JP2019052301A - Polymer being polyarylene with main chain having alicyclic skeleton, polymer production method, composition, film, film coated substrate, optical element, image display apparatus, coating material, and molding - Google Patents

Abstract

To provide: a polymer with excellent transparency, high thermal weight loss temperature (pyrolysis temperature), and high glass-transition temperature; a production method of the polymer; a composition; a film; a film coated substrate; an optical element; an image display apparatus; a coating material; and a molding.SOLUTION: The polymer comprises a structural unit represented by general formula (I) in the figure, where X1 and X2 each independently represent a specific divalent group, with X1 having no hydroxy group on an aromatic ring and X2 having a hydroxy group on an aromatic ring; Y each independently represent an alicycle-containing divalent group.SELECTED DRAWING: None

Description

  The present invention relates to a polymer that is a polyarylene having an alicyclic skeleton in the main chain, a method for producing the polymer, a composition, a film, a substrate with a film, an optical element, an image display device, a coating material, and a molded article.

  An aromatic polymer having an aromatic ring in the main chain has excellent heat resistance and mechanical properties, and is used as an engineering plastic (see, for example, Patent Document 1 and Patent Document 2). Among them, polymers having a structure having an aromatic ring and an alicyclic ring in the main chain are expected to be applied to optical components because they are excellent in heat resistance and transparency (see, for example, Patent Document 3).

JP-A-62-273030 JP 2005-272728 A JP 2013-53194 A

  Although the polymer having the heat resistance and transparency described in Patent Document 3 has a high thermogravimetric decrease temperature of 400 ° C. or higher, there is room for improvement in the glass transition temperature.

  The present invention has been made in view of the above circumstances, has excellent transparency, a high thermogravimetric reduction temperature (pyrolysis temperature), a high glass transition temperature, a polymer production method, a composition, It aims at providing a film | membrane, a base material with a film | membrane, an optical element, an image display apparatus, a coating material, and a molded object.

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

[In General Formula (I), each X1 is independently at least selected from the group consisting of General Formula (II-1), General Formula (II-2), and General Formula (II-3) below. Represents a divalent group represented by one type, and each X2 is independently selected from the group consisting of the following general formula (III-1), the following general formula (III-2), and the following general formula (III-3). The divalent group represented by at least 1 type selected is represented, Y represents the bivalent group containing an alicyclic ring each independently. m represents the number of structural units represented by -X1-Y- included in the general formula (I), and n represents a structural unit represented by -X2-Y- included in the general formula (I). The ratio of m to n (m: n) is 95: 5 to 5:95. ]



[In General Formulas (II-1), (II-2) and (II-3), each R ¹ independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. , R ² each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. o represents the integer of 0-3 each independently, and p represents the integer of 0-2. Z represents an oxygen atom or a divalent group containing at least one selected from the group consisting of the following general formulas (IV-1) to (IV-7). ]

[In General Formulas (IV-1) to (IV-7), each R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ² Each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ³ and R ⁴ may each independently have a hydrogen atom or a substituent. A C1-C30 hydrocarbon group is represented. n represents an integer of 0 to 4, each independently represents an integer of 0 to 2, and m represents an integer of 0 to 3, each independently. ]



[In General Formulas (III-1), (III-2), and (III-3), each R ² independently represents a hydrocarbon group having 1 to 30 carbon atoms that may have a substituent. . o independently represents an integer of 0 to 3, and p independently represents an integer of 0 to 2, respectively. Z represents an oxygen atom or a divalent group that is at least one selected from the group consisting of the following general formulas (IV-1) to (IV-7). ]

[In General Formulas (IV-1) to (IV-7), each R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ² Each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ³ and R ⁴ may each independently have a hydrogen atom or a substituent. A C1-C30 hydrocarbon group is represented. n represents an integer of 0 to 4, each independently represents an integer of 0 to 2, and m represents an integer of 0 to 3, each independently. ]
<2> In the general formula (I), Y is at least one selected from the group consisting of the following general formula (V-1), the following general formula (V-2), and the following general formula (V-3). The polymer as described in <1> containing group represented by these.

<3> At least one compound selected from the group consisting of the following general formula (VI-1), the following general formula (VI-2) and the following general formula (VI-3), and a dihalide containing an alicyclic ring, The method for producing a polymer according to <1> or <2>, which comprises a reaction step of reacting in a catalyst.



[In General Formulas (VI-1), (VI-2), and (VI-3), each R ¹ independently represents a hydrocarbon group having 1 to 30 carbon atoms that may have a substituent. R ² represents each independently a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. o represents the integer of 0-3 each independently, and p represents the integer of 0-2. Z represents an oxygen atom or a divalent group containing at least one selected from the group consisting of the following general formulas (IV-1) to (IV-7). ]

[In General Formulas (IV-1) to (IV-7), each R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ² Each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ³ and R ⁴ may each independently have a hydrogen atom or a substituent. A C1-C30 hydrocarbon group is represented. n represents an integer of 0 to 4, each independently represents an integer of 0 to 2, and m represents an integer of 0 to 3, each independently. ]
<4> The catalyst according to <3>, wherein the catalyst is at least one selected from the group consisting of copper (I) bromide, copper (II) bromide, hexacarbonylmolybdenum (0), and zinc (II) chloride. A method for producing the polymer.
<5> The polymer according to <3> or <4>, further comprising a step of allowing an organic halide derived from a hydrocarbon group having 1 to 30 carbon atoms to act in the presence of a base after the reaction step. Manufacturing method.
<6> A heavy compound represented by the following general formula (VII), in which an organic halide derived from a hydrocarbon group having 1 to 30 carbon atoms is allowed to act on the polymer according to <1> or <2> in the presence of a base. Manufacturing method of coalescence.

