CN104212160A - Transparent TPU (thermoplastic polyurethane) film with high yellowing-resistance and preparation method thereof - Google Patents
Transparent TPU (thermoplastic polyurethane) film with high yellowing-resistance and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a transparent TPU (thermoplastic polyurethane) film with high yellowing-resistance. The transparent TPU film comprises the following components: TPU particles, phosphate without a benzene ring, maleic anhydride-grafted co-polypropylene, an ultraviolet light absorber, hydrogen-containing silicone oil and an antioxidant. A preparation method for the highly-yellowing-resistant type transparent TPU film comprises the following steps: (1) pre-drying all components; (2) mixing all dried components, and extruding and molding by virtue of a casting machine to obtain the TPU film. The film has good yellowing resistance, long tensile elongation and high tensile strength.
Description
Technical field
The present invention relates to a kind of TPU film and preparation method thereof, particularly relate to a kind of high Yellowing-resistant transparent TPU film and preparation method thereof.
Background technology
TPU (Thermoplastic polyyrethane, thermoplastic polyurethane) be a kind of novel organic polymer synthetic materials, belong to compound, English trade(brand)name: Flexible polyurethane, that a kind of properties is excellent, rubber rubber can be replaced, soft polyvinyl chloride material PVC.Such as it has excellent physicals, such as wear resistance, and screen resilience is all better than conventional polyurethanes, PVC, and ageing resistance is better than rubber, can be described as the optimal material of alternative PVC and PU, is called novel polymer material in the world.
Thermoplastic polyurethane has many uses general, such as, can be used for footwear as sports shoes Logo, sports shoes air cushion, climbing boot, snowshoe, golf shoes, ice skate, fabric and laminated material inside, become clothing as snow clothing, raincoat, wind coat, cold-proof jacket, field jacket, paper diaper, physiological brief, in fabric matrix material (Waterproof Breathable), pharmaceutical is as operating coat, cap, footwear, hospital's mattress, ice bag, bandage, plasma bags, surgery wrapping cloth, mouth mask, Deng fabric and material inside, operation table air bag, national defence articles for use are as fuel tanker, and overlay film sealed up for safekeeping by weapon, camp window, military water bag, vestlifejacket, fills fabric and the fabric inside of motorboat etc., air bag, and sporting goods is as football surface and inner bag, air mattress, lister bag, ski glove (waterproof bag), submarine armor, snow clothing, swimsuit, ski, trade mark, air bag, sweater, the fabrics such as weight reducing clothing and inside material, industrial goods is as loudspeaker drum paper rubber edge, water-proof strip, sound insulation material, fire proofing wood, fire-protection suit, bunker clothing, the fabrics such as asbeston and inside matrix material, electric wire jacket material, other purposes are as mobile phone key, plastic inflatable toy, sheet, tablecloth, shower curtain, furniture cloth, apron, piano, computor-keyboard, the fabrics such as overlay film and inside material.
Polyurethane termoplastic elastomer has polyester type and polyether-type two class, and the random spherical or cylindrical particle of white, relative density 1.10-1.25, polyether-type relative density is less than polyester type.The outstanding feature of polyurethane termoplastic elastomer is excellent in abrasion resistance, ozone resistance is fabulous, hardness is large, intensity is high, good springiness, low temperature resistant, have good oil resistant, chemical-resistant resistance and environmental resistance, in wet environment, polyether-type Ester hydrolysis stability far exceedes polyester type.Polyether-type thermoplastic polyurethane elastomer is the large class of one in Polyurethane Thermoplastic Elastomer, is generally synthesized by polytetramethylene ether diol (PTMGE), MDI and small molecule chain extender.Compared with polyester type Polyurethane Thermoplastic Elastomer, Polyether-type thermoplastic polyurethane elastomer has excellent low-temperature performance, anti-hydrolytic performance and elasticity, obtain in film, electric wire, spandex fibre etc. and apply widely, also more and more deep to its research.
