CN101148493A - Polyester type ultra-low density polyurethane resin for shoes - Google Patents
Polyester type ultra-low density polyurethane resin for shoes Download PDFInfo
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- CN101148493A CN101148493A CNA2007101343691A CN200710134369A CN101148493A CN 101148493 A CN101148493 A CN 101148493A CN A2007101343691 A CNA2007101343691 A CN A2007101343691A CN 200710134369 A CN200710134369 A CN 200710134369A CN 101148493 A CN101148493 A CN 101148493A
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Abstract
The present invention is the recipe of three component polyurethane resin for insole. The polyurethane resin includes one component A of active hydrogen-containing mixture comprising long chain polyol polymer, chain expanding agent, cross-linking agent, surfactant, foaming agent and other assistants; one component B comprising polyester or polyether modified MDI pre-polymer; and one component C or catalyst component of glycol solution of triethylidene diamine. The polyurethane resin has density as low as 0.25-0.30 g/cu cm, capacity of making the product firm and good in appearance, and other advantages.
Description
Technical field
The present invention relates to a kind of three component resin for shoes, be meant a kind of polyester type ultra-low density polyurethane resin for shoes especially, be mainly used in the production of shoe-pad.The A component is hydroxyl (OH) class raw material, is the mixture that contains active hydrogen, mainly is made up of polymerized polyalcohol, chainextender, linking agent, tensio-active agent, whipping agent and other auxiliary agents of long-chain.The B component is isocyanic ester (NCO) class raw material, mainly is with polyester or polyether-modified 4.4 diphenylmethanediisocyanates (MDI) performed polymer.The C component is a catalyzer, is made up of the ethylene glycol solution of triethylenediamine.During use, generally be a certain amount of C component to be added in the A component go, mix, use as a component, again with the B component reaction.Wherein, A, C component are separately deposited, main purpose is to extend the shelf life, and is that resin is not perishable.
Technical background
At present, the polyurethane insole resin that uses on the market mainly contains two classes, and a class is a polyester, and a class is a polyether-type.The material characteristic of polyethers and polyester is different, and the two is incompatible.The shoe-pad resilience of polyether-type is good, and moulding is fast, shrinks for a short time, and density is low, but bad mechanical strength, cortex is thin, and material is easily aging.The characteristics of polyester type mainly are that material is mobile poor, and physical strength is good, and cortex is thicker relatively, and resilience is poor, and moulding is slow, easily shrinkage strain, and density is bigger than polyether-type.But, also having the resin of pair polyester type to carry out improved prescription on the market, mainly is to add the polyethers composition in the A component, reduces its shrinking percentage, increases its typing effect.Insole products after the improvement, resilience makes moderate progress, but moulding is still slow, still need 6～8 minutes just can the demoulding, and insole products still has the phenomenon of shrinking modification, density is also relatively large, and is totally unfavorable to production efficiency and economic benefit.
Summary of the invention
The objective of the invention is to develop polyester type ultra-low density footwear polyurethane resin for shoes, save the consumption of material, shorten the time of typing, improve the production efficiency and the economic benefit of Shoes Factory.
