CN106084747A - One has high hydrolytic stability TPU film and preparation method thereof - Google Patents
One has high hydrolytic stability TPU film and preparation method thereof Download PDFInfo
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- CN106084747A CN106084747A CN201610405300.7A CN201610405300A CN106084747A CN 106084747 A CN106084747 A CN 106084747A CN 201610405300 A CN201610405300 A CN 201610405300A CN 106084747 A CN106084747 A CN 106084747A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/353—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
- C08K5/58—Organo-tin compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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Abstract
A kind of TPU film with high hydrolytic stability and preparation method thereof.Described TPU film includes following component by weight: polyether-type TPU granule 100 parts, stabilizer against hydrolysis 5 20 parts, 0.1 5 parts of antioxidant, heat-resisting stabilizing agent 0.1 5 parts, wherein, stabilizer against hydrolysis is N, N ' two (2,6 diisopropyl phenyl) carbodiimide and singly 2 oxazolines are with the mixture of 1:0.3 2 mol ratio.The TPU film that the present invention provides has the anti-hydrolytic performance of excellence.
Description
Technical field
The present invention relates to a kind of TPU film and preparation method thereof, particularly relate to one and there is high hydrolytic stability TPU film
And preparation method thereof.
Background technology
TPU (Thermoplastic polyurethanes) entitled Polyurethane Thermoplastic Elastomer rubber, is broadly divided into
Have polyester-type and polyether-type point.Its hardness range width (60HA-85HD), wear-resisting, oil resistant, transparent, good springiness, article of everyday use,
It is used widely in the fields such as sports goods, toy, ornament materials.
TPU film is on the basis of TPU particulate material, through the thin film that the special process such as calendering, curtain coating, blown film, coating is made.
TPU (thermoplastic polyurethane) is increasingly subject to the welcome of people because of its superior performance and environmental protection concept.At present, every use
The place of PVC, TPU all can become the succedaneum of PVC.But the advantage that TPU is had, PVC is the most too far behind to catch up.TPU not only has
The high-tension of brilliance, high-tensile strength, tough and ageing-resistant characteristic, and be kind of ripe environment-friendly materials.At present, TPU is by extensively
General it is applied to: footwear material, ready-made clothes, inflatable toys, waterborne and sports equipment under water, medical device, body-building apparatus, automobile seat material
Material, umbrella, leather trunk, suitcase etc..
But the hydrolytic stability of existing TPU is poor, reason be water penetrate into after elastomer with there occurs of group in TPU
Learning reaction, create chemical degradation, the chemical composition of elastomer and physical arrangement are destroyed, and hydrolysis is irreversible.
In terms of improving TPU hydrolytic stability, it is presently mainly the hydrophobicity by strengthening polyurethane elastomer, or makes
The segment of fracture " is replanted " and is solved, and is summed up two aspects: one is the structure changing Polyurethane Thermoplastic Elastomer, but
Due to its complex process, relatively costly, and the proper property of Polyurethane Thermoplastic Elastomer also can be made to weaken, application is subject to
Certain restriction；Two is to add chemical assistant, and current industrial wide variety of hydrolysis auxiliary agent mainly has epoxy compound species
And Carbodiimides, epoxy compounds substantially can be divided into glycidyl derivatives and hydrocarbon substituted epoxy ethane compounds two
Big class.
As CN 101457018A discloses Polyurethane Thermoplastic Elastomer of a kind of hydrolysis and preparation method thereof, specifically
For a kind of organic diisocyanate containing carbodiimide modified as the Polyurethane Thermoplastic Elastomer of hydrolysis auxiliary agent.But its
Hydrolytic stability yet suffers from deficiency.
CN 104231598A discloses a kind of TPU film with high hydrolytic stability and preparation method thereof.Described TPU
Thin film includes following component by weight: TPU granule 100；Epoxy resin 12～25；Polycarbodiimide 3～8；Antioxidant
0.3～10.This invention adds epoxy resin in TPU granule and polycarbodiimide prepares the TPU with high hydrolytic stability
Thin film, makes the hydrolysis-stable of TPU film product increase, but still needs to be improved further.
