CN1281652C - Colloidal particles of thermoplastic PU soft resin and fabricating method - Google Patents
Colloidal particles of thermoplastic PU soft resin and fabricating method Download PDFInfo
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- CN1281652C CN1281652C CN 200410008663 CN200410008663A CN1281652C CN 1281652 C CN1281652 C CN 1281652C CN 200410008663 CN200410008663 CN 200410008663 CN 200410008663 A CN200410008663 A CN 200410008663A CN 1281652 C CN1281652 C CN 1281652C
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- thermoplastic polyurethane
- soft resin
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- micelle
- isocyanic acid
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Abstract
The present invention relates to a manufacturing method of thermoplastic PU flexible resin rubber particles, which is characterized in that organic isocyanic acid salts and diols or polyalcohols react on each other in a synthetic reaction to be matched with a lubricant, an antioxidant, a heat resisting auxiliary agent, etc. to prepare TPU flexible resin rubber particles with the hardness of Shore A50 to 80. The method of the thermoplastic PU flexible resin rubber particles comprises the steps that the polyalcohols, the diols, the auxiliary agent, etc. are evenly mixed by a stirring machine according to certain proportions and supplied into a kneading machine or a perfusing machine; then, the organic isocyanic acid salts in a specific proportion are added into the kneading machine or the perfusing machine, fully stirred, mixed and milled evenly so that the organic isocyanic acid salts fully react; the organic isocyanic acid salts are extruded into thermally melted strip-shaped TPUs by an extruding machine, immediately cooled and hardened in freezing water or placed into a containing disk and matured. The strip-shaped TPUs cooled are cut into particles by a particle cutting machine, or the strip-shaped TPUs are dried after the strip-shaped TPUs are pulverized by a pulverizing machine, the auxiliary agent is added and the strip-shaped TPUs and the auxiliary agent are evenly mixed, and finally, a finished product of the TPU flexible resin rubber particles with the hardness of Shore A50 to 80 is obtained.
Description
Technical field
The present invention relates to the manufacture method of a kind of thermoplastic polyurethane (PU (TPU)) soft resin micelle, especially refer to made TPU soft resin micelle, have the softness of hardness at Shore A 50 to 80, can use soft PVC (PVC) adhesive tape machine to carry out multiple post-treatment, and in the processing and manufacturing process, not have problem of environmental pollutions such as waste water, waste gas.
Background technology
The production of imitation leather in the past mainly based on synthetic skin of urethane (PU) and the synthetic skin of polyvinyl chloride (PVC), utilizes processing modes such as coating, applying to make the imitation leather product.Yet the synthetic skin of PU uses high solvent composition resin and diluting solvent to be main raw material, and in manufacturing processed, used solvent during urethane resin is filled a prescription can be derivatized to the problem of waste water, exhaust emission; And the synthetic skin of PVC uses powder polyvinyl chloride resin and liquid plasticizer to be main raw material, in mixing calender line, must operate in the high temperature open system for a long time, is easy to generate the problem that dust and plasticizer evaporate into exhaust emission.
Because in the manufacturing processed of synthetic skin of PU and the synthetic skin of PVC, environmental pollution problems such as waste water, waste gas are arranged all, each advanced country stops using and forbidding one after another at present.Especially, the rerum natura of synthetic skin of PU and the synthetic skin of PVC has following shortcoming again:
1. the hydrolytic resistance of synthetic polyurethane leather is relatively poor, and in the time of improving the hydrolysis rerum natura, rerum naturas such as surface abrasion resistance consumption intensity can relative variation.
2.PVC the anti-flexion of low temperature and the shock-resistant poor properties of synthetic skin generally only can be low temperature resistant to-10 ℃, when being in the low temperature that is lower than below-10 ℃, the synthetic skin of PVC just very easily breaks; If in the time of will improving low temperature resistant rerum natura, the surface of the synthetic skin of PVC, plasticizer is very easily arranged or add unusual surperficial that auxiliary agent spues, and during the refuse incineration of PVC goods, can produce the doubt of malicious dioxin, chlorine and the heavy metal particle in century, heavy metal can be separated out and contaminate environment when burying, not compliance with environmental protection requirements.
3. the synthetic skin of synthetic polyurethane leather or PVC is used in high friction bump purposes occasion, and its surface abrasion resistance consumption and stripping strength quality can't meet market demands fully.
Therefore, (Thermalplastic Polyurenthane TPU), has replaced the PVC material, and becomes the main material of imitation leather to possess all good thermoplastic polyurethane of environmental protection advantage and rerum natura, abrasion performance and flexibility.
