CN101429271B - Polyether type resin for low-rigidity transparent anti-skidding shoes - Google Patents
Polyether type resin for low-rigidity transparent anti-skidding shoes Download PDFInfo
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- CN101429271B CN101429271B CN2008102441198A CN200810244119A CN101429271B CN 101429271 B CN101429271 B CN 101429271B CN 2008102441198 A CN2008102441198 A CN 2008102441198A CN 200810244119 A CN200810244119 A CN 200810244119A CN 101429271 B CN101429271 B CN 101429271B
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Abstract
The invention belongs to three-component polyurethane resin for shoes, and in particular relates to low-hardness transparent polyether resin for antiskid shoes, wherein a component A refers to polyether glycol containing oxhydryl (OH) group, a component B refers to a performed polymer containing isocyanate NCO group, and a component C refers to a glycol solution containing trimethylene diamine; and the component A and the component C are mixed to form a material A, and the material A is taken as a component and subjected to chemical reaction with the component B. The low-hardness transparent polyether resin for the antiskid shoes is stirred at a high speed by a foaming machine for low-pressure shoes, injected into a die by means of injection molding, and is subjected to a one-step injection molding. Materials of the formula have low viscosity, good fluidity and wide foaming range, and are not required to be heated before use; and sole products are antiskid and transparent.
Description
Technical field
The invention belongs to a kind of polyurethane resin for shoes of three components, specifically a kind of polyether type resin for low-rigidity transparent anti-skidding shoes.The A component is for containing the polyether glycol of hydroxyl (OH) group, the B component is the performed polymer that contains isocyanic ester NCO group, the C component is the ethylene glycol solution that contains the trimethylene diamines, and A component and C component are mixed into the A material as a component and B component generation chemical reaction.Use foaming machine after high-speed stirring through the low pressure footwear, be injected in the mould once injection moulding.
Background technology
Because common polyurethane in use for shoes skidproof effect is relatively poor, especially the polyurethane in use for shoes medium bottom shoes bedding and padding that have, in order to satisfy client's skid-resistance requirements, must before middle bed material cast, pour into a mould the very thin polyether-type low-rigidity transparent anti-slip material of one deck earlier, increase the skidproof effect of goods, the sole that adopts resin for shoes of the present invention to produce, hardness is low, good antiskid effect, easily processing, good springiness, hydrolysis, and also good with urethane medium bottom shoes pad cohesiveness, by adding the mill base of different colours, make versicolor clear bottom and be subjected to liking of consumers in general deeply, but common polyether-type resin for shoes goods poor flexibility in the market, because the polyethers water content height that has, cause foaming easily, cause poor transparency, the product strength that has is relatively poor disconnected once tearing, and fraction defective is higher.
Summary of the invention
Purpose of the present invention is developed polyether type resin for low-rigidity transparent anti-skidding shoes exactly, and this formula materials viscosity is low, good fluidity, and the foaming wide ranges need not heat before using, and the goods of sole is anti-skidding transparent.
Be the concrete formation of A component, B component, C component below: (unit is a mass parts)
The A component:
(AV=0.01～0.05mgKOH/g, OH=15～20mgKOH/g) 100 for a, polyether glycol A
B, dibasic alcohol 1～4
The B component:
c、MDI 100
d、H
3PO
4 0.001-0.002
E, modification MDI 6～10
(AV=0.01～0.05mgKOH/g, OH=20～26mgKOH/g) 30～65 for f, polyether glycol B
The C component:
The C component is the ethylene glycol solution of trimethylene diamines, wherein trimethylene diamines and ethylene glycol mass ratio be 1: 2.0～2.1.
The method of producing described polyether type resin for low-rigidity transparent anti-skidding shoes is as follows: the order of the various compositions in the A component by following a, b joined in the reactor successively, stirred under 25～35 ℃ temperature 2.1～2.3 hours, the packing discharging; The order of addition(of ingredients) of described composition and add-on are: a, polyether glycol A:100 part, AV=0.01～0.05mgKOH/g of polyether glycol A, OH=15～20mgKOH/g, f=3,1～4 part of b, chainextender ethylene glycol;
Each raw material in the B component is joined in the reactor of nitrogen protection successively, and 70 ± 2 ℃ were stirred 2.1～2.3 hours, and it was terminal point at 210～220 o'clock that analytical test makes the NCO equivalent; The addition sequence of the raw material in the B component and add-on are: 100 parts of c, MDI; D, H
3PO
40.001-0.002 part; E, modification MDI6.0～10 part; F, polyether glycol B:30～65 part, AV=0.01～0.05mgKOH/g of polyether glycol B, OH=20～26mgKOH/g, f=2;
Is 1: 2.0～2.1 to be mixed with solution with the trimethylene diamines in the C component and ethylene glycol by mass ratio;
Unit is a mass parts.
