WO2019009079A1 - Polyketone composition containing hydrazide compound, polyketone cured product, optical element and image display device - Google Patents

Abstract

The polyketone composition contains a polyketone containing a structural unit represented by the general formula (I) and a hydrazide compound. In general formula (I), X each independently represents a divalent group having 1 to 50 carbon atoms which may have a substituent, and Y each independently has a substituent It also represents a bivalent hydrocarbon group having 1 to 30 carbon atoms, and n represents an integer of 1 to 1,500.

Description

Polyketone composition containing hydrazide compound, cured product of polyketone, optical element and image display device

The present disclosure relates to a polyketone composition, a cured polyketone 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 the polymers belonging to aromatic polyketones are aromatic polyether ketones polymerized using a nucleophilic aromatic substitution reaction, and have ether bonds in the main chain. On the other hand, aromatic polyketones having no ether bond in the main chain can exhibit better heat resistance and chemical resistance than aromatic polyether ketones (see, for example, Patent Documents 1 and 2) ).

In recent years, it has been reported that aromatic polyketones having both high transparency and heat resistance can be obtained by directly polymerizing alicyclic dicarboxylic acids and 2,2'-dialkoxybiphenyl compounds by Friedel-Crafts acylation. Application to optical parts is expected (see, for example, Patent Document 3).

Japanese Patent Application Laid-Open No. 62-7730 JP 2005-272728 A JP, 2013-53194, A

Here, the molecule itself of the aromatic polyketone described in Patent Document 3 is stable to a drug solution. However, a cured product obtained by forming this aromatic polyketone on a substrate may peel off or dissolve from the substrate when exposed to a chemical solution, and the practical chemical resistance of the cured product There is a problem.

The present disclosure provides a polyketone composition excellent in heat resistance, transparency and chemical resistance and a cured polyketone, and an optical element and an image display having the cured polyketone, when the cured product is made into a cured product. The purpose is

Means for solving the above problems include the following embodiments.

　一般式（Ｉ）中、Ｘは、それぞれ独立に、置換基を有していてもよい炭素数１～５０の２価の基を表し、Ｙは、それぞれ独立に、置換基を有していてもよい炭素数１～３０の２価の炭化水素基を表し、ｎは１～１５００の整数を表す。
＜２＞　前記一般式（Ｉ）において、Ｘが、それぞれ独立に、芳香環を含む炭素数６～５０の２価の基を含む、＜１＞に記載のポリケトン組成物。
＜３＞　前記一般式（Ｉ）において、Ｘが、それぞれ独立に、下記一般式（ＩＩ－１）～（ＩＩ－３）からなる群より選択される少なくとも１つで表される２価の基を含む、＜１＞又は＜２＞に記載のポリケトン組成物。

　一般式（ＩＩ－１）中、Ｒ^１は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１～３０の炭化水素基を表し、Ｒ^２は、それぞれ独立に、置換基を有していてもよい炭素数１～３０の炭化水素基を表し、ｍは、それぞれ独立に、０～３の整数を表す。

　一般式（ＩＩ－２）中、Ｒ^１は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１～３０の炭化水素基を表し、Ｒ^２は、それぞれ独立に、置換基を有していてもよい炭素数１～３０の炭化水素基を表し、ｍは、それぞれ独立に、０～３の整数を表し、Ｚは、酸素原子又は下記一般式（ＩＩＩ－１）～（ＩＩＩ－７）から選択される２価の基を表す。

　一般式（ＩＩＩ－１）～（ＩＩＩ－７）中、Ｒ^１は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１～３０の炭化水素基を表し、Ｒ^２は、それぞれ独立に、置換基を有していてもよい炭素数１～３０の炭化水素基を表し、Ｒ^３及びＲ^４は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１～３０の炭化水素基を表す。ｍは、それぞれ独立に、０～３の整数を表し、ｎは、それぞれ独立に、０～４の整数を表し、ｐは、それぞれ独立に、０～２の整数を表す。

　一般式（ＩＩ－３）中、Ｒ^５は、それぞれ独立に、置換基を有していてもよい炭素数１～３０の炭化水素基を表し、ｎは、それぞれ独立に、０～４の整数を表す。
＜４＞　前記一般式（Ｉ）において、Ｙが飽和炭化水素基を含む、＜１＞～＜３＞のいずれか１項に記載のポリケトン組成物。
＜５＞　前記一般式（Ｉ）において、Ｙが飽和脂環式炭化水素基を含む、＜１＞～＜４＞のいずれか１項に記載のポリケトン組成物。
＜６＞　前記一般式（Ｉ）において、Ｙの炭素数が６～３０である、＜１＞～＜５＞のいずれか１項に記載のポリケトン組成物。
＜７＞　前記ヒドラジド化合物が、分子中に２個以上のヒドラジド基を有する、＜１＞～＜６＞のいずれか１項に記載のポリケトン組成物。
＜８＞　前記ヒドラジド化合物が、芳香族ヒドラジド化合物を含む、＜１＞～＜７＞のいずれか１項に記載のポリケトン組成物。
＜９＞　溶剤をさらに含有する、＜１＞～＜８＞のいずれか１項に記載のポリケトン組成物。
＜１０＞　＜１＞～＜９＞のいずれか１項に記載のポリケトン組成物の硬化物である、ポリケトン硬化物。
＜１１＞　＜１０＞に記載のポリケトン硬化物を有する光学素子。
＜１２＞　＜１０＞に記載のポリケトン硬化物を有する画像表示装置。 <1> A polyketone composition containing a polyketone containing a structural unit represented by the following general formula (I) and a hydrazide compound.

In general formula (I), X each independently represents a divalent group having 1 to 50 carbon atoms which may have a substituent, and Y each independently has a substituent It also represents a bivalent hydrocarbon group having 1 to 30 carbon atoms, and n represents an integer of 1 to 1,500.
<2> The polyketone composition according to <1>, wherein in the general formula (I), each X independently includes an aromatic ring-containing divalent group having 6 to 50 carbon atoms.
<3> In the general formula (I), each of X's 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 as described in <1> or <2> containing <1> or <2>.