[In General Formula (VII), each X is independently selected from the group consisting of General Formula (II-1), General Formula (II-2), and General Formula (II-3) below. The divalent group represented by 1 type is represented, Y represents each independently the bivalent group containing an alicyclic ring. q represents the number of structural units represented by general formula (VII), and q is the total amount of m and n in general formula (I). ]



[In General Formulas (II-1), (II-2) and (II-3), each R ¹ independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. , R ² each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. o represents the integer of 0-3 each independently, and p represents the integer of 0-2. Z represents an oxygen atom or a divalent group containing at least one selected from the group consisting of the following general formulas (IV-1) to (IV-7). ]

[In General Formulas (IV-1) to (IV-7), each R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ² Each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ³ and R ⁴ may each independently have a hydrogen atom or a substituent. A C1-C30 hydrocarbon group is represented. n represents an integer of 0 to 4, each independently represents an integer of 0 to 2, and m represents an integer of 0 to 3, each independently. ]
<7> A composition comprising the polymer according to <1> or <2> and a solvent.
<8> A film comprising the polymer according to <1> or <2>.
<9> A substrate with a film having a substrate and the film according to <8> provided on at least a part of the surface of the substrate.
<10> An optical element having the film according to <8> or the substrate with a film according to <9>.
<11> An image display device comprising the film according to <8> or the substrate with a film according to <9>.
<12> A coating material comprising the polymer according to <1> or <2>.
<13> A molded article comprising the polymer according to <1> or <2>.

  According to the present invention, a polymer having excellent transparency, a high thermal weight loss temperature (thermal decomposition temperature) and a high glass transition temperature, a method for producing the polymer, a composition, a film, a substrate with a film, An optical element, an image display device, a coating material, and a molded body are provided.

Hereinafter, embodiments for carrying out 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 numerical values and ranges thereof, and the present invention is not limited thereto.
In the present disclosure, the term “process” includes a process that is independent of other processes and includes the process if the purpose of the process is achieved even if it cannot be clearly distinguished from the other processes. .
In the present disclosure, the numerical ranges indicated using “to” include numerical values described 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 another numerical description. . Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
In the present disclosure, a plurality of substances corresponding to each component may be included. When multiple types of substances corresponding to each component are present in the composition, the content or content of each component is the total content or content of the multiple types of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, a plurality of particles corresponding to each component may be included. When a plurality of particles corresponding to each component are present in the composition, the particle diameter of each component means a value for a mixture of the plurality of particles present in the composition unless otherwise specified.
In the present disclosure, the term “layer” or “film” includes only a part of the region in addition to the case where the layer or film is formed over the entire region. The case where it is formed is also included.
In the present disclosure, the term “lamination” refers to stacking layers, and two or more layers may be combined, or two or more layers may be detachable.
In the present disclosure, “transparency” means a property that the transmittance of visible light (at least the transmittance of visible light having a wavelength of 400 nm) is 80% or more (equivalent to a film thickness of 10 μm).
In the present disclosure, “heat resistance” means representing a high thermal decomposition temperature of 400 ° C. or higher and a high glass transition temperature of 230 ° C. or higher.

<Polymer>
The polymer of the present disclosure includes a structural unit represented by the following general formula (I).
As a result of studies by the present inventors, it has been found that the polymer of the present disclosure has excellent transparency, a high thermogravimetric reduction temperature (thermal decomposition temperature), and a high glass transition temperature. The reason for this is not clear, but it is considered that first, by having an aromatic ring and an alicyclic ring bonded to the aromatic ring, the thermogravimetric reduction temperature (thermal decomposition temperature) is high, and it has transparency. Next, it is thought that it has a high glass transition temperature by having a hydroxyl group in the polymer and strengthening the interaction between molecules.

  In the general formula (I), each X1 is independently at least one selected from the group consisting of the following general formula (II-1), the following general formula (II-2), and the following general formula (II-3). The bivalent group represented by these is represented.

In General Formula (II-1), each R ¹ independently represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R ² independently has a substituent. The C1-C30 hydrocarbon group which may have been represented. o represents an integer of 0 to 3 independently. Moreover, a wavy line represents a binding site, and so on.

In general formula (II-1), from the viewpoint of reaction control, each R ¹ is preferably independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
Examples of the hydrocarbon group represented by R ¹ include a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and combinations of these hydrocarbon groups. Examples of the substituent when the hydrocarbon group represented by R ¹ has a substituent include a halogen atom, a hydroxy group, an epoxy group, an oxetanyl group, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. Etc. When the hydrocarbon group represented by R ¹ 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 saturated aliphatic hydrocarbon group represented by R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, and 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, An n-triacontanyl group etc. are mentioned.

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.

Examples of the alicyclic hydrocarbon group represented by R ¹ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cycloalkyl group such as a norbornyl group, an adamantyl group, and a cyclohexenyl group. And the like, and the like.

From the viewpoint of reaction control, each R ² is preferably independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Examples of R ² include the same as those exemplified for R ¹ . As the substituent in the case having a hydrocarbon group substituents represented by R ^2, a halogen atom, hydroxy group, an epoxy group, an oxetanyl group, an alkoxy group having 1 to 5 carbon atoms, 2 to 5 carbon atoms An acyl group etc. are mentioned. o is preferably an integer of 0 to 2.

In General Formula (II-2), each R ¹ independently represents a hydrocarbon group having 1 to 30 carbon atoms that may have a substituent, and each R ² independently has a substituent. The C1-C30 hydrocarbon group which may have been represented. p represents an integer of 0 to 2.

For more information on ^{R 1} and ^{R 2} in formula (II-2), respectively Details regarding the general formula (II-1) ^{R 1} and ^{R 2} in the same manner.

In General Formula (II-3), each R ¹ independently represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R ² independently has a substituent. The C1-C30 hydrocarbon group which may have been represented. o represents the integer of 0-3 each independently. Z represents an oxygen atom or a divalent group containing at least one selected from the group consisting of the following general formulas (IV-1) to (IV-7). ^R 1, ^{R 2} in the general formula (II-3), and to a more o, respectively similar to the information about ^R 1, ^{R 2,} and o in the general formula (II-1).

