CN101021046A - Recipe and production process of artificial leather of thermoplastic polyurethane - Google Patents
Recipe and production process of artificial leather of thermoplastic polyurethane Download PDFInfo
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- CN101021046A CN101021046A CN 200610035730 CN200610035730A CN101021046A CN 101021046 A CN101021046 A CN 101021046A CN 200610035730 CN200610035730 CN 200610035730 CN 200610035730 A CN200610035730 A CN 200610035730A CN 101021046 A CN101021046 A CN 101021046A
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Abstract
The present invention is the recipe and production process of artificial leather of thermoplastic polyurethane. The artificial leather has thermoplastic polyurethane elastomer resin as the main material, acrylic resin, plasticizer of non-toxic polyol derivative, dispersant, stuffing, etc. The rolling process of producing thermoplastic polyurethane artificial leather includes the following steps: 1. sizing the base fabric; 2. rolling to compound TPU base material and top material; 3. adhering the compounded TPU base material and top material onto the base fabric; and 4. post-treatment of the artificial leather to obtain the thermoplastic polyurethane artificial leather product. The production process may be completed in a conventional rolling production line.
Description
Technical field
The present invention relates to a kind of prescription and manufacture method thereof of artificial leather, refer in particular to the prescription and the calendering autofrettage thereof of a kind of full environment protection thermoplastic polyurethane (TPU, Thermoplastic Polyurethane) artificial leather.
Background technology
The production of traditional artificial leather, mainly based on synthetic skin of PU and the synthetic skin of PVC, the main raw material that is used to make the synthetic skin of PU is PU resin and the retarder thinner that contains high solvent, the main raw material that is used to make the synthetic skin of PVC is PVC powder and liquid plasticizer, plasticizer adopts phthalate, and manufacture method is rubbing method, applying method, blown film method or T-mould The tape casting etc.The prescription of traditional artificial leather and manufacture method have following shortcoming:
(1) when synthesizing skin as main body with PU, when adopting rubbing method manufacturer fabricate-leather, because need in the coating process semi-finished product after cohesion, washing are carried out dried, used solvent will be derived in dry run and be become waste water, waste gas, contaminated environment in the PU resin formula; And, the hydrolytic resistance of the synthetic skin of PU is relatively poor, when improving its anti-hydrolytic performance as desire, the relative variation of performance such as its peel strength and surface abrasion resistance consumption intensity, especially when base fabric adopted nylon to weave cotton cloth, peel strength was used in high the friction when clashing into the purposes occasion below 0.5Kg/3cm, its surface abrasion resistance consumption and peel strength quality are difficult to meet market demands, and practicality is little.
(2) when synthesizing skin as main body with PVC, when adopting applying manufactured artificial leather, in mixing calender line, owing to operate for a long time, easily produce dust and plasticizer volatilization waste gas in the high temperature open system, environmental pollution is very big; And, can produce toxic gas dioxin (dioxin), chlorine and heavy metal particle during the incineration of garbage of PVC goods; The anti-flexion of low temperature and the impact resistance of the synthetic skin of PVC are poor, then plasticizer very easily occurs or add the anomaly that auxiliary agent spues in the surface if desire is improved its resistance to low temperature,
(3) phthalate is a toxic reagent, as plasticizer, contains poisonous prescription in the feasible artificial leather of making, and is applied in the daily life, and the harm people's is healthy.
Therefore, in order to solve above-mentioned variety of problems, the invention provides a kind of with thermoplastic polyurethane as the environment-protecting asepsis of major ingredient, degradable artificial leather prescription, and the method that is used to make this kind artificial leather.
Summary of the invention
The object of the present invention is to provide a kind of with thermoplastic polyurethane as the environment-protecting asepsis of major ingredient, degradable artificial leather prescription, and the method that is used to make this kind artificial leather: rolling process.
