JP2020193276A - Polymer which is polyarylene having alicyclic skeleton and fluorene skeleton in main chain, production method of polymer, composition, film, substrate with film, optical element, image display device, coating material and molded body - Google Patents

Abstract

To provide a polymer having excellent transparency, a high glass transition temperature and excellent weather resistance when formed into a molded article such as a film, a production method of 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.SOLUTION: A polymer has two types of a structural unit (X) and a structural unit (Y) different from each other. The structural unit (X) represents a divalent group expressed by general formula (II), and the structural unit (Y) represents a divalent group expressed by a crosslinked alicyclic structure including an adamantane skeleton or a norbornane skeleton. In general formula (II), R1 and R2 each independently represent a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and each p independently represents an integer of 0 to 3.SELECTED DRAWING: None

Description

The present invention relates to a polymer which is a polyarylene having an alicyclic skeleton and a fluorene 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 molding. Regarding the body.

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

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

The polymer described in Patent Document 3 is excellent in heat resistance and transparency, and has a high thermogravimetric reduction temperature of 400 ° C. or higher, but there is room for improvement in the glass transition temperature. Further, improvement in weather resistance when formed into a molded product such as a film is also desired.

The present invention has been made in view of the above circumstances, and is excellent in transparency, high glass transition temperature, and excellent weather resistance when formed into a molded product such as a film, a polymer production method, a composition, and a film. , A substrate with a film, an optical element, an image display device, a coating material, and a molded product.

Means for solving the above problems include the following embodiments.
<1> A polymer having a structural unit represented by the following general formula (I).

[In the general formula (I), X represents a divalent group represented by the following general formula (II), and Y represents the following general formula (III-1), the following general formula (III-2), and It represents a divalent group represented by at least one selected from the group consisting of the following general formula (III-3). Parentheses represent structural units. ]

[In the general formula (II), R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms which may independently have a substituent, and R ² each independently has a substituent. It represents a hydrocarbon group having 1 to 30 carbon atoms, and p represents an integer of 0 to 3 independently. The wavy line represents the binding site. ]

[In the general formulas (III-1), (III-2) and (III-3), the wavy line represents the binding site. ]
<2> Selected from the group consisting of the compound represented by the following general formula (IV), the following general formula (V-1), the following general formula (V-2), and the following general formula (V-3). The method for producing a polymer according to <1>, which comprises a reaction step of reacting with a compound represented by at least one kind in the presence of a catalyst.

[In the general formula (IV), R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms which may independently have a substituent, and R ² each independently has a substituent. It represents a hydrocarbon group having 1 to 30 carbon atoms, and p represents an integer of 0 to 3 independently. ]

[In the general formulas (V-1), (V-2) and (V-3), X independently represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. ]
<3> In <2>, the catalyst comprises at least one selected from the group consisting of copper (I) bromide, copper (II) bromide, hexacarbonyl molybdenum (0), and zinc chloride (II). The method for producing a polymer according to the above.
<4> A composition containing the polymer according to <1> and a solvent.
<5> A film containing the polymer according to <1>.
<6> A base material with a film having a base material and the film according to <5> provided on at least a part of the surface of the base material.
<7> An optical element having the film according to <5> or the substrate with a film according to <6>.
<8> An image display device having the film according to <5> or the substrate with a film according to <6>.
<9> A coating material containing the polymer according to <1>.
<10> A molded product containing the polymer according to <1>.

According to the present invention, a polymer having excellent transparency, a high glass transition temperature, and excellent weather resistance when formed into a molded product such as a film, a method for producing the polymer, a composition, a film, a substrate with a film, and optics. Elements, image display devices, coating materials and moldings 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 the numerical values and their ranges, and does not limit the present invention.
In the present disclosure, the term "process" includes not only a process independent of other processes but also the process if the purpose of the process is achieved even if it cannot be clearly distinguished from the other process. ..
The numerical range indicated by using "~" in the present disclosure includes the numerical values before and after "~" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, a plurality of types of substances corresponding to each component may be contained. When a plurality of substances corresponding to each component are present in the composition, the content rate or content of each component is the total content rate or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, a plurality of types of particles corresponding to each component may be contained. When a plurality of particles corresponding to each component are present in the composition, the particle size 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 "membrane" is used only in a part of the region in addition to the case where the layer or the membrane is formed in the entire region when the region in which the layer or the membrane exists is observed. The case where it is formed is also included.
In the present disclosure, the term "laminated" means stacking layers, and two or more layers may be bonded or two or more layers may be detachable.

