WO2001021713A1 - Composition de resine thermoplastique et procede de production correspondant - Google Patents

Composition de resine thermoplastique et procede de production correspondant Download PDF

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Publication number
WO2001021713A1
WO2001021713A1 PCT/JP2000/006567 JP0006567W WO0121713A1 WO 2001021713 A1 WO2001021713 A1 WO 2001021713A1 JP 0006567 W JP0006567 W JP 0006567W WO 0121713 A1 WO0121713 A1 WO 0121713A1
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WO
WIPO (PCT)
Prior art keywords
thermoplastic resin
conductivity
composition
phase
resin
Prior art date
Application number
PCT/JP2000/006567
Other languages
English (en)
Japanese (ja)
Inventor
Jiro Watanabe
Masuo Kuroda
Original Assignee
The Yokohama Rubber Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Yokohama Rubber Co., Ltd. filed Critical The Yokohama Rubber Co., Ltd.
Publication of WO2001021713A1 publication Critical patent/WO2001021713A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon

Definitions

  • the present invention relates to a thermoplastic resin composition and a method for producing the same, and more particularly, to a desired conductivity having a small variation in a semiconductive region (10 4 [ ⁇ ⁇ cn!] To 10 12 [ ⁇ ⁇ cm]).
  • the present invention relates to a thermoplastic resin composition having a (volume resistivity) and a method for producing the same.
  • the distribution of the conductivity imparting agent in the foam depends on the degree of foaming. It was difficult to control, and it was also difficult to obtain a semiconductive composition using a foam and having no variation in resistance value.
  • an object of the present invention is a semiconductive region (1 0 4 to 1 0 1 2 [Omega ⁇ cm]), the thermoplastic resin composition having a small desired conductivity field variability (the volume resistivity) Contact And a method for producing the same. Disclosure of the invention
  • a matrix phase containing a thermoplastic resin (A) and a domain phase containing a thermoplastic resin (B) and a conductivity-imparting agent (C) are provided.
  • a is not less than 1
  • volume resistivity 1 0 4 -1 0 1 the thermoplastic resin composition is 2 [Omega ⁇ cm] is provided.
  • the expression that the volume resistivity is 10 4 to 10 12 [ ⁇ ⁇ cm] means that the average value of the volume resistivity is in this order.
  • the domain phase contains the conductivity imparting agent (C) in a volume fraction of 5 to 25%, and the volume ratio of the matrix phase to the domain phase is
  • the thermoplastic resin composition having a domain phase of 90 to 10/25/75 is provided.
  • thermoplastic resin composition comprising mixing a thermoplastic resin (B) and a conductivity-imparting agent (C) in advance, and further mixing a thermoplastic resin (A).
  • FIG. 1 is an explanatory diagram showing a sea-island structure of a domain phase and a matrix phase.
  • FIG. 2 is an explanatory view showing an arrangement of force pump racks in a polymer.
  • the thermoplastic resin composition of the present invention includes a matrix phase (continuous phase) containing a thermoplastic resin (A), a thermoplastic resin (B), and a conductivity imparting agent ( C) and a domain phase (dispersed phase) containing Is the surface tension of the resin (A) a A and the surface tension of the resin (B)? ⁇
  • the difference from ⁇ B -7 A is 1 or more, preferably 1.5 or more, more preferably 3 or more.
  • the surface tension mentioned here indicates the surface tension at room temperature (at 20). reality To measure the surface tension at the temperature at which the thermoplastic resin (A) and the thermoplastic resin (B) are mixed, it is extremely difficult to measure the surface tension at high temperatures.
  • the tendency of the surface tension value to decrease from room temperature to high temperature is similar, so that the surface tension at room temperature is used here.
  • the intermolecular force acts uniformly on the molecules inside the substance, but the intermolecular attractive force acting on the molecules at the interface becomes uneven. Due to this microscopic difference in intermolecular force, molecules on the surface have larger free energy than molecules inside. This is the macroscopic free energy per unit area, that is, the surface tension.
  • the surface tension can be measured between the gas phase and the liquid phase by various measurement methods, and thermodynamically determined by theoretical and approximate formulas. This idea is extended to the solid phase to calculate the surface tension of various resins at each temperature. Specifically, it is described in Polymer Handbook (published by John Wiley and Sons).
