JP4517225B2 - Pressure sensitive conductive elastomer - Google Patents
Pressure sensitive conductive elastomer Download PDFInfo
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- JP4517225B2 JP4517225B2 JP2004175124A JP2004175124A JP4517225B2 JP 4517225 B2 JP4517225 B2 JP 4517225B2 JP 2004175124 A JP2004175124 A JP 2004175124A JP 2004175124 A JP2004175124 A JP 2004175124A JP 4517225 B2 JP4517225 B2 JP 4517225B2
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- 229920001971 elastomer Polymers 0.000 title claims description 39
- 239000000806 elastomer Substances 0.000 title claims description 38
- 239000002245 particle Substances 0.000 claims description 54
- 230000006835 compression Effects 0.000 claims description 29
- 238000007906 compression Methods 0.000 claims description 29
- 239000011231 conductive filler Substances 0.000 claims description 29
- 239000000919 ceramic Substances 0.000 claims description 27
- 150000002484 inorganic compounds Chemical class 0.000 claims description 17
- 229910010272 inorganic material Inorganic materials 0.000 claims description 17
- 150000002894 organic compounds Chemical class 0.000 claims description 11
- 238000009830 intercalation Methods 0.000 claims description 7
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 239000002131 composite material Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920002379 silicone rubber Polymers 0.000 description 6
- 239000004945 silicone rubber Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- -1 organometallic fatty acid salt Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Description
本発明は、無加圧・無変形状態では高い電気抵抗値を示し、圧縮変形時の荷重の増加に従って電気抵抗値が減少して導電性を示す感圧導電性エラストマーに関するものである。 The present invention relates to a pressure-sensitive conductive elastomer that exhibits a high electric resistance value in a non-pressurized / non-deformed state and exhibits conductivity by decreasing the electric resistance value as the load during compression deformation increases.
従来の感圧導電性エラストマーとしては、非導電性エラストマー中に、球状の導電性カーボンブラック粒子又は導電性カーボンブラックの造粒物と、シリコーンゴム粒子と、γ−アルミナ（Al2O3）粒子とを配合したものが知られている（例えば、特許文献１及び特許文献２参照。）。
しかしながら、球状の導電性カーボンブラック粒子を配合したものでは、見かけ上の硬度が高く、圧縮変形時の電気抵抗値変化が小さいので、感圧導電性センサとしての感度が悪いという問題点がある。 However, the blend of spherical conductive carbon black particles has a problem that the apparent hardness is high and the change in electric resistance value during compression deformation is small, so that the sensitivity as a pressure-sensitive conductive sensor is poor.
一方、導電性カーボンブラックの造粒物を配合したものでは、圧縮変形時の電気抵抗値変化は大きいものの、造粒物が破損し易いので、耐久性や安定性に欠けるという問題点がある。 On the other hand, in the case of blending a granulated product of conductive carbon black, although the change in electric resistance value during compression deformation is large, the granulated product is easily damaged, so that there is a problem that durability and stability are lacking.
更に、これらの感圧導電性エラストマーでは、引き裂き強度が低いと共に、繰り返しの圧縮変形に対する電気抵抗値変化の再現性（信頼性）が良くないという問題点がある。 Furthermore, these pressure-sensitive conductive elastomers have problems in that the tear strength is low and the reproducibility (reliability) of the change in electric resistance value due to repeated compression deformation is not good.
本発明は、以上のような事情や問題点に鑑みてなされたものであり、機械的強度が高く、繰り返しの圧縮変形に対する電気抵抗値変化の再現性が良好な感圧導電性エラストマーを提供することを目的とする。 The present invention has been made in view of the above-described circumstances and problems, and provides a pressure-sensitive conductive elastomer having high mechanical strength and good reproducibility of change in electric resistance value due to repeated compression deformation. For the purpose.
上記目的を達成するための請求項１の発明は、無加圧・無変形状態では高い電気抵抗値を示し、圧縮変形時の荷重の増加に従って電気抵抗が減少して導電性を示す感圧導電性エラストマーであって、非導電性エラストマー中に、１０〜４０ｗｔ％の配合割合で板状、針状（ウィスカー状）、又は繊維状の導電性フィラーと、２〜２０ｗｔ％の配合割合で有機化合物をインターカレートした層状無機化合物粒子であり粒径が５〜１００ｎｍのセラミック粒子とを分散させたものである。
In order to achieve the above object, the invention according to
請求項２の発明においては、前記層状無機化合物粒子は、有機化合物及び硬化前の非導電性エラストマーをインターカレートした層状無機化合物粒子である。 In the invention of claim 2, the layered inorganic compound particles are layered inorganic compound particles obtained by intercalating an organic compound and a non-conductive elastomer before curing.
