Enhanced outdoor colored resin thermal transfer ribbon and preparation method thereof

Abstract

The invention belongs to the technical field of colored resin thermal transfer ribbons, and particularly relates to an enhanced outdoor colored resin thermal transfer ribbon and a preparation method thereof. The enhanced outdoor colored resin thermal transfer ribbon comprises a second color layer, a first color layer, a stripping layer, a base material and a back coating layer which are arranged in sequence. According to the invention, the color layer is divided into multiple layers, so that various properties, such as grinding efficiency, ink stability, chemical resistance and weather resistance, can be effectively improved.

Description

Technical Field

[0001] The invention belongs to the technical field of color resin carbon ribbons, and in particular relates to an enhanced color resin carbon ribbon for outdoor use and a preparation method thereof. Background Art

[0002] With the continuous development of thermal transfer printing, traditional black monochrome printing can no longer meet the needs of customers. With the development of thermal transfer color ribbons and the emergence of wide-format thermal transfer equipment, thermal transfer outdoor signs have become an important type of outdoor signs. However, in actual use, more and more customers have reported that color thermal transfer signs are prone to fading, especially in special colors such as State Grid Green, Traffic Yellow, Traffic Orange, etc., where the fading phenomenon is extremely obvious. This is because in the existing pigment system, there are very few pigments that meet the needs of special colors and have good light resistance and weather resistance. For special colors, it is often necessary to use a variety of pigments for use, but most pigments have problems such as poor compatibility, poor light resistance and weather resistance, and inconsistent light resistance and weather resistance. As a result, when using multiple pigments for color matching, there are problems such as difficulty in grinding, poor stability after dispersion, and poor chemical resistance, light resistance, and weather resistance of the pattern after transfer. The present invention can effectively improve the convenience in preparing special color thermal transfer color carbon ribbons by designing the color carbon ribbon structure, and at the same time improve the chemical resistance, light resistance and weather resistance of the pattern after transfer. Summary of the invention

[0003] In order to solve the deficiencies of the prior art, the present invention provides an enhanced outdoor color resin carbon ribbon and a preparation method thereof. The enhanced outdoor color resin carbon ribbon provided by the present invention can be reliably used outdoors.

[0004] The technical solution provided by the present invention is as follows:

[0005] An enhanced outdoor color resin carbon ribbon comprises a second color layer, a first color layer, a peeling layer, a substrate and a back coating layer which are arranged in sequence.

[0006] Furthermore, the thickness of the substrate is 4-10 μm, and the substrate can be one of polyethylene terephthalate (PET) film, 1,4-polycyclohexylene dimethylene terephthalate film, polyethylene naphthalate (PEN) film, polyphenylene sulfide film, polystyrene (PS) film, polypropylene (PP) film, polyethylene (PE) film, polyvinyl chloride film, nylon film, polyimide film, etc., preferably with a thickness of 4-6 μm.

[0007] Furthermore, the back coating layer has a thickness of 0.1-0.5 μm. The purpose of the back coating layer is to prevent adverse effects such as stickiness or wrinkles caused by the temperature-sensitive heating head during thermal transfer. The main components of the back coating layer are cellulose acetate propionate, polyvinyl acetal resin, and polyvinyl butyral resin. The thickness is preferably 0.2-0.4 μm.

[0008] The back coating often also requires the addition of high-adhesive resins such as polyester, polyurethane, etc.

[0009] Lubricants such as phosphate esters, zinc stearate, glyceryl dioleate, glyceryl monooleate, etc. are often added to the back coating.

[0010] Fillers with self-cleaning effects are often added to the back coating, such as talcum powder, kaolin, calcium carbonate, aluminum hydroxide, silica, graphite, boron nitride and other inorganic particles.

[0011] The back coating often requires the addition of one or more of a leveling agent, a dispersant and an antistatic agent.

[0012] The back coating often requires the addition of a crosslinking agent such as an isocyanate compound.

[0013] The preparation method of the back coating layer is as follows: the above materials are dissolved in 2-butanone and toluene to prepare a back coating liquid, and then the back coating liquid is coated on the substrate using a 280-line ceramic anilox roller and a gravure coater, and dried at 60-100° C. with a coating speed of 60-100 m / min.

