Temperature-sensing reversible color-changing UV (ultraviolet) ink for PVC (polyvinyl chloride), and preparation method and use method thereof
Technical Field
The invention relates to the technical field of printing ink, and in particular relates to temperature-sensing reversible color-changing UV ink for PVC, a preparation method and a use method thereof.
Background
The UV ink is also called ultraviolet light curing ink, and refers to ink which is formed into a film and dried by polymerizing monomers in an ink binder into a polymer by using ultraviolet light with different wavelengths and energies under the irradiation of ultraviolet light. The UV ink has the advantages of gorgeous color, good printability, proper curing and drying rate, good adhesive force, wear resistance, corrosion resistance, weather resistance and the like, and also has the advantages of high curing speed, high printing quality, no VOC (volatile organic Compounds) emission and the like. UV ink is an economical, efficient ink and has covered all areas of printing. The most prominent markets for global UV inks are currently: in Europe and America, China and Japan, the market of the UV ink required by China at present is gradually expanding.
Reversible temperature-change color-change ink is a special anti-counterfeiting ink which changes the color of a material when reaching a certain specific temperature range and can recover the color after the temperature is recovered to the original temperature. The reversible temperature-change color-conversion ink has the advantages of convenience, rapidness, accuracy, no need of additional auxiliary equipment and the like, and has wide application prospect in package anti-counterfeiting printing. However, the ink is generally used on high-grade printing pieces due to high price, and is limited. At present, although there are many researches on temperature-sensitive color-changing materials, there are few researches on temperature-sensitive reversible color-changing UV ink systems and temperature-sensitive color-changing temperature control in the processes of temperature rise and temperature drop.
Disclosure of Invention
The invention aims to provide the temperature-sensing reversible color-changing UV ink for PVC, which has the advantages of convenience in detection, simplicity in curing, good adhesion and the like.
The invention also aims to provide a preparation method of the temperature-sensitive reversible color-changing UV ink for PVC, which is simple and easy to operate, and each parameter is easy to control.
The third purpose of the invention is to provide a use method of the temperature-sensitive reversible color-changing UV ink for PVC, which is convenient to use and has good performance.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides temperature-sensing reversible color-changing UV (ultraviolet) ink for PVC (polyvinyl chloride), which comprises the following raw materials in percentage by weight: 30-54% of prepolymer, 30-51% of monomer, 5-9% of photoinitiator, 3-7% of accelerator, 0.5-2% of dispersant, 1-2% of defoamer and 2-6% of thermochromic pigment.
The invention provides a preparation method of temperature-sensitive reversible color-changing UV (ultraviolet) ink for PVC (polyvinyl chloride), which comprises the following steps of:
premixing: mixing the prepolymer, the monomer, the accelerator and the defoaming agent, and stirring at 60-85 ℃ to obtain a mixture;
pigment dispersion: then adding the temperature-sensitive color-changing pigment, the photoinitiator and the dispersant into the mixture, and stirring.
The invention provides a use method of temperature-sensing reversible color-changing UV ink for PVC, which comprises the steps of filtering the temperature-sensing reversible color-changing UV ink for PVC by using a screen printing net, coating the filtered temperature-sensing reversible color-changing UV ink on PVC, and irradiating the PVC for 8-20 min by using ultraviolet light.
The temperature-sensitive reversible color-changing UV ink for PVC, the preparation method and the use method have the beneficial effects that:
the temperature-sensing reversible color-changing UV ink is prepared from specific raw materials and using amount, has the temperature-sensing reversible color-changing function, and can be applied to package anti-counterfeiting printing. The method has the advantages of convenience, rapidness, accuracy, no need of additional auxiliary equipment and the like, and has wide market prospect. The adhesive has strong adhesive force, simple curing, high speed, no cracking, scratch resistance and ink diffusion on materials, sufficient strength and resistance, and excellent ethanol resistance, acid resistance, alkali resistance, water resistance and the like.
The temperature-sensitive reversible color-changing UV ink is cured under ultraviolet irradiation, can reduce the interference of external temperature to a color-changing system, has excellent adhesive force on printing materials such as paper, plastics, metal and the like, and can greatly expand the application of the reversible temperature-sensitive reversible color-changing material in package anti-counterfeiting printing.
