UV mould pressing holographic plastic as well as preparation method and application thereof

Abstract

The invention discloses UV (ultraviolet) mould pressing holographic plastic as well as a preparation method and application thereof. The holographic plastic is prepared by photocuring holographic material mother liquor, the holographic material mother liquor formula comprises the following components in parts by mass: 1-10 parts of siloxane with a structure as shown in a formula I, 50-70 parts of an acrylate polymer, 10-50 parts of a photopolymerization monomer and 2-7 parts of a free radical type photoinitiator. The siloxane (such as dodecyltrimethoxysilane) used in the formula forms a hydrophobic monomolecular layer on the surface of the material, so that the surface energy is reduced. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of holographic plastic preparation, and more specifically, relates to UV molded holographic plastic and a preparation method and application thereof. Background Art

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

[0003] UV molding process: During the contact between the nickel plate and the PET film coated with the holographic material mother liquid, the holographic material mother liquid penetrates and fills into the microstructure grooves of the nickel plate. Then, UV light is used to cure it. After curing, the nickel plate is peeled off to obtain a UV molded holographic plastic product.

[0004] However, during the molding process, the holographic material mother liquid contacts the PET base film and the nickel plate at the same time. The different adhesion between the holographic material mother liquid, the nickel plate and the PET base film will affect the molding effect; when the holographic material mother liquid is solidified, the adhesion to the nickel plate is greater than its adhesion to the PET base film, and it will partially stick to the nickel plate. When peeling off the PET base film, the pattern transfer is incomplete, which contaminates the nickel plate. Summary of the invention

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

[0006] Based on this, the technical solution of the present invention is as follows:

[0007] A holographic material mother solution, comprising 1-10 parts by weight of a siloxane having a structure shown in formula I, 50-70 parts by weight of an acrylate polymer, 10-50 parts by weight of a photopolymerizable monomer, and 2-7 parts by weight of a free radical photoinitiator;

[0008]

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

[0010] R 2 , R 3 , R 4 The same or different, independently selected from C 1-4 alkyl.

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

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

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

[0014] According to an embodiment of the present invention, the mass parts of the siloxane 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 invention, the acrylate polymer is at least one of polyetheramine modified polyurethane acrylate, aliphatic polyurethane diacrylate, polyurethane acrylate oligomer, and aliphatic polyurethane diacrylate oligomer. Preferably, it is a mixture of polyetheramine modified polyurethane acrylate, aliphatic polyurethane diacrylate, polyurethane acrylate oligomer, and aliphatic polyurethane diacrylate oligomer. In the mixture, preferably, the mass ratio of the polyetheramine modified polyurethane acrylate, aliphatic polyurethane diacrylate, polyurethane acrylate oligomer, and aliphatic polyurethane diacrylate oligomer is 2-4:4-6:4-6:3-5.

[0016] According to an embodiment of the present invention, the mass fraction of the acrylic ester polymer is 50 parts, 55 parts, 60 parts, 65 parts or 70 parts.

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

[0018] According to an embodiment of the present invention, the mass fraction of the photopolymerizable monomer is 30-50 parts, for example, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts.

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

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

[0021] The present invention also provides a method for preparing the above-mentioned holographic material mother solution, the method comprising:

[0022] The siloxane having the structure shown in Formula I, the acrylate polymer, the photopolymerization monomer and the free radical photoinitiator are mixed to obtain the holographic material mother solution.

[0023] The invention also provides a UV molded holographic plastic, which is a photocured product of the holographic material mother solution.

[0024] The present invention also provides a method for preparing the above-mentioned UV molded holographic plastic, the method comprising the following steps:

[0025] 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.

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

[0027] According to an embodiment of the present invention, the holographic material mother solution is layered between a nickel plate and a PET film.

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

[0029] According to an embodiment of the present invention, the pattern grooves on the nickel plate have a depth of 2-2.5 μm and a width of 7-10 μm.

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

[0031] S1: mixing the siloxane of the structure shown in formula I, the acrylate polymer, the photopolymerization monomer and the free radical photoinitiator to obtain a holographic material mother solution;

[0032] S2: fix one end of the PET film with the release layer facing downward on the nickel plate, lift up the PET film, and drop the holographic material mother liquid obtained in S1 on one end of the nickel plate; use a UV laminator to evenly distribute the holographic material mother liquid between the nickel plate and the PET film and cover the pattern on the nickel plate;

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

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

[0035] The invention also provides an application of a holographic material mother solution or UV molded holographic plastic in the field of anti-counterfeiting, home appliance decoration or packaging.

