JP2000212364A - Poly(vinylidene fluoride) resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject poly(vinylidene fluoride) resin composition that stably, homogeneously and accurately reproduce a prescribed volume resistivity with reduced fluctuation of the volume resistivity depending on the environmental temperature and is useful as a belt or the like by adding a combination of a conductivity-imparting component with a specific tetra-ammonium salt and adding the combination to the resin. SOLUTION: This poly(vinylidene fluoride) resin composition comprises at least (A) 100 pts.wt. of poly(vinylidene fluoride), (B) 0.1-1,000 pts.wt., preferably 0.1-30 pts.wt. of an alkyl quaternary ammonium salt of an acid bearing a perfluoroalkyl group, and (C) 0.01-10 pts.wt. of a conductivity-imparting component. In a preferred embodiment, the component B is an alkyl quaternary ammonium salt of a perfluoroalkylsulfonic acid, particularly tetrabutylammonium perfluoroalkyl-sulfonate, its molecular weight is controlled to 500-800 and the component C is an alkyl quaternary ammonium sulfate or sulfite with a volume resistivity of 103-1013 Ωcm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyvinylidene fluoride resin composition, and more particularly, to a polyvinylidene fluoride resin composition which can be suitably used in a field requiring conductivity or semiconductivity. In the present invention, the semiconductive resin composition is a resin composition having a 10 ³ ~10 ^{1 3} Ωcm about a volume resistivity.

[0002] The resin composition of the present invention can be used without particular limitation in applications utilizing its conductivity or semiconductivity. The resin composition of the present invention can be suitably used, for example, as a material for forming at least a surface layer of a charging member such as a charging roll, a transfer roll, a developing roll, a charging belt, and a discharging belt in an electrophotographic image forming apparatus. .

[0003] Further, the resin composition of the present invention can be used for applications utilizing its antistatic property, antistatic property, dust adsorption preventing property, and the like.
For example, it can be suitably used as an electronic component packaging film, wallpaper, OA equipment exterior material, or antistatic partition. Furthermore, the resin composition of the present invention can be used for other uses, for example, a solid electrolyte in a secondary battery.

[0004]

2. Description of the Related Art In recent years, in the field of electric and electronic devices,
There is an increasing demand for semiconductive resin materials whose volume resistivity is precisely controlled. For example, in an image forming apparatus such as an electrophotographic copying machine, a facsimile, and a laser beam printer (an electrophotographic copying machine, an electrostatic recording device, and the like), the charging, exposing, developing, transferring, fixing, and discharging steps are performed. , An image is formed. In each of these steps, a resin material whose volume resistivity is precisely controlled is required from the viewpoints of adsorption and separation of paper and adsorption and removal of toner.

[0005] Members (related to charging or in contact with toner) such as a charging roll or belt, a transfer roll or belt, a developing roll, and a toner layer thickness regulating blade mounted on such an image forming apparatus include: Usually, the surface layer is semiconductive, specifically, 10 ³ to 1
It is often required to have an arbitrary volume resistivity of about 0 ¹³ Ωcm.

For example, in the charging system using the above-described charging roll or belt, a charging roll or belt to which a voltage is applied is brought into contact with a photosensitive drum (electrostatic latent image holding member) to directly charge the surface of the photosensitive drum. To uniformly and uniformly charge the drum.

[0007] In the developing method using a developing roll,
By the frictional force between the developing roll and the toner supply roll,
After the toner is adsorbed on the surface of the developing roll in a charged state, the toner is made uniform with a toner layer thickness regulating blade, and then the electrostatic latent image on the surface of the photosensitive drum is caused to fly by an electric attraction force and developed. I have. Further, in a transfer method using a transfer roll or a belt, a voltage having a polarity opposite to that of the toner is applied to the transfer roll or the belt to generate an electric field, and the toner on the photoconductor is transferred to the transfer material ( Paper).

Therefore, a charging member such as a charging roll or a belt in an image forming apparatus is generally required to have a low volume within a proper range and a uniform volume resistivity.
When a charging member having a different volume resistivity locally (locally) is used, a high quality toner image cannot be obtained.

For example, if the volume resistivity of the charging roll or belt is not uniform, the surface of the photoreceptor cannot be uniformly and uniformly charged, and the quality of an image is degraded. Also,
It is desirable that these charging members have a small change in volume resistivity and surface resistivity due to a change in humidity. This is because, if the volume resistivity or the surface resistivity of the charging member changes significantly due to a change in humidity under a normal use environment, it becomes difficult to stably obtain a high-quality image.

Outside the field of the image forming apparatus described above, there is a high need for a resin material having a predetermined volume resistivity. For example, exterior materials and components of OA equipment formed of a resin material are likely to impair the appearance or cause a failure when dust, toner or the like is sucked. Films and containers for packaging resinous devices and components used in the manufacturing process of semiconductor devices and LCDs (liquid crystal devices) in the electronics industry, and electronic components such as ICs and LSIs absorb dust due to static electricity. Then, there is a great possibility that the quality of the electronic component packaged by the film or the container is impaired. Therefore, it is required that a resin material used in these applications be given a volume resistivity of about 10 ³ to 10 ¹³ Ωcm to have an antistatic property.

