UV embossed holographic plastic and its preparation method and application

Abstract

The application discloses a UV moulded holographic plastic and a preparation method and application thereof. The holographic plastic is prepared by photo-curing of a holographic material mother liquor. The holographic material mother liquor formula comprises 1-10 mass parts of siloxane with a structure shown in formula I, 50-70 mass parts of an acrylate polymer, 10-50 mass parts of a photopolymerization monomer, and 2-7 mass parts of a free radical type photoinitiator. The siloxane (such as dodecyl trimethoxysilane) used in the formula forms a hydrophobic monolayer on the surface of the material, thereby reducing the surface energy.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of holographic plastic preparation, and more particularly relates to a UV mold pressing holographic plastic and a preparation method and application thereof. BACKGROUND

[0002] The UV mold pressing holographic plastic is an optical functional material obtained by transferring the micro-nano structure on a nickel plate to a plastic substrate through ultraviolet curing, and has important application value in the fields of anti-counterfeiting, home appliance decoration and packaging.

[0003] The UV mold pressing process is as follows: during the process of contacting the nickel plate with the PET film coated with the holographic material mother liquor, the holographic material mother liquor penetrates and fills into the microstructure grooves of the nickel plate. Then, UV light is used for irradiation to make it cured. After curing, the nickel plate is peeled off, and then the UV mold pressing holographic plastic product is obtained.

[0004] However, in the mold pressing process, the holographic material mother liquor simultaneously contacts the PET base film and the nickel plate. The adhesion between the holographic material mother liquor, the nickel plate and the PET base film will affect the mold pressing effect. When the adhesion of the holographic material mother liquor to the nickel plate after curing is greater than that to the PET base film, it will be partially adhered to the nickel plate. When the PET base film is peeled off, the pattern transfer is incomplete, and the nickel plate is contaminated. SUMMARY

[0005] In view of the above defects or improvement needs of the prior art, the purpose of the present application is to provide a UV mold pressing holographic plastic and a preparation method and application thereof. The UV mold pressing holographic plastic of the present application can significantly inhibit the plate sticking effect, and has good tensile properties and ultraviolet aging resistance, and can be applied in the fields of anti-counterfeiting, home appliance decoration and packaging.

[0006] Based on this, the technical scheme of the present application is as follows:

[0007] A holographic material mother liquor, which comprises 1-10 parts by mass of a siloxane having the structure shown in Formula I, 50-70 parts by mass of an acrylate polymer, 10-50 parts by mass of a photopolymerization monomer and 2-7 parts by mass of a free radical type photoinitiator;

[0008]

[0009] In Formula I, R 1 is selected from C 6-13 alkyl;

[0010] R 2 , R 3 , R 4 are the same or different, and are each independently selected from C 1-4 alkyl.

[0011] According to an embodiment of the present application, the R1 selected from C 8-12 alkyl.

[0012] According to an embodiment of the present application, R 2 , R 3 , R 4 are the same or different, each independently selected from methyl, ethyl, propyl or butyl.

[0013] According to an embodiment of the present application, the silane is, for example, dodecyltrimethoxysilane.

[0014] According to an embodiment of the present application, the mass parts of the silane are 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts.

[0015] According to an embodiment of the present application, the acrylate polymer is at least one of polyetheramine-modified polyurethane acrylate, aliphatic polyurethane diacrylate, polyurethane acrylate oligomer, aliphatic polyurethane diacrylate oligomer. Preferably, the mixture of polyetheramine-modified polyurethane acrylate, aliphatic polyurethane diacrylate, polyurethane acrylate oligomer, aliphatic polyurethane diacrylate oligomer. In the mixture, preferably, the mass ratio of the polyetheramine-modified polyurethane acrylate, aliphatic polyurethane diacrylate, polyurethane acrylate oligomer, aliphatic polyurethane diacrylate oligomer is 2-4:4-6:4-6:3-5.

[0016] According to an embodiment of the present application, the mass parts of the acrylate polymer are 50 parts, 55 parts, 60 parts, 65 parts or 70 parts.

[0017] According to an embodiment of the present application, the photopolymerization monomer is at least one of dipropylene glycol diacrylate and tripropylene glycol diacrylate. Preferably, the mixture of dipropylene glycol diacrylate and tripropylene glycol diacrylate. In the mixture, preferably, the mass ratio of dipropylene glycol diacrylate and tripropylene glycol diacrylate is 0.5-1.5:3-4.