  • thermoplastic resin (A) When the thermoplastic resin (A) is mixed with the thermoplastic resin (B) and the conductivity-imparting agent (C) such as carbon black, the conductivity-imparting agent (C) has a higher surface tension than the resin, so that when mixing, The transition to the resin side where the interfacial tension becomes smaller, that is, the resin (B) having a larger surface tension. For this reason, by substantially imparting conductivity only to the domain phase containing the resin (B), the volume specific resistance (electrical resistance) of the domain phase is changed to the volume specific resistance of the matrix phase of the thermoplastic resin composition. Thus, a composition that is smaller than the value (electric resistance value) is obtained.
  • thermoplastic resin composition of the present invention stabilizes the volume specific resistance value with a small variation and stabilization.
  • a method shown in FIG. 2 in which carbon black 2 is directly mixed with polymer 11 is used.
  • the pump rack 2 is added to the polymer 1, the carbon black 2 forms a conductive circuit at a certain amount, and the conductivity is suddenly improved. It was very difficult to control the resistance value.
  • the domain phase 3 containing the conductivity-imparting agent (C) such as carbon black and the matrix phase 4 may form a sea-island structure. Therefore, a conductive circuit as shown in Fig. 2 is not formed, and conductivity is developed by electrons jumping between the domain phases 3 containing a conductivity-imparting agent (C) called a tunnel effect.
  • C conductivity-imparting agent
  • the volume resistivity value is determined by the distance between the domain phases 3. Therefore, the volume resistivity can be freely controlled by the amount and the particle size of the domain phase 3 in the thermoplastic resin composition, and the particle size in the system becomes almost uniform. It becomes a small material.
  • the conductive composition of the present invention can be controlled by the semiconductive region (1 0 4 to 1 0 1 2 [Omega ⁇ cm]).
  • 1 0 5 - conventional as 1 0 1 1 [Omega ⁇ cm] can control the conductivity of it is difficult to obtain without variation region.
  • the control of the conductivity (volume resistivity) of the domain phase depends on the conductivity of the thermoplastic resin (B), which is a component of the domain phase, and the type and amount of the conductivity imparting agent (C) contained. be able to.
  • the domain phase contains the conductivity imparting agent (C) in a volume fraction of 5 to 25%, preferably 10 to 20%, and a matrix
  • the volume fraction of the conductivity-imparting agent (C) contained in the domain phase depends on the type of the thermoplastic resin (B) contained in the domain phase, but is preferably 5 to 25%. When the content is 5% or more, sufficient conductivity can be exhibited, and when the content is 25% or less, the kneading property in the resin composition can be improved.
  • the method for controlling the conductivity of the thermoplastic resin composition can be achieved by changing the type and amount of the conductivity-imparting agent (C) contained in the dispersed domain phase. It is easy to prepare a resin composition that forms a domain phase and a matrix phase containing a property imparting agent (C) in advance, and control the ratio by changing the ratio in the thermoplastic resin composition. Further, it is preferable from the viewpoint of the uniformity of dispersion of the conductivity imparting agent (C) in the resin composition. Further, the particle size of the domain phase is controlled by selecting the compatibility between the resin (A) and the resin (B), the kneading temperature, and the shear rate during the production of the composition of the present invention described below. Can be. The conductivity of the matrix phase can be controlled by selecting the type of the thermoplastic resin (A) contained in the composition of the present invention.
  • the composition of the present invention which can control the conductivity of the entire composition, has been conventionally used.
  • stable conductive semiconductive region of the composition resulting Rukoto is difficult 1 0 4 to 1 0 1 2 having a certain conductivity [Omega ⁇ cm], the double It can be easily and stably provided without requiring complicated control.
  • thermoplastic resins or compositions thereof can be used as the thermoplastic resin (A) contained in the matrix phase and the thermoplastic resin (B) contained in the domain phase used in the present invention. That is, it may be a single thermoplastic resin or composition, or a composition comprising a mixture thereof.
  • thermoplastic resin (A) examples include polyolefin resins such as polypropylene, polycarbonate, and high-density polyethylene.
  • thermoplastic resin (B) examples include linear low-density polyethylene and polyethylene. Examples include terephthalate and nylon 66.
  • conductivity-imparting agent (C) used in the present invention conventionally known conductivity-imparting agents can be used.
  • Preferred examples thereof include a metal-based filler and a carbon-based filler.
  • Metallic fillers include metal powders such as Ag powder, Ni powder, Cu powder, Ag powder, Cu powder, brass fiber, A1 fiber, Cu fiber, metal fiber such as stainless steel fiber, and metal. There are flakes both having a volume resistivity of about 1 0 _ 6 [Omega ⁇ cm].
