CN1321155C - Polyurethane composition for film and its use - Google Patents
Polyurethane composition for film and its use Download PDFInfo
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- CN1321155C CN1321155C CNB2004100069677A CN200410006967A CN1321155C CN 1321155 C CN1321155 C CN 1321155C CN B2004100069677 A CNB2004100069677 A CN B2004100069677A CN 200410006967 A CN200410006967 A CN 200410006967A CN 1321155 C CN1321155 C CN 1321155C
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- polyurethane
- urethane
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- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 239000004814 polyurethane Substances 0.000 title claims abstract description 41
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 claims abstract description 56
- 238000002844 melting Methods 0.000 claims abstract description 42
- 229920006264 polyurethane film Polymers 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 230000008018 melting Effects 0.000 claims abstract description 21
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 17
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 17
- 239000004744 fabric Substances 0.000 claims abstract description 15
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 56
- 229920000728 polyester Polymers 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 15
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- 238000012545 processing Methods 0.000 claims description 14
- 239000004677 Nylon Substances 0.000 claims description 11
- 229920001778 nylon Polymers 0.000 claims description 11
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical class C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 238000007766 curtain coating Methods 0.000 claims description 4
- 239000002759 woven fabric Substances 0.000 claims description 4
- 229920006226 ethylene-acrylic acid Polymers 0.000 claims description 3
- -1 ethylene-propylene acetoacetic ester Chemical compound 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
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- 239000002253 acid Substances 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 230000005684 electric field Effects 0.000 claims description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 2
- 239000005043 ethylene-methyl acrylate Substances 0.000 claims description 2
- 238000005098 hot rolling Methods 0.000 claims description 2
- 239000012943 hotmelt Substances 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 230000035699 permeability Effects 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 17
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- 230000000694 effects Effects 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
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Abstract
The present invention discloses a polyurethane composition for films, which is prepared from 95 wt% to 50 wt% of thermoplastic polyurethane and 5 wt% to 50 wt% of modifying agent. The present invention also discloses an application of the polyurethane composition for the films in preparing a composite film product. A polyurethane layer in the composite polyurethane film product can be formed by making raw materials into a film which is thermally bonded with another substrate, or the composite polyurethane film product can be formed by directly coating the raw materials on a fabric base for further thermal bonding. The polyurethane composition for the films not only can change the melting point of a film material to meet the requirements of a thermal bonding process, but also can regulate peel force between the polyurethane film layer and another substrate and can control the water vapor permeability of the composite product.
Description
Technical field
The present invention relates to a kind of polyurethane composition, especially relate to a kind of film polyurethane composition and the application in the film composite prod thereof.
Background technology
At present, people require more and more higher to the over-all properties of textile fabric, and the lamination of textiles compound be to make textiles obtain property, achieve the important means of high-performance, high added value.In flat woven fabric, be difficult to include many performances such as brute force, elasticity, wearing quality, comfortableness, aesthetic property, it is very difficult to develop the flat woven fabric that has several performances concurrently, complex process, cost is too high, and adopt lamination that two-layer or multiple layer fabric are bonded together or fabric and polymer film and other flexible materialss are bonded together, the various useful performance of fabric is merged, can form the mixture that has multiple function concurrently.This lamination compound mode is one of important channel of developing in recent years the weaving product innovation.As in U.S. Pat 6,420,625 mention by lamination compound mode and prepare not only moisture permeable, liquid but also impermeable fabric sandwich.
In general, can utilize modes such as stitching, tackiness agent are bonding, autoadhesion that various fabrics, film are connected to make laminar composite.Tackiness agent commonly used has solvent cement, water emulsion and hot melt adhesive etc.In recent years; along with the reinforcement of various countries' environmental protection consciousness and the strictness further of relevant law; the Solvent Adhesive method that environment is polluted is subjected to increasing restriction easily; and environment amenable hot melt adhesive method is subjected to increasing attention, plays the part of more and more important role in the lamination of textiles is compound.
