JPH107865A - Semiconductive thermoplastic fluororesin composition and semiconductive thermoplastic fluororestn film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition stably expressing a specified volume resistivity in high accuracy, low in change with the lapse of time and environmental dependency, large in surface contact angle, and excellent in processability, by incorporating a thermoplastic fluororesin with an antioxidant and an ionic electrolyte. SOLUTION: This semiconductive composition is obtained by incorporating (A) 100 pts.wt. of a blend of (A1 ) 98-85 pts.wt. of a thermoplastic fluororesin <190 deg.C in melting point such as polyvinylidene fluoride or vinylidene fluoride copolymer and (A2) 2-15 pts.wt. of a polyalkylene oxide containing >=30wt.% of propylene oxide unit (pref. >=240 deg.C in the 10% weight reduction temperature determined by thermogravimetric analysis) with (B) 0.03-3 pts.wt. of an antioxidant such as a phenolic antioxidant and (C) 0.02-3 pts.wt. of an ionic electrolyte such as lithium perchlorate or lithium thiocyanate, and as necessary, (D) 0.3-10 pts. e.g. electronic image-forming processes such as electrophotographs and facsimiles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition having properties suitable for an electronic image forming process such as electrophotography, facsimile, laser printer, etc., and a film obtained from the composition. The present invention relates to a semiconductive thermoplastic fluororesin composition containing an antioxidant, an antioxidant, and a silicone resin, and a semiconductive thermoplastic fluororesin film.

[0002]

2. Description of the Related Art Conventionally, organic antistatic agents and inorganic conductive materials such as carbon black and metal powder have been added for the purpose of imparting antistatic properties and conductivity to thermoplastic resins. I have. However, among these, inorganic conductive materials such as carbon black and metal powder can impart extremely high conductivity, but on the other hand, a slight change in the amount of addition or processing due to the development of conductivity due to their contact. The electrical resistance greatly changes depending on the conditions and the like, and it was extremely difficult to control the volume resistivity in the range of 1 × 10 ⁵ to 1 × 10 ¹² Ω · cm. Furthermore, when such an inorganic conductive material is added, the transparency of the thermoplastic resin is impaired, and when added in a large amount, there is a problem that the mechanical strength of the product is reduced or the surface is roughened. .

[0003] On the other hand, when an organic antistatic agent is used, there is little problem of a decrease in transparency and mechanical strength, but a normal addition amount exhibits a volume resistivity of 1 × 10 ¹¹ Ω · cm or less. It was difficult to do. In addition, organic antistatic agents generally have a low molecular weight, and since the antistatic agent bleeds out to the surface of the thermoplastic resin to exhibit antistatic properties, it contaminates the surroundings and has poor durability. There was also a problem that the surface specific resistance was changed by washing with water.

To solve such problems, for example, polyether-ester-amide having a specific structure, a polymer having a quaternary ammonium salt in a side chain, a polymer having a sulfonic acid salt in a side chain, High molecular weight antistatic agents such as polymers containing polyalkylene oxide chains have been proposed. These high molecular weight antistatic agents have permanent antistatic properties compared to conventional organic low molecular weight antistatic agents, have improved surface stickiness due to bleed-out, and can be blended in large amounts. From 10 ¹⁰ Ω
-It has become possible to achieve a volume resistivity level of about cm. Further, the polymer type antistatic agent has a feature that it can accurately reproduce a semiconductive region of 10 ⁹ Ω · cm to 10 ¹² Ω · cm as compared with the inorganic conductive material. However, these polymer-type antistatic agents have a large difference between the electric resistance under low temperature and low humidity and the electric resistance under high temperature and high humidity, that is, the environment dependence of electric resistance, as compared with inorganic conductive materials such as carbon black. In addition, the film surface condition is good under a normal environment, but the film surface becomes sticky under high temperature and high humidity.

Further, since these polymer type antistatic agents are designed to be applicable to general-purpose thermoplastic resins such as polyolefin resin, polystyrene, ABS resin, etc., they are non-staining, heat resistant, weather resistant, When applied to thermoplastic fluororesins that have excellent properties such as ozone resistance and flame retardancy, compatibility is poor, and when mixed in large amounts, processability and physical properties are reduced, making it difficult to obtain thin films. There was a problem. Also, by adding a polymer type antistatic agent,
Decreased non-staining properties, which are inherent properties of thermoplastic fluororesins,
That is, there is a disadvantage that the surface contact angle is reduced.

Further, a stabilized conductive halogen-containing resin composition in which a perchlorate and a polyether polymer are blended with a halogen-containing resin (JP-A-3-39346) is disclosed. Among resins, when perchlorate and polyether-based polymer are blended with polyvinyl fluoride, the melting point of polyvinyl fluoride is as high as 227 ° C.
The processing requires a considerable high temperature, and the heat of the processing reduces the molecular weight of the compounded polyether polymer, and the thermal decomposition products of this polyether polymer bleed out to the surface of the molded product. was there. Further, when a chlorine-based synthetic resin or a bromine-based synthetic resin is used as the halogen-containing resin, since the polarity of these resins is smaller than that of the fluorine-based resin, a polyether-based polymer, It is necessary to considerably increase the amount of the perchlorate, which causes a problem that the processability is reduced and a problem that the polyether-based polymer bleeds out to the surface of the molded article.

