CN111234407A - Scratch-resistant PVC door seal rubber sleeve material and preparation method thereof - Google Patents
Scratch-resistant PVC door seal rubber sleeve material and preparation method thereof Download PDFInfo
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- CN111234407A CN111234407A CN202010020353.3A CN202010020353A CN111234407A CN 111234407 A CN111234407 A CN 111234407A CN 202010020353 A CN202010020353 A CN 202010020353A CN 111234407 A CN111234407 A CN 111234407A
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
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Abstract
The invention discloses a scratch-resistant PVC door seal rubber sleeve material and a preparation method thereof, wherein the scratch-resistant PVC door seal rubber sleeve material consists of PVC resin, a plasticizer, a lubricant, a stabilizer, calcium carbonate, carbon black and a scratch-resistant auxiliary agent, and the preparation method of the scratch-resistant PVC door seal rubber sleeve material comprises the following steps: weighing; mixing the raw materials to prepare powder; granulating; and (5) extruding and molding the rubber sleeve. The door seal rubber sleeve solves the problem that the common PVC door seal rubber sleeve material and the dark door seal rubber sleeve are easy to scratch and scrape white in practical use, can reduce the friction coefficient of the surface of a door seal rubber sleeve product, enables the surface of the door seal rubber sleeve to be smooth, has excellent scratch resistance, can reduce the number of scrapped door seal rubber sleeve products in the production turnover process, improves the overall processing performance of the material, reduces the torque, reduces the equipment abrasion, and is suitable for manufacturing the PVC door seal product of a refrigerator.
Description
Technical Field
The invention relates to the field of refrigerator door sealing rubber sleeve materials and preparation methods thereof, and particularly belongs to a scratch-resistant PVC door sealing rubber sleeve material and a preparation method thereof.
Background
In recent years, with the rapid development of the household appliance industry, refrigerator host factories put higher and higher requirements on door sealant sleeves. The refrigerator door sealing rubber sleeve commonly used in the domestic refrigerator market at present is made of polyvinyl chloride (PVC) materials. However, in the actual use process, the whole PVC door seal rubber sleeve made of polyvinyl chloride (PVC) material is soft, in the transportation, assembly and use processes, the problems of scratch and white scraping are easily caused when a sharp object is encountered, the color change or color change is also caused, the whole attractiveness of the finished product of the PVC door seal rubber sleeve is seriously influenced, the stress concentration is also generated at the scratch, the durability of the finished product of the PVC door seal rubber sleeve is influenced, the whole service life of the finished product is shortened, and the use of the PVC door seal rubber sleeve in a high-end refrigerator is limited.
Therefore, technical research personnel of our company develop a scratch-resistant PVC door seal rubber sleeve material and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a scratch-resistant PVC door seal rubber sleeve material and a preparation method thereof, which can solve the problems mentioned in the background technology and are suitable for being popularized and used in the production of finished products of refrigerator door seal rubber sleeves.
The technical scheme adopted by the invention is as follows:
the scratch-resistant PVC door seal rubber sleeve material comprises PVC resin, a plasticizer, a lubricant, a stabilizer, calcium carbonate and carbon black, and is characterized by also comprising a scratch-resistant auxiliary agent, wherein the scratch-resistant auxiliary agent comprises the following components in parts by weight:
100 parts of PVC resin, 60-90 parts of plasticizer, 0.5-2 parts of lubricant, 3-6 parts of stabilizer, 30-70 parts of calcium carbonate, 0.5-2 parts of carbon black and 1-5 parts of scratch-resistant auxiliary agent, wherein the weight unit of each component is gram;
the PVC resin in the mixture is a polar non-crystalline polymer, is prepared by compounding and mixing one or more of polyvinyl chloride resins with the average polymerization degree of 800, 1000 and 1300, and is the production brand of S-60/S-65/S-70 of Taiwan plastic industry Co.Ltd;
the plasticizer is prepared by compounding tributyl citrate with one or more of dioctyl terephthalate, trioctyl trimellitate, epoxidized soybean oil, polyester, dioctyl sebacate and dioctyl adipate, wherein the tributyl citrate is produced by Wien chemical company, the dioctyl terephthalate is produced by blue sail chemical company, the trioctyl trimellitate is produced by Union chemical industry company, the epoxidized soybean oil is produced by environmental protection science and technology company, the polyester is produced by environmental protection science and technology company, the dioctyl sebacate is produced by environmental protection science and technology company, and the dioctyl adipate is produced by the chemical industry company;
the lubricant is prepared by compounding two or three or four of stearic acid, monoglyceride, paraffin and PE wax, wherein the monoglyceride is an essential component during the compounding of the lubricant, the monoglyceride in the lubricant is SP-4 produced by Jialishi additive limited company, the stearic acid is VA-1865 produced by eastern palm industry limited company, the paraffin is 58 produced by China Petroleum-treating petrochemical company, and the PE wax is PE-2 produced by Jiangxi Macro-Yuan chemical industry limited company;
the stabilizer is a calcium-zinc stabilizer which cannot contain lead, is prepared by compounding two or three of zinc stearate, calcium stearate and hydrotalcite, and is a Huizhou brocade source plasticizing material company Limited with the production brand of CZ-1012;
the calcium carbonate is one or two of light calcium carbonate and heavy calcium carbonate, and the calcium carbonate is HX-1250 brand produced by Jiangxi Guangxi Industrial and Industrial Limited liability company;
the carbon black is medium pigment channel black;
the scratch-resistant auxiliary agent is an ultrahigh molecular weight silicone master batch taking styrene-acrylonitrile copolymer SAN as a carrier.