A kind of thermoplastic polyurethane (Thermoplastic Polyurethane, TPU) prescription of artificial leather, be composited by bed material, lining and base fabric, component comprises at least: TPU(Thermoplastic polyurethanes), acrylic resin, plasticizer, foaming stabilization agent, foam control agent and blowing agent, wherein, plasticizer is the polyol derivative plasticizer.The prescription composition and the weight ratio of lining and bed material are as follows:
Lining:
TPU(Thermoplastic polyurethanes) 100
Acrylic resin 2----10
Polyol derivative plasticizer 1----50
Dispersant 0----1
Strengthen packing material 0----30
Stearic acid 0----1
Antioxidant 0----1
Ultra-violet absorber 0----1
Colorant 0----5
Bed material:
TPU(Thermoplastic polyurethanes) 100
Acrylic resin 2----10
Polyol derivative plasticizer 1----50
Foaming stabilization agent 2----3
Foam control agent 0.5---1.5
Blowing agent 4----6
Strengthen packing material 0----50
Colorant 0----5
Wherein, dispersant is selected polymer fatty acid fat dispersant for use, and the foaming stabilization agent is selected Ba/Zn foaming stabilization agent for use, and blowing agent is selected blowing agent AC for use, and polyol derivative is selected propylene glycol ester for use.
The present invention also provides a kind of method for making of artificial leather of thermoplastic polyurethane, and it adopts rolling process to make, and may further comprise the steps:
(1) with the base fabric starching;
(2) adopt compound TPU bed material of rolling process and lining;
(3) bed material and lining are carried out compound, fit on the base fabric again;
(4) artificial leather is carried out post processing, promptly make described artificial leather of thermoplastic polyurethane;
Wherein, in step (2), it is as follows to adopt rolling process to prepare the technological process of TPU lining and bed material: stir--〉banburying--〉and open refining--〉and filter--〉calendering--〉and draw and get.
In step (3), base fabric is selected knitted cloth for use, is rolled the pin cotton, Woven Fabrics, imitative in skin, impregnation cloth or the nonwoven fabric any one.
Compared with prior art, a kind of artificial leather of thermoplastic polyurethane of the present invention has adopted the Polyurethane Thermoplastic Elastomer resin as major ingredient, synthetic skin of traditional artificial leather major ingredient PU or the synthetic skin of PVC have been replaced, fusion acrylic resin, plasticizer, dispersant, packing material etc. are made, wherein, plasticizer has substituted poisonous phthalate by nontoxic polyol derivative, makes the artificial leather of making have environment-protecting asepsis, degradable characteristic.
In addition, the present invention adopts rolling process to prepare artificial leather of thermoplastic polyurethane, can use conventional press production line, do not need with blown film or T-mould curtain coating production line, like this, can make originally be used for poly-ammonia ethene (PVC) artificial leather production rolling equipment not can because of PVC based on environmental protection factor investment loss that market shrinkage causes, and calender must not made any machinery and changes, this production method can make the production cost of TPU artificial leather reduce greatly, makes market more accept TPU and uses as the environmental protection material.In preparation technology, major ingredient polyurethane resin and various additive auxiliary material add simultaneously at homogenizer, do not need to heat in advance, do not need granulation in advance yet, temperature during by control additives ratio and mixing stirring, use acrylic resin, dispersant polymeric fatty acid esters and stearic acid and reduce the intermolecular friction of raw material in the production process, and the melt temperature of reduction molten mass, thereby raising heat endurance, and prevent that molten mass is bonded on the metal wheel face, reduce machine burden, lower power consumption.
Description of drawings
Fig. 1 is the preparation flow figure of a kind of artificial leather of thermoplastic polyurethane of the present invention;
Fig. 2 is the compound TPU bed material of rolling process and the lining preparation flow figure of a kind of artificial leather of thermoplastic polyurethane of the present invention.
The specific embodiment
Below further set forth the prescription of artificial leather of thermoplastic polyurethane of the present invention.