In the present disclosure, "transparency" means a property that the transparency of visible light (transparency of visible light having a wavelength of at least 400 nm) is 80% or more (converted to a film thickness of 10 μm).
In the present disclosure, "heat resistance" means indicating a high thermal decomposition temperature of 400 ° C. or higher and a high glass transition temperature of 230 ° C. or higher.
In the present disclosure, "weather resistance" means a property that the decrease in transmittance at a wavelength of 400 nm is less than 5% when irradiated with ultraviolet rays of 365 nm at 50 J / cm ² .

<Polymer>
The polymer of the present disclosure has a structural unit represented by the following general formula (I).

In the general formula (I), X represents a divalent group represented by the following general formula (II), and Y represents the following general formula (III-1), the following general formula (III-2), and the following. Represents a divalent group represented by at least one selected from the group consisting of the general formula (III-3). Parentheses represent structural units.

In the general formula (II), R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms which may independently have a substituent, and R ² each independently has a substituent. It represents a hydrocarbon group having 1 to 30 carbon atoms which may be used. p represents an integer of 0 to 3 independently of each other. The wavy line represents the binding site, and the same applies thereafter.

According to the studies by the present inventors, it has been found that the polymer of the present disclosure has excellent transparency, a high glass transition temperature, and excellent weather resistance when formed into a molded product such as a film. The reason is not clear, but it can be thought of as follows. First, it is considered to have transparency by having an aromatic ring and a structure in which an alicyclic ring represented by the general formulas (III-1) to (III-3) is bonded to the aromatic ring. Further, it is considered that having a fluorene skeleton having a three-ring structure including an aromatic ring increases the glass transition temperature and has excellent weather resistance. In addition, by having an aromatic ring and a structure in which an alicyclic ring represented by the general formulas (III-1) to (III-3) is bonded to the aromatic ring, the thermogravimetric reduction temperature (pyrolysis temperature) can be set. The effect of becoming higher is also achieved.

From the viewpoint of reaction control, R ¹ in the general formula (II) is preferably a hydrocarbon group having 1 to 20 carbon atoms, which may independently have a substituent. 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 hydrocarbon group represented by R ¹ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination of these hydrocarbon groups. Examples of the aliphatic hydrocarbon group include a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, and a combination of these aliphatic hydrocarbon groups.
From the viewpoint of weather resistance, the hydrocarbon group represented by R ¹ is preferably an aliphatic hydrocarbon or an aromatic hydrocarbon group, more preferably contains an aromatic hydrocarbon.

Examples of the aromatic hydrocarbon group represented by R ¹ include a phenyl group, a naphthyl group, a fluorenyl group and the like, and a phenyl group is preferable from the viewpoint of heat resistance.

When the aromatic hydrocarbon group represented by R ¹ has a substituent, the substituents include a halogen atom, a hydroxy group, an epoxy group, an oxetanyl group, an alkyl group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. Examples thereof include an alkoxy group, a hydroxyalkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. Among these, the substituent of the aromatic hydrocarbon group is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and an alkyl group having 1 to 3 carbon atoms or 1 carbon group. It is more preferably an alkoxy group of ~ 3, particularly preferably a methyl group, an ethyl group, a methoxy group or an ethoxy group, and extremely preferably a methyl group or a methoxy group.

Saturated aliphatic hydrocarbon groups 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. Group, isopentyl group, sec-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-icosanyl group, Examples thereof include an n-triacontanyl group.

