JP2020105517A - Polyketone composition containing polyketone containing structural unit having chain group and hydrazide compound, polyketone cured product, optical element, and image display device - Google Patents

Abstract

To provide a polyketone composition that makes it possible to prepare a cured product having excellent breaking elongation and a cured product thereof, and an optical element and an image display device having the polyketone cured product.SOLUTION: A polyketone composition contains polyketone containing a structural unit of general formula (II), and a hydrazide compound.SELECTED DRAWING: None

Description

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

Aromatic polyketones having an aromatic ring and a carbonyl group in the main chain have excellent heat resistance and mechanical properties and are used as engineering plastics. Most of 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

Furthermore, when applying a polyketone to an optical member, it may be required to have excellent elongation at break in addition to heat resistance and transparency. However, the conventional aromatic polyketone may not be able to obtain sufficient elongation at break. In view of the above circumstances, the present disclosure aims to provide a polyketone composition capable of producing a cured product having excellent elongation at break, a cured product thereof, and an optical element and an image display device having the cured polyketone.

Means for solving the above problems include the following embodiments.

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

[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 composition according to <1>, wherein each R ² in the general formula (II) independently represents an alkoxy group, an amino group, or a hydrocarbon group having 1 to 30 carbon atoms.
<3> The polyketone composition 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 composition 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). Stuff.

[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 composition described in <1>.
<6> The structural unit of the general formula (II) is the structural unit of the general formula (II-1), and the structural unit of the general formula (II-1) is the structural unit of the following general formula (II-3). The polyketone composition according to <4> or <5>.

[In general formula (II-3), R< ² > represents a substituent each independently. R ³ represents a chain hydrocarbon group having 1 to 28 carbon atoms. ]
<7> Any one of <1> to <6>, in which the polyketone further contains a divalent group having 1 to 50 carbon atoms, which is linked to a group having the structural unit of the general formula (II) with a carbonyl group interposed therebetween. The polyketone composition according to Item 1.
<8> At least the divalent group having 1 to 50 carbon atoms, which is connected to the group having the structural unit of the general formula (II) via the carbonyl group, is selected from the group consisting of an alicyclic skeleton and an aromatic ring. The polyketone composition according to <7>, which comprises one kind.
<9> The polyketone composition according to any one of <1> to <8>, in which the hydrazide compound has two or more hydrazide groups in the molecule.
<10> The polyketone composition according to any one of <1> to <9>, wherein the hydrazide compound contains at least one selected from the group consisting of a chain aliphatic hydrazide compound and an aromatic hydrazide compound. ..
<11> The polyketone composition according to any one of <1> to <10>, further containing a solvent.
<12> A polyketone cured product, which is a cured product of the polyketone composition according to any one of <1> to <11>.
<13> An optical element having the polyketone cured product according to <12>.
<14> An image display device having the polyketone cured product according to <12>.

The present disclosure provides a polyketone composition capable of producing a cured product having excellent elongation at break, a cured product thereof, and an optical element and an image display device having the polyketone cured product.

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 heat resistance” means that the glass transition point (Tg) of the member containing polyketone is 140° C. or higher.
In the present disclosure, “excellent transparency” means that the transmittance of light having 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 6%.
In the present disclosure, “excellent flexibility” means that the film does not crack even when the cured product is subjected to a mandrel test using a core rod having a diameter of 2 mm by the method of the example.

<<Polyketone composition>>
The polyketone composition of the present disclosure contains a polyketone containing a structural unit represented by the following general formula (II) and a hydrazide compound.

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.

According to the polyketone composition of the present disclosure, the elongation at break when a cured product is excellent. The reason for this is not clear, but it is presumed as follows. The polyketone contained in the polyketone composition of the present disclosure has, between two aromatic rings, a chain group having at least one atom selected from the group consisting of carbon atoms and oxygen atoms in its main chain. From this, it is speculated that the rigidity of the molecule is relaxed and the elongation at break is improved.

Further, according to the polyketone composition of the present disclosure, excellent heat resistance tends to be maintained when a cured product is obtained. It is considered that the plurality of aromatic rings in the polyketone of the present disclosure contributes to heat resistance. Furthermore, 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 addition to this, since the polyketone composition contains a hydrazide compound, the hydrazine compound acts on the polyketone to form a crosslinked structure. Therefore, it is considered that when the polyketone composition is cured, it has an excellent breaking elongation and does not significantly reduce Tg.
Furthermore, the cured product obtained from the polyketone composition of the present disclosure tends to maintain good transparency and flexibility.
Hereinafter, each component contained in the polyketone composition will be described.