And according to the demand in market, the thermoplastic polyurethane micelle is divided into general ejaculation level, transparent ejaculations level, hydrolysis and penetrates various thermoplastic polyurethane micelles such as level, abrasion performance level, T-die pouring film adhesive plaster, low temperature resistant ejaculation level and extrusion level; Wherein, can be supplied to adhesive tape machine to make the thermoplastic polyurethane micelle raw material of film adhesive plaster, its hardness is all more than Shore A80, because thermoplastic polyurethane micelle on the market, hardness is if be lower than Shore A80 when following, glutinous wheel when mediating, adhesive tape machine can take place, and flowability is poor again, there are unusual phenomenoies such as flatness difference and generation white point on the film adhesive plaster surface that produces out, still, the hardness of thermoplastic polyurethane micelle is when Shore A80 is above, processing torsion for adhesive tape machine is quite big, must process at a slow speed with the 3-ROLL adhesive tape machine, can't use the flexible PVC adhesive tape machine to process the thermoplastic polyurethane micelle.
Summary of the invention
Still can not process the TPU micelle based on the soft adhesive tape machine of present PVC, be head it off, develop a kind of manufacture method of thermoplastic polyurethane soft resin micelle especially, to make the TPU soft resin micelle of hardness at Shore A 50 to 80, its flowability is good, and can use the flexible PVC adhesive tape machine to carry out multiple post-treatment.
Therefore, purpose of the present invention is promptly in the manufacture method that a kind of thermoplastic polyurethane soft resin micelle is provided, can make the soft micelle of the TPU of hardness between Shore A 50 to 80, with can use the flexible PVC adhesive tape machine to produce fabricate-heat plasticity-polyurethane film adhesive plaster next life, through fit with base cloth or applying PU release layer after, and can produce and provide high-intensity thermoplastic polyurethane (TPU) imitation leather, and, this kind imitation leather is compared with the synthetic leather of natural leather or other kind, has better abrasion performance intensity, advantages such as anti-flexion of low temperature and high frequency processing, be fit to multiple post-treatment purposes, and as other, do not producing waste water in the leather manufacturing processed in the manufacturing processed, problem of environmental pollutions such as waste gas.
Description of drawings
Fig. 1 is the manufacturing flow chart of thermoplastic polyurethane soft resin micelle shown in the present.
Embodiment
The manufacture method of thermoplastic polyurethane soft resin micelle shown in the present can be made into the thermoplastic polyurethane soft resin micelle of hardness between Shore A 50 to 80, and its detailed content is described as follows:
One, the adjustment of material choice and polymerizable molecular
1. for adjusting the composition composition and the data such as rerum natura, voltinism thereof of thermoplastic polyurethane micelle, the present invention selects organic isocyanic acid salt of suitable proportion to synthesize with glycols or polyalcohols.
Wherein, selected organic isocyanic acid salt comprises aliphatics, aromatic series, alicyclic diisocyanate etc.And, by trimethylammonium-hexane-methylene-vulcabond (trimethyl-hexane-methylene-diisocyanate); 5-isocyanic acid methyl-3,3,5-3-methyl cyclohexanol based isocyanate (isophrone-diisocyanate); Hexamethylene diisocyanate (hexamethylene-diisocyanate); 4, and the 4-dicyclohexyl methane diisocyanate (4,4-dicyclohexyl-methane-diisocyanate); Between-benzene-vulcabond (meta-phenylene-diisocyanate); 4,4-diphenylmethanediisocyanate (4,4 '-diphenyl-methane-diisocyanate); And 4, the 4-diphenyl diisocyanate (is selected wherein one or more for use in the middle of 4,4 '-diphenyl-diisocyanate) colony that is formed;
Selected glycols is by ethylene glycol (ethylene glycol); Propylene glycol (1,3-propyleneglycol); Butyleneglycol (butylene glycol); Hexylene glycol (1,6-hexamethylene glycol); And select for use wherein a kind of in the middle of the colony that formed of Diethylene Glycol (diethylene glycol);
Polyalcohols then comprises polyester type and polyether-type, for example: by oxyethane (ethyleneoxide); 1,2 propylene oxide (1,2propylene oxide); Tetrahydrochysene is rebuked the poly-alkane ether glycol (polyalkylene ether glycol) of muttering ring-opening polymerizations such as (tetra-hydrofuran) and getting, perhaps by Succinic Acid (succinic acid), pentanedioic acid (glutaric acid), suberic acid (suberic acid), hexanodioic acid aliphatic dicarboxylic acid and rudimentary aliphatics alcohols such as (adipic acid), as ethylene glycol (ethyleneglycol), butyleneglycol (butylene glycol), glycol ether (diethylene glycol), triglycol (tri-ethylene glycol), hexane diol (hexamethylene glycol), 2,2-dimethyl-1, the polyester glycol (polyester glycol) that ammediol (neopentyl glycol) reaction makes.
