CN108373786B - Anti-fog, gold-stamping and UV-LED (ultraviolet-light-emitting diode) curing varnish for cigarette paper packaging printed matter - Google Patents
Anti-fog, gold-stamping and UV-LED (ultraviolet-light-emitting diode) curing varnish for cigarette paper packaging printed matter Download PDFInfo
- Publication number
- CN108373786B CN108373786B CN201610988792.7A CN201610988792A CN108373786B CN 108373786 B CN108373786 B CN 108373786B CN 201610988792 A CN201610988792 A CN 201610988792A CN 108373786 B CN108373786 B CN 108373786B
- Authority
- CN
- China
- Prior art keywords
- curing
- parts
- led
- varnish
- fog
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
A kind of cigarette paper packs the printed matter and uses the waterproof fog, can gilt, UV-LED solidifies the gloss oil, the composition is (Wt%): 10-40 parts of bisphenol A epoxy acrylate, 10-30 parts of nine-functional polyester acrylate and 5-15 parts of aliphatic polyurethane acrylate; TMPTA 5-15; HDDA 10-50; 3-10 parts of active amine; 0.1-0.5 of leveling agent; 0.5-2 parts of mixed wax powder; photoinitiator (2): TPO 1-6, camphorquinone 0.5-5, N- [2- (dimethylamino) ethyl ester]-1, 8-naphthalimide 0.5-4, 8190-5, 4(2) -ITX 0-5. The viscosity was measured in a Zealan No. 4 cup for 60-120 seconds with a surface tension of 20-30 Dynes/cm. After coating, the central wavelength is 365-405 nm, and the illumination is 0.5-1.5W/cm2And the curing agent can be rapidly cured under the illumination of an LED at a distance of 5 mm. The surface water contact angle of the curing film is 80-120 degrees, the dynamic friction coefficient is 0.05-0.2, the static friction coefficient is 0.1-0.3, and the curing film has good water mist resistance and gilding performance.
Description
Technical Field
The application relates to a water mist-proof gold-stamping UV-LED curing varnish for cigarette paper packaging printed matters, belonging to the field of printing materials and technologies.
Background
After the paper package is printed, a layer of transparent gloss oil is coated on the surface of the printing ink layer in a full-page mode, and the transparent gloss oil is solidified to form a transparent coating after coating, so that the printing ink layer is protected, the water resistance and the wear resistance of a printed product are improved, and the glossiness of the surface of the printed product is improved or a special apparent effect is formed. After the varnish for packaging cigarette paper is cured, the varnish is required to have high transparency, no smell, strong gloss, rapid drying, good chemical corrosion resistance and good light resistance, a cured film has certain elasticity and flexibility, strong adhesion to ink, good leveling property, smooth film surface, wide post-press processing adaptability (capable of gold stamping) and excellent wear resistance. The requirement of abrasion resistance must be satisfied in order to be not easily scratched during the printing process, such as during handling and storage and on automatic cigarette packet packaging machines.
If the surface layer of the printed matter after being polished is easy to form water mist in the process of temperature and humidity change, the water mist is accumulated on the surface of the printed matter, and the packaged matter is affected with damp and deteriorated. Typically, temperature changes in the object can form a mist on the surface of the object. For example, a person wearing glasses can quickly walk from indoor high temperature to outdoor low temperature in winter, and water mist is accumulated on the glasses often; for another example, when an article is taken out of a refrigerator, water mist and water film are accumulated on the surface of the article. The current principle of preventing water mist includes: firstly, the method comprises the following steps: the surface of the material is hydrophilic, the surface energy of the material is reduced, a large number of hydrophilic groups are formed on the hydrophilic material, water molecules can be attracted, and fog drops can be quickly spread on the surface of the material to form a water film to reduce diffuse reflection of light, so that the aim of preventing fog is fulfilled. This method can accumulate water on the surface of the paper packaging printed matter, which can lead to the packaged matter becoming wet, which obviously does not conform to cigarette packaging materials. Secondly, the method comprises the following steps: compared with hydrophilic materials, the material surface is hydrophobic, and fog drops can roll easily on the material surface because the hydrophobic material cannot be soaked by water, so that the antifogging effect can be achieved theoretically. Thirdly, the method comprises the following steps: the surface temperature of the material is higher than the dew point temperature of water, and the aim of preventing fog is achieved because water vapor cannot be condensed on the surface. Obviously, only the second method is adopted to prevent the formation of water mist on the surface of the varnish cured film, that is, the larger the water contact angle of the surface of the cured film formed after the varnish is cured, the better.
