JPH0657075A - Heat-sensitive resin material and heat-sensitive heater - Google Patents
Heat-sensitive resin material and heat-sensitive heaterInfo
- Publication number
- JPH0657075A JPH0657075A JP21591892A JP21591892A JPH0657075A JP H0657075 A JPH0657075 A JP H0657075A JP 21591892 A JP21591892 A JP 21591892A JP 21591892 A JP21591892 A JP 21591892A JP H0657075 A JPH0657075 A JP H0657075A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- sensitive
- polyvinyl chloride
- resin material
- chloride resin
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 239000011347 resin Substances 0.000 title claims abstract description 67
- 229920005989 resin Polymers 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 38
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 31
- 239000000654 additive Substances 0.000 claims abstract description 30
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 30
- 230000000996 additive effect Effects 0.000 claims abstract description 28
- 239000004014 plasticizer Substances 0.000 claims abstract description 25
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 pyromellitic acid ester Chemical class 0.000 claims abstract description 13
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000012212 insulator Substances 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 6
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 238000013329 compounding Methods 0.000 abstract description 4
- 230000000740 bleeding effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000003878 thermal aging Methods 0.000 abstract 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 230000032683 aging Effects 0.000 description 9
- 230000001965 increasing effect Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229910020366 ClO 4 Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 229910001484 inorganic perchlorate Inorganic materials 0.000 description 4
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004808 2-ethylhexylester Substances 0.000 description 2
- OYDSANWSTXENCV-UHFFFAOYSA-N 2-hydroxyethyl-dimethyl-[3-(octadecanoylamino)propyl]azanium perchlorate Chemical compound [O-][Cl](=O)(=O)=O.CCCCCCCCCCCCCCCCCC(=O)NCCC[N+](C)(C)CCO OYDSANWSTXENCV-UHFFFAOYSA-N 0.000 description 2
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
Landscapes
- Surface Heating Bodies (AREA)
- Resistance Heating (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電気カーペット等に用
いられる感熱樹脂材料及び感熱発熱体に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive resin material and a heat-sensitive heating element used for electric carpets and the like.
【０００２】[0002]
【従来の技術】電気カーペット等の広面積暖房器具に
は、従来よりポリ塩化ビニル樹脂を主成分とする感熱樹
脂材料をサーミスタとして用いた面状の感熱発熱体やコ
ード状の感熱発熱体が使用されている。そして近年の電
気カーペットにあっては、カーペット地からなる表面材
や、電気カーペットに被せて使用するカバー材として、
本物志向や高級志向から分厚いものが好まれる傾向にあ
り、感熱発熱体の温度を従来よりも高くする必要が生じ
てきている。2. Description of the Related Art For wide area heating appliances such as electric carpets, a sheet-like heat-generating element or a cord-like heat-generating element using a heat-sensitive resin material mainly containing polyvinyl chloride resin as a thermistor has been conventionally used. Has been done. And in the recent electric carpet, as a surface material made of a carpet material or a cover material to be used by covering the electric carpet,
Thick ones tend to be favored from a genuine or high-class orientation, and it has become necessary to raise the temperature of the heat-sensitive heating element higher than before.
【０００３】[0003]
【発明が解決しようとする課題】しかし、感熱発熱体の
温度を従来よりも高温にすると、部分的に断熱状態にな
るときに生じる部分断熱高温部の温度が非常に高くな
り、ポリ塩化ビニル樹脂を主成分とする感熱樹脂材料で
は高温での熱老化のために温度センサーとしての固有イ
ンピーダンス（以下｜Ｚ｜と略記）と温度との関係の特
性が経時変化し、｜Ｚ｜の変化によって感知する温度が
危険な高温になってしまうおそれがあった。この現象は
ポリ塩化ビニル樹脂中の可塑剤が高温の作用でブリー
ドアウトしてポリ塩化ビニル樹脂のガラス転移点が高温
側にシフトしてしまう、ポリ塩化ビニル樹脂が高温に
さらされると脱塩素反応を起こして熱老化してしまう、
等が原因になっていると考えられる。However, when the temperature of the heat-sensitive heating element is set higher than that of the conventional one, the temperature of the partially adiabatic high temperature part generated when the part is in a heat insulating state becomes extremely high. In a heat-sensitive resin material containing as a main component, the characteristic of the relationship between the intrinsic impedance (hereinafter abbreviated as | Z |) and temperature as a temperature sensor changes with time due to heat aging at high temperature, and it is sensed by the change in | Z | There was a risk that the temperature would be dangerously high. This phenomenon is that the plasticizer in the polyvinyl chloride resin bleeds out due to the action of high temperature and the glass transition point of the polyvinyl chloride resin shifts to the high temperature side. When the polyvinyl chloride resin is exposed to high temperature, the dechlorination reaction occurs. Causes heat aging,
It is thought that the cause is.
【０００４】本発明は上記の点に鑑みてなされたもので
あり、ポリ塩化ビニル樹脂の熱老化を抑制して｜Ｚ｜の
変動を抑え、しかもサーミスタ特性を高めることができ
る感熱樹脂材料、及びこの感熱樹脂材料を用いた感熱発
熱体を提供することを目的とするものである。The present invention has been made in view of the above points, and a heat-sensitive resin material capable of suppressing the heat aging of a polyvinyl chloride resin to suppress the fluctuation of | Z | and further improving the thermistor characteristics, and The object is to provide a heat-sensitive heating element using this heat-sensitive resin material.