Further, a resin composition having excellent antistatic properties, in which an alkylene oxide copolymer and an ion dissociable metal salt are blended with a thermoplastic resin, has been proposed (JP-A-6-200171). However, polyolefin resins,
A composition in which a polyalkylene oxide and an ion dissociable metal salt are blended with a thermoplastic resin such as a styrene-based resin such as an ABS resin or a polymethacrylate-based resin imparts semiconductivity due to the small polarity of the thermoplastic resin. Therefore, it is necessary to considerably increase the blending amount of the polyalkylene oxide copolymer and the ion dissociable metal salt, and if the blending amount of the polyalkylene oxide copolymer is increased, the polyalkylene oxide copolymer formed during molding processing is increased. There is a problem that the thermal decomposition product of the coalescence bleeds out to the surface of the molded article. Further, when the polyalkylene oxide copolymer and the ion dissociable metal salt are blended into the thermoplastic fluororesin, there is a problem that the non-staining property which is a characteristic of the thermoplastic fluororesin is lost.

[0008] In OA equipment such as a copying machine, a facsimile, a laser printer, etc., to which the principle of electrophotography is applied,
Generally, each process includes charging, exposure, development, transfer, fixing, and charge removal, and various rolls, belts, and blades are used to precisely control static electricity in each process. When these are used, in addition to the above-mentioned conditions, even if the amount of the antistatic agent to be added is not strictly controlled, 1 × 10 ⁵ to 1 × 10 ¹² Ω · cm, especially 1 × 10 ⁵ to 1 It is desired that a volume specific resistance in the range of × 10 ¹¹ Ω · cm and a surface specific resistance in the range of 1 × 10 ⁵ to 1 × 10 ¹² Ω / □ be stably provided.
It is also desired to further reduce the environmental dependence of electrical resistance and the bleed-out of additives, and to increase the surface contact angle.

[0009]

DISCLOSURE OF THE INVENTION The present invention has good physical and mechanical properties and has a property of 1 × 10 ⁸ to 1 × 10 ¹² Ω · c.
The semi-conductivity suitable for the electronic image forming process that stably and accurately expresses the volume resistivity in the range of m, has little change over time, environment dependency, bleed-out, large surface contact angle, and excellent workability. An object is to provide a thermoplastic fluororesin composition and a film obtained from the composition.

[0010]

Means for Solving the Problems The present inventors have studied in detail the combination of a polymer type antistatic agent and a thermoplastic resin in order to achieve the above-mentioned object. Attention was paid to a remarkable thermoplastic fluororesin. As a result of intensive study, the melting point is 98 to 85 parts by weight of a thermoplastic fluororesin having a melting point of less than 190 ° C. and 2 to 15 parts by weight of a polyalkylene oxide containing 30% by weight or more of a propylene oxide unit which is a polymer type antistatic agent. A thermoplastic fluororesin composition containing 0.03 to 3 parts by weight of an antioxidant and 0.02 to 3 parts by weight of an ionic electrolyte with respect to 100 parts by weight of the mixture has a volume resistivity of about 1 ×.
In addition to exhibiting stable ionic conductivity of 10 ⁸ to 1 × 10 ¹² Ω · cm, there is little environmental dependence of electric resistance, and there is no stickiness of the film surface even under high temperature and high humidity, and excellent workability. And 98 to 85 parts by weight of a thermoplastic fluororesin having a melting point of less than 190 ° C. and 30% by weight of a propylene oxide unit as a polymer type antistatic agent.
The antioxidant is added to 100 parts by weight of the mixture comprising 2 to 15 parts by weight of the polyalkylene oxide contained above.
3 to 3 parts by weight, 0.3 to 10 parts by weight of silicone resin,
And a thermoplastic fluororesin composition containing 0.02 to 3 parts by weight of an ionic electrolyte has a volume resistivity of approximately 1 × 10 ⁸
Not only does it exhibit stable ionic conductivity of up to 1 × 10 ¹² Ω · cm, it also has little environmental dependence, especially of electrical resistance, has no stickiness on the film surface even under high temperature and high humidity, and has excellent workability. It has been found that the contact angle is large, and the above-mentioned semiconductive thermoplastic fluororesin composition can be easily prepared by adjusting the compounding ratio of the constituent thermoplastic fluororesin, polyalkylene oxide, and ionic electrolyte. The present inventors have found that the target electric resistance can be controlled accurately and precisely, and have completed the present invention.

