JPH0953002A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having excellent heat resistance and good compatibility and dispersibility with a photochromic material, an electrochromic material or an electroluminescent material and giving an element having excellent humidity resistance. SOLUTION: This thermoplastic resin composition comprises a thermoplastic norbornene resin (a) and at least one member (b) selected from among a photochromic material, an electrochromic material and an electroluminescent material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition provided with a photochromic function, an electrochromic function, or an electroluminescence function, which is particularly excellent in heat resistance and is a PC material, an EC material, or an EL material. The present invention relates to a thermoplastic resin composition having good compatibility and dispersibility with materials, excellent moisture resistance, and giving a clear image.

[0002]

2. Description of the Related Art Photochromic (PC) materials that develop color when irradiated with ultraviolet rays are used for light control applications such as sunglasses and light control glass, optical recording applications, and display element applications. In addition, a light control glass and a display element made of an electrochromic (EC) material whose color changes with the flow of current are also known. Furthermore, electroluminescence (EL) that emits light when an electric field is applied
The material is used for various lighting applications and display applications. When used for the above-mentioned applications, the above-mentioned PC material, EC material or EL material comprising an inorganic compound or an organic compound is formed into a thin film on the surface of various molded products by a method such as vacuum deposition or sputtering, or the above-mentioned material is a binder such as a resin. A method of forming a light emitting layer or a color forming layer by dispersing it inside and applying it on the surface of a molded article is used. As an example of such a binder, as a binder for a PC material, polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, phenolic resin, polyester resin, which are disclosed in JP-A-4-13128 and JP-A-4-63871, Resins such as polyamide-based resins, epoxy-based resins, polyurethane-based resins, vinyl acetate resins, and cellulose derivatives are known, and as binders for EC materials, ABS resins and poly-based resins disclosed in JP-A-2-153989 and the like. -Vinyl acetate polybutadiene, polyacrylamide, polyethylene, polystyrene, polypropylene, polycarbonate, polymethyl methacrylate, polyvinyl butyral, fluororesin,
Thermoplastic resin such as polyacetal, polyamide, polyester, polyacrylate, polyetherimide, polysulfone, polyphenylene sulfide, phenol resin, unsaturated polyester resin, polyurethane resin, vinyl ester resin, polyimide resin, epoxy resin and other thermosetting resin, Natural polymer derivatives such as cellulose acetate are known, and as binders for EL materials, cyanoethylated compounds disclosed in JP-A-6-349580 and acrylic resins disclosed in JP-A-6-267657. Resins, urethane resins, silicone resins, epoxy resins, phenol resins and other crosslinkable resins, polystyrene, polycarbonate, polyarylate disclosed in JP-A-7-3256 and the like.
Thermoplastic resins such as polyester, polyamide, and polymethyl (meth) acrylate are known. However, when these resins are used as a binder, it is not always possible to obtain an element with stable quality. For example, crosslinking with heat or curing agent such as epoxy resin or phenol resin
Since a crosslinkable resin and a thermosetting resin that cure are indispensable for the work of cross-linking and curing after being applied to the surface of a molded article, productivity is poor, and it is difficult to obtain a uniform coating film. Also, cyanoethylated products, polyvinyl butyral,
Resins such as polyvinyl alcohol, polyamide resins, and cellulose derivatives have a high water absorption rate, and there is a problem that the display performance is deteriorated due to the permeation of water into the element while the display element made of these resins is used for a long time. Further, a resin having almost zero water absorption such as a fluororesin and polyurethane has a poor dispersibility with a PC material, an EC material, and an EL material, so that it is difficult to obtain a uniform coating film. Since the film adhesion is poor, there is a problem that water enters between the electrodes and the display performance deteriorates. Further, many resins conventionally known as binder resins have insufficient transparency, and a coloring layer or a light emitting layer using such a resin as a binder has a problem of poor contrast and unclear display. Among known resins, polymethylmethacrylate and polycarbonate are resins that are widely used for various optical applications because of their excellent transparency.
Since polymethylmethacrylate has a low heat distortion temperature, it cannot be used in applications requiring heat resistance of 100 ° C. or higher, such as in-vehicle applications, so that the applications are extremely limited. Further, polycarbonate is inferior in dispersibility with the above-mentioned color-forming / light-emitting material, it is difficult to obtain a uniform coating film, and there is a problem that the surface hardness is low and the coating film is easily damaged. Under these circumstances, PC materials, which have excellent transparency and heat resistance,
There has been a demand for a binder which has good dispersibility with EC materials or EL materials and is also excellent in moisture resistance, and which gives a clear image especially when used in display devices.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a thermoplastic resin composition which is excellent in heat resistance, has good dispersibility in PC materials, EC materials, EL materials and the like, and gives an element excellent in moisture resistance. The purpose is to do.