【０００５】[0005]
【課題を解決するための手段】本発明に係る感熱樹脂材
料は、ポリ塩化ビニル系樹脂に、ピロメリット酸エステ
ル系の耐熱性可塑剤と、安定剤として酸化鉛（ＰｂＯ）
と二酸化珪素（ＳｉＯ 2 ）からなる珪酸鉛と、過塩素酸
からなるイオン性添加剤を配合して成ることを特徴とす
るものである。[Means for Solving the Problems] Thermosensitive resin material according to the present invention
Polyvinyl chloride resin, pyromellitic acid ester
-Based heat-resistant plasticizer and lead oxide (PbO) as stabilizer
And silicon dioxide (SiO 2) Lead silicate and perchloric acid
It is characterized by being mixed with an ionic additive consisting of
It is something.
【０００６】また本発明に係る感熱発熱体は、上記の感
熱樹脂材料を介して一対の電極を配置し、少なくとも一
方を発熱抵抗体としてこれらを絶縁体で覆って成ること
を特徴とするものである。以下、本発明を詳細に説明す
る。ポリ塩化ビニル系樹脂に配合される可塑剤として、
トリメリット酸エステル系や、ピロメリット酸エステル
系、ポリエステル系などの耐熱性可塑剤があるが、本発
明では上記の耐熱性可塑剤のなかでも耐熱性が優れてい
るピロメリット酸エステル系の耐熱性可塑剤を用いる。
感熱樹脂材料のサーミスタ特性の発現はポリ塩化ビニル
樹脂のガラス転移点に依存しており、高温の作用で可塑
剤がブリードアウトして抜けてしまうとガラス転移点が
変化し、｜Ｚ｜が変動してしまう。このために高温が作
用してもブリードアウトしない耐熱性可塑剤を用いるも
のである。耐熱性可塑剤の配合量は、ポリ塩化ビニル系
樹脂１００重量部に対して１０〜１００重量部が好まし
い。耐熱性可塑剤の配合量が少なすぎると他の配合剤と
の均一分散性や押し出し成形性、耐寒性等に問題が発生
し、多すぎると耐熱性可塑剤とはいえ高温の作用でブリ
ードアウトし易くなると共に、ポリ塩化ビニル系樹脂の
ガラス転移点が低くなり過ぎて｜Ｚ｜の値が温度に対し
て急激に変化する高感度領域が低温側にシフトしてしま
うことになる。このために耐熱性可塑剤の配合量の上限
と下限は上記のように設定されるものであり、特に３０
〜６０重量部の範囲が適する。Further, the heat-sensitive heating element according to the present invention is characterized in that a pair of electrodes are arranged with the above heat-sensitive resin material interposed therebetween, and at least one of them serves as a heating resistor and these are covered with an insulator. is there. Hereinafter, the present invention will be described in detail. As a plasticizer compounded in polyvinyl chloride resin,
There are heat-resistant plasticizers such as trimellitic acid ester-based, pyromellitic acid ester-based, and polyester-based heat-resistant plasticizers, but in the present invention, among the above heat-resistant plasticizers Use a plasticizer.
The expression of thermistor characteristics of the thermosensitive resin material depends on the glass transition point of the polyvinyl chloride resin, and if the plasticizer bleeds out and escapes by the action of high temperature, the glass transition point changes and | Z | fluctuates. Resulting in. For this reason, a heat resistant plasticizer which does not bleed out even when a high temperature acts is used. The blending amount of the heat resistant plasticizer is preferably 10 to 100 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin. If the amount of heat-resistant plasticizer is too small, problems such as uniform dispersibility with other compounding agents, extrusion moldability, and cold resistance will occur. In addition, the glass transition point of the polyvinyl chloride resin becomes too low, and the high-sensitivity region where the value of | Z | suddenly changes with temperature is shifted to the low temperature side. For this reason, the upper and lower limits of the amount of the heat-resistant plasticizer compounded are set as described above, and especially 30
A range of up to 60 parts by weight is suitable.
【０００７】また、ポリ塩化ビニル系樹脂に配合する安
定剤として、本発明では酸化鉛（ＰｂＯ）と二酸化珪素
（ＳｉＯ2 ）からなる珪酸鉛を用いる。ポリ塩化ビニル
系樹脂の安定剤としては従来から三塩基性硫酸鉛のなど
の塩基性鉛が使用されているが、塩基性の安定剤は可塑
剤を分解させてしまうおそれがある。これに対して珪酸
鉛はこのように可塑剤を分解させるおそれがないために
上記のような耐熱性可塑剤を用いることが可能になると
共に分子中の鉛成分がリッチであるために熱安定性を高
めることができるものである。珪酸鉛の配合量は、ポリ
塩化ビニル系樹脂１００重量部に対して５〜３０重量部
が好ましい。珪酸鉛の配合量が少なすぎると熱安定性が
不足することになり、また珪酸鉛は粉体状であるために
多量を安定して配合することができない。このために珪
酸鉛の配合量は上限と下限を上記のように設定されるも
のであり、特に１０〜２５重量部の範囲が適する。In the present invention, lead silicate composed of lead oxide (PbO) and silicon dioxide (SiO 2 ) is used as a stabilizer to be added to the polyvinyl chloride resin. Basic lead such as tribasic lead sulfate has been conventionally used as a stabilizer for polyvinyl chloride resins, but the basic stabilizer may decompose the plasticizer. On the other hand, lead silicate does not have the risk of decomposing the plasticizer in this way, so it becomes possible to use the heat-resistant plasticizer as described above, and the lead component in the molecule is rich, so the thermal stability is high. Can be increased. The lead silicate content is preferably 5 to 30 parts by weight per 100 parts by weight of the polyvinyl chloride resin. If the amount of lead silicate blended is too small, the thermal stability will be insufficient, and since lead silicate is in powder form, a large amount cannot be stably blended. For this reason, the upper limit and the lower limit of the lead silicate content are set as described above, and a range of 10 to 25 parts by weight is particularly suitable.
