CN114989672B

CN114989672B - Preparation and implementation method of photochromic anti-counterfeiting material

Info

Publication number: CN114989672B
Application number: CN202210604846.0A
Authority: CN
Inventors: 申立全; 岳绍杰; 刘朋飞; 马尧臣
Original assignee: Guangyi Technology Wuxi Co ltd
Current assignee: Guangyi Technology Wuxi Co ltd
Priority date: 2022-05-31
Filing date: 2022-05-31
Publication date: 2023-05-16
Anticipated expiration: 2042-05-31
Also published as: CN114989672A

Abstract

The invention discloses a preparation method and an implementation method of a photochromic anti-counterfeiting material. The invention uses solvent-free paint and EB electron beam curing technology to apply the photochromism technology to the packaging material, thus realizing the mass production of the novel anti-counterfeiting material. The invention prepares the anti-counterfeiting packaging material through special formula design and process control, and the process does not contain solvent and photoinitiator, is a novel and environment-friendly anti-counterfeiting packaging material, and can be applied to high-end industries such as food, medical treatment and the like.

Description

Preparation and implementation method of photochromic anti-counterfeiting material

Technical Field

The invention belongs to the field of packaging materials, and relates to a preparation method and an implementation method of a photochromic anti-counterfeiting material, which can be used for surface anti-counterfeiting of label materials such as paper, fabric, PE film, PET film, PP film, BOPP film, PVC film and the like or packaging materials.

Background

Color-changing anti-counterfeiting materials are divided into two types, one of which changes color by changing temperature and the other of which changes color by ultraviolet irradiation. The anti-counterfeiting material which changes the color by changing the temperature is mature, and related patents report that the traditional temperature-changing anti-counterfeiting material is solvent-based paint, is coated on packaging materials and is prepared by high-temperature curing, and the traditional technology changes the solvent-based paint into water-based paint, thereby meeting the environmental protection requirement. However, the photochromic cannot change the solvent type coating into the water type coating, and the main reason is that the photochromic dye cannot be dissolved in water, so that the environmental protection requirement cannot be met, and the traditional thermosetting process can be completely cured only by 50-100 meters on a production line, so that the cost is extremely high for the field of ink-jet printing and cannot be realized; the photochromic can not be changed into a UV light-cured coating, and the main reasons are that the photochromic dye can generate yellowing, service life reduction and incomplete curing under UV irradiation, and meanwhile, the UV coating also involves a light-shielding operation problem, and the irradiation before UV curing can influence the gel deterioration of the coating, so that construction can not be performed; the traditional thermosetting technology needs long-term high-temperature curing, the thickness of the packaging material is about 25 microns, BOPP, PP or PE is mainly used, the packaging material can be wrinkled and deformed at a high temperature for a long time, meanwhile, the surface polarity of the packaging material is very low, and good adhesive force of the photochromic coating on the packaging film is difficult to ensure, so that the thermosetting technology is difficult to realize standard mass production because of technology and technology. In summary, photochromic techniques are rarely applied to the field of security materials.

Disclosure of Invention

The invention aims to solve the problem that the photochromic technology cannot be applied to anti-counterfeiting packaging materials, and provides a preparation method and an implementation method of the photochromic anti-counterfeiting material. The invention uses self-developed coating and EB electron beam curing process to apply photochromic technology to packaging material, and realizes the scale production of novel anti-counterfeiting material by unique design and ink-jet process. Compared with the prior art, the photochromic anti-counterfeiting material has higher adhesive force and can be directly adhered to the surface of untreated BOPP; and has better chemical resistance and discoloration resistance.

The invention provides a photochromic anti-counterfeiting material, which comprises the following components in parts by weight:

preferably, the chlorine content of the chlorinated polypropylene is 20% -70%, and is preferably one or more of CY-9122P, CY-9124P, F-2P, 13-LP, 13-LLP, 14-LWP, 15-LP, 15-LLP, 16-LP, DX-523P, DX-526-P, HM-21P, CY-1321P, CY-1132, F-225P, F-6P and F-7P formed by the eastern ocean of Japan.