Preferably, the calcium carbonate is ground heavy calcium carbonate which is washed and milled by water, and the particle size of the ground heavy calcium carbonate is not more than 5 um.
Preferably, the carbon black is a mesochrome channel black manufactured by Mitsubishi chemical corporation, Japan, and the scratch resistant aid is a high-grade silicone particulate manufactured by Doctoria scientific Co., Ltd, LYSI-415.
The preparation method of the scratch-resistant PVC door seal rubber sleeve material comprises the following steps:
the method comprises the following steps: weighing: accurately weighing the components in the range of parts according to claim 1 to an accuracy of no more than 0.1 gram;
step two: mixing raw materials to prepare powder: adding the PVC resin and the plasticizer which are accurately weighed in the step one into a high-speed mixer through a charging barrel of the high-speed mixer, fully mixing for not less than 10min, raising the temperature of the high-speed mixer, adding the lubricant, the stabilizer, the calcium carbonate, the carbon black and the scratch-resistant auxiliary agent which are obtained after the accurate weighing in the step 1) into the high-speed mixer when the temperature of the high-speed mixer is raised to 80 ℃, fully mixing for not less than 10min, then continuing raising the temperature of the high-speed mixer, and discharging from the high-speed mixer when the temperature of the high-speed mixer is raised to 120 ℃ to obtain dry and uniform mixed powder;
step three: and (3) granulation: adding the mixed powder prepared in the step two into a double-stage extruder for extrusion granulation, wherein the temperature parameters of a double-screw extrusion section of the double-stage extruder are set as follows: the temperature of a first zone is 120-130 ℃, the temperature of a second zone is 125-135 ℃, the temperature of a third zone is 128-138 ℃, the temperature of a fourth zone is 130-140 ℃, the temperature of a fifth zone is 133-143 ℃, the temperature of a machine head is 135-145 ℃, the temperature parameters of seven-nine zones of a single-screw extrusion section screw of a double-stage extruder are set to be 135-145 ℃, the rotating speed of a main machine is 120-150 r/min, the residence time of mixed powder in a double-screw extrusion section is controlled, the residence time of the mixed powder in the double-screw extrusion section is 2-3 min, the mixed powder is ensured to be agglomerated, after the mixed powder is plasticized to be agglomerated, the residence time of the mixed powder in the double-screw extrusion section is reduced as much as possible, the temperature near a feeding hopper of the double-screw extrusion section should be the lowest temperature zone in the double-stage extruder, then is gradually increased, the temperature of a neck mold at the rear end, obtaining mixed granules;
step four: and (3) extrusion molding of the rubber sleeve: adding the mixed granules prepared in the third step into a single-screw extruder for extrusion molding, setting parameters of the single-screw extruder to be 100-130 ℃ in the first zone, 125-135 ℃ in the second zone, 135-140 ℃ in the third zone, 140-145 ℃ in the fourth zone, 140-145 ℃ in the fifth zone, 140-145 ℃ in the head and 35r/min in the main engine speed, extruding and molding the granules from the single-screw extruder, cooling the granules in a cold water tank, and cutting the granules by a saw blade type tracking cutting machine when the temperature of the extruded and molded material is reduced to 25-30 ℃ to obtain the scratch-resistant PVC door sealing rubber sleeve.
Compared with the prior art, the invention has the following beneficial effects:
the invention solves the problems of easy scratch and white scraping caused by the impact with sharp objects in the transportation, assembly and use processes of the common door seal rubber sleeve material in the actual use, the rejection rate of the finished product is low, meanwhile, the scratch-resistant PVC door seal rubber sleeve material contains the scratch-resistant auxiliary agent, so that the material has good fluidity, excellent demoulding performance, good appearance smoothness and small influence on the overall mechanical property of the material, and the finished product prepared from the material has good stability and non-mobility.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described below with specific embodiments, and the technical solutions in the embodiments of the present invention are clearly and completely described. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention will be described in further detail with reference to examples and specific embodiments.