Described resin in use, described C component accounts for 1.25～1.31% of A component; Described B component accounts for 35～50% of A component; Unit is a mass percent.
During use, earlier the C component is added in the A component, mixes, form compound; Again the B component is added in the described compound, mix cast, rise and send out time 10～15S, tack-free time 60～65S, resilience time of occurrence 100～120 seconds, the compact density 1.05～1.09g/cm of cast product through shoe machine
335～42 ℃ of product molding mould temperature.
Each component effect and technology are as follows: a, f are polyether polyol with high activity as the main reaction raw material; Wherein a is polyether glycol A, its AV=0.01～0.05mgKOH/g, OH=15～20mgKOH/g, f=3; F is polyether glycol B, its AV=0.01～0.05mgKOH/g, and OH=20～26mgKOH/g, f=2 uses the previous crops processed; B is chainextender ethylene glycol (EG), plays crosslinked and the effect of adjusting hardness, and c is 4.4 diphenyl diisocyanates (MDI), and e is modification 4.4 diphenyl diisocyanates (modification MDI), and c, e are as the main reaction raw material.In the A prescription, only used a kind of high reactivity high-molecular weight polyether glycol of three-functionality-degree, in order to improve the transparency of goods, do not add tensio-active agent, there is not the foaming of water and pneumatogen, because the density of goods is bigger, does not add tensio-active agent, and goods are not had bigger influence, do not add tensio-active agent, saved the tooling cost of material yet; A component prescription constitutes less, is convenient to the organization of production arrangement, shortens the production cycle simultaneously, and the quality of product is more stable.Also adopted high-molecular weight high reactivity low-unsaturated polyether polyatomic alcohol at the B component, the sole of producing, hardness is low, good antiskid effect, easily processing, good springiness, hydrolysis, intensity is good, can be processed into versicolor goods and be subjected to liking of consumers in general deeply.Simultaneously A of the present invention, B material manufacturing technique are simple, and A material and mould need not heat, and earlier with C component and A component premix, are packaged into the A material and expect one-time cast-forming with B.
Embodiment
The forming process condition of resin for shoes of the present invention is: A component and C component are pre-mixed earlier as the A material, take out directly and the reaction of B material the disposal pouring moulding.
(1) manual operations: 100 parts of weighing A components, 40 parts of B components, pour in the die cavity and foam for 5～9 second under the brute force of 2500r/min stirs.
(2) power operation: the A mixture joins in the A batch can of shoe machine, and the B component joins in the B batch can of shoe machine, through the moulding of head high-speed stirring disposal pouring.
(3) the mixing equivalent of A component is about 80, the pressure 0.35～0.40MPa of A pump, and 30～35 ℃ of material temperature are near ambient temperature.
The mixing equivalent of B component is 215 ± 5; Pressure 0.41～the 0.46MPa of pump, 35～42 ℃ of material temperature.
A/B measures discharging with 100: 35～50 ratio through volume pump, in the high-speed stirring hybrid reaction moulding of head through 4500r/min.The discharge-amount of shoe machine generally is 60～90 Grams Per Seconds.
Table 1 has been listed 6 kinds of prescriptions altogether, and promptly for 6 embodiment, unit is a mass parts
Polyether glycol A is used for the A component, and polyether glycol B is used for the B component, and A, B component are branch independent productions of coming.
Below to each component part when consumption changes, the variation of the physical property characteristic of finished product is narrated, and simultaneously proportionlity between A, B, the C each component and goods situation is narrated.
1. number prescription: the density of A component is at 1.07 ± 0.01g/cm
3, material viscosity: 725～800cps (40 ℃).During operation, earlier the A component is mixed mutually with the C component, composition mixture, wherein the C component accounts for 1.31% of A component.And then the B component joined in the mixture, the B component accounts for 35% of A component, through the mechanical high-speed hybrid reaction, rises and sends out time a 10～15S, tack-free time 60～65S, resilience time of occurrence 100～120 seconds.35～40 ℃ of product molding mould temperature, extrudate density are 1.08 ± 0.01g/cm
3, products appearance smooth finish is good, and hardness has only 30～35 degree C types, is placed on slidingly above the hyaline smooth glass of 45 degree not get off.