2. control molecular weight with NCO/OH, its scope is 0.8～1.4, and organic isocyanic acid salt proportion is between 15 to 45 weight %, and the part by weight of polyalcohols and glycols is between 70: 30 to 90: 10.The auxiliary agent that is aided with the particular functional base, for example: lubrication prescription, antioxidant, heat resistance accessory etc., to increase sliding property and thermotolerance and to increase the time that can process, avoid glutinous wheel transitivity to destroy.Wherein, lubrication prescription comprises organic ammonium wax, organic ester type waxes, organic ester alcohol wax, polyethylene wax, response type Teflon, response type silicone oil (Silicone) etc.; And heat resistance accessory comprises antioxidant, secondary antioxidant, UV light absorber etc.
Two, the procedure for producing of thermoplastic polyurethane resin micelle
The manufacturing process of thermoplastic polyurethane soft resin micelle shown in the present as shown in Figure 1, has two kinds of manufacture method, and first kind of manufacture method is:
1. with polyalcohols, glycols, auxiliary agent etc., press the thermoplastic polyurethane Resin adhesive granule product of different size, mix with stirrer earlier, introduce in the bottler according to certain proportion.Because the glycols addition very little, product can be soft partially, abrasive wear resistance is poor, and the glycols addition is too high, the product meeting is hard partially, the shortage flexibility, and, additive dosage very little, product can stick wheel, abrasive wear resistance is poor, addition is too many, product is can hard partially, anti-refrangibility poor, mixing uniformity difference etc., and therefore, adding proportion of the present invention is: with thermoplastic polyurethane resin micelle is 100 weight parts, polyalcohols 100 weight parts, glycols are at 0.1～10 weight part, and auxiliary agent is between 0.1～10 weight part.
2. again with organic isocyanic acid salt, diisocyanate class is for example pressed the thermoplastic polyurethane Resin adhesive granule product of different size, add in the bottler according to certain proportion, through fully stir, mixing, mixing evenly, it is fully reacted.
3. with step 1 and 2 compound; through extruder 120～230 ℃ of reactions; the control rotating speed is in 500～3600 Revolution Per Minutes (rpm) scope; the thermoplastic polyurethane that strip heat is melted is introduced hardening by cooling in refrigerated water or the normal-temperature water; the temperature of water coolant is between-5～35 ℃; refrigerative strip thermoplastic polyurethane after the dicing machine pelletizing, is promptly made thermoplastic polyurethane soft resin micelle according to the planning size, and packing gets product after the drying.
Second kind of manufacture method is:
1. with polyalcohols, glycols, auxiliary agent etc., press the thermoplastic polyurethane Resin adhesive granule product of different size, mix with stirrer earlier, introduce in the bottler according to certain proportion.Because the glycols addition very little, product can be soft partially, abrasive wear resistance is poor, and the glycols addition is too high, the product meeting is hard partially, the shortage flexibility, and, additive dosage very little, product can stick wheel, abrasive wear resistance is poor, addition is too many, product is can hard partially, anti-refrangibility poor, mixing uniformity difference etc., and therefore, adding proportion of the present invention is: with thermoplastic polyurethane resin micelle is 100 weight parts, polyalcohols 100 weight parts, glycols are at 0.1～10 weight part, and auxiliary agent is between 0.1～10 weight part.
2. again with organic isocyanic acid salt, diisocyanate class is for example pressed the thermoplastic polyurethane Resin adhesive granule product of different size, add in the bottler according to certain proportion, through fully stir, mixing, mixing evenly, it is fully reacted.
3. with the compound of step 1 and 2; through extruder in 120～230 ℃ of reactions; the control rotating speed is in 500～3600 Revolution Per Minutes (rpm) scope; the thermoplastic polyurethane that strip heat is melted is inserted in the Sheng dish; in 60～110 ℃ of temperature; the maturation of 12～72 hours time; cooling makes into solid-state; be ground into particle with pulverizer again; through adding various auxiliary agents and the modification agent blending is even; form thermoplastic polyurethane soft resin micelle through tablets press granulation, dehumidifying, drying, cooling again, get product through packing.
