CN113004584B - Low-temperature vulcanized rubber for balls and preparation method of low-temperature vulcanized rubber balls - Google Patents
Low-temperature vulcanized rubber for balls and preparation method of low-temperature vulcanized rubber balls Download PDFInfo
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- CN113004584B CN113004584B CN202110256884.7A CN202110256884A CN113004584B CN 113004584 B CN113004584 B CN 113004584B CN 202110256884 A CN202110256884 A CN 202110256884A CN 113004584 B CN113004584 B CN 113004584B
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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
- C08L7/00—Compositions of natural rubber
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- 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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Abstract
The invention relates to the technical field of rubber products, and discloses low-temperature vulcanized rubber for balls and a preparation method of low-temperature vulcanized rubber balls, wherein the low-temperature vulcanized rubber for the balls comprises the following components in parts by weight: 50-80 parts of natural rubber, 20-50 parts of styrene butadiene rubber, 80-100 parts of calcium carbonate, 30-50 parts of white carbon black, 5-10 parts of zinc oxide, 1-3 parts of stearic acid, 2-5 parts of tackifying resin, 2-5 parts of butylated hydroxytoluene, 1-3 parts of protective wax, 1-2 parts of MB, 2-4 parts of flow venting agent PW, 5-10 parts of white factice, 5-10 parts of naphthenic oil, 2-4 parts of accelerator BZ, 1-2 parts of accelerator PZ, 1-2 parts of accelerator SIP, 2-4 parts of sulfur and a plurality of parts of color rubber.
Description
Technical Field
The invention relates to the technical field of rubber products, in particular to low-temperature vulcanized rubber for balls and a preparation method of low-temperature vulcanized rubber balls.
Background
Rubber sports balls such as basketball, soccer, and volleyball are common sports balls and are commonly used in ball sports. The rubber football is made up by using rubber through the processes of mixing rubber into pieces, manually sticking rubber skin on the ball bladder (ball bladder and cloth ball) by using tool, directly making hot vulcanization treatment and forming under the condition of high-temp. and high-pressure, and its ball body surface is a whole body, and its surface grain is made up by pressing. The technology is characterized in that rubber is directly vulcanized and molded at high temperature, the texture is hard, and the comfort level of use is not high. The existing rubber sport ball is vulcanized under the conditions of high temperature and high pressure, and the temperature is as follows: 140-180 deg.C, pressure 9-11kgf/cm 2 After vulcanization, due to the arrangement of high temperature and high pressure, when the rubber skin reaches the same color, more color glue consumption is needed, and the rubber skin is cured at presentThe high-temperature vulcanized rubber ball has higher hardness and lower rebound resilience, and the rubber is more easily aged.
Disclosure of Invention
Therefore, the low-temperature vulcanized rubber for the balls and the preparation method of the low-temperature vulcanized rubber balls are needed to be provided, so that the problems of the existing equipment and the existing rubber sport balls in high-temperature vulcanization are solved.
In order to achieve the purpose, the invention provides low-temperature vulcanized rubber for balls, which comprises the following components in parts by weight:
50-80 parts of natural rubber, 20-50 parts of styrene butadiene rubber, 80-100 parts of calcium carbonate, 30-50 parts of white carbon black, 5-10 parts of zinc oxide, 1-3 parts of stearic acid, 2-5 parts of tackifying resin, 2-5 parts of dibutyl hydroxy toluene, 1-3 parts of protective wax, 1-2 parts of MB, 2-4 parts of flow exhaust agent PW, 5-10 parts of white factice, 5-10 parts of naphthenic oil, 2-4 parts of accelerator BZ, 1-2 parts of accelerator PZ, 1-2 parts of accelerator SIP, 2-4 parts of sulfur and a plurality of parts of color cement. The amount of the color glue is prepared according to the color of the rubber required to be prepared.
