Temperature-sensitive ink, preparation method thereof and printed product

Abstract

The invention provides temperature-sensitive ink suitable for various printing modes, a preparation method thereof and a printed product. The ink is prepared from the following raw materials in percentage by mass: 15 to 45 weight percent of aromatic polyurethane acrylic resin, 5 to 45 weight percent of modified epoxy acrylic resin, 5 to 10 weight percent of ethoxylated trimethylolpropane triacrylate, 5 to 10 weight percent of 1, 6-hexanediol diacrylate, 5 to 10 weight percent of tetrahydrofuran acrylate, 5 to 10 weight percent of acryloyl morpholine, 5 to 10 weight percent of co-initiator, 0.5 to 1.5 weight percent of polyethylene wax, 4 to 10 weight percent of photosensitizer, 0.5 to 1.5 weight percent of heat stabilizer and 5 to 15 weight percent of calcium carbonate. According to the invention, the resin which is easy to yellow in a high-temperature environment is added into the formula, and the excessive and active photosensitizer is combined, so that the coating can obtain an excellent temperature band color change effect and an irreversible color change effect under a high-temperature condition.

Description

Technical Field

[0001] The present application relates to the field of ink technology, and in particular to a temperature-variable ink suitable for various printing methods, a preparation method thereof, and printed products. Background Art

[0002] As an interesting anti-counterfeiting ink, temperature-sensitive ink has always appeared in people's daily necessities with its amazing color-changing effect. Most temperature-sensitive inks are reversible and can repeatedly present the required color change effect as the temperature changes; however, there are also some temperature-sensitive materials used in anti-counterfeiting products, which are irreversible. This material is generally used in anti-counterfeiting products, or food packaging and various indicators that are sensitive to temperature.

[0003] At present, the temperature color change range of irreversible temperature-changing inks on the market is about 50~80°C, which can only meet the color change effect within this temperature range, and the applicable customer groups are limited to a small range. For irreversible temperature-changing materials on the market, the color change is relatively single, and a temperature change effect only has a single color change, which is relatively boring. In the anti-counterfeiting material market, there is not much technical threshold.

[0004] The contents of the background technology section are merely the technologies known to the inventors and do not necessarily represent the prior art in the field. Summary of the invention

[0005] In view of at least one problem of the above-mentioned prior art, the first purpose of the present application is to provide a kind of temperature-changing ink that can present a multi-stage and irreversible color change effect in multiple temperature ranges, and the color gradually becomes darker as the temperature rises, thereby achieving an anti-counterfeiting effect. The temperature-changing ink includes the following raw materials in mass percentage:

[0006] 15~45wt% aromatic polyurethane acrylic resin, 5~45wt% modified epoxy acrylic resin, 5~10wt% ethoxylated trimethylolpropane triacrylate, 5~10wt% 1,6-hexanediol diacrylate, 5~10wt% tetrahydrofuran acrylate, 5~10wt% acryloyl morpholine, 5~10wt% co-initiator, 0.5~1.5wt% polyethylene wax, 4~10wt% photosensitizer, 0.5~1.5wt% heat stabilizer and 5~15wt% calcium carbonate.

[0007] In some embodiments of the present application, the aromatic polyurethane acrylic resin includes at least one of a difunctional aromatic polyurethane acrylic resin, a trifunctional aromatic polyurethane acrylic resin, a tetrafunctional aromatic polyurethane acrylic resin, and a hexafunctional aromatic polyurethane acrylic resin.

[0008] In some embodiments of the present application, the modified epoxy acrylic resin includes at least one of rosin-modified epoxy acrylic resin, aldehyde-ketone-modified epoxy acrylic resin, and phenol-formaldehyde-modified epoxy acrylic resin.

[0009] In some embodiments of the present application, the photosensitizer includes at least one of benzophenone, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, 2,4,6(trimethylbenzoyl)diphenylphosphine oxide, isopropylthioxanthine, 2,4-diethylthioxanthine, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone, and 1-hydroxy-cyclohexyl-phenyl ketone.

[0010] In some embodiments of the present application, the particle size range of the calcium carbonate is 1000~10000 mesh.

[0011] In some embodiments of the present application, the particle size of the temperature-variable ink is less than 5 μm.