請求項３の発明においては、前記導電性フィラーの体積抵抗率は１０6Ω／ｃｍ以下である。 In the invention of claim 3, the conductive filler has a volume resistivity of 10 6 Ω / cm or less.
請求項４の発明においては、前記導電性フィラーは、その面方向又は長さ方向を、シート状に形成された非導電性エラストマーの面方向に対して略平行に配向させたものである。 According to a fourth aspect of the present invention, the conductive filler has its surface direction or length direction oriented substantially parallel to the surface direction of the non-conductive elastomer formed in a sheet shape.
請求項１の発明によれば、機械的強度が高いと共に、繰り返しの圧縮変形に対する電気抵抗値変化の再現性が良好である。また、層状無機化合物粒子の２〜２０ｗｔ％の配合割合での添加で絶縁特性が得られると共に、引張強度や耐久性を向上させることができる。また、層状無機化合物粒子とマトリックス（母材）としての硬化後の非導電性エラストマーとの親和性が高くなる。そのため、複合体中における亀裂生成を阻害できると共に、仮に亀裂が生成したとしても分子スケール（１ｎｍ未満のスケール）又はナノメータースケール（１０００ｎｍ未満のスケール）で亀裂の伝播を抑制できるので、荷重を印加及び除加した場合や熱的な変化を受けた場合における複合体の機械的強度や耐久性を飛躍的に向上させることができる。
According to the present invention, the machine械的high strength, has good reproducibility of the electrical resistance value change against compressive deformation iteration. Further, the addition of the layered inorganic compound particles at a blending ratio of 2 to 20 wt% can obtain the insulation characteristics and improve the tensile strength and durability. Moreover, affinity with the non-conductive elastomer after curing as a layer-like inorganic compound particles and a matrix (base material) is high. Therefore, crack generation in the composite can be inhibited, and even if cracks are generated, propagation of cracks can be suppressed on a molecular scale (scale less than 1 nm) or nanometer scale (scale less than 1000 nm), so a load is applied. In addition, the mechanical strength and durability of the composite can be dramatically improved when it is added or subjected to thermal changes.
請求項２の発明によれば、請求項１の効果をより向上させることができる。
According to the invention of claim 2 , the effect of
請求項３の発明によれば、複合体の電気抵抗値がより低くなるので、複合体の電気抵抗値変化の範囲をより広くすることができる。 According to invention of Claim 3 , since the electrical resistance value of a composite_body | complex becomes lower, the range of the electrical resistance value change of a composite_body | complex can be made wider.
請求項４の発明によれば、繰り返しの圧縮変形に対する電気抵抗値変化の再現性や引張強度を更に向上させることができる。 According to invention of Claim 4 , the reproducibility and tensile strength of an electrical resistance value change with respect to repeated compression deformation can further be improved.
以下、本発明の実施形態について説明する。
本実施形態に係る感圧導電性エラストマーは、非導電性エラストマー中に、板状、針状、又は繊維状の導電性フィラーと、粒径がナノメーターサイズのセラミック粒子とを分散させたものである。
Hereinafter, embodiments of the present invention will be described.
The pressure-sensitive conductive elastomer according to this embodiment is obtained by dispersing a plate-like, needle-like, or fibrous conductive filler and ceramic particles having a particle size of nanometer in a non-conductive elastomer. is there.
非導電性エラストマーの種類は特に限定されるものではないが、１液型又は２液型の常温硬化シリコーンゴムが好適である。１液型の常温硬化シリコーンゴムとしては、空気中の湿気で加水分解を起こし、硬化（架橋）が進行する縮合型のもの等が挙げられ、オキシム型やアルコール型のもの等を使用することができる。２液型の常温硬化シリコーンゴムとしては、錫（Ｓｎ）化合物等の有機金属脂肪酸塩によって常温硬化する縮合型のもの等が挙げられる。 The type of non-conductive elastomer is not particularly limited, but a one-pack type or two-pack type room temperature curing silicone rubber is suitable. Examples of the one-pack type room-temperature-curing silicone rubber include condensation-type ones that undergo hydrolysis by moisture in the air and cure (cross-linking), and oxime-type and alcohol-type ones can be used. it can. Examples of the two-pack type room-temperature-curing silicone rubber include condensation-type ones that are cured at room temperature with an organometallic fatty acid salt such as a tin (Sn) compound.