In addition, the preparation method of the temperature-sensitive reversible color-changing UV ink is simple, the prepolymer, the monomer, the accelerator and the defoamer are premixed to obtain a mixture, and then the temperature-sensitive color-changing pigment, the photoinitiator and the dispersant are introduced into the mixture, so that the pigment is well dispersed in the ink, the effective mixing of various raw materials is ensured, and the reduction of the product quality caused by the early introduction of the temperature-sensitive color-changing pigment is avoided. The preparation method is simple, convenient to operate and suitable for industrial large-scale production.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The temperature-sensitive reversible color-changing UV ink for PVC according to the embodiment of the present invention will be specifically described below.
The temperature-sensitive reversible color-changing UV ink for PVC provided by the embodiment of the invention comprises the following raw materials in percentage by weight: 30-54% of prepolymer, 30-51% of monomer, 5-9% of photoinitiator, 3-7% of accelerator, 0.5-2% of dispersant, 1-2% of defoamer and 2-6% of thermochromic pigment.
Further, in a preferred embodiment of the present invention, the temperature-sensitive reversible color-changing UV ink for PVC comprises the following raw materials by weight: 31.25 to 50.11 percent of prepolymer, 45.35 to 50 percent of monomer, 6.02 to 8.04 percent of photoinitiator, 3.74 to 5.07 percent of accelerator, 0.7 to 1.25 percent of dispersant, 1 to 1.25 percent of defoamer and 5 to 5.26 percent of thermochromic pigment.
By using the specific raw material composition and the specific dosage proportion and utilizing the thermochromic pigment, the product has the temperature-sensing reversible color-changing function and can be applied to package anti-counterfeiting printing.
Further, in a preferred embodiment of the present invention, the thermochromic pigment is a thermochromic powder. The thermochromic powder in the embodiment of the invention is prepared by an electron transfer type organic compound system. The electron transfer type organic compound is an organic color system with a special chemical structure. The molecular structure of the organic substance is changed by electron transfer at a specific temperature, thereby realizing color conversion. The color-changing substance not only has bright color, but also can realize color change from a 'colored-colorless' state, which is not possessed by heavy metal double salt complex type and liquid crystal type reversible temperature-sensitive color-changing substances.
Further, the particle size of the thermochromic powder is preferably 200-800 meshes. The temperature-sensitive color-changing powder with the particle size can be well dispersed in a product, and the uniformity of the product quality is ensured.
Further, in a preferred embodiment of the present invention, the prepolymer is selected from one or more of epoxy acrylic resin, polyurethane acrylic resin, polyester acrylate resin, polyether acrylic resin, polypropylene acrylate, and unsaturated polyester resin. More preferably, the prepolymer is selected from epoxy acrylic resins.
The choice of the prepolymer has a great influence on the curing speed, hardness, sensitivity, stability and printability of the UV ink. In addition, the dispersibility, resistance, etc. of the prepolymer to the pigment all have an effect on the discoloration temperature. In the embodiment of the invention, the epoxy acrylic resin is selected as the prepolymer, so that the thermochromic pigment can form good dispersion in a product, has good adhesive force, and generates relatively obvious color change after reaching the expected temperature.
Further, in a preferred embodiment of the present invention, the monomer is selected from one or more of ethylene glycol diacrylate, ethoxyethoxyethyl acrylate, diethylene glycol diacrylate phthalate, dipropylene glycol diacrylate, tripropylene glycol diacrylate.
Further, the monomer is preferably HDDA (ethylene glycol diacrylate). The monomer has the advantages of convenient raw material source and low cost, and can effectively adjust the solubility and viscosity reduction performance of the UV printing ink, the adhesiveness of a cured product and the like.
Further, in a preferred embodiment of the present invention, the photoinitiator is selected from one or more of trimethylbenzoyldiphenylphosphine oxide, bisbenzoylphenylphosphine oxide, diphenylethanone.
The photoinitiator is a compound which is easy to be excited by light, and is excited into a free radical after absorbing light, and energy is transferred to photosensitive molecules to enable the UV printing ink to generate a curing reaction. In an embodiment of the present invention, the photoinitiator is preferably trimethylbenzoyldiphenylphosphine oxide (I1). The photoinitiator is very sensitive to light, and greatly promotes the polymerization and crosslinking of monomers.
Further, in a preferred embodiment of the invention, the accelerator is a reactive amine. Specifically, an active amine product consisting of TMPTA trimethylolpropane triacrylate, diethylamine and a polymerization inhibitor is selected. The active amine is an industrial product, and the raw materials are easy to obtain. The active amine can promote the curing of the resin, improve the photocuring speed of the product, improve the hardness of the cured product and the like.
