Protective resin thermal transfer ribbon with excellent waterproofness, preparation method and application

Abstract

The invention relates to the technical field of thermal transfer printing, in particular to a protective resin thermal transfer ribbon with excellent waterproofness, a preparation method and application. The component of the water vapor barrier layer of the protective resin thermal transfer ribbon comprises resin with extremely low water vapor transmittance; the component of the protective layer comprises first thermoplastic acrylic resin; the first thermoplastic acrylic resin is free radical polymerization resin, and the main body of the first thermoplastic acrylic resin is a methyl methacrylate monomer. The protective resin thermal transfer ribbon has the characteristics of excellent hydrophobicity, oleophobicity, stain resistance and the like; the coating is very stable to light, heat, acid and alkali, so that the coating has excellent weather resistance, corrosion resistance, chemical medium resistance, light transmission and the like; the moisture-proof performance of the printed matter can be obviously improved; the transfer printing ink can be widely applied to high-temperature and high-humidity tropical areas, and patterns and products transferred by the transfer printing ink have good high-temperature-resistant and moisture-resistant effects.

Description

Technical Field

[0001] This invention relates to the field of heat transfer technology, and more specifically, to a protective resin ribbon with excellent waterproof properties, its preparation method, and its application. Background Technology

[0002] Currently, heat transfer printing of signs is widely used in various industries, while some outdoor printed products require the images to withstand various complex environments, which places high demands on properties such as weather resistance and chemical resistance.

[0003] Existing protective ribbons used in outdoor printing products for heat transfer printing often have a protective layer covering the coloring layer, which provides certain weather resistance, chemical resistance, and dirt resistance when used outdoors to meet the needs of various environments.

[0004] However, while existing protective resin ribbons can meet environmental requirements under normal conditions, in actual use, it has been found that in tropical climates such as Hainan, the coating is easily penetrated by water vapor due to the high temperature and humidity, causing the interface between the protective coating and the color coating to separate, resulting in loss of marking effect and even deterioration of the image of printed materials. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a protective resin carbon ribbon with excellent waterproof properties, its preparation method and application.

[0006] The technical solution of the present invention to solve the above-mentioned technical problems is as follows: The present invention provides a protective resin ribbon with excellent waterproof properties, comprising a substrate, wherein a water vapor barrier layer and a protective layer are sequentially provided on one side of the substrate; The water vapor barrier layer comprises a resin with extremely low water vapor permeability. The protective layer comprises a first thermoplastic acrylic resin; the first thermoplastic acrylic resin is a free radical polymer resin, the main component of which is methyl methacrylate monomer.

[0007] Based on the above technical solution, the present invention can be further improved as follows.

[0008] Furthermore, the extremely low water vapor transmission rate resin includes thermoplastic resin and / or thermosetting resin, wherein the thermoplastic resin is one or more of polyethylene, polypropylene, acrylic resin, polyester resin, polyurethane resin, polyvinyl chloride resin, and polyvinylidene chloride resin, and the thermosetting resin includes one or more of the crosslinking products of each of the thermoplastic resins, epoxy resin, and melamine resin.

[0009] Furthermore, the extremely low water vapor transmission rate resin is polyvinylidene chloride resin, and the water vapor transmission rate of the polyvinylidene chloride resin is 0.7-24 g / (m²).2 •24h).

[0010] Furthermore, the water vapor barrier layer also includes fluorinated silicone oil, the mass of which is 0.1%-2% of the extremely low water vapor permeability resin.

[0011] Furthermore, the molecular weight (Mn) of the first thermoplastic acrylic resin is 80,000-150,000, and the glass transition temperature (Tg) is 40-120°C.

[0012] Furthermore, the protective layer is provided with an adhesive layer, the adhesive layer comprising a second thermoplastic acrylic resin, the second thermoplastic acrylic resin being a resin obtained by polymerizing acrylic acid, methacrylic acid and their derivatives, the second thermoplastic acrylic resin having a molecular weight Mn of 5000-300000 and a glass transition temperature Tg of 40-120℃.

[0013] Furthermore, a back coating is provided on the other side of the substrate, and the composition of the back coating includes polyurethane modified silicone resin and / or acrylic modified silicone resin.

[0014] Furthermore, the thickness of the adhesive layer is 0.2-2 μm, the thickness of the protective layer is 0.5-20 μm, the thickness of the water vapor barrier layer is 0.2-2 μm, and the thickness of the back coating layer is 0.5-1.2 μm.

