CN1225927A - Method for producing high-strength thermoplastic polyurethane artificial leather - Google Patents
Method for producing high-strength thermoplastic polyurethane artificial leather Download PDFInfo
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- CN1225927A CN1225927A CN 98100526 CN98100526A CN1225927A CN 1225927 A CN1225927 A CN 1225927A CN 98100526 CN98100526 CN 98100526 CN 98100526 A CN98100526 A CN 98100526A CN 1225927 A CN1225927 A CN 1225927A
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Abstract
The production method of high-strength thermoplastic polyurethane resin artificial leather includes the following steps: using thermoplastic polyurethane elastomer resin (TPU) 100 PHR, adding polyolefine 0-30 PHR, polyvinyl chloride 0-30 PHR, lubricant 0-20 PHR, filling agent 0-20 PHR, modifier 0-20 PHR and colouring agent 0-15 PHR to obtain mixed batch material, mixing and melting at 100-240 deg.C, film-forming by using film-forming machine to obtain thin film with thickness of 0.02mm-6.0 mm, sticking or applying the thin film over the base cloth, embossing or surface treatment to obtain the invented finished product.
Description
The present invention relates to the method for making of high-strength thermoplastic polyurethane artificial leather, refer to that especially the Polyurethane Thermoplastic Elastomer (TPU) with different soft and hard degree kind is the method that principal constituent prepares high-strength thermoplastic polyurethane artificial leather.
The production of imitation leather in the past, mainly based on synthetic skin of PU and the synthetic skin of PVC, the main raw material of making the synthetic skin use of PU is PU resin and the diluting solvent that contains the high solvent composition; The main raw material that the synthetic skin of manufacturing PVC uses is PVC powder and liquid plasticizer, utilizes modes such as coating, applying to make synthetic leather, and its shortcoming is:
(1) the synthetic skin of PU uses high solvent composition resin and diluting solvent to be main raw material, and manufacture method mainly is to coat the PU resin formula on the base cloth or on the separate-type paper, utilize explained hereafter such as cohesion, washing and drying with coating machine.Used solvent in the PU resin formula, deriving in manufacturing processed becomes waste water, waste gas, therefore must take precautions against the treatment facility of environmental pollution in waste water, waste gas etc. by a large amount of funds of investment, otherwise will cause environmental and ecological destruction is polluted.
(2) the synthetic skin of PVC uses powder-type polyvinyl chloride resin and liquid plasticizer to be main raw material, it is in mixing calender line, because operation is to carry out in the high temperature open system for a long time, easily produce the pollution of dust and plasticizer volatilization waste gas, must invest a large amount of funds in dust and waste gas treatment equipment, environmental and ecological destruction be polluted otherwise will cause.
(3) hydrolytic resistance of the synthetic skin of PU is relatively poor, when desire is improved anti-hydrolytic performance, and the relative variation of performance such as its stripping strength and surface abrasion resistance consumption intensity, especially base fabric is a nylon when weaving cotton cloth, and stripping strength is below 0.5Kg/3cm, and practicality is little.
(4) the anti-flexion of low temperature and the impact resistance of the synthetic skin of PVC are poor, generally only can be low temperature resistant to-10 ℃, very easily break when requiring more low temperature, and then plasticizer very easily occurs or add the unusual phenomenon that auxiliary agent spues in the surface if desire is improved resistance to low temperature.And can produce malicious dioxin, chlorine and the heavy metal particle in century during the refuse incineration of PVC goods, heavy metal can be separated out and contaminate environment when burying, and is not inconsistent environmental requirement.
(5) synthetic skin of PU or the synthetic skin of PVC, when being used in height friction bump purposes occasion, its surface abrasion resistance consumption and stripping strength quality still can't meet market demands fully.
The objective of the invention is to address the above problem, and a kind of method for making of high-strength thermoplastic polyurethane resin synthetic leather is provided.
