JPH11323052A - Poly(vinylidene fluoride)-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare the subject composition excellent in transparency and semiconductivity, hardly causing the change in volume resistivity and surface resistivity due to atmospheric humidity change and useful for an electrification member for an electrophotographic copier, etc., by adding a specific quaternary ammonium salt to poly(vinylidene fluoride)-based resin at the specific content ratio. SOLUTION: This composition is prepared by blending (A) 100 pts.wt. poly(vinylidene fluoride)-based resin [pref. poly(vinylidene fluoride) homopolymer] and (B) 0.03-10 pts.wt. quaternary ammonium compound (pref. tetrabutylammonium hydrogensulfate:) selected from a group consisting of (i) an alkyl quaternary ammonium sulfate of formula I (wherein, R<1> to R<4> are each an alkyl; R<5> is an alkyl or the like) and (ii) an alkyl quaternary ammonium sulfite of formula II (wherein, R<6> to R<9> are each an alkyl; R<10> is an alkyl or the like). The composition is useful as an elecrification-controlling material for an electronic part-packaging material, wallpaper, an antistatic partition, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyvinylidene fluoride-based resin composition, and more particularly, to a polyvinylidene fluoride-based resin which can be suitably used in a field requiring semiconductivity and / or transparency. Composition. The resin composition of the present invention makes use of semiconductivity, for example, a charging roll in an electrophotographic image forming apparatus,
It is suitable as a resin material for forming at least a surface layer of a charge control member (semiconductive member) such as a transfer roll, an image roll, a charging belt, and a discharging belt. In addition, the resin composition of the present invention is used for applications utilizing antistatic properties, antistatic properties, dust absorption preventing properties, and the like, for example, electronic component packaging materials (eg, films, bags, containers), wallpaper, OA equipment exterior materials. It is suitable as a charge control member such as an antistatic partition.

[0002] In the present invention, a semiconductive resin composition means a resin material having a volume resistivity located between an insulator and a metal conductor, and more specifically, from 10 ⁵ to 10 ¹³ Ωc.
It means a resin composition having a volume resistivity of about m. The resin composition of the present invention is suitable as a resin material for an optical member such as an optical fiber, a lens, a light-transmitting material for a solar cell, and a cover for lighting as an application utilizing transparency (high light transmittance and low haze). Used for The resin composition of the present invention,
Utilizing both the properties of semi-conductivity and transparency, it is suitably used for optical members such as a window glass for preventing dust adsorption and a protective material for a display.

[0003]

2. Description of the Related Art In the field of electric and electronic equipment, a resin material whose volume resistivity is precisely controlled is required as a semiconductive material. 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, etc.), each process of charging, exposure, development, transfer, fixing, and static elimination is performed. An image has been formed. In order to form various members used in each of these steps, a resin material whose volume resistivity is precisely controlled is required.

[0004] At least the surface layer of a charging roll or belt, a transfer roll or belt, a developing roll, a toner layer thickness regulating blade, or the like mounted on such an image forming apparatus must be semiconductive. 10
It is required to have a desired volume resistivity in the range of ⁵ to 10 ¹³ Ωcm. For example, in a charging method using a charging roll or a belt, a charging roller or a belt to which a voltage is applied is brought into contact with the photosensitive drum to directly apply a charge to the surface of the photosensitive drum to uniformly and uniformly charge. In the developing method using a developing roll, the frictional force between the developing roll and the toner supply roll causes the toner to be adsorbed on the surface of the developing roll in a charged state, and after uniformizing the toner with a toner layer thickness regulating blade, The electrostatic latent image on the surface of the photoreceptor drum is developed by flying by an electric attraction force. In the transfer method using a transfer roll or belt, a voltage having a polarity opposite to that of the toner is applied to the transfer roll or belt to generate an electric field, and the toner on the photoconductor is transferred onto a transfer material by an electron attraction force generated by the electric field. ing.

Therefore, charge control members such as a charging roll and a belt in an image forming apparatus are required to have a low volume resistivity in an appropriate range. Further, the volume resistivity needs to be uniform, and if the volume resistivity is different in place, a high quality image cannot be obtained. For example, if the volume resistivity of the charging roll or belt is not uniform, the surface of the photoconductor cannot be uniformly and uniformly charged, and the quality of an image is degraded. Further, it is desired that the volume resistivity and the surface resistivity of these members do not significantly change due to a change in humidity. If the volume resistivity or the surface resistivity of the charge control member significantly changes due to a change in humidity under a normal use environment, a stable high-quality image cannot be obtained.

[0006] In addition, the exterior materials and parts of the OA equipment formed of a resin material, if dust and toner are sucked, may impair the appearance or cause a failure. Films, bags, and containers for packaging electronic devices such as ICs and LSIs, and resin devices and parts used in the manufacturing process of semiconductor devices and LCDs in the electronics industry, when dust is absorbed by the generation of static electricity, Impairs the quality of electronic components. Therefore, it is required that the resin material used for these applications, especially for the surface layer material, be given a volume resistivity of about 10 ⁵ to 10 ¹³ Ωcm to have charge controllability.

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 a method of kneading an organic antistatic agent into a resin, a method of kneading a conductive filler such as carbon black or metal powder into a resin, and a method of kneading an ionic electrolyte into a resin.

