TW201906923A - Polyketone composition containing ruthenium compound, polyketone cured product, optical element, and image display device - Google Patents

Abstract

A polyketone composition includes a hydrazide compound and a polyketone including a structural unit represented by general formula (I). In general formula (I), X each independently represents a divalent group that has from 1 to 50 carbon atoms and that may include a substituent group; Y each independently represents a divalent hydrocarbon group that has 1 to 30 carbon atoms and that may include a substituent group; and n represents an integer from 1 to 1500.

Description

Polyketone composition containing polyhydrazine compound, polyketone hardened material, optical element and image display device

The invention relates to a polyketone composition, a polyketone hardened material, an optical element and an image display device.

Aromatic polyketones with aromatic rings and carbonyl groups in the main chain, which have excellent heat resistance and mechanical properties, have been used as engineering plastics. Almost all the polymers belonging to the aromatic polyketone are an aromatic polyether ketone, which is polymerized by using a nucleophilic aromatic substitution reaction, and the main chain has an ether bond. On the other hand, an aromatic polyketone having no ether bond in the main chain can exhibit superior heat resistance and chemical resistance than the aromatic polyetherketone (for example, refer to Patent Documents 1 and 2).

In recent years, the following reports have been proposed and are expected to be applied to optical parts: the alicyclic dicarboxylic acid and 2,2'-dialkoxybiphenyl are reacted by a Friedel-Crafts hydration reaction By directly polymerizing the compound, an aromatic polyketone can be obtained, which coexists high transparency and heat resistance. [Prior Art Literature] (Patent Literature)

Patent Document 1: Japanese Patent Application Publication No. 62-7730 Patent Document 2: Japanese Patent Application Publication No. 2005-272728 Patent Document 3: Japanese Patent Application Publication No. 2013-53194

[Problems to be Solved by the Invention] Here, the molecule of the aromatic polyketone described in Patent Document 3 is relatively stable to chemical agents. However, the cured product obtained by forming this aromatic polyketone on a substrate may be peeled off or dissolved from the substrate when exposed to a chemical agent, and it is a practical chemical-resistant chemical in the cured product. Sexually, there are still problems to be solved.

The present invention has been made in view of the above-mentioned circumstances, and an object thereof is to provide a polyketone composition and a polyketone hardened material, and an optical element and an image display device having the polyketone hardened material. Excellent transparency and chemical resistance. [Technical means to solve the problem]

The technical means for solving the problems to be solved includes the following implementation aspects.

<1> A polyketone composition containing a polyketone including a structural unit represented by the following general formula (I), and a hydrazide compound; In the general formula (I), X each independently represents a divalent group having 1 to 50 carbon atoms which may have a substituent, Y each independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and n represents 1 Integer to 1500. <2> The polyketone composition according to <1>, wherein in the general formula (I), X each independently contains a divalent group having 6 to 50 carbon atoms containing an aromatic ring. <3> The polyketone composition according to <1> or <2>, wherein in the aforementioned general formula (I), X is independently contained so as to be selected from the following general formulae (II-1) to (II- 3) At least one type of bivalent base selected from the group: In the 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 each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. m each independently represents an integer of 0 to 3; In the 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 each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. m each independently represents an integer of 0 to 3, and Z represents an oxygen atom or a divalent group selected from the following general formulae (III-1) to (III-7); In the general formulae (III-1) to (III-7), R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ² each independently represents a carbon number which may have a substituent. A hydrocarbon group of 1 to 30, R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group of 1 to 30 carbon atoms which may have a substituent, m each independently represents an integer of 0 to 3, and n each independently represents 0 to 4 Integers, p each independently represents an integer of 0 to 2; In the general formula (II-3), R ⁵ each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and n each independently represents an integer of 0 to 4. <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 includes a saturated alicyclic hydrocarbon group. <6> The polyketone composition according to any one of <1> to <5>, wherein the carbon number of Y in the general formula (I) is 6 to 30. <7> The polyketone composition according to any one of <1> to <6>, wherein the hydrazine compound has two or more hydrazine groups in a molecule. <8> The polyketone composition according to any one of <1> to <7>, wherein the hydrazine compound includes an aromatic hydrazine compound. <9> The polyketone composition according to any one of <1> to <8>, further comprising a solvent. <10> A polyketone cured product, which is a cured product of the polyketone composition according to any one of <1> to <9>. <11> An optical element comprising the polyketone cured product according to <10>. <12> An image display device comprising the polyketone cured product according to <10>. [efficacy]

According to the present invention, it is possible to provide a polyketone composition and a polyketone hardened material, and an optical element and an image display device having the polyketone hardened material. The polyketone composition has heat resistance, transparency, and resistance after being made into a hardened material. Excellent chemical properties.

The present invention is explained in detail below. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not necessary except for the case where it is specifically indicated. The numerical values and their ranges are also the same, and are not intended to limit the present invention.

In the present invention, the numerical range indicated by using "~" includes the numerical values described before and after "~" as the minimum and maximum values, respectively. In the numerical range described in stages in the present invention, the upper limit value or lower limit value in one numerical range may be replaced with the upper limit value or lower limit value in another numerical range described in stages. In addition, in the numerical range described in the present invention, the upper limit value or lower limit value of the numerical range may be replaced with a value disclosed in the embodiment. In the present invention, each component may include a plurality of substances corresponding to each component. When a plurality of substances corresponding to each component exist in the composition, unless otherwise specified, the content rate or content of each component means the total content rate or content of the plurality of substances present in the composition. In the present invention, the term "layer" or "film" includes a case where the layer or the film is formed only in a part of the area when the area is formed when the area where the layer or the film exists is observed. In the present invention, the term "lamination" means that layers are stacked, and two or more layers may be combined together, or two or more layers may be separated.