[0036] Beneficial effects of the present invention:

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

[0038] In addition, the UV molded holographic plastic obtained based on the holographic material mother liquor of the present invention has good tensile properties (such as elongation at break of more than 80%, more preferably more than 85%) and anti-ultraviolet aging performance (such as color difference values ​​are all within 2), and can be used in the fields of anti-counterfeiting, home appliance decoration, and packaging. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 The water contact angles of the UV molded holographic plastics obtained in Examples 1-4 of the present invention and Comparative Example 1.

[0040] Figure 2 It is the plate sticking ratio of the UV molded holographic plastics obtained in Examples 1-4 and Comparative Example 1.

[0041] Figure 3 It is the infrared spectra of the material mother solutions obtained in Example 1 and Comparative Example 1 before and after photocuring.

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

[0043] Figure 5 is the elongation at break of the UV molded holographic plastics obtained in Examples 1-4 and Comparative Example 1;

[0044] Among them, (a) is the UV molded holographic plastic of comparative example 1, (b) is the UV molded holographic plastic of example 4, (c) is the UV molded holographic plastic of example 3, (d) is the UV molded holographic plastic of example 2, and (e) is the UV molded holographic plastic of example 1. DETAILED DESCRIPTION

[0045] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[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 noted that the polyetheramine modified polyurethane acrylate is selected from Runao Chemical 5186, aliphatic polyurethane diacrylate is selected from Changxing Material ETERCURE 6112-100, polyurethane acrylate polymer is selected from Sartomer CN9010 NS, aliphatic polyurethane diacrylate polymer is selected from Sartomer CN8888NS.

[0048] Example 1

[0049] The holographic material mother liquor includes: 30 parts by mass of tripropylene glycol diacrylate, 10 parts by mass of dipropylene glycol diacrylate, 4 parts by mass of free radical photoinitiator 1-hydroxycyclohexyl phenyl ketone, 18 parts by mass of aliphatic polyurethane diacrylate, 18 parts by mass of polyurethane acrylate polymer, 8 parts by mass of polyetheramine modified polyurethane acrylate, 12 parts by mass of aliphatic polyurethane diacrylate polymer and 7 parts by mass of dodecyltrimethoxysilane.

[0050] Preparation of UV molded holographic plastic with high efficiency demoulding:

[0051] Weigh 30 parts by mass of tripropylene glycol diacrylate and 10 parts by mass of dipropylene glycol diacrylate, add 4 parts by mass of free radical photoinitiator thereto and stir evenly to dissolve the free radical photoinitiator, then add 18 parts by mass of aliphatic polyurethane diacrylate, 18 parts by mass of polyurethane acrylate polymer, 8 parts by mass of polyetheramine-modified polyurethane acrylate, 12 parts by mass of aliphatic polyurethane diacrylate polymer, and finally add 7 parts by mass of dodecyltrimethoxysilane; and stir evenly with ultrasound to obtain a holographic material mother liquor.

[0052] Fix one end of the PET film on the nickel plate under light-proof conditions (with the release layer of the PET film facing downward), and the PET film needs to cover the pattern; lift up the PET film, drip the holographic material mother liquid on one end of the nickel plate, and use a UV compounder to evenly distribute the holographic material mother liquid and cover the pattern on the nickel plate; cure the holographic material mother liquid and adhere it to the PET film by ultraviolet light, and the power density of the ultraviolet light is 300mW / cm 2 , the illumination time is 10s, and the wavelength of the ultraviolet light is 365nm; after curing, the nickel plate is peeled off to obtain the UV molded holographic plastic.

[0053] Example 2

[0054] The only difference between Example 2 and Example 1 is that 5 parts by mass of dodecyltrimethoxysilane is added when preparing the holographic material mother solution.

[0055] Example 3

[0056] The only difference between Example 3 and Example 1 is that 3 parts by mass of dodecyltrimethoxysilane is added when preparing the holographic material mother solution.