As a resin to be provided with a predetermined volume resistivity as described above, a polyvinylidene fluoride resin can be used. Polyvinylidene fluoride resins are generally used for such purposes because they have characteristics of being excellent in solvent resistance, stain resistance, and processability.

Conventionally, methods for lowering the electrical resistance (volume resistivity) of a polyvinylidene fluoride resin or a molded article thereof include (1) a method of applying an organic antistatic agent to the surface of a resin molded article, and (2) There are known methods of kneading an organic antistatic agent into a resin, (3) kneading a conductive filler such as carbon black or metal powder into a resin, and (4) kneading an ionic electrolyte into a resin. I have.

However, in the method (1) of applying an antistatic agent, since the polyvinylidene fluoride resin is excellent in non-adhesiveness, the surface of a molded article made of the resin is wiped or washed. The antistatic agent applied to the surface of the polyvinylidene fluoride resin tends to easily fall off.

In the method of kneading the antistatic agent (2), a surfactant or a hydrophilic resin is often used as the organic antistatic agent. Among these methods, the method using a surfactant employs a mechanism of bleeding out (leaching out) the surfactant from the surface of the molded article to impart an antistatic property. It is inevitable that the degree of the bleed-out changes due to the change, and the volume resistivity and the antistatic property largely change.
There is a high possibility that the stain resistance, which is an advantage of polyvinylidene fluoride resin, is impaired. On the other hand, in the method using a hydrophilic resin as an antistatic agent, a large amount of the hydrophilic resin must be blended in order to obtain a desired antistatic effect. However, there is a problem that physical properties such as resistance, weather resistance, ozone resistance, and solvent resistance are deteriorated, and that the volume resistivity and the antistatic property are largely dependent on humidity.

Among these properties, the stain resistance and the solvent resistance are also properties required for cleaning the toner adhered to a member disposed in an electrophotographic image forming apparatus when the toner adheres thereto. . Since an image forming apparatus equipped with a corona discharge device or the like generates ozone, the member is also required to have ozone resistance. The weather resistance is a property required when used as a surface protection material for a signboard or a window glass used outdoors.

The method (3) of kneading the conductive filler has been adopted in many fields. For example, the charging roll is formed by coating a core metal with a semiconductive resin composition obtained by kneading a conductive filler into a resin. However, a semiconductive resin composition in which a conductive filler is dispersed in a resin generally has a very non-uniform volume resistivity distribution, and its variation is often several orders of magnitude (for example, 10
⁽² times or more), there was a problem in practical performance. In particular, since the polyvinylidene fluoride resin has a small surface energy, when a conductive filler is dispersed in the resin, the conductive filler moves in the resin by application of a high voltage or the like, and as a result, the volume of the resin is reduced. There is a problem that the resistivity fluctuates.

Moreover, polyvinylidene fluoride resin compositions in which conductive fillers are dispersed generally have insufficient withstand voltage, and are not necessarily suitable for applications in which a high voltage is repeatedly applied. Further, in order to achieve the required semiconductivity level using a filler, it is necessary to increase the amount of the filler to be filled in the resin, and therefore, the molding processability of the polyvinylidene fluoride-based resin composition and There is a problem that the mechanical strength is lowered or the hardness is too high. Further, a polyvinylidene fluoride resin composition in which a conductive filler is dispersed is usually colored by a conductive filler (it has a color of itself) such as conductive carbon black. It is unsuitable for application to materials and wallpaper.

In the above method (4), in which the ionic electrolyte is kneaded into the resin, regarding the addition of the ionic electrolyte, it has long been known that polyvinylidene fluoride (PVDF) is a good conductor of ions (see, for example, Showa 51-32
330, JP-A-51-110658,
In view of JP-A-111337 and JP-A-54-127873, it is expected that polyvinylidene fluoride resin is effective in imparting semiconductivity.

However, a resin composition in which an inorganic metal salt such as lithium chloride or potassium chloride as a typical electrolyte is kneaded in a polyvinylidene fluoride resin, since these inorganic metal salts are only slightly dissolved in the resin, It was difficult to reduce the volume resistivity to 1 × 10 ¹³ Ωcm or less. Further, there has been a problem that aggregates of an excessively added inorganic metal salt cause so-called fish eyes (a phenomenon in which small spherical lumps appear in a transparent or translucent resin). If the kneading temperature is increased or the kneading time is lengthened in order to dissolve the aggregates in the polyvinylidene fluoride resin, the resin and / or the electrolyte may be decomposed, thereby substantially impairing the mechanical properties and appearance. Increase. Furthermore, when a deliquescent metal salt such as a Li salt is used, if the metal salt is filled in a large amount, the resin composition becomes hygroscopic, so that the volume resistivity greatly changes due to a change in humidity. And the surface of the molded article becomes sticky due to the bleeding-out of the bleed-out metal salt.

As a method for improving the solubility of an electrolyte in a resin, JP-A-60-177064 and JP-A-61-72061 disclose a method of including a polar solvent such as propylene carbonate in a resin. Proposed. However, in this method, since the electrolyte and the polar solvent easily bleed out, there were problems such as instability of the electrical properties of the resin and stickiness of the resin surface.

[0021]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyvinylidene fluoride resin composition which has solved the above-mentioned disadvantages of the prior art.