As CN 103193950 A discloses a kind of Polyether-type thermoplastic polyurethane elastomer and preparation method thereof, described Polyether-type thermoplastic polyurethane elastomer is made up of 40 ~ 55% oligopolymer dibasic alcohol, 30 ~ 45% isocyanic ester, 5 ~ 20% chainextenders and 0.05 ~ 0.2% oxidation inhibitor, namely its preparation method adds oxidation inhibitor in oligopolymer dibasic alcohol, vacuumizes the oligopolymer dibasic alcohol containing oxidation inhibitor that dewaters to obtain; By chainextender vacuum hydro-extraction process; Isocyanic ester constant temperature oil bath is dissolved; The chainextender of the oligopolymer dibasic alcohol containing oxidation inhibitor and vacuum hydro-extraction process is mixed and heat regulation mixes to 90-100 DEG C with the isocyanic ester that oil bath has been dissolved, obtain when being stirred to 150 DEG C block elements in 80 DEG C of baking oven slakings, pulverize, be placed in that twin-screw extrusion unit is extruded, Qie La, dry up rear injection moulding machine injection moulding, flatness modulus must be had, longer elongation at break, the Polyether-type thermoplastic polyurethane elastomer that tensile strength scope is adjustable.
In addition, the application of TPU film is now more and more extensive, and also more and more higher to its requirement, the transparent TPU film as yellowing resistance also becomes one of demand.
Summary of the invention
One of the object of the invention is to provide a kind of high Yellowing-resistant transparent TPU film.Described TPU film is transparent and has excellent anti-yellowing property, also has longer elongation at break and stronger tensile strength.
For reaching above-mentioned purpose, the present invention adopts following technical scheme:
A kind of high Yellowing-resistant transparent TPU film, by mass percentage, containing following component:
According to TPU film of the present invention, by mass percentage, containing following component:
According to TPU film of the present invention, the hardness of described TPU particle is 60-75HD.
According to TPU film of the present invention, described UV light absorber is 2-(2 ˊ-hydroxyl-5 ˊ-aminomethyl phenyl) benzotriazole.
Preferably, described oxidation inhibitor is oxidation inhibitor TPP and/or antioxidant TNP.
Preferably, described TPU particle is prepared from by following component, described component by mass percentage, containing polyoxyethylene glycol 20-35%, poly phosphazene 5-25%, tolylene diisocyanate 10-25%, butyleneglycol
10-30%, without the phosphorous acid ester 1-5% of phenyl ring, containing hydrogen silicone oil 1-5%, and adopts preparation with the following method:
(1) polyoxyethylene glycol is vacuumized dehydration at 70-80 DEG C under 0.2-0.5kPa vacuum;
(2) dewater under butyleneglycol 0.2-0.5kPa vacuum 85-95 DEG C; Melt at tolylene diisocyanate 57-68 DEG C;
(3) more than 0.5h is heated at the butyleneglycol after step (1) gained mixture and step (2) being dewatered is blended in 80-90 DEG C;
(4) tolylene diisocyanate after step (2) being melted mixes with step (3) gained mixture and other components, stirs more than 0.5h, then more than slaking 12h at 85-95 DEG C at 145-155 DEG C;
(5) by step (4) products therefrom granulation and get final product.
An object of the present invention is also to provide the preparation method according to TPU film of the present invention, comprises the steps:
(1) all components is dry in advance;
(2) by all dried component mixing, described TPU film is namely obtained through casting machine extrusion moulding.
According to preparation method of the present invention, the temperature of step (1) described drying is 80 ~ 90 DEG C, such as, be 83 DEG C, 86 DEG C, 89 DEG C etc., and the dry time is 2 ~ 3h, such as, be 2.1h, 2.5h, 2.8h etc.
According to preparation method of the present invention, each section of temperature of step (2) described casting machine arranges as follows: barrel temperature is 125-145 DEG C; Filter screen temperature is 160-170 DEG C; Elbow temperature is 210-230 DEG C; Connection temperature is 210-230 DEG C; Die head temperature is 210-230 DEG C.
The TPU film that the present invention obtains is transparent and has higher elongation at break, tensile strength, has excellent anti-yellowing property simultaneously.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.
A kind of high resistance to yellow type transparent TPU film, by mass percentage, containing following component:
(1) by all components at 80 ~ 90 DEG C of dry 2-3h in advance;
(2) by all dried component mixing, described TPU film is namely obtained through casting machine extrusion moulding.