【０００８】また本発明では、ポリ塩化ビニル系樹脂に
過塩素酸塩をイオン性添加剤として配合することによっ
て、温度上昇に伴ってイオン伝動によりインピーダンス
低下を引き起こさせ、｜Ｚ｜〜温度特性の変化率を大き
くすることによってサーミスタ特性を高めて温度検知の
精度を高めるようにしている。本発明では、過塩素酸塩
よりなるイオン性添加剤として式（１）の構造式で表さ
れるステアラミドプロピルジメチル−β−ヒドロキシエ
チルアンモニウム過塩素酸塩を用いる。他の過塩素酸塩
よりなるイオン性添加剤は、一般式が式（２）及び式
（３）で表される第四級アンモニウム塩（有機過塩素酸
塩）や一般式が式（４）で表されるアルカリ金属塩（無
機過塩素酸塩）をポリオール系高分子に溶解させたもの
等がある。イオン添加剤としてこのような過塩素酸（式
（５））タイプのものを用いるのは、式（６）、式
（７）、式（８）、式（９）等のタイプのものに比べて
耐熱性が高いためである。Further, in the present invention, by adding perchlorate as an ionic additive to the polyvinyl chloride resin, the impedance is lowered by the ionic transmission as the temperature rises, and the | Z | By increasing the rate of change, the thermistor characteristics are enhanced and the accuracy of temperature detection is enhanced. In the present invention, stearamidopropyldimethyl-β-hydroxyethylammonium perchlorate represented by the structural formula (1) is used as the ionic additive composed of perchlorate. Other ionic additives composed of perchlorates include quaternary ammonium salts (organic perchlorates) represented by the general formulas (2) and (3) and the general formula (4). There is a solution in which an alkali metal salt (inorganic perchlorate) represented by is dissolved in a polyol polymer. The use of such a perchloric acid (formula (5)) type as an ionic additive is more effective than that of formula (6), formula (7), formula (8), formula (9), etc. It has high heat resistance.
【０００９】[0009]
【化１】 [Chemical 1]
【００１０】 式（４） Ｌｉ+ ・ＣｌＯ4 - 式（５） ＣｌＯ4 - 式（６） Ｃ2 Ｈ5 ＳＯ4 - 式（７） Ｈ2 ＰＯ4 - 式（８） ＮＯ3 - 式（９） Ｃｌ- また上記のイオン性添加剤として用いる有機および無機
の過塩素酸塩の配合量は、ポリビニル系樹脂１００重量
部に対して０．５〜５重量部の範囲が好ましい。イオン
添加剤の配合量が少ないと｜Ｚ｜〜温度特性の変化率を
大きくしてサーミスタ特性を高める効果を十分に得るこ
とができないために上記のような下限が設定されるもの
である。逆にイオン性添加剤の配合量が多すぎるとポリ
塩化ビニル系樹脂の熱安定性を低下させるおそれがあ
り、イオン性添加剤の上限は製造バラツキが発生しにく
く、配合を増加してもサーミスタ特性がそれ以上良くな
らない限界の飽和添加量より少しだけ過飽和の量になる
ように設定するのがよい。このためにイオン性添加剤の
配合量は上限と下限を上記のように設定されるものであ
り、特に２〜４重量部の範囲が適する。[0010] Equation (4) Li + · ClO 4 - Equation (5) ClO 4 - formula (6) C 2 H 5 SO 4 - Equation (7) H 2 PO 4 - Formula (8) NO 3 - (9 ) Cl − The amount of organic and inorganic perchlorates used as the ionic additive is preferably 0.5 to 5 parts by weight based on 100 parts by weight of the polyvinyl resin. If the blending amount of the ionic additive is small, the effect of increasing the change rate of | Z | to temperature characteristics and enhancing the thermistor characteristics cannot be sufficiently obtained, and therefore the above lower limit is set. On the contrary, if the amount of the ionic additive compounded is too large, the thermal stability of the polyvinyl chloride resin may be reduced, and the upper limit of the ionic additive is less likely to cause manufacturing variations, and even if the compounding amount is increased, It is preferable to set the amount of supersaturation to be a little less than the limit of the amount of saturated addition that does not further improve the characteristics. For this reason, the upper limit and the lower limit of the blending amount of the ionic additive are set as described above, and the range of 2 to 4 parts by weight is particularly suitable.