Another object of the present invention is to provide 10 ³ to 10 ¹³ Ωc.
An object of the present invention is to provide a polyvinylidene fluoride-based resin composition that stably reproduces a predetermined volume resistivity uniformly and accurately within a range of m and that has a small change in volume resistivity due to a change in environmental humidity.

Still another object of the present invention is to provide a belt, a tube, and the like using such a resin composition having excellent semiconductivity.
An object of the present invention is to provide various semiconductive molded articles such as sheets, fibers, and injection molded articles.

[0024]

Means for Solving the Problems As a result of diligent studies, the present inventors have found that the addition of a specific alkyl quaternary ammonium salt to a polyvinylidene fluoride resin in combination with a conductivity-imparting component is described above. Has been found to be extremely effective in achieving the objectives.

The polyvinylidene fluoride resin composition of the present invention is based on the above findings. More specifically, 100 parts by weight of the polyvinylidene fluoride resin (A) and an alkyl quaternary acid having a perfluoroalkyl group are used. It contains at least 0.1 to 1000 parts by weight of an ammonium salt (B) and 0.01 to 10 parts by weight of a conductivity-imparting component (C).

According to the knowledge of the present inventor, the above alkyl quaternary ammonium salt (B) is a plasticizer-like or non-plasticizer with respect to the combination of the polyvinylidene fluoride resin (A) and the conductivity-imparting component (C). It is presumed that a suitable conductivity is obtained while suppressing bleed-out in order to achieve appropriate integration of these three components by acting as a solvent. As a result of further research based on the above findings, the present inventor found that an alkyl quaternary ammonium salt of an acid having a perfluoroalkyl group was contained in 100 parts by weight of a polyvinylidene fluoride resin.
By adding 1 to 30 parts by weight and 0.1 to 10 parts by weight of the conductivity-imparting component, in addition to the above characteristics, there is no formation of aggregates or fish eyes, and good processability is obtained.
It has also been found that a resin composition that can be molded into various molded articles can be obtained by a general melt processing method.

According to the present invention, for example, the following preferred embodiments are provided. (1) With respect to 100 parts by weight of a polyvinylidene fluoride resin (A), 0.1 to 30 parts by weight of an alkyl quaternary ammonium salt (B) of an acid having a perfluoroalkyl group and 0 parts by weight of a conductivity-imparting component (C) The above resin composition containing 0.1 to 10 parts by weight. (2) The above resin composition, wherein the alkyl quaternary ammonium salt (B) is an alkyl quaternary ammonium salt of perfluoroalkylsulfonic acid. (3) The alkyl quaternary ammonium salt has a molecular weight of 50
The above resin composition having a value of 0 or more and less than 800. (4) The above resin composition wherein the alkyl quaternary ammonium salt is tetrabutylammonium perfluoroalkylsulfonate. (5) The resin composition as described above, wherein the conductivity imparting component (C) is a sulfate or sulfite of an alkyl quaternary ammonium. (6) The volume resistivity is 10 ³ Ωcm or more and 10 ¹³ Ωcm.
The above resin composition which is as follows. (7) a sheet, belt made of each of the resin compositions described above,
Tubes, fibers or injection moldings. (8) The resin composition having the form of a charging member for an electrophotographic device or an electrostatic recording device.

[0028]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described more specifically with reference to the drawings as necessary. In the following description, “parts” and “%” representing quantitative ratios are based on weight unless otherwise specified.

(Polyvinylidene fluoride resin)
Polyvinylidene Fluoride Resin (A)
Is a homopolymer of vinylidene fluoride (ie, poly
Vinylidene fluoride; PVDF), and vinylidene fluoride
Copolymerizable with vinylidene fluoride whose main structural unit is
And copolymers with functional monomers. Workability
From the viewpoint of (ease of processing), the polyvinylidene fluoride-based
GPC (gel permeation chromatography) of resin (A)
Weight average molecular weight (Mw) is 2 × 10
^Five~ 6 × 10^Five(And 3 × 10 ^Five~ 5 × 10^Five) About
Preferably.

In the latter copolymer, as the other “copolymerizable monomer”, a fluorine-containing monomer can be suitably used from the viewpoint of solvent resistance and stain resistance. In the above copolymer, when the number of moles of the polyvinylidene fluoride monomer constituting the copolymer is 100, the number of moles of the other “copolymerizable monomer” is 1 to 50.
It is preferably about mol% (more preferably 5 to 15 mol%).

The vinylidene fluoride copolymer preferably usable in the present invention includes vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene-copolymer. Hexafluoropropylene copolymer and the like. In the present invention, the polyvinylidene fluoride-based resins can be used alone or in combination of two or more as required.

Among the polyvinylidene fluoride resins, PVDF, which is a homopolymer of vinylidene fluoride, is preferred from the viewpoints of stain resistance, ozone resistance and solvent resistance. From the viewpoint of flexibility and tear strength, a vinylidene fluoride copolymer having vinylidene fluoride as a main component alone is used,
Alternatively, it is preferable to use it by blending with PVDF.

For the purpose of improving the adhesiveness and the like, a vinylidene fluoride copolymer into which a functional group has been introduced may be used as necessary. Examples of such a functional group include a carboxyl group, a carbonyl group, a sulfonic group, a nitro group,
Examples include an acetyl group, a hydroxy group, and an amino group.