That is, according to the present invention, 100 to 100 parts by weight of a mixture comprising 98 to 85 parts by weight of a thermoplastic fluororesin having a melting point of less than 190 ° C. and 2 to 15 parts by weight of a polyalkylene oxide containing 30% by weight or more of propylene oxide units. The semiconductive thermoplastic fluororesin composition is characterized by containing 0.03 to 3 parts by weight of an antioxidant and 0.02 to 3 parts by weight of an ionic electrolyte per part by weight. Further, a thermoplastic fluororesin having a melting point of less than 190 ° C.
85 parts by weight and 100 parts by weight of a mixture of 2 to 15 parts by weight of a polyalkylene oxide containing 30% by weight or more of a propylene oxide unit are added with 0.03 of an antioxidant.
The present invention provides a semiconductive thermoplastic fluororesin composition characterized by containing 0.3 to 3 parts by weight, 0.3 to 10 parts by weight of a silicone resin, and 0.02 to 3 parts by weight of an ionic electrolyte. Particularly, the semiconductive thermoplastic fluororesin composition, wherein the thermoplastic fluororesin having a melting point of less than 190 ° C. is one selected from polyvinylidene fluoride or a copolymer thereof, or a mixture of two or more types. Product, preferably, the vinylidene fluoride copolymer is a vinylidene fluoride-propylene hexafluoride copolymer,
One or a mixture of two or more selected from vinylidene fluoride-ethylene tetrafluoride-propylene hexafluoride copolymer or a graft copolymer of vinylidene fluoride-propylene hexafluoride copolymer and vinylidene fluoride And a semiconductive thermoplastic fluororesin composition is provided. Also particularly the polyalkylene oxide is
It is a copolymer of ethylene oxide and propylene oxide, or one selected from thermoplastic polyalkylene oxide in which the main chain is extended between polyethylene oxide and polypropylene oxide, or polypropylene oxide, or a mixture of two or more kinds. Preferably, the polyalkylene oxide has a 10% weight loss temperature by thermogravimetric analysis (TGA) of 240.
The semiconductive thermoplastic fluororesin composition, wherein the composition is not less than ℃. In particular, there is provided the semiconductive thermoplastic fluororesin composition, wherein the antioxidant is a phenolic antioxidant, and in particular, the silicone resin represented by the following formula (1): And the proportion of the substituent introduced into the silicone resin is not more than 75% by weight of the entire silicone resin, and the semiconductive thermoplastic fluororesin composition according to any of the above is provided. And

Embedded image (R _{1 to} R ₃ represent a methyl group, an alkyl group having 8 to 30 carbon atoms, a phenyl group, a substituent having a polyalkylene oxide chain represented by the formula (2), a polycaprolactone chain represented by the formula (3) Any of the substituents

Embedded image (R ₄ is an alkylene group having 1 to 8 carbon atoms, R ₅ is H or CH ₃ , and O is an integer of 2 or more)

Embedded image (R ₆ is an alkylene group having 1 to 8 carbon atoms, p is an integer of 2 or more.) Furthermore, particularly, the ionic electrolyte is preferably an alkali metal thiocyanate, phosphate, sulfate, or an alkali metal and a halogen-containing oxygen. The semiconductive thermoplastic fluororesin composition is provided, wherein the composition is one kind selected from acid salts or a mixture of two or more kinds. Further, according to the present invention, there is provided a semiconductive thermoplastic fluororesin film obtained by molding the above semiconductive thermoplastic fluororesin composition at a processing temperature of less than 240 ° C.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described more specifically. Examples of the thermoplastic fluororesin having a melting point of less than 190 ° C. used in the present invention include polyvinylidene fluoride, vinylidene fluoride-propylene hexafluoride copolymer, and vinylidene fluoride.
Examples include a graft copolymer of ethylene tetrafluoride-propylene hexafluoride copolymer, vinylidene fluoride-propylene hexafluoride copolymer and vinylidene fluoride, and particularly, polyvinylidene fluoride, or a copolymer thereof. Is preferred from the viewpoint of moldability. The melting point of the thermoplastic fluororesin must be lower than 190 ° C. in order to prevent the thermal decomposition of the polyalkylene oxide during the molding process.
For a thermoplastic fluororesin of 90 ° C. or higher, the processing temperature needs to be raised to a higher temperature, so that the polyalkylene oxide undergoes thermal decomposition during kneading, or during molding,
It is not preferable because decomposition products bleed out on the surface of the molded product.

On the other hand, as the polyalkylene oxide constituting the semiconductive thermoplastic fluororesin composition of the present invention, a polyalkylene oxide containing 30% by weight or more of a propylene oxide unit is used. Specifically, a copolymer of ethylene oxide and propylene oxide; a polyethylene oxide and polypropylene oxide, or a thermoplastic polyalkylene oxide obtained by extending the main chain of polypropylene oxides with a dibasic acid, dibasic acid chloride, diisocyanate, or the like ( Even if it is partially crosslinked, it can be used as long as it has thermoplasticity.). These polyalkylene oxides can be used alone or in combination of two or more.