In the present invention, "excellent transparency" means that the transmittance of visible light (transmittance of visible light having a wavelength of at least 400 nm) is 80% or more (equivalent to a film thickness of 1 μm).

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

In the present invention, "excellent chemical resistance of the cured product" means that the film-like polyketone cured product formed on the silicon substrate is exposed to a chemical even under the following conditions (a) and (b), The polyketone hardened | cured material does not peel from a base material, nor does a polyketone hardened | cured material melt | dissolve. Condition (a): a mixed solution (DMSO: 2AE, 7: 3 in volume ratio) of dimethylsulfinium sulfide (DMSO) and 2-ethanolamine (2AE) is heated to 60 ° C, and then formed on a silicon substrate The hardened polyketone was immersed for 30 minutes. (1) Condition (b): A polyketone hardened material formed on a silicon substrate was immersed in a 0.5 mass% hydrogen fluoride (HF) aqueous solution at 23 ° C for 30 minutes.

<Polyketone composition> The polyketone composition of the present invention contains a polyketone (hereinafter also referred to as a "specific polyketone") containing a structural unit represented by the following general formula (I), and a hydrazine compound.

In the general formula (I), X each independently represents a divalent group having 1 to 50 carbon atoms which may have a substituent, Y each independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and n represents 1 Integer to 1500.

The polyketone composition of the present invention has the above-mentioned configuration, and after being made into a cured product, it has excellent heat resistance, transparency, and chemical resistance. The reason is not clear, but it is considered as follows. Specific polyketones are excellent in heat resistance and transparency. In addition, since the main chain of certain polyketones is almost all formed by C-C bonds, the molecule itself is more stable to chemical agents. In addition, when the polyketone composition contains a hydrazine compound, the hydrazine compound can act on a specific polyketone to form a crosslinked structure. Therefore, a high Tg appears after the polyketone composition is made into a cured product. In addition, peeling of the cured product from the substrate, dissolution of the cured product, and the like can be suppressed, and chemical resistance can be further improved. Hereinafter, each component will be described.

(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 divalent group having 1 to 50 carbon atoms which may have a substituent. Y each 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 1,000, and more preferably an integer of 5 to 500. When the divalent group or the divalent hydrocarbon group has a substituent, the carbon number of the divalent group or the divalent hydrocarbon group is the number of carbons not including the substituent. The same applies to the following. The specific polyketone may include a structural unit represented by the general formula (I) in the main chain, or may include a structural unit represented by the general formula (I) in a side chain, and preferably includes the general unit (I) in the main chain. Building blocks.

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 that X can have is not particularly limited, and specific examples include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a fluorenyl group having 2 to 5 carbon atoms, and the like.

The divalent group represented by X is preferably a hydrocarbon group, and more preferably contains an aromatic ring. If X has an aromatic ring, it tends to be able to express higher heat resistance.

From the viewpoint of achieving high heat resistance, X is preferably a divalent group having 6 to 50 carbon atoms containing an aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fused tetraphenyl ring, a 1,2-chrysene ring, a pyrene ring, a triphenylene ring, and a fused ring. Pentabenzene ring, benzofluorene ring, etc.

In addition, the divalent group represented by X preferably includes a plurality of aromatic rings, and more preferably a divalent group (hereinafter also referred to as a "specific aromatic ring group"), in which the plurality of aromatic rings are non-conjugated to each other, or The mutual conjugate relationship is weak. Thereby, when synthesizing a polyketone, a good dihydration reaction can be achieved 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 preferably has a carbon number of 12 to 50.

Here, the term "a plurality of aromatic rings are non-conjugated to each other or have a weak conjugate relationship with each other" means that a plurality of aromatic rings are bonded together via an ether bond or a methylene bond, or like 2, 2 The '-substituted biphenyls thus suppress the conjugation of the aromatic rings to each other based on the steric effect caused by the substituent.

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

In the 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 each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. m each independently represents an integer of 0 to 3. The part marked with a wavy line means a bond. The same applies to the following.

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 hydrocarbyl group has a substituent, the carbon number of the hydrocarbyl group is a carbon number that does not include a substituent. The same applies to the following.

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

Examples of the saturated aliphatic hydrocarbon group represented by R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, and n-pentyl. , Isopentyl, secondary pentyl, neopentyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-icosyl, n-tridecyl . The saturated aliphatic hydrocarbon group may have an alicyclic hydrocarbon group described later at a terminal portion thereof.

Examples of the unsaturated aliphatic hydrocarbon group represented by R ¹ include alkenyl groups such as vinyl and allyl groups; alkynyl groups such as ethynyl and the like. The unsaturated aliphatic hydrocarbon group may have an alicyclic hydrocarbon group described later at a terminal portion thereof.

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. The alicyclic hydrocarbon group may have at least one kind of alicyclic ring selected from the group consisting of a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group.

The substituent that the hydrocarbon group represented by R ¹ can have is not particularly limited, and examples thereof include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and a fluorenyl group having 2 to 5 carbon atoms.

