CN101543325B - Anti-crocking rubber sole - Google Patents
Anti-crocking rubber sole Download PDFInfo
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- CN101543325B CN101543325B CN2009101115020A CN200910111502A CN101543325B CN 101543325 B CN101543325 B CN 101543325B CN 2009101115020 A CN2009101115020 A CN 2009101115020A CN 200910111502 A CN200910111502 A CN 200910111502A CN 101543325 B CN101543325 B CN 101543325B
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- rubber
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- crocking
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 65
- 239000005060 rubber Substances 0.000 title claims abstract description 65
- 239000002994 raw material Substances 0.000 claims abstract description 34
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008117 stearic acid Substances 0.000 claims abstract description 10
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000003213 activating effect Effects 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000011787 zinc oxide Substances 0.000 claims abstract description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims abstract description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 28
- 238000007670 refining Methods 0.000 claims description 17
- 239000005864 Sulphur Substances 0.000 claims description 16
- 238000007599 discharging Methods 0.000 claims description 14
- 238000004513 sizing Methods 0.000 claims description 14
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 claims description 13
- 229960004029 silicic acid Drugs 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000013461 design Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 244000043261 Hevea brasiliensis Species 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005062 Polybutadiene Substances 0.000 claims description 6
- 238000010009 beating Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 229920003052 natural elastomer Polymers 0.000 claims description 6
- 229920001194 natural rubber Polymers 0.000 claims description 6
- 229920002857 polybutadiene Polymers 0.000 claims description 6
- 125000006850 spacer group Chemical group 0.000 claims description 6
- 238000002474 experimental method Methods 0.000 claims description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 239000004200 microcrystalline wax Substances 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000003921 oil Substances 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005259 measurement Methods 0.000 abstract description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 abstract 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 abstract 1
- 239000002530 phenolic antioxidant Substances 0.000 abstract 1
- 229920001195 polyisoprene Polymers 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 229920003048 styrene butadiene rubber Polymers 0.000 abstract 1
- 238000013329 compounding Methods 0.000 description 30
- 239000004615 ingredient Substances 0.000 description 30
- 238000005516 engineering process Methods 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 241000218691 Cupressaceae Species 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 3
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- 229960002447 thiram Drugs 0.000 description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- UEZWYKZHXASYJN-UHFFFAOYSA-N cyclohexylthiophthalimide Chemical compound O=C1C2=CC=CC=C2C(=O)N1SC1CCCCC1 UEZWYKZHXASYJN-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000010721 machine oil Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- MNDJKTIGCWCQIG-UHFFFAOYSA-N 4-n-naphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(C=CC=C2)C2=C1 MNDJKTIGCWCQIG-UHFFFAOYSA-N 0.000 description 1
- JFISFZKKYWLPPP-UHFFFAOYSA-N 4-sulfanyl-3h-1,3-benzothiazole-2-thione Chemical compound C1=CC=C2SC(S)=NC2=C1S JFISFZKKYWLPPP-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- KYYWBEYKBLQSFW-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCC(O)=O KYYWBEYKBLQSFW-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 230000010181 polygamy Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000013138 pruning Methods 0.000 description 1
- 230000000306 recurrent effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- NCSQKSMOKBZEDF-UHFFFAOYSA-L zinc;n-methyl-n-phenylcarbamodithioate Chemical compound [Zn+2].[S-]C(=S)N(C)C1=CC=CC=C1.[S-]C(=S)N(C)C1=CC=CC=C1 NCSQKSMOKBZEDF-UHFFFAOYSA-L 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an anti-crocking rubber sole and relates to a rubber sole. The invention provides the anti-crocking rubber sole with low production cost, long service life, ageing resistance and no crocking and a method for manufacturing the same. Raw materials comprise A and B; the raw material A comprises 72.9 percent of cis-1,4-polybutadiene rubber, 20.2 percent of caoutchouc, 6.9 percent of styrene-butadiene rubber, 44.5 percent of precipitated hydrated silicon dioxide, 0.8 percent of bi-(3- propyl triethoxysilane)- tetrasulfide, 5.3 percent of zinc oxide, 3.5 to 4.5 percent of polyethylene glycol, 1.0 to 2.0 percent of stearic acid, 1.1 percent of rubber viscosity increaser, 0.8 percent of activating agent, 0.3 to 0.6 percent of phenolic antioxidant, 0.4 percent of tackifying resin and 1.0 percent of antifogging agent; the raw material B comprises insoluble sulfur, tetramethylthiuram monosulfide and an accelerant; and the ratio of the A to the insoluble sulfur to the tetramethylthiuram monosulfide to the accelerant is 500 : 1.0-2.5 :1.0 : 0.7. The anti-crocking rubber sole is prepared by banburying, mill opening, sulfur treatment, measurement of a vulcanizing curve, oil pressure molding and a crocking test.