For polyvinylidene fluoride resin,
Other thermoplastic resins such as acrylic resins and other fluororesins may be blended and used within a range not to impair the object of the present invention. When the total volume of the blended resin obtained by blending the polyvinylidene fluoride-based resin (that is, the polyvinylidene fluoride-based resin + other resin) is 100 parts, the amount of the “other resin” added is 1 to 50% by weight. Parts (more preferably 1 to 30 parts by volume).

(Alkyl quaternary ammonium salt of acid having a perfluoroalkyl group) The alkyl quaternary ammonium salt of an acid having a perfluoroalkyl group (B) used in the present invention has the following formula (1):

Embedded image (In the above formula, A represents an acid, R ¹ represents perfluoroalkyl, and R ^{2 to} R ⁵ represent the same or different alkyl groups, or fluorine-containing alkyl groups, or perfluoroalkyl groups.) It is a compound represented by these.

These alkyl quaternary ammonium chlorides
As a specific example of the product, for example, (C_TwoH_Five)_FourN⁺, (C_ThreeH
₇)_FourN⁺, (C_FourH₉)_FourN⁺, (C_FiveH₁₁)_FourN⁺, (C
_TwoF_Five)_FourN⁺, (C_ThreeF₇)_FourN⁺, (C_FourF₉)_FourN⁺, (C_Five
F₁₁)_FourN⁺A quaternary ammonium cation such as₈F
₁₇SO_Four ^-, C₆F₁₃SO_Four ^-, C₈F₁₇SO_Three ^-, C₆F₁₃S
O _Three, C₈F₁₇COO^-, C₆F₁₃COO^-, Etc.
List salts composed of anions containing an oloalkyl group
Can be.

The total number of carbon atoms of the four alkyl groups of the quaternary ammonium cation is usually from 8 to 30 (and more preferably from 12 to 30).
To 24, especially 15 to 20) are preferred. On the other hand, the carbon number of the anion containing a perfluoroalkyl group is usually 5 to 2
0 (more preferably 5 to 15, particularly 5 to 10) is preferred. If the number of carbon atoms of both anions and cations is too small, the alkyl quaternary ammonium salt (B) tends to bleed out, while if the number of carbon atoms is too large, the effect of imparting conductivity tends to decrease. In order to balance these, the molecular weight of the alkyl quaternary ammonium salt (B) of the acid having a perfluoroalkyl group is preferably about 500 to 800 (more preferably about 600 to 700).

Further, these compounds may be salts formed by combining two or more kinds of anions and / or cations. The four alkyl groups of the quaternary ammonium may be the same or different. Among these, a quaternary ammonium salt of perfluoroalkylsulfonic acid is preferred, and a tetrabutylammonium salt of perfluoroalkylsulfonic acid is particularly preferred from the viewpoint of the balance between the difficulty in bleeding out and the effect of imparting conductivity.

According to the knowledge of the present inventor, rather than adding the alkyl quaternary ammonium salt (B) alone to the polyvinylidene fluoride resin (A), the quaternary ammonium salt (B) can be used as a component for imparting conductivity. It has been found that by adding to polyvinylidene fluoride resin (A) in combination with (C), the conductive contribution effect can be enhanced. this is,
According to the knowledge of the present inventors, an alkyl quaternary ammonium salt (B) added to a polyvinylidene fluoride resin (A)
Is dispersed in the resin in the form of a salt (without ion dissociation), and the ion of the electrolyte of the conductivity-imparting component (C) combined therewith is an alkyl quaternary ammonium salt. It is presumed that the transfer of ions derived from (B) in the resin (A) is promoted.

In an embodiment in which the resin composition of the present invention is used for a solid electrolyte or the like of a secondary battery, the amount of the alkyl quaternary ammonium salt (B) added is 100 parts by weight of the polyvinylidene fluoride resin (A). It is usually preferred that the amount be 1 to 1000 parts by weight (more preferably 10 to 500 parts by weight, particularly 30 to 200 parts by weight). If the addition amount of the salt (B) is too small, the volume resistance value of the resin composition tends not to be sufficiently reduced, while if the addition amount is too large, the electrode between the electrodes constituting the secondary battery or the like tends to be low. Tends to be difficult to maintain the shape of the resin composition.

A material for forming at least a surface layer of a charging member such as a charging roll, a transfer roll, a developing roll, a charging belt, and a charge removing belt in an electrophotographic image forming apparatus, a film for packaging electronic parts, wallpaper,
In embodiments where the bleed-out of additives is more strictly limited, such as OA equipment exterior materials and antistatic partitions, the amount of the alkyl quaternary ammonium salt (B) to be added is limited to the polyvinylidene fluoride resin ( A) Usually, 0.1 to 30 parts by weight (further 1 to 20 parts by weight) per 100 parts by weight
Parts by weight, especially 5 to 10 parts by weight).
If the amount of the salt (B) is too small, it tends not to be sufficiently low, while if the amount is too large, bleed out from the resin composition tends to occur.