[0018] According to an embodiment of the present application, the mass parts of the photopolymerization monomer are 30-50 parts, for example, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts.

[0019] According to an embodiment of the present application, the free radical type photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4'-(methylthio)-2-morpholinobutyrophenone, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide or 3,3'-carbonylbis(7-diethylaminocoumarin) / N-phenylglycine.

[0020] According to an embodiment of the present application, the mass fraction of the radical photoinitiator is 3 parts, 4 parts, 5 parts, 6 parts or 7 parts.

[0021] The present application also provides a preparation method of the holographic material mother liquor, and the method comprises the following steps:

[0022] The siloxane, the acrylate polymer, the photopolymerization monomer and the radical photoinitiator are mixed to obtain the holographic material mother liquor.

[0023] The present application also provides a UV molding holographic plastic, which is a photocured product of the holographic material mother liquor.

[0024] The present application also provides a preparation method of the UV molding holographic plastic, and the method comprises the following steps:

[0025] The holographic material mother liquor is placed on a nickel plate, and then a PET film is placed on the holographic material mother liquor, and the holographic material mother liquor is photocured to obtain the UV molding holographic plastic.

[0026] According to an embodiment of the present application, the PET film release layer is in contact with the holographic material mother liquor.

[0027] According to an embodiment of the present application, the holographic material mother liquor is placed between the nickel plate and the PET film.

[0028] According to an embodiment of the present application, the photocuring is performed under ultraviolet light. Preferably, the power density of the ultraviolet light is 200-400 mW / cm 2 , for example, 300 mW / cm 2 , the illumination time is 5-120 s, and the wavelength of the ultraviolet light is 365 nm.

[0029] According to an embodiment of the present application, the pattern groove depth of the nickel plate is 2-2.5 μm, and the width is 7-10 μm.

[0030] As an exemplary embodiment of the present application, the preparation method of the UV molding holographic plastic is specifically as follows:

[0031] S1: the siloxane, the acrylate polymer, the photopolymerization monomer and the radical photoinitiator are uniformly mixed to obtain a holographic material mother liquor;

[0032] S2: one end of the PET film release layer is fixed on the nickel plate with the release layer facing down, the PET film is lifted up, and the holographic material mother liquor obtained in S1 is added dropwise on one end of the nickel plate; the holographic material mother liquor is uniformly distributed between the nickel plate and the PET film and covers the pattern on the nickel plate by using a UV compound machine.

[0033] S3: placing the nickel plate coated with the holographic material mother liquor obtained in step S2 and the PET film under ultraviolet light for photocuring to obtain the UV embossed holographic plastic.

[0034] According to the embodiment of the present application, step S1 and step S2 are operated under light-proof conditions.

[0035] The present application also provides an application of the holographic material mother liquor or the UV embossed holographic plastic in the field of anti-counterfeiting, the field of home appliance decoration or the field of packaging.

[0036] The present application has the following advantages:

[0037] Compared with the prior art, the holographic material mother liquor formula of the present application comprises: 1-10 parts by mass of siloxane with the structure shown in formula I, 50-70 parts by mass of acrylate polymer, 10-50 parts by mass of photopolymerization monomer, and 2-7 parts by mass of free radical type photoinitiator. The siloxane (such as dodecyltrimethoxysilane) used in the formula forms a hydrophobic monolayer on the surface of the material, thereby reducing the surface energy and significantly inhibiting the plate sticking effect. Specifically, the plate sticking area ratio of the mother liquor without adding siloxane is reduced by at least 90%, preferably by at least 95%, and more preferably by 98%.

[0038] In addition, the UV embossed holographic plastic obtained based on the holographic material mother liquor of the present application has good tensile properties (such as elongation at break of more than 80%, more preferably more than 85%) and ultraviolet aging resistance (such as color difference value of less than 2), and can be applied in the field of anti-counterfeiting, the field of home appliance decoration or the field of packaging. BRIEF DESCRIPTION OF DRAWINGS

[0039] Figure 1 The UV embossed holographic plastic obtained in Examples 1-4 and Comparative Example 1 is the water contact angle.

[0040] Figure 2 The UV embossed holographic plastic obtained in Examples 1-4 and Comparative Example 1 is the plate sticking ratio.

[0041] Figure 3 The UV embossed holographic plastic obtained in Examples 1-4 and Comparative Example 1 is the infrared spectrum before and after photocuring of the material mother liquor.

