CN108373787B - Hydrophobic light-resistant UV-LED curing glazing oil for paper packaging printed matter - Google Patents

Hydrophobic light-resistant UV-LED curing glazing oil for paper packaging printed matter Download PDF

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CN108373787B
CN108373787B CN201610988793.1A CN201610988793A CN108373787B CN 108373787 B CN108373787 B CN 108373787B CN 201610988793 A CN201610988793 A CN 201610988793A CN 108373787 B CN108373787 B CN 108373787B
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monomer
curing
viscosity
nano
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CN108373787A (en
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黄江伟
毛科林
肖勇
成竹良
蒙瑞强
何迪
李晓丽
许文才
罗世永
吴长茂
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Guangxizhenlong Colour Printing & Packing Co ltd
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Guangxizhenlong Colour Printing & Packing Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/32—Radiation-absorbing paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

1-10% of cerium dioxide or zinc oxide or titanium dioxide which has improved dispersion performance through plasma polymerization and has powder D50 diameter of 10-60nm is added into the varnish. The light resistance of the printed matter is improved by the use of the nano powder with the forbidden band width of about 3eV, and the nano powder can absorb the ultraviolet rays in sunlight or illumination light. By utilizing the synergistic effect of the inorganic nano powder and the flatting agent, the inorganic nano powder forms a random island-shaped distributed rough surface on the surface of a printed matter, so that the effect of surface hydrophobic is achieved. The synergistic effect of the polyester acrylate with low viscosity and 9 functional groups, the monomer with high reactivity, the photoinitiator and the active amine is selected, so that the reactivity of the prepared glazing oil is improved, and the purpose of rapid curing even if the LED illumination intensity is weak is achieved. After the glazing oil is cured, various performances of the cigarette paper package meet various performance requirements of the glazing oil.

Description

Hydrophobic light-resistant UV-LED curing gloss oil for paper packaging printed matter
Technical Field
The application relates to hydrophobic light-resistant UV-LED curing varnish for paper packaging printed matters, and belongs to the field of printing materials and technologies.
Background
After the paper package is printed, a layer of transparent gloss oil is usually coated on the surface of the printing ink layer in a full-page manner, and the transparent coating is formed after the coating is cured, so that the printing ink layer is protected, and the water resistance and the wear resistance of a printed product are improved; and to improve the gloss of the surface of the packaging print or to create special appearance effects. After the glazing oil for paper packaging is cured, the glazing oil is required to have high transparency, no smell, strong gloss, rapid drying, good chemical corrosion resistance and good light resistance, and a cured film has certain elasticity and flexibility, strong adhesion to ink, good leveling property, smooth film surface, wide post-press processing adaptability and excellent wear resistance.
Paper packaging paper is used as a printing base material, online glazing is carried out through offset printing or gravure, if the surface of the glazing oil is too hydrophilic, water mist or water film is easily formed on the surface of the curing film layer, the mechanical strength of the paper packaging material is reduced, and further, water can penetrate through the paper packaging material and enter the packaged article, so that the packaged article is affected with damp and goes bad. Therefore, if the varnish is cured and has good hydrophobicity, water mist or water film is not easy to form. On the other hand, most of paper package printing currently adopts water-based ink, and most of the paper package printing currently adopts organic dye or organic pigment, so that the color of the printed pictures and texts of the paper package can be seriously faded under the action of sunlight and ultraviolet rays, and great color difference is generated due to serious fading along with the time lapse. Because the outer package color of the product fades and becomes light, consumers easily regard the commodity with long storage time as old commodity, even counterfeit commodity. Based on the above, the application discloses a glazing oil with good hydrophobicity and light resistance for paper packaging printed matters.
The varnish is one of important basic materials for packaging printed matters, and can be divided into three types, namely oil type varnish (solvent type varnish), water-based varnish and UV (ultraviolet) varnish according to different curing modes. The water-based varnish has the defects of slow drying, easy set-off and the like. The UV gloss oil is widely applied due to rapid curing, no solvent volatilization and good curing film performance. In recent years, the UV-LED curing technology developed in the UV curing mode adopts a 365-420nm light source emitted by an LED to replace the conventional light source commonly used in UV light curing, such as a mercury lamp, a metal halogen lamp or an excimer lamp, and irradiates the varnish, and the varnish performs photopolymerization reaction under the action of light to change from a liquid state to a solid state, i.e., curing.
The traditional UV curing most commonly adopts low, medium and high pressure mercury lamps, and the light emitting wavelength is in a wide range of 200-380 nm. The light emitted by the UV-LED lamp is similar to monochromatic light and is generally described by a central wavelength, the light emitting wavelength is in the range of 20-30nm around the central wavelength, and the relationship between the light emitting intensity and the wavelength is in Gaussian distribution. According to the difference of wavelength conversion fluorescent powder for LEDs and the packaging mode, the fluorescent powder is generally called UV-LED curing, but the central wavelength is respectively 365nm, 385nm, 395nm, 405nm or 420nm and the like. In addition, the illuminance and the overall energy density of the LED luminous radiation on the surface of the varnish are weaker than those of the traditional mercury lamp. Therefore, gloss oil is required to have higher photopolymerization activity. On the other hand, the prepolymer for photopolymerization, also called resin, the raw materials such as active monomer and photoinitiator are still the raw materials for traditional UV curing, and have no raw materials compatible with the UV-LED curing technology. The photoinitiator plays a very critical role in the photocuring process, and the most basic requirement is that the photoinitiator can generate active groups only by absorption in the luminous wavelength range of a light source for curing so as to initiate photopolymerization. Most of photoinitiators in the market at present have absorption wavelength less than 365nm, and because UV-LED curing is a new technology, photoinitiators with strong absorption in the wavelength range of 365-420 are seriously lacked at present, only a few of traditional photoinitiators for UV curing have weak absorption in the wavelength range of 365-420nm, and the initiation efficiency of the photoinitiators is not high. Due to the two reasons, the UV-LED curing speed of the gloss oil is low, the curing degree is low, and the UV-LED curing speed of the gloss oil is far lower than the printing speed.
