Heat preservation and insulation type PETG light blocking film and processing technology thereof

Abstract

The invention relates to the technical field of research and development of PETG-based functional film materials, and discloses a heat-preservation and heat-insulation PETG light-blocking film and a processing technology thereof.The heat-preservation and heat-insulation PETG light-blocking film is prepared by synthesizing a light-blocking silane coupling agent based on a substitution reaction between a chlorine-based functional group and an amino functional group, performing surface modification treatment on nano titanium dioxide by using the light-blocking silane coupling agent, and performing heat-preservation and heat-insulation treatment on nano titanium dioxide by using the light-blocking silane coupling agent; then the light-blocking type silane coupling agent modified heat-insulation type nano filler is used as a modifier to prepare heat-insulation type printing ink; finally, the heat insulation type ink is printed on the front face of the milky white PETG film through gravure printing, two layers of black ink are printed on the back face of the milky white PETG material through inner printing, the heat preservation and heat insulation type PETG light blocking film is prepared, the light blocking rate of the heat preservation and heat insulation type PETG light blocking film within the wavelength range of 200-800 nm can reach 100%, the heat insulation capacity is very excellent, the production process is simple, operation is easy, and the heat preservation and heat insulation type PETG light blocking film is suitable for industrial production. The milky white PETG film is used for replacing a black and white film, so that the production cost can be effectively reduced.

Description

Technical Field

[0001] The invention relates to the technical field of research and development of PETG-based functional film materials, in particular to a heat-insulating PETG light-blocking film and a processing technology thereof. Background Art

[0002] PETG is a transparent, non-crystalline copolyester. The commonly used comonomer of PETG is 1,4-cyclohexanedimethanol (CHDM), whose full name is polyethylene terephthalate-1,4-cyclohexanedimethanol. It is a product of terephthalic acid (PTA), ethylene glycol (EG) and 1,4-cyclohexanedimethanol (CHDM) by ester exchange polycondensation. Compared with PET, it has more 1,4-cyclohexanedimethanol comonomer, and compared with PCT, it has more ethylene glycol comonomer. Therefore, the performance of PETG is very different from that of PET and PCT.

[0003] PETG sheet has outstanding toughness and high impact strength. Its impact strength is 3-10 times that of modified polyacrylates. It has a wide processing range, high mechanical strength and excellent flexibility. Compared with PVC, it has higher transparency, better gloss, is easy to print and has environmental advantages. It is widely used in various long-lasting daily necessities.

[0004] Light-blocking film, also known as black and white film, is mainly used for sunshade and heat insulation, preventing light penetration, and also plays a role in cooling. Black and white film has two sides, one is white and the other is black. At present, the black and white film process on the market uses white high-density PET film, one side of which is coated with a black nano-technology coating, and the other side is bonded with a bubble insulation film by Velcro. The production process is complicated, so its price cost is relatively high. In addition, the heat insulation effect of the black and white film by bonding the bubble insulation film with Velcro is not good, and the light-blocking effect is not very perfect. Summary of the invention

[0005] Black and white films are expensive and have imperfect heat-insulating and light-blocking properties. In order to improve the heat-insulating and light-blocking properties of the light-blocking film and reduce the production cost of the light-blocking film, the present invention provides a heat-insulating and heat-insulating PETG light-blocking film and a processing technology thereof.

[0006] A processing technology for heat-insulating PETG light-blocking film comprises the following steps:

[0007] Step 1: prepare heat-insulating ink. The specific process is as follows:

[0008] Synthesizing a light-blocking silane coupling agent, and using the light-blocking silane coupling agent to perform surface modification on nano-titanium dioxide to obtain a heat-insulating nano-filler modified with the light-blocking silane coupling agent;

[0009] The connecting material, the heat-insulating nanofiller modified by the light-blocking silane coupling agent, the additive, propylene glycol methyl ether, ethanol, deionized water and the adhesion promoter are uniformly mixed to form a pre-dispersed color paste, and the pre-dispersed color paste is ground to obtain the heat-insulating ink;

[0010] Step 2, preparing black ink: adding carbon black, a binder, an additive, ethanol, propylene glycol methyl ether and deionized water into a disperser and mixing them evenly to form a pre-dispersed color paste, and grinding to obtain black ink;

[0011] Step three, printing is performed in a manner of inner printing and surface printing. The raw material film adopts a milky white PETG film, the surface printing is gravure printing, the gravure printing ink is a heat-insulating ink, and the inner printing is performed by printing two layers of black ink on the back of the milky white PETG material. The inner printing is performed on a printing machine with a 2-color flip frame through two black laser plates to obtain a heat-insulating PETG light-blocking film.