In general formula (II-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 is independently substituted Represents a hydrocarbon group having 1 to 30 carbon atoms which may have a group; m independently represents an integer of 0 to 3;

In general formula (II-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 R ² is independently substituted Group each independently represent an integer of 0 to 3 and Z represents an oxygen atom or a group represented by the following general formula (III-1): (III-7) represents a divalent group selected from (III-7).

In general formulas (III-1) to (III-7), R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ² represents And each independently represent a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ³ and R ⁴ each independently represent a hydrogen atom or a carbon optionally having a substituent It represents several 1 to 30 hydrocarbon groups. m independently represents an integer of 0 to 3, n independently represents an integer of 0 to 4, and p independently represents an integer of 0 to 2.

In general formula (II-3), each R ⁵ independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and n is independently an integer of 0 to 4 Represents
<4> The polyketone composition according to any one of <1> to <3>, wherein Y in the general formula (I) contains a saturated hydrocarbon group.
<5> The polyketone composition according to any one of <1> to <4>, wherein in the general formula (I), Y contains a saturated alicyclic hydrocarbon group.
<6> The polyketone composition according to any one of <1> to <5>, wherein in the general formula (I), Y has 6 to 30 carbon atoms.
<7> The polyketone composition according to any one of <1> to <6>, wherein the hydrazide compound has two or more hydrazide groups in the molecule.
<8> The polyketone composition according to any one of <1> to <7>, wherein the hydrazide compound comprises an aromatic hydrazide compound.
<9> The polyketone composition according to any one of <1> to <8>, further comprising a solvent.
<10> A cured polyketone that is a cured product of the polyketone composition according to any one of <1> to <9>.
The optical element which has a polyketone cured material as described in <11><10>.
The image display apparatus which has a polyketone cured material as described in <12><10>.

According to the present disclosure, it is possible to provide a polyketone composition and a cured polyketone having excellent heat resistance, transparency and chemical resistance when made into a cured product, and an optical element and an image display device having the cured polyketone. .

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, a numerical range indicated by using “to” indicates a range including numerical values described before and after “to” as the minimum value and the maximum value, respectively.
The upper limit value or the lower limit value described in one numerical value range may be replaced with the upper limit value or the lower limit value of the other stepwise description numerical value range in the numerical value range described stepwise in the present disclosure. . In addition, 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 example.
In the present disclosure, each component may contain a plurality of corresponding substances. When a plurality of substances corresponding to each component are present in the composition, the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, the words “layer” or “film” mean that when the region in which the layer or film is present is observed, in addition to the case where the region is entirely formed, only a part of the region The case where it is formed is also included.
The term "laminate" in the present disclosure refers to stacking layers, two or more layers may be combined, and two or more layers may be removable.

In the present disclosure, “excellent in transparency” means that the visible light transmittance (at least the transmittance of visible light with a wavelength of 400 nm) is 80% or more (film thickness is 1 μm).

In the present disclosure, “excellent in heat resistance” means that the thermal decomposition temperature is 400 ° C. or higher and the glass transition point (Tg) is 270 ° C. or higher in the member containing the polyketone.

In the present disclosure, “excellent chemical resistance of the cured product” means that the cured polyketone is obtained by exposing the cured film-like polyketone formed on a silicon substrate to a chemical solution under the following conditions (a) and (b): It means that it does not peel from the substrate and the polyketone cured product does not dissolve.
Condition (a): A mixed solution of dimethyl sulfoxide (DMSO) and 2-ethanolamine (2AE) (DMSO: 2AE in a volume ratio of 7: 3) is heated to 60 ° C. to form a cured polyketone formed on a silicon substrate Soak for 30 minutes.
Condition (b): The cured polyketone formed on a silicon substrate is immersed in a 0.5% by mass aqueous solution of hydrogen fluoride (HF) at 23 ° C. for 30 minutes.

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

In general formula (I), X each independently represents a divalent group having 1 to 50 carbon atoms which may have a substituent, and Y each independently has a substituent It also represents a bivalent hydrocarbon group having 1 to 30 carbon atoms, and n represents an integer of 1 to 1,500.

The polyketone composition of this indication is excellent in heat resistance, transparency, and chemical resistance, when it is set as the hardened | cured material by setting it as the said structure. Although the reason is not clear, it is considered as follows.
The specific polyketone is excellent in heat resistance and transparency. In addition, the molecule itself is stable to a drug solution since the specific polyketone is formed with almost a C—C bond in the main chain. Furthermore, when the polyketone composition contains a hydrazide compound, the hydrazide compound can act on a specific polyketone to form a crosslinked structure. Therefore, when a polyketone composition is made into a hardened material, high Tg is expressed. Moreover, it is thought that peeling from a base material, dissolution of a cured product, and the like are suppressed, and chemical resistance is further improved.
Each component will be described below.

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

In the general formula (I), X each independently represents a bivalent group having 1 to 50 carbon atoms which may have a substituent. Each Y independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. n represents an integer of 1 to 1500, preferably an integer of 2 to 1000, and more preferably an integer of 5 to 500. In addition, when a divalent group or a divalent hydrocarbon group has a substituent, the number of carbons of the substituent is not included in the number of carbons of the divalent group or the divalent hydrocarbon group. The same applies thereafter. The specific polyketone may contain the structural unit represented by the general formula (I) in the main chain or in the side chain, and preferably in the main chain.

The carbon number of the divalent group represented by X is 1 to 50, preferably 1 to 30, and more preferably 1 to 24.

The substituent which X may have is not particularly limited, and specific 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 divalent group represented by X is preferably a hydrocarbon group, and more preferably an aromatic ring. When X has an aromatic ring, higher heat resistance tends to be realized.