【００１１】上記のように作成される本発明に係る感熱
樹脂材料をサーミスタとして用いて、図３に示すような
面状の感熱発熱体Ａや、図４に示すようなコード状の感
熱発熱体Ａを製造することができる。図３の面状の感熱
発熱体は、感熱樹脂材料１を成形した感熱樹脂シートの
一方の片面に銅箔などの金属箔をジクザグ状のパターン
に加工して形成した電極２と、この電極２と近接する位
置において金属箔を加工して形成した電極３とを貼り付
け、感熱樹脂材料１のシートの他方の片面に電極２，３
間に渡るように金属箔を加工して形成した分割反射電極
５を貼り付け、感熱樹脂材料１のシートの両面を絶縁樹
脂シートなどの絶縁体４で被覆することによって作成す
ることができる。このものでは電極２が発熱抵抗体（発
熱回路）として、電極３が温度検知電極として使用され
るものであり、電極２に通電して発熱させると感熱樹脂
材料１は温度変化に伴って｜Ｚ｜が変化するために、電
極３に生じる電位を検出することによって発熱温度を検
知することができるものである。Using the thermosensitive resin material according to the present invention produced as described above as a thermistor, a sheet-shaped heat-sensitive heating element A as shown in FIG. 3 or a cord-shaped heat-sensitive heating element as shown in FIG. A can be produced. The sheet-like heat-sensitive heating element of FIG. 3 includes an electrode 2 formed by processing a metal foil such as a copper foil into a zigzag pattern on one surface of a heat-sensitive resin sheet obtained by molding the heat-sensitive resin material 1, and the electrode 2 And an electrode 3 formed by processing a metal foil at a position close to the electrode 3 are attached, and the electrodes 2 and 3 are attached to the other surface of the sheet of the thermosensitive resin material 1.
It can be prepared by pasting the divided reflective electrodes 5 formed by processing a metal foil so as to extend between them, and covering both sides of the sheet of the thermosensitive resin material 1 with the insulator 4 such as an insulating resin sheet. In this device, the electrode 2 is used as a heating resistor (heating circuit), and the electrode 3 is used as a temperature detection electrode. When the electrode 2 is energized to generate heat, the heat-sensitive resin material 1 | Z Since | changes, the heat generation temperature can be detected by detecting the potential generated in the electrode 3.
【００１２】また図４のコード状の感熱発熱体Ａは、絶
縁性の芯糸７に金属線をスパイラル状に巻いて内巻の電
極２とし、感熱樹脂材料１を例えば押し出し成形して内
巻電極２の外側に被覆し、その外側に金属線を巻いて外
巻の電極３とし、さらにその外側に樹脂フィルムを巻い
て分離層１０を形成した後に、その外側に絶縁体４を被
覆することによって作成することができる。内巻の電極
２と外巻の電極３の少なくとも一方を発熱抵抗体として
通電することによって発熱させることができ、電極３に
生じる電位を検出することによって発熱温度を検知する
ことができるものである。このように製造される感熱発
熱体Ａを例えば図５及び図６に示すように、ポリエステ
ル繊維等の厚さ１０ｍｍ程度の裏面布１１と厚さ９μ程
度の均熱アルミニウム平面体１２との間に挟んで、ジグ
ザグ状に配置し、そして均熱アルミニウム平面体１２の
上にポリエステル繊維等の厚さ５ｍｍ程度の表面布１３
を積層することによって電気カーペットＢを作成するこ
とができる。図５において１４は電源コード、１５は温
度コントローラである。In the cord-shaped heat-sensitive heating element A of FIG. 4, a metal wire is spirally wound around an insulative core thread 7 to form an inner wound electrode 2, and a heat-sensitive resin material 1 is extruded to form an inner wound electrode 2. Covering the outside of the electrode 2, winding a metal wire around the outside to form the outer wound electrode 3, further winding a resin film around the outside to form the separation layer 10, and then covering the outside with the insulator 4. Can be created by. Heat can be generated by energizing at least one of the inner wound electrode 2 and the outer wound electrode 3 as a heating resistor, and the heat generation temperature can be detected by detecting the potential generated in the electrode 3. . As shown in FIGS. 5 and 6, for example, the heat-sensitive heating element A manufactured in this way is provided between a back cloth 11 having a thickness of about 10 mm and a soaking aluminum flat body 12 having a thickness of about 9 μ, such as polyester fiber. It is sandwiched and arranged in a zigzag shape, and a surface cloth 13 such as polyester fiber having a thickness of about 5 mm is placed on the soaking aluminum flat body 12.
The electric carpet B can be produced by stacking the above. In FIG. 5, 14 is a power cord, and 15 is a temperature controller.
【００１３】[0013]
【実施例】次に、本発明を実施例によってさらに説明す
る。 （実施例 １）平均重合度が１３００のポリ塩化ビニル
樹脂１００重量部に、可塑剤として式（１０）に示すピ
ロメリット酸オクチルエステル（ＴＯＰＭ）を４５重量
部、安定剤として珪酸鉛を２５重量部、イオン性添加剤
として式（１）に示す過塩素酸よりなる第四級アンモニ
ウム塩を３重量部配合して、感熱樹脂材料を調製した。EXAMPLES The present invention will be further described with reference to examples. Example 1 100 parts by weight of polyvinyl chloride resin having an average degree of polymerization of 1300, 45 parts by weight of octyl pyromellitic acid octyl ester (TOPM) represented by the formula (10) as a plasticizer, and 25 parts by weight of lead silicate as a stabilizer. Parts, 3 parts by weight of a quaternary ammonium salt of perchloric acid represented by the formula (1) as an ionic additive was blended to prepare a heat-sensitive resin material.
