CN103184018B - Natural rubber sole surface defect Rapid-Repair glue and preparation method thereof - Google Patents
Natural rubber sole surface defect Rapid-Repair glue and preparation method thereof Download PDFInfo
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- CN103184018B CN103184018B CN201310126766.XA CN201310126766A CN103184018B CN 103184018 B CN103184018 B CN 103184018B CN 201310126766 A CN201310126766 A CN 201310126766A CN 103184018 B CN103184018 B CN 103184018B
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Abstract
The invention discloses a kind of natural rubber sole surface defect Rapid-Repair glue and preparation method thereof, wherein the composition of promoting agent comparatively prior art add magnesium oxide, be not only applicable to the sulfuration under lesser temps, also accelerate vulcanization rate, facilitate concrete operations; Adopt natural rubber sole surface defect Rapid-Repair glue prepared by the present invention and sole bonding good, the Chemical bond of higher degree can be had with its mend a shoe sole sole and repair sheets behind the end, can not come off, effectively can repair defective footwear boots.The present invention is applicable to the Rapid-Repair among a small circle of the defect such as surperficial starved, bubble of the rubber soles caused due to reasons such as forming pressure, rubber, moulds in footwear boots production process.
Description
Technical field
The invention belongs to field of rubber technology, specifically a kind of natural rubber sole surface defect Rapid-Repair glue and preparation method thereof.
Background technology
In natural rubber shoe sole production process, due to the impact of the various factors such as mobility, mold shape of sulfide stress, sizing material, individually can there are some defects as bubble, starved etc. with rear surface in sole at vulcanization forming, though these surface imperfection can not cause quality influence to wearing, affect attractive in appearance.Therefore need to modify this.After modification, these become footwear can to demote sale of dispatching from the factory.Now current method for repairing and mending is at sole defective part site wax.But these paraffin wear in process the actual of footwear boots, because it and rubber soles do not form effective combination, it can be caused to come off from sole, thus not reach real effect of repairing.
Summary of the invention
Technical problem solved by the invention, be to provide a kind of natural rubber sole surface defect Rapid-Repair glue and preparation method thereof, solve to due to reasons such as forming pressure, rubber, moulds in footwear boots production process, the defects such as surperficial starved, bubble carry out the problem of repairing to cause sole to occur.The natural rubber sole surface defect Rapid-Repair glue adopting this formula obtained and sole bonding well, can have the Chemical bond of higher degree with its mend a shoe sole sole and repair sheets behind the end, can not come off, effectively can repair defective footwear boots.
For this reason, the technical solution used in the present invention is:
A kind of natural rubber sole surface defect Rapid-Repair glue, raw material composition, with weight parts, comprising:
| Title material | Parts by weight |
| Natural rubber | 100 |
| Promoting agent | 8-11 |
| Anti-aging agent | 1.8-3.2 |
| Carbon black | 35-45 |
| Softening agent | 15-20 |
| Tackifier | 7-9 |
| Vulcanizing agent | 1.8-2.2 |
| Promotor | 1.6-2.4 |
Wherein: promoting agent comprises zinc oxide, magnesium oxide and stearic acid;
Anti-aging agent comprises heterocyclic anti-aging agent and amines antioxidants;
Promotor comprises thiazole accelerator and thiuram type accelerator.
Limit as one of the present invention, with weight parts:
1. consisting of of described promoting agent:
4 ~ 5 parts, zinc oxide, magnesium oxide 2-3 part, stearic acid 2 ~ 3 parts;
2. described anti-aging agent is:
0.8 ~ 1.2 part, heterocyclic anti-aging agent, amines antioxidants 1.0 ~ 2.0 parts;
3. described promotor is:
Thiazole accelerator 0.8 ~ 1.2 part, thiuram type accelerator 0.8 ~ 1.2 part.
Limit as another kind of the present invention, described carbon black is high abrasion furnace carbon black N330.
Limit as of the present invention the third, described heterocyclic anti-aging agent chemical name is 2-mercaptobenzimidazole; Described amines antioxidants chemical name is anti-aging agent N-sec.-propyl N`-diphenyl-para-phenylene diamine (antioxidant 4010NA);
Described thiazole accelerator chemical name is 2-benzothiazolyl mercaptan; Described thiuram type accelerator chemical name is tetramethyl-thiuram disulfide.
As the 4th kind of restriction of the present invention, described tackifier are terpine resin and Stockholm tar.
