JP2017197687A - Polymer comprising aromatic ring and quaternary carbon atom-containing alicycle, method for producing polymer, composition, film, base material with film, optical element, image display device, coating material and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer having excellent heat resistance and transparency and also having a low water absorption and a method for producing the same, and a composition comprising a polymer, a film, a base material with a film, an optical element, an image display device, a coating material and a molding.SOLUTION: A polymer comprises an aromatic ring, and an alicycle having a quaternary carbon atom bound to the aromatic ring.SELECTED DRAWING: None

Description

  The present invention relates to a polymer containing an aromatic ring and a quaternary carbon atom-containing alicyclic ring, 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). In particular, a polymer having a bulky and rigid skeleton in the molecular structure can be expected to have excellent heat resistance and transparency.

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

When a resin material is applied to an optical component, it is often used in combination with various materials including a metal material. Therefore, from the viewpoint of dimensional stability and reliability, it is desirable that the water absorption is low in addition to being excellent in heat resistance and transparency.
However, a polymer having high heat resistance such as polyimide generally contains many functional groups having polarity and tends to have a high water absorption rate.

  The present invention has been made in view of the above circumstances, and has a polymer having excellent heat resistance and transparency, a low water absorption rate, a method for producing the same, a composition containing the polymer, a film, and a substrate with a film An object of the present invention is to provide an optical element, an image display device, a coating material, and a molded body.

<1> A polymer comprising an aromatic ring and an alicyclic ring having a quaternary carbon atom bonded to the aromatic ring.
<2> The polymer according to <1>, comprising a structural unit represented by the following general formula (I).

[In General Formula (I), X represents a divalent group containing an aromatic ring, and Y represents a divalent group containing an alicyclic ring having a quaternary carbon atom bonded to the aromatic ring. n represents the number of structural units represented by the general formula (I). ]
<3> In the general formula (I), Y represents at least one selected from the group consisting of the following general formula (IV-1), the following general formula (IV-2), and the following general formula (IV-3). <2> The polymer according to <2>.

<4> The polymer according to <2> or <3>, wherein, in the general formula (I), X includes a divalent group including two or more aromatic rings.
<5> In the general formula (I), X is 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). <2>-<4> The polymer of any one of <2> containing the bivalent group of these.

[In General Formula (II-1), each R ¹ independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R ² independently represents a substituent. The C1-C30 hydrocarbon group which may have is shown. Each m independently represents an integer of 0 to 3. ]

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

[In General Formula (III), R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. ]

[In General Formula (II-3), each R ⁵ independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. n shows the integer of 0-4 each independently. ]
<6> The polymer according to any one of <1> to <5>, further including a carbonyl group.
<7> The compound according to any one of <1> to <6>, comprising a reaction step of reacting a compound represented by the following general formula (VI) with a compound containing an aromatic ring in an acidic medium. Manufacturing method of coalescence.

[In General Formula (VI), Y represents an alicyclic ring containing a carbon atom that is bonded to the aromatic ring of the compound containing the aromatic ring to form a quaternary carbon atom. ]
<8> The compound containing an aromatic ring includes at least one selected from the group consisting of the following general formula (VII-1), the following general formula (VII-2), and the following general formula (VII-3). <7> The method for producing a polymer according to item 7.

[In General Formula (VII-1), each R ¹ independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R ² independently represents a substituent. The C1-C30 hydrocarbon group which may have is shown. Each m independently represents an integer of 0 to 3. ]

[In General Formula (VII-2), each R ¹ independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R ² independently represents a substituent. Represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom, and Z represents an oxygen atom or a divalent group represented by the following general formula (III). Each m independently represents an integer of 0 to 3. ]

[In General Formula (III), R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. ]

In General Formula (VII-3), each R ⁵ independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. n shows the integer of 0-4 each independently.
<9> The reaction step includes a step of preparing a mixture of the compound represented by the general formula (VI) and an acidic medium, and a step of adding the compound containing the aromatic ring to the mixture in this order. The manufacturing method of the polymer as described in 7> or <8>.
<10> A composition comprising the polymer according to any one of <1> to <6>.
<11> A film comprising the polymer according to any one of <1> to <6>.
<12> A substrate with a film having a substrate and the film according to <11> provided on at least part of the surface of the substrate.
<13> An optical element having the film according to <11> or the substrate with a film according to <12>.
<4> An image display device having the film according to <11> or the film-coated substrate according to <12>.
<15> A coating material comprising the polymer according to any one of <1> to <6>.
<16> A molded article comprising the polymer according to any one of <1> to <6>.

