JPH08176411A - Thermoplastic norbornene resin composition - Google Patents

Abstract

PURPOSE: To obtain a liq. thermoplastic norbornene resin compsn. which gives a coating film excellent in abrasion resistance and clarity and is suitable esp. for a binder of a photoreceptor for a copying machine. CONSTITUTION: This compsn. contains a thermoplastic norbornene resin, a thermoplastic elastomer having a refractive index of 1.48-1.55, and a charge- generating substance and/or a charge-transporting substance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic norbornene resin solution composition which provides a coating film having excellent abrasion resistance and transparency and is particularly suitable as a binder for a photoconductor for a copying machine.

[0002]

2. Description of the Related Art Conventionally, as a photoconductor used in an electrophotographic machine such as a copying machine, a photoconductor made of an inorganic photoconductive material or an organic photoconductive material has been widely used. Polycarbonate resin (PC) having a bisphenol A skeleton is generally used as a binder for these photoconductors because it has good transparency, strength, and electrical characteristics, but it does not have sufficient abrasion resistance and is repeatedly copied. Moreover, there is a problem that the copy image is affected by the abrasion of the binder layer. Moreover, these binders have problems such as hydrolysis and gelation of the solution, and it has been difficult to obtain a good quality photoreceptor layer. Also, since it is a PC, it is easily scratched,
There is also a problem that the image quality of the copy deteriorates as the number of scratches increases as the copying is repeated.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art, and provides a coating film having excellent abrasion resistance, transparency and adhesion, and an organic photoconductor for a copying machine. It is an object of the present invention to provide a thermoplastic norbornene-based resin solution composition suitable as a binder or a material for EL devices.

[0004]

The resin solution composition of the present invention comprises (A) a thermoplastic norbornene-based resin, (B) a thermoplastic elastomer having a refractive index in the range of 1.48 to 1.55, and (C). It is characterized by containing a charge generating substance and / or a charge transfer substance. The thermoplastic norbornene resin used in the present invention has a norbornane skeleton in its repeating unit. For example, the thermoplastic resin includes a norbornane skeleton represented by any of the general formulas (I) to (IV).

[0005]

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[0006]

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[0007]

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[0008]

[Chemical 4]

(In the formula, A, B, C and D represent a hydrogen atom or a monovalent organic group.) Examples of the thermoplastic resin having a norbornane skeleton which can be used in the present invention include those disclosed in Japanese Patent Laid-Open No. 60-168708, JP-A-62-252406, JP-A-62-25240.
7, JP-A-2-133413, JP-A-63
-145324, JP-A-63-264626, JP-A-1-240517, and JP-B-57-88.
Examples thereof include resins described in Japanese Patent Publication No. 15 and the like.

As a specific example of this thermoplastic resin, at least one tetracyclododecene derivative represented by the following general formula (V) or an unsaturated cyclic compound copolymerizable with the tetracyclododecene is metathesized. The hydrogenated polymer obtained by hydrogenating the polymer obtained by superposition | polymerization can be mentioned.

[0011]

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(In the formula, A to D are the same as above.) In the tetracyclododecene derivative represented by the general formula (V), a polar group may be contained in A, B, C and D. It is preferable in terms of adhesion to other materials and heat resistance.
Further, the polar group ^{_{- (CH 2) n COOR 3}} ( wherein, R ³ is a hydrocarbon group having 1 to 20 carbon atoms, n represents 0
It is preferable that the hydrogenated polymer to be obtained has a high glass transition temperature. In particular, the - polar substituent represented by (CH _{2) n} COOR ^3, the general formula () 1 is preferably contained in one molecule of the tetracyclododecene derivatives. 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. Particularly, the tetracyclododecene derivative represented by the general formula (V) in which the substituent is a methyl group or an ethyl group is preferable in that the synthesis thereof is easy. Specifically, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 1 ^7,10] dodeca-8-ene are preferred. These tetracyclododecene derivatives or a mixture of unsaturated cyclic compounds copolymerizable therewith are disclosed, for example, in JP-A-4-77520, No.
By the method described in page 12, upper right column, line 12 to page 6, lower right column, line 6, metathesis polymerization, hydrogenation, and a thermoplastic resin to be used in the present invention can be made. 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 60 MHz, ¹ H-N
The value measured by MR 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.