[0012] The second object of the present application is to provide a method for preparing any of the above-mentioned temperature-variable inks, characterized in that it comprises the following steps: S1: mixing aromatic polyurethane acrylic resin, modified epoxy acrylic resin, ethoxylated trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, tetrahydrofuran acrylate, acryloyl morpholine, co-initiator, polyethylene wax, photosensitizer, heat stabilizer and calcium carbonate, stirring evenly and leaving for a predetermined time to fully wet the mixed pigment; and S2: Grinding the mixed pigment after being placed for the predetermined time, so that the mixed pigment reaches a predetermined fineness.

[0013] In some embodiments of the present application, the stirring time is 30-50 min, and the predetermined time is >4 h.

[0014] In some embodiments of the present application, the aromatic polyurethane acrylic resin includes at least one of a difunctional aromatic polyurethane acrylic resin, a trifunctional aromatic polyurethane acrylic resin, a tetrafunctional aromatic polyurethane acrylic resin, and a hexafunctional aromatic polyurethane acrylic resin.

[0015] In some embodiments of the present application, the modified epoxy acrylic resin includes at least one of rosin-modified epoxy acrylic resin, aldehyde-ketone-modified epoxy acrylic resin, and phenol-formaldehyde-modified epoxy acrylic resin.

[0016] In some embodiments of the present application, the photosensitizer includes at least one of benzophenone, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, 2,4,6(trimethylbenzoyl)diphenylphosphine oxide, isopropylthioxanthine, 2,4-diethylthioxanthine, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone, and 1-hydroxy-cyclohexyl-phenyl ketone.

[0017] In some embodiments of the present application, the particle size range of the calcium carbonate is 1000~10000 mesh.

[0018] In some embodiments of the present application, the predetermined fineness is less than 5 μm.

[0019] The third object of the present application is to provide a printed product, comprising a base paper and an ink layer, wherein the ink layer is formed by printing any of the above-mentioned temperature-variable inks on the base paper.

[0020] In some embodiments of the present application, the ink layer has different colors in different temperature ranges.

[0021] The present invention adds aromatic benzene ring group materials, co-initiators, modified epoxy acrylic resins, and active photosensitizer materials with thermochromic properties into the ink formula, so that the ink layer has a significant color change effect under high temperature conditions after drying. The temperature-changing ink of the present invention has diversified color change effects at multiple ultra-high temperature sections, with color changes from 140 to 220°C: colorless-slightly yellow-dark yellow-light brown, and the color change effect is irreversible.

[0022] Additional aspects and advantages of the present invention will be given in part in the following description and in part will be obvious from the following description, or will be learned through practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The drawings constituting a part of the present disclosure are used to provide a further understanding of the present disclosure. The illustrative embodiments of the present disclosure and their descriptions are used to explain the present disclosure and do not constitute an improper limitation on the present disclosure. In the drawings:

[0024] Figure 1 The figure is a schematic diagram of a process flow for preparing ink according to an embodiment of the present invention.

[0025] Figure 2 The figure shows the color change effect of the printed product prepared in Example 1 of the present invention.

[0026] Figure 3 The color changing effect of the standard sample used in the embodiment of the present invention is shown.

[0027] Figure 4 The color change effect of the printed product prepared in Example 2 of the present invention is shown.

[0028] Figure 5 The color change effect of the printed product prepared in Example 3 of the present invention is shown.

[0029] Figure 6 The discoloration effect of the printed product prepared in Comparative Example 1 of the present invention is shown.

[0030] Figure 7 The color change effect of the printed product prepared in Comparative Example 2 of the present invention is shown. DETAILED DESCRIPTION

[0031] In the following, only some exemplary embodiments are briefly described. As those skilled in the art will appreciate, the described embodiments may be modified in various ways without departing from the spirit or scope of the present invention. Therefore, the drawings and descriptions are considered to be exemplary and non-restrictive in nature.

[0032] The disclosure below provides many different embodiments or examples to realize different structures of the present invention. In order to simplify the disclosure of the present invention, the parts and settings of specific examples are described below. Of course, they are only examples, and the purpose is not to limit the present invention. In addition, the present invention can repeat reference numbers and / or reference letters in different examples, and this repetition is for the purpose of simplicity and clarity, which itself does not indicate the relationship between the various embodiments and / or settings discussed. In addition, the present invention provides various specific examples of processes and materials, but those of ordinary skill in the art can be aware of the application of other processes and / or the use of other materials.

[0033] As used herein, "about" or "approximately" is inclusive of the stated value and means within an acceptable range of deviation from the particular value as determined by one skilled in the art, taking into account the measurement in question and the errors associated with the measurement of the particular quantity (i.e., the limitations of the measurement system). For example, "about" can mean within one or more standard deviations, or within ±30%, ±20%, ±10%, or ±5% of the stated value.