The thermoplastic resin composition of the present invention comprises (a) a thermoplastic norbornene resin and (b)
It comprises at least one of a photochromic material, an electrochromic material, and an electroluminescent material. Further, there is also provided a thermoplastic resin composition characterized in that (a) the thermoplastic norbornene-based resin contains a polar substituent in its norbornane skeleton. The (a) thermoplastic norbornene-based resin used in the thermoplastic resin composition of the present invention has a norbornane skeleton in its repeating unit. For example,
This thermoplastic resin contains a norbornane skeleton represented by the general formulas (I) to (IV).

[0004]

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[0005]

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[0006]

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[0007]

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(In the formula, A, B, C and D represent a hydrogen atom or a monovalent organic group.) The thermoplastic resin having a norbornane skeleton used in the present invention has sufficient strength. And its weight average molecular weight is 5,000 to 1,000,000, preferably 8,000 to 20.
In many cases. Examples of the thermoplastic resin having a norbornane skeleton that can be used in the present invention include, for example, JP-A-60-168708 and JP-A-62-25240.
6, JP-A-62-252407, JP-A-2
-133413, JP-A-63-145324, JP-A-63-264626, JP-A 1-24
Examples thereof include resins described in Japanese Patent No. 0517, Japanese Patent Publication No. 57-8815, and the like. In the present invention, in the above general formulas (I) to (IV), it is preferable that A, B, C and D contain a polar group.
It is preferable in terms of compatibility with materials, EL materials and other additives, coatability, adhesion with other laminates, and heat resistance. Those that do not contain polar groups at all have excellent moisture resistance, but their compatibility with PC materials, EC materials, EL materials and other additives is limited, and bleeding on the surface may occur if a large amount of the above materials is added. A molded product of high quality such as color unevenness cannot be obtained, and when it is used as a paint, the coating property is poor, and it is difficult to obtain a thin film having a uniform thickness, so that the application may be limited. However, if the number of polar groups contained per repeating unit represented by the above general formula is too large, the water absorbency becomes too large, and a molded article obtained from a resin composition containing such a resin as a binder will show a lapse of time. Performance is likely to deteriorate due to absorption of ambient moisture, and productivity is poor due to the need to newly provide a moisture-proof layer. Therefore, in order to balance water absorbency with coatability, adhesiveness, and heat resistance, the saturated water absorption of the thermoplastic resin composition of the present invention is 0.05 to 1.0% by weight, preferably 0.
It is preferable to select the type and number of polar groups and other substituents so as to be in the range of 1 to 0.5% by weight. Specific examples of the thermoplastic resin include metathesis polymerization of at least one tetracyclododecene derivative represented by the following general formula (V) or an unsaturated cyclic compound copolymerizable with the tetracyclododecene. A hydrogenated polymer obtained by hydrogenating the obtained polymer can be exemplified.

[0009]