導電性フィラーとしては、板状、針状、又は繊維状のフィラー（セラミックフィラー、ガラスフィラー、ポリマーフィラー等）の表面に導電性物質（カーボン、金属、導電性セラミック等）をコーティングしたもの等が挙げられる。導電性物質のコーティング方法としては、ＣＶＤ（chemical vapor deposition，化学的蒸着）、ＰＶＤ（physical vapor deposition，物理的蒸着）、焼き付け、メッキ、析出、塗布等が挙げられる。セラミックフィラーとしては、マイカ（雲母，弾力に富む六角板状のアルミニウムけい酸塩鉱物）、アルミナ（Al2Ｏ3）、シリカ（SiＯ2）、サファイヤ、炭化ケイ素（SiＣ）等が挙げられる。ポリマーフィラーとしては、ポリスチレン、ポリエチレン、エポキシ樹脂、ポリテトラフルオロエチレン等が挙げられる。 Examples of the conductive filler include a plate-like, needle-like, or fibrous filler (ceramic filler, glass filler, polymer filler, etc.) coated with a conductive substance (carbon, metal, conductive ceramic, etc.), etc. Can be mentioned. Examples of the conductive material coating method include CVD (chemical vapor deposition), PVD (physical vapor deposition), baking, plating, deposition, and coating. Examples of the ceramic filler include mica (a mica, a hexagonal plate-like aluminum silicate mineral rich in elasticity), alumina (Al 2 O 3 ), silica (SiO 2 ), sapphire, silicon carbide (SiC), and the like. Examples of the polymer filler include polystyrene, polyethylene, epoxy resin, polytetrafluoroethylene, and the like.
導電性フィラーのサイズ（粒径又は最大長さ）としては、１〜３０μｍが好適である。これに対し、導電性フィラーのサイズが１μｍ未満であれば複合体（感圧導電性エラストマー）の電気抵抗値変化が小さくなる一方、３０μｍを超えれば複合体の繰り返しの圧縮変形に対する電気抵抗値変化の再現性が悪くなるので、いずれの場合も望ましくない。 The size (particle size or maximum length) of the conductive filler is preferably 1 to 30 μm. On the other hand, if the size of the conductive filler is less than 1 μm, the change in the electrical resistance value of the composite (pressure-sensitive conductive elastomer) is small, whereas if it exceeds 30 μm, the change in the electrical resistance value against repeated compression deformation of the composite. In both cases, the reproducibility of the image quality is undesirable.
ここで、導電性フィラーのアスペクト比が２〜３０であれば、導電性フィラー同士が接触し易くなるので、複合体の圧縮変形に対する電気抵抗値変化の範囲を広げることができると共に、複合体の機械的強度を高くすることができるという利点がある。これに対し、導電性フィラーのアスペクト比が２未満であれば複合体中における導電性フィラーの配向度が低いために強度の改善ができない一方、３０を越えれば複合体の圧縮変形に対する電気抵抗値変化が急激で広い荷重範囲での使用ができないので、いずれの場合も望ましくない。なお、ここでいうアスペクト比とは、板状の導電性フィラーではその厚みに対する等価円直径の比をいい、針状又は繊維状の導電性フィラーではその断面の等価円直径に対する長さの比をいう。 Here, if the aspect ratio of the conductive filler is 2 to 30, the conductive fillers can easily come into contact with each other, so that the range of the electrical resistance value change with respect to the compression deformation of the composite can be expanded, and the composite There is an advantage that the mechanical strength can be increased. On the other hand, if the aspect ratio of the conductive filler is less than 2, the strength cannot be improved due to the low degree of orientation of the conductive filler in the composite, whereas if it exceeds 30, the electrical resistance value against compressive deformation of the composite In either case, the change is abrupt and cannot be used in a wide load range. The aspect ratio here means the ratio of the equivalent circular diameter to the thickness of the plate-like conductive filler, and the ratio of the length to the equivalent circular diameter of the cross-section of the needle-like or fibrous conductive filler. Say.