The present invention is main composition with the Polyurethane Thermoplastic Elastomer resin, mix and be equipped with polyolefine, polyvinyl chloride, lubrication prescription, weighting agent, tinting material and modification agent and make composition, wherein the Polyolefin and polyvinyl chloride can optionally add one or both, its adding proportion out of the ordinary is between 0PHR～30PHR, generally below adding 15PHR, be advisable, can influence the wear resistant of finished product too much; Lubrication prescription can be improved the processibility of extrusion, and addition generally to be advisable below the 10PHR, can influence the wear resistant of finished product between 0PHR～20PHR when too many; Weighting agent can reduce cost, and addition is between 0PHR～20PHR, generally to be advisable below the 12PHR, can influence wear resistant when too many and tear, tension intensity; Can add according to need as for tinting material and modification agent.Mentioned component can simultaneously or add in the groove in batches, makes it be molten state with 100 ℃ to 240 ℃ temperature, with the continuous extrusion plastic film of T-mould extruder, and still is heat in the plastic film extrusion and melts under the state with preheating or the base fabric that is not preheated and fit; Perhaps mixingly roll into film after roll the roller of turbine and rolling press with mixing machine, on the applying embossing machine, fit with preheating or the base fabric that is not preheated, and can when fitting, use general iron embossed wheel to extrude lines, perhaps use the embossing of special substance embossed wheel on special embossing machine, surface abrasion resistance consumption height is provided in manufacturing, stripping strength is high and the high-strength artificial leather of low temperature tolerance characteristics.The present invention utilizes one, two, three layer or common extruder of multilayer T-mould or rolling press roller calendered film technology manufacturing imitation leather, main raw material because of use in the manufacturing is the 100% solid granular TPU micelle of shape, do not need again with any solvent cut dissolving, can directly come into operation, can not produce problem of environmental pollutions such as waste gas, waste water, dust; According to plastic layer film thickness, performance, soft durometer requirement, which kind of explained hereafter decision is selected with, to produce low-cost satisfactory high-performance artificial leather, to be fit to multiple processing purposes.The present invention be utilize one, two, three layer or multilayer T-mould altogether extruder or rolling press roller calendered film make the method for imitation leather, below the operating method of different extruders is described respectively.
One, for one deck extruder:
(1) will be based on the composition of thermoplasticity PU elastomerics, direct extrusion is also drenched film on base fabric, and thermoplasticity PU elastomerics itself has the dual function of sticking with paste layer glued membrane and surface layer glued membrane concurrently.
Two, be total to extruder to two layers:
(1) is composition material (hereinafter to be referred as sticking with paste a layer glued membrane) near one deck of applying base fabric, is mainly and improves base fabric and follow intensity based on thermoplasticity PU elastomerics.
(2) adjacency is stuck with paste one deck of layer glued membrane for the composition material based on thermoplasticity PU elastomerics, as surperficial plastic cement rete (hereinafter to be referred as the surface layer glued membrane).
Three, for being total to extruder more than three layers or three layers:
(1) one deck near the applying base fabric is the admixtion (sticking with paste layer with two layers of extruder, hereinafter to be referred as sticking with paste layer glued membrane) based on thermoplasticity PU elastomerics, and main function is followed intensity for improving base fabric.
(2) one deck of the top is surperficial plastic layer (hereinafter to be referred as the surface layer glued membrane), and its raw material is the admixtion based on thermoplasticity PU elastomerics, and the main function of surface layer glued membrane is to give the surface required rerum natura and feel.
(3) boundary as middle plastic layer (hereinafter to be referred as the middle level glued membrane), adjusts product thickness and soft durometer in sticking with paste between layer glued membrane and the surface layer glued membrane one or more layers for the admixtion based on thermoplasticity PU elastomerics or polyolefine or polyvinyl chloride.
Four, for the rolling press processing procedure:
(1) base cloth is after sewing up pressing, with lathering machine coating paste on base cloth, make when fitting can with well follow based on the admixtion of thermoplasticity PU elastomerics.
(2) select suitable admixtion according to the soft durometer that requires based on thermoplasticity PU elastomerics, utilize the roller of rolling press to roll into the film of desired thickness, directly fit with sticking with paste cloth by the embossed wheel embossing in discharging place, perhaps on the applying embossing machine again with preheating or be not preheated on stick with paste the base fabric embossing and fit.