In the 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 carbons represented by R ² include the same groups as the hydrocarbon groups having 1 to 30 carbons exemplified in R ¹ . Examples of the substituent that the hydrocarbon group represented by R ² may have include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a fluorenyl group having 2 to 5 carbon atoms, and the like.

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

In the 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 each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. m each independently represents an integer of 0 to 3, and Z represents an oxygen atom or a divalent group selected from the following general formulae (III-1) to (III-7). Formula (II-2) in R ^1, R ² and m are the details of each of the general formula R (II-1) ^1, R ² and m are the same.

In the general formulae (III-1) to (III-7), R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ² each independently represents a carbon number which may have a substituent. A hydrocarbon group of 1 to 30, R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group of 1 to 30 carbon atoms which may have a substituent, m each independently represents an integer of 0 to 3, and n each independently represents 0 to 4 Integer, p each independently represents an integer of 0 to 2. From the viewpoint of heat resistance, R ³ and R ^{4 are} preferably a hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ³ and R ⁴ include the same group as the hydrocarbon group having 1 to 30 carbon atoms exemplified in R ¹ in the general formula (II-1). Examples of the substituent that R ³ and R ⁴ can have include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a fluorenyl group having 2 to 5 carbon atoms, and the like. n each independently represents an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1. p each independently represents an integer of 0 to 2, preferably 0 or 1. R & lt details ^1, R ² and m are, respectively, the general formula R (II-1) ^1, R ² and m are the same.

In the general formula (II-3), R ⁵ each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and n each independently represents an integer of 0 to 4. 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 group as the hydrocarbon group having 1 to 30 carbon atoms exemplified in R ¹ in the general formula (II-1). Examples of the substituent that R ⁵ may have include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and a fluorenyl group having 2 to 5 carbon atoms.

In the 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 even more preferably 0 or 1.

In the general formula (I), Y each 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 from 4 to 30, and from the viewpoint of heat resistance, it is preferably from 6 to 30.

From the viewpoint of transparency, the hydrocarbon group represented by Y preferably contains a saturated hydrocarbon group. The saturated hydrocarbon group may be a saturated acyclic aliphatic hydrocarbon group or a saturated alicyclic hydrocarbon group. From the viewpoint of coexisting higher heat resistance and transparency, the hydrocarbon group represented by Y preferably contains a saturated alicyclic hydrocarbon group. Since an alicyclic hydrocarbon group is larger than an acyclic aliphatic hydrocarbon group having the same carbon number, it tends to have excellent solubility in a solvent while maintaining high heat resistance and transparency. In addition, the hydrocarbon group represented by Y may have a plurality of saturated acyclic aliphatic hydrocarbon groups, a plurality of saturated alicyclic hydrocarbon groups, or any combination of a saturated acyclic aliphatic hydrocarbon group and a saturated alicyclic hydrocarbon group. 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, examples of the hydrocarbon group represented by Y include methylene, ethylene, trimethylene, methylethylene, tetramethylene, and 1-methyl. Trimethylene, 2-methyltrimethylene, ethylidene, 1,1-dimethylethylene, 1,2-dimethylethylene, pentyl, 1-methyltetramethylene Methyl, 2-methyltetramethylene, 1-ethyltrimethylene, 2-ethyltrimethylene, 1,1-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1 , 2-dimethyltrimethylene, propyl-ethylidene, ethylmethyl-ethylidene, hexyl, 1-methyl-pentyl, 2-methyl-pentyl, 3-methyl-pentyl, 1-ethyltetramethylene, 2-ethyltetramethylene, 1-propyltrimethylene, 2-propyltrimethylene, butylethylene, 1,1-dimethyltetramethylene , 2,2-dimethyltetramethylene, 1,2-dimethyltetramethylene, 1,3-dimethyltetramethylene, 1,4-dimethyltetramethylene, 1 , 2,3-trimethyltrimethylene, 1,1,2-trimethyltrimethylene, 1,1,3-trimethyltrimethylene, 1,2,2-trimethyltrimethylene , 1-ethyl-1-methyltrimethylene, 2-ethyl-2-methyl Trimethylene, 1-ethyl-2-methyltrimethylene, 2-ethyl-1-methyltrimethylene, 2,2-ethylmethyltrimethylene, heptyl, octyl, Nonyl, decyl, icosyl, icosyl, etc.

Among them, from the standpoint of heat resistance, preferred examples of the hydrocarbon group include tetramethylene, hexyl, methylpentyl, ethyltetramethylene, propyltrimethylene, and butylethylene. , Dimethyltetramethylene, trimethyltrimethylene, ethylmethyltrimethylene, heptyl, octyl, hexanonyl, decyl, icodecyl, hexadecane Base etc.

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, examples of the hydrocarbon group represented by Y include a bivalent hydrocarbon group having the following skeleton: cyclopropane skeleton, cyclobutane skeleton, cyclopentane skeleton, cyclohexane skeleton, cycloheptane Alkane skeleton, cyclooctane skeleton, cubic alkane skeleton, norbornane skeleton, tricyclic [5.2.1.0] decane skeleton, adamantane skeleton, double adamantane skeleton, bicyclo [2.2.2] octane skeleton, ten Hydronaphthalene skeleton and the like.