When utilizing the hot melt adhesive method to prepare composite prod, both raw material can be made film, again with itself and fabricbase heat bonding, also can be directly with the raw material squeezing and coating on fabricbase, base material itself also can make film and directly carry out hot melt adhesive.Introduce a kind of hot melting cohesion film and the bonding waterproof that is used for goods of fabric as Japanese Patent JP 4189959-A; Japanese Patent JP 8209558-A mentions and is used to prepare label with a kind of hot melting cohesion film and fabric are sticking mutually.Work in the application and development that concentrates on goods in a large number in the above-mentioned research and the research of recombining process on, and few to hot sticky study on the modification with raw material itself.
Because the diversity that goods use, different requirements has been proposed for the performance of composite product.Some goods require its bonding strength height, and other goods require it to have higher water vapour permeability, and some products are less demanding to water vapour permeability, cohesiveness, and the flexibility of composite product is had higher requirement.Some product requirements have lower heat bonding temperature.Therefore, when preparation lamination composite prod, need provide a kind of mode that can regulate performances such as cohesive force, overall water vapour permeability, snappiness between film and the base cloth, to satisfy the service requirements of different goods.
Thermoplastic polyurethane (PU) material has excellent extension recovery because soft, the hard segment molecule structure of its uniqueness makes it when having good strength, in very wide temperature range, particularly under the cold condition, still can keep good snappiness.Matrix material after polyurethane film and various types of materials are laminated can be used for preparing sports goods, footwear, bag, case, clothes and medical treatment product, and in recent years, the composite prod of polyurethane film and base material has become the important laminar composite of a class.
But general thermoplastic polyurethane fusing point is higher, the film of preparation is softer, heat bonding temperature height, when under comparatively high temps, adopting hot melting mode to prepare matrix material, be easy to stick together, can not satisfy technology and products thereof performance demands, be necessary polyurethane material is carried out modification, make it can satisfy the needs of preparation different composite product.
Summary of the invention
The object of the present invention is to provide a kind of film polyurethane composition, said composition can reduce the fusing point of thin-film material, satisfies the requirement of thermal bonding technology, and can regulate the cohesiveness and the water vapour permeability of composite prod effectively.
Another object of the present invention is to provide the application of polyurethane composition in preparation laminated film product of a kind of film.
A kind of film polyurethane composition of the present invention includes the properties-correcting agent of weight percentage 95%～50% thermoplastic polyurethane and weight percentage 5%～50%.
Wherein, preferred package contains the properties-correcting agent of weight percentage 95%～70% thermoplastic polyurethane and weight percentage 5%～30%.
Described urethane is polyester type, polyether-type or polyester polyether-type etc., and durometer level can be between 75A～95A.
Described properties-correcting agent be low-melting point polyester, low melting point nylon, ethylene-acrylate class, ethylene-acrylic acid or vinyl acetate with multipolymer of ethene etc. in any one or a few mix, blending ratio can be 1-4: 1-4 or 1-4: 1-4: 1-4.
Described low-melting point polyester, intrinsic viscosity [η] 〉=0.55, fusing point is about 80～150 ℃.
Described low melting point nylon, hot melt scope are 90～150 ℃.
Described ethylene-acrylate class can be wherein a kind of such as ethylene-methyl acrylate, ethylene-methyl methacrylate methyl esters, ethylene-propylene acetoacetic ester or ethylene-propylene acid butyl ester, the content of esters of acrylic acid can be in 2%～30% scope, and melting index can be between 1～30g/10min.
Described ethylene-acrylic acid copolymer, acrylic acid content can be 4%～30%, and melting index can be between 2～30g/10min.
The multipolymer of described vinyl acetate and ethene, wherein the content of vinyl acetate can be between 5%～45%.
The present invention can reduce heat bonding temperature, an envelope temperature of urethane by adding properties-correcting agent, and can regulate the bonding force and the water vapour permeability of composite prod to a certain extent.As in urethane raw, adding low-melting nylon raw material, can reduce rising between polyurethane film and the base material and seal temperature.And in urethane raw, add low-melting polyester raw material, in the water vapour permeability of not obvious reduction film and base material composite prod, can improve the heat bonding intensity between polyurethane film and the base material largely.In urethane raw, add ethylene-acrylate, in an envelope temperature that changes between polyurethane film and the base material, can change the water vapour permeability of polyurethane film and base material composite prod.By selection and control to the use raw material, reduce heat bonding temperature, an envelope temperature of urethane, and can control, regulate the peeling force between layer of polyurethane and the institute's matrix material and the water vapour permeability of composite prod preferably, satisfy the service requirements of different composite product.