【００１４】（実施例 ２）平均重合度が１３００のポ
リ塩化ビニル樹脂１００重量部に、可塑剤として式（１
０）に示すピロメリット酸オクチルエステル（ＴＯＰ
Ｍ）を４５重量部、安定剤として珪酸鉛を２５重量部、
イオン性添加剤として式（１）に示す過塩素酸よりなる
第四級アンモニウム塩を５重量部配合して、感熱樹脂材
料を調製した。Example 2 100 parts by weight of a polyvinyl chloride resin having an average degree of polymerization of 1300 was added as a plasticizer of the formula (1)
0) Pyromellitic acid octyl ester (TOP
M) 45 parts by weight, lead silicate 25 parts by weight as a stabilizer,
A thermosensitive resin material was prepared by blending 5 parts by weight of a quaternary ammonium salt of perchloric acid represented by the formula (1) as an ionic additive.
【００１５】（比較例 １）平均重合度が１３００のポ
リ塩化ビニル樹脂１００重量部に、可塑剤として式（１
０）に示すピロメリット酸オクチルエステル（ＴＯＰ
Ｍ）を４５重量部、安定剤として三塩基性硫酸鉛を２５
重量部、イオン性添加剤として式（１）に示す過塩素酸
よりなる第四級アンモニウム塩を３重量部配合して、感
熱樹脂材料を調製した。Comparative Example 1 100 parts by weight of a polyvinyl chloride resin having an average degree of polymerization of 1300 was added as a plasticizer with the formula (1).
0) Pyromellitic acid octyl ester (TOP
45 parts by weight of M) and 25 parts of tribasic lead sulfate as a stabilizer.
3 parts by weight of a quaternary ammonium salt of perchloric acid represented by the formula (1) as an ionic additive was blended to prepare a heat-sensitive resin material.
【００１６】（比較例 ２）平均重合度が１３００のポ
リ塩化ビニル樹脂１００重量部に、可塑剤として式（１
１）に示すトリメリット酸オクチルエステル（ＴＯＴ
Ｍ）を４５重量部、安定剤として珪酸鉛を２５重量部、
イオン性添加剤として式（１）に示す過塩素酸よりなる
第四級アンモニウム塩を３重量部配合して、感熱樹脂材
料を調製した。Comparative Example 2 100 parts by weight of a polyvinyl chloride resin having an average degree of polymerization of 1300 was added as a plasticizer with the formula (1).
Octyl ester of trimellitic acid (TOT shown in 1)
M) 45 parts by weight, lead silicate 25 parts by weight as a stabilizer,
A thermosensitive resin material was prepared by mixing 3 parts by weight of a quaternary ammonium salt of perchloric acid represented by the formula (1) as an ionic additive.
【００１７】（比較例 ３）平均重合度が１３００のポ
リ塩化ビニル樹脂１００重量部に、可塑剤として式（１
１）に示すトリメリット酸オクチルエステル（ＴＯＴ
Ｍ）を４５重量部、安定剤として三塩基性硫酸鉛を２５
重量部、イオン性添加剤として式（１）に示す過塩素酸
よりなる第四級アンモニウム塩を３重量部配合して、感
熱樹脂材料を調製した。Comparative Example 3 100 parts by weight of a polyvinyl chloride resin having an average degree of polymerization of 1300 was added as a plasticizer with the formula (1).
Octyl ester of trimellitic acid (TOT shown in 1)
45 parts by weight of M) and 25 parts of tribasic lead sulfate as a stabilizer.
3 parts by weight of a quaternary ammonium salt of perchloric acid represented by the formula (1) as an ionic additive was blended to prepare a heat-sensitive resin material.
【００１８】[0018]
【化２】 [Chemical 2]
【００１９】実施例（１）及び比較例（１）〜（３）で
得た感熱樹脂材料について１９０℃で加熱して劣化促進
テストをおこない、脱塩酸による分解が急激に発生する
までの時間を測定して熱安定性を調べた。またこの感熱
樹脂材料を０．５ｍｍ厚のシートにプレスした状態で１
３６℃で１６８時間（７日間）加熱し、揮発減量と８０
℃での｜Ｚ｜の変化量を測定した。これらの結果を表１
に示す。The heat-sensitive resin materials obtained in Example (1) and Comparative Examples (1) to (3) were heated at 190 ° C. to carry out a deterioration acceleration test, and the time until decomposition by dehydrochlorination suddenly occurred was conducted. It measured and investigated thermal stability. In addition, the heat-sensitive resin material is pressed into a 0.5 mm thick sheet to
Heat at 36 ° C for 168 hours (7 days) and reduce volatilization to 80%.
The amount of change in | Z | at ° C was measured. These results are shown in Table 1.
Shown in.
