CN110982119A - Use of triazole compound as thermoplastic resin material additive for low-voltage electric appliance shell - Google Patents
Use of triazole compound as thermoplastic resin material additive for low-voltage electric appliance shell Download PDFInfo
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- CN110982119A CN110982119A CN201911323183.XA CN201911323183A CN110982119A CN 110982119 A CN110982119 A CN 110982119A CN 201911323183 A CN201911323183 A CN 201911323183A CN 110982119 A CN110982119 A CN 110982119A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
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- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention discloses application of a triazole compound as an additive of a thermoplastic resin material for a low-voltage electric appliance shell, and particularly relates to the triazole compound added when the thermoplastic resin material for the low-voltage electric appliance shell is prepared. The triazole compound is used as the additive of the thermoplastic resin material for the low-voltage apparatus shell, so that the surface of the low-voltage apparatus shell can be effectively prevented from generating pits, and the problem that the surface of the low-voltage apparatus shell is easy to generate pits is effectively solved.
Description
Technical Field
The invention relates to the technical field of modified engineering plastics, in particular to application of a triazole compound as an additive of a thermoplastic resin material for a low-voltage electrical apparatus shell.
Background
The plastic shell made of the modified engineering plastic is widely applied to the industry of low-voltage electrical appliances, such as a shell of a circuit breaker, because various electronic components assembled inside the circuit breaker are mostly metal parts (copper coils and copper wires), welding can be used in the assembly process of the circuit breaker, in order to ensure the welding firmness, welding-aid phosphorus copper powder is usually introduced in the welding process, and in addition, the welding and the assembly processes are basically manual operation, so that tiny copper powder cannot be prevented from falling or being adhered to the surface of the plastic shell in the assembly process.
In addition, the assembled circuit breaker is mostly stored in kraft paper (corrugated paper) packing boxes, and then one box of circuit breaker is orderly stacked in a large kraft paper box and sealed and stored in a warehouse. Kraft paper is manufactured by adopting sulfate softwood pulp as a raw material through the working procedures of papermaking forming, water pressing, drying in a drying cylinder, press polishing and the like, sodium hydroxide and sodium sulfide are added in the manufacturing process to steam and boil slurry, partial active sulfides (such as hydrogen sulfide, sodium sulfide and the like) can be remained in the kraft paper due to incomplete desizing in the manufacturing process, and copper powder on the surface of a plastic shell can chemically react with the active sulfides in the storage process, so that pits with different depths are formed on the part, to which the copper powder is adhered, of the surface of the plastic shell, and the appearance and the service performance of a product are influenced.
Disclosure of Invention
The invention provides an application of a triazole compound as an additive of a thermoplastic resin material for a low-voltage apparatus shell, aiming at solving the problem that pockmarks with different depths are easy to appear on the surface of the low-voltage apparatus shell in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme: the application of the triazole compound as an additive of a thermoplastic resin material for a low-voltage electric appliance shell and the application of the triazole compound as an additive for preventing pockmarks on the surface of the low-voltage electric appliance shell in preparing the thermoplastic resin material for the low-voltage electric appliance shell. The triazole compound belongs to organic heterocyclic compounds, is generally used as a sterilization component in a bactericide for plant fungal diseases, has the common characteristic of containing a hydroxyl (ketone group), a substituted phenyl group and a1, 2, 4-triazole group compound on a main chain in chemical structure, and the inventor finds that the triazole compound is used as an additive of a thermoplastic resin material for a low-voltage electric appliance shell, and the triazole compound is added when the thermoplastic resin material for the low-voltage electric appliance shell is prepared, so that pockmarks on the surface of the low-voltage electric appliance shell can be effectively avoided, and the excellent pockmark prevention effect is achieved.
Preferably, the raw materials of the thermoplastic resin material for the low-voltage electric appliance shell at least comprise the following components in parts by weight: 40-70 parts of thermoplastic resin and 0.2-1 part of triazole compound.
Preferably, the thermoplastic resin material for the low-voltage electrical appliance shell further comprises 7-30 parts of a flame retardant and 20-40 parts of a reinforcing filler by weight. In the actual production, other conventional auxiliary agents in the field, such as toughening agents, lubricants, antioxidants, coloring agents, flow improvers, heat stabilizers, light stabilizers, ester exchangers, marking agents, nucleating agents and the like, can be added into the formula according to the performance requirements of the thermoplastic resin material for the low-voltage electric appliance shell.