In order to solve the problem, the polyester acrylic prepolymer with low viscosity and super-polyfunctional groups, the high-reactivity monomer, the active amine and the photoinitiator which is matched appropriately are adopted, and the synergistic effect of all the components is utilized, so that the photopolymerization activity of the gloss oil is obviously improved, and the curing rate and the curing degree of the photopolymerization are improved, and the UV-LED curing rate of the gloss oil is matched with the printing rate of the traditional offset printing, flexo printing and gravure printing.
Disclosure of Invention
The nano TiO is used 2 Nano ZnO and nano CeO 2 The D50 diameter of the powder is between 10nm and 60 nm.
Firstly, the synthesized nano TiO is mixed with water 2 Or nano ZnO or nano CeO 2 Plasma polymerization to form a transparent SiO layer x (x = 0.3-2) thin layers, the thin layers having a thickness of less than 10 angstroms.
In a closed glass container, the nano powder body is moved under the action of mechanical stirring, a plasma discharge system is formed in a closed space by using a power supply with the frequency of 13.56MHz and the maximum power of 1000W, when the vacuum degree reaches about 20Pa, a reaction monomer hexamethyldisiloxane or dimethyl siloxane or tetramethyl siloxane which takes Ar as a carrier gas is introduced, and transparent SiO with the thickness of less than 10 angstroms is formed on the surface of the powder body by polymerization x (x = 0.3-2) film, improving the dispersibility of the powder in the active monomer.
Secondly, the surface modified nano TiO is treated 2 Or nano ZnO or nano CeO 2 Uniformly dispersing in tripropylene glycol diacrylate (TPGDA) or hexanediol diacrylate (HDDA) or trifunctional trimethylolpropane triacrylate (TMPTA) or N-acryloyl morpholine (acmo) active monomer. Under the condition of not adding a wetting dispersant, adding the powder into the active monomer, dispersing at a high speed, and sanding by using a sand mill, wherein the sand mill uses zirconia beads with the diameter of 0.05mm, and the sanding is continuously carried out until the powder is observed to be in a nano dispersion state under an electron microscope. Because most of the wetting dispersants in the current market can not participate in photopolymerization reaction, in order to ensure that the curing speed and the curing degree of the prepared gloss oil are not influenced by the wetting dispersant which can not perform photopolymerization reaction, the application adopts plasma polymerization to form transparent SiO with the thickness of less than 10 angstroms on the surface of powder x (x = 0.3-2) film, improving the dispersibility of the powder in the active monomer. On the other hand, the unique sand milling process is adopted, so that the single nano-particle can be dispersed on the premise of not adding a wetting dispersant.
And thirdly, reasonably preparing the UV-LED gloss oil according to a formula.
Typically, the gloss oil resin, also referred to as a prepolymer, has a number of functional groups that can react of 2, more that is 4, 5 or 6 functional groups. The greater the number of functional groups, the greater the photopolymerization activity, but at the same time the greater the prepolymer viscosity. The prepared printing product glazing oil has different viscosity requirements according to different glazing modes and glazing amounts. For the surface glazing of paper by an anilox roller, the coating dry weight is usually controlled to be 4-12 g/m 2 . The viscosity was required to be measured in a zeien No. 4 cup for 60-120 seconds. Thus, the high viscosity of the prepolymer multi-functional groups is disadvantageous in that low-viscosity reactive monomers, also referred to as reactive diluents, have to be matched. The viscosity of the reactive monomer is still proportional to the number of functional groups that can undergo photopolymerization. That is, in order to increase the rate of photopolymerization of the gloss oil, it is difficult to significantly increase the reaction rate by selecting a commonly used multifunctional prepolymer since it must be compounded with a reactive monomer having a low functional group. The polyester acrylic prepolymer with 9 functional groups is adopted, the viscosity of the prepolymer is much lower than that of the common prepolymer, the viscosity at 25 ℃ is 300cps, and is equivalent to that of a reactive diluent, the defect of high viscosity is overcome, and the photopolymerization reaction rate of the prepared gloss oil can be greatly improved.
The other prepolymer adopted by the application, namely the difunctional epoxy acrylate prepolymer, is low in cost, has high chemical reactivity, and endows a cured film with high chemical stability, hardness and scratch resistance.
Photoinitiators are one of the key components in gloss oils. After the varnish is cured, residual ultraviolet initiator in the varnish can also generate chemical migration or pollute food in a package through physical contact under certain conditions, thereby causing potential harm to human health. According to the list of licensed substances for use of low migration UV photoinitiators, the list of licensed substances for use of smoking materials (YQ 15.4-2012), the framework paper, the cigarette wrapping paper (strips and boxes) and the sealing paper: the selection of 8 initiators is permitted in the official license of 33 + the temporary license.
Photoinitiators absorb light energy under the illumination of the LED to initiate photopolymerization, and must absorb light within the narrow wavelength range (20-30 nm) emitted by the LED.
The UV-LED curing rate of the glazing oil is improved by adopting the photoinitiator with the absorption wavelength being absorbed at the narrow central wavelength of the LED and matching with proper active amine. According to the absorption spectra of the commonly used photoinitiators tested by the applicant, only 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), camphorquinone, N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (819), 4-ethylenepropylene thioxanthone, 2-ethylenepropylene thioxanthone have weak absorption in the range of 360-420nm, and thus, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), camphorquinone, N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (819), 4-ethylenepropylene thioxanthone or 2-ethylenepropylene thioxanthone is used as photoinitiator, which allows for both deep curing and surface curing of the gloss oil by the synergistic combination of these photoinitiators.
The acrylic acid esterification active amine is used as a reactive amine co-initiator which is completely mutually soluble with active monomers, polyurethane acrylate and the like, is a low-viscosity crosslinkable amine co-initiator, and is used as a synergist to be mixed with a proper photoinitiator so as to improve the photocuring speed, particularly accelerate the surface curing speed. The acrylic acid esterified active amine can not migrate to the surface so as to avoid surface blooming, and the active amine polymer with double bond groups has good compatibility, high oil/water balance, low volatility, anti-migration, anti-oxygen polymerization inhibition function and low smell.