The thermoplasticity PU elastomerics paste raw material that each layer glued membrane is used, its major ingredient is a thermoplasticity PU elastomerics, and its hardness is between 20～100A (Shore hardness), and proportion is between 1.00～1.40, melt flow index is 1～50gm/10 branch, and the melting point scope is 80 ℃～190 ℃; But can add lubrication prescription, antioxidant, UV light absorber, flame retardant, antistatic agent, colorant, weighting agent congruent melting blended resin and other performance improvers according to various performance needs in addition.
Therefore, the present invention is a principal constituent with the Polyurethane Thermoplastic Elastomer (TPU) of different soft and hard degree kind, mix and be equipped with polyolefine, polyvinyl chloride, lubrication prescription, weighting agent, tinting material and modification agent and make admixtion, warp is with the continuous extrusion plastic film of T-mould extruder, and still be heat in plastic film and melt under the state with preheating or the base cloth that is not preheated and fit: perhaps mixingly roll into film, on the applying embossing machine, make the high-strength artificial leather with preheating or the base cloth applying embossing that is not preheated, cooling after roll the roller of turbine and rolling press with mixing machine.Compare with natural leather or other kind synthetic leathers, this kind leather has characteristics such as better abrasion performance intensity, stripping strength, the anti-flexion of low temperature, be fit to multiple post-treatment purposes, and in manufacturing processed, do not have to produce environmental pollution problems such as waste water, waste gas in other general leather manufacturing process.
Fig. 1 is for being the course of processing figure of the present invention of example with one deck extruder.
Fig. 2 is the section of structure with the plastic cement skin of explained hereafter shown in Figure 1.
Fig. 3 is a process flow sheet of the present invention.
Following conjunction with figs. further specifies technology contents of the present invention, and procedure for processing of the present invention please refer to Fig. 1 (being total to extruder with one deck is example).Have the admixtion based on thermoplasticity PU elastomerics of sticking with paste layer glued membrane and the dual function of surface layer glued membrane concurrently, by glued membrane extruder (Fig. 1 (1)) extrusion, the processing temperature scope is 100 ℃～240 ℃; When the extruder processing temperature was lower than this temperature range, resin extrusion extensibility was poor, and productivity is not good, and when the extruder processing temperature was higher than this temperature, resin is easy crossed thermolysis, and causes the transverse gage distributional difference, and productivity is not good yet.
The extrusion film thickness is 0.02～6.0mm; When being lower than this film thickness scope, the transverse gage difference intensity that easily causes fitting is not good, and influences surface physical property, and when adhesive film thickness was higher than this thickness range, finished product materials amount was many and price is higher, and the market acceptance level is little.
Base fabric (Fig. 1 (7)) after preliminary heating device (Fig. 1 (2)) preheating, enter applying rubber wheel (Fig. 1 (4)) and embossed wheel (Fig. 1 (5)) with from the T-mould (after the melt plastic cement film applying embossing of Fig. 1 (3) extrusion, through cooling wheel (Fig. 1 (6)) cooling, can become plastic film finished product (Fig. 1 (8)) again; Base fabric preheating temperature scope can be room temperature～200 ℃, the base fabric preheating temperature is looked cloth kind thermotolerance difference and is changed, main purpose is for increasing applying intensity, base fabric can be without the preheating extrusion plastic film of fitting at once, but the applying stripping strength is relatively poor, the base fabric preheating temperature heals, and then finished product applying intensity is better for height, the base fabric preheating temperature is just optionally fitted stripping strength and cloth kind and is decided, but preheating temperature can not surpass the base fabric heat resisting temperature, otherwise shrink and melting phenomenon, general polypropylene (PP) material base fabric preheating temperature is room temperature～130 ℃, the preheating temperature of nylon material base fabric is room temperature～160 ℃, polyester, material such as rayon and cotton base fabric, its preheating temperature scope are room temperature～200 ℃, the base fabric preheating temperature can influence applying intensity below room temperature, do not consider; More than the top temperature scope, to shrink and melting phenomenon because of causing base fabric easily, productivity is poor, does not also consider; Embossed wheel and cooling wheel can lead to water coolant, and rubber wheel need not cool off.