Polyester type ultra-low density polyurethane resin for shoes comprises A component, B component and C component, it is characterized in that,
The A component comprises:
A. polyester polyol A (AV=0.1～0.8, OH=79～85mgKOH/g) 40～70 parts,
B. polyester polyol B (AV=0.1～0.8, OH=53～59mgKOH/g) 30～60 parts,
C. polyester polyol C (AV=0.1～0.8, OH=58～63mgKOH/g) 10～30 parts,
D. the graftomer polyester polyol (AV=0.1～0.8, OH=71～79mgKOH/g) 15～40 parts,
E. ethylene glycol is 1.0～6.0 parts,
F. silicone oil DC3041 is 0.4～0.8 part,
G. silicone oil DC3042 is 0.2～0.6 part,
H. trolamine is 0.5～1.5 part,
I. water is 0.4～1.5 part,
2.0～6.0 parts of j.HCFC-141b,
The B component comprises:
K.4.4 diphenylmethanediisocyanate MDI is 100 parts,
L.H
3PO
40.001 part,
M. polyester polyol D (AV=0.1～0.8, OH=79～85mgKOH/g) 25～30 parts,
N. polyether glycol E (AV=0.03～0.1, OH=25～40mgKOH/g) 15～25 parts,
O. liquefied mdi is 5.0～10 parts,
The C component comprises:
1 part of triethylenediamine and 1.5～2.3 parts of ethylene glycol solutions, unit is a weight part; AV wherein refers to the acid number of polyester polyol, and OH refers to the hydroxyl value of polyester polyol.
The finished product density of described polyurethane resin for shoes is 0.25～0.30g/cm
3
In use, earlier with the preheating 4～6 hours in 60 ± 5 ℃ baking oven of A component and B component; Again the C component is added in the A component and goes, mix, form a blending ingredients; Be to stir for 5～9 seconds under the condition of 2200～2800r/min then with this blending ingredients and B component, be poured into foaming in the die cavity again at rotating speed; Its add-on is 100 parts for the A component, and the B component is 56～64 parts, and the C component is 1.2～1.5 parts, and unit is a weight part.
Perhaps, in use, earlier with the preheating 4～6 hours in 60 ± 5 ℃ baking oven of A component and B component; Again the C component is added in the A component, mix, form blending ingredients; This blending ingredients is poured in the A batch can of shoes making machine then, at the shoes making machine internal recycle, measures during cast by volume pump; The B component is poured in the B batch can of shoes making machine,, measures during cast at the shoes making machine internal recycle by volume pump; The mixing equivalent of A component is 120.9 ± 5, and the mixing equivalent of B component is 200 ± 5; Pressure 0.35～the 0.40MPa of the volume pump that the A component is used, the pressure of the pump that 42～45 ℃ of B components of material temperature are used is 0.40～0.45MPa, 40～43 ℃ of material temperature; When the cast metering, because the C component only plays katalysis, do not react with A component or B component, therefore still measure discharging with 100: 56～64 ratio through volume pump usually with A component and B component, head at shoes making machine mixes foaming through the rotating speed of 4200～4800r/min.
Each component effect and technology are as follows:
In the A component, a, b, c, d are polyester polyol.A and b are the polyester polyols of being produced through the high temperature dehydration polymerization by ethylene glycol (EG), Diethylene Glycol (DEG), hexanodioic acid (AA).C is the polyester polyol of being produced by DEG, TriMethylolPropane(TMP) (TMP), AA.D is the polyester polyol of being produced through high temperature dehydration by EG, DEG, AA, after the styrene monomer graft modification.Produce AV=0.1～0.8 with EG, DEG, AA earlier, the polyester polyol of OH=71～79mgKOH/g utilizes its batch technology to come the polyester polyol of production modification again.Generally be that mixtures such as part base polyester polyvalent alcohol and styrene-based monomers, initiator slowly are added drop-wise in the stirred reactor of dispersion agent and part base polyester mixture, 100～130 ℃, reacted 3～5 hours, vacuumize 0.08～0.09MPa then, 3～5 hours or remove unreacted monomer more for a long time, promptly get the graftomer polyester polyol.A, b, c, d are the effects of playing skeleton and support.C, d also play typing to goods, accelerate curing speed, prevent to shrink the effect of modification.E mainly is a chainextender.Silicone oil is tensio-active agent, mainly plays the reduction surface tension, and evenly foam is eliminated bubble, increases the effect of the stability of material.Use two kinds of silicone oil better, more stable than a kind of, foam is fine and smooth more, and cortex is more abundant, and the stability of material is also better.Trolamine mainly is a linking agent, mainly plays the speed of accelerating moulding, reduces distortion, the effect of enhancing productivity.I and j are whipping agents, and i is a chemical foaming agent, and j is a pneumatogen, can both increase the foaming power of material, reduce the density of product.