Further, it is more preferable that these polyalkylene oxides are selected from those having a 10% weight loss temperature of 240 ° C. or higher by thermogravimetric analysis (TGA). In the present invention, the thermogravimetric analysis (TGA) of the polyalkylene oxide was performed under the following conditions, and the 10% weight loss temperature mentioned here means the thermogravimetric analysis (TG).
It means the temperature at which the weight of the polyalkylene oxide read from the chart obtained in A) is reduced by 10% compared to the initial weight. <Conditions of thermogravimetric analysis (TGA)>-Sample amount: 10 mg-Cell: made of aluminum-Carrier gas: air-Initial temperature: 23 ° C-Heating rate: 10 ° C / min Polyalkylene oxide whose temperature is 240 ° C or more Is preferably used because the reduction in molecular weight due to heat during molding is suppressed.

As the polyalkylene oxide having a 10% weight loss temperature of 240 ° C. or more by thermogravimetric analysis, a copolymer of ethylene oxide and propylene oxide having a number average molecular weight of 3,000 or more; polyethylene oxide and polypropylene oxide, or polypropylene A thermoplastic polyalkylene oxide in which the main chains of the oxides are extended; and the like. However, in the present invention, propylene oxide is preferred in that the resulting semiconductive thermoplastic fluororesin composition has a reduced environmental dependence of electric resistance. A polyalkylene oxide containing 30% by weight or more of a unit is preferably used.

The mixing ratio of these polyalkylene oxides is preferably 2 to 15 parts by weight, more preferably 2 to 12 parts by weight, and more preferably 2 to 12 parts by weight based on 100 parts by weight of the mixture of the thermoplastic fluororesin and the polyalkylene oxide. 1
0 parts by weight is more preferred. If the compounding ratio exceeds 15 parts by weight, the compatibility with the thermoplastic fluororesin is deteriorated, so that not only the processability is lowered, but also the bleed-out of the component whose molecular weight is reduced by the heat at the time of processing is not preferable. On the other hand, if the blending ratio of the polyalkylene oxide is less than 2 parts by weight, the desired volume specific resistance cannot be exhibited, which is not preferable.

The antioxidants used in the present invention include:
Phenol-based, amine-based, sulfur-based, and phosphorus-based ones are used alone or in combination of two or more, and a phenolic antioxidant is most preferably used in view of its effect. As phenolic antioxidants, for example, 2,6
-Di-t-butylphenol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, 2,2-thio-diethylenebis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 2-t-butyl-6- (3'-t-
Butyl-5'-methyl-2'-hydroxybenzyl)-
4-methylphenyl acrylate, 2,4-di-t-butyl-6- [1- (3,5-di-t-butyl-2-hydroxyphenyl) ethyl] phenyl acrylate, and the like. The addition amount of the antioxidant is preferably 0.03 to 3 parts by weight, more preferably 0.05 to 2 parts by weight, per 100 parts by weight of the mixture of the thermoplastic fluororesin and the polyalkylene oxide.
Parts by weight are preferred. If the amount of the antioxidant is less than 0.03 parts by weight, a part of the polyalkylene oxide is decomposed during molding and the decomposition product bleeds out to the surface, which is not preferable. If the amount exceeds the above range, the effect corresponding to the compounding amount cannot be improved, which is not preferable.

The silicone resin used in the present invention includes a fluorine-containing alkyl group at the end of the polyorganosiloxane or a part of the alkyl group in the side chain, a substituent containing a polyalkylene oxide chain, and a C8-30 carbon atom. Is preferably substituted with a long-chain alkyl group, a substituent containing a polycaprolactone chain, or a phenyl group. The silicone resin is represented by the following formula (1), and It is more preferable to use those having a ratio of the introduced substituent of 75% by weight or less based on the entire silicone resin from the viewpoint of processability and the effect of increasing the surface contact angle.

Embedded image (R _{1 to} R ₃ represent a methyl group, an alkyl group having 8 to 30 carbon atoms, a phenyl group, a substituent having a polyalkylene oxide chain represented by the formula (2), a polycaprolactone chain represented by the formula (3) Any of the substituents

Embedded image (R ₄ is an alkylene group having 1 to 8 carbon atoms, R ₅ is H or CH ₃ , o is an integer of 2 or more)

Embedded image (R ₆ is an alkylene group having 1 to 8 carbon atoms, and p is an integer of 2 or more). The amount of the silicone resin added is a mixture of a thermoplastic fluororesin and a polyalkylene oxide.
0.3 to 10 parts by weight, preferably 0.5 to 7 parts by weight, per 100 parts by weight. If the addition amount is less than 0.3 part by weight, the surface contact angle of the obtained product will hardly increase, and if the addition amount exceeds 10 parts by weight, the processability will be reduced, which is not preferable.