By the made thermoplastic polyurethane micelle of above two kinds of manufacture method, have that rerum natura is good, pliability is good and good characteristics such as solvent-free, and, have the softness of hardness between Shore A 50 to 80, its outward appearance is between translucent and transparent, its molecular weight is between 50000 to 250000, fusing point is between 130 to 190 ℃, but add its cheap and long processing time, can be processed into the film of thickness 0.1mm to 6.0mm for the flexible PVC adhesive tape machine, the adhesive tape machine processing temperature is between 150 to 190 ℃, and process period is between 20 to 60 minutes.
Again with above-mentioned thermoplastic polyurethane film adhered or coat that surface temperature is weaved cotton cloth at 60 to 200 ℃ all types of, on tNonwovens or the dry type polyurethane film, wherein, weave cotton cloth or the material of tNonwovens such as polyester, spiral shell are entangled, on any base cloth of cotton, nylon, wool, fiber crops, polyurethane(s), polypropylene, polyhutadiene, polystyrene, polymethylmethacrylate and derivative thereof, through embossing or surface treatment, promptly can be made into a kind of high-intensity thermoplastic polyurethane synthetic leather again.
Three, processing instance
Embodiment one
According to the composition of raw materials ratio, with polyalcohols A 50 weight parts, another kind of polyalcohols B 50 weight parts, glycols 6 weight parts, diisocyanate class 36 weight parts etc., mix with stirrer earlier, and adding is pre-mixed lubrication prescription 0.5 weight part that stirs, antioxidant 2.5 weight parts, the mixture of UV light absorber 1.5 weight parts etc., in the introducing bottler, stir, ℃ squeeze out with heater heats to 160～200 at extruder through pumping, the thermoplastic polyurethane that strip heat is melted in 5～10 ℃ of refrigerated waters, cool off make into solid-state, cut into particle with cutting knife again, again through dehumidifying, dry, cooling forms thermoplastic polyurethane soft resin micelle particle, get product through packing, and, the rerum natura of this kind thermoplastic polyurethane soft resin micelle, as shown in Table 1.
Table one
| Project | Unit | Actual |
| Hardness | Shore A | 78 |
| Tension intensity | Kg/cm 2 | 300 |
| Elongation | ％ | 600 |
| Tear strength | Kg/cm | 70 |
| Test roll mill (TEST | ℃ | 160～180 |
| ROLL) processing temperature | ||
| TEST ROLL process period | Min. | 40 |
Embodiment two
According to the composition of raw materials ratio; with polyalcohols A 50 weight parts; polyalcohols B 20 weight parts; polyalcohols C 30 weight parts; glycols 5 weight parts; diisocyanate class 25 weight parts etc.; mix with stirrer earlier; and adding is pre-mixed lubrication prescription 0.5 weight part that stirs; antioxidant 2.5 weight parts; the mixture of UV light absorber 1.5 weight parts etc.; in the introducing bottler; stir; ℃ squeeze out with heater heats to 160～200 at extruder through pumping; the thermoplastic polyurethane that strip heat is melted places the Sheng dish; through 75 ℃ of temperature; the maturation of 20 hours time; cooling makes into solid-state, cuts into particle with cutting knife again, again through the tablets press granulation; dehumidifying; dry; cooling forms thermoplastic polyurethane soft resin micelle; get product through packing; and, the rerum natura of this kind thermoplastic polyurethane soft resin micelle, as shown in Table 2.
Table two
| Project | Unit | Actual |
| Hardness | Shore A | 58 |
| Tension intensity | Kg/cm 2 | 250 |
| Elongation | ％ | 700 |
| Tear strength | Kg/cm | 45 |
| TEST ROLL processing temperature | ℃ | 150～160 |
| TEST ROLL process period | Min. | 40 |
Embodiment three post-treatment embodiment
With embodiment two made thermoplastic polyurethane soft resin micelles, rolled material 5～10 minutes with ten thousand horsepowers of machines, become the semi-melting state, be discharged in the two insulation wheels, the material temperature control is at 80～120 ℃, draw material after continuing to mix 5～10 minutes and go into the four-wheel adhesive tape machine, 170～190 ℃ of control adhesive tape machine front-wheel temperature, 170～190 ℃ of last wheel temperature, 160～180 ℃ of middle wheel temperature, 145～160 ℃ of lower whorl temperature, adjusting the extrusion gap is 1.0mm, batch after wheel is drawn cooling through drawing, be the thermoplastic polyurethane finished film, and, the rerum natura of this kind thermoplastic polyurethane film, as shown in Table 3.