Description
Technical field
The present invention relates to a kind of rubber soles, especially relate to a kind of factory formula of anti-bloom rubber soles.
Background technology
China is the footwear producing country and the exported country of whole world maximum at present, yet the recurrent bloom problem of rubber soles has become one of limiting factor of present Chinese shoe industry, and bloom also has certain seasonality, and to summer and autumn, the probability that the bloom problem occurs is higher.The rubber surface bloom has not only seriously influenced the presentation quality of product, and also affects to a certain extent the serviceability and the life-span of rubber, also affects the processing performance and the physical and mechanical properties of sizing material.Bloom also can cause sizing material incipient scorch and goods aging, and it is aging so just to have accelerated goods, has shortened service life.The harm of bloom brings enormous economic loss for sole manufacturer.
The bloom of rubber soles is meant the compounding ingredients such as sulphur, wax class, promoter, age resistor, plasticizer and filler that cooperate in the rubber, from sizing material or goods internal migration to the surface and separate out phenomenon like materials such as frosts.The consumption that its essential reason is these compounding ingredients has exceeded the solubility in sizing material or vulcanizate, turns to due to the stable state from metastable state.
The rubber bloom is that by the top layer migration precipitation of interior course, when compounding ingredient was reduced to its saturation state in rubber, precipitation process just came to an end again because after the inner compounding ingredient of rubber reached hypersaturated state, the compounding ingredient on the nearly top layer of rubber was at first separated out.Make compounding ingredient reach hypersaturated state, cause the main cause of rubber bloom to have: sizing compound formula design is improper, technological operation is improper, raw material quality fluctuation, ageing of rubber etc., below makes simple analysis with regard to the problems referred to above.
(1) the prescription design is improper
The consumption of the prescription improper main assignment mixture of design in rubber surpasses its maximum use amount.(mainly being temperature, secondly is pressure) general compounding ingredient all has certain solubility in rubber under certain condition, and the use level that reaches compounding ingredient solubility is called the maximum use amount of compounding ingredient.During the prescription design, the compounding ingredient consumption surpasses its maximum use amount, and compounding ingredient just can not be dissolved in the rubber fully, makes compounding ingredient reach hypersaturated state in rubber.The state because compounding ingredient finally will reach capacity in rubber, therefore in being tending towards the saturation state process, excess is used, undissolvable compounding ingredient just will be separated out, and forms bloom at rubber surface.Generally, the improper compounding ingredient of bloom that causes easily of prescription design has vulcanizing agent: sulphur; Promoter: dibenzothiazyl disulfide (DM), tetramethylthiuram disulfide (TMTD), 2-benzothiazolyl mercaptan (M), tetramethylthiuram monosulfide (TMTM), ethylene thiourea (NA-22) etc.; Age resistor: N-PBNA (D), N, N '-diphenyl-para-phenylene diamine and PBNA mixture (H), CPPD N cyclohexyl N (4010), N, N ' two (betanaphthyl) p-phenylenediamine (PPD) (DNP), 2 mercapto benzimidazole (MB), paraffin etc.; Plasticizer: machine oil, ester class wet goods; Activating agent: zinc oxide, stearic acid etc.; Filler: fine particle calcium carbonate, magnesium carbonate etc.; Antiscorching agent: N-cyclohexylthiophthalimide (CTP) etc.
(2) technological operation is improper
When sizing material was produced, at first the compounding ingredient weighing was wanted accurately, in order to avoid cause polygamy, made the consumption of compounding ingredient surpass its maximum consumption in rubber, and caused bloom.Secondly, smash the glue inequality in order to avoid cause by the abundant pressing of technological operation, compounding ingredient disperses irregular, makes that compounding ingredient local concentration in sizing material is excessive, reaches hypersaturated state, and causes bloom.