The film of the present invention application of polyurethane composition in preparation laminated film product.Described film can be processed into the thin polyurethane rete with polyurethane composition, and its thickness can be chosen between 15 μ m～80 μ m.
For realizing another goal of the invention of the present invention, adopt the preparation of described thin polyurethane rete both can adopt to extrude curtain coating and also can adopt modes such as extrusion-blown modling to carry out.Adopting the processing mode of blowing is that urethane raw is extruded by die head, through overcooling, lead, be wound into polyurethane film, and mode and the bonding formation polyurethane film of the base material composite prod by hot melt adhesive again; Also can adopt extrude curtain coating mode with the direct squeezing and coating of urethane raw on fabricbase, the mode by hot melt adhesive forms the polyurethane film composite prod again.
Specifically, the polyurethane film composite prod that the present invention is mentioned is composited with the technology of heat bonding by thermoplastic polyurethane and properties-correcting agent mode and the base material by extruding processing.Mentioned its layer of polyurethane of polyurethane film composite prod of the present invention both can be that raw material is made film again with itself and other base material heat bonding, also can be directly with the further heat bonding again on base material of the direct squeezing and coating of above-mentioned raw materials.In the present invention, the water vapour permeability of peeling force between polyurethane film and base material and polyurethane film composite prod can be regulated within the specific limits.
Film polyurethane composition of the present invention can utilize forcing machine that composition is extruded processing, specifically, be with urethane and properties-correcting agent predrying after, add in the forcing machine through material suction device, it is plastified, compresses, extrude through die head again by forcing machine.The length-to-diameter ratio of used forcing machine is 20～50, is preferably 25～35, and the processing temperature scope in each district of screw rod is controlled at 150 ℃～300 ℃, and head temperature is controlled at 150 ℃, and the forcing machine rotating speed is controlled at 30rpm～60rpm.
Polyurethane film by polyurethane composition of the present invention processes plays the heat bonding effect in the laminated film product, described laminated film product comprises polyurethane film and base material, and described polyurethane film can be individual layer; Also can be the composite bed that one deck or two-layer other films are arranged on the basis of described individual layer layer of polyurethane again, its structure can be urethane/polymethylmethacrylate+urethane, urethane/ethylene-vinyl acetate copolymer+urethane.Urethane/polymeric amide+urethane or polyurethane/polyester+urethane.
Compound tense is base materials employed to adopt apparel textile commonly used, can be looped fabric, woven fabrics, also can be non-woven.
Hot melt adhesive between polyurethane film and the base material can adopt hot rolling, ultrasonic wave, high-frequency electric field or hot gas flow etc. wherein any one mode carry out.
Zhi Bei polyurethane film composite prod can reduce the heat bonding temperature greatly according to the method described above, satisfies processing requirement; And the peeling force between thin polyurethane rete and textiles or other base materials can be adjusted between 0.3N/cm～4.2N/cm in the described composite prod, and the water vapour permeability of composite prod can be at 110～3800g/24h.m
2Between regulate, satisfy the service requirements of different composite product.
The testing method that the present invention adopts is as follows:
1, the measuring method of stripping strength (FZ T 01010-91)
The polyurethane film composite prod is tailored into following batten, the batten width is (25 ± 0.5) mm, along the specimen length direction with film and the about 30mm of base cloth strip off in advance, batten is placed in the tensile test machine, detachment rate by 100mm/min is peeled off, and the stripping strength record result between film and base cloth is unit with N/cm.
2, the testing method of film stretching intensity (GB13022-91)
Utilize the stamping knife punching out to become dumbbell specimen the polyurethane film of preparation, the sample total length is (110 ± 1) mm, and the parallel portion width is (6.5 ± 0.1) mm.Sample is placed two anchor clamps of tensile testing machine, the sample longitudinal axis and the upper and lower anchor clamps line of centres are coincided, it is stretched and obtain intensity level by the speed of 200 ± 20mm/min, tensile strength is unit with MPa.