  According to the present invention, a polymer having excellent heat resistance and transparency and a low water absorption rate, a method for producing the same, a composition containing the polymer, a film, a substrate with a film, an optical element, and 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 this specification, 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. It is.
In the present specification, the numerical ranges indicated by 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 this specification, 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. Good. Further, in the numerical ranges described in this specification, 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 specification, the content rate or content of each component in the composition is such that when there are a plurality of substances corresponding to each component in the composition, the plurality of kinds present in the composition unless otherwise specified. It means the total content or content of substances.
In the present specification, the particle diameter of each component in the composition is a mixture of the plurality of types of particles present in the composition unless there is a specific indication when there are a plurality of types of particles corresponding to each component in the composition. Means the value of.
In this specification, the term “layer” or “film” refers to a part of the region in addition to the case where the layer or the film is formed when the region where the layer or film exists is observed. It is also included when it is formed only.
In this specification, the term “lamination” indicates that layers are stacked, and two or more layers may be combined, or two or more layers may be detachable.
In the present specification, the “transparency” means a property that the visible light transmittance (visible light transmittance of at least 400 nm wavelength) is 80% or more (in terms of film thickness of 10 μm).
As used herein, “heat resistance” means a property that does not cause visible yellowing or deformation even when heated at 200 ° C. for 10 minutes in air.

<Polymer>
The polymer of this embodiment includes an aromatic ring and an alicyclic ring having a quaternary carbon atom bonded to the aromatic ring (hereinafter also referred to as a quaternary carbon atom-containing alicyclic ring). As a result of studies by the present inventors, it has been found that the polymer of the present embodiment has excellent heat resistance and transparency, and has a low water absorption rate. The reason for this is not clear, but first, it is considered to have heat resistance and transparency by having an aromatic ring and an alicyclic ring bonded to the aromatic ring. Furthermore, since the quaternary carbon atom has no C—H bond having a slight polarity, the interaction with the water molecule is weak, and the water molecule penetrates into an aggregate or aggregate of polymer molecular chains. As a result, the water absorption rate is considered to be low.

  The structure of the aromatic ring contained in the polymer of this embodiment is not particularly limited. From the viewpoint of transparency, it is preferably an aromatic ring having 3 to 24 carbon atoms. Examples of such an aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. Among these, a benzene ring is preferable from the viewpoint of increasing the polymerization reactivity. Moreover, the aromatic ring may have a substituent. Examples of the substituent include an alkyl group, a halogen atom, a hydroxy group, an epoxy group, an oxetanyl group, an alkoxy group, and an acyl group.

  The quaternary carbon atom-containing alicyclic ring contained in the polymer of this embodiment is not particularly limited. From the viewpoint of heat resistance, an alicyclic ring having 5 to 30 carbon atoms is preferable. Examples of such alicyclic rings include cubane skeleton, norbornane skeleton, tricyclo [5.2.1.0] decane skeleton, adamantane skeleton, diadamantane skeleton, bicyclo [2.2.2] octane skeleton, decahydronaphthalene skeleton, and the like. Is mentioned.

  The alicyclic ring having a quaternary carbon atom may contain an unsaturated bond. Moreover, the alicyclic ring having a quaternary carbon atom may have a substituent. Examples of the substituent include an alkyl group, a halogen atom, a hydroxy group, an epoxy group, an oxetanyl group, an alkoxy group, and an acyl group.

  The polymer of the present embodiment preferably contains a divalent group containing an aromatic ring and a divalent group containing a quaternary carbon atom-containing alicyclic ring. The divalent group containing an aromatic ring, More preferably, it includes a structure in which divalent groups containing a secondary carbon atom-containing alicyclic ring are alternately bonded (that is, includes a structural unit represented by the following general formula (I)).

  In the general formula (I), X represents a divalent group containing an aromatic ring, and Y represents a divalent group containing a quaternary carbon atom-containing alicyclic ring. In general formula (I), X in n structural units may be the same or different, and Y may be the same or different. n represents the number of structural units represented by the general formula (I). n is not particularly limited, and may be an integer of 3 to 1000.

  The carbon number of the divalent group containing an aromatic ring is not particularly limited, and may be 6 to 50, for example. From the viewpoint of the heat resistance of the polymer, at least a part of the divalent group containing an aromatic ring preferably contains two or more aromatic rings. When the bivalent group containing an aromatic ring contains two or more aromatic rings, the two or more aromatic rings may be bonded with a single bond or may be bonded with a divalent linking group.

  Examples of the divalent linking group that connects two or more aromatic rings include an oxygen atom, a sulfur atom, an alkylene group that may have a substituent, an alkenylene group that may have a substituent, and a substituent. An alkynylene group, an imino group, a carbonyl group, and the like, which may have an alkyl group. Furthermore, the bivalent coupling group which connected two or more arbitrary coupling groups chosen from the above-mentioned coupling group is mentioned. Among these, as the divalent linking group, an oxygen atom or an alkylene group which may have a substituent is preferable.