(3) raw material quality fluctuation
Rubber mostly belongs to industrial goods with compounding ingredient, and purity is not high, and its composition and usually said chemicals have a great difference.Chemical composition such as vulcanization accelerator and antiaging agent is still more clearly in any case, and other compounding ingredient is very rough.For example, the rubber stearic acid is a kind of fatty acid mixed, is not pure stearic acid, and it only is equivalent to the mixture of hexadecanoic acid (palmitic acid) and oleic acid.Other materials such as zinc oxide, magnesia and carbon black are sneaked into a lot of impurity in the mill.Material such as fine particle calcium carbonate, potter's clay has very big difference because of place of production material difference, method for making difference, technology difference, batch difference.Fluctuation takes place the compounding ingredient quality will cause that its purity, moisture, ash content, pH value, physical property etc. change, and these factor affecting its solubility in rubber.If solubility descends, just bloom can take place compounding ingredient.
(4) ageing of rubber
Ageing of rubber mostly causes the network structure of the complete equilibrium of vulcanizate to destroy, thereby also destroyed the chemistry between the various compounding ingredients and rubber molecule and compounding ingredient in the rubbery system or physics combines, and has reduced the solubility of compounding ingredient in rubbery system.Therefore, those parts are in the compounding ingredient of hypersaturated state just can emanate out from the rubber middle reaches, forms bloom.The bloom that ageing of rubber causes is different with the bloom of other type.It is not occur in easily that temperature is low, the winter of high humidity and autumn, but occur in the environment of high summer of temperature and exposure in sunshine.
Publication number provides a kind of factory formula for aging-resistant rubber strip for the application for a patent for invention of CN101104711, and this prescription is made up of neoprene, natural gum, sulphur, vulcanizing agent DTDM, zinc oxide, antioxidant 4010 Na, age resistor ODA, stearic acid, paraffin, high abrasion carbon black, altax, accelerant N a-22 and machine oil.Its preparation method is, earlier with material after the refining of face refining machine side, and then take by weighing sizing material after the face refining of constant weight and put into vulcanizer and vulcanize, after sulfuration finished, product was finished product through pruning.It is low, ageing-resistant that this product has a production cost, long service life, the advantage of outer surface no blooming.
Notification number provides a kind of preparation method of EPDM rubber waterproof rolling material for the patent of invention of CN1281886.This method adopts the vulcanizing system that adds low temperature short vulcanization auxiliary agent with sulphur.Auxiliary agent is: dimercapto benzothiazole, dibenzothiazyl disulfide, tetramethylthiuram disulfide, zinc methylphenyldithiocarbamate, ethylene thiourea.This invention has also added anti-spray pitch except that selecting the anti-bloom of mixed aid, improved the reliability of blowout prevention, is beneficial to bonding.Pitch has improved processing characteristics again in whole system, make the easier mixing of sizing material, helps improving the physical property of waterproof roll.Add the making that the anti-bloom of mixed aid is used for EPDM rubber waterproof rolling material, help improving the physical property of waterproof roll.
Publication number provides a kind of high elastic semitransparent rubber particle surface for table tennis bat for the application for a patent for invention of CN1911989, comprise matrix material, solubilizer, Sulfur, vulcanizing activator and the vulcanization accelerator be made up of natural rubber and butadiene rubber blend, its prescription quality consists of: natural rubber 40-80 part; Butadiene rubber 20-60 part; Solubilizer 1-5 part; Sulphur 1.5-3.5 part; Vulcanizing activator 2-5 part; Vulcanization accelerator 1-2.5 part.
Although above-mentioned patent documentation has been done suitable research to the anti-bloom of some materials,, make that it can only be as the reference of preventing the bloom shoe sole production because the footwear material has than big-difference with above-mentioned in manufacture craft, raw material.And up to the present, yet there are no about the relevant patent in the anti-bloom aspect of material for sole of shoe.
Summary of the invention
The objective of the invention is provides a kind of not only production cost low, long service life, ageing-resistant, and does not have anti-bloom rubber soles of bloom and preparation method thereof at the existing bloom difficult problem of existing rubber soles.