The alicyclic hydrocarbon groups represented by R ^1, from the viewpoint of achieving both solubility heat resistance and solvent is preferably an n- propyl group.

When the saturated aliphatic hydrocarbon group represented by R ¹ has a substituent, the substituents include a halogen atom, a hydroxy group, an epoxy group, an oxetanyl group, an alkoxy group having 1 to 5 carbon atoms, and 2 to 5 carbon atoms. Examples thereof include the acyl group of.

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.

When the unsaturated aliphatic hydrocarbon group represented by R ¹ has a substituent, the substituent includes a halogen atom, a hydroxy group, an epoxy group, an oxetanyl group, an alkoxy group having 1 to 5 carbon atoms, and 2 to 2 carbon atoms. Examples thereof include an acyl group of 5.

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

When the alicyclic hydrocarbon group represented by R ¹ has a substituent, the substituent includes a halogen atom, a hydroxy group, an epoxy group, an oxetanyl group, an alkyl group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. Examples thereof include an alkoxy group of 2 to 5 and an acyl group having 2 to 5 carbon atoms.

Among these, the hydrocarbon group represented by R ¹ is a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, 2 , 5-Dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 2,3,5-trimethylphenyl group , 2,3,6-trimethylphenyl group, 2,4,5-trimethylphenyl group, methyl group, ethyl group, or n-propyl group, preferably from the viewpoint of achieving both heat resistance and solubility in a solvent. Therefore, it is more preferably a phenyl group, a p-tolyl group, or an n-propyl group.

From the viewpoint of reaction control, it is preferable that R ² in the general formula (II) is a hydrocarbon group having 1 to 20 carbon atoms, which may independently have a substituent. Examples of R ² include saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and combinations of these hydrocarbon groups. Examples of the substituent in the case where the hydrocarbon group represented by R ² has a substituent, a halogen atom, hydroxy group, an epoxy group, an oxetanyl group, an alkoxy group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms And so on. When the hydrocarbon group represented by R ² has a substituent, the carbon number of the hydrocarbon group does not include the carbon number of the substituent.

The saturated aliphatic hydrocarbon group represented by R ^2, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, t- butyl group, n- pentyl Group, isopentyl group, sec-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-icosanyl group, Examples thereof include an n-triacontanyl group.

Examples of the unsaturated aliphatic hydrocarbon group represented by R ² 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 ² include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group and an adamantyl group, and a cyclohexenyl group. Cycloalkenyl groups and the like can be mentioned.

In the general formula (II), p is preferably an integer of 0 to 2, and more preferably 0 from the viewpoint of heat resistance and weather resistance.

Y in the general formula (I) is represented by 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) 2 Represents the basis of valence.

The polymer having the structural unit represented by the general formula (I) may contain one divalent group represented by the general formula (II) alone, or two or more in combination. You may. Further, the polymer having a structural unit represented by the general formula (I) has a divalent group represented by the general formula (III-1), (III-2), or the general formula (III-3). One type may be contained alone, or two or more types may be contained in combination.

<Method for producing a polymer having a structural unit represented by the general formula (I)>
The method for producing a polymer having a structural unit represented by the general formula (I) is not particularly limited, and for example, a compound represented by the general formula (IV) and a general formula (V-1), general. It may be produced by a method including a reaction step of reacting a compound represented by at least one selected from the group consisting of the formula (V-2) and the general formula (V-3) in the presence of a catalyst. ..

In the general formula (IV), R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms which may independently have a substituent, and R ² each independently has a substituent. It represents a hydrocarbon group having 1 to 30 carbon atoms, and p represents an integer of 0 to 3 independently.

In the general formula ^{(IV), R 1, R} 2, and details of p, is the same as the detailed general formula in ^{(II) R 1, R 2} , and p of.

In the general formulas (V-1), (V-2) and (V-3), X independently represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. From the viewpoint of polymerization reactivity, X is preferably a chlorine atom or a bromine atom.

