WO2021208506A1 - Temperature-resistant lettering film and preparation method therefor - Google Patents

Abstract

A temperature-resistant lettering film and a preparation method therefor. Raw materials for preparing the temperature-resistant lettering film comprise the following components in parts by weight: 90-100 parts by weight of TPU particles, 10-30 parts by weight of methyl vinyl silicone rubber, 5-15 parts by weight of polyethylene terephthalate, 0.1-5.0 parts by weight of a processing lubricant, 0.1-5.0 parts by weight of an antioxidant, and 0.1-5.0 parts by weight of an anti-UV agent. The combination of the TPU particles, methyl vinyl silicone rubber, and polyethylene terephthalate enables a TPU material to have high heat resistance, thereby improving the temperature resistance of the lettering film. The lettering film is stable in quality, environmentally-friendly, and good in wear resistance, high temperature resistance, and flexural resistance, and has extremely good stability in the production process and a good surface effect, and thus has a good surface lettering effect.

Description

Temperature-resistant lettering film and preparation method thereof

This disclosure is based on a Chinese patent application with an application number of 202010298559.2 and an application date of April 16, 2020, and claims the priority of the Chinese patent application. The entire content of the Chinese patent application is hereby incorporated by reference into this application.

Technical field

The invention belongs to the technical field of polymer materials, and relates to a temperature-resistant lettering film and a preparation method thereof.

Background technique

With the improvement of people’s living standards, people’s pursuit of enzymes is also getting higher and higher, especially people expect to show different patterns on clothes, shoes, gloves, hats and other daily necessities to get better visual effects and good visual effects. The touch.

In the prior art, the patterns are mostly obtained by silk printing, but its production efficiency is low, the defective products are high, the production site requirements are many, and the technical requirements for workers are high. Thermal transfer is a more novel method than silk printing on fabrics or textiles. In the process of making patterns, most of the lettering films on the market are mostly TPU lettering films, but the TPU thermal transfer lettering films currently on the market have a stiff hand feel, poor softness, and poor weather resistance. It is easy to change in the sun, especially easy to yellow, which reduces the appearance and has a short service life.

Therefore, in this field, it is desired to obtain a lettering film that is abrasion-resistant, weather-resistant, flex-resistant, stable, and resistant to yellowing.

Summary of the invention

In view of the shortcomings of the prior art, the purpose of the present invention is a temperature-resistant lettering film and a preparation method thereof.

To achieve this goal, the present invention adopts the following technical solutions:

In one aspect, the present invention provides a temperature-resistant lettering film. The raw materials for preparing the temperature-resistant lettering film include the following components by weight:

In the present invention, the combination of TPU particles, methyl vinyl silicone rubber and polyethylene terephthalate can make the TPU material have higher heat resistance and improve the temperature resistance of the lettering film.

In the present invention, in the raw material for preparing the temperature-resistant lettering film, the amount of the TPU particles can be 90 parts by weight, 91 parts by weight, 92 parts by weight, 93 parts by weight, 94 parts by weight, 95 parts by weight, 96 parts by weight. Parts by weight, 97 parts by weight, 98 parts by weight, 99 parts by weight or 100 parts by weight.

In the present invention, in the raw material for preparing the temperature-resistant lettering film, the amount of the methyl vinyl silicone rubber may be 10 parts by weight, 12 parts by weight, 15 parts by weight, 17 parts by weight, 19 parts by weight, 20 parts by weight. Parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, or 30 parts by weight.

In the present invention, in the raw material for preparing the temperature-resistant lettering film, the amount of polyethylene terephthalate may be 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight , 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight or 15 parts by weight.

In the present invention, in the preparation raw material of the temperature-resistant lettering film, the amount of the processing slip agent may be 0.1 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 1.3 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.3 parts by weight, 2.5 parts by weight, 2.8 parts by weight, 3 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.5 parts by weight, 4.8 parts by weight, or 5 parts by weight.