The raw material of anti-bloom rubber soles of the present invention is formed and is comprised A part and B part, the raw material of A part is formed and by the prescription of mass ratio is: butadiene rubber 72.9, natural rubber 20.2; butadiene-styrene rubber 6.9; precipitated hydrated silica (have another name called: white carbon) 44.5; two-(3-triethoxysilane propyl group)-tetrasulfide 0.8; zinc oxide 5.3; polyethylene glycol 3.5～4.5, stearic acid 1.0～2.0, rubber tackifier 1.1; activating agent 0.8; phenol antiager 0.3～0.6, tackifying resin 0.4, antifoggant 1.0; The raw material of B part consists of: insoluble sulfur, tetramethylthiuram monosulfide and promoter, press mass ratio, A part gross mass: insoluble sulfur: tetramethylthiuram monosulfide: promoter (MIX-2) is 500: (1.0～2.5): 1.0: 0.7.
Described antifoggant can adopt fully refined paraffin wax, microwax and hydride mixture etc.
The PEG-4000 type polyethylene glycol product that described polyethylene glycol preferably adopts Dongguan, Guangdong grand cypress chemistry Co., Ltd to produce, the RX-80 type rubber tackifier product that rubber tackifier preferably adopts Dongguan, Guangdong grand cypress chemistry Co., Ltd to produce, the MIX-2 type promoter product that the AT-55 type activating agent product that activating agent preferably adopts Dongguan, Guangdong grand cypress chemistry Co., Ltd to produce, promoter preferably adopt Dongguan, Guangdong grand cypress chemistry Co., Ltd to produce.Phenol antiager preferably adopts the Jinchang, Guangzhou to contain the SPB type phenol antiager product that Science and Technology Ltd. produces, antifoggant preferably adopts the Jinchang, Guangzhou to contain the 1956 type antifoggant products that Science and Technology Ltd. produces, insoluble sulfur preferably adopts the Jinchang, Guangzhou to contain the IS type insoluble sulfur product that Science and Technology Ltd. produces, the P-90 type tackifying resin product that tackifying resin preferably adopts east, Jinjiang industrial chemicals Co., Ltd of association to produce.
Described butadiene rubber, natural rubber, butadiene-styrene rubber can adopt the product of Taiwan company of Taiwan Plastic Group, precipitated hydrated silica and two-(3-triethoxysilane propyl group)-tetrasulfide can adopt the product of Jinjiang City Shi Naibao Science and Technology Ltd., and zinc oxide and stearic acid can adopt Hangzhou Oil and Fat Chemical Co., Ltd.'s product.
The preparation method of anti-bloom rubber soles of the present invention may further comprise the steps:
1) material weighing
Prescription raw materials weighing by design;
2) banburying
Rubber-like is mixed with tackifier class raw material, start the banbury banburying, make mixing of materials even, add 2/3 precipitated hydrated silica, continue banburying, rubber and precipitated hydrated silica mix, again caking when treating that temperature reaches 100 ℃, adds other all raw materials and remaining precipitated hydrated silica, when temperature continued to be elevated to 100 ℃, the mixture of all raw materials lumpd once more;
3) open refining
Open refining, sizing material is with the sheet material discharging;
4) add sulphur
Be put in dry place and leave standstill opening the sheet material of producing, bring into use mill to add sulphur, earlier sheet material is played the first time and the triangle bag second time in mill, played triangle bag for the third time again, above roll spacing, leave spacer gel, simultaneously sulphur, vulcanization accelerator and coloring agent are added on the spacer gel, then smash glue, mix, open the refining play and be changed to triangle bag and the clot method of beating, after mixing, discharging;
5) survey curing curve and oil pressure moulding
Clip one small pieces material, become instrument with sulphur and survey curing curve, record time of scorch and sulfurizing time are according to the cure time of record time of scorch and sulfurizing time adjusting hydraulic press, above material is cut into the sole shape be put in oil pressure moulding in the hydraulic press, promptly get the sole sample;
6) hydrolysis bloom experiment
The sole of making is cut a fritter put in the hydrolysis bloom machine, observe after the placement, record bloom phenomenon.
In step 2) in, the turn-on temperature of banbury is preferably 20～30 ℃.
In step 3), the roller spacing of opening refining has just begun to be preferably 3mm, is preferably 7.5mm during discharging, and the main purpose of opening refining is that rubber, compounding ingredient are mixed is more even, and another purpose is to make sizing material with the sheet discharging, is convenient to further processing and handles.
In step 4), described beating is preferably 0.5～1mm with the roll spacing of triangle bag for the second time the first time, and the thickness of discharging is preferably 2.5mm.
In step 6), described placement was preferably placed 3 days.