[0034] The following is a more detailed description of the specific embodiments of the present invention in conjunction with the accompanying drawings and examples, so that the scheme of the present invention and its advantages in various aspects can be better understood. However, the specific embodiments and examples described below are only for the purpose of illustration, rather than for limiting the present invention.

[0035] The temperature-variable ink provided in the present application includes the following raw materials: aromatic polyurethane acrylic resin, modified epoxy acrylic resin, ethoxylated trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, tetrahydrofuran acrylate, acryloyl morpholine, co-initiator, polyethylene wax, photosensitizer, heat stabilizer and calcium carbonate.

[0036] In the present invention, aromatic polyurethane acrylic resin and modified epoxy acrylic resin are the main resins, and due to the characteristics of their own groups, they can change color at high temperatures. Ethoxylated trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, tetrahydrofuran acrylate, and acryloyl morpholine play a diluting role on the resin, and the viscosity of the ink can be adjusted according to the situation. In addition, in addition to diluting the ink, 1,6-hexanediol diacrylate, tetrahydrofuran acrylate, and acryloyl morpholine can also provide the ink with good adhesion and flexibility.

[0037] Wherein, the content of the aromatic polyurethane acrylic resin is 15-45wt%. In some embodiments of the present application, the content may be 15wt%, 17wt%, 19wt%, 21wt%, 23wt%, 25wt%, 28wt%, 30wt%, 33wt%, 35wt%, 37wt%, 40wt% or 45wt%. Optionally, the aromatic polyurethane acrylic resin used in the present application includes at least one of a difunctional aromatic polyurethane acrylic resin, a trifunctional aromatic polyurethane acrylic resin, a tetrafunctional aromatic polyurethane acrylic resin and a hexafunctional aromatic polyurethane acrylic resin.

[0038] The content of the modified epoxy acrylic resin is 5-45wt%. In some embodiments of the present application, the content may be 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 17wt%, 19wt%, 22wt%, 24wt%, 26wt%, 28wt%, 30wt%, 33wt%, 35wt%, 37wt%, 40wt% or 45wt%. Optionally, the modified epoxy acrylic resin includes at least one of rosin-modified epoxy acrylic resin, aldehyde-ketone-modified epoxy acrylic resin and phenol-modified epoxy acrylic resin.

[0039] The content of ethoxylated trimethylolpropane triacrylate (EO3TMPTA) is 5-10 wt %. In some embodiments of the present application, the content may be 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt % or 10 wt %.

[0040] The content of 1,6-hexanediol diacrylate (HDDA) is 5-10 wt %. In some embodiments of the present application, the content may be 5 wt %, 7 wt %, 9 wt % or 10 wt %.

[0041] The content of tetrahydrofuran acrylate (THFA) is 5-10 wt %. In some embodiments of the present application, the content may be 5 wt %, 7 wt %, 9 wt % or 10 wt %.

[0042] The content of acryloylmorpholine (ACMO) is 5-10 wt %. In some embodiments of the present application, the content may be 5 wt %, 7 wt %, 9 wt % or 10 wt %.

[0043] The content of the co-initiator is 5-10 wt %. In some embodiments of the present application, the content may be 5 wt %, 7 wt %, 9 wt % or 10 wt %. Optionally, the co-initiator is an active amine, such as active amine P113.

[0044] The content of polyethylene wax is 0.5-1.5wt%. Polyethylene wax mainly plays a role of wear resistance in the present invention. In some embodiments of the present application, the content of polyethylene wax can be 0.5wt%, 1wt% or 1.5wt%.

[0045] The content of the photosensitizer is 4 to 10 wt%. Optionally, the photosensitizer includes at least one of benzophenone, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 2,4,6(trimethylbenzoyl)diphenylphosphine oxide, isopropylthioanthraquinone (2, 4 isomer mixture), 2,4-diethylthioanthraquinone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and 1-hydroxy-cyclohexyl-phenyl ketone. When used in combination, the drying time of the ink can be reduced. In some embodiments of the present application, the content of the photosensitizer may be 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt% or 10%. For example, the content of 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone may be 3-5 wt %, the content of 2,4-diethylthioxanthone may be 1-3 wt %, and the content of 2-phenylbenzyl-2-dimethylamino-1-(4-morpholinobenzylphenyl)butanone may be 1-3 wt %.