[0015] The present invention also provides a method for preparing a protective resin ribbon with excellent waterproof properties as described above, wherein the coating liquid for the water vapor barrier layer and the coating liquid for the protective layer are prepared separately, and then coated and cured sequentially on the substrate.

[0016] The present invention also provides an application of the protective resin ribbon with excellent waterproof properties as described above. The protective resin ribbon and its transfer pattern can be applied in high temperature and high humidity environments, wherein the temperature of the high temperature and high humidity environment is greater than or equal to 35°C and the humidity is greater than or equal to 85%.

[0017] The beneficial effects of this invention are as follows: (1) The protective resin carbon ribbon of the present invention has excellent waterproof properties. It is provided with a resin component containing a resin with extremely low water vapor permeability as a water vapor barrier layer, so that it has excellent hydrophobic, oleophobic and stain-resistant properties. (2) The protective resin carbon ribbon of the present invention with excellent waterproof properties uses a free radical polymer resin with methyl methacrylate monomer as the main component as the protective layer resin, which makes the protective carbon ribbon very stable against light, heat, acid and alkali, thereby having excellent weather resistance, corrosion resistance, chemical resistance and light transmittance. (3) The protective resin carbon ribbon of the present invention, which has excellent waterproof properties, can significantly improve the waterproof and vapor-proof performance of printed materials; (4) The protective resin carbon ribbon of the present invention has excellent waterproof properties and can be widely used in tropical regions with high temperature and high humidity. The patterns and products transferred by it have good high temperature and water vapor resistance. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of the layer structure of the protective resin carbon ribbon with excellent waterproof properties according to the present invention.

[0019] The attached diagram lists the components represented by each number as follows: 1. Adhesive layer; 2. Protective layer; 3. Water vapor barrier layer; 4. Substrate; 5. Back coating. Detailed Implementation

[0020] The principles and features of the present invention are described below. The examples given are only for explaining the present invention and are not intended to limit the scope of the present invention.

[0021] The protective resin ribbon of the present invention with excellent waterproof properties includes a substrate 4, and a water vapor barrier layer 3 and a protective layer 2 are sequentially provided on one side of the substrate 4; the water vapor barrier layer 3 includes a resin with extremely low water vapor permeability and fluorine-modified silicone oil; the protective layer 2 includes a first thermoplastic acrylic resin; the first thermoplastic acrylic resin is a free radical polymer resin, the main component of which is methyl methacrylate monomer.

[0022] The protective resin ribbon of the present invention, possessing excellent waterproof properties, incorporates a resin component containing a resin with extremely low water vapor permeability as the water vapor barrier layer 3, exhibiting excellent hydrophobic, oleophobic, and stain-resistant properties. Furthermore, the use of the aforementioned free radical polymerized resin as the resin in the protective layer 2 makes the protective ribbon highly stable against light, heat, acids, and alkalis, thereby possessing excellent weather resistance, corrosion resistance, chemical resistance, and light transmittance.

[0023] The protective resin ribbon of the present invention, which has excellent water resistance, can significantly improve the water and vapor resistance of printed materials.

[0024] Preferably, the resin with extremely low water vapor permeability includes thermoplastic resin and / or thermosetting resin. The thermoplastic resin is one or more of polyethylene, polypropylene, acrylic resin, polyester resin, polyurethane resin, polyvinyl chloride resin, and polyvinylidene chloride resin. The thermosetting resin includes one or more of the crosslinking products of each thermoplastic resin, epoxy resin, and melamine resin.

[0025] Since thermosetting resins can have an adverse effect on the heat transfer process, thermoplastic resins are preferred for the water vapor barrier layer.

[0026] Preferably, the resin with low water vapor permeability is polyvinylidene chloride resin.

[0027] Polyvinylidene chloride resin has the lowest water vapor permeability and is the most effective.

[0028] Preferably, the water vapor barrier layer 3 also includes fluorinated silicone oil; fluorinated silicone oil can further improve the hydrophobic, oleophobic, and stain-resistant properties of the extremely low water vapor permeability resin. After adding fluorinated silicone oil, during the film formation process, the fluorinated alkyl groups with extremely low surface energy will preferentially migrate to the surface, giving the coating surface excellent hydrophobic, oleophobic, and stain-resistant properties.

[0029] Preferably, the mass of the fluorinated modified silicone oil is 0.1%-2% of the extremely low water vapor permeability resin.