【００２０】さらに実施例（１）および（２）で得た感
熱樹脂材料を０．５ｍｍ厚にプレスしたシートで初期の
｜Ｚ｜〜温度特性を測定した。その結果を図１に示す。Further, the initial | Z | -temperature characteristics were measured using a sheet obtained by pressing the thermosensitive resin materials obtained in Examples (1) and (2) to a thickness of 0.5 mm. The result is shown in FIG.
【００２１】[0021]
【表１】 [Table 1]
【００２２】表１にみられるように、実施例（１）のも
のでは熱安定性が高まり、また揮発減量が小さくなると
共に｜Ｚ｜の変化も小さくなることが確認される。すな
わち実施例（１）と比較例（１）より、ＴＯＴＭより耐
ブリード性の優れるＴＯＰＭを用いても三塩基性硫酸鉛
を安定剤として使用すると、感熱材料樹脂内の塩基性が
強くなりＴＯＰＭが分解されて、揮発減量、｜Ｚ｜変化
とも大きくなる。これは珪酸鉛を使用すると著しく改善
される。またこの改善効果は、比較例（２）と（３）よ
りＴＯＴＭでも同様な傾向が見られるが、本発明の実施
例（１）のような組成において特に効果が大きく、本発
明に至ったものである。As can be seen from Table 1, in Example (1), it is confirmed that the thermal stability is increased, the volatilization loss is reduced, and the change in | Z | is reduced. That is, from Example (1) and Comparative Example (1), even if TOPM having superior bleeding resistance to TOTM is used, if tribasic lead sulfate is used as a stabilizer, the basicity in the heat-sensitive material resin becomes stronger and TOPM becomes higher. When decomposed, the volatilization loss and the | Z | change also increase. This is significantly improved with the use of lead silicate. This improvement effect is similar to that of Comparative Examples (2) and (3) in the case of TOTM, but the composition of Example (1) of the present invention has a particularly large effect and has led to the present invention. Is.
【００２３】さらに図１に見られるように実施例（２）
ではイオン性添加剤を５重量部添加しているにもかかわ
らず、３重量部添加した実施例（１）のものと｜Ｚ｜〜
温度特性に変化がないことから実施例（１）のものは過
塩素酸よりなる第四級アンモニウム塩を増量してもサー
ミスタ特性がそれ以上良くならない過飽和量であること
が分かる。Further, as shown in FIG. 1, the embodiment (2)
In spite of the fact that 5 parts by weight of the ionic additive is added, the amount of the compound of Example (1) added with 3 parts by weight and | Z |
Since there is no change in the temperature characteristics, it can be seen that in Example (1), the amount of supersaturation is such that the thermistor characteristics are not improved even if the amount of the quaternary ammonium salt of perchloric acid is increased.
【００２４】また実施例（１）及び比較例（３）で作成
した感熱樹脂材料を用いて図４のワイヤー状の感熱発熱
体Ａを作成した。すなわち、全芳香族ポリエステル系１
０００デニール繊維で形成した芯糸７に銅合金よりなる
０．１１ｍｍφの金属線５本をピッチ１．２５ｍｍでス
パイラル状に巻いて内巻電極２とし、その外側に感熱樹
脂材料１を押し出し成形して被覆し、その外側にＮｉメ
ッキした幅０．５ｍｍ、厚み０．０５ｍｍの金属線をピ
ッチ１．８ｍｍでスパイラル状に巻いて外巻電極３と
し、さらにその外側に厚み１２μのポリエチレンテレフ
タレートフィルムを巻いて分離層１０を形成した後に、
厚み０．４ｍｍの耐熱ポリ塩化ビニル樹脂の絶縁体４で
絶縁被覆することによって、内巻電極２を発熱抵抗体と
して用いる感熱発熱体Ａを作成した。Further, the heat-sensitive resin material prepared in Example (1) and Comparative Example (3) was used to prepare a wire-shaped heat-sensitive heating element A shown in FIG. That is, wholly aromatic polyester system 1
A core yarn 7 made of 000 denier fiber is spirally wound with five 0.11 mmφ metal wires made of a copper alloy at a pitch of 1.25 mm to form an inwardly wound electrode 2, and the thermosensitive resin material 1 is extruded and molded on the outside thereof. And a Ni-plated metal wire having a width of 0.5 mm and a thickness of 0.05 mm is spirally wound on the outside at a pitch of 1.8 mm to form the outer wound electrode 3, and a polyethylene terephthalate film having a thickness of 12 μ is further provided on the outer side thereof. After winding to form the separation layer 10,
A heat-sensitive heating element A using the inner winding electrode 2 as a heating resistor was prepared by insulating and covering with an insulator 4 of a heat-resistant polyvinyl chloride resin having a thickness of 0.4 mm.
【００２５】このように作成される感熱発熱体の感熱樹
脂材料について、｜Ｚ｜〜温度特性と１１０℃雰囲気中
に２０００時間放置して熱老化処理したあとの｜Ｚ｜〜
温度特性を、周波数６０Ｈｚ、感熱発熱体の長さ３６ｍ
の条件でそれぞれ測定した。結果を図２に示す。図２に
みられるように、実施例（１）のものは比較例（３）の
ものに比べて熱老化が進行しないために｜Ｚ｜の変化が
小さくなることが確認される。Regarding the heat-sensitive resin material of the heat-sensitive heating element produced in this way, | Z | -after temperature aging and heat aging treatment at 110 ° C. for 2000 hours | Z |
Temperature characteristics, frequency 60Hz, length of heat-sensitive heating element 36m
Was measured under each condition. The results are shown in Figure 2. As shown in FIG. 2, it is confirmed that in Example (1), the change in | Z | becomes smaller than that in Comparative Example (3) because the heat aging does not proceed.