Further, in a preferred embodiment of the present invention, the defoaming agent is a silicone oil type defoaming agent (F810). The defoaming agent is used for improving the leveling property of the ink layer, preventing the generation of shrinkage cavities, enabling the surface of the ink film to be smooth and simultaneously increasing the glossiness of ink printing. The defoaming agent has chemical inertia, wide applicable temperature range and outstanding heat resistance, cold resistance, weather resistance and aging resistance. And the better effect can be obtained by using less amount.
Further, in a preferred embodiment of the present invention, the dispersant is an active high-molecular-weight dispersant (D-265). The dispersant can make the pigment and resin in the ink have low wetting, so that the pigment has good dispersibility in the ink and the coagulation and precipitation of ink particles are prevented. The dispersing agent contains more adsorption groups, is beneficial to stirring and dispersing of the pigment, and ensures that the pigment can achieve good dispersion at a lower stirring speed.
The invention provides a preparation method of temperature-sensitive reversible color-changing UV (ultraviolet) ink for PVC (polyvinyl chloride), which comprises the following steps of:
premixing: mixing the prepolymer, the monomer, the accelerator and the defoaming agent, and stirring at 60-85 ℃ to obtain a mixture;
pigment dispersion: then adding the temperature-sensitive color-changing pigment, the photoinitiator and the dispersant into the mixture, and stirring.
The prepolymer, the monomer, the accelerator and the defoaming agent are premixed at a certain temperature through a premixing process, and the temperature is relatively high in the process, so that the materials can be effectively mixed. In addition, the raw materials are firstly preliminarily stirred and mixed to form a uniform and stable mixture, so that the subsequent pigment is more conveniently added. In addition, the premixing process can avoid the phenomenon that the pigment, the photoinitiator and the like are added early and are greatly influenced in the subsequent operation process to influence the product quality.
Further, in a preferred embodiment of the present invention, in the pre-mixing step, the stirring speed is 100 to 150 rpm, and the stirring time is 10 to 18 minutes.
Further, in a preferred embodiment of the present invention, in the pigment dispersing step, the stirring speed is 30 to 50 rpm, and the stirring time is 3 to 5 minutes.
The premixing process and the pigment dispersing process are both stirred at a lower speed, so that the phenomenon that part of raw materials are polymerized due to overhigh speed is avoided. And the premixing process uses relatively high speed stirring for a relatively long time, while the pigment dispersing process uses relatively low speed stirring for a relatively short time, so as to obtain the product with the best quality.
The invention provides a use method of temperature-sensing reversible color-changing UV ink for PVC, which comprises the steps of filtering the temperature-sensing reversible color-changing UV ink for PVC by using a screen printing net, coating the filtered temperature-sensing reversible color-changing UV ink on PVC, and irradiating the PVC for 8-20 min by using ultraviolet light. Furthermore, the ultraviolet irradiation time is 10-18 min.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The temperature-sensitive reversible color-changing UV ink for PVC provided by the embodiment comprises the following raw materials in percentage by weight: 37.41% of epoxy acrylic resin, 45.35% of hexanediol diacrylate, 6.02% of trimethylbenzoyl diphenyl phosphine oxide, 3.74% of active amine, 1.2% of active high-molecular-weight dispersant, 1.02% of organic silicon oil defoaming agent and 5.26% of thermochromic powder.
The raw materials are all analytically pure.
The temperature-sensitive reversible color-changing UV ink for PVC is prepared by the following steps:
a. preparing materials: and (b) weighing the epoxy acrylic resin, the hexanediol diacrylate, the trimethyl benzoyl diphenyl phosphine oxide (I1), the active amine, the organic silicon oil defoaming agent, the active high-molecular-weight dispersing agent and the thermochromic powder one by one according to the composition of the raw materials for later use, and taking the photoinitiator for later use in the step b.
b. Premixing: b, stirring the prepolymer, the monomer, the accelerator and the defoaming agent which are weighed in the step a at a constant temperature of 75 ℃ at a low speed of 150 revolutions per minute in a water bath for 18 minutes;
c. pigment dispersion: and c, adding the temperature-sensitive color-changing pigment, the photoinitiator and the dispersant into the mixture heated and stirred uniformly in the step b, and stirring the mixture at a constant speed of 50 revolutions per minute by using a glass rod for 5 minutes. In this embodiment, the basic temperature of the thermochromic powder is 31 ℃.