Reactive monomers, also known as reactive diluents, have functional groups that participate in photopolymerization reactions. The solubility to solid photoinitiators is high. Through the comparative experiment of the curing rate of the common reactive diluent, the application selects trifunctional trimethylolpropane triacrylate (TMPTA), difunctional 1, 6-hexanediol diacrylate (HDDA) and monofunctional N-acryloyl morpholine (acmo) as the reactive monomer combination for use. TMPTA has three functional groups, has a fast curing rate, and additionally imparts good water resistance, chemical resistance, abrasion resistance and high flexibility to the cured film. HDDA is a typical low viscosity, fast curing commonly used reactive monomer that can be used to adjust the viscosity of the varnish over a wide range, while HDDA also imparts higher hydrophobic properties to the cured film. The N-acryloyl morpholine (acmo) nitrogen-containing monomer has strong adhesive force to paper base materials, ultralow odor, low shrinkage rate and high curing rate.
The leveling agent can strongly reduce the surface tension of the glazing oil, and polyester modified polydimethylsiloxane grafted with acrylic acid functional groups is selected, and the acrylic acid functional groups can be subjected to crosslinking reaction and curing under the action of a photoinitiator. And the leveling agent adopted by the common UV-cured glazing oil has no reactive active group and does not participate in photopolymerization. The leveling agent capable of generating a crosslinking reaction is used for adjusting the surface tension of the gloss oil within a certain range, namely the leveling rate of the surface of the coated gloss oil is controlled, and the geometric appearance, namely the roughness, of the surface of the cured film is regulated. The surface roughness is different, and the dynamic friction coefficient and the static friction coefficient of the solidified film are different, so that the requirements of an automatic packaging machine on the dynamic friction coefficient and the static friction coefficient are met.
Through repeated experimental tests, the preferable formula of the light-resistant, hydrophobic and UV-LED curing gloss oil for the cigarette paper packaging printed matter is represented by the following mass percent (Wt%):
nanopowder (TiO) 2 Or ZnO or CeO 2 )：1-10；
Prepolymer, also known as resin: 10-40 parts of bifunctional bisphenol A epoxy acrylate and 10-30 parts of nine-functional polyester acrylate;
reactive monomers, also known as reactive diluents: trifunctional trimethylolpropane triacrylate (TMPTA) 5-15; 10-50 of bifunctional 1, 6-hexanediol diacrylate (HDDA); 0-30 parts of N-acryloyl morpholine (acmo).
Active amine: 3-10 parts of acrylated reactive amine;
leveling agent: polyester-modified, acrylic functional group grafted polydimethylsiloxane 0.1 to 0.5;
photoinitiator (2): 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) 1-6, camphorquinone 0.5-5, N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide 0.5-4, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide (819) 0-4,4 (2) -ethylenepropylenethioamine thioxanthone 0-4.
Accurately weighing the components according to a designed formula, adding the components into a stainless steel reaction kettle at room temperature, stirring for 12 hours at a rotating speed of 800-1000r/min to completely dissolve a solid initiator without visible solid particles, adjusting the viscosity by using a small amount of HDDA (high-density digital-analog) and adjusting the surface tension by using a leveling agent, filtering, and checking the viscosity and the surface tension. The viscosity of the varnish is detected by a Zeian No. 4 cup within 60-120 seconds, and the surface tension of the varnish is controlled to be between 20 and 30Dynes/cm by the leveling agent. Packaging with metal barrel. Namely the product of the application. All operations are preferably performed under yellow illumination.
The prepared gloss oil is evenly coated on 80 g/m 2 The curing light source on the transfer paper is an LED light source, the central wavelengths are 365nm, 385nm, 395nm and 405nm respectively, and the illumination intensity is about 0.5-15W/cm 2 The paper feeding speed is 120-180 m/min, and the gloss oil is at 810cm by infrared spectrum test before and after gloss oil curing -1 The absorption band of (a) disappears after the curing by LED illumination, thus proving that the C = C conversion is complete and the curing is complete. The surface of the cured film was pressed with a finger without leaving a fingerprint, and the completion of curing was also confirmed from another point of view.
And fourthly, after the gloss oil is coated and cured, inorganic nano-powder cerium dioxide, zinc oxide and titanium dioxide in the gloss oil cooperate with polyester-modified polydimethylsiloxane grafted with acrylic acid functional groups to construct a rough appearance on the surface of a printed matter, and the gloss oil cured film forms a random rough surface structure shown in the attached drawing of the specification. The rough surface is utilized to obtain the surface hydrophobic performance, and the water contact angle is controlled within the range of 120-145 degrees, so that the surface hydrophobic effect is achieved. As the size of the used nano powder is 10-60nm, the visible light transparency of a cured film formed after the gloss oil is cured is not affected basically.
The prepared varnish was tested for surface tension using a K100 surface tensiometer.
And testing the friction resistance of the cured film: the prepared gloss oil is evenly coated on 80 g/m 2 The coating weight of the transfer paper is about 4 to 6 g/m 2 After being cured by an LED light source, the decorative presswork of the 7705-2008 planographic printing plate has no phenomena of scratch, ink drop and the like.
And (3) testing the water contact angle of the cured film: the prepared gloss oil is evenly coated on 80 g/m 2 The coating weight of the transfer paper is about 4 to 6 g/m 2 After curing with an LED light source, the water contact angle was measured using a DSA100 video contact angle meter.
The lightfastness of the cured films was tested in accordance with ISO 12040-1997 "printing technology-prints and stamp-ink-evaluation using a filtered xenon arc lamp".
And (3) testing the dynamic and static friction coefficients: the prepared gloss oil is evenly coated on 80 g/m 2 The coating weight of the transfer paper is about 4 to 6 g/m 2 After being cured by an LED light source, the sample is cut into a specification of 65 multiplied by 90mm, and the plastic film is cut into a specification of 150 multiplied by 400mm and used as a substrate to be attached to a sliding block to rub with the substrate. And (3) detecting according to GB/T10006-1988 plastic film and sheet friction coefficient measuring method.
And (3) waterproof fog test: the prepared gloss oil is evenly coated on 80 g/m 2 The coating weight of the transfer paper is about 4 to 6 g/m 2 After curing with an LED light source, the test was performed as follows.