White cardboard or transfer paper is used as a base material for cigarette packaging, and after offset printing or gravure printing, online glazing is performed, and local bronzing pictures and texts are often needed after the glazing oil is cured. The gold stamping process is to adhere a layer of aluminum layer on the surface of the gloss oil curing film by an adhesive under the action of heat and pressure. If the surface of the glazing oil is too hydrophobic, the adhesive is difficult to firmly adhere the aluminum layer on the glazing oil curing film, and the quality defects of incomplete hot stamping, complete hot stamping, insufficient hot stamping fastness and the like are caused. Therefore, the requirement of the gloss oil for preventing water mist is that the surface of the cured film has higher hydrophobicity and better hydrophobicity, and the requirement of gold stamping is that the surface of the cured film has higher hydrophilicity and better hydrophilicity, which is a pair of contradictory requirements. In order to achieve both of the good mist-proof property and the good bronzing effect of the varnish, the surface energy and the surface roughness of the surface layer formed after the varnish is cured are required to be controlled within a certain range. The surface tension, the surface dynamic friction coefficient and the static friction coefficient of the gloss oil are controlled within a certain range by adopting a proper auxiliary agent and the gloss oil raw material with the hydrophobic group, so that the surface of the UV-LED gloss oil after being cured has proper surface roughness, surface energy and surface friction coefficient, and the water mist prevention and gilding performance of the paper-based printed matter after being polished are considered.
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, 365-420nm light sources emitted by LEDs are adopted in the UV-LED curing technology developed in a UV curing mode to replace the traditional light sources commonly adopted by UV photocuring, such as mercury lamps, metal halogen lamps or excimer lamps, so that the gloss oil is irradiated, and the gloss oil is subjected to photopolymerization reaction under the action of light, so that the gloss oil is converted from a liquid state to a solid state, namely, the curing is carried out.
The conventional UV curing most commonly adopts low, medium and high pressure mercury lamps, and the light-emitting wavelength is in a wider 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. Although the wavelength conversion phosphor for LED and the packaging method are referred to as UV-LED curing, the central wavelengths are different from each other, such as 365nm, 385nm, 395nm, 405nm, and 420 nm. In addition, the LED luminous radiation is weaker than the traditional mercury lamp in illuminance and overall energy density on the surface of the varnish. Therefore, gloss oil is required to have higher photopolymerization activity. On the other hand, prepolymers for photopolymerization, also called resins, reactive monomers, photoinitiators and other raw materials are still the raw materials for traditional UV curing, and at present, no raw materials for matching with UV-LEDs are available. 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 range of the luminous center wavelength of a light source for curing so as to initiate photopolymerization. Most of the photoinitiators in the market at present have absorption wavelength less than 365nm, and because UV-LED curing is a new technology, the photoinitiator with strong absorption in the wavelength range of 365-. Due to the two reasons, the UV-LED curing speed of the gloss oil is far less than the printing speed, and the curing degree of the gloss oil is low.
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 matched photoinitiator are adopted, and the photopolymerization activity of the gloss oil is obviously improved through the synergistic effect of all the components, so that 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. And the formula is adjusted, so that the fog resistance and the gilding performance of the cured film are both considered.
Disclosure of Invention
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 gloss oil has different gloss modes and gloss amounts and has all viscosity requirementsDifferent. For the surface glazing of paper by anilox roller, the coating dry weight is usually controlled to be 4-6 g/m2. The viscosity is required to be 60-120 seconds with a zeien No. 4 cup. 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 in the application, namely the difunctional epoxy acrylate prepolymer, has high chemical reactivity and endows a cured film with high chemical stability, hardness and scratch resistance.