The plastic cement skin finished product structure of Sheng Chaning please refer to Fig. 2 in the above described manner, and Fig. 2 (1) is for having surface layer concurrently and sticking with paste the glued membrane of the dual function of layer, and Fig. 2 (2) is a base fabric; Plastic cement skin surface can impose printing again or surface color optical haze degree is handled, to increase product feeling of high class and value added.
According to the prepared imitation leather plastic cement of the inventive method leatherware following characteristics are arranged:
(1) the plastic cement rete of imitation leather (the used fiber material of base fabric comprises materials such as nylon, polyester, rayon, cotton, polypropylene, polyacrylonitrile, wool, fiber crops) and the stripping strength between base fabric can reach more than the 9.6Kg/3cm.
(2) the abrasion performance intensity on imitation leather surface is splendid, according to JIS-K6328 method test, can reach more than #H22 emery wheel * 1Kg * 10000 time, can not break in the surface.
(3) anti-flexing rerum natura is good, and normal temperature can reach more than 125000 times, and-10 ℃ can reach more than 30000 times, after 70 ℃ * 95%RH * 1 week hydrolysis test, tests the anti-flexing rerum natura of its normal temperature according to the JIS-K6545 method and still can reach more than 125000 times.
(4) in plastic film and base fabric, can change being pressed into imitation leather according to the embossed wheel lines with beautiful decorative pattern with applying embossed wheel applying extrusion.
(5) imitation leather after the applying can print or optical haze degree processing arbitrarily.
Your auditor the invention people makes further understand the technology contents of this case, as the prescription of thermoplasticity PU elastomer resin admixtion how, make imitation leather of the present invention, with following embodiment technology contents of the present invention is described now, but be not to limit category of the present invention with this.Embodiment 1
Adopt one deck extruder manufacturing altogether, used prescription, extrusion thickness and base fabric kind are as shown in table 1, extrusion arbor cylinder temperature is by 130 ℃ of cold zones to the high-temperature zone 190 ℃, T mould temperature is 190 ℃, the base fabric preheating temperature is 100 ℃, (temperature is 30 ℃～50 ℃ to deliver to the applying embossed wheel after the base fabric preheating, the embossed wheel rotating speed is 6 yards/minute) fit into the plastic cement skin that thickness is 1.4mm with the plastic film of extrusion, directly cutting after cooling wheel (temperature is 28 ℃) cooling, batch packing for 50 yards with every bundle, be finished product; Finished product base fabric stripping strength is more than the 12Kg/3cm, can be used for the purposes of footwear processing for downstream source mill.The rerum natura of itself and PVC and PU plastic cement skin relatively, and is as shown in table 2.
Table 1
| Admixtion is formed (weight part) | The TPU micelle | ????100 |
| The look grain | ????8 | |
| Antioxidant | ????0.5 | |
| Stearic acid | ????0.2 | |
| Film thickness (mm) | ????0.35 | |
| Base fabric | Polyester non woven fabric (cloth thickness 1.0mm) | |
| Finished product total thickness (mm) | ????1.40+0.05 | |
Table 2
Embodiment 2
| 1.4mm footwear goods | TPU goods of the present invention | The wet-type PU goods | The PVC goods |
| Tension intensity (Kg/3mm) | ??45↑ | ????35↑ | ??35↑ |
| Elongation (%) | ?100↓ | ????100↓ | ?100↓ |
| Tear strength (Kg) | ?9.5↑ | ????9.5↑ | ?9.5↑ |
| Stripping strength (Kg/3cm) | ?9.6↑ | ????8.6↑ | ?9.0↑ |
| The abrasion performance number of times (#H22 * 1Kg) | 10000 times ↑ | 800 times ↓ | 1000 times ↓ |
| Hydrolysis (75%RH * 75 ℃ * 14 days) | By | By | By |
| The intensity that rises brokenly Kg/cm 2 | ?26 | ?????25 | ?24 |
| Winter hardiness-10 ℃ | 30000 times ↑ | 20000 times ↑ | 20000 times ↑ |
Adopt one deck extruder manufacturing altogether, used prescription, extrusion thickness and base fabric kind are as shown in table 3, extrusion arbor cylinder temperature is by 125 ℃ of cold zones to the high-temperature zone 185 ℃, T mould temperature is 180 ℃, the base fabric preheating temperature is 100 ℃, (temperature is 30 ℃～50 ℃ to deliver to the applying embossed wheel after the base fabric preheating, the embossed wheel rotating speed is 7 yards/minute) fit into the plastic cement skin that thickness is 1.0mm with the plastic film of extrusion, after cooling wheel (temperature is 30 ℃) cooling, batch in reeling machine, deliver to embossing machine then with special embossed wheel embossing lines, batch and pack to tie 50 yards with cutting machine then, be finished product.The stripping strength of finished product base fabric is more than the 9.6Kg/3cm, and surface abrasion resistance consumption number of times can reach more than #H22 * 1Kg * 10000 time, can be used for the purposes of footwear processing for downstream source mill.
