TW574717B - Positive temperature coefficient (PTC) element - Google Patents

Description

574717

574717 V. Description of the invention (2) The specific resistance of the electrode formed under 2 Ω * cmvx is at 20 ° C, i is based on the foregoing system, and the electrode is based on the above-mentioned present invention. Element, of which electrode is the ptc element of item 2 of the present invention. Patent application of the present invention: the ore nickel (Ni) layer is characterized by electrolytic nickel plating.) The layer is a PTC element of the third item of the present invention. Components, of which the PTC component of item 4 is based on the above-mentioned demineralized nickel ⑷) layer ;;: K (N1) layer and the upper layer of the electrical component; two: " the scope of profit No. 5 The m element of the term is characterized by the aforementioned .T ^ p \ Ni: p ^; ^ Nl} ^ ^ ^ M tt *% is too pm +1 and the nickel plating (N1) layer is characterized. The 6th PTC element of the patent scope of the element is characterized by the aforementioned .Bθ \ electroless nickel (H) layer. Element, " ΐr: The PTC element of item 7 of the patent scope is based on the above-mentioned Shizhi Mine Record (Nl) layer is a graphite dispersed electrolytic ore nickel (Nι) layer containing dispersed graphite in the recording film As a feature. … The PTC element in the eighth item of the “Political Stone Element” is based on the foregoing, and the thickness of the middle electrode is 5 to 40 cores. ^ The implementation of Deng Ming is as follows: 2: ==: 二 ^ After careful research [Find out that 91043-TYKIIU.ptd is made from the matrix of hydrate and conductive filler, orally, day by day. Page 6 574717 V. Description of the invention (3) Nickel plating is formed on both sides of the conductive plate When the (N i) layer is used as the provided electrode, the amount of the reducing agent derived from the non-conductive P or B contained in the nickel-plated (N 1) coating is reduced, and the specific resistance at 20 ° C is 1 PTC elements that are stable below 2 Ω · cm and have sufficiently low specific resistance. The present invention will be described in detail below. The crystalline polymer used in the present invention is not particularly limited, and examples thereof include polymers such as polyethylene and polypropylene. Olefins, halogenated vinyl, or vinylidene polymers, and these modified substances, the use of crystalline polyolefins is preferred, high density polyethylene is particularly suitable. As for conductive fillers, Carbon black, graphite, carbon fiber, and metal particles or metal fibers such as nickel, copper, and silver. Mixing ratio of conductive polymer and conductive filler, for crystalline polymer: 20 to 80% by weight, preferably conductive filler: 80 to 20% by weight, for crystalline polymer: 3 to 70 Conductive filler: 70% to 30% by weight is preferred. When the crystalline polymer is less than 20% by weight, the strength of the conductive plate tends to weaken. If it exceeds 80% by weight, then It is difficult to obtain sufficient conductivity. After the crystalline polymer and conductive filler are mixed at a specified mixing ratio by dry blending or melt kneading, etc., the mixture is formed into a sheet or film. Next, the sheet or film is here The surface of the shaped compact is subjected to mechanical polishing such as sandblasting and / or etching treatment using a mixed solution of chromic acid and sulfuric acid to expose the conductive filler on the surface of the compact and apply plating thereto Nickel (N i) can be used to form an electrode, and the nickel (N i) plating layer can be formed by either electroless plating or electrolytic plating.

