JP6874470B2 - Polyketone resin composition, cured polyketone, optical element, image display device, coating material and molded product - Google Patents

Description

The present invention relates to a polyketone resin composition, a cured polyketone product, an optical element, an image display device, a coating material, and a molded product.

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 polyetherketones polymerized by utilizing the nucleophilic aromatic substitution reaction, and also have an ether bond in the main chain. On the other hand, it is known that aromatic polyketones having no ether bond in the main chain are more excellent in heat resistance and chemical resistance than aromatic polyetherketones (for example, Patent Document 1 and Patent Documents). 2).

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

When a resin material such as an aromatic polyketone is applied to an optical component, it is desirable to be able to exhibit properties that cannot be obtained with an inorganic material, and such properties include, for example, light weight and flexibility. Examples of applications utilizing light weight include glass substitute materials and coating materials for portable devices, and examples of applications utilizing flexibility include flexible displays and organic EL (organic electroluminescence) displays. In particular, the application of resin materials to organic EL displays has attracted particular attention in recent years.

Japanese Unexamined Patent Publication No. 62-7730 Japanese Unexamined Patent Publication No. 2005-272728 Japanese Unexamined Patent Publication No. 2013-53194

Materials such as organic EL displays are required to have high surface hardness and high barrier property against oxygen and water vapor in addition to high transparency and heat resistance. However, although the film formed from the aromatic polyketone described in the above patent document is excellent in transparency and heat resistance, there is room for improvement in surface hardness and barrier property against oxygen and water vapor. Therefore, it is desired to develop an aromatic polyketone having good surface hardness and high barrier property against oxygen and water vapor while maintaining high transparency and heat resistance.

One embodiment of the present invention has been made in view of the above situation, and when used as a cured film, a polyketone resin composition having excellent transparency and heat resistance, high surface hardness, and high barrier property against oxygen and water vapor. The purpose is to provide. Further, one embodiment of the present invention is an optical element, an image display device, a coating material and a molding having a polyketone cured product and a polyketone cured product which are excellent in transparency and heat resistance and exhibit high surface hardness and high barrier property against oxygen and water vapor. The purpose is to provide the body.

Means for solving the above problems include the following embodiments.
<1> At least one selected from the group consisting of a polyketone and a nitrogen atom having a structural unit represented by the following general formula (I) in the main chain, and a hydroxymethyl group and an alkoxymethyl group bonded to the nitrogen atom. Contains nitrogen-containing compounds having a group and inorganic particles,
A polyketone resin composition in which the content of the inorganic particles is 10 parts by mass to 70 parts by mass with respect to 100 parts by mass of the total amount of the polyketone, the nitrogen-containing compound and the inorganic particles.

[In the general formula (I), X represents a divalent group having 1 to 50 carbon atoms which may have a substituent, and Y represents a divalent group having 1 to 30 carbon atoms which may have a substituent. Represents the divalent hydrocarbon group of, and n represents an integer of 1 to 1500. ]
<2> The polyketone resin composition according to <1>, wherein the average particle size of the inorganic particles is 10 nm to 200 nm.
<3> The polyketone resin composition according to <1> or <2>, wherein X is a divalent group having 6 to 50 carbon atoms containing an aromatic ring in the general formula (I).
<4> In the general formula (I), X is a divalent group represented by at least one selected from the group consisting of the following general formulas (II-1) to the following general formulas (II-3). The polyketone resin composition according to any one of <1> to <3>.

[In the general formula (II-1), R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms which may independently have a hydrogen atom or a substituent, and R ² independently represents a hydrocarbon group having 1 to 30 carbon atoms. It represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and m independently represents an integer of 0 to 3. ]

[In the general formula (II-2), R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms which may independently have a hydrogen atom or a substituent, and R ² independently represents a hydrocarbon group having 1 to 30 carbon atoms. It represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, m represents an integer of 0 to 3 independently, and Z represents an oxygen atom or the following general formula (III-1). -Represents a divalent group represented by any of the following general formulas (III-7). ]

[In the general formulas (III-1) to (III-7), R ¹ independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent. R ² represents a hydrocarbon group having 1 to 30 carbon atoms which may independently have a substituent, and R ³ and R ⁴ each independently have a hydrogen atom or a substituent. It represents a hydrocarbon group having 1 to 30 carbon atoms, where m independently represents an integer of 0 to 3, n represents an integer of 0 to 4 independently, and p represents an integer of 0 to 4, respectively. , Represents an integer of 0-2. ]

[In the general formula (II-3), R ⁵ independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and n is independently 0 to 4, respectively. Represents an integer. ]
<5> The polyketone resin composition according to any one of <1> to <4>, wherein Y is a divalent saturated hydrocarbon group in the general formula (I).
<6> The polyketone resin composition according to any one of <1> to <5>, wherein Y is a divalent saturated alicyclic hydrocarbon group in the general formula (I).
<7> The polyketone resin composition according to any one of <1> to <6>, wherein the carbon number of Y is 6 to 30 in the general formula (I).
<8> The polyketone resin composition according to any one of <1> to <7>, wherein the inorganic particles are silica particles.
<9> The polyketone according to any one of <1> to <8>, wherein the total number of the hydroxymethyl group and the alkoxymethyl group contained in the molecule of the nitrogen-containing compound is 2 to 6. Resin composition.
<10> The polyketone resin composition according to any one of <1> to <9>, which further contains a thermolatent acid generator.
<11> The polyketone resin composition according to any one of <1> to <10>, which further contains a solvent.
<12> A cured polyketone, which is a cured product of the polyketone resin composition according to any one of <1> to <11>.
<13> The polyketone cured product according to <12>, wherein the haze when the thickness is 10 μm is less than 1%.
<14> The polyketone cured product according to <12> or <13>, wherein the transmittance at 400 nm is 85% or more in terms of a film thickness of 1 μm.
<15> An optical element having the polyketone cured product according to any one of <12> to <14>.
<16> An image display device having the polyketone cured product according to any one of <12> to <14>.
<17> A coating material having the polyketone cured product according to any one of <12> to <14>.
<18> A molded product having the polyketone cured product according to any one of <12> to <14>.

According to one embodiment of the present invention, it is possible to provide a polyketone resin composition which is excellent in transparency and heat resistance when formed into a cured film, and exhibits high surface hardness and high barrier property against oxygen and water vapor. Further, according to one embodiment of the present invention, an optical element, an image display device, and a coating material having a polyketone cured product and a polyketone cured product having excellent transparency and heat resistance, high surface hardness, and high barrier property against oxygen and water vapor. And a molded body can be provided.