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(In the formulas, A to D are the same as above.) When the tetracyclododecene derivative represented by the general formula (V) has a polar group, the polar group is-(CH ₂ ) _n.
It is a group represented by COOR ³ (wherein R ³ is a hydrocarbon group having 1 to 20 carbon atoms, n is an integer of 0 to 10), and the hydrogenated polymer obtained has a high glass transition temperature. It is preferable that it has In particular, this-(CH ₂ ) _n
It is preferable that one polar substituent represented by COOR ³ is contained per molecule of the tetracyclododecene derivative represented by the general formula (V). In the above-mentioned general formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, but it is preferable that the hydrogen absorption of the obtained hydrogenated polymer becomes smaller as the number of carbons increases, but From the viewpoint of balance with the glass transition temperature, a chain alkyl group having 1 to 4 carbon atoms or a (poly) cyclic alkyl group having 5 or more carbon atoms is preferable, and a methyl group, an ethyl group, or a cyclohexyl group is particularly preferable. Is preferred. Furthermore, since the tetracyclododecene derivative of the general formula (V) in which a hydrocarbon group having 1 to 10 carbon atoms is simultaneously bonded as a substituent to the carbon atom to which the carboxylic acid ester group is bonded reduces hygroscopicity. preferable. In particular, the tetracyclododecene derivative of the general formula (V) in which the substituent is a methyl group or an ethyl group is preferable in that the synthesis is easy. Specifically, 8-methyl-8
-Methoxycarbonyltetracyclo [4.4.0.1
^{2,5 17,10} ] dodeca-8-ene is preferred. These tetracyclododecene derivatives or a mixture of unsaturated cyclic compounds copolymerizable therewith are disclosed, for example, in JP-A-4-77.
No. 520, page 4, upper right column, line 12 to page 6, lower right column, sixth
The thermoplastic resin used in the present invention can be obtained by metathesis polymerization and hydrogenation according to the method described in the row. From the viewpoint of heat resistance, it is preferable that the hydrogenated polymer has a softening temperature of 90 ° C. or higher and a glass transition temperature of 100 ° C. or higher. The hydrogenation rate of the hydrogenated polymer is 6
The value measured by 0 H, ¹ H-NMR is 50% or more, preferably 90% or more, more preferably 98% or more. The higher the hydrogenation rate, the better the stability to heat and light. The hydrogenated polymer used as the thermoplastic resin having a norbornane skeleton of the present invention contains a gel contained in the hydrogenated polymer from the viewpoint of preventing the occurrence of defects such as roughening of the coating film surface and the film surface. The amount is preferably 5% by weight or less, more preferably 1% by weight. Of the thermoplastic norbornene-based resin thus obtained,
The total light transmittance measured by ASTM D-1003 is 8
5% or more, preferably 90% or more, more preferably 9
It is 2% or more.

In the thermoplastic resin composition of the present invention, P
A known material is preferably used as the C material, and examples thereof include inorganic materials such as silver, tungsten, mercury, molybdenum, and titanium compounds, spiropyran-based, spirooxazine-based, spirothiopyran-based, indigo-based, and fulgide-based materials. An organic compound such as an azo compound type, an aromatic olefin type, or a porphyrin / cyanine type can be used. As the EC material used in the present invention, known materials are preferably used, and examples thereof include inorganic materials such as tungsten oxide and titanium oxide, viologen, quinone, phthalocyanine, fluoran series, styryl series, polythiophene, polypyrrole, polyaniline and the like. The following organic compounds can be used. Further, when the thermoplastic resin composition of the present invention contains an EC material, an electrolyte may be blended with the EC material. Such an electrolyte is a salt containing a cation such as an alkali metal ion, a quaternary ammonium ion or the like, or a halide ion, or an anion such as perchlorate ion, and examples thereof include KBr, KCl, NaCl and Ba.
Cl ₂ , LiCl, KI, H ₃ PO ₄ , K ₂ SO ₄ , Na ₂ S
O ₄ , FeSO ₄ , KClO ₄ , LiClO ₄ , NH ₄ Cl
O ₄ , AgClO ₄ , KBF ₄ , LiBF ₄ , AgBF ₄ ,
Inorganic compounds such as LiPF ₆ , KH ₂ PO ₄ , KNO ₃ , and CH ₃ COOK, tetramethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium cyanide, tetraethylammonium perchlorate, tetrabutylammonium bromide , Tetrabutylammonium iodide, tetrabutylammonium perchlorate, tetrabutylammonium borofluoride, tetrahexylammonium chloride, tetrahexylammonium iodide, n-dodecyltrimethylammonium bromide, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, etc. The organic compounds of

A known material is preferably used as the EL material used in the present invention. For example, as the inorganic material, at least one selected from calcium sulfide, magnesium sulfide, tin sulfide, barium sulfide, and cadmium sulfide.
With at least one kind of base material, as an activator (including co-activator or additive), from copper, silver, manganese, molybdenum, tungsten, thorium, uranium, aluminum, lithium, beryllium, fluorine, chlorine, bromine, iodine, etc. Examples of the organic material include at least one selected from the group consisting of cyclopentadiene, perinone, oxadiazole, bisstyrylbenzene, perylene, coumarin, rare earth complex, distyrylpyrazine, thiadiazolopyridine, pyrrolo. Examples thereof include derivatives such as pyridine and naphthyridine. In the thermoplastic resin composition of the present invention, the blending amount of the above-mentioned PC material, EC material or EL material, or when two or more materials from these materials are used, the total amount thereof is the thermoplastic norbornene resin 1
The amount is 0.001 to 200 parts by weight, preferably 0.1 to 100 parts by weight, relative to 00 parts by weight. If the blending amount of the above-mentioned materials is less than 0.001 part by weight, the desired function cannot be sufficiently exhibited, and if it exceeds 200 parts by weight, the compatibility with the thermoplastic norbornene-based resin as the binder deteriorates, and It is difficult to make uniform molded products such as bleeding and uneven color. The PC used in the present invention
When the material, the EC material and the EL material are inorganic materials, it is preferable to specify the average particle diameter in consideration of the balance with the dispersibility with the binder, the color forming property and the light emitting property, and specifically, 0 .1 to 50 μm, preferably 0.5 to
It is in the range of 30 μm.

