CN110835462A - High-wear-resistance printable TPU film and preparation method thereof - Google Patents
High-wear-resistance printable TPU film and preparation method thereof Download PDFInfo
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- CN110835462A CN110835462A CN201911194973.2A CN201911194973A CN110835462A CN 110835462 A CN110835462 A CN 110835462A CN 201911194973 A CN201911194973 A CN 201911194973A CN 110835462 A CN110835462 A CN 110835462A
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Abstract
The invention provides a high-wear-resistance printable TPU film and a preparation method thereof, wherein the preparation raw materials of the printable TPU film comprise the following components: 40-80 parts of toluene diisocyanate, 30-40 parts of polyester polyol, 20-30 parts of polyether polyol, 5-8 parts of alkoxy poly (oxyalkylene) glycol, 2-6 parts of dipentaerythritol hexaacrylate, 4-7 parts of a chain extender and 2-4 parts of a catalyst; according to the printable TPU film provided by the invention, through the matched use of the polyether polyol, the alkoxy poly (alkylene oxide) glycol and the dipentaerythritol hexaacrylate, the TPU film has good printing performance, meanwhile, the wear resistance of the TPU film is improved, the good use performance can be still maintained for 600-800 times, the TPU film has good application prospect in the printing field, the application range of the TPU film is expanded, and the application value is high.
Description
Technical Field
The invention belongs to the field of high polymer materials, relates to a TPU film and a preparation method thereof, and particularly relates to a high-wear-resistance printable TPU film and a preparation method thereof.
Background
TPU (Thermoplastic polyurethane) is a novel organic polymer synthetic material, and has a trade name of: the Flexible polyurethane is a high molecular material generated by the joint reaction of diisocyanate, macromolecular polyol and a chain extender. The expandable multifunctional cable has multiple expandable functions and good performance, thereby having wide application prospect. The polyurethane elastomer is a material with stronger cohesive energy, has excellent wear resistance, and can improve the wear resistance by 2-10 times compared with natural rubber. Meanwhile, the rubber material has higher mechanical strength and tearing strength, and has excellent damping and buffering performance, so that the rubber material has better 'Israel' ability.
CN103802416A discloses a high-brightness wear-resistant building material decorative film and a production method thereof, which comprises the following seven steps: firstly, preparing materials, secondly, preparing a polyurethane resin dissolving and separating liquid, thirdly, preparing UV oil, fourthly, printing with high-precision color register and temperature control, fifthly, coating a chemical separating liquid on the bottom surface of a base film, sixthly, coating the UV oil, and seventhly, adhering a PET protective film. The decorative film is a five-layer laminated structure film and sequentially comprises a PET protective film layer, a UV oil layer, an ink printing layer, a base film layer and a polyurethane separation liquid coating from top to bottom.
CN105860658A discloses a high-wear-resistance modified aqueous polyurethane ink, the printing ink introduces aramid pulp into the aqueous polyurethane ink, the aramid pulp can obtain excellent dispersibility after being dispersed in a composite emulsion, the mechanical property of the polyurethane ink can be effectively improved, and the polyurethane after being modified by hexafluorobutyl methacrylate and glycidyl methacrylate has better water resistance, so that the environment-friendly aqueous ink with high hydrophobicity, high strength, high adsorption force, high wear resistance and high temperature resistance is prepared, and the application range of the traditional aqueous polyurethane ink is widened. This method is developed as a humorous, and cannot form a thin film, thus limiting the application.
CN108330704A discloses a graphene superfine fiber polyurethane synthetic leather and a preparation method thereof, wherein the graphene superfine fiber polyurethane synthetic leather comprises a surface layer, a middle layer and a bonding layer which are prepared from the following raw materials: the high-performance aqueous non-yellowing polyurethane resin comprises high-performance aqueous non-yellowing polyurethane resin, nylon, graphene, superfine fiber polyurethane synthetic base material, wear-resisting agent, light-resisting agent, flame-retardant color master batch and pure water; the preparation method comprises the following steps: s1, weighing the raw materials according to the proportion; s2, processing graphene; s3, mixing and stirring the raw materials; s4, filtering the solution by using a filter screen, and preparing the automobile microfiber leather by using a dry synthetic leather production line. The prepared graphene superfine fiber polyurethane synthetic leather has excellent comprehensive performance, good test results in all aspects, basically the same physical indexes as those of common superfine fiber automobile interiors, excellent moisture permeability and air permeability and wear resistance, and natural leather touch.