[0012] Preferably, the light-blocking silane coupling agent is: hindered aminotrimethoxysilane and / or hindered aminotriazinetrimethoxysilane.

[0013] Preferably, the formula of the thermal insulation ink is: 8-15 parts by weight of thermal insulation nanofiller modified with a light-blocking silane coupling agent, 30-50 parts by weight of polyamide resin, 10-30 parts by weight of styrene acrylic emulsion, 2-5 parts by weight of polyethylene micropowder wax with an average particle size of about 4.5-5.5 μm, 3-6 parts by weight of propylene glycol methyl ether, 3-6 parts by weight of ethanol, 8-12 parts by weight of deionized water, and 1-2 parts by weight of adhesion promoter ADP-W450.

[0014] Preferably, the formula of the black ink is: 10-15 parts by weight of carbon black, 30-50 parts by weight of alcohol-soluble polyurethane, 5-20 parts by weight of styrene acrylic emulsion, 2-5 parts by weight of oxidized polyethylene wax powder with an average particle size of about 7-9 μm, 5-9 parts by weight of ethanol, 5-10 parts by weight of propylene glycol methyl ether and 8-12 parts by weight of deionized water.

[0015] Preferably, the heat-insulating PETG light-blocking film has a light blocking rate of 100% within the wavelength range of 200-800nm.

[0016] The present invention has the following beneficial technical effects:

[0017] The invention uses 3-aminopropyltrimethoxysilane, 4-amino-2,2,6,6-tetramethylpiperidine and cyanuric chloride as raw materials, and utilizes the substitution reaction between chlorine functional groups and amino functional groups to synthesize light-blocking silane coupling agents (hindered aminotrimethoxysilane and hindered aminotriazinetrimethoxysilane); uses the light-blocking silane coupling agent to perform surface modification treatment on nano titanium dioxide to obtain heat-insulating nano fillers modified by the light-blocking silane coupling agent, and uses the fillers as modifiers to prepare heat-insulating ink; and uses the inner printing and outer printing method to print, wherein the raw material film adopts an opalescent PETG film, the outer printing is gravure printing, the gravure printing ink is a heat-insulating ink, and two layers of black ink are printed on the back of the opalescent PETG material for the inner printing, so as to prepare a heat-insulating PETG light-blocking film, wherein the light blocking rate of the film can reach 100% within the wavelength range of 200-800nm, and the film has very excellent heat-insulating capacity.

[0018] The production process of the invention is simple and easy to operate. The black and white film is expensive, about 42,000 yuan per ton, and the milky white PETG film is about 30,000 yuan per ton. Using the PETG film as the raw material film for processing instead of the black and white film can fully reduce the production cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is the spectrum scanning curve of thermal insulation PETG light-blocking film. DETAILED DESCRIPTION

[0020] Embodiment 1:

[0021] The hindered amino trimethoxysilane is synthesized by a method comprising: a substitution reaction between the amino (NH2) functional group of 4-amino-2,2,6,6-tetramethylpiperidine and the chlorine functional group of 3-chloropropyl trimethoxysilane, and a molar ratio of 4-amino-2,2,6,6-tetramethylpiperidine to 3-chloropropyl trimethoxysilane is controlled to be (1.01-1.03):1, thereby obtaining the hindered amino trimethoxysilane. The synthesis steps are as follows: 16.1 g of 4-amino-2,2,6,6-tetramethylpiperidine, 19.9 g of 3-chloropropyltrimethoxysilane, 41.5 g of potassium carbonate, 1.66 g of potassium iodide and 120 mL of anhydrous toluene are added into a flask, and the mixture is reacted at 60° C. for 10 h under nitrogen protection. After the reaction is completed, the mixture is filtered, the excess solvent is removed, and the mixture is dried to obtain hindered aminotrimethoxysilane, and the chemical structure and hydrogen spectrum characterization results are as follows:

[0022]

[0023] 1H NMR (400MHz, DMSO-d6, δ): 0.68-0.71 (t, 2H), 1.21-1.26 (d, 12H), 1.53-1.65 ( m, 6H), 1.82-1.85 (m, 2H), 2.59-2.62 (m, 2H), 3.08-3.15 (m, 1H), 3.56 (s, 9H);

