Anti-copy holographic polymer material composition, anti-copy coating and anti-counterfeit label

Abstract

The invention discloses an anti-copy holographic high-molecular material composition, an anti-copy coating and an anti-counterfeit label, the anti-copy holographic high-molecular material composition forms an anti-copy function by adding beta-Al (OH) 3 and gamma-Al2O3, and is compatible with components such as organic high-molecular resin and rosin-based modified phenolic resin to avoid agglomeration and sedimentation of inorganic materials; and the self-layering effect is generated, the self-layering coating can be fused with existing composite material resin or transfer material resin, migration of the self-layering coating to the surface of a coating is promoted, the anti-copying effect is achieved, and the self-layering coating has important significance for preventing anti-fake patterns from being cracked and stolen and improving the safety coefficient.

Description

Technical Field

[0001] The present invention relates to the technical field of anti-counterfeiting materials, in particular to an anti-copying holographic polymer material composition, an anti-copying coating and an anti-counterfeiting label. Background Art

[0002] Anti-counterfeiting is a technical means to identify authenticity and prevent forgery, alteration, and cloning. Product anti-counterfeiting usually uses an anti-counterfeiting coating containing anti-counterfeiting patterns or information to hide the anti-counterfeiting information, prevent multiple queries, enhance the durability of the label, improve the visual effect and provide additional anti-counterfeiting functions, making it technically difficult for counterfeiters to forge.

[0003] With existing anti-counterfeiting coatings, counterfeiters can completely separate the anti-counterfeiting film from the security film by cleaning and peeling it with acid or alkaline solutions. Although the security pattern will corrode to a certain extent after prolonged contact with acid or alkaline solutions, some skilled professionals can still quickly peel the anti-counterfeiting film with alkaline solutions while ensuring the security pattern on the security film remains intact. They can then use identification and reading equipment to illegally steal the security pattern or information, and then use the security pattern on counterfeit products to forge them.

[0004] Therefore, designing an anti-counterfeiting coating that can prevent duplication is of great significance for preventing the anti-counterfeiting pattern from being cracked and stolen and improving the security factor. Summary of the Invention

[0005] The invention provides a holographic polymer material composition capable of preventing duplication, which is used to produce an anti-counterfeiting coating with an anti-duplication effect after being cured, thereby preventing the anti-counterfeiting pattern from being cracked and stolen and improving the safety factor.

[0006] In view of this, the solution of the present invention is:

[0007] The first aspect of the present invention is to provide a holographic polymer material composition capable of preventing duplication, comprising a resin A and a resin B, wherein the solid mass ratio of the resin A to the resin B is (3-9): (10-20); The resin A comprises, by weight, 50-70 parts of polyacrylic acid, 1-5 parts of hydroxyethyl cellulose, 65-80 parts of rosin-based modified phenolic resin, 12-15 parts of inorganic material, 85-122 parts of alcohol solvent, and 0.2-0.5 parts of silane coupling agent. The inorganic material includes β-Al(OH)3 and γ-Al2O3; The resin B is a composite material resin or a transfer material resin.

[0008] Furthermore, the mass proportion of β-Al(OH)3 in the inorganic material is 45-60%.

[0009] Furthermore, the composite resin comprises, by weight, 15-26 parts of vinyl chloride-vinyl acetate copolymer, 5-12 parts of acrylate resin, 4-11 parts of cellulose, 5-9 parts of rosin-based hyperbranched polyester, 0.5-1.8 parts of high molecular weight polyurethane, and 0.1-0.3 parts of functional additives and performance regulators.

[0010] Furthermore, the transfer material resin comprises, by mass, 15-21 parts of acrylic resin, 17-26 parts of cellulose, and 0.5-2.1 parts of functional additives.

[0011] Preferably, in the composite material resin or the transfer material resin, the cellulose is selected from at least one of cellulose acetate, cellulose acetate propionate and cellulose acetate butyrate; The molecular weight of the high molecular weight polyurethane exceeds 110,000; The functional additive is selected from at least one of a leveling agent, a defoaming agent, and a defoaming agent; The performance regulator is selected from at least one of a plasticizer, a heat stabilizer, and an adhesion promoter.

[0012] Furthermore, the composite material resin and the transfer material resin use a single or mixed organic solvent.

[0013] Preferably, the solvent used for the composite material resin is at least one selected from n-hexane, butanone, ethyl acetate, butyl acetate, and n-propyl acetate. The solvent used for the transfer material resin is at least one selected from ethyl acetate, butanone, n-propyl acetate, and butyl acetate.

