TW201219479A - Covering layer of lead-free PVC resin composition and wire, cable thereof - Google Patents

Abstract

A covering layer made of PVC composition containing lead less than 1000ppm is disclosed. The PVC composition includes (A) PVC resin, (B) CaCO3, (C) clay (D) Ca-Zn stabilizer, and (E) plasticizer.

Description

201219479 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to: a type _, particularly a package having a gas content of less than 〇〇 _ _ _ _ _ _ _ _ _ _ _ Deep,, and mouth [previous technology] The power of electricity (4) is related to people's 4 activities, especially under the gradual development, people must upgrade the power and technology wheel to meet the demand. And == also: Increased 'also makes the pipeline to exercise for many years, its importance since the use of electricity (4) 3, the use of polyethylene (PVC) original: - ΐ poly =:::, the high-voltage grade of heavy metal long-term use has caused environmental disputes, In particular, the fixative is used as a lead-safety stearate for the addition of a heat-reinforcing gas-gathering vinyl resin, or a divalent (tetra)-Wer salt, a bivalent bismuth bismuth dichloride; The agent has a point, so = 対 gas is excellent in heat resistance and sealing climate stability === for the long-term resistance characteristics of the second:::= that need to be used for a long time, the poison is fixed, and it belongs to the accumulation itself. Sexual metal female sputum' is the goal of development; 3/19 2012 19479 Mesh has been found in a variety of stabilizers that can be used to make cables, for example - "mixed metals using hydrotalcites and antimony trioxide, stabilizers, but the properties of S stabilizers are significantly lower in terms of long-term stability: In addition, due to the improvement of environmental awareness, the size of the product is limited by the specifications of the raw materials and products of the industry. Therefore, how to = meet the R〇HS directive with the wrong amount, and make the manufactured plastics have the characteristics of resistance to temperature and good physical properties, which is the primary purpose of the research and development personnel. The inventor of the door case has been carefully researched in view of the above-mentioned techniques in actual application, and has accumulated many years of experience in the practice of related production (four), and finally proposed that the design is reasonable and effective in improving the above problems. The object of the invention is to provide a coating layer comprising a polyvinyl chloride resin composition having a lead content of less than 100 pm to conform to the specifications of the r〇hs directive; and the (four) coating layer The wires and cables formed by the m body can be applied to a high temperature environment. The present invention provides a coating layer of a m-chloro-baked resin composition, which comprises a gas-containing ethylene tree having a mis-quantity of less than 1000, and a gas of the product H. The vinyl resin composition includes the following components: Component (A): Polyethylene resin; Component (8): Calcium carbonate; Component (c): calcined clay; Component (D): Ma Zinc stabilizer; Component (E): a plasticizer. The present invention also provides a wire structure comprising: at least a conductor; and 4/19 201219479 - an insulating layer coated on the material; wherein the insulating layer contains a polystyrene resin composition containing i_ppm. The gas gathering system: = group, the composition includes the following components: component (4): polyethylene resin; component '曰 carbon (four); component (C): burnt clay; component (9): mother zinc Sense and component (5): plasticizer. The invention further provides an electrical winding structure comprising: a plurality of wire structures comprising: at least a conductor; and - a coating layer covering the == the plurality of wire structures; wherein the insulation = Lit! The gas-bearing vinyl resin composition includes the following components: a component (A; a resin; a component (B): carbonic acid; a component (9): a dance stabilizer; and a component (8): a) =: a clay , private notice, the following two have the effect of profit: the invention uses! Bow zinc stability, j P system ^ vinyl resin thermal cracking 'and further mention; : layer, one cover two for reference and description, not used The present invention is limited to the following figure: [Embodiment] The present invention provides a gold-free L flat/layer which contains a composition of a coating of a composition of The coating can be applied to long-term high-temperature use (for example, ==. 5 5/19 201219479 C temperature $(iil ). The above-mentioned polyethylene alloy resin composition The materials include: site (A). Polyethylene resin, component (B): calcium carbonate (CaC〇3), (c): calcined clay (Clay), component (D): zinc stabilizer; And component (8): soil-poor i. The constituent materials of the polyethylene-based resin composition of the present invention do not contain a lead compound, so that the requirements of the R〇HS directive can be met. '下下洋,.' ^ The composition of the above-mentioned composition of the polyethylene-rich bismuth resin having a lead content of less than 1 〇〇〇卯 claw: μ component of the invention (A): polystyrene (pvc) resin, which is the main polymer' It is also possible to use ethylene ethylene and a soft vinyl polymer (also known as ethylene-vinyl acetate g copolymer, coffee café, EEA), and materials. Forming a graft-like material as the main polymer. 'And knife (B) · Calcium carbonate (CaC〇3), component (8): calcined clay y) and group knife (E). Plasticizer, add In the poly-ethylene main resin, the physical properties and electrical requirements (such as cns _, =:, CNS 2655) of the prepared coating layer are up to the national standard, and the control cost = fruit can be achieved. Where component (8): the amount of carbon dance added relative to the component (4)