Preferably, the reactive diluent is one or more of toluene, xylene, cyclohexane, methylcyclohexane, methyl ethyl ketone, methyl isobutyl ketone, butyl ester, ethyl acetate, vinyl cyclohexane and styrene.

Preferably, the photochromic dye is a spiropyran or a material having a spiropyran structure; preferably UK Vilman chemistry Reversacol Sea Green, reversacol Velvent Rlue, reversacol Sunflower one or more of Reversacol Ruby, reversacol Ocean Blue.

In some embodiments, the photochromic materials described above may also be other materials having similar properties to spiropyrans, such as diarylethenes, salicylaldoanilides, spiro well throat, fulgides, spiropyrans, spirooxazines, azobenzene, hexaphenyl bis-Miwa, or similar compounds having these structural units.

As preferable:

the antioxidant is aromatic amine antioxidant, hindered phenol antioxidant or sulfur-containing antioxidant, preferably one or more of constant bridge chemistry Chemfos-36, chemfos-626 or Chemfos-619;

the ultraviolet light absorber is one or more of benzophenone, salicylate, benzotriazole, triazine or substituted acrylonitrile, preferably constant bridge chemistry chemsellib-BP 3, chemsellib-BP 6, chemsellib-327, chemsellib-328 or chemsellib-329;

the light stabilizer is one or more of diphenyl ketone, salicylate, benzotriazole, triazine, substituted acrylonitrile, hindered amine, oxamide or organic nickel compound, preferably constant bridge chemistry chemmorb-LS 944, chemmorb-LS 622 or chemmorb-LS 144.

Preferably, the chlorinated polypropylene is F-2P; the reactive diluent is vinyl cyclohexane; the ultraviolet absorbent is Chemsorb-329; the antioxidant is Chemfos-36; the light stabilizer is Chemsorb-LS944.

Preferably, the components are as follows:

the invention also provides a preparation method of the photochromic anti-counterfeiting material, which comprises the following steps:

firstly, adding chlorinated polypropylene and an active diluent into a four-neck flask, heating to 90 ℃ and uniformly stirring, and finally gradually adding an ultraviolet light absorber, a light stabilizer, an antioxidant and a photochromic dye, and uniformly stirring at 90 ℃ to obtain the photochromic anti-counterfeiting coating.

The invention also provides a spraying method of the photochromic anti-counterfeiting material, which comprises the following steps of:

the photochromic inkjet coating is sprayed on the substrate by using a UV inkjet process, and a continuous interphase pattern is obtained on the substrate by EB curing.

Preferably, the EB curing voltage is 80-200 kv, the dosage is 10KGy-200KGy, and the oxygen content is 100PPM-500PPM; the substrate includes, but is not limited to, fabric, paper, PET, PE, PP, BOPP, PVC, PC, PU, or PUE.

The invention aims to realize the design and production of novel anti-counterfeiting materials by utilizing a photochromic technology, adopts a unique spraying process and a curing process, sprays logo or pattern appointed by a customer on a packaging material and cures and forms, when sunlight or a fluorescent pen (lamp) irradiates, the logo or pattern with a certain color can appear, and when no sunlight or fluorescent pen (lamp) irradiates, the logo or pattern gradually returns to the original colorless and transparent state.

The unique spraying process and the curing process are to combine UV ink-jet printing with EB electron beam curing, and finally realize the cross-field application of the photochromic coating on the packaging material.

The beneficial effects of the invention are as follows:

the photochromic coating provided by the invention is a solvent-free coating, the viscosity of the coating is controlled, the coating is suitable for ink-jet printing and is combined with EB curing, the distance from ink-jet to curing is less than 1 meter, compared with solvent-based thermosetting coating, the VOC emission is basically zero, the method meets the national environment-friendly requirement, a production line does not need a drying tunnel, an exhaust gas combustion device RTO is not required to be installed, and therefore, the production cost is saved, the product competitiveness is improved; and secondly, the invention adopts a process combining UV ink-jet printing and EB electron beam curing to realize the application of the photochromic technology on the anti-counterfeiting material, and logo or pattern can be customized according to the requirements of customers to realize mass production on any base material. The UV ink-jet printing is adopted, so that the production line speed of 100-200 meters per minute can be realized, the production efficiency can be improved, and the production cost can be reduced. By adopting EB electron beam curing, the paint does not need to be added with a photoinitiator, the UV ink-jet nozzle does not need to be blocked due to paint deterioration, a production workshop does not need to be subjected to light-shielding treatment, the paint does not need to worry about deterioration of the paint due to illumination gel, meanwhile, the EB can break down chemical bonds of packaging materials such as BOPP, PE or PP and the like, and form chemical links with the photochromic paint, so that better adhesive force of the photochromic paint on the packaging materials is realized, the EB curing belongs to room temperature curing, no heat is generated, and the packaging materials cannot deform due to high temperature generated during curing.

The reactive diluent adopted by the invention not only can reduce the curing cost, but also has better compatibility with the photochromic dye; secondly, the photochromic coating provided by the application also has good surface adhesion, and can be sprayed on the surface of a substrate which is difficult to attach, such as BOPP and the like. In addition, the compound has better chemical resistance and discoloration resistance compared with the prior art.

Detailed Description

The following will explain the embodiments of the present application in detail by way of examples, whereby the implementation process of how the present application applies technical means to solve technical problems and achieve technical effects can be fully understood and implemented accordingly.

The raw materials and equipment used in the present application are common raw materials and equipment used in the field and are commercially available products unless otherwise specified. The methods used in the present application are conventional in the art unless otherwise specified.

There are many other embodiments that can be implemented, and none of them are listed here, but the embodiments claimed in the claims of this application are all applicable.

"comprising" or "including" is intended to mean that the compositions (e.g., media) and methods include the recited elements, but not exclude other elements. When used to define compositions and methods, "consisting essentially of … …" means excluding other elements that have any significance to the combination for the purpose. Thus, a composition consisting essentially of the elements defined herein does not exclude other materials or steps that do not materially affect the basic and novel characteristics of the claimed application. "consisting of … …" means the process steps excluding trace elements and essential elements of other components. Embodiments defined by each of these transitional terms are within the scope of this application.

Chlorinated polypropylene: the Japanese eastern chemical into CY-9122P, the Japanese eastern chemical into CY-9124P, the Japanese eastern chemical into F-2P, the Japanese eastern chemical into 13-LP, the Japanese eastern chemical into 13-LLP and the Japanese eastern chemical into 14-LWP;

a diluent: vinyl cyclohexane of national medicine group;

photochromic dyes: UK Vilman chemistry Reversacol Sea Green;

ultraviolet light absorber: constant bridge chemistry chemorb-329;

an antioxidant: constant bridge chemistry Chemfos-36;

light stabilizers: constant bridge chemistry Chemsorb-LS944.

Example 1:

5g CY-9122P and 95g vinylcyclohexane are put into a flask, then the temperature is raised to 90 ℃, after the mixture is stirred at the temperature of 90 ℃ until the mixture is dissolved, 0.2g Chemsorb-329, 0.2g Chemfos-36, 0.2g Chemsorb-LS944 and 5g Reversacol Sea Green,90 ℃ are put into the flask, and the mixture is stirred at the temperature of 1 hour, thus obtaining the photochromic inkjet coating with the viscosity of 5.3mPa.s.

The UV ink-jet machine is arranged on a coating production line, then the ink-jet coating tank is arranged on the UV ink-jet printer, the ink-jet speed and the coating production line speed are set at a matched numerical value, a continuous alternate pattern is obtained on the PET substrate, finally, the continuous alternate pattern is formed by EB electron beam curing, the electron beam voltage is 120kv, the dosage is 120kGy, and the oxygen content is controlled to be about 200 PPM.

Example 2:

5g CY-9124P and 95g vinylcyclohexane are put into a flask, then the temperature is raised to 90 ℃, after the mixture is stirred at the temperature of 90 ℃ until the mixture is dissolved, 0.2g Chemsorb-329, 0.2g Chemfos-36, 0.2g Chemsorb-LS944 and 5g Reversacol Sea Green,90 ℃ are put into the flask, and the mixture is stirred at the temperature of 1 hour, thus obtaining the photochromic inkjet paint with the viscosity of 5.1 Pa.s.