In the present invention, in the raw material for preparing the temperature-resistant lettering film, the amount of the antioxidant may be 0.1 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 1.3 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.3 parts by weight, 2.5 parts by weight, 2.8 parts by weight, 3 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.5 parts by weight, 4.8 parts by weight, or 5 parts by weight.

In the present invention, in the raw material for preparing the temperature-resistant lettering film, the amount of the anti-UV agent can be 0.1 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 1.3 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.3 parts by weight, 2.5 parts by weight, 2.8 parts by weight, 3 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.5 parts by weight, 4.8 parts by weight, or 5 parts by weight.

Preferably, the raw materials for preparing the TPU particles include the following components in parts by weight:

In the present invention, the amount of diisocyanate used in the preparation of the TPU particles can be 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight. Parts, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, or 30 parts by weight.

Preferably, the diisocyanate is any one or a combination of at least two of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate or hexamethylene diisocyanate .

In the present invention, the amount of polyester polyol used in the preparation of the TPU particles can be 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, or 50 parts by weight.

Preferably, the polyester polyol is polyethylene adipate diol, polyethylene adipate-1,2-propylene glycol ester diol, polyethylene adipate-1,4- Any one or a combination of at least two of butanediol ester diol or poly-1,4-butanediol adipate diol.

Preferably, the number average molecular weight of the polyester polyol is 1000-5000, such as 1000, 1200, 1400, 1600, 1800, 2000, 2300, 2500, 2800, 3000, 3300, 3500, 3800, 4000, 4300, 4500 , 4800 or 5000.

In the present invention, in the raw material for preparing the TPU particles, the amount of chain extender can be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight. Parts by weight, 9 parts by weight, or 10 parts by weight.

In the present invention, in the raw material for preparing the TPU particles, the chain extender is 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol or 1,3-butanediol. Any one or a combination of at least two of the diols.

In the present invention, the amount of catalyst used in the preparation of the TPU particles can be 3 parts by weight, 3.3 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.2 parts by weight, 4.5 parts by weight, 4.8 parts by weight. Or 5 parts by weight.

Preferably, the catalyst is any one or a combination of at least two of organic bismuth, organic tin or titanate catalysts.

In the present invention, in the raw material for the preparation of TPU particles, the amount of white carbon black can be 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight. Parts by weight, 13 parts by weight, 14 parts by weight, or 15 parts by weight.

In the present invention, the amount of mimontmorillonite used in the preparation of the TPU particles can be 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, or 15 parts by weight.

In the present invention, in the preparation of the TPU particles, the amount of antioxidant can be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight Parts by weight, 9 parts by weight, or 10 parts by weight.

Preferably, the antioxidant of the present invention is any one or a mixture of at least two of antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant TPP or antioxidant TNP.

Preferably, the number average molecular weight of the polyethylene terephthalate is 2000-8000, for example 2000, 2300, 2500, 2800, 3000, 3500, 4000, 4500, 5000, 5500, 5800, 6000, 6500, 6800 , 7000, 7500, 7800 or 8000.

Preferably, the processing slip agent is any one or a combination of at least two of calcium stearate, magnesium stearate, zinc stearate or barium stearate.

Preferably, the anti-UV agent includes salicylate anti-UV agent, benzophenone anti-UV agent, benzotriazole anti-UV agent, substituted acrylonitrile anti-UV agent, triazine anti-UV agent or hindered Any one or a combination of at least two of the amine anti-UV agents.

On the other hand, the present invention provides a method for preparing the temperature-resistant lettering film as described above, and the preparation method includes the following steps:

The TPU particles, processing slip agent, antioxidant, and anti-UV agent are evenly mixed, dried, and extruded to obtain a temperature-resistant lettering film.

Preferably, the drying is dried in a desiccant dryer for 4-6 hours, for example, 4 hours, 4.3 hours, 4.5 hours, 4.8 hours, 5 hours, 5.3 hours, 5.5 hours, 5.8 hours, or 6 hours.

Preferably, the drying temperature is 85-100°C, such as 85°C, 88°C, 90°C, 93°C, 95°C, 98°C or 100°C.

