CN1177607A - Film and object obtained from material comprising polyurethane and polyamide and polyether block polymer - Google Patents
Film and object obtained from material comprising polyurethane and polyamide and polyether block polymer Download PDFInfo
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- CN1177607A CN1177607A CN 97118590 CN97118590A CN1177607A CN 1177607 A CN1177607 A CN 1177607A CN 97118590 CN97118590 CN 97118590 CN 97118590 A CN97118590 A CN 97118590A CN 1177607 A CN1177607 A CN 1177607A
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- polymkeric substance
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Abstract
The invention provide a film and an article obtained from a material comprising thermoplastic polyurethane; and block polymer of polyamide and polyether PE. The latter is used for the production of film and article. The film is gas-breathable and liquid-impermeable, while the article is antistaticity.
Description
The present invention relates to relate to the purposes that the latter is used to produce described film and goods by comprising urethane and having polymeric amide and the film and the goods of the preparation of the material of polyether block.Film of the present invention is impermeable but respirable, and goods of the present invention are antistatic.
EP-A-0,476,963 disclose based on the polymkeric substance with polymeric amide and polyoxyethylene glycol block and the block polymer that (a) does not contain the polyoxyethylene glycol block, (b) polymeric amide, (c) polyester or (d) film of the water vapor permeable of the blend of urethane.In all embodiments, at first only provided the embodiment of polymeric amide, next amount of polymkeric substance with polymeric amide and polyoxyethylene glycol block is quite big, is 75 or 50wt%.Show that to the embodiment of water vapour permeability to(for) the polymkeric substance with polymeric amide and polyoxyethylene glycol block of 50wt% consumption is half of 75wt% consumption.
EP-A-0,442,786 disclose the method for extruding processing thermoplastic urethane, comprise adding 5 to 45wt% segment polyetheramides, for example have the polymkeric substance of polyamide-block and polyether block.In the embodiment that is given, have the polymkeric substance of polymeric amide and polyether block, comprise the polyamide-block of PA12 block form and the polyether block of PEG or PTMG block form.The not mentioned film performance that can obtain by present patent application instruction is particularly such as the performance of infiltration and/or impermeable gas (as water vapour) or liquid (as water).Simultaneously, the not mentioned static resistance that can obtain goods by described method.
EP-A-0,526,858 disclose the film based on the urethane that comprises 5 to 20wt% segment polyetheramides.The end-use of this film is a covering substrates, and this film has the bonds well performance on base material.Give among the embodiment therein, have the polymkeric substance of polymeric amide and polyether block, comprise the polyamide-block of PA12 block form and the polyether block of PTMG block block form.At EP-A0, in 526,858, the performance of not mentioned film permeation and/or impermeable gas (as water vapour) or liquid (as water).
None instruction of these documents or hint the present invention.
According to first aspect, the present invention relates to a kind of by the material that comprises following component (by weight) make impermeable-can breathe film or have the goods of antistatic property:
(a) 50 to 95% thermoplastic polyurethane;
(b) 5 to 50% have polymeric amide PA11, PA12 or PA11, a polymkeric substance of 12 blocks and polyethers PE block.
According to second aspect, the invention provides produce with the material (by weight) that comprises following component impermeable-can breathe the purposes of film:
(a) 50 to 95% thermoplastic polyurethane;
(b) 5 to 50% have polymeric amide PA11, PA12 or PA11, a polymkeric substance of 12 blocks and polyethers PE block.
In first embodiment, the polyethers PE block in the polymkeric substance (b) is the PEG block.
In second embodiment, the polyether block PE in the polymkeric substance (b) is the PTMG block.
In the 3rd embodiment, the polyamide-block in the polymkeric substance (b) is the PA12 block.
In one embodiment, thermoplastic polyurethane is a polyether(poly)urethane.
In addition, thermoplastic polyurethane is a polyester-polyurethane.
Described material preferably includes (by substance weight):
(a) 90 to 65% thermoplastic polyurethane;
(b) 10 to 35% have polymeric amide PA11, PA12 or PA11, a polymkeric substance of 12 blocks and polyethers PE block.
This material also comprises the third polymkeric substance, and the amount of described the third polymkeric substance is at the most 100%, preferably 50% (by the weight of described material) at the most.
Be described in more detail below the present invention.
Term " thermoplastic polyurethane " (being designated hereinafter simply as TPU) uses by the known conventional meaning of those skilled in the art.