2. number prescription: the A component is mixed mutually with the C component, composition mixture, wherein the C component accounts for 1.33% of A component, the B component is joined in the mixture again, and the B component accounts for 40% of A component.A component density is at 1.08 ± 0.01g/cm
3, material viscosity 620～725cps (40 ℃).Through the shoe machine cast, rise and send out time 11～15S, tack-free time 60～65S, resilience time of occurrence 100～120 seconds, the compact density 1.09 ± 0.01g/cm of cast product
335～40 ℃ of product molding mould temperature.Products appearance smooth finish is good, and integral body is more complete, does not have bigger bubble and pore, and hardness 34～37 degree C types are placed on and slidingly above the hyaline smooth glass of 45 degree do not get off.
3. number prescription: the A component is mixed mutually with the C component, composition mixture, wherein the C component accounts for 1.30% of A component, the B component is joined in the mixture again, and the B component accounts for 42% of A component.A component density is at 1.07 ± 0.01g/cm
3, material viscosity 600～680cps (40 ℃).Through the shoe machine cast, rise and send out time 10～15S, tack-free time 60～65S, resilience time of occurrence 100～120 seconds, 38～42 ℃ of product molding mould temperature, the compact density 1.09 ± 0.01g/cm of cast product
3Products appearance smooth finish is good, and resilience is good, does not have bigger bubble and pore, and goods hardness 40～45 degree C types are placed on and slidingly above the hyaline smooth glass of 45 degree do not get off.
4. number prescription: the A component is mixed mutually with the C component, composition mixture, wherein the C component accounts for 1.25% of A component, the B component is joined in the mixture again, and the B component accounts for 45% of A component.A component density is at 1.07 ± 0.01g/cm
3, material viscosity 650～720cps (40 ℃).Mix cast through shoe machine, rise and send out time 10～15S, tack-free time 60～70S, resilience time of occurrence 100～120 seconds, the compact density 1.05 ± 0.01g/cm of cast product
338～42 ℃ of product molding mould temperature.Products appearance smooth finish is good, and integral body is more complete, does not have bigger bubble and pore, and goods hardness 43～48 degree C types are placed on and slidingly above the hyaline smooth glass of 45 degree do not get off.
5. number prescription: the A component is mixed mutually with the C component, composition mixture, wherein the C component accounts for 1.3% of A component, the B component is joined in the mixture again, and the B component accounts for 45% of A component.A component density is at 1.04 ± 0.01g/cm
3, material viscosity 650～770cps (40 ℃).Mix cast through shoe machine, rise and send out time 10～15S, tack-free time 60～70S, resilience time of occurrence 100～120 seconds, the compact density 1.05 ± 0.01g/cm of cast product
338～42 ℃ of product molding mould temperature.Products appearance smooth finish is good, and integral body is more complete, does not have bigger bubble and pore, and goods hardness 46～50 degree C types are placed on and slidingly above the hyaline smooth glass of 45 degree do not get off.
6. number prescription: the A component is mixed mutually with the C component, composition mixture, wherein the C component accounts for 1.3% of A component, the B component is joined in the mixture again, and the B component accounts for 50% of A component.A component density is at 1.07 ± 0.01g/cm
3, material viscosity 1250～1350cps (40 ℃).Mix cast through shoe machine, rise and send out time 10～15S, tack-free time 60～70S, resilience time of occurrence 100～120 seconds, the compact density 1.05 ± 0.01g/cm of cast product
338～42 ℃ of product molding mould temperature.Products appearance smooth finish is good, and integral body is more complete, does not have bigger bubble and pore, and goods hardness 50～55 degree C types are placed on slightly slip above the 45 hyaline smooth glass of spending.
Come as can be seen by top embodiment, along with the increase of chain extension dosage, the hardness of goods increases to some extent, and the skidproof effect of goods slightly descends.
The invention belongs to the resin for shoes prescription, is the three-component polyurethane resin of polyether-type.The A component is a hydroxyl OH class raw material, is the mixture that contains active hydrogen, mainly is made up of the three-functionality-degree high activity polyether.The B component is an isocyanic ester NCO class raw material, mainly is 4.4 diphenyl diisocyanates (MDI) performed polymer with the modification of high reactivity low-unsaturated polyether polyatomic alcohol.The C component is a catalyzer, is made up of the ethylene glycol solution of triethylenediamine.The present invention has only adopted a kind of polyether glycol in the A component, need not add water and add tensio-active agent, has optimized prescription, has simplified technical process, has saved cost, from energy-saving and emission-reduction with to raise the efficiency be a quantum jump.In addition, the present invention is strict control moisture in operating process, has increased the transparent effect of goods, and product quality is more stable.Moreover the present invention adopts high reactivity high-molecular weight polyether glycol, increased the tear strength of goods, added a spot of chainextender and made that the non-skid property of goods is superior, this kind resin can be used for producing the non-skid finish of urethane medium bottom shoes bedding and padding, it is convenient and reliable to operate, and use range is extensive.