Example 2
The temperature-sensitive reversible color-changing UV ink for PVC provided by the embodiment comprises the following raw materials in percentage by weight: 50.11% of epoxy acrylic resin, 30.04% of hexanediol diacrylate, 8.04% of trimethyl benzoyl diphenyl phosphine oxide, 5.07% of active amine, 0.7% of active high-molecular dispersing agent, 1.04% of organic silicon oil defoaming agent and 5% of thermochromic powder.
The raw materials are all analytically pure.
The temperature-sensitive reversible color-changing UV ink for PVC is prepared by the following steps:
a. preparing materials: and (b) weighing the epoxy acrylic resin, the hexanediol diacrylate, the trimethyl benzoyl diphenyl phosphine oxide (I1), the active amine, the organic silicon oil defoaming agent, the active high-molecular-weight dispersing agent and the thermochromic powder one by one according to the composition of the raw materials for later use, and taking the photoinitiator for later use in the step b.
b. Premixing: b, stirring the prepolymer, the monomer, the accelerator and the defoaming agent which are weighed in the step a at a constant temperature of 65 ℃ in a water bath at a low speed of 100 revolutions per minute for 15 minutes;
c. pigment dispersion: and c, adding the temperature-sensitive color-changing pigment, the photoinitiator and the dispersant into the mixture heated and stirred uniformly in the step b, and stirring the mixture at a constant speed of 40 revolutions per minute by using a glass rod for 5 minutes. In this embodiment, the basic temperature of the thermochromic powder is 31 ℃.
Example 3
The temperature-sensitive reversible color-changing UV ink for PVC provided by the embodiment comprises the following raw materials in percentage by weight: 50% of epoxy acrylic resin, 30% -51% of hexanediol diacrylate, 6.25% of trimethylbenzoyl diphenyl phosphine oxide, 5% of active amine, 1.25% of active high-molecular-weight dispersing agent, 1.25% of organic silicon oil defoaming agent and 5% of thermochromic powder.
The raw materials are all analytically pure.
The temperature-sensitive reversible color-changing UV ink for PVC is prepared by the following steps:
a. preparing materials: and (b) weighing the epoxy acrylic resin, the hexanediol diacrylate, the trimethyl benzoyl diphenyl phosphine oxide (I1), the active amine, the organic silicon oil defoaming agent, the active high-molecular-weight dispersing agent and the thermochromic powder one by one according to the composition of the raw materials for later use, and taking the photoinitiator for later use in the step b.
b. Premixing: b, stirring the prepolymer, the monomer, the accelerator and the defoaming agent which are weighed in the step a at a constant temperature of 70 ℃ in a water bath at a low speed of 100 revolutions per minute for 10 minutes;
c. pigment dispersion: and c, adding the temperature-sensitive color-changing pigment, the photoinitiator and the dispersant into the mixture heated and stirred uniformly in the step b, and stirring the mixture at a constant speed of 30 revolutions per minute by using a glass rod for 5 minutes. In this embodiment, the basic temperature of the thermochromic powder is 31 ℃.
Example 4
The temperature-sensitive reversible color-changing UV ink for PVC provided by the embodiment comprises the following raw materials in percentage by weight: 30% of polyurethane acrylic resin, 44% of diethylene glycol diacrylate phthalate, 9% of diphenylethanone, 7% of active amine, 2% of high-activity high-molecular dispersing agent, 2% of organic silicon oil defoaming agent and 6% of thermochromic powder.
The raw materials are all analytically pure.
The temperature-sensitive reversible color-changing UV ink for PVC is prepared by the following steps:
a. preparing materials: and (c) weighing the prepolymer, the monomer, the accelerator, the defoaming agent, the dispersing agent and the thermochromic pigment one by one according to the composition of the raw materials for later use, and taking the photoinitiator for later use in the step (b).
b. Premixing: b, stirring the prepolymer, the monomer, the accelerator and the defoaming agent which are weighed in the step a at a constant temperature of 60 ℃ at a low speed of 150 revolutions per minute in a water bath kettle for 10 minutes;
c. pigment dispersion: and c, adding the temperature-sensitive color-changing pigment, the photoinitiator and the dispersant into the mixture heated and stirred uniformly in the step b, and stirring the mixture at a constant speed of 30 revolutions per minute by using a glass rod for 5 minutes. In this embodiment, the basic temperature of the thermochromic powder is 39 ℃.