導電性フィラーの配合割合としては、１０〜４０ｗｔ％が好適である。これに対し、導電性フィラーの配合割合が１０ｗｔ％未満であれば複合体の電気抵抗値が高くなる一方、４０ｗｔ％を超えれば複合体の伸びや弾性が低下すると共に、無加圧時の複合体の絶縁性が保たれないので、いずれの場合も望ましくない。なお、導電性フィラーの体積抵抗率が１０6Ω／ｃｍ以下、好ましくは１０Ω／ｃｍ以下、より好ましくは１０-1Ω／ｃｍ以下であれば、複合体の電気抵抗値がより低くなるので、複合体の電気抵抗値変化の範囲をより広くできるという利点がある。 The blending ratio of the conductive filler is preferably 10 to 40 wt%. On the other hand, when the blending ratio of the conductive filler is less than 10 wt%, the electrical resistance value of the composite increases, whereas when it exceeds 40 wt%, the elongation and elasticity of the composite decrease and the composite without pressure is applied. In any case, it is not desirable because the insulation of the body is not maintained. In addition, if the volume resistivity of the conductive filler is 10 6 Ω / cm or less, preferably 10 Ω / cm or less, more preferably 10 −1 Ω / cm or less, the electrical resistance value of the composite becomes lower. There is an advantage that the range of change in the electrical resistance value of the composite can be made wider.
セラミック粒子としては、粒径がナノメーターサイズの等軸状セラミック粒子、板状セラミック結晶、針状セラミック結晶、セラミック単結晶粒子、セラミック多結晶粒子、造粒セラミック粉体、セラミック顆粒、後述する層状無機化合物粒子等が挙げられる。 Ceramic particles include nanometer-sized equiaxed ceramic particles, plate-shaped ceramic crystals, needle-shaped ceramic crystals, ceramic single crystal particles, ceramic polycrystalline particles, granulated ceramic powder, ceramic granules, and a layered form described later. Examples include inorganic compound particles.
セラミック粒子の粒径としては、５〜１００ｎｍが好適である。これに対し、セラミック粒子の粒径が５ｎｍ未満であればセラミック粒子の均一分散が困難になると共に、複合体の電気抵抗値変化が小さくなる一方、１００ｎｍを超えれば複合体の繰り返しの圧縮変形に対する電気抵抗値変化の再現性が悪くなるので、いずれの場合も望ましくない。 The particle size of the ceramic particles is preferably 5 to 100 nm. On the other hand, if the particle size of the ceramic particles is less than 5 nm, uniform dispersion of the ceramic particles becomes difficult and the change in the electric resistance value of the composite is reduced. On the other hand, if the particle size exceeds 100 nm, the composite is repeatedly compressed and deformed. In any case, the reproducibility of the change in the electric resistance value is deteriorated.
セラミック粒子の配合割合としては、２〜２０ｗｔ％が好適である。これに対し、セラミック粒子の配合割合が２ｗｔ％未満であれば複合体の電気抵抗値が低くなると共に、複合体の強度を高くすることができないために繰り返しの圧縮変形に対する電気抵抗値変化の再現性が悪くなる一方、２０ｗｔ％を超えれば複合体の伸びや弾性が低下するので、いずれの場合も望ましくない。 The mixing ratio of the ceramic particles is preferably 2 to 20 wt%. On the other hand, if the blending ratio of the ceramic particles is less than 2 wt%, the electrical resistance value of the composite is lowered and the strength of the composite cannot be increased, so that the electrical resistance value change due to repeated compression deformation is reproduced. On the other hand, if it exceeds 20 wt%, the elongation and elasticity of the composite will be lowered, so that it is not desirable in either case.