Among these, from the viewpoint of heat resistance, preferred examples of the hydrocarbon group include a divalent hydrocarbon group having the following skeleton: a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cubic alkane skeleton, and a norbornane skeleton. , Tricyclic [5.2.1.0] decane skeleton, adamantane skeleton, double adamantane skeleton, bicyclo [2.2.2] octane skeleton, decalin skeleton, etc.

Examples of the substituent that the hydrocarbon group represented by Y may have include an amine group, an oxo group (a side oxygen group), a hydroxyl group, and a halogen atom.

Y preferably contains at least one 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), and more preferably Preferably, it contains at least a divalent hydrocarbon group represented by the following general formula (IV).

The hydrogen atom of the adamantane skeleton in the general formula (IV), the hydrogen atom of the cyclohexane skeleton in the general formula (V-1), the hydrogen atom of the decahydronaphthalene skeleton in the general formula (V-2), and the general formula The hydrogen atom of the norbornane skeleton in (V-3) may be substituted with an amine group, a keto group, a hydroxyl group or a halogen atom, respectively. In the general formula (IV) and the general formulas (V-1) to (V-3), Z each independently represents a single bond or a divalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. From the viewpoint of obtaining a soft hardened product, Z is preferably a divalent saturated hydrocarbon group having 1 to 10 carbon atoms which may each independently have a substituent, and from the viewpoint of heat resistance, Z is preferably independently Divalent saturated hydrocarbon group having 1 to 5 carbon atoms having a substituent. In addition, from the viewpoint of obtaining high hardness, Z is preferably a single bond.

Examples of the divalent hydrocarbon group represented by Z include methylene, ethylene, trimethylene, methylethylene, tetramethylene, 1-methyltrimethylene, and 2-methyltrimethylene. Ethyl, ethylidene, 1,1-dimethylethylene, 1,2-dimethylethylene, pentyl, 1-methyltetramethylene, 2-methyltetramethylene , 1-ethyltrimethylene, 2-ethyltrimethylene, 1,1-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1,2-dimethyltrimethylene, Propylethyl, ethylmethylethyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-ethyltetramethylene, 2 -Ethyltetramethylene, 1-propyltrimethylene, 2-propyltrimethylene, butylethylene, 1,1-dimethyltetramethylene, 2,2-dimethyltetramethylene Methyl, 1,2-dimethyltetramethylene, 1,3-dimethyltetramethylene, 1,4-dimethyltetramethylene, 1,2,3-trimethyltrimethylene Group, 1,1,2-trimethyltrimethylene, 1,1,3-trimethyltrimethylene, 1,2,2-trimethyltrimethylene, 1-ethyl-1-methyl Trimethylene, 2-ethyl-2-methyltrimethylene, 1-ethyl-2-methyltrimethylene , 2-ethyl-1-methyltrimethylene, heptyl, octyl, nononyl, decyl 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 a fluorenyl group having 2 to 5 carbon atoms. When the divalent hydrocarbon group represented by Z has a substituent, the carbon number of the divalent saturated hydrocarbon group is the number of carbons that does not include a substituent.

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

In the general formula (IV-1), the general formula (VI-1), the general formula (VI-2), and the general formula (VI-3), Z can be exemplified by the general formula (IV) and the general formula (V-1). ) To (V-3) have the same Z group.

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

The weight average molecular weight (Mw) of a specific polyketone is measured by standard gel permeation chromatography (GPC) in terms of polystyrene, and is 500 or more from the viewpoint of maintaining heat resistance. It is preferably from 10,000 to 1,000,000 from the viewpoint of higher heat resistance and solubility in a solvent. When 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 a specific polyketone is a value measured by the method described in an Example.

The specific polyketone may be used singly or in combination of two or more kinds. In addition, the polyketone composition may contain a polyketone other than the specific polyketone. Hereinafter, a specific polyketone and other polyketones are sometimes referred to as a "polyketone". From the viewpoints of heat resistance, transparency, and chemical resistance after production of a cured product, the content rate of the specific polyketone with respect to the total amount of the polyketone is preferably 50% by mass or more, and more preferably 60% by mass or more. It is more preferably 70% by mass or more.

From the viewpoints of heat resistance, transparency, and chemical resistance after production into a cured product, the total content of the polyketone is 50 to 99 parts by mass relative to 100 parts by mass of the total amount of the polyketone and the hydrazine compound. Preferably, it is 50 to 95 parts by mass.

<Hydrazine compound> The polyketone composition of the present invention contains a hydrazine compound.

The hydrazine compound preferably has two or more hydrazine groups in the molecule. Among them, the hydrazine compound preferably has 2 to 6 hydrazino groups in the molecule, more preferably has 2 to 4 hydrazino groups in the molecule, and even more preferably has 2 or 3 hydrazino groups in the molecule. Particularly preferred is that it has 2 hydrazino groups in the molecule. The hydrazino group is a group represented by the following chemical formula (VII).

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

When the hydrazine compound is an acyclic aliphatic hydrazine compound, the portion of the hydrazine compound other than the hydrazine group (hereinafter also referred to as a backbone portion) is preferably an acyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms. An acyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferred, and an acyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferred. In addition, the acyclic aliphatic hydrazine compound may be a hydrazine compound, which does not have a backbone portion such as ethylenedihydrazine (ie, the hydrazine groups are directly linked together). Acyclic aliphatic hydrocarbon group may be linear or branched, and linear is preferred. Acyclic aliphatic hydrocarbon group may or may not have a substituent. When the acyclic 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 a fluorenyl group having 2 to 5 carbon atoms. When the hydrocarbyl group has a substituent, the carbon number of the hydrocarbyl group is a carbon number that does not include a substituent. The same applies to the following. Acyclic aliphatic hydrocarbon groups may or may not have unsaturated bonds, and preferably have no unsaturated bonds.