(Conductivity-imparting Component) In the present invention, as the electroconductivity-imparting component (C), an electrolyte which is a salt comprising an anion and a cation and which can be ion-dissociated in a polyvinylidene fluoride resin (A) is used. Here, the fact that the conductivity imparting component (C) is “ion dissociable in the resin (A)” means that
For example, it can be confirmed by the following method. From the viewpoint of the conductivity-imparting effect, the volume resistivity measured by the following method is 10 ¹⁵ Ωcm or less (furthermore, 10 ¹² Ωcm or less).
It is preferable to use the component (C) that gives the volume resistivity of

<Method for Confirming Ion Dissociation> Vinylidene fluoride homopolymer (weight average molecular weight Mw = 3.6 × 10
⁵ ; number average molecular weight Mn = 1.8 × 10 ⁵ ; trade name: KF # 1000, manufactured by Kureha Chemical Industry Co., Ltd.) 100 parts by weight, and 1 part by weight of component (C) for which the effect of imparting conductivity should be confirmed Into a mixer (trade name: Super Mixer, manufactured by Kawada Seisakusho Co., Ltd.), and sufficiently stirred and mixed at a rotation speed of 1,000 rpm for about 2 minutes. Then, the obtained mixture is subjected to a single screw extruder (Pla Giken Co., Ltd.). And pelletized to a diameter of about 3 mm. Immediately after the pellets are molded by a hot press (trade name: F-50 type compression molding machine manufactured by Shinto Metal Industry Co., Ltd.), the pellets are rapidly cooled at 20 ° C. to obtain a 0.25 mm thick sheet. The volume resistivity of the sheet thus obtained is 2
The measurement is performed under the conditions of 3 ° C. and 50% RH by the method described below (method using a resiliency cell).

In the present invention, from the viewpoint of suppressing the decomposition of the component (C), it is preferable that the resin (A) does not substantially decompose at a normal melt molding temperature of 200 to 280 ° C. Further, from the viewpoint of suppressing the decomposition and denaturation of the resin (A),
The pH of a 1% aqueous solution of the component (C) is 7 or less (furthermore, pH 6
To about 2). In the present invention, the above-mentioned “not substantially decomposed” or “pH of 7 or less” can be confirmed, for example, by the following method.

<Method of confirming that no substantial decomposition occurs> When the thermogravimetric measurement was performed under the following conditions, the processing temperature (200 to 2)
Weight at 80 ° C.) is 99.5% of the initial weight (30 ° C.).
It is confirmed that it is more than the above (further 99.9%).

The conductivity-imparting component (C) is vacuum-dried at 60 ° C. for 24 hours or more using a vacuum dryer (trade name: DP-43, manufactured by Yamato Scientific Co., Ltd.). The dried component (C) was subjected to an initial temperature of 3 using a thermogravimeter (trade name: TG / DTA220, manufactured by Seiko Instruments Inc.).
The weight change is measured under the conditions of 0 ° C., an end temperature of 300 ° C., and a heating rate of 10 ° C./min.

<Method for confirming that pH is 7 or less> 9
1 g of the conductivity-imparting component (C) is added to 9 g of distilled water,
Prepare a 1% by weight aqueous solution (if the component (C) is not completely dissolved in distilled water, prepare a saturated solution in which undissolved substances are precipitated). The above-mentioned 1% by weight aqueous solution was adhered to each of a methyl red test paper, a cresollet test paper, and a bromthymol blue test paper (all manufactured by Toyo Roshi Kaisha) using a glass rod. Compare the color with a standard color change table (manufactured by Toyo Roshi Kaisha) to confirm that the pH is 7 or less.

Specific examples of the conductivity imparting component (C) include alkylbenzenesulfonic acid such as dodecylbenzenesulfonic acid, fatty acid such as lauryl sulfate, alkylnaphthalenesulfonic acid, dialkylsulfosuccinic acid, alkylphosphoric acid, alkanesulfonic acid, alkyl Examples of the electrolyte include an electrolyte comprising an anion such as diphenyl ether sulfate and dialkyl succinate and a cation such as sodium, potassium, rubidium, cesium, tetrofluoroborate, and hexafluorophosphate. In particular, tetrapropyl ammonium hydrogen sulfate,
Tetrabutylammonium hydrogen sulfate,
Quaternary ammonium salts such as tetrapropylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, tetrapropylammonium hexafluorophosphate, tetrabutylammonium hexafluorophosphate, or potassium perfluoroalkylsulfonate, sodium perfluoroalkylsulfonate, Perfluoroalkylsulfonic acid salts such as rubidium perfluoroalkylsulfonate, cesium perfluoroalkylsulfonate and lithium perfluoroalkylsulfonate are preferred as the conductivity-imparting component (C).

Of these, sulfates or sulfites of alkyl quaternary ammonium salts are particularly preferred as the conductivity-imparting component (C). The addition amount of the conductivity-imparting component (C) is based on the polyvinylidene fluoride resin (A).
Usually, at least 0.01 parts by weight (and even at least 0.01 part by weight).
1 part by weight, more preferably at least 0.3 part by weight, more preferably at least 0.5 part by weight, particularly preferably at least 1 part by weight). The upper limit of the addition amount of the component (C) is a range in which the resin is not decomposed and foamed at the time of processing and molding the resin, and this usually differs depending on the type of the conductivity imparting component (C). For example, when the component (C) is tetrabutylammonium hydrogen sulfate, the resin starts to be colored at an added amount exceeding 3 parts by weight, and foams and decomposes at an added amount exceeding 10 parts by weight, making molding difficult. In the present invention, the "do not decompose and foam" means, for example,
It can be confirmed by the following method.