The catalyst used in producing the polymer having the structural unit represented by the general formula (I) is not particularly limited, and is usually used for, for example, Friedel-Crafts alkylation reaction and Friedel-Crafts acylation reaction. , Aluminum chloride (III), Iron (III) Chloride, Lewis Acids such as Trifluoromethanesulfonyl Samalium (III), Copper Bromide (I), Copper Bromide (II), Hexacarbonyl Molybdenum (0), Zinc Chloride (II) ) Etc. may be used. Other known catalysts used in polymer production methods may be used.

Copper bromide (I), copper bromide (II), hexacarbonyl molybdenum (0), and zinc chloride are used as catalysts for producing a polymer having a structural unit represented by the general formula (I). It is preferable to use at least one selected from the group consisting of (II).
The use of the above catalysts tends to facilitate control of the Friedel-Crafts alkylation reaction. From this point of view, it is more preferable to use at least one selected from the group consisting of copper (I) bromide and zinc (II) chloride.

The amount of the catalyst used is preferably adjusted as appropriate. For example, when at least one selected from the group consisting of copper (I) bromide and zinc (II) chloride is used as the catalyst, the general formula (IV) is used. For 1 mol of the total amount of the represented compound and the compound represented by at least one selected from the group consisting of the general formula (V-1), the general formula (V-2), and the general formula (V-3). Therefore, the catalyst may be used in an amount of about 0.05 mol to 0.5 mol.

Examples of the solvent used for producing the polymer having the structural unit represented by the general formula (I) include o-dichlorobenzene, o-bromotoluene, mesitylene, nitrobenzene, N-methyl-2-pyrrolidone, N, It is preferable to use N-dimethylacetamide, sulfolane or the like.
When the above solvent is used, the compound represented by the general formula (IV), the compound represented by the general formula (V-1), the compound represented by the general formula (V-2), and the general formula (V-3) are used. ), And the polymer having the structural unit represented by the general formula (I) are easily dissolved or dispersed, and the reaction tends to be easily controlled.
Further, from the viewpoint that the molecular weight of the obtained polymer is increased and the thermal decomposition temperature and the glass transition temperature are increased, it is more preferable to use mesitylene as the solvent. In addition, since mesitylene is a non-halogen solvent, it is also excellent in that it can suppress the influence on the environment. On the other hand, from the viewpoint of excellent solubility of the polymer having the structural unit represented by the general formula (I), it is more preferable to use bromotoluene as the solvent.
The amount of the solvent used is preferably adjusted as appropriate. The amount of the solvent used is specifically a group consisting of the compound represented by the general formula (IV), the general formula (V-1), the general formula (V-2), and the general formula (V-3). The solvent can be in the range of 0.1 L to 10 L per 1 mol of the total amount of the compound represented by at least one selected from the above.

The reaction temperature at the time of producing the polymer having the structural unit represented by the general formula (I) can be appropriately adjusted according to the desired molecular weight, and can be, for example, 100 ° C to 200 ° C.

The reaction time for producing the polymer having the structural unit represented by the general formula (I) can be appropriately adjusted according to the desired molecular weight, and can be, for example, 1 hour to 50 hours.

The molecular weight of the polymer is not particularly limited and can be selected according to the intended use. From the viewpoint of heat resistance, the weight average molecular weight (Mw) of the polymer is preferably 3,000 or more, more preferably 10,000 or more, and further preferably 20,000 or more. It is particularly preferably 30,000 or more. The number average molecular weight (Mn) is preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 3,000 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 300,000 or less. The number average molecular weight (Mn) is preferably 200,000 or less, and more preferably 100,000 or less.

The molecular weight (Mw and Mn) of the polymer is a value obtained by measuring by the GPC method using tetrahydrofuran (THF) as an eluent and converting to standard polystyrene.
-Device name: Ecosec HLC-8320GPC (Tosoh Corporation)
-Column: TSKgel Supermultipore HZ-M (Tosoh Corporation)
・ Detector: UV detector and RI detector combined ・ Flow velocity: 0.35 ml / min

<Composition>
The composition of the polymer 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 the like, and examples thereof include varnish and slurry. The compositions of the present disclosure may contain other components in addition to the polymers of the present disclosure. Examples of other components include additives, cross-linking agents and the like.

