CN116215099A

CN116215099A - Resin carbon tape with excellent weather resistance, preparation method and application

Info

Publication number: CN116215099A
Application number: CN202211610625.0A
Authority: CN
Inventors: 汪鑫; 王懿君; 唐国初
Original assignee: Hunan Dingyi Zhizao Digital Equipment Technology Development Co ltd; Hunan Dingyi Zhiyuan Technology Development Co Ltd
Current assignee: Hunan Dingyi Zhizao Digital Equipment Technology Development Co ltd; Hunan Dingyi Zhiyuan Technology Development Co Ltd
Priority date: 2022-12-12
Filing date: 2022-12-12
Publication date: 2023-06-06

Abstract

The invention relates to a resin carbon tape with excellent weather resistance, a preparation method and application thereof, and relates to the technical field of thermal transfer printing; the ink layer is formed by coating ink layer paint, wherein the ink layer paint comprises, by weight, 50-70 parts of organosilicon-acrylic composite resin, 50-70 parts of pigment, 5-15 parts of dispersing agent, 0-2.1 parts of light stabilizer and 2-3.5 parts of curing agent; the release layer is formed by coating release layer paint. Compared with the existing printed products of acrylic acid or organic silicon systems in the traffic industry, the printed products of the resin carbon tape have better weather resistance and have the advantages of both the acrylic acid and the organic silicon systems.

Description

Resin carbon tape with excellent weather resistance, preparation method and application

Technical Field

The invention relates to the technical field of thermal transfer printing, in particular to a resin carbon ribbon with excellent weather resistance, a preparation method and application thereof.

Background

Since the traffic sign needs to be exposed outdoors for a long period of time to cope with various environments, printed products in the traffic industry are required to have excellent weather resistance, thermoplastic acrylic resins are often selected in the industry, but weather resistance and solvent resistance of the thermoplastic acrylic resins are not optimal, and in order to increase the stain resistance, a methyl silicone or fluorine-containing auxiliary agent is generally required to be added to the acrylic resins, but the addition of these auxiliary agents often affects the transfer effect of the carbon tape.

From the viewpoint of printing modes, common printing modes in the market include screen printing, UV ink jet and thermal transfer printing, and thermal transfer printing in these printing modes has been rapidly developed in recent years due to higher environmental friendliness and relatively simple process flow.

Aiming at the special requirement that the traffic sign requires high weather resistance, the invention provides a resin carbon tape with excellent weather resistance, a preparation method and application. The applicant who needs to say has filed patent CN 202111612885.7-a gasoline-resistant resin carbon tape for traffic printing and a preparation method thereof, and CN 202111611831.9-a heat transfer resin carbon tape capable of being rapidly printed and a preparation method thereof, and so on.

Disclosure of Invention

The invention aims to provide a resin carbon tape with excellent weather resistance, a preparation method and application thereof. The purpose is to provide a resin carbon tape with excellent weather resistance based on thermal transfer printing for the transportation industry. The resin in the weather-resistant resin carbon tape adopts the organic silicon-acrylic acid composite resin, and when the organic silicon-acrylic acid composite resin is used together with the curing agent, the formed curing system has excellent weather resistance, and the adhesion with a base material is quite excellent, meanwhile, the transparency is quite high, the influence on the retroreflection coefficient is small, and meanwhile, the weather-resistant resin carbon tape has the performances of organic silicon and acrylic acid.

The invention aims to solve the technical problems, and a first object of the invention is to provide a resin carbon tape with excellent weather resistance, which comprises an ink layer, a release layer, a base material and a back coating which are sequentially attached from top to bottom;

the ink layer is formed by coating ink layer paint, and the ink layer paint comprises the following components in parts by weight: 50-70 parts of organosilicon-acrylic composite resin, 50-70 parts of pigment, 5-15 parts of dispersing agent, 0-2.1 parts of light stabilizer and 2-3.5 parts of curing agent, wherein the curing agent is methyl-containing siloxane;

the release layer is formed by coating release layer paint, and the release layer paint comprises the following components in parts by weight: 50-70 parts of (methyl) acrylic resin, 0.05-1.4 parts of light stabilizer and 0.25-2.5 parts of wax powder, wherein the number average molecular weight (Mn) of the (methyl) acrylic resin is 10000-20000, and the glass transition temperature Tg is 60-95.