From the viewpoint of achieving high heat resistance, X is preferably a divalent group having 6 to 50 carbon atoms including an aromatic ring. Examples of the aromatic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, naphthacene ring, chrysene ring, pyrene ring, triphenylene ring, pentacene ring, benzopyrene ring and the like.

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 a divalent group having a weak mutual conjugation relationship (hereinafter referred to as It is more preferable that it is "a specific aromatic ring group". By this, when synthesizing a polyketone, it is possible to realize good diacylation at a low reaction temperature, and it tends to be a polyketone having a high molecular weight and excellent heat resistance. 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 weakly conjugated to each other" means that a plurality of aromatic rings are bonded via an ether bond or a methylene bond, or 2, Steric hindrance due to substituents like 2'-substituted biphenyl means that conjugation of aromatic rings is suppressed.

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 general formula (II-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 is independently substituted Represents a hydrocarbon group having 1 to 30 carbon atoms which may have a group; m independently represents an integer of 0 to 3; The wavy part indicates a bond. The same applies thereafter.

From the viewpoint of heat resistance, the carbon number of the hydrocarbon group represented by R ¹ is 1 to 30, preferably 1 to 10, and more preferably 1 to 6. 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, a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, alicyclic hydrocarbon group and the like. Moreover, what combined these hydrocarbon groups may be used.

As the saturated aliphatic hydrocarbon group represented 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 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. In addition, the saturated aliphatic hydrocarbon group may have an alicyclic hydrocarbon group described later at its terminal portion.

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. In addition, the unsaturated aliphatic hydrocarbon group may have an alicyclic hydrocarbon group described later at its terminal portion.

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. Further, the alicyclic hydrocarbon group may have at least one selected from the group consisting of saturated aliphatic hydrocarbon groups and unsaturated aliphatic hydrocarbon groups in its alicyclic group.

The substituent which 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.

In General Formula (II-1), R ² each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. From the viewpoint of heat resistance, the carbon number of the hydrocarbon group represented by R ² is preferably 1 to 10, and more preferably 1 to 5.

Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ² include the same ones as the hydrocarbon groups having 1 to 30 carbon atoms exemplified for R ¹ . Further, examples of the substituent which the hydrocarbon group represented by R ² may have include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms.

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

In general formula (II-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 R ² is independently substituted A hydrocarbon group having 1 to 30 carbon atoms which may have a group, m independently represents an integer of 0 to 3, and Z represents an oxygen atom or the following general formula (III-1) It represents a divalent group selected from III-7).
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 formulas (III-1) to (III-7), R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ² represents And each independently represent a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ³ and R ⁴ each independently represent a hydrogen atom or a carbon optionally having a substituent It represents several 1 to 30 hydrocarbon groups. m independently represents an integer of 0 to 3, n independently represents an integer of 0 to 4, and p independently represents an integer of 0 to 2.
R ³ and R ⁴ are each preferably a hydrocarbon group of 1 to 5 carbon atoms which may have a substituent, from the viewpoint of heat resistance. Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ³ and R ⁴ include the same ones as the hydrocarbon group having 1 to 30 carbon atoms exemplified for R ¹ in the general formula (II-1) Be Further, examples of the substituent that R ³ and R ⁴ may have include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms.
Each n independently represents an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1.
Each p independently represents an integer of 0 to 2, preferably 0 or 1.
The R ^{1, R 2,} and each of the details of m, is the same as ^R 1, ^{R 2,} and m in Formula (II-1).

In general formula (II-3), each R ⁵ independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and n is independently an integer of 0 to 4 Represents
From the viewpoint of heat resistance, the carbon number of the hydrocarbon group represented by R ⁵ is preferably 1 to 10, and more preferably 1 to 5.
Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ⁵ include the same ones as the hydrocarbon groups having 1 to 30 carbon atoms exemplified for R ¹ in the general formula (II-1). Further, examples of the substituent that R ⁵ may have include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms.

In General Formula (II-3), n independently represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, 0 or 1 It is further preferred that

In the general formula (I), each Y independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. The carbon number of the hydrocarbon group represented by Y is preferably 4 to 30, and more preferably 6 to 30 from the viewpoint of heat resistance.

The hydrocarbon group represented by Y preferably contains a saturated hydrocarbon group from the viewpoint of transparency. The saturated hydrocarbon group may be a saturated acyclic aliphatic hydrocarbon group or a saturated alicyclic hydrocarbon group. From the viewpoint of achieving both higher heat resistance and transparency, the hydrocarbon group represented by Y preferably contains a saturated alicyclic hydrocarbon group. Since the alicyclic hydrocarbon group is bulkier than acyclic aliphatic hydrocarbon groups having the same carbon number, it tends to be excellent in solubility in solvents while maintaining high heat resistance and transparency.
The hydrocarbon group represented by Y is a plurality of saturated acyclic aliphatic hydrocarbon groups, a plurality of saturated alicyclic hydrocarbon groups, or a saturated acyclic aliphatic hydrocarbon group and a saturated alicyclic ring. It may be a hydrocarbon group having any combination of formula hydrocarbon groups. When Y is a hydrocarbon group having a saturated acyclic aliphatic hydrocarbon group and a saturated alicyclic hydrocarbon group, the Y is classified as a saturated alicyclic hydrocarbon group.