In addition, in the thermoplastic resin composition of the present invention, known antioxidants such as 2,6-di-t-butyl-4-methylphenol and 2,2'-dioxy-3 may be added, if desired. , 3'-di-t-butyl-5,5'-dimethylphenylmethane, tetrakis [methylene-3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl-4)
-Hydroxy-5-t-butylphenyl) butane, 1,
3,5-Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl-benzene, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate, 2,2'-dioxy-
3,3′-di-t-butyl-5,5′-diethylphenylmethane, 3,9-bis [1,1-dimethyl-2- [β
-(3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl], 2,4,8,1
0-tetraoxpyro [5,5] undecane, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-)
t-Butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl-4)
-Methylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite can be added. The amount of these antioxidants added is usually 0.1 to 3 parts by weight, preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the thermoplastic norbornene-based resin. When the amount of the antioxidant used is too small, the effect of improving the durability is insufficient, and when it is too large, problems such as bleeding from the molding surface and deterioration of transparency are unfavorable. In the resin composition of the present invention, in addition to the above-mentioned antioxidant, an ultraviolet absorber such as p-t-butylphenyl salicylate, 2, if necessary.
2'-dihydroxy-4-methoxybenzophenone,
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2- (2'-dihydroxy-4'-m-octoxyphenyl) benzotriazole; inorganic fillers such as calcium carbonate, carbon fiber, metal oxides Stabilizers, antistatic agents, dyes, pigments, flame retardants, impact resistance improving elastomers, etc. may be added. Further, additives such as a lubricant may be added for the purpose of improving processability. Furthermore, when casting the resin composition of the present invention to cast a cast film, a leveling agent may be added. As the leveling agent, for example, a fluorine-based nonionic surfactant, a special acrylic resin-based leveling agent, a silicone-based leveling agent, etc. can be used.

In the present invention, as a method of mixing the PC material, the EC material, or the EL material with the thermoplastic norbornene-based resin, the material and the thermoplastic norbornene-based resin, or if necessary, various additives described above are added. ,
A method of mixing with a twin-screw extruder, a Brabender, a roll kneader, etc., and pelletizing with an extruder, or a method of pulverizing pellets into a powder by a pulverizer, or a suitable solvent with the above materials and thermoplastic norbornene Examples thereof include a method of dissolving or dispersing the system resin and, if necessary, the above various additives. The solvent that can be used in the resin composition of the present invention is not particularly limited as long as it is a solvent that dissolves or disperses the thermoplastic norbornene-based resin, PC material, EC material, or EL material that is a solute and does not cause modification or reaction. Examples of such solvents include benzene,
Aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, trimethylbenzene, diethylbenzene and isopropylbenzene, aliphatic hydrocarbon solvents such as alkanes and cycloalkanes, dichloromethane, 1,2
-Halogenated hydrocarbon solvents such as dichloroethane, tetrachloroethane, trichloroethylene, methyl iodide, chloroform, carbon tetrachloride, chlorobenzene, dichloronaphthalene, acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone Ketone solvents such as diethyl ether, dimethoxyethane, diethoxyethane, tetrahydrofuran, ether solvents such as tetrahydropyran, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl formate, butyl formate, cellosolve acetate, carbitol acetate Ester solvent such as, methanol, ethanol, isopropyl alcohol, butanol, cellosolve, ethyl cellosolve, butyl celloso Bed, carbitol, ethyl carbitol, butyl carbitol, include alcohol solvents such as diacetone alcohol. These solvents may be used alone, or two or more kinds of solvents may be mixed and used. Further, a mixture of a solvent that dissolves the thermoplastic norbornene-based resin and a solvent that does not dissolve it may be used. Water or fat may be used as a material that does not dissolve the thermoplastic norbornene-based resin. Among the above solvents,
Hydrocarbon-based solvents, halogenated hydrocarbon-based solvents, and ether-based solvents such as tetrahydrofuran are preferred.