In order to further improve the hydrophobic property of the cured film, hydrophobic aliphatic urethane acrylate prepolymer is added.
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: and selecting from 33 formal licenses and 8 temporary licenses.
Photoinitiators absorb light energy under the illumination of the LED to initiate photopolymerization, and must absorb light within the narrow wavelength range (20-30nm) 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 applicants, 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 and 2-ethylenepropylene thioxanthone have weak absorption in the range of 360 and 420nm, and thus, 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), camphorquinone, N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide and ylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide (819), 4-ethylenepropylene thioxanthone and 2-ethylenepropylene thioxanthone are selected as photoinitiators for the developed top oils Through the compounding and cooperation of the photoinitiators, the deep curing and surface curing rate and curing degree of the gloss oil are considered.
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) and difunctional 1, 6-hexanediol diacrylate (HDDA) 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 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, the dynamic friction coefficient and the static friction coefficient of the solidified film are different, and the water mist forming speed and the gold stamping performance are different.
In addition, the components of the paint are added with a polytetrafluoroethylene/polyethylene micronized mixed wax powder, the dosage range is 0.5-2 Wt%, and the polytetrafluoroethylene/polyethylene micronized mixed wax powder has good solubility in gloss oil, no delamination and no skinning, smooth hand feeling and good wear resistance. The coating is used for further regulating and controlling the dynamic friction coefficient and the static friction coefficient of the surface after the varnish is cured, and the wear resistance and the blocking resistance of the surface of a cured film (when two surfaces are tightly attached, particularly under the condition of heating and extrusion, two pieces of wrapping paper are easy to be adhered together). If the addition amount is too large, the defects of incomplete gilding, poor adhesion of a gilding film and the like can be caused.
Through repeated experimental tests, the preferable formula of the waterproof fog, gildable and UV-LED curing varnish for the cigarette paper packaging printed matter is represented by the following mass percent (Wt%):
prepolymer, also known as resin: 10-40 parts of bifunctional bisphenol A epoxy acrylate, 10-30 parts of nine-functional polyester acrylate and 5-15 parts of hydrophobic aliphatic polyurethane acrylate;
reactive monomers, also known as reactive diluents: trifunctional trimethylolpropane triacrylate (TMPTA) 5-15; 10-50 parts of bifunctional 1, 6-hexanediol diacrylate (HDDA);
active amine: 3-10 parts of acrylated reactive amine;
leveling agent: polyester-modified, acrylic functional group grafted polydimethylsiloxane 0.1 to 0.5;
wax powder: 0.5-2 parts of polytetrafluoroethylene/polyethylene micronized mixed wax powder;
photoinitiator (2): 1-6 parts of 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 0.5-5 parts of camphorquinone, 0.5-4 parts of N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide; 0-5 parts of bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 0-5 parts of ethylene-propylene-thioxanthone.
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-. 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/m2The curing light source on the transfer paper is an LED light source, the central wavelength is 365nm, 385nm, 395nm and 405nm respectively, and the illumination is 0.5-15W/cm2The paper can be cured quickly under the illumination of an LED at a distance of 5mm, the paper feeding speed is 120-180 m/min, and the gloss oil is 810cm through infrared spectrum tests before and after the gloss oil is cured-1The absorption band disappears after the LED is cured by illumination, and 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 testing the surface tension of the prepared varnish. The test was carried out using a K100 surface tensiometer.
And testing the friction resistance of the cured film: the prepared gloss oil is evenly coated on 80 g/m2The coating weight of the transfer paper is about 4 to 6 g/m2After the curing by the LED light source, the phenomena of scratch, ink drop and the like do not occur according to 7705-2008 detection of the planographic decoration printed matter.
And (3) testing the water contact angle of the cured film: the prepared gloss oil is evenly coated on 80 g/m2The coating weight of the transfer paper is about 4 to 6 g/m2After being cured by LED light sourceThe water contact angle was measured using a DSA100 model video contact angle meter.