【００２６】[0026]
【発明の効果】上記のように本発明は、ポリ塩化ビニル
系樹脂に、ピロメリット酸エステル系の耐熱性可塑剤
と、安定剤として酸化鉛（ＰｂＯ）と二酸化珪素（Ｓｉ
Ｏ2 ）からなる珪酸鉛と、過塩素酸塩からなるイオン性
添加剤を配合して感熱樹脂材料を調製したので、ピロメ
リット酸エステル系の耐熱性可塑剤のブリードアウトを
防止すると共に酸化鉛（ＰｂＯ）と二酸化珪素（ＳｉＯ
2 ）からなる珪酸鉛の配合で熱安定性を高め、ポリ塩化
ビニル樹脂の熱老化を抑制して｜Ｚ｜の変動を抑え、し
かもイオン性添加剤として配合する過塩素酸によってサ
ーミスタ特性を高めることができるものである。As described above, according to the present invention, a polyvinyl chloride resin is used in addition to a pyromellitic ester heat-resistant plasticizer, and lead oxide (PbO) and silicon dioxide (Si) as stabilizers.
Since a heat-sensitive resin material was prepared by mixing lead silicate composed of O 2 ) and an ionic additive composed of perchlorate, bleed-out of pyromellitic ester heat-resistant plasticizer was prevented and lead oxide (PbO) and silicon dioxide (SiO
2 ) Lead silicate compounded to improve the thermal stability, suppress the heat aging of polyvinyl chloride resin to suppress the variation of | Z |, and enhance the thermistor property by the perchloric acid compounded as an ionic additive. Is something that can be done.
【００２７】従って、感熱発熱体の感熱温度を高温に設
定しても｜Ｚ｜の変動を低く抑えることができるため
に、断熱性の大きいカバー材等を使用する電気カーペッ
トに使用しても十分に暖かさを感じる温度に設定するこ
とが可能になるものである。Therefore, even if the heat-sensitive temperature of the heat-sensitive heating element is set to a high temperature, the fluctuation of | Z | can be suppressed to a low level, so that it can be sufficiently used for an electric carpet using a cover material having a large heat insulating property. It is possible to set the temperature to feel warmth.
【図１】感熱樹脂材料の固有インピーダンス〜温度曲線
のグラフである。FIG. 1 is a graph of a characteristic impedance-temperature curve of a thermosensitive resin material.
【図２】感熱樹脂材料の熱老化処理前と熱老化処理後の
固有インピーダンス〜温度曲線のグラフである。FIG. 2 is a graph of a specific impedance-temperature curve of a heat-sensitive resin material before heat aging treatment and after heat aging treatment.
【図３】面状感熱発熱体の断面図である。FIG. 3 is a cross-sectional view of a planar heat-sensitive heating element.
【図４】コード状感熱発熱体の正面図である。FIG. 4 is a front view of a cord-shaped heat-sensitive heating element.
【図５】電気カーペットの斜視図である。FIG. 5 is a perspective view of an electric carpet.
【図６】電気カーペットの拡大した断面図である。FIG. 6 is an enlarged sectional view of the electric carpet.
１ 感熱樹脂材料 ２ 電極 ３ 電極 ４ 絶縁体 1 Thermosensitive resin material 2 Electrode 3 Electrode 4 Insulator
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年９月２８日[Submission date] September 28, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００８[Correction target item name] 0008
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００８】また本発明では、ポリ塩化ビニル系樹脂に
過塩素酸塩をイオン性添加剤として配合することによっ
て、温度上昇に伴ってイオン伝導によりインピーダンス
低下を引き起こさせ、｜Ｚ｜〜温度特性の変化率を大き
くすることによってサーミスタ特性を高めて温度検知の
精度を高めるようにしている。本発明では、過塩素酸塩
よりなるイオン性添加剤として式（１）の構造式で表さ
れるステアラミドプロピルジメチル−β−ヒドロキシエ
チルアンモニウム過塩素酸塩を用いる。他の過塩素酸塩
よりなるイオン性添加剤は、一般式が式（２）及び式
（３）で表される第四級アンモニウム塩（有機過塩素酸
塩）や一般式が式（４）で表されるアルカリ金属塩（無
機過塩素酸塩）をポリオール系高分子に溶解させたもの
等がある。イオン添加剤としてこのような過塩素酸（式
（５））タイプのものを用いるのは、式（６）、式
（７）、式（８）、式（９）等のタイプのものに比べて
耐熱性が高いためである。Further, in the present invention, by adding perchlorate as an ionic additive to the polyvinyl chloride resin, the impedance is lowered due to ionic conduction as the temperature rises. By increasing the rate of change, the thermistor characteristics are enhanced and the accuracy of temperature detection is enhanced. In the present invention, stearamidopropyldimethyl-β-hydroxyethylammonium perchlorate represented by the structural formula (1) is used as the ionic additive composed of perchlorate. Other ionic additives composed of perchlorates include quaternary ammonium salts (organic perchlorates) represented by the general formulas (2) and (3) and the general formula (4). There is a solution in which an alkali metal salt (inorganic perchlorate) represented by is dissolved in a polyol polymer. Such perchloric acid (formula (5)) type is used as the ionic additive compared to formula (6), formula (7), formula (8), formula (9) and other types. It has high heat resistance.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１０】 式（４） Ｌｉ+ ・ＣｌＯ4 - 式（５） ＣｌＯ4 - 式（６） Ｃ2 Ｈ5 ＳＯ4 - 式（７） Ｈ2 ＰＯ4 - 式（８） ＮＯ3 - 式（９） Ｃｌ- また上記のイオン性添加剤として用いる有機および無機
の過塩素酸塩の配合量は、ポリ塩化ビニル系樹脂１００
重量部に対して０．５〜５重量部の範囲が好ましい。イ
オン添加剤の配合量が少ないと｜Ｚ｜〜温度特性の変化
率を大きくしてサーミスタ特性を高める効果を十分に得
ることができないために上記のような下限が設定される
ものである。逆にイオン性添加剤の配合量が多すぎると