When the thermoplastic norbornene resin is dissolved in the solvent, it may be at room temperature or at high temperature. A uniform solution can be obtained by sufficient stirring. The concentration of this solution is
It can be freely selected according to the molecular weight of the solute resin, the type of application, and the required physical properties, but the viscosity is 100 cp.
It is preferably in the range of 100,000 cp. 1
If it is less than 00 cp, the viscosity is too low to make coating difficult, and it is difficult to obtain a uniform coating film or film, and it takes time to remove the solvent after coating. If it exceeds 100,000 cp, the fluidity is poor and it is difficult to obtain a coating film or film having a good surface condition. The thermoplastic resin composition of the present invention can be made into a desired molded article by a known molding method such as injection molding, extrusion molding, compression molding or the like. When the resin composition is dissolved or dispersed in a solvent, it can be used as a paint or formed into a film by a casting method. A known method can be used as a method for forming a coating film on a predetermined substrate using the thermoplastic resin composition of the present invention as a coating material, for example, a vapor deposition method, a dry method such as a sputtering method or a brush coating method, Wet coating methods such as dip coating method, spray coating method, plate coating method, spinner coating method, bead coating method, curtain coating method, gravure printing method, screen printing method, offset printing method, letterpress printing method, etc. Can be mentioned. The film thickness in this case varies depending on the application and purpose, but is 0.01 in order not to impair the coloring and light emission performance.
μm to 3.0 mm, preferably 0.05 μm to 1.0 m
m. When the film thickness is less than 0.01 μm, the film thickness is too thin and the color development performance or the light emission performance becomes insufficient, and 3.0 mm
If it exceeds, it is difficult to form a smooth coating film over the entire surface,
In addition, the transparency of the coating film becomes poor.

Further, the thermoplastic resin composition of the present invention may be used for various display devices in the form of a composition solution obtained by dissolving and dispersing it in a solvent. The thermoplastic resin composition of the present invention is an alternative to silver salt photosensitive materials, copying materials, printing photoreceptors, cathode ray photosensitive recording materials, various recording materials such as laser photosensitive materials,
Photochromic moldings such as sunglasses, optical filter materials, display materials, photometers, decoration materials, etc .; electrochromic applications such as large or small display elements, light control glass, light quantity adjusting filters, optical switches; OA computers It can be used for flat panel displays such as TVs and wall-mounted TVs, light sources for copiers, light sources such as liquid crystal displays and backlights for measuring instruments, display panels, and electroluminescence applications such as marker lights. Suitable for required applications. As an example of the above-mentioned application, when the resin composition of the present invention is used as an EC element, the constitution is not particularly limited, and as an example, the thermoplastic resin is provided between a pair of electrodes consisting of a transparent electrode and a counter electrode. An example is one in which a color-forming layer made of a thermoplastic resin composition containing a norbornene-based resin and the above EC material and an electrolyte layer containing the above electrolyte are sandwiched. This electrolyte may be mixed with the EC material in the thermoplastic norbornene-based resin so as to serve as both the color-developing layer and the electrolyte layer, or may be structured to be in contact with the color-developing layer as an electrolyte layer separately from the color-developing layer. When the electrolyte is provided independently of the coloring layer,
The form may be solid or liquid. A known method is used to form the color forming layer on the electrode, and it may be applied on the conductive substrate of the transparent electrode or the counter electrode by the film forming method described above. Further, as another example of the above-mentioned application, when the thermoplastic resin composition of the present invention is used as an EL device, the constitution is not particularly limited, but basically, a pair of an anode and a cathode is used. A structure in which a light emitting layer made of the thermoplastic resin composition containing the thermoplastic norbornene-based resin and the EL material is sandwiched between the electrodes, and a hole transport layer or an electron transport layer may be provided between the light emitting layer and the electrode as necessary. It can be interposed.