However, in the method (1), since the polyvinylidene fluoride resin is excellent in non-adhesiveness, the antistatic agent is easily dropped off by wiping or washing the surface of the molded article. I will. In the method (2), a surfactant or a hydrophilic resin is used as the organic antistatic agent. The method using a surfactant employs a mechanism that imparts antistatic properties by bleeding out the surfactant from the surface of the molded product. Preventability changes greatly. In addition, stain resistance, which is an advantage of polyvinylidene fluoride resin, is impaired. In the method using a hydrophilic resin, in order to obtain a desired antistatic effect, it is necessary to mix a large amount of the hydrophilic resin. Therefore, the inherent stain resistance, weather resistance, ozone resistance, There is a problem that physical properties such as solvent properties are deteriorated, and that the volume resistivity and the antistatic property are largely dependent on humidity. Stain resistance and solvent resistance are also properties required for cleaning a member disposed in an electrophotographic image forming apparatus when toner adheres thereto. An image forming apparatus equipped with a corona discharge device generates ozone,
Ozone resistance is also a property required for members. The weather resistance is
This property is required when used as a surface protection material for signboards and window glasses used outdoors.

The method (3) has been adopted in many fields. For example, the charging roll is formed by coating a core metal with a semiconductive resin composition in which a conductive filler is kneaded 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. There was a performance problem. In particular, since polyvinylidene fluoride resin has a small surface energy, when a conductive filler is dispersed, the conductive filler moves in the resin due to application of a high voltage, and as a result, the volume resistivity fluctuates. There was a problem. In addition, 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. In addition, in order to achieve the required level of semiconductivity using a conductive filler, it is necessary to increase the filling amount, and therefore, the processability and mechanical strength of the polyvinylidene fluoride resin composition are increased. Or the hardness becomes too high. Furthermore, since a polyvinylidene fluoride resin composition in which a conductive filler is dispersed is often colored by a conductive filler such as conductive carbon black, for example, it is used for applications such as exterior materials of OA equipment and wallpaper. Not suitable for application.

The method of kneading the ionic electrolyte of the above (4) is based on the fact that polyvinylidene fluoride (PVDF) has long been known to be a good conductor of ions (see, for example, JP-A-51-32330, Kaisho 51-11065
No. 8, JP-A-51-111337, JP-A-5-11337
In view of the above, it is expected that the method is effective for imparting semiconductivity to polyvinylidene fluoride resin. However, a resin composition obtained by kneading an inorganic metal salt such as lithium chloride or potassium chloride as an electrolyte into a polyvinylidene fluoride resin has a low volume resistivity because these inorganic metal salts are only slightly dissolved in the resin. To 1 × 10 ¹³ Ωcm or less was difficult. In addition, there has been a problem that aggregates of an inorganic metal salt added excessively cause fish eyes. 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 is decomposed, which substantially impairs the mechanical properties and appearance. Further, in the case of a deliquescent metal salt such as a Li salt, when the resin is filled in a large amount, the resin composition becomes hygroscopic, so that a change in humidity causes a large change in volume resistivity or bleeding. A problem arises in that the surface of the molded article becomes sticky due to the deliquescence of the metal salt that has gone out.

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, this method has problems that the Young's modulus of the resin is remarkably reduced and the resin surface is sticky by the bleed-out electrolyte and solvent.

Conventionally, a method has been proposed in which a quaternary ammonium salt is used as an antistatic agent for a resin. For example, JP-A-46-64989 discloses an antistatic coating material in which a quaternary ammonium salt and a resin are dissolved in an organic solvent. However, this coating material easily falls off by washing, and it is difficult to maintain the antistatic effect for a long time. JP-A-47-3835 discloses an antistatic sheet in which a quaternary ammonium salt is kneaded into a polyolefin. However,
This antistatic sheet is a mechanism that exhibits an antistatic effect by bleeding out the quaternary ammonium salt from the resin, so that its conductivity and antistatic effect greatly change due to environmental changes such as temperature and humidity. Would. In addition, in a resin having a small polarity such as polyolefin, the electrolyte is hardly ionized, so that the surface resistivity can be reduced, but the volume resistivity cannot be reduced. Furthermore, since most quaternary ammonium salts, particularly quaternary ammonium halide salts, are inferior in thermal stability, when melt-mixed with a polyvinylidene fluoride resin (the processing temperature of this resin is about 220 to 270 ° C.) ,
Problems such as foaming and coloring occur in the molded product.

In addition, many metal salts and quaternary ammonium salts are liable to bleed out, especially in a high humidity environment. For example, in a semiconductor device manufacturing process, metal impurities on the surface of an antistatic packaging material may cause a defective product. In the case of transfer rolls and belts attached to electrophotographic image forming apparatuses, the volume resistance of the surface layer changes due to the decrease in the amount of electrolyte in the resin, and the image quality deteriorates. there were.

With respect to optical materials, in recent years, in the field of optoelectronics, a transparent resin material which is light and has excellent workability has been strongly demanded. However, transparent resin materials usable for optical applications have been limited to polymethyl methacrylate, polycarbonate, polystyrene, some olefin resins having an aliphatic cyclic structure, and the like. However, when such a conventional resin is used for a pickup lens of a compact disk or a magneto-optical disk, for example, resins that easily absorb moisture such as polymethyl methacrylate, polystyrene, and polycarbonate change in dimensions and refractive index due to moisture absorption. Proceeds from the surface of the lens, and the characteristics of the entire lens become non-uniform. As a result, there is a problem that the wavefront of the laser light is disturbed, which adversely affects both writing and reading. Further, a pickup lens of a compact disk player mounted on an automobile is required to have a heat resistance of 100 to 130 ° C. or higher, but it has been difficult for polymethyl methacrylate to satisfy the requirement.

Further, in a general optical system such as a projection television or a camera, a single lens inevitably causes chromatic aberration whose focal length differs depending on the wavelength of light, so that a plurality of materials having different refractive indices and Abbe numbers are used. In order to eliminate chromatic aberration, a design called “color achromatism” is required. In a glass lens, the achromatic design is relatively easy because there are more than 200 types of glass having different refractive indexes and Abbe numbers. However, when only a plastic lens is used, a transparent resin material that can be used as described above is used. Has only several types, and the refractive index of each resin material is 1.5 to 1.6.
Because it is concentrated near, it is very difficult to achromatic design,
In this field, a new transparent resin material has always been required.