Because the present invention has carried out deep analysis to the anti-bloom prescription of the sole factor, drawing insoluble sulfur is most important compounding ingredient, and whether its consumption successfully has key effect to sulfuration, and consumption too much can cause sulfuring up.Because the hydrogen bond action power of white carbon is strong, therefore adding polyethylene glycol can effectively improve its dispersiveness, and large usage quantity easily causes bloom because of supersaturation.Because stearic acid is indispensable activating agent in the vulcanizing system, but the amount that is to use has strict requirement, as selects improper easy supersaturation and cause bloom.Phenol antiager can prevent heat ageing, but consumption too much also can cause bloom.This shows that compare with existing rubber soles, the prepared rubber soles of the present invention does not have bloom, product quality is up to state standards.
The specific embodiment
Following examples will the present invention is further illustrated
Embodiment 1: the preparation method of anti-bloom rubber soles of the present invention may further comprise the steps:
1) material weighing
Composition of raw materials sees Table 1, wherein, the addition of insoluble sulfur, tetramethylthiuram monosulfide and promoter is to be that 500g calculates by A part (raw material of A part is formed and comprised butadiene rubber, natural rubber, butadiene-styrene rubber, precipitated hydrated silica, two-(3-triethoxysilane propyl group)-tetrasulfide, zinc oxide, polyethylene glycol, stearic acid, rubber tackifier, activating agent, phenol antiager, tackifying resin and antifoggant) gross mass.
Table 1
2) banburying
Rubber-like is mixed with tackifier class raw material, start the banbury banburying, make mixing of materials even, add 2/3 precipitated hydrated silica, continue banburying, rubber and precipitated hydrated silica mix, and lump again, when treating that temperature reaches 100 ℃, add other all raw materials and remaining precipitated hydrated silica, when temperature continued to be elevated to 100 ℃, the mixture of all raw materials lumpd once more, and the turn-on temperature of banbury is 20 ℃.
3) open refining
Open refining, sizing material is with the sheet material discharging, and the roller spacing of opening refining has just begun to be 3mm, is 7.5mm during discharging, and the main purpose of opening refining is that rubber, compounding ingredient are mixed is more even, and another purpose is to make sizing material with the sheet discharging, is convenient to further processing and handles.
4) add sulphur
Be put in dry place and leave standstill opening the sheet material of producing, bring into use mill to add sulphur, earlier sheet material is played the first time and the triangle bag second time in mill, play triangle bag for the third time again, above roll spacing, leave spacer gel, simultaneously sulphur, vulcanization accelerator and coloring agent are added on the spacer gel, then smash glue, mix, open the refining play and be changed to dozen triangle bag and clot method, after mixing, discharging, describedly beat the first time and the roll spacing of triangle bag for the second time is 0.5mm, the thickness of discharging is 2.5mm.
5) survey curing curve and oil pressure moulding
Clip one small pieces material, become instrument with sulphur and survey curing curve, record time of scorch and sulfurizing time are according to the cure time of record time of scorch and sulfurizing time adjusting hydraulic press, above material is cut into the sole shape be put in oil pressure moulding in the hydraulic press, promptly get the sole sample;
6) hydrolysis bloom experiment
The sole of making is cut a fritter put in the hydrolysis bloom machine, place and observe after 3 days, record bloom phenomenon.
Embodiment 2: similar to Example 1, its difference is that composition of raw materials sees Table 2, and the turn-on temperature of banbury is 25 ℃, and beating is 1mm with the roll spacing of triangle bag for the second time for the first time.
Table 2
Embodiment 3: similar to Example 1, its difference is that composition of raw materials sees Table 3, and the turn-on temperature of banbury is 30 ℃.
Table 3
Embodiment 4: similar to Example 1, its difference is that composition of raw materials sees Table 4, and the turn-on temperature of banbury is 25 ℃, and beating is 1mm with the roll spacing of triangle bag for the second time for the first time.
Table 4
Embodiment 5: similar to Example 1, its difference is that composition of raw materials sees Table 5, and beating is 1mm with the roll spacing of triangle bag for the second time for the first time.
Table 5
Embodiment 6: similar to Example 1, its difference is that composition of raw materials sees Table 6, and the turn-on temperature of banbury is 25 ℃.
Table 6
Embodiment 7: similar to Example 1, its difference is that composition of raw materials sees Table 7, and the turn-on temperature of banbury is 25 ℃.