  Specifically, the divalent group containing an aromatic ring is 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). And the groups shown.

In General Formula (II-1), each R ¹ independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R ² independently represents a substituent. The C1-C30 hydrocarbon group which may have is shown. Each m independently represents an integer of 0 to 3. Moreover, a wavy line shows a coupling | bond part and it is the same after that.

In general formula (II-1), from the viewpoint of reaction control, R ¹ is preferably a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
Examples of the hydrocarbon group represented by R ¹ include saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, 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. Is mentioned. 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, n -A triacontanyl group etc. are mentioned.

Examples of the unsaturated aliphatic hydrocarbon group represented by R ¹ include alkenyl groups such as vinyl groups and allyl groups, and alkynyl groups such as ethynyl groups.

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, a cyclohexenyl group, and the like. And the like.

From the viewpoint of reaction control, the hydrocarbon group represented by R ² is preferably a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Examples of the hydrocarbon group represented by R ² include the same as those exemplified for R ¹ . Examples of the 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. m is preferably an integer of 0 to 2.

In general formula (II-2), each R ¹ independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R ² independently represents a substituent. A hydrocarbon group having 1 to 30 carbon atoms which may be present, and Z represents an oxygen atom or a divalent group represented by the following general formula (III). Each m independently represents an integer of 0 to 3. Each of the details of the ^R 1, ^{R 2} and m in formula (II-2), the same as in the general formula (II-1) of ^R 1, ^{R 2} and m in detail.

In general formula (III), R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. From the viewpoint of reaction control, R ³ and R ⁴ are preferably a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. As the hydrocarbon group represented by R ³ and R ⁴ , the same groups as those exemplified for R ¹ in formula (II-1) can be mentioned. Examples of the 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.

In General Formula (II-3), each R ⁵ independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. n shows the integer of 0-4 each independently.

From the viewpoint of reaction control, R ⁵ is preferably a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group represented by R ⁵ include the same groups as those exemplified for R ¹ in formula (II-1). Examples of the 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. n is preferably an integer of 0 to 2.

  As a bivalent group containing a quaternary carbon atom containing alicyclic ring, the bivalent group containing the quaternary carbon atom containing alicyclic ring mentioned above is mentioned. From the viewpoint of paralleling heat resistance, transparency, low water absorption, and solubility in a solvent, the divalent group containing a quaternary carbon atom-containing alicyclic ring is represented by the following general formula (IV-1) or the following general formula. A group represented by at least one selected from the group consisting of (IV-2) and the following general formula (IV-3) is preferable.

  From the viewpoint of the solubility of the polymer in the solvent, the polymer of this embodiment preferably contains a carbonyl group. For example, it is preferable to include a structural unit represented by the following general formula (V).

  In the general formula (V), X represents a divalent group containing an aromatic ring, and Y represents a divalent group containing an alicyclic ring having a quaternary carbon atom bonded to a carbon atom of a carbonyl group. The details of X are the same as the details of X in general formula (I). The details of Y are the same as the details of Y in formula (I) (wherein the quaternary carbon atom is bonded to the carbon atom of the carbonyl group instead of the aromatic ring). m represents the number of structural units represented by the general formula (V). The value of m is not particularly limited and can be selected according to the desired amount of the carbonyl group contained in the polymer. For example, the ratio (n: m) to n, which is the number of structural units represented by the general formula (I), can be selected from a range of 100: 0 to 5:95.

  When the polymer of this embodiment includes the structural unit represented by the general formula (I) and the structural unit represented by the general formula (V), the structural unit represented by the general formula (I) and the general formula (V) The arrangement state of the structural unit represented by is not particularly limited. For example, the structural unit represented by the general formula (I) and the structural unit represented by the general formula (V) may be alternately arranged, randomly arranged, or arranged in blocks.

  The molecular weight of the polymer of the present embodiment 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 of the present embodiment is preferably 10,000 or more, and more preferably 20,000 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 of this embodiment 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 of the present embodiment 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 combined use
・ Flow rate: 0.4ml / min

  The polymer of this embodiment is excellent in transparency and heat resistance. And the film | membrane and other embodiment containing the polymer of this embodiment mentioned later have a low water absorption, and it is hard to raise | generate malfunctions, such as a dimensional change by water absorption. Therefore, the polymer of this embodiment can be suitably used for members used in a high temperature and high humidity environment.

