JPH07247397A - Semiconductive fluororesin composition - Google Patents

Abstract

PURPOSE:To provide a semiconductive resin compsn. which can accurately develop a predetermined volume resistivity in the range of from 1X10<5> to 1X10<11>OMEGA.cm and is less likely to be influenced by environment. CONSTITUTION:To a mixture of 95 to 30wt.% thermoplastic fluororesin with 5 to 70wt.% polymer of an epihalohydrin is added an ionic electrolyte in an amt. of 0.05 to 5wt.% based on the mixture.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductive fluororesin composition which can be suitably used in electrophotographic image forming processes such as copying machines, facsimiles and laser printers.

[0002]

2. Description of the Related Art OA devices such as copying machines, facsimiles, laser printers, etc., which apply the principle of electrophotography, generally have processes of charging, exposing, developing, transferring, fixing, and neutralizing, Various rolls, belts and blades are used to precisely control static electricity in each process. At present, most of the semiconductive resins used in this field are those obtained by adding a conductive substance to an insulating polymer to give it a semiconductive function. Rubber such as silicone rubber and butadiene rubber, and various thermoplastic resins are used as the insulating polymer, and inorganic conductive materials such as carbon powder and metal powder and organic antistatic agents are generally used as the conductive material. Target. In recent years, technological developments have been actively made in order to speed up the process and improve the image quality as well as the size and weight reduction of the device, and the following requirements have been made for the semiconductive resin.

Even if the addition amount of the antistatic agent is not strictly controlled, 1 × 10 ⁵ to 1 × 10 ¹² Ω · cm, particularly 1 × 10 ⁵
A predetermined volume resistivity can be stably applied in the range of 1 × 10 ¹¹ Ω · cm. Environmental dependence of volume resistivity is small. Have good physical properties and mechanical strength.

When an inorganic conductive material such as carbon powder or metal powder is added, almost satisfactory results can be obtained with respect to the above requirement. Since the resistance changes greatly, there is a problem with the requirement. For example, in a carbon powder addition system, 1 × 10 ⁵ to 1 × 10 ¹¹ Ω ·
The range of cm is called an unstable region, and is said to be a region that is particularly difficult to control. Further, if the compounding ratio of the inorganic conductive material is increased, there arises a problem that the mechanical strength of the product is lowered and the surface is roughened.

On the other hand, when an organic antistatic agent is used as a conductive material, the usual organic antistatic agent has a low molecular weight, which is unsatisfactory. Also, in terms of the above, it is difficult to develop a volume resistivity of 1 × 10 ¹¹ Ω · cm or less with a normal addition amount. Recently, for example, a permanent antistatic resin composition using a polyether-ester-amide having a specific structure (Japanese Patent Publication No. 4-72855) and a semi-conductive transfer roll to which the composition is applied (Japanese Patent Laid-Open No. 5-28755). Since a polymer type organic antistatic agent such as 107794 gazette) has been developed and the problem of has been considerably improved and a large amount of compounding has become possible, 10 ¹⁰ Ω · cm
The level before and after has come to be achieved. However, even in these cases, the dependency on the environment is great, and it was extremely difficult to satisfy both of them at the same time.

[0006]

SUMMARY OF THE INVENTION The present invention has good physical and mechanical properties, and is 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm.
It is an object of the present invention to provide a semiconductive resin that stably exhibits a predetermined volume specific resistance in the range of 1) with high accuracy and is suitable for an electronic image forming process with little change over time and environmental dependence.

[0007]

According to the present invention, a polymer 5 of 95 to 30% by weight of a thermoplastic fluororesin and epihalohydrin is used.
To 70% by weight of the mixture, and 0.05 to 5% by weight of the ionic electrolyte is added to the mixture, to provide a semiconductive fluororesin composition, further comprising:
Provided is the above semiconductive fluororesin composition, wherein the thermoplastic fluororesin is polyvinylidene fluoride, or a copolymer thereof, and further, a polymer of epihalohydrin is a homopolymer of epichlorohydrin or a copolymer of epichlorohydrin. The semiconductive fluororesin composition characterized by being a united body is provided, and furthermore, the ionic electrolyte is at least one of alkali metal thiocyanate, phosphate, sulfate and halogen oxyacid salt. The semiconductive fluororesin composition is provided.