[0046] The content of the heat stabilizer is 0.5-1.5 wt%. The heat stabilizer in the present invention mainly plays a role in improving the storage stability of the ink. In some embodiments of the present application, the content of the heat stabilizer can be 0.5 wt%, 1 wt% or 1.5 wt%.

[0047] The content of calcium carbonate is 5-15wt%. The particle size of the calcium carbonate used in the present invention is less than 5μm, and the particle size distribution is 1000 mesh to 10000 mesh. In some specific embodiments, the mass percentage of calcium carbonate can be 5wt%, 7wt%, 9wt%, 11wt%, 13wt% or 15wt%.

[0048] Optionally, the particle size of the temperature-variable ink is less than 5 μm.

[0049] The present invention adds a material containing an aromatic benzene ring group, a co-initiator, a modified epoxy acrylic resin, and a photosensitizer material with thermochromic properties into the ink formula, so that the ink layer has a significant color change effect under high temperature conditions after drying. The temperature-changing ink of the present invention has a diversified color change effect at multiple ultra-high temperature sections, and has a color change effect of: colorless-slightly yellow-dark yellow-light brown between 140 and 210°C, and the color change effect is irreversible.

[0050] Figure 1 A method for preparing the above-mentioned ink provided in an embodiment of the present application is shown, comprising the following steps S1 and S2.

[0051] S1: Aromatic polyurethane acrylic resin, modified epoxy acrylic resin, ethoxylated trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, tetrahydrofuran acrylate, acryloylmorpholine, co-initiator, polyethylene wax, photosensitizer, heat stabilizer and calcium carbonate are mixed and stirred evenly and then placed for a predetermined time to allow the mixed pigment to be fully wetted.

[0052] Optionally, a planetary mixer is used for stirring. Further optionally, the stirring time is 30 to 50 minutes. In some specific embodiments, the stirring time can be 30 minutes, 35 minutes, 40 minutes, 45 minutes or 50 minutes.

[0053] Optionally, the predetermined time is greater than 4 hours. The mixed pigment is allowed to stand for more than 4 hours to be fully moistened before grinding.

[0054] S2: Grinding the mixed pigment after being placed for a predetermined time to make the mixed pigment reach a predetermined fineness.

[0055] Optionally, a three-roll mill is used to grind at least 2 times so that the mixed pigment reaches a predetermined fineness. The pressure of the three-roll mill can be set according to the fineness requirement, and the fineness can be detected using a fineness meter. Optionally, the predetermined fineness is <5 μm.

[0056] Optionally, the prepared ink is subjected to a three-roll mill to remove air bubbles and is then ready for packaging.

[0057] The present application further provides a printed product, which includes a base paper and an ink layer, wherein the ink layer is formed by printing any of the above-mentioned inks on the base paper. The ink can be printed on the paper surface by offset printing, flexographic printing, silk screen printing or roller coating.

[0058] The ink layer of the printed product provided by the present invention has different colors in different temperature ranges, and the color change effect is diversified. The color changes from 140 to 210°C are: colorless-slightly yellow-dark yellow-light brown, and the color change effect is irreversible.

[0059] The present invention is described below with reference to specific embodiments. The process condition values ​​taken in the following embodiments are all exemplary, and the possible numerical ranges are as shown in the above invention content. For process parameters not specifically noted, conventional techniques can be used. Unless otherwise specified, the detection methods used in the following embodiments are conventional detection methods in the industry. Unless otherwise specified, the reagents and instruments used in the technical solutions provided by the present invention can be purchased from conventional channels or the market.

[0060] Example 1 This embodiment prepares a printed product, the base material of which is a PVC film material. The specific preparation steps are as follows:

[0061] First, a difunctional aromatic polyurethane acrylic resin, a rosin-modified epoxy acrylic resin, ethoxylated trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, tetrahydrofuran acrylate, acryloyl morpholine, a co-initiator, polyethylene wax, a photosensitizer, a heat stabilizer and calcium carbonate were mixed and stirred uniformly according to the mass percentage in Table 1 to obtain a mixed pigment. The mixed pigment was then placed for 6.5 hours to fully wet the mixed pigment. The mixed pigment was then ground in a three-roll mill so that the fineness of the mixed pigment was less than 5 μm to obtain the desired ink.