As the further restriction of above-mentioned restriction, described terpine resin counts 2-3 part with parts by weight, and Stockholm tar counts 5-6 part with parts by weight.
As the 5th kind of restriction of the present invention, described softening agent is machine oil.
As the 6th kind of restriction of the present invention, described vulcanizing agent is the SULPHUR POWDER of more than fineness 200 order.
As to detailed statement of the present invention, particular content is as follows:
In promoting agent of the present invention, not only employ zinc oxide and stearic acid, also use magnesium oxide, be not only applicable to the sulfuration under lesser temps, also accelerate vulcanization rate; Generally, the curing temperature of rubber is about 150 DEG C, curing temperature is higher, and the curing temperature used in the present invention can realize sulfidation at about 100 DEG C, when being heated to about 100 DEG C by repair sheets, sole and repair sheets just can being made can to have the Chemical bond of higher degree, can not come off, effectively can repair defective footwear boots, greatly facilitate the carrying out of patch work.
Use anti-aging agent 2-mercaptobenzimidazole MB in the present invention, good protective effect can be played to the thermo-oxidative ageing, Weather etc. of rubber soles; Use anti-aging agent N-sec.-propyl N '-diphenyl-para-phenylene diamine 4010NA, to the ozone-resistant aging resistance, the effect of being very helpful of flex cracking resistance performance that improve rubber soles; Antioxidant MB and 4010NA with the use of, to preventing rubber thermal ageing, oxygen aging, photoaging, dynamic fatigue and resisting that the catalysis of the poisonous metal such as copper, manganese is aging efficient synergy.
The use of promotor 2-benzothiazolyl mercaptan MBT in the present invention, serve the technique effect improving rubber vulcanization speed and state of vulcanization, the sulfuration feature due to thiazole accelerator promotor self: play sulphur early, vulcanization rate is fast, state of vulcanization is high, and vulcanizating glue physical performance is good.Thus this vulcanization characteristics is well suited for carrying out Rapid-Repair to natural rubber sole surface defect: because repair sheets are heated to react under relatively low working temperature (100 DEG C-120 DEG C), so compared with general rubber unvulcanizate, repair sheets need vulcanization rate faster, and the shorter incipient scorch phase is to make repair sheets can bond with at the bottom of glue under lower curing temperature.
Use accelerant disulfide tetra methylthiuram TMTD in the present invention simultaneously.The use of Vulcanization accelerator TMTD, at initial vulcanization step, has slight restraining effect to accelerant MBT, so this vulcanization system can ensure that sizing material has enough safety in production.The other important feature of this vulcanization system is exactly after sizing material plays sulphur, and the vulcanization rate of sizing material is exceedingly fast.So at a lower temperature can fast-curing sizing material so be well suited for repair sheets.
In the present invention, the accelerant MBT of 0.8-1.2 weight part can ensure that cross-linked rubber has suitable state of vulcanization, if exceed this number, vulcanization rate can be too fast, unfavorable to the safety in production of sizing material.If lower than this number, the state of vulcanization of cross-linked rubber can be caused not enough, the possibility of owing sulphur strengthens, the physicals of cross-linked rubber declines, and can not meet the specification of quality of repair sheets.
Vulcanization accelerator TMTD use level and accelerant MBT are equivalent loading in the present invention, because only have when equivalent uses, both just can be formed in initial vulcanization step and mutually suppress, the vulcanization characteristics of sulfuration middle and later periods acceleration.
In the present invention, the use of tackifier terpine resin, mainly increases the autohension of sizing material, to facilitate the use of repair sheets.
In the present invention, the use of softening agent mainly reduces the hardness of sizing material, convenient operation.
If it is too many that softening agent adds, rubber unvulcanizate can be too soft, is unfavorable for that workman refines the operations such as glue, is also unfavorable for the Chemical bond of repair sheets and sole because gum content is low simultaneously; On the contrary, if plasticizer loading very little, sizing material is difficulty when mixing, and other dispersion of materials is bad, does not have suitable hardness, is also not easy to operative, so the add-on of softening agent is moderate.
In the present invention, the use of vulcanizing agent, rubber unvulcanizate can be made chemical reaction can to occur after being heated, vulcanization crosslinking, and rubber is transformed into build macromole from linear macromolecule, and then becomes the cross-linked rubber having stable chemical state.