In general formulas (IV-1) to (IV-7), each R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ² represents Each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ³ and R ⁴ each independently represent a carbon atom which may have a hydrogen atom or a substituent. The hydrocarbon group of number 1-30 is represented. n represents an integer of 0 to 4, each independently represents an integer of 0 to 2, and m represents an integer of 0 to 3, each independently.

R ³ and R ⁴ in the general formula (IV-1) are preferably each independently a hydrocarbon group having 1 to 5 carbon atoms which may have a substituent, from the viewpoint of heat resistance. Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ³ and R ⁴ include the same as the hydrocarbon group having 1 to 30 carbon atoms exemplified by R ¹ in the general formula (II-1). It is done. Examples of the substituent R ³ and R ⁴ may have, a halogen atom, an alkoxy group having 1 to 5 carbon atoms and an acyl group having 2 to 5 carbon atoms.
N in the general formulas (IV-2) and (IV-3) each independently represents an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2. Preferably, 0 or 1 is more preferable.
O in general formula (IV-4), (IV-5) and general formula (IV-7) represents the integer of 0-2 each independently, and it is preferable that it is 0 or 1.
For more information on ^{R 1} and ^{R 2} in the general formula (IV-2) ~ (IV -7), respectively similar to the details regarding the general formula (II-1) ^{R 1} and ^{R 2} in.
m represents the integer of 0-3 each independently, and it is preferable that it is an integer of 0-2.

In general formula (I), each X2 is independently at least one selected from the group consisting of the following general formula (III-1), the following general formula (III-2), and the following general formula (III-3). The bivalent group represented by these is represented.

Formula (III-1), ^{R 2} each independently represent a hydrocarbon group of 1 to 30 carbon atoms which may have a substituent. o represents the integer of 0-3 each independently.

For more information on ^{R 2} and o in the general formula (III-1), respectively Details regarding ^{R 2} and o in the general formula (II-1) as well.

In General Formula (III-2), each R ² independently represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and p is each independently an integer of 0 to 2. Represents.

For more information on ^{R 2} and p in the general formula (III-2), respectively similar to the details regarding the ^{R 2} and p in the general formula (II-2).

In General Formula (III-3), each R ² independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. o represents the integer of 0-3 each independently. Z represents an oxygen atom or a divalent group that is at least one selected from the group consisting of the following general formulas (IV-1) to (IV-7).
For more information on ^{R 2} and o in the general formula (III-3), respectively Details regarding general formula (II-3) in the ^{R 2} and o similar.

Details regarding R ¹ , R ² , R ³ , R ⁴ , n, o, and m in General Formulas (IV-1) to (IV-7) representing Z in General Formula (III-3) are The details of R ¹ , R ² , R ³ , R ⁴ , n, o, and m in general formulas (IV-1) to (IV-7) representing Z in (II-3) are the same. .

  In general formula (I), Y represents a bivalent group containing an alicyclic ring each independently. As the divalent group containing an alicyclic ring, any divalent alicyclic hydrocarbon group derived from an alicyclic compound can be used without particular limitation. As the divalent alicyclic hydrocarbon group, cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, cycloheptanediyl group, cyclooctanediyl group, decahydronaphthalenediyl group, norbornanediyl group, Examples thereof include cycloalkanediyl groups such as an adamantanediyl group, bicyclo [2.2.2] octanediyl group, and cycloalkenediyl groups such as cyclohexenediyl group.

Y in the general formula (I) is represented by at least one selected from the group consisting of the following general formula (V-1), the following general formula (V-2), and the following general formula (V-3). Preferably it contains a group.

In general formula (I), m represents the number of structural units represented by -X1-Y- included in general formula (I), and n represents -X2-Y- included in general formula (I). The ratio of m to n (m: n) is 95: 5 to 5:95.
From the viewpoint of increasing the thermogravimetry temperature (pyrolysis temperature) and transparency, it is preferable to increase the ratio of m. Specifically, m: n is preferably 50:50 to 95: 5, More preferably, it is 60: 40-95: 5.
From the viewpoint of increasing the glass transition temperature and the adhesiveness, it is preferable to increase the ratio of n. Specifically, m: n is preferably 50:50 to 5:95, and 40:60 to 5: More preferably, it is 95.

<Method for Producing Polymer Represented by General Formula (I)>
The method for producing the polymer represented by the general formula (I) is not particularly limited. For example, the following general formula (VI-1), the following general formula (VI-2), and the following general formula (VI-3) It may be produced by a method including a reaction step of reacting at least one compound selected from the group consisting of) and a dihalide containing an alicyclic ring in a catalyst.

In General Formula (VI-1), each R ¹ independently represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R ² independently has a substituent. The C1-C30 hydrocarbon group which may be sufficient. o represents an integer of 0 to 3 independently.

In the general formula ^(VI-1), more of R 1, ^{R 2,} and o, are the same as in the general formula (II-1) Medium ^R 1, ^{R 2,} and o details.

In General Formula (VI-2), each R ¹ independently represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R ² independently has a substituent. The C1-C30 hydrocarbon group which may be sufficient. p represents the integer of 0-2 each independently.

In general formula (VI-1), the details of R ¹ , R ² , and p are the same as the details of R ¹ , R ² , and o in general formula (II-2).

In General Formula (VI-3), each R ¹ independently represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R ² independently has a substituent. The C1-C30 hydrocarbon group which may be sufficient. o represents an integer of 0 to 3 independently. Z represents an oxygen atom or a divalent group that is at least one selected from the group consisting of the following general formulas (IV-1) to (IV-7).

Details regarding R ¹ , R ² , R ³ , R ⁴ , n, o, and m in the general formulas (IV-1) to (IV-7) representing Z in the general formula (VI-3) are as follows. The details regarding R ¹ , R ² , R ³ , R ⁴ , n, o, and m in General Formulas (IV-1) to (IV-7) representing Z in (II-3) are the same as each other.