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

The numerical range indicated by using "~" in the present disclosure indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively.
In the numerical range 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 another numerical range described stepwise. Further, in the numerical range described in the present specification, 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, the content rate or content of each component in the composition is the same when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. Means the total content or content of.
In the present disclosure, the term "layer" or "membrane" refers to only a part of the region, in addition to the case where the layer or the membrane is formed in the entire region when the region where the layer or the membrane exists is observed. The case where it is formed is also included.
In the present disclosure, the term "laminated" refers to stacking layers, and two or more layers may be bonded or the two or more layers may be removable.
In the present disclosure, the "average particle size" is synonymous with the "average primary particle size" unless otherwise specified.
In the present disclosure, the cured product of the polyketone resin composition is also referred to as a cured product or a cured product of the polyketone resin.
In the present disclosure, a film which is a form of a cured product of a polyketone resin composition is also referred to as a cured film or a polyketone film.

As used herein, "a plurality of aromatic rings are unconjugated to each other or have a weak mutual coupling relationship" means that the two aromatic rings are mediated by an ether bond or a methylene bond, or 2,2'. -It means that the conjugation between aromatic rings is suppressed by steric hindrance due to substituents such as substituted biphenyl.

In the present specification, "excellent in transparency" means that the transparency of visible light (transparency of visible light having a wavelength of at least 400 nm) is 85% or more (converted to a film thickness of 1 μm).

As used herein, the term "heat resistance" means that the glass transition temperature (Tg) of a member containing a polyketone is at least 180 ° C. or higher.

As used herein, the term "high surface hardness" means that the pencil hardness of the cured film is 2H or more.

As used herein, the term "high barrier property" means that the water vapor permeability of the cured membrane is 5 g / m ² / day or less and the oxygen permeability of the cured membrane is 5 cc / m ² / day or less. ..

<Polyketone resin composition>
The polyketone resin composition of the present disclosure includes a polyketone (hereinafter, also referred to as “specific polyketone”) containing a structural unit represented by the following general formula (I) in the main chain, a nitrogen atom, and a hydroxymethyl bonded to the nitrogen atom. It contains a nitrogen-containing compound having at least one group selected from the group consisting of a group and an alkoxymethyl group (hereinafter, also referred to as “specific nitrogen-containing compound”), and inorganic particles.

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

The polyketone resin composition of the present disclosure has excellent transparency and heat resistance when formed into a cured film, has high surface hardness, and exhibits high barrier property against oxygen and water vapor. The reason is not clear, but it is presumed as follows.
Since the specific polyketone contains a carbonyl group in the main chain, it has excellent heat resistance and transparency. Further, when the specific nitrogen-containing compound functions as a cross-linking agent, the polyketone main chains are cross-linked, and as a result, the specific polyketones are more entangled with each other and the structure becomes dense. It is considered that a high barrier property against water vapor is exhibited.

Hereinafter, each component will be described.

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

In the general formula (I), X represents a divalent group having 1 to 50 carbon atoms which may have a substituent. Y represents a divalent group having 1 to 30 carbon atoms which may have a substituent. n represents an integer of 1 to 1500, preferably 2 to 1000, and more preferably 5 to 500. When the divalent group has a substituent, the carbon number of the divalent group does not include the carbon number of the substituent. The same applies thereafter.
When n is 2 or more, the plurality of Xs and Ys may be the same or different.

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

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

The divalent group represented by X is preferably a hydrocarbon group, and more preferably contains an aromatic ring. When X has an aromatic ring, the heat resistance tends to be further improved.

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

Further, the divalent group represented by X preferably contains a plurality of aromatic rings, and the plurality of aromatic rings are divalent groups that are non-conjugated to each other or have a weak conjugation relationship with each other (hereinafter referred to as “divalent groups”). It is more preferably (also referred to as "specific aromatic ring group"). As a result, good diacylation can be realized at a low reaction temperature during polyketone synthesis, and the polyketone tends to have a high molecular weight and excellent heat resistance. The specific aromatic ring group preferably has 12 to 50 carbon atoms.

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

In the general formula (II-1), R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms which may independently have a hydrogen atom or a substituent, and R ² is an independent substitution. It represents a hydrocarbon group having 1 to 30 carbon atoms which may have a group, and m independently represents an integer of 0 to 3. The wavy part means a bond. The same applies thereafter.

From the viewpoint of heat resistance, the ^{hydrocarbon group represented by R1 has 1} to 30 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. When the hydrocarbon group has a substituent, the carbon number of the hydrocarbon group does not include the carbon number of the substituent. The same applies thereafter.

Examples of the hydrocarbon group represented by R ¹ include a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, and an alicyclic hydrocarbon group.

Examples of the saturated aliphatic hydrocarbon group represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group and an n-pentyl group. Group, isopentyl group, sec-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-icosanyl group, Examples thereof include an n-triacanthanyl group. Further, it may have an alicyclic hydrocarbon group described later at the terminal portion of the saturated aliphatic hydrocarbon group.

Examples of the unsaturated aliphatic hydrocarbon group represented by R ¹ include an alkenyl group such as a vinyl group and an allyl group, and an alkynyl group such as an ethynyl group. Further, it may have an alicyclic hydrocarbon group described later at the terminal portion of the unsaturated aliphatic hydrocarbon group.

Examples of the alicyclic hydrocarbon group represented by R ¹ include a cycloalkyl group such as a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a norbornyl group, and a cycloalkenyl group such as a cyclohexenyl group. Further, the ring of the alicyclic hydrocarbon group may have at least one selected from the group consisting of a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group.

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

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

Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ² include those similar to the hydrocarbon group having 1 to 30 carbon atoms exemplified in ^{R 1.} Examples of the substituent may have a hydrocarbon group represented by R ^2, a halogen atom, an alkoxy group having 1 to 5 carbon atoms and an acyl group having 2 to 5 carbon atoms.

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

In the general formula (II-2), R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms which may independently have a hydrogen atom or a substituent, and R ² is an independent substitution. It represents a hydrocarbon group having 1 to 30 carbon atoms which may have a group, m represents an integer of 0 to 3 independently, and Z is an oxygen atom or the following general formula (III-1) to the following. Represents a divalent group represented by any of the general formulas (III-7).

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

^{From the viewpoint of heat resistance, R 3} and R ⁴ in the general formula (III-1) are preferably hydrocarbon groups having 1 to 5 carbon atoms which may have a substituent. Examples of the hydrocarbon groups having 1 to 30 carbon atoms represented by R ³ and R ⁴ include those similar to the hydrocarbon groups having 1 to 30 carbon atoms exemplified by ^{R 1 in the general formula (II-1).} Be done. Examples of the substituent that R ³ and R ⁴ can have include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms.