When Y contains a saturated acyclic aliphatic hydrocarbon group, the carbon number of the hydrocarbon group represented by Y is 1 to 30, and preferably 3 to 30.
When Y contains a saturated acyclic aliphatic hydrocarbon group, the hydrocarbon group represented by Y is a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, a 1-methyltrimethylene group, 2-methyltrimethylene group, ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, pentylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1-ethyltrimethylene group , 2-ethyltrimethylene group, 1,1-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, propylethylene group, ethylmethylethylene group, hexylene group, 1-methyl Pentylene group, 2-methyl pentylene group, 3-methyl pentylene group, 1-ethyl tetramethylene group, 2-ethyl teto Methylene group, 1-propyltrimethylene group, 2-propyltrimethylene group, butylethylene group, 1,1-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 1, 3-dimethyltetramethylene group, 1,4-dimethyltetramethylene group, 1,2,3-trimethyltrimethylene group, 1,1,2-trimethyltrimethylene group, 1,1,3-trimethyltrimethylene group, 1 , 2,2-Trimethyltrimethylene, 1-ethyl-1-methyltrimethylene, 2-ethyl-2-methyltrimethylene, 1-ethyl-2-methyltrimethylene, 2-ethyl-1-methyl Trimethylene group, 2,2-ethylmethyltrimethylene group, heptylene group, octylene group, nonylene group, decylene group, icosanylene group, Riakontaniren group, and the like.

Among them, from the viewpoint of heat resistance, the hydrocarbon group is preferably tetramethylene group, hexylene group, methyl pentylene group, ethyl tetramethylene group, propyltrimethylene group, butyl ethylene group, dimethyl tetramethylene group, trimethyl. A trimethylene group, an ethylmethyl trimethylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an icosanylene group, a triacontanylene group etc. are mentioned.

When Y contains a saturated alicyclic hydrocarbon group, the carbon number of the hydrocarbon group represented by Y is 3 to 30, preferably 4 to 30, and more preferably 6 to 30. .
When Y contains a saturated alicyclic hydrocarbon group, the hydrocarbon group represented by Y is cyclopropane skeleton, cyclobutane skeleton, cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cubane skeleton, norbornane Examples thereof include bivalent hydrocarbon groups having a skeleton, a tricyclo [5.2.1.0] decane skeleton, an adamantane skeleton, a diadamantane skeleton, a bicyclo [2.2.2] octane skeleton, a decahydronaphthalene skeleton and the like.

Among them, from the viewpoint of heat resistance, as a hydrocarbon group, preferably, 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, Examples thereof include divalent hydrocarbon groups having a diadamantane skeleton, a bicyclo [2.2.2] octane skeleton, a decahydronaphthalene skeleton and the like.

As a substituent which the hydrocarbon group represented by Y may have, an amino group, an oxo group, a hydroxyl group, a halogen atom etc. are mentioned.

Y preferably contains at least a divalent hydrocarbon group represented by at least one selected from the group consisting of the following general formula (IV) and the following general formulas (V-1) to (V-3) It is more preferable to include at least a divalent hydrocarbon group represented by the following general formula (IV).

Hydrogen atom of adamantane skeleton in general formula (IV), hydrogen atom of cyclohexane skeleton in general formula (V-1), hydrogen atom of decahydronaphthalene (decalin) skeleton in general formula (V-2), and general formula (V The hydrogen atoms of the norbornane skeleton in -3) may be substituted with a hydrocarbon group, an amino group, an oxo group, a hydroxyl group or a halogen atom.
Also, in the general formula (IV) and the general formulas (V-1) to (V-3), each Z independently has a single bond or a carbon number of 1 to 10 which may have a substituent. Represents a divalent saturated hydrocarbon group.
From the viewpoint of obtaining a soft cured product, each Z is preferably independently a divalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and from the viewpoint of heat resistance Therefore, Z is preferably a divalent saturated hydrocarbon group having 1 to 5 carbon atoms. Further, from the viewpoint of obtaining high hardness, Z is preferably a single bond.

Examples of the divalent saturated hydrocarbon group represented by Z include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, an ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, pentylene group, 1-methyl tetramethylene group, 2-methyl tetramethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 1,1 -Dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, propylethylene group, ethylmethylethylene group, hexylene group, 1-methylpentylene group, 2-methylpentylene group, 3-Methyl pentylene group, 1-ethyl tetramethylene group, 2-ethyl tetramethylene group, 1-propyltrile Tylene group, 2-propyltrimethylene group, butylethylene group, 1,1-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 1,4-dimethyltetramethylene, 1,2,3-trimethyltrimethylene, 1,1,2-trimethyltrimethylene, 1,1,3-trimethyltrimethylene, 1,2,2-trimethyltrile Methylene group, 1-ethyl-1-methyltrimethylene group, 2-ethyl-2-methyltrimethylene group, 1-ethyl-2-methyltrimethylene group, 2-ethyl-1-methyltrimethylene group, heptylene group, Examples include octylene group, nonylene group, decylene group and the like.

Examples of the substituent which the divalent saturated hydrocarbon group represented by Z may have include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. In addition, when the bivalent hydrocarbon group represented by Z has a substituent, carbon number of a substituent shall not be included in carbon number of a bivalent saturated hydrocarbon group.

The divalent hydrocarbon group represented by the general formula (IV) may be a divalent hydrocarbon group represented by the following general formula (IV-1).
The divalent hydrocarbon group represented by the general formula (V-1) may be a divalent hydrocarbon group represented by the following general formula (VI-1).
The divalent hydrocarbon group represented by the general formula (V-2) may be a divalent hydrocarbon group represented by the following general formula (VI-2).
The divalent hydrocarbon group represented by the general formula (V-3) may be a divalent hydrocarbon group represented by the following general formula (VI-3).

Z in the general formula (IV-1), the general formula (VI-1), the general formula (VI-2) and the general formula (VI-3) is a group represented by the general formula (IV) and the general formula (V-1) The same as Z in V-3) can be mentioned.

