CN110577680A - light anti-skid rubber sole material and manufacturing method thereof - Google Patents
light anti-skid rubber sole material and manufacturing method thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/0023—Use of organic additives containing oxygen
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2323/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2407/00—Characterised by the use of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
Abstract
The invention discloses a light anti-slip rubber sole material and a manufacturing method thereof, wherein the sole material is prepared by blending and foaming the following materials in parts by weight: 15-30 parts of brominated butyl rubber, 15-30 parts of solution-polymerized styrene-butadiene rubber, 15-30 parts of neodymium butadiene rubber, 10-30 parts of syndiotactic polybutadiene resin, 5-20 parts of natural rubber, 1-2 parts of tackifying resin, 10-15 parts of fumed silica, 3-5 parts of zinc oxide, 1-3 parts of a silica activator, 0.5-2.0 parts of a silane coupling agent, 0.5-1.0 part of stearic acid, 3-4 parts of a chemical anti-aging agent, 0.5-1.0 part of a physical anti-aging agent, 0.5-1.5 parts of insoluble sulfur and 1-2 parts of an accelerator. The rubber sole provided by the invention can realize light weight and good slip resistance at the same time, and has good market prospect.
Description
Technical Field
the invention relates to the technical field of shoe manufacturing, in particular to a light anti-skid rubber sole material and a manufacturing method thereof.
Background
the sole material is an important component of a shoe, and the quality of the sole material not only determines the performance of a pair of shoes, but also influences the comfort of a wearer. With the improvement of living standard and body-building consciousness, people pay more and more attention to the performance requirements of sole materials, and the sole is required to be antiskid and wear-resistant, and have multiple additional functions of light weight, softness, comfort and the like or be suitable for specific purposes. Rubber is the sole material of most shoes at present due to relatively good wear resistance. However, the existing rubber soles are more focused on improving the wear resistance and the skid resistance, and the defect of higher density of the rubber outsole is ignored. Because a large amount of reinforcing agent and filler are added, the density of the rubber outsole is 1.0g/cm3Above, even above 1.2g/cm3Resulting in a heavy shoe and poor wearing comfort. Patent application CN101643562A discloses a novel formulation with high slip resistance, which can produce soles with slip resistance coefficient of dry 1.0 and wet 0.8, but it is not mentioned that the formulation can achieve light weight at the same time. Patent application CN109054114A discloses a method for manufacturing an anti-slip rubber sole, the anti-slip coefficient can reach dry 0.9 and wet 0.6, the formula is not mentioned to achieve light weight, and simultaneously, the formula adds a peeling procedure, and the process is complicated.
Some manufacturers also begin to select the EVA wear-resistant undersoles as soles of shoes with light weight requirements. However, the anti-slip performance, especially the wet slip performance, of the EVA wear-resistant outsole is very poor, and the EVA wear-resistant outsole is very easy to fall down in rainy days and cannot meet the normal safety performance requirement. Therefore, it is one of the research hotspots in the industry to improve the physical properties of the rubber sole and make the rubber sole have the advantages of light weight, slip resistance, wear resistance, and the like.
Disclosure of Invention
In order to solve the technical problems, the invention provides a light anti-slip rubber sole material with low density and good anti-slip performance and a manufacturing method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
The light anti-slip rubber sole material is prepared by blending and foaming materials, wherein the materials comprise the following components in parts by weight:
The brominated butyl rubber contains 1-3% of bromine, has a Mooney viscosity of 25-50, and is preferably selected from Langshen X2. The brominated butyl rubber has a wider damping temperature range, has a higher damping factor at room temperature, and has excellent dry and wet slip resistance.
the styrene content of the solution polymerized styrene-butadiene rubber is 25-46%, the Mooney viscosity is 25-60, and the solution polymerized styrene-butadiene rubber is preferably Asahi chemical 303. The solution polymerized styrene butadiene rubber has higher damping factor at 0 ℃, and can improve the wet-type slip resistance of the sole.
The cis-structure of the neodymium butadiene rubber is more than 95 percent, the Mooney viscosity is 40-70, and Langshan CB24 is preferred. The neodymium series butadiene rubber is also called rare earth butadiene rubber, is a novel butadiene rubber variety which is further upgraded and developed on the basis of the traditional titanium, cobalt and nickel series butadiene, has polybutadiene with high cis-1, 4-structure content in the structure, has high structure regularity, can show induced crystallization performance similar to isoprene rubber in a stretching state, and has better performance in the aspects of abrasion, heat generation, aging and the like than the traditional butadiene rubber.