A. Cutting the main part of the cigarette box paper coated with the gloss oil into small pieces by using scissors;
B. attaching the cut sample to the surface of a cylinder, wherein the printing surface faces outwards;
C. tightly attaching a plastic film on the surface of the sample, and tightly adhering and fixing the sample by using an adhesive tape;
D. the outlet of the air blowing cylinder is aligned with the sample, and hot air is blown out to heat the sample for about 1 minute;
E. and after cooling, observing whether the surface of the sample has water mist phenomenon.
And (3) testing the flexibility of the cured film: the prepared gloss oil is evenly coated on 80 g/m 2 The coating weight of the transfer paper is about 4 to 6 g/m 2 After the printed matter is solidified by LED light source, it can be folded for more than 5 times, and has no defects of colour burst and burst, etc.
The surface water mist prevention and the automatic packaging machine have requirements on the surface flatness, the smoothness and the surface energy of the solidified gloss oil. The surface energy is described by a surface water contact angle, and the water contact angle of the transfer paper for cigarette packaging before being coated with the gloss oil is 55-60 degrees. Repeated experiments show that if the surface tension of the gloss oil is controlled to be between 20 and 30Dynes/cm under the premise of ensuring that other properties such as flexibility, light resistance, wear resistance and the like of the cured film meet the requirements of cigarette packaging materials, the surface water contact angle is 120 to 145 degrees after the cured film is coated and an LED light source is cured. The dynamic coefficient of friction of the surface of the cured film is controlled to be 0.050 to 0.200, and the static coefficient of friction is controlled to be 0.100 to 0.300. The cured film on the surface of the printed matter has good light resistance and hydrophobicity.
The beneficial effect of this application is: adding 1-10% of nano cerium dioxide or zinc oxide or titanium dioxide in percentage by mass into the gloss oil. The forbidden band widths of the three powders are about 3eV, and the purpose of protecting the light resistance of printed matters is achieved by absorbing ultraviolet rays in sunlight or illumination light by using cerium dioxide, zinc oxide or titanium dioxide. Inorganic nano-powder cerium dioxide or zinc oxide or titanium dioxide is utilized to cooperate with a leveling agent to form random rough morphology on the surface of a printed matter, so that the effect of surface hydrophobicity is achieved. The synergistic effect of low-viscosity 9-functional-group polyester acrylate, high-reactivity monomer, photoinitiator and active amine is selected to improve the reactivity of the prepared glazing oil, so that the purpose of rapid curing even if the LED illumination intensity is weak is achieved. The viscosity of the varnish is detected by a Chuanyn 4# cup within 60-120 seconds, and the surface tension of the varnish is controlled to be between 20 and 30Dynes/cm by the leveling agent; through the synergistic effect of the components in the formula, the dynamic coefficient of friction is controlled to be between 0.050 and 0.200, the static coefficient of friction is controlled to be between 0.100 and 0.300, and the requirements of the automatic cigarette packaging machine on the friction coefficient and the surface scratch resistance of the cigarette packaging paper box are met. The application considers that the photoinitiator residues and the volatile organic compounds meet the requirements of cigarette packaging materials after the varnish on the printed matter is cured, can be used for surface glazing of the cigarette packaging printed matter, and improves the hydrophobicity of the printed matter and the light resistance of printing colors.
Drawings
The attached drawing is a scanning electron microscope photo of the surface of the solidified gloss oil, and the small spheres in the drawing are nano cerium dioxide, zinc oxide or titanium dioxide powder, so that a rough structure is formed on the surface of a printed matter, and the hydrophobic property of the surface of the printed matter is improved.
Detailed Description
The patent application is further illustrated by the following specific examples.
Example 1
The formula of the UV-LED curing gloss oil is expressed by the following mass percent (Wt%):
firstly, synthesizing the nano TiO with the D50 diameter of 30nm 2 Plasma polymerization was used to form a thin layer of transparent SiOx (x = 0.3-2).
In a closed glass container, the powder body moves under the action of mechanical stirring, a plasma discharge system is formed in a closed space by using a power supply with the frequency of 13.56MHz and the maximum power of 1000W, when the vacuum degree reaches about 20Pa, a reaction monomer hexamethyldisiloxane with Ar as a carrier gas is introduced, and transparent SiO with the thickness of about a few angstroms is formed on the surface of the powder body x (x = 0.3-2) film, improving the dispersibility of the powder in the active monomer.
Secondly, the surface modified nano TiO is treated 2 Uniformly dispersed in tripropylene glycol diacrylate (TPGDA) reactive monomer. Under the condition of not adding wetting dispersant, add the powder in the active monomer, through high-speed dispersion, then sand mill sanding, the zirconia pearl that the sanding was used for diameter to be 0.05mm, continuous sanding is until observing under the electron microscope that the powder becomes nanometer dispersed state. The mass ratio of the nano particles to the active monomer is 25: 75.
Prepolymer: difunctional bisphenol A epoxy acrylate 20, nine functional polyester acrylate 28;
reactive monomer: trifunctional trimethylolpropane triacrylate (TMPTA) 5; 1, 6-hexanediol diacrylate (HDDA) 5 with double functional groups, dispersed with nano TiO 2 Tripropylene glycol diacrylate (TPGDA) monomer 21, n-acryloyl morpholine (acmo) 6;
active amine: acrylated reactive amine 8;
leveling agent: polyester-modified polydimethylsiloxane grafted with acrylic functional groups 0.1;
photoinitiator (2): 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) 3, camphorquinone 0.5, N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide 2.5, 4-ethylenepropylenethioaminones 1.
Accurately weighing the components according to a designed formula, adding the components into a stainless steel reaction kettle at room temperature, stirring for 12 hours at a rotating speed of 800r/min to completely dissolve a solid initiator without visible solid particles, adjusting the viscosity by using a small amount of HDDA (high-density digital-analog) and adjusting the surface tension by using a leveling agent, filtering, checking that the viscosity and the surface tension are qualified, and packaging by using a metal barrel.
The gloss oil was checked for viscosity using a Zeian # 4 cup for 78 seconds and a surface tension of 28Dynes/cm.