The specific polyketone is represented by Y as a divalent hydrocarbon group represented by the above general formula (IV), and at least one selected from the group consisting of the above general formulas (V-1) to (V-3) It may be a polyketone containing both of the represented divalent hydrocarbon groups. The specific polyketone is at least one selected from the group consisting of a divalent hydrocarbon group represented by the above general formula (IV) as Y and a group consisting of the above general formulas (V-1) to (V-3) When containing both of the represented divalent hydrocarbon groups, the content of the divalent hydrocarbon group represented by the general formula (IV) and the general formulas (V-1) to (V-3) The mass ratio ((IV): (V-1) to (V-3)) to the total content of divalent hydrocarbon groups represented by is not particularly limited. From the viewpoint of heat resistance and elongation, the mass ratio is preferably 5:95 to 95: 5, and more preferably 5:95 to 90:10 from the viewpoint of heat resistance and solubility.

From the viewpoint of maintaining heat resistance, the weight average molecular weight (Mw) of the specific polyketone is preferably 500 or more in polystyrene equivalent standard GPC (gel permeation chromatography), and the heat resistance and solvent are higher. From the viewpoint of solubility in water, it is more preferably 10,000 to 1,000,000. If higher heat resistance is required, the weight average molecular weight (Mw) is more preferably 20,000 to 1,000,000. The weight average molecular weight (Mw) of the specific polyketone refers to a value measured by the method described in the examples.

The specific polyketones may be used alone or in combination of two or more.
Also, the polyketone composition may contain other polyketone other than the specific polyketone. Hereinafter, the specific polyketone and the other polyketone may be collectively referred to as "polyketone".
From the viewpoint of heat resistance, transparency, and chemical resistance when it is a cured product, the content of the specific polyketone relative to the total amount of polyketone is preferably 50% by mass or more, and 60% by mass or more More preferably, the content is 70% by mass or more.

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 of the polyketone and the hydrazide compound from the viewpoints of heat resistance, transparency and chemical resistance when made into a cured product Is preferable, and 50 parts by mass to 95 parts by mass is more preferable.

<Hydrazide compound>
The polyketone compositions of the present disclosure contain hydrazide compounds.

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 2 or 3 hydrazide groups. Are more preferred, and it is particularly preferred to have 2 hydrazide groups. The hydrazide group represents a group represented by the following chemical formula (VII).

As a hydrazide compound, an acyclic 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.

When the hydrazide compound is an acyclic aliphatic hydrazide compound, the portion excluding the hydrazide group of the hydrazide compound (hereinafter also referred to as a skeleton) is an acyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms Is preferably a non-cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms, and more preferably a non-cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms. The acyclic aliphatic hydrazide compound may be, for example, a hydrazide compound having no skeleton (that is, a hydrazide group is directly linked) such as oxalic acid dihydrazide.
The acyclic aliphatic hydrocarbon group may be linear or branched, and is preferably linear.
The acyclic aliphatic hydrocarbon group may or may not have a substituent. When the noncyclic 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. When the hydrocarbon group has a substituent, the number of carbons contained in the substituent is not included in the number of carbons of the hydrocarbon group. The same applies to the following.
The acyclic 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 of the hydrazide compound is preferably, for example, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an alicyclic hydrocarbon having 3 to 8 carbon atoms It is more preferably a group, and still more preferably an alicyclic hydrocarbon group having 3 to 6 carbon atoms. The alicyclic hydrocarbon group is a hydrocarbon group having an alicyclic structure at least in part, and may have an acyclic aliphatic hydrocarbon group in addition to the alicyclic group.
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, and an acyl group having 2 to 5 carbon atoms.
The alicyclic hydrocarbon group may or may not have an unsaturated bond.

When the hydrazide compound is an aromatic hydrazide compound, the skeleton of the hydrazide compound is, for example, preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, and is an aromatic hydrocarbon group having 6 to 12 carbon atoms The aromatic hydrocarbon group is more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms. The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring at least in part, and in addition to the aromatic ring, it has an acyclic aliphatic hydrocarbon group, an alicyclic hydrocarbon group or a combination thereof. It may be done.
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 may be a compound having both an alicyclic and an aromatic ring in the molecule. That is, the compound may be a compound corresponding to both an alicyclic hydrazide compound and an aromatic hydrazide compound.

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

In formula (VIII), W represents a hydrocarbon group, and n represents an integer of 2 to 6.
The hydrocarbon group represented by W may be an acyclic aliphatic hydrocarbon group, may be an alicyclic hydrocarbon group, may be an aromatic hydrocarbon group, and may be an aromatic hydrocarbon It is preferably a group. The details of the acyclic aliphatic hydrocarbon group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group are the same as the respective details in the skeleton of the hydrazide compound.
n is preferably 2 to 4, more preferably 2 or 3, and still more preferably 2.

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, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, Examples include fumaric acid dihydrazide and itaconic acid dihydrazide 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.

A hydrazide compound may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the hydrazide compound is 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the total amount of the polyketone and the hydrazide compound from the viewpoint of heat resistance, transparency and chemical resistance when it is a cured product. It is preferably 5 parts by mass to 50 parts by mass, and 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. As the solvent, 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, 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, ether Rubenzen, propylbenzene, cumene, diisopropylbenzene, hexyl benzene, anisole, diglyme, dimethyl sulfoxide, chloroform, dichloromethane, dichloroethane, chlorobenzene and the like. One of these solvents may be used alone, or two or more thereof may be used in combination.

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

<Other additives>
The polyketone composition may further contain other additives. Other additives include adhesion assistants, surfactants, leveling agents, antioxidants, ultraviolet light deterioration inhibitors, sliding agents (polytetrafluoroethylene particles etc.), light diffusing agents (acrylic crosslinked particles, silicone crosslinked particles) Ultrathin glass flakes, calcium carbonate particles, etc.), fluorescent dyes, inorganic phosphors (phosphoruss containing aluminates as mother crystals), antistatic agents, crystal nucleating agents, inorganic antibacterial agents, organic antibacterial agents, photocatalysts Examples include antifouling agents (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, the polyketone composition is applied to at least a part of the surface of a substrate to form a composition layer, and the composition layer is dried to remove the solvent from the composition layer or to cure along with the removal of the solvent. A polyketone cured product can be made. The method for applying the polyketone composition to the substrate is not particularly limited as long as the composition layer can be formed in an arbitrary shape at any place on the substrate. Examples of the method for applying the polyketone composition to a substrate include an immersion 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 glass, semiconductor, metal oxide insulator (titanium oxide, silicon oxide etc.), inorganic material such as silicon nitride, triacetylcellulose, transparent polyimide, polycarbonate, Examples of the transparent substrate include transparent resins such as acrylic polymers and cycloolefin resins. The shape of the substrate is not particularly limited, and may be plate-like or film-like. The polyketone composition of the present disclosure is excellent in chemical resistance when made into a cured product, and thus can be suitably used as a coating material of a substrate, a molded product, and the like.