Examples of the site containing an alicyclic ring in a dihalide containing an alicyclic ring include a divalent group containing an alicyclic ring represented by Y in the above general formula (I). Same as Y in I).
Moreover, as a halogen atom in the dihalide containing an alicyclic ring, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
The dihalide containing an alicyclic ring is a dihalide containing a group represented by at least one selected from the group consisting of the general formulas (V-1), (V-2) and (V-3). Preferably, it is a dichloride or dibromide containing a group represented by at least one selected from the group consisting of the general formulas (V-1), (V-2) and (V-3). Is more preferable.

  The catalyst used in producing the polymer represented by the general formula (I) is not particularly limited, and examples thereof include aluminum chloride (usually used in Friedel-Crafts alkylation reaction and Friedel-Crafts acylation reaction). III), Lewis acid such as iron (III) chloride, trifluoromethanesulfonyl samarium (III), copper (I) bromide, copper (II) bromide, molybdenum hexacarbonyl (0), zinc (II) chloride, etc. May be. In addition, you may use the catalyst used for the known polymer manufacturing method.

As a catalyst used in producing the polymer represented by the general formula (I), copper bromide (I), copper bromide (II), hexacarbonylmolybdenum (0), and zinc chloride (II) are used. It is preferable to use at least one selected from the group consisting of
When the catalyst is as described above, the control of the reaction tends to be facilitated in the Friedel-Crafts alkylation reaction. From such a viewpoint, it is more preferable to use at least one selected from the group consisting of copper (I) bromide and zinc (II) chloride.

As a solvent used in producing the polymer represented by the general formula (I), o-dichlorobenzene, nitrobenzene, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, etc. may be used. preferable.
When the above solvent is used, the compound represented by the general formulas (VI-1) to (VI-3), the dihalide containing an alicyclic ring, the catalyst, and the polymer represented by the general formula (I) are dissolved. Or it tends to disperse and it becomes easy to control reaction easily.
From the viewpoint of increasing the transmittance of the polymer represented by the general formula (I), it is more preferable to use sulfolane as the solvent.

  Moreover, when manufacturing the polymer represented by general formula (I), you may add bases, such as sodium carbonate and sodium hydrogencarbonate. When a base is added, the m / n ratio of the polymer represented by the general formula (I) tends to increase.

  The molecular weight of the polymer is not particularly limited, and can be selected according to the use. From the viewpoint of heat resistance, the weight average molecular weight (Mw) of the polymer is preferably 5000 or more, more preferably 10,000 or more, and further preferably 20000 or more. Further, the number average molecular weight (Mn) is preferably 1000 or more, and more preferably 2000 or more.

  From the viewpoint of solubility in a solvent, the weight average molecular weight (Mw) of the polymer is preferably 350,000 or less, and more preferably 300000 or less. The number average molecular weight (Mn) is preferably 200000 or less, and more preferably 100000 or less.

The molecular weight (Mw and Mn) of the polymer is a value determined by standard polystyrene conversion, measured by GPC method using tetrahydrofuran (THF) as an eluent.
-Device name: Ecosec HLC-8320GPC (Tosoh Corporation)
-Column: TSKgel Supermultipore HZ-M (Tosoh Corporation)-Detector: UV detector and RI detector used together-Flow rate: 0.4 ml / min

After the reaction step, a step of allowing an organic halide derived from a hydrocarbon group having 1 to 30 carbon atoms to act in the presence of a base may be further included. By performing this step, the hydroxyl group on the aromatic ring represented by X2 in the general formula (I) can be alkoxylated, and the ratio of n in the general formula (I) is decreased and the ratio of m is increased. be able to. Therefore, the ratio of m and n in the general formula (I) can be appropriately adjusted according to the purpose.
The base and the organic halide used in this step will be described in the following “Method for producing polymer represented by general formula (VII)”.

<Method for Producing Polymer Represented by General Formula (VII)>
By reacting the polymer represented by the general formula (I) with an organic halide derived from a hydrocarbon group having 1 to 30 carbon atoms in the presence of a base, the polymer represented by the following general formula (VII) is reacted. A coalescence may be produced.

  In general formula (VII), each X is independently at least one selected from the group consisting of general formula (II-1), general formula (II-2), and general formula (II-3) below. And Y represents a divalent group containing an alicyclic ring independently. q represents the number of structural units represented by general formula (VII), and q is the total amount of m and n in general formula (I).

In general formulas (II-1), (II-2) and (II-3), R ¹ each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, R < ² > represents the C1-C30 hydrocarbon group which may have a substituent each independently. o represents the integer of 0-3 each independently, and p represents the integer of 0-2. Z represents an oxygen atom or a divalent group containing at least one selected from the group consisting of the following general formulas (IV-1) to (IV-7).

In general formulas (IV-1) to (IV-7), each R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ² represents Each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ³ and R ⁴ each independently represent a carbon atom which may have a hydrogen atom or a substituent. The hydrocarbon group of number 1-30 is represented. n represents an integer of 0 to 4, each independently represents an integer of 0 to 2, and m represents an integer of 0 to 3, each independently.

In the general formula (VII), details regarding R ¹ , R ² , o, and p in the general formulas (II-1), (II-2), and (II-3) are the same as those in the general formula (I). The details regarding R ¹ , R ² , o, and p in the formulas (II-1), (II-2), and (II-3) are the same.
Moreover, in general formula (VII), details regarding R ¹ , R ² , R ^3, and R ⁴ in (IV-1) to (IV-7) are the general formula (IV-1) in general formula (I). It is the same as the detail regarding R < ¹ >, R < ² >, R < ³ > and R < ⁴ > in-(IV-7).

  It does not restrict | limit especially as a base used for reaction, For example, you may use a cesium carbonate.

The organic halide is not particularly limited, and examples thereof include fluoride, chloride, bromide, and iodide. Carbon number of the hydrocarbon group induced | guided | derived to an organic halide is 1-30, it is preferable that it is 1-12, and it is more preferable that it is 1-6.
Specific examples of the organic halide derived from a hydrocarbon group having 1 to 30 carbon atoms include methyl fluoride, ethyl fluoride, propyl fluoride, butyl fluoride, methyl chloride, ethyl chloride, propyl chloride, and chloride. Examples thereof include butyl, methyl bromide, ethyl bromide, propyl bromide, butyl bromide, hexyl bromide, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, hexyl iodide and the like.