TPU is based on the multipolymer of urethane, and it can be by polymer diol (for example having molecular weight between 1000 to 3500) and non-essential glycol (or lower molecular weight (being usually less than 300) chainextender) and di-isocyanate reaction preparation.Should syntheticly can be undertaken by a step or two steps.Polymer diol by representing thermoplastic polymer block and chainextender provide elastomeric hard and soft section respectively.The hard section is by hydrogen bond association, and the isocyanate groups of adjacent chain associates mutually to constitute the crystalline matrix in the soft chain simultaneously; The equivalent of the thermoplastics of partial crystallization so is provided.
In TPU, can distinguish and be: wherein polymer diol be polyester (glycol) type such as polyethylene glycol adipate, poly-hexanodioic acid tetramethylene glycol ester, poly-(E-caprolactone) those and wherein polymer diol be those of polyethers (glycol) type such as polypropylene glycol, polyoxygenated tetramethylene glycol, polyoxytrimethylene polyoxyethylene enediol.
Polymer diol also can be mixed form, i.e. polyether ester.
Diphenylene methane vulcabond (MDI) is general vulcabond, and uses 1 usually, and the 4-butyleneglycol is a chainextender.
The example of commercial product is Elastollan 1185 and 1190 (a PU ether), Elastollan C85 and C90 (PU-ester), and Desmopan 588 and 385 (PU-ether-ether).The polymkeric substance of Elastollan scope can be available from BASF, Desmopan scope available from Bayer.
Also can imagine the mixture of TPU.
Polymkeric substance with polyamide (PA) block and polyethers (PE) block is to make material of the present invention have the component of useful performance.
This polymkeric substance with polymeric amide and polyether block is to make from polyamide segment with reactive behavior end and the copolycondensation with polyether segment of reactive behavior end, wherein:
-polyamide segment with diamines end and polyoxy alkylidene segment copolycondensation with dicarboxylic acid end;
-have a dicarboxylic acid end polyamide segment with by polyoxy alkylidene segment copolycondensation with diamines end with aliphatic dihydroxyl a-ω polyoxy alkylidene segment (being called polyether glycol) cyanoethylation and hydrogenation acquisition;
-have the polyamide segment and the copolycondensation of polyether glycol segment of diamines end, at this in particular cases, the product of acquisition is polyether ester amides (being designated hereinafter simply as PEEA).
These polymkeric substance be disclosed in (for example) French Patent serial number 7418913 and 7726678 and following United States Patent (USP) in: 4,331,786,4,115,475,4,195,015,4,839,441,4,864,014,4,230,838 and 4,332,920.
Polyamide segment with dicarboxylic acid end makes in the presence of chain restriction dicarboxylic acid by the mixture of (for example) amino a-ω carboxylic acid, lactan or stoichiometric basically dicarboxylic acid and diamines.Polyamide-block is PA11, PA12 or PA11,12.Polyamide-block is PA12.Advantageously, the average molecular mass Mn of polyamide segment PA can be 300 to 15,000, and preferred 600 to 5,000.
Polyethers can be (for example) polyoxyethylene glycol (PEG), polytetramethylene glycol (PTMG) or polypropylene glycol (PPG), and preceding two kinds is preferred.
No matter whether polyether block is included in the polymer chain with polymeric amide and polyether block with glycol or diamines form, and they all are called as PEG block or PTMG block for the sake of simplicity.The average molecular mass Mn of polyether segment is 100 to 6,000, preferred 300 to 3,000.
Polymkeric substance with polymeric amide and polyether block also can comprise the part of random distribution.These polymkeric substance can be by polyethers and polyamide-block precursor while prepared in reaction.For example, this reaction can be carried out between polyether glycol, lactan (or corresponding α-omega amino acid) and chain restriction diacid in the presence of less water.The polymkeric substance that makes has the very big polyamide-block of most of polyether block, length variations and has carried out random reaction and the random distribution all ingredients in polymer chain.
Have the Shore hardness that the polymkeric substance of polymeric amide PA block and polyethers PE block has and be generally 20 to 75, preferred 30 to 70, logarithmic viscosity number is 0.8 to 2.5 (measuring under the starting point concentration 0.8g/100ml in meta-cresol under 25 ℃).
Polymkeric substance with PA block and PE block can be by 5 to 85wt%PE (with 95 to 15%PA), preferred 20 to 80wt%PE (with 80 to 20%PA), more preferably 30 to 70wt%PE (with 70 to 30%PA) form.
