JP7522092B2 - Composite material and its manufacturing method - Google Patents
Composite material and its manufacturing method Download PDFInfo
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- JP7522092B2 JP7522092B2 JP2021209829A JP2021209829A JP7522092B2 JP 7522092 B2 JP7522092 B2 JP 7522092B2 JP 2021209829 A JP2021209829 A JP 2021209829A JP 2021209829 A JP2021209829 A JP 2021209829A JP 7522092 B2 JP7522092 B2 JP 7522092B2
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- 239000002131 composite material Substances 0.000 title claims description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000002245 particle Substances 0.000 claims description 86
- 239000000463 material Substances 0.000 claims description 58
- 229920001971 elastomer Polymers 0.000 claims description 40
- 239000011159 matrix material Substances 0.000 claims description 31
- 239000004020 conductor Substances 0.000 claims description 25
- 239000011247 coating layer Substances 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229920002379 silicone rubber Polymers 0.000 description 9
- 239000004945 silicone rubber Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010058 rubber compounding Methods 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 229920001973 fluoroelastomer Polymers 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000013500 performance material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- -1 Vol. 12 Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Conductive Materials (AREA)
Description
本発明は、複合材及びその製造方法に関する。 The present invention relates to a composite material and a method for manufacturing the same.
エピクロロヒドリンゴムは、半導電性を示すゴム材料として知られている（例えば非特許文献１）。 Epichlorohydrin rubber is known as a rubber material that exhibits semiconductivity (e.g., Non-Patent Document 1).
エピクロロヒドリンゴムを用いることにより半導電性を得ることはできるが、それに加えて、例えば高耐熱性のようなエピクロロヒドリンゴムが有さない特性も得たい場合には、エピクロロヒドリンゴムの適用は困難である。 Although it is possible to obtain semiconductivity by using epichlorohydrin rubber, it is difficult to apply epichlorohydrin rubber if you also want to obtain properties that epichlorohydrin rubber does not have, such as high heat resistance.
本発明の課題は、半導電性も含む導電性制御を行うことができる複合材を提供することである。 The objective of the present invention is to provide a composite material that can control electrical conductivity, including semiconductivity.
本発明は、絶縁性のマトリクスと、前記マトリクス内に設けられた導電性粒子とを備えた複合材であって、前記導電性粒子は、ＪＩＳ Ｚ８８０１－１：２０１９に規定される目開き１ｍｍのふるいを透過する大きさの粒子本体と、前記粒子本体の表面を被覆する導電性コート層とを含み、前記導電性コート層は、ベース材と、前記ベース材内に設けられた導電材とを有し、前記導電性粒子における前記導電材の含有量が０．５質量％以上１．５質量％以下であり、前記複合材における前記導電性粒子の含有量が３０質量部以上８０質量部以下であり、前記複合材における前記導電性コート層の含有量が３質量部以上８質量部以下であり、前記複合材における前記導電材の含有量が０．１５質量部以上０．４質量部以下であり、前記複合材の体積抵抗率が１．３×１０ ４ 以上５．７×１０ ４ 以下である。 The present invention provides a composite material including an insulating matrix and conductive particles provided within the matrix, the conductive particles including a particle body having a size that allows the conductive particles to pass through a sieve having an opening of 1 mm as defined in JIS Z8801-1:2019, and a conductive coating layer covering a surface of the particle body , the conductive coating layer including a base material and a conductive material provided within the base material, the conductive particles having a content of the conductive material of 0.5% by mass or more and 1.5% by mass or less, the conductive particles having a content of 30 parts by mass or more and 80 parts by mass or less, the conductive coating layer having a content of 3 parts by mass or more and 8 parts by mass or less, the conductive material having a content of 0.15 parts by mass or more and 0.4 parts by mass or less, and the composite material having a volume resistivity of 1.3 x 10 4 or more and 5.7 x 10 4 or less .
本発明は、絶縁性のマトリクスと、前記マトリクス内に設けられた導電性粒子とを備えた複合材の製造方法であって、前記導電性粒子を、ＪＩＳ Ｚ８８０１－１：２０１９に規定される目開き１ｍｍのふるいを透過する大きさの粒子本体の表面を被覆するようにコーティング材により導電性コート層を形成することにより作製した後、前記マトリクスを形成するマトリクス形成材料と混合する。 The present invention provides a method for producing a composite material comprising an insulating matrix and conductive particles provided within the matrix, in which the conductive particles are produced by forming a conductive coating layer using a coating material so as to cover the surfaces of particle bodies having a size that allows passage through a sieve with a mesh size of 1 mm as specified in JIS Z8801-1:2019, and then mixing the conductive particles with a matrix-forming material that forms the matrix.