That is, the inventors of the present invention have studied in detail the combination of a polymer type antistatic agent and a thermoplastic resin in order to achieve the above-mentioned object. As a result, a thermoplastic fluororesin with a polymer of epihalohydrin is used as a polymer type. When used as an antistatic agent and used in combination with an ionic electrolyte, a semiconductive composition having a stable volume resistivity in the range of approximately 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm can be obtained. I found it.

The present invention will be described in detail below. The thermoplastic fluororesin used in the present invention, polyvinylidene fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer Combined, polytrifluoroethylene chloride, polytrifluoroethylene chloride-vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-6 Examples thereof include a graft copolymer of a propylene fluoride copolymer and vinylidene fluoride, and polyvinylidene fluoride or a copolymer thereof is particularly preferable in terms of moldability.

Examples of the polymer of epihalohydrin include homopolymers and copolymers of epichlorohydrin, epibromhydrin, epiiodohydrin and epifluorohydrin. Examples of the monomer copolymerized with epihalohydrin include: Examples thereof include ethylene oxide, propylene oxide, butylene oxide, and allyl glycidyl ether. In particular, a copolymer of epichlorohydrin and ethylene oxide, a copolymer of epichlorohydrin and propylene oxide, a copolymer of epichlorohydrin and allyl glycidyl ether, a terpolymer of epichlorohydrin and ethylene oxide, and an allyl glycidyl ether terpolymer Preference is given to using.

In the case of the epihalohydrin copolymer, the content of epihalohydrin is preferably 30 mol% or more. If the content of epihalohydrin in the copolymer is less than this, the ozone resistance, which is a characteristic of epihalohydrin rubber, decreases, and the semiconducting fluororesin composition obtained becomes highly environmentally dependent, which is not preferable.

The thermoplastic fluororesin and epihalohydrin polymer described above are preferably mixed in the range of 95 to 30% by weight of the thermoplastic fluororesin and 5 to 70% by weight of the epihalohydrin polymer. When the content of the polymer of epihalohydrin exceeds 70% by weight, the content of the thermoplastic fluororesin decreases, so that not only the characteristics of the fluororesin are lost but also the product becomes tacky. It is not preferable because the volume resistivity cannot be expressed.

As the ionic electrolyte used in the present invention, alkali metal thiocyanates, phosphates, sulfates and halogen oxyacid salts can be used. Of these, lithium perchlorate and perchlorate are particularly preferable. Sodium acid salt, potassium perchlorate, lithium thiocyanate, sodium thiocyanate and potassium thiocyanate are preferable. The ionic electrolyte is preferably used in an amount of 0.05 to 5% by weight based on the total amount of the thermoplastic fluororesin and epihalohydrin polymer.

In the semiconductive fluororesin composition of the present invention, the above-mentioned thermoplastic fluororesin, the polymer of epihalohydrin, and the ionic electrolyte are kneaded by an ordinary kneader, mixing roll, Banbury mixer, biaxial kneader or the like. Can be manufactured by, depending on the application, film,
It is used after being molded into the shape of a sheet, tube, etc. If necessary, a small amount of synthetic resin other than the thermoplastic fluororesin may be added.

[0015]

EXAMPLES Next, the present invention will be described in detail with reference to Examples. Further, the volume resistivity in the examples was measured by using a Hiresta HRS probe manufactured by Mitsubishi Petrochemical Co., Ltd.
It is the result measured at 00V. The volume resistivity was measured at 23 ° C. and 50% RH unless otherwise specified. Furthermore, the thermoplastic fluororesin used in the examples,
The polymer of epihalohydrin and the ionic electrolyte are as follows.

Thermoplastic Fluorocarbon Resin Fluorocarbon Resin A: Vinylidene Fluoride-Propylene Hexafluoropropylene Copolymer Grafted with Vinylidene Fluoride (Central Glass: Cefralsoft G180) Fluorocarbon Resin B: Polyvinylidene Fluoride (Mitsubishi Yuka: Kainer 2800) Fluororesin C: Polytrifluoroethylene chloride (Daikin Industries: NEOFLONCTFE) Fluororesin D: Tetrafluoride ethylene-ethylene copolymer (Daikin Industries: NEOFLON ETFE EP-
610)