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, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethylketone, diisobutylketone, methylamylketone, cyclohexanone, propylene glycol monomethyl ether , Propropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, xylene, mecitylene, ethylbenzene, propylbenzene, cumene, diisopropylbenzene, hexylbenzene, anisole, diglime, dimethyl sulfoxide, chloroform, dichloromethane, dichloroethane, chlorobenzene, etc. Can be mentioned. One of these solvents may be used alone, or two or more of these solvents may be used in combination.

Examples of the additive include an adhesive aid, a surfactant, a leveling agent, an antioxidant, an ultraviolet deterioration inhibitor and the like. These additives may be used alone or in combination of two or more.

Examples of the cross-linking agent include a polyfunctional epoxy compound, a polyfunctional acrylic compound, a polyfunctional oxetane compound, a compound having a plurality of hydroxy groups, a compound having a plurality of hydroxymethyl groups, a compound having a plurality of alkoxymethyl groups, and the like. These cross-linking agents may be used alone or in combination of two or more.

<Membrane>
The membranes of the present disclosure include the polymers of the present disclosure. The film of the present disclosure has a glass transition temperature comparable to that of a polyimide film, and has a lower water absorption rate than that of a polyimide film. It also has excellent weather resistance. Therefore, the film of the present disclosure is excellent in dimensional stability, reliability, etc. even when used in a high humidity environment.

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

The dried polymer membrane of the present disclosure may be further heat-treated, if necessary. The heat treatment method is not particularly limited, and is a box-type dryer, hot-air conveyor-type dryer, quartz tube furnace, hot plate, rapid thermal annealing, vertical diffusion furnace, infrared curing furnace, electron beam curing furnace, microwave curing furnace. It can be carried out using an oven such as. Further, as the atmospheric condition in the heat treatment step, either the air or an inert atmosphere such as nitrogen can be selected.

<Base material with film>
The base material with a film of the present disclosure includes a base material and a film of the present disclosure provided on at least a part of the surface of the base material. The substrate with a film of the present disclosure may have a film on one surface of the substrate or may have a film on both sides. Further, the film formed on the base material may be one layer or a multi-layer structure in which two or more layers are laminated.

The type of base material is not particularly limited. Examples of the substrate 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, and acrylic resins. , A resin substrate such as a cycloolefin resin can be exemplified. The substrate may or may not be transparent. The shape of the base material 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 have the film or the substrate with a film of the present disclosure, respectively.

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 it to a member.

The optical element of the present disclosure can be preferably used as a polarizing plate or the like in various image display devices such as a liquid crystal display device. The image display device may have the same configuration as the conventional image display device except that the 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 a lighting 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 TN type, STN type, π type and the like can be used.

The use of the image display device is not particularly limited. For example, OA devices such as desktop PCs, laptop computers, and copy machines; mobile devices such as mobile phones, clocks, digital cameras, mobile information terminals (PDAs), and portable game machines; household electricity such as video cameras, televisions, and microwave ovens. Equipment; In-vehicle equipment such as back monitors, car navigation system monitors, car audios; Exhibition equipment such as information monitors for commercial stores; Security equipment such as monitoring monitors; Nursing equipment such as nursing care monitors; Medical monitors, etc. Medical equipment and the like.

<Coating material>
The coating materials of the present disclosure include the polymers of the present disclosure. The object covered with the covering material is not particularly limited, and examples thereof include the above-mentioned 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, and for example, the coating may be formed by adhering the film-like coating material to the object to be coated by a method such as laminating, or coating the liquid coating material. It may be applied to the subject and then dried to form a coating.