<Composition>
The polymer composition of the present disclosure includes the polymer of the present disclosure and a solvent. The state of the composition is not particularly limited and can be selected according to the use of the composition, and examples thereof include varnish, slurry, mixed powder and the like. The composition of the present disclosure may contain other components in addition to the polymer of the present disclosure. Examples of other components include additives and crosslinking agents.

  The solvent is not particularly limited, and γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, butyl acetate, benzyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, xylene, mesitylene, ethyl Benzene, propyl benzene, cumene, diisopropylbenzene, hexyl benzene, anisole, diglyme, dimethyl sulfoxide, chloroform, dichloromethane, dichloroethane, chlorobenzene and the like. These solvents may be used alone or in combination of two or more.

  Examples of the additive include an adhesion assistant, a surfactant, a leveling agent, an antioxidant, and an ultraviolet deterioration preventing agent. These additives may be used individually by 1 type, or may use 2 or more types together.

  Examples of the crosslinking agent include polyfunctional epoxy compounds, polyfunctional acrylic compounds, polyfunctional oxetane compounds, compounds having a plurality of hydroxy groups, compounds having a plurality of hydroxymethyl groups, compounds having a plurality of alkoxymethyl groups, and the like. These crosslinking agents may be used individually by 1 type, or may use 2 or more types together.

<Membrane>
The membrane of the present disclosure includes the polymer of the present disclosure. The film of the present disclosure has heat resistance (thermal decomposition temperature and glass transition temperature) comparable to that of a polyimide film, and has a lower water absorption rate than the polyimide film. Therefore, the membrane of the present disclosure is excellent in dimensional stability, reliability, and the like even when used in a high humidity environment.

The manufacturing method of the film | membrane of this indication is not specifically limited. For example, the composition of the present disclosure is produced by applying the composition of the present disclosure containing a solvent to the surface of the substrate to form a composition layer, and drying the composition as necessary to remove the solvent from the composition layer. can do. The produced membrane may be used as a substrate with a film without being separated from the substrate, or may be used after being separated from the substrate.
The method for applying the composition to the substrate is not particularly limited, and examples include dipping, spraying, screen printing, bar coating, and spin coating. The method for drying the composition layer is not particularly limited, and examples thereof include a method of heating using a hot plate and an oven, and natural drying.

  The dried polymer film of the present disclosure may be further heat-treated as necessary. The heat treatment method is not particularly limited, and is 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 performed using an oven. In addition, as an atmospheric condition in the heat treatment step, any of air or an inert atmosphere such as nitrogen can be selected.

<Substrate with membrane>
The substrate with a film of the present disclosure includes the substrate and the film of the present disclosure provided on at least a part of the surface of the substrate. The film-coated substrate of the present disclosure may have a film on one surface of the substrate or may have a film on both surfaces. The film formed on the substrate may be a single layer or a multi-layer structure in which two or more layers are laminated.

  The type of substrate is not particularly limited. Base materials include glass substrates, semiconductor substrates, metal oxide insulator substrates (for example, titanium oxide substrates and silicon oxide substrates), inorganic substrates such as silicon nitride substrates, triacetyl cellulose, polyimide, polycarbonate, acrylic resins Examples thereof include resin substrates such as cycloolefin resins. The substrate may be transparent or not transparent. The shape of the substrate is not particularly limited, and examples thereof include a plate shape and a film shape.

<Optical element and image display device>
The optical element and the image display device of the present disclosure each have the film or the substrate with the film of the present disclosure.

  The optical element and the image display device use, for example, the base material side of the base material on which the film of the present disclosure is formed for an LCD (liquid crystal display), an ELD (electroluminescence display), or the like via an adhesive, an adhesive, or the like. It can be obtained by sticking to the member.

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

  The use of the image display device is not particularly limited. For example, OA equipment such as desktop personal computers, notebook personal computers, and copy machines; portable equipment such as mobile phones, watches, digital cameras, personal digital assistants (PDAs), and portable game machines; Equipment: Vehicle monitors, back monitors, car navigation system monitors, car audio equipment, etc .; Display equipment such as commercial store information monitors; Security equipment such as monitoring monitors; Care equipment such as nursing monitors; Medical monitors, etc. Medical equipment.

<Coating material>
The coating material of the present disclosure includes the polymer of the present disclosure. The target to be coated with the coating material is not particularly limited, and examples include the above-described image display device, window glass, in-vehicle glass, and camera lens. The method of forming the coating using the coating material is not particularly limited. For example, the coating may be formed by adhering a film-shaped coating material to the object to be coated by a method such as laminating, or coating a liquid coating material. The coating may be formed by applying to an object and then drying.

<Molded body>
The molded body of the present disclosure includes the polymer of the present disclosure. The method for producing the molded body is not particularly limited, and a method known in the technical field can be used. For example, extrusion molding method, injection molding method, calender molding method, blow molding method, FRP (Fiber Reinforced Plastic) molding method, laminate molding method, casting method, powder molding method, solution casting method, vacuum molding method, compressed air molding Method, extrusion composite molding method, stretch molding method, foam molding method and the like.

  The molded article of the present disclosure may further contain various additives for imparting a desired function, improving characteristics, improving moldability, and the like as necessary. Additives include sliding agents (eg, polytetrafluoroethylene particles), light diffusing agents (acrylic crosslinked particles, silicone crosslinked particles, ultrathin glass flakes, calcium carbonate particles, etc.), fluorescent dyes, inorganic phosphors (aluminum) Phosphors having acid salts as mother crystals), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (titanium oxide particles, zinc oxide particles, etc.), crosslinking agents, curing agents, reactions Accelerators, infrared absorbers (heat absorbers), photochromic agents and the like can be mentioned.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Example 1]
(Synthesis of polyarylene “BP1” having an alicyclic skeleton in the main chain)
In a flask equipped with a magnetic stir bar and a nitrogen balloon, 0.5 mmol of 1,3-dibromoadamantane, 0.5 mmol of 2,2′-dimethoxybiphenyl, 0.2 mmol of copper (I) bromide, N-methyl- 2-Pyrrolidone (NMP) 1 ml was added and stirred at 150 ° C. for 48 hours. After the reaction, the reaction solution was poured into 50 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 BP1 (isolation yield: 93% by mass).
When the molecular weight of BP1 was measured by the method described later, the weight average molecular weight was 27,400 and the number average molecular weight was 3,300. Moreover, when the methylation rate (m / (m + n) × 100 [%]) of BP1 was measured by the method described later, it was 38%.