Embodiment 1
A kind of high resistance to yellow type transparent TPU film, by mass percentage, containing following component:
(1) by all components at 80 DEG C of dry 3h in advance;
(2) by all dried component mixing, namely obtain described TPU film through casting machine extrusion moulding, each section of temperature of described casting machine arranges as follows: barrel temperature is 145 DEG C; Filter screen temperature is 170 DEG C; Elbow temperature is 210 DEG C; Connecting temperature is 210 DEG C; Die head temperature is 230 DEG C;
Wherein, described TPU particle by mass percentage, containing following component:
(1) polyoxyethylene glycol is vacuumized dehydration at 80 DEG C under 0.2kPa vacuum;
(2) dewater at lower for butyleneglycol 0.5kPa vacuum 85 DEG C; Melt at tolylene diisocyanate 57 DEG C;
(3) 1h is heated at the butyleneglycol after step (1) gained mixture and step (2) being dewatered is blended in 80 DEG C;
(4) tolylene diisocyanate after step (2) being melted mixes with step (3) gained mixture and other components, stirs 0.5h, then slaking 20h at 85 DEG C at 155 DEG C;
(5) by step (4) products therefrom granulation and get final product.
The thickness of obtained film is 0.04mm.
Embodiment 2
A kind of high resistance to yellow type transparent TPU film, by mass percentage, containing following component:
(1) by all components at 90 DEG C of dry 2h in advance;
(2) by all dried component mixing, namely obtain described TPU film through casting machine extrusion moulding, each section of temperature of described casting machine arranges as follows: barrel temperature is 125 DEG C; Filter screen temperature is 160 DEG C; Elbow temperature is 230 DEG C; Connecting temperature is 230 DEG C; Die head temperature is 210 DEG C;
Wherein, described TPU particle by mass percentage, containing following component:
(1) polyoxyethylene glycol is vacuumized dehydration at 70 DEG C under 0.5kPa vacuum;
(2) dewater at lower for butyleneglycol 0.2kPa vacuum 95 DEG C; Melt at tolylene diisocyanate 68 DEG C;
(3) 0.5h is heated at the butyleneglycol after step (1) gained mixture and step (2) being dewatered is blended in 90 DEG C;
(4) tolylene diisocyanate after step (2) being melted mixes with step (3) gained mixture and other components, stirs 3h, then slaking 12h at 90 DEG C at 150 DEG C;
(5) by step (4) products therefrom granulation and get final product.
The thickness of obtained film is 0.03mm.
Embodiment 3
A kind of high resistance to yellow type transparent TPU film, by mass percentage, containing following component:
(1) by all components at 85 DEG C of dry 2.5h in advance;
(2) by all dried component mixing, namely obtain described TPU film through casting machine extrusion moulding, each section of temperature of described casting machine arranges as follows: barrel temperature is 130 DEG C; Filter screen temperature is 165 DEG C; Elbow temperature is 220 DEG C; Connecting temperature is 220 DEG C; Die head temperature is 210 DEG C;
Wherein, TPU particle by mass percentage, containing following component:
(1) polyoxyethylene glycol is vacuumized dehydration at 75 DEG C under 0.4kPa vacuum;
(2) dewater at lower for butyleneglycol 0.3kPa vacuum 90 DEG C; Melt at tolylene diisocyanate 60 DEG C;
(3) 2h is heated at the butyleneglycol after step (1) gained mixture and step (2) being dewatered is blended in 85 DEG C;
(4) tolylene diisocyanate after step (2) being melted mixes with step (3) gained mixture and other components, stirs 3h, then slaking 30h at 95 DEG C at 145 DEG C;
(5) by step (4) products therefrom granulation and get final product.
The thickness of obtained film is 0.06mm.
Respectively the TPU film of gained in above-described embodiment 1-3 is cut into long 25mm, wide 6.1mm, the test piece of thick 2mm, then GB/T 528-1998 (ISO 37:2005) is pressed on electronic universal tension testing machine, in temperature (23 ± 2) DEG C, humidity (50 ± 2%), draw speed is measure its mechanics performance determining under the condition of 200mm/min, and measures the yellowness index change of transparency and UV illumination 24h; The results are shown in following table 1.
Table 1
As can be seen from the table, the TPU film that the present invention obtains not only length of fracture, tensile strength is high, and anti-yellowing property is excellent.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (8)
1. a high resistance to yellow type transparent TPU film, is characterized in that, by mass percentage, containing following component:
2. TPU film according to claim 1, is characterized in that, by mass percentage, containing following component:
3. TPU film according to claim 1 and 2, is characterized in that, the hardness of described TPU particle is 60-75HD.
4. the TPU film according to any one of claim 1-3, is characterized in that, described UV light absorber is 2-(2 ˊ-hydroxyl-5 ˊ-aminomethyl phenyl) benzotriazole;
Preferably, described oxidation inhibitor is oxidation inhibitor TPP and/or antioxidant TNP.