[0030] Preferably, the polyvinylidene chloride resin can be a solvent-based polyvinylidene chloride resin or a polyvinylidene chloride emulsion. However, polyvinylidene chloride emulsion has a lower water vapor permeability. Therefore, emulsion-type polyvinylidene chloride is preferred as the resin component of the water vapor barrier layer 3.

[0031] Preferably, the water vapor permeability of the polyvinylidene chloride resin is 0.7-24 g / (m²). 2 •24h).

[0032] Preferably, the polyvinylidene chloride resin is solvent-based PVDC / F310, solvent-based PVDC / R204, or PVDC emulsion / L813D.

[0033] Preferably, the thickness of the water vapor barrier layer 3 is 0.2-2μm, and more preferably 0.4-1μm. When the thickness is less than 0.4μm, the water vapor barrier layer 3 cannot effectively block water vapor. When the thickness of the water vapor barrier layer 3 is greater than 1μm, it is easy to cause poor transfer during the heat transfer process.

[0034] Preferably, in order to have good outdoor weather resistance, the molecular weight (Mn) of the first thermoplastic acrylic resin is 80,000-150,000 and the glass transition temperature (Tg) is 40-120℃.

[0035] More preferably, the molecular weight (Mn) of the first thermoplastic acrylic resin is 90,000-120,000, and the glass transition temperature is 70-110℃.

[0036] Preferably, in order to better adhere the protective layer 2 to the substrate (printing substrate), an adhesive layer 1 must be provided on the side of the protective layer 2 away from the substrate 4.

[0037] Preferably, the component of the next layer 1 includes a second thermoplastic acrylic resin, which is a resin obtained by polymerizing acrylic acid, methacrylic acid and their derivatives (such as esters, nitriles, amides), and the above resin can provide good adhesion.

[0038] Preferably, the second thermoplastic acrylic resin is a thermoplastic acrylic resin prepared by free radical polymerization with methyl methacrylate monomer as the main component.

[0039] Preferably, the second thermoplastic acrylic resin has a molecular weight (Mn) of 5000-300000 and a glass transition temperature (Tg) of 40-120℃.

[0040] Preferably, the second thermoplastic acrylic resin has a molecular weight (Mn) of 25,000-150,000 and a glass transition temperature (Tg) of 60-110°C.

[0041] Preferably, the other side of the substrate 4 is provided with a back coating 5, which serves to protect the print head by resisting heat during printing.

[0042] Preferably, the back coating 5 comprises polyurethane-modified silicone resin and / or acrylic-modified silicone resin.

[0043] Preferably, the substrate 4 is a transparent flexible plastic film, such as polypropylene (PP), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyethylene (PE), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), etc. PET and PEN are preferred.

[0044] The protective resin carbon ribbon of the present invention has an adhesive layer 1 with a thickness of 0.2-2 μm, a protective layer 2 with a thickness of 0.5-20 μm, a water vapor barrier layer 3 with a thickness of 0.2-2 μm, a back coating layer 5 with a thickness of 0.5-1.2 μm, and a substrate 4 with a thickness of 4-25 μm.

[0045] The thickness of the adhesive layer 1 is preferably 0.3-0.9 μm; the thickness of the protective layer 2 is preferably 1-10 μm; and the thickness of the substrate 4 is preferably 4-10 μm.

[0046] In addition, the thickness of the water vapor barrier layer 3 is 0.2-2μm, preferably 0.4-1μm; when the thickness is less than 0.4μm, the water vapor barrier layer 3 cannot effectively block water vapor; when the thickness of the water vapor barrier layer 3 is greater than 1μm, it is easy to cause poor transfer during the heat transfer process.

[0047] The pattern obtained by transferring the protective resin carbon ribbon according to the present invention has a surface layer of water vapor barrier layer 3, the water vapor permeability of which is less than 1 g / (m 2 • 24h), effectively preventing water vapor from penetrating the bottom protective layer 2, significantly improving the weather resistance of printed products in high temperature and high humidity environments.

[0048] The present invention provides a method for preparing a protective resin ribbon with excellent waterproof properties by preparing a coating liquid for the water vapor barrier layer 3 and a coating liquid for the protective layer 2, and then coating and curing them sequentially on a substrate 4.

[0049] Specifically, the preparation method of the present invention includes the following steps: (1) Disperse the extremely low water vapor permeability resin in water and isopropanol according to the required amount, and then obtain the coating liquid of water vapor barrier layer 3. Then coat it on one side surface of substrate 4 by gravure coating or slit coating and dry it to obtain water vapor barrier layer 3.