The molecular weight of BP1 was measured by the GPC method using N-methyl-2-pyrrolidone as an eluent, and determined in terms of standard polystyrene. Details are as follows.
-Device name: Ecosec HLC-8320GPC (Tosoh Corporation)
・ Column: TSKgel Super AW (Tosoh Corporation)
・ Detector: UV detector and RI detector combined ・ Flow rate: 0.4ml / mIn

The methylation rate of BP1 is determined by proton nuclear magnetic resonance spectroscopy (1H-NMR), the proton of the methoxy group observed at δ3.5 to 4.5, and the aromatic ring observed at δ6.5 to 7.5. It was calculated from the integral ratio of protons.
・ Device name: AVANCE300 (Bruker)
・ Resonance frequency: 300 MHz (as proton nucleus)
Solvent: N, N-dimethylformamide-d7

(Preparation of varnish)
BP1 was dissolved in N-methyl-2-pyrrolidone so as to have a concentration of 20% by mass and filtered through a polytetrafluoroethylene membrane filter (pore diameter: 5 μm) to obtain a BP1 varnish.

(Production of substrate with film)
BP1 varnish is applied onto a glass substrate by spin coating, dried on a 120 ° C hot plate for 3 minutes, and further dried in a nitrogen gas oven at 200 ° C for 1 hour to produce a glass plate with a BP1 film did. Using this, the transparency and adhesion of BP1 were evaluated by the methods described below. The results are shown in Table 1.

(Evaluation of transparency)
The transmittance of the BP1 film-coated glass plate at a wavelength of 400 nm was measured by an ultraviolet-visible absorption spectrum method using an ultraviolet-visible spectrophotometer (“U-3310 Spectrophotometer”, Hitachi High-Tech Co., Ltd.). Using a glass substrate without a film as a reference, a value converted to a film thickness of 10 μm was defined as transmittance (%). The film thickness was the number average value of the values measured at three points using a stylus profilometer ("Dektak 3 ST", ULVAC, Inc. (Veeco)).

(Evaluation of adhesion)
The BP1 film of the BP1 film-attached glass plate was divided into 100 squares at 1 mm square, peeled with a scotch tape, and the number of squares remaining on the substrate was counted. 90 or more squares were evaluated as A, and 80 to 89 squares as B.

(Measurement of thermal decomposition temperature)
The powder of BP1 was weighed on an aluminum pan and the weight loss was measured using a thermogravimetric balance (“TG-DTA6300”, Hitachi High-Tech Science Co., Ltd.). The intersection of the tangents of the curves where the weight is greatly reduced by heating is defined as the pyrolysis temperature. The results are shown in Table 1.

(Measurement of glass transition temperature)
The powder of BP1 is weighed into an aluminum pan, and the temperature at which the baseline changes (second order transition) is defined as the glass transition temperature using a differential scanning calorimeter (DSC) (“DSC8500”, Perkin Elmer). The results are shown in Table 1.

[Example 2]
(Synthesis of polyarylene “BP2” having an alicyclic skeleton in the main chain)
In a screw-necked flask equipped with a magnetic stir bar, 0.5 mmol of 1,3-dibromoadamantane, 0.5 mmol of 2,2′-dimethoxybiphenyl, 0.2 mmol of hexacarbonylmolybdenum (0), and 1 ml of nitrobenzene were added. In addition, the mixture was stirred at 150 ° C. for 24 hours. After the reaction, the reaction solution was poured into 50 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 BP2.
When the molecular weight was measured by the same method as in Example 1, the weight average molecular weight of BP2 was 8,500 and the number average molecular weight was 2,100. The methylation rate of BP2 was 55%. Table 1 shows the evaluation results of transparency, thermal decomposition temperature, glass transition temperature, and adhesion of BP2.

[Example 3]
(Synthesis of polyarylene “PH1” having an alicyclic skeleton in the main chain)
To a flask equipped with a magnetic stirring bar and a nitrogen balloon, 0.5 mmol of 1,3-dibromoadamantane, 0.5 mmol of 1,3-dimethoxybenzene, 0.2 mmol of copper (I) bromide, and 1 ml of NMP were added. , And stirred at 150 ° C. for 48 hours. After the reaction, the reaction solution was poured into 50 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 PH1.
When the molecular weight was measured in the same manner as in Example 1, the weight average molecular weight of PH1 was 37,000, and the number average molecular weight was 5,200. The methylation rate of PH1 was 31%. Table 1 shows the evaluation results of transparency, thermal decomposition temperature, glass transition temperature, and adhesion of PH1.

[Example 4]
(Synthesis of polyarylene “PH2” having an alicyclic skeleton in the main chain)
To the same apparatus as in Example 3, 0.5 mmol of 1,3-dibromoadamantane, 0.5 mmol of 1,3-dimethoxybenzene, 0.2 mmol of copper (I) bromide, and 1 ml of NMP were added. Stir at 150 ° C. for 24 hours. After the reaction, PH2 was obtained in the same manner as in Example 3.
When the molecular weight was measured in the same manner as in Example 1, the weight average molecular weight of PH2 was 19,900, and the number average molecular weight was 4,900. The methylation rate of PH2 was 46%. Table 1 shows the evaluation results of transparency, thermal decomposition temperature, glass transition temperature, and adhesion of PH2.