[0062] Table 1 Raw materials used in Example 1 type factory model Mass percentage (wt%) Performance Indicators Bifunctional aromatic polyurethane acrylic resin China Zhongshan Qianyou Chemical Materials Co., Ltd. UV2021 25 Elongation 6%, high temperature discoloration Rosin modified epoxy acrylic resin Xiamen Aikema Chemical Co., Ltd., China UV-100A 10 Plant-based content: >20%, discoloration at high temperature Ethoxylated trimethylolpropane triacrylate China Taiwan Evergreen Materials Industry Co., Ltd. EM2380TF 10 Viscosity (cps at 25℃): 50~70 1,6-Hexanediol diacrylate China Taiwan Evergreen Materials Industry Co., Ltd. EM221TF 8 Viscosity (cps at 25℃): 5~10 Tetrahydrofuran acrylate Korea Miwon Special Chemical Co., Ltd. M150 8 Viscosity (cps at 25℃): 5~6, increase flexibility and adhesion Acryloylmorpholine China Guangdong Lancolu New Materials Co., Ltd. L6102 8 Viscosity (cps at 25℃): 5~6, increase flexibility and adhesion Co-initiator China Zhongshan Qianyou Chemical Materials Co., Ltd. Active amine P113 8 Co-initiator, high temperature discoloration Polyethylene wax Clariant Chemicals (China) Co., Ltd. 9610F 1 Increased scratch resistance 2-Methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone Tianjin Jiuri New Materials Co., Ltd. JRcure1107 3 Surface drying, high temperature discoloration 2,4-Diethylthioxanthone Tianjin Jiuri New Materials Co., Ltd. JRcure1106 3 Deep curing, high temperature discoloration 2-phenylbenzyl-2-dimethylamino-1-(4-morpholinobenzylphenyl)butanone ‌Aigenmon Group of the Netherlands Omnirad369 2 Deep curing, high temperature discoloration Heat Stabilizer Rhodia Group MEHQ 1 Provides storage stability Nano Calcium Carbonate Shanghai Excellence Nano New Materials Co., Ltd., China SP-100 13 Particle size: 20-100nm Example 2 This embodiment prepares a printed product, the substrate material of which is a PVC film material. The specific preparation steps are the same as those in the first embodiment.

[0063] Table 2 Raw materials used in Example 2 type factory model Mass percentage (wt%) Performance Indicators Bifunctional aromatic polyurethane acrylic resin China Zhongshan Qianyou Chemical Materials Co., Ltd. UV2021 20 Elongation 6%, high temperature discoloration Rosin modified epoxy acrylic resin Xiamen Aikema Chemical Co., Ltd., China UV-100A 6 Plant-based content: >20%, discoloration at high temperature Phenolic modified epoxy acrylic resin Allnex EB9636 4 Viscosity (cps at 25℃): 25000 Ethoxylated trimethylolpropane triacrylate China Taiwan Evergreen Materials Industry Co., Ltd. EM2380TF 10 Viscosity (cps at 25℃): 50~70 1,6-Hexanediol diacrylate China Taiwan Evergreen Materials Industry Co., Ltd. EM221TF 8 Viscosity (cps at 25℃): 5~10 Tetrahydrofuran acrylate Korea Miwon Special Chemical Co., Ltd. M150 10 Viscosity (cps at 25℃): 5~6, increase flexibility and adhesion Acryloylmorpholine China Guangdong Lancolu New Materials Co., Ltd. L6102 8 Viscosity (cps at 25℃): 5~6, increase flexibility and adhesion Co-initiator China Zhongshan Qianyou Chemical Materials Co., Ltd. Active amine P113 10 Co-initiator, high temperature discoloration Polyethylene wax Clariant Chemicals (China) Co., Ltd. 9610F 1.2 Increased scratch resistance 2-Methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone Tianjin Jiuri New Materials Co., Ltd. JRcure1107 8 Surface drying, high temperature discoloration Heat Stabilizer Rhodia Group MEHQ 0.8 Provides storage stability Nano Calcium Carbonate Shanghai Excellence Nano New Materials Co., Ltd., China SP-100 14 Particle size: 20-100nm Example 3 This embodiment prepares a printed product, the substrate material of which is a PVC film material. The specific preparation steps are the same as those in the first embodiment.