Preferably, after the extrusion, the mirror surface is pressed, cooled, trimmed, and rewinded under pressure to obtain the temperature-resistant lettering film.

Preferably, the TPU particles are prepared by the following method:

A. Add white carbon black, rice montmorillonite, and antioxidant to the polyester polyol and mix uniformly to obtain the first mixture;

B. Add the catalyst to the chain extender and mix evenly to obtain a second mixture;

C. The diisocyanate is mixed with the first mixture and the second mixture, reacted, and then extruded, pelletized, and vacuum dried to obtain the TPU particles.

Preferably, the temperature of the reaction in step C is 70-100°C, such as 70°C, 75°C, 78°C, 80°C, 82°C, 85°C, 88°C, 90°C, 92°C, 95°C, 98°C or 100°C.

Preferably, the reaction time in step C is 2-10h, such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 6h, 7h, 8h, 9h or 10h.

Preferably, the temperature of the extrusion in step C is 150°C to 200°C, such as 150°C, 155°C, 158°C, 160°C, 165°C, 168°C, 170°C, 175°C, 178°C, 180°C, 185°C ℃, 188℃, 190℃, 195℃, 198℃ or 200℃.

Compared with the prior art, the present invention has the following beneficial effects:

In the present invention, the combination of TPU particles, methyl vinyl silicone rubber and polyethylene terephthalate can make the TPU material have higher heat resistance and improve the temperature resistance of the lettering film. The engraving film of the invention has stable quality, is green and environmentally friendly, has good wear resistance, high temperature resistance, and flexural resistance, and has excellent stability and surface effect during the production process, and its surface engraving effect is very good.

Detailed ways

The technical solution of the present invention will be further explained by specific embodiments below.

Example 1

In this embodiment, a temperature-resistant lettering film is provided, and the raw materials for preparing the temperature-resistant lettering film include the following components by weight:

The raw materials for the preparation of TPU particles include the following components in parts by weight:

The preparation method of the temperature-resistant lettering film is as follows:

(1) Preparation of TPU particles:

A. Add white carbon black, rice montmorillonite, and antioxidant to the polyester polyol and mix uniformly to obtain the first mixture;

B. Add the catalyst to the chain extender and mix evenly to obtain a second mixture;

C. Mix the diisocyanate with the first mixture and the second mixture, react at 80°C for 5 hours, then extrude at 160°C, pelletize, and dry in vacuum to obtain the TPU particles.

(2) Mix the TPU particles, processing slip agent, antioxidant, and anti-UV agent uniformly, and dry it in a desiccant dryer at 85°C for 6 hours, extrude, press on the mirror, cool, trim, and rewind under pressure , Get a temperature-resistant lettering film.

Example 2

In this embodiment, a temperature-resistant lettering film is provided, and the raw materials for preparing the temperature-resistant lettering film include the following components by weight:

The raw materials for the preparation of TPU particles include the following components in parts by weight:

The preparation method of the temperature-resistant lettering film is as follows:

(1) Preparation of TPU particles:

A. Add white carbon black, rice montmorillonite, and antioxidant to the polyester polyol and mix uniformly to obtain the first mixture;

B. Add the catalyst to the chain extender and mix evenly to obtain a second mixture;

C. Mix the diisocyanate with the first mixture and the second mixture, react at 70°C for 10 hours, then extrude at 150°C, pelletize, and dry in vacuum to obtain the TPU particles.

(2) Mix the TPU particles, processing slip agent, antioxidant, and anti-UV agent evenly, dry them in a desiccant dryer at 90°C for 5 hours, extrude, press on the mirror, cool, trim, and rewind under pressure , Get a temperature-resistant lettering film.