[0014] Furthermore, the molecular weight of the polyacrylic acid is 20,000-30,000; and / or the alcohol solvent is a mixed solvent of ethanol and isopropanol.

[0015] Furthermore, the silane coupling agent is methacryloxypropyltrimethoxysilane and / or aminopropyltrimethoxysilane.

[0016] The second aspect of the present invention is to provide an anti-copy coating, which is prepared from the composition of the first aspect, comprising the steps of mixing resin A and resin B, coating to form a film, and thermally curing.

[0017] Furthermore, the heat curing temperature is selected in the art according to the properties of the heat curing type resin, such as 70-120°C; preferably, when resin B is a composite material resin, the curing temperature is 95-105°C, and when resin B is a transfer material resin, the curing temperature is 75-85°C.

[0018] A third aspect of the present invention is to provide an anti-copy holographic anti-counterfeiting label comprising a base film provided with an anti-copy coating on which a holographic pattern is heat-embossed; the anti-copy coating is prepared from the composition of the first aspect, comprising the steps of mixing resin A and resin B, coating the mixture on the base film, and heat-curing the mixture.

[0019] Furthermore, the base film includes but is not limited to common base films such as PVC film, PET film, self-adhesive paper, and coated paper.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] The anti-copying holographic polymer material composition provided by the present invention forms an anti-copying function by adding β-Al(OH)3 and γ-Al2O3, and is compatible with components such as organic polymer resin and rosin-based modified phenolic resin to prevent inorganic material agglomeration and sedimentation, and produce a self-stratification effect. It can be integrated with existing composite material resin or transfer material resin to promote its migration to the coating surface, exerting an anti-copying effect, which is of great significance for preventing the cracking and theft of anti-counterfeiting patterns and improving the safety factor. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a comparison diagram of the anti-counterfeiting coating obtained in one embodiment of the present invention before and after alkaline solution corrosion. DETAILED DESCRIPTION

[0023] The technical solutions of the present invention will be clearly and completely described below in conjunction with preferred embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0024] In one embodiment, a holographic polymer material composition capable of preventing duplication is provided, comprising a resin A and a resin B, wherein the solid mass ratio of the resin A to the resin B is (3-9): (10-20);

[0025] The resin A comprises, by weight, 50-70 parts of polyacrylic acid, 1-5 parts of hydroxyethyl cellulose, 65-80 parts of rosin-based modified phenolic resin, 12-15 parts of inorganic material, 85-122 parts of alcohol solvent, and 0.2-0.5 parts of silane coupling agent.

[0026] The inorganic material includes β-Al(OH)3 and γ-Al2O3, and preferably the mass proportion of β-Al(OH)3 in the inorganic material is 45-60%; the resin B is a composite material resin or a transfer material resin, which is a thermosetting base resin material commonly used in anti-counterfeiting coatings in the field.

[0027] In the above embodiment, the anti-copying holographic polymer material composition forms an anti-copying function by adding β-Al(OH)3 and γ-Al2O3, and is combined with organic polymer resin, rosin-based modified phenolic resin and other ingredients to prevent inorganic material agglomeration and sedimentation, and produce a self-stratification effect. It can be integrated with existing composite material resin or transfer material resin to promote its migration to the coating surface, thereby exerting an anti-copying effect.

[0028] In the above embodiment, Resin A is mixed and dispersed by introducing β-Al(OH)3 and a polymer resin. The simultaneous introduction of linear polyacrylic acid and γ-Al2O3 synergistically promotes the formation of a stable, transparent composition. The main mechanism of action of polyacrylic acid is its linear molecular chain, making it suitable for thickening and dispersion. Its properties are utilized to increase the miscibility of β-Al(OH)3 and γ-Al2O3 in polyacrylic acid, thereby improving the stability of the mixed solution. β-Al(OH)3 has a high specific surface area and porosity, which increases the material's contact area with the outside world. The cubic molecular structure of γ-Al2O3 produces a steric hindrance effect in the mixed solution, preventing inorganic material agglomeration and sedimentation.

[0029] In the above embodiments, the solids refer to the components of resin A and resin B excluding volatile solvents, and the proportion of resin A in the solids is the ratio of the sum of the components excluding the alcohol solvent to the mass of the total solids.

[0030] In a preferred embodiment, the composite resin comprises, by weight, 15-26 parts of vinyl chloride-vinyl acetate copolymer, 5-12 parts of acrylate resin, 4-11 parts of cellulose, 5-9 parts of rosin-based hyperbranched polyester, 0.5-1.8 parts of high molecular weight polyurethane, and 0.1-0.3 parts of functional additives and performance regulators.