[0014] Furthermore, the peeling layer has a thickness of 0.1-0.3 μm, preferably 0.1-0.2 μm. The peeling layer is composed of thermoplastic polymethyl methacrylate, micro wax powder and the like.

[0015] The thermoplastic polymethyl methacrylate accounts for 95-98% of the peeling layer, has a molecular weight of 5000-20000, preferably 10000-15000, and a Tg value of 50-110°C, preferably 60-100°C.

[0016] The micro wax powder can be PE wax, Fischer-Tropsch wax, etc., preferably PE wax, the wax accounts for 2-5% in the peeling layer, the particle size is between 1-10 μm, preferably less than 7 μm, and the melting point is between 80-120°C.

[0017] The preparation method of the peeling layer is as follows: dissolving, grinding and dispersing the above materials with a solvent to prepare a peeling layer coating liquid, and then using a 400-line ceramic anilox roller and a gravure coater to coat the back coating liquid on the substrate, drying at 80-100°C, and a coating speed of 60-100m / min.

[0018] When the color of the color ribbon needs to be realized by mixing two kinds of pigments, the two pigments are used separately, and the first color layer and the second color layer are set respectively; if the color of the color ribbon requires three kinds of pigments, additional color layers can also be added.

[0019] It is preferred that the pigment in the first color layer has better light resistance and weather resistance than the pigment in the second color layer.

[0020] More preferably, the pigment in the first color layer has high transparency.

[0021] With this solution, each individual color layer generally contains only one pigment, thus avoiding the problems of low grinding efficiency, easy color floating, and easy pigment agglomeration after grinding and dispersion when multiple pigments are ground together.

[0022] At the same time, this scheme makes the chemical resistance of the pattern after transfer better. This may be because after a single pigment is ground and dispersed, its uniformity is good. After the pattern is formed, the coating density of the pattern is good, which can effectively prevent the penetration of chemical substances and has good chemical resistance. However, when only one color layer is used and multiple pigments are in one layer, due to the difference of pigments and poor compatibility, the pattern layer formed by coating generally has many gaps, poor barrier to chemical substances, and poor chemical resistance.

[0023] At the same time, with this solution, the first color layer, which is more weather-resistant after transfer, is on the surface of the pattern. During outdoor use, the first color layer covers the second color layer. When used outdoors, the first color layer of the upper coating layer is exposed to more water, oxygen and absorbs more ultraviolet energy, which can effectively protect the second color layer of the lower coating layer, avoid premature fading of the pigment in the second color layer with poor light resistance and weather resistance, and effectively increase the overall reliability of the printed pattern in outdoor use.

[0024] The color layer is composed of chloroacetic acid resin, thermoplastic methyl methacrylate, pigment, plasticizer and the like.

[0025] The molecular weight of the thermoplastic methyl methacrylate is 80000-300000, preferably 100000-150000, Tg>100℃, preferably 100-105℃, and the weight percentage of the thermoplastic methyl methacrylate in the color layer is between 30%-45%. The thermoplastic methyl methacrylate has good light transmittance, good light resistance and weather resistance, and good transferability, which can ensure that the carbon tape has good transfer ability. The high molecular weight selection effectively ensures the outdoor use reliability of the pattern after transfer. At the same time, with the precise design of the peeling layer, it can effectively avoid problems such as insufficient resolution. The weight percentage of vinyl chloride in the chlorovinyl resin is greater than 85%, the degree of polymerization K>15, and the weight percentage is 5%-15%; the excellent pigment dispersibility and film-forming property of the chlorovinyl resin provide good help for the coating and film-forming of the carbon tape, and the high polar groups contained in it have good transfer adaptability and adhesion on the PVC tape after transfer. The color layer resin is mainly composed of the thermoplastic methyl methacrylate resin, which ensures the light resistance and weather resistance of the transferred pattern. If the weight percentage of chloroacetic acid resin in the color layer is too high, the light resistance and weather resistance will be reduced;