91043-TYK1IU. Ptd Page 7 574717 V. Description of the invention (4) Unplating, although hypophosphite is used, but hypophosphite is used:; for wind and / ammonia () ^, for mineral coating Medium; surrounded by ί ;; ===, if the person ^ P or B in the nickel-plated (Ni) coating becomes non-conductive because the specific resistance becomes larger and becomes less than 3, P or B is coated. When the room temperature is sufficiently low and the specific resistance of ρτ is stable and the electroless nickel with acid salt is the reducing agent, it is necessary to make the P in the secondary coating film less than 2% by weight. When the plating conditions are such that the electroless nickel (Nl) plating of the original agent is performed, it is necessary to always make B in the coating with boron hydride as the coating to be 2% by weight or less. For PTC elements with & conditions where the non-conductive material is not sufficiently low as the reducing agent for the coating when the plating bath is used for plating. G 'is stable and, as for electrolytic plating, a well-known nickel (Ni) bath such as a compound bath and a sulfamic acid bath can be applied. , W a 11) bath, gas gloss agent in these plating baths, half of the plating bath and twisted organic added can also be applied. "Plating and gloss plating are used to connect the PTC element to the electrical equipment." In order to reduce the contact resistance, if it is divided into points: a nickel-plated (Ni) layer to be used is used as nickel plating. The (Ni) layer is formed of graphite. The graphite with excellent electrical dispersion is dispersed in a point manner and the conductivity with the surface in contact with the plating layer is improved, which can reduce the contact resistance. As for the graphite that makes electrical contact between the two, any one of natural graphite or artificial graphite— ^, 50% of the finely pulverized graphite with a cumulative diameter of less than 10 mm in the coating film may be used. Finely pulverized graphite with a cumulative diameter below 5 // m is optimal. The average grain size of those who use 5 0 0 / 〇 # is 91043-TYKHU.ptd Page 8

574717

V. Description of the invention (5) Graphitized carbon mist with a degree of concentration around 0 · 1 " m is a centripetal agent diluted with a certain amount of water; stone: etc. After fine graphite is dispersed, it is added to the plating, Yeer 2 = graphite dispersant kneaded, it is appropriate to charge to about 0.5 ~ 10% by weight. ^. The blending amount of the dispersant is 100g / L for graphite. The addition amount is aw. The bonding liquid is adjusted to-the tube and other methods to make it healthy.吹入 介 #, 10% and 9% cycle rate, and it is advisable to set it in a frequently dispersed state. Such as :::: Stirring and other stirring methods to maintain a content ratio of 25% by weight. The dispersion state is well-preserved. It can be ink-dispersed or graphite-dispersed in the coating film. The management of the dispersion of this graphite is: two corners: plating can be performed, but bath or stone plating, nickel plating (Kawasaki line electrolytic bonding is more suitable. Electrolytic plating of the upper layer (Nn two lower layers) The electroless nickel (Ni) plating layer is timely, so that the formed two nickel plating layer can be used. In this case, the electroless deposits can be used in both layers, but only 2 weights! The amount of the non-thermoelectric substance of the spoon or B # may be set to the thickness of the chain (Nl) layer described in Λ is preferably 5 to 40 mm, and 15 to 25 mm to argue ... If the thickness of the landing layer is less than 5 V m, the high-electricity sheet is applied .: 、, Man Cheng lacks the voltage resistance, and the nickel-plated (N i) coating will be separated from the conductive layer by one degree. In addition, if the thickness of the plating layer exceeds 40 / ζιι, the 20C specific resistance of the object of the present invention is economical even if the thickness of the plating layer exceeds 40 / ζιι. The cost becomes unfavorable, so the upper limit is 40 " m. As described above, by controlling the thickness of the Ni-plated film or the hafnium-plated film 91043-TYKHU. Ptd