As the ionic electrolyte used in the present invention, a thiocyanate, a phosphate, a sulfate, or a salt obtained from an alkali metal and a halogen-containing oxygen acid of an alkali metal may be used alone or in combination. Of these, potassium perchlorate, sodium perchlorate, lithium perchlorate, potassium thiocyanate,
Sodium thiocyanate and lithium thiocyanate are preferred. The amount added is 0.0 parts by weight based on 100 parts by weight of the mixture of the thermoplastic fluororesin and the polyalkylene oxide.
The amount is preferably 2 to 3 parts by weight, more preferably 0.05 to 2 parts by weight, and further preferably 0.07 to 1.5 parts by weight. If the added amount of the ionic electrolyte is less than 0.02 parts by weight, sufficient semiconductivity is not exhibited, which is not preferable. Conversely, if the added amount of the ionic electrolyte exceeds 3 parts by weight, thermal decomposition of the polyalkylene oxide during processing is performed. Not only is promoted, but also the environment dependence of the electrical properties of the obtained composition is increased, which is not preferable.

If necessary, a lubricant, a compatibilizer, a pigment, a reinforcing agent, etc. can be added to the semiconductive thermoplastic fluororesin composition of the present invention as long as the semiconductive property is not impaired. .

The semiconductive thermoplastic fluororesin composition of the present invention comprises a thermoplastic fluororesin having a melting point of less than 190 ° C., a polyalkylene oxide, an antioxidant, an ionic electrolyte and, if necessary, a silicone resin. Can be produced by kneading with a usual kneader, roll, Banbury mixer, twin-screw kneader or the like, and depending on its use, it is used after being shaped into a film, sheet, tube, molded product or the like. In addition, a small amount of a synthetic resin other than the thermoplastic fluororesin can be blended as required, for example, to improve workability.

The method of obtaining the semiconductive thermoplastic fluororesin film of the present invention is not particularly limited. For example, the semiconductive thermoplastic fluororesin composition obtained as described above is used. Into a film, supplying the pellet to an extruder equipped with an annular die or a T-die, forming a film, a method of forming a film by a calender method, a method of hot-pressing, and the like. Here, the processing temperature needs to be less than 240 ° C.,
Preferably, it is lower than 235 ° C. If the temperature is higher than 240 ° C., the polyalkylene oxide is reduced in molecular weight by heat during processing, and the reduced molecular weight polyalkylene oxide bleeds out to the surface of the product, which is not preferable.

[0023]

The reason why the thermoplastic fluororesin composition of the present invention can exhibit electric resistance until it reaches the semiconductive region is that the CF bond in the thermoplastic fluororesin has the highest electronegativity among all elements. Because it is polarized by fluorine atoms, it promotes dissociation of the ionic electrolyte, and lone electron pairs of oxygen atoms forming ether bonds in polyalkylene oxide form complexes with metal ions in a matrix resin having polarity, It is thought to be to promote the movement significantly. Furthermore, since the polyalkylene oxide containing a propylene oxide unit in an amount of 30% by weight or more is used, it is hardly affected by humidity, so that the environment dependency is small,
By adding an antioxidant, the thermal decomposition of the polyalkylene oxide during molding can be suppressed, so there is no stickiness of the product surface especially under high temperature and high humidity, and furthermore, the polyalkylene can be reduced by using a silicone resin together. It is considered that the reduced surface contact angle was significantly increased by the addition of the oxide. Therefore, the semiconductive thermoplastic fluororesin composition of the present invention can be easily adjusted to 1 × 10 ⁸ to 1 by adjusting the mixing ratio of the constituent thermoplastic fluororesin, polyalkylene oxide, and ionic electrolyte. In addition to being able to accurately and stably express a predetermined volume resistivity in the range of × 10 ¹² Ω · cm, there is little difference between the electrical resistance under high temperature and high humidity and the electrical resistance under low temperature and low humidity, and it is used. It exhibits stable ionic conductivity even when the environment changes, has no stickiness on the product surface under high temperature and high humidity, and has a feature that the surface contact angle can be increased by adding a silicone resin. Further, the semiconductive thermoplastic fluororesin composition of the present invention can set the processing temperature low, and by adding an antioxidant, minimizes the reduction of the molecular weight of the polyalkylene oxide due to heat during processing. Since it is suppressed, there is almost no bleed-out of additives and the like, and the surface contact angle can be greatly increased by using a silicone resin in combination. Further, the semiconductive thermoplastic fluororesin film of the present invention also has excellent physical properties such as the inherent non-staining property, antifouling property, heat resistance, weather resistance, ozone resistance and flame retardancy of the thermoplastic fluororesin. Therefore, it is suitably used as a resin for an electronic image forming process.

[0024]

Next, the present invention will be described in detail with reference to examples. Parts in Examples are parts by weight, and the blending ratio is on a weight basis. The thermoplastic fluororesin, polyalkylene oxide, antioxidant, silicone resin, and ionic electrolyte used in the examples are as follows.