The prepared gloss oil is evenly coated on 80 g/m 2 On the transfer paper of (2), the dry coating weight is about 4-6 g/m 2 Using a central wavelength of 395nm and an illumination of 0.5W/cm 2 The LED lamp of (1) is cured. The paper feeding speed is 150m/min. After curing, the test was performed with the following results:
and (3) testing the water contact angle of the cured film: 130 deg. The coefficient of dynamic friction was 0.154 and the coefficient of static friction was 0.210. The light fastness of the cured films was tested according to ISO 12040-1997 "printing technology-prints and stamp-inks-evaluated using a filtered xenon arc lamp" and was rated 6.
Other properties meet the fourth part of the YQ15.4-2012 permitted materials list for cigarettes: the prepared glazing oil can be used for curing and glazing by using an LED light source after printing of cigarette package presswork.
Example 2
The formula of the UV-LED curing gloss oil is expressed by the following mass percent (Wt%):
firstly, the synthesized nano ZnO with the D50 diameter of 40nm is polymerized by plasma to form a layer of transparent SiO x A thin layer.
In a closed glass container, the powder body is moved under the action of mechanical stirring, a plasma discharge system is formed in a closed space by using a power supply with the frequency of 13.56MHz and the maximum power of 1000W, when the vacuum degree reaches about 20Pa, a reaction monomer dimethyl disiloxane with Ar as a carrier gas is introduced, and the vacuum degree is controlled by controlling the vacuum degree in a closed glass containerThe surface of the powder forms transparent SiO with the thickness of about a few angstroms x (x 0.3-2.0) film to improve the dispersion performance of powder in active monomer.
And step two, uniformly dispersing the surface modified nano ZnO in a trifunctional trimethylolpropane triacrylate (TMPTA) active monomer. Under the condition of not adding wetting dispersant, add the powder in the active monomer, through high-speed dispersion, then sand mill sanding, the zirconia pearl that the sanding was used for diameter to be 0.05mm, continuous sanding is until observing under the electron microscope that the powder becomes nanometer dispersed state. The mass ratio of the nano particles to the active monomer is 30: 70.
Prepolymer: difunctional bisphenol a epoxy acrylate 22, nine functional polyester acrylate 25;
reactive monomer: trifunctional trimethylolpropane triacrylate (TMPTA) 23 dispersed with nano zinc oxide; difunctional 1, 6-hexanediol diacrylate (HDDA) 18;
active amine: acrylated reactive amine 6;
leveling agent: polyester-modified polydimethylsiloxane grafted with acrylic functional groups 0.2;
photoinitiator (2): 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) 2, camphorquinone 1, N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide 1.5, 2-ethylenepropylenethioanthrone 1.
Accurately weighing the components according to a designed formula, adding the components into a stainless steel reaction kettle at room temperature, stirring for 12 hours at a rotating speed of 900r/min to completely dissolve a solid initiator without visible solid particles, adjusting the viscosity by using a small amount of HDDA (high-density digital data acquisition) and adjusting the surface tension by using a leveling agent, filtering, checking that the viscosity and the surface tension are qualified, and packaging by using a metal barrel.
The gloss oil was checked for viscosity in a Zealan # 4 cup at 85 seconds and a surface tension of 27Dynes/cm.
The prepared gloss oil is evenly coated on 80 g/m 2 On the transfer paper of (2), the dry coating weight is about 4-6 g/m 2 Using a central wavelength of 385nm and an illuminance of 15W/cm 2 The LED lamp of (1) is cured. The paper feeding speed is 160m/min. After curing, the test was performed with the following results:
and (3) testing the water contact angle of the cured film: 135 deg. The coefficient of dynamic friction was 0.081, and the coefficient of static friction was 0.158. The lightfastness of the cured films was tested according to ISO 12040-1997 "printing technology-prints and stamp-pad ink-evaluation using a filtered xenon arc lamp" and was rated 7.
Other properties meet the fourth part of the YQ15.4-2012 permitted materials list for cigarettes: the prepared glazing oil can be used for curing and glazing by using an LED light source after printing cigarette package presswork.
Example 3
Firstly, the synthesized nano cerium oxide with the diameter of D50 being 10nm is polymerized by plasma to form a layer of transparent SiO x A thin layer.
In a closed glass container, the powder body is moved under the action of mechanical stirring, a plasma discharge system is formed in a closed space by using a power supply with the frequency of 13.56MHz and the maximum power of 1000W, when the vacuum degree reaches about 20Pa, a reaction monomer tetramethyldisiloxane with Ar as a carrier gas is introduced, and transparent SiO with the thickness of about a few angstroms is formed on the surface of the powder body x (x 0.3-2.0) film to improve the dispersion performance of powder in active monomer.
And step two, uniformly dispersing the surface-modified nano cerium oxide in an N-acryloyl morpholine (acmo) active monomer. Under the condition of not adding a wetting dispersant, adding the powder into the active monomer, dispersing at a high speed, and sanding by using a sand mill, wherein the sand mill uses zirconia beads with the diameter of 0.05mm, and the sanding is continuously carried out until the powder is observed to be in a nano dispersion state under an electron microscope. The mass ratio of the nano particles to the active monomer is 20: 80.
The formula of the UV-LED curing gloss oil is expressed by the following mass percent (Wt%):
prepolymer (c): 10 parts of bifunctional bisphenol A epoxy acrylate and 24 parts of nine-functional polyester acrylate;
reactive monomer: trifunctional trimethylolpropane triacrylate (TMPTA) 8; n-acryloyl morpholine (acmo) active monomer 37 with nano cerium oxide dispersed therein;
active amine: acrylated reactive amines 4;
leveling agent: polyester-modified polydimethylsiloxane grafted with acrylic functional groups 0.2;
photoinitiator (2): 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) 3, camphorquinone 1, N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide 1, bis (2, 4, 6-trimethylbenzoyl) phosphine oxide 1.5.
Accurately weighing the components according to a designed formula, adding the components into a stainless steel reaction kettle at room temperature, stirring for 12 hours at a rotating speed of 1000r/min to completely dissolve a solid initiator without visible solid particles, adjusting the viscosity by using a small amount of HDDA (high-density digital data acquisition) and adjusting the surface tension by using a leveling agent, filtering to obtain the product, inspecting the qualified viscosity and surface tension, and packaging by using a metal barrel.
The gloss oil was checked for viscosity in a Zealan # 4 cup for 68 seconds and a surface tension of 25Dynes/cm.