As the optical fiber, a plastic optical fiber having both a core component and a sheath component made of plastic is known in addition to a glass-based optical fiber using quartz glass or multi-component glass as a core component and a sheath component. ing. Plastic optical fibers are easier to manufacture and handle and are less expensive than glass optical fibers, but have the disadvantages of poor durability and heat resistance and high transmission loss.

Polyvinylidene fluoride (PVDF) has excellent heat resistance and weather resistance, has low moisture absorption, and has a refractive index of 1.4.
Since it is about 2 and smaller than other transparent resins, it is expected as a sheath component of plastic optical fibers. However, PVDF is liable to be clouded due to crystallization at the time of processing and molding. For example, JP-A-63-22872, JP-A-1-97901, and JP-A-5-609.
No. 31, JP-A-8-106019, etc.
A method of blending with an acrylic resin to make it transparent has been proposed. However, blending PVDF with an acrylic resin has disadvantages such as a decrease in heat resistance, weather resistance, and non-hygroscopicity, which are characteristics of PVDF, and a refractive index approaching that of an acrylic resin. Furthermore, a blend system of resins has a problem in that it tends to be optically non-uniform and light scattering is large.

[0018] Polyvinylidene fluoride resin is used as a surface protective material for office supplies, signboards, building materials, etc., taking advantage of its excellent weather resistance. Dissatisfied with transparency.

As a method for improving the transparency of a polyvinylidene fluoride resin, a method using an inorganic salt such as KCl or NaCl as a crystal nucleating agent, a method for forming a substantially unstretched sheet or thread, and the like have heretofore been used. Are stretched under cold or high temperature and high pressure conditions. However, the method of adding an inorganic salt has a problem that aggregates cause fish eyes. The method of drawing a substantially undrawn sheet or thread-like molded product under cold drawing or high-temperature and high-pressure conditions requires enormous processing equipment, and has a problem in productivity. Further, both methods were insufficient in the effect of improving transparency.

[0020]

SUMMARY OF THE INVENTION The object of the present invention is to
^A polyvinylidene fluoride resin composition that can stably and uniformly exhibit a desired volume resistivity within a range of ⁵ to 10 ¹³ Ωcm and has small changes in volume resistivity and surface resistivity due to environmental humidity changes. To provide.

Another object of the present invention is to provide a polyvinylidene fluoride resin composition having high light transmittance and low haze value and excellent transparency. Furthermore, an object of the present invention is to provide a semiconductive and / or transparent resin such as a tube, a sheet, a fiber, and an injection molded product by using such a resin composition having excellent semiconductive and / or transparent properties. It is to provide a molded article.

The present inventors have conducted intensive studies to overcome the above-mentioned problems of the prior art, and as a result, a resin obtained by adding a sulfate or sulfite of an alkyl quaternary ammonium to a polyvinylidene fluoride resin at a specific ratio. The composition is excellent in transparency, has a volume resistivity of a semiconductive region, has no variation in volume resistivity depending on a place, and can exhibit a desired volume resistivity stably and accurately. I found it. In addition, this resin composition does not generate aggregates or fish eyes, and does not bleed out additives. Furthermore, this resin composition has good processability,
It can be formed into various molded products by a general melt processing method. The present invention has been completed based on these findings.

[0023]

According to the present invention, the formula (1) is added to 100 parts by weight of the polyvinylidene fluoride resin (A).

[0024]

Embedded image

(Wherein, R ^{1 to} R ⁴ are the same or different alkyl groups, and R ⁵ is an alkyl group, a fluoroalkyl group, or a hydrogen atom). Salt (B1), and formula (2)

[0026]

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(Wherein, R ^{6 to} R ⁹ are the same or different alkyl groups, and R ¹⁰ is an alkyl group, a fluoroalkyl group, or a hydrogen atom). At least one compound (B) selected from the group consisting of salts (B2) by 0.03 to
There is provided a polyvinylidene fluoride resin composition containing 10 parts by weight. Further, according to the present invention, there is provided a molded article comprising the polyvinylidene fluoride-based resin composition.

[0028]

Means for Solving the Problems Polyvinylidene fluoride-based
Resin As the polyvinylidene fluoride resin (A) used in the present invention, a homopolymer of vinylidene fluoride (ie,
Polyvinylidene fluoride (PVDF), and copolymers of vinylidene fluoride having vinylidene fluoride as a main constituent unit and other copolymerizable monomers can be mentioned. As the vinylidene fluoride copolymer, vinylidene fluoride-
Hexafluoropropylene copolymers, vinylidene fluoride-tetrafluoroethylene copolymers, and vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymers are preferred. These polyvinylidene fluoride resins can be used alone or in combination of two or more.

Among 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 constituent unit alone is used,
Alternatively, it is preferable to use it by blending with PVDF. In order to improve the adhesiveness, a vinylidene fluoride copolymer having a functional group introduced is preferably used. As the polyvinylidene fluoride-based resin, another thermoplastic resin such as an acrylic resin or another fluororesin may be blended and used as long as the object of the present invention is not hindered.

Alkyl quaternary ammonium sulfates and salts
Sulfate The alkyl quaternary ammonium sulfate used in the present invention (B
1) is given by the equation (1)

[0031]

Embedded image

(Wherein R ^{1 to} R ⁴ are the same or different alkyl groups, and R ⁵ is an alkyl group, a fluoroalkyl group, or a hydrogen atom). The alkyl quaternary ammonium sulfite (B2) used in the present invention has the formula (2)

[0033]

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(Wherein, R ^{6 to} R ⁹ are the same or different alkyl groups, and R ¹⁰ is an alkyl group, a fluoroalkyl group, or a hydrogen atom). Among these compounds, alkyl quaternary ammonium sulfate (B1) is preferable because of its excellent stability.