Summary of the invention
For solving the problems referred to above, an object of the present invention is to provide a kind of TPU film with high hydrolytic stability.This
The TPU film that invention provides has the anti-hydrolytic performance of excellence.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that
A kind of TPU film with high hydrolytic stability, includes following component by weight:
Wherein, stabilizer against hydrolysis is N, N '-two (2,6-diisopropyl phenyl) carbodiimide with single 2-oxazoline with 1:
0.3-2, for example, mixture of 1:0.4,1:0.6,1:0.8,1:1.1,1:1.3,1:1.5,1:1.7,1:1.9 equimolar ratio.
Described stabilizer against hydrolysis can be such as 6 parts, 8 parts, 9 parts, 11 parts, 13 parts, 15 parts, 17 parts, 19 parts etc..
Described antioxidant can be such as 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1.0 parts, 1.5 parts, 2.0 parts, 2.5 parts, 3.1
Part, 3.6 parts, 4.0 parts, 4.4 parts, 4.8 parts etc..
Described heat-resisting stabilizing agent can be such as 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1.0 parts, 1.5 parts, 2.0 parts, 2.5
Part, 3.1 parts, 3.6 parts, 4.0 parts, 4.4 parts, 4.8 parts etc..
Use said components proportioning and polyether-type TPU granule can improve significantly with the combination of specific stabilizer against hydrolysis
Preparing the anti-hydrolytic performance of thin film, mechanical property conservation rate is obviously improved.The component only selected in the present invention and content range
Inside can be only achieved expected effect, in above-mentioned component and content range, then do not reach intended technique effect.Visible, this
Cooperate between the said components of invention, jointly act on, in the component concentration ranges limited, achieve unforeseeable skill
Art effect, it is seen that the performance test of embodiment part.
As preferably, the TPU film with high hydrolytic stability of the present invention, include following component by weight:
Wherein, stabilizer against hydrolysis is N, N '-two (2,6-diisopropyl phenyl) carbodiimide with single 2-oxazoline with 1:
The mixture of 0.5-1 mol ratio.
As preferably, the TPU film with high hydrolytic stability of the present invention, described antioxidant is that polyphenol antioxidant is with sub-
The combination of phosphate ester antioxidant.
Preferably, described polyphenol antioxidant is antioxidant 1010 and/or antioxidant 1076.
Preferably, described phosphite antioxidant is irgasfos 168 and/or 618.
Preferably, the mol ratio of described polyphenol antioxidant and phosphite antioxidant is 1:0.2-5, for example, 1:0.4,1:
0.7,1:1.1,1:1.5,1:2,1:2.6,1:3.3,1:3.8,1:4.2,1:4.7 etc., the polyphenol antioxidant under this ratio is with sub-
Phosphate ester combination can obtain the antioxidant effect of excellence, preferably 1:1-3.
Preferably, described heat-resisting stabilizing agent is the combination of stannum stabilizer and zinc stearate.
Preferably, described stannum stabilizer is that in organic tin stabilizer, one or more combination, preferably mercaptan have
One or more combination, more preferably carbomethoxy mercaptan tin stabilizer in machine stannum stabilizer.
Preferably, the mol ratio of described stannum stabilizer and zinc stearate is 1:0.5-3, for example, 1:0.6,1:0.9,1:
1.1,1:1.5,1:2,1:2.6,1:2.9 etc., preferably 1:1-2.
The heat-resisting stabilizing agent combination of the present invention and suitable proportioning considerably increase the Heat-resistant stable performance of prepared thin film.
" including " of the present invention, it is intended that it is in addition to described component, it is also possible to include other components, these other components
Give the characteristic that described TPU film is different.In addition, " including " of the present invention, it is also possible to replace with enclosed
" be " or " by ... composition ".
An object of the present invention also resides in provides a kind of TPU film with high hydrolytic stability of the present invention
Preparation method, comprises the steps:
(1) will mix after raw material drying；
(2) mixed material melt blending is obtained composite master batch；
(3) masterbatch is carried out blown film, calendering or casting film-forming processing, obtains described TPU film.