[0024] The hindered amino triazine trimethoxysilane is synthesized by the following method: firstly, the amino functional group of 3-aminopropyl trimethoxysilane is subjected to substitution reaction with the chloro functional group of cyanuric chloride, and then the amino (NH2) functional group of 4-amino-2,2,6,6-tetramethylpiperidine is subjected to substitution reaction with the chloro functional group of cyanuric chloride, and the molar ratio of cyanuric chloride, 3-aminopropyl trimethoxysilane and 4-amino-2,2,6,6-tetramethylpiperidine is controlled to be 1:(1.01-1.03):(2.05-2.2) , and obtain hindered amino triazine trimethoxysilane. The specific synthesis steps are: 6.1g of cyanuric chloride, 6.2g of 3-aminopropyl trimethoxysilane, 41.5g of potassium carbonate, 1.66g of potassium iodide and 120mL of anhydrous toluene are added to a flask, and nitrogen protection is used to react at room temperature for 4h, and then 10.8g of 4-amino-2,2,6,6-tetramethylpiperidine is added, and the reaction is carried out at 80°C for 10h, and the excess solvent is filtered off and dried to obtain hindered amino triazine trimethoxysilane. Its chemical structure and hydrogen spectrum characterization results are as follows:

[0025]

[0026] 1 H NMR (400MHz, DMSO-d6, δ): 0.66-0.69 (t, 2H), 0.88 (s, 2H), 1.2-1.25 (d, 24H), 1.76-1.82 (m, 8H), 1.84-1.88(m, 2H), 3.5-3.53(m, 2H), 3.57(s, 9H), 3.86-.394(m, 2H), 6.84-6.92(m, 3H).

[0027] Embodiment 2:

[0028] A thermal insulation nanofiller modified with hindered aminotrimethoxysilane is prepared. The specific preparation method is as follows: 1 g of nano titanium dioxide, 0.2 g of hindered aminotrimethoxysilane, 10 mL of deionized water, and 20 mL of anhydrous ethanol are added to a conical flask, the pH value is adjusted to 4.5 with glacial acetic acid and 25% ammonia water, ultrasonically dispersed at 45° C. for 1 hour, and the thermal insulation nanofiller modified with hindered aminotrimethoxysilane is obtained by washing, filtering, and drying;

[0029] The method for preparing a thermal insulation nanofiller modified with hindered aminotriazinetrimethoxysilane is different from the method for preparing a thermal insulation nanofiller modified with hindered aminotrimethoxysilane in that hindered aminotriazinetrimethoxysilane is used to replace hindered aminotrimethoxysilane.

[0030] Among them, nano titanium dioxide is fumed titanium dioxide NT-50 nanometers, purchased from Hubei Huifu Nanomaterials Co., Ltd.;

[0031] Preparation of thermal insulation ink a: 55 g of a binder (the mass ratio of polyamide resin and styrene acrylic emulsion is 40:15), 10 g of a thermal insulation nanofiller modified with hindered aminotrimethoxysilane, 3 g of an additive (polyethylene micropowder wax with an average particle size of about 4.5-5.5 μm), 5 mL of propylene glycol methyl ether, 6 mL of ethanol, 10 mL of deionized water, and 1.5 g of an adhesion promoter are added into a disperser and stirred for 30 minutes to mix evenly to form a pre-dispersed color paste, and then the pre-dispersed color paste is pumped into a grinder for grinding until the material fineness is about 10 μm, thereby obtaining thermal insulation ink a;

[0032] Preparation of thermal insulation ink b, which differs from the method steps of preparing thermal insulation ink a only in that: using hindered amino triazine trimethoxy silane-modified thermal insulation nanofiller to replace the hindered amino trimethoxy silane-modified thermal insulation nanofiller;

[0033] Wherein, the connecting material is any one or more combinations of aminated resin liquid, styrene-acrylic emulsion, and polyamide resin, and the present invention selects polyamide resin and styrene-acrylic emulsion;

[0034] The polyamide resin has a viscosity of about 200 cP and was purchased from Shenzhen Jitian Chemical Co., Ltd.;

[0035] The viscosity of styrene acrylic emulsion was 2000 mPa·s and was purchased from Shandong Xintengyue Chemical Co., Ltd.;

[0036] The auxiliary agent is one or more combinations of polyethylene micro-powder wax, calcium carbonate, and corn starch. The present invention selects polyethylene micro-powder wax PEW-0276, which is purchased from Nanjing Tianshi New Material Technology Co., Ltd.;

[0037] The adhesion promoter model is ADP-W450, purchased from Nanjing Nengde New Material Technology Co., Ltd.