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

The molded article of the present disclosure may further contain various additives in order to impart desired functions, improve properties, improve moldability, and the like, if necessary. As additives, sliding agents (for example, polytetrafluoroethylene particles), light diffusers (acrylic crosslinked particles, silicone crosslinked particles, ultrathin glass flakes, calcium carbonate particles, etc.), fluorescent dyes, inorganic phosphors (alumin). Phosphores with acid salts as mother crystals, etc.), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (titanium oxide particles, zinc oxide particles, etc.), cross-linking agents, curing agents, reactions Examples include accelerators, infrared absorbers (heat ray absorbers), and photochromic agents.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

[Example 1]
(Synthesis of polyarylene "FL (Pr)" having an alicyclic skeleton and a fluorene 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 9,9-dipropylfluorene, 0.2 mmol of zinc (II) chloride, and 1 ml of mesitylene were placed. In addition, the mixture was stirred at 150 ° C. for 24 hours to obtain a reaction solution. The reaction solution was poured into 50 ml of methanol, and the formed precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain FL (Pr) (isolation yield 90% by mass).
When the molecular weight of FL (Pr) was measured by the method described later, the weight average molecular weight was 54,000, and the number average molecular weight was 9,300.

The molecular weight of FL (Pr) was measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent, and was determined in terms of standard polystyrene. The details are as follows.
-Device name: Ecosec HLC-8320GPC (Tosoh Corporation)
-Column: TSKgel Supermultipore HZ-M (Tosoh Corporation)
・ Detector: UV detector and RI detector combined ・ Flow velocity: 0.35 ml / min

(Preparation of varnish)
FL (Pr) was dissolved in mesitylene so as to have a concentration of 20% by mass, and filtered through a membrane filter (pore size: 5 μm) made of polytetrafluoroethylene to obtain a FL (Pr) varnish.

(Preparation of substrate with film)
The FL (Pr) varnish is applied onto a glass substrate by a spin coating method, 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 obtain FL (Pr). A glass plate with a film was produced. Using this, the transparency and weather resistance of FL (Pr) were evaluated by the method described later. The results are shown in Table 1.

(Evaluation of transparency)
The transmittance of a glass plate with an FL (Pr) film at a wavelength of 400 nm was measured by an ultraviolet-visible absorption spectrum method using an ultraviolet-visible near-infrared spectrophotometer (“V-570”, JASCO Corporation). Using a glass substrate without a film as a reference, the value converted to a film thickness of 10 μm was defined as the transmittance (%). The film thickness was taken as a number average value of values measured at three points using a stylus type step meter (“Dectak3 ST”, ULVAC, Inc. (Veco)).

(Measurement of pyrolysis temperature)
The FL (Pr) powder was weighed in an aluminum pan, and the weight loss was measured using a thermogravimetric balance (“TG-DTA6300”, Hitachi High-Tech Science Corporation). The intersection of the tangents of a curve whose weight is greatly reduced by heating is defined as the pyrolysis temperature. The results are shown in Table 1.

(Measurement of glass transition temperature)
FL (Pr) powder is weighed in an aluminum pan, and the temperature at which the baseline changes (secondary transition) is defined as the glass transition temperature using a differential scanning calorimeter (DSC) (“DSC8500”, PerkinElmer). To do. The results are shown in Table 1.

(Evaluation of weather resistance)
The glass plate with FL (Pr) film was put into an exposure apparatus (“Eye Grantage 3KW standard conveyor type exposure apparatus”, using Eye Graphics Co., Ltd., metal halide lamp) and irradiated with ultraviolet rays of 365 nm at 50 J / cm ² . Before and after irradiation, the transmittance of the glass plate with FL (Pr) film at a wavelength of 400 nm was measured, the rate of decrease in transmittance after irradiation was calculated by the following formula, and the weather resistance was evaluated according to the following criteria. The results are shown in Table 1.
Decrease rate of transmittance after irradiation (%) = (transmittance before irradiation-transmittance after irradiation) / transmittance before irradiation x 100
~Evaluation criteria~
A: Less than 5% B: 5% or more and less than 10% C: 10% or more

