JPS5936860B2 - Method for producing crosslinked polyolefin extrusion molded products - Google Patents
Method for producing crosslinked polyolefin extrusion molded productsInfo
- Publication number
- JPS5936860B2 JPS5936860B2 JP52103904A JP10390477A JPS5936860B2 JP S5936860 B2 JPS5936860 B2 JP S5936860B2 JP 52103904 A JP52103904 A JP 52103904A JP 10390477 A JP10390477 A JP 10390477A JP S5936860 B2 JPS5936860 B2 JP S5936860B2
- Authority
- JP
- Japan
- Prior art keywords
- extruder
- extrusion molded
- crosslinked polyolefin
- polyolefin
- molded products
- 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.)
- Expired
Links
- 238000001125 extrusion Methods 0.000 title claims description 18
- 229920000098 polyolefin Polymers 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 229920005672 polyolefin resin Polymers 0.000 claims 1
- 239000000376 reactant Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 238000004898 kneading Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
- B29C48/38—Plasticisers, homogenisers or feeders comprising two or more stages using two or more serially arranged screws in the same barrel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Specially Adapted For Manufacturing Cables (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Description
【発明の詳細な説明】
＜発明の対象＞
本発明はシリコーングラフト化による架橋ポリオレフィ
ン押出成型品（例えば架橋ポリオレフィン絶縁電線）を
得るための製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Object of the Invention> The present invention relates to a manufacturing method for obtaining a crosslinked polyolefin extrusion molded product (for example a crosslinked polyolefin insulated wire) by silicone grafting.
＜従来技術＞ポリエチレンなどのポリオレフィン系重合
体とビニルトリメトキシシラン、ラジカル発生剤などの
グラフト反応剤を一定の条件下で加熱することにより反
応させ、得られたシリル変性ポリオレフィンをシロキサ
ン縮合触媒の存在下で水分と反応させ最終的に架橋ポリ
オレフィン生成物を得る方法は既に公知である。<Prior art> A polyolefin polymer such as polyethylene is reacted with a graft reactant such as vinyltrimethoxysilane or a radical generator by heating under certain conditions, and the resulting silyl-modified polyolefin is reacted with the presence of a siloxane condensation catalyst. Processes for reacting with moisture to ultimately obtain crosslinked polyolefin products are already known.
しかし、従来の押出加工法は次のような欠点があつた。However, conventional extrusion processing methods have the following drawbacks.
（ハ ポリオレフィンとグラフト反応剤を押出混練し、
架橋性グラフトポリマを製造し、これをあらかじめマス
ターバッチ化した触媒（例えばジブチル錫ジラウレート
）と一緒に加熱押出することにより架橋性製品を得る。(c. Extrusion kneading of polyolefin and grafting reactant,
A crosslinkable product is obtained by producing a crosslinkable graft polymer and extruding it under heat together with a pre-masterbatched catalyst (for example, dibutyltin dilaurate).
このような２段階法では架橋性グラフトポリマー及びマ
スターバッチを微少量の水分から絶縁管理することが必
要であり、管理が困難である上、２段階製法はコスト高
となる。（２）１段階押出法を使用した１段階法による
製造法例えば特開昭５０−１３２０５４、特開昭５０−
１３５１３８では、シロキサン縮合触媒を押出スクリュ
ー溶融域以降にポンプにより注入し、その他の液状グラ
フト反応剤をホッパーより投入する方法がある。In such a two-step method, it is necessary to insulate the crosslinkable graft polymer and masterbatch from minute amounts of moisture, which is difficult to manage, and the two-step production method is expensive. (2) One-step manufacturing method using one-step extrusion method For example, JP-A-50-132054, JP-A-Sho 50-
In No. 135138, there is a method in which a siloxane condensation catalyst is injected by a pump after the extrusion screw melting zone, and other liquid graft reactants are introduced from a hopper.
しかしこの方法では充分な架橋度を得るための注入量を
ホッパーに投入することが難しい。即ちホッパー中のポ
リオレフィンペレットが液状グラフト反応剤により湿潤
し、ペレットがスリップし、スクリュウ供給部に一定に
食込まず、押出量に変動を発生するからである。（３）
同じような１段階法において１台の押出機のシリンダー
あるいはスクリュウに複数個の注入孔を設けて、グラフ
ト反応剤を別々に注入する方法（例えば特開昭５０−１
３８０４２）があるが、ポリオレフインペレツト中の水
分を１段階法において充分に脱気することが難かしく、
更に微少量のグラフト反応剤を一定量、長時間にわたつ
て注入するための複数個の注入ポンプが必要である。However, with this method, it is difficult to charge the amount into the hopper to obtain a sufficient degree of crosslinking. That is, the polyolefin pellets in the hopper become wet with the liquid grafting reactant, causing the pellets to slip and not to feed into the screw feeder constantly, resulting in fluctuations in the extrusion rate. (3)
In a similar one-step method, a plurality of injection holes are provided in the cylinder or screw of one extruder, and the grafting reagent is separately injected (for example, in JP-A-50-1
38042), but it is difficult to sufficiently degas the moisture in the polyolef impeller in a one-step method;
Furthermore, a plurality of injection pumps are required to inject a constant amount of a minute amount of the grafting reagent over a long period of time.