As preferably, in the preparation method of the present invention, it is dried under vacuo at 50-70 DEG C described in step (1), for example,
53 DEG C, 57 DEG C, 60 DEG C, 64 DEG C, carry out under 68 DEG C etc. more than 2h, for example, 2.2h, 2.6h, 3.3h, 3.9h, 4.5h, 5.7h,
7.5h etc., preferably 3-6h.
Preferably, it is blended in described in high-speed mixer and carries out.
Preferably, the time of described mixing is more than 1min, for example, 2min, 2.5min, 3.4min, 4min, 4.5min
Deng, preferably 3-5min.
Preferably, during described mixing, mixer rotating speed is more than 20000r/min, preferably 30000-50000r/min.
As preferably, in the preparation method of the present invention, described in step (2), the temperature of melt blending is 150-230 DEG C, example
As for 155 DEG C, 160 DEG C, 163 DEG C, 168 DEG C, 172 DEG C, 177 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 202 DEG C, 210 DEG C, 216 DEG C,
223 DEG C, 229 DEG C etc., the time is 0.5-5h, for example, 0.8h, 1.5h, 3h, 3.6h, 4.5h etc., preferably 1-2h.
The present invention adds N, N '-two (2,6-diisopropyl phenyl) carbodiimide and single 2-oxazoline group in TPU granule
The stabilizer against hydrolysis preparation closed has the TPU film of high hydrolytic stability, makes the heat resistant hydrolysis of TPU film product stably carry
Height, mechanical property conservation rate, antioxidation, light fastness stability relatively existing product makes moderate progress to a great extent.The present invention prepares
Elastic polyurethane body thin film after 6 weeks tensile strength keep more than 96%, after 6 weeks elongation at break be initial 1.45 times with
On, all it is far superior to comparative example.
Detailed description of the invention
For the present invention is better described, it is simple to understand technical scheme, the present invention's is typical but non-limiting
Embodiment is as follows:
Embodiment 1
A kind of TPU film with high hydrolytic stability, includes following component by weight:
Wherein, stabilizer against hydrolysis is N, N '-two (2,6-diisopropyl phenyl) carbodiimide with single 2-oxazoline with 1:
The mixture of 0.3 mol ratio；
Described antioxidant is antioxidant 1010 and phosphite antioxidant 618 mol ratio is the combination of 1:5；
Described heat-resisting stabilizing agent is carbomethoxy mercaptan tin stabilizer and zinc stearate mol ratio is the combination of 1:2.
And be prepared by the following method:
(1) raw material is dried under vacuo at 60 DEG C mixing after more than 3h；
(2) by mixed material in high-speed mixer at 230 DEG C, rotating speed is that 40000r/min melt blending 3h must answer
Combination master batch；
(3) masterbatch is carried out blown film processing, obtain described TPU film.
Embodiment 2
A kind of TPU film with high hydrolytic stability, includes following component by weight:
Wherein, stabilizer against hydrolysis is N, N '-two (2,6-diisopropyl phenyl) carbodiimide with single 2-oxazoline with 1:1
The mixture of mol ratio；
Described antioxidant is antioxidant 1076 and phosphite antioxidant 168 mol ratio is the combination of 1:0.2；
Described heat-resisting stabilizing agent is stannum stabilizer and zinc stearate mol ratio is the combination of 1:0.5；
And be prepared by the following method:
(1) raw material is dried under vacuo at 70 DEG C mixing after more than 5h；
(2) by mixed material in high-speed mixer at 150 DEG C, rotating speed is that 50000r/min melt blending 0.5h obtains
Composite master batch；
(3) masterbatch is carried out casting film-forming processing, obtain described TPU film.
Embodiment 3
A kind of TPU film with high hydrolytic stability, includes following component by weight:
Wherein, stabilizer against hydrolysis is N, N '-two (2,6-diisopropyl phenyl) carbodiimide with single 2-oxazoline with 1:2
The mixture of mol ratio；
Described antioxidant be polyphenol antioxidant 1010 be the combination of 1:1 with phosphite antioxidant 168 mol ratio；
Described heat-resisting stabilizing agent is carbomethoxy mercaptan tin stabilizer and zinc stearate mol ratio is the combination of 1:3；
And be prepared by the following method:
(1) mix after raw material being dried 2h under vacuo at 50 DEG C；
(2) by mixed material in high-speed mixer at 200 DEG C, rotating speed is that 20000r/min melt blending 2.5h obtains
Composite master batch；
(3) carry out masterbatch rolling film forming processing, obtain described TPU film.