[0042] Figure 4 The UV embossed holographic plastic obtained in Examples 1-4 and Comparative Example 1 is the color difference value after ultraviolet aging.

[0043] Figure 5 The UV embossed holographic plastic obtained in Examples 1-4 and Comparative Example 1 is the elongation at break.

[0044] wherein (a) is the UV embossing holographic plastic of Comparative Example 1, (b) is the UV embossing holographic plastic of Example 4, (c) is the UV embossing holographic plastic of Example 3, (d) is the UV embossing holographic plastic of Example 2, and (e) is the UV embossing holographic plastic of Example 1. DETAILED DESCRIPTION

[0045] The technical solutions of the present application will be further described in detail below in combination with specific examples. It should be understood that the following examples are only illustratively described and explained the present application, and should not be interpreted as limiting the scope of protection of the present application. Any technology achieved based on the above description of the present application is covered within the scope intended to be protected by the present application.

[0046] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0047] It should be particularly noted that the polyether amine modified polyurethane acrylate is selected from Runao Chemical 5186, the aliphatic polyurethane diacrylate is selected from Changxing Material ETERCURE 6112-100, the polyurethane acrylate oligomer is selected from Sartomer CN9010 NS, and the aliphatic polyurethane diacrylate oligomer is selected from Sartomer CN8888 NS.

[0048] Example 1

[0049] The holographic material mother liquor comprises 30 parts by mass of tripropylene glycol diacrylate, 10 parts by mass of dipropylene glycol diacrylate, 4 parts by mass of a free radical type photoinitiator 1-hydroxycyclohexyl phenyl ketone, 18 parts by mass of an aliphatic polyurethane diacrylate, 18 parts by mass of a polyurethane acrylate oligomer, 8 parts by mass of a polyether amine modified polyurethane acrylate, 12 parts by mass of an aliphatic polyurethane diacrylate oligomer, and 7 parts by mass of dodecyl trimethoxysilane.

[0050] Preparation of a UV embossing holographic plastic with high demolding efficiency:

[0051] 30 parts by mass of tripropylene glycol diacrylate and 10 parts by mass of dipropylene glycol diacrylate are weighed, 4 parts by mass of a free radical type photoinitiator is added and stirred uniformly to dissolve the free radical type photoinitiator, then 18 parts by mass of an aliphatic polyurethane diacrylate, 18 parts by mass of a polyurethane acrylate oligomer, 8 parts by mass of a polyether amine modified polyurethane acrylate, 12 parts by mass of an aliphatic polyurethane diacrylate oligomer are added, and finally 7 parts by mass of dodecyl trimethoxysilane is added; the mixture is uniformly stirred by ultrasonic to obtain a holographic material mother liquor.

[0052] The PET film is fixed on the nickel plate under light-proof condition (the release layer of the PET film faces downward), and the PET film needs to cover the pattern; the PET film is lifted, and the holographic material mother liquor is added on one end of the nickel plate, and the UV compound machine is used to make the holographic material mother liquor uniformly distributed and cover the pattern on the nickel plate; the holographic material mother liquor is cured and attached to the PET film by ultraviolet light irradiation, the power density of the ultraviolet light is 300 mW / cm 2 , the irradiation time is 10 s, and the wavelength of the ultraviolet light is 365 nm; after curing, the nickel plate is peeled off to obtain the UV molded holographic plastic.

[0053] Example 2

[0054] Example 2 is different from example 1 only in that 5 parts by mass of dodecyltrimethoxysilane is added when preparing the holographic material mother liquor.

[0055] Example 3

[0056] Example 3 is different from example 1 only in that 3 parts by mass of dodecyltrimethoxysilane is added when preparing the holographic material mother liquor.

[0057] Example 4

[0058] Example 4 is different from example 1 only in that 1 part by mass of dodecyltrimethoxysilane is added when preparing the holographic material mother liquor.

[0059] Example 5

[0060] Example 5 is different from example 1 only in that 8 parts by mass of dodecyltrimethoxysilane is added when preparing the holographic material mother liquor.

[0061] The pattern has poor apparent effect, appears mottling and foggy texture, and the clarity of the pattern is reduced.

[0062] Comparative Example 1

[0063] Comparative Example 1 is different from example 1 only in that no dodecyltrimethoxysilane is added when preparing the holographic material mother liquor.