The syndiotactic polybutadiene resin has 1, 2-butadiene structure content of more than 90 percent, crystallinity of 15-35 percent, preferably JSR RB 840. The syndiotactic polybutadiene resin is a poly 1, 4-butadiene structure which is polymerized by using cis-butadiene as a raw material and is different from butadiene rubber, and the molecular structure of the syndiotactic polybutadiene resin is that the syndiotactic content containing 1, 2 double bonds exceeds more than 90 percent, and the syndiotactic polybutadiene resin has rubber physical property and plastic processability. The preferable RB840 resin has the crystallinity of 34 percent and the Shore hardness of 97A, and can obviously improve the hardness of the product only by proper dosage. Meanwhile, the syndiotactic butadiene resin has good compatibility with other materials in the formula, has little influence on abrasion and mechanical property after being added, and is superior to thermoplastic materials such as POE, EVA and the like.
The grade of the natural rubber is selected from Vietnam SVR-3L standard rubber. SVR-3L natural rubber is a common natural rubber product, has balanced comprehensive performance and cost, and is widely applied to rubber sole formulations. Compared with the artificial synthetic rubber, the natural rubber has the optimal mechanical property, and the proper amount of the natural rubber can ensure that the mechanical properties such as the tensile strength, the elongation at break, the tearing strength and the like of the formula can reach the standard.
The tackifying resin is selected from one of C5 petroleum resin, C9 petroleum resin and terpene resin, and is preferably C5 petroleum resin. The petroleum resin is a thermoplastic resin produced by processing and polymerizing C5 and C9 components after petroleum cracking, has the molecular weight of 300-3000, and can play roles of tackifying and softening in a rubber formula. The C5 petroleum resin has low softening point, light color, less peculiar smell, low unsaturation degree, good compatibility with rubber, and good mechanical property, and the sole is not easy to yellow compared with other tackifying resins.
The white carbon black is fumed silica. The white carbon black commonly used at present is precipitated white carbon black with the specific surface area of 160m2Per g, whereas fumed silica can usually reach 200m2more than g, the larger the specific surface area of the white carbon black is, the higher the reinforcing capacity is, and the product with the same filling amount in the formula has higher hardness and mechanical property; meanwhile, the fumed silica is not easy to generate stress whitening phenomenon in the stretching process, namely the fatigue resistance of the fumed silica after repeated bending is more excellent.
The white carbon black active agent is selected from one or two of diethylene glycol and PEG4000, and PEG4000 is preferred.
The silane coupling agent type number is selected from Texaco SI 69.
The chemical anti-aging agent is selected from one or more of SP, BHT and MB, preferably SP.
The physical anti-aging agent is selected from microcrystalline paraffin.
The promoter is selected from one or more of D, DM and TS, and is preferably DM.
The manufacturing method of the light anti-slip rubber sole material comprises the following steps:
(1) Weighing the components in parts by weight respectively;
(2) placing brominated butyl rubber, solution polymerized butadiene styrene rubber, neodymium series butadiene rubber, syndiotactic butadiene resin, natural rubber, tackifying resin, gas phase white carbon black, zinc oxide, white carbon black active agent, silane coupling agent, stearic acid, chemical anti-aging agent and physical anti-aging agent into an internal mixer for banburying, discharging rubber at 115 ℃ and 120 ℃ and discharging sheets, and placing for more than 24 hours at room temperature;
(3) continuously mixing the mixed components obtained in the step (2) in an open type rubber mixing mill, adding insoluble sulfur and an accelerant, uniformly mixing, and uniformly discharging pieces according to the required specification;
(4) and (3) cutting the obtained mixed sheet into a sole shape, putting the sole shape into a rubber sole mold, and vulcanizing and molding at the molding temperature of 155 ℃ to obtain the light anti-skid rubber sole material.
According to the technical scheme, brominated butyl rubber and solution-polymerized butadiene styrene rubber with excellent dry-wet skid resistance are selected, high-crystalline syndiotactic polybutadiene resin is matched to improve the hardness of the main rubber, filling reinforcing agents are reduced, and meanwhile, neodymium series butadiene rubber and natural rubber are added to ensure the wear resistance and the tensile property balance of the material. The filler is selected from fumed silica with high specific surface area, the reinforcing effect is better than that of the common precipitated silica, and the over-high density of the finished product under high filling is avoided.
The invention has the beneficial effects that: by providing the foamable composition with a proper proportion and carrying out foaming production, the rubber sole material with the advantages of light weight, skid resistance and the like can be produced. Compared with most of the existing commercially available rubber sole materials, the density of the light anti-skid sole can be lower than 1.0g/cm3At the same time, rubThe coefficient is not less than 0.9 in a dry mode, and not less than 0.6 in a wet mode, so that the antiskid sports shoe has good antiskid performance, simultaneously realizes a light weight effect, can greatly reduce the running gravity burden of sports shoe wearers, improves the wearing comfort of consumers, and has good market prospect.
Detailed Description
In order that the present invention and the claims thereof may be fully understood, preferred embodiments of the present invention are illustrated below, but not limited thereto.