<Thermoplastic Fluororesin> Fluororesin A: Polyvinylidene fluoride (Atochem:
KYNAR710 melting point: 170 ° C.) Fluororesin B: polychlorotrifluoroethylene (manufactured by Daikin Co., Ltd .: NEOFLON CTFE melting point: 210-2)
12 ° C)

<Polyalkylene oxide> PAO-A: thermoplastic polyalkylene oxide obtained by extending the main chain of polyethylene oxide and polypropylene oxide with diisocyanate (40% by weight of propylene oxide units in polyalkylene oxide).・
PAO-B: thermoplastic polyalkylene oxide obtained by extending the main chain of polyethylene oxide and polypropylene oxide with diisocyanate (propylene oxide units in polyalkylene oxide 60% by weight). PAO-C: thermoplastic polyalkylene oxide in which the main chain of polypropylene oxide is extended with diisocyanate (100% by weight of propylene oxide units in polyalkylene oxide). PAO-D: a thermoplastic polyalkylene oxide obtained by elongating the main chain of polyethylene oxide with diisocyanate (0% by weight of propylene oxide units in polyalkylene oxide). PAO-E: thermoplastic polyalkylene oxide obtained by extending the main chain of polyethylene oxide and polypropylene oxide with diisocyanate (propylene oxide units in polyalkylene oxide: 20% by weight). The polyalkylene oxide was subjected to thermogravimetric analysis (TGA) under the following conditions. From the obtained chart, the temperature at which the weight of the polyalkylene oxide was reduced by 10%,
That is, the 10% weight loss temperature was read. Table 1 shows the results. << Thermogravimetric analysis (TGA) condition >>-Measuring instrument: Thermogravimetric analyzer (SSC / 5200 series TG / DTA220 manufactured by Seiko Instruments Inc.)-Sample amount: 10 mg-Cell: made of aluminum-Carrier gas: air-Initial temperature: 23 ° C · Temperature rise rate: 10 ° C / min

[0027]

[Table 1]

<Antioxidant> Antioxidant A: pentaerythrityl-tetrakis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] (IRGANOX 1010, manufactured by Nippon Ciba Geigy Co., Ltd.) <Silicone-based resin>-Silicone-based resin A: polyethylene oxide on the side chain of organopolysiloxane -Based resin, polyethylene oxide content 10% by weight (F1-
024-01, manufactured by Nippon Unicar Co., Ltd.)-Silicone resin B: a silicone resin in which polycaprolactone is grafted to the side chain of organopolysiloxane, polycaprolactone content 70% by weight (F-201-
01, manufactured by Nihon Unicar Co., Ltd.) <Ion electrolyte>-Ion electrolyte A: lithium perchlorate

The method for evaluating the semiconductive thermoplastic fluororesin composition in the examples is as follows. <Volume specific resistance> The volume specific resistance was measured at an applied voltage of 500 V using a Hiresta HRS probe manufactured by Mitsubishi Yuka Corporation. The measurement of the volume resistivity was performed at 23 ° C. and 50% RH unless otherwise specified. <Haze on film surface under high temperature and high humidity> The film obtained by hot pressing was placed in 30 ° C., 80% RH for 24 hours.
The film was left for a time, and the presence or absence of fogging on the film surface was observed. <Evaluation of Environmental Dependence of Electric Resistance> The volume resistivity (LL) at 10 ° C. and 30% RH of the film obtained by hot pressing and the volume resistivity (HH) at 30 ° C. and 80% RH were measured. And LL / HH. <Surface contact angle> The contact angle was measured by a droplet method using a contact angle meter manufactured by Kyowa Interface Chemistry.

Example 1 PAO- containing 95 parts by weight of a fluororesin A and 40% by weight of a propylene oxide unit
A5 parts by weight of A, 0.5 parts by weight of antioxidant A, and 0.5 parts by weight of ionic electrolyte A were uniformly kneaded with a mixing roll at 180 ° C. and then press-molded to produce a film having a thickness of about 120 μm. Table 2 shows the properties of the obtained film.
Shown in

Comparative Example 1 95 parts by weight of fluororesin A, 5 parts by weight of PAO-D containing no propylene oxide unit, 0.5 parts by weight of antioxidant A, and ionic electrolyte A
0.5 parts by weight were uniformly kneaded with a mixing roll at 180 ° C. and then press-molded to produce a film having a thickness of about 120 μm. Table 2 also shows various properties of the obtained film.

Comparative Example 2 95 parts by weight of fluororesin A, 5 parts by weight of PAO-D containing no propylene oxide unit, and 0.5 parts by weight of ionic electrolyte A were uniformly kneaded with a mixing roll at 180.degree. A film having a thickness of about 120 μm was produced. Table 2 also shows various properties of the obtained film.

Comparative Example 3 95 parts by weight of polychlorotrifluoroethylene, 5 parts by weight of PAO-A, antioxidant A
0.5 parts by weight and 0.5 parts by weight of ionic electrolyte A
The mixture was uniformly kneaded with a mixing roll at 45 ° C., and then press-molded to produce a 120 μm thick film. Table 2 also shows various properties of the obtained film.