Polymer of epihalohydrin EpCl resin A: Copolymer of epichlorohydrin and ethylene oxide (Nippon Zeon: HERCLOR
C) EpCl resin B: a copolymer of epichlorohydrin and ethylene oxide (manufactured by Zeon Corporation: Gechron 2
000) EpCl resin C: terpolymer of epichlorohydrin, ethylene oxide and allyl glycidyl ether (manufactured by Zeon Corporation: Gechron 3100) EpCl resin D: copolymer of epichlorohydrin and allyl glycidyl ether (manufactured by Nippon Zeon: Gechro)
n 1100) EpCl resin E: terpolymer of epichlorohydrin, ethylene oxide, and allyl glycidyl ether (Daiso: epichromer CG) EpCl resin F: copolymer of epichlorohydrin and ethylene oxide (daiso: epichromer C)

Ion Electrolyte Ion Electrolyte A: Lithium Perchlorate Ion Electrolyte B: Potassium Thiocyanate Ion Electrolyte C: Sodium Thiocyanate

Example 1 A 3: 1 (weight ratio) mixture of fluororesin A and fluororesin B was used as the thermoplastic fluororesin, and the total mixing ratio was changed to 10 by changing the compounding ratio of the thermoplastic fluororesin and EpCl resin A.
After adjusting the amount to 0 parts by weight, 0.5 parts by weight of ionic electrolyte A was added and uniformly kneaded with a 180 ° C. mixing roll to obtain a semiconductive fluororesin composition. The composition obtained was press-molded to form a film having a thickness of about 100 μm, which was used as a test piece. FIG. 1 shows the relationship between the compounding amount of EpCl resin A and the volume resistivity of the obtained film.

Comparative Example 1 100 parts by weight of the same thermoplastic fluororesin as in Example 1 was blended with a predetermined amount of carbon black (Ketjen Black) and uniformly kneaded with a mixing roll at 180 ° C. to give a semiconductive fluororesin. A composition was obtained. The composition obtained was press-molded to form a film having a thickness of about 100 μm, which was used as a test piece. FIG. 1 also shows the relationship between the blending amount of carbon black and the volume resistivity of the obtained film.

Comparative Example 2 97 parts by weight of thermoplastic fluororesin and 3 parts of EpCl resin A
A semiconductive fluororesin composition was obtained in the same manner as in Example 1 except that the parts by weight were used. This composition was press-molded to form a film having a thickness of about 100 μm, which was used as a test piece. The volume resistivity of the test piece was 1.5 × 10 ¹¹ Ω · cm.

As is apparent from FIG. 1, the composition of Comparative Example 1 containing carbon black as the conductivity-imparting agent was
The volume resistivity decreases 100,000 times or more when the amount of carbon black added is increased by only 1 part by weight, whereas in the case of the composition of the present invention, even if the amount of EpCl resin is increased. , Volume resistivity is 1 × 10 ¹² to 1 × 1
Gradually decreases to × 10 ⁷ Ω · cm. Therefore, it can be understood that the composition of the present invention can express the desired predetermined volume resistivity with high accuracy without strictly controlling the blending amount of the EpCl resin.

When the amount of the EpCl resin compounded exceeds 70 parts by weight based on 100 parts by weight of the total amount of the thermoplastic fluororesin and the EpCl resin, not only the effect of lowering the volume specific resistance is reduced but also it is obtained. The resulting composition became tacky. On the other hand, when the compounding amount was as small as 3 parts by weight as in Comparative Example 2, only those having the same volume specific resistance as the conventional antistatic agent were obtained.

Example 2 20 parts by weight of EpCl resin A and a predetermined amount of ionic electrolyte A were mixed with a mixture of 60 parts by weight of fluororesin A and 20 parts by weight of fluororesin B, and the mixture was uniformly kneaded with a mixing roll at 180 ° C. Thus, a semiconductive fluororesin composition was obtained. The obtained composition is press-molded to a thickness of about 100μ.
A film of m was prepared and used as a test piece. FIG. 2 shows the relationship between the amount of ionic electrolyte A added and the volume resistivity of the obtained film.

Example 3 20 parts by weight of EpCl resin B and 0.5 parts by weight of ionic electrolyte A were added to a mixture of 60 parts by weight of fluororesin A and 20 parts by weight of fluororesin B, and the mixture was uniformly mixed with a mixing roll at 180 ° C. The mixture was kneaded to obtain a semiconductive fluororesin composition. Then, the obtained composition was press-molded to form a film having a thickness of about 100 μm, which was used as a test piece. Table 1 shows the volume resistivity of the obtained film under various environments.