The present invention comprises the above-mentioned thermoplastic norbornene resin and a thermoplastic elastomer dissolved or dispersed in a solvent, wherein the thermoplastic elastomer has an Izod impact strength of 10 kg.cm/cm or more. Those are preferably used. Further, the refractive index of the thermoplastic elastomer is preferably in the range of 1.48 to 1.55. Anything outside the above range will lack transparency. Examples of such thermoplastic elastomers include aromatics such as styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, styrene-isoprene block copolymers, hydrogenated styrene-isoprene block copolymers. Examples thereof include vinyl-conjugated diene-based block copolymers, urethane-based elastomers, low crystalline polybutadiene resins, ethylene-propylene elastomers, styrene-grafted ethylene-propylene elastomers, thermoplastic polyester elastomers and ethylene-based ionomer resins. In order to obtain a coating film having particularly excellent transparency, an aromatic vinyl-conjugated diene system such as a hydrogenated styrene-butadiene random copolymer, a block copolymer or a block-random copolymer is used as the thermoplastic elastomer. It is preferable to use hydrogenated products of block copolymers and urethane elastomers. The aromatic vinyl-conjugated diene block copolymer has a styrene content of 20 to 45% by weight, and is a copolymer of butadiene and an acrylic ester, and the weight ratio of butadiene and an acrylic ester is 10 to 10. 90:90 to 10, 100 parts by weight of these and styrene and / or acrylonitrile copolymerized at a ratio of 0 to 30 parts by weight, and hydrogenated products thereof. Further, these thermoplastic elastomers are modified with a specific functional group such as an epoxy group, a carboxyl group, a hydroxyl group, an amino group, an acid anhydride group, or an oxazoline group for the purpose of improving compatibility with the thermoplastic norbornene-based resin. It may have been done. The urethane elastomer has both a hard phase and a soft phase in one molecule, and has a polyurethane structure in the hard phase and a polyester or polyether structure in the soft phase. The hard phase of the urethane elastomer is formed by reacting diisocyanate, glycol, and, if necessary, diamine or water. Examples of the diisocyanate include 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, silylylene diisocyanate, and hexamethylene diisocyanate. On the other hand, as the soft phase, aliphatic polyethers such as polyether glycol and polytetramethylene glycol, and aliphatic polyesters such as polytetramethylene adipate and poly-ε-caprolactone are generally used. Specifically, Kuramiron (made by Kuraray Co., Ltd.), Miractolan (made by Nippon Miractolan Co., Ltd.), Paraprene (made by Nippon Polyurethane Co., Ltd.), Pandex (made by Dainippon Ink Co., Ltd.), Takelac, Elastollan (made by Takeda-Bardish Urethane Co., Ltd.). , Iron Liver (manufactured by Nippon Oil Seal Co., Ltd.), Resamine (manufactured by Dainichiseika Co., Ltd.), Pyoprene (manufactured by Mitsui Nisso Urethane Co., Ltd.), Eagle Run (manufactured by Hokushin Chemical Co., Ltd.) and the like.

In the present invention, the abrasion resistance of the coating film obtained from the thermoplastic norbornene-based resin solution composition can be controlled by changing the blending amount of the above-mentioned thermoplastic elastomer depending on the kind of purpose and purpose. From the balance of transparency and abrasion resistance,
It is preferably contained in the range of 5 to 50% by weight, particularly 1 to 20% by weight. Here, the method for obtaining the thermoplastic norbornene-based resin solution composition of the present invention is not particularly limited, and pellets or powdery thermoplastic norbornene-based resin and thermoplastic elastomer are dissolved or dispersed in an appropriate solvent. The above-mentioned thermoplastic elastomer may be added directly to the reaction solution after polymerization or hydrogenation of the thermoplastic norbornene-based resin.
In the latter method, a solution of an ultra-high molecular weight thermoplastic norbornene-based resin can be prepared, and a coating film having extremely excellent strength can be obtained.

In the present invention, the solvent in the resin solution composition is not particularly limited as long as it is a solvent capable of dissolving or dispersing the thermoplastic norbornene-based resin or the thermoplastic elastomer which is a solute. Examples of such solvents include benzene, toluene, xylene, ethylbenzene, chlorobenzene, trimethylbenzene, diethylbenzene,
Aromatic hydrocarbon solvents such as isopropylbenzene and chlorobenzene, aliphatic hydrocarbon solvents such as alkanes, cycloalkanes, alkenes and cycloalkenes,
Acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and other ketone solvents, diethyl ether, dimethoxyethane, diethoxyethane, tetrahydrofuran, tetrahydropyran and other ether solvents, methyl acetate, ethyl acetate , Butyl acetate, isoamyl acetate, ethyl formate, butyl formate, cellosolve acetate, ester solvent such as carbitol acetate,
Examples thereof include alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, cellosolve, ethyl cellosolve, butyl cellosolve, carbitol, ethyl carbitol, butyl carbitol and 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, a hydrocarbon solvent,
Halogenated hydrocarbon solvents and ether solvents such as tetrahydrofuran are preferable in that both the thermoplastic norbornene resin and the thermoplastic elastomer are compatible with each other.