surface

Page 9 574717 V. The amount of non-conductive materials such as P or B enclosed in the description of the invention (6), can obtain a PTC device with a specific resistance of 20 ° C below 1 · 2 Ω · cm. f Shilong 丨 Examples are given below to explain the present invention in more detail. (Poor Example) In a plastic grinder (P 1 as tom i 1 1), 45% by weight of high-density polyethylene #melting point (melting point · 1 35 ° C, manufactured by Dow Chemical Co., Ltd.) and spherical 酴Acid resin is sintered at 1900 ° C to produce a granular slope with an average particle diameter of 1 5 // m. Glassy carbon black (GPC-30Η, manufactured by UNITIKA) has been 5% by weight at the kneading temperature. 15 (TC melt-kneading for 10 minutes. This kneaded material was formed into a sheet having a wall thickness of 0 mm to 3 mm by a hot press. From this sheet, a test piece with 1 Ocin in length and 8 cm in width was cut out. This test piece was etched in a mixed solution of chromic acid and lithosauric acid at 70 ° C, washed with water, and then immersed in a catalyst solution (W 〇 1 dmeta 1 Manufactured by the company: p] \ | p and) 1 50mL / L and hydrochloric acid 1 50mL / L in an aqueous solution for 10 minutes and washed with water. $ Immerse in a 50mL / L sulfuric acid solution for 3 minutes, and then wash with water again and touch ' Media treatment. In this way, various nickel-plated (Ni) layers were formed on both sides of the surface-activated test piece under the conditions shown, and 15 types of test phases were produced; A ~ shown in Table 1 E The composition of various bond nickel (Ni baths is as follows. When forming a plating film that is only electrolytically plated, strike plating is applied under the conditions listed in Table 1 below.) The degree of plating is shown as the change in the immersion time or the energization time. The upper layer of Zhou, Jinyou 574717 V. The conditions shown in (7) of the invention make a plating film. In the obtained plating film, The contents of P and B are obtained by fluorescent X-rays. The plating film is obtained by measuring the weight before and after plating [A 1: electroless plating bath]

35 g / L 5 g / L 15 g / L Nickel sulfate Sodium underfill Sodium citrate [A 2: Electroless plating bath]

25 g / L 10 g / L 30 g / L Nickel Sulfate Sodium Hypophosphate Sodium Gluconate [B 1: Electroless plating bath]

Nibol〇n-5M (made by world metal company): 200mL / L Nibol〇n-5B (made by world metal company): 70mL / L

[B2: Electroless plating bath] Nickel sulfate, sodium succinate, boric acid, ammonium chloride

3 0 g / L 55 g / L 30 g / L 30 g / L 2 g / L

91043-TYKHU.ptd p. 11 574717

91043-TYK1IU. Pld Page 12 574717 V. Description of Invention (9)

Dispersant (sodium fumarate): 5 m L / L

Dentless agent (sodium lauryl sulfate): 2 m L / L Yan 1 material number nickel (Ni) plating beryllium) V (degrees (β m) coated with A (P, · B or imc)) ί 丨 丨 1: (丨%) Μ points h * Up Μ species: bath temperature (° C) vii flow density (A / dm2) plating bath bath temperature (° C) VII flow density (A / dm2) 1 A1 85 5 P: 1.5 The present invention 2 A1 85 25 P: 1.5 The present invention 3 A1 85 3 P: 1.5 The present invention 4 A2 90 25 P: 2.2 Comparative example 5 B1 60 16 B: 0.1 The present invention 6 B2 60 17 Β: 1.8 The present invention 7 B3 60 25 Β: 2.1 Comparative Example 8 C 95 15 The present invention 9 D 55 0.5 D 55 5 5 Wood invention 10 D 55 0.5 D 55 5 25 The invention 11 D 55 0.5 D 55 5 3 This Invention 12 E 55 1 E 55 20 25 C: 3.0 Invention 13 A1 85 D 55 5 25 P: 1.5 Invention 14 A1 85 — E 55 20 25 P: 1.5 C: 3.0 Invention

91043-TYKI1U. Ptd page 13 V. Description of the invention (10) The PTC element obtained by the above method. After measuring this PTC element, a disc with a diameter of 15 mm was punched out and the specific resistance (p: Ω · M) was made. The resistance is calculated by the following formula: P · A / t

PTC

In the formula, ·, each symbol indicates the resistance value of the ptc element (Ω)-the area of the J electrode of the ptc element (⑽2), the number of pulses, the thickness of the cow (㈤ is the electrical check when a high voltage is applied to the PTC element ,, The durability of the coating was tested with a withstand voltage. The withstand voltage test was performed after applying 50V and 50A to the PTC element and holding it for 10 minutes. The change in the nickel (Ni) coating was observed and it was judged that there was swelling and peeling on the coating. As a bad film, there is very little swelling to a practically non-problematic degree, and the phenomenon of peeling is considered to be good, and the film is swollen, and no peeling is considered to be superior. Measurement results of specific resistance and withstand voltage test The results are shown in Table 2.