The scratch-resistant PVC door seal gum cover material consists of PVC resin, a plasticizer, a lubricant, a stabilizer, calcium carbonate, carbon black and a scratch-resistant auxiliary agent, wherein the weight ratio of the components is as follows: 100 parts of PVC resin, 60-90 parts of plasticizer, 0.5-2 parts of lubricant, 3-6 parts of stabilizer, 30-70 parts of calcium carbonate, 0.5-2 parts of carbon black and 1-5 parts of scratch-resistant auxiliary agent, wherein the weight unit is gram, the PVC resin is a polar non-crystalline polymer and is prepared by compounding and mixing one or more polyvinyl chloride resins with the average polymerization degrees of 800, 1000 and 1300, the plasticizer is prepared by compounding and mixing tributyl citrate, dioctyl terephthalate, trioctyl trimellitate, epoxidized soybean oil, polyester, dioctyl sebacate and dioctyl adipate, the lubricant is prepared by compounding one or more of stearic acid, monoglyceride, paraffin and PE wax, the monoglyceride is an essential component when the lubricant is compounded, the stabilizer is a calcium-zinc stabilizer, no lead is contained in the calcium-zinc stabilizer, and the stabilizer comprises zinc stearate, calcium-zinc stabilizer and polyethylene wax, The PVC resin is prepared by compounding two of calcium stearate and hydrotalcite, the compatibility of PVC resin can be improved, the melting of the material is promoted, the strength of the material is improved, the calcium carbonate is formed by mixing one or two of light calcium carbonate and heavy calcium carbonate, the heavy calcium carbonate after washing and grinding has a better using effect, the carbon black is medium pigment channel black and has the advantages of moderate viscosity, high blackness, high glossiness and the like, the scratch resistance auxiliary agent is an ultrahigh molecular weight silicone master batch taking styrene-acrylonitrile copolymer SAN as a carrier, and the material can have better fluidity, demolding performance and better apparent smoothness, wherein the PVC resin is produced by Taiwan plastic industry Limited company with the production brand of S-60/S-65/S-70; the tributyl citrate is produced by Vila En chemical Co., Ltd, the dioctyl terephthalate is produced by blue Sail chemical Co., Ltd, the trioctyl trimellitate is produced by Co-chemical industry Co., Ltd, the epoxidized soybean oil is produced by Jia ao environmental protection science and technology Co., Ltd, the polyester is produced by Co-chemical industry Co., Ltd, the dioctyl sebacate is produced by Jia ao environmental protection science and technology Co., Ltd, and the dioctyl adipate is produced by Co-chemical industry Co., Ltd; in the lubricant, the production brand of a good Lishi additive company Limited is SP-4, the production brand of a palm industry corporation Limited is VA-1865, the production brand of paraffin wax is 58, the production brand of a petroleum smooth petrochemical company in China is PE wax, and the production brand of a Jiangxi Macro-telechemical industry corporation Limited is PE-2; the stabilizer is a Huizhou brocade source plasticizing material company Limited with the production brand of CZ-1012; the calcium carbonate is HX-1250 for Jiangxi Guanghuai Industrial and Industrial liability company.
Preferably, the calcium carbonate is ground heavy calcium carbonate which is washed and milled by water, and the particle size of the ground heavy calcium carbonate is not more than 5 um.
Preferably, the carbon black is a mesochrome channel black manufactured by Mitsubishi chemical corporation, Japan, and the scratch resistant aid is a high-grade silicone particulate manufactured by Doctoria scientific Co., Ltd, LYSI-415.
The preparation method of the scratch-resistant PVC door seal rubber sleeve material comprises the following specific steps:
the method comprises the following steps: weighing: accurately weighing the components in the range of parts according to claim 1 to an accuracy of no more than 0.1 gram;
step two: mixing raw materials to prepare powder: adding the PVC resin and the plasticizer which are accurately weighed in the step one into a high-speed mixer through a charging barrel of the high-speed mixer, fully mixing for not less than 10min, raising the temperature of the high-speed mixer, adding the lubricant, the stabilizer, the calcium carbonate, the carbon black and the scratch-resistant auxiliary agent which are obtained after the accurate weighing in the step 1) into the high-speed mixer when the temperature of the high-speed mixer is raised to 80 ℃, fully mixing for not less than 10min, then continuing raising the temperature of the high-speed mixer, and discharging from the high-speed mixer when the temperature of the high-speed mixer is raised to 120 ℃ to obtain dry and uniform mixed powder;
step three: and (3) granulation: adding the mixed powder prepared in the step two into a double-stage extruder for extrusion granulation, wherein the temperature parameters of a double-screw extrusion section of the double-stage extruder are set as follows: the temperature of a first zone is 120-130 ℃, the temperature of a second zone is 125-135 ℃, the temperature of a third zone is 128-138 ℃, the temperature of a fourth zone is 130-140 ℃, the temperature of a fifth zone is 133-143 ℃, the temperature of a machine head is 135-145 ℃, the temperature parameters of seven-nine zones of a single-screw extrusion section screw of a double-stage extruder are set to be 135-145 ℃, the rotating speed of a main machine is 120-150 r/min, the residence time of mixed powder in a double-screw extrusion section is controlled, the residence time of the mixed powder in the double-screw extrusion section is 2-3 min, the mixed powder is ensured to be agglomerated, after the mixed powder is plasticized to be agglomerated, the residence time of the mixed powder in the double-screw extrusion section is reduced as much as possible, the temperature near a feeding hopper of the double-screw extrusion section should be the lowest temperature zone in the double-stage extruder, then is gradually increased, the temperature of a neck mold at the rear end, obtaining mixed granules;
step four: and (3) extrusion molding of the rubber sleeve: adding the mixed granules prepared in the third step into a single-screw extruder for extrusion molding, setting parameters of the single-screw extruder to be 100-130 ℃ in the first zone, 125-135 ℃ in the second zone, 135-140 ℃ in the third zone, 140-145 ℃ in the fourth zone, 140-145 ℃ in the fifth zone, 140-145 ℃ in the head and 35r/min in the main engine speed, extruding and molding the granules from the single-screw extruder, cooling the granules in a cold water tank, and cutting the granules by a saw blade type tracking cutting machine when the temperature of the extruded and molded material is reduced to 25-30 ℃ to obtain the scratch-resistant PVC door sealing rubber sleeve.