このように、板状、針状、又は繊維状の導電性フィラーを用いれば、複合体中の導電パスが生じ易くなるので、複合体の電気抵抗値変化の範囲を広げることができる。また、導電性フィラーの他に粒径がナノメーターサイズのセラミック粒子も配合しておけば、導電性フィラーが均一に分散すると共に、複合体の機械的強度も高くなる。そのため、このような感圧導電性エラストマーによれば、機械的強度が高く、繰り返しの圧縮変形に対する電気抵抗値変化の再現性が良好であるという利点がある。 As described above, if a plate-like, needle-like, or fibrous conductive filler is used, a conductive path in the composite is easily generated, and thus the range of change in the electrical resistance value of the composite can be expanded. If ceramic particles having a particle size of nanometer in addition to the conductive filler are blended, the conductive filler is uniformly dispersed and the mechanical strength of the composite is increased. Therefore, according to such a pressure-sensitive conductive elastomer, there is an advantage that the mechanical strength is high and the reproducibility of the change in electric resistance value with respect to repeated compression deformation is good.
ここで、セラミック粒子が極めて大きい表面積を有する層状無機化合物粒子であれば、少量の添加で絶縁特性が得られると共に、引張強度や耐久性を向上させることができるという利点がある。このような層状無機化合物粒子としては、粘土鉱物（モンモリロナイト、スメクタイト、ハイドロタルサイト、バイデライト、ノントロナイト、ヘクトライト、サボナイト、ソーコナイト、スチブンサイト、ベントナイト、雲母鉱物、チタン酸化合物等）等が挙げられる。 Here, if the ceramic particles are layered inorganic compound particles having an extremely large surface area, there are advantages that insulation properties can be obtained with a small amount of addition, and tensile strength and durability can be improved. Examples of such layered inorganic compound particles include clay minerals (montmorillonite, smectite, hydrotalcite, beidellite, nontronite, hectorite, saponite, soconite, stevensite, bentonite, mica mineral, titanic acid compound, etc.). .
また、有機化合物をインターカレートした層状無機化合物粒子を配合すれば、層状無機化合物粒子とマトリックス（母材）としての硬化後の非導電性エラストマーとの親和性が高くなる。そのため、複合体中における亀裂生成を阻害できると共に、仮に亀裂が生成したとしても分子スケール又はナノメータースケールで亀裂の伝播を抑制できるので、荷重を印加及び除加した場合や熱的な変化を受けた場合における複合体の機械的強度や耐久性を飛躍的に向上させることができるという利点がある。 In addition, if layered inorganic compound particles intercalated with an organic compound are blended, the affinity between the layered inorganic compound particles and the non-conductive elastomer after curing as a matrix (base material) increases. Therefore, crack generation in the composite can be inhibited, and even if cracks are generated, propagation of cracks can be suppressed on a molecular scale or nanometer scale. There is an advantage that the mechanical strength and durability of the composite can be dramatically improved.
有機化合物としては、炭素数６以上のアルキル基を有しかつ末端にイオン化可能な極性基（アミノ基、ヒドロキシ基、カルボキシル基、アルデヒド基等）を有するアミン、アルコール、カルボン酸、アルデヒド等が挙げられる。層状無機化合物粒子に有機化合物をインターカレートする方法としては、層状無機化合物粒子の懸濁液に有機化合物を添加、溶解させて所定時間撹拌する方法等が挙げられる。この場合、混合液に超音波を照射しながら撹拌すれば、より効率良くインターカレートできるという利点がある。 Examples of the organic compound include amines, alcohols, carboxylic acids, aldehydes, etc., having an alkyl group having 6 or more carbon atoms and having a polar group (amino group, hydroxy group, carboxyl group, aldehyde group, etc.) that can be ionized at the terminal. It is done. Examples of the method of intercalating the organic compound into the layered inorganic compound particles include a method of adding and dissolving the organic compound in the suspension of the layered inorganic compound particles and stirring for a predetermined time. In this case, there is an advantage that intercalation can be performed more efficiently if the mixture is stirred while irradiating ultrasonic waves.
更に、有機化合物及び硬化（架橋）前の非導電性エラストマーをインターカレートした層状無機化合物粒子を配合すれば、より効果的である。有機化合物及び硬化前の非導電性エラストマーをインターカレートする方法としては、上記のようにして有機化合物をあらかじめインターカレートしておいた層状無機化合物粒子を硬化前の非導電性エラストマーの溶液に添加し、この混合液を所定時間撹拌する方法等が挙げられる。この場合、混合液に超音波を照射しながら撹拌すれば、上記と同様、より効率良くインターカレートできるという利点がある。 Furthermore, it is more effective if layered inorganic compound particles intercalated with an organic compound and a non-conductive elastomer before curing (crosslinking) are blended. As a method for intercalating the organic compound and the non-conductive elastomer before curing, the layered inorganic compound particles in which the organic compound is pre-intercalated as described above are added to the non-conductive elastomer solution before curing. The method of adding and stirring this liquid mixture for a predetermined time etc. are mentioned. In this case, if the mixture is stirred while irradiating with ultrasonic waves, there is an advantage that the intercalation can be performed more efficiently as described above.