Claims (2)
1. a method of producing polyether type resin for low-rigidity transparent anti-skidding shoes is characterized in that: the order of the various compositions in the A component by following a, b joined in the reactor successively, stirred under 25～35 ℃ temperature 2.1～2.3 hours, the packing discharging; The order of addition(of ingredients) of described composition and add-on are: a, polyether glycol A:100 part, AV=0.01～0.05mgKOH/g of polyether glycol A, OH=15～20mgKOH/g, f=3,1～4 part of b, chainextender ethylene glycol;
Each raw material in the B component is joined in the reactor of nitrogen protection successively, and 70 ± 2 ℃ were stirred 2.1～2.3 hours, and it was terminal point at 210～220 o'clock that analytical test makes the NCO equivalent; The addition sequence of the raw material in the B component and add-on are: 100 parts of c, MDI; D, H
3PO
40.001-0.002 part; 6.0～10 parts of e, modification MDI; F, polyether glycol B:30～65 part, AV=0.01～0.05mgKOH/g of polyether glycol B, OH=20～26mgKOH/g, f=2;
Is 1: 2.0～2.1 to be mixed with solution with the trimethylene diamines in the C component and ethylene glycol by mass ratio;
Unit is a mass parts;
Described resin in use, described C component accounts for 1.25～1.31% of A component; Described B component accounts for 35～50% of A component; Unit is a mass percent;
Earlier the C component is added in the A component, mixes, form compound; Again the B component is added in the described compound, mix cast, rise and send out time 10～15S, tack-free time 60～65S, resilience time of occurrence 100～120 seconds, the compact density 1.05～1.09g/cm of cast product through shoe machine
335～42 ℃ of product molding mould temperature.
2. a polyether type resin for low-rigidity transparent anti-skidding shoes that utilizes the method acquisition of the described production polyether type resin for low-rigidity transparent anti-skidding shoes of claim 1 comprises A component, B component and C component; It is characterized in that the A component comprises: a, polyether glycol A:100 part, b, chainextender ethylene glycol (EG): 1～4 part, AV=0.01～0.05mgKOH/g of described polyether glycol A, OH=15～20mgKOH/g, f=3; Described B component comprises: c, MDI:100 part, d, H
3PO
4: 0.001-0.002 part, e, modification MDI:6～10 part, f, polyether glycol B:30～65 part, AV=0.01～0.05mgKOH/g of described polyether glycol B, OH=20～26mgKOH/g, f=2; Described C component is the ethylene glycol solution of trimethylene diamines, and wherein the mass ratio of trimethylene diamines and ethylene glycol is 1: 2.0～2.1; Unit is a mass parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102441198A CN101429271B (en) | 2008-12-08 | 2008-12-08 | Polyether type resin for low-rigidity transparent anti-skidding shoes |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102441198A CN101429271B (en) | 2008-12-08 | 2008-12-08 | Polyether type resin for low-rigidity transparent anti-skidding shoes |
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| CN101429271A CN101429271A (en) | 2009-05-13 |
| CN101429271B true CN101429271B (en) | 2010-10-13 |
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| CN2008102441198A Expired - Fee Related CN101429271B (en) | 2008-12-08 | 2008-12-08 | Polyether type resin for low-rigidity transparent anti-skidding shoes |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945889A (en) * | 2015-07-28 | 2015-09-30 | 佛山市南方鞋材有限公司 | Shoe outsole material high in non-skid property |
| CN105622882A (en) * | 2016-02-04 | 2016-06-01 | 福州美创美工艺品有限公司 | Light-permeable polyurethane artificial material manufacturing method and light-permeable polyurethane artificial material manufacturing composition |
| CN110431164B (en) * | 2017-03-28 | 2021-11-16 | 科思创德国股份有限公司 | Translucent polyurethane or polyisocyanurate foams |
| CN107868224A (en) * | 2017-12-12 | 2018-04-03 | 温州市小林鞋材有限公司 | A kind of polyurethane Antiskid sole and preparation method thereof |
| CN110183711A (en) * | 2019-05-18 | 2019-08-30 | 陈建飞 | One kind being used in casting type camouflage color colour mixture polyurathamc manufacture method of sole |
| CN110423330A (en) * | 2019-07-30 | 2019-11-08 | 广东康诚新材料科技股份有限公司 | Integrally formed shoes outsole and preparation method thereof |
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