The first embodiment is as follows:
the refrigerator door sealing rubber sleeve material is accurately weighed according to the following material parts, wherein the weight of each component is gram;
adding 100 parts of accurately weighed PVC resin and 60 parts of plasticizer into a high-speed mixer through a charging barrel of the high-speed mixer, fully mixing for 10min, increasing the temperature of the high-speed mixer, adding 2 parts of accurately weighed lubricant, 6 parts of stabilizer, 30 parts of calcium carbonate, 2 parts of carbon black and 5 parts of scratch-resistant auxiliary agent into the high-speed mixer when the temperature of the high-speed mixer is increased to 80 ℃, continuously increasing the temperature of the high-speed mixer after mixing for 10min at low speed, and discharging from the high-speed mixer when the temperature of the high-speed mixer is increased to 120 ℃ to obtain dry and uniform mixed powder;
extruding and granulating the prepared mixed powder through a double-stage extruder, wherein the temperature parameters of a double-screw extrusion section of the double-stage extruder are as follows: the temperature of the first zone is 120 ℃, the temperature of the second zone is 128 ℃, the temperature of the third zone is 132 ℃, the temperature of the fourth zone is 138 ℃, the temperature of the fifth zone is 140 ℃, the temperature of the sixth zone is 142 ℃, and the temperature parameters of the single-screw extrusion section are set as follows: the temperature of a seventh zone is 142 ℃, the temperature of an eighth zone is 142 ℃, the temperature of a ninth zone is 142 ℃, the rotating speed of a main machine is 125 rpm, the residence time of the powder in a double-screw extrusion section is controlled, the residence time of the mixed powder in the double-screw extrusion section is 2min to 3min, the mixed powder is ensured to be plasticized into a mass, the residence time of the mixed powder in the double-screw extrusion section is reduced as much as possible after the mixed powder is plasticized into the mass, the temperature near a feeding hopper of the double-screw extrusion section is the lowest region in the double-stage extruder, then the temperature is gradually increased, the temperature of a neck ring at the rear end of the single-screw extrusion section of the double-stage extruder is highest, and the extruded material is air-cooled to;
adding the mixed granules extruded by the double-screw extruder into a single-screw extruder for extrusion molding, setting parameters of the single-screw extruder to be 120 ℃ in the first zone, 130 ℃ in the second zone, 135 ℃ in the third zone, 140 ℃ in the fourth zone, 142 ℃ in the fifth zone, 145 ℃ in the head, and 35 rpm in the main machine, setting the parameters of the single-screw extruder to be 130 ℃ in the second zone, 135 ℃ in the third zone, 140 ℃ in the fourth zone, 142 ℃ in the fifth zone, cooling the head in the cold water tank after the single-screw extruder is demoulded, and cutting the extruded materials by a saw blade type tracking cutting machine when the temperature of the extruded materials is reduced to 25-30 ℃ to obtain the scratch-resistant PVC door sealing rubber sleeve.
Then cutting, penetrating magnetism and heat welding are carried out to obtain a complete finished product of the refrigerator door seal.
The refrigerator door seal rubber sleeve prepared by the formula and the process has the advantages that the scratch-resistant auxiliary agent is the ultra-high molecular weight silicone master batch taking the styrene-acrylonitrile copolymer SAN as the carrier, so that the material has better fluidity, demoulding performance and appearance smoothness; the stabilizer can improve the compatibility of the PVC resin, promote the melting of the material and improve the strength of the material; the calcium carbonate has better use effect with the ground calcium carbonate which is washed and milled by water.
Compared with the common refrigerator door seal rubber sleeve PVC material, the material solves the problems of easy scratch and white scraping caused by the impact with sharp objects in the transportation, assembly and use processes of the common door seal rubber sleeve material when in actual use, has low rejection rate of finished products, and simultaneously contains a scratch-resistant auxiliary agent, so that the material has good fluidity, excellent demoulding performance, good apparent smoothness and small influence on the overall mechanical performance of the material.