The polyurethane materials disclosed at present have no material with both abrasion resistance and printability, so how to develop a TPU film with good abrasion resistance and printability is of great significance for the application.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a TPU film and a preparation method thereof, in particular to a high-wear-resistance printable TPU film and a preparation method thereof, so as to solve the problems that the existing TPU film is poor in wear resistance and the printing performance cannot meet the daily use requirement.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a printable TPU film prepared from raw materials comprising the following components:
according to the printable TPU film provided by the invention, the polyether polyol, the alkoxy poly (alkylene oxide) glycol and the dipentaerythritol hexaacrylate are used in a matched manner, so that the TPU film has good printing performance, meanwhile, the wear resistance of the TPU film is improved, and the good use performance can still be maintained after 600-800 times of friction.
In the invention, the high wear resistance means that when a sample is rubbed by using a friction resistance tester (MCJ-01A, Jinan Languang electromechanical technology, Inc.) under a load of 4 pounds, the sample still can maintain good service performance after being rubbed for 600-800 times.
The toluene diisocyanate of the present invention is 40 to 80 parts by weight, and may be, for example, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, or the like.
The polyester polyol of the present invention is 30 to 40 parts by weight, and may be, for example, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, or the like.
Preferably, the number average molecular weight of the polyester polyol is 600-1800, such as 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700 or 1800.
The polyether polyol of the present invention may be 20 to 30 parts by weight, for example, 20 parts, 21 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, or 30 parts, and the like.
In the invention, the polyether polyol contains carbon-oxygen bonds, so that the toughness of the formed material is improved, and the wear resistance of the TPU film can be improved.
Preferably, the polyether polyol has a number average molecular weight of 3000-.
Preferably, the polyether polyol is an acrylonitrile graft-modified polyether polyol. The solid content is 40-45%, and the functionality is 2-3. The polyether polyol is of type KE-880S, preferably manufactured by the company Liya polyol (Nanjing) Ltd.
The alkoxy poly (oxyalkylene) glycol of the present invention is used in an amount of 5 to 8 parts by weight, for example, 5 parts, 6 parts, 7 parts, or 8 parts.
In the invention, the alkoxy group and the oxyalkylene group can improve the hydrophilicity of the mixed raw materials, thereby endowing the TPU film with better hydrophilicity and toughness and improving the wear resistance.
Preferably, the alkoxy poly (oxyalkylene) glycol has a number average molecular weight of 1000-1500, which may be, for example, 1000, 1100, 1200, 1300, 1400, 1500, or the like.
Preferably, in the alkoxy poly (oxyalkylene) glycol, the alkoxy group has 1 to 5, for example, 1, 2, 3, 4 or 5 carbon atoms, and the oxyalkylene group has 2 to 4, for example, 2, 3 or 4 carbon atoms.
The dipentaerythritol hexaacrylate of the present invention is present in an amount of 2 to 6 parts by weight, for example, 2 parts, 3 parts, 4 parts, 5 parts, or 6 parts, etc.
In the invention, the dipentaerythritol hexaacrylate can improve the fluidity of the mixture, so that the TPU film can be endowed with good printability, and the abrasion resistance of the alkoxy poly (oxyalkylene) glycol and the polyether polyol can be improved, and the influence on the performance of the TPU film is important.
The weight part of the chain extender in the invention is 4-7 parts, and can be 4 parts, 5 parts, 6 parts or 7 parts, for example.
The catalyst of the present invention is 2-4 parts by weight, for example, 2 parts, 3 parts, 4 parts, etc.
In the present invention, the chain extender and the catalyst used are all those commonly used in the art, and for example, the chain extender may be ethylene glycol, ethylenediamine, 1, 3-propanediol, 1, 4-butanediol, etc.; the catalyst may be an organotin catalyst, and specifically may be stannous octoate, dibutyltin dioctoate or dibutyltin monthly silicate, or the like.
In another aspect, the present invention provides a method of making a printable TPU film, as described above, comprising the steps of:
(1) adding toluene diisocyanate, polyester polyol, polyether polyol, alkoxy poly (oxyalkylene) glycol and dipentaerythritol hexaacrylate into a container, and dehydrating in vacuum under the stirring condition;
(2) adding a chain extender and a catalyst into the material obtained in the step (1) for mixing reaction;
(3) and (3) adding the material reacted in the step (2) into a double-screw extruder for extrusion molding to obtain the printable TPU film.