When the thermoplastic norbornene resin or the thermoplastic elastomer 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 the resin solution composition of the present invention can be freely selected depending on the molecular weight of the solute resin, the type of application, and the required physical properties, but the total of the thermoplastic norbornene resin and the thermoplastic elastomer is relative to the solvent. It is preferably contained in the range of 5% by weight to 80% by weight.
It is preferably in the range of 00 cp to 100,000 cp. If it is less than 100 cp, the viscosity is too low to apply the coating, 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 coating film obtained from the resin solution composition of the present invention preferably does not soften at room temperature, and particularly preferably has a softening temperature of 50 ° C. or higher. The thermoplastic norbornene-based resin solution composition of the present invention includes known antioxidants such as 2,6-di-t-butyl-4-methylphenol and 2,2'-dioxy-3,3'-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], 2,4,8,10-tetraoxpyro [5,5]
Undecane, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,2 6
-Di-t-butyl-4-methylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite can be added. The addition amount of these antioxidants is usually 0.1 to 3 parts by weight, preferably 0.1 to 100 parts by weight of the specific polymer.
It is 2 to 2 parts by weight. 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 addition to the above-mentioned antioxidants, the resin solution composition of the present invention may optionally contain an ultraviolet absorber such as p-t-butylphenyl salicylate or 2,2'-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,
Elastomers for improving impact resistance can be added. Further, additives such as a lubricant may be added for the purpose of improving processability. Further, when the resin solution composition of the present invention is cast to form a cast film, a leveling agent can 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 the charge generating substance and / or the charge transfer substance, which are known as the charge generating substance and / or the charge transferring substance, which are added to the resin solution prepared by dissolving or dispersing the thermoplastic norbornene resin and the thermoplastic elastomer in the solvent. As an example of the charge generating substance, amorphous selenium, crystalline selenium-tellurium alloy, selenium-arsenic alloy, other selenium compounds and selenium alloys, zinc oxide, inorganic photoconductive materials such as titanium oxide can be used. Body, azo pigment, perylene pigment, polycyclic quinone pigment, indigoid pigment, phthalocyanine pigment, carbonium pigment, quinoneimine pigment, methine pigment, quinoline pigment, benzoquinone pigment, naphthalimide pigment, perinone Pigments, azurenium pigments, squarylium pigments, thiapyrylium pigments It can be used organic pigments. Examples of charge transfer substances include carbazole derivatives, oxazole derivatives, oxadiazole derivatives, pyrazoline derivatives, hydrazone derivatives, aromatic amines,
A substance such as a stilbene derivative or a triphenylmethane derivative can be used. The coating composition of the present invention containing the above charge generating substance or charge transfer substance as a photosensitive layer is used as a dip coating method, spray coating method, plate coating method, spinner coating method, bead coating method, curtain coating method, etc. It may be applied on the conductive substrate by the well-known coating method. Here, even if the photosensitive layer has a single-phase structure that includes both a charge generation substance and a charge transfer substance at the same time, a laminated structure in which the charge generation layer containing the charge generation substance and the charge transfer layer containing the charge transfer substance are functionally separated May be In the present invention, the amount of the charge generating substance and / or the charge transfer substance added to the resin solution of the thermoplastic norbornene resin and the thermoplastic elastomer is 100 parts by weight in total of the thermoplastic norbornene resin and the thermoplastic elastomer. For 10
It is preferably in the range of 300 parts by weight to 300 parts by weight. The thermoplastic norbornene-based resin solution composition of the present invention can be used for various photoconductors in addition to the above-mentioned use as the electrophotographic photoconductor.