The gas b-baked resin is divided into 1 part by weight, and is divided into 2 by a weight of about 5 to 100 by ^ 1 A. h. . The weight is equally divided, and it is more preferably about (10) by weight or the like. Component (C): Addition amount of calcined clay, phase gas, ethylene resin, 1GG weight, aliquot, Ming 5, 仏A, Juli inch knife, 0 5 to 30, etc., and equal to 5 to 25 weight. Equally divided into better, and then with 4 knives as the best 冉 冉 from about 1 〇 weight divided into more 6/19 201219479 component (E): the amount of plasticizer added phase vinyl resin 〇〇 weight equal parts, The polychlorinated chlorine of ' ', 71 ) is preferably equal to two weights of 2-3 to 7 〇, etc., and the plasticizer can be phthalic acid, dicarboxylic acid, diterpene, quinone, and hydrazine. Diisohydrazine (_), trimellitic acid di-benzene:

Si plastic t or more. Component (E): Adding two plasticizers: The coating is suitable for long-term high temperature applications.

Solution=2) The dicalcium zinc stabilizer can inhibit the thermal cracking of the polyvinyl chloride main resin, and the "peptide example" is a heat-resistant two-layer used in the coating of stearic acid and hardened at a high temperature; J = wide heat resistance, _ stabilizer can also contain ... another 6 SBM 1 CStear〇yl ben2〇yl, 嶋) 'to increase the heat resistance level to (four) or more, for example 3 ΓΓ Wei temperature. In the present invention, touch The amount of the stabilizer is added, and the weight of the gas-containing vinyl resin of the knife (Α) is equally divided into 10 parts by weight, and the weight is equally divided into 4 parts by weight, and 4 parts by weight is preferably divided into 4 parts by weight. It is more preferable. Pingyijia further includes the component (f) of the polyvinyl chloride resin composition of the present invention: an additive such as a flame retardant, a toner, etc., the amount of which is extracted for the component (A) J> ^Polyethylene vinyl resin 10 〇 weight aliquot, divided into about 2 to 3 weights, and the proposed composition containing less than the rigid group of polyvinyl chloride can be used to make The high temperature resistant cladding layer is applied to the insulating layer or the coating layer in the wire structure/cable structure. Please refer to Fig. 1 'which shows a wire structure丄〇 It includes a conductor 1 7/19 201219479 overlying the conductor; [the main unit 1 of the transmission power in the insulating layer 10 of 1 is a wire structure, as in the present embodiment, the material of the guide wire, etc., '冓 ❹ ❹ , , , , , , , , , , , , , , , 单 单 单 单 单 单 单 单 单 单 单 单 单 单 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体2 is the coating layer described above, so it can be referred to the foregoing and will not be described here.

