JP2020105286A - Polyketone containing structural unit having aromatic ring and chain group, polyketone composition, polyketone film, optical element, image display device, and method for producing polyketone - Google Patents

Abstract

To provide polyketone having excellent flexibility and breaking elongation, a polyketone composition and a polyketone film containing the same, an optical element and an image display device having the polyketone film, and a method for producing polyketone having excellent flexibility and breaking elongation.SOLUTION: A polyketone contains a structural unit of general formula (II). R1 is a divalent a chain group having 2-30 C and/or O atoms in the main chain. R2 independently represent a substituent. Of R1, if an atom adjacent to an aromatic ring is O, x that represents the number of substituents R2 of the aromatic ring adjacent to O is an integer of 0-4. Of R1, if an atom adjacent to an aromatic ring is C, x that represents the number of substituents R2 of the aromatic ring adjacent to C is an integer of 1-4. At least one of substituents R2 of the aromatic ring adjacent to C represents an electron-donating group.SELECTED DRAWING: None

Description

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 the aromatic polyketone are aromatic polyether ketones polymerized by utilizing a nucleophilic aromatic substitution reaction, and have an ether bond in the main chain. On the other hand, an aromatic polyketone that does not have an ether bond in the main chain can exhibit more excellent heat resistance than an aromatic polyether ketone (see, for example, Patent Document 1 and Patent Document 2).

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

JP 62-7730 A JP 2005-272728 A JP, 2013-53194, A

It is expected that an optical component to which a resin material is applied will have characteristics that cannot be obtained with an inorganic material. For example, the lightness and the flexibility compared to the inorganic material can be mentioned. Examples of the application destination of the resin material include a coating material that makes use of light weight, a glass substitute material, and a flexible display that makes use of flexibility.

Furthermore, when a molded product molded from a resin material is used for a flexible display or the like, it is required that the molded product has excellent flexibility and elongation at break. On the other hand, conventional aromatic polyketones have room for improvement in flexibility and elongation at break for application to optical members such as substrates for flexible displays.

In view of the above circumstances, the present disclosure provides a polyketone excellent in flexibility and elongation at break, a polyketone composition and a polyketone film containing the same, an optical element and an image display device having the polyketone film, and a polyketone excellent in flexibility and elongation at break. It aims at providing the manufacturing method of.

Means for solving the above problems include the following embodiments.

<1> A polyketone containing a structural unit represented by the following general formula (II).

[In the general formula (II), R ¹ represents a divalent chain group having 2 to 30 atoms of at least one kind selected from the group consisting of carbon atoms and oxygen atoms in the main chain. R ^2's each independently represent a substituent. When the atom adjacent to the aromatic ring in R ¹ is an oxygen atom, x representing the number of the substituents R ^{2 on} the aromatic ring adjacent to the oxygen atom represents an integer of 0 to 4. When the atom adjacent to the aromatic ring in R ¹ is a carbon atom, x representing the number of the substituents R ^{2 on} the aromatic ring adjacent to the carbon atom represents an integer of 1 to 4 and is adjacent to the carbon atom. At least one of the substituents R ² on the aromatic ring represents an electron donating group. ]
<2> The polyketone according to <1>, wherein in the general formula (II), each R ² independently represents an alkoxy group, an amino group, or a hydrocarbon group having 1 to 30 carbon atoms.
<3> The polyketone according to <1> or <2>, wherein in the general formula (II), R ¹ has an oxygen atom at one or both ends of the main chain.
<4> The polyketone according to <1>, wherein the structural unit represented by the general formula (II) is selected from structural units represented by the following general formula (II-1) or structural units represented by the following general formula (II-2).

[In general formula (II-1), R< ² > represents a substituent each independently. R ³ represents a chain hydrocarbon group having 1 to 28 carbon atoms. x represents an integer of 0 to 4. ]

[In general formula (II-2), R< ² > represents a substituent each independently, and in each aromatic ring, at least one R< ² > represents an electron-donating group. R ⁴ represents a chain hydrocarbon group having 2 to 30 carbon atoms. x represents an integer of 1 to 4. ]
<5> In the general formulas (II-1) and (II-2), R ² 's each independently represent an alkoxy group, an amino group, or a hydrocarbon group having 1 to 30 carbon atoms, <4 > The polyketone described in.
<6> The method according to any one of <1> to <5>, further including a divalent group having 1 to 50 carbon atoms, which is linked to the group having the structural unit of the general formula (II) with a carbonyl group interposed therebetween. The described polyketone.
<7> At least the divalent group having 1 to 50 carbon atoms, which is connected to the group having the structural unit represented by the general formula (II) by separating the carbonyl group, is selected from the group consisting of an alicyclic skeleton and an aromatic ring. The polyketone according to <6>, which comprises one kind.
<8> A polyketone composition containing the polyketone according to any one of <1> to <7> and a solvent.
<9> A polyketone film containing the polyketone according to any one of <1> to <7>.
<10> An optical element having the polyketone film according to <9>.
<11> An image display device having the optical element according to <10>.
<12> A method for producing a polyketone, which comprises subjecting a monomer containing a structural unit of the following general formula (IIA) and a dicarboxylic acid to a condensation reaction in an acidic medium.

[In the general formula (IIA), R ¹ represents a divalent chain group having 2 to 30 atoms of at least one kind selected from the group consisting of carbon atoms and oxygen atoms in the main chain. R ^2's each independently represent a substituent. When the atom adjacent to the aromatic ring in R ¹ is an oxygen atom, x representing the number of the substituents R ^{2 on} the aromatic ring adjacent to the oxygen atom represents an integer of 0 to 4. When the atom adjacent to the aromatic ring in R ¹ is a carbon atom, x representing the number of the substituents R ^{2 on} the aromatic ring adjacent to the carbon atom represents an integer of 1 to 4 and is adjacent to the carbon atom. At least one of the substituents R ² on the aromatic ring represents an electron donating group. ]
<13> The method for producing a polyketone according to <12>, wherein in the general formula (II), each R ² independently represents an alkoxy group, an amino group, or a hydrocarbon group having 1 to 30 carbon atoms.
<14> The method for producing a polyketone according to <12> or <13>, wherein in the general formula (II), R ¹ has an oxygen atom at one or both ends of the main chain.