[0050] In this step, a certain amount of additives can also be added. These additives can be conventional additives such as leveling agents and defoamers to improve the leveling and bubble problems of the coating liquid.

[0051] (2) Dissolve methacrylic resin in methyl ethyl ketone-toluene solvent according to the required amount to obtain the coating liquid of protective layer 2. Then, coat it on the surface of water vapor barrier layer 3 by gravure coating or slit coating and dry it to obtain protective layer 2.

[0052] (3) Dissolve the thermoplastic acrylic resin, light stabilizer and light absorber in methyl ethyl ketone-toluene solvent according to the required amount to obtain the coating liquid of adhesive layer 1. Then coat it on the surface of protective layer 2 by gravure coating or slit coating and dry it to obtain adhesive layer 1.

[0053] (4) Dissolve polyurethane modified silicone resin and acrylic modified silicone resin in methyl ethyl ketone-toluene solvent according to the required amount, and add a certain amount of additives to obtain the coating liquid of the back coating 5. Then, coat it on the other side of the substrate 4 by gravure coating or slit coating and dry it to obtain the back coating 5.

[0054] The present invention relates to the application of a protective resin ribbon with excellent waterproof properties. This protective resin ribbon and its transfer pattern can be applied in high temperature and high humidity environments, where the temperature is greater than or equal to 35°C and the humidity is greater than or equal to 85%.

[0055] The effects of the present invention will be illustrated below through specific embodiments and comparative examples.

[0056] Table 1 shows the specific composition, mass fraction, and thickness of the water vapor barrier layer 3 in Comparative Examples 1-6 of the present invention: Table 1 In the carbon ribbons of Examples 1-3 and Comparative Examples 1-3, the protective layer 2 is composed of 100 parts by weight of methacrylic resin. The adhesive layer 1 consists of 80 parts by weight of thermoplastic acrylic resin, 10 parts by weight of light stabilizer, and 10 parts by weight of light absorber. The back coating layer 5 consists of 50 parts by weight of polyurethane modified silicone resin and 50 parts by weight of acrylic modified silicone resin. The thickness of the back coating layer 5 is 0.2 μm.

[0057] In Examples 1-3 and Comparative Examples 1-3, the substrate 4 was a 5.3μm PET substrate, and the transfer body (printing substrate) was a white reflective film.

[0058] The specific methods for preparing carbon ribbons in Examples 1-3 and Comparative Examples 1-3 are as follows: (1) Disperse the extremely low water vapor permeability resin in water and isopropanol according to the required amount to obtain the coating liquid of water vapor barrier layer 3. Then, coat it on one side surface of substrate 4 by gravure coating or slit coating and dry it to obtain water vapor barrier layer 3.

[0059] (2) Dissolve methacrylic resin in methyl ethyl ketone-toluene solvent according to the required amount to obtain the coating liquid of protective layer 2. Then, coat it on the surface of water vapor barrier layer 3 by gravure coating or slit coating and dry it to obtain protective layer 2.

[0060] (3) Dissolve the thermoplastic acrylic resin, light stabilizer and light absorber in methyl ethyl ketone-toluene solvent according to the required amount to obtain the coating liquid of adhesive layer 1. Then coat it on the surface of protective layer 2 by gravure coating or slit coating and dry it to obtain adhesive layer 1.

[0061] (4) Dissolve polyurethane modified silicone resin and acrylic modified silicone resin in methyl ethyl ketone-toluene solvent according to the required amount to obtain the coating liquid of the back coating 5. Then coat it on the other side of the substrate 4 by gravure coating or slot coating and dry it to obtain the back coating 5.

[0062] After completing the above process, the ribbon is obtained. The obtained ribbon is printed onto the surface of a white reflective film using a heat transfer printing machine and then subjected to a water vapor resistance test.

[0063] Comparative Example 4 uses the same protective layer 2, adhesive layer 1 and back coating layer 5 as Comparative Example 1, and the coating thickness, coating method and printing method are the same. The only difference is that the water vapor barrier layer 3 is not added.

[0064] Comparative Example 5 used the same protective layer 2, adhesive layer 1, and back coating layer 5 as Comparative Example 1, and the coating thickness, coating method, and printing method were also the same. The only difference was that the water vapor barrier layer 3 was composed of polyvinyl chloride resin, and its water vapor permeability was 39 g / (m²). 2 (24h). The thickness of the water vapor barrier layer 3 is 0.8μm.