In the present invention, the parts by weight of vulcanizing agent are 1.8-2.2, if higher than this number, have following two disadvantages:
1. cross-linked rubber state of vulcanization can be made higher than expection, and cross-linked rubber hardness is higher, bad with sole bonding;
2. the sulfuration of rubber unvulcanizate can be made too short for inductive phase, and sizing material does not have enough safety in production, and the bonding of repair sheets and sole is also bad simultaneously.
If but lower than this number, have following two disadvantages:
1. vulcanization rate can be caused excessively slow, be unfavorable for workman's execute-in-place.
2. cross-linked rubber state of vulcanization can be made too low, and vulcanizating glue physical performance is bad, thus has influence on the quality of repair sheets self;
Present invention also offers the concrete grammar preparing above-mentioned repair sheets, it carries out according to following steps order:
(1) the plasticating of natural rubber
Natural rubber is dropped in 450 type mills and plasticate, according to rubber Wei Lianshi plasticity and nerve test method, survey its plasticity, require 0.55-0.60, the natural rubber that obtained plasticity meets the requirements;
(2) weighing of raw material prepares
By the natural rubber of plasticating and other desired raw material by recipe requirements precise, for subsequent use;
(3) sizing material banburying
The raw materials such as above-mentioned ready natural rubber, promoting agent, anti-aging agent, carbon black, tackifier, softening agent are dropped into Banbury mixer and carries out banburying, when sizing material temperature reaches 120 DEG C, binder removal;
(4) rubber compounding
Fall behind under sizing material, bag roller, adds vulcanizing agent, promotor, after treating that above-mentioned powder is mixed into sizing material, sizing material is played five triangle bags and powder is uniformly dispersed in sizing material, then slice, cooling, obtained rubber unvulcanizate, for subsequent use;
(5) inspection of rubber unvulcanizate
Above-mentioned rubber unvulcanizate is left standstill 24 hours, therefrom extracts sample, carry out the inspection of vulcanization characteristics, physicals, after qualified, carry out next step;
(6) sizing material is shaped
The above-mentioned rubber unvulcanizate be up to the standards is gone up mill mixing again, after sizing material is heated deliquescing bag roller, uses cutter the shape being cut into regulation under sizing material, mending a shoe sole at the end for becoming footwear workshop.
Owing to have employed above-mentioned technical scheme, compared with prior art, acquired technical progress is in the present invention:
Mend a shoe sole the end compared with the common cured repairing of point by natural rubber sole surface defect Rapid-Repair glue provided by the present invention, avoid the obscission using paraffin to exist in the place of repairing, when natural rubber sole defect mending glue provided by the present invention is for repairing, repair sheets can be made to be combined completely with rubber soles, and merge, difficult drop-off, and repair conveniently.
In the present invention, the use level of Vulcanization accelerator TMTD use level and accelerant MBT is equivalent, because only have when equivalent uses, both just can be formed in initial vulcanization step and mutually suppress, the vulcanization characteristics of sulfuration middle and later periods acceleration.The accelerant MBT of 0.8-1.2 weight part can ensure that cross-linked rubber has suitable state of vulcanization, if exceed this number, vulcanization rate can be too fast, unfavorable to the safety in production of sizing material.If lower than this number, the state of vulcanization of cross-linked rubber can be caused not enough, the possibility of owing sulphur strengthens, the physicals of cross-linked rubber declines, and can not meet the specification of quality of repair sheets.
The composition of promoting agent comparatively prior art adds magnesium oxide, is not only applicable to the sulfuration under lesser temps, also accelerates vulcanization rate; Generally, the curing temperature of rubber is about 150 DEG C, curing temperature is higher, and the present invention can realize sulfuration at middle used curing temperature at about 100 DEG C, when being heated to about 100 DEG C by repair sheets, just can make to mend a shoe sole sole and repair sheets behind the end can have the Chemical bond of higher degree, can not come off, also greatly facilitate the carrying out of patch work simultaneously.
The present invention be applicable to in footwear boots production process due to reasons such as forming pressure, rubber, moulds, rubber soles occurs that the defects such as surperficial starved, bubble carry out Rapid-Repair among a small circle.
The present invention is described in further detail below in conjunction with embodiment.