3, the vapor transfer rate of composite prod (GB/T 12704-91)
Composite prod is made circular specimen, and specimen finish is (70 ± 1) mm.Inject 10mL water to cleaning, in the exsiccant moisture vapor transmission cup, sample testing is faced down to be placed on the moisture vapor transmission cup, seals after loading onto packing ring and pressure ring, forms the test group zoarium.The test group zoarium is lain in a horizontal plane in the proofing box that reaches the regulation test conditions, and (test conditions of regulation is as follows: 38 ℃ of probe temperatures, relative humidity 2%, gas velocity 0.5m/s.Weighed every 1 hour, calculate the loss of gross weight in 24 hours, to obtain the vapor transfer rate of composite prod.
Urethane composite prod of the present invention, by to the screening of urethane raw and in raw material, add properties-correcting agent, reduce the fusing point of thin-film material, satisfy the requirement of thermal bonding technology, regulate the peeling force between thin polyurethane rete and other base materials and control the water vapour permeability of this type of composite prod.
This type of film can carry out heat bonding with various types of materials such as fabricbase, thin film based etc. and make matrix material, after this type of film can being cut into certain width, is used for the heat sealing to clothes fabricbase crease place.Because the heat bonding temperature of film can be adjusted in certain temperature range in this product, therefore, during as the heat sealing bar, the heat sealing temperature can be turned down with this type of film, in wide temperature range, carry out heat bonding.Utilize this type of film to make the heat sealing film and can overcome pure polyurethane film as heat-sealing during bar, the heat bonding temperature is higher, and itself blocking under warming appears in polyurethane film, influences the phenomenon of the planeness at polyurethane film and fabricbase crease place.
Because the diversity of composite material goods, some occasions need with the thermal caking aspect directly and fabricbase bonding, other occasions then need thermal caking aspect and other faces bonding, make the composite prod of different structures.In the recombination process, hot sticky layer the cohesive force size that plays adhesive effect there is different requirements.Cross when low when hot sticky relay, the heat bonding film does not have bonding effect; And when hot sticky relay is too high, bonding with other materials, when particularly further sticking mutually with the film that has been bonded together with other materials, when original film and the bonding force between the other materials are low, if it is excessive that play film and original film bonding force of heat bonding effect this moment, then the problem that original film and other materials are peeled off can occur, destroy the integrity of material.
The present invention reaches by the screening to urethane raw and add properties-correcting agent in raw material, not only can change the fusing point of thin-film material, satisfy the requirement of thermal bonding technology, but also thermal caking power can be adjusted in proper range, can effectively keep keeping the globality of matrix material preferably under the condition of cohesive strength between the composite material.
Embodiment
Following embodiment is for further describing the present invention, but described embodiment only is used to illustrate the present invention rather than restriction the present invention.
Comparative Examples
A kind of urethane raw, its shore hardness A is 85, density is 1.12g/cm
3, produce by BASF AG.The thin polyurethane rete adopts the mode of blowing to process, the TPU raw material is adopted the mode of automatic suction, joining screw diameter is in φ 35 single screw extrusion machines, the length-to-diameter ratio of extruder screw is 24: 1, forcing machine is the syllogic heating, the processing temperature of each section of TPU is controlled to be 160 ℃, 180 ℃, 180 ℃ respectively, and the temperature of mouthful mould is controlled to be 160 ℃, and the forcing machine rotating speed is 40rpm.Above-mentioned raw materials extruded by forcing machine make film, thickness is 20 μ m.
With of bonding mode and the fabricbase heat bonding of this film by hot gas flow, hot stream temperature is 440 ℃, the fabricbase that experiment is selected for use is the terylene drills, Zhi Bei polyurethane film composite prod as stated above, wherein the stripping strength between thin polyurethane rete and fabricbase is 3N/cm, and the whole water vapour permeability of composite prod is 750g/24h.m
2, tensile strength is 27MPa.
Embodiment 1
Film of the present invention is made up of 80% urethane raw and 20% low melting point nylon with polyurethane composition.