The physical property test result of the refrigerator door seal material is as follows:
wherein:
the method for testing the molecular mobility comprises the following steps: firstly, preparing the scratch-resistant PVC door seal rubber sleeve material prepared according to the embodiment 1 into a vulcanized sheet with uniform overall thickness and 2mm thickness, cutting the vulcanized sheet into test pieces (with the size deviation of plus or minus 0.3mm) with the specification of 50mm by 10mm by 2mm, wherein the surface is free from pollution, and the cut edges are uniform; the test piece is put in a dryer to be dried for 24 hours and then weighed, and then the weight is recorded as M1; then clamping the test piece between two plates (standard HIPS plates) made of standard modified high-impact polystyrene to form a test sample;
the test specimen was horizontally placed in an oven, and then a 1.1kg weight or an iron block (equivalent to 0.22 kg/cm) was loaded thereon2Load of (b), placed in an oven at 70 ℃ ± 2 ℃, after 72h the test specimen is taken out, then the test piece is separated from a standard modified high impact polystyrene board (standard HIPS board), placed in a desiccator to be cooled to room temperature and then weighed, after which the weight is recorded as M2;
according to the formula: the molecular mobility% M is calculated as M1-M2/M1 100%, and the final result is obtained as the arithmetic mean of the three groups.
The scratch resistance test method comprises the steps of fixedly loading a 1.1Kg weight on a grinding head of a scratch resistance tester at the temperature of 23 +/-2 ℃, reciprocating and stroking the grinding head on the surface of a scratch resistant PVC door sealant sleeve material sample manufactured according to the first embodiment at the speed of 25rpm for 20 times to form a cycle, stopping reciprocating and stroking the grinding head after the cycle, measuring the front and back color difference △ E by a spectrocolorimeter (a Konika minometric spectrocolorimeter, the model is CM-2600d), and measuring three groups in total, wherein the arithmetic mean value is the final result.
Example two:
the refrigerator door sealing rubber sleeve material is accurately weighed according to the following material parts, wherein the weight of each component is calculated according to the parts by weight:
adding 100 parts of accurately weighed PVC resin and 70 parts of plasticizer into a high-speed mixer through a charging barrel of the high-speed mixer, fully mixing for 10min, increasing the temperature of the high-speed mixer, adding 1 part of accurately weighed lubricant, 5 parts of stabilizer, 50 parts of calcium carbonate, 1 part of carbon black and 3 parts of scratch-resistant auxiliary agent into the high-speed mixer when the temperature of the high-speed mixer is increased to 80 ℃, continuously increasing the temperature of the high-speed mixer after mixing for 10min at low speed, and discharging from the high-speed mixer when the temperature of the high-speed mixer is increased to 120 ℃ to obtain dry and uniform mixed powder;
extruding and granulating the prepared mixed powder through a double-stage extruder, wherein the temperature parameters of a double-screw extrusion section of the double-stage extruder are as follows: the temperature of the first zone is 120 ℃, the temperature of the second zone is 125 ℃, the temperature of the third zone is 132 ℃, the temperature of the fourth zone is 135 ℃, the temperature of the fifth zone is 138 ℃, the temperature of the sixth zone is 138 ℃, and the temperature parameters of the single-screw extrusion section are set as follows: the temperature of a seventh zone is 138 ℃, the temperature of an eighth zone is 138 ℃, the temperature of a ninth zone is 138 ℃, the rotating speed of a main machine is 130 r/min, the residence time of the powder in a double-screw extrusion section is controlled, the residence time of the mixed powder in the double-screw extrusion section is 2min to 3min, the mixed powder is ensured to be plasticized into a mass, the residence time of the mixed powder in the double-screw extrusion section is reduced as far as possible after the mixed powder is plasticized into the mass, the temperature near a feeding hopper of the double-screw extrusion section is the lowest region in the double-stage extruder, then the temperature is gradually increased, the temperature of a neck ring at the rear end of a single-screw extrusion section of the double-stage extruder is highest, and the extruded material is air-;
adding the mixed granules extruded by the double-screw extruder into a single-screw extruder for extrusion molding, setting parameters of the single-screw extruder to be 110 ℃ in the first zone, 125 ℃ in the second zone, 130 ℃ in the third zone, 135 ℃ in the fourth zone, 140 ℃ in the fifth zone, 142 ℃ in the head, and 35 rpm in the main machine, setting parameters of the single-screw extruder to be 110 ℃ in the second zone, 125 ℃ in the third zone, 135 ℃ in the fourth zone, 140 ℃ in the fifth zone, cooling the extrusion head at the speed of 35 rpm in the main machine, discharging the extrusion materials from the single-screw extruder, cooling the extrusion materials in a cold water tank, and cutting the extrusion materials by using a saw blade type tracking cutting machine when the temperature of the extrusion materials is reduced to 25-30 ℃ to obtain the scratch-resistant.
Then cutting, penetrating magnetism and heat welding are carried out to obtain a complete finished product of the refrigerator door seal.
The refrigerator door seal rubber sleeve prepared by the formula and the process has the advantages that the scratch-resistant auxiliary agent is the ultra-high molecular weight silicone master batch taking SAN as a carrier, so that the material has better fluidity, demoulding performance and appearance smoothness; the stabilizer can improve the compatibility of the PVC resin, promote the melting of the material and improve the strength of the material; the calcium carbonate has better use effect with the ground calcium carbonate which is washed and milled by water.