Embodiment
embodiment 1a kind of natural rubber sole surface defect Rapid-Repair glue and preparation method thereof
The preparation method of above-mentioned natural rubber sole surface defect Rapid-Repair glue, it carries out according to following steps order:
(1) the plasticating of natural rubber
Natural rubber is put into 450 type mills to plasticate, the roller distance of mill is adjusted to 1.5mm-2mm, natural gum thin-pass six times to seven times, carry out the detection of natural gum plasticity, require that plasticity is 0.55-0.60, if nonconforming, continue thin-pass, until qualified.The obtained like this natural rubber meeted the requirements of plasticating;
(2) preparation of raw material
By the natural rubber of plasticating and other desired raw material according to the form below precise, for subsequent use;
| Title material | Weight (kilogram) |
| Natural rubber | 100 |
| Zinc oxide | 5 |
| Magnesium oxide | 3 |
| Stearic acid | 3 |
| Antioxidant MB | 1 |
| Antioxidant 4010NA | 1.5 |
| Carbon black N330 | 40 |
| Softening agent machine oil | 20 |
| Tackifier terpine resin | 5 |
| Tackifier Stockholm tar | 3 |
| Vulcanizing agent SULPHUR POWDER | 2 |
| Accelerant MBT | 1 |
| Add up to | 184.5 |
(3) sizing material banburying
The raw materials such as the natural rubber of plasticating, zinc oxide, magnesium oxide, stearic acid, 2-mercaptobenzimidazole MB, antioxidant 4010NA, high wear-resistant carbon black, machine oil, tackifier terpine resin and Stockholm tar are dropped into Banbury mixer and carries out banburying, after banburying 3min, when sizing material temperature reaches 120 DEG C, binder removal, obtained banburying rubber;
(4) rubber compounding
By above-mentioned banburying sizing material bag roller, after adding SULPHUR POWDER, dimercapto benzothiazole MBT that load weighted fineness is more than 200 orders, treating that these powders are mixed into sizing material, play five triangle bags, slice, cooling, obtained mixing of rubber, for subsequent use;
(5) secondary charging of sizing material
From above-mentioned sizing material, take out 922.5g, the small-sized mill of upper 150 type, after bag roller, add accelerant disulfide tetra methylthiuram TMTD 5g, eat powder complete, play five triangle bags, get off, cooling, standby inspection;
(6) inspection of mixing of rubber
Glue stuff compounding is left standstill 24h, and sampling, carries out vulcanization rate inspection, carries out next step after qualified;
(7) sizing material slice
In advance 2mm is adjusted in 150 type mill roll spacings, by mill on the rubber unvulcanizate that is up to the standards, sizing material is subject to the shearing action post softening of roller, allows sizing material bag roller, after mixing one minute, and bottom sheet.
The above-mentioned sizing material prepared is processed into thickness 2mm, the India-rubber strip of width 2mm, is transported to into footwear workshop.When the one-tenth footwear finding that there is surface imperfection need to repair, open electric iron, the above-mentioned India-rubber strip electric iron got ready is heated, then these hot glues is adhered to rejected region, ironing, waits to be tested.
embodiment 2-7
The difference of embodiment 2-7 and embodiment 1, be only the difference of the consumption of involved raw material composition, its preparation method is identical, and concrete difference is as shown in the table:
Claims (8)
1. a natural rubber sole surface defect Rapid-Repair glue, is characterized in that its raw material composition is with weight parts, bag
Draw together:
Natural rubber 100 parts, promoting agent 8-11 part, anti-aging agent 1.8-3.2 part, carbon black 35-45 part,
Softening agent 15-20 part, tackifier 7-9 part, vulcanizing agent 1.8-2.2 part, promotor 1.6-2.4 part;
Wherein:
Promoting agent comprises zinc oxide, magnesium oxide and stearic acid;
Anti-aging agent comprises heterocyclic anti-aging agent and amines antioxidants;
Promotor comprises thiazole accelerator and thiuram type accelerator;
Wherein, with weight parts:
1. consisting of of described promoting agent:
4 ~ 5 parts, zinc oxide, magnesium oxide 2-3 part, stearic acid 2 ~ 3 parts;
2. described anti-aging agent is:
0.8 ~ 1.2 part, heterocyclic anti-aging agent, amines antioxidants 1.0 ~ 2.0 parts;
3. described promotor is:
Thiazole accelerator 0.8 ~ 1.2 part, thiuram type accelerator 0.8 ~ 1.2 part.
2., according to the natural rubber sole surface defect Rapid-Repair glue described in claim 1, it is characterized in that: described charcoal
Black is high abrasion furnace carbon black N330.