The beneficial effects of the invention are as follows: when the organosilicon-acrylic composite resin is used together with a curing agent, the formed curing system has excellent weather resistance, excellent adhesiveness with a base material, high transparency and small influence on the retroreflection coefficient, and has the performances of organosilicon and acrylic acid. Compared with the existing printed products of acrylic acid or organic silicon systems in the traffic industry, the printed products obtained by printing the resin carbon tape have the advantages of more excellent weather resistance and both. The release layer is positioned on one side of the ink layer away from the traffic sign substrate after printing is finished, and mainly plays a role in helping the ink layer to separate from the substrate; the back coating is used for heat transfer and friction prevention and protecting the printing head and the printing base material.

On the basis of the technical scheme, the invention can be improved as follows.

Further, the ink layer coating comprises the following components in parts by weight: 55-65 parts of organosilicon-acrylic composite resin, 55-65 parts of pigment, 7-15 parts of dispersing agent, 0.25-2.1 parts of light stabilizer and 2.5-3 parts of curing agent;

the release layer coating comprises the following components in parts by weight: 55-65 parts of (methyl) acrylic resin, 0.1-1 part of light stabilizer and 0.5-2 parts of wax powder.

Further, the organic silicon-acrylic composite resin comprises the following components in percentage by weight (3-4): the end-capping structure of the chemical combination of polysiloxane and acrylic acid of (6-7) (the organosilicon-acrylic composite resin is a product of DIC corporation, product name: organosilicon-acrylic composite resin aqueous dispersion CERANATE WSA-1070), and the pH is 7.5-8.5; the pigment inorganic pigment and/or organic pigment; the curing agent is gamma- (methacryloyloxy) propyl trimethoxy siloxane; the light stabilizer comprises one or more than two of salicylate, benzene ketone, benzotriazole and triazine ultraviolet absorbers; the dispersing agent comprises a carboxyl-containing polymer organic solvent solution, a modified polysiloxane solution, an anionic surfactant, a high molecular weight carboxylic acid organic solution, an organic solution of a mixture of electrically neutral polyamide and polyester, an electrically neutral polycarboxylic acid ammonium salt, a mixture organic solution of high molecular weight carboxylic acid and modified polysiloxane, an organic solution of polyurethane and the like; the (methyl) acrylic resin comprises one or more than two of methyl methacrylate, acrylonitrile, ethyl acrylate, butyl acrylate, isooctyl acrylate and isobutyl methacrylate; the wax powder comprises one or more of carnauba wax, PE wax and EVA wax.

Further, the substrate is a transparent flexible plastic film;

the back coating comprises one or more than two of ester modified organic silicon resin, acrylic acid modified organic silicon resin, polyvinyl acetal resin and polyvinyl butyral resin.

Further, the transparent flexible plastic film includes polypropylene (PP), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyethylene (PE), polyvinyl alcohol (PVA), or polymethyl methacrylate (PMMA). Among them, PET is preferable.

The inorganic pigment comprises one or more than two of oxide, chromate, sulfate, silicate, borate, molybdate, phosphate, vanadate, ferricyanide, hydroxide, sulfide and metal;

the organic pigment comprises one or more than two of azo pigment, phthalocyanine pigment, polycyclic pigment and aromatic methane pigment, and the polycyclic pigment comprises anthraquinone, indigo group, quinacridone and dioxazine;

the release layer coating, the printing ink layer coating and the back coating also comprise 0.1-1 part of leveling agent and 0.1-1 part of defoaming agent.

Further, the thickness of the ink layer is 0.5-1.5 μm; the thickness of the release layer is 0.5-2 mu m; the thickness of the base material is 4-25 mu m; the thickness of the back coating is 0.2-1.0 mu m.

Further, the thickness of the ink layer is 0.8-1.2 μm; the thickness of the release layer is 0.5-1.5 mu m; the thickness of the base material is 4-10 mu m; the thickness of the back coating is 0.5-0.8 mu m.