Table three
| Project | Unit | Actual |
| Hardness | Shore A | 61 |
| Tension intensity | Kg/cm 2 | 260 |
| Elongation | ％ | 670 |
| Tear strength | Kg/cm | 48 |
| TEST ROLL processing temperature | ℃ | 150～160 |
| TEST ROLL process period | Min. | 40 |
Claims (7)
1. the manufacture method of a thermoplastic polyurethane soft resin micelle, select organic isocyanic acid salt 15～45 weight % for use, and polyalcohols and the glycols building-up reactions of part by weight between 70: 30 and 90: 10, collocation lubrication prescription, antioxidant or heat resistance accessory, and control molecular weight with NCO/OH, and make molecular weight 50000 to 250000, fusing point is at 130 to 190 ℃, hardness is at the thermoplastic polyurethane soft resin micelle of Shore A 50 to 80, and its step comprises:
(1) is 100 weight parts with the resin micelle, after polyalcohols 100 weight parts, glycols 0～10 weight part, auxiliary agent 0～10 weight part are mixed with stirrer, introduces bottler;
(2) the organic isocyanic acid salt through selecting for use is added in the bottler of step poly-(1) fully stirring, mixing and mixing even; Wherein, organic isocyanic acid salt is selected from trimethylammonium-hexane-methylene-vulcabond, 5-isocyanic acid methyl-3,3,5-3-methyl cyclohexanol based isocyanate, hexamethylene diisocyanate, 4, the 4-dicyclohexyl methane diisocyanate ,-benzene-vulcabond, 4,4-diphenylmethanediisocyanate and 4, the colony that the 4-diphenyl diisocyanate is formed wherein one or more;
(3) compound that step (2) has fully been reacted is extruded into heat via the extruder signature and melts the strip thermoplastic polyurethane, and introduces temperature hardening by cooling in-5～35 ℃ water, again via the dicing machine pelletizing, and makes thermoplastic polyurethane soft resin micelle.
2. the manufacture method of thermoplastic polyurethane soft resin micelle according to claim 1; wherein; step (3) is given as security via extruder and is extruded into after heat melts the strip thermoplastic polyurethane; heat is melted the strip thermoplastic polyurethane to be inserted in the Sheng dish; under 60～110 ℃ of temperature; the maturation of 12～72 hours elapsed time; and be cooled to solid-state; be ground into particle with pulverizer again; after adding various auxiliary agents and modification agent blending evenly, form thermoplastic polyurethane soft resin micelle through tablets press granulation, dehumidifying, drying, cooling again.
3. the manufacture method of thermoplastic polyurethane soft resin micelle as claimed in claim 1 or 2, wherein, glycols is selected from the wherein a kind of of the colony that is made up of ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol and Diethylene Glycol.
4. as the manufacture method of thermoplastic polyurethane soft resin micelle as described in the claim 3, wherein, polyalcohols is selected from the wherein a kind of of the colony that is made up of poly-alkane ether glycol and polyester glycol.
5. as the manufacture method of thermoplastic polyurethane soft resin micelle as described in the claim 4, wherein, lubrication prescription is selected from the wherein a kind of of the colony that is made up of organic ammonium wax, organic ester type waxes, organic ester alcohol wax, polyethylene wax, response type Teflon and response type silicone oil.
6. as the manufacture method of thermoplastic polyurethane soft resin micelle as described in the claim 4, wherein, heat resistance accessory is selected from the wherein a kind of of the colony that is made up of antioxidant, secondary antioxidant and a UV light absorber.
7. a hardness is at the thermoplastic polyurethane soft resin micelle of Shore A 50 to 80, method according to claim 1 is made, and its molecular weight is 50000 to 250000, and fusing point is at 130 to 190 ℃, can supply the flexible PVC adhesive tape machine process, and make the film of thickness 0.1mm to 6.0mm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410008663 CN1281652C (en) | 2004-03-16 | 2004-03-16 | Colloidal particles of thermoplastic PU soft resin and fabricating method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410008663 CN1281652C (en) | 2004-03-16 | 2004-03-16 | Colloidal particles of thermoplastic PU soft resin and fabricating method |
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| CN1563133A CN1563133A (en) | 2005-01-12 |
| CN1281652C true CN1281652C (en) | 2006-10-25 |
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| CN 200410008663 Expired - Fee Related CN1281652C (en) | 2004-03-16 | 2004-03-16 | Colloidal particles of thermoplastic PU soft resin and fabricating method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101235596B (en) * | 2008-03-07 | 2010-06-16 | 李勇 | Method for preparing artificial polyurethane leather |
| CN104460231B (en) * | 2013-09-18 | 2020-03-13 | 东友精细化工有限公司 | Colored curable resin composition |
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