3., according to the natural rubber sole surface defect Rapid-Repair glue described in claim 1, it is characterized in that:
Described heterocyclic anti-aging agent is 2-mercaptobenzimidazole; Described amines antioxidants is anti-aging agent N-sec.-propyl
N`-diphenyl-para-phenylene diamine;
Described thiazole accelerator is 2-benzothiazolyl mercaptan; Described thiuram type accelerator is tetramethyl
Thiuram.
4., according to the natural rubber sole surface defect Rapid-Repair glue described in claim 1, it is characterized in that: described increasing
Stick is terpine resin and Stockholm tar.
5., according to the natural rubber sole surface defect Rapid-Repair glue described in claim 4, it is characterized in that: described terpene
Olefine resin counts 2-3 part with parts by weight, and Stockholm tar counts 5-6 part with parts by weight.
6., according to the natural rubber sole surface defect Rapid-Repair glue described in claim 1, it is characterized in that: described increasing
Moulding agent is machine oil.
7., according to the natural rubber sole surface defect Rapid-Repair glue described in claim 1, it is characterized in that: described sulphur
Agent is the SULPHUR POWDER of more than fineness 200 order.
8. prepare the side of the natural rubber sole surface defect Rapid-Repair glue according to any one of claim 1 ~ 7 for one kind
Method, is characterized in that it carries out according to following steps order:
(1) the plasticating of natural rubber
Dropped into by natural rubber in 450 type mills and carry out plasticating and survey its plasticity, require 0.55-0.60, obtained plasticity conforms with
The natural rubber required;
(2) weighing of raw material prepares
By the natural rubber of plasticating and other desired raw material by recipe requirements precise, for subsequent use;
(3) sizing material banburying
The raw materials such as above-mentioned ready natural rubber, promoting agent, anti-aging agent, carbon black, tackifier, softening agent are dropped into Banbury mixer enter
Row banburying, when sizing material temperature reaches 120 DEG C, binder removal;
(4) rubber compounding
Fall behind under sizing material, bag roller, adds vulcanizing agent, promotor, after treating that above-mentioned powder is mixed into sizing material, sizing material is made a call to five triangles
Bag makes powder be uniformly dispersed in sizing material, then slice, cooling, obtained rubber unvulcanizate, for subsequent use;
(5) inspection of rubber unvulcanizate
Above-mentioned rubber unvulcanizate is left standstill 24 hours, therefrom extracts sample, carry out the inspection of vulcanization characteristics, physicals, qualified laggard
Go next step;
(6) sizing material is shaped
The above-mentioned rubber unvulcanizate be up to the standards is gone up mill mixing again, after sizing material is heated deliquescing bag roller, uses cutter handle
Sizing material is cut into the shape of needs, mends a shoe sole at the end for becoming footwear workshop.
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| CN201310126766.XA CN103184018B (en) | 2013-04-12 | 2013-04-12 | Natural rubber sole surface defect Rapid-Repair glue and preparation method thereof |
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| CN201310126766.XA CN103184018B (en) | 2013-04-12 | 2013-04-12 | Natural rubber sole surface defect Rapid-Repair glue and preparation method thereof |
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| CN103184018B true CN103184018B (en) | 2015-09-30 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104130463A (en) * | 2014-07-21 | 2014-11-05 | 南通迅达橡塑制造有限公司 | Preparation method of efficient damping rubber for passenger elevator and goods elevator |
| CN104788748B (en) * | 2015-04-17 | 2017-05-24 | 广西藤县通轩立信化学有限公司 | rubber containing modified terpene resin |
| CN114685864A (en) * | 2020-12-28 | 2022-07-01 | 双安科技（天津）有限公司 | Insulating trousers for water under live working |
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| CN101543325A (en) * | 2009-04-14 | 2009-09-30 | 泰亚(泉州)鞋业有限公司 | Anti-crocking rubber sole |
| CN102964644A (en) * | 2012-12-19 | 2013-03-13 | 际华三五一四制革制鞋有限公司 | Special sizing material for foaming rubber sole |
-
2013
- 2013-04-12 CN CN201310126766.XA patent/CN103184018B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101543325A (en) * | 2009-04-14 | 2009-09-30 | 泰亚(泉州)鞋业有限公司 | Anti-crocking rubber sole |
| CN102964644A (en) * | 2012-12-19 | 2013-03-13 | 际华三五一四制革制鞋有限公司 | Special sizing material for foaming rubber sole |
Non-Patent Citations (2)
| Title |
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| 吴海若等.主要配合剂.《产品材料基础》.中国人民大学出版社,2010,第115页. * |
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