[Example 2]
(Synthesis of polyarylene "FL (Ph) 1" having an alicyclic skeleton and a fluorene 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 9,9-diphenylfluorene, 0.2 mmol of zinc (II) chloride, and 1 ml of o-bromotoluene were added. , And stirred at 150 ° C. for 24 hours to obtain a reaction solution. The reaction solution was poured into 50 ml of methanol, and the formed precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain FL (Ph) 1.
When the molecular weight was measured by the same method as in Example 1, the weight average molecular weight of FL (Ph) 1 was 69,000, and the number average molecular weight was 5,900. Table 1 shows the evaluation results of the transparency, thermal decomposition temperature, glass transition temperature, and weather resistance of FL (Ph) 1.

[Example 3]
(Synthesis of polyarylene "FL (Ph) 2" having an alicyclic skeleton and a fluorene skeleton in the main chain)
To a flask equipped with a magnetic stir bar and a nitrogen balloon, 0.5 mmol of 1,3-dibromoadamantane, 0.5 mmol of 9,9-diphenylfluorene, 0.2 mmol of zinc (II) chloride, and 1 ml of mesitylene were added. , 150 ° C. for 18 hours to obtain a reaction solution. The reaction solution was poured into 50 ml of methanol, and the formed precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain FL (Ph) 2.
When the molecular weight was measured by the same method as in Example 1, the weight average molecular weight of FL (Ph) 2 was 100,000, and the number average molecular weight was 8,000. Table 1 shows the evaluation results of the transparency, thermal decomposition temperature, glass transition temperature, and weather resistance of FL (Ph) 2.

[Example 4]
(Synthesis of polyarylene "FL (Tol) 1" having an alicyclic skeleton and a fluorene 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 9,9-di (p-tolyl) fluorene, 0.2 mmol of zinc (II) chloride, and o -Bromotoluene (1 ml) was added, and the mixture was stirred at 150 ° C. for 24 hours to obtain a reaction solution. The reaction solution was poured into 50 ml of methanol, and the formed precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain FL (Tol) 1.
When the molecular weight was measured by the same method as in Example 1, the weight average molecular weight of FL (Tol) 1 was 50,000, and the number average molecular weight was 7,800. Table 1 shows the evaluation results of the transparency, thermal decomposition temperature, glass transition temperature, and weather resistance of FL (Tol) 1.

[Example 5]
(Synthesis of polyarylene "FL (Tol) 2" having an alicyclic skeleton and a fluorene 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 9,9-di (p-tolyl) fluorene, 0.2 mmol of zinc (II) chloride, and mesitylene. 1 ml and the like were added, and the mixture was stirred at 150 ° C. for 18 hours to obtain a reaction solution. The reaction solution was poured into 50 ml of methanol, and the formed precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain FL (Tol) 2.
When the molecular weight was measured by the same method as in Example 1, the weight average molecular weight of FL (Tol) 2 was 79,000, and the number average molecular weight was 9,000. Table 1 shows the evaluation results of the transparency, thermal decomposition temperature, glass transition temperature, and weather resistance of FL (Tol) 2.

[Comparative Example 1]
(Synthesis of polymethylmethacrylate "PMMA")
Methyl methacrylate (100 parts by mass), water (58 parts by mass), and isopropyl alcohol (185 parts by mass) were weighed and mixed in a 100 ml three-necked flask equipped with a magnetic stir bar, a thermometer, and a cooler. Nitrogen was bubbled for 30 minutes at room temperature (25 ° C.) to remove dissolved oxygen. Then, the temperature was raised to 60 ° C., and nitrogen was bubbled for another 30 minutes to obtain a reaction solution. Azobisisobutyronitrile (4 parts by mass) was added to the reaction mixture, and the mixture was reacted at 60 ° C. for 9 hours. The solution after the reaction was recovered as it was and used as a PMMA varnish.
When the molecular weight was measured by the same method as in Example 1, the weight average molecular weight of PMMA was 64,000, and the number average molecular weight was 25,900.