[0031] In a preferred embodiment, the transfer material resin comprises, by mass, 15-21 parts of acrylic resin, 17-26 parts of cellulose, and 0.5-2.1 parts of functional additives.

[0032] Preferably, among the above composite material resins or transfer material resins:

[0033] The cellulose is selected from at least one of cellulose acetate, cellulose acetate propionate and cellulose acetate butyrate; The molecular weight of the high molecular weight polyurethane is greater than 110,000, and preferably the molecular weight range is 110,000-150,000.

[0034] The functional additive is selected from at least one of a leveling agent, a defoaming agent, and a defoaming agent; The performance regulator is selected from at least one of a plasticizer, a heat stabilizer, and an adhesion promoter.

[0035] Optionally, the aforementioned leveling agents, defoamers, defoamers, plasticizers, thermal stabilizers, and adhesion promoters can be selected based on the resin system. These additives aim to improve physical properties such as leveling, thermal stability, and enhance adhesion to the substrate after curing. These are optional additions considered in the field to address the overall performance of the resin solution and are not directly related to anti-copying functionality. For example, adhesion promoters can be selected from high molecular weight block copolymers; defoamers can be selected from polysiloxanes or terminal esterified polyethers; and leveling agents can be selected from wetting and dispersing agents such as alkanolammonium salts of polymers or alkanolammonium salts of polycarboxylic acids. Surface additives such as polyether-modified polydimethylsiloxane and polyacrylates can be used as defoamers.

[0036] In a preferred embodiment, the composite material resin and transfer material resin utilize a single or mixed organic solvent. Preferably, the composite material resin comprises at least one solvent selected from n-hexane, butanone, ethyl acetate, butyl acetate, and n-propyl acetate; and the transfer material resin comprises at least one solvent selected from ethyl acetate, butanone, n-propyl acetate, and butyl acetate. The amounts of these organic solvents added ensure that the solids content of the composite material resin and transfer material resin is within the range of 10-50%, preferably 20-28% for the composite material resin and 18-25% for the transfer material resin.

[0037] In a preferred embodiment, the components in resin A are:

[0038] The rosin-based hyperbranched modified polyester is a modified polyester known in the art, such as that obtained by copolymerizing maleopimaric acid (MPA), trimethylolpropane (TMP) and glycerol.

[0039] The molecular weight of the polyacrylic acid is preferably 20,000-30,000; The alcohol solvent is a mixed solvent of ethanol and isopropanol, preferably with an ethanol content of 25-50%; The silane coupling agent is at least one of methacryloxypropyltrimethoxysilane and aminopropyltrimethoxysilane.

[0040] In another embodiment, a method for preparing an anti-copy coating is provided, using the composition described above, comprising the steps of mixing resin A and resin B, applying the mixture to form a film, and thermally curing the mixture. After the two resins are mixed, the inorganic material migrates to the coating surface, and thermal curing cross-links the resin components, thereby providing the coating with an anti-copy function.

[0041] In a preferred embodiment, the heat curing temperature is selected in the art according to the properties of the heat curing type resin, such as 70-120°C; preferably, when resin B is a composite material resin, the curing temperature is 95-105°C, and when resin B is a transfer material resin, the curing temperature is 75-85°C.

[0042] In a preferred embodiment, an ultrasonic-assisted method may be used to improve the dispersion uniformity of the resin A, and a small amount of insoluble matter may be removed by filtration.

[0043] The following are preferred implementation examples. Unless otherwise specified, the selected reagents are commercially available and the experimental methods used are well known in the art.

[0044] Resin A Formula 1

[0045] 60 parts of polyacrylic acid, 3 parts of hydroxyethyl cellulose, 70 parts of rosin-based modified phenolic resin, 36 parts of β-Al(OH) and 7 parts of γ-Al2O3, 100 parts of alcohol solvent (ethanol: isopropanol = 30:70), and 0.3 parts of methacryloxypropyltrimethoxysilane.

[0046] Resin A Formula 2

[0047] 55 parts of polyacrylic acid, 2 parts of hydroxyethyl cellulose, 65 parts of rosin-based modified phenolic resin, 38 parts of β-Al(OH) and 6 parts of γ-Al2O3, 90 parts of alcohol solvent (ethanol:isopropanol = 40:60), 0.2 parts of methacryloxypropyltrimethoxysilane, and 0.1 parts of aminopropyltrimethoxysilane.

[0048] Resin A Formula 3

[0049] 70 parts of polyacrylic acid, 5 parts of hydroxyethyl cellulose, 80 parts of rosin-based modified phenolic resin, 39 parts of β-Al(OH) and 5 parts of γ-Al2O3, 120 parts of alcohol solvent (ethanol: isopropanol = 50:50), 0.2 parts of methacryloxypropyltrimethoxysilane, and 0.2 parts of aminopropyltrimethoxysilane.