[0026] The first color layer preferably has highly weather-resistant pigments that meet color requirements, and the second color layer can select pigments that meet color requirements according to the overall color requirements, and the requirements for light resistance and weather resistance can be reduced. In the color layer, the pigment accounts for 45%-60%. Insufficient weight percentage of pigments in the color layer will lead to reduced light resistance and weather resistance;

[0027] The plasticizer may be selected from commonly used plasticizers such as epoxy soybean oil, dioctyl phthalate, dibutyl phthalate, etc., and the weight percentage is generally 1%-10% of the methacrylic copolymer. The use of the plasticizer can improve the reliability of the printed pattern.

[0028] The pigment in the first color layer can be selected from commonly used pigments, such as Pigment Yellow 150R, etc.;

[0029] The pigment in the second color layer can be selected from commonly used pigments, such as Pigment Red 254 or Pigment Red 149.

[0030] At the same time, in order to further improve the weather resistance of the printed pattern, anti-aging additives such as light absorbers, light stabilizers, antioxidants, etc. can also be added to the color layer.

[0031] The preparation method of the color layer is as follows: the above materials are dissolved in butanone and toluene, and then ground to prepare a color layer coating liquid, the pigment particle size is 0.1-0.2 μm, a 230-250 line ceramic anilox roller is used, a gravure coater is used for coating, and the coating is dried at 80-100° C. The coating speed is 60-100 m / min.

[0032] The present invention also provides a method for preparing an enhanced outdoor colored resin carbon ribbon, comprising the following steps: 1) applying corona to both sides of a substrate; 2) coating a heat-resistant and smooth back coating layer on the substrate; 3) coating a peeling layer on the reverse side of the back coating layer; 4) coating a first color layer on top of the peeling layer; 5) coating a second color layer on top of the first color layer.

[0033] The present invention arranges the color layer in multiple layers, which can effectively improve various performances, such as grinding efficiency, ink stability, chemical resistance, and weather resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is a schematic diagram of the structure of the enhanced outdoor color resin carbon ribbon provided by the present invention.

[0035] Figure 2 The traffic yellow pattern printed by embodiment 1 is adopted.

[0036] Figure 3 The traffic orange pattern printed by Embodiment 2 is adopted.

[0037] Attached Figure 1 The structures represented by the labels are listed below:

[0038] 1. Base material; 2. Peeling layer; 3. First color layer; 4. Second color layer; 5. Back coating layer. DETAILED DESCRIPTION

[0039] The principles and features of the present invention are described below. The examples given are only used to explain the present invention and are not used to limit the scope of the present invention.

[0040] Unless otherwise specified, the test methods used in the examples are conventional methods; the materials and reagents used are commercially available reagents and materials unless otherwise specified.

[0041] In a specific embodiment, Figure 1 As shown, the enhanced outdoor color resin carbon ribbon comprises a second color layer 4, a first color layer 3, a peeling layer 2, a substrate 1 and a back coating layer 5 which are arranged in sequence.

[0042] Example

[0043] In Examples 1-2, the back coating solution is prepared by weighing the raw materials according to the following proportions:

[0044] 2-Butanone 60 parts

[0045] Toluene 25 parts

[0046] Cellulose acetate propionate 10 parts Eastman CAP-482-0.5

[0047] Polyester resin 0.5 parts Toyobo GK888

[0048] Zinc stearate 0.3 parts Sunas SAK-ZS-PLB

[0049] Phosphate ester 0.25 parts Chengbei Chemical JP-502

[0050] 0.2 parts of glyceryl dioleate Binzhou Jinsheng GDO

[0051] Isocyanate 2 parts Covestro N3390

[0052] 0.3 parts of talcum powder

[0053] Silicon dioxide 0.2 parts Evonik OK630

[0054] Antistatic agent 0.3 parts Aidiko AS-301E

[0055] First, cellulose acetate propylene and polyester resin are added to a mixed solvent of 2-butanone and toluene to dissolve, and then zinc stearate, phosphate ester, glycerol dioleate, talc, silica and antistatic agent are added and stirred for 2 hours, and then isocyanate is added and stirred for 0.5 hours to obtain a back coating liquid.