Artificial leather is fitted by the lining after calendering and bed material and base fabric and makes, wherein, artificial leather lining and bed material all adopt TPU(Thermoplastic polyurethanes) as major ingredient, also include auxiliary material in the backing material formula: plasticizer, foaming stabilization agent, foam control agent, reinforcement packing material; Also include auxiliary material in the lining prescription: plasticizer, dispersant, reinforcement packing material, antioxidant, ultra-violet absorber and colorant.In the present invention, plasticizer is selected the polyol derivative plasticizer for use; Dispersant is selected polymer fatty acid fat dispersant for use; The foaming stabilization agent is selected Ba/Zn foaming stabilization agent for use; Blowing agent is selected blowing agent AC for use; Strengthen packing material and can select calcene for use; Colorant can be selected PU type color chips for use; Polyol derivative can be selected propylene glycol ester for use.Base fabric can be selected knitted cloth for use, rolls the pin cotton, Woven Fabrics, imitative in various cloth kinds such as skin, impregnation cloth or nonwoven fabric.The color of the selected decider's fabricate-leather by colorant can be colouredly or colourless, and thickness range is 0.05mm-5.00mm.
The prescription of bed material following (weight ratio):
Thermoplastic polyurethane 100
Acrylic resin 2---10
Polyol derivative plasticizer 1----50
Foaming stabilization agent 2----3
Foam control agent 0.5---1.5
Blowing agent AC 4-----6
Strengthen packing material 0-----50
Colorant 0-----5
The prescription of lining following (weight ratio):
TPU(Thermoplastic polyurethanes) 100
Acrylic resin 2---10
Polyol derivative plasticizer 1----50
Dispersant 0----1
Strengthen packing material 0----30
Stearic acid 0-----1
Antioxidant 0-----1
Ultra-violet absorber 0-----1
Colorant 0-----5
Specifically set forth artificial leather manufacture method of the present invention below in conjunction with Fig. 1-2:
Step 1) is produced the base fabric starching at slurry cloth machine:
The equipment of use: starch the cloth machine, go up paste wheel (generally taking turns), be coated with cutter with 30-60 purpose intaglio plate;
Technological process: use and be coated with the method for scraping with being coated with the cutter frictioning and it being coated on the base fabric, wherein, glue generally uses two liquid type polyurethane glue.
Process conditions: bake out temperature: 120-135 ℃; Drying time: 1-2 minute
Purpose: base fabric and sizing material are pasted firmly.
Step 2) adopts the compound TPU bed material of rolling process;
The equipment that uses: homogenizer, banbury, mill, filter, 4 roll calendars, draw and get wheel, applying wheel, cooling wheel and winding wheel, wherein, rolling process adopts conventional press production line, do not need with blown film or T-mould curtain coating production line, both applicable to the manufacturing of polyvinyl chloride (PVC) artificial leather, again applicable to the manufacturing of thermoplastic polyurethane (TPU) artificial leather.
Technological process: stir--〉banburying--〉and open refining--〉filtration--〉calendering--〉draw and get
Preparation process is as described below:
Step 21) in homogenizer, throws bed material (polyurethane resin, acrylic resin, polyol derivative plasticizer, Ba/Zn foaming stabilization agent, foam control agent, reinforcement packing material) by said ratio, and carry out the high-speed stirred mixing;
Process conditions: first stirring at low speed 30 seconds, back high-speed stirred 5-6 minute, temperature range 102-108 ℃.
Purpose: fully mix various materials.
Step 22) bed material behind the high-speed stirred mixing falls into banbury, treats that blowing agent AC and colorant are dropped in half back of blanking in the homogenizer, continues to have thrown bed material then;
Process conditions: 4.5-5.5 minute banburying time
Purpose: material is further mixed and preliminary gel.
Step 23) will drop in regular turn through the bed material of banburying among mill A, the B, and open refining through twice and handle;
Process conditions: mixing temperature 110-130 ℃
Purpose: with complete gel of material and feed.
Step 24) will put into filter through the bed material of opening refining and filter, remove impurity;
Process conditions: die head temperature 90-130 ℃; Filtering mesh is 8 orders * 20 orders
Purpose: with Impurity removal.
Step 25) will put into 4 roll calendars through the bed material that filters rolls;
Process conditions: rolling temperature 115-145 ℃
Purpose: sizing material is pressed into sheet and adjustment thickness.
Step 26) bed material after will rolling is sent into to draw and is got wheel;
Process conditions: temperature is 120-145 ℃
Purpose: get wheel stretching adjustment and go out the film ideal thickness by drawing.
Step 3) adopts the compound TPU lining of rolling process; The equipment that uses and technological process and compound TPU bed material identical.