A kind of thermoplastic polyurethane raw material, its shore hardness A is 85, density is 1.12g/cm
3, produce by BASF AG.
Add total amount 20% low melting point nylon in above-mentioned raw materials, fusing point is 95 ℃, and the place of production is a China Textile Academy.
Processing units, the same Comparative Examples of bonding process, and according to testing method stripping strength between polyurethane film and the fabricbase and vapor transfer rate are measured.Hot stream temperature is 370 ℃, and the stripping strength between thin polyurethane rete and fabricbase is 3.6N/cm, and the whole water vapour permeability of composite prod is 300g/24h.m
2
Embodiment 2
Film of the present invention is made up of 80% urethane raw and 20% low-melting point polyester with polyurethane composition.
A kind of urethane raw, its shore hardness A is 85, density is 1.12g/cm
3, produce by BASF AG.In above-mentioned raw materials, add 2 and go into total amount 20% low-melting point polyester, intrinsic viscosity [η] 〉=0.55,110 ℃ of fusing points, the place of production is a China Textile Academy.Join in the forcing machine after the mixing back is even.
The processing temperature of each section of forcing machine is 140 ℃, 150 ℃, 150 ℃, prepares polyurethane film.
Prepared film is utilized the mensuration of carrying out stripping strength and vapor transfer rate after hot-gas reflow soldering equipment and the fabricbase heat bonding.Hot stream temperature is 380 ℃, and measured stripping strength is 3.2N/cm, and vapor transfer rate is 885g/24h.m
2, tensile strength is 29Mpa.
Embodiment 3
Film of the present invention is made up of urethane raw and low-melting point polyester raw material.
Urethane raw, its shore hardness A is 85, density is 1.12g/cm
3, be polyether(poly)urethane, produce by U.S. Gu Lide company.The low-melting point polyester raw material, intrinsic viscosity [η] 〉=0.55,110 ℃ of fusing points, the place of production is a China Textile Academy.
Present embodiment has shown by the control to two kinds of raw material blend ratios, has made polyurethane film have different numerical value with the cohesive force and the water vapour permeability of base cloth.
Polyester is joined respectively in the forcing machine by different proportionings with urethane raw, the processing conditions of forcing machine is adjusted, be prepared into film according to the different proportionings of blend.
Carry out bondingly with fabricbase the bonding mode of above-mentioned film by hot gas flow respectively, the temperature of hot gas flow is 400 ℃, and tests according to relevant criterion, and the stripping strength and the vapor transfer rate of different films and fabricbase see the following form.
The low-melting point polyester of different mixture ratio/thin polyurethane film properties relatively
| Low-melting point polyester/urethane | Stripping strength N/cm | Tensile strength MPa | Vapor transfer rate g/24h.m 2 |
| 0/100 | 2.4 | 18.3 | 4100 |
| 10/90 | 3.5 | 19.2 | 3800 |
| 20/80 | 4.0 | 23.6 | 3300 |
| 30/70 | 4.2 | 27.8 | 2800 |
Embodiment 4
Film of the present invention is made up of urethane raw and low-melting point polyester raw material.
Urethane raw, its shore hardness A is 85, density is 1.12g/cm
3, produce by U.S. Gu Lide company.The low-melting point polyester raw material, intrinsic viscosity [η] 〉=0.55,110 ℃ of fusing points, the place of production is a China Textile Academy.
In the present embodiment to the working method of the control of two kinds of raw material blend ratios, polyurethane film with embodiment 3, being the temperature of above-mentioned film and the used hot gas flow of fabricbase heat bonding low is 330 ℃, at this moment, the film of different proportionings and the stripping strength of fabricbase have bigger variation, see the following form.
The low-melting point polyester of different mixture ratio/thin polyurethane film properties relatively
| Low-melting point polyester/urethane | Stripping strength N/cm | Tensile strength MPa | Vapor transfer rate g/24h.m 2 |
| 0/100 | 0 | 18.3 | 4100 |
| 10/90 | 0.9 | 19.2 | 3700 |
| 20/80 | 1.4 | 23.6 | 3300 |
| 30/70 | 3.0 | 27.8 | 2800 |
Embodiment 5
Compound in the present embodiment with the preparation of polyurethane film employing coextrusion unit, two-layerly make by thermoplastic polyurethane, thermoplastic polyurethane and low-melting point polyester blend respectively, wherein blend is made up of 80% urethane raw and 20% low-melting point polyester, and is raw materials used with embodiment 1.