本発明によれば、絶縁性のマトリクス内に設けられた多数の導電性粒子のそれぞれが、粒子本体の表面が導電性コート層で被覆された構成を有することにより、半導電性も含む導電性制御を行うことができる。 According to the present invention, each of the numerous conductive particles provided in the insulating matrix has a configuration in which the surface of the particle body is covered with a conductive coating layer, making it possible to control the conductivity, including semiconductivity.
以下、実施形態について詳細に説明する。 The following describes the embodiments in detail.
図１は、実施形態に係る複合材１０を示す。この複合材１０は、例えば半導電性が求められるプリンタや複写機の帯電ロール、転写ロール、現像ロール等に適用することができる。また、この複合材１０は、例えば導電性が求められる導電性マット等にも適用することができる。 Figure 1 shows a composite material 10 according to an embodiment. This composite material 10 can be used, for example, in charging rolls, transfer rolls, and developing rolls of printers and copiers that require semiconductivity. This composite material 10 can also be used, for example, in conductive mats that require conductivity.
実施形態に係る複合材１０は、絶縁性のマトリクス１１と、そのマトリクス１１内にランダムに設けられた多数の導電性粒子１２とを備える。 The composite material 10 according to the embodiment comprises an insulating matrix 11 and a large number of conductive particles 12 randomly arranged within the matrix 11.
マトリクス１１としては、例えばゴムや樹脂が挙げられる。マトリクス１１は、複合材１０の導電性を制御する観点から、これらのうちのゴムが好ましい。ゴムのマトリクス１１は、ポリマー単体であっても、ポリマーにゴム配合剤が配合されたゴム組成物であっても、どちらでもよい。ゴムのマトリクス１１は、ポリマー鎖間が架橋された架橋ゴムであっても、未架橋ゴムであっても、どちらでもよい。ゴムのマトリクス１１を構成するポリマーとしては、例えば、シリコーンゴム、フッ素ゴム等が挙げられる。マトリクス１１は、ポリマーを架橋させる硬化剤、架橋剤、触媒等を含有していてもよい。 Examples of the matrix 11 include rubber and resin. From the viewpoint of controlling the electrical conductivity of the composite material 10, rubber is preferred as the matrix 11. The rubber matrix 11 may be either a polymer alone or a rubber composition in which a rubber compounding agent is compounded with a polymer. The rubber matrix 11 may be either a crosslinked rubber in which polymer chains are crosslinked or an uncrosslinked rubber. Examples of the polymer constituting the rubber matrix 11 include silicone rubber and fluororubber. The matrix 11 may contain a curing agent, a crosslinking agent, a catalyst, etc. that crosslink the polymer.
マトリクス１１は、絶縁性である。ここで、本出願における「絶縁性」とは、ＪＩＳ Ｋ６２７１－１：２０１５に基づいて測定される体積抵抗率が１．０×１０１３Ω・ｃｍ以上であることをいう。 The matrix 11 is insulating. In this application, the term "insulating" refers to a volume resistivity of 1.0×10 13 Ω·cm or more as measured based on JIS K6271-1:2015.
導電性粒子１２は、粒子本体１２１と、その粒子本体１２１の表面を被覆する導電性コート層１２２とを含む。 The conductive particle 12 includes a particle body 121 and a conductive coating layer 122 that covers the surface of the particle body 121.
複合材１０における導電性粒子１２の総含有量は、複合材１０の導電性を制御する観点から、好ましくは２０質量％以上９０質量％以下、より好ましくは３０質量％以上７０質量％以下である。導電性粒子１２における導電性コート層１２２の含有量は、同様の観点から、好ましくは１質量％以上２０質量％以下、より好ましくは５質量％以上１０質量％以下である。複合材１０における導電性コート層１２２の総含有量は、複合材１０の導電性を制御する観点から、好ましくは０．５質量％以上１５質量％以下、より好ましくは１質量％以上１０質量％以下である。 From the viewpoint of controlling the conductivity of the composite 10, the total content of the conductive particles 12 in the composite 10 is preferably 20% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 70% by mass or less. From the same viewpoint, the content of the conductive coating layer 122 in the conductive particles 12 is preferably 1% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 10% by mass or less. From the viewpoint of controlling the conductivity of the composite 10, the total content of the conductive coating layer 122 in the composite 10 is preferably 0.5% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass or less.