[0038] Embodiment 3:

[0039] Preparation of black ink: 12g of carbon black (carbon black for printing ink, purchased from Kasong Chemical), 52g of a binder (the mass ratio of alcohol-soluble polyurethane and styrene-acrylic emulsion is 40:12), 3g of an additive (oxidized polyethylene wax powder with an average particle size of about 7-9 μm), 10mL of ethanol, 8mL of propylene glycol methyl ether, and 10mL of water were added to a disperser and stirred for 30 minutes to mix evenly to form a pre-dispersed color paste, and then the pre-dispersed color paste was pumped into a grinder for grinding until the material fineness was about 10 μm;

[0040] The connecting material is one or more combinations of alcohol-soluble polyurethane, styrene-acrylic emulsion, and dry vegetable oil. The present invention selects alcohol-soluble polyurethane and styrene-acrylic emulsion;

[0041] The alcohol-soluble polyurethane had a viscosity of 3000 mPa·s and was purchased from Sansheng Trading Co., Ltd., Shunde District, Foshan City;

[0042] The auxiliary agent is one or more combinations of calcium carbonate, oxidized polyethylene wax powder, and corn starch. The present invention selects oxidized polyethylene wax powder, model Neptune 5223N4, purchased from Sanye Technology Co., Ltd.

[0043] Embodiment 4:

[0044] Preparation of PETG film: injecting PETG particles into a film blowing machine, setting the temperature range to 180-220°C and the blowing ratio to 3, to prepare a milky white PETG film;

[0045] Among them, the PETG model is PETG S2008, purchased from Shenzhen Dilingwei Technology Co., Ltd.

[0046] Embodiment 5:

[0047] Preparation of thermal insulation PETG light-blocking film: Printing is performed in the manner of inner printing and outer printing, the raw material film is a milky white PETG film, the outer printing is gravure printing (the gravure printing ink is a heat-insulating ink), and the inner printing is performed by printing two layers of black ink on the back of the milky white PETG material (the inner printing is performed on a printer with a two-color flip frame through two black laser plates), to obtain a thermal insulation PETG light-blocking film with a thickness of 0.054 mm;

[0048] According to the processing technology of the thermal insulation type PETG light-blocking film, when the thermal insulation type ink a is used for the gravure printing ink, the thermal insulation type PETG light-blocking film a is prepared;

[0049] According to the processing technology of the above-mentioned thermal insulation type PETG light-blocking film, when the thermal insulation type ink b is used as the gravure printing ink, the thermal insulation type PETG light-blocking film b is prepared.

[0050] Embodiment 6:

[0051] The above-mentioned thermal insulation PETG light-blocking film was tested for transmittance, with the scanning wavelength set to 200-800nm, the wavelength interval 5nm, the scanning speed slow, the experimental environment temperature 23±2℃, the humidity (50±5)%RH, and the test results showed that within the wavelength range of 200-800nm, the thermal insulation PETG light-blocking film had a light blocking rate of 100%, and the light transmittance tester measured that it was not transparent. Its spectral scanning curve is as follows: Figure 1 As shown;

[0052] The thermal insulation performance of the thermal insulation PETG light-blocking film was tested: the thermal insulation PETG light-blocking film was placed at the top center opening of the thermal insulation box, the temperature control probe of the electronic thermometer was placed inside the thermal insulation box, and an incandescent lamp (power 0.6W / cm 2 ) as the light source, the room temperature is kept constant, the initial temperature in the incubator is recorded, and the timing is started at the same time. The test time is 5 minutes. The temperature change value is calculated according to the difference between the temperature in the incubator and the initial temperature. The thermal insulation performance of the thermal insulation type PETG light-blocking film is evaluated. The experimental results are shown in Table 1;

[0053] Table 1 Experimental results of thermal insulation performance of thermal insulation PETG light-blocking film

[0054]

[0055] The experimental results show that compared with PETG film, under the same conditions, the temperature change value of thermal insulation PETG light-blocking film is smaller and has better thermal insulation performance;

[0056] It can be seen from the above experimental results that the heat-insulating PETG light-blocking film prepared by the present invention not only has a very excellent light-blocking ability, with a light-blocking rate of 100%, but also has a significantly improved heat-insulating ability.