[0056] In Examples 1-2, the peeling layer formulation is as shown in the following table:

[0057] wt% Thermoplastic Methyl Methacrylate 9.5 Micro wax powder 0.5 Anti-aging additives 0 2-Butanone 45 Toluene 45

[0058] In Examples 1-2, the substrate is

[0059] 4.5μm polyethylene terephthalate.

[0060] In Example 1, the formulas of color layer 1 (i.e., the first color layer) and color layer 2 (i.e., the second color layer) of the traffic yellow resin carbon ribbon are as shown in the following table:

[0061]

[0062] In Example 2, the formulas of the color layer 1 and the color layer 2 of the traffic orange resin ribbon are as shown in the following table:

[0063]

[0064] One choice of thermoplastic methyl methacrylate is BR80 from Mitsubishi Chemical;

[0065] One choice of chloroacetic acid resin is H15 / 42 from Wacker;

[0066] The preparation steps are: 1. Apply corona on both sides of the substrate; 2. Apply a heat-resistant and smooth back coating layer on the PET substrate; 3. Apply a peeling layer on the reverse side of the back coating layer; 4. Apply color layer 1 on the peeling layer; 5. Apply color layer 2 on color layer 1.

[0067] The grinding efficiency of the color layer of the resin carbon ribbon, the ink stability of the color layer after grinding, the solvent resistance of the transfer pattern, and the weather resistance of the transfer pattern were accelerated aging tests according to the following method.

[0068] Color layer grinding efficiency test:

[0069] The above-mentioned color layer preparation method was adopted, and the particle size of the ink after grinding for 30 minutes was tested using an OMEC laser particle size analyzer, and the D50 particle size of the ink was recorded.

[0070] Ink stability test of color layer after grinding:

[0071] The color layer preparation method described above was adopted, and the ink was ground for 30 minutes and placed at 50°C for 24 hours using an OMEC laser particle size analyzer to test the particle size, and the ink D50 particle size was recorded.

[0072] Chemical resistance test of transfer pattern:

[0073] Use a thermal transfer traffic sign printer (manufactured by Hunan Dingyi Intelligent Manufacturing Co., Ltd., model DTP-1300) to print on 3M V-type white reflective film Figure 2 Traffic yellow pattern and Figure 3 Traffic orange pattern.

[0074] An alcohol friction test was performed using an alcohol friction tester, and the number of frictions when the test pattern turned white under a load of 1 kg was recorded.

[0075] Accelerated aging test of the transferred pattern:

[0076] Use a thermal transfer traffic sign printer (manufactured by Hunan Dingyi Intelligent Manufacturing Co., Ltd., model DTP-1300) to print on 3M V-type white reflective film Figure 2 , 3 The pattern shown.

[0077] According to the operating method of GBT18833-2012 Road Traffic Reflective Sheeting, the test cycle is 1800h.

[0078] The formed images were visually confirmed and evaluated according to the following evaluation criteria:

[0079] OK: passed the national standard (photometric performance, chromaticity performance) test;

[0080] NG: failed the national standard (photometric performance, chromaticity performance) test;

[0081] Test results:

[0082]

[0083]

[0084] Comparative Example

[0085] In the comparative example, the back coating layer and the peeling layer are consistent with those in the embodiment, and the color layer scheme adopts one color layer, and the pigment in the color layer uses multiple pigments, which are as follows:

[0086] Color Layer

[0087]

[0088] Comparative Example Test: All test methods are the same as those in the embodiment.

[0089]

[0090] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. An enhanced outdoor color resin ribbon, characterized in that: The invention comprises a second color layer, a first color layer, a peeling layer, a substrate and a back coating layer which are arranged in sequence.

2. The enhanced outdoor color resin ribbon according to claim 1, characterized in that: The light fastness of the pigment in the first color layer is higher than the light fastness of the pigment in the second color layer; The weather resistance of the pigment in the first color layer is higher than the weather resistance of the pigment in the second color layer; The pigment in the first color layer is a high-transmittance pigment.