[0019]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited by this. In addition,
In the examples, parts and% are based on weight unless otherwise specified. Reference Example 1 8-Methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-en 10
2. 0 g, 1,2-dimethoxyethane 60 g, cyclohexane 240 g, 1-hexene 9 g, and a solution of diethylaluminum chloride 0.96 mol / l in toluene 3.
4 ml was added to an autoclave having an internal volume of 1 liter. On the other hand, in another flask, a solution of tungsten hexachloride (0.1%) 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 1/8 (weight ratio) of 1,2-dimethoxyethane and cyclohexane was added to make the polymer / solvent 1/10 (weight ratio), and then triethanolamine 20 g Was added and stirred for 10 minutes. To this polymerization solution, 500 g of methanol was added, 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 repeated twice, and the resulting lower layer was mixed with cyclohexane and 1,
Dilute appropriately with 2-dimethoxyethane to give a polymer concentration of 10
% Cyclohexane-1,2-dimethoxyethane solution was obtained. To this solution, 20 g of palladium / silica magnesia [manufactured by JGC Chemical Co., Ltd., palladium amount = 5%] was added, and the mixture was reacted in an autoclave at a hydrogen pressure of 40 kg / cm ² at 165 ° C. for 4 hours, and then a hydrogenation catalyst. Was removed by filtration to obtain a hydrogenated polymer solution. In addition, the hydrogenated polymer solution was mixed with pentaerythrityl-
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 charge generating layer made of a vinyl polymer was formed on a glass substrate.
After forming by coating, 100 parts of thermoplastic resin A and hydrogen
Styrene-butadiene block polymer (hydrogenation rate 98
%, Molecular weight 16 × 10^Four, Refractive index 1.515) 10 parts
30 parts of amine dye and dichloromethane / dichlore
Resin solution having a concentration of 10% by weight dissolved in a tan mixed solution
Is applied and dried at 90 ° C for 1 hour to give a film thickness of 20μ.
A photoreceptor is obtained by forming a charge transfer layer of m or more.
Was. This photoreceptor was evaluated for wear resistance and photoreceptor characteristics.
Was. The evaluation results are shown in Table 1. In addition, each measurement is as follows
Went to.Wear resistance Cut the cast film into a circle with a diameter of 13 cm.
The wear test is performed with a taper wear tester using
No, the test method determined from the wear loss is JIS-
According to K7240. Worn wheel CS-5 (250g overweight) Rotation speed 3000 rotations Rotation speed 3000 rotations / 42.5 minutesPhotoconductor characteristics Charge the photoreceptor with a corona charger (the surface potential at that time)
To V_i(V) After leaving for 1 second (at that time)
Surface voltage is V₀(V)), monochromatic laser light (78
0 nm, 2 μW / cm²) Is continuously exposed to the surface potential
The following characteristics were obtained by attenuating. Charge retention rate D₁  The surface potential (V_i, V₀From the measured value of
It was calculated. D₁= V₀/ V_i× 100 (%) Half exposure amount E_1/2 Surface potential is V from the start of exposure₀Needed to decay to half of
Time t_1/2(S) and irradiation light intensity 2 (μW / cm²)
The product of and_1/2(ΜJ / cm²). Residual potential V_r Time from exposure start 10 × t_1/2(S) Table when elapsed
The surface potential is the residual potential V_r(V).

Example 2 A photoreceptor was obtained in the same manner as in Example 1 except that the thermoplastic resin B was used instead of the thermoplastic resin A. This photoreceptor was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Example 3 A photoconductor was obtained in the same manner as in Example 1 except that the urethane-based elastomer; Kuramilon-3190 (manufactured by Kuraray Co., Ltd.) was used in place of the hydrogenated styrene-butadiene block copolymer. This photoreceptor was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Example 4 Example 1 was repeated except that the thermoplastic resin B was used in place of the thermoplastic resin A, and the hydrogenated styrene-butadiene block copolymer was replaced with a urethane-based elastomer; Kuramilon-3190 (manufactured by Kuraray Co., Ltd.). A photoconductor was obtained by the same method. This photoreceptor was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Comparative Example Instead of the thermoplastic resin A, bisphenol A type polycarbonate (“Panlite” K-130 manufactured by Teijin Chemicals Ltd.)
A photosensitive member was obtained in the same manner as in Example 1 except that (0) was used. This photoreceptor was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

[0023]

[Table 1]

[0024]

INDUSTRIAL APPLICABILITY The thermoplastic norbornene-based resin solution composition of the present invention provides a coating film excellent in transparency and abrasion resistance, and is particularly excellent when used as a binder for a photoconductor such as electrophotography. It has excellent characteristics.

Continuation of front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location // C09D 145/00 PGM (72) Inventor Kikuko Honda 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Naru Rubber Co., Ltd.

Claims (1)

[Claims] 1. A thermoplastic norbornene-based resin (A),
A thermoplastic norbornene-based resin solution composition containing (B) a thermoplastic elastomer having a refractive index in the range of 1.48 to 1.55 and (C) a charge generating substance and / or a charge transfer substance.