The preparation technology of A component is: each component is joined in the reactor in order successively, and 70 ℃ of stirrings can be packed discharging in two hours.
In the B component, add polyester with polyethers and come the modification performed polymer, increased the elasticity of goods, reduced the shrinking percentage of goods, make the surface effect of goods better, outward appearance is perfect more.
The preparation technology of B component: each raw material is joined successively in the reactor of nitrogen protection, 70 ℃ were stirred two hours, and it was terminal point at 195～205 o'clock that analytical test makes the NCO equivalent.Because heat release during reaction, polyester and polyethers add fashionable, add several times, and controlled temperature are below 80 ℃.
The C component is a catalyzer, prepares fairly simplely, is 1: 1.5～2.3 to be mixed with solution and to get final product by weight with triethylenediamine and ethylene glycol.
The shoe-pad resilience that this prescription is produced is better than the prescription of other polyester type, reaches the requirement of the high resilience of polyether-type.Mainly we have done improvement from skeleton for this, quote big polyester polyvalent alcohol of degree of crosslinking and graftomer polyester polyol in the A component and produce shoe-pad.The B component has also been used highly active polyether components inside, has improved the characteristic of performed polymer, makes it to have the advantage of polyether-type material, and its stability is also stable many than being added in the A component, effect might as well many.The viscosity of this formula materials is low, good fluidity, and foaming power is good, mainly is that we have done technical improvement and adjusting in conjunction with polyester and polyethers foaming characteristics.We have used water and HCFC-141b to make whipping agent, and reduce surface tension, have used two kinds of highly active tensio-active agents to increase the stability of material.We have also used linking agent to increase the typing effect, have made things convenient for the client when concrete operations are used, and the center is judged well, operates quick and convenient.Like this, fast with the shoe-pad typing speed that this prescription is produced, surface effect is good, and pouring behind the mould 2.5～3.5 minutes just can depanning, and goods are flexible type not, and fraction defective is low, and the density of shoe-pad is than 0.35～0.40g/m of polyether-type
3Also low, reach extremely-low density 0.25～0.30g/m
3, improved production efficiency and economic benefit greatly.In addition, because the present invention is polyester type, improve greatly with the consistency of other resin for shoes.Because present footwear material all is a polyester type, the trouble of cleaning of evaporator can not appear wanting when different resins uses like this, promptly saved raw material, saved the time again.
Advantage of the present invention: 1, adopted four kinds of polyester polyols in the A component, changed the skeleton of two kinds of polyvalent alcohols in the past, and increased b and two kinds of polyvalent alcohols of d, the consumption of c also increases to some extent, and degree of crosslinking is than increasing greatly in the past.Improved breakthrough from the skeleton has also changed the structure of material, thereby has also done place mat and support for material in the change aspect outward appearance and the rerum natura.2, adopt two kinds of whipping agents and two kinds of silicone oil, increased the foaming power and the flowability of material greatly, made the density of goods lower, more stable, saved the consumption of material.Density is also much lower than similar polyester product, and general density can reach 0.25～0.30g/cm
33, the B component is improved, significantly reduced the shrinkage phenomenon of goods, cortex is more abundant, and the appearance surfaces better effects if has promoted product specification.4, goods typings is fast, and slaking is fast, from the mould time by original 7～9 minutes, dropping to present 2.5～3.5 minutes can improve production efficiency greatly from mould.5, since the present invention to be the consistency of the prescription of polyester type and other materials good, be convenient on same machine, produce different footwear materials.The footwear material requires good mechanical property now, is polyester substantially on the market.Need not use up after the polyethers as the polyethers material like this, do the material of polyester again, must wash several defective materials and irritate, not only bother but also waste raw material, the client's is more convenient to use.