[0064] Table 3 Raw materials used in Example 3 type factory model Mass percentage (wt%) Performance Indicators Hexafunctional aromatic polyurethane acrylic resin China Taiwan Evergreen Materials Industry Co., Ltd. Etercure6145-100 20 Elongation 6%, high temperature discoloration Aldehyde ketone modified epoxy acrylic resin China Zhongshan Qianyou Chemical Materials Co., Ltd. UV1005-65 10 Viscosity (cps at 25℃): 30000-50000 Ethoxylated trimethylolpropane triacrylate China Taiwan Evergreen Materials Industry Co., Ltd. EM2380TF 10 Viscosity (cps at 25℃): 50~70 1,6-Hexanediol diacrylate China Taiwan Evergreen Materials Industry Co., Ltd. EM221TF 10 Viscosity (cps at 25℃): 5~10 Tetrahydrofuran acrylate Korea Miwon Special Chemical Co., Ltd. M150 10 Viscosity (cps at 25℃): 5~6, increase flexibility and adhesion Acryloylmorpholine China Guangdong Lancolu New Materials Co., Ltd. L6102 10 Viscosity (cps at 25℃): 5~6, increase flexibility and adhesion Co-initiator China Zhongshan Qianyou Chemical Materials Co., Ltd. Active amine P113 8 Co-initiator, high temperature discoloration Polyethylene wax Clariant Chemicals (China) Co., Ltd. 9610F 1 Increased scratch resistance Benzophenone Tianjin Jiuri New Materials Co., Ltd. JRCure-1020 3 Surface drying, high temperature discoloration N-(Ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine Qingdao Jiedejia New Material Technology Co., Ltd., China UV 1 2 Provide stability Heat Stabilizer Rhodia Group MEHQ 1 Provides storage stability Nano Calcium Carbonate Shanghai Excellence Nano New Materials Co., Ltd., China SP-100 15 Particle size: 20-100nm Comparative Example 1 This comparative example prepares a printed product, the substrate material of which is a PVC film material. The specific preparation steps are the same as those in Example 1.

[0065] Table 4 Raw materials used in Comparative Example 1 type factory model Mass percentage (wt%) Performance Indicators Rosin modified epoxy acrylic resin Xiamen Aikema Chemical Co., Ltd., China UV-100A 26 Plant-based content: >20%, discoloration at high temperature Ethoxylated trimethylolpropane triacrylate China Taiwan Evergreen Materials Industry Co., Ltd. EM2380TF 10 Viscosity (cps at 25℃): 50~70 1,6-Hexanediol diacrylate China Taiwan Evergreen Materials Industry Co., Ltd. EM221TF 10 Viscosity (cps at 25℃): 5~10 Tetrahydrofuran acrylate Korea Miwon Special Chemical Co., Ltd. M150 10 Viscosity (cps at 25℃): 5~6, increase flexibility and adhesion Acryloylmorpholine China Guangdong Lancolu New Materials Co., Ltd. L6102 10 Viscosity (cps at 25℃): 5~6, increase flexibility and adhesion Co-initiator China Zhongshan Qianyou Chemical Materials Co., Ltd. Active amine P113 10 Co-initiator, high temperature discoloration Polyethylene wax Clariant Chemicals (China) Co., Ltd. 9610F 1 Increased scratch resistance 2-Methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone Tianjin Jiuri New Materials Co., Ltd. JRcure1107 3 Surface drying, high temperature discoloration 2,4-Diethylthioxanthone Tianjin Jiuri New Materials Co., Ltd. JRcure1106 3 Deep curing, high temperature discoloration 2-phenylbenzyl-2-dimethylamino-1-(4-morpholinobenzylphenyl)butanone AEGON Group Omnirad369 3 Deep curing, high temperature discoloration Heat Stabilizer Rhodia Group MEHQ 1 Provides storage stability Nano Calcium Carbonate Shanghai Excellence Nano New Materials Co., Ltd., China SP-100 13 Particle size: 20-100nm Comparative Example 2 This comparative example prepares a printed product, the substrate material of which is a PVC film material. The specific preparation steps are the same as those in Example 1.