<Method for producing polymer>
The method for producing a polymer according to this embodiment comprises a compound represented by the following general formula (VI) (hereinafter referred to as a dicarboxylic acid monomer) and a compound containing an aromatic ring (hereinafter also referred to as an aromatic monomer). A step of reacting in a medium (hereinafter also referred to as a reaction step).

  In general formula (VI), Y represents an alicyclic ring containing a carbon atom that is bonded to an aromatic ring of a compound containing an aromatic ring to form a quaternary carbon atom. The details and preferred aspects of Y are the same as the details and preferred aspects of the quaternary carbon atom-containing alicyclic ring contained in the polymer of the embodiment described above.

  According to the said method, the polymer of this embodiment containing an aromatic ring and the alicyclic ring which has the quaternary carbon atom couple | bonded with the said aromatic ring is efficiently compoundable. That is, the dicarboxylic acid monomer represented by the general formula (VI) first becomes an acyl cation in an acidic medium. Thereafter, the carbonyl moiety is eliminated to become an alkyl cation. Thus, a polymer containing an aromatic ring and an alicyclic ring having a quaternary carbon atom bonded to the aromatic ring can be obtained by a condensation reaction with an aromatic monomer in a state of being an alkyl cation. .

  When an acyl cation generated from a dicarboxylic acid monomer is reacted with an aromatic monomer before becoming an alkyl cation in an acidic medium, a carbonyl group is formed. Therefore, a desired amount of carbonyl group can be introduced into the structure of the polymer by controlling the conditions for reacting the dicarboxylic acid monomer and the aromatic monomer in an acidic medium. By introducing a carbonyl group, the solubility of the polymer in the solvent tends to be improved.

  From the viewpoint of sufficiently controlling the conditions for reacting the dicarboxylic acid monomer and the aromatic monomer, the reaction step includes a step of preparing a mixture of the dicarboxylic acid monomer and the acidic medium, and a step of adding the aromatic monomer to the mixture. Are preferably provided in this order.

  The aromatic monomer to be reacted with the dicarboxylic acid monomer is not particularly limited, and can be selected according to the desired characteristics of the polymer. From the viewpoint of heat resistance, it is preferable to use an aromatic monomer containing two or more aromatic rings. Examples of the aromatic monomer containing two or more aromatic rings include a biphenyl monomer, a diphenyl ether monomer, a bisphenol monomer, a fluorene monomer, and the like.

  In one embodiment, the aromatic monomer is at least one selected from the group consisting of the following general formula (VII-1), the following general formula (VII-2), and the following general formula (VII-3).

In General Formula (VII-1), each R ¹ independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R ² independently represents a substituent. The C1-C30 hydrocarbon group which may have is shown. Each m independently represents an integer of 0 to 3.

Details of ^R 1, ^{R 2} and m in the general formula (VII-1), the same as in the general formula (II-1) of ^R 1, ^{R 2} and m in detail.

In General Formula (VII-2), each R ¹ independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R ² independently represents a substituent. A hydrocarbon group having 1 to 30 carbon atoms which may be present, and Z represents an oxygen atom or a divalent group represented by the following general formula (III). Each m independently represents an integer of 0 to 3.

In general formula (III), R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.

Details of R ¹ , R ² , Z and m in the general formula (VII-2) and details of R ³ and R ⁴ in the general formula (III) are as follows: R ¹ , R in the general formula (II-2) ² , Z and m, and the details of R ³ and R ⁴ in formula (III) are the same.

In General Formula (VII-3), each R ⁵ independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. n shows the integer of 0-4 each independently.

The general formula (VII-3) ^{R 5} and n details in, is the same as the general formula (II-3) ^{R 5} and n in detail.

  The dicarboxylic acid monomer represented by the general formula (VI) is represented by the following general formula (VIII-1) and the following general formula (VIII) from the viewpoint of making heat resistance, transparency, low water absorption, and solubility in a solvent side by side. -2) and a dicarboxylic acid monomer represented by at least one selected from the group consisting of the following general formula (VIII-3).

  The acidic medium used in the above method is not particularly limited. In this specification, the “acidic medium” means a medium containing an acidic substance (Bronsted acid or Lewis acid), and the acidic substance may be an organic acid or an inorganic acid. The acidic medium is preferably liquid under the reaction conditions. For example, an organic solvent solution of aluminum chloride, an organic solvent solution of trifluoroalkanesulfonic acid, polyphosphoric acid, a mixture of diphosphorus pentoxide and organic sulfonic acid, or the like can be used. From the viewpoint of reactivity and ease of handling, a mixture of diphosphorus pentoxide and an organic sulfonic acid is preferable. From the viewpoint of the transparency of the obtained polymer, it is preferable to use methanesulfonic acid as the organic sulfonic acid. An acidic medium may be used individually by 1 type, or may use 2 or more types together.