Example 3

In this embodiment, a temperature-resistant lettering film is provided, and the raw materials for preparing the temperature-resistant lettering film include the following components by weight:

The raw materials for the preparation of TPU particles include the following components in parts by weight:

The preparation method of the temperature-resistant lettering film is as follows:

(1) Preparation of TPU particles:

A. Add white carbon black, rice montmorillonite, and antioxidant to the polyester polyol and mix uniformly to obtain the first mixture;

B. Add the catalyst to the chain extender and mix evenly to obtain a second mixture;

C. Mix the diisocyanate with the first mixture and the second mixture, react at 100°C for 2 hours, then extrude at 180°C, pelletize, and dry in vacuum to obtain the TPU particles.

(2) Mix the TPU particles, processing slip agent, antioxidant, and anti-UV agent evenly, dry in a dehumidifying dryer at 100°C for 4 hours, extrude, press on the mirror, cool, trim, and rewind under pressure , Get a temperature-resistant lettering film.

Example 4

In this embodiment, a temperature-resistant lettering film is provided, and the raw materials for preparing the temperature-resistant lettering film include the following components by weight:

The raw materials for the preparation of TPU particles include the following components in parts by weight:

The preparation method of the temperature-resistant lettering film is as follows:

(1) Preparation of TPU particles:

A. Add white carbon black, rice montmorillonite, and antioxidant to the polyester polyol and mix uniformly to obtain the first mixture;

B. Add the catalyst to the chain extender and mix evenly to obtain a second mixture;

C. Mix the diisocyanate with the first mixture and the second mixture, react at 90°C for 4 hours, and then extrude at 200°C, pelletize, and dry in vacuum to obtain the TPU particles.

(2) Mix the TPU particles, processing slip agent, antioxidant and anti-UV agent uniformly, dry in a dehumidifying dryer at 95°C for 5 hours, extrude, press on the mirror, cool, trim, and rewind under pressure , Get a temperature-resistant lettering film.

Example 5

In this embodiment, a temperature-resistant lettering film is provided, and the raw materials for preparing the temperature-resistant lettering film include the following components by weight:

The raw materials for the preparation of TPU particles include the following components in parts by weight:

The preparation method of the temperature-resistant lettering film is as follows:

(1) Preparation of TPU particles:

A. Add white carbon black, rice montmorillonite, and antioxidant to the polyester polyol and mix uniformly to obtain the first mixture;

B. Add the catalyst to the chain extender and mix evenly to obtain a second mixture;

C. Mix the diisocyanate with the first mixture and the second mixture, react at 80°C for 6 hours, and then extrude at 170°C, pelletize, and dry in vacuum to obtain the TPU particles.

(2) Mix the TPU particles, processing slip agent, antioxidant, and anti-UV agent uniformly, dry in a dehumidifying dryer at 85°C for 4 hours, extrude, press on the mirror, cool, trim, and rewind under pressure , Get a temperature-resistant lettering film.

Comparative example 1

This comparative example is different from Example 1 only in that the raw material for the preparation of the temperature-resistant lettering film does not include methyl vinyl silicone rubber, and the amount of polyethylene terephthalate is 23 parts by weight.

Comparative example 2

This comparative example is different from Example 1 only in that the raw materials for the preparation of the temperature-resistant lettering film do not include polyethylene terephthalate, and the amount of methyl vinyl silicone rubber is 23 parts by weight.

Comparative example 3

This comparative example is different from Example 1 only in that the amount of methyl vinyl silicone rubber used in the preparation of the temperature-resistant lettering film is 5 parts by weight.

Comparative example 4

This comparative example is different from Example 1 only in that the amount of methyl vinyl silicone rubber used in the preparation of the temperature-resistant lettering film is 40 parts by weight.

Comparative example 5

This comparative example is different from Example 1 only in that the amount of polyethylene terephthalate in the raw material for the preparation of the temperature-resistant lettering film is 1 part by weight.

Comparative example 6

This comparative example is different from Example 1 only in that the amount of polyethylene terephthalate in the raw material for the preparation of the temperature-resistant lettering film is 20 parts by weight.

The above Examples 1-5 and Comparative Examples 1-6 were tested for tensile strength, tear strength, weather resistance, washing resistance, etc. The test methods are as follows:

Tensile strength: GB/T 34220-2017

Tearing strength: GB/T529-2008;

Weather resistance: the time for no yellowing and detachment of the lettering film when exposed to the sun at 30-38°C.