[0064] Test Example 1

[0065] (1) Sticking area ratio: the sticking area and total area of each group of patterns in examples 1-4 and comparative example 1 are calculated by image-J; the ratio of the sticking area to the total area is the sticking area ratio. The sticking area ratio results of the UV molded holographic plastics obtained in examples 1-4 and comparative example 1 are shown in Table 1. Figure 2 The sticking area ratio of the material obtained in comparative example 1 is 0.377, and the sticking area ratio of the material obtained in example 1 is 0.007.

[0066] (2) Infrared test: infrared spectrum tester was used to test the changes of the material mother liquor before and after light curing under the conditions of Example 1 and Comparative Example 1, and the test results are shown in Table 1. Figure 3

[0067] (3) Haze test: under the conditions of 22℃ and doctor blade thickness of 10μm, the holographic material mother liquor under the conditions of Examples 1-5 and Comparative Example 1 was coated on a PET film with a thickness of 50μm, and cured into a film under the irradiation of 365nm ultraviolet light for 90s. The haze of the sample was tested by a haze tester, and the test results are shown in Table 1.

[0068] Table 1 Haze of the coated samples of Examples 1-5 and Comparative Example 1

[0069]

[0070] (4) Color difference value: color difference tester was used for testing. Examples 1-4 and Comparative Example 1 were simultaneously placed in an ultraviolet aging box with an irradiance of 0.89W / m 2 for 168h, and then tested by a color difference tester. The color difference test results of the UV molded holographic plastics of Examples 1-4 and Comparative Example 1 are shown in Table 2. Figure 4 Figure 4 It can be seen from Table 2 that the color difference values of the samples prepared in Examples 1-4 are all within 2. The holographic plastics prepared in the present application have good ultraviolet aging resistance.

[0071] (5) Tensile property: universal testing machine was used for testing. The results of the elongation at break are shown in Table 3. The elongation at break of the material prepared in Comparative Example 1 is 71.568%, and the elongation at break of the material prepared in Example 1 is 86.538%. The holographic plastics prepared have good tensile property. Figure 5

[0072] The above has exemplarily described the embodiments of the present application. However, the protection scope of the present application is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made by those skilled in the art within the spirit and principle of the present application shall be included in the protection scope of the present application.​​​

Claims

1. A holographic material mother solution, characterized in that: It comprises 1-10 parts by mass of a siloxane having a structure represented by formula I, 50-70 parts by mass of an acrylate polymer, 10-50 parts by mass of a photopolymerizable monomer, and 2-7 parts by mass of a free radical photoinitiator; Formula I In Formula I, R 1 Selected from C 6-13 alkyl; R 2 、R 3 、R 4 The same or different, independently selected from C 1-4 alkyl; The acrylate polymer is at least one of polyetheramine modified polyurethane acrylate, aliphatic polyurethane diacrylate, and polyurethane acrylate oligomer; The photopolymerizable monomer is at least one of dipropylene glycol diacrylate and tripropylene glycol diacrylate.

2. The holographic material mother solution according to claim 1, characterized in that: The free radical photoinitiator is selected from one or more of 1-hydroxycyclohexylphenyl ketone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide or 3,3'-carbonylbis(7-diethylaminocoumarin) / N-phenylglycine.

3. The method for preparing a holographic material mother solution according to claim 1 or 2, characterized in that: The method is: The siloxane with the structure shown in formula I, the acrylate polymer, the photopolymerizable monomer and the free radical photoinitiator are mixed to obtain the holographic material mother solution.

4. A UV molded holographic plastic, characterized in that: The photocured product is the holographic material mother solution according to claim 1 or 2.

5. The method for preparing the UV molded holographic plastic according to claim 4, characterized in that: The method comprises the following steps: The holographic material mother liquid is spread on a nickel plate, and then a PET film is placed on the holographic material mother liquid, and the PET film is photocured to obtain the UV molded holographic plastic.

6. The method according to claim 5, characterized in that The photocuring is performed under ultraviolet light.

7. The method according to claim 6, wherein The power density of the ultraviolet light is 200-400 mW / cm 2 , the illumination time is 5-120 s, and the wavelength of the ultraviolet light is 365 nm.

8. Use of the holographic material mother solution according to claim 1 or 2 or the UV molded holographic plastic according to claim 4 in the fields of anti-counterfeiting, home appliance decoration or packaging.

Images