Preparation process is as described below:
Step 31) in homogenizer, throws lining (polyurethane resin, acrylic resin, polyol derivative plasticizer, polymer fatty acid fat dispersant, stearic acid, antioxidant and ultra-violet absorber) by said ratio, and carry out the high-speed stirred mixing;
Process conditions: first stirring at low speed 30 seconds, back high-speed stirred 5-6 minute
Purpose: fully mix various materials.
Step 32) lining behind the high-speed stirred mixing falls into banbury, drops into colorant again;
Process conditions: 4.5-5.5 minute banburying time
Purpose: material is further mixed and preliminary gel.
Step 33) will drop in regular turn through the lining of banburying among mill A, the B, and open refining through twice and handle;
Process conditions: mixing temperature 110-130 ℃
Purpose: with complete gel of material and feed.
Step 34) will put into filter through the lining of opening refining and filter, remove impurity;
Process conditions: die head temperature 90-130 ℃; Filtering mesh is 20 * 40 * 80 orders
Purpose: with Impurity removal.
Step 35) will put into 4 roll calendars through the lining that filters rolls;
Process conditions: rolling temperature 140-165 ℃
Purpose: sizing material is pressed into sheet and adjustment thickness.
Step 36) lining after will rolling is sent into to draw and is got wheel;
Process conditions: temperature is 140-165 ℃
Purpose: get wheel stretching adjustment and go out the film ideal thickness by drawing.
Step 4) is carried out bed material and lining compound, fits on the base fabric again;
At this moment, to and draw the bed material that takes out and lining is delivered to the wheel of fitting in the lump together with base fabric be pressed into artificial leather under normal temperature condition through calendering, thickness is 0.05mm-5.00mm, then these artificial leather semi-finished product is cooled off through cooling wheel, is taken out by winding wheel at last;
Step 5) is to the artificial leather processing of foaming;
The equipment that uses: foaming furnace.Foaming furnace generally has 3-5 the thermal treatment zone, when using 3 thermals treatment zone foaming, because of the body of heater heat supply at least heat time heating time longer; When using 5 thermals treatment zone foaming because of the body of heater heat supply at most heat time heating time shorter.The present invention finishes foaming process with 4 thermals treatment zone.
The oily foamable stove in 4 districts:
180-210 ℃ in 1# district
190-220 ℃ in 2# district
180-190 ℃ in 3# district
170-180 ℃ in 4# district
Speed 12-22mpm
Step 6) is carried out surface treatment to artificial leather;
The equipment that uses: processor, mesh: 80-120 order
Surface conditioning agent: polyurethane series surface conditioning agent
Step 7) is last, will pack bundling after the artificial leather cutting, is the artificial leather of thermoplastic polyurethane finished product.
Below specify the manufacture method of a kind of artificial leather of thermoplastic polyurethane of the present invention by an embodiment.
The specification requirement of TPU artificial leather:
Embossing: DN2 (shallow dermatoglyph) look number: U5175 (black) luminosity: T6W1 (on-slip sense)
The name of an article: TPU black 130g rolls cotton thickness: the 1.4mm of pin
Width: 1370mm orders and makes quantity: 500 yards purposes: baseball glove
Manufacturing step is as follows:
Step 1) uses two liquid polyurethane glues with the base fabric starching;
Process conditions: bake out temperature: go up the paddle wheel order for 135 ℃: 40 orders
Starching number of times: 2 subline speed: 25mpm
Step 2) compound TPU bed material (rubberizing thickness: 0.42mm; Rubberizing width: 1422mm)
Step 21) proportioning by following bed material feeds intake in homogenizer, and carries out the high-speed stirred mixing;
Process conditions: first stirring at low speed 30 seconds, back high-speed stirred 5 minutes, temperature reach 105 ℃.