Further, the paint comprises the following components in parts by weight:
60 parts of natural rubber, 40 parts of styrene-butadiene rubber, 90 parts of calcium carbonate, 40 parts of white carbon black, 5 parts of zinc oxide, 2 parts of stearic acid, 3 parts of tackifying resin, 3 parts of dibutyl hydroxy toluene, 2 parts of protective wax, 1.5 parts of MB, 3 parts of flow exhaust agent PW, 8 parts of white factice, 8 parts of naphthenic oil, 3 parts of accelerator BZ, 1 part of accelerator PZ, 1 part of accelerator SIP, 2 parts of sulfur and a plurality of parts of color cement.
A low-temperature vulcanized rubber ball comprises a bladder and a rubber skin attached to the outer surface of the bladder, wherein the rubber skin is any one of the rubbers.
The preparation method of the low-temperature vulcanized rubber ball comprises the following steps:
(1) Weighing natural rubber, styrene butadiene rubber, calcium carbonate, white carbon black, zinc oxide, stearic acid, dibutyl hydroxy toluene, protective wax, MB, a flow exhaust agent PW, white factice and naphthenic oil, and mixing by using an internal mixer to form unprimed rubber compound;
(2) Weighing an accelerator BZ, an accelerator PZ, an accelerator SIP, sulfur and colored rubber, and uniformly mixing the accelerator BZ, the accelerator PZ, the accelerator SIP, the sulfur, the colored rubber and unpromoted rubber compound on an open mill to form the promoted rubber;
(3) Preparing the rubber sheet from the accelerated rubber through a calender, and cooling and shaping the prepared rubber sheet;
(4) Cutting the rubber sheet into rubber skin by using a cutting die after cooling and shaping, and attaching the rubber skin to the surface of the bladder by using an attaching and attaching machine to form an unvulcanized rubber ball;
(5) And vulcanizing the unvulcanized rubber ball by using a vulcanizing machine to obtain a vulcanized rubber ball.
Further, in the step (1), the temperature of an internal mixer is 110-135 ℃, and the mixing time is 4-6min.
Further, in the step (2), the temperature of a roller of the open mill is controlled to be 35-55 ℃, and the mixing time is 3-4min.
Further, in the step (3), the temperature of a roller of the calender is 50-65 ℃, the cooling and shaping temperature is below 22 ℃, and the cooling and shaping time is 1-3h.
Further, in the step (4), after the rubber skin is attached to the surface of the bladder, the attaching machine is continuously used for attaching leather to the outer surface of the rubber skin.
Further, in the step (5), the vulcanizing temperature of the vulcanizing machine is 90-110 ℃, the vulcanizing time is 13-18min, and the air pressure is 4-6kgf/cm 2 。
The technical scheme has the following beneficial effects:
1. according to the invention, the natural rubber with good elasticity, wear resistance and water resistance is used as a main material, after the styrene butadiene rubber is added, the anti-aging performance is improved, the zinc oxide is a good activator of the accelerator and the sulfur, so that the accelerator and the sulfur can play a role more quickly and deeply, the activation effect is stronger by matching with stearic acid, and the calcium carbonate and the white carbon black are compounded for use, so that the product has better wear resistance and is easy to process. Naphthenic oil is a good plasticizer of rubber, so that the rubber is plasticated more easily, after the accelerator BZ, the accelerator PZ and the accelerator SIP are matched for use, the rubber is combined with sulfur more quickly, so that the vulcanization is completed more quickly and deeply, after the sulfur is added, the internal molecules of the rubber are rearranged, and when the rubber ball is vulcanized, the vulcanization temperature is only required to be ensured to be 90-110 ℃, and the air pressure is 4-6kgf/cm 2 Then can finishVulcanization and can ensure that the surface of the vulcanized rubber ball does not cause frost.
2. According to the invention, the dosage of the accelerator BZ, the accelerator PZ and the accelerator SIP is proportioned, so that vulcanization can be completed only at a lower temperature when the rubber ball is vulcanized, and after vulcanization is completed, the ball body has lower hardness and higher experimental rebound height, which shows that the rubber ball has higher elasticity.