Compared with the common refrigerator door seal rubber sleeve PVC material, the material solves the problems of easy scratch and white scraping caused by the impact with sharp objects in the transportation, assembly and use processes of the common door seal rubber sleeve material when in actual use, has low rejection rate of finished products, and simultaneously contains a scratch-resistant auxiliary agent, so that the material has good fluidity, excellent demoulding performance, good apparent smoothness and small influence on the overall mechanical performance of the material.
The physical property test result of the refrigerator door seal material is as follows:
wherein:
the method for testing the molecular mobility comprises the following steps: firstly, preparing the scratch-resistant PVC door seal rubber sleeve material prepared according to the embodiment 1 into a vulcanized sheet with uniform overall thickness and 2mm thickness, cutting the vulcanized sheet into test pieces (with the size deviation of plus or minus 0.3mm) with the specification of 50mm by 10mm by 2mm, wherein the surface is free from pollution, and the cut edges are uniform; the test piece is put in a dryer to be dried for 24 hours and then weighed, and then the weight is recorded as M1; then clamping the test piece between two plates (standard HIPS plates) made of standard modified high-impact polystyrene to form a test sample;
the test specimen was horizontally placed in an oven, and then a 1.1kg weight or an iron block (equivalent to 0.22 kg/cm) was loaded thereon2Load of (b), placed in an oven at 70 ℃ ± 2 ℃, after 72h the test specimen is taken out, then the test piece is separated from a standard modified high impact polystyrene board (standard HIPS board), placed in a desiccator to be cooled to room temperature and then weighed, after which the weight is recorded as M2;
according to the formula: the molecular mobility% M is calculated as M1-M2/M1 100%, and the final result is obtained as the arithmetic mean of the three groups.
The scratch resistance test method comprises the steps of fixedly loading a 1.1Kg weight on a grinding head of a scratch resistance tester at the temperature of 23 +/-2 ℃, reciprocating and stroking the grinding head on the surface of a scratch resistant PVC door sealant sleeve material sample manufactured according to the second embodiment at the speed of 25rpm for 20 times to form a cycle, stopping reciprocating and stroking the grinding head after the cycle, measuring the front and back color difference △ E by a spectrocolorimeter (a Konika minometric spectrocolorimeter, the model is CM-2600d), and measuring three groups in total, wherein the arithmetic mean value is the final result.
Example three:
the refrigerator door sealing rubber sleeve material is accurately weighed according to the following material parts, wherein the weight of each component is calculated according to the parts by weight:
adding 100 parts of accurately weighed PVC resin and 90 parts of plasticizer into a high-speed mixer through a charging barrel of the high-speed mixer, fully mixing for 10min, increasing the temperature of the high-speed mixer, adding 0.5 part of accurately weighed lubricant, 3 parts of stabilizer, 70 parts of calcium carbonate, 0.5 part of carbon black and 1 part of scratch-resistant auxiliary agent into the high-speed mixer when the temperature of the high-speed mixer is increased to 80 ℃, continuously increasing the temperature of the high-speed mixer after mixing for 10min at low speed, and discharging from the high-speed mixer when the temperature of the high-speed mixer is increased to 120 ℃ to obtain dry and uniform mixed powder;
extruding and granulating the prepared mixed powder through a double-stage extruder, wherein the temperature parameters of a double-screw extrusion section of the double-stage extruder are as follows: the temperature of the first zone is 120 ℃, the temperature of the second zone is 125 ℃, the temperature of the third zone is 130 ℃, the temperature of the fourth zone is 132 ℃, the temperature of the fifth zone is 135 ℃, the temperature of the sixth zone is 135 ℃, and the temperature parameters of the single-screw extrusion section are set as follows: the temperature of a seventh zone is 135 ℃, the temperature of an eighth zone is 135 ℃, the temperature of a ninth zone is 135 ℃, the rotating speed of a main machine is 140 r/min, the residence time of the powder in a double-screw extrusion section is controlled, the residence time of the mixed powder in the double-screw extrusion section is 2min to 3min, the mixed powder is ensured to be plasticized into a mass, the residence time of the mixed powder in the double-screw extrusion section is reduced as much as possible after the mixed powder is plasticized into the mass, the temperature near a feeding hopper of the double-screw extrusion section is the lowest region in the double-stage extruder, then the temperature is gradually increased, the temperature of a neck ring at the rear end of a single-screw extrusion section of the double-stage extruder is highest, and the extruded material is air-;
adding the mixed granules extruded by the double-screw extruder into a single-screw extruder for extrusion molding, setting parameters of the single-screw extruder to be 100 ℃ in the first zone, 120 ℃ in the second zone, 125 ℃ in the third zone, 130 ℃ in the fourth zone, 140 ℃ in the fifth zone, 140 ℃ in the head, and 35 rpm in the main machine, setting parameters of the single-screw extruder to be 100 ℃, setting parameters of the single-screw extruder to be 120 ℃, setting parameters of the single-screw extruder to be 125 ℃, setting parameters of the single-screw extruder to be 130 ℃ in the third zone, setting parameters of the single-screw extruder to be 140 ℃ in the fifth zone, cooling the single-screw extruder in a cold water tank, and cutting the single-screw extruder by using a saw blade type tracking cutting machine when the temperature of the extruded materials is reduced to.