粒子本体１２１としては、例えば、ゴム粒子、樹脂粒子等が挙げられる。粒子本体１２１は、複合材１０の導電性を制御する観点から、これらのうちのゴム粒子が好ましい。ゴム粒子の粒子本体１２１は、ポリマー単体で形成されていても、ポリマーにゴム配合剤が配合されたゴム組成物で形成されていても、どちらでもよい。ゴム粒子の粒子本体１２１は、カーボンブラック等の導電材料が配合された導電性を有するゴム組成物で形成されていてもよい。ゴム粒子の粒子本体１２１は、架橋ゴムで形成されていても、未架橋ゴムで形成されていても、どちらでもよい。ゴム粒子の粒子本体１２１を形成するポリマーとしては、例えば、シリコーンゴム、フッ素ゴム等が挙げられる。ゴム粒子の粒子本体１２１は、資源の再利用の観点から、使用済みゴム製品から回収された廃棄ゴムで構成されていることが好ましい。粒子本体１２１の粒径は、マトリクス１１への導電性粒子１２の混合性を高め、粉砕により粒子本体１２１を効率的に得るとともに、複合材１０の導電性を制御する観点から、好ましくは１２５μｍ以上２ｍｍ以下である。粒子本体１２１は、同様の観点から、ＪＩＳ Ｚ８８０１－１：２０１９に規定される目開き１ｍｍのふるいを透過する大きさであることが好ましい。 Examples of the particle body 121 include rubber particles and resin particles. From the viewpoint of controlling the conductivity of the composite material 10, the particle body 121 is preferably a rubber particle. The particle body 121 of the rubber particle may be formed of a polymer alone or a rubber composition in which a rubber compounding agent is mixed with a polymer. The particle body 121 of the rubber particle may be formed of a rubber composition having conductivity in which a conductive material such as carbon black is mixed. The particle body 121 of the rubber particle may be formed of a crosslinked rubber or an uncrosslinked rubber. Examples of the polymer forming the particle body 121 of the rubber particle include silicone rubber and fluororubber. From the viewpoint of recycling resources, the particle body 121 of the rubber particle is preferably composed of waste rubber recovered from used rubber products. The particle diameter of the particle body 121 is preferably 125 μm or more and 2 mm or less from the viewpoint of increasing the mixability of the conductive particles 12 in the matrix 11, efficiently obtaining the particle body 121 by pulverization, and controlling the conductivity of the composite material 10. From the same viewpoint, it is preferable that the particle body 121 is of a size that allows it to pass through a sieve with 1 mm openings as specified in JIS Z8801-1:2019.
導電性コート層１２２は、図２に示すように、ベース材１２２ａと、そのベース材１２２ａ内に設けられた多数の導電材１２２ｂとを有する。 As shown in FIG. 2, the conductive coating layer 122 has a base material 122a and a number of conductive materials 122b provided within the base material 122a.
複合材１０におけるベース材１２２ａの総含有量は、複合材１０の導電性を制御する観点から、好ましくは０．４５質量％以上１４．５質量％以下、より好ましくは０．９５質量％以上９．９５質量％以下である。導電性粒子１２におけるベース材１２２ａの含有量は、同様の観点から、好ましくは０．９０質量％以上１９．９質量％以下、より好ましくは４．８質量％以上９．９質量％以下である。導電性コート層１２２におけるベース材１２２ａの含有量は、同様の観点から、好ましくは６０質量％以上９９質量％以下、より好ましくは７０質量％以上９５質量％以下である。 From the viewpoint of controlling the electrical conductivity of the composite material 10, the total content of the base material 122a in the composite material 10 is preferably 0.45% by mass or more and 14.5% by mass or less, more preferably 0.95% by mass or more and 9.95% by mass or less. From the same viewpoint, the content of the base material 122a in the conductive particles 12 is preferably 0.90% by mass or more and 19.9% by mass or less, more preferably 4.8% by mass or more and 9.9% by mass or less. From the same viewpoint, the content of the base material 122a in the conductive coating layer 122 is preferably 60% by mass or more and 99% by mass or less, more preferably 70% by mass or more and 95% by mass or less.