Detailed Description
In order to explain technical contents, structural features, and objects and effects of the technical means in detail, the following detailed description is given with reference to specific embodiments.
Example 1
The low-temperature vulcanized rubber for the balls comprises the following components in parts by weight:
60 parts of natural rubber, 40 parts of styrene-butadiene rubber, 90 parts of calcium carbonate, 40 parts of white carbon black, 5 parts of zinc oxide, 2 parts of stearic acid, 3 parts of tackifying resin, 3 parts of Butylated Hydroxytoluene (BHT), 2 parts of protective wax, 1.5 parts of 2-Mercaptobenzimidazole (MB), 3 parts of flowing gas exhauster PW, 8 parts of white factice, 8 parts of naphthenic oil, 3 parts of accelerant BZ, 1 part of accelerant PZ, 1 part of accelerant SIP, 2 parts of sulfur and 1 part of color cement.
The low-temperature vulcanized rubber comprises a bladder and a rubber skin attached to the outer surface of the bladder, wherein the rubber skin is the rubber for the ball.
The preparation method of the rubber ball comprises the following steps:
(1) Weighing natural rubber, styrene butadiene rubber, calcium carbonate, white carbon black, zinc oxide, stearic acid, tackifying resin, dibutyl hydroxy toluene, protective wax, MB, a flow exhaust agent PW, white factice and naphthenic oil, and mixing by using an internal mixer to form un-promoted rubber compound; the temperature of the internal mixer is 120 ℃, and the mixing time is 5min;
(2) Weighing an accelerator, an accelerator PZ, an accelerator SIP, sulfur and colored rubber, and uniformly mixing the accelerator, the accelerator PZ, the accelerator SIP, the sulfur, the colored rubber and unpromoted rubber compound on an open mill to form the promoted rubber; controlling the temperature of a roller of the open mill at 50 ℃, and mixing for 3min;
(3) Preparing the rubber sheet from the accelerated rubber through a calender, and cooling and shaping the prepared rubber sheet; the temperature of a roller of the calender is 60 ℃, the cooling and shaping temperature is below 22 ℃, and the cooling and shaping time is 3 hours;
(4) Cutting the rubber sheet into rubber skin by using a cutting die after cooling and shaping, and attaching the rubber skin to the surface of the bladder by using an attaching machine to form an unvulcanized rubber ball;
(5) Vulcanizing unvulcanized rubber balls by using a vulcanizing machine to obtain vulcanized rubber balls, wherein the vulcanizing temperature of the vulcanizing machine is 100 ℃, the vulcanizing time is 15min, and the air pressure is 5kgf/cm 2 。
Examples 2 to 3: the low-temperature rubber ball is different from the rubber ball in example 1 in that the components and the corresponding parts by weight of the rubber are shown in Table 1.
Comparative examples 1 to 3: a low temperature vulcanized rubber ball is different from example 1 in that the rubber components and the corresponding parts by weight are shown in Table 1.
Comparative example 4: a low-temperature vulcanized rubber ball, which is different from comparative example 1 in that the vulcanization temperature is 160 ℃ and the air pressure is 10kgf/cm 2 。
The rubber balls prepared in examples 1 to 3 and comparative examples 1 to 4 were observed for blooming on the surface, and the hardness of the ball was measured by a Shore A hardness tester, and the rebound height of the rubber ball was measured by dropping at a height of 1800 MM. The results are shown in Table 1.
In table 1, it can be seen from example 1 and comparative examples 1 to 4 that the combination of the accelerator BZ, the accelerator PZ and the accelerator SIP in the present invention makes the rubber ball of the present invention not generate blooming even if the vulcanized state is maintained at low temperature and low pressure during the vulcanization process, and the ball hardness is low and has high rebound height, whereas in contrast, the three accelerators of comparative example 1 are used in excess, comparative example 2 and comparative example 3 do not use all three accelerators, so the vulcanized rubber ball generates blooming phenomenon, and the hardness is higher than that of example 1, when the vulcanization is performed at higher temperature and pressure, a high temperature vulcanization accelerator is required, and the accelerator CZ is a high temperature accelerator, and although the blooming phenomenon can be avoided, the hardness of the product is increased and the rebound performance is decreased.