<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.

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. In R ¹ , the atoms adjacent to each aromatic ring are independently an oxygen atom or a carbon atom.

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 having a main chain in which carbon atoms and oxygen atoms are present in the main chain and a chain hydrocarbon group and an oxygen atom are combined.

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. When the chain hydrocarbon group has a branched chain, the branched chain is not included in the substituents of the chain hydrocarbon group.

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 having a main chain 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 the like, and an alkoxy group, an amino group, or a hydrocarbon group having 1 to 30 carbon atoms. Is preferred.

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 , N-icosanyl group, n-triacontanyl group and like saturated chain hydrocarbon groups; and vinyl group, alkenyl groups such as allyl groups, and unsaturated chain hydrocarbon groups such as alkynyl groups such as ethynyl groups; substitution Alternatively, an aromatic hydrocarbon group such as an unsubstituted phenyl group and a substituted or unsubstituted benzyl group can be used. In one preferred embodiment, R ² may be a methyl group or a phenyl group.

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 a saturated chain hydrocarbon group or an unsaturated chain hydrocarbon group described above as a specific example when R ² is a hydrocarbon group having 1 to 30 carbon atoms. And an alkoxy group in which an oxygen atom is linked to.

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. Details of R ² and x, "of R ^1, atom adjacent to the aromatic ring may be oxygen atom" formula in (II) is similar to the embodiment of R ² and x can be employed.

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.

As an example of a preferred embodiment, the structural unit of the general formula (II) is the structural unit of the general formula (II-1), and the structural unit of the general formula (II-1) is the following general formula (II- The embodiment which is the structural unit of 3) is mentioned.

In formula (II-3), R ^2's each independently represent a substituent. R ³ represents a chain hydrocarbon group having 1 to 28 carbon atoms.

Details of R ^2, is in the general formula (II) x is 1 "of R ^1, atom adjacent to the aromatic ring may be an oxygen atom" is similar to the embodiment of R ² which may be employed in. Details of R ^3, is similar to the details of the ^{R 3} in the general formula (II-1).

In the structural unit of general formula (II-3), R ² is substituted at the 2-position of the aromatic ring. A polyketone containing such a structural unit tends to have particularly good elongation at break and glass transition temperature when made into a cured product. The reason for this is not clear, but it is presumed that adjacent aromatic rings have a more planar structure.

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. Details of R ² and x, "of R ^1, atom adjacent to the aromatic ring is if a carbon atom" formula in (II) is similar to the embodiment of R ² and x can be employed.

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 connected to the group having 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 5,000 to 1,000,000. When higher heat resistance is required, the weight average molecular weight (Mw) is more preferably 10,000 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 1,000 to 100, from the viewpoint of higher thermal decomposition resistance. It is more preferably 000, and even more preferably 2,000 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 more preferably 60% by mass or more, from the viewpoint of elongation at break. It is preferably 70% by mass or more, and further preferably.

[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. Examples thereof include diacid, isophthalic acid, terephthalic acid, diphenic acid, and 2,6-naphthalenedicarboxylic acid.

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

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

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

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

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

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

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

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

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

<Hydrazide compound>
The polyketone composition of the present disclosure contains a hydrazide compound. When the polyketone composition of the present disclosure contains a hydrazide compound in combination with the above-mentioned polyketone, it tends to be able to maintain good heat resistance as well as excellent elongation at break. Although the detailed reason is not clear, it is presumed that the use of a hydrazide compound as the curing agent stabilizes the crosslinked structure and exerts the above effects well. The above-mentioned effect tends to be excellently exhibited, for example, as compared with the case where an amine compound is used as a curing agent.

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

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

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

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

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

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

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

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

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

The hydrazide compounds may be used alone or in combination of two or more. The content of the hydrazide compound is preferably 1 part by mass to 50 parts by mass, more preferably 5 parts by mass to 50 parts by mass, based on 100 parts by mass of all polyketones contained in the polyketone composition. More preferably, it is from 30 to 30 parts by mass. When the content of the hydrazide compound is 1 part by mass or more based on 100 parts by mass of the polyketone, good heat resistance tends to be easily maintained. In addition, good transparency and chemical resistance tend to be easily obtained. When the content of the hydrazide compound is 50 parts by mass or less with respect to 100 parts by mass of polyketone, heat resistance and elongation at break tend to be favorably maintained.