複合材１０における導電材１２２ｂの総含有量は、複合材１０の導電性を制御する観点から、好ましくは０．０５質量％以上５質量％以下、より好ましくは０．１質量％以上３質量％以下である。導電性粒子１２における導電材１２２ｂの含有量は、同様の観点から、好ましくは０．１質量％以上３質量％以下、より好ましくは０．２質量％以上１．５質量％以下である。導電性コート層１２２における導電材１２２ｂの含有量は、同様の観点から、好ましくは１質量％以上４０質量％以下、より好ましくは５質量％以上３０質量％以下である。 From the viewpoint of controlling the conductivity of the composite 10, the total content of the conductive material 122b in the composite 10 is preferably 0.05% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less. From the same viewpoint, the content of the conductive material 122b in the conductive particles 12 is preferably 0.1% by mass or more and 3% by mass or less, more preferably 0.2% by mass or more and 1.5% by mass or less. From the same viewpoint, the content of the conductive material 122b in the conductive coating layer 122 is preferably 1% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 30% by mass or less.
ベース材１２２ａとしては、例えばゴムや樹脂が挙げられる。ベース材１２２ａは、複合材１０の導電性を制御する観点から、ゴム又は樹脂であることが好ましく、ゴムであることがより好ましい。ゴムのベース材１２２ａは、ポリマー単体であっても、ポリマーにゴム配合剤が配合されたゴム組成物であっても、どちらでもよい。ゴムのベース材１２２ａは、ポリマー鎖間が架橋された架橋ゴムであっても、未架橋ゴムであっても、どちらでもよい。ゴムのベース材１２２ａを構成するポリマーとしては、例えば、シリコーンゴム、イソプレンゴム、ウレタンゴム等が挙げられる。マトリクス１１及びベース材１２２ａのいずれもゴムの場合、ベース材１２２ａを構成するポリマーは、マトリクス１１への導電性粒子１２の混合性を高める観点から、マトリクス１１を構成するポリマーと同種ポリマーであることが好ましい。具体的には、例えば、マトリクス１１がシリコーンゴムである場合、ベース材１２２ａもシリコーンゴムであることが好ましい。ベース材１２２ａは、ポリマーを架橋させる硬化剤、架橋剤、触媒等を含有していてもよい。 The base material 122a may be, for example, rubber or resin. From the viewpoint of controlling the conductivity of the composite material 10, the base material 122a is preferably rubber or resin, and more preferably rubber. The rubber base material 122a may be either a polymer alone or a rubber composition in which a rubber compounding agent is compounded with a polymer. The rubber base material 122a may be either a crosslinked rubber in which polymer chains are crosslinked or an uncrosslinked rubber. Examples of the polymer constituting the rubber base material 122a include silicone rubber, isoprene rubber, and urethane rubber. When both the matrix 11 and the base material 122a are rubber, the polymer constituting the base material 122a is preferably the same type of polymer as the polymer constituting the matrix 11 from the viewpoint of increasing the mixability of the conductive particles 12 with the matrix 11. Specifically, for example, when the matrix 11 is silicone rubber, the base material 122a is preferably silicone rubber. The base material 122a may contain a curing agent, a crosslinking agent, a catalyst, etc. that crosslinks the polymer.
導電材１２２ｂとしては、例えば、炭素系導電材、金属系導電材等が挙げられる。炭素系導電材としては、例えば、カーボンナノチューブ（ＣＮＴ）、カーボンナノファイバー（ＣＮＦ）、炭素繊維などの繊維状炭素系導電材；アセチレンブラック、ケッチェンブラックなどの粒子状炭素系導電材等が挙げられる。金属系導電材としては、例えば、金、銀、銅、その他の金属、及びそれらの合金の金属粒子が挙げられる。導電材１２２ｂは、これらのうちの１種又は２種以上を含むことが好ましく、複合材１０の導電性を制御する観点から、炭素系導電材を含むことがより好ましく、繊維状炭素系導電材を含むことが更に好ましく、カーボンナノチューブ（ＣＮＴ）を含むことがより更に好ましい。導電材１２２ｂの大きさは、導電性粒子１２の粒子本体１２１の大きさよりもはるかに小さい。 Examples of the conductive material 122b include carbon-based conductive materials and metal-based conductive materials. Examples of the carbon-based conductive materials include fibrous carbon-based conductive materials such as carbon nanotubes (CNT), carbon nanofibers (CNF), and carbon fibers; and particulate carbon-based conductive materials such as acetylene black and ketjen black. Examples of the metal-based conductive materials include metal particles of gold, silver, copper, other metals, and alloys thereof. The conductive material 122b preferably contains one or more of these, and from the viewpoint of controlling the conductivity of the composite material 10, it is more preferable to contain a carbon-based conductive material, even more preferable to contain a fibrous carbon-based conductive material, and even more preferable to contain a carbon nanotube (CNT). The size of the conductive material 122b is much smaller than the size of the particle body 121 of the conductive particle 12.