Figure 2 shows a wire-lined Η-Α, I = and an insulating layer 2 coated on the conductor 21; conductor = transmission power in the wire structure 20 = guide: 21-series material, as in It is formed by a good conductive copper wire, and in the embodiment, the conductor 21 is a plurality of single wires, a circular biting wire, etc.; The structure may have a plurality of aspects, for example, including at least one conductor 2 Τ and FIG. 2 and FIG. 2 'wire structure 2 〇 9 , ' A 2 1 and insulating layer 2 ^ structure 2 包覆 coated with conductor 2 1 A wire containing less than 1GGGppm (or less error), which conforms to the R〇HS Directive and is applicable to the operating environment of D. 7 1 week for question/dish cover: 3 2:3: The clear structure 3 〇, which uses -1 to wrap two strands of wire structure 1 ,, wherein the wire structure 舜; </, can refer to the content of Figure 1, and in this embodiment, by n Μ / Or the insulating layer i 2 is the coating layer described above, so that the material of the covering layer 1 can make the material of the cable structure 3 符合 conform to the R 〇 ' and can be applied to high temperature conditions. 8/19 201219479 Please refer to 4 to 6, which respectively show a cable structure 40, 50, 60, which uses a coating layer 4 1 , 5 1 , 6 1 to form the two-, three-, and four-wire structure 2 shown in FIG. 0 is coated, wherein the description of the wire structure 20 can refer to FIG. 2, and in the specific embodiment, the cover layer 31 and/or the insulating layer 2 2 are as described above. The coating layer, so the material properties of the coating layer 3 1 can make the material of the cable structure 40, 50, 60 comply with the R〇HS directive, and can be applied to high temperature conditions. The following will explain the present invention by a specific experimental example. The lead content of the resulting cladding layer (ie, the insulating layer and the coating layer): numbered 彳 insulating layer 1 2 3 4 5 6 7 8 9 10 PVC 100 100 100 100 100 100 100 100 100 100 CaC〇3 10 20 40 60 80 10 20 40 60 80 Clay 5 10 15 20 25 5 10 15 20 25 60 ° C calcium zinc stabilizer 4 4.5 5 5.5 6 105 ° C calcium zinc stabilizer (SMB) — — 6 6.5 7 7.5 8 60 °C lead system stabilizer ---- ——————— — — ——————— 1〇5°C lead system stabilizer — — — DINP 30 35 45 40 35 — — — — — TOTM 10 20 30 35 45 50 60 Toner (RoHS compliant) Addition ratio: 0.01~2.6 (according to product hue requirements) RoHS Direct (Pb < 1000 ppm) nd (MDL.= 2 ppm) Money (Cd < 100 ppm) Mercury (Hg < 1000 ppm) Hexavalent Chromium (Cr6+<1000 ppm) Polybrominated Link (PBBs < 1000 ppm) nd (MDL.= 5 ppm) Polybrominated Diphenyl Ether (PBDEs < 1000 ppm)

Table 1 9/19 201219479 Table 1 shows the lead content test of the insulating layer made of the gas-gathered vinyl resin composition at various composition ratios. For example, in Experimental Example 1, the weight of the component (A) is divided into 100. The weight of component (B) is divided into 10; the weight of component (C) is divided into 5; the component (D) is 6 (TC calcium zinc stabilizer (without adding SMB), and its weight is divided into 4; component (E) is Diisononyl Phthalate (DINP), its weight is divided into 30; and according to the test results, the lead content is much smaller than the 1000 ppm specified in the RoHS Directive. Adding coating 11 12 13 14 15 16 PVC 100 100 100 100 100 100 CaC〇3 40 80 100 20 20 20 Clay 5 10 20 60°C calcium zinc stabilizer 4 5 6 105°C calcium zinc stabilizer (SMB) 6.5 7 7.5 60°C lead system stabilizer—————— 1〇5°C lead system stabilizer—————— DINP 40 50 65 30 TOTM 40 40 20 Toner (RoHS compliant) Adding ratio: 0.01~2.6( According to product hue requirements) RoHS Direct Lead (Pb < 1000 ppm) nd (MDL. = 2 ppm) Money (Cd < 100 ppm) Mercury (Hg < 1000 ppm) Hexavalent chromium (Cr6+<1000 ppm) Polybrominated stupid (PBBs < 1000 ppm) nd (MDL.= 5 ppm) Polybrominated diphenyl ethers (PBDEs < 1000 ppm) Table 2 10/19 201219479 Table 2 shows various The test for the error amount of the coating layer made of the polyvinyl chloride resin composition at the composition ratio, for example, in Experimental Example 16, the weight of the component (A) is divided into 100; the weight of the component (B) is divided into equal parts. 20; component (C) weight is divided into 20; component (D) is 105 ° C calcium zinc stabilizer (added SMB), its weight is equal to 7.5; component (E) is 30 weight An aliquot of diisononyl phthalate with 20 weight aliquots of trioctyl triacetate; and according to the test results, the lead content is much less than the 10,000 ppm of the RoHS standard. A preferred embodiment of the invention is compared to a conventional PVC coating with a lead-containing stabilizer.