Preferably, the temperature of the vacuum dehydration in the step (1) is 60 to 80 ℃, for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃ and the like can be used.
Preferably, the vacuum dehydration time in step (1) is 2-6 hours, such as 2 hours, 3 hours, 4 hours, 5 hours or 6 hours.
Preferably, the stirring rate in step (1) is 100-170r/min, such as 100r/min, 110r/min, 120r/min, 130r/min, 140r/min, 150r/min, 160r/min or 170 r/min.
Preferably, the temperature of the mixing reaction in step (2) is 50 to 80 ℃, and may be, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃.
Preferably, the mixing reaction in step (2) is carried out for 1 to 5 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, or the like.
Preferably, the temperature of the feeding section of the twin-screw extruder in step (3) is 120-.
Compared with the prior art, the invention has the following beneficial effects:
according to the printable TPU film provided by the invention, through the matched use of the polyether polyol, the alkoxy poly (alkylene oxide) glycol and the dipentaerythritol hexaacrylate, the TPU film has good printing performance, meanwhile, the wear resistance of the TPU film is improved, the good service performance can be still maintained after 600-800 times of friction, the TPU film has good application prospect in the printing field, the application range of the TPU film is expanded, and the application value is high.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The preparation raw materials of the printable TPU film provided in this example include the following components in parts by weight:
the preparation method comprises the following steps:
(1) toluene diisocyanate, polyester polyol (the number average molecular weight is 1200), KE-880S (the number average molecular weight is 4000), ethoxy poly (ethylene oxide) glycol (the number average molecular weight is 1100) and dipentaerythritol hexaacrylate are added into a container, and vacuum dehydration is carried out for 4 hours at 70 ℃ under the condition of stirring at the speed of 120 r/min;
(2) adding ethylene glycol and stannous octoate into the material obtained in the step (1), and mixing and reacting for 4 hours at 70 ℃;
(3) and (3) adding the material reacted in the step (2) into a double-screw extruder, and extruding and molding to obtain the printable TPU film, wherein the temperature of a feeding section of the double-screw extruder is 125 ℃, the temperature of a mixing section of the double-screw extruder is 145 ℃, the temperature of an extrusion section of the double-screw extruder is 170 ℃, and the temperature of a machine head of the double-screw extruder is 155 ℃.
Example 2
The preparation raw materials of the printable TPU film provided in this example include the following components in parts by weight:
the preparation method comprises the following steps:
(1) toluene diisocyanate, polyester polyol (the number average molecular weight is 1500), KE-880S (the number average molecular weight is 3000), n-propoxy poly (n-propylene oxide) glycol (the number average molecular weight is 1100) and dipentaerythritol hexaacrylate are added into a container, and vacuum dehydration is carried out for 2 hours at 80 ℃ under the stirring condition of 170 r/min;
(2) adding 1, 3-propylene glycol and dibutyltin dioctoate into the material in the step (1), and mixing and reacting for 1 hour at the temperature of 80 ℃;
(3) and (3) adding the material reacted in the step (2) into a double-screw extruder, and extruding and molding to obtain the printable TPU film, wherein the temperature of a feeding section of the double-screw extruder is 120 ℃, the temperature of a mixing section of the double-screw extruder is 140 ℃, the temperature of an extrusion section of the double-screw extruder is 170 ℃, and the temperature of a machine head of the double-screw extruder is 150 ℃.
Example 3
The preparation raw materials of the printable TPU film provided in this example include the following components in parts by weight:
the preparation method comprises the following steps:
(1) toluene diisocyanate, polyester polyol (with the number average molecular weight of 600), KE-880S (with the number average molecular weight of 5000), ethoxy poly (ethylene oxide) diol (with the number average molecular weight of 1000) and dipentaerythritol hexaacrylate are added into a container, and vacuum dehydration is carried out for 6 hours at 60 ℃ under the condition of stirring at the speed of 100 r/min;
(2) adding 1, 3-propylene glycol and dibutyltin dioctoate into the material in the step (1), and mixing and reacting for 5 hours at 50 ℃;
(3) and (3) adding the material reacted in the step (2) into a double-screw extruder, and extruding and molding to obtain the printable TPU film, wherein the temperature of a feeding section of the double-screw extruder is 130 ℃, the temperature of a mixing section of the double-screw extruder is 160 ℃, the temperature of an extrusion section of the double-screw extruder is 180 ℃, and the temperature of a machine head of the double-screw extruder is 160 ℃.