Testing the dynamic and static friction coefficients: the prepared gloss oil is evenly coated on 80 g/m2The coating weight of the transfer paper is about 4 to 6 g/m2After the sample is solidified by an LED light source, the sample is cut into a size of 65 × 90mm, and the plastic film is cut into a size of 150 × 400mm and used as a substrate to be attached to a slide block to rub with the substrate, and the detection is carried out according to GB/T10006-1988 measuring method for friction coefficients of the plastic film and the sheet.
And (3) waterproof fog test: the prepared gloss oil is evenly coated on 80 g/m2The coating weight of the transfer paper is about 4 to 6 g/m2After 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. aligning the outlet of the air blowing cylinder to the sample, blowing hot air to heat the sample for about 1 minute;
E. and observing the surface of the sample after cooling to avoid water mist.
And (3) testing the flexibility of the cured film: the prepared gloss oil is evenly coated on 80 g/m2The coating weight of the transfer paper is about 4 to 6 g/m2After 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.
Testing the gilding performance: the prepared gloss oil is evenly coated on 80 g/m2The coating weight of the transfer paper is about 4 to 6 g/m2After the LED light source is used for curing, local hot gold stamping is carried out by an automatic gold stamping machine, and the hot stamping quality is detected. The gold stamping film has the advantages of good quality, flat and solid appearance, good finish and no scratch phenomenon; the thermoprinted characters, patterns and lines are clear and clean, and the thermoprinted characters, patterns and lines are free from white marks, color change, dirty spots and missing spots. The hot stamped alumite layer is tightly combined with the glazing oil curing film, and the firmness is good.
Hot stamping, surface water mist prevention and automatic packaging machine have requirements on surface flatness, smoothness and surface energy after the gloss oil is solidified. 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 fastness, wear resistance and the like of the cured film meet the requirements of cigarette packaging materials, the surface water contact angle is 80 to 120 degrees after the surface of the cured film is coated and an LED light source is cured. The dynamic friction coefficient of the surface of the cured film is controlled to be 0.050-0.200, and the static friction coefficient is controlled to be 0.100-0.300. The solidified film on the surface of the printed matter has good water mist resistance and hot stamping quality.
The beneficial effect of this application is: 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 hydrophobic aliphatic polyurethane acrylate with the hydrophobic function and the HDDA are added, so that the anti-water-fog performance of the cured film is improved; 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, particularly the dosage of the mixed wax powder, the water contact angle on the surface of the cured film is adjusted and controlled to be between 80 and 120 degrees, the dynamic friction coefficient is between 0.050 and 0.200, the static friction coefficient is between 0.100 and 0.300, and the cured film on the surface of the printed matter has good water mist resistance and thermoprinting performance. The application gives consideration to the performances of water mist prevention and bronzing after the varnish for the printed matter is cured, the photoinitiator residue and the volatile organic matter meet the requirements of cigarette packaging materials, and the varnish can be used for surface glazing of the cigarette packaging printed matter.
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%):
prepolymer: bifunctional bisphenol A epoxy acrylate 15, nine-functional polyester acrylate 25, and hydrophobic aliphatic urethane acrylate 8;
reactive monomer: trifunctional trimethylolpropane triacrylate (TMPTA) 5; bifunctional 1, 6-hexanediol diacrylate (HDDA) 31;
active amine: acrylated reactive amine 8;
leveling agent: polyester-modified polydimethylsiloxane grafted with acrylic functional groups 0.1;
wax powder: 1, polytetrafluoroethylene/polyethylene micronized mixed wax powder;
photoinitiator (2): 4% of 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 0.5% of camphorquinone, 1% of N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide and 1.5% of 4-ethylene-propylene-thioanthrone.
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 and wax powder 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 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 78 seconds and a surface tension of 28 Dynes/cm.
The prepared gloss oil is evenly coated on 80 g/m2On the transfer paper of (2), the dry coating weight is about 4-6 g/m2Using a central wavelength of 385nm and an illumination of 0.5W/cm2The LED lamp of (1) is cured. The paper feeding speed is 150 m/min. After curing, the test was performed with the following results:
and (3) testing the water contact angle of the cured film: 110 deg.