  When a mixture of diphosphorus pentoxide and organic sulfonic acid is used as the acidic medium, the mixing ratio of diphosphorus pentoxide and organic sulfonic acid is a mass ratio (diphosphorus pentoxide: organic from the viewpoint of control of the mixing ratio and reactivity. The sulfonic acid) is preferably 1: 5 to 1:20, more preferably 1: 5 to 1:10. As the ratio of diphosphorus pentoxide is larger, the reactivity between the dicarboxylic acid monomer and the aromatic monomer tends to be improved.

  The mixture of the dicarboxylic acid monomer and the acidic medium may be prepared with stirring. The stirring time is not particularly limited, and can be selected according to the type and amount of the dicarboxylic acid monomer and the amount when introducing a carbonyl group. For example, it may be 1 minute to 60 minutes. The stirring method is not particularly limited, and the stirring can be performed by a general method using a magnetic stirrer, a mechanical stirrer, or the like.

  The amount of the acidic medium used in the above method is not particularly limited as long as it can dissolve the aromatic monomer and the dicarboxylic acid monomer, and can be used in a range from a catalyst amount to a solvent amount. From the viewpoint of reactivity and ease of handling, the amount of the acidic medium is preferably in the range of 5 to 100 parts by mass with respect to 1 part by mass of the dicarboxylic acid monomer.

  The temperature at the time of reacting the aromatic monomer and the dicarboxylic acid monomer is preferably 10 ° C. to 100 ° C. from the viewpoint of suppressing coloring and side reaction of the polymer as the reaction product, and increases the reaction rate. From the viewpoint of improving productivity, the temperature is more preferably 20 ° C to 100 ° C.

  The atmosphere of the reaction in the condensation reaction between the aromatic monomer and the dicarboxylic acid monomer is not particularly limited, and may be a closed system or an open system. From the viewpoint of suppressing the decrease in the reactivity of the acidic medium due to the presence of moisture, an inert gas atmosphere such as dry air or nitrogen or argon is preferable. From the viewpoint of preventing an unexpected side reaction, an inert gas atmosphere such as nitrogen or argon is more preferable.

  When the dicarboxylic acid monomer and the aromatic monomer are reacted, the reaction may be promoted by stirring an acidic medium containing the dicarboxylic acid monomer and the aromatic monomer. The stirring method is not particularly limited, and the stirring can be performed by a general method using a magnetic stirrer, a mechanical stirrer, or the like.

  The time for reacting the aromatic monomer and the dicarboxylic acid monomer can be adjusted by the reaction temperature, the molecular weight of the target polymer, the kind of monomer used for the reaction, and the like. From the viewpoint of obtaining a polymer having a sufficiently high molecular weight, the reaction time is preferably about 1 hour to 120 hours, and more preferably 1 hour to 72 hours from the viewpoint of productivity.

  The pressure when the aromatic monomer and the dicarboxylic acid monomer are reacted is not particularly limited, and the reaction may be performed under normal pressure, increased pressure, or reduced pressure. From the viewpoint of cost, it is preferable to carry out the reaction under normal pressure.

  The method for taking out the polymer after reacting the aromatic monomer and the dicarboxylic acid monomer is not particularly limited. For example, a reaction solution (an acidic catalyst containing a reaction product) is contacted with a poor solvent of a polymer that is a reaction product to precipitate a polymer, and impurities are extracted into a poor solvent layer. It can be separated and removed from the reaction solution by methods such as filtration, decantation, and centrifugation. Further, after that, the separated polymer is dissolved again in the good solvent of the polymer, and again brought into contact with the poor solvent of the polymer to precipitate the polymer, the impurities are extracted into the poor solvent layer, and the precipitated polymer is filtered. The step of separating from the liquid by a method such as decantation or centrifugation may be repeated.

<Composition>
The polymer composition of the present embodiment includes the polymer of the present embodiment. The state of the composition is not particularly limited and can be selected according to the use of the composition. For example, varnish, slurry, mixed powder, etc. are mentioned. The composition of this embodiment may contain other components in addition to the polymer of this embodiment. Examples of other components include a solvent, an additive, and a crosslinking agent.

  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 alone or in combination of two or more.

  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 alone or in combination of two or more.

  Solvents include 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, ethylbenzene, pro Rubenzen, 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.

<Membrane and substrate with membrane>
The film of this embodiment includes the polymer of this embodiment. The film of this embodiment has heat resistance comparable to that of a polyimide film, and has a lower water absorption rate than the polyimide film. Therefore, the film of this embodiment is excellent in dimensional stability and reliability even when used in a high humidity environment.