In these compounds (B), R ^{1 to} R
The total number of carbon atoms of the alkyl group in ⁴ or R ^{6 to} R ⁹ is usually 4 or more, preferably 8 to 30, more preferably 12 to 24, and particularly preferably 15 to 20. Examples of the alkyl group include a short-chain alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. R
When ⁵ and R ¹⁰ are alkyl groups are short-chain alkyl groups such as methyl group and ethyl group are representative. R
^{When 5} and R ¹⁰ are fluoroalkyl groups, CF
_3, short-chain fluoroalkyl group such as C ₂ F ₅ are representative.

As specific examples of these compounds (B),
For example, (C_TwoH_Five)_FourN⁺, (C_ThreeH₇) _FourN⁺, (C_FourH₉)_Four
N⁺, (C_FiveH₁₁)_FourN⁺ Alkyl quaternary ammonium such as
Cation and CF_ThreeSO_Four ^-, CH_ThreeSO_Four ^-, HSO_Four ^-, C
F_ThreeSO_Three ^-, CH_ThreeSO_Three ^-, HSO_Three ^-Such as sulfuric acid or zinc
And salts comprising sulfuric acid-containing anions.
You. These compounds (B) have two or more anions and
And a salt combining cations. Also, four
The four alkyl groups of the quaternary ammonium are each
They may be the same or different. Among these,
Hydrogen sulfate of alkyl quaternary ammonium is preferred,
Trabutylammonium hydrogen sulfate
[(C_TwoH_Five)_FourNHSO_FourIs particularly preferred. These transformations
Compounds may be used alone or in combination of two or more.
Let it be used.

Polyvinylidene fluoride resins usually have an α-type structure simply by being melt-mixed with other substances. However, when a sulfate or sulfite of an alkyl quaternary ammonium is added, the polyvinylidene fluoride resin becomes polyfluorinated in the process of melt-mixing. The vinylidene resin has a β-type structure. From these facts, it is considered that these compounds act as a β-type crystal nucleating agent for the polyvinylidene fluoride resin.

Polyvinylidene fluoride resin composition The polyvinylidene fluoride resin composition of the present invention is a resin composition containing a polyvinylidene fluoride resin (A) and the compound (B). The compounding ratio of the compound (B)
It is in the range of 0.03 to 10 parts by weight, preferably 0.05 to 8 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the polyvinylidene fluoride resin (A). Particularly preferably, it is 0.3 to 2 parts by weight. If the compounding ratio is too small, the improvement effect by the addition of the compound (B) is small. If the compounding ratio is too large, coloring of the resin or decomposition and foaming during processing may occur. In addition, the preferable compounding ratio of the compound (B) can be appropriately determined depending on required physical properties.

JP-A-8-99374 and JP-A-7-99
As disclosed in Japanese Patent No. 28266, a transfer belt used in an electrophotographic copying machine, a laser beam printer, or the like preferably has a high elastic modulus. Specifically, the Young's modulus of the belt is preferably 1.0 GPa or more, and particularly preferably 1.5 GPa or more. However, when the amount of the compound (B) added increases, the Young's modulus of the sheet formed from the resin composition tends to extremely decrease. Therefore, when such a resin composition is used for a charging belt of an electrophotographic image forming apparatus, there is a problem that the charging belt expands with time, and an image shift occurs in a transfer process. When the polyvinylidene fluoride resin composition of the present invention is used as a transfer belt in an electrophotographic copying machine, a laser beam printer, or the like, the compound (B) is used with respect to 100 parts by weight of the polyvinylidene fluoride resin (A). Is preferably 0.03 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, further preferably 0.3 to 2 parts by weight,
0.5 to 1 part by weight is particularly preferred.

When the polyvinylidene fluoride resin composition of the present invention is used in a field where transparency is required, it is more specifically used as, for example, office supplies, office automation equipment, building materials, and surface protection materials for signboards. In this case, the absorbance ratio Rα defined by the formula (I) is preferably 0.8 or less,
0.5 or less is more preferable, 0.3 or less is more preferable, and 0.1 or less is especially preferable. On the other hand, when the resin composition of the present invention is used for an optical lens, an optical fiber, an optical filter, or the like, Rα is preferably 0.5 or less,
0.3 or less is more preferable, 0.1 or less is more preferable, and 0.05 or less is especially preferable. Rα can be 0.02 or less, if desired.

The absorbance varies depending on the monomer composition of the polyvinylidene fluoride resin (A), the type of the compound (B), the amount of the compound (B) added, the presence or absence of stretching, and the like. Therefore, the adjustment of the absorbance ratio is suitably performed by selecting the type of the polyvinylidene fluoride resin (A) or the compound (B), adjusting the amount of the compound (B) added, adjusting the stretching conditions, or a combination thereof. be able to. For example,
As shown in FIG. 3, as the amount of compound (B) added increases, the absorbance ratio decreases. Further, Example 11 described later.
As shown in Nos. To 12, for example, when a sheet of the polyvinylidene fluoride resin composition is stretched, the absorbance ratio can be significantly reduced. Adjustment of the amount of compound (B) to be added and stretching may be combined. The lower limit of the absorbance ratio is 0 when Dα is zero.