Testing the dynamic and static friction coefficients: the coefficient of dynamic friction was 0.154 and the coefficient of static friction was 0.210.
The curing film has good fog-proof performance and gold stamping performance.
Other properties meet the fourth part of the list of licensed materials for YQ15.4-2012 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%):
prepolymer: difunctional bisphenol A epoxy acrylate 20, nine-functional polyester acrylate 20, hydrophobic aliphatic urethane acrylate 7;
reactive monomer: trifunctional trimethylolpropane triacrylate (TMPTA) 10; bifunctional 1, 6-hexanediol diacrylate (HDDA) 31;
active amine: acrylated reactive amine 6;
leveling agent: polyester-modified polydimethylsiloxane grafted with acrylic functional groups 0.2;
wax powder: 0.5 of polytetrafluoroethylene/polyethylene micronized mixed wax powder;
photoinitiator (2): 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO)2, camphorquinone 2, N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide 1.0, bis (2, 4, 6-trimethylbenzoyl) phosphine oxide 0.5.
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 and wax powder 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 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 at 85 seconds and a surface tension of 26 Dynes/cm.
The prepared gloss oil is evenly coated on 80 g/m2Is coated on the transfer paper with the coating amount of about 4 to 6 g/m2Using a central wavelength of 395nm and an illuminance of 15W/cm2The LED lamp of (1) is cured. The paper feeding speed is 160 m/min. After curing, the test was performed with the following results:
and (3) testing the water contact angle of the cured film: 98 deg.
Testing the dynamic and static friction coefficients: the coefficient of dynamic friction was 0.081, and the coefficient of static friction was 0.158.
The curing film has good fog-proof performance and gold stamping performance.
Other properties meet the fourth part of the list of licensed materials for YQ15.4-2012 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 3
The formula of the UV-LED curing gloss oil is expressed by the following mass percent (Wt%):
prepolymer: 10 parts of bifunctional bisphenol A epoxy acrylate, 24 parts of nine-functional polyester acrylate and 10 parts of hydrophobic aliphatic polyurethane acrylate;
reactive monomer: trifunctional trimethylolpropane triacrylate (TMPTA) 8; difunctional 1, 6-hexanediol diacrylate (HDDA) 37;
active amine: acrylated reactive amine 4;
leveling agent: polyester-modified polydimethylsiloxane grafted with acrylic functional groups 0.2;
wax powder: 0.5 of polytetrafluoroethylene/polyethylene micronized mixed wax powder;
photoinitiator (2): 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO)3, camphorquinone 1, N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide 2.5.
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 the rotating speed of 1000r/min to completely dissolve the solid initiator and the wax powder 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 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 68 seconds and a surface tension of 25 Dynes/cm.
The prepared gloss oil is evenly coated on 80 g/m2On the transfer paper of (2), the dry coating weight is about 4-6 g/m2Using a central wavelength of 405nm and an illuminance of 1.2W/cm2The LED lamp of (1) is cured. The paper feeding speed is 150 m/min. After curing, the test was carried out, and the test results are as follows：
And (3) testing the water contact angle of the cured film: 85 degrees.
Testing the dynamic and static friction coefficients: the coefficient of dynamic friction was 0.077 and the coefficient of static friction was 0.112.
The curing film has good fog-proof performance and gold stamping performance.
Other properties meet the fourth part of the list of licensed materials for YQ15.4-2012 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%):
prepolymer: 18 parts of bifunctional bisphenol A epoxy acrylate, 20 parts of nine-functional polyester acrylate and 8 parts of hydrophobic aliphatic polyurethane acrylate;
reactive monomer: trifunctional trimethylolpropane triacrylate (TMPTA) 5; difunctional 1, 6-hexanediol diacrylate (HDDA) 35;
active amine: acrylated reactive amine 6;
leveling agent: polyester-modified polydimethylsiloxane grafted with acrylic functional groups 0.3;
wax powder: 1.2 of polytetrafluoroethylene/polyethylene micronized mixed wax powder;
photoinitiator (2): 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO)4.5, camphorquinone 0.5, N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide 1, 2-ethylenepropylenethionamide 0.5.