When the hydrazine compound is an alicyclic hydrazine compound, the skeleton portion of the hydrazine compound is preferably, for example, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an alicyclic hydrocarbon group having 3 to 8 carbon atoms is preferred. An alicyclic hydrocarbon group having 3 to 6 carbon atoms is more preferable. An alicyclic hydrocarbon group is a hydrocarbon group having an alicyclic structure in at least a part thereof, and may have an acyclic aliphatic hydrocarbon group in addition to the alicyclic ring. 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 a fluorenyl group having 2 to 5 carbon atoms. The alicyclic hydrocarbon group may or may not have an unsaturated bond.

When the hydrazine compound is an aromatic hydrazine compound, the skeleton portion of the hydrazine compound is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, and An aromatic hydrocarbon group of 6 to 10 is more preferable. The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring in at least a part thereof, and may have an acyclic aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a combination thereof in addition to the aromatic ring. The fluorene 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 a fluorenyl group having 2 to 5 carbon atoms.

The hydrazine compound may be a compound having both an alicyclic ring and an aromatic ring in its molecule. In other words, it may be a compound corresponding to both an alicyclic hydrazine compound and an aromatic hydrazine compound.

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

In the formula (VIII), W represents a hydrocarbon group, and n represents an integer of 2 to 6.烃 The hydrocarbon group represented by W may be an acyclic aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, and an aromatic hydrocarbon group is preferred. The details of the acyclic aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group are the same as those of the acyclic aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group of the skeleton portion of the hydrazine compound, respectively. N is preferably 2 to 4, more preferably 2 or 3, and even more preferably 2.

As specific examples of the hydrazine compound, for example, ethylene dihydrazide, malonyl hydrazine, succinimide, glutar hydrazine, hexamethylene hydrazine, phthalimide, and m-xylazine , P-xylylene hydrazine, decanediozine, maleic hydrazine, fumaric hydrazine, Ikon dihydrazine, lemon trihydrazine. From the viewpoint of heat resistance, hexamethylene hydrazine and m-xylylenedihydrazine are preferable, and m-xylylene hydrazine is more preferable. The hydrazine compound can be a commercially available product or can be synthesized by a conventional method.

The hydrazine compound may be used individually by 1 type, and may use 2 or more types together. From the viewpoints of heat resistance, transparency, and chemical resistance after production into a cured product, the content of the hydrazine compound is 1 to 50 parts by mass based on 100 parts by mass of the total amount of the polyketone and the hydrazine compound. Preferably, 5 to 50 parts by mass is more preferable, and 5 to 30 parts by mass is more preferable.

<Solvent> The fluorene polyketone composition may further contain a solvent. The solvent is not particularly limited as long as it can dissolve or disperse 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-dimethylformamidine, N, N-dimethylethyl Pyridamine, hexamethylphosphamide, cyclobutane, diethyl ketone, diisobutanone, methylpentyl ketone, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol Monobutyl ether, dipropylene glycol monomethyl ether, xylene, trimethylbenzene, ethylbenzene, propylbenzene, cumene, diisopropylbenzene, hexylbenzene, anisole, diethylene glycol dimethyl ether, diethylene glycol Methyl sulfene, chloroform, dichloromethane, dichloroethane, chlorobenzene, etc. These solvents can be used singly or in combination of two or more kinds.

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

<Other additives> The fluorene polyketone composition may further contain other additives. Other additives include, for example, adhesion promoters, surfactants, leveling agents, antioxidants, ultraviolet deterioration inhibitors, slip agents (such as polytetrafluoroethylene particles), and light diffusing agents (acrylic crosslinking). Particles, silicon-oxygen crosslinked particles, ultra-thin glass flakes, calcium carbonate particles, etc.), fluorescent dyes, inorganic phosphors (fluorescent bodies with aluminate as parent crystal, etc.), antistatic agents, crystal nucleating agents , Inorganic antibacterial agent, organic antibacterial agent, photocatalytic antifouling agent (titanium oxide particles, zinc oxide particles, etc.), crosslinker, hardener, reaction accelerator, infrared absorber (heat ray absorber), photochromic agent Wait.

<Polyketone hardened | cured material> The polyketone hardened | cured material of this invention is a hardened | cured material of the polyketone composition of this invention. The fluorene polyketone hardened | cured material can be manufactured by the following method, for example. First, a polyketone composition is supplied to at least a part of the surface of a substrate to form a composition layer and dried. After removing the solvent from the composition layer or curing it together with the solvent, the polymer of the present invention can be produced. Ketone hardener. The method for supplying the polyketone composition to the substrate is not particularly limited as long as it is a method capable of forming a composition layer at an arbitrary position on the substrate in an arbitrary shape. Examples of the method for supplying 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 be supplied with the polyketone composition is not particularly limited, and examples thereof include transparent substrates composed of glass, semiconductors, metal oxide insulators (titanium oxide, silicon oxide, etc.), inorganic materials such as silicon nitride, and the like. ; Transparent resins such as cellulose triacetate, transparent polyimide, polycarbonate, acrylic polymers, and cycloolefin resins. The shape of the substrate is not particularly limited, and may be a plate shape or a film shape. Since the polyketone composition of the present invention is excellent in chemical resistance after being made into a cured product, it can be suitably used as a coating material, a molded product, or the like for a substrate.