Other Additives When the polyvinylidene fluoride resin composition of the present invention is used in the field of transparency, it is desirable not to contain other additives as much as possible. If desired, other additives can be contained.
As other additives, for example, talc, mica, silica, alumina, kaolin, ferrite, potassium titanate, titanium oxide, zinc oxide, iron oxide, magnesium hydroxide, calcium carbonate, nickel carbonate, calcium sulfate,
Granular or powdered fillers such as barium sulfate, aluminum hydroxide, glass powder, quartz powder, graphite, inorganic pigments, organic metal salts, and other metal oxides; carbon fiber, glass fiber, asbestos fiber, silica fiber, alumina fiber, zirconia Fiber, boron nitride fiber, silicon nitride fiber, boron fiber,
Fibrous fillers such as potassium titanate fiber; and the like. These fillers can be appropriately compounded according to the purpose of use within a range not to impair the object of the present invention.

Further, the polyvinylidene fluoride resin composition includes, for example, an antioxidant, a lubricant, a plasticizer, an organic pigment,
A general-purpose additive such as an inorganic pigment, an ultraviolet absorber, a surfactant, an inorganic acid, an organic acid, a pH adjuster, a cross-linking agent, and a coupling agent is appropriately compounded within a range not to impair the effects of the present invention. Can be.

Method for Preparing Resin Composition, Molding Method, and Use There are no particular restrictions on the method for preparing the polyvinylidene fluoride resin composition of the present invention.
Powder or pellets of polyvinylidene fluoride resin,
A method of mixing the compound (B) with a mixer such as a mixer, a method of mixing the components with a mixer and then pelletizing the mixture by a melt extrusion method, and a method of mixing each component with water or water and a water-soluble solvent. A method of dissolving or dispersing in a mixed solvent, mixing with a mixer such as a mixer, followed by drying, and melt-extruding the obtained dried product to form a pellet is exemplified.

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. In addition, a masterbatch in which the compound (B) is contained in the polyvinylidene fluoride resin (A) at a high concentration is prepared in advance, and the resin is adjusted so that the concentration of the compound (B) becomes necessary at the time of molding. Molding can be performed after dilution.

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 manufactured using the polyvinylidene fluoride-based resin composition of the present invention, a single-screw or two-shaft
Using a screw extruder and a T-die, the resin composition in a molten state is extruded immediately below the lip, and cooled and solidified while being closely adhered to a cooling drum by an air knife or the like. In order to solidify the polyvinylidene fluoride resin composition of the present invention from a molten state, it is preferable to control the cooling temperature within a range of -30 to 100 ° C, and particularly to control the cooling temperature within a range of 0 to 30 ° C. preferable.

The polyvinylidene fluoride 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, a conductive member, a lens, and an optical filter. , Transparent film, transparent container and the like. 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 a fiber by a known molding method such as injection molding or melt extrusion. It is possible. After processing, it is possible to further stretch or heat set. The polyvinylidene fluoride resin composition of the present invention may be used alone,
If necessary, it may be compounded with another resin layer or the like, and used as a laminated sheet or a composite yarn.

[0048]

The present invention will be described below more specifically with reference to examples and comparative examples. The measuring method of the physical properties is as follows. (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,
Inner electrode diameter 26.0 mm, outer electrode inner diameter 3
8.0mm, outer diameter of outer electrode 40.0mm) and load 7k
g between the inner electrode and the counter electrode
The volume resistivity ρ _v when a voltage of V was applied for 1 minute (in the thickness direction) was determined with a resistance meter (trade name: High Resistance Meter HP4339A, manufactured by Hewlett-Packard Company). For details of such a volume resistivity measurement method using the ring electrode method, JIS-K6911 can be referred to. 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 diameter 5.9 mm, outer electrode inner diameter 11.0 mm, outer electrode outer diameter 17.8 mm)
And a measurement stage (trade name: cashier table FL, manufactured by Mitsubishi Chemical Co., Ltd.), a sample is sandwiched between them, and a voltage of 500 V is applied between the inner electrode of the probe and the measurement stage while pressing the sample with a pressure of about 3 kg weight. And a resistivity measuring device (trade name:
The volume resistivity ρ _v was determined using Hiresta IP (manufactured by Mitsubishi Chemical Corporation). For details of such a volume resistivity measurement method using the ring electrode method, JIS-K6911 can be referred to.

(3) Calculation of average value In the above-mentioned measurement of the thickness and the volume resistivity, these values were measured at 20 measurement points arbitrarily selected per 1 m ² of the surface area of the sample to be measured, or at 20 measurement points selected arbitrarily. One point (a total of 20 points) was measured for each molded product, and the maximum value, the minimum value, and the average value (arithmetic mean) were obtained. (4) Young's modulus According to JIS-K7113, width 10 mm, length 100
mm test strip (TENSIL)
ON RTM100 type, manufactured by Orientec Co., Ltd.) under the conditions of a tensile speed of 50 mm / min and a distance between chucks of 50 mm.

(5) 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, inner electrode diameter: 26.0 mm, outer electrode: (38.0 mm inner diameter, 40.0 mm outer diameter of outer electrode)
After holding the sample with a load of 7 kg in a constant temperature and humidity chamber (trade name: LH30-13M, manufactured by Nagano Kagaku Seisakusho Co., Ltd.) for 24 hours, the inner electrode and the counter electrode were During the application of a voltage of 100 V for 1 minute (in the thickness direction), the volume resistivity ρ _v was determined with a resistance meter (trade name: High Resistance Meter HP4339A, manufactured by Hewlett-Packard Company). For details of such a volume resistivity measurement method using the ring electrode method, see JIS-K
6911 can be referred to. The volume resistivity was measured after adjusting the relative humidity for 24 hours in each humidity environment in the order of 30%, 50%, 70%, and 90%.