A second object of the present invention is to provide a method for producing a resin carbon tape having excellent weather resistance, characterized by comprising the steps of:

s1: preparing liquid:

and (3) coating an ink layer: dissolving organosilicon-acrylic acid composite resin in butanone and toluene solvent, then adding pigment, dispersant and light stabilizer, stirring and mixing, and finally adding curing agent to prepare ink layer coating for later use;

and (3) release layer coating: dissolving acrylic resin in butanone and toluene solvent, adding light stabilizer and wax powder, stirring and mixing to obtain release coating;

back coating paint: one or more than two of polyurethane modified organic silicon resin, acrylic acid modified organic silicon resin, polyvinyl acetal resin and polyvinyl butyral resin are dissolved in butanone and toluene solvent, and are stirred and mixed to prepare back coating paint for standby;

s2: corona is performed;

providing a substrate, and beating corona on two opposite surfaces of the substrate;

s3: coating;

coating the back coating prepared in the step S1 on one surface of the substrate in the step S2, and then drying to form a back coating for later use;

coating the release layer coating prepared in the step S1 on one surface of the back coating, which is far away from the base material, and then drying to form a release layer for later use;

and (2) coating the ink layer coating prepared in the step (S1) on one surface of the release layer far away from the base material, and then drying to form an ink layer, so as to obtain the resin carbon tape with excellent weather resistance.

The beneficial effects of adopting above-mentioned scheme are: the preparation method provided by the invention can be used for efficiently and rapidly completing the preparation of the resin carbon tape with excellent weather resistance.

In the step S3, gravure coating or slit coating is adopted to coat back coating, the drying temperature is 50-100 ℃, and the drying time is 40-60S; the gravure coating or slit coating release coating is adopted, the drying temperature is 50-100 ℃, and the drying time is 40-60s; and (3) coating an ink layer by adopting gravure coating or slit coating, wherein the drying temperature is 40-100 ℃ and the drying time is 1-4h.

A third object of the present invention is to provide the use of a resin carbon tape with excellent weather resistance for thermal transfer transportation substrates.

The layer structure of the resin carbon tape after printing on the surface of the traffic base material is as follows: the white light-reflecting film comprises a white light-reflecting film, an ink layer on the surface of the white light-reflecting film and a release layer on one side, far away from the white light-reflecting film, of the surface of the ink layer.

Drawings

Fig. 1 is a structural view of a resin carbon tape having excellent weather resistance according to the present invention.

In the drawings, the list of components represented by the various numbers is as follows:

1-ink layer, 2-release layer, 3-substrate, 4-back coating.

Detailed Description

The principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the invention.

Example 1

The embodiment relates to a resin carbon tape with excellent weather resistance, which comprises an ink layer, a release layer, a base material and a back coating, wherein the ink layer, the release layer, the base material and the back coating are sequentially attached from top to bottom; the details are shown in the table 1,

the ink layer is formed by coating ink layer paint, and in the ink layer paint, organic silicon-acrylic acid composite resin comprises the following components in percentage by weight: 6, a polysiloxane and acrylic acid chemically combined end-capping structure, and the pH is 7.5-8.5; the pigment is azo pigment; the dispersing agent is modified polyester organic solution; the light stabilizer is salicylate; the curing agent is gamma- (methacryloyloxy) propyl trimethoxy siloxane;

the release layer is formed by coating release layer paint, wherein in the release layer paint, (methyl) acrylic resin is methyl methacrylate; the light stabilizer is salicylate; the wax powder is carnauba wax; the (meth) acrylic resin has a number average molecular weight (Mn) of 20000 and a glass transition temperature Tg of 60.

The preparation method of the resin carbon tape with excellent weather resistance comprises the following steps:

s1: preparing liquid:

and (3) release layer coating: dissolving (methyl) acrylic resin in butanone and toluene solvent, adding light stabilizer and wax powder, stirring and mixing to prepare release layer coating for later use;

s2: corona is performed;

s3: coating;

In the step S3, gravure coating or slit coating is adopted to coat back coating paint, wherein the drying temperature is 100 ℃, and the drying time is 60 seconds; the gravure coating release layer coating is adopted, the drying temperature is 100 ℃, and the drying time is 60s; and (3) coating an ink layer by adopting gravure coating or slit coating, wherein the drying temperature is 100 ℃, and the drying time is 2 hours.

After obtaining the resin carbon tape with excellent weather resistance, printing the ink layer and the release layer on the surface of the white reflecting film by using a printer based on thermal transfer printing, and performing weather resistance test.