Polymkeric substance with polyamide-block and polyether block preferably includes the polyamide-block of single type and the polyether block of single type.Use has the polymkeric substance of PA12 block and PEG block and has the PA12 block and the polymkeric substance of PTMG block is favourable.
Yet also can use the blend of polymkeric substance with polyamide-block and polyether block.
These polymkeric substance with polyamide-block and polyether block can have been bought from Elf Atochem by trade(brand)name Pebax .
These polymkeric substance with PA block and PE block have the vapor permeation characteristic, and are called " wetting ability ", and hydrophilic connotation is that those skilled in the art know usually.
These polymkeric substance make and wherein are mixed with the TPU that seldom measures this polymkeric substance and have astonishing characteristic:
-have for the film that makes by material of the present invention impermeable-can breathe performance;
-have antistatic property for the goods that obtain by material of the present invention.
Even forming principal phase, TPU also can obtain these performances.This is astonishing because usually received in the prior art be to give performance by principal phase, particularly ventilation property.This amazing and beyond thought result, making can the very a spot of hydrophilic substance of blending, and still can obtain desired properties, reduces the cost of the finished product thus.Simultaneously, be also noted that then perviousness and static resistance become better if increase the amount (as 15 to 30%) of PEEA.This result also is astonishing, and matrix still is TPU matrix because those skilled in the art are contemplated that, so these performances are constant basically in whole compositing range.
(for example) term that uses among the present invention " the third compound " representative can with TPU or PEEA with itself or as any polymkeric substance of compatilizer blend.
The third polymkeric substance (for example) can be by polyolefine, as with grafting or copolyreaction in addition functionalized polyolefin form.The example of the third polymkeric substance is PE, ethylene copolymer, these polymkeric substance can with various monomers such as maleic anhydride or glycidyl methacrylate graft or with these monomer copolymerizations.
Material of the present invention also can mix with conventional additives.
The film that makes by material of the present invention be impermeable-respirable, in other words water vapor permeable but impermeable water, in brief permeable gas but liquid impermeable.These films can be used any currently known methods in this area, as by extruding preparation.The thickness that these films have is (for example) 5 to 500 μ m, preferred 10 to 250 μ m.These films can bond with other film and/or base material.
Goods are defined as " anlistatig ", because they have static resistance, meaning is that their surface resistivity is 10
9To 10
11Ohms/square.These goods can be with any method known in the art, as by extrude, preparation such as injection moulding, molding.
The following example explanation the present invention, but do not limit the present invention.
Embodiment
In an embodiment, water vapour permeability is measured perviousness with every m according to DIN standard 53122 under 23 ℃, relative humidity RH85%
2Gram number (the g/m of every day
2/ d) expression.
Embodiment 1 to 3
In these embodiments, use the polyester-polyurethane (PU-ester) that is called Elastollan C85 available from the commodity of BASF.Also use have weight ratio 50/50, polyether ester acid amides (PEEA) polymkeric substance of the Shore hardness D40 of PA12 that molecular-weight average is respectively Mn=1500 and Mn=1500 and PEG block.
Make polyester-polyurethane and polyesteramide blend by batching, curtain coating forms film then.Ratio is a weight ratio.
Following table 1 has provided the result:
Table 1
| Composition | Perviousness (g/m2/d) | Thickness (μ m) |
| PU-ester 100% | ??????112 | ????105 |
| PU-ester 100% | ???????90 | ????126 |
| PU-ester/PEEA 85/15 | ????190-200 | ????110 |
| PU-ester/PEEA 70/30 | ???????260 | ????110 |
| PEEA?100％ | ??????3000 | ?????50 |
Embodiment 4 to 6
In these embodiments, carry out, but use polyether-polyurethane (PU-ether) available from the commodity Elastollan 1185 by name of BASF according to the step identical with embodiment 1 to 3.
The results are shown in the table 2.
Table 2
| Composition | Perviousness (g/m2/d) | Thickness (μ m) |
| PU-ester 100% | ???????120 | ??????109 |
| PU-ester/PEEA 85/15 | ???????174 | ??????109 |
| PU-ester/PEEA 70/30 | ???????290 | ??????100 |
The result proves, uses the polymkeric substance and the big weight polyurethane that have PA12 and PEG block on a small quantity, can obtain impermeable-respirable film.
Obviously, the invention is not restricted to described embodiment, can carry out the various variations that those skilled in the art realize easily.