TABLE 1 preparation conditions and test results of examples 1 to 3, comparative examples 1 to 4.
Example 4
The preparation method of the low-temperature vulcanized rubber ball is different from the embodiment 1 in that the temperature of an internal mixer is 110 ℃, the mixing time is 4min, the temperature of a roller of an open mill is controlled to be 55 ℃, the mixing time is 3min, the temperature of a roller of a calender is 50 ℃, the vulcanization temperature of a vulcanizer is 90 ℃, the vulcanization time is 18min, and the air pressure is 6kgf/cm 2 。
Example 5
The preparation method of the low-temperature vulcanized rubber ball is different from the embodiment 1 in that the temperature of an internal mixer is 135 ℃, the mixing time is 3min, the temperature of a roller of an open mill is controlled at 50 ℃, the mixing time is 4min, the temperature of a roller of a calender is 65 ℃, the vulcanization temperature of a vulcanizer is 110 ℃, the vulcanization time is 16min, and the air pressure is 4kgf/cm 2 。
Comparative example 5: the difference compared to example 1 is that the temperature of the internal mixer is 140 ℃ and the mixing time is 4min.
Comparative example 6: the difference compared to example 1 is that the roll temperature of the open mill was controlled at 65 ℃.
Comparative example 7: compared with example 1, except that the vulcanization temperature was 160 ℃ and the air pressure was 10kgf/cm 2 。
The rubber balls prepared in examples 1, 4 to 5 and comparative examples 5 to 7 were observed for blooming on the surface, and the hardness of the ball was measured by a Shore A durometer, and the rebound height of the rubber ball was measured by dropping at a height of 1800 MM. The results are shown in Table 2.
TABLE 2 test results of examples 1, 4, 5 and comparative examples 5 to 7.
| Example 1 | Example 4 | Example 5 | Comparative example 5 | Comparative example 6 | Comparative example 7 | |
| Shore A hardness/HA | 62 | 67 | 67 | 73 | 72 | 70 |
| Rebound height/mm | 1369 | 1362 | 1380 | 1371 | 1362 | 1310 |
As can be seen from Table 2, comparative examples 5 and 6 show that in the case of rubber compositions identical to those of example 1, temperatures of the internal mixer and the open mill outside the range of the process of the invention lead to an increase in the hardness of the spheres after vulcanization, while comparative example 7 shows that higher vulcanization temperatures and vulcanization gas pressure drops lower the rebound height of the finished spheres, i.e.the elasticity of the spheres, in the case of identical compositions.
Example 6
A preparation method of a low-temperature vulcanized rubber ball is different from that of the embodiment 1 in that in the step (4), after a rubber skin is attached to the surface of a bladder, an attaching machine is continuously used for attaching leather to the outer surface of the rubber skin, and rubber has fluidity under the low-temperature vulcanization condition, so that rubber materials are promoted to better flow and penetrate into a fabric layer at the bottom of the leather, and the rubber skin is firmly connected with the leather.
In the present invention, the amount of the color gum component varies with the color requirement of the spheres, and example 7 is performed below by taking PB11 malachite blue as an example in the GSB national standard color number.
Example 7: the difference from example 1 is that the amount of the color paste used is 4 parts.
Comparative example 8: the difference from example 1 is that the vulcanization temperature is 160 ℃ and the air pressure is 10kgf/cm 2 . The dosage of the color glue is 4 parts, and the color of the prepared rubber ball is PB06 light blue in GSB national standard color number
Comparative example 9: the difference from example 1 is that the vulcanization temperature was 160 ℃ and the air pressure was 10kgf/cm 2 . The amount of the color glue is 4.2 parts, and the color of the prepared rubber ball is PB11 peacock blue in GSB national standard color number.