Example 3:

5.5 g F-2P and 95g of vinylcyclohexane are put into a flask, then the temperature is raised to 90 ℃, the mixture is stirred at a constant temperature until the mixture is dissolved, and then 0.2g of Chemsorb-329, 0.2g of Chemfos-36, 0.2g of Chemsorb-LS944 and 5g Reversacol Sea Green,90 ℃ are put into the flask, and the mixture is stirred at a constant temperature for 1 hour, so that the photochromic inkjet paint with the viscosity of 4.3mPa.s is obtained.

Example 4:

5g of 13-LP and 95g of vinylcyclohexane are put into a flask, then the temperature is raised to 90 ℃, the mixture is stirred at a constant temperature until the mixture is dissolved, and then 0.2g of Chemsorb-329, 0.2g of Chemfos-36, 0.2g of Chemsorb-LS944 and 5g Reversacol Sea Green,90 ℃ are put into the flask, and the mixture is stirred at a constant temperature for 1 hour, so that the photochromic inkjet paint with the viscosity of 5.5 Pa.s is obtained.

Example 5:

5g of 13-LLP and 95g of vinylcyclohexane are put into a flask, then the temperature is raised to 90 ℃, the mixture is stirred at a constant temperature until the mixture is dissolved, and then 0.2g of Chemsorb-329, 0.2g of Chemfos-36, 0.2g of Chemsorb-LS944 and 5g Reversacol Sea Green,90 ℃ are put into the flask, and the mixture is stirred at a constant temperature for 1 hour, so that the photochromic inkjet paint with the viscosity of 5.5 Pa.s is obtained.

Example 6:

5g of 14-LWP and 95g of vinylcyclohexane are put into a flask, then the temperature is raised to 90 ℃, the mixture is stirred at a constant temperature until the mixture is dissolved, and then 0.2g of Chemsorb-329, 0.2g of Chemfos-36, 0.2g of Chemsorb-LS944 and 5g Reversacol Sea Green,90 ℃ are put into the flask, and the mixture is stirred at a constant temperature for 1 hour, so that the photochromic inkjet paint with the viscosity of 5.7mPa.s is obtained.

The test results of the photochromic anti-counterfeiting materials obtained in examples 1 to 6 after spraying are shown in Table 1.

TABLE 1

As can be seen from Table 1, the chlorinated polypropylene CY-9122P, CY-9124P and F-2P of examples 1-3 are modified by maleic acid to obtain better adhesive force and alcohol resistance, and the chlorinated polypropylene 13-LP, 13-LLP and 14-LWP of examples 4-6 are free of unsaturated double bonds, so that the adhesive force and alcohol resistance are slightly insufficient; because CY-9122P, CY-9124P and F-2P have molecular weights of 60000, 60000 and 65000 respectively, melting points of 82 ℃, 80 ℃ and 70 ℃ respectively, F-2P has higher molecular weight and lowest melting point and better flexibility corresponding to F-2P, a faster fading speed can be obtained, and the comprehensive performance of the embodiment 3 is optimal according to the optimal physical examination of customers on anti-counterfeiting performance.

In addition to the large impact of the labeling properties of chlorinated polypropylene on the present application, its ratio to reactive diluent can also have a large impact. Examples 7-11 will mainly investigate the effect of different proportions of chlorinated polypropylene and reactive diluent on its viscosity.

Example 7:

3g F-2P and 94g of vinylcyclohexane are put into a flask, then the temperature is raised to 90 ℃, after the mixture is stirred at the temperature of 90 ℃ until the mixture is dissolved, 0.2g of Chemsorb-329, 0.2g of Chemfos-36, 0.2g of Chemsorb-LS944 and 5g Reversacol Sea Green,90 ℃ are put into the flask, and the mixture is stirred at the temperature of 1 hour, so that the photochromic inkjet paint with the viscosity of 3.8mPa.s is obtained.