  • carbon-based fillers include carbon black such as Ketjen black, furnace black, acetylene black, and thermal black, graphite, and carbon fiber.
  • the composition of the present invention includes a metal-based filler Carbon-based fillers may be added alone or in combination.
  • the amount of the conductivity-imparting agent (C) can be appropriately determined depending on the type of the conductivity-imparting agent (C) to be used and the size of the conductivity required for the resin particles and the composition of the present invention.
  • the amount of the metal powder or metal fiber added may be appropriately determined according to the conductivity to be imparted to the composition of the present invention and the conductivity depending on the type of metal used, and is not particularly limited.
  • the conductive carbon black used in the present invention is added for imparting conductivity to the composition, and is separated from carbon black used as a filler and a Z reinforcing agent, and has DBP (dibutyl phthalate) oil absorption.
  • the amount is 90 (m1 / 100 g or more, preferably 100 (ml Zl00 g) or more, more preferably 150 to
  • the type of the conductive carbon black may be appropriately determined according to the conductivity as long as the final thermoplastic resin J5 has a volume resistivity in the range of 10 4 to 10 12 ( ⁇ cm) as the composition.
  • Examples of such conductive carbon include Mitsubishi Chemical Corporation's # 3050B, # 3150B, # 3750B, # 3950B, Axo Corporation's Ketjen Black EC, DJ-600, # 4500, # made by Tokai Carbon
  • the amount of the conductive carbon black to be added may be appropriately determined according to the conductivity of the resin particles contained in the composition of the present invention and, consequently, the conductivity imparted to the composition of the present invention, and is not particularly limited. . Further, it is preferable that the conductive black is not substantially contained in the matrix phase but is contained in the resin particles. This is because the volume resistivity of the composition can be more reliably controlled.
  • a plasticizer, a compatibilizer, a vulcanization accelerator, an antioxidant, an antioxidant as long as the object of the present invention is not impaired. Agents, ultraviolet absorbers, coloring agents such as pigments and dyes, and additives such as processing aids.
  • the composition of the present invention can be produced by simultaneously kneading the thermoplastic resin (A), the thermoplastic resin (B), and the conductivity-imparting agent (C). It is preferable to mix the conductivity-imparting agent (C) in advance and further mix the thermoplastic resin (A) because the conductivity-imparting agent (C) is effectively incorporated into the thermoplastic resin (B). .
  • the model used for mixing is not particularly limited, and examples thereof include a screw extruder, a kneader, a Banbury mixer, and a twin-screw kneading extruder.
  • the above two-stage mixing may be continuously performed by one type of mixer, or may be sequentially performed by using two or more types of kneaders.
  • the melt viscosity refers to the melt viscosity of the component at an arbitrary temperature during kneading
  • the melt viscosity of each resin composition material is defined by the temperature, shear rate (sec- ') and shear stress.
  • the stress and shear rate of each resin composition material are measured at any temperature in the molten state that flows through the cell, especially at the temperature range during kneading, and the shear stress is divided by the shear rate. Thereby, the melt viscosity is calculated.
  • a capillary rheometer capiograph 1C manufactured by Toyo Seiki may be used.
  • the conductivity of the domain phase dispersed in the composition is controlled by adding the conductivity-imparting agent to the domain phase, and the dispersion state of the domain phase and the resistance value of the matrix phase are controlled. Therefore, the conductivity can be controlled in the semiconductive region.
  • Such a control is a method that can be easily controlled such as the amount and dispersion state of the conductivity-imparting agent (C) in the conductive domain phase, and is therefore more controlled than the conventional control of the resistance value of the conductive resin composition and the like. Can be easily achieved, and furthermore, stable and reliable control of the resistance value can be achieved, so that the effect of increasing the yield in the production of the composition can be obtained.
  • the structure of the composition of the present invention is also a pressure-sensitive conductive structure, it can be used as a pressure-sensitive conductive composition.
  • the conductive compositions of the present invention 1 0 4 ⁇ 1 0 1 2 [ ⁇ - cm), preferably from 1 0 5 ⁇ : L 0 1 1 conductive semiconductive region of [Omega ⁇ cm) of It can be controlled to have.