According to the present disclosure, a polyketone having excellent flexibility and elongation at break, a polyketone composition and a polyketone film containing the same, an optical element and an image display device having the polyketone film, and a method for producing polyketone excellent in flexibility and elongation at break Will be provided.

Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and does not limit the present invention.

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

In the present disclosure, “excellent flexibility” means that even if the cured film is subjected to a mandrel test using a core rod having a diameter of 2 mm by the method of the example, the film does not crack.
In the present disclosure, “excellent transparency” means that the visible light transmittance (the light transmittance of at least a wavelength of 400 nm) is 80% or more (converted to a film thickness of 1 μm).
In the present disclosure, “excellent elongation at break” means that the elongation at break of the cured product measured by the method of Examples exceeds 3%.

≪Polyketone≫
The polyketone of the present disclosure includes a structural unit represented by the following general formula (II).

In the general formula (II), R ¹ represents a divalent chain group having 2 to 30 at least one atom selected from the group consisting of carbon atoms and oxygen atoms in the main chain. R ^2's each independently represent a substituent. When the atom adjacent to the aromatic ring in R ¹ is an oxygen atom, x representing the number of the substituents R ^{2 on} the aromatic ring adjacent to the oxygen atom represents an integer of 0 to 4. When the atom adjacent to the aromatic ring in R ¹ is a carbon atom, x representing the number of the substituents R ^{2 on} the aromatic ring adjacent to the carbon atom represents an integer of 1 to 4 and is adjacent to the carbon atom. At least one of the substituents R ² on the aromatic ring represents an electron donating group.

The polyketone of the present disclosure has excellent flexibility and elongation at break. The reason is not necessarily clear, but since the main chain has a chain group having two or more atoms of at least one kind selected from the group consisting of carbon atoms and oxygen atoms between the two aromatic rings, It is presumed that the rigidity of is relaxed.

The polyketone of the present disclosure tends to have excellent transparency and heat resistance. It is considered that the plurality of aromatic rings in the polyketone of the present disclosure contributes to heat resistance. Further, since the plurality of aromatic rings in the formula (II) are non-conjugated to each other or have a weak conjugation relationship with each other, good diacylation can be achieved at a low reaction temperature when synthesizing a polyketone, It is considered to be a polyketone having a high molecular weight and excellent heat resistance.

In formula (II), R ¹ represents a divalent chain group having 2 to 30 atoms of at least one kind selected from the group consisting of carbon atoms and oxygen atoms in the main chain. The number of atoms present in the main chain is preferably 2 to 20, more preferably 2 to 15, and even more preferably 2 to 10. In the present disclosure, the main chain of R ¹ refers to an atom chain connecting two aromatic rings of general formula (II). In addition, the chain group refers to a group that does not include a cyclic structure on the main chain.

The number of carbon atoms and oxygen atoms present in the main chain of R ¹ is not particularly limited as long as the total number is 2 to 30. For example, R ¹ may be a chain hydrocarbon group in which all the atoms present in the main chain are carbon atoms (also simply referred to as chain hydrocarbon group), and all the atoms present in the main chain are oxygen. It may be a chain group which is an atom, or may be a chain group which is a combination of a chain hydrocarbon group and an oxygen atom having a carbon atom and an oxygen atom in the main chain.

When R ¹ is a chain hydrocarbon group, the chain hydrocarbon group may or may not have a substituent. Examples of the substituent include a hydroxyl group, an amino group, an alkoxy group, a halogen atom and an acyl group.

When R ¹ is a chain hydrocarbon group, the chain hydrocarbon group may be a straight chain hydrocarbon group or a branched hydrocarbon group.

When R ¹ is a chain hydrocarbon group, the chain hydrocarbon group may or may not contain an unsaturated bond.

When R ¹ is a chain hydrocarbon group, R ¹ is preferably a chain hydrocarbon group having 2 to 20 carbon atoms, more preferably a chain hydrocarbon group having 2 to 15 carbon atoms, More preferably, it is a chain hydrocarbon group having 2 to 10 carbon atoms. In the present disclosure, the carbon number of the hydrocarbon group does not include the carbon number of the substituent. Moreover, when the chain hydrocarbon group has a branched chain, the branched chain is not included in the substituent.

When R ¹ is a chain group in which all atoms existing in the main chain are oxygen atoms, examples of the chain group include groups in which 2 to 30 oxygen atoms are linearly bonded. The number of oxygen atoms is preferably 2 to 20, more preferably 2 to 15, and even more preferably 2 to 10.

When R ¹ is a chain group in which a chain hydrocarbon group and an oxygen atom are combined, the chain group may or may not have a substituent. Examples of the substituent include a hydroxyl group, an amino group, an alkoxy group, a halogen atom and an acyl group.

When R ¹ is a chain group in which a chain hydrocarbon group and an oxygen atom are combined, the chain hydrocarbon group in R ¹ may be a straight chain hydrocarbon group or a branched hydrocarbon group. Good.

When R ¹ is a chain group in which a chain hydrocarbon group and an oxygen atom are combined, the chain hydrocarbon group may or may not contain an unsaturated bond.

When R ¹ is a chain group in which a chain hydrocarbon group and an oxygen atom are combined, the total number of carbon atoms of the chain hydrocarbon group in R ¹ is preferably 1 to 18, and 1 to 13 Is more preferable, and 1 to 8 is further preferable.

When R ¹ is a chain group in which a chain hydrocarbon group and an oxygen atom are combined, the position of the oxygen atom in R ¹ is not particularly limited as long as it is on the main chain. In one preferable embodiment, R ¹ has an oxygen atom at one or both ends of the main chain. The oxygen atom present at one end or both ends of the main chain of R ¹ can act as an electron-donating group for the aromatic ring in the synthesis of polyketone. Further, R ¹ may be a chain group having no oxygen atom at one or both ends of the main chain but having an oxygen atom inside. R ¹ may be a chain group having an oxygen atom at one or both ends of the main chain and also having an oxygen atom inside.