When the polyketone composition contains a solvent, it can be dried before and after curing. The drying method is not particularly limited, and examples thereof include a method of performing heat treatment using a device such as a hot plate and an oven, and a method of natural drying. The conditions for performing the heat treatment and drying are not particularly limited as long as the solvent in the polyketone composition is sufficiently volatilized, and may be about 50 ° C to 150 ° C for 1 minute to 90 minutes.

The method for hardening the polyketone is not particularly limited, and it can be hardened by heat treatment or the like. Hardening by heat treatment can be performed using a box-type dryer, a hot-air conveyor-type dryer, a quartz tube furnace, a heating plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, and an electron beam curing furnace. , Microwave hardening furnace, etc.

The environment at the time of hardening can be selected from the atmosphere and an inert gas such as nitrogen. From the viewpoint of preventing oxidation of the polyketone composition, it is preferably performed in a nitrogen environment.的 The temperature and time of the heat treatment for hardening can be arbitrarily set in consideration of composition conditions, operation efficiency, etc., and can be performed at 60 ° C to 200 ° C for about 30 minutes to 2 hours.

The dried polyketone hardened product of the present invention may be further heat-treated as necessary to remove residual solvents. The method of the heat treatment is not particularly limited, and can be performed using a box dryer, a hot-air conveyor belt dryer, a quartz tube furnace, a heating plate, a rapid thermal annealing, a vertical diffusion furnace, an infrared hardening furnace, and electronics Beam hardening furnace, microwave hardening furnace, vacuum dryer, etc. In addition, in the heat treatment step, the gas environment is not particularly limited, and examples thereof include, for example, the atmosphere, an inert gas environment such as nitrogen, and the like. The conditions for performing the heat treatment are not particularly limited, and may be performed at 150 ° C to 250 ° C for about 1 minute to 90 minutes. Further heat treatment tends to increase the density of the obtained polyketone cured product.

When the polyketone hardened material has a thickness of 10 μm, the haze is preferably less than 1%. In addition, the transmittance at 400 nm of the cured polyketone is preferably 85% or more in terms of a film thickness of 1 μm.

The obtained polyketone hardened material can also be used directly as a base material with a polyketone hardened material in a state of being added to the base material, and can also be used after being peeled from the base material as needed.中 In the base material with a polyketone hardened material, the polyketone hardened material may be provided on at least a part of the surface of the base material, and may be provided on only one side of the base material or on both sides of the base material. Moreover, a polyketone hardened | cured material may have a single layer structure or a multiple layer structure which laminated | stacked two or more layers.

<Optical element and image display device> The optical element and image display device of the present invention each include the polyketone cured product of the present invention. The polyketone hardened material suitable for an optical element and an image display device can be used as it is as a base material with a polyketone hardened | cured material in the state added to a base material as mentioned above. Moreover, if a base material is a transparent base material, it can be used suitably for an optical element. As a transparent base material, the base material illustrated in the manufacture of a polyketone hardened | cured material is mentioned, for example.

An optical element and an image display device can be obtained, for example, by adhering a substrate side of a substrate with a polyketone hardened material to a liquid crystal display (LCD) or an electroluminescent display via an adhesive, an adhesive, or the like. (ELD), organic EL display, etc.

Various optical elements such as a polyketone hardened material and a polarizing plate using the polyketone hardened material can be preferably used for various image display devices such as a liquid crystal display device. The video display device may have the same configuration as a conventional video display device except that the polyketone cured product of the present invention is used. When the image display device is a liquid crystal display device, it can be manufactured by appropriately assembling optical elements such as a liquid crystal cell, a polarizing plate, and other components such as a lighting system (backlight, etc.) as required, and adding a driving circuit, and the like. The liquid crystal cell is not particularly limited, and various types such as a twisted nematic (TN) type, a super twisted nematic (STN) type, and a π type can be used.

Examples of applications for image display devices include office automation (OA) devices such as desktop computers, notebook computers, and photocopiers; mobile phones, clocks, digital cameras, mobile information terminals (PDAs), and portable game consoles. Carrying equipment; household appliances such as cameras, televisions, microwave ovens; on-board equipment such as rear screens, screens for car navigation systems, car stereos; display equipment such as information screens for commercial shops; surveillance equipment such as monitor screens; monitor screens, etc. Nursing equipment; medical equipment such as medical monitors. [Example]

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

<Polyketone composition> 实施 The components (A) to (C) were blended at the ratios shown in Tables 1 and 2, and filtered with a filter made of polytetrafluoroethylene (PTFE) to obtain examples and comparative examples. Polyketone composition. The numerical values in parentheses indicate the blending ratio (parts by mass). "-" Means that the component is not contained. Each component in Table 1 and Table 2 is as follows.