(Preparation of substrate with film)
The PMMA varnish is applied onto a glass substrate by a spin coating method, 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 prepare a glass plate with a PMMA film. did. Using this, the transparency and weather resistance of PMMA were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2]
(Synthesis of polyarylene "BP" having an alicyclic skeleton in the main chain and a hydroxyl group on the aromatic ring)
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, and N-methyl- 1 ml of 2-pyrrolidone (NMP) was added, and the mixture was stirred at 150 ° C. for 48 hours to obtain a reaction solution. The reaction solution was poured into 50 ml of methanol, and the formed precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain BP (isolation yield 93% by mass).
When the molecular weight was measured by the same method as in Example 1, the weight average molecular weight of BP was 27,400, and the number average molecular weight was 3,300. Moreover, when the methylation rate of BP was measured by the method described later, it was 38%. When BP was not methylated, the site was a hydroxyl group. Table 1 shows the evaluation results of BP transparency, thermal decomposition temperature, glass transition temperature, and weather resistance.

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

From Table 1, the polymers of the present disclosure, polyarylenes having an alicyclic skeleton and a fluorene skeleton in the main chain (FL (Pr), FL (Ph) 1, FL (Ph) 2, FL (Tol) 1, And FL (Tol) 2) show a high transmittance of 90% or more, a high thermal decomposition temperature of 400 ° C. or higher, a high glass transition temperature of 230 ° C. or higher, and the weather resistance of the film obtained from the polymer. Was expensive.
On the other hand, the transparent resin polymethylmethacrylate (PMMA) shown in Comparative Example 1 had high transmittance but low weather resistance.
Further, the polyarylene (BP) having an alicyclic skeleton in the main chain and a hydroxyl group on the aromatic ring shown in Comparative Example 2 had high transmittance, thermal decomposition temperature and glass transition temperature. However, the weather resistance of BP was inferior to that of the polymer of the present disclosure, polyarylene having an alicyclic skeleton and a fluorene skeleton in the main chain.

Claims (10)

A polymer having a structural unit represented by the following general formula (I).

[In the general formula (I), X represents a divalent group represented by the following general formula (II), and Y represents the following general formula (III-1), the following general formula (III-2), and It represents a divalent group represented by at least one selected from the group consisting of the following general formula (III-3). Parentheses represent structural units. ]

[In the general formula (II), R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms which may independently have a substituent, and R ² each independently has a substituent. It represents a hydrocarbon group having 1 to 30 carbon atoms which may be present, and p independently represents an integer of 0 to 3. The wavy line represents the binding site. ]

[In the general formulas (III-1), (III-2) and (III-3), the wavy line represents the binding site. ] At least one selected from the group consisting of the compound represented by the following general formula (IV), the following general formula (V-1), the following general formula (V-2), and the following general formula (V-3). The method for producing a polymer according to claim 1, which comprises a reaction step of reacting the represented compound with the compound in the presence of a catalyst.

[In the general formula (IV), R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms which may independently have a substituent, and R ² each independently has a substituent. It represents a hydrocarbon group having 1 to 30 carbon atoms which may be present, and p independently represents an integer of 0 to 3. ]

[In the general formulas (V-1), (V-2) and (V-3), X independently represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. ] The weight according to claim 2, wherein the catalyst comprises at least one selected from the group consisting of copper (I) bromide, copper (II) bromide, hexacarbonyl molybdenum (0), and zinc chloride (II). Manufacturing method of coalescence. A composition containing the polymer according to claim 1 and a solvent. A film containing the polymer according to claim 1. A base material with a film having a base material and the film according to claim 5 provided on at least a part of the surface of the base material. An optical element having the film according to claim 5 or the substrate with a film according to claim 6. An image display device having the film according to claim 5 or the substrate with a film according to claim 6. A coating material containing the polymer according to claim 1. A molded product containing the polymer according to claim 1.