In formula (II), R ^2's each independently represent a substituent. Examples of the substituent represented by R ² include a hydroxyl group, an alkoxy group, an amino group, a hydrocarbon group having 1 to 30 carbon atoms, and an alkoxy group, an amino group, or a hydrocarbon group having 1 to 30 carbon atoms. preferable.

When R ² is a hydrocarbon group having 1 to 30 carbon atoms, the hydrocarbon group may or may not have a substituent. Examples of the substituent include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, and the like.

When R ² is a hydrocarbon group having 1 to 30 carbon atoms, the hydrocarbon group may be a straight chain hydrocarbon group or a branched hydrocarbon group.

When R ² is a hydrocarbon group having 1 to 30 carbon atoms, the hydrocarbon group may or may not contain an unsaturated bond.

As the hydrocarbon group having 1 to 30 carbon atoms represented by R ² , a hydrocarbon group having 1 to 20 carbon atoms is preferable, a hydrocarbon group having 1 to 15 carbon atoms is more preferable, and a hydrocarbon group having 1 to 10 carbon atoms. A hydrogen group is more preferred.

When R ² is a hydrocarbon group having 1 to 30 carbon atoms, specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t- Butyl group, n-pentyl group, isopentyl group, sec-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group And saturated chain hydrocarbon groups such as n-icosanyl group and n-triacontanyl group; and unsaturated chain hydrocarbon groups such as alkenyl groups such as vinyl group and allyl group and alkynyl groups such as ethynyl group. To be

When R ² is an alkoxy group, R ² is preferably an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. Is more preferable.

Specific examples of the case where R ² is an alkoxy group include, for example, the saturated chain hydrocarbon group or the unsaturated chain carbon group described above as a specific example of the case where R ² is a hydrocarbon group having 1 to 30 carbon atoms. An alkoxy group in which an oxygen atom is linked to a hydrogen group can be mentioned.

When R ² is an amino group, the amino group may be an unsubstituted amino group or a substituted amino group in which 1 or 2 hydrogen atoms are substituted with an alkyl group. As the substituted amino group, a substituted amino group having one or two hydrocarbon groups having 1 to 30 carbon atoms is preferable. Specific examples of the hydrocarbon group having 1 to 30 carbon atoms in the substituted amino group include the saturated chain hydrocarbon group and unsaturated groups described above as specific examples when R ² is a hydrocarbon group having 1 to 30 carbon atoms. Examples thereof include chain hydrocarbon groups.

In the general formula (II), in R ¹ , when the atom adjacent to the aromatic ring is an oxygen atom, x representing the number of the substituents R ^{2 on} the aromatic ring adjacent to the oxygen atom is an integer of 0 to 4. Represent In this case, R ² may or may not be an electron-donating group because an oxygen atom adjacent to the aromatic ring can act as an electron-donating group in the synthesis of polyketone. When the atom adjacent to the aromatic ring is an oxygen atom, x, which represents the number of the substituent R ² of the aromatic ring adjacent to the oxygen atom, is preferably 0 to ² from the viewpoint of easy availability. From the viewpoint of solubility in a solvent, x is preferably 1 to 4.
When the atom adjacent to the aromatic ring in R ¹ is a carbon atom, x representing the number of the substituents R ^{2 on} the aromatic ring adjacent to the carbon atom represents an integer of 1 to 4 and is adjacent to the carbon atom. At least one of the substituents R ² on the aromatic ring represents an electron donating group. From the viewpoint of easy availability, when the atom adjacent to the aromatic ring is a carbon atom, x is preferably 1 or 2.
Examples of the electron donating group include a hydroxyl group, an alkoxy group and an amino group.

The bonding position of the structural unit of general formula (II) to the adjacent group is not particularly limited. In a preferred embodiment, when the atom adjacent to the aromatic ring in R ¹ is an oxygen atom, it is located at the para-position or ortho-position, preferably the para-position with respect to the oxygen atom. In another preferred embodiment, when R ² is an electron-donating group, it is located in the para-position or ortho-position, preferably the para-position with respect to the electron-donating group.

As one preferable embodiment of the structural unit of general formula (II), the structural unit of general formula (II-1) and the structural unit of general formula (II-2) can be mentioned.

In formula (II-1), R ^2's each independently represent a substituent. R ³ represents a chain hydrocarbon group having 1 to 28 carbon atoms. x represents an integer of 0 to 4. The details of R ² and x are the same as those in the case where the atom of R ¹ adjacent to the aromatic ring is an oxygen atom in the general formula (II).

The chain hydrocarbon group represented by R ³ may or may not have a substituent. Examples of the substituent include a hydroxyl group, an amino group, an alkoxy group, a halogen atom and an acyl group.
The chain hydrocarbon group represented by R ³ may be a straight chain hydrocarbon group or a branched hydrocarbon group.
The chain hydrocarbon group represented by R ³ may or may not contain an unsaturated bond.
The chain hydrocarbon group represented by R ³ preferably has 1 to 18 carbon atoms, more preferably 1 to 13 carbon atoms, and further preferably 1 to 8 carbon atoms.

The bonding position of the structural unit of the general formula (II-1) to the adjacent group is not particularly limited, and it is located at the para position or ortho position with respect to the oxygen atom existing between the aromatic ring and R ³ . Preferably, it is more preferably located in the para position. When an electron donating group is present as R ² , the electron donating group is preferably located in the para position or the ortho position, more preferably in the para position.

In formula (II-2), R ^2's each independently represent a substituent, and at least one R ^{2 in} each aromatic ring represents an electron-donating group. R ⁴ represents a chain hydrocarbon group having 2 to 30 carbon atoms. x represents an integer of 1 to 4. The details of R ² and x are the same as those in the case where the atom of R ¹ adjacent to the aromatic ring is a carbon atom in the general formula (II).