Claims (9)
- One kind comprise that following material (by weight) makes impermeable-can breathe film:(a) 50 to 95% thermoplastic polyurethane;(b) 5 to 50% have polymeric amide PA11, PA12 or PA11, a polymkeric substance of 12 blocks and polyethers PE block.
- 2. antistatic article that makes by the material that comprises following component (by weight):(a) 50 to 95% thermoplastic polyurethane;(b) 5 to 50% have polymeric amide PA11, PA12 or PA11, a polymkeric substance of 12 blocks and polyethers PE block.
- Respectively according to claim 1 or 2 impermeable-can breathe film or antistatic article, wherein the polyethers PE block in the polymkeric substance (b) is the PEG block.
- Respectively according to claim 1 or 2 impermeable-can breathe film or antistatic article, wherein the polyether block PE in the polymkeric substance (b) is the PTMG block.
- Respectively according to claim 12 or according to claim 3 or 4 impermeable-can breathe film or antistatic article, wherein thermoplastic polyurethane is a polyether-polyurethane.
- Respectively according to claim 12 or according to claim 3 or 4 impermeable-can breathe film or antistatic article, wherein thermoplastic polyurethane is a polyester-polyurethane.
- Respectively according to claim 12 or according to claim 3 to 6 any one impermeable-can breathe film or antistatic article, wherein the polyamide-block in the polymkeric substance (b) is the PA12 block.
- Respectively according to claim 12 or according to claim 3 to 7 any one impermeable-can breathe film or antistatic article, can make by the material that comprises following component (by weight):(a) 90 to 65% thermoplastic polyurethane;(b) 10 to 35% polymkeric substance with polymeric amide PA block and polyethers PE block.
- Respectively according to claim 12 or according to claim 3 to 8 any one impermeable-can breathe film or antistatic article, wherein said material comprises the third polymkeric substance, the amount of described the third polymkeric substance is at the most 100%, preferably 50% (by the weight of described material) at the most.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97118590 CN1177607A (en) | 1996-08-23 | 1997-08-22 | Film and object obtained from material comprising polyurethane and polyamide and polyether block polymer |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9610464 | 1996-08-23 | ||
| CN 97118590 CN1177607A (en) | 1996-08-23 | 1997-08-22 | Film and object obtained from material comprising polyurethane and polyamide and polyether block polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1177607A true CN1177607A (en) | 1998-04-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97118590 Pending CN1177607A (en) | 1996-08-23 | 1997-08-22 | Film and object obtained from material comprising polyurethane and polyamide and polyether block polymer |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460201C (en) * | 2003-10-20 | 2009-02-11 | 阿托菲纳公司 | Polyamide/polyurethane multilayer structures for decorated articles |
| CN107383858A (en) * | 2017-07-17 | 2017-11-24 | 宁波市鄞州红岩汽配厂 | A kind of automobile radiators water-supplying chamber |
| CN109370046A (en) * | 2018-10-09 | 2019-02-22 | 仲恺农业工程学院 | Method for improving air permeability of polypropylene film, modified polypropylene film and application |
| CN111040420A (en) * | 2019-09-04 | 2020-04-21 | 晋江兴迅新材料科技有限公司 | Method for preparing TPV (thermoplastic vulcanizate) foam material from PEBAX (polyethylene-ethylene-butylene-styrene copolymer) and TPV foam material |
-
1997
- 1997-08-22 CN CN 97118590 patent/CN1177607A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460201C (en) * | 2003-10-20 | 2009-02-11 | 阿托菲纳公司 | Polyamide/polyurethane multilayer structures for decorated articles |
| CN107383858A (en) * | 2017-07-17 | 2017-11-24 | 宁波市鄞州红岩汽配厂 | A kind of automobile radiators water-supplying chamber |
| CN109370046A (en) * | 2018-10-09 | 2019-02-22 | 仲恺农业工程学院 | Method for improving air permeability of polypropylene film, modified polypropylene film and application |
| CN109370046B (en) * | 2018-10-09 | 2021-03-16 | 仲恺农业工程学院 | Method for improving air permeability of polypropylene film, modified polypropylene film and application |
| CN111040420A (en) * | 2019-09-04 | 2020-04-21 | 晋江兴迅新材料科技有限公司 | Method for preparing TPV (thermoplastic vulcanizate) foam material from PEBAX (polyethylene-ethylene-butylene-styrene copolymer) and TPV foam material |
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