Additives Preferred Embodiment (Lead-free PVC) Comparative Example (Lead-based PVC) 1 2 1 2 PVC 100 100 100 100 CaC〇3 80 80 80 80 Clay 10 10 10 10 Calcium stabilizer 4 4 Lead-based stabilizer 4 4 Lubricant 0.5 0.5 0.5 0.5 DINP 50 50 TOTM 50 50 RoHS Directive^(Pb < 1000 ppm) nd (MDL= 2 ppm) nd (MDL.= 2 ppm) Approx. 10,000 Approx. 10,000 lli (Cd < 100 ppm) nd (MDL_= 2 ppm) nd (MDL= 2 ppm) Mercury (Hg < 1000 ppm) 11/19 201219479 Hexavalent chromium (Cr6+ <1000 ppm) Polybrominated biphenyls (PBBs < 1000 ppm) Polybrominated diphenyl ethers (PBDEs < 1000 Pd) nd (MDL= 5 PPm) nd (MDL= 5 ppm) nd (MDL .= 5 ppm) nd (MDL.= 5 ppm) Table 3 According to the experimental results in Table 3, Comparative Examples 1 and 2 were added with lead system. The stabilizer, which contains a coating containing about 0.001 ppm of the wrong amount, does not comply with the RoHS directive. On the contrary, the error amount of the preferred embodiments 1 and 2 of the present invention is much smaller than the 10,000 ppm specified in the RoHS Directive. In addition, please refer to FIG. 7 , which shows the comparison of the aging test of the lead-free polyvinyl chloride resin composition of the present invention with the conventional miscible polyvinyl chloride resin composition, as shown in the figure, the aging performance comparison according to CNS 679 test. As a result, the lead-free polyvinyl chloride-based resin composition of the present invention is superior to the general lead-based polyvinyl chloride-based resin composition, and shows that the quality of the electric wire and cable of the lead-free-based resin composition of the present invention has better high-temperature reliability. . The table below shows the results of testing the physical/electrical properties of the preferred embodiment of the present invention with a PVC coating of a conventional lead-containing stabilizer. Project ship-free PVC resin composition heat-resistant grade heat-resistant 60 ° c heat-resistant 90 ° C heat-resistant 1 〇 5 ° C insulation material covering insulation material coating insulation material coating 1. Physical properties 1.1. Normal temperature tensile strength kgf / mm2 1.4 1.4 1.5 1.5 1.7 1.7 1.2. Elongation at room temperature % 150 150 200 200 200 200 1.3. Tensile strength after aging % 88 88 90 90 90 85 1.4. Elongation after aging % 85 85 85 85 85 80 12/19 201219479 1.5. Tensile strength after oil resistance% 80 80 85 80 85 85 ' 1.6. Elongation after oil resistance % 60 60 85 60 85 85 2. Electrical properties 2.1. Volume resistance Ω-cm 4.0 E14 5.0 E13 5.0 E14 5.0 E13 5.0 E14 5.0 E13 Table 4 Item Lead-based PVC resin composition Heat-resistant grade heat-resistant 60 °C Heat-resistant 90 °C Heat-resistant 1〇5 °C Insulation material coating Insulation material coating Insulation material coating 1. Physical properties 1.1. Normal temperature tensile strength kgf/mm2 1.4 1.4 1.5 1.5 1.8 1.8 1.2. Normal temperature elongation % 150 150 200 200 200 200 1.3. Tensile strength after aging % 85 85 85 85 85 80 1.4. Elongation after aging % 80 80 80 80 80 75 1.5. Tensile strength residual rate after oil resistance 80 80 85 80 85 85 1.6. Elongation at oil resistance % 60 60 85 60 85 85 2. Electrical properties 2.1. Volume resistance Ω-cm 3.0 E14 5.0 E13 3.0 E14 5.0 E13 3.0 E14 5.0 E13