[Example 5]
(Synthesis of polyarylene “BF1” having an alicyclic skeleton in the main chain)
In a flask equipped with a magnetic stir bar and a nitrogen balloon, 0.5 mmol of 1,3-dibromoadamantane, 0.5 mmol of 2,2′-dimethoxydiphenylmethane, 0.2 mmol of copper (II) bromide, and 1 ml of NMP were added. In addition, the mixture was stirred at 150 ° C. for 48 hours. After the reaction, the reaction solution was poured into 50 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 BF1.
When the molecular weight was measured in the same manner as in Example 1, the weight average molecular weight of BF1 was 86,000, and the number average molecular weight was 4,100. The methylation rate of BF1 was 21%. Table 1 shows the evaluation results of transparency, thermal decomposition temperature, glass transition temperature, and adhesion of BF1.

[Example 6]
(Synthesis of polyarylene “BP3” having an alicyclic skeleton in the main chain)
In a screw-necked flask equipped with a magnetic stirring bar, 0.5 mmol of 1,3-dibromoadamantane, 0.5 mmol of 2,2′-dimethoxybiphenyl, 0.1 mmol of zinc (II) chloride, 0.5 mmol of sodium carbonate, And 1 ml of sulfolane were added and stirred at 150 ° C. for 24 hours. After the reaction, the reaction solution was poured into 50 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 BP3.
When the molecular weight was measured by the same method as in Example 1, BP3 had a weight average molecular weight of 12,500 and a number average molecular weight of 4,400. The methylation rate of BP3 was 70%. Table 1 shows the evaluation results of transparency, thermal decomposition temperature, glass transition temperature, and adhesion of BP3.

[Example 7]
(Synthesis of polyarylene “PH3 (PH1 ′)” having an alicyclic skeleton in the main chain)
In a flask equipped with a magnetic stir bar and a nitrogen balloon, 0.5 mmol of 1,3-dibromoadamantane, 0.5 mmol of 1,4-dimethoxybenzene, 0.1 mmol of zinc (II) chloride, and 0.5 mmol of sodium bicarbonate And 1 ml of sulfolane were added and stirred at 150 ° C. for 24 hours. After the reaction, the reaction solution was poured into 50 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 PH3 (PH1 ′).
When the molecular weight was measured by the same method as in Example 1, the (PH1 ′) weight average molecular weight of PH3 was 120,000, and the number average molecular weight was 7,200. The methylation rate of PH′1 was 65%. Table 1 shows the evaluation results of transparency, thermal decomposition temperature, glass transition temperature, and adhesion of PH3 (PH1 ′).

[Comparative Example 1]
(Synthesis of polyketone "AD1" having alicyclic skeleton in the main chain)
In a flask equipped with a stirrer and a nitrogen balloon, 4 mmol of 1,3-adamantane dicarboxylic acid, 4 mmnol of 2,2′-dimethoxybiphenyl, diphosphorus pentoxide and methanesulfonic acid (mass ratio 1:10) 12 ml was added and stirred at 60 ° C. for 24 hours. After the reaction, the mixed solution was poured into 300 ml of distilled water, and the produced precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and dried to obtain AD1.
When the molecular weight was measured in the same manner as in Example 1, the weight average molecular weight of AD1 was 60,000, and the number average molecular weight was 3,000. Table 1 shows the evaluation results of transparency, thermal decomposition temperature, glass transition temperature, and adhesion of AD1.

[Comparative Example 2]
(Synthesis of polyarylene “AD2” having an alicyclic skeleton in the main chain and no hydroxyl group on the aromatic ring)
To a four-necked flask equipped with a stirrer and a nitrogen balloon, 10 mmol of 1,3-adamantane dicarboxylic acid and 30 ml of a mixed solution of diphosphorus pentoxide and methanesulfonic acid (mass ratio 1:10) were added, For 10 minutes. Subsequently, 10 mmol of 2,2′-dimethoxybiphenyl was added to the flask and stirred at 60 ° C. for 40 hours. After the reaction, the reaction solution was poured into 500 ml of methanol, and the produced precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain AD2.
When the molecular weight was measured in the same manner as in Example 1, the weight average molecular weight of AD2 was 52,000, and the number average molecular weight was 9,100. Table 1 shows the evaluation results of transparency, thermal decomposition temperature, glass transition temperature, and adhesion of AD2.

From Table 1, the polyarylenes (BP1, BP2, BP3, PH1, PH2, PH3 (PH1 ′), BF1) having the alicyclic skeleton in the main chain and having a hydroxyl group on the aromatic ring, which are the polymers of the present disclosure. ) Shows a high transmittance of 90% or higher, a high thermal decomposition temperature of 400 ° C. or higher, a high glass transition temperature of 230 ° C. or higher, and adhesion between a film obtained from a polymer and a glass substrate. Was expensive.
On the other hand, the polyketone (AD1) having an alicyclic skeleton in the main chain shown in Comparative Example 1 has high transmittance and thermal decomposition temperature and is excellent in adhesion. However, the glass transition temperature of AD1 was as low as 172 ° C.
Moreover, the polyarylene (AD2) which has an alicyclic skeleton in the main chain and does not have a hydroxyl group on the aromatic ring shown in Comparative Example 2 has high transmittance and thermal decomposition temperature. However, the glass transition temperature of AD2 was as low as 220 ° C., and the adhesion was poor.

[Synthesis Example 1]
(Methylation of polyarylene “BP1” having an alicyclic skeleton in the main chain: synthesis of polyarylene having no hydroxyl group on the aromatic ring)
In a flask equipped with a magnetic stirrer and a nitrogen balloon, 0.3 g of polyarylene “BP1” obtained in Example 1, 3 ml of methyl iodide, 2 mmol of cesium carbonate, and 3 ml of N, N-dimethylacetamide were added. In addition, the mixture was stirred at room temperature for 7 days. After the reaction, the reaction solution was poured into 50 ml of distilled water, and the produced precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain a methylated product of “BP1”.
When the molecular weight was measured in the same manner as in Example 1, the methylated product of “BP1” had a weight average molecular weight of 29,000 and a number average molecular weight of 3,400. The methylation rate was almost 100%. The methylated product of “BP1” had a transmittance of 98%, a thermal decomposition temperature of 464 ° C., a glass transition temperature of 226 ° C., and an adhesiveness of B evaluation.