5. the TPU film according to any one of claim 1-4, it is characterized in that, described TPU particle is prepared from by following component, described component by mass percentage, containing polyoxyethylene glycol 20-35%, poly phosphazene 5-25%, tolylene diisocyanate 10-25%, butyleneglycol 10-30%, without the phosphorous acid ester 1-5% of phenyl ring, containing hydrogen silicone oil 1-5%, and adopt preparation with the following method:
(1) polyoxyethylene glycol is vacuumized dehydration at 70-80 DEG C under 0.2-0.5kPa vacuum;
(2) dewater under butyleneglycol 0.2-0.5kPa vacuum 85-95 DEG C; Melt at tolylene diisocyanate 57-68 DEG C;
(3) more than 0.5h is heated at the butyleneglycol after step (1) gained mixture and step (2) being dewatered is blended in 80-90 DEG C;
(4) tolylene diisocyanate after step (2) being melted mixes with step (3) gained mixture and other components, stirs more than 0.5h, then more than slaking 12h at 85-95 DEG C at 145-155 DEG C;
(5) by step (4) products therefrom granulation and get final product.
6. the preparation method of the TPU film described in any one of claim 1-5, comprises the steps:
(1) all components is dry in advance;
(2) by all dried component mixing, described TPU film is namely obtained through casting machine extrusion moulding.
7. preparation method according to claim 6, is characterized in that, the temperature of step (1) described drying is 80 ~ 90 DEG C, and the dry time is 2 ~ 3h.
8. preparation method according to claim 6, is characterized in that, each section of temperature of step (2) described casting machine arranges as follows: barrel temperature is 125-145 DEG C; Filter screen temperature is 160-170 DEG C; Elbow temperature is 210-230 DEG C; Connection temperature is 210-230 DEG C; Die head temperature is 210-230 DEG C.
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| CN201410479946.0A CN104212160A (en) | 2014-09-18 | 2014-09-18 | Transparent TPU (thermoplastic polyurethane) film with high yellowing-resistance and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906780A (en) * | 2016-07-05 | 2016-08-31 | 安徽三彩工贸有限责任公司 | Low temperature resistant polyurethane rigid foamed plastic |
| CN107857986A (en) * | 2017-11-28 | 2018-03-30 | 广东聚航新材料研究院有限公司 | A kind of transparent yellowing-resistant TPU casting films and its processing method |
| CN113930004A (en) * | 2021-12-17 | 2022-01-14 | 河北环宸科技有限公司 | Transparency modifier for gas-phase anti-rust film |
| CN115340762A (en) * | 2021-10-25 | 2022-11-15 | 德星技术（苏州）有限公司 | High-transparency anti-yellowing automobile protection film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101061067A (en) * | 2003-07-14 | 2007-10-24 | 罗迪亚公司 | Improved color stability of isocyanates |
| CN102782037A (en) * | 2009-12-11 | 2012-11-14 | 陶氏环球技术有限责任公司 | Thermoplastic polymer blends comprising dynamically crosslinked polyurethane in an olefin polymer matrix |
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2014
- 2014-09-18 CN CN201410479946.0A patent/CN104212160A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101061067A (en) * | 2003-07-14 | 2007-10-24 | 罗迪亚公司 | Improved color stability of isocyanates |
| CN102782037A (en) * | 2009-12-11 | 2012-11-14 | 陶氏环球技术有限责任公司 | Thermoplastic polymer blends comprising dynamically crosslinked polyurethane in an olefin polymer matrix |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906780A (en) * | 2016-07-05 | 2016-08-31 | 安徽三彩工贸有限责任公司 | Low temperature resistant polyurethane rigid foamed plastic |
| CN107857986A (en) * | 2017-11-28 | 2018-03-30 | 广东聚航新材料研究院有限公司 | A kind of transparent yellowing-resistant TPU casting films and its processing method |
| CN115340762A (en) * | 2021-10-25 | 2022-11-15 | 德星技术（苏州）有限公司 | High-transparency anti-yellowing automobile protection film and preparation method thereof |
| CN113930004A (en) * | 2021-12-17 | 2022-01-14 | 河北环宸科技有限公司 | Transparency modifier for gas-phase anti-rust film |
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