Above-mentioned two kinds of raw materials are joined respectively in the different forcing machines, be processed into the co-extrusion film of urethane, low-melting point polyester blend.
The processing equipment used is that double-layer coextrusion goes out production unit, and the prepared film total thickness is 20 μ m.
Heat bonding recombining process mode, base materials employed, the same Comparative Examples of testing method.Hot stream temperature is 380 ℃, and measured stripping strength is 3.2N/cm.
Embodiment 6
The utilization of this kind composite prod extrude curtain coating more further the mode of heat bonding process.
A kind of thermoplastic polyurethane raw material, shore hardness A are 85, and density is 1.12g/cm
3, for Bayer A.G produces.
A kind of ethylene-methyl methacrylate methyl terpolymer raw material, the content of methyl methacrylate is 20%, and melting index is 6.0g/10min, and Vicat softening point is 54 ℃, for E.I.Du Pont Company produces.
Behind urethane raw with 80%, 20% the ethylene-methyl methacrylate methyl terpolymer combination drying, join in the single screw extrusion machine,, extrude downwards by T pattern head through behind the spiro rod plasticizing, fabricbase unreels with the speed of 20m/min, and the direct squeezing and coating of the polyurethane film of extruding are on fabricbase.By ultrasonic welding device and the further heat bonding of fabricbase, be 1.3S heat-up time between film and fabricbase again, and amplitude is 100%.The fabricbase selected for use of experiment is the terylene drills, Zhi Bei polyurethane film composite prod as stated above, and wherein the stripping strength between thin polyurethane rete and fabricbase is 4N/cm, the vapor transfer rate of composite prod is 120g/24h.m
2, tensile strength is 10Mpa.
Embodiment 7
A kind of thermoplastic polyurethane raw material, its shore hardness A is 85, density is 1.12g/cm
3, produce by BASF AG.
A kind of ethylene-methyl methacrylate methyl terpolymer raw material, the content of methyl methacrylate is 20%, and melting index is 6.0, and Vicat softening point is 54 ℃, for E.I.Du Pont Company produces.
Behind urethane raw with 80%, 20% the ethylene-methyl methacrylate methyl terpolymer combination drying, join in the single screw extrusion machine, adopting screw diameter is the forcing machine of φ 30, the processing temperature of each section of forcing machine is controlled to be 140 ℃, 155 ℃, 155 ℃ respectively, the temperature of mouth mould is controlled to be 150 ℃, the forcing machine rotating speed is 40rpm, is prepared into film, and film thickness is 20 μ m.
With of mode and the fabricbase heat bonding of this film by hot gas flow, bonding mode, the same Comparative Examples of testing method, hot stream temperature is 420 ℃, the whole water vapour permeability of composite prod is 495g/24h.m
2, tensile strength is 12MPa.
Embodiment 8
Film of the present invention is made up of 80% polyester urethane raw, 5% low melting point nylon, 10% low-melting point polyester and 5% ethylene-methyl methacrylate methyl terpolymer with polyurethane composition.
A kind of polyester urethane raw, its shore hardness A is 85, density is 1.12g/cm
3, produce by BASF AG.
A kind of low melting point nylon, fusing point are 95 ℃, and the place of production is a China Textile Academy; A kind of low-melting point polyester raw material, intrinsic viscosity [η] 〉=0.55,110 ℃ of fusing points, the place of production is a China Textile Academy; A kind of acrylic polymers, its density are 0.938g/cm
3, acrylic acid content 15%, melting index are 20g/10min, by Dow Chemical's preparation, above-mentioned raw materials is answered vacuum-drying before processing.
80% is thermoplastic polyurethane in the above-mentioned raw materials, 20% be the acrylic polymers blend after, join in the forcing machine, the preparation polyurethane film.