  As shown in Synthesis Example 1, a polyarylene having an alicyclic skeleton in the main chain and a hydroxyl group on an aromatic ring, which is a polymer of the present disclosure, is carbonized with 1 to 30 carbon atoms in the presence of a base. It was found that when an organic halide derived from a hydrogen group was allowed to act, it could be converted to polyarylene having a reduced hydroxyl group on the aromatic ring.

Claims (13)

The polymer containing the structural unit represented by the following general formula (I).

[In General Formula (I), each X1 is independently at least selected from the group consisting of General Formula (II-1), General Formula (II-2), and General Formula (II-3) below. Represents a divalent group represented by one type, and each X2 is independently selected from the group consisting of the following general formula (III-1), the following general formula (III-2), and the following general formula (III-3). The divalent group represented by the at least 1 type selected is represented, Y represents the bivalent group containing an alicyclic ring each independently. m represents the number of structural units represented by -X1-Y- included in the general formula (I), and n represents a structural unit represented by -X2-Y- included in the general formula (I). The ratio of m to n (m: n) is 95: 5 to 5:95. ]



[In General Formulas (II-1), (II-2) and (II-3), each R ¹ independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. , R ² each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. o represents the integer of 0-3 each independently, and p represents the integer of 0-2. Z represents an oxygen atom or a divalent group containing at least one selected from the group consisting of the following general formulas (IV-1) to (IV-7). ]

[In General Formulas (IV-1) to (IV-7), each R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ² Each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ³ and R ⁴ may each independently have a hydrogen atom or a substituent. A C1-C30 hydrocarbon group is represented. n represents an integer of 0 to 4, each independently represents an integer of 0 to 2, and m represents an integer of 0 to 3, each independently. ]



[In General Formulas (III-1), (III-2), and (III-3), each R ² independently represents a hydrocarbon group having 1 to 30 carbon atoms that may have a substituent. . o independently represents an integer of 0 to 3, and p independently represents an integer of 0 to 2, respectively. Z represents an oxygen atom or a divalent group that is at least one selected from the group consisting of the following general formulas (IV-1) to (IV-7). ]

[In General Formulas (IV-1) to (IV-7), each R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ² Each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ³ and R ⁴ may each independently have a hydrogen atom or a substituent. A C1-C30 hydrocarbon group is represented. n represents an integer of 0 to 4, each independently represents an integer of 0 to 2, and m represents an integer of 0 to 3, each independently. ] In the general formula (I), Y is represented by at least one selected from the group consisting of the following general formula (V-1), the following general formula (V-2), and the following general formula (V-3). The polymer according to claim 1, comprising a group.
A catalyst comprising at least one compound selected from the group consisting of the following general formula (VI-1), the following general formula (VI-2) and the following general formula (VI-3), and a dihalide containing an alicyclic ring The manufacturing method of the polymer of Claim 1 or Claim 2 including the reaction process made to react in.



[In General Formulas (VI-1), (VI-2), and (VI-3), each R ¹ independently represents a hydrocarbon group having 1 to 30 carbon atoms that may have a substituent. R ² represents each independently a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. o represents the integer of 0-3 each independently, and p represents the integer of 0-2. Z represents an oxygen atom or a divalent group containing at least one selected from the group consisting of the following general formulas (IV-1) to (IV-7). ]

[In General Formulas (IV-1) to (IV-7), each R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ² Each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ³ and R ⁴ may each independently have a hydrogen atom or a substituent. A C1-C30 hydrocarbon group is represented. n represents an integer of 0 to 4, each independently represents an integer of 0 to 2, and m represents an integer of 0 to 3, each independently. ]   The polymer according to claim 3, wherein the catalyst is at least one selected from the group consisting of copper (I) bromide, copper (II) bromide, hexacarbonylmolybdenum (0), and zinc (II) chloride. Manufacturing method.   The method for producing a polymer according to claim 3 or 4, further comprising a step of allowing an organic halide derived from a hydrocarbon group having 1 to 30 carbon atoms to act after the reaction step in the presence of a base. . Production of a polymer represented by the following general formula (VII), wherein an organic halide derived from a hydrocarbon group having 1 to 30 carbon atoms is allowed to act on the polymer according to claim 1 or 2 in the presence of a base. Method.

[In General Formula (VII), each X is independently selected from the group consisting of General Formula (II-1), General Formula (II-2), and General Formula (II-3) below. The divalent group represented by 1 type is represented, Y represents each independently the bivalent group containing an alicyclic ring. q represents the number of structural units represented by general formula (VII), and q is the total amount of m and n in general formula (I). ]



[In General Formulas (II-1), (II-2) and (II-3), each R ¹ independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. , R ² each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. o represents the integer of 0-3 each independently, and p represents the integer of 0-2. Z represents an oxygen atom or a divalent group containing at least one selected from the group consisting of the following general formulas (IV-1) to (IV-7). ]

[In General Formulas (IV-1) to (IV-7), each R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ² Each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ³ and R ⁴ may each independently have a hydrogen atom or a substituent. A C1-C30 hydrocarbon group is represented. n represents an integer of 0 to 4, each independently represents an integer of 0 to 2, and m represents an integer of 0 to 3, each independently. ]   A composition comprising the polymer according to claim 1 or 2 and a solvent.   A film comprising the polymer according to claim 1 or 2.   The base material with a film | membrane which has a base material and the film | membrane of Claim 8 provided in at least one part of the surface of the said base material.   An optical element comprising the film according to claim 8 or the film-coated substrate according to claim 9.   An image display device comprising the film according to claim 8 or the film-coated substrate according to claim 9.   A coating material comprising the polymer according to claim 1.   The molded object containing the polymer of Claim 1 or Claim 2.