Examples of such EL devices are: anode / light emitting layer / cathode anode / hole transport layer / light emitting layer / cathode anode / hole transport layer / light emitting layer / electron transport layer / cathode anode / light emitting layer / electron transport layer. / A constitution such as a cathode can be mentioned. The hole transport layer and the electron transport layer can improve the light emission performance. The hole transport material forming the hole transport layer is disclosed in JP-A-3-47890.
Known compounds can be used according to JP-A-5-311161, JP-A-7-3256, and the like. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, Pyrazolone derivative, phenylenediamine derivative, arylamine derivative, amino-substituted chalcone derivative, oxazole derivative, styrylanthracene derivative, fluorenone derivative, hydrazone derivative, stilbene derivative, porphyrin compound, phthalocyanine compound, naphthalocyanine compound, aromatic tertiary amine compound Compounds such as styrylamine compounds, silazane compounds, polyvinylcarbazole, and polysilane are preferably used. Further, known compounds can also be used as the electron transporting material constituting the electron transporting layer,
For example, fluorenone derivatives, thiopyran dioxide derivatives, diphenylquinone derivatives, anthraquinodimethane derivatives, fluorenylidenemethane derivatives, anthrone derivatives, oxadiazole derivatives, aromatic compounds such as tetraphenylbutadiene, and 8-hydroxyquinoline Al complexes. Compounds such as metal complexes such as cyclopentadiene derivative, perinone derivative, bisstyrylbenzene derivative, perylene derivative, coumarin compound, rare earth complex, distyrylpyrazine derivative, thiadiazolopyridine derivative, pyrrolopyridine derivative and naphthyridine derivative are preferably used. To be In the present invention, the hole-transporting material and the electron-transporting material are added to a light-emitting layer composed of the EL material and the thermoplastic norbornene-based resin to form a single-layer EL.
It may be an element and may be formed between the electrode and the light emitting layer as a hole transport layer and an electron transport layer independently of the light emitting layer. Further, a hole transport layer or an electron transport layer may be further provided between the electrode and the light emitting layer containing the hole transport material or the electron transport material. In the present invention, the method for forming the light emitting layer and, if necessary, the hole transporting layer or the electron transporting layer is not particularly limited, and is applied on the conductive substrate of the anode or the cathode by the film forming method described above. do it.

[0018]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited by this. In addition,
In Examples, parts and% are based on weight unless otherwise specified. The various measurements in the examples were performed as follows. Heat resistance The PC coating film, EC coating film, or EL coating film after being placed in an air oven at 120 ° C. for 24 hours was visually observed, and the heat resistance was evaluated according to the following evaluation criteria. ◯: A coating film which is not deformed or discolored and has excellent smoothness. X: Deformation, discoloration or turbidity is observed in the coating film. Moisture resistance After being kept at 80 ° C and 90% relative humidity for 1000 hours. The PC coating film, the EC coating film, or the EL coating film was visually observed, and the moisture resistance was evaluated according to the following evaluation criteria. ◯: A coating film with excellent transparency without discoloration or turbidity X: Discoloration or turbidity in the coating film Photochromic (PC) characteristics PC coating film exposed to ultraviolet rays of 1000 mJ / c by a high pressure mercury lamp
The coating film when irradiated with m ² to develop color was visually observed, and the display characteristics were evaluated according to the following evaluation criteria. ◯: The PC coating film is transparent without turbidity, and the color development is even and uniform. X: The PC coating film is discolored or turbid, or the color development is uneven and the appearance is unsatisfactory. Electrochromic. (EC) Characteristics The appearance of the display screen of the EC element was visually observed when a voltage was applied between the electrodes of the EC element by a DC power source, and the display characteristics were evaluated according to the following evaluation criteria. ◯: EC element screen is transparent without turbidity and color development is uniform without unevenness ×: EC element screen is discolored or turbid Electroluminescence (EL) characteristics a) Luminance Luminance Current density in EL element Luminance meter (BM-8 type manufactured by Tokyo Optical Co., Ltd.) that measures the emission brightness when a current of 10 mA / cm ² is applied.
It measured using. b) Appearance of Light-Emitting Layer The appearance of the light-emitting layer when a current having a current density of 10 mA / cm ² was applied to the EL element was visually observed, and the display characteristics were evaluated according to the following evaluation criteria. ◯: The light emission is uniform and the screen is good without discoloration. ×: The light emission is uneven or the screen has discoloration or turbidity.