91043-TYKHU.ptd Page 14 574717 V. Description of the invention (π) ^ 2, sample number than attached (Ω · cm) 丨 order rtiM sex distinction 1 1.1 Excellent invention 2 1.1 Excellent invention 3 1.1 Excellent wood hair叨 4 2.2 悛 Comparative example 5 1.1 Excellent present invention 6 1.2 Excellent present invention 7 2.0 Excellent comparative example 8 1.0 Excellent present hair 9 0.9 Excellent present invention 10 0.9 Excellent present hair 11 0.9 Excellent present 12 0.9 Excellent present 13 1.0 The present invention 14 1.0 The present invention 91043-TYKHU.ptd Page 15 574717 V. Description of the invention U2) As can be seen from Table 2, the amount of P or B in the nickel-plated (N i) coating used as an electrode is 2 PTC elements with a weight percentage of less than 1% represent extremely low specific resistance values. In addition, it was found that the PTC element having the thickness of the mineral coating was greater than that in terms of t-voltage characteristics.

91043-TYKI1U. Ptd Page 16 ^ Shang Gu 襕 Filled by the Bureau) Chinese Patent Specification for Positive Temperature Coefficient (> TC) Element One 574717 Inventor (4 people in total) Invention Name 2 Total English (fx) ιΜ) / Residence (Chinese) / Residence (English) Name or Name (Chinese)

POSITIVE TEM ^ KATURE COEFFICIENT (PTC) ELEMENT

1.ECHIG0 YOSHIAKI

1. Japanese JP 1. Japanese 23, Uji Sakura, Uji City, Kyoto Prefecture, Japan, and two public research institutes in the public limited company 1.23, Ujiosakura, Uji-shi, Kyoto JAPAN Research & Development Center of Unitika Ltd. 1. Steel Sheet Industry Co., Ltd. 2. Toyo Steel Sheet Co., Ltd. 1. Κ0ΗΑΝ KOGYO CO., LTD 2. T0Y0 KOHAN CO., LTD. · Name or name (English)

1. Japan JP 2. Japan JP Office, resident residence in the camp: 4 9 13 Machii Panyu Shisi-ku, Shimomatsu, Shimochi Prefecture, Tokyo Metropolitan City, Japan and the Republic of Japan} Those who are not in the same phase, please apply to the Bureau Guigui moved forward with the address book C κί \ Resident Residence & Estate (Central) 2.1394, Nishitoyoi, Kudamatsu-shi, Yamaguchi, JAPAN Co., LTD.

1.2-12, Yonbancho, Chiyoda-ku, Tokyo, 102-8447 JAPAN 1. Iwasaki Mori 2. Tanabe Denichi

l.IWASAKI MAM0RU 2.ΤΑΝΑΒΕ HIR0KAZU

KOHAN KOGYO

H7-Qm / jrFYTr

Claims (1)

The electrode formed by Ni-p or Ni-b electroless nickel (Ni) plating and nickel (Ni) plating containing p or b in an amount of 2% by weight or less was 20%. The specific resistance of 〇 is 12Q • cm or less. -A positive temperature coefficient (PTC) element as described in item 1 of the patent application, where the electrode is electrolessly plated with nickel (Ni). • A positive temperature coefficient (pTC) element such as the one in the scope of patent application, where the electrode is electrolytically plated with nickel (Ni). · 4 · For example, the positive temperature coefficient (pTC) element of the scope of application for patent, in which the electrode is a two-layer nickel plating made of an electroless nickel (Ni) layer on the lower layer and an electrolytic nickel (Ni) layer on the upper layer. (Ni) layer. T ^ Γ w Patent 1 & around the positive temperature coefficient (PTC) element of item 3 or 4, the intermediate electrolytic nickel (Ni) plating layer is a graphite dispersion electrolytic plating containing dispersed graphite in the coating film Nickel (Ni) layer.