以上の構成の実施形態に係る複合材１０によれば、絶縁性のマトリクス１１内に設けられた多数の導電性粒子１２のそれぞれが、粒子本体１２１の表面が導電性コート層１２２で被覆された構成を有することにより、半導電性も含む導電性制御を行うことができる。 According to the composite material 10 according to the embodiment of the above configuration, each of the numerous conductive particles 12 provided in the insulating matrix 11 has a configuration in which the surface of the particle body 121 is covered with a conductive coating layer 122, thereby making it possible to control the conductivity, including semiconductivity.
実施形態に係る複合材１０が半導電性である場合、その体積抵抗率は１．０×１０３Ω・ｃｍ以上１．０×１０８Ω・ｃｍ以下である。ここで、本出願における複合材１０の体積抵抗率は、次のようにして求められる。複合材１０の円盤状等のシート状の試験片について、その上下面の全面にそれぞれ電極を押し当て、両電極間に電圧を変化させて印加し、各電圧で流れる電流を測定する。そして、電流と電圧との関係を求め、それを線形近似したときの傾きを抵抗値とし、その抵抗値に試験片の面積を乗じるとともに、厚さで除したものを体積抵抗率とする。 When the composite material 10 according to the embodiment is semiconductive, its volume resistivity is 1.0×10 3 Ω·cm or more and 1.0×10 8 Ω·cm or less. Here, the volume resistivity of the composite material 10 in the present application is obtained as follows. For a disk-shaped or sheet-shaped test piece of the composite material 10, electrodes are pressed against the entire upper and lower surfaces, respectively, and a voltage is applied between the two electrodes while varying, and the current flowing at each voltage is measured. Then, the relationship between the current and the voltage is obtained, and the slope when the relationship is linearly approximated is taken as the resistance value, and the resistance value is multiplied by the area of the test piece and divided by the thickness to obtain the volume resistivity.
次に、実施形態に係る複合材１０の製造方法について説明する。 Next, we will explain the manufacturing method of the composite material 10 according to the embodiment.
まず、液状ベース材に導電材１２２ｂを混合したコーティング材を調製する。液状ベース材は、加熱されて固化することによりベース材１２２ａに形成される液状材料である。コーティング材は、液状ベース材及び導電材１２２ｂ以外に、粘度調整等のための溶媒を含有していてもよい。コーティング材は、液状ベース材のポリマーが架橋する場合、硬化剤、架橋剤、触媒を含有していてもよい。 First, a coating material is prepared by mixing a liquid base material with conductive material 122b. The liquid base material is a liquid material that is formed on the base material 122a by being heated and solidified. In addition to the liquid base material and conductive material 122b, the coating material may contain a solvent for viscosity adjustment, etc. If the polymer of the liquid base material is crosslinked, the coating material may contain a curing agent, a crosslinking agent, and a catalyst.
次いで、多数の粒子本体１２１のそれぞれについて、その表面にコーティング材を付着させる。この付着手段としては、例えば、粒子本体１２１のコーティング材への浸漬、粒子本体１２１の表面へのコーティング材のスプレー等が挙げられる。 Next, a coating material is applied to the surface of each of the numerous particle bodies 121. Examples of the application method include immersing the particle bodies 121 in the coating material, spraying the coating material onto the surface of the particle bodies 121, etc.
続いて、表面にコーティング材が付着した粒子本体１２１を加熱し、液状ベース材を固化させて導電性コート層１２２を形成し、これにより、各々、粒子本体１２１の表面を導電性コート層１２２で被覆した多数の導電性粒子１２を作製する。 Next, the particle body 121 with the coating material attached to its surface is heated to solidify the liquid base material and form a conductive coating layer 122, thereby producing a large number of conductive particles 12, each of which has the surface of the particle body 121 coated with a conductive coating layer 122.