In the general formula (III-2) and the general formula (III-3), n independently represents an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1. preferable.
P in the general formula (III-4), the general formula (III-5) and the general formula (III-7) independently represents an integer of 0 to 2, and is preferably 0 or 1.

Formula (II-2), the general formula (III-2) ^R 1 in ~ formula ^{(III-7), R 2} , and each of the details of m, the general formula ^{(II-1) R} 1 in , R ² , and m.

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

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

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

The divalent hydrocarbon group represented by Y preferably contains a divalent saturated hydrocarbon group from the viewpoint of transparency. The divalent saturated hydrocarbon group may be a divalent saturated aliphatic hydrocarbon group or a divalent saturated alicyclic hydrocarbon group. From the viewpoint of achieving both higher heat resistance and transparency, the divalent hydrocarbon group represented by Y preferably contains a divalent saturated alicyclic hydrocarbon group. Since divalent alicyclic hydrocarbon groups are bulkier than divalent aliphatic hydrocarbon groups having the same number of carbon atoms, they tend to have excellent solubility in solvents while maintaining high heat resistance and transparency. is there.
Further, the divalent hydrocarbon group represented by Y may contain a plurality of types of divalent saturated aliphatic hydrocarbon groups or a plurality of types of divalent saturated alicyclic hydrocarbon groups. Further, Y may contain a combination of a divalent saturated aliphatic hydrocarbon group and a divalent saturated alicyclic hydrocarbon group.

The divalent saturated aliphatic hydrocarbon group represented by Y has 1 to 30 carbon atoms, preferably 3 to 30 carbon atoms.
Examples of the divalent saturated aliphatic hydrocarbon group include 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 Methylene group, 2,2-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, propylethylene group, ethylmethylethylene group, hexylene group, 1-methylpentylene group, 2-methylpentylene group, 3-methyl Pentylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 1-propyltrimethylene group, 2-propyltrimethylene group, butylethylene group, 1,1-dimethyltetramethylene group, 2,2-dimethyl Tetramethylene group, 1,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 1,4-dimethyltetramethylene group, 1,2,3-trimethyltrimethylene group, 1,1,2-trimethyltri Methylene 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, decylene group, icosanylene group, triactanylene group, etc. Can be mentioned.

From the viewpoint of heat resistance, the divalent saturated aliphatic hydrocarbon group is preferably a hexylene group, a methylpentylene group, an ethyltetramethylene group, a propyltrimethylene group, a butylethylene group, a dimethyltetramethylene group, or a trimethyltri. Examples thereof include a methylene group, an ethylmethyltrimethylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an icosanylene group, a triacontanilen group and the like.

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

From the viewpoint of heat resistance, the divalent saturated alicyclic hydrocarbon group is preferably a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cubane skeleton, a norbornane skeleton, or a tricyclo [5.2.1.0] decane skeleton. , Adamantane skeleton, diadamantane skeleton, bicyclo [2.2.2] octane skeleton, decahydronaphthalene skeleton and the like, and examples thereof include divalent hydrocarbon groups.

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

Y 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 formula (V-1) to the following general formula (V-3). It is preferable, and it is more preferable to contain at least a divalent hydrocarbon group represented by the following general formula (IV).

In the general formula (IV), the hydrogen atom of the adamantan skeleton may be substituted with a hydrocarbon group, an amino group, an oxo group, a hydroxyl group or a halogen atom. Further, in the general formula (IV), Z represents a divalent saturated hydrocarbon group having 1 to 10 carbon atoms, which may independently have a single bond or a substituent.
From the viewpoint of obtaining a flexible film, Z is preferably a divalent saturated hydrocarbon group having 1 to 10 carbon atoms, which may independently have a substituent, and from the viewpoint of heat resistance. , Z is more preferably a divalent saturated hydrocarbon group having 1 to 5 carbon atoms.

Examples of the divalent saturated hydrocarbon group represented by Z include methylene group, ethylene group, trimethylene group, methylethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group and 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 1-ethyl-2-methyltrimethylene group, 2-ethyl-1-methyltrimethylene group, heptylene group, octylene group, nonylene group and decylene group.

Examples of the substituent that the divalent saturated hydrocarbon group represented by Z can have include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. When the divalent saturated hydrocarbon group represented by Z has a substituent, the carbon number of the divalent saturated hydrocarbon group does not include the carbon number of the substituent. The same applies hereinafter.

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

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

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

From the viewpoint of maintaining heat resistance, the weight average molecular weight (Mw) of the specific polyketone is preferably 500 or more in terms of polystyrene-equivalent standard GPC (gel permeation chromatography), and has higher heat resistance and a solvent. From the viewpoint of solubility in, 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 (Mw) of the specific polyketone refers to a value measured by the method described in Examples.

As the specific polyketone, one type may be used alone, or two or more types may be used in combination.
Moreover, the polyketone resin composition may contain a polyketone other than the specific polyketone. Hereinafter, the specific polyketone and other polyketones may be collectively referred to as "polyketone". From the viewpoint of heat resistance and transparency when the cured film is formed, the content of the specific polyketone with respect to the total amount of the polyketone is preferably 50% by mass or more, more preferably 60% by mass or more, and 70. It is more preferably mass% or more.

From the viewpoint of transparency when the cured film is formed, the total content of the polyketone is preferably 30 parts by mass to 90 parts by mass with respect to 100 parts by mass of the total amount of the polyketone, the specific nitrogen-containing compound and the inorganic particles. , 40 parts by mass to 80 parts by mass, more preferably.

<Specific nitrogen-containing compound>
The polyketone resin composition of the present disclosure is a nitrogen-containing compound (specific nitrogen-containing compound) having a nitrogen atom and at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group bonded to the nitrogen atom. ) Is contained.
The use of a specific nitrogen-containing compound is preferable in terms of excellent heat resistance of the cured product and high barrier property against oxygen and water vapor. The specific nitrogen-containing compound is preferably a compound having both a hydroxymethyl group and an alkoxymethyl group or a compound having no hydroxymethyl group and having an alkoxymethyl group, and a compound having no hydroxymethyl group and having an alkoxymethyl group is more preferable. preferable.