When the polyketone composition contains a solvent, drying may be performed before and after curing. The drying method is not particularly limited, and examples thereof include a method of heat treatment using an apparatus 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 about 50 to 150 ° C. for about 1 to 90 minutes.

The method for curing the polyketone is not particularly limited, and can be cured by heat treatment or the like. Hardening by heat treatment is carried out using a box-type drier, hot-air type conveyor drier, quartz tube furnace, hot plate, rapid thermal annealing, vertical diffusion furnace, infrared curing furnace, electron beam curing furnace, microwave curing furnace etc. It can be done.

The atmosphere for curing may be selected from the atmosphere, an inert atmosphere such as nitrogen, etc., and from the viewpoint of preventing the oxidation of the polyketone composition, it is preferable to carry out under a nitrogen atmosphere.
The temperature and time of heat treatment for curing can be arbitrarily set in view of composition conditions, working efficiency and the like, and may be about 30 minutes to 2 hours at 60 ° C. to 200 ° C.

If necessary, the dried cured polyketone of the present disclosure may be further heat-treated to remove residual solvent. The method of heat treatment is not particularly limited, and a box dryer, a hot air conveyor type 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 It can be carried out using a vacuum dryer or the like. Further, 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 about 150 ° C. to 250 ° C., for about 1 minute to 90 minutes. Further heat treatment tends to increase the density of the obtained cured polyketone product.

The haze when the cured polyketone has a thickness of 10 μm is preferably less than 1%.
Moreover, it is preferable that the transmittance | permeability of 400 nm of a polyketone cured material is 85% or more in conversion of 1 micrometer of film thickness.

The resulting cured polyketone can be used as a substrate bearing a cured polyketone with the substrate attached, and can be peeled off from the substrate and used if necessary.
In the cured polyketone substrate, the cured polyketone may be provided on at least a part of the surface of the substrate, and may be provided only on one side of the substrate or may be provided on both sides. In addition, the cured polyketone may have a single-layer or 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 have the polyketone cured product of the present disclosure. The cured polyketone applied to the optical element and the image display device may be applied as a substrate bearing the cured polyketone while the substrate is attached as described above. Moreover, if a base material is a transparent base material, it can use suitably for an optical element. As the transparent substrate, those exemplified for the production of a cured polyketone can be mentioned.

An optical element and an image display apparatus apply an LCD (liquid crystal display), an ELD (electroluminescence display), an organic EL display, etc. via an adhesive, an adhesive, etc., for example in the substrate side in a polyketone cured substrate. It can be obtained by pasting to a place.

The cured polyketone and various optical elements such as a polarizing plate using the same can be preferably used for various image display devices such as liquid crystal display devices. The image display device may have the same configuration as a conventional image display device except that the cured polyketone of the present disclosure is used. When the image display device is a liquid crystal display device, the drive circuit may be assembled by appropriately assembling the respective components such as a liquid crystal cell, an optical element such as a polarizing plate, and an illumination system (backlight etc.) as necessary. It 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 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, electronic devices Electric appliances for home use such as ranges, back monitors, monitors for car navigation systems, in-vehicle devices such as car audio, display devices such as information monitors for commercial stores, security devices such as monitoring monitors, nursing care such as nursing care monitors The devices include medical devices such as medical monitors and the like.

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

<Polyketone composition>
The components (A) to (C) were blended in the proportions shown in Table 1 and Table 2 and filtered through a filter made of PTFE (polytetrafluoroethylene) to obtain the polyketone compositions of Examples and Comparative Examples. . The numerical values in the parentheses represent the blending ratio (parts by mass). "-" Indicates that the component is not contained. Each component in Table 1 and Table 2 is shown below.

Component (A): Polyketone (Synthesis Example 1) Synthesis of Polyketone PK-1 In a flask containing 10 mmol of 2,2′-dimethoxybiphenyl and 10 mmol of cis-1,4-cyclohexanedicarboxylic acid as monomers, diphosphorus pentaoxide and 30 ml of a mixed solution of methanesulfonic acid (mass ratio 1:10) was added and stirred at 60.degree. After the reaction, the contents were poured into 500 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 polyketone PK-1.
The weight average molecular weight of the obtained polyketone PK-1 was 20,000, and the number average molecular weight was 8,000. In addition, a weight average molecular weight and a number average molecular weight are measured by the below-mentioned method, and are computed. The weight average molecular weight (Mw) and number average molecular weight (Mn) of polyketone PK-2 to polyketone PK-15 described later were also measured by the same method.

Synthesis Example 2 Synthesis of Polyketone PK-2 In the same manner as in Example 1 except that 10 mmol of 2,2′-dimethoxybiphenyl and 13 mmol of 1,3-adamantanedicarboxylic acid were used as monomers, a polyketone PK-2 was obtained. The The weight average molecular weight of the obtained polyketone PK-2 was 280,000, and the number average molecular weight was 44,000.

Synthesis Example 3 Synthesis of Polyketone PK-3 A polyketone PK-3 was obtained in the same manner as Example 1, except that 10 mmol of 2,2′-dimethoxybiphenyl and 10 mmol of 1,3-adamantanediacetic acid were used as monomers. The
The weight average molecular weight of the obtained polyketone PK-3 was 42,000, and the number average molecular weight was 12,000.