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

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

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

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

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

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

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

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

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

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

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

From the viewpoint of transparency, the polyketone cured product has a transmittance of light having a wavelength of 400 nm (converted to a film thickness of 1 μm) of preferably 80% or more, more preferably 90% or more, and more preferably 97% or more. Is more preferable. The transmittance of light having a wavelength of 400 nm can be obtained by an ultraviolet-visible absorption spectrum method using a spectrophotometer (for example, V-570, JASCO Corporation). Specifically, it can be determined by the method described in the examples.

From the viewpoint of heat resistance, the glass transition point of the polyketone cured product is preferably 140°C or higher, and 150°C or higher, 160°C or higher, 170°C or higher, 180°C or higher, 190°C or higher, 200°C or higher, 210°C. As described above, the higher the temperature is 220° C. or higher, the higher temperature is 230° C. or higher, the more preferable. The upper limit of the glass transition point is not particularly limited and may be, for example, 300°C. The glass transition point is a value measured using a viscoelasticity measuring device (for example, RSA-II, Rheometric Scientific F.E. Co., Ltd.) under conditions of 1 Hz and 25° C. to 300° C. ..

The elongation percentage at break of the polyketone cured product is preferably 7% or more, more preferably 9% or more, and further preferably 11% or more. From the viewpoint of avoiding a decrease in strength, the upper limit of the elongation at break may be, for example, 20%. The elongation at break can be determined by using a tensile tester (for example, AUTOGRAPH EZ-TEST EZ-S, manufactured by Shimadzu Corporation) to perform a tensile test on the polyketone cured product at a speed of 5 mm/min.

The flexibility of the polyketone cured product can be determined by a mandrel test (cylindrical mandrel method) according to JIS K5600-5-1:1999. The minimum diameter of the crack-free mandrel obtained by the method described in the examples is preferably 2 mm or less.

<<Optical element and image display device>>
The optical element and the image display device of the present disclosure each include the polyketone cured product of the present disclosure. The polyketone cured product applied to the optical element and the image display device may be applied as a substrate with a polyketone cured product with the substrate attached as described above. Moreover, if the base material is a transparent base material, it can be suitably used for an optical element. Examples of the transparent base material include base materials composed of resins such as triacetyl cellulose, transparent polyimide, polycarbonate, acrylic polymer, and cycloolefin resin.

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

A cured product of polyketone and various optical elements such as a polarizing plate using the same can be preferably used in various image display devices such as liquid crystal display devices. The image display device may have the same configuration as the conventional image display device except that the polyketone cured product 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.

<Polyketone composition>
The following components (A) to (C) are blended in the proportions shown in Tables 4 and 5, filtered through a filter made of PTFE (polytetrafluoroethylene) having 5 μm pores, and the polyketones of Examples and Comparative Examples are given. A composition was obtained. In Tables 4 and 5, the numerical value in parentheses represents the compounding ratio (parts by mass). In Table 5, "-" indicates that the component is not contained. Each component in Table 4 and Table 5 is shown below.

Component (A): Polyketone (Synthesis Example 1) Synthesis of Polyketone PK-1 A flask containing 10 mmol of 1,2-diphenoxyethane and 10 mmol of 4,4′-dicarboxybiphenyl ether as monomers was charged with diphosphorus pentoxide and 30 ml of a mixed solution of methanesulfonic acid (mass ratio 1:10) was added, and the mixture was stirred at 60°C. After the reaction, the content was thrown into 500 ml of methanol, and the produced precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain polyketone PK-1.
The obtained polyketone PK-1 had a weight average molecular weight of 16,000 and a number average molecular weight of 8,000. The weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured and calculated by the method described below.

(Synthesis examples 2 to 22) Synthesis of polyketones PK-2 to PK-22 Polyketones PK-2 to PK-same as in Synthesis example 1 except that the monomers were changed to the components shown in Tables 1 to 3. I got 22. The unit of the numerical values in Tables 1 to 3 is mmol, and the blank indicates that the corresponding component is not used. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyketone PK-2 to PK-22 were measured by the same method as PK-1.