その後、導電性粒子１２をマトリクス形成材料と混合する。マトリクス形成材料は、マトリクス１１を形成する材料であって、固体材料であっても、液体材料であっても、どちらでもよい。固体材料のマトリクス形成材料の場合、混練により導電性粒子１２をマトリクス形成材料と混合することができる。液体材料のマトリクス形成材料には、撹拌により導電性粒子１２をマトリクス形成材料と混合することができる。マトリクス形成材料は、ポリマーが架橋する場合、硬化剤、架橋剤、触媒を含有していてもよい。 Then, the conductive particles 12 are mixed with the matrix-forming material. The matrix-forming material is a material that forms the matrix 11, and may be either a solid material or a liquid material. In the case of a solid matrix-forming material, the conductive particles 12 can be mixed with the matrix-forming material by kneading. In the case of a liquid matrix-forming material, the conductive particles 12 can be mixed with the matrix-forming material by stirring. In the case where the polymer is crosslinked, the matrix-forming material may contain a curing agent, a crosslinking agent, and a catalyst.
そして、導電性粒子１２を混合したマトリクス形成材料を所定形状に成形し、必要に応じて加熱等してマトリクス形成材料のポリマーを架橋等させることにより実施形態に係る複合材１０を得る。 The matrix-forming material mixed with the conductive particles 12 is then molded into a predetermined shape, and heated, if necessary, to crosslink the polymer of the matrix-forming material, thereby obtaining the composite material 10 according to the embodiment.
（複合材）
＜マトリクス形成材料の準備＞
マトリクス形成材料として、液状シリコーンゴム（ＫＥ－１９５０－７０Ａ／Ｂ 信越化学工業社製）を準備した。
(Composite materials)
<Preparation of matrix-forming material>
As a matrix-forming material, liquid silicone rubber (KE-1950-70A/B, manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared.
＜導電性粒子の作製＞
シリコーンゴム（ＫＥ１９５０－４０Ａ／Ｂ 信越化学工業社製）を架橋させた架橋ゴムを、カッターミルを用いて粉砕し、それをＪＩＳ Ｚ８８０１－１：２０１９に規定される目開き１ｍｍのふるいにかけて透過したゴム粒子を回収し、それを粒子本体とした。
<Preparation of conductive particles>
A crosslinked rubber obtained by crosslinking silicone rubber (KE1950-40A/B manufactured by Shin-Etsu Chemical Co., Ltd.) was pulverized using a cutter mill, and the pulverized rubber was passed through a sieve having an opening of 1 mm as specified in JIS Z8801-1:2019 to recover the rubber particles that passed through the sieve, which were used as the particle body.
シリコーンワニス（ＴＳＲ１１２２ モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）と、その触媒（ＹＣ８１０８ モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）と、多層長尺カーボンナノチューブ分散液（９３２６ＭＷＬ トクシキ社製）とを混合してコーティング材原液を得た。このコーティング材原液を、後述する導電性粒子における導電性コート層の含有量が５質量％、８質量％、及び１０質量％となるように酢酸ブチルで希釈し、シリコーンゴム及びその触媒を含有するとともに酢酸ブチルを含む溶剤を含有する液状ベース材に導電材のカーボンナノチューブ（ＣＮＴ）が分散した３種のコーティング材１乃至３を調製した。 A coating material stock solution was obtained by mixing silicone varnish (TSR1122, Momentive Performance Materials Japan), its catalyst (YC8108, Momentive Performance Materials Japan), and a multi-layer long carbon nanotube dispersion (9326MWL, Tokushiki). This coating material stock solution was diluted with butyl acetate so that the conductive coating layer content in the conductive particles described below was 5 mass%, 8 mass%, and 10 mass%, and three types of coating materials 1 to 3 were prepared in which conductive carbon nanotubes (CNTs) were dispersed in a liquid base material containing silicone rubber and its catalyst and a solvent containing butyl acetate.
コーティング材１乃至３のそれぞれに、粒子本体のゴム粒子を浸漬して混合し、それをホットプレート上で十分に乾燥させ、その後、１８０℃に温度設定した大気オーブンに２０分間入れてシリコーンゴムを架橋させることにより、各々、粒子本体の表面が導電性コート層で被覆された導電性粒子１乃至３を作製した。導電性粒子１乃至３の構成については表１に示す。 The rubber particles of the particle body were immersed in and mixed with each of the coating materials 1 to 3, then thoroughly dried on a hot plate, and then placed in an atmospheric oven set at 180°C for 20 minutes to crosslink the silicone rubber, producing conductive particles 1 to 3, each of which had the surface of the particle body covered with a conductive coating layer. The composition of conductive particles 1 to 3 is shown in Table 1.