ポリ塩化ビニル系樹脂の熱安定性を低下させるおそれが
あり、イオン性添加剤の上限は製造バラツキが発生しに
くく、配合を増加してもサーミスタ特性がそれ以上良く
ならない限界の飽和添加量より少しだけ過飽和の量にな
るように設定するのがよい。このためにイオン性添加剤
の配合量は上限と下限を上記のように設定されるもので
あり、特に２〜４重量部の範囲が適する。[0010] Equation (4) Li + · ClO 4 - Equation (5) ClO 4 - formula (6) C 2 H 5 SO 4 - Equation (7) H 2 PO 4 - Formula (8) NO 3 - (9 ) Cl - Also, the blending amount of the organic and inorganic perchlorates used as the above-mentioned ionic additive is 100% by weight of the polyvinyl chloride resin.
The range of 0.5 to 5 parts by weight is preferable with respect to parts by weight. If the blending amount of the ionic additive is small, the effect of increasing the change rate of | Z | to temperature characteristics and enhancing the thermistor characteristics cannot be sufficiently obtained, and therefore the above lower limit is set. On the contrary, if the amount of the ionic additive compounded is too large, the thermal stability of the polyvinyl chloride resin may be reduced, and the upper limit of the ionic additive is less likely to cause manufacturing variations, and even if the compounding amount is increased, It is preferable to set the amount of supersaturation to be a little less than the limit of the amount of saturated addition that does not further improve the characteristics. For this reason, the upper limit and the lower limit of the blending amount of the ionic additive are set as described above, and the range of 2 to 4 parts by weight is particularly suitable.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１８[Correction target item name] 0018
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１８】[0018]
【化２】 [Chemical 2]
【手続補正４】[Procedure amendment 4]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図２[Name of item to be corrected] Figure 2
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図２】 [Fig. 2]
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図６[Name of item to be corrected] Figure 6
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図６】 [Figure 6]
Claims (2)
酸エステル系の耐熱性可塑剤と、安定剤として酸化鉛
（ＰｂＯ）と二酸化珪素（ＳｉＯ2 ）からなる珪酸鉛
と、過塩素酸塩からなるイオン性添加剤を配合して成る
ことを特徴とする感熱樹脂材料。1. A polyvinyl chloride resin containing a pyromellitic acid ester heat-resistant plasticizer, lead silicate composed of lead oxide (PbO) and silicon dioxide (SiO 2 ) as a stabilizer, and perchlorate. A heat-sensitive resin material, characterized by being mixed with an ionic additive.
一対の電極を配置し、少なくとも一方を発熱抵抗体とし
てこれらを絶縁体で覆って成ることを特徴とする感熱発
熱体。2. A heat-sensitive heating element, characterized in that a pair of electrodes are disposed with the heat-sensitive resin material according to claim 1 interposed therebetween, and at least one of them serves as a heating resistor and is covered with an insulator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21591892A JPH0657075A (en) | 1992-08-13 | 1992-08-13 | Heat-sensitive resin material and heat-sensitive heater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21591892A JPH0657075A (en) | 1992-08-13 | 1992-08-13 | Heat-sensitive resin material and heat-sensitive heater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0657075A true JPH0657075A (en) | 1994-03-01 |
Family
ID=16680417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21591892A Pending JPH0657075A (en) | 1992-08-13 | 1992-08-13 | Heat-sensitive resin material and heat-sensitive heater |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0657075A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000136279A (en) * | 1998-11-04 | 2000-05-16 | Achilles Corp | Self-tacky vinyl chloride-based resin sheet |
| JP2001266649A (en) * | 2000-03-22 | 2001-09-28 | Kansai Electric Power Co Inc:The | Polyvinyl chloride composition and electric cable using the same |
-
1992
- 1992-08-13 JP JP21591892A patent/JPH0657075A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000136279A (en) * | 1998-11-04 | 2000-05-16 | Achilles Corp | Self-tacky vinyl chloride-based resin sheet |
| JP2001266649A (en) * | 2000-03-22 | 2001-09-28 | Kansai Electric Power Co Inc:The | Polyvinyl chloride composition and electric cable using the same |
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| Date | Code | Title | Description |
|---|---|---|---|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20001128 |