(6) Humidity Dependence of Surface Resistivity In the present invention, a resiliency cell having a ring-shaped electrode (trade name: HP16008B, manufactured by Hewlett-Packard Company, inner electrode diameter: 26.0 mm, outer electrode: (38.0 mm inner diameter, 40.0 mm outer diameter of outer electrode)
After holding the sample under a load of 7 kg in a thermo-hygrostat (trade name: LH30-13M, manufactured by Nagano Kagaku Seisakusho Co., Ltd.) adjusted to a predetermined temperature and humidity for 24 hours, the inner electrode and the outer electrode The surface resistivity ρ _s when a voltage of 10 V was applied for 1 minute (in the surface direction) during this period was determined with a resistance meter (trade name: High Resistance Meter HP4339A, manufactured by Hewlett-Packard Company). Details of such a surface resistivity measurement method using the ring electrode method are described in JIS-K69.
11 can be referred to. The surface resistivity was measured after adjusting the relative humidity for 24 hours in each humidity environment in the order of relative humidity of 30%, 50%, 70%, and 90%.

(7) Haze Value (Haze) The haze value was measured using a haze meter (trade name: $ 80, manufactured by Nippon Denshoku Industries Co., Ltd.). For details on how to measure the haze, see J
IS-K7015 can be referred to. (8) Infrared absorption spectrum (IR) The infrared absorption spectrum was obtained by Fourier transform infrared spectrophotometer (trade name: FTIR-8200, manufactured by Shimadzu Corporation), total reflection measurement cell (trade name: ATR-8000, Shimadzu Corporation) Manufactured), and prism (KRS-5, manufactured by Shimadzu Corporation)
Using the ATR method (Attenuated Tota)
l Reflectance) in the range of 400 cm ^-1 to 1000 cm ^-1 . (9) Absorbance D of infrared absorption spectrum at absorbance ratio Rα 531 cm ^-1
α and the absorbance Dβ of the infrared absorption spectrum at 511 cm ⁻¹ were determined from the formula (I).

[0053]

(Equation 2)

[0054] However, the absorbance Dx of infrared absorption spectra in xcm ^-1 is obtained from the formula (II) formula from the intensity I of the intensity I0 of incident light transmitted light in xcm ^-1.

[0055]

(Equation 3)

As shown in FIGS. 8B and 8C, the baseline at which the absorbance was determined was around 500 cm ^-1 and 545.
If a tangent is drawn to the peak near cm ⁻¹ or Dβ is extremely large, such a tangent will cause a tangent to the peak near 520 cm ⁻¹ , as shown in FIG. 5
A tangent line a ₁ contacting the peak near 45 cm ⁻¹ and the peak near 520 cm ⁻¹ , and the peak near 520 cm ⁻¹ and 500 cm ⁻¹
It is determined by drawing a tangent line a ₂ tangent to a nearby mountain, and Dα and Dβ are determined based on this baseline. (10) Differential scanning calorimetry (DSC) Differential scanning calorimeter (product name: DSC30, Mett)
er) and data processor (product name: TC10)
A, manufactured by Mettler Co., Ltd.) and the DSC method under the following conditions. Conditions: sample weight 10 mg, measurement start temperature 30 ° C, measurement end temperature 250 ° C, heating rate 10 ° C / min

[Examples 1 to 7 and Comparative Examples 2 to 6] Table 1
Was added to a mixer (trade name: Super Mixer, manufactured by Kawada Seisakusho Co., Ltd.), and the mixture was sufficiently stirred and mixed at 1,000 rpm for about 5 minutes. Next, the obtained mixture was pelletized to a diameter of about 3 mm at a die temperature of 240 ° C. using a single screw extruder (manufactured by Plagiken Co., Ltd.). This pellet was immediately cooled at 230 ° C. and immediately cooled at 20 ° C. to obtain a sheet having a thickness of 0.25 mm. Table 1 shows the measurement results of the physical properties.

Example 8 The procedure of Examples 1 to 7 was repeated except that a resin powder having the composition shown in Table 1 and additives were used, and the mixture was gradually cooled at 100 ° C. immediately after press molding.
Sheet was obtained. Table 1 shows the measurement results of the physical properties.

[Examples 9 and 10] A resin powder having the composition shown in Table 1 and an additive were mixed with a mixer (manufactured by Kawada Seisakusho Co., Ltd., trade name:
Super Mixer) and rotate at 1000rpm
For about 5 minutes. Then, the obtained mixture was subjected to single-screw extruder (Pla Giken Co., Ltd.)
The pellet was formed into a diameter of about 5 mm at a die temperature of 240 ° C. The raw material thus pelletized is supplied to a T-type die (die temperature 240 ° C.) having a lip clearance of 0.7 mm using a single screw extruder (manufactured by Plagiken Co., Ltd.), and the molten resin extruded from the die is discharged. It was formed into a sheet by a cooling roll at 90 ° C. Table 1 shows the measurement results of the physical properties.

Example 11 The sheet obtained in Example 10 was stretched 3.5 times in the machine direction by a tenter clip type stretching machine adjusted to 140 ° C. to obtain a uniaxially oriented film having a thickness of 35 μm. . The absorbance ratio Rα of this film is
It was 0.05. Table 1 shows the measurement results of the physical properties.

Example 12 The sheet obtained in Example 10 was stretched 3.5 times in the longitudinal direction by a tenter clip type stretching machine adjusted to 140 ° C., and further 3.5 in the transverse direction.
The film was stretched twice to obtain a biaxially oriented film having a thickness of 10 μm. The absorbance ratio Rα of this film was 0.02. Table 1 shows the measurement results of the physical properties.

[Comparative Example 1] PVDF pellets at 230 ° C
And then quenched at 20 ° C to a thickness of 0.25
mm sheet was obtained. Table 1 shows the measurement results of the physical properties.