Preferably, the thermoplastic resin is one or more of polyamide, polycarbonate, polyethylene terephthalate and polybutylene terephthalate.
Preferably, the thermoplastic resin is polyamide, and the polyamide is one or more of PA6, PA66, PA56, PA1010 and PA 610.
Preferably, the triazole compound is one or more of triadimefon, triadimenol, diniconazole, tebuconazole, hexaconazole, propiconazole, triflumizole, cyproconazole, flusilazole, difenoconazole and tetraconazole.
Preferably, the flame retardant is one or more of a nitrogen flame retardant, a phosphorus flame retardant and a bromine flame retardant.
Preferably, the flame retardant is a nitrogen flame retardant, and the nitrogen flame retardant is melamine cyanurate or melamine polyphosphate.
Preferably, the reinforcing filler is a fibrous filler and/or an inorganic mineral powder.
Preferably, the fiber filler is one or more of glass fiber, basalt fiber and potassium titanate fiber; the inorganic mineral powder is one or more of talcum powder, wollastonite, mica, calcium carbonate, attapulgite, montmorillonite, zeolite and kaolin.
The thermoplastic resin material for the low-voltage electric appliance shell is prepared by the following method: the method comprises the steps of uniformly mixing the raw materials of the components weighed according to the weight ratio in a high-speed mixing pot, feeding the materials from a main feeding port of a double-screw extruder, carrying out melt extrusion by the double-screw extruder, cooling, drying and granulating to obtain the thermoplastic resin material for the shell of the low-voltage apparatus, wherein the working temperature of the double-screw extruder is 200-230 ℃ in a feeding section, the temperature of a melt plasticizing section is 230-280 ℃, the temperature of a mixing and homogenizing section is 200-260 ℃, the temperature of a melt conveying section is 230-280 ℃, the residence time is 0.5-1 minute, and the rotating speed of a main engine of the double-screw extruder.
Therefore, the invention has the following beneficial effects: the triazole compound is used as the additive of the thermoplastic resin material for the low-voltage apparatus shell, and the triazole compound is added when the thermoplastic resin material for the low-voltage apparatus shell is prepared, so that the pits on the surface of the low-voltage apparatus shell can be effectively avoided, and the problem that the pits are easily generated on the surface of the low-voltage apparatus shell is effectively solved.
Drawings
Fig. 1 is a surface view of a breaker case made of a thermoplastic resin material for a low-voltage device case in example 1, which was subjected to a copper-carrying pock test.
Fig. 2 is a surface view of a breaker case made of the thermoplastic resin material for a low-voltage device case in comparative example 1, after the copper-carrying pockmark test result.
Fig. 3 is a surface view of the breaker case made of the thermoplastic resin material for the low-voltage device case of example 2, which was subjected to the copper-carrying pock test.
Fig. 4 is a surface view of a breaker case made of a thermoplastic resin material for a low-voltage device case in comparative example 2 after a copper-carrying pockmark acceleration test.
Fig. 5 is a surface view of the breaker case made of the thermoplastic resin material for the low-voltage device case in example 3 after the copper-carrying pockmark acceleration test.
Fig. 6 is a surface view of a breaker case made of a thermoplastic resin material for a low-voltage device case in comparative example 3, which was subjected to a copper-carrying pockmark acceleration test.
Fig. 7 is a surface view of the breaker case made of the thermoplastic resin material for the low-voltage device case of example 4 after the copper-carrying pockmark acceleration test.
Fig. 8 is a surface view of a breaker case made of a thermoplastic resin material for a low-voltage device case in comparative example 4 after a copper-carrying pockmark acceleration test.
Fig. 9 is a surface view of the breaker case made of the thermoplastic resin material for the low-voltage device case of example 5 after the copper-carrying pockmark acceleration test.