The prepared gloss oil is evenly coated on 80 g/m 2 On the transfer paper of (2), the dry coating weight is about 4-6 g/m 2 Using a central wavelength of 405nm and an illumination of 0.95W/cm 2 The LED lamp of (1) is cured. The paper feeding speed is 150m/min. After curing, the test was performed with the following results:
and (3) testing the water contact angle of the cured film: 137 deg. The coefficient of dynamic friction was 0.077 and the coefficient of static friction was 0.112. The lightfastness of the cured films was tested according to ISO 12040-1997 "printing technology-prints and stamp-pad ink-evaluation using a filtered xenon arc lamp" and was rated 6.
Other properties meet the fourth part of the YQ15.4-2012 permitted materials list for cigarettes: the prepared glazing oil can be used for curing and glazing by using an LED light source after printing of cigarette package presswork.
Example 4
The formula of the UV-LED curing gloss oil is expressed by the following mass percent (Wt%):
firstly, the synthesized nano cerium oxide with the D50 diameter of 50nm is polymerized by plasma to form a layer of transparent SiO x A thin layer.
In a sealed glass container, the powder is on machineMoving under the action of mechanical stirring, forming a plasma discharge system in a closed space by using a power supply with the frequency of 13.56MHz and the maximum power of 1000W, introducing a reaction monomer tetramethyldisiloxane taking Ar as a carrier gas when the vacuum degree reaches about 20Pa, and forming transparent SiO with the thickness of about a few angstroms on the surface of powder x (x = 0.3-2.0) film, improving the dispersibility of the powder in the active monomer.
And step two, uniformly dispersing the surface-modified nano cerium oxide in an N-acryloyl morpholine (acmo) active monomer. Under the condition of not adding wetting dispersant, add the powder in the active monomer, through high-speed dispersion, then sand mill sanding, the zirconia pearl that the sanding was used for diameter to be 0.05mm, continuous sanding is until observing under the electron microscope that the powder becomes nanometer dispersed state. The mass ratio of the nano particles to the active monomer is 35: 65.
Prepolymer: difunctional bisphenol a epoxy acrylate 22, nine functional polyester acrylate 24;
reactive monomer: trifunctional trimethylolpropane triacrylate (TMPTA) 5; difunctional 1, 6-hexanediol diacrylate (HDDA) 15; an N-acryloyl morpholine (acmo) active monomer 20 dispersed with nano cerium oxide;
active amine: acrylated reactive amines 6;
leveling agent: polyester-modified polydimethylsiloxane grafted with acrylic functional groups 0.3;
photoinitiator (2): 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) 4, camphorquinone 0.5, N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide 1, bis (2, 4, 6-trimethylbenzoyl) phosphine oxide 1.
Accurately weighing the components according to a designed formula, adding the components into a stainless steel reaction kettle at room temperature, stirring for 12 hours at a rotating speed of 1000r/min to completely dissolve a solid initiator without visible solid particles, adjusting the viscosity by using a small amount of HDDA (high-density digital-analog) and adjusting the surface tension by using a leveling agent, filtering, checking that the viscosity and the surface tension are qualified, and packaging by using a metal barrel.
The gloss oil was checked for viscosity in a Zealan # 4 cup for 77 seconds and a surface tension of 20Dynes/cm.
Will be describedThe prepared gloss oil is uniformly coated on 80 g/m 2 On the transfer paper of (2), the dry coating weight is about 4-6 g/m 2 The central wavelength is 365nm, and the illumination is 1.7W/cm 2 The LED lamp of (1) is cured. The paper feeding speed is 160m/min. After curing, the test was performed with the following results:
and (3) testing the water contact angle of the cured film: 140 degrees. The coefficient of dynamic friction was 0.058, and the coefficient of static friction was 0.183. The lightfastness of the cured films was tested according to ISO 12040-1997 "printing technology-prints and stamp-pad ink-evaluation using a filtered xenon arc lamp" and was rated 6.
Other properties meet the fourth part of the YQ15.4-2012 permitted materials list for cigarettes: the prepared glazing oil can be used for curing and glazing by using an LED light source after printing of cigarette package presswork.
Example 5
The formula of the UV-LED curing gloss oil is expressed by the following mass percent (Wt%):
firstly, synthesizing the nano TiO with the D50 diameter of 60nm 2 Plasma polymerization to form a transparent SiO layer x A thin layer.
In a closed glass container, the powder body moves under the action of mechanical stirring, a plasma discharge system is formed in a closed space by using a power supply with the frequency of 13.56MHz and the maximum power of 1000W, when the vacuum degree reaches about 20Pa, a reaction monomer hexamethyldisiloxane with Ar as a carrier gas is introduced, and transparent SiO with the thickness of about a few angstroms is formed on the surface of the powder body x (x 0.3-2) film, improving the dispersion performance of the powder in the active monomer.
Secondly, the surface modified nano TiO is treated 2 Uniformly dispersed in trifunctional trimethylolpropane triacrylate (TMPTA) reactive monomer. Under the condition of not adding wetting dispersant, add the powder in the active monomer, through high-speed dispersion, then sand mill sanding, the zirconia pearl that the sanding was used for diameter to be 0.05mm, continuous sanding is until observing under the electron microscope that the powder becomes nanometer dispersed state. The mass ratio of the nano particles to the active monomer is 25: 75.
Prepolymer (c): difunctional bisphenol a epoxy acrylate 19, nine functional polyester acrylate 25;
reactive monomer: dispersed with nano TiO 2 Trifunctional trimethylolpropane triacrylate (TMPTA) 29; difunctional 1, 6-hexanediol diacrylate (HDDA) 9.5;
active amine: acrylated reactive amines 9;
leveling agent: polyester-modified polydimethylsiloxane grafted with acrylic functional groups 0.2;
photoinitiator (2): 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) 5, camphorquinone 0.8, N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide 0.5, bis (2, 4, 6-trimethylbenzoyl) phosphine oxide 1.
Accurately weighing the components according to a designed formula, adding the components into a stainless steel reaction kettle at room temperature, stirring for 12 hours at a rotating speed of 1000r/min to completely dissolve the solid initiator without visible solid particles, adjusting the viscosity by using a small amount of HDDA (high density data acquisition) and adjusting the surface tension by using a flatting agent, filtering, checking that the viscosity and the surface tension are qualified, and packaging by using a metal barrel.