Example 4 A mixture of 53 parts by weight of fluororesin A and 17 parts by weight of fluororesin C was mixed with 30 parts by weight of EpCl resin B and 0.5 parts by weight of ionic electrolyte B, and uniformly mixed with a mixing roll at 180 ° C. The mixture was kneaded to obtain a semiconductive fluororesin composition. Then, the obtained composition was press-molded to form a film having a thickness of about 100 μm, which was used as a test piece. Table 1 shows the volume resistivity of the obtained film under various environments.

Example 5 A mixture of 53 parts by weight of fluororesin A and 17 parts by weight of fluororesin B was mixed with 30 parts by weight of EpCl resin B and 0.5 part by weight of ionic electrolyte C, and uniformly mixed with a 180 ° C. mixing roll. The mixture was kneaded to obtain a semiconductive fluororesin composition. Then, the obtained composition was press-molded to form a film having a thickness of about 100 μm, which was used as a test piece. Table 1 shows the volume resistivity of the obtained film under various environments.

Comparative Example 3 A mixture of 70 parts by weight of fluororesin A and 24 parts by weight of fluororesin B was mixed with 6 parts by weight of a commercially available polyether ester amide as an antistatic agent and 0.25 part by weight of sodium dodecylbenzenesulfonate. The mixture was uniformly kneaded with a 180 ° C. mixing roll to obtain a semiconductive fluororesin composition. The resulting composition is press molded to a thickness of about 1
A 00 μm film was prepared and used as a test piece. Table 1 shows the volume resistivity of the obtained film under various environments.

Comparative Example 4 A mixture of 60 parts by weight of fluororesin A and 20 parts by weight of fluororesin B was mixed with 20 parts by weight of a commercially available polyether ester amide as an antistatic agent and 0.5 parts by weight of ionic electrolyte A, and the mixture was heated at 180 ° C. Was uniformly kneaded with a mixing roll of No. 1 to obtain a semiconductive fluororesin composition. Then, the obtained composition was press-molded to form a film having a thickness of about 100 μm, which was used as a test piece. Table 1 shows the volume resistivity of the obtained film under various environments.

[0030]

[Table 1]

From Table 1, the composition of the present invention is
Comparative Example 3 not only showing the desired volume resistivity at 0% RH, but using polyetheresteramide instead of the polymer of epihalohydrin, and increasing the amount of polyetheresteramide compounded to lower the volume resistivity. It can be seen that the value of LL / HH is smaller than that of Comparative Example 4 and the environmental dependence is small.

Examples 6 to 10 A mixture of fluororesin A and fluororesin B was added with EpC.
A predetermined amount of a resin and an ionic electrolyte were mixed and uniformly kneaded with a mixing roll at 180 ° C. to obtain a semiconductive fluororesin composition. Then, the obtained composition was press-molded to form a film having a thickness of about 100 μm, which was used as a test piece. Table 2 shows the blending ratios thereof and the volume resistivity of the obtained film.

Comparative Example 5 A semiconductive fluororesin composition was obtained by uniformly kneading a mixture of polypropylene, EpCl resin A and ionic electrolyte B with a mixing roll at 180 ° C. Then
The composition obtained was press-molded to form a film having a thickness of about 100 μm, which was used as a test piece. Table 2 also shows the blending ratios thereof and the volume resistivity of the obtained film.

Comparative Example 6 A predetermined amount of ionic electrolyte B was mixed with a mixture of fluororesin A and fluororesin B, and the mixture was uniformly kneaded with a mixing roll at 180 ° C. to obtain a semiconductive fluororesin composition. Then, the obtained composition is press-molded to have a thickness of about 100 μm.
A film of m was prepared and used as a test piece. Table 2 also shows the blending ratios thereof and the volume resistivity of the obtained film.

Comparative Example 7 EpCl was added to a mixture of fluororesin A and fluororesin B.
A predetermined amount of Resin A was mixed and uniformly kneaded with a 180 ° C. mixing roll to obtain a semiconductive fluororesin composition. Then, the obtained composition is press-molded to have a thickness of about 100 μm.
A film of m was prepared and used as a test piece. Table 2 also shows the blending ratios thereof and the volume resistivity of the obtained film.