  • the composition of the present invention includes various types of charging rollers for OA equipment, antistatic sheets, conductive belts, semiconductive belts, semiconductive rolls, vacuum cleaners, equipment panel covers, clean room interiors, IC-related parts and housings for IC products, It can be suitably used for products using thermoplastic and conductive compositions such as fuel tanks, sensor electrodes, ground rods, planar heating elements, inner and outer tubes for antistatic hoses, flooring materials for buildings, etc. it can.
  • thermoplastic and conductive compositions such as fuel tanks, sensor electrodes, ground rods, planar heating elements, inner and outer tubes for antistatic hoses, flooring materials for buildings, etc. it can.
  • Examples 1 to 8 and Comparative Examples 1 to 4 First, a master batch (MB 1 to MB 6) as a domain phase composition was charged into a twin-screw kneader at a weight ratio shown in Table 1 below. The mixture was kneaded at 250 and a shear rate of 100 Osec- ', and the composition released for the kneaded MBs 1 to 5 was pelletized with a resin pelletizer.
  • the obtained pellets (MB 1 to MB 5) and the thermoplastic resin (A) were charged into a twin-screw kneader at a weight ratio such that the total amount of the resin components shown in Table 2 was 100, and 200 to 250, and kneaded at a shear rate of 100 Osec one 1, a twin-screw kneader thermoplastic resin sets forming material extruded in strands from the discharge port of the water-cooled, and pelletized with a resin for pelletizer scratch.
  • HPDE carbon black and thermoplastic resin (A) were dry-blended and fed into a twin-screw kneading extruder without using one master batch.
  • this pellet was sheeted from a single-screw extruder through a T-die to a thickness of 100 m, and the volume resistivity at room temperature was measured for any 10 points of the obtained sheet, and the average value was calculated.
  • the results are shown in Table 2 below.
  • log volume resistivity
  • the difference between the highest value and the lowest value was shown in the following Table 2 as the variation (power).
  • the sheet was cut into ultra-thin sections, and the transmission electron microscope (TEM) was used to observe where the carbon black was unevenly distributed in the matrix phase and the domain phase.
  • L-LDPE 30 One-one-one-----one
  • HDPE high density polyethylene, HIZEX 2100], Mitsui Chemicals, Inc.
  • PET 'one-piece, bi-mouthed pet EMC 560 PET 'one-piece, bi-mouthed pet EMC 560
  • N66 Nylon 66, Amilan CM3006, Toray,
  • L-LDPE Linear low-density polyethylene, ULTZEX 20100 J
  • Comparative Example 1 in which conductive carbon black was blended in advance without being blended in the domain phase was used for the conductive carbon black during the biaxial kneading process. Cannot be unevenly distributed in the domain phase, but remains in the matrix phase, and the dispersion is not uniform, so that the variation in the volume resistivity value has increased. However, it was also recognized that even when the components were manufactured in the same composition and in the same mixing order as in Comparative Example 1, if the kneading was performed for a considerably long time, there was almost no variation in the volume resistivity. In Comparative Example 2, the amount of the domain phase containing the conductive black was small.
  • thermoplastic resin composition comprising a matrix phase (continuous phase) containing a thermoplastic resin (A) and a domain phase (dispersed phase) containing a thermoplastic resin (B) and a conductivity-imparting agent (C).
  • the semiconductive region (10 4 to 10 12 [ ⁇ ⁇ cm]) can be obtained by setting the difference TB-r A between the surface tension a A of the resin (A) and the surface tension of the resin (B) to 1 or more.
  • thermoplastic resin composition having a desired conductivity (volume resistivity) having a small variation and a method for producing the same.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette invention se rapporte à une composition de résine thermoplastique, qui comprend une phase matrice contenant une résine thermoplastique (A) et une phase domaine contenant une résine thermoplastique (B) et un agent lui conférant une conductivité électrique (C), le rapport en volume entre la phase matrice et la phase domaine étant compris entre 90/10 et 25/75. La différence (ηA-ηB) entre la tension de surface (ηA) de la résine (A) et celle (ηB) de la résine (B) est égale ou supérieure à 1 et ladite composition présente une résistivité volumique comprise entre 10?4 et 1012¿ [Φ < cm]; cette invention se rapportant également à un procédé de production de cette composition. Cette composition de résine thermoplastique possède la conductivité souhaitée (résistivité volumique) avec une dispersion réduite dans la zone semi-conductrice.
PCT/JP2000/006567 1999-09-24 2000-09-25 Composition de resine thermoplastique et procede de production correspondant WO2001021713A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/269664 1999-09-24
JP26966499A JP2001089674A (ja) 1999-09-24 1999-09-24 熱可塑性樹脂組成物およびその製造方法