[0066] Table 5 Raw materials used in Comparative Example 2 type factory model Mass percentage (wt%) Performance Indicators Bifunctional aromatic polyurethane acrylic resin China Zhongshan Qianyou Chemical Materials Co., Ltd. UV2021 30 Elongation 6%, high temperature discoloration Ethoxylated trimethylolpropane triacrylate China Taiwan Evergreen Materials Industry Co., Ltd. EM2380TF 10 Viscosity (cps at 25℃): 50~70 1,6-Hexanediol diacrylate China Taiwan Evergreen Materials Industry Co., Ltd. EM221TF 8 Viscosity (cps at 25℃): 5~10 Tetrahydrofuran acrylate Korea Miwon Special Chemical Co., Ltd. M150 10 Viscosity (cps at 25℃): 5~6, increase flexibility and adhesion Acryloylmorpholine China Guangdong Lancolu New Materials Co., Ltd. L6102 8 Viscosity (cps at 25℃): 5~6, increase flexibility and adhesion Co-initiator China Zhongshan Qianyou Chemical Materials Co., Ltd. Active amine P113 10 Co-initiator, high temperature discoloration Polyethylene wax Clariant Chemicals (China) Co., Ltd. 9610F 1 Increased scratch resistance 2-Methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone Tianjin Jiuri New Materials Co., Ltd. JRcure1107 3 Surface drying, high temperature discoloration 2,4-Diethylthioxanthone Tianjin Jiuri New Materials Co., Ltd. JRcure1106 3 Deep curing, high temperature discoloration 2-phenylbenzyl-2-dimethylamino-1-(4-morpholinobenzylphenyl)butanone AEGON Group Omnirad369 3 Deep curing, high temperature discoloration Heat Stabilizer Rhodia Group MEHQ 1 Provides storage stability Calcium carbonate Shanghai Excellence Nano New Materials Co., Ltd., China SP-100 13 Particle size: 20-100nm Experimental example The following methods were used to test the ink properties in the examples and comparative examples.

[0067] Use an ink knife to take an appropriate amount of temperature-changing ink, add it to the base material PVC film, and use a 10-micron wire rod to evenly apply it on the base material. After the sample is displayed, it is dried in a UV machine; after drying, use an oven to set 126 °C, 137 °C, 148 °C, 180 °C, and 210 °C to test the high-temperature color change effect. The color change effect is consistent with the standard sample and is qualified. See the color change effect Figure 2 , the color change effect of the standard sample is shown in Figure 3 Among them, the standard sample is the ink coated on the PVC film material, and after drying, the high temperature color change effect is obtained in the laboratory using an oven set at 140 °C, 180 °C, 200 °C, and 220 °C respectively.

[0068] At the same time, the fineness, viscosity and fluidity of the ink were measured using a fineness plate, a viscosity meter and a fluidity meter. Finally, the drying property was determined by a drying experiment. The measurement results are shown in Table 2.

[0069] Then fold the sample in half and check if there are any cracks. The result shows no cracks.

[0070] Use 3M610 tape to compact the ink printed surface of the sample, pull it up vertically 90 degrees quickly, and observe whether there is ink falling off. The result shows that there is no ink falling off.

[0071] Table 6 Performance parameters of inks in examples and comparative examples Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Fineness / μm 5 5 5 5 5 Viscosity / mpa.s 800 750 920 1300 760 <![CDATA[Drying energy (mj / cm 2 )]]> 280 280 280 280 280 Adhesion (3M tape method) 100 / 100 100 / 100 20 / 100 10 / 100 100 / 100 from Figure 2 It can be seen that the printed product provided in Example 1 of the present application has no color change at 140°C, and slowly changes color from 160°C. At 220°C, the color changes from colorless to slightly yellow to dark yellow to brown, and the color change effect is irreversible. Figure 2 , Figure 3 It can be seen that the color change effect of the printed product provided in this application is basically consistent with that of the standard sample.

[0072] from Figure 4 It can be seen that the printed product provided in Example 2 of the present application has no color change at 140°C, and slowly changes color from 160°C. At 220°C, the color changes from colorless-slightly yellow-dark yellow-light brown, and the color change effect is irreversible.

[0073] from Figure 5 It can be seen that the printed product provided in Example 3 of the present application has no color change at 140°C, and slowly changes color from 160°C. At 220°C, the color changes from colorless-slightly yellow-dark yellow-light brown, and the color change effect is irreversible.

[0074] from Figure 6 and Figure 7 It can be seen that the printed products provided in Comparative Examples 1 and 2 of the present application have no color change at 140°C and 160°C, and gradually change color from 180°C. At 220°C, the color changes from colorless to slightly yellowish to yellow to light brown.