Example 8:

7g F-2P and 93g of vinylcyclohexane are put into a flask, then the temperature is raised to 90 ℃, after the mixture is stirred at the temperature of 90 ℃ until the mixture is dissolved, 0.2g of Chemsorb-329, 0.2g of Chemfos-36, 0.2g of Chemsorb-LS944 and 5g Reversacol Sea Green,90 ℃ are put into the flask, and the mixture is stirred at the temperature of 1 hour, thus obtaining the photochromic inkjet paint with the viscosity of 10.7mPa.s.

Example 9:

9g F-2P and 92g of vinylcyclohexane are put into a flask, then the temperature is raised to 90 ℃, the mixture is stirred at a constant temperature until the mixture is dissolved, and then 0.2g of Chemsorb-329, 0.2g of Chemfos-36, 0.2g of Chemsorb-LS944 and 5g Reversacol Sea Green,90 ℃ are put into the flask, and the mixture is stirred at a constant temperature for 1 hour, so that the photochromic inkjet paint with the viscosity of 20.3mPa.s is obtained.

Example 10:

11g F-2P and 91g of vinylcyclohexane are put into a flask, then the temperature is raised to 90 ℃, the mixture is stirred at a constant temperature until the mixture is dissolved, and then 0.2g of Chemsorb-329, 0.2g of Chemfos-36, 0.2g of Chemsorb-LS944 and 5g Reversacol Sea Green,90 ℃ are put into the flask, and the mixture is stirred at a constant temperature for 1 hour, so that the photochromic inkjet paint with the viscosity of 28.6mPa.s is obtained.

Example 11:

13g F-2P and 90g of vinylcyclohexane are put into a flask, then the temperature is raised to 90 ℃, the mixture is stirred at a constant temperature until the mixture is dissolved, and then 0.2g of Chemsorb-329, 0.2g of Chemfos-36, 0.2g of Chemsorb-LS944 and 5g Reversacol Sea Green,90 ℃ are put into the flask, and the mixture is stirred at a constant temperature for 1 hour, so that the photochromic inkjet paint with the viscosity of 40.8mPa.s is obtained.

TABLE 2

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As can be seen from Table 2, as the addition ratio of F-2P is proportional to the alcohol resistance and the fading speed, but the addition amount exceeds a certain ratio, the viscosity of the inkjet paint increases, and the solubility of the photochromic dye decreases, resulting in clogging of the inkjet head. From examples 3, 7, 8, 9, 10, and 11, the addition ratio of example 8 was most suitable.

Example 13: the effect of the species of reactive diluent on the coating.

7g F-2P and 93g of reactive diluent are put into a flask, then the temperature is raised to 90 ℃, after the mixture is stirred at the temperature of 90 ℃ until the mixture is dissolved, 0.2g of Chemsorb-329, 0.2g of Chemfos-36, 0.2g of Chemsorb-LS944 and 5g of photochromic dye are put into the flask, and after the mixture is stirred at the temperature of 90 ℃ for 1 hour, the photochromic inkjet paint is obtained.

And (3) standing the photochromic coating, and observing uniformity and layering phenomena of the photochromic coating.

The results are shown in Table 3.

TABLE 3 Table 3

Example 14: testing of different substrates

The UV inkjet printer was mounted on the coating line, the coating material obtained in example 8 was then mounted on the UV inkjet printer, the inkjet speed and the coating line speed were set to a matched value, the substrates were subjected to corona treatment first, then continuous alternating patterns were obtained on the different substrates, and finally, the patterns were formed by EB electron beam curing, the electron beam voltage was 120kv, the dose was 120kGy, and the oxygen content was controlled at about 200 PPM.

TABLE 4 Table 4

Example 15: influence of adhesion

The coating obtained in example 8 was compared with the BOPP surface adhesion of a commercially available conventional photochromic coating, and BOPP was used both surface treated and untreated.

The coating obtained in example 8 of the present application was sprayed: the method comprises the steps of installing a UV ink jet machine on a coating production line, then installing an ink jet coating tank on a UV ink jet printer, setting the ink jet speed and the coating production line speed at a matched numerical value, carrying out corona treatment on BOPP, obtaining continuous alternate patterns on the BOPP, and finally curing and forming through EB (electron beam) electron beam, wherein the electron beam voltage is 120kv, the dosage is 120kGy, and the oxygen content is controlled to be about 200 PPM.