Film and fabricbase are with the bonding mode bonding of hot gas flow in the polyurethane film composite prod, and hot stream temperature is 410 ℃, by testing method water vapour permeability, stripping strength is tested, and the whole water vapour permeability of composite prod is 110g/24h.m
2, tensile strength is 10MPa.
Embodiment 9
Film of the present invention is made up of 95% polyester polyether(poly)urethane raw material and 5% low melting point nylon.
Urethane raw, its shore hardness A is 80, density is 1.12g/cm
3, produce by BASF AG.Low melting point nylon, the place of production are China Textile Academy.
Adopt the method for embodiment 1 to be processed into film, with mode and the fabricbase heat bonding of this film by hot gas flow, the same Comparative Examples of testing method.Hot stream temperature is reduced to 420 ℃, and the whole water vapour permeability of composite prod is 650g/24h.m
2, stripping strength 3.2N/cm.
Embodiment 10
Film of the present invention is made up of 50% urethane raw, 50% low-melting point polyester raw material.
Urethane raw, its shore hardness A is 95, density is 1.10g/cm
3, produce by U.S. Gu Lide company.The low-melting point polyester raw material, intrinsic viscosity [η] 〉=0.55,110 ℃ of fusing points, the place of production is a China Textile Academy.
Adopt the method for embodiment 1 to be processed into film, with of mode and the fabricbase heat bonding of this film by hot gas flow, bonding mode, the same Comparative Examples of testing method, hot stream temperature can be reduced to 320 ℃.
Although the present invention has been done detailed explanation and has quoted some specific exampless as proof, for a person skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (8)
1. film polyurethane composition, it is characterized in that described composition is made up of the thermoplastic polyurethane of weight percentage 95%～50% and the properties-correcting agent of weight percentage 5%～50%, described thermoplastic polyurethane is polyester type, polyether-type or polyester polyether-type, and durometer level is between 75A～95A; Described properties-correcting agent by fusing point between 80～150 ℃, the content of nylon between 90～150 ℃ of the polyester of intrinsic viscosity 〉=0.55, hot melt scope, acrylate is between 2%～30%, melting index in the ethylene-acrylate class between 1～30g/10min, acrylic acid content between 4%～30%, melting index between 2～30g/10min ethylene-acrylic acid or the content of vinyl acetate be 5%～45% vinyl acetate and ethene multipolymer in any one or a few mix.
2. a kind of film polyurethane composition according to claim 1 is characterized in that, said composition is made up of the thermoplastic polyurethane of weight percentage 95%～70% and the properties-correcting agent of weight percentage 5%～30%.
3. a kind of film polyurethane composition according to claim 1 and 2 is characterized in that, described ethylene-acrylate class is a kind of in ethylene-methyl acrylate, ethylene-methyl methacrylate methyl esters, ethylene-propylene acetoacetic ester or the ethylene-propylene acid butyl ester.
4. a kind of film polyurethane composition according to claim 1 and 2, it is characterized in that, described properties-correcting agent by fusing point between 80～150 ℃, the polyester of intrinsic viscosity 〉=0.55, the nylon of fusing point between 90～150 ℃, the content of acrylate is between 2%～30%, the ethylene-acrylate class of melting index between 1～30g/10min, acrylic acid content is between 4%～30%, melting index between 2～30g/10min ethylene-acrylic acid or the content of vinyl acetate be 5%～45% vinyl acetate and ethene multipolymer in any two or three mix, blending ratio is 1-4: 1-4 or 1-4: 1-4: 1-4.
5. any one described a kind of film of the claim 1-4 application of polyurethane composition in preparation urethane composite prod, it is characterized in that polyurethane film required in the urethane composite prod adopts the processing mode preparation of extruding curtain coating or extrusion-blown modling, extrude the employing forcing machine, the length-to-diameter ratio of described forcing machine is 20～50, the processing temperature scope in each district of screw rod is controlled at 150 ℃～300 ℃, head temperature is controlled at 150 ℃～240 ℃, and the screw extrusion press rotating speed is controlled at 30rpm～60rpm.