The chain hydrocarbon group represented by R ⁴ may or may not have a substituent. Examples of the substituent include a hydroxyl group, an amino group, an alkoxy group, a halogen atom and an acyl group.
The chain hydrocarbon group represented by R ⁴ may be a straight chain hydrocarbon group or a branched hydrocarbon group.
The chain hydrocarbon group represented by R ⁴ may or may not contain an unsaturated bond.
The chain hydrocarbon group represented by R ⁴ preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and further preferably 1 to 10 carbon atoms.

The bonding position of the structural unit of general formula (II-2) with the adjacent group is preferably located at the para position or ortho position with respect to R ² which is an electron donating group, and located at the para position. Is more preferable.

The polyketone may further include a divalent group having 1 to 50 carbon atoms, which is linked to the structural unit represented by the general formula (II) via a carbonyl group. The divalent group is preferably a divalent hydrocarbon group having 1 to 50 carbon atoms, and preferably contains an alicyclic skeleton or an aromatic ring from the viewpoint of both heat resistance and elongation at break. The details of Y in the general formula (I) described later can be applied to the details of the divalent group having 1 to 50 carbon atoms.

The polyketone is preferably a polyketone having a structural unit represented by the following general formula (I).

In the general formula (I), X's each independently represent a divalent group containing the structural unit of the general formula (II), and Y's each independently represent a divalent group having 1 to 50 carbon atoms. , N represents the number of structural units.

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

In the general formula (I), each X may independently be a divalent group containing the structural unit of the general formula (II), and another divalent group is linked to the structural unit of the general formula (II). Or a group consisting of the structural unit represented by the general formula (II).
The number of carbon atoms contained in the divalent group represented by X is preferably 12 to 50, more preferably 12 to 40, and further preferably 12 to 30.
Examples of the divalent group that can be linked to the general formula (II) include a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. Specifically, examples of the divalent group that can be connected to the general formula (II) include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, a 1-methyltrimethylene group, and a 2-methyltrimethylene group. 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 Methylene 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-methylpentylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 1-propyltrimethylene group, 2-propyltrimethylene group, butylethylene group, 1,1-dimethyl Tetramethylene 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 group, 1-ethyl-1-methyltrimethylene group, 2-ethyl-2 -Methyltrimethylene group, 1-ethyl-2-methyltrimethylene group, 2-ethyl-1-methyltrimethylene group, heptylene group, octylene group, nonylene group, decylene group and the like.

In general formula (I), each Y independently represents a divalent group having 1 to 50 carbon atoms, preferably a divalent hydrocarbon group having 1 to 50 carbon atoms. From the viewpoint of achieving both heat resistance and elongation at break, Y preferably contains an alicyclic skeleton or an aromatic ring.

The divalent group represented by Y preferably contains an aromatic ring from the viewpoint of achieving both elongation at break and heat resistance. In addition, the divalent group represented by Y preferably contains a saturated hydrocarbon group from the viewpoint of elongation at break and transparency. The saturated hydrocarbon group may be a saturated chain hydrocarbon group or a saturated alicyclic hydrocarbon group. From the viewpoints of elongation at break, heat resistance and transparency, the divalent group represented by Y preferably contains a saturated alicyclic hydrocarbon group. Since the alicyclic hydrocarbon group is bulkier than the chain hydrocarbon group having the same carbon number, it tends to have excellent solubility in a solvent while maintaining high heat resistance and transparency.
The divalent group represented by Y may contain a plurality of types of saturated chain hydrocarbon groups or a plurality of types of saturated alicyclic hydrocarbon groups. Further, Y may contain a combination of a saturated chain hydrocarbon group and a saturated alicyclic hydrocarbon group.

When Y contains a saturated chain hydrocarbon group, the divalent group represented by Y has 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, and more preferably 3 to 30 carbon atoms. ..
When Y contains a saturated chain hydrocarbon group, the divalent group represented by Y is a methylene group, ethylene group, trimethylene group, methylethylene group, tetramethylene group, 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-methylpentylene group Group, 2-methylpentylene group, 3-methylpentylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene 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-trimethyl Trimethylene group, 1,1,2-trimethyltrimethylene group, 1,1,3-trimethyltrimethylene group, 1,2,2-trimethyltrimethylene group, 1-ethyl-1-methyltrimethylene group, 2- Ethyl-2-methyltrimethylene group, 1-ethyl-2-methyltrimethylene group, 2-ethyl-1-methyltrimethylene group, 2,2-ethylmethyltrimethylene group, heptylene group, octylene group, nonylene group, Examples thereof include a decylene group, an icosanylene group, and a triacontanylene group.

Among them, from the viewpoint of heat resistance, the divalent group represented by Y is preferably a tetramethylene group, a hexylene group, a methylpentylene group, an ethyltetramethylene group, a propyltrimethylene group, a butylethylene group, Examples thereof include a dimethyltetramethylene group, a trimethyltrimethylene group, an ethylmethyltrimethylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an icosanylene group, and a triacontanylene group.

When Y contains a saturated alicyclic hydrocarbon group, the divalent group represented by Y has 3 to 50 carbon atoms, preferably 3 to 30 carbon atoms, and more preferably 4 to 30 carbon atoms. It is preferably 6 to 30, and more preferably 6 to 30.
When Y contains a saturated alicyclic hydrocarbon group, the divalent group represented by Y includes a cyclopropane skeleton, a cyclobutane skeleton, a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cubane skeleton, A divalent hydrocarbon group having a norbornane 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, or the like can be given. ..

Among them, from the viewpoint of heat resistance, the divalent group represented by Y is preferably a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cubane skeleton, a norbornane skeleton, tricyclo[5.2.1.0]. A divalent hydrocarbon group having a decane skeleton, an adamantane skeleton, a diadamantane skeleton, a bicyclo[2.2.2]octane skeleton, a decahydronaphthalene skeleton, or the like can be given.

Examples of the substituent that the divalent group represented by Y may have include an amino group, an oxo group, a hydroxyl group, and a halogen atom.