Fig. 10 is a surface view of a breaker case made of a thermoplastic resin material for a low-voltage device case in comparative example 5 after a copper-carrying pockmark acceleration test.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
In the following examples and comparative examples, the concrete steps of the copper-loaded pockmark acceleration test are as follows:
(1) adding 5% NaCl solution into phosphorus-copper powder (soldering flux) to obtain phosphorus-copper powder dispersion liquid, wherein the concentration of the phosphorus-copper powder in the phosphorus-copper powder dispersion liquid is 0.2g/10 ml;
(2) uniformly coating the phosphorus-copper powder dispersion liquid on the outer surface of the circuit breaker plastic shell, and observing by adopting a metallographic microscope to confirm that copper powder is loaded on the surface of the circuit breaker plastic shell;
(3) the low-voltage electrical appliance with copper powder loaded on the surface is molded and arranged in a kraft paper box, the kraft paper box is placed in a high-low temperature damp-heat test box for 120 hours (the parameters of the test box are that the temperature is 85 ℃ and the relative humidity is 85 percent), and the kraft paper box is taken out and wiped to observe the surface condition of the shell.
Example 1
Weighing 70kg of thermoplastic resin (PA 6) and 1kg of triazole compound (0.5 kg of triadimenol and 0.5kg of diniconazole) according to the weight ratio, uniformly mixing the raw materials through a high-speed mixing pot, feeding the raw materials from a main feeding port of a double-screw extruder, carrying out melt extrusion through the double-screw extruder, cooling, drying and granulating to obtain the thermoplastic resin material for the low-voltage electric appliance shell, wherein the working temperature of the double-screw extruder is 200 ℃ in a feeding section, 230 ℃ in a melt plasticizing section, 200 ℃ in a mixing and homogenizing section, 230 ℃ in a melt conveying section, the retention time is 0.5 minute, and the main machine rotating speed of the double-screw extruder is 280 rpm.
Comparative example 1
Comparative example 1 compared with example 1, the triazole compound is not added, and the rest is completely the same as example 1.
The thermoplastic resin materials for the low-voltage apparatus casings obtained in example 1 and comparative example 1 were respectively prepared into the breaker casings, and then copper-loaded pockmark tests were respectively performed to observe the generation of pockmarks on the casing surfaces, and the surface conditions of the breaker plastic casings at this time were respectively shown in fig. 1 and fig. 2.
Example 2
Weighing raw materials according to the weight ratio of 55kg of thermoplastic resin (45 kg of PA6+10kg of PA 66), 12kg of flame retardant (melamine cyanurate), 32kg of reinforcing filler (12 kg of glass fiber +20kg of wollastonite) and 0.5kg of triazole compound (tebuconazole), uniformly mixing the raw materials through a high-speed mixing pot, feeding the raw materials from a main feeding port of a double-screw extruder, carrying out melt extrusion through the double-screw extruder, cooling, drying and granulating to obtain the thermoplastic resin material for the low-voltage electric appliance shell, wherein the working temperature of the double-screw extruder is 220 ℃, the temperature of a melt homogenizing section is 240 ℃, the temperature of a mixing section is 220 ℃, the temperature of a melt conveying section is 250 ℃, the residence time is 0.6 min, and the main machine rotating speed of the double-screw extruder is 300 rpm.
Comparative example 2
Comparative example 2 is identical to example 2 except that no triazole-based compound is added, and the procedure is identical to example 2.
The thermoplastic resin materials for the low-voltage apparatus casings obtained in example 2 and comparative example 2 were respectively prepared into the breaker casings, and then copper-loaded pockmark tests were respectively performed to observe the generation of pockmarks on the casing surfaces, and the surface conditions of the breaker plastic casings at this time were respectively shown in fig. 3 and 4.
Example 3
Weighing the raw materials according to the weight ratio of 40kg of thermoplastic resin (10 kgPA56+15kgPA1010+15kgPA 610), 7kg of flame retardant (red phosphorus master batch), 20kg of reinforcing filler (talcum powder), 0.2kg of triazole compound (propiconazole) and 0.5kg of lubricant (pentaerythrite stearate), uniformly mixing the raw materials through a high-speed mixing pot, feeding the raw materials from a main feeding port of a double-screw extruder, performing melt extrusion through the double-screw extruder, cooling, drying and granulating to obtain the thermoplastic resin material for the low-voltage apparatus shell, wherein the working temperature of the double-screw extrusion is 230 ℃, the temperature of a melt plasticizing section is 280 ℃, the temperature of a mixing homogenizing section is 260 ℃, the melt conveying section is 280 ℃, the residence time is 1 minute, and the main machine rotating speed of the double-screw extruder is 350 rpm.
Comparative example 3
Comparative example 3 is identical to example 3 except that no triazole-based compound is added, and the procedure is identical to example 3.