＜複合材の作製＞
マトリクス形成材料及び導電性粒子１を、前者の含有量が７０質量％及び後者の含有量が３０質量％となるように混合して撹拌することにより塊状材料を調製した。この塊状材料０．３５ｇを、金型の内径１０ｍｍ及び深さ３ｍｍの円盤状のキャビティに充填し、１３０℃の温度下で９．８ＭＰａの圧力を負荷して５分間保持するプレス成形により円盤状の複合材を作製した。そして、この複合材を実施例１－１とした。
<Preparation of composite material>
A bulk material was prepared by mixing and stirring the matrix-forming material and the conductive particles 1 so that the content of the former was 70% by mass and the content of the latter was 30% by mass. 0.35 g of this bulk material was filled into a disk-shaped cavity of a mold having an inner diameter of 10 mm and a depth of 3 mm, and a disk-shaped composite material was produced by press molding at a temperature of 130° C. and a pressure of 9.8 MPa, which was maintained for 5 minutes. This composite material was designated Example 1-1.
マトリクス形成材料及び導電性粒子１の含有量がそれぞれ６０質量％及びが４０質量％、５０質量％及びが５０質量％、４０質量％及びが６０質量％、３０質量％及びが７０質量％、並びに２０質量％及びが８０質量％である塊状材料も調製し、これらを用いて実施例１－１と同様の複合材を作製した。そして、それらをそれぞれ実施例１－２乃至１－６とした。実施例１－１乃至１－６の構成については表２Ａに示す。 Block materials were also prepared in which the contents of the matrix forming material and conductive particles 1 were 60% by mass and 40% by mass, 50% by mass and 50% by mass, 40% by mass and 60% by mass, 30% by mass and 70% by mass, and 20% by mass and 80% by mass, respectively, and were used to make composite materials similar to those in Example 1-1. These were then designated Examples 1-2 to 1-6, respectively. The configurations of Examples 1-1 to 1-6 are shown in Table 2A.
導電性粒子１に代えて導電性粒子２を用いたことを除いて、実施例１－１乃至１－６と同一構成の複合材を作製した。そして、それらの複合材を実施例２－１乃至２－６とした。実施例２－１乃至２－６の構成については表２Ｂに示す。同様に、導電性粒子１に代えて導電性粒子３を用いたことを除いて、実施例１－１乃至１－６と同一構成の複合材を作製した。そして、それらの複合材を実施例３－１乃至３－６とした。実施例３－１乃至３－６の構成については表２Ｃに示す。 Composite materials with the same configuration as Examples 1-1 to 1-6 were prepared, except that conductive particle 2 was used instead of conductive particle 1. These composite materials were then designated Examples 2-1 to 2-6. The configurations of Examples 2-1 to 2-6 are shown in Table 2B. Similarly, composite materials with the same configuration as Examples 1-1 to 1-6 were prepared, except that conductive particle 3 was used instead of conductive particle 1. These composite materials were then designated Examples 3-1 to 3-6. The configurations of Examples 3-1 to 3-6 are shown in Table 2C.
（試験方法）
実施例１－１乃至１－６、実施例２－１乃至２－６、及び実施例３－１乃至３－６のそれぞれの円盤状の複合材について、その上下面のそれぞれに厚さ１ｍｍの２０ｍｍ角の銅板電極を押し当てて０．２ＭＰａの圧力で挟持するとともに、両銅板電極間に０Ｖ、３０Ｖ、５０Ｖ、８０Ｖ、及び１００Ｖの電圧を段階的に変化させて印加し、各電圧で流れる電流を測定した。そして、電流と電圧との関係を求め、それを線形近似したときの傾きを抵抗値とし、その抵抗値に試験片の面積（０．５２πｃｍ２）を乗じるとともに、厚さ（０．３ｃｍ）で除したものを体積抵抗率とした。
(Test method)
For each of the disk-shaped composite materials of Examples 1-1 to 1-6, Examples 2-1 to 2-6, and Examples 3-1 to 3-6, a 20 mm square copper plate electrode with a thickness of 1 mm was pressed against the top and bottom surfaces of the composite material, respectively, and the composite material was clamped under a pressure of 0.2 MPa, and a voltage of 0 V, 30 V, 50 V, 80 V, and 100 V was applied between the two copper plate electrodes while being changed in stages, and the current flowing at each voltage was measured. The relationship between the current and the voltage was then calculated, and the slope of the linear approximation was taken as the resistance value. The resistance value was multiplied by the area (0.5 2 π cm 2 ) of the test piece and divided by the thickness (0.3 cm) to obtain the volume resistivity.