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). More preferably, it contains 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 decalin skeleton in general formula (V-2), and norbornane in general formula (V-3). Each hydrogen atom in the skeleton may be substituted with a hydrocarbon group, an amino group, an oxo group, a hydroxyl group or a halogen atom.
In general formula (IV) and general formulas (V-1) to (V-3), Z is independently a single bond or a substituted or unsubstituted divalent saturated group having 1 to 10 carbon atoms. Represents a hydrocarbon group.
From the viewpoint of obtaining a flexible molded product, Z is preferably each independently a substituted or unsubstituted divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and from the viewpoint of heat resistance, Z is It 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-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-methylpentylene group, 2-methylpentylene group, 3-methylpentylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene 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 group, 1-ethyl-1-methyltrimethylene group, 2-ethyl-2-methyltrimethylene group, Examples thereof include a 1-ethyl-2-methyltrimethylene group, a 2-ethyl-1-methyltrimethylene group, a heptylene group, an octylene group, a nonylene group and a decylene group.

Examples of the substituent that the divalent saturated hydrocarbon group represented by Z may have include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, and the like.

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 general formula (V-2) may be a divalent hydrocarbon group represented by the following general formula (VI-2).
The divalent hydrocarbon group represented by 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 Z in the general formula (IV) and the general formulas (V-1) to (V-1). The same as Z in V-3) can be mentioned.

The polyketone is represented by Y as at least one selected from the group consisting of the divalent hydrocarbon group represented by the general formula (IV) and the general formulas (V-1) to (V-3). It may be a polyketone containing both of the above-mentioned divalent hydrocarbon group. The polyketone is represented by Y as at least one selected from the group consisting of the divalent hydrocarbon group represented by the general formula (IV) and the general formulas (V-1) to (V-3). And a divalent hydrocarbon group represented by the formula (V-1) to (V-3), the content of the divalent hydrocarbon group represented by the general formula (IV) The mass ratio ((IV):(V-1) to (V-3)) to the total content of the divalent hydrocarbon groups 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.

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

The number average molecular weight (Mn) of the polyketone of the present disclosure is preferably 500 or more in terms of standard GPC in terms of polystyrene from the viewpoint of maintaining heat resistance, and 2,500 to 100, from the viewpoint of higher thermal decomposition resistance. It is more preferably 5,000, and even more preferably 5,000 to 75,000. The number average molecular weight of the polyketone is a value measured by the method described in Examples.

The polyketone of this indication may be used individually by 1 type and may be used in combination of 2 or more type. Further, the polyketone of the present disclosure may be used in combination with another polyketone. When the polyketone of the present disclosure is used in combination with another polyketone, the content ratio of the polyketone of the present disclosure to the total polyketone is preferably 50% by mass or more, and 60% by mass or more from the viewpoint of flexibility and elongation at break. It is more preferable that the content is 70% by mass or more.

[Method for producing polyketone]
The method for producing the polyketone of the present disclosure is not particularly limited, and examples thereof include a method of subjecting a monomer containing the structural unit of the general formula (II) and a dicarboxylic acid to a condensation reaction in an acidic medium. Preferred is a method in which a monomer of the following general formula (IIA) and a dicarboxylic acid are subjected to a condensation reaction in an acidic medium.

In formula (IIA), R ¹ represents a divalent chain group having 2 to 30 at least one atom selected from the group consisting of carbon atoms and oxygen atoms in the main chain. R ^2's each independently represent a substituent. When the atom adjacent to the aromatic ring in R ¹ is an oxygen atom, x representing the number of the substituents R ^{2 on} the aromatic ring adjacent to the oxygen atom represents an integer of 0 to 4. When the atom adjacent to the aromatic ring in R ¹ is a carbon atom, x representing the number of the substituents R ^{2 on} the aromatic ring adjacent to the carbon atom represents an integer of 1 to 4 and is adjacent to the carbon atom. At least one of the substituents R ² on the aromatic ring represents an electron donating group.

The details of R ¹ , R ² and x in the general formula (IIA) can be applied to the details of R ¹ , R ² and x in the general formula (II), respectively.

Specific examples of the monomer of general formula (IIA) include 1,2-diphenoxyethane, 1,2-bis(3-methylphenoxy)ethane, 1,3-bis(2-methoxyphenoxy)-2-propanol, 4-[(2S,3R)-4-(3,4-dimethoxyphenyl)-2,3-dimethylbutyl]-1,2-dimethoxybenzene and the like can be mentioned.

Examples of the dicarboxylic acid include dicarboxylic acids having 1 to 50 carbon atoms. In the present disclosure, the carbon number of the dicarboxylic acid does not include the carbon of the carboxy group. The same applies hereinafter. The dicarboxylic acid preferably contains an alicyclic skeleton or an aromatic ring.

As the dicarboxylic acid, a dicarboxylic acid represented by the following general formula (6A) is preferable.

In formula (6A), Y represents a divalent hydrocarbon group having 1 to 50 carbon atoms. As the details of Y, the details of Y in the general formula (I) can be applied.

Specific examples of the dicarboxylic acid include 1,3-adamantanedicarboxylic acid, 1,3-adamantanediacetic acid, 4,4′-dicarboxydiphenyl ether, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dodecane. Diacid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, dodecanedioic acid and the like can be mentioned.

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

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

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

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

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

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

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

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

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

<<Polyketone composition>>
The polyketone composition of the present disclosure contains the polyketone of the present disclosure and a solvent. The polyketone composition may further contain a polyketone other than the polyketone of the present disclosure, an additive, and the like. The polyketone composition can be obtained by, for example, dissolving the polyketone of the present disclosure in a solvent. The method of dissolving the polyketone in the solvent is not particularly limited, and a method known in the art can be used. Insoluble components may be filtered off, if necessary.

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

The content of the solvent is preferably 5 parts by mass to 95 parts by mass, and more preferably 10 parts by mass to 90 parts by mass, based on 100 parts by mass of the total amount of all the polyketones of the polyketone composition and the solvent.