The thermoplastic resin materials for the low-voltage apparatus casings obtained in example 3 and comparative example 3 were respectively prepared into the breaker casings, and then copper-loaded pockmark tests were respectively performed to observe the generation of pockmarks on the casing surfaces, and the surface conditions of the breaker plastic casings at this time were respectively shown in fig. 5 and 6.
Example 4
Weighing the raw materials according to the weight ratio of 53kg of thermoplastic resin (PA 66), 14kg of flame retardant (decabromodiphenylethane), 30kg of reinforcing filler (glass fiber), 0.5kg of triazole compound (hydroxyconazole), 3kg of lubricant (ethylene bis stearamide) and 0.1kg of antioxidant (Pasteur IRGANOX 1010), uniformly mixing the raw materials through a high-speed mixing pot, feeding the raw materials from a main feeding port of a double-screw extruder, performing melt extrusion through the double-screw extruder, cooling, drying and granulating to obtain the thermoplastic resin material for the low-voltage apparatus shell, wherein the working temperature of the double-screw extrusion is 220 ℃, the temperature of a melt plasticizing section is 260 ℃, the temperature of a mixing homogenizing section is 260 ℃, the temperature of a melt conveying section is 230 ℃, the residence time of the double-screw extruder is 1 minute, and the main machine rotating speed of the double-screw extruder is 300 rpm.
Comparative example 4
Comparative example 4 is identical to example 4 except that no triazole-based compound is added, and the procedure is identical to example 4.
The thermoplastic resin materials for low-voltage apparatus casings obtained in example 4 and comparative example 4 were respectively prepared into breaker casings, copper-loaded pockmark tests were respectively performed, and the occurrence of pockmarks on the casing surface was observed, and the surface conditions of the breaker plastic casings at this time were respectively shown in fig. 7 and 8.
Example 5
Weighing the raw materials according to the weight ratio of 56kg of thermoplastic resin (50 kg of PA6+6kg of polyethylene terephthalate), 10.5kg of flame retardant (brominated epoxy resin), 30kg of reinforcing filler (glass fiber), 0.7kg of triazole compound (0.5 kg of triadimenol +0.5kg of cyproconazole), 0.5kg of lubricant (pentaerythritol stearate) and 0.1kg of light stabilizer (Pasteur Tinuvin XT 55), uniformly mixing the raw materials except the reinforcing filler, feeding the raw materials from a main feeding port of a double-screw extruder, feeding the reinforcing filler from a side feeding port, performing melt extrusion by the double-screw extruder, cooling, drying and dicing to obtain the thermoplastic resin material for the shell of the low-voltage apparatus, wherein the working temperature of the double-screw extruder is 220 ℃ in a feeding section, 210 ℃ in a melt plasticizing section, 230 ℃ in a mixing and homogenizing section, 250 ℃ in a melt conveying section, the retention time is 1 minute, and the rotating speed of a main machine of the double-screw extruder is 300 rpm.
Comparative example 5
Comparative example 5 is identical to example 5 except that no triazole-based compound is added, and the procedure is identical to example 5.
The thermoplastic resin materials for low-voltage apparatus casings obtained in example 5 and comparative example 5 were respectively prepared into breaker casings, copper-loaded pockmark tests were respectively performed, and the occurrence of pockmarks on the casing surface was observed, and the surface conditions of the breaker plastic casings at this time were respectively shown in fig. 9 and 10.
As is apparent from fig. 1 to 10, the surface of the molded case of the circuit breaker in fig. 1, 3, 5, 7 and 9 is smooth and free from generation of pockmarks, while the surface of the molded case of the circuit breaker in fig. 2, 4, 6, 8 and 10 has a large amount of pockmarks. Therefore, when the low-voltage electric appliance shell is prepared, the triazole compound is added into the raw materials, so that pockmarks on the surface of the low-voltage electric appliance shell can be effectively avoided.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (10)
1. The application of the triazole compound as an additive of a thermoplastic resin material for a low-voltage electric appliance shell is characterized by being applied to the preparation of the thermoplastic resin material for the low-voltage electric appliance shell as the additive for preventing pockmarks on the surface of the low-voltage electric appliance shell.
2. The use of the triazole-based compound as an additive for a thermoplastic resin material for a low-voltage electrical apparatus housing according to claim 1, wherein the raw material of the thermoplastic resin material for a low-voltage electrical apparatus housing comprises at least the following components in parts by weight: 40-70 parts of thermoplastic resin and 0.2-1 part of triazole compound.