The total number of hydroxymethyl groups and alkoxymethyl groups contained in the molecule of the specific nitrogen-containing compound is not particularly limited as long as it is one or more. The total number of hydroxymethyl groups and alkoxymethyl groups contained in the molecule of the specific nitrogen-containing compound is preferably 2 to 6, and from the viewpoint of the barrier property of the cured film, it is preferably 4 to 6. More preferred.

The number of carbon atoms of the alkoxy group in the alkoxymethyl group is preferably 1 to 30, more preferably 1 to 15, further preferably 1 to 10, and particularly preferably 1 to 3. It is extremely preferable that the number of carbon atoms is 1.

Examples of the specific nitrogen-containing compound include compounds represented by the following general formula (VII-1) and the following general formula (VII-2).

In the general formula (VII-1), A represents an n-valent organic group, and W ¹ and W ² are independently hydrogen atoms, the following general formula (VIII-1) or the following general formula (VIII-2). It is a group represented by, and n represents 2 or 3. However, among the plurality of ^{W 1} and ^{W 2,} at least one is a group represented by the following general formula (VIII-1) or the following general formula (VIII-2), a plurality of ^{W 1} and ^{W 2} It is preferable that two or more of them are groups represented by the following general formula (VIII-1) or the following general formula (VIII-2).

In the general formula (VIII-2), R ¹ represents an alkyl group having 1 to 30 carbon atoms which may have a substituent. The ^{number of carbon atoms of the alkyl group represented by R 1} is preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 3, and particularly preferably 1. The general formula (VIII-2) of ^{R 1} in detail, the same as ^{R 1} in Formula (II-1).

In the general formula (VII-1), examples of the organic group represented by A include groups represented by the following general formula (IX-1) and the following general formula (IX-2).

In the general formula (VII-2), W ^{3 to} W ⁶ are independent hydrogen atoms or groups represented by the general formula (VIII-1) or the general formula (VIII-2). ^However, of W 3 to ^W-6, at least one is a group represented by the general formula (VIII-1) or general formula ^(VIII-2), 2 or more of W 3 to ^W-6 is, It is preferably a group represented by the general formula (VIII-1) or the general formula (VIII-2).

Examples of the specific nitrogen-containing compound include compounds represented by the following general formulas (X-1) to the following general formulas (X-3).

In the general formulas (X-1) to (X-3), R ¹ independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent. Details of R ^1, is the same as ^{R 1} in the general formula (VIII-2).

The specific nitrogen-containing compound may be a monomer or an oligomer, or may be a mixture of a monomer and an oligomer. Examples of the oligomer include those formed by self-reaction of compounds (monomers) represented by the general formulas (X-1) to (X-3).

One specific nitrogen-containing compound may be used alone, or two or more thereof may be used in combination. The content of the specific nitrogen-containing compound is 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the total amount of the specific polyketone, the specific nitrogen-containing compound and the inorganic particles from the viewpoint of heat resistance and barrier property when the cured film is formed. The amount is preferably 5 parts by mass, more preferably 5 parts by mass to 50 parts by mass, and further preferably 5 parts by mass to 20 parts by mass.

<Thermal latent acid generator>
The polyketone resin composition may further contain a thermolatent acid generator. A thermolatent acid generator is a compound that generates an acid when heated. When the polyketone resin composition contains a thermolatent acid generator, the cross-linking reaction of the specific nitrogen-containing compound is promoted, and a stronger cured product can be obtained, so that the barrier property of the cured film tends to be improved. ..

Examples of the acid generated from the thermolatent acid generator include aryl sulfonic acids such as p-toluene sulfonic acid and benzene sulfonic acid, and per (±) -10-campar sulfonic acid, trifluoromethane sulfonic acid, and nonafluorobutane sulfonic acid. Examples thereof include alkyl sulfonic acids such as fluoroalkyl sulfonic acid, methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid.

As the thermal latent acid generator, one type may be used alone, or two or more types may be used in combination. The content of the thermal latent acid generator is preferably 0.05 parts by mass to 30 parts by mass with respect to 100 parts by mass of the total amount of the specific polyketone, the specific nitrogen-containing compound and the thermal latent acid generator. It is more preferably 1 part by mass to 20 parts by mass, and further preferably 0.2 part by mass to 10 parts by mass.

<Inorganic particles>
The polyketone resin composition contains inorganic particles.
Examples of the inorganic particles include silica, alumina, natural mica, synthetic mica, talc, calcium oxide, calcium carbonate, zirconium oxide, titanium oxide, antimony oxide, barium titanate, kaolin, bentonite, diatomaceous earth, boron nitride, aluminum nitride, and the like. Particles of silicon carbide, zinc oxide, cerium oxide, cesium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and graphite can be mentioned. From the viewpoint of transparency, it is preferable to use silica particles.
One type of inorganic particles may be used alone, or two or more types may be used in combination.

The shape of the inorganic particles is not particularly limited, but a spherical shape is preferable from the viewpoint of transparency of the polyketone resin composition.

Inorganic particles can be produced by known methods such as the flame hydrolysis method, the flame thermal decomposition method, and the plasma method described in International Publication No. 96/31572. As the inorganic particles, a nano-dispersed sol of stabilized colloidal inorganic particles can be preferably used, such as colloidal silica manufactured by Admatex Co., Ltd., TiO ₂ sol manufactured by Merck Co., Ltd., and SiO manufactured by Nissan Chemical Industry Co., Ltd. _{Commercially available products such as 2} , ZrO ₂ , Al ₂ O ₃ and Sb ₂ O ₃ sol, and silica (product name, Aerosil) manufactured by Nippon Aerosil Co., Ltd. are available.

The surface of the inorganic particles may be modified. The surface modification of the inorganic particles can be performed using a known surface modifier. As such a surface modifier, for example, a compound capable of interacting with a functional group existing on the surface of the inorganic particles such as covalent bond and complex formation can be used. Examples of such a surface modifier include a carboxy group, a (primary, secondary or tertiary) amino group, a quaternary ammonium group, a carbonyl group, a glycidyl group, a vinyl group, and a (meth) group in the molecule. ) A compound having a functional group such as an acryloxy group or a mercapto group can be used. The surface modifier is usually preferably liquid under standard temperature and pressure conditions.

Surface modifiers include formic acid, acetic acid, propionic acid, butyric acid, pentanic acid, hexanoic acid, acrylic acid, methacrylic acid, crotonic acid, citric acid, adipic acid, succinic acid, glutaric acid, oxalic acid, maleic acid, and fumal. Saturated or unsaturated mono- and polycarboxylic acids (preferably monocarboxylic acids) having 1 to 12 carbon atoms such as acids; these esters (preferably alkyl esters having 1 to 4 carbon atoms such as methyl methacrylate); Amidos; β-dicarbonyl compounds such as acetylacetone, 2,4-hexanedione, 3,5-heptandione, acetoacetic acid, alkylacetoacetic acids having 1 to 4 carbon atoms; silane coupling agents and the like.