加えて、導電性フィラーの面方向又は長さ方向を、シート状に形成された非導電性エラストマーの面方向に対して略平行に配向させておけば、繰り返しの圧縮変形に対する電気抵抗値変化の再現性や引張強度を更に向上させることができるという利点がある。導電性フィラーの面方向又は長さ方向を非導電性エラストマーの面方向に対して略平行に配向させる方法としては、カレンダー成形等により複合体を所定厚さのシート状に圧延する方法等が挙げられる。 In addition, if the surface direction or length direction of the conductive filler is oriented substantially parallel to the surface direction of the non-conductive elastomer formed in a sheet shape, the electric resistance value changes due to repeated compression deformation. There is an advantage that reproducibility and tensile strength can be further improved. Examples of the method of orienting the surface direction or length direction of the conductive filler substantially parallel to the surface direction of the non-conductive elastomer include a method of rolling the composite into a sheet having a predetermined thickness by calendar molding or the like. It is done.
次に、本発明の実施例について説明する。
非導電性エラストマーとしては、１液型の常温硬化シリコーンゴム（信越化学工業株式会社製，ＫＥ−４４５）を用いた。導電性フィラーとしては、板状の導電性セラミック粉末（大塚化学株式会社製，ＢＫ４００Ｍ，サイズ：３〜８μｍ，平均アスペクト比：２．７）を用いた。セラミック粒子としては、ヘキサデシルアミンをインターカレートしたモンモリロナイト粉末（クニミネ工業株式会社製，クニピアＦ，平均２次粒子径：５μｍ）を用いた。
Next, examples of the present invention will be described.
As the non-conductive elastomer, one-pack type room temperature curing silicone rubber (manufactured by Shin-Etsu Chemical Co., Ltd., KE-445) was used. As the conductive filler, a plate-shaped conductive ceramic powder (manufactured by Otsuka Chemical Co., Ltd., BK400M, size: 3 to 8 μm, average aspect ratio: 2.7) was used. As the ceramic particles, montmorillonite powder intercalated with hexadecylamine (Kunimine Industries, Ltd., Kunipia F, average secondary particle size: 5 μm) was used.
感圧導電性エラストマーの作製に際しては、まず、硬化前の非導電性エラストマーを表１の配合量でヘキサン溶媒に溶かして非導電性エラストマー溶液とし、これに導電性フィラーやセラミック粒子を表１の割合で配合し、混合機で充分に混合した。 In preparing the pressure-sensitive conductive elastomer, first, the non-conductive elastomer before curing is dissolved in a hexane solvent at the blending amount shown in Table 1 to obtain a non-conductive elastomer solution. It mix | blended in the ratio and mixed thoroughly with the mixer.
次いで、混合物に超音波（振動数：２２．９ｋＨｚ，２時間）を照射して硬化前の非導電性エラストマーをセラミック粒子にインターカレートしながらエバポレーションによりヘキサン溶媒を留去し、充分に脱泡した。脱泡後の混合物をカレンダー成形機により圧延し、その圧延物を室温で２４時間放置して硬化させ、厚さ１ｍｍの感圧導電性エラストマーシートを作製した。 Next, the mixture is irradiated with ultrasonic waves (frequency: 22.9 kHz, 2 hours) to evaporate the hexane solvent by evaporation while intercalating the non-conductive elastomer before curing into the ceramic particles, and the mixture is sufficiently removed. Foamed. The defoamed mixture was rolled by a calendering machine, and the rolled product was allowed to stand at room temperature for 24 hours to be cured to produce a pressure-sensitive conductive elastomer sheet having a thickness of 1 mm.