(Synthesis Example 23) Synthesis of polyketone PK-23 As monomers, 10 mmol of 1,2-bis(2-methylphenoxy)ethane, 5 mmol of 4,4'-dicarboxybiphenyl ether and 5 mmol of 1,4-cyclohexanedicarboxylic acid were added. 30 ml of a mixed solution of diphosphorus pentoxide and methanesulfonic acid (mass ratio 1:10) was added to the flask and stirred at 60°C. After the reaction, the content was thrown into 500 ml of methanol, and the produced precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain polyketone PK-23.
The obtained polyketone PK-23 had a weight average molecular weight of 38,000 and a number average molecular weight of 9,900. The weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured and calculated by the same method as PK-1.

(Synthesis example 24) Synthesis of polyketone PK-24 As a monomer, 10 mmol of 1,3-bis(2-phenylphenoxy)propane, 5 mmol of 4,4'-dicarboxybiphenyl ether and 5 mmol of 1,4-cyclohexanedicarboxylic acid were added. 30 ml of a mixed solution of diphosphorus pentoxide and methanesulfonic acid (mass ratio 1:10) was added to the flask and stirred at 60°C. After the reaction, the content was thrown into 500 ml of methanol, and the produced precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain polyketone PK-24.
The obtained polyketone PK-24 had a weight average molecular weight of 16,000 and a number average molecular weight of 4,800. The weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured and calculated by the same method as PK-1.

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

B2: compound represented by the following formula (XII)

B3: compound represented by the following formula (XIII)

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

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

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

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

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

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

<Transmissivity measurement>
The transmittance of the polyketone cured product for light having a wavelength of 400 nm was measured by an ultraviolet-visible absorption spectrum method using a spectrophotometer (V-570, JASCO Corporation). Table 6 shows the transmittance of the cured product converted into a film thickness of 1 μm, using the glass substrate having no polyketone cured product as a reference.

<Tg measurement>
Using a viscoelasticity measuring device (RSA-II, Rheometric Scientific FE Co., Ltd.), Tg of the polyketone cured product was measured under the conditions of 1 Hz and 25°C to 300°C. The peak top of tan δ is defined as Tg. The results are shown in Table 6.

<Measurement of elongation at break>
Using a tensile tester (AUTOGRAPH EZ-TEST EZ-S, manufactured by Shimadzu Corporation), the polyketone cured product was subjected to a tensile test at a speed of 5 mm/min to measure the elongation at break. The results are shown in Table 6.

<Flexibility measurement>
The cured polyketone was evaluated by the mandrel test (cylindrical mandrel method). The test was performed according to JIS K5600-5-1:1999. The diameter of the mandrel was changed from 25 mm to 2 mm, and the presence or absence of cracks was visually confirmed. Table 6 shows the minimum diameter of the mandrel which does not cause cracks.

It can be seen that the polyketone cured products obtained from the polyketone compositions of Examples have a high elongation at break. In addition, it can be seen that the polyketone cured products obtained from the polyketone compositions of the examples have good transmittance, Tg, and flexibility.

Further, in particular, in the case of a polyketone composition using PK-23, which is a polyketone containing a structural unit in which R ² is substituted at the 2-position of an aromatic ring in the above general formula (II-3), the obtained polyketone is cured. The product had a Tg of 285° C. (Example 26).

Claims (14)

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

[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 composition 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 composition according to claim 1 or 2, wherein in the general formula (II), R ¹ has an oxygen atom at one end or both ends of the main chain. The polyketone composition 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 composition of. The structural unit of the general formula (II) is a structural unit of the general formula (II-1), and the structural unit of the general formula (II-1) is a structural unit of the following general formula (II-3), The polyketone composition according to claim 4 or claim 5.

[In general formula (II-3), R< ² > represents a substituent each independently. R ³ represents a chain hydrocarbon group having 1 to 28 carbon atoms. ] 7. The polyketone further comprises 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) across a carbonyl group. The polyketone composition described in 1. 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. 8. The polyketone composition of claim 7 comprising. The polyketone composition according to any one of claims 1 to 8, wherein the hydrazide compound has two or more hydrazide groups in the molecule. The polyketone composition according to any one of claims 1 to 9, wherein the hydrazide compound contains at least one selected from the group consisting of a chain aliphatic hydrazide compound and an aromatic hydrazide compound. The polyketone composition according to any one of claims 1 to 10, further comprising a solvent. A polyketone cured product, which is a cured product of the polyketone composition according to any one of claims 1 to 11. An optical element comprising the cured polyketone according to claim 12. An image display device comprising the polyketone cured product according to claim 12.