Table 3
| Admixtion is formed (weight part) | The TPU micelle | ????100 |
| The look grain | ????6 | |
| The PE micelle | ????6 | |
| Weighting agent | ????10 | |
| Stearic acid | ????0.2 | |
| Antioxidant | ????0.5 | |
| Film thickness (mm) | ????0.35 | |
| Base fabric | Polyester non woven fabric (cloth thickness 0.7mm) | |
| Finished product total thickness (mm) | ????1.40+0.05 | |
Claims (1)
1. the method for making of a high-strength thermoplastic polyurethane synthetic leather, add polyolefine 0～30PHR by Polyurethane Thermoplastic Elastomer resin (TPU) 100PHR, lubrication prescription 0～20PHR, weighting agent 0～20PHR, modification agent 0～20PHR, tinting material 0～15PHR and make admixtion, this admixtion is behind 100 ℃～240 ℃ mixed meltings, via one deck, two layers, three layers or the common extruder of multilayer, the film forming machine that rolling press is selected, obtain the film of thickness 0.02mm to 6.0mm, fit again or coat surface temperature and remain on room temperature to a kind of base cloth of 200 ℃ of preheatings, through embossing or surface treatment and make synthetic leather, described base cloth is selected from by polyester again, rayon, cotton, nylon, polypropylene, wool, fiber crops, polyurethane(s), polyacrylonitrile, polyhutadiene, polystyrene, what polymethylmethacrylate and derivative thereof were made weaves cotton cloth or non woven fabric.
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| Application Number | Priority Date | Filing Date | Title |
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| CN98100526A CN1125111C (en) | 1998-02-12 | 1998-02-12 | Method for producing high-strength thermoplastic polyurethane artificial leather |
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| CN98100526A CN1125111C (en) | 1998-02-12 | 1998-02-12 | Method for producing high-strength thermoplastic polyurethane artificial leather |
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| CN1225927A true CN1225927A (en) | 1999-08-18 |
| CN1125111C CN1125111C (en) | 2003-10-22 |
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| CN98100526A Expired - Fee Related CN1125111C (en) | 1998-02-12 | 1998-02-12 | Method for producing high-strength thermoplastic polyurethane artificial leather |
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| CN1314854C (en) * | 2005-07-07 | 2007-05-09 | 靳爱晨 | Production of thermoplastic polyurethane leather with figure on surface |
| CN101363192B (en) * | 2008-09-26 | 2010-06-09 | 李勇 | Method for producing polyvinyl chloride imitation leather using waste polystyrol foam material |
| CN102416751A (en) * | 2010-09-27 | 2012-04-18 | 刘坤钟 | Manufacturing method of synthetic leather |
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| CN103015220A (en) * | 2012-12-20 | 2013-04-03 | 陕西科技大学 | Preparation method of thermoplastic polyurethane synthetic leather |
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| CN101363192B (en) * | 2008-09-26 | 2010-06-09 | 李勇 | Method for producing polyvinyl chloride imitation leather using waste polystyrol foam material |
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| CN103422359A (en) * | 2013-08-13 | 2013-12-04 | 易杨波 | Artificial leather preparation technology and artificial leather |
| CN103434244A (en) * | 2013-08-27 | 2013-12-11 | 无锡翔隆高分子面料有限公司 | Method for manufacturing high-strength thermoplastic polyurethane (TPU) multi-layer composite fabric |
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