Bed material proportioning (weight ratio)
TPU(Thermoplastic polyurethanes) 100kg
Acrylic resin 2.3kg
Polyol derivative 20kg
Ba/Zn foaming stabilization agent 2.3kg
Foam control agent 1.2kg
Strengthen packing material 35kg
Black patch 0.35kg
Step 22) bed material behind the high-speed stirred mixing falls into banbury, treats that blowing agent AC 5.8kg and colorant black patch 0.35kg are dropped in half back of blanking in the homogenizer, continues to have thrown remaining bed material then;
Process conditions: banburying time: 5 minutes; Blanking electric current: 352A
Step 23) will drop in regular turn through the bed material of banburying among mill A, the B, and open refining through twice and handle;
Process conditions: 120 ℃ of mixing temperatures
Step 24) will put into filter through the bed material of opening refining and filter, remove impurity;
Process conditions: 110 ℃ of die head temperatures; Filtering mesh is 8 orders * 20 orders
Step 25) will put into 4 roll calendars through the bed material that filters rolls;
Process conditions: front-wheel temperature: 134 ℃; Last wheel temperature: 134 ℃;
Middle wheel temperature: 126 ℃; Lower whorl temperature: 126 ℃
Step 26) bed material after will rolling is sent into to draw and is got wheel;
Process conditions: temperature is 128 ℃
Step 3) adopts the compound TPU lining of rolling process; The equipment that uses and technological process and compound TPU bed material identical.(rubberizing thickness: 0.18mm; Rubberizing width: 1422mm)
Preparation process is as described below:
Step 31) feeds intake in homogenizer by proportioning, and carry out the high-speed stirred mixing as lower fabric;
Process conditions: first stirring at low speed 30 seconds, back high-speed stirred 6 minutes; Temperature reaches 102 ℃
Lining proportioning (weight ratio)
TPU(Thermoplastic polyurethanes) 100kg
Acrylic resin 11.6kg
Polyol derivative 20kg
Polymer fatty acid fat 0.58kg
Strengthen packing material 28kg
Black patch 1.6kg
Step 32) lining behind the high-speed stirred mixing is fallen into banbury, drop into colorant black patch 1.6kg again;
Process conditions: 4 minutes banburying time; Blanking electric current: 281A
Step 33) will drop in regular turn through the lining of banburying among mill A, the B, and open refining through twice and handle;
Process conditions: 120 ℃ of mixing temperatures
Step 34) will put into filter through the lining of opening refining and filter, remove impurity;
Process conditions: 120 ℃ of die head temperatures; Filter mesh: 20 * 40 * 80 orders
Step 35) will put into 4 roll calendars through the lining that filters rolls;
Process conditions: front-wheel temperature: 160 ℃; Last wheel temperature: 160 ℃;
Middle wheel temperature: 154 ℃; Lower whorl temperature: 154 ℃
Step 36) lining after will rolling is sent into to draw and is got wheel;
Process conditions: temperature is 154 ℃
Step 4) is carried out bed material and lining compound;
At this moment, will and draw the bed material that takes out and lining is delivered to the wheel of fitting in the lump carry out the pressing artificial leather under normal temperature condition through calendering, then with these artificial leather semi-finished product through cooling wheel cooling, take out by winding wheel at last.
Step 5) is to the artificial leather processing of foaming;
The equipment that uses: foaming furnace
The oily foamable stove in 4 districts:
1# district: 200 ℃ of embossed wheel: DN2
2# district: 200 ℃ of speed: 20.6mpm
3# district: 1 90 ℃ of pressure: 2kgf/cm
2
4# district: 188 ℃
Step 6) is carried out surface treatment to artificial leather;
The equipment that uses: processor
Surface conditioning agent: on-slip sense polyurethane surface treating agent
Mesh: 80 orders
Number of processes: 1 time
Step 7) is last, will pack bundling after the artificial leather cutting, is the artificial leather of thermoplastic polyurethane finished product.
Above disclosed only is preferred embodiment of the present invention, can not limit the present invention's interest field certainly with this, and therefore the equivalent variations of being done according to the present patent application claim still belongs to the scope that the present invention is contained.
Claims (10)
1. thermoplastic polyurethane (Thermoplastic Polyurethane, TPU) prescription of artificial leather, be composited by bed material, lining and base fabric, it is characterized in that component comprises at least: TPU(Thermoplastic polyurethanes), acrylic resin, plasticizer, foaming stabilization agent, foam control agent and blowing agent, wherein, plasticizer is the polyol derivative plasticizer.