3. The use of the triazole compound as an additive of a thermoplastic resin material for a low-voltage electrical apparatus shell according to claim 2, wherein the raw material of the thermoplastic resin material for a low-voltage electrical apparatus shell further comprises 7-30 parts by weight of a flame retardant and 20-40 parts by weight of a reinforcing filler.
4. The use of the triazole-based compound as an additive to a thermoplastic resin material for a low-voltage electrical apparatus housing according to claim 2, wherein the thermoplastic resin is one or more of polyamide, polycarbonate, polyethylene terephthalate and polybutylene terephthalate.
5. Use of the triazole-based compound as an additive to a thermoplastic resin material for a low-voltage electrical apparatus housing according to claim 4, wherein the thermoplastic resin is polyamide, and the polyamide is one or more of PA6, PA66, PA56, PA1010 and PA 610.
6. Use of the triazole-based compound as an additive for a thermoplastic resin material for a low-voltage electrical apparatus housing according to claim 1 or 2, wherein the triazole-based compound is one or more of triadimefon, triadimenol, diniconazole, tebuconazole, hexaconazole, propiconazole, triflumizole, cyproconazole, flusilazole, difenoconazole, and tetraconazole.
7. The use of the triazole-based compound as an additive for a thermoplastic resin material for a low-voltage electrical apparatus housing according to claim 3, wherein the flame retardant is one or more of a nitrogen-based flame retardant, a phosphorus-based flame retardant and a bromine-based flame retardant.
8. The use of the triazole-based compound as an additive for a thermoplastic resin material for a low-voltage electrical apparatus housing according to claim 7, wherein the flame retardant is a nitrogen-based flame retardant, and the nitrogen-based flame retardant is melamine cyanurate or melamine polyphosphate.
9. Use of the triazole-based compound according to claim 3 as an additive to a thermoplastic resin material for a low-voltage electrical apparatus case, wherein the reinforcing filler is a fibrous filler and/or an inorganic mineral powder.
10. The use of the triazole-based compound as an additive to a thermoplastic resin material for a low-voltage electrical apparatus housing according to claim 9, wherein the fibrous filler is one or more of glass fiber, basalt fiber, potassium titanate fiber; the inorganic mineral powder is one or more of talcum powder, wollastonite, mica, calcium carbonate, attapulgite, montmorillonite, zeolite and kaolin.
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| WO1993007909A1 (en) * | 1991-10-17 | 1993-04-29 | Solvay Interox Limited | Compositions and uses thereof |
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| CN104629268A (en) * | 2013-11-06 | 2015-05-20 | 金发科技股份有限公司 | Spraying-free polyester composition having special aesthetic effects and preparation method and application thereof |
| CN104629165A (en) * | 2013-11-06 | 2015-05-20 | 金发科技股份有限公司 | Spraying-free thermoplastic resin composition with special aesthetic effect and a preparation method and application thereof |
| CN104693790A (en) * | 2011-05-09 | 2015-06-10 | 本松工程塑料（杭州）有限公司 | Low-cost halogen-free and flame-retarding polyamide material for low-voltage appliance housings |
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- 2019-12-20 CN CN201911323183.XA patent/CN110982119B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993007909A1 (en) * | 1991-10-17 | 1993-04-29 | Solvay Interox Limited | Compositions and uses thereof |
| CN104693790A (en) * | 2011-05-09 | 2015-06-10 | 本松工程塑料（杭州）有限公司 | Low-cost halogen-free and flame-retarding polyamide material for low-voltage appliance housings |
| CN103225085A (en) * | 2013-04-25 | 2013-07-31 | 中国科学院海洋研究所 | Application of triazole compound containing salicylaldehyde as high efficiency corrosion inhibitor |
| CN104327907A (en) * | 2013-07-22 | 2015-02-04 | 中国石油化工股份有限公司 | Copper corrosion resistant additive composition |
| CN104629268A (en) * | 2013-11-06 | 2015-05-20 | 金发科技股份有限公司 | Spraying-free polyester composition having special aesthetic effects and preparation method and application thereof |
| CN104629165A (en) * | 2013-11-06 | 2015-05-20 | 金发科技股份有限公司 | Spraying-free thermoplastic resin composition with special aesthetic effect and a preparation method and application thereof |
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