<Other additives>
The polyketone composition may further contain other additives. Other additives include adhesion promoters, surfactants, leveling agents, antioxidants, ultraviolet deterioration inhibitors, sliding agents (polytetrafluoroethylene particles, etc.), light diffusing agents (acrylic crosslinked particles, silicone crosslinked). Particles, ultra-thin glass flakes, calcium carbonate particles, etc., fluorescent dyes, inorganic phosphors (such as phosphors having aluminate as a mother crystal), antistatic agents, crystal nucleating agents, inorganic antibacterial agents, organic antibacterial agents, Photocatalyst antifouling agent (titanium oxide particles, zinc oxide particles, etc.), cross-linking agent (epoxy compound, isocyanate compound, hydrazide compound, phenol compound, etc.), curing agent, reaction accelerator, infrared absorber (heat ray absorber), photochromic Agents and the like.

≪Polyketone film≫
The polyketone film of the present disclosure contains the polyketone of the present disclosure. The polyketone film can be produced, for example, by the following method. First, the above-mentioned polyketone composition is applied to at least a part of the surface of the substrate to form a composition layer. Then, the composition layer is dried to obtain a polyketone film.

The method for applying the polyketone composition to the substrate is not particularly limited as long as it is a method capable of forming the composition layer in an arbitrary shape on the substrate at an arbitrary position. Examples of the method for applying the polyketone composition to the substrate include a dipping method, a spray method, a screen printing method, a spin coating method, a spin coating method, and a bar coating method.

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

The method for drying the composition layer is not particularly limited, and examples thereof include a method of heating using a device such as a hot plate and an oven and a method of natural drying.

If desired, the dried polyketone film may be further heat treated. The method of heat treatment is not particularly limited, and is a box dryer, a hot air conveyor dryer, a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace. And the like. The atmospheric conditions for the heat treatment may be in the air or an inert atmosphere such as nitrogen. The temperature and time of the heat treatment for drying can be arbitrarily set in view of work efficiency, and are usually 60°C to 300°C and about 30 minutes to 2 hours. Further heat treatment tends to increase the film density of the obtained polyketone film.

The obtained polyketone film can be used as a substrate with a polyketone film while the substrate is still attached, or can be peeled off from the substrate and used as necessary. In the base material with a polyketone film, the polyketone film may be provided on at least a part of the surface of the base material, and may be provided on only one surface of the base material or on both surfaces. In the substrate with a polyketone film, the polyketone film may have a single layer or a multi-layer structure in which two or more layers are laminated.

The polyketone film may include a crosslinker component that reacts with the polyketone. Examples of the crosslinking agent component that reacts with the polyketone include an epoxy compound, an isocyanate compound, a hydrazide compound, and a phenol compound.

When the cross-linking agent component is contained in the polyketone film, the polyketone may be cured using a device such as a hot plate or an oven. The temperature for curing can be arbitrarily set in view of work efficiency, and is generally preferably 60°C to 300°C, more preferably 80°C to 250°C, and further preferably 100°C to 200°C. .. The time for curing the polyketone film can be arbitrarily set in view of work efficiency, and is usually preferably about 30 minutes to 2 hours.

The content of all polyketones in the polyketone film is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more, when a cross-linking agent component other than the polyketone is not contained. Is more preferable. When the polyketone film contains a crosslinking agent component other than polyketone, the content of all polyketones in the polyketone film is preferably 20% by mass to 95% by mass, and 30% by mass to 85% by mass. Is more preferable, and it is further preferable that the content is 50% by mass to 80% by mass or more. When the content of polyketone is 20% by mass or more, the polyketone film tends to maintain excellent transparency and heat resistance.

<<Optical element and image display device>>
The optical element and the image display device of the present disclosure each include the polyketone film of the present disclosure. The polyketone film in the optical element and the image display device may be the above-mentioned base material with a polyketone film.

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

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

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

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

Example 1 Synthesis of Polyketone PK1 A flask containing 5.0 mmol of 1,2-diphenoxyethane and 5.0 mmol of 1,3-adamantanedicarboxylic acid was placed in a mixture of diphosphorus pentoxide and methanesulfonic acid (mass). 10 ml of the ratio 1:10) was added, and the mixture was stirred with a nitrogen balloon at 60° C. for 10 hours. After the reaction, the reaction solution was poured into 500 ml of methanol, and the produced precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain polyketone PK1. The obtained polyketone PK1 had a weight average molecular weight of 21,000 and a number average molecular weight of 3,800.
At this time, when the obtained polyketone is visually colored, the polyketone is dissolved in 5 g of N-methyl-2-pyrrolidone (NMP), the solution is thrown in 200 ml of distilled water, and the produced precipitate is The steps of filtering, washing and drying were repeated until the polyketone was no longer visible.

Example 2 Synthesis of Polyketone PK2 Example 1 except that 4.0 mmol of 1,2-diphenoxyethane, 1.0 mmol of 2,2′-dimethoxybiphenyl and 5.0 mmol of 1,3-adamantanedicarboxylic acid were used as monomers. Polyketone PK2 was obtained in the same manner as described above. The obtained polyketone PK2 had a weight average molecular weight of 30,000 and a number average molecular weight of 4,400.

(Example 3) Synthesis of polyketone PK3 Polyketone PK3 was obtained in the same manner as in Example 1 except that 5.0 mmol of 1,2-diphenoxyethane and 5.0 mmol of cyclohexane-1,3-dicarboxylic acid were used as monomers. .. The obtained polyketone PK3 had a weight average molecular weight of 32,000 and a number average molecular weight of 4,800.

(Example 4) Synthesis of polyketone PK4 Example except that 5.0 mmol of 1,2-diphenoxyethane, 3.0 mmol of 1,3-adamantanedicarboxylic acid and 2.0 mmol of cyclohexane-1,3-dicarboxylic acid were used as monomers. Polyketone PK4 was obtained in the same manner as in 1. The obtained polyketone PK4 had a weight average molecular weight of 44,000 and a number average molecular weight of 5,100.

(Example 5) Synthesis of polyketone PK5 Polyketone was prepared in the same manner as in Example 1 except that 5.0 mmol of 1,2-bis(3-methylphenoxy)ethane and 5.0 mmol of 1,3-adamantanedicarboxylic acid were used as monomers. PK5 was obtained. The obtained polyketone PK5 had a weight average molecular weight of 40,000 and a number average molecular weight of 4,700.