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 the rotating speed of 1000r/min to completely dissolve the solid initiator and the wax powder 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 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 77 seconds and a surface tension of 20 Dynes/cm.
The prepared gloss oil is evenly coated on 80 g/m2On the transfer paper of (2), the dry coating weight is about 4-6 g/m2The central wavelength is 365nm, and the illumination is 0.8W/cm2The LED lamp of (1) is cured. The paper feeding speed is 160 m/min. After curing, the test was performed with the following results:
and (3) testing the water contact angle of the cured film: 85 degrees.
Testing the dynamic and static friction coefficients: the coefficient of dynamic friction was 0.058 and the coefficient of static friction was 0.183.
The curing film has good fog-proof performance and gold stamping performance.
Other properties meet the fourth part of the list of licensed materials for YQ15.4-2012 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%):
prepolymer: bifunctional bisphenol A epoxy acrylate 16, nine-functional polyester acrylate 22, hydrophobic aliphatic urethane acrylate 6;
reactive monomer: trifunctional trimethylolpropane triacrylate (TMPTA) 9; 29.5 difunctional 1, 6-hexanediol diacrylate (HDDA);
active amine: acrylated reactive amine 9;
leveling agent: polyester-modified polydimethylsiloxane grafted with acrylic functional groups 0.2;
wax powder: 1.0 of polytetrafluoroethylene/polyethylene micronized mixed wax powder;
photoinitiator (2): 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO)4, camphorquinone 0.8, N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide 0.5, bis (2, 4, 6-trimethylbenzoyl) phosphine oxide 1, 4(2) -ethylenepropylenethioaminole 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 the rotating speed of 1000r/min to completely dissolve the solid initiator and the wax powder 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 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 Chuanyn # 4 cup for 99 seconds and a surface tension of 28 Dynes/cm.
The prepared gloss oil is evenly coated on 80 g/m2On the transfer paper of (2), the dry coating weight is about 4-6 g/m2The central wavelength is 395nm, and the illumination is 6.5W/cm2The LED lamp of (1) is cured. The paper feeding speed is 160 m/min. After curing, the test was performed with the following results:
and (3) testing the water contact angle of the cured film: 105 deg..
Testing the dynamic and static friction coefficients: the coefficient of dynamic friction was 0.068 and the coefficient of static friction was 0.158.
The curing film has good fog-proof performance and gold stamping performance.
Other properties meet the fourth part of the list of licensed materials for YQ15.4-2012 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 is weak is achieved. Respectively has central wavelength of 365nm, 385nm, 395nm and 405nm and illuminance of 0.5-15W/cm2Under the illumination of LED, the curing is fast. The hydrophobic aliphatic polyurethane acrylate with the hydrophobic function and the HDDA are added, so that the anti-water-fog performance of the cured film is improved; 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, especially the dosage of wax powder, the water contact angle of the surface of the cured film is adjusted to be between 80 and 120 degrees, the dynamic friction coefficient is between 0.050 and 0.200, the static friction coefficient is between 0.100 and 0.300, and the surface of the printed matter is fixedThe film coating has good water mist resistance and hot stamping quality. The application considers the performances of water mist prevention and gold stamping after the varnish on the printed matter is solidified, the photoinitiator residue and the volatile organic matter meet the requirements of cigarette packaging materials, and the photoinitiator residue and the volatile organic matter are used for LED glazing on the surface of the cigarette packaging printed matter and are 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 (9)
1. The oil for preventing water mist, gilding and curing and polishing UV-LED for the cigarette paper packaging printed matter is characterized by comprising the following components in percentage by mass (Wt%): prepolymer: 10-40 parts of bifunctional bisphenol A epoxy acrylate, 10-30 parts of nine-functional polyester acrylate and 5-15 parts of hydrophobic aliphatic polyurethane acrylate; reactive monomer: trifunctional trimethylolpropane triacrylate (TMPTA) 5-15; 10-50 parts of bifunctional 1, 6-hexanediol diacrylate (HDDA); active amine: 3-10 parts of acrylated reactive amine; leveling agent: polyester-modified, acrylic functional group grafted polydimethylsiloxane 0.1 to 0.5; wax powder: 0.5-2 parts of polytetrafluoroethylene/polyethylene micronized mixed wax powder; photoinitiator (2): 1-6 parts of 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 0.5-5 parts of camphorquinone, 0.5-4 parts of N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide, 0-5 parts of bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 0-5 parts of 4(2) -ethylene-propylene-thioxanthone; accurately metering according to the formula, stirring in a stainless steel reaction kettle for 12 hours at room temperature to obtain 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 oil according to claim 1, which is prepared from a reasonable formula, namely, a high-reactivity resin, a high-reactivity monomer and lightThe photopolymerization activity of the prepared gloss oil is obviously improved under the synergistic effect of the initiator, the active amine and the flatting agent with the reaction group; the central wavelength is 365, 385, 395 and 405nm, and the illumination is 0.5-15W/cm2And the curing agent can be rapidly cured under the illumination of an LED at a distance of 5 mm.