＜発明の目的＞
本発明の目的は前記した従来技術の欠点を一掃すること
の出来た新規、有用な架橋ポリオレフイン押出成型品の
製造方法を提供することにある。<Object of the Invention> An object of the present invention is to provide a new and useful method for producing a crosslinked polyolefin extrusion molded product, which can eliminate the drawbacks of the prior art described above.
＜発明の要旨＞本発明の要旨は次の通りである。<Summary of the Invention> The gist of the present invention is as follows.
゛第１押出機のホツパ一からポリオレフインペレツトと
シロキサン縮合触媒を供給し、加熱溶融し、第２押出機
の樹脂供給部に圧入し、さらにその他のグラフト反応剤
は、第１押出機と第２押出機の接続部からある距離を有
して押出方向とは反対側の位置に設けられた第２押出機
のグラフト反応剤注入口から、注入ポンプを使用するこ
となく、第１押出機の押出速度＜第２押出機の押出速度
とすることによつてグラフト反応剤を定量的に計量し注
入する。゛The polyolefin impellets and siloxane condensation catalyst are supplied from the hopper of the first extruder, heated and melted, and then press-fitted into the resin supply section of the second extruder. From the grafting reagent inlet of the second extruder, which is located at a certain distance from the connection point of the two extruders and on the opposite side of the extrusion direction, the grafting agent of the first extruder is injected without using an injection pump. By setting the extrusion speed<the extrusion speed of the second extruder, the graft reactant is quantitatively measured and injected.
しかる後に第２押出機スクリユウ混練部によつて均一混
練し押出成型する架橋ポリオレフイン押出成型品の製造
方法である。In this method, the crosslinked polyolefin extrusion molded product is then uniformly kneaded in a screw kneading section of a second extruder and extrusion molded.
＜実施例＞ 添付図面を引用して本発明の一実施例を説明する。<Example> An embodiment of the present invention will be described with reference to the accompanying drawings.
第１押出機１のホツパ一９よりポリオレフインペレツト
とシロキサン縮合触媒を第１押出機内に供給する。Ｌ／
Ｄ＝２０〜２４、圧縮比２．５〜４のスローコンプレツ
シヨンタイプのスクリユウを使用し、ペレット内の水分
を充分に脱気すると共に、分散しにくい触媒を均一に混
練、分散させる。A polyolefin pellet and a siloxane condensation catalyst are fed into the first extruder from the hopper 9 of the first extruder 1. L/
Using a slow compression type screw with D=20 to 24 and a compression ratio of 2.5 to 4, the moisture in the pellets is sufficiently degassed, and the hard-to-disperse catalyst is uniformly kneaded and dispersed.
第１押出機１と第２押出機１０の接続は球面接※手２に
よつて接続され、第２押出機１０のホツパ一のセンター
から３Ｄ〜７Ｄ（４部相当長、Ｄは第２押出機の口径）
の位置に第１押出機内の溶融物を注入する。The first extruder 1 and the second extruder 10 are connected by a spherical surface*hand 2, and from the center of the hopper of the second extruder 10 to 3D to 7D (length equivalent to 4 parts, D is the second extruder machine caliber)
The melt in the first extruder is injected into the position.
第２押出機のホツパー上にはグラフト反応剤タンク５、
流量計４が設置されていると共に、第２押出機のスクリ
ユウ６の端末には液体シール装置３を設け、注入グラフ
ト反応剤の漏れを防止する。On the hopper of the second extruder is a graft reactant tank 5,
A flow meter 4 is installed, and a liquid sealing device 3 is installed at the end of the screw 6 of the second extruder to prevent leakage of the injected graft reactant.
グラフト反応剤の注入量の計量化は、第１押出機の押出
速度＜第２押出機の押出速度とし、その差の大小によつ
て微調節が可能である。第２押出機はその長さ方向に３
つのゾーンに区分されている。The amount of graft reactant to be injected can be finely adjusted by setting the extrusion speed of the first extruder<the extrusion speed of the second extruder, and depending on the magnitude of the difference. The second extruder has three
It is divided into two zones.