Then cutting, penetrating magnetism and heat welding are carried out to obtain a complete finished product of the refrigerator door seal.
The refrigerator door seal rubber sleeve prepared by the formula and the process has the advantages that the scratch-resistant auxiliary agent is the ultra-high molecular weight silicone master batch taking SAN as a carrier, so that the material has better fluidity, demoulding performance and appearance smoothness; the stabilizer can improve the compatibility of the PVC resin, promote the melting of the material and improve the strength of the material; the calcium carbonate has better use effect with the ground calcium carbonate which is washed and milled by water.
Compared with the common refrigerator door seal rubber sleeve PVC material, the material solves the problems of easy scratch and white scraping caused by the impact with sharp objects in the transportation, assembly and use processes of the common door seal rubber sleeve material when in actual use, has low rejection rate of finished products, and simultaneously contains a scratch-resistant auxiliary agent, so that the material has good fluidity, excellent demoulding performance, good apparent smoothness and small influence on the overall mechanical performance of the material.
The physical property test result of the refrigerator door seal material is as follows:
| test items | Test method | Unit of | Test results |
| Density of | GB/T1033-2018 | g/cm3 | 1.32 |
| Shore hardness | GB/T2411-2018 | ShoreA | 63 |
| Tensile strength | GB/T1040-2006 | MPa | 11.08 |
| Elongation at break | GB/T1040-2006 | ％ | 262.48 |
| Mobility of molecules | QMB-J032.2003-2017 | ％ | 0.34 |
| Scratch resistance | / | / | 0.19 |
Wherein:
the method for testing the molecular mobility comprises the following steps: firstly, preparing the scratch-resistant PVC door seal rubber sleeve material prepared according to the embodiment 1 into a vulcanized sheet with uniform overall thickness and 2mm thickness, cutting the vulcanized sheet into test pieces (with the size deviation of plus or minus 0.3mm) with the specification of 50mm by 10mm by 2mm, wherein the surface is free from pollution, and the cut edges are uniform; the test piece is put in a dryer to be dried for 24 hours and then weighed, and then the weight is recorded as M1; then clamping the test piece between two plates (standard HIPS plates) made of standard modified high-impact polystyrene to form a test sample;
the test specimen was horizontally placed in an oven, and then a 1.1kg weight or an iron block (equivalent to 0.22 kg/cm) was loaded thereon2Load of (b), placed in an oven at 70 ℃ ± 2 ℃, after 72h the test specimen is taken out, then the test piece is separated from a standard modified high impact polystyrene board (standard HIPS board), placed in a desiccator to be cooled to room temperature and then weighed, after which the weight is recorded as M2;
according to the formula: the molecular mobility% M is calculated as M1-M2/M1 100%, and the final result is obtained as the arithmetic mean of the three groups.
The scratch resistance test method comprises the steps of fixedly loading a 1.1Kg weight on a grinding head of a scratch resistance tester at the temperature of 23 +/-2 ℃, reciprocating and stroking the grinding head on the surface of a scratch resistant PVC door sealant sleeve material sample manufactured according to the third embodiment at the speed of 25rpm for 20 times to form a cycle, stopping reciprocating and stroking the grinding head after the cycle, measuring the front and back color difference △ E by a spectrocolorimeter (a Konika minometric spectrocolorimeter, the model is CM-2600d), and measuring three groups in total, wherein the arithmetic mean value is the final result.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (4)
1. The scratch-resistant PVC door seal rubber sleeve material comprises PVC resin, a plasticizer, a lubricant, a stabilizer, calcium carbonate and carbon black, and is characterized by also comprising a scratch-resistant auxiliary agent, wherein the scratch-resistant auxiliary agent comprises the following components in parts by weight:
100 parts of PVC resin, 60-90 parts of plasticizer, 0.5-2 parts of lubricant, 3-6 parts of stabilizer, 30-70 parts of calcium carbonate, 0.5-2 parts of carbon black and 1-5 parts of scratch-resistant auxiliary agent, wherein the weight unit of each component is gram;
the PVC resin in the mixture is a polar non-crystalline polymer, is prepared by compounding and mixing one or more of polyvinyl chloride resins with the average polymerization degree of 800, 1000 and 1300, and is the production brand of S-60/S-65/S-70 of Taiwan plastic industry Co.Ltd;
the plasticizer is prepared by compounding tributyl citrate with one or more of dioctyl terephthalate, trioctyl trimellitate, epoxidized soybean oil, polyester, dioctyl sebacate and dioctyl adipate, wherein the tributyl citrate is produced by Wien chemical company, the dioctyl terephthalate is produced by blue sail chemical company, the trioctyl trimellitate is produced by Union chemical industry company, the epoxidized soybean oil is produced by environmental protection science and technology company, the polyester is produced by environmental protection science and technology company, the dioctyl sebacate is produced by environmental protection science and technology company, and the dioctyl adipate is produced by the chemical industry company;
the lubricant is prepared by compounding two or three or four of stearic acid, monoglyceride, paraffin and PE wax, wherein the monoglyceride is an essential component during the compounding of the lubricant, the monoglyceride in the lubricant is SP-4 produced by Jialishi additive limited company, the stearic acid is VA-1865 produced by eastern palm industry limited company, the paraffin is 58 produced by China Petroleum-treating petrochemical company, and the PE wax is PE-2 produced by Jiangxi Macro-Yuan chemical industry limited company;
the stabilizer is a calcium-zinc stabilizer which cannot contain lead, is prepared by compounding two or three of zinc stearate, calcium stearate and hydrotalcite, and is a Huizhou brocade source plasticizing material company Limited with the production brand of CZ-1012;
the calcium carbonate is one or two of light calcium carbonate and heavy calcium carbonate, and the calcium carbonate is HX-1250 brand produced by Jiangxi Guangxi Industrial and Industrial Limited liability company;
the carbon black is medium pigment channel black;
the scratch-resistant auxiliary agent is an ultrahigh molecular weight silicone master batch taking styrene-acrylonitrile copolymer SAN as a carrier.