The manufacturing method of the film | membrane of this embodiment is not specifically limited. For example, the film of the present embodiment is formed by applying the composition of the present embodiment containing a solvent to the surface of the substrate to form a composition layer, and drying it as necessary to remove the solvent from the composition layer. Can be manufactured. 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.

  If necessary, the dried polymer film of this embodiment may be further heat-treated. 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.

  The base material with a film according to the present embodiment includes the base material and the film according to the present embodiment provided on at least a part of the surface of the base material. The film-coated substrate of the present embodiment 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. For example, glass substrate, semiconductor substrate, metal oxide insulator substrate (for example, titanium oxide substrate and silicon oxide substrate), inorganic substrate such as silicon nitride substrate, triacetyl cellulose, polyimide, polycarbonate, acrylic resin, cycloolefin A resin substrate such as a resin can be exemplified. 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 embodiment each have the film or the substrate with the film of the present embodiment.

  The optical element and the image display device, for example, the substrate side of the substrate on which the film according to the present embodiment is formed, to 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 bonding to a member that is being used.

  The optical element of this embodiment 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 that of the conventional image display device except that the film of the present embodiment 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, copiers, mobile phones, watches, digital cameras, personal digital assistants (PDAs), portable devices such as portable game machines, home electric appliances such as video cameras, televisions, microwave ovens, etc. Equipment, back monitor, car navigation system monitor, in-car equipment such as car audio, display equipment such as information monitor for commercial stores, security equipment such as monitoring monitor, care equipment such as care monitor, medical monitor, etc. Medical equipment.

<Coating material>
The coating material of this embodiment contains the polymer of this embodiment. The object to be coated with the coating material is not particularly limited, and is an OA device such as a desktop personal computer, a notebook personal computer, a copy machine, a mobile phone, a digital camera, a personal digital assistant (PDA), a portable device such as a portable game machine, a video camera, TV, various displays, window glass, in-vehicle glass, camera lens, and the like. 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 embodiment includes the polymer of the present embodiment. 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.

  Various additives may be added to the molded product of the present embodiment as necessary to impart a desired function, improve characteristics, improve moldability, and the like. 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 (aluminic acid) Phosphors with a salt as a mother crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (titanium oxide particles, zinc oxide particles, etc.), crosslinking agents, curing agents, reaction acceleration Agents, infrared absorbers (heat ray absorbers), photochromic agents and the like.

  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 polymer "AD" containing aromatic ring and quaternary carbon atom-containing alicyclic 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 AD. When the molecular weight of AD was measured by the method described later, the weight average molecular weight was 52,000 and the number average molecular weight was 9,100. Further, the thermal decomposition temperature of AD was measured by the method described later. The results are shown in Table 1.

The fact that AD contains an aromatic ring and an alicyclic ring having a quaternary carbon atom bonded to the aromatic ring indicates that an aromatic quaternary carbon atom bonded by carbon-13 nuclear magnetic resonance spectroscopy ( ¹³ C-NMR). This was confirmed by the presence of a carbon peak on the ring at 142 ppm. Details are as follows.
・ Device name: AVANCE300 (Bruker)
・ Resonance frequency: 300 MHz (as proton nucleus)
・ Solvent: Deuterated chloroform

(Preparation of varnish)
AD was dissolved in N-methyl-2-pyrrolidone (NMP) to a concentration of 20% by mass and filtered through a polytetrafluoroethylene membrane filter (pore size: 5 μm) to obtain an AD varnish.

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

(Evaluation of water absorption)
An AD varnish was applied onto a polyimide film by a bar coating method and dried on a hot plate at 120 ° C. for 3 minutes, and then the polymer AD film was peeled off from the polyimide film to obtain an AD single film. The obtained single membrane was fixed on a plate made of polytetrafluoroethylene and dried in a nitrogen gas oven at 200 ° C. for 1 hour. Using this, the water absorption of AD was measured by the method described later. The results are shown in Table 1.

[Example 2]
(Synthesis of polymer "BO" containing aromatic ring and quaternary carbon atom-containing alicyclic ring)
BO was obtained in the same manner as in Example 1 except that 10 mmol of 1,4-bicyclo [2.2.2] octane dicarboxylic acid was used instead of 1,3-adamantane dicarboxylic acid. When the molecular weight of BO was measured by the method described later, the weight average molecular weight was 65,000 and the number average molecular weight was 10,000. Further, in the same manner as in Example 1, it was confirmed that BO contains an aromatic ring and an alicyclic ring having a quaternary carbon atom bonded to the aromatic ring, and the thermal decomposition temperature was measured. The results are shown in Table 1.

  A varnish was prepared in the same manner as in Example 1 using BO, and the transparency of the BO and the water absorption rate were evaluated. The results are shown in Table 1.