<Method for confirming that no decomposition foaming occurs> When "decomposition foaming" occurs, air bubbles are mixed in the resin molded product, a colored material is mixed in the resin molded product, or the color of the entire resin is changed. Phenomena such as blackening and off-flavor (especially hydrofluoric acid odor) are observed. Therefore, "Do not decompose and foam"
Can be easily confirmed by the absence of these phenomena.

(Other Additives) The polyvinylidene fluoride resin (A) composition of the present invention may contain various additives, if necessary. Such "other additives"
As, talc, mica, silica, alumina, kaolin, ferrite, potassium titanate, titanium oxide, zinc oxide, iron oxide, magnesium hydroxide, calcium carbonate,
Granular or powdery fillers such as nickel carbonate, calcium sulfate, barium sulfate, aluminum hydroxide, glass powder, quartz powder, carbon black, graphite, inorganic pigments, organic metal salts, and metal oxides; carbon fibers, glass fibers, asbestos fibers, Silica fiber, alumina fiber, zirconia fiber,
Fibrous fillers such as boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber; and the like. These fillers can be appropriately compounded according to the purpose of use as long as the object of the present invention (providing conductivity while suppressing bleed-out) is not hindered.

Further, the polyvinylidene fluoride resin composition of the present invention includes, for example, an antioxidant, a lubricant, a plasticizer, an organic pigment, an inorganic pigment, an ultraviolet absorber, a surfactant, an inorganic acid, an organic acid, a pH, General-purpose additives such as an adjusting agent, a cross-linking agent, and a coupling agent can be appropriately compounded within a range that does not impair the effects of the present invention.

(Method for Preparing Resin Composition) The method for preparing the polyvinylidene fluoride resin composition of the present invention is not particularly limited. From the viewpoint of making the composition uniform, the following methods (1) to (3) can be suitably used. (1) A method of mixing vinylidene fluoride resin powder or pellets, an alkyl quaternary ammonium salt (B) and a conductivity-imparting component (C) with a mixer or the like, and (2) mixing each component with a mixer. Thereafter, the mixture is pelletized by a melt extrusion method, (3) each component is dissolved or dispersed in water or a mixed solvent of water and a water-soluble solvent, mixed with a mixer such as a mixer, and dried. A method in which the obtained dried product is melt-extruded and pelletized.

The polyvinylidene fluoride resin composition of the present invention can be formed into various molded articles and coated molded articles by various molding methods such as a press molding method, a melt extrusion method, an injection molding method, a solution casting method, and a coating method. Can be processed. Also, a masterbatch in which a polyvinylidene fluoride resin (A) contains a high concentration of an alkyl quaternary ammonium salt (B) and a conductivity-imparting component (C) is prepared in advance, and the concentration is adjusted as required during molding. The resin may be diluted with the resin (A) and molded.

When extruding the polyvinylidene fluoride resin composition of the present invention into a seamless belt, a continuous melt extrusion molding method is preferably used. As a desirable continuous melt extrusion molding method of the seamless belt, there is a method in which a single-screw extruder and a spiral annular die are used to extrude directly from a lip of the die, and to take out while controlling the inner diameter by an internal cooling mandrel method. When a sheet is produced using the polyvinylidene fluoride resin composition of the present invention, as a continuous extrusion molding method, using a single-screw or twin-screw extruder and a T-die, the molten resin composition is removed from a lip. A method of extruding immediately below and cooling and solidifying while closely adhering to the cooling drum with an air knife or the like can be used.

The method for molding the polyvinylidene fluoride resin composition of the present invention is not particularly limited, and may be formed into a sheet or fiber by a known molding method such as injection molding or melt extrusion. Forming is possible. After processing, it is possible to further stretch or heat set. The polyvinylidene fluoride-based resin composition of the present invention may be used alone, or may be combined with another resin layer or the like, if necessary, to be used as a laminated sheet or composite yarn.

(Use of Resin Composition) The polyvinylidene fluoride-based resin composition of the present invention can be used as an antistatic film for packaging electronic parts, an antistatic container, a dust adsorption preventing member used for various OA equipment, a static eliminating member, It can be suitably used for semiconductive members, conductive members, and the like.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

[0059]