3. The enhanced outdoor color resin ribbon according to claim 2, characterized in that: The first color layer comprises the following components in parts by weight: chlorovinyl resin, thermoplastic methyl methacrylate, a first pigment and a plasticizer; The second color layer comprises the following components in parts by weight: chlorovinyl resin, thermoplastic methyl methacrylate, a second pigment and a plasticizer.

4. The enhanced outdoor color resin ribbon according to claim 3, characterized in that: Thermoplastic methyl methacrylate has a molecular weight of 80,000-300,000, Tg>100°C, and a weight percentage of methyl methacrylate in the first color layer or the second color layer is between 30% and 45%; The weight content of vinyl chloride in the chlorovinyl resin is greater than 85%, the degree of polymerization K>15, and the weight percentage of vinyl chloride in the first color layer or the second color layer is between 5% and 15%; The weight percentage of the plasticizer in the first color layer or the second color layer is between 1% and 10%; The weight percentage of the pigment in the first color layer is between 45% and 60%; The weight percentage of the pigment in the second color layer is between 45% and 60%.

5. The enhanced outdoor color resin ribbon according to claim 4, characterized in that: The molecular weight of thermoplastic methyl methacrylate is 100,000-150,000, and Tg is 100-105°C; Plasticizer choices include, but are not limited to, epoxidized soybean oil, dioctyl phthalate, or dibutyl phthalate.

6. The enhanced outdoor color resin ribbon according to claim 1, characterized in that: The thickness of the substrate is 4-10 μm, and the substrate may be selected from, but is not limited to, polyethylene terephthalate film, 1,4-polycyclohexylene dimethylene terephthalate film, polyethylene naphthalate film, polyphenylene sulfide film, polystyrene film, polypropylene film, polyethylene film, polyvinyl chloride film, nylon film or polyimide film; The thickness of the back coating layer is 0.1-0.5 μm, and the back coating layer can be selected from, but not limited to, cellulose acetate propionate, polyvinyl acetal resin or polyvinyl butyral resin; The peeling layer has a thickness of 0.1-0.3 μm and comprises thermoplastic polymethyl methacrylate and micro wax powder.

7. The enhanced outdoor color resin ribbon according to claim 6, characterized in that: The back coating layer further comprises any one or more of a high-adhesive resin, a lubricant, a self-cleaning filler, a leveling agent, a dispersant, an antistatic agent or a cross-linking agent; The weight percentage of the polythermoplastic methyl methacrylate in the peeling layer is 95%-98%, the molecular weight is between 5000-20000, and the Tg value is 50-110°C; The weight percentage of the micro wax powder in the peeling layer is 2%-5%. The micro wax powder includes but is not limited to PE wax and Fischer-Tropsch wax. The particle size is between 1-10 μm and the melting point is between 80-120° C.

8. The enhanced outdoor color resin ribbon according to claim 7, characterized in that: The thickness of the substrate is 4-6 μm; The molecular weight of the thermoplastic polymethyl methacrylate is 10000-15000, and the Tg value is 60-100°C; The particle size of the micro wax powder is below 7 μm.

9. The enhanced outdoor color resin ribbon according to claim 8, characterized in that: The selection of high-adhesive resins in the back coating includes, but is not limited to, polyesters and polyurethanes; The choice of lubricant in the back coating includes, but is not limited to, phosphate esters, zinc stearate, glyceryl dioleate, or glyceryl monooleate; The selection of self-cleaning fillers in the back coating includes, but is not limited to, talc, kaolin, calcium carbonate, aluminum hydroxide, silica, graphite or boron nitride; The selection of cross-linking agents in the back coating includes, but is not limited to, isocyanate compounds; The micro wax powder is PE wax.

10. A method for preparing an enhanced outdoor color resin ribbon according to any one of claims 1 to 9, characterized in that: The following steps are involved: 1) Apply corona on both sides of the substrate; 2) applying a back coating layer on the substrate; 3) Applying a release layer on the reverse side of the back coating; 4) coating a first color layer on the release layer; 5) Apply a second color layer on top of the first color layer.

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