[0034]

[Table 2]

As is clear from Table 2, the composition of Example 1 using a thermoplastic fluororesin having a melting point of 190 ° C. or less as the matrix resin was obtained from a polyalkylene oxide containing propylene oxide units in an amount of 30% by weight or more. Contains a propylene oxide unit, while exhibiting good ionic conductivity by combining an inhibitor and an ionic electrolyte, without causing fogging on the film surface even under high temperature and high humidity, and having low environmental dependence of electrical resistance. The film of Comparative Example 1 using a polyalkylene oxide that does not have good ionic conductivity has a large environmental dependence of electric resistance. Further, the film of Comparative Example 2 in which no antioxidant was used was fogged on the film surface under high temperature and high humidity, and the environment dependence of electric resistance was large.
On the other hand, in Comparative Example 3 in which polychlorotrifluoroethylene having a high melting point was used as the thermoplastic fluororesin, the kneading temperature by the mixing roll had to be increased to 245 ° C., so that the polyalkylene oxide was decomposed and volatilized during kneading. The volume resistivity was hardly reduced. Therefore, in order to obtain good ion conductivity with a small blending amount, it is understood that it is essential to use a thermoplastic fluororesin having a melting point of less than 190 ° C. as the matrix resin.

[Examples 2 and 3] PAO-B (propylene oxide unit was 60% by weight based on 95 parts by weight of fluororesin)
5 parts by weight of PAO-C (containing 100% by weight of propylene oxide units), 0.5 parts by weight of an antioxidant A, and 0.5 parts by weight of an ionic electrolyte A.
The mixture was uniformly kneaded with a mixing roll at 80 ° C. and then press-molded to obtain a film having a thickness of about 120 μm. Table 3 shows the composition and Table 4 shows various properties.

[Examples 4 and 5] 5 parts by weight of PAO-C (containing 100% by weight of propylene oxide unit), 0.5 parts by weight of antioxidant A, 2 parts by weight of silicone resin, and 95 parts by weight of fluororesin A 0.5 part by weight of the ionic electrolyte A was added, and the mixture was uniformly kneaded with a mixing roll at 180 ° C. and then press-molded to obtain a film having a thickness of about 120 μm. Table 3 shows the composition and Table 4 shows various properties.

Comparative Example 4 P to 95 parts by weight of fluororesin A
After adding 5 parts by weight of AO-E (containing 20% by weight of propylene oxide unit), 0.5 parts by weight of antioxidant A, and 0.5 parts by weight of ionic electrolyte A, and uniformly kneading with a 180 ° C. mixing roll Press molding was performed to obtain a film having a thickness of about 120 μm. Table 3 shows the composition.
Table 4 shows various properties.

[0039]

[Table 3]

[0040]

[Table 4]

From the results shown in Table 4, the film of the present invention shows that 2
At 3 ° C. and 50% RH, the desired volume resistivity is exhibited, the value of LL / HH is small, the environment dependency is low, and the product surface does not fog even under high temperature and high humidity. It can be seen that it can be used well even under wet conditions. Further, in Examples 4 and 5, the addition of the modified silicone resin not only significantly increased the surface contact angle but also reduced the environmental dependence of electric resistance.
On the other hand, since the film of Comparative Example 4 uses a polyalkylene oxide having a small content of propylene oxide units, the value of LL / HH is large. Thus, the semiconductive thermoplastic fluororesin film obtained by molding the semiconductive thermoplastic fluororesin composition of the present invention can exhibit a stable function under various environments,
It can be seen that it also has the non-staining property which is an inherent property of the thermoplastic fluororesin.

[0042]