Table 7
Make sample by above prescription, and be put in the bloom experiment that is hydrolyzed under the hot and humid environment.Take out after 3 days, the record phenomenon, all normal, no bloom.The sole physical property measurement result of embodiment 1～7 is referring to table 8, and is provable thus, by the mentioned above principle component design, can effectively prevent the aging bloom that causes under hot and humid condition.
Table 8
Comparative example 1 (bloom occurring): composition of raw materials sees Table 9.
Table 9
Comparative example 2 (bloom occurring): composition of raw materials sees Table 10.
Table 10
Comparative example 3 (bloom occurring): composition of raw materials sees Table 11.
Table 11
Prescription by above Comparative Examples 1～3 is made sample, and is put in the bloom experiment that is hydrolyzed under the hot and humid environment.Take out after 3 days, the record phenomenon finds that bloom is serious.
Claims (8)
1. anti-bloom rubber soles is characterized in that its raw material is formed and comprises A part and B part, the raw material composition of A part and be butadiene rubber 72.9 by the prescription of mass ratio, natural rubber 20.2, butadiene-styrene rubber 6.9, precipitated hydrated silica 44.5, two-(3-triethoxysilane propyl group)-tetrasulfide 0.8, zinc oxide 5.3, polyethylene glycol 3.5～4.5, stearic acid 1.0～2.0, rubber tackifier 1.1, activating agent 0.8, phenol antiager 0.3～0.6, tackifying resin 0.4, antifoggant 1.0; The raw material of B part consists of: insoluble sulfur, tetramethylthiuram monosulfide and promoter, press mass ratio, A part gross mass: insoluble sulfur: tetramethylthiuram monosulfide: promoter is 500: (1.0～2.5): 1.0: 0.7.
2. a kind of anti-bloom rubber soles as claimed in claim 1 is characterized in that antifoggant is fully refined paraffin wax, microwax and hydride three's a mixture.
3. a kind of according to claim 1 preparation method of anti-bloom rubber soles is characterized in that may further comprise the steps:
1) material weighing
Prescription raw materials weighing by design;
2) banburying
Rubber-like is mixed with tackifier class raw material, start the banbury banburying, make mixing of materials even, add 2/3 precipitated hydrated silica, continue banburying, rubber and precipitated hydrated silica mix, again caking when treating that temperature reaches 100 ℃, adds all remaining raw materials of A part and remaining precipitated hydrated silica, when temperature continued to be elevated to 100 ℃, the mixture of all raw materials lumpd once more;
3) open refining
Open refining, sizing material is with the sheet material discharging;
4) add sulphur
Be put in dry place and leave standstill opening the sheet material of producing, bring into use mill to add sulphur, earlier sheet material is played the first time and the triangle bag second time in mill, played triangle bag for the third time again, above roll spacing, leave spacer gel, partly be added in B on the spacer gel simultaneously, then smash glue, mix, open the refining play and be changed to triangle bag and the clot method of beating, after mixing, discharging;
5) survey curing curve and oil pressure moulding
Clip one small pieces material, become instrument with sulphur and survey curing curve, record time of scorch and sulfurizing time are according to the cure time of record time of scorch and sulfurizing time adjusting hydraulic press, above material is cut into the sole shape be put in oil pressure moulding in the hydraulic press, promptly get the sole sample;
6) hydrolysis bloom experiment
The sole of making is cut a fritter put in the hydrolysis bloom machine, observe after the placement, record bloom phenomenon.
4. as the preparation method of a kind of anti-bloom rubber soles as described in the claim 3, it is characterized in that in step 2) in, the turn-on temperature of banbury is 20～30 ℃.
5. as the preparation method of a kind of anti-bloom rubber soles as described in the claim 3, it is characterized in that in step 3) the roller spacing of opening refining has just begun to be 3mm, is 7.5mm during discharging.
6. as the preparation method of a kind of anti-bloom rubber soles as described in the claim 3, it is characterized in that in step 4), describedly beat the first time and the roll spacing of triangle bag for the second time is 0.5～1mm.
7. as the preparation method of a kind of anti-bloom rubber soles as described in the claim 3, it is characterized in that in step 4) the thickness of discharging is 2.5mm.
8. as the preparation method of a kind of anti-bloom rubber soles as described in the claim 3, it is characterized in that in step 6) that described placement is to place 3 days.
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