[Comparative Example 1]
(Synthesis of transparent polyimide "PI" precursor)
In a four-necked flask equipped with a stirrer and a nitrogen balloon, 49 g of N-methyl-2-pyrrolidone and 30 mmol of trans-1,4-cyclohexanediamine were added and dissolved by stirring. Thereafter, 30 mmol of 3,3,4,4-biphenyltetracarboxylic dianhydride was added. At this time, a white solid (acid and amine salt) was formed. Subsequently, the mixture was stirred in a hot water bath at 80 ° C. for 10 minutes to completely dissolve the produced salt. Thereafter, the mixture was stirred at room temperature for 70 hours to obtain a PI precursor (PI precursor) solution. When the molecular weight of the obtained PI precursor was measured by the method described later, the weight average molecular weight of the PI precursor was 53,000, and the number average molecular weight was 14,000. Further, the thermal decomposition temperature was measured in the same manner as in Example 1. The results are shown in Table 1.

(Preparation of varnish)
The PI precursor was dissolved in N-methyl-2-pyrrolidone (NMP) to a concentration of 20% by mass, filtered through a polytetrafluoroethylene membrane filter (pore size: 5 μm), and the PI precursor varnish. Got.

(Evaluation of transparency)
The PI precursor varnish was applied onto a glass substrate by spin coating, dried on a hot plate at 120 ° C. for 3 minutes, and further dried in a nitrogen gas oven at 300 ° C. for 1 hour to completely remove the PI precursor. A glass plate with a PI film was prepared by changing to PI. Using this, the transparency of PI was evaluated by the method described later. The results are shown in Table 1.

(Evaluation of water absorption)
The PI precursor varnish was applied onto a silicon substrate by a bar coating method, dried on a hot plate at 120 ° C. for 3 minutes, and then the PI precursor film was peeled off from the silicon substrate to obtain a single film of the PI precursor. It was. The obtained single membrane was fixed on a plate made of polytetrafluoroethylene and dried in a nitrogen gas oven at 300 ° C. for 1 hour to change the PI precursor into complete PI. Using this, the water absorption of PI was measured by the method described later. The results are shown in Table 1.

[Comparative Example 2]
(Synthesis of cycloolefin polymer “COP”)
In a four-necked flask equipped with a stirrer and a nitrogen balloon, 500 parts by mass of dehydrated cyclohexane, 0.55 parts by mass of 1-hexene, 0.30 parts by mass of diisopropyl ether, 0.20 parts by mass of triisobutylaluminum, Then, 0.075 parts by mass of isobutyl alcohol was added and mixed by stirring. Thereafter, while maintaining the temperature at 55 ° C., 250 parts by mass of 2-norbornene and 15 parts by mass of a 1.0 mass% toluene solution of tungsten hexachloride were continuously added over 2 hours to cause a polymerization reaction. The resulting reaction solution was filtered through a filter equipped with a stainless steel wire mesh using diatomaceous earth as a filter aid to remove the catalyst. Next, the reaction solution was poured into 3000 parts by mass of isopropyl alcohol, and the produced precipitate was collected by filtration. The solid collected by filtration was washed with acetone and then dried to obtain COP. When the molecular weight of the obtained COP was measured by the method described later, the weight average molecular weight was 62,000 and the number average molecular weight was 33,000. Further, the thermal decomposition temperature was measured in the same manner as in Example 1. The results are shown in Table 1.

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

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

(Evaluation of water absorption)
A COP varnish was applied on a polyimide film by a bar coating method and dried on a hot plate at 120 ° C. for 3 minutes, and then the COP film was peeled off from the polyimide film to obtain a COP single film. The obtained single membrane was fixed on a plate made of polytetrafluoroethylene and dried in a nitrogen gas oven at 300 ° C. for 1 hour. Using this, the water absorption of COP was measured by the method described later. The results are shown in Table 1.

(Measurement of molecular weight)
In Example 1, Example 2, and Comparative Example 2, the molecular weight was measured by GPC method using tetrahydrofuran (THF) as an eluent, and determined in terms of standard polystyrene. 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 use
・ Flow rate: 0.4ml / min

In Comparative Example 1, the molecular weight was measured by the GPC method using N-methyl-2-pyrrolidone (NMP) 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 use
・ Flow rate: 0.4ml / min

(Measurement of thermal decomposition temperature)
The polymer powders obtained in Example 1, Example 2, Comparative Example 1 and Comparative Example 2 were weighed into an aluminum pan and reduced in weight using a thermogravimetric balance (“TG-DTA6300”, Hitachi High-Tech Science Co., Ltd.). Was measured. The intersection of the tangents of the curves where the weight is greatly reduced by heating is defined as the pyrolysis temperature.