Example 1
A manufacturing method of a light anti-skid rubber sole material comprises the following steps:
(1) Weighing the following components in parts by weight: 20 parts of brominated butyl rubber (BIIR), 30 parts of solution polymerized styrene-butadiene rubber (SSBR), 20 parts of neodymium butadiene rubber (NdBR), 20 parts of syndiotactic polybutadiene Resin (RB), 10 parts of Natural Rubber (NR), 1 part of tackifying resin, 15 parts of white carbon black, 4 parts of zinc oxide, 1 part of white carbon black active agent, 1 part of silane coupling agent, 0.5 part of stearic acid, 4 parts of chemical anti-aging agent, 0.5 part of physical anti-aging agent, 1 part of insoluble sulfur and 2 parts of accelerator;
(2) placing brominated butyl rubber, solution polymerized butadiene styrene rubber, neodymium series butadiene rubber, syndiotactic butadiene resin, natural rubber, tackifying resin, white carbon black, zinc oxide, white carbon black active agent, silane coupling agent, stearic acid, chemical anti-aging agent and physical anti-aging agent into an internal mixer for banburying, discharging rubber at 120 ℃ and discharging sheets, and placing for 24 hours at room temperature;
(3) Continuously mixing the obtained mixed components in an open rubber mixing mill, adding insoluble sulfur and a vulcanization accelerator, uniformly mixing, and uniformly discharging sheets according to required specifications;
(4) And (3) cutting the mixing sheets into a sole shape, putting the mixture into a rubber sole mold, and vulcanizing and molding at the molding temperature of 155 ℃ to obtain the light anti-slip rubber sole.
wherein, the components of the formula related by the invention are all normal commercial products. The preparation equipment is common rubber and plastic processing equipment, and can realize the production of products without changing the existing production home processing system.
Examples 2 to 6
Preparation of light anti-skid rubber sole material
following the same procedure as in example 1, examples 2-6 and comparative examples 1-3 were obtained by replacing only the raw materials and their parts by weight as listed in Table 1.
TABLE 1 raw material formulation of anti-slip rubber sole material
The formulations of comparative examples 1-3 were fine-tuned based on example 6 and the articles were tested for other physical properties at the same hardness.
TABLE 2 Properties of the products of the examples and comparative examples
As can be seen from Table 2, the density of the products of examples 1 to 6 was less than 1.0g/cm3However, the slip resistance performance of the examples 2 and 4 is poor, and the other examples can reach the set index. From the above data, it can be seen that the density of the sole prepared from the light anti-slip rubber prepared by the example of the present invention is less than 1.0g/cm3The friction coefficient is not less than 0.9 in dry type and not less than 0.6 in wet type.
From comparative example 1 and example 6, it can be seen that if syndiotactic polybutadiene resin is not added, more fumed silica must be added to the formulation to balance the hardness of the product, and the test result shows that the density is much higher than 1.0g/m3。
As can be seen from comparative example 2 and example 6, the precipitated silica is used in an amount higher than that of fumed silica, and the tested density is more than 1.0g/m3。
As can be seen from comparative example 3 and example 6, the wear resistance of the product is poor and the wet slip is slightly low by replacing neodymium butadiene rubber with common butadiene rubber.
By adding syndiotactic polybutadiene resin with the crystallinity of 15-29 percent, the hardness requirement of the sole can be met without adding a large amount of filling reinforcing agent, thereby reducing the using amount of the filling reinforcing agent and effectively reducing the density. The wear-resistant wet-skid performance of the sole can be further improved by selecting the neodymium butadiene rubber with better physical properties.
The friction coefficient of the light anti-skidding sole prepared by the invention is not lower than 0.9 in a dry mode and not lower than 0.6 in a wet mode, and the density is 1.0g/cm3The product is wear-resistant and folding-resistant, and the light-colored product is not easy to yellow and discolor.
Claims (10)
1. The light anti-slip rubber sole material is characterized in that: the foaming agent is prepared by blending and foaming materials, wherein the materials comprise the following components in parts by weight:
Brominated butyl rubber 15-30 parts
15-30 parts of solution polymerized styrene-butadiene rubber
15-30 parts of neodymium butadiene rubber
10-30 parts of syndiotactic polybutadiene resin
5-20 parts of natural rubber
1-2 parts of tackifying resin
10-15 parts of fumed silica
3-5 parts of zinc oxide
1-2 parts of white carbon black active agent
0.5-2.0 parts of silane coupling agent
0.5 to 1.0 portion of stearic acid
3-4 parts of chemical anti-aging agent
0.5 to 1.0 portion of physical anti-aging agent
0.5 to 1.5 portions of insoluble sulfur
1-2 parts of an accelerator.