[0065] Comparative Example 6 used the same protective layer 2, adhesive layer 1, and back coating layer 5 as Comparative Example 1, and the coating thickness, coating method, and printing method were also the same. The only difference was that the water vapor barrier layer 3 was composed of polyester resin, and its water vapor permeability was 18 g / (m²). 2 (24h). The thickness of the water vapor barrier layer 3 is 0.8μm.

[0066] For the ribbons of Comparative Examples 4-6, printing and water vapor resistance tests were also conducted using a heat transfer-based printer.

[0067] The method for testing water vapor resistance is as follows: Place the printed sample in a constant temperature and humidity test chamber, set the parameters to 60℃ and 90% humidity, and after 168 hours, remove the sample and observe its surface condition. Rate the sample according to the following standards: A: The sample's appearance showed no obvious changes. B: A small amount of hazy or cloudy phenomenon appeared on the sample surface. C: A large amount of hazy, cloudy phenomenon appeared on the sample surface. D: Coating peeling The performance test results of each embodiment and comparative example are shown in Tables 2 and 3: Table 2 Table 3 As can be seen from the above embodiments and comparative examples, the protective resin ribbon of the present invention with excellent waterproof properties can significantly improve the waterproof and vapor-proof performance of printed materials.

[0068] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A protective resin ribbon with excellent waterproof properties, characterized in that, The substrate (4) includes a water vapor barrier layer (3) and a protective layer (2) sequentially disposed on one side of the substrate (4). The water vapor barrier layer (3) comprises a resin with extremely low water vapor permeability. The protective layer (2) comprises a first thermoplastic acrylic resin; the first thermoplastic acrylic resin is a free radical polymer resin, the main component of which is methyl methacrylate monomer.

2. The protective resin carbon ribbon with excellent waterproof properties according to claim 1, characterized in that, The extremely low water vapor transmission rate resin includes thermoplastic resin and / or thermosetting resin. The thermoplastic resin is one or more of polyethylene, polypropylene, acrylic resin, polyester resin, polyurethane resin, polyvinyl chloride resin, and polyvinylidene chloride resin. The thermosetting resin includes one or more of the crosslinking products of the thermoplastic resin, epoxy resin, and melamine resin.

3. The protective resin ribbon with excellent waterproof properties according to claim 2, characterized in that, The extremely low water vapor transmission rate resin is polyvinylidene chloride resin, and the water vapor transmission rate of the polyvinylidene chloride resin is 0.7-24 g / (m²). 2 •24h).

4. The protective resin ribbon with excellent waterproof properties according to claim 1, characterized in that, The water vapor barrier layer (3) also includes fluorinated silicone oil, the mass of which is 0.1%-2% of the extremely low water vapor permeability resin.

5. The protective resin carbon ribbon with excellent waterproof properties according to claim 1, characterized in that, The first thermoplastic acrylic resin has a molecular weight (Mn) of 80,000-150,000 and a glass transition temperature (Tg) of 40-120°C.

6. A protective resin ribbon with excellent waterproof properties according to any one of claims 1-5, characterized in that, The protective layer (2) is provided with an adhesive layer (1), the adhesive layer (1) is composed of a second thermoplastic acrylic resin, the second thermoplastic acrylic resin is a resin obtained by polymerizing acrylic acid, methacrylic acid and its derivatives, the molecular weight Mn of the second thermoplastic acrylic resin is 5000-300000, and the glass transition temperature Tg is 40-120℃.

7. The protective resin ribbon with excellent waterproof properties according to claim 6, characterized in that, The other side of the substrate (4) is provided with a back coating (5), the composition of which includes polyurethane modified silicone resin and / or acrylic modified silicone resin.

8. The protective resin ribbon with excellent waterproof properties according to claim 7, characterized in that, The thickness of the adhesive layer (1) is 0.2-2 μm, the thickness of the protective layer (2) is 0.5-20 μm, the thickness of the water vapor barrier layer (3) is 0.2-2 μm, and the thickness of the back coating layer (5) is 0.5-1.2 μm.

9. A method for preparing a protective resin carbon ribbon with excellent waterproof properties as described in any one of claims 1-8, characterized in that, The coating liquids for the water vapor barrier layer (3) and the protective layer (2) are prepared separately and then coated and cured sequentially on the substrate (4).

10. The application of a protective resin ribbon with excellent waterproof properties as described in any one of claims 1-8, characterized in that, The protective resin ribbon and its transfer pattern can be applied to high temperature and high humidity environments, wherein the temperature is greater than or equal to 50°C and the humidity is greater than or equal to 85%.

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