2. The scratch-resistant PVC door sealing rubber sleeve material as claimed in claim 1, wherein the calcium carbonate is ground heavy calcium carbonate which is washed and milled, and the particle size of the ground heavy calcium carbonate is not more than 5 um.
3. The scratch-resistant PVC door sealant sleeve material as claimed in claim 1, wherein the carbon black is a mesochrome channel black of Mitsubishi chemical corporation, Japan, trade name MA-100, and the scratch-resistant aid is a silicone particulate of high grade, produced by Dow Sishi, science and technology Limited, trade name LYSI-415.
4. The preparation method of the scratch-resistant PVC door sealant sleeve material as claimed in any one of claims 1 to 3, which is characterized by comprising the following steps:
1) weighing: accurately weighing the components in the range of parts according to claim 1 to an accuracy of no more than 0.1 gram;
2) mixing raw materials to prepare powder: adding the PVC resin and the plasticizer which are accurately weighed in the step 1) into a high-speed mixer through a charging barrel of the high-speed mixer, fully mixing for not less than 10min, raising the temperature of the high-speed mixer, adding the lubricant, the stabilizer, the calcium carbonate, the carbon black and the scratch-resistant auxiliary agent which are obtained after the accurate weighing in the step 1) into the high-speed mixer when the temperature of the high-speed mixer is raised to 80 ℃, fully mixing for not less than 10min, then continuing raising the temperature of the high-speed mixer, and discharging from the high-speed mixer when the temperature of the high-speed mixer is raised to 120 ℃ to obtain dry and uniform mixed powder;
3) and (3) granulation: adding the mixed powder prepared in the step 2) into a double-stage extruder for extrusion granulation, wherein the temperature parameters of a double-screw extrusion section of the double-stage extruder are set as follows: the temperature of a first zone is 120-130 ℃, the temperature of a second zone is 125-135 ℃, the temperature of a third zone is 128-138 ℃, the temperature of a fourth zone is 130-140 ℃, the temperature of a fifth zone is 133-143 ℃, the temperature of a machine head is 135-145 ℃, the temperature parameters of seven-nine zones of a single-screw extrusion section screw of a double-stage extruder are set to be 135-145 ℃, the rotating speed of a main machine is 120-150 r/min, the residence time of mixed powder in a double-screw extrusion section is controlled, the residence time of the mixed powder in the double-screw extrusion section is 2-3 min, the mixed powder is ensured to be agglomerated, after the mixed powder is plasticized to be agglomerated, the residence time of the mixed powder in the double-screw extrusion section is reduced as much as possible, the temperature near a feeding hopper of the double-screw extrusion section should be the lowest temperature zone in the double-stage extruder, then is gradually increased, the temperature of a neck mold at the rear end, obtaining mixed granules;
4) and (3) extrusion molding of the rubber sleeve: adding the mixed granules prepared in the step 3) into a single-screw extruder for extrusion molding, setting parameters of the single-screw extruder to be 100-130 ℃ in the first zone, 125-135 ℃ in the second zone, 135-140 ℃ in the third zone, 140-145 ℃ in the fourth zone, 140-145 ℃ in the fifth zone, 140-145 ℃ in the head temperature, and 35r/min in the main machine rotation speed after the mixed granules are extruded and molded from the single-screw extruder and are discharged from a die, cooling the mixed granules in a cold water tank, and cutting the extruded and molded material by using a saw blade type tracking cutting machine when the temperature of the extruded and molded material is reduced to 25-30 ℃ to obtain the scratch-resistant PVC door sealing rubber sleeve.
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