（試験結果）
試験結果を表２Ａ乃至２Ｃに示す。表２Ａ乃至２Ｃによれば、実施例１－１乃至１－６、実施例２－１乃至２－６、及び実施例３－１乃至３－６のいずれの複合材も、体積抵抗率が１．０×１０３Ω・ｃｍ以上１．０×１０８Ω・ｃｍ以下の範囲にあって、半導電性を示すことが分かる。
(Test results)
The test results are shown in Tables 2A to 2C. It can be seen from Tables 2A to 2C that the composite materials of Examples 1-1 to 1-6, Examples 2-1 to 2-6, and Examples 3-1 to 3-6 all had a volume resistivity in the range of 1.0×10 3 Ω·cm or more and 1.0×10 8 Ω·cm or less, and thus exhibited semiconductivity.
本発明は、複合材の技術分野について有用である。 The present invention is useful in the field of composite materials.
１０ 複合材
１１ マトリクス
１２ 導電性粒子
１２１ 粒子本体
１２２ 導電性コート層
１２２ａ ベース材
１２２ｂ 導電材
10 Composite material 11 Matrix 12 Conductive particle 121 Particle body 122 Conductive coating layer 122a Base material 122b Conductive material
Claims (4)
前記導電性粒子は、ＪＩＳ Ｚ８８０１－１：２０１９に規定される目開き１ｍｍのふるいを透過する大きさの粒子本体と、前記粒子本体の表面を被覆する導電性コート層と、を含み、
前記導電性コート層は、ベース材と、前記ベース材内に設けられた導電材と、を有し、
前記導電性粒子における前記導電材の含有量が０．５質量％以上１．５質量％以下であり、
前記複合材における前記導電性粒子の含有量が３０質量部以上８０質量部以下であり、
前記複合材における前記導電性コート層の含有量が３質量部以上８質量部以下であり、
前記複合材における前記導電材の含有量が０．１５質量部以上０．４質量部以下であり、
前記複合材の体積抵抗率が１．３×１０ ４ 以上５．７×１０ ４ 以下である複合材。 A composite material comprising an insulating matrix and conductive particles disposed within the matrix,
The conductive particles include a particle body having a size that allows the particle body to pass through a sieve having an opening of 1 mm as defined in JIS Z8801-1:2019, and a conductive coating layer that covers a surface of the particle body,
The conductive coating layer has a base material and a conductive material provided in the base material,
The content of the conductive material in the conductive particles is 0.5% by mass or more and 1.5% by mass or less,
The content of the conductive particles in the composite material is 30 parts by mass or more and 80 parts by mass or less,
The content of the conductive coating layer in the composite material is 3 parts by mass or more and 8 parts by mass or less,
The content of the conductive material in the composite material is 0.15 parts by mass or more and 0.4 parts by mass or less,
The volume resistivity of the composite material is 1.3 x 10 4 or more and 5.7 x 10 4 or less .
前記ベース材がゴム又は樹脂である複合材。 2. The composite material according to claim 1 ,
A composite material in which the base material is rubber or resin.
前記マトリクスがゴムである複合材。 The composite material according to claim 1 or 2 ,
A composite material in which the matrix is rubber.
前記導電性粒子を、ＪＩＳ Ｚ８８０１－１：２０１９に規定される目開き１ｍｍのふるいを透過する大きさの粒子本体の表面を被覆するようにコーティング材により導電性コート層を形成することにより作製した後、前記マトリクスを形成するマトリクス形成材料と混合する複合材の製造方法。 1. A method for producing a composite material comprising an insulating matrix and conductive particles disposed within the matrix, the method comprising the steps of:
A method for producing a composite material, comprising the steps of: preparing the conductive particles by forming a conductive coating layer using a coating material so as to cover the surface of a particle body having a size that allows the conductive particles to pass through a sieve with a mesh size of 1 mm as specified in JIS Z8801-1:2019; and then mixing the conductive particles with a matrix forming material that forms the matrix.
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