The gloss oil was checked for viscosity in a Chuanyn # 4 cup for 99 seconds and a surface tension of 28Dynes/cm.
The prepared gloss oil is evenly coated on 80 g/m 2 On the transfer paper of (2), the dry coating weight is about 4-6 g/m 2 With a central wavelength of 405nm and an illuminance of 1.25W/cm 2 The LED lamp of (1) is cured. The paper feeding speed is 160m/min. After curing, the test was performed with the following results:
and (3) testing the water contact angle of the cured film: 120 degrees. The coefficient of dynamic friction was 0.068 and the coefficient of static friction was 0.158. The light fastness of the cured films was tested according to ISO 12040-1997 "printing technology-prints and stamp-inks-evaluated using a filtered xenon arc lamp" and was rated 6.
Other properties meet the fourth part of the YQ15.4-2012 permitted materials list for cigarettes: the prepared glazing oil can be used for curing and glazing by using an LED light source after printing of cigarette package presswork.
Example 6
The formula of the UV-LED curing gloss oil is expressed by the following mass percent (Wt%):
firstly, the synthesized nano ZnO with the D50 diameter of 20nm is polymerized by plasma to form a layer of transparent SiO x A thin layer.
In a closed glass container, the powder body is moved under the action of mechanical stirring, a plasma discharge system is formed in a closed space by using a power supply with the frequency of 13.56MHz and the maximum power of 1000W, when the vacuum degree reaches about 20Pa, a reaction monomer tetramethyldisiloxane with Ar as a carrier gas is introduced, and transparent SiO with the thickness of about a few angstroms is formed on the surface of the powder body x (x 0.3-2.0) film to improve the dispersion performance of the powder in the active monomer.
And secondly, uniformly dispersing the surface-modified nano ZnO in a bifunctional 1, 6-hexanediol diacrylate (HDDA) active monomer. Under the condition of not adding wetting dispersant, add the powder in the active monomer, through high-speed dispersion, then sand mill sanding, the zirconia pearl that the sanding was used for diameter to be 0.05mm, continuous sanding is until observing under the electron microscope that the powder becomes nanometer dispersed state. The mass ratio of the nano particles to the active monomer is 30: 70.
Prepolymer: difunctional bisphenol a epoxy acrylate 22, nine functional polyester acrylate 25;
reactive monomer: trifunctional trimethylolpropane triacrylate (TMPTA) 10; bifunctional 1, 6-hexanediol diacrylate (HDDA) 21 dispersed with nano zinc oxide; n-acryloyl morpholine (acmo) 10;
active amine: acrylated reactive amine 6;
leveling agent: polyester-modified polydimethylsiloxane grafted with acrylic functional groups 0.2;
photoinitiator (2): 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) 2, camphorquinone 1, N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide 1, 5, 4-ethylenepropylenethioanthrone 1.
Accurately weighing the components according to a designed formula, adding the components into a stainless steel reaction kettle at room temperature, stirring for 12 hours at a rotating speed of 900r/min to completely dissolve a solid initiator without visible solid particles, adjusting the viscosity by using a small amount of HDDA (high-density digital data acquisition) and adjusting the surface tension by using a leveling agent, filtering, checking that the viscosity and the surface tension are qualified, and packaging by using a metal barrel.
The gloss oil was checked for viscosity in a Zealan # 4 cup at 85 seconds and a surface tension of 23Dynes/cm.
The prepared gloss oil is evenly coated on 80 g/m 2 On the transfer paper of (2), the dry coating weight is about 4-6 g/m 2 Using a central wavelength of 385nm and an illuminance of 15W/cm 2 The LED lamp of (1) is cured. The paper feeding speed is 160m/min. After curing, the test was performed with the following results:
and (3) testing the water contact angle of the cured film: and 142 deg.
Testing the dynamic and static friction coefficients: the coefficient of dynamic friction was 0.075 and the coefficient of static friction was 0.138.
The light fastness of the cured films was tested according to ISO 12040-1997 "printing technology-prints and stamp-inks-evaluated using a filtered xenon arc lamp" and was rated 6.
Other performances satisfy the fourth part of the YQ15.4-2012 permitted materials list for cigarettes: the prepared glazing oil can be used for curing and glazing by using an LED light source after printing cigarette package presswork.
Example 7
The formula of the UV-LED curing gloss oil is expressed by the following mass percent (Wt%):
firstly, synthesizing nano TiO with D50 diameter of 20nm 2 Plasma polymerization to form a transparent SiO layer x A thin layer.
In a closed glass container, the powder body is moved under the action of mechanical stirring, a plasma discharge system is formed in a closed space by using a power supply with the frequency of 13.56MHz and the maximum power of 1000W, when the vacuum degree reaches about 20Pa, a reaction monomer dimethyl disiloxane with Ar as a carrier gas is introduced, and transparent SiO with the thickness of about a few angstroms is formed on the surface of the powder body x (x = 0.3-2) film, improving the dispersibility of the powder in the active monomer.
Secondly, the surface modified nano TiO is treated 2 Uniformly dispersing in the N-acryloyl morpholine active monomer. Without moisteningUnder the condition of the dispersing agent, adding the powder into the active monomer, dispersing at a high speed, and then sanding by using a sanding machine, wherein the sanding machine uses zirconia beads with the diameter of 0.05mm, and sanding is continuously carried out until the powder is observed to be in a nano dispersion state under an electron microscope. The mass ratio of the nano particles to the active monomer is 25: 75.
Prepolymer: 24 difunctional bisphenol A epoxy acrylate and 23 nonafunctional polyester acrylate;
reactive monomer: trifunctional trimethylolpropane triacrylate (TMPTA) 13; dispersed with nano TiO 2 The monomer N-acryloyl morpholine (acmo) 18, difunctional 1, 6-hexanediol diacrylate (HDDA) 8;
active amine: acrylated reactive amine 8; leveling agent: polyester-modified polydimethylsiloxane grafted with acrylic functional groups 0.1;
photoinitiator (2): 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) 1.5, camphorquinone 1.5, N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide 1.5, 4-ethylenepropylenethioanthrone 1.5.