Example 4
The preparation raw materials of the printable TPU film provided in this example include the following components in parts by weight:
the preparation method comprises the following steps:
(1) adding toluene diisocyanate, polyester polyol (the number average molecular weight is 1800), KE-880S (the number average molecular weight is 3400), ethoxy poly (ethylene oxide) glycol (the number average molecular weight is 1500) and dipentaerythritol hexaacrylate into a container, and carrying out vacuum degassing at 60 ℃ for 3 hours under the condition of stirring at the speed of 100 r/min;
(2) adding 1, 4-butanediol and stannous octoate into the material in the step (1), and mixing and reacting for 3 hours at 60 ℃;
(3) and (3) adding the material reacted in the step (2) into a double-screw extruder, and extruding and molding to obtain the printable TPU film, wherein the temperature of a feeding section of the double-screw extruder is 125 ℃, the temperature of a mixing section of the double-screw extruder is 145 ℃, the temperature of an extrusion section of the double-screw extruder is 170 ℃, and the temperature of a machine head of the double-screw extruder is 155 ℃.
Example 5
The preparation raw materials of the printable TPU film provided in this example include the following components in parts by weight:
the preparation method comprises the following steps:
(1) toluene diisocyanate, polyester polyol (with the number average molecular weight of 600), KE-880S (with the number average molecular weight of 4500), ethoxy poly (ethylene oxide) glycol (with the number average molecular weight of 1000) and dipentaerythritol hexaacrylate are added into a container, and vacuum dehydration is carried out for 4 hours at 70 ℃ under the condition of stirring at the speed of 120 r/min;
(2) adding ethylenediamine and stannous octoate into the material obtained in the step (1), and mixing and reacting for 4 hours at 70 ℃;
(3) and (3) adding the material reacted in the step (2) into a double-screw extruder, and extruding and molding to obtain the printable TPU film, wherein the temperature of a feeding section of the double-screw extruder is 125 ℃, the temperature of a mixing section of the double-screw extruder is 145 ℃, the temperature of an extrusion section of the double-screw extruder is 170 ℃, and the temperature of a machine head of the double-screw extruder is 155 ℃.
Example 6
This example differs from example 1 in that the same procedure as in example 1 was repeated except that KE-880S was replaced with polytetrahydrofuran diol to obtain a TPU film.
Comparative example 1
This comparative example differs from example 1 in that the comparative example does not include KE-880S, 16 parts by weight of ethoxylated poly (oxyethylene) glycol and 18 parts by weight of dipentaerythritol hexaacrylate, and a TPU film was prepared in the same manner as in example 1.
Comparative example 2
This comparative example differs from example 1 in that no ethoxylated poly (oxyethylene) glycol was included, 26 parts by weight of KE-880S and 8 parts by weight of dipentaerythritol hexaacrylate were included in the comparative example, and TPU films were prepared as in example 1.
Comparative example 3
This comparative example differs from example 1 in that dipentaerythritol hexaacrylate was not included in the comparative example, 26 parts by weight of KE-880S and 8 parts by weight of ethoxylated poly (oxyethylene) glycol were included in the comparative example, and TPU films were prepared in the same manner as in example 1.
Comparative example 4
This comparative example differs from example 1 in that KE-880S and ethoxylated poly (oxyethylene) glycol are not included in the comparative example, 34 parts by weight of dipentaerythritol hexaacrylate are included in the comparative example, and TPU films are prepared in the same manner as in example 1.
Comparative example 5
This comparative example differs from example 1 in that KE-880S, ethoxylated poly (oxyethylene) glycol and dipentaerythritol hexaacrylate are not included in the comparative example and a TPU film is prepared in the same manner as in example 1.
The TPU films provided in examples 1 to 6 and comparative examples 1 to 3 were subjected to an abrasion resistance test, and the samples were rubbed under a load of 4 lbs using an abrasion resistance meter (MCJ-01A, denland optomechanical and electrical technologies limited) at normal temperature and the number of rubs was counted.
Evaluation was based on the following criteria:
○, the friction times are 600-800 times;
△, the rubbing times are 300-600 times;
x: the number of rubbing is 300 or less.