(Example 6) Synthesis of polyketone PK6 As a monomer, 4.0 mmol of 1,2-bis(3-methylphenoxy)ethane, 1.0 mmol of 2,2'-dimethoxybiphenyl and 5.0 mmol of 1,3-adamantanedicarboxylic acid were used. Polyketone PK6 was obtained in the same manner as in Example 1 except for the above. The obtained polyketone PK6 had a weight average molecular weight of 25,000 and a number average molecular weight of 3,000.

Example 7 Synthesis of Polyketone PK7 As a monomer, 5.0 mmol of 1,2-bis(3-methylphenoxy)ethane, 4.0 mmol of 4,4′-dicarboxydiphenyl ether and 1.0 mmol of cyclohexane-1,3-dicarboxylic acid. Polyketone PK7 was obtained in the same manner as in Example 1 except that The obtained polyketone PK7 had a weight average molecular weight of 35,000 and a number average molecular weight of 5,800.

Example 8 Synthesis of Polyketone PK8 As monomers, 5.0 mmol of 1,2-bis(3-methylphenoxy)ethane, 4.0 mmol of 1,3-adamantanediacetic acid and 1.0 mmol of cyclohexane-1,3-dicarboxylic acid were used. Polyketone PK8 was obtained in the same manner as in Example 1 except that it was used. The obtained polyketone PK8 had a weight average molecular weight of 40,000 and a number average molecular weight of 5,000.

(Example 9) Synthesis of polyketone PK9 Example except that 5.0 mmol of 1,2-bis(3-methylphenoxy)ethane, 4.5 mmol of 1,3-adamantanediacetic acid and 0.5 mmol of dodecanedioic acid were used as monomers. Polyketone PK9 was obtained in the same manner as in 1. The obtained PK9 had a weight average molecular weight of 31,000 and a number average molecular weight of 3,800.

(Example 10) Synthesis of polyketone PK10 Same as Example 1 except that 5.0 mmol of 1,3-bis(2-methoxyphenoxy)-2-propanol and 5.0 mmol of 1,3-adamantanediacetic acid were used as monomers. Thus, polyketone PK10 was obtained. The obtained PK10 had a weight average molecular weight of 11,000 and a number average molecular weight of 2,800.

Example 11 Synthesis of Polyketone PK11 4-[(2S,3R)-4-(3,4-dimethoxyphenyl)-2,3-dimethylbutyl]-1,2-dimethoxybenzene 5.0 mmol and 4 as monomers Polyketone PK11 was obtained in the same manner as in Example 1 except that 2.5 mmol of 4,4'-dicarboxydiphenyl ether and 2.5 mmol of cyclohexane-1,3-dicarboxylic acid were used. The obtained PK11 had a weight average molecular weight of 22,500 and a number average molecular weight of 4,200.

(Comparative Example 1) Synthesis of polyketone PK12 Polyketone PK12 was obtained in the same manner as in Example 1 except that 5.0 mmol of 2,2'-dimethoxybiphenyl and 5.0 mmol of 1,3-adamantanedicarboxylic acid were used as monomers. The obtained PK12 had a weight average molecular weight of 40,000 and a number average molecular weight of 5,000.

(Comparative Example 2) Synthesis of Polyketone PK13 Polyketone PK13 was obtained in the same manner as in Example 1 except that 5.0 mmol of 2,2'-dimethoxybiphenyl and 5.0 mmol of cyclohexane-1,3-dicarboxylic acid were used as monomers. .. The obtained polyketone PK13 had a weight average molecular weight of 38,000 and a number average molecular weight of 4,400.

(Comparative Example 3) Synthesis of Polyketone PK14 Polyketone PK14 was obtained in the same manner as in Example 1 except that 5.0 mmol of 2,2'-dimethoxybiphenyl and 5.0 mmol of terephthalic acid were used as monomers. The obtained polyketone PK14 had a weight average molecular weight of 10,000 and a number average molecular weight of 3,700.

(Comparative Example 4) Synthesis of Polyketone PK15 Synthesis was performed in the same manner as in Example 1 except that 5.0 mmol of 2,2'-dimethoxybiphenyl and 5.0 mmol of dodecanedioic acid were used as monomers, but gelation proceeded during the synthesis. However, the target product was not obtained.

(Example 12) Varnish using polyketone PK1 PK1 obtained in Example 1 was dissolved in 1-methyl-2-pyrrolidone (NMP) at a concentration of 20% by mass, and a membrane made of polytetrafluoroethylene was used. Filtration with a filter (pore size 5 μm) gave PK1 varnish.

Examples 13 to 22 Varnishes Using PK2 to PK11 Polyketone varnishes were prepared in the same manner as in Example 1 except that PK2 to PK11 obtained in Examples 2 to 11 were used.

(Comparative Examples 5 to 7) Varnishes using PK12 to PK14 Polyketone varnishes were prepared in the same manner as in Example 1 except that PK12 to PK14 obtained in Comparative Examples 1 to 3 were used.

(Comparative Example 8)
Since PK15 obtained in Comparative Example 4 had gelation progressed during synthesis, the intended product could not be obtained and a varnish could not be produced.

(Example 23) Film using varnish of polyketone PK1 The varnish of PK1 obtained in Example 12 was applied on a glass substrate and a polyimide film by a bar coating method to obtain a substrate with a film of PK1. Each of the obtained film-coated substrates was dried on a hot plate heated to 120° C. for 3 minutes, and then placed in a nitrogen-substituted high-temperature clean oven (Koyo Thermo System Co., Ltd.), CLH-21CD(III), at 25° C. To 200° C. in 1 hour, further heated at 200° C. for 1 hour to dry the solvent, and then lowered in temperature from 200° C. to 80° C. in 1 hour to obtain a test substrate, which was evaluated as described below. ..

(Examples 24 to 33) Film using varnish of polyketone PK2 to PK11 Films were prepared in the same manner as in Example 23 except that the varnish of polyketone obtained in Examples 13 to 22 was used instead of the varnish of PK1. The attached substrate was obtained and evaluated as described below.