[0035]

[Table 2]

As shown in Table 2, the compositions of the present invention (Examples 6 to 10) have a volume resistivity of 1 × 10 ¹¹ Ω · cm or less, while polypropylene is used instead of the thermoplastic fluororesin. In the case of Comparative Example 5 used, a desired volume resistivity was not obtained. Moreover, when the epihalohydrin polymer was not used (Comparative Example 6) and when the ionic electrolyte was not used (Comparative Example 7), the volume resistivity was 100 times higher than that of the Examples.

Examples 11 and 12 EpCl resin and ionic electrolyte were mixed in a predetermined amount with a fluororesin and uniformly kneaded with a mixing roll at 180 ° C. to obtain a semiconductive fluororesin composition. Then, the obtained composition was press-molded to form a film having a thickness of about 100 μm, which was used as a test piece. Table 3 shows the blending ratios thereof and the volume resistivity of the obtained film.

[0038]

[Table 3]

[0039]

The semiconductive fluororesin composition of the present invention comprises a thermoplastic fluororesin, a polymer of epihalohydrin,
By appropriately changing the compounding ratio of the ionic electrolyte and the ionic electrolyte, the target volume resistivity can be easily expressed, and it has been considered extremely difficult to achieve 1 × 10 ⁵ to 1 × 1.
The volume resistivity in the region of 0 ¹¹ Ω · cm can be accurately controlled. In particular, the volume resistivity of 1 × 10 ⁹ Ω · cm or less can be realized because the C—F bond in the thermoplastic fluororesin is polarized by the fluorine atom having the highest electronegativity, so that the ionic electrolyte dissociates. This is probably because the ether bond in the polymer of epihalohydrin significantly accelerates the movement of the dissociated metal ion in the matrix resin having polarity.

Further, although the semiconductive fluororesin composition of the present invention contains an ionic electrolyte, the difference between the volume resistivity under high temperature and high humidity and the volume resistivity under low temperature and low humidity is small. The feature is that it exhibits relatively stable ionic conductivity even when the use environment changes.

The semiconductive fluororesin composition of the present invention can be easily molded into films, sheets, tubes and the like, and further has the characteristics of fluororesin such as non-adhesiveness, antifouling property, heat resistance and weather resistance. Property, ozone resistance, and flame retardancy are also retained, and it has excellent properties suitable for a semiconductive resin for an electronic image forming process. As described above, the semiconductive fluororesin composition of the present invention has excellent physical properties such as non-staining property, antifouling property, heat resistance, weather resistance, ozone resistance and flame retardancy. It is suitable for use as a resin for an electronic image forming process because it can accurately and stably develop a predetermined volume resistivity in the range of 10 ⁵ to 1 × 10 ¹¹ Ω · cm and has little environmental dependence. It is something.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the blending amount of a conductive material and the volume resistivity of the films obtained in Example 1 and Comparative Examples 1 and 2.

FIG. 2 is a graph showing the relationship between the amount of added ionic electrolyte and the volume resistivity of the film obtained in Example 2.

[Explanation of symbols]

 ◯: A film containing an EpCl resin. ●: A film containing carbon black.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location H01B 1/06 A (72) Inventor Shigetoshi Takechi 1515 Nakatsu-cho, Marugame-shi, Kagawa Okura Industrial Co., Ltd. (72 Inventor Takanori Okamoto 1515 Nakatsu-cho, Marugame-shi, Kagawa Okura Industrial Co., Ltd. (72) Inventor Hoju Nomura 1515 Nakatsu-cho, Marugame, Kagawa Okura Industrial Co., Ltd.

Claims (4)

[Claims] 1. A mixture comprising 95 to 30% by weight of a thermoplastic fluororesin and 5 to 70% by weight of a polymer of epihalohydrin, and further comprising 0.05 to 5% by weight of an ionic electrolyte with respect to the mixture. A characteristic semiconductive fluororesin composition. 2. The semiconductive fluororesin composition according to claim 1, wherein the thermoplastic fluororesin is polyvinylidene fluoride or a copolymer thereof. 3. The semiconductive fluororesin composition according to claim 1, wherein the epihalohydrin polymer is an epichlorohydrin homopolymer or copolymer. 4. The semiconductive fluororesin composition according to claim 1, wherein the ionic electrolyte is at least one of an alkali metal thiocyanate, a phosphate, a sulfate and a halogen oxyacid salt.