Comparative example
Embodiment 1 in comparative example 1:CN 104231598A.
Comparative example 2: difference from Example 1 is: stabilizer against hydrolysis is N, N '-two (2,6-diisopropyl phenyl)
Carbodiimide and single 2-oxazoline are with the mixture of 1:0.1 mol ratio；Described antioxidant is that antioxidant 1010 resists with phosphite ester
Oxygen agent 618 mol ratio is the combination of 1:0.1；Described heat-resisting stabilizing agent is carbomethoxy mercaptan tin stabilizer and zinc stearate mol ratio
Combination for 1:0.1.
Comparative example 3: difference from Example 2 is: stabilizer against hydrolysis is N, N '-two (2,6-diisopropyl phenyl)
Carbodiimide；Described antioxidant is phosphite antioxidant 618；Described heat-resisting stabilizing agent is carbomethoxy mercaptan tin stabilizer.
Comparative example 4: difference from Example 3 is: stabilizer against hydrolysis 1 part, 8 parts of antioxidant, heat-resisting stabilizing agent 8
Part.
Performance test
Be hydrolyzed in 80 DEG C of tanks stability test by the film product that embodiment 1-3 and comparative example prepare, necessarily
Carry out physical property measurement by ASTMD412 (American Society Testing and Materials's standard) after time, the results are shown in Table 1.
Table 1
As known from Table 1, the elastic polyurethane body thin film of embodiment of the present invention 1-3 is tensile strength holding more than 96% after 6 weeks,
And comparative example 1 is 94.5%, comparative example 2 is 94%, and comparative example 3 is 92%, and comparative example 4 is 93.5%；Elongation at break after 6 weeks
For initial more than 1.45 times, and comparative example 1 is 1.39, and comparative example 2 is 1.3, and comparative example 3 is 1.35, and comparative example 4 is 1.34.
The concrete ratio of the material that the stabilizer against hydrolysis of comparative example 2, antioxidant, heat-resisting stabilizing agent use is not in the application
In the range of, then use stabilizer against hydrolysis, antioxidant, the heat-resisting stabilizing agent of comparative example 3 are not that the application limits, contrast
The stabilizer against hydrolysis of example 4, antioxidant, heat-resisting stabilizing agent amount not within the scope of this application.But, result but shows, this
The tensile strength of the product of invention keeps and elongation at break is superior to comparative example over time, it is seen that only at this
Preferable effect could be obtained in the component of bright restriction and corresponding content range.
Applicant states, person of ordinary skill in the field is on the basis of above-described embodiment, by above-described embodiment
The concrete content point value of component, combined with the technical scheme of Summary, thus the new numerical range produced, also it is
One of record scope of the present invention, the application, for making description simple and clear, no longer enumerates these numerical rangies.
Applicant states, the present invention illustrates the present invention by above-described embodiment, but the invention is not limited in above-mentioned
Operating procedure, does not i.e. mean that the present invention has to rely on aforesaid operations step and could implement.Person of ordinary skill in the field
It will be clearly understood that any improvement in the present invention, the equivalence to raw material selected by the present invention is replaced and the interpolation of auxiliary element, concrete
Way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the technology concept of the present invention, technical scheme can be carried out multiple simple variant, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, at not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy illustrates the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. there is a TPU film for high hydrolytic stability, include following component by weight:
Wherein, stabilizer against hydrolysis is N, N '-two (2,6-diisopropyl phenyl) carbodiimide with single 2-oxazoline with 1:0.3-2
The mixture of mol ratio.
TPU film the most according to claim 1, it is characterised in that include following component by weight:
Wherein, stabilizer against hydrolysis is N, N '-two (2,6-diisopropyl phenyl) carbodiimide with single 2-oxazoline with 1:0.5-1
The mixture of mol ratio.