[Comparative Example 7] Using a single screw extruder (manufactured by Plagiken Co., Ltd.), PVDF pellets were T-shaped with 0.7 mm lip clearance (die temperature 240 ° C).
And the molten resin extruded from the die was formed into a sheet by a cooling roll at 90 ° C. Table 1 shows the measurement results of the physical properties.

Comparative Example 8 The sheet obtained in Comparative Example 7 was stretched by a tenter clip type stretching machine adjusted to 140 ° C.
The film was stretched 3.5 times in the machine direction to obtain a uniaxially oriented film having a thickness of 35 μm. The absorbance ratio Rα of this film is 0.
97. Table 1 shows the measurement results of the physical properties.

[Comparative Example 9] The sheet obtained in Comparative Example 7 was stretched with a tenter clip type stretching machine adjusted to 140 ° C.
The film was stretched 3.5 times in the machine direction and further 3.5 times in the transverse direction to obtain a biaxially oriented film having a thickness of 10 μm.
The absorbance ratio Rα of this film was 0.59. Table 1 shows the measurement results of the physical properties.

[0066]

[Table 1]

Footnotes: (1) PVDF: polyvinylidene fluoride (KF # 1000, manufactured by Kureha Chemical Industry Co., Ltd.) (2) VPFP: vinylidene fluoride-propylene hexafluoride copolymer [Kureha Chemical Industry Co., Ltd.] , KF # 2300] (3) TBAHS: (C ₄ H ₉ ) ₄ NHSO ₄ [manufactured by Toyama Pharmaceutical Co., Ltd.] (4) TEABr: (C ₂ H ₅ ) ₄ NBr [manufactured by Wako Pure Chemical Industries, Ltd.] (5) TBABr: [CH ₃ (CH ₂ ) ₃ ] ₄ NBr [manufactured by Wako Pure Chemical Industries, Ltd.] (6) TEACl: (C ₂ H ₅ ) ₄ NCl [manufactured by Wako Pure Chemical Industries, Ltd.] (7) MAC1: CH ₃ NH ₃ Cl [manufactured by Wako Pure Chemical Industries, Ltd.]

As is clear from the results in Table 1, the polyvinylidene fluoride resin compositions of the present invention (Examples 1 to 10)
Has a moderately low volume resistivity, small variation, and low haze. In addition, the polyvinylidene fluoride resin composition of the present invention can significantly reduce the haze value by selecting the mixing ratio and the molding conditions (Examples 4 to 10). Furthermore, in Examples 1 to 10, no aggregates or fish eyes were observed in the sample, and no bleed out of the additive was observed.

On the other hand, when there is no additive (Comparative Examples 1 and 7) and when the compounding ratio of the compound (B) is too large (Comparative Example 2), additives other than the compound (B) of the present invention are used. When they are added (Comparative Examples 3 to 6), only unsatisfactory results can be obtained. Particularly in Comparative Examples 2 to 6, the resin composition was colored brown and decomposed and foamed during pelletization. Therefore, the physical properties of Comparative Examples 2 to 6 shown in Table 1 are measured values for the colored foamed sheet. Also,
The press sheets of Comparative Examples 3 to 6 had an ammonia odor.

Measurement of Young's Modulus Young's modulus was measured using each of the samples prepared in Examples 1 to 6 and Comparative Example 1. The results are shown in FIG. As is apparent from FIG. 1, the Young's modulus of the sheet tends to sharply decrease as the amount of TBAHS added increases. Measurement of HAZE HAZE was measured using each of the samples prepared in Examples 1 to 6 and Comparative Example 1. The results are shown in FIG. As is clear from FIG. 2, when the amount of TBAHS added increases,
The HAZE of the sheet tends to decrease sharply and the transparency tends to increase. Measurement of Rα Rα was measured using the samples prepared in Examples 1 to 5 and Comparative Example 1. The results are shown in FIG. As is clear from FIG. 3, as the amount of TBAHS added increases, Rα of the sheet tends to decrease sharply.

DSC Measurement 1 DSC measurement was performed using each sample prepared in Example 2, Example 4, Example 5, and Comparative Example 1. Fig. 4 shows the results.
Shown in As is clear from FIG. 4, the DSC charts of Example 2, Example 4, and Example 5 show 185 to 20.
In the range of 0 ° C., a peak not observed in Comparative Example 1 is observed. DSC Measurement 2 Using each sample prepared in Examples 4 and 8, D
SC was measured. FIG. 5 shows the results. As is clear from FIG. 5, in the DSC chart of Example 8 in which the temperature was gradually cooled after press molding, the peak in the range of 185 to 200 ° C. observed in Example 4 disappeared.

Measurement of Volume Resistivity Using the sample prepared in Example 10, the humidity dependency of the volume resistivity was measured. FIG. 6 shows the results. As is clear from FIG. 6, the sheet obtained from the polyvinylidene fluoride resin composition of the present invention has a small humidity dependency of the volume resistivity. Measurement of Surface Resistivity Using the sample prepared in Example 10, the humidity dependency of the surface resistivity was measured. FIG. 7 shows the results. As is clear from FIG. 7, the sheet obtained from the polyvinylidene fluoride resin composition of the present invention has a small humidity dependency of the surface resistivity.

[0073]

According to the present invention, 10 ⁵ to 10 ¹³ Ωcm
The present invention provides a polyvinylidene fluoride-based resin composition that can stably exhibit a desired volume resistivity uniformly and accurately within the range described above, and has a small change in volume resistivity and surface resistivity due to a change in environmental humidity. Using this polyvinylidene fluoride resin composition, semiconductive molded articles such as tubes, sheets, fibers, and injection molded articles can be obtained. Further, according to the present invention, a polyvinylidene fluoride resin composition having a low haze value and excellent transparency is provided. Using this polyvinylidene fluoride resin composition, a transparent molded product such as a tube, a sheet, a fiber, and an injection molded product can be obtained.

