000 and a number average molecular weight of 3,000.

(Synthesis example 13) Synthesis of polyketone PK-13 Polyketone PK was carried out in the same manner as in Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of terephthalic acid and 5 mmol of 2,6-naphthalenedicarboxylic acid were used as monomers. -13 was obtained. The obtained polyketone PK-13 had a weight average molecular weight of 5,000 and a number average molecular weight of 3,000.

(Synthesis Example 14) Synthesis of polyketone PK-14 In the same manner as in Example 1 except that 10 mmol of 2,2'-bis(2-methoxyphenyl)propane and 10 mmol of 4,4'-dicarboxybiphenyl ether were used as monomers. Thus, polyketone PK-14 was obtained. The obtained polyketone PK-14 had a weight average molecular weight of 20,000 and a number average molecular weight of 10,000.

(Synthesis Example 15) Synthesis of polyketone PK-15 Polyketone PK-15 was obtained in the same manner as in Example 1 except that 10 mmol of biphenyl ether and 10 mmol of diphenic acid were used as monomers. The obtained polyketone PK-15 had a weight average molecular weight of 20,000 and a number average molecular weight of 9,800.

(Synthesis Example 16) Synthesis of polyketone PK-16 Polyketone PK-16 was obtained in the same manner as in Example 1 except that 10 mmol of the following compound (VII) and 10 mmol of 4,4'-dicarboxybiphenyl ether were used as monomers. It was The obtained polyketone PK-16 had a weight average molecular weight of 20,000 and a number average molecular weight of 12,000.

(B) Component B1: Compound represented by the following formula (VIII)

B2: a compound represented by the following formula (VIV)

B3: a compound represented by the following formula (X)

Component (C): solvent C1: mixed solvent of N-methyl-2-pyrrolidone and dimethyl sulfoxide (mass ratio 1:1)

<Preparation of evaluation sample>
Using the obtained polyketone composition, a polyketone cured product was produced by the following method, and a sample for evaluation described below was prepared.

(1) Sample for transmittance measurement A glass substrate was coated with the polyketone composition by a spin coating method and dried for 3 minutes on a hot plate heated to 120°C. The obtained glass substrate was heat-treated in an inert gas oven (Koyo Thermo System Co., Ltd.) under a nitrogen stream at 250° C. for 1 hour to form a polyketone cured product having a thickness of 10 μm on the glass substrate and permeating the same. It was used as a sample for rate measurement.

(2) Sample for Tg and CTE measurement A polyketone composition was applied on a glass substrate by a bar coating method, dried in the same manner as (1), and heat-treated to give a polyketone cured product having a thickness of 10 μm on the glass substrate. Formed. This polyketone cured product was peeled from the glass substrate to obtain a polyketone cured product, which was used as a sample for Tg and CTE measurement.

(3) Sample for flexibility test A 10 μm polyketone cured product obtained in the same manner as in (2) was used as a sample for flexibility test.

<Molecular weight measurement of polyketone>
The molecular weight (weight average molecular weight and number average molecular weight) of the polyketone was measured by the GPC method using tetrahydrofuran (THF) as an eluent, and determined in terms of standard polystyrene. The details are as follows.

・Device name: Ecosec HLC-8320GPC (Tosoh Corporation)
・Column: TSKgel Supermultipore HZ-M (Tosoh Corporation) ・Detector: UV detector, RI detector combined ・Flow rate: 0.4 ml/min

<Transmissivity measurement>
The transmittance of the polyketone cured product for light having a wavelength of 400 nm was measured by an ultraviolet-visible absorption spectrum method using a spectrophotometer (V-570, JASCO Corporation). Table 4 shows the transmittance of the cured product converted into a film thickness of 1 μm, using the glass substrate having no polyketone cured product as a reference.

<Tg measurement>
Using a viscoelasticity measuring device (RSA-II, Rheometric Scientific FE Co., Ltd.), Tg of the polyketone cured product was measured under the conditions of 1 Hz and 25°C to 300°C. The peak top of tan δ is defined as Tg. The results are shown in Table 4.

<CTE measurement>
Using a thermomechanical analyzer (Seiko Instruments Inc., TMA/SS6000), the measurement was performed under the conditions of 50° C. to 300° C. and a tensile load of 0.5 MPa with respect to the cross-sectional area of the polyketone cured product. The average linear expansion coefficient in the temperature range of 50°C to 250°C was calculated. The results are shown in Table 4.

<Flexibility measurement>
The cured polyketone was evaluated by the mandrel test (cylindrical mandrel method). The test was performed according to JIS K5600-5-1:1999. The diameter of the mandrel was changed from 25 mm to 2 mm, and the presence or absence of cracks was visually confirmed. Table 4 shows the minimum diameter of the mandrel which does not cause cracks.

It was found that the polyketone cured products obtained from the polyketone compositions of Examples had excellent heat resistance and had a low CTE. In addition, the polyketone cured products obtained from the polyketone compositions of Examples were also excellent in transparency and flexibility.
On the other hand, in Comparative Examples 1 to 4 which did not contain a hydrazide compound, none of the Examples had both high Tg and low CTE, as in the Examples.

Claims (9)

A polyketone composition containing a polyketone containing a structural unit represented by the following general formula (I) and a hydrazide compound.

[In the general formula (I), X's each independently represent a divalent group having 6 to 50 carbon atoms containing an aromatic ring, and Y's each independently represent 2 having 2 to 6 carbon atoms containing an aromatic ring. Represents a valent group, and n represents the number of structural units. ] In the general formula (I), each X independently contains a divalent group represented by at least one selected from the group consisting of the following general formulas (II-1) to (II-3), The polyketone composition according to claim 1.

[In the general formula ^{(II-1), R} 1 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, ^{R 2} each independently represents a substituent, m, respectively It independently represents an integer of 0 to 3. ]

[In the general formula (II-2), ^{R 1} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, ^{R 2} each independently represents a substituent, m, respectively Independently, it represents the integer of 0-3 and Z represents the divalent group selected from an oxygen atom or the following general formula (III-1)-(III-7). ]

[In general formulas (III-1) to (III-7), R ^1's each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and R ^2's each independently represent a substituent. R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. m represents the integer of 0-3 each independently, n represents the integer of 0-4 each independently, p represents the integer of 0-2 each independently. ]


[In the general formula (II-3), ^{R 5} each independently represent a substituent, n is independently an integer of 0-4. ] In the general formula (I), Y contains at least one divalent group selected from the group consisting of the following general formulas (IV-1) to (IV-5). A polyketone composition as described.

[In general formulas (IV-1) to (IV-5), each R ⁶ independently represents a substituent. In formula (IV-5), R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. n represents the integer of 0-4 each independently. m independently represents an integer of 0 to 3. ] The polyketone composition according to any one of claims 1 to 3, wherein the hydrazide compound has two or more hydrazide groups in the molecule. The polyketone composition according to any one of claims 1 to 4, wherein the hydrazide compound is an aromatic hydrazide compound. The polyketone composition according to any one of claims 1 to 5, further comprising a solvent. A polyketone cured product, which is a cured product of the polyketone composition according to any one of claims 1 to 6. An optical element comprising the polyketone cured product according to claim 7. An image display device comprising the cured product of the polyketone according to claim 7.