[0057] Example 4

[0058] The only difference between Example 4 and Example 1 is that 1 part by mass of dodecyltrimethoxysilane is added when preparing the holographic material mother solution.

[0059] Example 5

[0060] The only difference between Example 5 and Example 1 is that 8 parts by mass of dodecyltrimethoxysilane is added when preparing the holographic material mother solution.

[0061] The pattern appearance is poor, with mottled and foggy textures, and the clarity of the pattern is reduced.

[0062] Comparative Example 1

[0063] The only difference between Comparative Example 1 and Example 1 is that dodecyltrimethoxysilane is not added when preparing the holographic material mother solution.

[0064] Test Example 1

[0065] (1) Plate sticking area ratio: Use image-J to calculate the plate sticking area and total area of ​​each pattern group in Examples 1-4 and Comparative Example 1; the ratio of the plate sticking area to the total area is the plate sticking area ratio. The plate sticking ratio results of the UV molded holographic plastics obtained in Examples 1-4 and Comparative Example 1 are as follows: Figure 2 The material adhesion ratio of the comparative example 1 is 0.377, and the material adhesion ratio of the embodiment 1 is 0.007.

[0066] (2) Infrared test: An infrared spectrometer was used to test the changes in the material before and after photocuring of the material mother solution under the conditions of Example 1 and Comparative Example 1. The test results are as follows: Figure 3 shown.

[0067] (3) Haze test: At 22°C and with a blade thickness of 10 μm, the holographic material mother solution of Examples 1-5 and Comparative Example 1 was scraped onto a PET film with a thickness of 50 μm, and then irradiated under 365 nm ultraviolet light for 90 seconds to form a film. The haze of the sample was tested with a haze meter, and the test results are shown in Table 1.

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

[0069]

[0070] (4) Color difference: Tested using a colorimeter. 2 The color difference test results of the UV molded holographic plastics obtained in Examples 1-4 and Comparative Example 1 are as follows: Figure 4 As shown by Figure 4 It can be seen that the color difference values ​​of the samples prepared in Examples 1-4 are all within 2. The holographic plastic obtained in the present invention has good anti-ultraviolet aging performance.

[0071] (5) Tensile properties: Tested using a universal testing machine. The elongation at break results are as follows: Figure 5 The elongation at break of the material obtained in comparative example 1 is 71.568%, and the elongation at break of the material obtained in example 1 is 86.538%. The obtained holographic plastic has good tensile properties.

[0072] The above is an exemplary description of the embodiments of the present invention. However, the protection scope of the present invention is not limited to the above embodiments. Any modification, equivalent substitution, improvement, etc. made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A holographic material mother solution, characterized in that: It comprises 1-10 parts by weight of a siloxane having a structure shown in formula I, 50-70 parts by weight of an acrylate polymer, 10-50 parts by weight of a photopolymerizable monomer, and 2-7 parts by weight of a free radical photoinitiator; 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.

2. The holographic material mother solution according to claim 1, characterized in that: The acrylate polymer is at least one of polyetheramine modified polyurethane acrylate, aliphatic polyurethane diacrylate, polyurethane acrylate oligomer, and aliphatic polyurethane diacrylate oligomer.

3. The holographic material mother solution according to claim 1, characterized in that: The photopolymerizable monomer is at least one of dipropylene glycol diacrylate and tripropylene glycol diacrylate.

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

5. The method for preparing a holographic material mother solution according to any one of claims 1 to 4, characterized in that: The method is: The siloxane having the structure shown in Formula I, the acrylate polymer, the photopolymerization monomer and the free radical photoinitiator are mixed to obtain the holographic material mother solution.

6. A UV molded holographic plastic, characterized in that: It is a photocured product of the holographic material mother solution according to any one of claims 1 to 4.

7. The method for preparing the UV molded holographic plastic according to claim 6, 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.

8. The method according to claim 7, characterized in that The photocuring is performed under ultraviolet light.

9. The method according to claim 8, characterized in that The power density of the ultraviolet light is 200-400 mW / cm 2 The illumination time is 5-120s, and the wavelength of the ultraviolet light is 365nm.

10. Use of the holographic material mother solution according to any one of claims 1 to 4 or the UV molded holographic plastic according to claim 6 in the field of anti-counterfeiting, home appliance decoration or packaging.

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