Example 2

In this example, 70 parts of (meth) acrylic resin was used in the release layer compared with example 1, and the remainder was the same as in comparative document 1. Details are shown in Table 1.

Example 3

In this example, compared with example 1, in the ink layer coating, the organosilicon-acrylic composite resin comprises the following components in weight ratio: 7 with a polysiloxane and acrylic acid chemically combined end-capping structure, and the pH is 7.5-8.5; the pigment is azo pigment; the (meth) acrylic resin Mn is 10000, tg is 95, and the remainder is the same as in comparative document 1. Details are shown in Table 1.

Example 4

In this example, compared with example 1, in the ink layer coating, the organosilicon-acrylic composite resin comprises the following components in weight ratio of 3.5:6.5 a polysiloxane and acrylic acid chemically bonded end-capping structure; the pigment is phthalocyanine pigment; the thickness of the release layer is 0.6 mu m; the remainder is the same as comparative document 1. Details are shown in Table 1.

Example 5

In this example, compared with example 1, the wax powder in the release layer was 1 part, and the remainder was the same as in comparative document 1. Details are shown in Table 1.

Example 6

In this example, 2.66 parts of gamma- (methacryloyloxy) propyl trimethoxysiloxane was used in the ink layer, 10000 parts of (meth) acrylic resin Mn, 95 parts of Tg, and the remainder was the same as in comparative document 1. Details are shown in Table 2.

Example 7

In this example, compared with example 1, the silicone-acrylic composite resin in the ink layer was 70 parts, the γ - (methacryloyloxy) propyl trimethoxy siloxane was 2.66 parts, the (meth) acrylic resin Mn was 10000, tg was 95, and the rest was the same as in comparative document 1. Details are shown in Table 2.

Example 8

In this example, compared with example 1, the pigment in the ink layer was 70 parts, gamma- (methacryloyloxy) propyl trimethoxysiloxane was 2.66 parts, the (meth) acrylic resin Mn was 10000, tg was 95, and the remainder was the same as in comparative document 1. Details are shown in Table 2.

Example 9

In this example, compared with example 1, 2.66 parts of gamma- (methacryloyloxy) propyl trimethoxysiloxane, 10000 parts of (meth) acrylic resin Mn, 95 parts of Tg, and 0.8 μm of ink layer thickness were obtained, and the remainder was the same as in comparative document 1. Details are shown in Table 2.

Example 10

In this example, compared with example 1, the (meth) acrylic resin Mn was 10000, tg was 95, and the remainder was the same as in comparative document 1. Details are shown in Table 2.

TABLE 1 Components and amounts of ink layer, release layer, substrate and Back coating in examples 1-5

TABLE 2 Components and amounts of ink layer, release layer, substrate and Back coating in examples 1-5

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Comparative example 1

The same release and back coat formulations, coating thickness, coating pattern, printing pattern as in example 3 were used, but the resin in the ink layer was replaced with a conventional acrylic resin.

Comparative example 2

The same ink layer and back coat formulation, coating thickness, coating mode, and printing mode as in example 3 were used, but no release layer was applied.

Comparative example 3:

the ink layer resin in example 3 was replaced with a common acrylic resin and the release layer was not applied.

Experimental example

Whether have to fall the piece during printing, whether glue the carbon tape, the side cut nature is good not good etc. phenomenon come the printing effect to the carbon tape to evaluate when the rendition, according to road traffic reflective film national standard: GB/T18833-2012. The results are detailed in tables 3 to 5.

The weather resistance of the samples was evaluated by:

(1) Using a xenon lamp aging test box for 1800 hours, and observing whether the surface of the xenon lamp aging test box has the phenomena of wrinkling, foaming, cracking and the like;

(2) Measuring the residual percentage of the retroreflection coefficient of the material after accelerated aging by using a xenon lamp aging test box for 1800 hours;

(3) The color difference values before and after accelerated aging were measured using a xenon lamp aging test chamber for 1800 hours.

Table 3 comparative performance tables for examples 1 to 5

Table 4 comparative performance tables for examples 6 to 10

Table 5 comparative examples 1 to 3 performance comparative tables

In summary, the silicone-acrylic composite resin is adopted, and when the silicone-acrylic composite resin is used together with a curing agent, the formed curing system has excellent weather resistance, excellent adhesiveness to a substrate, high transparency, less influence on the retroreflection coefficient and performance of silicone and acrylic acid. Compared with the existing printed products of acrylic acid or organic silicon systems in the traffic industry, the printed products obtained by printing the resin carbon tape have the advantages of more excellent weather resistance and both.