[0075] As can be seen from Table 6, the printing adaptability of the temperature-changing ink provided by the present application is also very good. According to Comparative Example 1, the aromatic polyurethane acrylic resin component is not added in the comparative example, resulting in a high viscosity of the ink prepared therefrom, and a relatively serious adhesion problem. In the adhesion test, the temperature-changing coating basically fell off, and the high-temperature color change effect was acceptable, but the color change was not as deep as that in Example 1. Figure 6 In Comparative Example 2, no modified epoxy acrylic resin component was added, and there was no problem with adhesion, but the color change was not as obvious as in Example 1. Figure 7 In Example 3, due to the different modified epoxy acrylate used in the formula, the color change effect obtained is not as good as that of Example 1. Figure 5 As shown; in Example 2, as the amount of rosin-modified epoxy acrylate decreases, the color changes accordingly, and the color is not as deep as in Example 1, as shown in FIG. Figure 4 shown.

[0076] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A temperature-variable ink, characterized in that: The following raw materials are included in mass percentage: 15-45wt% aromatic polyurethane acrylic resin, 5-45wt% modified epoxy acrylic resin, 5-10wt% ethoxylated trimethylolpropane triacrylate, 5-10wt% 1,6-hexanediol diacrylate, 5-10wt% tetrahydrofuran acrylate, 5-10wt% acryloylmorpholine, 5-10wt% co-initiator, 0.5-1.5wt% polyethylene wax, 4-10wt% photosensitizer, 0.5-1.5wt% heat stabilizer and 5-15wt% calcium carbonate.

2. The temperature-variable ink according to claim 1, characterized in that: The aromatic polyurethane acrylic resin includes at least one of a difunctional aromatic polyurethane acrylic resin, a trifunctional aromatic polyurethane acrylic resin, a tetrafunctional aromatic polyurethane acrylic resin and a hexafunctional aromatic polyurethane acrylic resin.

3. The temperature-variable ink according to claim 1, characterized in that: The modified epoxy acrylic resin includes at least one of rosin modified epoxy acrylic resin, aldehyde ketone modified epoxy acrylic resin, and phenol formaldehyde modified epoxy acrylic resin.

4. The temperature-variable ink according to claim 1, characterized in that: The photosensitizer includes at least one of benzophenone, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, 2,4,6(trimethylbenzoyl)diphenylphosphine oxide, isopropylthioxanthine, 2,4-diethylthioxanthine, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone, and 1-hydroxy-cyclohexyl-phenyl ketone.

5. The temperature-variable ink according to claim 1, characterized in that: The particle size range of the calcium carbonate is 1000 to 10000 meshes.

6. The temperature-variable ink according to claim 1, characterized in that: The particle size of the temperature-variable ink is less than 5 μm.

7. A method for preparing a temperature-variable ink, characterized in that: The following steps are involved: S1: mixing and stirring aromatic polyurethane acrylic resin, modified epoxy acrylic resin, ethoxylated trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, tetrahydrofuran acrylate, acryloyl morpholine, a co-initiator, polyethylene wax, a photosensitizer, a thermal stabilizer and calcium carbonate to obtain a mixed pigment; and S2: Grinding the mixed pigment to achieve a predetermined fineness.

8. The preparation method according to claim 7, characterized in that: The stirring time is 30 to 50 minutes, and the predetermined time is greater than 4 hours.

9. The preparation method according to claim 7, characterized in that: The aromatic polyurethane acrylic resin includes at least one of a difunctional aromatic polyurethane acrylic resin, a trifunctional aromatic polyurethane acrylic resin, a tetrafunctional aromatic polyurethane acrylic resin and a hexafunctional aromatic polyurethane acrylic resin.

10. The preparation method according to claim 7, characterized in that: The modified epoxy acrylic resin includes at least one of rosin modified epoxy acrylic resin, aldehyde ketone modified epoxy acrylic resin, and phenol formaldehyde modified epoxy acrylic resin.

11. The preparation method according to claim 7, characterized in that: The photosensitizer includes at least one of benzophenone, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, 2,4,6(trimethylbenzoyl)diphenylphosphine oxide, isopropylthioxanthine, 2,4-diethylthioxanthine, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone, and 1-hydroxy-cyclohexyl-phenyl ketone.

12. The preparation method according to claim 7, characterized in that: The particle size range of the calcium carbonate is 1000 to 10000 meshes.

13. The preparation method according to claim 7, characterized in that: The predetermined fineness is less than 5 μm.

14. A printed product, characterized in that: The invention comprises a base paper and an ink layer, wherein the ink layer is formed by printing the temperature-variable ink described in any one of claims 1 to 6 on the base paper.

15. The printed product according to claim 14, characterized in that The ink layer has different colors in different temperature ranges.

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