The polyvinylidene fluoride resin composition of the present invention can be used in the field of semiconductivity in the field of charge control members such as a charging roll, a transfer roll, a developing roll, a charging belt, and a discharging belt in an electrophotographic image forming apparatus. It is suitable as a material for forming at least the surface layer. Examples of the roll-shaped member include those in which a polyvinylidene fluoride-based resin composition layer is formed on the outermost layer directly or via another resin layer and / or rubber layer on a cored bar. In addition, the resin composition of the present invention may be used for electronic component packaging materials (for example,
It is suitable as various charge control members such as bags, containers, wallpaper, OA equipment exterior materials, antistatic partitions, and transfer tubes for powder coating materials. The polyvinylidene fluoride resin composition of the present invention includes, as a field of transparency, an optical fiber, a sheath component of an optical fiber, an optical lens, a window glass, a window glass protective material, a display protective material, a CRT protective material, a solar cell translucent material, It is suitable as an optical member such as a cover for lighting.

[Brief description of the drawings]

FIG. 1 is a diagram showing the Young's modulus of each sample prepared in Examples 1 to 6 and Comparative Example 1 in relation to the addition amount of tetrabutylammonium hydrogen sulfate (TBAHS).

FIG. 2 is a diagram showing the haze value of each sample prepared in Examples 1 to 6 and Comparative Example 1 in relation to the amount of TBAHS added.

FIG. 3 is a diagram showing Rα of each sample prepared in Examples 1 to 5 and Comparative Example 1 in relation to the amount of TBAHS added.

FIG. 4 is a diagram showing the results of DSC measurement using the samples prepared in Example 2, Example 4, Example 5, and Comparative Example 1.

FIG. 5 is a diagram showing a result of performing a DSC measurement using each sample prepared in Example 4 and Example 8.

FIG. 6 is a diagram showing the volume resistivity in relation to humidity using the sample prepared in Example 10.

FIG. 7 is a diagram showing the surface resistivity in relation to humidity using the sample prepared in Example 10.

FIG. 8 is a diagram showing a method for determining a baseline for determining the absorbance of an infrared absorption spectrum.

Claims (20)

[Claims] 1. Polyvinylidene fluoride resin (A) 10
With respect to 0 parts by weight, the formula (1) (Wherein, R ^{1 to} R ⁴ are the same or different alkyl groups, and R ⁵ is an alkyl group, a fluoroalkyl group, or a hydrogen atom). ) And formula (2) (Wherein, R ^{6 to} R ⁹ are the same or different alkyl groups, and R ¹⁰ is an alkyl group, a fluoroalkyl group, or a hydrogen atom). A) a polyvinylidene fluoride resin composition containing at least one compound (B) selected from the group consisting of: 0.03 to 10 parts by weight; 2. Polyvinylidene fluoride resin (A) is:
The resin composition according to claim 1, which is a homopolymer of vinylidene fluoride. 3. The polyvinylidene fluoride resin (A)
The resin composition according to claim 1, which is a copolymer of vinylidene fluoride and another copolymerizable monomer. 4. The vinylidene fluoride copolymer is a vinylidene fluoride-hexafluoropropylene copolymer, a vinylidene fluoride-tetrafluoroethylene copolymer, or a vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer The resin composition according to claim 3, which is 5. An alkyl quaternary ammonium sulfate (B)
The resin composition according to claim 1, wherein 1) is an alkyl quaternary ammonium hydrogen sulfate. 6. The resin composition according to claim 5, wherein the alkyl quaternary ammonium hydrogen sulfate is tetrabutyl ammonium hydrogen sulfate. 7. The resin composition according to claim 1, which has a haze value of 40% or less. 8. The resin composition according to claim 1, wherein the volume resistivity is in the range of 10 ⁵ to 10 ¹³ Ωcm. 9. the Dα the absorbance of the infrared absorption spectrum in 531cm ^-1, when a Dβ the absorbance of the infrared absorption spectrum in 511cm ^-1, the formula (I) ## EQU1 ## 2. The polyvinylidene fluoride resin composition according to claim 1, wherein the absorbance ratio Rα defined by the formula is in the range of 0 to 0.8. 10. At least one endothermic peak within a temperature range of 185 to 200 ° C. when measured using a differential scanning calorimeter at a temperature rising start temperature of 30 ° C. and a temperature rising rate of 10 ° C./min. The resin composition according to claim 1, which shows: 11. The resin composition according to claim 1, which is a resin material used for a charging member of an electrophotographic device or an electrostatic recording device. 12. A molded article comprising the polyvinylidene fluoride resin composition according to claim 1. Description: 13. The molded article according to claim 12, which is a sheet, a fiber, or an injection molded article. 14. The molded article according to claim 12, which is a charge control member. 15. The molded article according to claim 14, wherein the charge control member is a semiconductive member in an electrophotographic device or an electrostatic recording device. 16. The semiconductive member has a Young's modulus of 1.0 GP.
16. A belt-shaped or sheet-shaped member of at least a.
The molded article as described. 17. The molded article according to claim 14, wherein the semiconductive member is a roll-shaped member having a surface layer formed from a polyvinylidene fluoride-based resin composition. 18. The molded article according to claim 14, wherein the charge control member is an electronic component packaging material, a wallpaper, an OA equipment exterior material, an antistatic partition, or a transfer tube of a powder coating material. 19. The molded article according to claim 12, which is an optical member. 20. The optical member according to claim 19, wherein the optical member is an optical fiber, a sheath component of the optical fiber, an optical lens, a window glass, a window glass protective material, a display protective material, a CRT protective material, a light transmitting material for a solar cell, or a cover for lighting. The molded article as described.