Test by repeatedly constantly improves, debugs and tries out, and this product is suitability for industrialized production, is subjected to client's favorable comment on market deeply.
Embodiment
The forming process condition of polyester type ultra-low density polyurethane resin for shoes is: the preheating 4～6 hours in 60 ± 5 ℃ of baking ovens earlier of A component, B component, and take out the C component is joined in the A component, form the A component mixture.The consumption of C is generally 1.22～1.5% of A.
(1) manual operations: 100 parts of weighing A components, 62 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: blending ingredients is poured in the A batch can of shoes making machine,, measures during pouring operation at the shoes making machine internal recycle by volume pump.The B component is poured in the B batch can of shoes making machine,, measures during pouring operation at the shoes making machine internal recycle by volume pump.
(3) the mixing equivalent of blending ingredients is about 120 ± 5
The mixing equivalent of B component is 200 ± 5
(4) being used to carry the pressure of the volume pump A of blending ingredients is 0.35～0.40MPa, and the temperature of blending ingredients is 42～45 ℃
Being used to carry the pressure of the volume pump B of B component is 0.40～0.45MPa, 40～43 ℃ of the temperature of B component;
A component and B component are measured discharging with 100: 56～64 ratio through volume pump, in the high-speed stirring hybrid reaction moulding of shoes making machine head through 4200～4800r/min.The discharge-amount of shoe machine generally is 60～70 Grams Per Seconds, and actual discharge-amount can be regulated by the measuring apparatus of shoe machine according to goods.
The use of polyester type ultra-low density polyurethane resin for shoes mainly A component (general B component is fixed comparatively speaking), adapts to mould complicated and changeable according to the adjusting of A component, makes different colours, the different product that requires.Table has been listed 6 kinds of prescriptions altogether, promptly for 6 embodiment.
Table one
| Material | No. 1 prescription | No. 2 prescriptions | No. 3 prescriptions | No. 4 prescriptions | No. 5 prescriptions | No. 6 prescriptions |
| The A component | ||||||
| Polyester polyol A | 40 | 50 | 60 | 60 | 70 | 70 |
| Polyester polyol B | 60 | 50 | 40 | 40 | 30 | 30 |
| Polyester polyol C | 10 | 30 | 20 | 10 | 20 | 25 |
| The graftomer polyester polyol | 20 | 15 | 25 | 40 | 20 | 30 |
| Ethylene glycol | 3 | 4 | 5 | 1 | 2 | 6 |
| Silicone oil DC3041 | 0.4 | 0.5 | 0.8 | 0.7 | 0.5 | 0.6 |
| Silicone oil DC3042 | 0.4 | 0.6 | 0.3 | 0.5 | 0.2 | 0.4 |
| Trolamine | 0.5 | 0.8 | 1.0 | 1.5 | 0.7 | 1.2 |
| Water | 0.4 | 1.0 | 1.2 | 1.5 | 0.6 | 0.8 |
| HCFC-141b | 6.0 | 3 | 3.5 | 2.0 | 5.0 | 4.0 |
| The B component | ||||||
| MDI | 100 | 100 | 100 | 100 | 100 | 100 |
| H3PO4 | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Polyester polyol D | 25 | 28 | 30 | 27 | 29 | 26 |
| Polyether glycol E | 25 | 23 | 15 | 18 | 16 | 20 |
| Liquefied mdi | 5 | 6 | 9 | 10 | 8 | 7 |
| The C component | ||||||
| Triethylenediamine | 30 | 35 | 35 | 38 | 40 | 30 |
| Ethylene glycol | 70 | 65 | 65 | 62 | 60 | 70 |
The unit of each component is a weight part in the table.
Below to each integral part when consumption changes, the physical property characteristic of finished product changes to be narrated, and simultaneously proportionlity and goods situation between A, B, each component of C is narrated.