6. a kind of film according to claim 5 application of polyurethane composition in preparation urethane composite prod, it is characterized in that, polyurethane film in the described urethane composite prod is an individual layer, or the composite bed of one deck or two-layer other films is arranged on the basis of described individual layer urethane again, its structure is urethane/polymethylmethacrylate+urethane, urethane/ethylene-vinyl acetate copolymer+urethane, urethane/polymeric amide+urethane or polyurethane/polyester+urethane.
7. a kind of film according to claim 5 application of polyurethane composition in preparation urethane composite prod, it is characterized in that the polyurethane film in the described urethane composite prod is compound by any one mode and base material in hot rolling, ultrasonic wave, high-frequency electric field or the hot gas flow.
8. a kind of film according to claim 7 is characterized in that with the application of polyurethane composition in preparation urethane composite prod described base material is an apparel textile, can be in looped fabric, woven fabrics or the non-woven any one.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100069677A CN1321155C (en) | 2004-03-03 | 2004-03-03 | Polyurethane composition for film and its use |
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|---|---|---|---|
| CNB2004100069677A CN1321155C (en) | 2004-03-03 | 2004-03-03 | Polyurethane composition for film and its use |
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| CN1664005A CN1664005A (en) | 2005-09-07 |
| CN1321155C true CN1321155C (en) | 2007-06-13 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781858B (en) * | 2009-09-30 | 2012-05-09 | 安徽安利合成革股份有限公司 | Dry veneering process of high weather-resistant fluorescent polyamide synthetic leather |
| CN103192567B (en) * | 2012-01-09 | 2016-05-11 | 佛山金万达科技股份有限公司 | Thermoplastic resin film layer compound and preparation method thereof |
| CN103507191B (en) * | 2012-06-22 | 2015-08-26 | 东莞市雄林新材料科技股份有限公司 | A kind of curtain coating batches middle permeation waterproof humidity-permeant TPU membrane |
| CN104263259B (en) * | 2014-09-18 | 2016-12-07 | 东莞市雄林新材料科技股份有限公司 | A kind of low melting point high-adhesive-strength TPU hot melt adhesive film and preparation method thereof |
| CN104589559B (en) * | 2014-12-01 | 2017-08-22 | 杭州绿兴环保材料有限公司 | A kind of ultra-thin polyurethane-hot melt gum resin film processing technology |
| CN107501911B (en) * | 2017-09-29 | 2018-08-24 | 安徽嘉明新材料科技有限公司 | A method of preparing high-quality TPU film |
| CN107936538A (en) * | 2017-12-04 | 2018-04-20 | 王荷香 | A kind of modified polyurethane and its synthetic method |
| CN111349333A (en) * | 2020-04-21 | 2020-06-30 | 东莞市雄林新材料科技股份有限公司 | TPU film for surfing kite and preparation method thereof |
| CN115232464A (en) * | 2022-08-12 | 2022-10-25 | 广东汇齐新材料有限公司 | Easily-dried waterproof moisture-permeable film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4342847A (en) * | 1978-12-16 | 1982-08-03 | Bayer Aktiengesellschaft | Process for the production of thermoplastic synthetic materials |
| CN1041427C (en) * | 1990-02-13 | 1998-12-30 | 阿托化学公司 | Process for working thermoplastic TPU by extrusion and modifier for use in this process |
| CN1408768A (en) * | 2001-09-30 | 2003-04-09 | 叶志成 | Formulation of full environment protection thermoplastic polyurethane (TPU) film and its calendering production method |
-
2004
- 2004-03-03 CN CNB2004100069677A patent/CN1321155C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4342847A (en) * | 1978-12-16 | 1982-08-03 | Bayer Aktiengesellschaft | Process for the production of thermoplastic synthetic materials |
| CN1041427C (en) * | 1990-02-13 | 1998-12-30 | 阿托化学公司 | Process for working thermoplastic TPU by extrusion and modifier for use in this process |
| CN1408768A (en) * | 2001-09-30 | 2003-04-09 | 叶志成 | Formulation of full environment protection thermoplastic polyurethane (TPU) film and its calendering production method |
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| CN1664005A (en) | 2005-09-07 |
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