The average particle size of the inorganic particles is not particularly limited, but is preferably 10 nm to 200 nm, more preferably 10 nm to 150 nm, and even more preferably 10 nm to 100 nm. If it is 10 nm or more, a desired surface hardness can be easily obtained, and if it is 200 nm or less, an increase in haze tends to be suppressed. Inorganic particles having an average particle size of less than 10 nm are difficult to manufacture and obtain due to dispersion stability.

In the present disclosure, the average particle size of the inorganic particles is a value measured after the film is formed by using the method described in Examples.

The content of the inorganic particles is preferably 10 parts by mass to 70 parts by mass and preferably 20 parts by mass to 60 parts by mass with respect to 100 parts by mass of the total amount of the specific polyketone, the specific nitrogen-containing compound and the inorganic particles. It is more preferably 30 parts by mass to 60 parts by mass. When the content of the inorganic particles is 10 parts by mass or more, the surface hardness of the polyketone film tends to be effectively improved, and when it is 70 parts by mass or less, the transparency of the polyketone film is excellent and the increase in haze is suppressed. It tends to have excellent toughness.

When a nano-dispersion sol of stabilized colloidal inorganic particles is used as the inorganic particles, a dispersion liquid containing the inorganic particles may be used as it is.

<Solvent>
The polyketone resin composition may further contain a solvent. The solvent is not particularly limited as long as it dissolves or disperses each component. As the solvent, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, butyl acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-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, mecitylene, ethylbenzene, propylbenzene, cumene, diisopropylbenzene, hexylbenzene, anisole, diglime, dimethylsulfoxide, chloroform, dichloromethane, dichloroethane, chlorobenzene And so on. These solvents may be used alone or in combination of two or more.

When the polyketone resin composition contains a solvent, the content of the solvent is the total of the polyketone, the nitrogen-containing compound, the inorganic particles, and the thermolatent acid generator contained as necessary, and other additives and solvents described below. The amount is preferably 5 parts by mass to 95 parts by mass, and more preferably 10 parts by mass to 90 parts by mass with respect to 100 parts by mass.

<Other additives>
The polyketone resin composition may further contain other additives. Other additives include adhesive aids, surfactants, leveling agents, antioxidants, UV deterioration inhibitors, sliding agents (polytetrafluoroethylene particles, etc.), light diffusers (acrylic crosslinked particles, silicone crosslinked particles, etc.). , Ultra-thin glass flakes, calcium carbonate particles, etc.), fluorescent dyes, inorganic phosphors (fluorescents whose mother crystal is aluminate, etc.), antistatic agents, crystal nucleating agents, inorganic antibacterial agents, organic antibacterial agents, photocatalysts Examples thereof include antifouling agents (titanium oxide particles, zinc oxide particles, etc.), cross-linking agents, curing agents, reaction accelerators, ultraviolet absorbers (heat ray absorbers), photochromic agents, and the like.

<Polyketone cured product>
The cured polyketone of the present disclosure is a cured product of the polyketone resin composition of the present disclosure.
The method for producing the cured polyketone product of the present disclosure is not particularly limited. For example, the polyketone resin composition of the present disclosure containing a solvent is applied to the surface of at least a part of a base material to form a composition layer, and the composition layer is dried to be cured after removing the solvent from the composition layer or with the removal of the solvent. By doing so, the polyketone cured product of the present disclosure can be produced.
The method of applying the polyketone resin composition to the base material is not particularly limited as long as the composition layer can be formed at an arbitrary place on the base material in an arbitrary shape. Examples of the method for applying the polyketone resin composition to the substrate include a dipping method, a spray method, a screen printing method, a rotary coating method, a spin coating method, and a bar coating method.

The base material to which the polyketone resin composition is applied is not particularly limited, and is limited to glass, semiconductors, metal oxide insulators (titanium oxide, silicon oxide, etc.), inorganic materials such as silicon nitride, triacetyl cellulose, transparent polyimide, and polycarbonate. , A transparent base material composed of a transparent resin such as an acrylic polymer or a cycloolefin resin can be exemplified. The shape of the base material is not particularly limited, and may be plate-shaped or film-shaped. The polyketone resin composition of the present disclosure can be suitably used as a coating material for a base material, a molded product, or the like.

If the polyketone resin composition contains a solvent, it may be dried. The drying method is not particularly limited, and examples thereof include a method of heat treatment using an apparatus such as a hot plate and an oven, and a method of natural drying. The conditions for drying by heat treatment are not particularly limited as long as the solvent in the polyketone resin composition is sufficiently volatilized, and are usually about 1 minute to 90 minutes at 50 ° C. to 150 ° C.

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

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

If necessary, the dried polyketone cured product of the present disclosure may be further heat-treated in order to remove the residual solvent. The heat treatment method is not particularly limited, and is a box dryer, a hot air conveyor dryer, a quartz tube furnace, a hot plate, a rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace. , It can be performed using a vacuum dryer or the like. The atmosphere in the heat treatment step is not particularly limited, and examples thereof include an atmosphere and an inert atmosphere such as nitrogen. The conditions for performing the heat treatment are not particularly limited, and may be about 1 minute to 90 minutes at 150 ° C. to 250 ° C. Further heat treatment tends to increase the density of the obtained polyketone cured product.

The haze when the polyketone cured product has a thickness of 10 μm is preferably less than 1%.
The transmittance of the cured polyketone product at 400 nm is preferably 85% or more in terms of film thickness of 1 μm.

The obtained cured polyketone product can be used as a base material with a cured polyketone product with the base material attached, or can be peeled off from the base material if necessary.
In the base material with a cured polyketone, the cured polyketone 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 sides. Further, the cured polyketone product may have a single layer or a multi-layer structure in which two or more layers are laminated.

<Optical element and image display device>
The optical element and the image display device of the present disclosure each have a cured polyketone of the present disclosure. The polyketone cured product applied to the optical element and the image display device may be the above-mentioned base material with the polyketone cured product. Further, if the base material is a transparent base material, it can be suitably used for an optical element. Examples of the transparent substrate include those exemplified in the production of a cured polyketone product.

For the optical element and the image display device, for example, the base material side of the base material with a cured polyketone is applied to an LCD (liquid crystal display), ELD (electroluminescence display), organic EL display, etc. via an adhesive, an adhesive, or the like. It can be obtained by pasting it on a place.