2. the prescription of a kind of artificial leather of thermoplastic polyurethane according to claim 1 is characterized in that:
The prescription composition and the weight ratio of lining and bed material are as follows:
Lining:
TPU(Thermoplastic polyurethanes) 100
Acrylic resin 2----10
Polyol derivative plasticizer 1----50
Dispersant 0----1
Strengthen packing material 0----30
Stearic acid 0----1
Antioxidant 0----1
Ultra-violet absorber 0----1
Colorant 0----5
Bed material:
TPU(Thermoplastic polyurethanes) 100
Acrylic resin 2----10
Polyol derivative plasticizer 1----50
Foaming stabilization agent 2----3
Foam control agent 0.5---1.5
Blowing agent 4----6
Strengthen packing material 0----50
Colorant 0----5
3. the prescription of a kind of artificial leather of thermoplastic polyurethane according to claim 2, it is characterized in that: dispersant is selected polymer fatty acid fat dispersant for use.
4. the prescription of a kind of artificial leather of thermoplastic polyurethane according to claim 2 is characterized in that: the foaming stabilization agent is selected Ba/Zn foaming stabilization agent for use, and blowing agent is selected blowing agent AC (Azodicarbonamide) for use.
5. the prescription of a kind of artificial leather of thermoplastic polyurethane according to claim 2, it is characterized in that: polyol derivative is selected propylene glycol ester for use.
6. according to the prescription of claim 2 or 3 described a kind of artificial leather of thermoplastic polyurethane, it is characterized in that: the prescription composition and the weight ratio of lining and bed material are as follows:
Lining:
TPU(Thermoplastic polyurethanes) 100
Acrylic resin 11.6
Polyol derivative plasticizer 20
Polymer fatty acid fat dispersant 0.58
Strengthen packing material 28
Black patch 1.6
Bed material:
TPU(Thermoplastic polyurethanes) 100
Acrylic resin 2.3
Polyol derivative plasticizer 20
The Ba/Zn stabilization agent 2.3 that foams
Foam control agent 1.2
Blowing agent AC 5.8
Strengthen packing material 35
Black patch 0.35
7. the method for making of an artificial leather of thermoplastic polyurethane is characterized in that may further comprise the steps:
(1) with the base fabric starching;
(2) compound TPU bed material and lining;
(3) bed material and lining are carried out compound, fit on the base fabric again;
(4) artificial leather is carried out post processing, promptly make described artificial leather of thermoplastic polyurethane.
8. the method for making of a kind of artificial leather of thermoplastic polyurethane according to claim 7, it is characterized in that: the method for making of described artificial leather of thermoplastic polyurethane is a rolling process.
9. the method for making of a kind of artificial leather of thermoplastic polyurethane according to claim 7 is characterized in that: base fabric is selected knitted cloth for use, is rolled the pin cotton, Woven Fabrics, imitative in skin, impregnation cloth or the nonwoven fabric any one.
10. the method for making of a kind of artificial leather of thermoplastic polyurethane according to claim 7 is characterized in that: in step 2) in, the technological process of preparation TPU lining and bed material is as follows: stir--〉banburying--〉and open refining--〉filtration--〉calendering--〉draw and get.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100357300A CN100485119C (en) | 2006-05-31 | 2006-05-31 | Thermoplastic polyurethane artificial leather |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100357300A CN100485119C (en) | 2006-05-31 | 2006-05-31 | Thermoplastic polyurethane artificial leather |
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| CN101021046A true CN101021046A (en) | 2007-08-22 |
| CN100485119C CN100485119C (en) | 2009-05-06 |
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| CNB2006100357300A Expired - Fee Related CN100485119C (en) | 2006-05-31 | 2006-05-31 | Thermoplastic polyurethane artificial leather |
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| CN102199882A (en) * | 2011-04-02 | 2011-09-28 | 江苏国信合成革有限公司 | TPU modified high performance PVC ball leather and its preparation method |
| CN102168382A (en) * | 2011-04-02 | 2011-08-31 | 江苏国信合成革有限公司 | High-cold-resistant synthetic leather and preparation method of the high-cold-resistant synthetic leather |
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