(A) Ingredient: Polyketone (Synthesis Example 1) Synthesis of polyketone PK-1 Into a flask, 10 mmol of 2,2'-dimethoxybiphenyl and 10 mmol of cis 1,4-cyclohexanedicarboxylic acid were added. After serving as a monomer, 30 mL of a mixed solution of phosphorus pentoxide and methanesulfonic acid (mass ratio 1:10) was added to the flask, and stirred at 60 ° C. After the reaction, the content was poured into 500 mL of methanol, and the resulting precipitate was filtered out. 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. The weight-average molecular weight and the number-average molecular weight are measured and calculated by a method described later. 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) The synthesis of polyketone PK-2 was the same as Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl and 13 mmol of 1,3-adamantane dicarboxylic acid were used as monomers. In this way, polyketone PK-2 was obtained. 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) The synthesis of polyketone PK-3 was the same as Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl and 10 mmol of 1,3-adamantane diacetic acid were used as monomers. In this way, polyketone PK-3 was obtained. 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) In the synthesis of polyketone PK-4, except that 2,2'-dimethoxybiphenyl 10 mmol, 1,3-adamantane dicarboxylic acid 5 mmol, and cis 1,4-cyclohexanedicarboxylic acid were used. Except that 5 mmol was used as a monomer, the rest was performed in the same manner as in Example 1 to obtain a polyketone PK-4. 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) In the synthesis of polyketone PK-5, 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of 1,3-adamantane dicarboxylic acid, and 5 mmol of dodecanedioic acid were used as monomers. Other than that, it carried out similarly to Example 1, and obtained polyketone 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) In the synthesis of polyketone PK-6, 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of 1,3-adamantane diacetic acid, and 5 mmol of dodecanedioic acid were used as monomers. Other than that, it carried out similarly to Example 1, and obtained polyketone 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 except that 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of adamantane diacetic acid, and 5 mmol of adipic acid were used as monomers. The rest was carried out in the same manner as in Example 1 to obtain polyketone 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 except that 2,2'-dimethoxybiphenyl 10 mmol, 1,3-adamantane diacetic acid 5 mmol, and cis 1,4-cyclohexanedicarboxylic acid were used. Except for 5 mmol, the rest was carried out in the same manner as in Example 1 to obtain 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) Polyketone PK-9 was synthesized by using 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of 1,3-adamantandiacetic acid, and trans 1,4-cyclohexanedicarboxylic acid. Except that 5 mmol was used as a monomer, the rest was performed in the same manner as in Example 1 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) Polyketone PK-10 was synthesized by using 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of 1,3-adamantandiacetic acid, and 1,4-cyclohexanedicarboxylic acid (cis A mixture of formula and trans, cis: trans (mol ratio) = 7: 3) 5 mmol was used as a monomer, and the rest were carried out in the same manner as in Example 1 to obtain polyketone PK-10. 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 except that 2,2'-dimethoxybiphenyl 10 mmol, 1,3-adamantane diacetic acid 5 mmol, and decalin-2,6-dicarboxylic acid 5 were used. Except that mmol was used as a monomer, the rest was performed in the same manner as in Example 1 to obtain polyketone PK-11. 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) In addition to the synthesis of polyketone PK-12, 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of 1,3-adamantane diacetic acid, and norbornane dicarboxylic acid (2,4-, 2,5-mixture) 5 mmol was used as a monomer, and the rest were carried out in the same manner as in Example 1 to obtain a polyketone PK-12. 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 except for the use of 2,2'-dimethoxybiphenyl 10 mmol, 1,3-adamantane diacetic acid 5 mmol and trans 2,3-norbornane dicarboxylic acid Except that 5 mmol was used as a monomer, the rest was performed in the same manner as in Example 1 to obtain a polyketone PK-13. 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 except that 2,2'-bis (2-methoxyphenyl) propane 10 mmol, 1,3-adamantane diacetic acid 5 mmol, and 1,4-cyclohexane were used. Except for 5 mmol of alkanedicarboxylic acid (mixture of cis and trans, cis: trans (mol ratio) = 7: 3) as monomers, the rest was performed in the same manner as in Example 1 to obtain polyketone PK-14. . 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 except that 10 mmol of diphenyl ether, 5 mmol of 1,3-adamantane diacetic acid, and 1,4-cyclohexanedicarboxylic acid (a mixture of cis and trans, Cis: trans (mol ratio) = 7: 3) 5 mmol was used as a monomer, and the rest was carried out in the same manner as in Example 1 to obtain polyketone PK-15. The weight average molecular weight of the obtained polyketone PK-15 was 27,000, and the number average molecular weight was 8,000.

(B) Component: hydrazine compound B1: a compound represented by the following formula (XII)

B2: Compound represented by the following formula (XIII)

(C) Component: Solvent C1: Mixed solvent of N-methyl-2-pyrrolidone and dimethylsulfinium (mass ratio 1: 1)

[Table 1]

[Table 2]

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

(1) Sample for transmittance measurement A polyketone composition was coated on a glass substrate by a spin coating method, and dried on a hot plate heated to 120 ° C for 3 minutes. An inert gas oven (Koyo Thermo Systems Co., Ltd.) was used to heat-treat the obtained glass substrate at 200 ° C. for 1 hour in a nitrogen gas flow, and then a polyketone hardened product having a thickness of 10 μm was formed on the glass substrate, and then This polyketone hardened | cured material was made into the sample for transmittance | permeability measurement.

(2) Sample for measuring thermal decomposition temperature After the polyketone composition was dropped into an aluminum cup, it was dried in the same manner as in (1) and heat-treated to obtain a cured polyketone formed in the aluminum cup. After peeling this polyketone hardened | cured material from an aluminum cup, this polyketone hardened | cured material was made into the sample for thermal decomposition temperature measurement.