A cured polyketone product and various optical elements such as a polarizing plate using the cured product can be preferably used in various image display devices such as a liquid crystal display device. 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 a lighting system (backlight, etc.) as necessary, and incorporating a drive circuit, etc. Can be manufactured. The liquid crystal cell is not particularly limited, and various types such as TN type, STN type, and π type can be used.

Applications of image display devices include OA devices such as desktop personal computers, laptop computers, and copy machines, mobile phones, clocks, digital cameras, mobile information terminals (PDAs), portable devices such as portable game machines, video cameras, televisions, and electronic devices. Household electrical equipment such as range, back monitor, car navigation system monitor, in-vehicle equipment such as car audio, exhibition equipment such as information monitor for commercial stores, security equipment such as monitoring monitor, nursing care such as nursing monitor Examples include devices, medical devices such as medical monitors, and the like.

<Coating material>
The coating material of the present disclosure includes a cured product of the polyketone resin composition of the present disclosure. The target covered with the coating material is not particularly limited, and OA devices such as desktop personal computers, laptop computers, and copy machines, mobile phones, digital cameras, personal digital assistants (PDAs), portable devices such as portable game machines, video cameras, etc. Examples include TVs, various displays, window glasses, in-vehicle glasses, and camera lenses. The method of forming a coating using the polyketone resin composition of the present disclosure is not particularly limited. For example, the polyketone resin composition of the present disclosure in the form of a film is adhered to a coating target by a method such as laminating and cured. A coating may be formed, or a liquid polyketone resin composition of the present disclosure may be applied to a coating object, dried and cured to form a coating.

<Molded body>
The molded article of the present disclosure includes a cured product of the polyketone resin composition of the present disclosure. The method for producing the molded product is not particularly limited, and a method known in the art can be used. For example, extrusion molding method, injection molding method, calendar molding method, blow molding method, FRP (Fiber Reinforced Plastic) molding method, laminated molding method, casting method, powder molding method, solution casting method, vacuum molding method, pneumatic molding. Examples thereof include a method of obtaining a molded product before curing by a method, an extrusion composite molding method, a stretch molding method and a foam molding method, and then curing.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the present invention is not limited to the following examples.

<Measurement of molecular weight 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 and RI detector combined ・ Flow velocity: 0.4 ml / min

<Polyketone resin composition>
The components (A) to (D) are blended so as to have the mass ratio of the solid content shown in Table 1 or Table 2, stirred, and filtered through a filter (pore diameter 5 μm) made of PTFE (polytetrafluoroethylene). Then, the polyketone resin compositions of Examples and Comparative Examples were obtained. "-" Indicates that the component is not contained. Each component in Table 1 or Table 2 is shown below. The numerical values in Tables 1 and 2 represent the compounding ratio (mass standard) of each component. Further, the solid content means the balance after removing the solvent of each component.

(A) Ingredient [Specific Polyketone]
(Synthesis Example 1) Synthesis of Polyketone PK-1 As a monoma, a mixed solution of diphosphorus pentoxide and methanesulfonic acid (mass) in a flask containing 10 mmol of 2,2'-dimethoxybiphenyl and 10 mmol of 1,3-adamantandicarboxylic acid. 30 ml of a ratio of 1:10) was added, and the mixture was stirred at 60 ° C. After the reaction, the contents were poured into 500 ml of methanol, and the formed precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain a polyketone PK-1.
The obtained polyketone PK-1 had a weight average molecular weight of 20,000 and a number average molecular weight of 8,000.
Polyketone PK-1 was dissolved in N-methyl-2-pyrrolidone to prepare a 20% by mass solution, which was used in the experiment.

(Synthesis Example 2) Synthesis of Polyketone PK-2 As a monoma, 10 mmol of 2,2'-dimethoxybiphenyl and 1,4-cyclohexanedicarboxylic acid (mixture of cis and trans, cis: trans (molar ratio) = 7: 3) Polyketone PK-2 was obtained in the same manner as in Example 1 except that 10 mmol was used. The obtained polyketone PK-2 had a weight average molecular weight of 25,000 and a number average molecular weight of 9,000.
Polyketone PK-2 was dissolved in N-methyl-2-pyrrolidone to prepare a 20% by mass solution, which was used in the experiment.

(Synthesis Example 3) Synthesis of polyketone PK-3 Polyketone PK-3 was obtained in the same manner as in Example 1 except that 2,2'-dimethoxybiphenyl 10 mmol and 1,3-adamantane diacetic acid 10 mmol were used as monomas. It was. The obtained polyketone PK-3 had a weight average molecular weight of 42,000 and a number average molecular weight of 12,000.
Polyketone PK-3 was dissolved in N-methyl-2-pyrrolidone to prepare a 20% by mass solution, which was used in the experiment.

(Synthesis Example 4) Synthesis of polyketone PK-4 Polyketone in the same manner as in Example 1 except that 2,2'-dimethoxybiphenyl 10 mmol, 1,3-adamantane dicarboxylic acid 5 mmol and dodecane diacid 5 mmol were used as monomas. PK-4 was obtained. The weight average molecular weight of the obtained polyketone PK-4 was 36,000, and the number average molecular weight was 13,000.
Polyketone PK-4 was dissolved in N-methyl-2-pyrrolidone to prepare a 20% by mass solution, which was used in the experiment.

(Synthesis Example 5) Synthesis of polyketone PK-5 Polyketone in the same manner as in Example 1 except that 2,2'-dimethoxybiphenyl 10 mmol, 1,3-adamantane diacetic acid 5 mmol and dodecane diic acid 5 mmol were used as monomas. PK-5 was obtained. The weight average molecular weight of the obtained polyketone PK-5 was 39,000, and the number average molecular weight was 12,000.
Polyketone PK-5 was dissolved in N-methyl-2-pyrrolidone to prepare a 20% by mass solution, which was used in the experiment.

(Synthesis Example 6) Synthesis of polyketone PK-6 Polyketone in the same manner as in Example 1 except that 2,2'-dimethoxybiphenyl 10 mmol, 1,3-adamantane diacetic acid 5 mmol and hexane diic acid 5 mmol were used as monomas. PK-6 was obtained. The weight average molecular weight of the obtained polyketone PK-6 was 39,000, and the number average molecular weight was 12,000.
Polyketone PK-6 was dissolved in N-methyl-2-pyrrolidone to prepare a 20% by mass solution, which was used in the experiment.