[0050] Resin A Comparative Formula 1

[0051] Same as Resin A Formula 1, except that the amount of polyacrylic acid used is 35 parts.

[0052] Resin A Comparative Formula 2

[0053] The difference from Resin A Formula 1 is that α-Al2O3 is added instead of γ-Al2O3.

[0054] Resin A Comparative Formula 3

[0055] The difference from Resin A Formula 1 is that ordinary Al(OH)3 is added instead of β-Al(OH)3.

[0056] Resin A Comparative Formula 4

[0057] The difference from Resin A Formulation 1 is that no rosin-based modified phenolic resin is added.

[0058] Composite resin formula 1

[0059] 20 parts of vinyl chloride-vinyl acetate copolymer, 8 parts of acrylic resin, 6 parts of cellulose, 6 parts of rosin-based hyperbranched polyester, 1.0 part of high molecular weight polyurethane, 20 parts of n-hexane; 50 parts of butanone; 45 parts of ethyl acetate; 10 parts of butyl acetate; 0.1 parts each of leveling agent and defoaming agent.

[0060] Composite resin formula 2

[0061] 25 parts of vinyl chloride-vinyl acetate copolymer, 10 parts of acrylic resin, 11 parts of cellulose, 9 parts of rosin-based hyperbranched polyester, 1.5 parts of high molecular weight polyurethane, 30 parts of n-hexane; 60 parts of butanone; 50 parts of ethyl acetate; 15 parts of butyl acetate; 10 parts of n-propyl acetate; 0.1 parts each of leveling agent and defoaming agent.

[0062] Composite resin formula 3

[0063] 15 parts of vinyl chloride-vinyl acetate copolymer, 12 parts of acrylic resin, 8 parts of cellulose, 8 parts of rosin-based hyperbranched polyester, 1.5 parts of high molecular weight polyurethane, 20 parts of n-hexane; 50 parts of butanone; 42 parts of ethyl acetate; 15 parts of n-propyl acetate; 0.1 parts each of leveling agent and defoaming agent.

[0064] Transfer material resin formula 1

[0065] 20 parts of acrylic resin; 25 parts of cellulose; 120 parts of ethyl acetate; 20 parts of butanone; 30 parts of n-propyl acetate; 0.1 parts each of leveling agent and defoaming agent.

[0066] Transfer material resin formula 2

[0067] 15 parts of acrylic resin; 18 parts of cellulose; 100 parts of ethyl acetate; 15 parts of butanone; 30 parts of n-propyl acetate; 15 parts of butyl acetate; 0.1 parts each of leveling agent and defoaming agent.

[0068] Transfer material resin formula 3

[0069] 18 parts of acrylic resin; 20 parts of cellulose; 130 parts of ethyl acetate; 30 parts of butanone; 0.1 parts each of leveling agent and defoaming agent.

[0070] Example

[0071] After the resin A of the above formula was dispersed by ultrasonic stirring, it was mixed with the composite material resin or the transfer material resin according to the compounding method shown in Table 1 (control groups 1 and 2 were the composite material resin and transfer material resin without compounding, respectively) to prepare a mixed resin liquid.

[0072] Table 1:

[0073]

[0074] *Note: The mass ratio of resin A:resin B is the mass ratio of their solid contents.

[0075] Examples 1-3 and Comparative Examples 1-4 in Table 1 above were respectively coated on a PET base film (thermal effective temperature 102° C., coating speed 90 m / min) to obtain a cured coating; and Examples 4-6 and Comparative Examples 5-8 were respectively coated on a PET base film (thermal effective range 80° C., coating speed 105 m / min) to obtain a cured coating.

[0076] Test Case

[0077] 1. The light transmittance of the above coatings was tested using an optical densitometer (Linshang LS117). The results are shown in Table 2.

[0078] Table 2:

[0079]

[0080] 2. Molding and anti-copying performance test

[0081] The coating was embossed with a metal nickel plate engraved with a holographic pattern. The embossing conditions were as follows: pressure: 2.0 MPa; temperature: 168° C.; speed: 55 m / min.

[0082] 1) Check whether the mold is sticky during the molding process and the brightness after molding

[0083] Table 3:

[0084]

[0085] 2) Anti-copying performance test of the coating after molding

[0086] To simulate the replication process of a holographic coating, 0.5 mol / L sodium hydroxide and 0.5 mol / L hydrochloric acid solutions were used to erode the coating for 30 minutes, respectively. The changes in pattern clarity and brightness relative to the original coating after erosion were observed. The results are shown in Table 4. The lower the pattern clarity and brightness, the more severe the coating damage during the erosion process, and the better the anti-copying performance.