８部：供給ゾーン６ 〜１０Ｄ，０部：混練ゾーン４〜
６Ｄ，０部：計量化ゾーン８〜１２Ｄを有し、均一混練
と溶融ポリオレフインの計量化をおこなう。8 parts: Supply zone 6 ~ 10D, 0 parts: Kneading zone 4 ~
6D, 0 parts: It has metering zones 8 to 12D, and performs uniform kneading and metering of molten polyolefin.
しかるのち溶融ポリオレフインはブレーカープレート１
２を通つてクロスヘツド７より走行する導線Ｗの周上に
押出される。この押出線条体は、その後水分にさらされ
て架橋化される。押出機はサーモカツプル１１、ヒータ
ー８、温度調節計等によりある温度勾配をもつて温度コ
ントロールされる。Afterwards, the molten polyolefin is applied to the breaker plate 1.
2 and is pushed out onto the circumference of the conducting wire W running from the crosshead 7. This extruded filament is then exposed to moisture and crosslinked. The temperature of the extruder is controlled with a certain temperature gradient using a thermocouple 11, a heater 8, a temperature controller, etc.
＜実施例の補足説明＞
（１）第２押出機のスクリユ一のＬ ／ Ｄ ＝ ２６
〜３２、好ましくはＬ／Ｄ−２８〜３０が有効である。<Supplementary explanation of the examples> (1) L/D of the screw of the second extruder = 26
-32, preferably L/D-28-30 are effective.
混練ゾーンｏ部のスクリユウ形状はフルフライトスクリ
ユウで発生するような層流を発生させないような構造例
えばダルメージ混練装置（ダルメージ歯数１２〜３０枚
、進み角度１５゜〜３００）ダルメージ層は４Ｄ〜６Ｄ
）等が有効である。（２）第２押出機の温度勾配は、ポ
リエチレンを採用した場合には、次のようになる。The shape of the screw in the kneading zone o section is designed to avoid the laminar flow that occurs with full-flight screws, for example, a dalmage kneading device (number of dalmage teeth: 12 to 30, advance angle 15° to 300), and the dalmage layer is 4D to 300. 6D
) etc. are valid. (2) The temperature gradient of the second extruder is as follows when polyethylene is used.
この場合、第１押出機の温度勾配は、シリンダ部分１２
０℃、第２押出機との接続部付近１４０℃程度が適切で
ある。In this case, the temperature gradient of the first extruder is
Appropriate temperatures are 0°C and about 140°C near the connection with the second extruder.
＜別の実施例＞
第１押出機は所要押出量を決定し、第２押出機はグラフ
ト反応剤の計量と混練をおこなう。<Another Example> The first extruder determines the required extrusion rate, and the second extruder measures and kneads the grafting reactant.
従つて第２押出機ホツパー部の流量計の設定値からの大
小を検出し、第２押出機スクリユウ速度を自動コントロ
ールすることにより一定の注入をおこなう方法としても
よい。＜作用効果＞
本発明の作用効果を列挙する。Therefore, a method may be adopted in which a constant injection is carried out by detecting the magnitude of the set value of the flow meter in the hopper section of the second extruder and automatically controlling the screw speed of the second extruder. <Effects> The effects of the present invention are listed below.
（１）第１押出機内でポリオレフインペレツト中の水分
は十分脱気されると共にシロキサン縮合触媒を均一に分
散させることが可能である。(1) In the first extruder, the moisture in the polyolefin pellet is sufficiently degassed, and the siloxane condensation catalyst can be uniformly dispersed.
（２）第１押出機と第２押出機との押出速度を調節する
ことによつて生じた負圧の作用により、注入ポンプ無し
にグラフト反応剤を計量注入することができる。(2) Due to the effect of negative pressure created by adjusting the extrusion speed of the first extruder and the second extruder, the grafting reagent can be metered without an injection pump.
（３）また、第２押出機の８部はグラフト反応剤が反応
しない温度にコントロールすることができるので、Ｏ部
でグラフト反応剤を均一に混練し、Ｏ部に送込めるので
、架橋製品の外観悪化の原因となるヤケを発生しない。(3) In addition, since the temperature of the 8th part of the second extruder can be controlled to a temperature at which the graft reactant does not react, the graft reactant can be uniformly kneaded in the O part and sent to the O part, so that the crosslinked product can be Does not cause discoloration that causes deterioration of appearance.
（４）従来法の欠点を全て解消できた。(4) All the drawbacks of the conventional method were eliminated.