As can be seen from the example 7 and the comparison groups 8-9, the use amount of the color rubber can be reduced in the example, so that the color rubber has brighter color under the action of the same color rubber amount, and the use amount of the color rubber is reduced by 5% under the low-temperature condition.
It should be noted that, in this document, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the phrases "comprising 8230; \8230;" or "comprising 8230; \8230;" does not exclude additional elements from existing in a process, method, article, or terminal device that comprises the element. Further, in this document, "greater than," "less than," "more than," and the like are understood to not include the present numbers; the terms "above", "below", "within" and the like are to be understood as including the number.
Although the embodiments have been described, other variations and modifications of the embodiments may occur to those skilled in the art once they learn of the basic inventive concepts, so that the above description is only for the embodiments of the present invention, and does not limit the scope of the invention.
Claims (5)
1. The low-temperature vulcanized rubber ball is characterized by comprising the following components in parts by weight:
50-80 parts of natural rubber, 20-50 parts of styrene butadiene rubber, 80-100 parts of calcium carbonate, 30-50 parts of white carbon black, 5-10 parts of zinc oxide, 1-3 parts of stearic acid, 2-5 parts of tackifying resin, 2-5 parts of dibutyl hydroxy toluene, 1-3 parts of protective wax, 1-2 parts of MB, 2-4 parts of flow exhaust agent PW, 5-10 parts of white factice, 5-10 parts of naphthenic oil, 2-4 parts of accelerator BZ, 1-2 parts of accelerator PZ, 1-2 parts of accelerator SIP, 2-4 parts of sulfur and a plurality of parts of color cement;
the preparation method of the low-temperature vulcanized rubber ball comprises the following steps:
(1) Weighing natural rubber, styrene butadiene rubber, calcium carbonate, white carbon black, zinc oxide, stearic acid, tackifying resin, dibutyl hydroxy toluene, protective wax, MB, a flow exhaust agent PW, white factice and naphthenic oil, and mixing by using an internal mixer to form unpromoted rubber, wherein the temperature of the internal mixer is 110-135 ℃, and the mixing time is 4-6min;
(2) Weighing an accelerator BZ, an accelerator PZ, an accelerator SIP, sulfur and colored rubber, uniformly mixing the accelerator BZ, the accelerator PZ, the accelerator SIP, the sulfur, the colored rubber and unpromoted rubber compound on an open mill to form promoted rubber, controlling the temperature of a roller of the open mill to be 35-55 ℃, and mixing for 3-4min;
(3) Preparing the accelerated rubber into a rubber sheet through a calender, and cooling and shaping the prepared rubber sheet;
(4) Cooling and shaping the rubber sheet, cutting the rubber sheet into rubber skin by using a cutting die, and attaching the rubber skin to the surface of the bladder by using an attaching machine to form an unvulcanized rubber ball;
(5) Vulcanizing the unvulcanized rubber ball by using a vulcanizing machine at 90-110 deg.C for 13-18min under 4-6kgf/cm 2 。
2. The low temperature vulcanized rubber ball of claim 1, which comprises the following components in parts by weight:
60 parts of natural rubber, 40 parts of styrene-butadiene rubber, 90 parts of calcium carbonate, 40 parts of white carbon black, 5 parts of zinc oxide, 2 parts of stearic acid, 3 parts of tackifying resin, 3 parts of dibutyl hydroxy toluene, 2 parts of protective wax, 1.5 parts of MB, 3 parts of flow exhaust agent PW, 8 parts of white factice, 8 parts of naphthenic oil, 3 parts of accelerator BZ, 1 part of accelerator PZ, 1 part of accelerator SIP, 2 parts of sulfur and a plurality of parts of color cement.