TPU film the most according to claim 1 and 2, it is characterised in that described antioxidant is polyphenol antioxidant and phosphorous acid
The combination of ester antioxidant.
TPU film the most according to claim 3, it is characterised in that described polyphenol antioxidant is antioxidant 1010 and/or resists
Oxygen agent 1076；
Preferably, described phosphite antioxidant is irgasfos 168 and/or 618；
Preferably, described polyphenol antioxidant is 1:0.2-5, preferably 1:1-3 with the mol ratio of phosphite antioxidant.
5. according to the TPU film described in any one of claim 1-3, it is characterised in that described heat-resisting stabilizing agent is stannum stabilizer
Combination with zinc stearate.
TPU film the most according to claim 5, it is characterised in that described stannum stabilizer is a kind of in organic tin stabilizer
Or one or more combination, more preferably carbomethoxy in two or more combinations, preferably thiol organotin stabilizer
Mercaptan tin stabilizer；
Preferably, described stannum stabilizer is 1:0.5-3, preferably 1:1-2 with the mol ratio of zinc stearate.
7. the preparation method of the TPU film described in any one of claim 1-6, comprises the steps:
(1) will mix after raw material drying；
(2) mixed material melt blending is obtained composite master batch；
(3) masterbatch is carried out blown film, calendering or casting film-forming processing, obtains described TPU film.
Preparation method the most according to claim 7, it is characterised in that be dried under vacuo at 50-70 described in step (1)
More than 2h, preferably 3-6h is carried out at DEG C.
9. according to the preparation method described in claim 7 or 8, it is characterised in that step is blended in high-speed mixer described in (1)
In carry out；
Preferably, the time of described mixing is more than 1min, preferably 3-5min；
Preferably, during described mixing, mixer rotating speed is more than 20000r/min, preferably 30000-50000r/min.
10. according to the preparation method described in any one of claim 7-9, it is characterised in that melt blending described in step (2)
Temperature is 150-230 DEG C, and the time is 0.5-5h, preferably 1-2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610405300.7A CN106084747A (en) | 2016-06-08 | 2016-06-08 | One has high hydrolytic stability TPU film and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610405300.7A CN106084747A (en) | 2016-06-08 | 2016-06-08 | One has high hydrolytic stability TPU film and preparation method thereof |
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| CN201610405300.7A Pending CN106084747A (en) | 2016-06-08 | 2016-06-08 | One has high hydrolytic stability TPU film and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112694742A (en) * | 2020-12-30 | 2021-04-23 | 浙江祥隆科技有限公司 | High-transparency hydrolysis-resistant TPU film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153855A (en) * | 2011-02-25 | 2011-08-17 | 深圳职业技术学院 | Hydrolysis-resistant thermoplastic polyurethane elastomer and manufacture method thereof |
| CN103568387A (en) * | 2013-10-08 | 2014-02-12 | 东莞市雄林新材料科技有限公司 | Wet-type PU (polyurethane) thin film attached with TPU (thermoplastic polyurethane) thin film |
| CN104231598A (en) * | 2014-09-18 | 2014-12-24 | 苏州市雄林新材料科技有限公司 | TPU (thermoplastic polyurethane) film with high hydrolytic stability and preparation method of TPU film |
-
2016
- 2016-06-08 CN CN201610405300.7A patent/CN106084747A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153855A (en) * | 2011-02-25 | 2011-08-17 | 深圳职业技术学院 | Hydrolysis-resistant thermoplastic polyurethane elastomer and manufacture method thereof |
| CN103568387A (en) * | 2013-10-08 | 2014-02-12 | 东莞市雄林新材料科技有限公司 | Wet-type PU (polyurethane) thin film attached with TPU (thermoplastic polyurethane) thin film |
| CN104231598A (en) * | 2014-09-18 | 2014-12-24 | 苏州市雄林新材料科技有限公司 | TPU (thermoplastic polyurethane) film with high hydrolytic stability and preparation method of TPU film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112694742A (en) * | 2020-12-30 | 2021-04-23 | 浙江祥隆科技有限公司 | High-transparency hydrolysis-resistant TPU film and preparation method thereof |
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Application publication date: 20161109 |