Synthesis Example 4 Synthesis of Polyketone PK-4 Example 1 except that 10 mmol of 2,2′-dimethoxybiphenyl, 5 mmol of 1,3-adamantanedicarboxylic acid and 5 mmol of cis-1,4-cyclohexanedicarboxylic acid were used as monomers. In the same manner as in, polyketone PK-4 was obtained. The weight average molecular weight of the obtained polyketone PK-4 was 36,000, and the number average molecular weight was 12,000.

Synthesis Example 5 Synthesis of Polyketone PK-5 Polyketone was prepared in the same manner as Example 1, except that 10 mmol of 2,2′-dimethoxybiphenyl, 5 mmol of 1,3-adamantane dicarboxylic acid and 5 mmol of dodecanedioic acid were used as monomers. I got PK-5. The weight average molecular weight of the obtained polyketone PK-5 was 36,000, and the number average molecular weight was 13,000.

Synthesis Example 6 Synthesis of Polyketone PK-6 A polyketone was prepared in the same manner as Example 1, except that 10 mmol of 2,2′-dimethoxybiphenyl, 5 mmol of 1,3-adamantanediacetic acid and 5 mmol of dodecanedioic acid were used as monomers. I got PK-6. The weight average molecular weight of the obtained polyketone PK-6 was 39,000, and the number average molecular weight was 12,000.

Synthesis Example 7 Synthesis of Polyketone PK-7 A polyketone was prepared in the same manner as Example 1, except that 10 mmol of 2,2′-dimethoxybiphenyl, 5 mmol of 1,3-adamantanediacetic acid and 5 mmol of hexanedioic acid were used as monomers. I got PK-7. The weight average molecular weight of the obtained polyketone PK-7 was 39,000, and the number average molecular weight was 12,000.

Synthesis Example 8 Synthesis of Polyketone PK-8 Same as Example 1 except that 10 mmol of 2,2′-dimethoxybiphenyl, 5 mmol of 1,3-adamantanediacetic acid and 5 mmol of cis-1,4-cyclohexanedicarboxylic acid were used. , Obtained polyketone PK-8. The weight average molecular weight of the obtained polyketone PK-8 was 45,000, and the number average molecular weight was 11,000.

Synthesis Example 9 Synthesis of Polyketone PK-9 Example 1 except that 10 mmol of 2,2′-dimethoxybiphenyl, 5 mmol of 1,3-adamantanediacetic acid and 5 mmol of trans-1,4-cyclohexanedicarboxylic acid were used as monomers. The same procedure was followed to obtain polyketone PK-9. The weight average molecular weight of the obtained polyketone PK-9 was 37,000, and the number average molecular weight was 10,000.

Synthesis Example 10 Synthesis of Polyketone PK-10 As monomers, 10 mmol of 2,2′-dimethoxybiphenyl, 5 mmol of 1,3-adamantanediacetic acid, and 1,4-cyclohexanedicarboxylic acid (a mixture of cis and trans, cis: trans) (Molar ratio) = 7: 3) In the same manner as in Example 1 except that 5 mmol was used, polyketone PK-10 was obtained. The weight average molecular weight of the obtained polyketone PK-10 was 33,000, and the number average molecular weight was 11,000.

Synthesis Example 11 Synthesis of Polyketone PK-11 Example 1 was repeated except that 10 mmol of 2,2′-dimethoxybiphenyl, 5 mmol of 1,3-adamantanediacetic acid and 5 mmol of decalin-2,6-dicarboxylic acid were used as monomers. In the same manner, polyketone PK-11 was obtained. The weight average molecular weight of the obtained polyketone PK-11 was 33,000, and the number average molecular weight was 10,000.

Synthesis Example 12 Synthesis of Polyketone PK-12 As monomers, 10 mmol of 2,2′-dimethoxybiphenyl, 5 mmol of 1,3-adamantanediacetic acid and 5 mmol of norbornane dicarboxylic acid (a mixture of 2,4- and 2,5-) were used. A polyketone PK-12 was obtained in the same manner as in Example 1 except that it was used. The weight average molecular weight of the obtained polyketone PK-12 was 27,000, and the number average molecular weight was 9,200.

Synthesis Example 13 Synthesis of Polyketone PK-13 Example 1 except that 10 mmol of 2,2′-dimethoxybiphenyl, 5 mmol of 1,3-adamantanediacetic acid and 5 mmol of trans-2,3-norbornane dicarboxylic acid were used as monomers. Polyketone PK-13 was obtained in the same manner as in. The weight average molecular weight of the obtained polyketone PK-13 was 26,000, and the number average molecular weight was 8,100.

Synthesis Example 14 Synthesis of Polyketone PK-14 As monomers, 10 mmol of 2,2′-bis (2-methoxyphenyl) propane, 5 mmol of 1,3-adamantanediacetic acid and 1,4-cyclohexanedicarboxylic acid (cis and trans A polyketone PK-14 was obtained in the same manner as in Example 1 except that 5 mmol of a mixture of cis: trans (molar ratio) = 7: 3 was used. The weight average molecular weight of the obtained polyketone PK-14 was 28,000, and the number average molecular weight was 8,300.

Synthesis Example 15 Synthesis of Polyketone PK-15 As monomers, 10 mmol of diphenyl ether, 5 mmol of 1,3-adamantanediacetic acid and 1,4-cyclohexanedicarboxylic acid (a mixture of cis and trans, cis: trans (molar ratio) = 7 : 3) In the same manner as in Example 1 except that 5 mmol was used, polyketone PK-15 was obtained. The weight average molecular weight of the obtained polyketone PK-15 was 27,000, and the number average molecular weight was 8,000.

Component (B): Hydrazide compound B1: Compound represented by the following formula (XII)

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

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 cured polyketone product was produced by the following method, and a sample for evaluation described later was prepared.