得られた感圧導電性エラストマーシートから５ｍｍ×５ｍｍ角（面積：２５ｍｍ2）の角形シートを切り取り、繰り返し（２〜１０回）の圧縮変形に対する電気抵抗値変化特性（Ｆ−Ｒ特性）を調べた。その結果を図１に示す。なお、電気抵抗値の測定に際しては、１対の電極を上面に有する電極基板上に角形シートを載置し、更にその上をゴムカバーで覆うことにより、角形シートの上面全体に負荷（荷重）が加わるようにした。 A 5 mm × 5 mm square (area: 25 mm 2 ) square sheet is cut out from the obtained pressure-sensitive conductive elastomer sheet, and the electrical resistance value change characteristic (FR characteristic) against repeated (2 to 10 times) compression deformation is examined. It was. The result is shown in FIG. In measuring the electrical resistance value, a square sheet is placed on an electrode substrate having a pair of electrodes on the upper surface, and further covered with a rubber cover, so that a load (load) is applied to the entire upper surface of the square sheet. Was added.
更に、繰り返し（２０００回、２００００回、１０００００回、２０００００回）の圧縮変形に対する電気抵抗値変化特性（耐久特性）を調べた。その結果を図２に示す。なお、圧縮サイクルは、３０００ｇｆの負荷を１秒−ＯＮ（印加）、１秒−ＯＦＦ（除加）のサイクルとした。 Furthermore, the electrical resistance value change characteristic (durability characteristic) with respect to repeated compression deformation (2000 times, 20000 times, 100000 times, 200000 times) was examined. The result is shown in FIG. The compression cycle was a load of 3000 gf with a cycle of 1 second-ON (application) and 1 second-OFF (addition).
次に、得られた感圧導電性エラストマーシートの機械的特性（引張強度、伸び率、硬度）を調べた。その結果を表２に示す。 Next, the mechanical properties (tensile strength, elongation rate, hardness) of the obtained pressure-sensitive conductive elastomer sheet were examined. The results are shown in Table 2.
〔比較例１〕
導電性フィラーとしてカーボンブラック粒子（日本カーボン株式会社製，粒径：1〜１０μｍ，平均粒径：５μｍ）を用い、セラミック粒子の代わりにシリコーンゴム粒子（東レダウコウニング株式会社製，粒径：２０〜１２０μｍ，平均粒径：７０μｍ）を用いた他は、実施例と同様の操作を行った。その結果を図３、図４、及び表２に示す。なお、耐久特性については、繰り返し回数を４０００回と１７０００回とした。
[Comparative Example 1]
Carbon black particles (manufactured by Nippon Carbon Co., Ltd., particle size: 1 to 10 μm, average particle size: 5 μm) are used as the conductive filler, and silicone rubber particles (manufactured by Toray Dow Corning Co., Ltd., particle size: The same operation as in the example was performed except that 20 to 120 μm and an average particle size: 70 μm) were used. The results are shown in FIGS. 3 and 4 and Table 2. In addition, about durability characteristics, the repetition frequency was 4000 times and 17000 times.
図１〜図４から明らかなように、比較例１では圧縮変形の回数による電気抵抗値変化特性のばらつきが大きいのに対し、実施例ではそのばらつきが小さく、繰り返しの圧縮変形に対する電気抵抗値変化の再現性（ヒステリシス）や耐久性が良好であることが分かる。また、表２から明らかなように、実施例の引張強度や伸び率は比較例１よりも向上していることが分かる。 As apparent from FIGS. 1 to 4, the variation in the electrical resistance value change characteristic due to the number of compression deformations is large in Comparative Example 1, whereas the variation is small in the example, and the electrical resistance value change due to repeated compression deformations. It can be seen that the reproducibility (hysteresis) and durability are good. Further, as is apparent from Table 2, it can be seen that the tensile strength and the elongation rate of the examples are higher than those of Comparative Example 1.
〔比較例２〕
導電性フィラーとして針状の導電性セラミック粉末（大塚化学株式会社製，ＢＫ４００Ｗ，サイズ（長さ）：１０〜２０μｍ，平均アスペクト比：４３）を用い、セラミック粒子を添加しない他は、実施例と同様にして繰り返し（２〜１０回）の圧縮変形に対する電気抵抗値変化特性（Ｆ−Ｒ特性）を調べた。その結果を図５及び表２に示す。
[Comparative Example 2]
Except for using a needle-shaped conductive ceramic powder (manufactured by Otsuka Chemical Co., Ltd., BK400W, size (length): 10 to 20 μm, average aspect ratio: 43) as the conductive filler, and without adding ceramic particles, Similarly, the electrical resistance value change characteristic (FR characteristic) with respect to repeated (2 to 10 times) compression deformation was examined. The results are shown in FIG.