Claims

1. A processing technology for heat-insulating PETG light-blocking film, characterized in that: The following steps are involved: Step 1: prepare heat-insulating ink, the specific process is as follows: Synthesizing a light-blocking silane coupling agent, and using the light-blocking silane coupling agent to perform surface modification on nano-titanium dioxide to obtain a heat-insulating nano-filler modified with the light-blocking silane coupling agent; The connecting material, the heat-insulating nanofiller modified by the light-blocking silane coupling agent, the additive, propylene glycol methyl ether, ethanol, deionized water and the adhesion promoter are uniformly mixed to form a pre-dispersed color paste, and the pre-dispersed color paste is ground to obtain the heat-insulating ink; Step 2: Evenly mix carbon black, a binder, an additive, ethanol, propylene glycol methyl ether and deionized water to form a pre-dispersed color paste, and grind to obtain a black ink; Step three, printing is performed in a manner of inner printing and surface printing. The raw material film adopts a milky white PETG film, the surface printing is gravure printing, the gravure printing ink is a heat-insulating ink, and the inner printing is performed by printing two layers of black ink on the back of the milky white PETG material. The inner printing is performed on a printing machine with a 2-color flip frame through two black laser plates to obtain a heat-insulating PETG light-blocking film.

2. The processing technology of a heat-insulating PETG light-blocking film according to claim 1, characterized in that: The light-blocking silane coupling agent is hindered aminotrimethoxysilane and / or hindered aminotriazinetrimethoxysilane.

3. The processing technology of a heat-insulating PETG light-blocking film according to claim 2, characterized in that: The chemical structural formula of the hindered aminotrimethoxysilane is:

4. The processing technology of a heat-insulating PETG light-blocking film according to claim 2, characterized in that: The preparation method of the hindered aminotrimethoxysilane is as follows: the amino NH2 functional group of 4-amino-2,2,6,6-tetramethylpiperidine and the chlorine functional group of 3-chloropropyltrimethoxysilane undergo a substitution reaction, and the molar ratio of 4-amino-2,2,6,6-tetramethylpiperidine to 3-chloropropyltrimethoxysilane is controlled to be (1.01-1.03):1, thereby obtaining the hindered aminotrimethoxysilane.

5. The processing technology of the heat-insulating PETG light-blocking film according to claim 2, characterized in that: The chemical structural formula of the hindered aminotriazinetrimethoxysilane is:

6. The processing technology of the heat-insulating PETG light-blocking film according to claim 2, characterized in that: The preparation method of the hindered amino triazine trimethoxysilane comprises the following steps: firstly, the amino functional group of 3-aminopropyl trimethoxysilane is subjected to a substitution reaction with the chloro functional group of cyanuric chloride, and then the amino NH2 functional group of 4-amino-2,2,6,6-tetramethylpiperidine is subjected to a substitution reaction with the chloro functional group of cyanuric chloride, and the amount ratio of cyanuric chloride, 3-aminopropyl trimethoxysilane and 4-amino-2,2,6,6-tetramethylpiperidine is controlled to be 1:(1.01-1.03):(2.05-2.2), so as to obtain the hindered amino triazine trimethoxysilane.

7. The processing technology of the heat-insulating PETG light-blocking film according to claim 1, characterized in that: The formula of the thermal insulation ink is: 8-15 parts by weight of thermal insulation nano filler modified by a light-blocking silane coupling agent, 30-50 parts by weight of a polyamide resin, 10-30 parts by weight of a styrene-acrylic emulsion, 2-5 parts by weight of polyethylene micropowder wax with an average particle size of about 4.5-5.5 μm, 3-6 parts by weight of propylene glycol methyl ether, 3-6 parts by weight of ethanol, 8-12 parts by weight of deionized water, and 1-2 parts by weight of an adhesion promoter ADP-W450.

8. The processing technology of the heat-insulating PETG light-blocking film according to claim 1, characterized in that: The formula of the black ink is: 10-15 parts by weight of carbon black, 30-50 parts by weight of alcohol-soluble polyurethane, 5-20 parts by weight of styrene-acrylic emulsion, 2-5 parts by weight of oxidized polyethylene wax powder with an average particle size of about 7-9 μm, 5-9 parts by weight of ethanol, 5-10 parts by weight of propylene glycol methyl ether and 8-12 parts by weight of deionized water.

9. A heat-insulating PETG light-blocking film obtained by the processing technology according to any one of claims 1 to 8, characterized in that: The heat-insulating PETG light-blocking film has a light blocking rate of 100% within the wavelength range of 200 to 800 nm.

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