Accurately weighing the components according to a designed formula, adding the components into a stainless steel reaction kettle at room temperature, stirring for 12 hours at a rotating speed of 900r/min to completely dissolve a solid initiator without visible solid particles, adjusting the viscosity by using a small amount of HDDA (high-density digital data acquisition) and adjusting the surface tension by using a leveling agent, filtering to obtain the product, inspecting the viscosity and the surface tension to be qualified, and packaging by using a metal barrel.
The gloss oil was checked for viscosity in a Zealan # 4 cup for 88 seconds and a surface tension of 25Dynes/cm.
The prepared gloss oil is evenly coated on 80 g/m 2 On the transfer paper of (2), the dry coating weight is about 4-6 g/m 2 Using a central wavelength of 385nm and an illumination of 12W/cm 2 The LED lamp of (1) is cured. The paper feeding speed is 160m/min. After curing, tests were performed with the following results:
and (3) testing the water contact angle of the cured film: 138 deg.. The coefficient of dynamic friction was 0.075 and the coefficient of static friction was 0.138. The light fastness of the cured films was tested according to ISO 12040-1997 "printing technology-prints and stamp-inks-evaluated using a filtered xenon arc lamp" and was rated 6.
Other properties meet the fourth part of the YQ15.4-2012 permitted materials list for cigarettes: the prepared glazing oil can be used for curing and glazing by using an LED light source after printing of cigarette package presswork.
By combining the above embodiments, the synergistic effect of the low-viscosity 9-functional-group polyester acrylate, the high-reactivity active monomer, the photoinitiator and the active amine is adopted, so that the reactivity of the prepared glazing oil is improved, and the purpose of rapid curing even if the LED illumination intensity is weak is achieved. The polishing oil has central wavelength of 365nm, 385nm, 395nm and 405nm, and illuminance of 0.5-15W/cm 2 And the curing is fast under the illumination of an LED with the irradiation distance of 5 mm. Adding 1-10% by mass of cerium dioxide, zinc oxide and titanium dioxide with the D50 diameter of 10-60nm into gloss oil; the cerium dioxide, the zinc oxide and the titanium dioxide are used for absorbing ultraviolet rays in sunlight or illumination light to achieve the aim of protecting the presswork against light; the inorganic nano-powder cerium dioxide, zinc oxide and titanium dioxide are utilized to construct a rough appearance on the surface of a printed matter, so that the effect of surface hydrophobicity is achieved. The viscosity of the varnish is detected by a Chuanyn 4# cup within 60-120 seconds, and the surface tension of the varnish is controlled to be between 20 and 30Dynes/cm by the leveling agent; through the synergistic effect of the components in the formula, the dynamic coefficient of friction of the cured film is controlled to be between 0.050 and 0.200, and the static coefficient of friction is controlled to be between 0.100 and 0.300. The application improves the light resistance and hydrophobic property of the cured varnish on the printed matter, and the photoinitiator residue and the volatile organic matter meet the requirements of cigarette packaging materials and are used for LED (light-emitting diode) glazing on the surface of the cigarette packaging printed matter, which is not listed. The above embodiments are merely illustrative and not restrictive of the technical solutions of the present patent application, and it should be understood by those skilled in the art that various changes and equivalents may be made therein without departing from the principle and scope of the technical solutions of the present patent application and are intended to be covered by the claims of the present patent application.

Claims (2)

1. Hydrophobic light-resistant UV-LED curing glazing oil for paper packaging printed matterThe quantity percentages are expressed as: nano TiO 2 2 Or ZnO or CeO 2 Powder: 1-10; prepolymer, also known as resin: 10-40 parts of bifunctional bisphenol A epoxy acrylate and 10-30 parts of nine-functional polyester acrylate; reactive monomer: 5-15 parts of trifunctional trimethylolpropane triacrylate; 10-50 parts of difunctional 1, 6-hexanediol diacrylate; 0-30 parts of N-acryloyl morpholine; active amine: 3-10 parts of acrylated reactive amine; leveling agent: polyester-modified, acrylic-functional grafted polydimethylsiloxane 0.1 to 0.5; photoinitiator (2): 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide 1-6, camphorquinone 0.5-5, N- [2- (dimethylamino) ethyl group]-1, 8-naphthalimide 0.5-4, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide 0-4, 4-isopropylthioxanthone or 2-isopropylthioxanthone 0-4;
the viscosity of the nine-functional polyester acrylate at 25 ℃ is 300cps;
the preparation method comprises the following steps:
firstly, synthesizing nano TiO in a closed glass container 2 Or ZnO or CeO 2 The powder moves under the action of mechanical stirring, a plasma discharge system is formed in a closed space by using a power supply with the frequency of 13.56MHz and the maximum power of 1000W, when the vacuum degree reaches about 20Pa, a reaction monomer hexamethyldisiloxane or tetramethyldisiloxane with Ar as a carrier gas is introduced, and transparent SiO with the thickness of less than 10 angstroms is formed on the surface of the powder through polymerization x A film, wherein x =0.3-2, improving the dispersibility of the powder in the reactive monomer;
secondly, the surface modified nano TiO is treated 2 Or ZnO or CeO 2 Uniformly dispersing in trifunctional trimethylolpropane triacrylate or bifunctional 1, 6-hexanediol diacrylate or N-acryloyl morpholine active monomer; dispersing at high speed without adding wetting dispersant, and sanding with a sand mill, wherein the sand mill uses zirconia beads with the diameter of 0.05mm, and sanding is continued until the powder is in a nano-dispersion state under the observation of an electron microscope;
and thirdly, accurately metering according to the formula, stirring for 12 hours in a stainless steel reaction kettle at room temperature, converting into a solution without visible solids, filtering, adjusting the viscosity by using an active monomer, detecting the viscosity by using a Chuanyn No. 4 cup within 60-120 seconds, and adjusting the surface tension of the gloss oil to be between 20 and 30Dynes/cm by using a leveling agent.
2. The hydrophobic light-resistant UV-LED curing varnish for the paper packaging printed matter as claimed in claim 1, wherein the nano TiO is used 2 Or ZnO or CeO 2 The D50 diameter of the powder is between 10nm and 60 nm.
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