[0087] Table 4:

[0088]

[0089] Taking Example 1 as an example, the comparison results of the holographic coating before and after being corroded by 0.5 mol / L sodium hydroxide are as follows: Figure 1 As shown, it can be clearly seen that the pattern clarity and brightness of the original coating (Figure A) after corrosion (Figure B) are significantly damaged.

[0090] It is not difficult to see from the above results that after Examples 1-3 and Examples 4-6 respectively compounded Resin A with Base Resin B and thermally cured to form a coating, the light transmittance of the coating was not significantly changed, and the mold test was unaffected, which could meet the performance requirements of a normal coating. In addition, under the conditions of acid and alkali simulated replication, the coating was eroded, the anti-counterfeiting pattern was significantly damaged, and it could play a significant anti-copying effect. In contrast, Comparative Examples 1-4 or Comparative Examples 5-8, due to changes in the formula of Resin A, under the same compounding conditions, decreased in light transmittance and mold resistance relative to Example 1 or Example 4. The possible reasons are: the reduced amount of polyacrylic acid reduced the dispersibility of the inorganic material; the replacement of β-Al(OH)3 resulted in a reduction in specific surface area, which was not conducive to dispersion; the replacement or loss of γ-Al2O3 or rosin-based modified phenolic resin easily caused inorganic material agglomeration, affecting the self-stratification effect. The above defects that are not conducive to material dispersion affect the coating thermal curing effect to varying degrees, thereby leading to defects such as sticking to the plate or low mold brightness.

[0091] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A holographic polymer material composition capable of preventing duplication, characterized in that: It is composed of resin A and resin B, and the solid mass ratio of resin A to resin B is (3-9): (10-20); The resin A comprises, by weight, 50-70 parts of polyacrylic acid, 1-5 parts of hydroxyethyl cellulose, 65-80 parts of rosin-based modified phenolic resin, 12-15 parts of inorganic material, 85-122 parts of alcohol solvent, and 0.2-0.5 parts of silane coupling agent. The inorganic material includes β-Al(OH)3 and γ-Al2O3; The resin B is a composite material resin or a transfer material resin.

2. The composition according to claim 1, characterized in that The mass proportion of β-Al(OH)3 in the inorganic material is 45-60%.

3. The composition according to claim 1, characterized in that The composite resin comprises, by weight, 15-26 parts of vinyl chloride-vinyl acetate copolymer, 5-12 parts of acrylate resin, 4-11 parts of cellulose, 5-9 parts of rosin-based hyperbranched polyester, 0.5-1.8 parts of high molecular weight polyurethane, and 0.1-0.3 parts of functional additives and performance regulators. And / or, the transfer material resin comprises, by mass, 15-21 parts of acrylic resin, 17-26 parts of cellulose, and 0.5-2.1 parts of functional additives.

4. The composition according to claim 3, characterized in that The cellulose is selected from at least one of cellulose acetate, cellulose acetate propionate and cellulose acetate butyrate; and / or, the molecular weight of the high molecular weight polyurethane exceeds 110,000; And / or, the functional additive is selected from at least one of a leveling agent, a defoaming agent, and a defoaming agent; And / or, the property regulator is selected from at least one of a plasticizer, a heat stabilizer, and an adhesion promoter.

5. The composition according to claim 1, characterized in that The composite material resin and / or transfer material resin uses a mixed organic solvent.

6. The composition according to claim 1, characterized in that The molecular weight of the polyacrylic acid is 20,000-30,000; And / or, the alcohol solvent is a mixed solvent of ethanol and isopropanol.

7. The composition according to claim 1, characterized in that The silane coupling agent is methacryloxypropyltrimethoxysilane and / or aminopropyltrimethoxysilane.

8. An anti-copy coating, characterized in that The method is prepared from the composition according to any one of claims 1 to 7, comprising the steps of mixing resin A and resin B, followed by coating and heat curing.

9. The anti-copy coating according to claim 8, characterized in that The heat curing temperature is 70-120°C. 10.Anti-copy holographic anti-counterfeiting label, characterized in that: The invention comprises a base film provided with an anti-copy coating, and a holographic pattern is hot-pressed on the anti-copy coating; the anti-copy coating is made from the composition according to any one of claims 1 to 7, and comprises the steps of mixing resin A and resin B, coating the mixture on the base film, and heat-curing.

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