While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.

Claims

1. The resin carbon tape with excellent weather resistance is characterized by comprising an ink layer, a release layer, a base material and a back coating which are sequentially attached from top to bottom;

the release layer is formed by coating release layer paint, and the release layer paint comprises the following components in parts by weight: 50-70 parts of (methyl) acrylic resin, 0.05-1.4 parts of light stabilizer and 0.25-2.5 parts of wax powder, wherein the number average molecular weight Mn of the (methyl) acrylic resin is 10000-20000, and the glass transition temperature Tg is 60-95.

2. The resin carbon tape of claim 1, wherein the resin carbon tape has excellent weather resistance,

the ink layer coating comprises the following components in parts by weight: 55-65 parts of organosilicon-acrylic composite resin, 55-65 parts of pigment, 7-15 parts of dispersing agent, 0.25-2.1 parts of light stabilizer and 2.5-3 parts of curing agent;

3. The resin carbon tape with excellent weather resistance according to claim 1 or 2, wherein the silicone-acrylic composite resin is prepared from (3-4) by weight: the end-capping structure of (6-7) wherein polysiloxane and acrylic acid are chemically combined, having a pH of 7.5-8.5; the pigment is an inorganic pigment and/or an organic pigment; the curing agent is gamma- (methacryloyloxy) propyl trimethoxy siloxane; the light stabilizer comprises one or more than two of salicylate, benzene ketone, benzotriazole and triazine ultraviolet absorbers; the dispersing agent comprises one or more than two of polymer organic solvent solution containing carboxyl, modified polysiloxane solution, anionic surfactant, high molecular weight carboxylic acid organic solution, organic solution of mixture of electrically neutral polyamide and polyester, electrically neutral polycarboxylic acid ammonium salt, mixture organic solution of high molecular weight carboxylic acid and modified polysiloxane and organic solution of polyurethane; the (methyl) acrylic resin comprises one or more than two of methyl methacrylate, acrylonitrile, ethyl acrylate, butyl acrylate, isooctyl acrylate and isobutyl methacrylate; the wax powder comprises one or more of carnauba wax, PE wax and EVA wax.

4. A resin carbon tape having excellent weather resistance according to claim 3, wherein the base material is a transparent flexible plastic film;

5. The resin carbon tape having excellent weather resistance according to claim 4,

the organic pigment comprises one or more than two of azo pigment, phthalocyanine pigment, polycyclic pigment and aromatic methane pigment;

the transparent flexible plastic film comprises polypropylene, polyethylene naphthalate, polyethylene terephthalate, polyethylene, polyvinyl alcohol or polymethyl methacrylate.

6. The resin carbon tape with excellent weather resistance according to claim 1, wherein the thickness of the ink layer is 0.5 to 1.5 μm; the thickness of the release layer is 0.5-2 mu m; the thickness of the base material is 4-25 mu m; the thickness of the back coating is 0.2-1.0 mu m.

7. The resin carbon tape with excellent weather resistance according to claim 6, wherein the thickness of the ink layer is 0.8 to 1.2 μm; the thickness of the release layer is 0.5-1.5 mu m; the thickness of the base material is 4-10 mu m; the thickness of the back coating is 0.5-0.8 mu m.

8. A method for producing a resin carbon tape having excellent weather resistance based on any one of claims 1 to 7, characterized by comprising the steps of:

s1: preparing liquid:

s2: corona is performed;

s3: coating;

9. The method for producing a resin carbon tape having excellent weather resistance according to claim 8, wherein in step S3, gravure coating or slot coating is used as a back coating material, the drying temperature is 50 to 100 ℃ and the drying time is 40 to 60 seconds; the gravure coating or slit coating release coating is adopted, the drying temperature is 50-100 ℃, and the drying time is 40-60s; and (3) coating an ink layer by adopting gravure coating or slit coating, wherein the drying temperature is 40-100 ℃ and the drying time is 1-4h.

10. Use of a resin carbon tape with excellent weatherability based on any one of claims 1 to 7, characterized in that the resin carbon tape is used for thermal transfer transportation substrates.