EXAMPLES In the following examples, physical properties were measured by the following measuring methods. (1) Thickness Measurement The thickness of the molded product was measured with a dial gauge thickness meter (trade name: DG-911, manufactured by Ono Sokki Co., Ltd.). (2) Volume resistivity In the present invention, a sample having a volume resistivity of 10 ¹⁰ Ωcm or more is a resiliency cell having a ring-shaped electrode (trade name: HP16008B, manufactured by Hewlett-Packard Company,
Outer diameter of inner electrode 26.0 mm, inner diameter of outer electrode 3
8.0mm, outer diameter of outer electrode 40.0mm) and load 7k
g, the sample is sandwiched, and the volume resistivity ρ _V when a voltage of 1 kV is applied for 1 minute (in the thickness direction) between the inner electrode and the counter electrode is measured with a resistance measuring instrument (trade name: High Resistance Meter HP4339A, Hewlett) (Packard)
I asked for it. The details of such a volume resistivity measurement method using the ring electrode method can be referred to JIS-K6911. In the present invention, a sample having a volume resistivity of less than 10 ¹⁰ Ωcm is a ring-shaped probe (trade name: HRS probe,
(Mitsubishi Chemical Corporation, inner electrode outer diameter 5.9 mm, outer electrode inner diameter 11.0 mm, outer electrode outer diameter 17.8 mm)
While holding the sample between the probe and the measurement stage (trade name: cashier table FL, manufactured by Mitsubishi Chemical Corporation) and pressing the sample with a pressure of about 3 kg, a voltage of 500 V is applied between the electrode inside the probe and the measurement stage. And a resistivity measurement device (trade name: Hiresta IP, manufactured by Mitsubishi Chemical Corporation). Details of such a volume resistivity measurement method using the ring electrode method are described in JIS-K
6911 can be referred to. (3) Calculation of Average Value In the measurement of the thickness and the volume resistivity described above, these values were arbitrarily selected per 1 m ² of the surface area of the sample to be measured.
One point (20 points in total) was measured for each of zero measurement points or arbitrarily selected 20 molded articles, and the maximum value, minimum value, and average value (arithmetic mean) were obtained. (4) Humidity Dependence of Volume Resistivity In the present invention, a resiliency cell having a ring-shaped electrode (trade name: HP16008B, manufactured by Hewlett-Packard Company, outer diameter of inner electrode 26.0 mm, inner diameter of outer electrode) 38.0 mm, outer diameter of outer electrode 40.0 m
m) with a load of 7 kg, and a thermo-hygrostat (trade name: LH30-13) adjusted to a predetermined temperature and humidity.
M, manufactured by Nagano Scientific Machinery Co., Ltd.) for 24 hours, and then a voltage of 100 V was applied between the inner electrode and the counter electrode for 1 hour.
For a minute (in the thickness direction), the volume resistivity ρ _V is measured with a resistance measuring instrument (trade name: High Resistance Meter HP433)
9A, manufactured by Hewlett-Packard Company). Details of such a method of measuring volume resistivity by the ring electrode method can be found in JI
SK6911 can be referred to. Volume resistivity, relative humidity 30%, 50%, 70%, 90% in order,
The measurement was performed after conditioning for 24 hours in each humidity environment. (5) Bleed-out The sample was left in an environment of 23 ° C. and a relative humidity of 50% for 30 days, and the presence or absence of bleed-out of the additive was confirmed visually and by touch. In this case, when powder observation, whitening, and precipitation of recrystallized matter are not observed by visual observation, and there is no stickiness due to touch (using a hand after normalizing by wiping sweat etc. in advance with ethanol) Was determined to have no bleed-out. (6) Thermal Stability of Volume Resistivity After the sample was left in an environment of 60 ° C. for 150 hours, the volume resistivity was measured, and the change in volume resistivity before and after the test was compared. However, this volume resistivity was measured in an environment of 23 ° C. and 50% in accordance with JIS-K6911.

Examples 1 to 8 and Comparative Examples 1 to 9 Each composition (Examples 1 to 8 and Comparative Examples 1 to 9 ) shown in the following (Table 1)
9; the meaning of each abbreviation will be described later)
Mixer (Kawada Seisakusho, product name: Super Mixer)
And sufficiently stirred and mixed at a rotation number of 1000 rpm for about 2 minutes. The resulting mixture was pelletized to a diameter of about 3 mm using a single screw extruder (Pla Giken Co., Ltd.). Immediately after the pellets were molded by a hot press (trade name: F-50 type compression molding machine manufactured by Shinto Metal Industry Co., Ltd.), the pellets were rapidly cooled at 20 ° C. to obtain a 0.25 mm thick sheet. However, Examples 1 to 8 and Comparative Examples 5 to 9 are 230
Comparative Examples 1 and 2 at 220 ° C., Comparative Example 3 at 190 ° C.
At 0 ° C, pelletization and press molding were performed.

Example 9 The raw material obtained in the same manner as in Example 1 was supplied to a T-type die having a lip clearance of 0.7 mm (die temperature 240 ° C.) using a single screw extruder (Pla Giken Co., Ltd.). Then, the molten resin extruded from the die was formed into a film by a cooling roll at 40 ° C. Table 1 shows the physical properties of the obtained composition.

[0062] The resin powder additive and dimethylacetamide 250 parts by weight of the composition shown in Example 10 the following Table 1 (Example 10), was placed in a glass beaker, stirred with a glass rod while heating to 120 ° C., the overall Was uniformly dissolved. This solution was extruded into water using a syringe (nozzle diameter: 1 mm) to form a strand.

The obtained strand is immersed in water for 48 hours,
After replacing dimethylacetamide in the resin with water, the strand was taken out, and the strand was taken out at 95 ° C for 24 hours and at 120 ° C for 80 hours.
Dried for hours. Further, the strand was cut into an appropriate length and immediately after being formed by a hot press at 230 ° C.
To obtain a sheet having a thickness of 0.25 mm.

Comparative Example 10 PVDF pellets were pressed at 250 ° C. and then pressed at 20 ° C.
To obtain a sheet having a thickness of 0.25 mm. Table 1 shows the physical properties of the obtained composition.