The specific steps of the washing resistance test are: place the test sample in a washing machine with warm water at 40°C, add washing powder, and wash it at 30 min/time, and test the number of times the sample's lettering film peels off or interlayer separation occurs. .

The test results are shown in Table 1.

It can be seen from the test results in Table 1 that the engraving film of the present invention has good stability, good temperature resistance, stable quality of the engraving film, and is not easy to peel off or interlayer detachment, and is not easy to yellow.

The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the temperature-resistant lettering film of the present invention and the preparation method thereof, but the present invention is not limited to the above-mentioned embodiments, which does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc. fall within the scope of protection and disclosure of the present invention.

Claims (10)

1. A temperature-resistant lettering film, characterized in that the raw materials for preparing the temperature-resistant lettering film include the following components by weight:

   
2. The temperature-resistant lettering film according to claim 1, wherein the raw materials for the preparation of the TPU particles comprise the following components by weight:

   
3. The temperature-resistant lettering film according to claim 1 or 2, wherein the diisocyanate is toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, or hexamethylene diisocyanate. Any one or a combination of at least two of the methylene diisocyanates;

   Preferably, the polyester polyol is polyethylene adipate diol, polyethylene adipate-1,2-propylene glycol ester diol, polyethylene adipate-1,4- Any one or a combination of at least two of butanediol ester diol or poly-1,4-butanediol adipate diol;

   Preferably, the number average molecular weight of the polyester polyol is 1000-5000.
4. The temperature-resistant lettering film according to any one of claims 1-3, wherein the chain extender is 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-propanediol, and 1,4-propanediol. Any one or a combination of at least two of butanediol or 1,3-butanediol;

   Preferably, the catalyst is any one or a combination of at least two of organic bismuth, organic tin or titanate catalysts.
5. The temperature-resistant lettering film according to any one of claims 1-4, wherein the antioxidant is antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant TPP or antioxidant Any one or a mixture of at least two of the oxygen agents TNP.
6. The temperature-resistant lettering film according to any one of claims 1-5, wherein the number average molecular weight of the polyethylene terephthalate is 2000-8000;

   Preferably, the processing slip agent is any one or a combination of at least two of calcium stearate, magnesium stearate, zinc stearate or barium stearate.
7. The temperature-resistant lettering film according to any one of claims 1-6, wherein the anti-UV agent comprises a salicylate anti-UV agent, a benzophenone anti-UV agent, and a benzotriazole Any one or a combination of at least two of the anti-UV agent, substituted acrylonitrile-based anti-UV agent, triazine-based anti-UV agent, or hindered amine-based anti-UV agent.
8. The method for preparing a temperature-resistant lettering film according to any one of claims 1-7, wherein the method is: mixing TPU particles, processing slip agent, antioxidant, and anti-UV agent uniformly, and drying , Extrusion, to get temperature-resistant lettering film.
9. The preparation method according to claim 8, wherein the drying is dried in a dehumidifying dryer for 4-6 hours;

   Preferably, the drying temperature is 85-100°C;

   Preferably, after the extrusion, the mirror surface is pressed, cooled, trimmed, and rewinded under pressure to obtain the temperature-resistant lettering film.
10. The preparation method according to claim 8 or 9, wherein the TPU particles are prepared by the following method:

    A. Add white carbon black, rice montmorillonite, and antioxidant to the polyester polyol and mix uniformly to obtain the first mixture;

    B. Add the catalyst to the chain extender and mix evenly to obtain a second mixture;

    C. Mixing the diisocyanate with the first mixture and the second mixture, reacting, and then extruding, granulating, and vacuum drying to obtain the TPU particles;

    Preferably, the temperature of the reaction in step C is 70-100°C;

    Preferably, the reaction time of step C is 2-10h;

    Preferably, the temperature of the extrusion in step C is 150°C to 200°C.