1. number prescription: the density of A component is at 1.17 ± 0.01g/cm
3, material viscosity: 1230～1330cps (40 ℃).During operation, earlier the A component is mixed mutually with the C component, composition mixture, wherein, 1.31% of C ingredients constitute A component.And then the B component joined in the mixture, 56% of B ingredients constitute A component, through the mechanical high-speed hybrid reaction, the density of free foaming is 0.136g/cm
3, rise and send out time 6～9S, tack-free time 49～56S, resilience time of occurrence 1 minute and 35 seconds, the compact density 0.27～0.29g/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.
2. number prescription: the A component is mixed mutually with the C component, composition mixture, wherein, 1.33% of C ingredients constitute A component joins the B component in the mixture again, 62% of B ingredients constitute A component.The A density of fraction is at 1.18 ± 0.01g/cm
3, material viscosity 1330～1430cps (40 ℃).Through shoe machine cast, free foaming density 0.135g/cm
3, rise and send out time 6～9S, tack-free time 45～55S, resilience time of occurrence 1 minute and 30 seconds, the compact density 0.26～0.28g/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.
3. number prescription: the A component is mixed mutually with the C component, composition mixture, wherein, 1.30% of C ingredients constitute A component joins the B component in the mixture again, 63.5% of B ingredients constitute A component.The A density of fraction is at 1.17 ± 0.01g/cm
3, material viscosity 1280～1380cps (40 ℃).Through shoe machine cast, free foaming density 0.130g/cm
3, rise and send out time 6～9S, tack-free time 44～54S, resilience time of occurrence 1 minute and 25 seconds, the compact density 0.27～0.29g/cm of cast product
338～42 ℃ of product molding mould temperature.Products appearance smooth finish is good, and resilience is good, does not have bigger bubble and pore.
4. number prescription: the A component is mixed mutually with the C component, composition mixture, wherein, 1.25% of C ingredients constitute A component joins the B component in the mixture again, 63% of B ingredients constitute A component.The A density of fraction is at 1.17 ± 0.01g/cm
3, material viscosity 1350～1450cps (40 ℃).Mix cast, free foaming density 0.132g/cm through shoe machine
3, rise and send out time 7～9S, tack-free time 43～52S, resilience time of occurrence 1 minute and 25 seconds, the compact density 0.26～0.29g/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.
5. number prescription: the A component is mixed mutually with the C component, composition mixture, wherein, 1.40% of C ingredients constitute A component joins the B component in the mixture again, 61% of B ingredients constitute A component.The A density of fraction is at 1.18 ± 0.01g/cm
3, material viscosity 1340～1450cps (40 ℃).Mix cast, free foaming density 0.129g/cm through shoe machine
3, rise and send out time 7～9S, tack-free time 45～55S, resilience time of occurrence 1 minute and 30 seconds, the compact density 0.25～0.28g/cm of cast product
335～40 ℃ of product molding mould temperature.Products appearance smooth finish is good, and is more complete, do not have bigger bubble and pore.
6. number prescription: the A component is mixed mutually with the C component, composition mixture, wherein, 1.30% of C ingredients constitute A component joins the B component in the mixture again, 64% of B ingredients constitute A component.The A density of fraction is at 1.17 ± 0.01g/cm
3, material viscosity 1320～1420cps (40 ℃).Mix cast, free foaming density 0.135g/cm through shoe machine
3, rise and send out time 7～9S, tack-free time 45～55S, resilience time of occurrence 1 minute and 30 seconds, the compact density 0.26～0.28g/cm of cast product
335～40 ℃ of product molding mould temperature.Resin Flow is good, and reactivity still can.Products appearance smooth finish is good, does not have bigger bubble and pore.