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WO2001021713A1 true WO2001021713A1 (fr) 2001-03-29

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Publication number Priority date Publication date Assignee Title
JP2018123266A (ja) * 2017-02-02 2018-08-09 古河電気工業株式会社 導電性樹脂成形体および導電性樹脂組成物

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50149735A (fr) * 1974-05-22 1975-12-01
JPS624749A (ja) * 1985-07-02 1987-01-10 Asahi Chem Ind Co Ltd ブレンド型導電性複合材料
EP0337487A1 (fr) * 1988-04-15 1989-10-18 Showa Denko Kabushiki Kaisha Composition polymère électroconductrice
JPH04306582A (ja) * 1990-04-21 1992-10-29 Matsushita Electric Works Ltd Ｐｔｃ発熱体材料
JPH0636859A (ja) * 1992-07-14 1994-02-10 Matsushita Electric Works Ltd Ｐｔｃ発熱体の製法
JPH10204305A (ja) * 1996-11-25 1998-08-04 Cosmo Sogo Kenkyusho:Kk 電磁波遮蔽性樹脂組成物、及び同組成物を用いた成形加工品
JPH1135835A (ja) * 1997-07-22 1999-02-09 Toyo Ink Mfg Co Ltd 導電性樹脂組成物
JPH11100512A (ja) * 1997-09-26 1999-04-13 Yokohama Rubber Co Ltd:The 熱可塑性エラストマー組成物
JPH11116732A (ja) * 1997-10-14 1999-04-27 Kakizaki Seisakusho:Kk 樹脂組成物

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50149735A (fr) * 1974-05-22 1975-12-01
JPS624749A (ja) * 1985-07-02 1987-01-10 Asahi Chem Ind Co Ltd ブレンド型導電性複合材料
EP0337487A1 (fr) * 1988-04-15 1989-10-18 Showa Denko Kabushiki Kaisha Composition polymère électroconductrice
JPH04306582A (ja) * 1990-04-21 1992-10-29 Matsushita Electric Works Ltd Ｐｔｃ発熱体材料
JPH0636859A (ja) * 1992-07-14 1994-02-10 Matsushita Electric Works Ltd Ｐｔｃ発熱体の製法
JPH10204305A (ja) * 1996-11-25 1998-08-04 Cosmo Sogo Kenkyusho:Kk 電磁波遮蔽性樹脂組成物、及び同組成物を用いた成形加工品
JPH1135835A (ja) * 1997-07-22 1999-02-09 Toyo Ink Mfg Co Ltd 導電性樹脂組成物
JPH11100512A (ja) * 1997-09-26 1999-04-13 Yokohama Rubber Co Ltd:The 熱可塑性エラストマー組成物
JPH11116732A (ja) * 1997-10-14 1999-04-27 Kakizaki Seisakusho:Kk 樹脂組成物

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