(1) Sample for transmittance measurement A polyketone composition was applied to a glass substrate by a spin coating method, and dried for 3 minutes on a hot plate heated to 120 ° C. The obtained glass substrate is heat-treated at 200 ° C. for 1 hour in a nitrogen stream using an inert gas oven (Koyo Thermo Systems Co., Ltd.) to form a 10 μm thick polyketone cured product on the glass substrate and transmit it. It was used as a sample for rate measurement.

(2) Thermal decomposition temperature measurement sample The polyketone composition was dropped onto an aluminum cup, dried as in (1), and heat treated to obtain a cured polyketone molded in the aluminum cup. The cured polyketone was peeled off from the aluminum cup and used as a thermal decomposition temperature measurement sample.

(3) Sample for Tg measurement The polyketone composition was applied on a glass substrate by bar coating, dried as in (1), and heat treated to form a 10 μm thick cured polyketone on the glass substrate. . The cured polyketone was peeled from the glass to obtain a cured polyketone, which was used as a sample for Tg measurement.

(4) Chemical resistance test sample A polyketone composition is applied to a silicon substrate by spin coating, dried as in (1), and heat treated to form a 10 μm thick cured polyketone on the silicon substrate. This was used as a sample for chemical resistance test.

<Molecular weight measurement of polyketone>
The molecular weight (weight average molecular weight and number average molecular weight) of the polyketone was measured by 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

<Transmittance measurement>
The transmittance of ultraviolet light at 400 nm of the cured polyketone was measured by UV-visible absorption spectroscopy using a spectrophotometer (V-570, JASCO Corporation). The transmittance of the cured product converted to a film thickness of 1 μm is shown in Table 3 with a glass substrate having no cured polyketone as a reference.

<Thermal decomposition temperature measurement>
The weight loss of the cured polyketone was measured using a thermogravimetric balance TG-DTA 6300 (Hitachi High-Tech Science, Inc.). The point of intersection of the tangents of the curve whose weight is greatly reduced by heating is defined as the pyrolysis temperature. The results are shown in Table 3.

<Tg measurement>
The Tg of the cured polyketone was measured under the conditions of 1 Hz and 25 ° C. to 300 ° C. using a viscoelasticity measuring apparatus (RSA-II, Rheometric Scientific F. Inc.). The peak top of Tan δ is defined as Tg. The results are shown in Table 3.

<Chemical resistance test>
The sample for chemical resistance test was singulated to prepare a test piece. The test pieces were immersed in the chemical solution under the following conditions (a) and (b), respectively. It was observed whether the cured polyketone dissolved or the cured polyketone peeled off from the silicon substrate during immersion. The observation results are shown in Table 3. In this test, when no dissolution and peeling were observed, it was considered "no change".

Condition (a): A mixed solution of dimethylsulfoxide (DMSO) and 2-ethanolamine (2AE) (DMSO: 2AE in a volume ratio of 7: 3) was heated to 60 ° C., and the test piece was immersed for 30 minutes.
Condition (b): The test piece was immersed in a 0.5 mass% hydrogen fluoride (HF) aqueous solution at 23 ° C. for 30 minutes.

It was found that the cured polyketone product obtained from the polyketone composition of the example is excellent in chemical resistance, transparency and heat resistance.
On the other hand, Comparative Examples 1 to 3 not containing a hydrazide compound were inferior in chemical resistance and low in Tg.

The disclosure of Japanese Patent Application No. 2017-130 597 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are as specific and individually as individual documents, patent applications, and technical standards are incorporated by reference. Hereby incorporated by reference.

Claims (12)

The polyketone composition containing the polyketone containing the structural unit represented with following General formula (I), and a hydrazide compound.

In general formula (I), X each independently represents a divalent group having 1 to 50 carbon atoms which may have a substituent, and Y each independently has a substituent It also represents a bivalent hydrocarbon group having 1 to 30 carbon atoms, and n represents an integer of 1 to 1,500. The polyketone composition according to claim 1, wherein in the general formula (I), each X independently comprises an aromatic ring-containing divalent group having 6 to 50 carbon atoms. In the general formula (I), each X independently includes a divalent group represented by at least one selected from the group consisting of the following general formulas (II-1) to (II-3): A polyketone composition according to claim 1 or claim 2.

In general formula (II-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 is independently substituted Represents a hydrocarbon group having 1 to 30 carbon atoms which may have a group; m independently represents an integer of 0 to 3;

In general formula (II-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 R ² is independently substituted Group each independently represent an integer of 0 to 3 and Z represents an oxygen atom or a group represented by the following general formula (III-1): (III-7) represents a divalent group selected from (III-7).

In general formulas (III-1) to (III-7), R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ² represents And each independently represent a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ³ and R ⁴ each independently represent a hydrogen atom or a carbon optionally having a substituent It represents several 1 to 30 hydrocarbon groups. m independently represents an integer of 0 to 3, n independently represents an integer of 0 to 4, and p independently represents an integer of 0 to 2.

In general formula (II-3), each R ⁵ independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and n is independently an integer of 0 to 4 Represents The polyketone composition according to any one of claims 1 to 3, wherein Y in the general formula (I) contains a saturated hydrocarbon group. The polyketone composition according to any one of claims 1 to 4, wherein in the general formula (I), Y contains a saturated alicyclic hydrocarbon group. The polyketone composition according to any one of claims 1 to 5, wherein in the general formula (I), Y has 6 to 30 carbon atoms. The polyketone composition according to any one of claims 1 to 6, wherein the hydrazide compound has two or more hydrazide groups in the molecule. The polyketone composition according to any one of claims 1 to 7, wherein the hydrazide compound comprises an aromatic hydrazide compound. The polyketone composition according to any one of claims 1 to 8, 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 9. An optical element comprising the cured polyketone according to claim 10. The image display apparatus which has a polyketone cured material of Claim 10.