3. A method for preparing low temperature vulcanized rubber balls as claimed in any one of claims 1 to 2, comprising the steps of:
(1) Weighing natural rubber, styrene butadiene rubber, calcium carbonate, white carbon black, zinc oxide, stearic acid, tackifying resin, dibutyl hydroxy toluene, protective wax, MB, a flow exhaust agent PW, white factice and naphthenic oil, and mixing by using an internal mixer to form unpromoted rubber, wherein the temperature of the internal mixer is 110-135 ℃, and the mixing time is 4-6min;
(2) Weighing an accelerator BZ, an accelerator PZ, an accelerator SIP, sulfur and colored rubber, and uniformly mixing the accelerator BZ, the accelerator PZ, the accelerator SIP, the sulfur, the colored rubber and unpromoted rubber compound on an open mill to form the promoted rubber, wherein the temperature of a roller of the open mill is controlled at 35-55 ℃, and the mixing time is 3-4min;
(3) Preparing the accelerated rubber into a rubber sheet through a calender, and cooling and shaping the prepared rubber sheet;
(4) Cooling and shaping the rubber sheet, cutting the rubber sheet into rubber skin by using a cutting die, and attaching the rubber skin to the surface of the bladder by using an attaching machine to form an unvulcanized rubber ball;
(5) Vulcanizing unvulcanized rubber balls by using a vulcanizing machine at the vulcanizing temperature of 90-110 ℃ for 13-18min and under the air pressure of 4-6kgf/cm to obtain vulcanized rubber balls 2 。
4. The method for preparing low-temperature vulcanized rubber balls as claimed in claim 3, wherein in the step (3), the temperature of the roller of the calender is 50-65 ℃, the temperature for cooling and shaping is below 22 ℃, and the time for cooling and shaping is 1-3h.
5. The method for preparing low-temperature vulcanized rubber balls according to claim 3, wherein in the step (4), after the rubber skin is attached to the surface of the bladder, leather is attached to the outer surface of the rubber skin by using an attaching machine.
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| US2764572A (en) * | 1952-11-04 | 1956-09-25 | Columbia Southern Chem Corp | Compounded rubber stock |
| JP2002020537A (en) * | 2000-07-11 | 2002-01-23 | Jsr Corp | Rubber composition |
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| CN108440775A (en) * | 2018-02-22 | 2018-08-24 | 山东星宇手套有限公司 | A kind of preparation method of the natural rubber gloves of no blooming |
| CN109517229A (en) * | 2018-11-30 | 2019-03-26 | 上海双浦橡胶防腐衬里有限公司 | A kind of low-temp low-pressure vulcanized rubber liner compositions and its application method |
| FR3074183A1 (en) * | 2017-11-30 | 2019-05-31 | Compagnie Generale Des Etablissements Michelin | HIGH MODULE RUBBER COMPOSITION COMPRISING AN EFFECTIVE SELF-RETICULATING SYSTEM |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2764572A (en) * | 1952-11-04 | 1956-09-25 | Columbia Southern Chem Corp | Compounded rubber stock |
| JP2002020537A (en) * | 2000-07-11 | 2002-01-23 | Jsr Corp | Rubber composition |
| CN107141510A (en) * | 2017-06-26 | 2017-09-08 | 常州市五洲环保科技有限公司 | Easy decentralized zinc-base vulcanization accelerator and preparation method thereof |
| FR3074183A1 (en) * | 2017-11-30 | 2019-05-31 | Compagnie Generale Des Etablissements Michelin | HIGH MODULE RUBBER COMPOSITION COMPRISING AN EFFECTIVE SELF-RETICULATING SYSTEM |
| CN108440775A (en) * | 2018-02-22 | 2018-08-24 | 山东星宇手套有限公司 | A kind of preparation method of the natural rubber gloves of no blooming |
| CN109517229A (en) * | 2018-11-30 | 2019-03-26 | 上海双浦橡胶防腐衬里有限公司 | A kind of low-temp low-pressure vulcanized rubber liner compositions and its application method |
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