A common photochromic coating (a us litadau UV ink) was sprayed according to its instructions.

The pre-treatment method of the BOPP surface comprises the following steps: the BOPP is subjected to corona treatment, and then the water-based PP water coated on the BOPP is solidified into a film by a thermosetting method.

TABLE 5

What is not described in detail in the present specification is common general knowledge of a person skilled in the art.

As used throughout the specification and claims, the word "comprise" is an open-ended term, and thus should be interpreted to mean "include, but not limited to. By "substantially" is meant that within an acceptable error range, a person skilled in the art is able to solve the technical problem within a certain error range, substantially achieving the technical effect.

It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such product or system. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a commodity or system comprising such elements.

While the foregoing description illustrates and describes the preferred embodiments of the present application, it is to be understood that this application is not limited to the forms disclosed herein, but is not to be construed as an exclusive use of other embodiments, and is capable of many other combinations, modifications and environments, and adaptations within the scope of the inventive concept described herein, through the foregoing teachings or through the skill or knowledge of the relevant arts. And that modifications and variations which do not depart from the spirit and scope of the present invention are intended to be within the scope of the appended claims.

Claims

1. The photochromic anti-counterfeiting material is characterized by comprising the following components in parts by weight:

1-10 parts by weight of chlorinated polypropylene;

90-100 parts by weight of a reactive diluent;

1-10 parts by weight of a photochromic dye;

0.1-1 parts by weight of an ultraviolet light absorber;

0.1-1 parts by weight of an antioxidant;

0.1-1 parts by weight of a light stabilizer;

the chlorinated polypropylene is selected from F-2P formed by the eastern ocean of Japan;

the reactive diluent is selected from vinyl cyclohexane;

the photochromic dye is selected from UK Vilman chemical Reversacol Sea Green Reversacol Sunflower, reverse Ruby, reversacol Ocean Blue;

the ultraviolet light absorber is one or more of constant bridge chemistry Chemsorb-BP3, chemsorb-BP6, chemsorb-327, chemsorb-328 and Chemsorb-329;

the light stabilizer is one or more selected from the group consisting of Chemsorb-LS944, chemsorb-LS622 and Chemsorb-LS144 of constant bridge chemistry.

2. The photochromic anti-counterfeiting material according to claim 1, wherein,

the antioxidant is one or more selected from Chemfos-36, chemfos-626 and Chemfos-619.

3. The photochromic anti-counterfeiting material according to claim 1, wherein the chlorinated polypropylene is F-2P; the reactive diluent is vinyl cyclohexane; the ultraviolet light absorber is Chemsorb-329; the antioxidant is Chemfos-36; the light stabilizer is Chemsorb-LS944.

4. The photochromic anti-counterfeiting material according to claim 3, wherein the weight parts of the components are as follows:

7 parts by weight of chlorinated polypropylene;

93 parts by weight of a reactive diluent;

5 parts by weight of a photochromic dye;

0.2 parts by weight of an ultraviolet light absorber;

0.2 parts of antioxidant;

0.2 parts by weight of light stabilizer.

5. A method of preparing a photochromic anti-counterfeiting material according to claim 1, comprising the steps of:

firstly, adding chlorinated polypropylene and an active diluent into a four-neck flask, heating to 90 ℃ and uniformly stirring, and finally gradually adding an ultraviolet light absorber, a light stabilizer, an antioxidant and a photochromic dye, and uniformly stirring at 90 ℃ to obtain the photochromic anti-counterfeiting material.

6. A method of spraying a photochromic anti-counterfeiting material according to claim 1, comprising the steps of:

and spraying the photochromic anti-counterfeiting material on the base material by using a UV ink-jet process, and curing the base material by EB to obtain a continuous alternate pattern.

7. The spraying method according to claim 6, wherein the EB curing voltage is 80kv-200kv, the dose is 10KGy-200KGy, and the oxygen content is 100PPM-500PPM; the substrate is fabric, paper, PET, PE, PP, BOPP, PVC, PC or PU.