(Evaluation of transparency)
The transmittance of a polymer-coated glass substrate prepared in Example 1, Example 2, Comparative Example 1 and Comparative Example 2 at a wavelength of 400 nm was measured using an ultraviolet-visible spectrophotometer (“U-3310 Spectrophotometer”, Hitachi High-Tech, Ltd.). ) And UV-visible absorption spectrum method. 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)).

(Measurement of water absorption)
Samples for measuring water absorption were prepared by cutting the polymer single membranes prepared in Example 1, Example 2, Comparative Example 1 and Comparative Example 2. This was dried at 50 ° C. for 24 hours, and then cooled to room temperature (25 ° C.) in a desiccator. The mass of the sample cooled to room temperature was measured with a precision balance and then immersed in ion-exchanged water for 24 hours. Then, the moisture adhering to the surface of the sample was wiped off with a Kim towel, and the mass of the sample was measured with a precision balance. The water absorption was calculated based on the following equation, where W1 was the mass of the sample before being immersed in ion-exchanged water, and W2 was the mass of the sample after being immersed in ion-exchanged water.

  As shown in Table 1, the polymer of this embodiment had transparency and heat resistance equal to or higher than those of conventional transparent polyimides, and had a lower water absorption than transparent polyimides. Moreover, the water absorption rate of the polymer of this embodiment is equivalent to the cycloolefin polymer known as resin with a low water absorption rate, and its thermal decomposition temperature was higher than that of the cycloolefin polymer.

  As mentioned above, it turned out that the polymer of this embodiment is excellent in transparency, heat resistance, and low water absorption.

Claims (16)

  A polymer comprising an aromatic ring and an alicyclic ring having a quaternary carbon atom bonded to the aromatic ring. The polymer of Claim 1 containing the structural unit shown by the following general formula (I).

[In General Formula (I), X represents a divalent group containing an aromatic ring, and Y represents a divalent group containing an alicyclic ring having a quaternary carbon atom bonded to the aromatic ring. n represents the number of structural units represented by the general formula (I). ] In the general formula (I), Y represents a group represented by at least one selected from the group consisting of the following general formula (IV-1), the following general formula (IV-2), and the following general formula (IV-3). The polymer of Claim 2 containing.
  The polymer according to claim 2 or 3, wherein, in the general formula (I), X includes a divalent group including two or more aromatic rings. In the general formula (I), X is at least one divalent 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 polymer of any one of Claims 2-4 containing the group of these.

[In General Formula (II-1), each R ¹ independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R ² independently represents a substituent. The C1-C30 hydrocarbon group which may have is shown. Each m independently represents an integer of 0 to 3. ]

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

[In General Formula (III), R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. ]

[In General Formula (II-3), each R ⁵ independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. n shows the integer of 0-4 each independently. ]   The polymer according to any one of claims 1 to 5, further comprising a carbonyl group. The production of the polymer according to any one of claims 1 to 6, comprising a reaction step of reacting a compound represented by the following general formula (VI) with a compound containing an aromatic ring in an acidic medium. Method.

[In General Formula (VI), Y represents an alicyclic ring containing a carbon atom that is bonded to the aromatic ring of the compound containing the aromatic ring to form a quaternary carbon atom. ] The compound containing an aromatic ring contains at least one selected from the group consisting of the following general formula (VII-1), the following general formula (VII-2), and the following general formula (VII-3). A method for producing the polymer described in 1.

[In General Formula (VII-1), each R ¹ independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R ² independently represents a substituent. The C1-C30 hydrocarbon group which may have is shown. Each m independently represents an integer of 0 to 3. ]

[In General Formula (VII-2), each R ¹ independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R ² independently represents a substituent. Represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom, and Z represents an oxygen atom or a divalent group represented by the following general formula (III). Each m independently represents an integer of 0 to 3. ]

[In General Formula (III), R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. ]

[In General Formula (VII-3), each R ⁵ independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. n shows the integer of 0-4 each independently. ]   The reaction step includes, in this order, a step of preparing a mixture of the compound represented by the general formula (VI) and an acidic medium, and a step of adding the compound containing the aromatic ring to the mixture. The manufacturing method of the polymer of Claim 8.   The composition containing the polymer of any one of Claims 1-6.   The film | membrane containing the polymer of any one of Claims 1-6.   The base material with a film | membrane which has a base material and the film | membrane of Claim 11 provided in at least one part of the surface of the said base material.   An optical element having the film according to claim 11 or the film-coated substrate according to claim 12.   An image display device comprising the film according to claim 11 or the film-coated substrate according to claim 12.   The coating material containing the polymer of any one of Claims 1-6.   The molded object containing the polymer of any one of Claims 1-6.