Table 4 bis Note 1. Aging test conditions: heat resistance 60 ° C: l 〇〇 ° C / 48 h, heat resistance 90. (:: 12 Γ (: / 168 h, heat resistance 105 ° C: 136 ° C / 168 h. Note 2. Oil resistance test conditions: 70 ° C / 4 h. Note 3. The data in the table are all minimum. According to Table IV In the case of the aging test results, the lead-free polyvinyl chloride-based resin composition of the present invention is superior to the general lead-based polyvinyl chloride-based resin composition; similarly, in terms of electrical characteristics, the present invention The lead-free polyvinyl chloride-based resin composition is superior to the general lead-based polystyrene-based resin composition. In summary, the present invention has the following advantages: 1. The lead-free polyvinyl chloride plastic of the present invention is a calcium-zinc stabilizer. Inhibition of polystyrene B 13/19 201219479 olefin resin thermal cracking 'According to the experimental results? Plastics have better heat resistance, can meet the heat resistance = 鬲 temperature operation. 2: The second invention of the error-free polyethylene alloy resin composition can be Long-term use in the temperature range of 60 to 105t: February added various raw materials such as dance zinc stabilizer, carbonic acid, calcined: soil, flame retardant, plasticizer, toner, etc., are not containing the original :Materials made of plastic, such as cladding, insulation, : The lead content of the layer is less than the 1000 ppm specified in the HSR Directive. The above description is only a preferred and feasible method of the present invention, and is not limited to the scope of the patent, so the specification of the present invention is used. And the equivalent technical changes of the contents of the drawings are included in the scope of the present invention. [Simplified Schematic] FIG. 1 is a wire structure according to a first embodiment of the present invention. FIG. 2 is a second embodiment of the present invention. Fig. 3 is a cable structure according to a first embodiment of the present invention. Fig. 4 is a cable structure according to a second embodiment of the present invention. Fig. 5 is a cable structure according to a third embodiment of the present invention. The cable structure of the fourth embodiment of the present invention is shown in Fig. 7. Fig. 7 is a graph showing the aging test of the present invention and the conventional PVC plastic. Wire structure [Signature of main components] 1 〇, 2 〇14/19 201219479 1 1, 2 1 Conductor 1 2 ' 2 2 Insulation layer 30, 40, 50, 60 Cable structure 3 1 , 4 1 , 5 1 , 6 1 Coating

15/19

Claims (1)