The TPU film materials provided in examples 1-6 and comparative examples 1-3 above were subjected to printability testing and observed for smoothness of printing. Specific results are shown in table 1:
TABLE 1
| Sample (I) | Wear resistance | Fluency of printing |
| Example 1 | ○ | Fluency |
| Example 2 | ○ | Fluency |
| Example 3 | ○ | Fluency |
| Example 4 | ○ | Fluency |
| Example 5 | ○ | Fluency |
| Example 6 | △ | Fluency |
| Comparative example 1 | △ | With slight jamming |
| Comparative example 2 | × | With slight jamming |
| Comparative example 3 | × | With slight jamming |
| Comparative example 4 | × | Catton |
| Comparative example 5 | × | Catton |
The results in the table 1 show that the printable TPU film provided by the invention has better wear resistance, and can still maintain good performance after being rubbed for 600-800 times.
In contrast, when the polyether polyol is changed from example 6 to example 1, the abrasion resistance is lowered.
As can be seen by comparing comparative examples 1-5 with example 1, when any one or more of KE-880S, ethoxylated poly (oxyethylene) glycol, and dipentaerythritol hexaacrylate is absent, the abrasion resistance of the TPU film becomes poor and the printability of the material is affected.
The applicant states that the present invention is illustrated by the above examples of highly abrasion resistant printable TPU films of the present invention and the process for making the same, but the present invention is not limited to the above detailed process, i.e. it is not meant that the present invention must rely on the above detailed process to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A printable TPU film characterized by being prepared from a feedstock comprising the following components:
2. the printable TPU film of claim 1 wherein the polyester polyol has a number average molecular weight of 600-1800.
3. The printable TPU film of claim 1 or 2 wherein the polyether polyol has a number average molecular weight of 3000-5000; preferably 3400 and 3800.
4. The printable TPU film of any of claims 1-3 where the polyether polyol is an acrylonitrile graft modified polyether polyol.
5. The printable TPU film of any of claims 1-4 where the alkoxy poly (oxyalkylene) glycol has a number average molecular weight of 1000-1500;
preferably, in the alkoxy poly (oxyalkylene) glycol, the number of carbon atoms of the alkoxy group is 1 to 5 and the number of carbon atoms of the oxyalkylene group is 2 to 4.
6. The method of making a printable TPU film of any of claims 1-5 where the method of making comprises the steps of:
(1) adding toluene diisocyanate, polyester polyol, polyether polyol, alkoxy poly (oxyalkylene) glycol and dipentaerythritol hexaacrylate into a container, and dehydrating in vacuum under the stirring condition;
(2) adding a chain extender and a catalyst into the material obtained in the step (1) for mixing reaction;
(3) and (3) adding the material reacted in the step (2) into a double-screw extruder for extrusion molding to obtain the printable TPU film.
7. The method according to claim 6, wherein the temperature of the vacuum dehydration in the step (1) is 60 to 80 ℃;
preferably, the vacuum dehydration time in step (1) is 2 to 6 hours.
8. The method as claimed in claim 6 or 7, wherein the stirring rate in step (1) is 100-170 r/min.
9. The production method according to any one of claims 6 to 8, wherein the temperature of the mixing reaction in step (2) is 50 to 80 ℃;
preferably, the time of the mixing reaction in the step (2) is 1 to 5 hours.
10. The method as claimed in any one of claims 6 to 9, wherein the temperature of the feeding section of the twin-screw extruder in step (3) is 120-.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103890113A (en) * | 2012-05-30 | 2014-06-25 | Lg化学株式会社 | Aqueous composition, optical film including the same, polarizing plate using the same, and liquid crystal display device using the same |
| US20140275305A1 (en) * | 2013-03-15 | 2014-09-18 | Imperial Sugar Company | Polyurethanes, polyurethane foams and methods for their manufacture |
| CN109564321A (en) * | 2016-08-17 | 2019-04-02 | 株式会社Lg化学 | Optical film with excellent adhesive strength and durability and including its light polarizing film |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103890113A (en) * | 2012-05-30 | 2014-06-25 | Lg化学株式会社 | Aqueous composition, optical film including the same, polarizing plate using the same, and liquid crystal display device using the same |
| US20140275305A1 (en) * | 2013-03-15 | 2014-09-18 | Imperial Sugar Company | Polyurethanes, polyurethane foams and methods for their manufacture |
| CN109564321A (en) * | 2016-08-17 | 2019-04-02 | 株式会社Lg化学 | Optical film with excellent adhesive strength and durability and including its light polarizing film |
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