Reference Example 1 8-Methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-en 10
2. A toluene solution of 0 g, 60 g of 1,2-dimethoxyethane, 240 g of cyclohexane, 9 g of 1-hexene, and 0.96 mol / l of diethylaluminum chloride.
4 ml was added to an autoclave having a volume of 1 liter. On the other hand, in another flask, 0.1 kg of tungsten hexachloride was added.
20 ml of a 05 mol / l 1,2-dimethoxyethane solution
And 10 ml of a 0.1 mol / l 1,2-dimethoxyethane solution of paraaldehyde were mixed. This mixed solution 4.9
ml was added to the mixture in the autoclave. After sealing, the mixture was heated to 80 ° C. and stirred for 4 hours.
To the obtained polymer solution, a mixed solvent of 2/8 (weight ratio) of 1,2-dimethoxyethane and cyclohexane was added to make the polymer / solvent 1/10 (weight ratio), and then 20 g of triethanolamine was added. Was added and stirred for 10 minutes. 500 g of methanol was added to the polymerization solution, and the mixture was stirred for 30 minutes and allowed to stand. The upper layer separated into two layers was removed, methanol was added again, and the mixture was stirred and allowed to stand, and then the upper layer was removed. The same operation was further performed twice, and the obtained lower layer was cyclohexane, 1,
Dilute appropriately with 2-dimethoxyethane and polymer concentration is 10
% Cyclohexane-1,2-dimethoxyethane solution. 20 g of palladium / silica magnesia [manufactured by Nikki Chemical Co., Ltd., palladium amount = 5%] was added to this solution, and the mixture was reacted in an autoclave at 165 ° C. under a hydrogen pressure of 40 kg / cm ² for 4 hours. Was removed by filtration to obtain a hydrogenated polymer solution. Further, pentaerythrityl-, an antioxidant, was added to this hydrogenated polymer solution.
Tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was added to the hydrogenated polymer in an amount of 0.1%, and the solvent was removed under reduced pressure at 380 ° C. Next, the molten resin was pelletized by an extruder in a nitrogen atmosphere, and the weight average molecular weight was 7.0 × 1.
A thermoplastic resin A having a 0 ⁴ , hydrogenation rate of 99.5% and a glass transition temperature of 168 ° C. was obtained.

Reference Example 2 6-Etylidene-2-tetracyclododecene was subjected to metathesis ring-opening polymerization and hydrogenation in the same manner as in Example,
The hydrogenation catalyst was removed by filtration to obtain a hydrogenated polymer solution. The same antioxidant as in Example 1 was added to the hydrogenated polymer solution in an amount of 0.1% with respect to the hydrogenated polymer, and the solvent was removed under reduced pressure at 360 ° C. Then, the molten resin was pelletized by an extruder in an atmosphere of nitrogen to obtain a thermoplastic resin B having a weight average molecular weight of 5.5 × 10 ⁴ , a hydrogenation rate of 99.5% and a glass transition temperature of 140 ° C. Example 1 A solution obtained by dissolving 100 parts of the thermoplastic resin A obtained in Reference Example 1 and 50 parts of the photochromic spiropyran compound in dichloromethane was cast on a colorless and transparent glass substrate with a bar coater, and the temperature was 100 ° C. The solvent was removed by leaving it on the hot plate for about 10 minutes to obtain a photochromic coating film having a film thickness of 20 μm. The coating film was evaluated for heat resistance, moisture resistance, and photochromic properties. Table 1 shows the evaluation results.

Example 2 A photochromic coating film was prepared and evaluated in the same manner as in Example 1 except that the thermoplastic resin B obtained in Reference Example 2 was used in place of the thermoplastic resin A. Table 1 shows the evaluation results. Comparative Example 1 A polymethylmethacrylate resin (“Acrypet VH” manufactured by Mitsubishi Rayon Co., Ltd.) was used in place of the thermoplastic resin A, and the solvent was removed at 60 ° C., and the same evaluation as in Example 1 was performed. Table 1 shows the evaluation results. Comparative Example 2 The evaluation was performed in the same manner as in Example 1 except that a polycarbonate resin (“Panlite” K-1300 manufactured by Teijin Chemicals Ltd.) was used instead of the thermoplastic resin A. Table 1 shows the evaluation results.