201219479 七1 A patent scope - a kind of material without m material and resin composition, the right one is a coffee, 1 is covered with a layer of loyalty: 000 ppm of gas-rich vinyl resin 祉 component (Α) group Fraction (Β) Component (C) Polyethylene Ethylene Resin; Calcium Carbonate; Calcined Clay; Composition, the polychloroethylene-resin composition includes the following main components of the October f f ::: each, μ. " . ' 73 ', and knife (D). Zinc stabilizer; and component (Ε): plasticizer. 2'It please cover the coating of the gas-free vinyl resin composition described in item 1 of the patent scope. 'The zinc stabilizer of the component (D) is any one or more of calcium stearate and zinc stearate. 3. 3. The chloroform-free resin composition as described in Item 2 (4) The coating layer, wherein the component (D) of the mother's repellent further comprises a melting point of 56 to 65. 硬 硬 硬 醯 醯 醯 。 。 4 4 4 4 4 4 4 4 4 4 4 4 4 4 a coating layer of the (4) resin composition, wherein the plasticizer of the component (8) is o-p-dicarboxylic acid: isodecyl ester diisodecyl phthalate, trimellitic acid Any one or more of an octyl ester and a polymer plasticizer. 3. A coating layer of a shipless polyvinyl chloride-resin composition according to the fourth aspect of the invention, wherein the polyvinyl chloride resin composition is further The coating layer of the lead-free polystyrene-based resin composition according to claim 5, wherein the polyvinyl chloride-based resin composition is relative to the component ( A) Polyethylene vinyl resin 等 aliquot, containing 16/19 201219479 5 to 100 parts by weight of component (B): calcium carbonate, 5 to 3 〇 by weight aliquot (C): calcined Clay, component of 1-2 parts by weight (D): calcium zinc stabilizer, component of 3 〇 to 7 〇 by weight (E): plasticizer, and group of 0.2 to 3.0 weight aliquot Sub-(F): an additive. 7. A wire structure comprising: at least one conductor; and an insulating layer coated on the conductor; wherein the insulating layer comprises a polystyrene resin composition having a lead content of less than 1000 Ppm The polystyrene resin composition comprises the following components: component (A): polystyrene resin; component (B): Acid|bow; component (C): calcined clay; component (D): zinc-dabilizing agent; and component (E): plasticizer. 8. The wire structure according to claim 7, wherein The calcium zinc stabilizer of the component (D) is any one of calcium stearate and zinc stearate, and the simple stabilizer of the component (9) further comprises a hard fat phenyl hydrazine having a bright point of 56 to 65C. 9. The electric wire structure according to claim 8, wherein the polyvinyl chloride resin composition further comprises a component (F): an additive, and the polystyrene resin composition is relatively 100 parts by weight of the polystyrene resin of component (A), containing 5 to 1 〇〇 by weight of the component (B-Guang-calcium carbonate, 5 to 30 parts by weight of component (c): calcined & Clay, 2 to 10 parts by weight and divided into (D): Calcium stabilizer, component of Sichuan to 70 parts by weight (E): plasticizer, and 〇·2 to 3.0 weight 17/19 201219479 quantity, etc. Sub-component (F): Add Μ. 10, an electric winding structure, comprising: a multi-strand wire structure 'each wire structure comprises: at least one conductor; and an insulating layer covering the conductor; and a coating layer coated on the multi-strand wire structure; Wherein, the insulating layer and the § hai coating layer each comprise a gas-containing ethylene ruthenium resin composition containing gold, I Μ 1 ΛΛΛ / ^ 3 blunt and less than 10 (8) Ppm, and the composition of the reduction __ is also divided into the following: Component (A). Polyvinyl chloride resin; Component (B): Carbonic acid | Bow; Component (C): Calcined clay; Group knife (D). Stationary stabilizer; and Component (E): Plasticizer . The electric winding structure of claim 1, wherein the component (D) is any one or more of calcium stearate and zinc stearate, and the component The calcium zinc stabilizer of (D) further comprises stearin benzamidine methane having a melting point of 56 to 65 °C. 1. The cable structure according to claim 11, wherein the polyvinyl chloride resin composition further comprises a component (F): an additive, and the polyvinyl chloride resin composition is relative to Polyethylene resin of component (A) 100 parts by weight 'component containing 5 to 1 〇〇 by weight (B) __ calcium carbonate, 5 to 30 parts by weight of component (c): calcined clay 2 to 10 parts by weight of the component (D): calcium zinc stabilizer "30 to 70 parts by weight of the component (E) · plasticizer, and 〇. 2 18/19 201219479 to 3.0 weight equal parts Component (F): additive. 19/19