(Comparative Examples 9 to 11) Film using varnish of polyketone PK12 to PK14 Films were prepared in the same manner as in Example 23 except that the varnish of polyketone obtained in Comparative Examples 5 to 7 was used instead of the varnish of PK1. The attached substrate was obtained and evaluated.

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

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

[Evaluation of transparency]
The transmittance of light having a wavelength of 400 nm of the glass substrate with a polyketone film obtained in Examples 23 to 33 and Comparative Examples 9 to 11 was measured using an ultraviolet-visible spectrophotometer (“U-3310 Spectrophotometer”, Hitachi High-Tech Co., Ltd.). It was measured by a visible absorption spectrum method. Table 1 and Table 2 show the transmittance converted to a film thickness of 1 μm using a glass substrate having no film as a reference.

[Evaluation of heat resistance]
The polyketone film-coated glass substrates obtained in Examples 23 to 33 and Comparative Examples 9 to 11 were allowed to stand in an oven at 200° C. for 24 hours, and the transmittance of light having a wavelength of 400 nm was measured by an ultraviolet-visible spectrophotometer (“U-3310 Spectrophotometer”). , Hitachi High-Tech Co., Ltd.). Table 1 and Table 2 show the transmittance converted to a film thickness of 1 μm using a glass substrate having no film as a reference.

[Evaluation of flex resistance]
The Kapton substrates with a polyketone film obtained in Examples 23 to 33 and Comparative Examples 9 to 11 were evaluated by a mandrel test (cylindrical mandrel method). The test was performed according to JIS K5600-5-1 (1999). The diameter of the mandrel was changed from 25 mm to 2 mm, and the presence or absence of cracks was visually confirmed. Tables 1 and 2 show the minimum diameters of the mandrels in which cracks do not occur.

[Evaluation of breaking elongation]
The polyketone film was peeled off from the glass substrate with a polyketone film obtained in Examples 23 to 33 and Comparative Examples 9 to 11, and the elongation at break was evaluated by a tensile tester (Shimadzu small bench tester EZ-S, Shimadzu Corporation). did.

As can be seen by comparing Examples 23 to 33 and Comparative Examples 9 to 11, the polyketones of Examples 23 to 33 are excellent in elongation at break and flexibility. In addition, the polyketones of Examples 23 to 33 have good permeability and heat resistance.

Claims (14)

A polyketone containing a structural unit represented by the following general formula (II).

[In the general formula (II), R ¹ represents a divalent chain group having 2 to 30 atoms of at least one kind selected from the group consisting of carbon atoms and oxygen atoms in the main chain. R ^2's each independently represent a substituent. When the atom adjacent to the aromatic ring in R ¹ is an oxygen atom, x representing the number of the substituents R ^{2 on} the aromatic ring adjacent to the oxygen atom represents an integer of 0 to 4. When the atom adjacent to the aromatic ring in R ¹ is a carbon atom, x representing the number of the substituents R ^{2 on} the aromatic ring adjacent to the carbon atom represents an integer of 1 to 4 and is adjacent to the carbon atom. At least one of the substituents R ² on the aromatic ring represents an electron donating group. ] The polyketone according to claim 1, wherein in the general formula (II), each R ² independently represents an alkoxy group, an amino group, or a hydrocarbon group having 1 to 30 carbon atoms. The polyketone according to claim 1 or 2, wherein in the general formula (II), R ¹ has an oxygen atom at one or both ends of the main chain. The polyketone according to claim 1, wherein the structural unit of the general formula (II) is selected from the structural unit of the following general formula (II-1) or the structural unit of the following general formula (II-2).

[In general formula (II-1), R< ² > represents a substituent each independently. R ³ represents a chain hydrocarbon group having 1 to 28 carbon atoms. x represents an integer of 0 to 4. ]

[In general formula (II-2), R< ² > represents a substituent each independently, and in each aromatic ring, at least one R< ² > represents an electron-donating group. R ⁴ represents a chain hydrocarbon group having 2 to 30 carbon atoms. x represents an integer of 1 to 4. ] In the said General formula (II-1) and General formula (II-2), R< ² > represents an alkoxy group, an amino group, or a C1-C30 hydrocarbon group each independently. Polyketone. The polyketone according to any one of claims 1 to 5, further comprising a divalent group having 1 to 50 carbon atoms, which is connected to a group having the structural unit represented by the general formula (II) with a carbonyl group interposed therebetween. .. The divalent group having 1 to 50 carbon atoms, which is connected to the group having the structural unit represented by the general formula (II) by separating the carbonyl group, is at least one selected from the group consisting of an alicyclic skeleton and an aromatic ring. 7. The polyketone of claim 6 comprising. A polyketone composition containing the polyketone according to any one of claims 1 to 7 and a solvent. A polyketone film containing the polyketone according to any one of claims 1 to 7. An optical element comprising the polyketone film according to claim 9. An image display device comprising the optical element according to claim 10. A method for producing a polyketone, which comprises subjecting a monomer containing a structural unit of the following general formula (IIA) and a dicarboxylic acid to a condensation reaction in an acidic medium.

[In the general formula (IIA), R ¹ represents a divalent chain group having 2 to 30 atoms of at least one kind selected from the group consisting of carbon atoms and oxygen atoms in the main chain. R ^2's each independently represent a substituent. When the atom adjacent to the aromatic ring in R ¹ is an oxygen atom, x representing the number of the substituents R ^{2 on} the aromatic ring adjacent to the oxygen atom represents an integer of 0 to 4. When the atom adjacent to the aromatic ring in R ¹ is a carbon atom, x representing the number of the substituents R ^{2 on} the aromatic ring adjacent to the carbon atom represents an integer of 1 to 4 and is adjacent to the carbon atom. At least one of the substituents R ² on the aromatic ring represents an electron donating group. ] The method for producing a polyketone according to claim 12, wherein in the general formula (II), R ² 's each independently represent an alkoxy group, an amino group, or a hydrocarbon group having 1 to 30 carbon atoms. The method for producing a polyketone according to claim 12 or 13, wherein in the general formula (II), R ¹ has an oxygen atom at one or both ends of the main chain.