(Synthesis Example 7) Synthesis of polyketone PK-7 Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of 1,3-adamantane diacetic acid and 5 mmol of cis-1,4-cyclohexanedicarboxylic acid were used as monomas. In the same manner as above, a polyketone PK-7 was obtained. The obtained polyketone PK-7 had a weight average molecular weight of 45,000 and a number average molecular weight of 11,000.
Polyketone PK-7 was dissolved in N-methyl-2-pyrrolidone to prepare a 20% by mass solution, which was used in the experiment.

(Synthesis Example 8) Synthesis of polyketone PK-8 Except that 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of 1,3-adamantane diacetic acid and 5 mmol of decalin-2,6-dicarboxylic acid were used as monomas, the same as in Example 1. Similarly, polyketone PK-8 was obtained. The obtained polyketone PK-8 had a weight average molecular weight of 33,000 and a number average molecular weight of 10,000.
Polyketone PK-8 was dissolved in N-methyl-2-pyrrolidone to prepare a 20% by mass solution, which was used in the experiment.

(Synthesis Example 9) Synthesis of polyketone PK-9 As a monoma, 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of 1,3-adamantane diacetic acid and 5 mmol of norbornane dicarboxylic acid (2,4-, 2,5-mix) were used. Polyketone PK-9 was obtained in the same manner as in Example 1 except that it was used. The obtained polyketone PK-9 had a weight average molecular weight of 27,000 and a number average molecular weight of 9,200.
Polyketone PK-9 was dissolved in N-methyl-2-pyrrolidone to prepare a 20% by mass solution, which was used in the experiment.

(Synthesis Example 10) Synthesis of polyketone PK-10 As monomas, 10 mmol of 2,2'-bis (2-methoxyphenyl) propane, 5 mmol of 1,3-adamantane diacetic acid and 1,4-cyclohexanedicarboxylic acid (cis and trans) Polyketone PK-10 was obtained in the same manner as in Example 1 except that the mixture, cis: trans (molar ratio) = 7: 3) 5 mmol was used. The obtained polyketone PK-10 had a weight average molecular weight of 28,000 and a number average molecular weight of 8,300.
Polyketone PK-10 was dissolved in N-methyl-2-pyrrolidone to prepare a 20% by mass solution, which was used in the experiment.

(Synthesis Example 11) Synthesis of polyketone PK-11 As monomas, 10 mmol of diphenyl ether, 5 mmol of 1,3-adamantane diacetic acid and 1,4-cyclohexanedicarboxylic acid (mixture of cis and trans, cis: trans (molar ratio) = 7) : 3) Polyketone PK-11 was obtained in the same manner as in Example 1 except that 5 mmol was used. The obtained polyketone PK-11 had a weight average molecular weight of 27,000 and a number average molecular weight of 8,000.
Polyketone PK-11 was dissolved in N-methyl-2-pyrrolidone to prepare a 20% by mass solution, which was used in the experiment.

(B) Component [Specific nitrogen-containing compound]
B1: Compound represented by the following formula (XII) (Me represents a methyl group)

B2: Compound represented by the following formula (XIII)

B3: Compound represented by the following formula (XIV) (Me represents a methyl group)

B4: Compound represented by the following formula (XV) (Bu represents a butyl group)

Ingredient (C) [Thermal latent acid generator]
C1: Compound represented by the following formula (XVI)

Component (D) [Inorganic particles]
Particle A: Cyclohexanone dispersion of silica particles (CHO-ST-M manufactured by Nissan Chemical Industries, Ltd., solid content of silica particles is 30% by mass)
Particle B: Silica particles (SC1050-SXT manufactured by Admatex Co., Ltd.)
Particle C: Titanium oxide particles (637254 manufactured by Sigma-Aldrich)

<Preparation and evaluation of evaluation samples>
Using the obtained polyketone resin composition, a cured film was prepared by the following method, a sample for evaluation described later was prepared, and the following evaluation was performed.

(1) Measurement of average particle size The obtained polyketone resin composition was applied onto a glass substrate by a bar coating method, dried on a hot plate heated to 120 ° C. for 3 minutes, and a polyketone film having a thickness of 10 μm was obtained. A glass substrate with a polyketone film having a polyketone film was prepared. This glass substrate with a polyketone film is heat-treated at 200 ° C. for 1 hour using a nitrogen-substituted inert gas oven, then cut using a diamond cutter, and the cut surface (film cross section) is subjected to a scanning electron microscope (manufactured by Philipps Co., Ltd.). Observation was performed using XL-30). From the obtained observation image, the major axis of 50 primary particles of inorganic particles was measured, and the average value thereof was taken as the average particle diameter. The results obtained are shown in Table 3.

Here, the major axis means that for the particles appearing on the cut surface, a combination of two parallel lines tangent to the outside of the particles is selected so as to sandwich the particles, and the two parallel lines having the longest distance among those combinations are selected. Is the distance.

(1) Haze measurement The obtained polyketone resin composition was applied onto a glass substrate by a bar coating method, dried on a hot plate heated to 120 ° C. for 3 minutes, and polyketone having a polyketone film having a thickness of 10 μm. A glass substrate with a film was produced. This glass substrate with a polyketone film was heat-treated at 200 ° C. for 1 hour using a nitrogen-substituted inert gas oven, and then haze was measured using a haze meter (NDH 2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.) using the glass substrate as a blank. .. Table 3 shows the transmittance (%) converted to a film thickness of 1 μm using a glass substrate without a film as a reference. The film thickness was taken as the number average value of the values measured at three points using a stylus type step meter (“Dectak3 ST”, ULVAC, Inc. (Veco)).

(2) Evaluation of Transparency The obtained polyketone resin composition was applied onto a glass substrate by a bar coating method and dried on a hot plate heated to 120 ° C. for 3 minutes to form a polyketone film having a thickness of 10 μm. A glass substrate with a polyketone film having a polyketone film was prepared. This glass substrate with a polyketone film is heat-treated at 200 ° C. for 1 hour using a nitrogen-substituted inert gas oven, and then the transmittance at a wavelength of 400 nm is measured using an ultraviolet-visible spectrophotometer (“U-3310 Spectrophotometer” Hitachi High-Tech Co., Ltd.). It was measured by the ultraviolet-visible absorption spectroscopy method. Table 3 shows the transmittance (%) converted to a film thickness of 1 μm using a glass substrate without a film as a reference. The film thickness was taken as the number average value of the values measured at three points using a stylus type step meter (“Dectak3 ST”, ULVAC, Inc. (Veco)).