図５及び図１から明らかなように、比較例２では圧縮変形の回数による電気抵抗値変化特性のばらつきが大きく、高い荷重値において圧縮変形の増大に伴う電気抵抗値の低下が認められないのに対し、実施例ではそのばらつきが小さく、繰り返しの圧縮変形に対する電気抵抗値変化の再現性や高い荷重値における電気抵抗値変化の度合いが良好であることが分かる。また、表２から明らかなように、伸び率は実施例よりも比較例２の方がわずかに高いものの、実施例の強度及び硬度は比較例２よりも向上していることが分かる。 As apparent from FIGS. 5 and 1, in Comparative Example 2, the variation in the electrical resistance value variation characteristic due to the number of compression deformations is large, and a decrease in the electrical resistance value accompanying an increase in compression deformation is not observed at high load values. On the other hand, in the examples, the variation is small, and it can be seen that the reproducibility of the change in the electric resistance value due to repeated compression deformation and the degree of the change in the electric resistance value at a high load value are good. Further, as apparent from Table 2, although the elongation rate is slightly higher in Comparative Example 2 than in Example, it can be seen that the strength and hardness of Example are improved as compared with Comparative Example 2.
以上のように、本発明の感圧導電性エラストマーは、無加圧・無変形状態では高い電気抵抗値を示し、圧縮変形時の荷重の増加に従って電気抵抗値が減少して導電性を示す感圧導電性センサとして有用であり、特に、板状、針状、又は繊維状の導電性フィラーの他に粒径がナノメーターサイズのセラミック粒子も添加することにより、高い機械的強度と繰り返し圧縮変形に対する電気抵抗値変化の良好な再現性（信頼性）を与えるのに適している。 As described above, the pressure-sensitive conductive elastomer of the present invention exhibits a high electric resistance value in a non-pressurized and non-deformed state, and the electric resistance value decreases as the load during compression deformation increases and exhibits a conductive property. It is useful as a pressure-conducting sensor. Especially, by adding ceramic particles with a particle size of nanometer in addition to plate-like, needle-like or fibrous conductive fillers, high mechanical strength and repeated compression deformation It is suitable for giving good reproducibility (reliability) of the electric resistance value change with respect to.
Claims (4)
非導電性エラストマー中に、１０〜４０ｗｔ％の配合割合で板状、針状、又は繊維状の導電性フィラーと、２〜２０ｗｔ％の配合割合で有機化合物をインターカレートした層状無機化合物粒子であり粒径が５〜１００ｎｍのセラミック粒子とを分散させたことを特徴とする感圧導電性エラストマー。 A pressure-sensitive conductive elastomer that exhibits a high electrical resistance value in a non-pressurized / non-deformed state, and exhibits electrical conductivity by decreasing its electrical resistance with increasing load during compression deformation,
During the non-conductive elastomer, plate the proportions of 10 to 40 wt%, acicular, or a conductive filler fibrous organic compound in proportion of 2 to 20 wt% with intercalated layered inorganic compound particles A pressure-sensitive conductive elastomer in which ceramic particles having a particle diameter of 5 to 100 nm are dispersed.
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| US20120073388A1 (en) * | 2009-05-22 | 2012-03-29 | University Of New Brunswick | Force sensing compositions, devices and methods |
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| JPH02186604A (en) * | 1986-11-20 | 1990-07-20 | Yokohama Rubber Co Ltd:The | Pressure-sensitive resistance changing type conductive composition |
| JPH0790236A (en) * | 1993-09-24 | 1995-04-04 | Soken Kagaku Kk | Adhesive having anisotropic conductivity |
| JP2000299016A (en) * | 1999-04-15 | 2000-10-24 | Koichi Niihara | Deformed conductive elastomer and its manufacture |
| WO2003002682A1 (en) * | 2001-06-29 | 2003-01-09 | 3M Innovative Properties Company | Devices, compositions, and methods incorporating adhesives whose preformance is enhanced by organophilic clay constituents |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019049605A1 (en) | 2017-09-06 | 2019-03-14 | シンジーテック株式会社 | Pressure-sensitive elastomer porous body |
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| JP2005350614A (en) | 2005-12-22 |
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