Comparative Example 11 VDFP pellets were pressed at 250 ° C. and then pressed at 20 ° C.
To obtain a sheet having a thickness of 0.25 mm. Tables 1 and 2 show the physical properties of the obtained composition.

[0066]

[Table 1]

[Table 2] In Examples 1 to 10 above, the sample (manufactured composition) was visually observed, but no aggregates, fish eyes, etc. were observed in the sample.

The abbreviations used in the above table have the following meanings.
It is on the street. PVDF: polyvinylidene fluoride (Kureha Chemical Industry Co., Ltd.)
VDFP: vinylidene fluoride-propylene hexafluoride copolymer
Combination (KF # 2300, manufactured by Kureha Chemical Industry Co., Ltd.) TBAHS: Tetrabutylammonium hydrogensa
Rufate ((C_FourH₉) _FourNHSO_FourPFASC: Cesium perfluoroalkyl sulfonate
(C₈F₁₇SO_ThreeCs) PFASTEA: Tetra perfluoroalkylsulfonic acid
Laethylammonium (C₈F₁₇SO_ThreeN (C_TwoH_Five)_Four) PFASTPA: perfluoroalkylsulfonic acid tet
Lapropyl ammonium (C₈F₁₇SO_ThreeN (C
_ThreeH₇)_Four) PFASTBA: Perfluoroalkylsulfonic acid tet
Labutylammonium (C₈F₁₇SO_ThreeN (C_FourH₉)_FourEC: ethylene carbonate PC: propylene carbonate NMP: N-methylpyrrolidone PDE: diethyl phthalate

(Evaluation of Humidity Dependence of Volume Resistivity) Using the sample prepared in Example 2, the humidity dependence of volume resistivity was measured. The results are shown in FIG. As is clear from FIG. 1, the sheet obtained from the polyvinylidene fluoride resin composition of the present invention has a small humidity dependency of the volume resistivity.

(Evaluation of bleed-out) In Examples 1 to 9 and Comparative Examples 5 to 11 described above, no bleed-out of the additive was observed, but in Example 10 and Comparative Examples 1 to 4, the bleed-out of the additive was Was observed.

(Thermal Stability of Volume Resistivity) The thermal stability evaluation results of the volume resistivity are shown in the following (Table 3). As is clear from Table 3, the sheet obtained from the polyvinylidene fluoride resin composition of the present invention has a small change in volume resistivity even after being left for 150 hours in an environment of 60 ° C.

[0071]

[Table 3]

[0072]

According to the present invention, 10 ³ to 10 ¹³ Ωcm
In this range, it is possible to provide a polyvinylidene fluoride-based resin composition that stably reproduces a predetermined volume resistivity uniformly and accurately and has a small change in volume resistivity due to a change in environmental humidity. Further, according to the present invention, it is possible to provide various semiconductive molded articles such as tubes, belts, sheets, and fiber injection molded articles having excellent semiconductivity.

The polyvinylidene fluoride resin composition of the present invention is suitable as a material for forming at least a surface layer such as a charging roll, a transfer roll, a developing roll, a charging belt, and a charge removing belt in an electrophotographic image forming apparatus. . It is also suitable as a film for packaging electronic parts, wallpaper, OA equipment exterior materials, and a transfer tube for powder coating materials.
Further, it is suitable as a solid electrolyte in a secondary battery.

[Brief description of the drawings]

FIG. 1 is a graph showing the results obtained when the relationship between humidity and volume resistivity was determined using the samples prepared in the examples.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yoshiyoshi Teramoto 18-13 Kamitamari, Tamari-mura, Niiji-gun, Ibaraki Pref. Resin Processing Technology Center, Kureha Chemical Industry Co., Ltd. EN137 FD117 GM01

Claims (9)

[Claims] 1. Polyvinylidene fluoride resin (A) 10
Polyfluoride containing at least 0 part by weight, 0.1 to 1000 parts by weight of an alkyl quaternary ammonium salt of an acid having a perfluoroalkyl group (B), and 0.01 to 10 parts by weight of a conductivity-imparting component (C). Vinylidene resin composition. 2. The alkyl quaternary ammonium salt (B)
2. The resin composition according to claim 1, comprising 0.1 to 30 parts by weight of the resin composition. 3. The alkyl quaternary ammonium salt (B)
Is an alkyl quaternary ammonium salt of a perfluoroalkylsulfonic acid. 4. The resin composition according to claim 3, wherein the molecular weight of the alkyl quaternary ammonium salt is 500 or more and less than 800. 5. The resin composition according to claim 3, wherein the alkyl quaternary ammonium salt of perfluoroalkylsulfonic acid is tetrabutylammonium perfluoroalkylsulfonic acid. 6. The conductive component (C) is a sulfate or sulfite of an alkyl quaternary ammonium.
The resin composition according to any one of the above. 7. A volume resistivity of 10 ³ Ωcm or more and 10 ¹³ Ω.
cm or less. 8. A resin molded product comprising the resin composition according to claim 2, wherein the resin molded product is selected from the group consisting of a sheet, a belt, a tube, a fiber, and an injection molded product. . 9. The resin molded product according to claim 8, which has a form of a charging member for an electrophotographic apparatus or an electrostatic recording apparatus.