(3) Evaluation of heat resistance The obtained polyketone resin composition was applied onto a polyimide (Kapton) film by a bar coating method and dried on a hot plate heated to 120 ° C. for 3 minutes to a thickness of 10 μm. A polyimide base material with a polyketone film having a polyketone film was prepared. The polyketone film was peeled off from the polyimide substrate and heat-treated at 200 ° C. for 1 hour in a nitrogen-substituted inert gas oven. Then, the glass transition temperature (Tg) of the film was measured by a dynamic viscoelasticity measuring method (tensile mode) using a dynamic viscoelasticity measuring device (“RSA-II” by Rheometrics). The values (° C.) of the obtained glass transition temperature are shown in Table 3.

(4) Evaluation of Pencil Hardness The obtained polyketone resin composition was applied onto a glass substrate by a bar coating method and dried on a hot plate heated to 120 ° C. for 3 minutes to form a polyketone film having a thickness of 10 μm. A glass substrate with a polyketone film having a polyketone film was prepared. This glass substrate with a film was heat-treated at 200 ° C. for 1 hour using a nitrogen-substituted inert gas oven, and then evaluated by a pencil hardness test. The test was conducted according to JIS K5600-5-4: 1999. The test results are shown in Table 3.

(5) Measurement of Water vapor Permeability The obtained polyketone resin composition was applied onto a polyimide (Kapton) film by a bar coating method and dried on a hot plate heated to 120 ° C. for 3 minutes to form a polyketone film. A polyimide base material with a polyketone film having a polyketone film was prepared. The polyketone film was peeled off from the polyimide substrate and heat-treated at 200 ° C. for 1 hour in a nitrogen-substituted inert gas oven. The water vapor permeability [g / m ² / day] of the obtained polyketone membrane was measured according to JIS K7129: 2008. The film thickness was 50 μm, and the conditions for the constant temperature and humidity treatment were a temperature of 40 ° C. and a humidity of 90% RH. The test results are shown in Table 3.

(6) Measurement of Oxygen Permeability The obtained polyketone resin composition was applied onto a polyimide (Kapton) film by a bar coating method and dried on a hot plate heated to 120 ° C. for 3 minutes to form a polyketone film. A polyimide base material with a polyketone film having a polyketone film was prepared. The polyketone film was peeled off from the polyimide substrate and heat-treated at 200 ° C. for 1 hour in a nitrogen-substituted inert gas oven. The oxygen permeability [cc / m ² / day] of the obtained polyketone membrane was measured according to JIS K7126-2: 2006. The film thickness was 50 μm. The test results are shown in Table 3.

It can be seen that the cured product of the polyketone resin composition of the example is excellent in heat resistance and transparency, and further has high surface hardness and high barrier property against oxygen and water vapor.
In Table 3, "single film not possible" means that the polyketone film could not be peeled off from the polyimide substrate.

Claims (17)

A polyketone containing a structural unit represented by the following general formula (I) in the main chain, a nitrogen atom, and at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group bonded to the nitrogen atom. Contains nitrogen-containing compounds, as well as inorganic particles,
A polyketone resin composition in which the content of the inorganic particles is 10 parts by mass to 70 parts by mass with respect to 100 parts by mass of the total amount of the polyketone, the nitrogen-containing compound and the inorganic particles.

[In the general formula (I), X represents a divalent group having 6 to 50 carbon atoms including an aromatic ring , and Y is a divalent hydrocarbon having 1 to 30 carbon atoms which may have a substituent. It represents a hydrogen group and n represents an integer of 1 to 1500. ] The polyketone resin composition according to claim 1, wherein the average particle size of the inorganic particles is 10 nm to 200 nm. Claimed that in the general formula (I), X is a divalent group represented by at least one selected from the group consisting of the following general formulas (II-1) to the following general formulas (II-3). The polyketone resin composition according to claim 1 or 2.

[In the general formula ^{(II-1), R} 1 each independently is also a hydrogen atom a hydrocarbon group having a carbon number of 1-30, ^{R 2} are each independently a hydrocarbon having a carbon number of 1 to 30 Represents a group, and m independently represents an integer of 0 to 3. ]

[In the general formula (II-2), ^{R 1} each independently is also a hydrogen atom a hydrocarbon group having a carbon number of 1-30, ^{R 2} are each independently a hydrocarbon having a carbon number of 1 to 30 Representing a group, m independently represents an integer of 0 to 3, and Z is an oxygen atom or 2 represented by any of the following general formulas (III-1) to the following general formula (III-7). Represents a valence group. ]

[In the general formula (III-1) ~ formula (III-7), ^{R 1} each independently represents a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 30, ^{R 2} are each independently, represents a hydrocarbon group having a carbon number of 1 to 30, ^{R 3} and ^{R 4} are each independently, also a hydrogen atom a hydrocarbon group of carbon number 1 to 30, m is independently 0-3 of Represents an integer, n independently represents an integer of 0 to 4, and p independently represents an integer of 0 to 2. ]

[In the general formula (II-3), ^{R 5} each independently represents a hydrocarbon group having a carbon number of 1 to 30, n each independently represents an integer of 0-4. ] The polyketone resin composition according to any one of claims 1 to 3 , wherein Y is a divalent saturated hydrocarbon group in the general formula (I). The polyketone resin composition according to any one of claims 1 to 4 , wherein Y is a divalent saturated polyketone hydrocarbon group in the general formula (I). The polyketone resin composition according to any one of claims 1 to 5 , wherein the carbon number of Y in the general formula (I) is 6 to 30. The polyketone resin composition according to any one of claims 1 to 6 , wherein the inorganic particles are silica particles. The polyketone resin composition according to any one of claims 1 to 7 , wherein the total number of the hydroxymethyl group and the alkoxymethyl group contained in the molecule of the nitrogen-containing compound is 2 to 6. .. The polyketone resin composition according to any one of claims 1 to 8 , further comprising a thermolatent acid generator. The polyketone resin composition according to any one of claims 1 to 9 , further comprising a solvent. A cured polyketone resin composition according to any one of claims 1 to 10. The cured polyketone product according to claim 11 , wherein the haze when the thickness is 10 μm is less than 1%. The cured polyketone product according to claim 11 or 12 , wherein the transmittance at 400 nm is 85% or more in terms of a film thickness of 1 μm. An optical element having the polyketone cured product according to any one of claims 11 to 13. An image display device comprising the polyketone cured product according to any one of claims 11 to 13. A coating material having the polyketone cured product according to any one of claims 11 to 13. A molded product having the cured polyketone product according to any one of claims 11 to 13.