[0022]

[Table 1] As is clear from Table 1, the PC coating films of Examples 1 and 2 have excellent heat resistance and moisture resistance, and also have excellent dispersibility with PC materials and give uniform color development. On the other hand, Comparative Example 1 using polymethylmethacrylate resin has heat resistance,
The moisture resistance was poor, and Comparative Example 2 using a polycarbonate resin had poor dispersibility of the PC material and had uneven coloring. Example 3 A solution prepared by dissolving 100 parts of the thermoplastic resin A obtained in Reference Example 1 and 50 parts of tetrabutyl pyromelliticate as an EC material in dichloromethane was prepared using indium-tin oxide (ITO) coated glass having a sheet resistance of 20Ω / □. A film is formed on a substrate (manufactured by Asahi Glass Co., Ltd.) by a spin coating method to a film thickness of 1.
An EC layer of 0 μm was formed. The EC layer was evaluated for heat resistance and moisture resistance. Next, an ITO-coated glass substrate was also used as the counter electrode of the electrode on which the EC layer was formed, and a 1 mol / l propylene carbonate solution of lithium perchlorate was filled between the electrodes with an electrolyte solution and sealed with an epoxy resin. EC
The device was obtained. The EC characteristics of this EC device were evaluated. Table 2 shows the evaluation results.

Example 4 Evaluation was carried out in the same manner as in Example 3 except that the thermoplastic resin B obtained in Reference Example 2 was used in place of the thermoplastic resin A. Table 2 shows the evaluation results. Comparative Example 3 Evaluations were made in the same manner as in Example 3 except that polymethylmethacrylate resin was used instead of the thermoplastic resin A. Table 2 shows the evaluation results. Comparative Example 4 Evaluation was made in the same manner as in Example 3 except that a polycarbonate resin was used instead of the thermoplastic resin A. Table 3 shows the evaluation results.

[Table 2] As is clear from Table 2, the EC devices of Examples 3 and 4 were E
It has excellent characteristics as a C element and has excellent heat resistance and moisture resistance. On the other hand, Comparative Example 3 using the polymethylmethacrylate resin was inferior in heat resistance and moisture resistance, and Comparative Example 4 using the polycarbonate resin was inferior in dispersibility of the EC material and had uneven coloring. there were. Example 5 100 parts of the thermoplastic resin A obtained in Reference Example 1, 70 parts of coumarin-6 as an EL material, and N, N 'as a hole transport material.
-Diphenyl-N, N'-bis (3-methylphenyl)
-1,1'-biphenyl-4,4'-diamine 20 parts,
2,5-bis (1-naphthyl)-as electron transport material
10 parts of 1,3,4-oxadiazole was dissolved in dichloromethane, and this was dissolved into indium with a sheet resistance of 20Ω / □.
Tin oxide (ITO) coated glass substrate (Asahi Glass Co., Ltd.)
Was manufactured by a spin coating method to form a light emitting layer having a film thickness of 10 μm. The heat resistance and moisture resistance of this light emitting layer were evaluated. Next, MgAg was further vacuum-deposited on this light emitting layer to form a cathode, and an EL device was obtained. The EL characteristics of this EL element were evaluated. Table 3 shows the evaluation results. Example 6 An EL device was prepared and evaluated in the same manner as in Example 5 except that the thermoplastic resin B obtained in Reference Example 2 was used instead of the thermoplastic resin A. Table 3 shows the evaluation results. Comparative Example 5 An EL device was prepared and evaluated in the same manner as in Example 5 except that polymethylmethacrylate resin was used instead of the thermoplastic resin A. Table 3 shows the evaluation results. Comparative Example 6 An EL device was prepared and evaluated in the same manner as in Example 5 except that a polycarbonate resin was used instead of the thermoplastic resin A. Table 3 shows the evaluation results.

[0024]

[Table 3] As is clear from Table 3, Examples 5 and 6 are excellent in durability, heat resistance and humidity resistance as EL elements. On the other hand, Comparative Example 5 using the polymethylmethacrylate resin was inferior in heat resistance and moisture resistance, and Comparative Example 6 using the polycarbonate resin was poor in dispersibility of the EL material and had uneven light emission and The brightness was also lowered.

Since the thermoplastic resin composition of the present invention uses the thermoplastic norbornene-based resin as the binder resin, it has excellent compatibility and dispersibility with PC materials, EC materials or EL materials, and heat resistance, Since it is also excellent in moisture resistance, it is intended to provide a display element capable of maintaining a clear display performance for a long period of time, particularly when used for a display element.

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Claims (2)

[Claims] 1. A thermoplastic norbornene resin (a),
(B) A thermoplastic resin composition containing at least one of a photochromic material, an electrochromic material, and an electroluminescent material. 2. The (a) thermoplastic norbornene-based resin,
The thermoplastic resin composition according to claim 1, which has a polar substituent in its norbornane skeleton.