2. The lightweight non-slip rubber sole material as set forth in claim 1, wherein: the brominated butyl rubber contains 1-3% of bromine and has a Mooney viscosity of 25-50%.
3. The lightweight non-slip rubber sole material as set forth in claim 1, wherein: the styrene content of the solution polymerized styrene-butadiene rubber is 25-46%, and the Mooney viscosity is 25-60%.
4. The lightweight non-slip rubber sole material as set forth in claim 1, wherein: the cis-structure of the neodymium butadiene rubber is more than 95 percent, and the Mooney viscosity is 40-70.
5. The lightweight non-slip rubber sole material as set forth in claim 1, wherein: the syndiotactic polybutadiene resin has 1, 2-butadiene structure content over 90% and crystallinity of 15-35%.
6. The lightweight non-slip rubber sole material as set forth in claim 1, wherein: the natural rubber is Vietnam SVR-3L standard rubber, and the tackifying resin is selected from one of C5 petroleum resin, C9 petroleum resin and terpene resin.
7. The lightweight non-slip rubber sole material as set forth in claim 1, wherein: the white carbon black active agent is one or two of diethylene glycol and PEG4000, and the silane coupling agent is Degussa SI 69.
8. The lightweight non-slip rubber sole material as set forth in claim 1, wherein: the chemical anti-aging agent is selected from one or a combination of more of SP, BHT and MB, the physical anti-aging agent is microcrystalline paraffin, and the accelerator is selected from one or a combination of more of D, DM and TS.
9. A method of manufacturing a lightweight non-slip rubber sole material as claimed in any one of claims 1 to 8, wherein: which comprises the following steps:
(1) Weighing the components in parts by weight respectively;
(2) Placing brominated butyl rubber, solution polymerized butadiene styrene rubber, neodymium series butadiene rubber, syndiotactic butadiene resin, natural rubber, tackifying resin, gas phase white carbon black, zinc oxide, white carbon black active agent, silane coupling agent, stearic acid, chemical anti-aging agent and physical anti-aging agent into an internal mixer for banburying, discharging rubber at 115 ℃ and 120 ℃ and discharging sheets, and placing for more than 24 hours at room temperature;
(3) continuously mixing the mixed components obtained in the step (2) in an open type rubber mixing mill, adding insoluble sulfur and an accelerant, uniformly mixing, and uniformly discharging pieces according to the required specification;
(4) And (3) blanking the obtained mixing sheet into a sole shape, putting the mixture into a rubber sole mold, and vulcanizing and molding to obtain the light anti-slip rubber sole material.
10. The method for manufacturing a lightweight non-slip rubber sole material as claimed in claim 9, wherein: the molding temperature in the step (4) was 155 ℃.
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| CN111363233A (en) * | 2020-04-26 | 2020-07-03 | 李忠欣 | High-performance odorless thermoplastic rubber and preparation method thereof |
| CN112029165A (en) * | 2020-08-27 | 2020-12-04 | 茂泰(福建)鞋材有限公司 | Ozone-aging-resistant light-colored rubber sole and preparation method thereof |
| CN112574478A (en) * | 2020-11-24 | 2021-03-30 | 福建省莆田市联盛鞋业有限公司 | Composition of ice top-dead-slip sheet, preparation method and ice top-dead-slip sole material |
| CN113444303A (en) * | 2021-07-28 | 2021-09-28 | 茂泰(福建)鞋材有限公司 | Anti-slippery bio-based rubber sole and preparation method and mold thereof |
| CN113683821A (en) * | 2021-08-31 | 2021-11-23 | 安踏（中国）有限公司 | Noise-reducing soft rubber outsole and preparation method and application thereof |
| CN115260616A (en) * | 2022-08-31 | 2022-11-01 | 泉州匹克鞋业有限公司 | Anti-slip rubber sole material and manufacturing method thereof |
| CN115304837A (en) * | 2021-08-09 | 2022-11-08 | 温州市优联新材料有限公司 | Antiskid sole material and preparation method thereof |
| CN117247610A (en) * | 2023-10-10 | 2023-12-19 | 广东力宇益宝鞋材有限公司 | Vegetarian leather sole material and preparation method thereof |
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| CN112029165B (en) * | 2020-08-27 | 2022-08-19 | 茂泰(福建)鞋材有限公司 | Ozone aging resistant light-colored rubber sole and preparation method thereof |
| CN112574478A (en) * | 2020-11-24 | 2021-03-30 | 福建省莆田市联盛鞋业有限公司 | Composition of ice top-dead-slip sheet, preparation method and ice top-dead-slip sole material |
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| CN113683821A (en) * | 2021-08-31 | 2021-11-23 | 安踏（中国）有限公司 | Noise-reducing soft rubber outsole and preparation method and application thereof |
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Application publication date: 20191217 |