The semiconductive thermoplastic fluororesin composition of the present invention comprises a thermoplastic fluororesin having a melting point of less than 190 ° C. as a matrix resin and three propylene oxide units.
By using a combination of a polyalkylene oxide, an antioxidant, an ionic electrolyte, and a silicone-based resin, if necessary, containing 0% by weight or more, the excellent interaction between them makes it possible to obtain 1 × 10 ⁸ to 1 × 10 ¹² Ω · cm. A predetermined volume specific resistance within the range can be accurately expressed. Further, the semiconductive fluororesin composition of the present invention, despite containing an ionic electrolyte, by adding an antioxidant, and a silicone-based resin, provides electrical resistance at low temperature and low humidity and high temperature and high humidity. In this case, there is little difference between the electric resistances, that is, the environment dependence of the electric resistance is small and stable ionic conductivity is exhibited, and the product has a property that no fogging occurs on the product surface even under high temperature and high humidity. Furthermore, the surface contact angle reduced by the addition of the polyalkylene oxide is greatly increased by the addition of the silicone resin, that is, the original property of the thermoplastic fluororesin, which is non-staining, is restored. Further, since there is almost no thermal decomposition product due to the polyalkylene oxide at the time of processing, there is no bleed-out due to additives and the workability is excellent.
Further, the semiconductive thermoplastic fluororesin composition of the present invention retains excellent physical properties such as non-adhesiveness, heat resistance, ozone resistance, and flame retardancy, which are characteristics of the fluororesin. Therefore, the semiconductive thermoplastic fluororesin composition of the present invention,
As a semiconductive resin for an electronic image forming process that requires accurate semiconductivity, it is suitably used in the field of, for example, electrophotographic materials. Furthermore, the semiconductive thermoplastic fluororesin composition of the present invention can be easily formed into films, sheets, tubes, and other molded products.
Further, the semiconductive thermoplastic fluororesin film of the present invention obtained by molding the semiconductive thermoplastic fluororesin composition also has the above-mentioned performance as it is, and is a semiconductive resin for an electronic image forming process. Are suitably used in the field of, for example, electrophotographic materials.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C08L 71:02 83:04) (72) Inventor Shigetoshi Takechi 1515 Nakatsucho, Marugame-shi, Kagawa Okura Industry Inside the Company (72) Inventor Takanori Okamoto 1515 Nakatsu-cho, Marugame-shi, Kagawa Prefecture Inside the Okura Kogyo Co., Ltd.

Claims (10)

[Claims] 1. A method according to claim 1, wherein 98 to 85 parts by weight of a thermoplastic fluororesin having a melting point of less than 190.degree.
2 to 15% by weight of polyalkylene oxide
0.03 to 3 parts by weight of an antioxidant and 0.02 to 3 parts by weight of an ionic electrolyte per 100 parts by weight of a mixture consisting of parts by weight
A semiconductive thermoplastic fluororesin composition comprising parts by weight. 2. A composition comprising 98 to 85 parts by weight of a thermoplastic fluororesin having a melting point of less than 190 ° C. and 30 parts of propylene oxide units.
2 to 15% by weight of polyalkylene oxide
It is characterized by containing 0.03 to 3 parts by weight of an antioxidant, 0.3 to 10 parts by weight of a silicone resin, and 0.02 to 3 parts by weight of an ionic electrolyte with respect to 100 parts by weight of a mixture consisting of parts by weight. A semiconductive thermoplastic fluororesin composition. 3. The thermoplastic fluororesin having a melting point of less than 190 ° C. is one kind selected from polyvinylidene fluoride or a copolymer thereof, or a mixture of two or more kinds. 3. The semiconductive thermoplastic fluororesin composition according to item 1. 4. The vinylidene fluoride copolymer is a vinylidene fluoride-propylene hexafluoride copolymer, a vinylidene fluoride-ethylene tetrafluoride-ethylene hexafluoropropylene copolymer, or a vinylidene fluoride-hexafluoride copolymer. 4. The semiconductive thermoplastic fluororesin composition according to claim 3, wherein the composition is one selected from graft copolymers of fluorinated propylene copolymers and vinylidene fluoride, or a mixture of two or more thereof. 5. The polyalkylene oxide is a copolymer of ethylene oxide and propylene oxide,
Or one or more selected from polyethylene oxide and polypropylene oxide, or a thermoplastic polyalkylene oxide in which the main chain of polypropylene oxide is extended.
A semiconductive thermoplastic fluororesin composition according to any one of claims 1 to 4. 6. The polyalkylene oxide has a 10% weight loss temperature by thermogravimetric analysis (TGA) of 240 ° C.
The semiconductive thermoplastic fluororesin composition according to any one of claims 1 to 5, characterized in that: 7. The semiconductive thermoplastic fluororesin composition according to claim 1, wherein the antioxidant is a phenolic antioxidant. 8. The method according to claim 1, wherein the silicone resin is represented by the following formula (1), and the ratio of the substituent introduced into the silicone resin is 75% by weight or less of the whole silicone resin. The semiconductive thermoplastic fluororesin composition according to any one of claims 2 to 7, wherein: Embedded image (R _{1 to} R ₃ are a methyl group, a long-chain alkyl group having 8 to 30 carbon atoms, a phenyl group, a substituent having a polyalkylene oxide chain represented by the formula (2), a poly-alkyl group represented by the formula (3) Any of the substituents having a caprolactone chain) (R ₄ is an alkylene group having 1 to 8 carbon atoms, R ₅ is H or CH ₃ , and o is an integer of 2 or more.) (R ₆ is an alkylene group having 1 to 8 carbon atoms, p is an integer of 2 or more) 9. The method according to claim 1, wherein the ionic electrolyte is one or more selected from alkali metal thiocyanates, phosphates, sulfates, and halogen-containing oxyacid salts. 9. The semiconductive thermoplastic fluororesin composition according to any one of 1 to 8. 10. A semiconductive thermoplastic fluororesin film obtained by molding the semiconductive thermoplastic fluororesin composition according to claim 1 at a processing temperature of less than 240 ° C.