(3) The sample for Tg is coated with a polyketone composition on a glass substrate by a rod coating method, dried in the same manner as in (1), and heat-treated to form a 10 μm-thick film on the glass substrate. Polyketone hardened. This polyketone hardened | cured material was peeled from the glass substrate, and the polyketone hardened | cured material was obtained, and this polyketone hardened | cured material was set as the sample for Tg measurement.

(4) The sample for chemical resistance test was coated with a polyketone composition on a silicon substrate by a spin coating method, dried in the same manner as in (1), and heat-treated to form a thickness on the silicon substrate. A polyketone hardened product of 10 μm was used as a sample for a chemical resistance test.

<Molecular weight measurement of polyketone> The molecular weight (weight average molecular weight and number average molecular weight) of polyketone is measured by GPC method using tetrahydrofuran (THF) as the eluent, and converted by standard polystyrene Find out later. The details are as follows.

・ Device name: Ecosec HLC-8320GPC (Tosoh Corporation) ・ Stem: TSKgel Supermultipore HZ-M (Tosoh Corporation) ・ Detector: Combined with ultraviolet (UV) detector, refractive index (RI) Detector ・ Flow rate: 0.4 mL / min

<Transmittance measurement> 400 The ultraviolet transmittance of 400 nm of the polyketone cured product was measured by ultraviolet-visible absorption spectroscopy using a spectrophotometer (V-570, Japan Spectroscopy Corporation). Using a glass substrate without a polyketone hardened material as a reference group, the transmittance of the hardened material converted to a film thickness of 1 μm is shown in Table 3.

<Measurement of Thermal Decomposition Temperature> 热 The weight loss of the cured polyketone was measured using a thermogravimetric balance TG-DTA6300 (Hitachi High-Tech Science Co., Ltd.). The intersection point of the tangent of the curve whose weight is greatly reduced by heating is defined as the thermal decomposition temperature. The results are shown in Table 3.

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

<Chemical resistance test> (1) A sample for a chemical resistance test is singulated to prepare a test piece. The test pieces were each immersed in a chemical agent under the following conditions (a) and (b). Observe that the polyketone hardened | cured material melt | dissolved in the immersion, or the polyketone hardened | cured material peeled from the silicon substrate. The observation results are shown in Table 3. In this test, when no dissolution or peeling was observed, it was set to "no change".

Condition (a): A mixed solution (DMSO: 2AE, 7: 3 by volume ratio) of dimethylsulfinium sulfide (DMSO) and 2-ethanolamine (2AE) is heated to 60 ° C, and the test piece is immersed for 30 minutes . (1) Condition (b): The test piece was immersed in a 0.5 mass% hydrogen fluoride (HF) aqueous solution at 23 ° C for 30 minutes.

[table 3]

From the above, it is understood that the polyketone hardened material obtained from the polyketone composition of the example is excellent in chemical resistance, transparency, and heat resistance. On the other hand, in Comparative Examples 1 to 3 containing no hydrazine compound, the chemical resistance was poor, and Tg was also low.

In this case, the entire disclosure of Japanese Patent Application No. 2017-130597 is incorporated in this specification by reference.文献 All documents, patent applications, and technical specifications described in this specification refer to each document, patent application, and technical specification in this specification by referring to each of them specifically and to the same extent as when they are separately described.

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Claims (12)

A polyketone composition comprising a polyketone including a structural unit represented by the following general formula (I), and a hydrazine compound; In the general formula (I), X each independently represents a divalent group having 1 to 50 carbon atoms which may have a substituent, Y each independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and n represents 1 Integer to 1500. The polyketone composition according to claim 1, wherein in the general formula (I), X each independently contains a divalent group having 6 to 50 carbon atoms containing an aromatic ring. The polyketone composition according to claim 1 or 2, wherein in the aforementioned general formula (I), X is each independently contained so as to consist of the following general formulae (II-1) to (II-3) The divalent base of at least one selected from the group: In the 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 each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. m each independently represents an integer of 0 to 3; In the 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 each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. m each independently represents an integer of 0 to 3, and Z represents an oxygen atom or a divalent group selected from the following general formulae (III-1) to (III-7); In the general formulae (III-1) to (III-7), R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ² each independently represents a carbon number which may have a substituent. A hydrocarbon group of 1 to 30, R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group of 1 to 30 carbon atoms which may have a substituent, m each independently represents an integer of 0 to 3, and n each independently represents 0 to 4 Integers, p each independently represents an integer of 0 to 2; In the general formula (II-3), R ⁵ each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and n each independently represents an integer of 0 to 4. The polyketone composition according to any one of claims 1 to 3, wherein in the general formula (I), Y 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), the carbon number of Y is 6 to 30. The polyketone composition according to any one of claims 1 to 6, wherein the molecule of the hydrazine compound has two or more hydrazine groups. The polyketone composition according to any one of claims 1 to 7, wherein the hydrazine compound includes an aromatic hydrazine compound. The polyketone composition according to any one of claims 1 to 8, further comprising a solvent. A hardened polyketone, which is a hardened polyketone composition according to any one of claims 1 to 9. An optical element comprising the polyketone cured product according to claim 10. An image display device comprising the polyketone cured product according to claim 10.