Claims (4)
1. polyester type ultra-low density polyurethane resin for shoes comprises A component, B component and C component, it is characterized in that,
The A component comprises:
A. polyester polyol A (AV=0.1～0.8, OH=79～85mgKOH/g) 40～70 parts,
B. polyester polyol B (AV=0.1～0.8, OH=53～59mgKOH/g) 30～60 parts,
C. polyester polyol C (AV=0.1～0.8, OH=58～63mgKOH/g) 10～30 parts,
D. the graftomer polyester polyol (AV=0.1～0.8, OH=71～79mgKOH/g) 15～40 parts,
E. ethylene glycol is 1.0～6.0 parts,
F. silicone oil DC3041 is 0.4～0.8 part,
G. silicone oil DC3042 is 0.2～0.6 part,
H. trolamine is 0.5～1.5 part,
I. water is 0.4～1.5 part,
2.0～6.0 parts of j.HCFC-141b,
The B component comprises:
K.4.4 diphenylmethanediisocyanate MDI is 100 parts,
1.H
3PO
40.001 part,
M. polyester polyol D (AV=0.1～0.8, OH=79～85mgKOH/g) 25～30 parts,
N. polyether glycol E (AV=0.03～0.1, OH=25～40mgKOH/g) 15～25 parts,
O. liquefied mdi is 5.0～10 parts,
The C component comprises:
1 part of triethylenediamine and 1.5～2.3 parts of ethylene glycol solutions, unit is a weight part; AV wherein refers to the acid number of polyester polyol, and OH refers to the hydroxyl value of polyester polyol.
2. polyester type ultra-low density polyurethane resin for shoes as claimed in claim 1 is characterized in that, the density of described polyurethane resin for shoes is 0.25～0.30g/cm
3
3. polyester type ultra-low density polyurethane resin for shoes as claimed in claim 1 is characterized in that: in use, and earlier with the preheating 4～6 hours in 60 ± 5 ℃ baking oven of A component and B component; Again the C component is added in the A component and goes, mix, form a blending ingredients; Be to stir for 5～9 seconds under the condition of 2200～2800r/min then with this blending ingredients and B component, be poured into foaming in the die cavity again at rotating speed; Its add-on is 100 parts for the A component, and the B component is 56～64 parts, and the C component is 1.2～1.5 parts, and unit is a weight part.
4. polyester type ultra-low density polyurethane resin for shoes as claimed in claim 1 is characterized in that: in use, and earlier with the preheating 4～6 hours in 60 native 5 ℃ baking ovens of A component and B component; Again the C component is added in the A component, mix, form blending ingredients; This blending ingredients is poured in the A batch can of shoes making machine then, at the shoes making machine internal recycle, measures during cast by volume pump; The B component is poured in the B batch can of shoes making machine,, measures during cast at the shoes making machine internal recycle by volume pump; The mixing equivalent of A component is 120 ± 5, and the mixing equivalent of B component is 200 ± 5; Pressure 0.35～the 0.40MPa of the volume pump that the A component is used, 42～45 ℃ of material temperature; The pressure of the pump that the B component is used is 0.40～0.45MPa, 40～43 ℃ of material temperature; In when metering cast, A component and B component are measured discharging with 100: 56～64 ratio through volume pump, mix foaming through the rotating speed of 4200～4800r/min at the head of shoes making machine.
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| CN101503503B (en) * | 2008-12-01 | 2011-04-13 | 无锡双象化学工业有限公司 | Preparation of wood-like sulfuration resistant material for polyether type polyurethane shoes |
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| CN101962432A (en) * | 2010-07-20 | 2011-02-02 | 温州市登达化工有限公司 | Synthesis process of low-density polyurethane sole stock solution |
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| US20200198278A1 (en) * | 2018-12-21 | 2020-06-25 | Zhongshan Cheng Shing Plastic Co., Ltd. | Sole and Method for Preparing Same |
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| CN113354793A (en) * | 2021-05-20 | 2021-09-07 | 华大化学集团有限公司 | Polyurethane resin for insole of high-resilience insole and preparation method thereof |
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