Example 5
The temperature-sensitive reversible color-changing UV ink for PVC provided by the embodiment comprises the following raw materials in percentage by weight: 54% of phthalic acid diethylene glycol diacrylate, 34.5% of hexanediol diacrylate, 5% of trimethylbenzoyl diphenyl phosphine oxide, 3% of active amine, 0.5% of active high-molecular-weight dispersant, 1% of organic silicon oil defoaming agent and 2% of thermochromic powder.
The raw materials are all analytically pure.
The temperature-sensitive reversible color-changing UV ink for PVC is prepared by the following steps:
a. preparing materials: and (c) weighing the prepolymer, the monomer, the accelerator, the defoaming agent, the dispersing agent and the thermochromic pigment one by one according to the composition of the raw materials for later use, and taking the photoinitiator for later use in the step (b).
b. Premixing: b, stirring the prepolymer, the monomer, the accelerator and the defoaming agent which are weighed in the step a at a constant temperature of 85 ℃ in a water bath at a low speed of 100 revolutions per minute for 18 minutes;
c. pigment dispersion: and c, adding the temperature-sensitive color-changing pigment, the photoinitiator and the dispersant into the mixture heated and stirred uniformly in the step b, and stirring the mixture at a constant speed of 50 revolutions per minute by using a glass rod for 3 minutes. In this embodiment, the basic temperature of the thermochromic powder is 35 ℃.
Test example 1
The PVC in the embodiments 1 to 5 uses the temperature-sensitive reversible color-changing UV ink to respectively detect the hue, the consistency and the solid content, and after the detection is qualified, the PVC is filtered by a silk screen and is uniformly coated on the PVC. And then, putting the printing ink coated on the PVC into an ultraviolet irradiation box, irradiating for 15min, and taking out to obtain samples 1-5 respectively.
And (5) carrying out performance detection on the sample.
The main performance test method in the test example of the invention is as follows:
1) testing of light solid velocity
Level 1: has no stickiness. The ink was not sticky to the touch.
Level 2: no stickiness when twisted by thumb. The ink film was not broken by rotational twisting with a thumb on the ink film with about 5kg of downward pressure.
Level 3: and (4) no scratch and curing. The ink film is scratched by a fingernail without cracking.
2) Examination of adhesion
The ink film was scribed with a needle point in a x shape and then attached to the score with cellophane adhesive tape and pulled to see if the ink film was pulled away from the glass substrate.
Level 0 (poor): the scored ink film can be substantially pulled off;
level 1 (medium) has a small amount of ink film pulled off;
level 2 (good) very few ink films were pulled off;
grade 3 (good) did not drop off at all.
3) Detection of resistance Performance
The method adopts a soaking method which is an ethanol-resistant, acid-resistant, alkali-resistant and water-resistant test method, and refers to the standard QB 568-1983. And (3) checking the principle: the dried ink samples were immersed in 1% sodium hydroxide solution, 1% hydrochloric acid solution, 95% ethanol solution and water, respectively, and after immersion for 24 hours, the samples were taken out, and the evaluation grades are shown in table 1 according to the change of the sample hanging.
TABLE 1 evaluation table of resistance rating
The detection results are shown in the following table 2, and the results show that the UV ink prepared in the embodiment of the invention can be directly cured under ultraviolet light, has an excellent curing effect, and has excellent adhesion. In addition, the obtained sample has excellent resistance, acid resistance, alkali resistance, ethanol resistance, water resistance, excellent quality, long service life and wide market application prospect.
TABLE 2 Performance results Table
In summary, the temperature-sensitive reversible color-changing UV ink for PVC of the embodiment of the present invention uses the epoxy acrylic resin as the prepolymer, uses the temperature-sensitive color-changing powder as the pigment, and defines the specific raw material composition and raw material ratio to obtain the temperature-sensitive reversible color-changing UV ink with excellent quality. The temperature-sensitive reversible color-changing printing ink has the functions of temperature sensing and reversible color changing, is wide in raw material source and low in cost, can be applied to package anti-counterfeiting printing, has the advantages of convenience, rapidness, accuracy, no need of additional auxiliary equipment and the like, and has a wide application prospect in package anti-counterfeiting printing. The preparation method is simple, easy to operate, convenient to use and short in curing time. The obtained product has good curing performance, strong adhesive force, acid and alkali resistance, water resistance and organic solvent resistance, and has wide application prospect.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.