図は本発明の製造方法の一実施例に用いる装置構成の一
例を示す説明図である。
１：第１押出機、９：ホツパ一 １０：第２押出機、２
：球面接手、５：グラフト反応剤タンク、４：流量計、
６：第２押出機のスクリユウ、３：液体シール装置、１
２：プレーカープレート、７リクロスヘツド、Ｗ：導線
、１１：サーモカツプル、８：ヒータ一。The figure is an explanatory diagram showing an example of an apparatus configuration used in an embodiment of the manufacturing method of the present invention. 1: 1st extruder, 9: hopper 10: 2nd extruder, 2
: Spherical hand, 5: Grafting reactant tank, 4: Flow meter,
6: Screw of second extruder, 3: Liquid sealing device, 1
2: Preaker plate, 7 recross head, W: Conductor, 11: Thermocouple, 8: Heater.
Claims (1)
の押出機中を経て２台目の押出機中へ供給すると共に、
両押出機のスクリュウ回転数を調節することにより２台
目の押出機内を負圧状態としこの状態で２台目の押出機
内にグラフト反応剤を注入することを特徴とする架橋ポ
リオレフィン押出成型品の製造方法。1. Supplying the polyolefin resin and siloxane condensation catalyst through the first extruder and into the second extruder,
A cross-linked polyolefin extrusion molded product characterized in that the second extruder is brought into a negative pressure state by adjusting the screw rotation speed of both extruders, and a grafting reagent is injected into the second extruder in this state. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52103904A JPS5936860B2 (en) | 1977-08-30 | 1977-08-30 | Method for producing crosslinked polyolefin extrusion molded products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52103904A JPS5936860B2 (en) | 1977-08-30 | 1977-08-30 | Method for producing crosslinked polyolefin extrusion molded products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5437167A JPS5437167A (en) | 1979-03-19 |
| JPS5936860B2 true JPS5936860B2 (en) | 1984-09-06 |
Family
ID=14366403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP52103904A Expired JPS5936860B2 (en) | 1977-08-30 | 1977-08-30 | Method for producing crosslinked polyolefin extrusion molded products |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5936860B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7558407B2 (en) | 1994-11-28 | 2009-07-07 | Yt Acquisition Corporation | Tokenless electronic transaction system |
| US7565329B2 (en) | 2000-05-31 | 2009-07-21 | Yt Acquisition Corporation | Biometric financial transaction system and method |
| US7606401B2 (en) | 1994-11-28 | 2009-10-20 | Yt Acquisition Corporation | System and method for processing tokenless biometric electronic transmissions using an electronic rule module clearinghouse |
| US7698567B2 (en) | 1994-11-28 | 2010-04-13 | Yt Acquisition Corporation | System and method for tokenless biometric electronic scrip |
| US7882032B1 (en) | 1994-11-28 | 2011-02-01 | Open Invention Network, Llc | System and method for tokenless biometric authorization of electronic communications |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5460358A (en) * | 1977-10-20 | 1979-05-15 | Toshiba Machine Co Ltd | Twooaxis extruder for blending use |
-
1977
- 1977-08-30 JP JP52103904A patent/JPS5936860B2/en not_active Expired
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7558407B2 (en) | 1994-11-28 | 2009-07-07 | Yt Acquisition Corporation | Tokenless electronic transaction system |
| US7606401B2 (en) | 1994-11-28 | 2009-10-20 | Yt Acquisition Corporation | System and method for processing tokenless biometric electronic transmissions using an electronic rule module clearinghouse |
| US7613659B1 (en) | 1994-11-28 | 2009-11-03 | Yt Acquisition Corporation | System and method for processing tokenless biometric electronic transmissions using an electronic rule module clearinghouse |
| US7620605B2 (en) | 1994-11-28 | 2009-11-17 | Yt Acquisition Corporation | System and method for processing tokenless biometric electronic transmissions using an electronic rule module clearinghouse |
| US7698567B2 (en) | 1994-11-28 | 2010-04-13 | Yt Acquisition Corporation | System and method for tokenless biometric electronic scrip |
| US7882032B1 (en) | 1994-11-28 | 2011-02-01 | Open Invention Network, Llc | System and method for tokenless biometric authorization of electronic communications |
| US8260716B2 (en) | 1994-11-28 | 2012-09-04 | Open Invention Network, Llc | System and method for processing tokenless biometric electronic transmissions using an electronic rule module clearinghouse |
| US8831994B1 (en) | 1994-11-28 | 2014-09-09 | Open Invention Network, Llc | System and method for tokenless biometric authorization of electronic communications |
| US7565329B2 (en) | 2000-05-31 | 2009-07-21 | Yt Acquisition Corporation | Biometric financial transaction system and method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5437167A (en) | 1979-03-19 |
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