3. The anti-fog, gold-stamping and UV-LED curing varnish for the cigarette paper packaging printed matter as claimed in claim 1, is characterized in that the varnish prepared according to reasonable formula composition is uniformly coated on 80 g/m2The coating weight of the transfer paper is 4 to 6 g/m2After the curing is carried out by using an LED light source, the surface water contact angle of the curing film is between 80 and 120 degrees, the dynamic friction coefficient is between 0.050 and 0.200, the static friction coefficient is between 0.100 and 0.300, and the curing film on the surface of the paper has good water mist resistance and thermoprinting performance.
4. The anti-fog, gold-stamping and UV-LED curing varnish for the cigarette paper packaging printed matter as claimed in claim 1, is characterized in that hydrophobic aliphatic urethane acrylate and 1, 6-hexanediol diacrylate (HDDA) with nonpolar hydrophobic long chain are adopted to improve the hydrophobic property of the curing film, so as to achieve the aim of preventing fog of the curing film.
5. The oil according to claim 1, wherein the oil has the following properties in the fourth part of YQ15.4-2012 permitted materials list for cigarette paper: frame paper, cigarette packaging paper (strips and boxes) and sealing paper meet the requirements of cigarette packaging on polishing oil.
6. The oil for preventing water mist, gilding and UV-LED curing and polishing used for the cigarette paper packaging printed matter as claimed in claim 1 is characterized in that the used resin, also called prepolymer, is bifunctional bisphenol A epoxy acrylate, nine-functional polyester acrylate and hydrophobic aliphatic polyurethane acrylate, has high photopolymerization activity and endows a cured film with proper hydrophobic property.
7. The oil according to claim 1, wherein the photoinitiator is 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), camphorquinone, N- [2- (dimethylamino) ethyl ester ] -1, 8-naphthalimide, bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, and 4(2) -ethyl-propyl thioxanthone, and can meet the requirement of cigarette packaging materials on photoinitiator residues and have relatively strong absorption in the LED luminescence wavelength ranges of 365nm, 385nm, 395nm and 405 nm.
8. The anti-fog, bronzing and UV-LED curing varnish for the cigarette paper packaging printing matter as claimed in claim 1, characterized in that the surface tension of the varnish is adjusted to be between 20 and 30Dynes/cm by using polyester-modified polydimethylsiloxane grafted with acrylic functional groups; the polytetrafluoroethylene/polyethylene micronized mixed wax powder is cooperatively used for regulating and controlling the dynamic friction coefficient, the static friction coefficient and the surface smoothness of the surface of the cured film, and the wear resistance of the surface film is improved.
9. The anti-fog, gold-stamping and UV-LED curing varnish for the cigarette paper packaging printed matter as claimed in claim 1, is characterized in that the viscosity of the varnish is suitable for the varnishing of a 120-wire-mesh wire-lined roller, the varnish is coated on the cigarette packaging paper in a line with common offset printing, gravure printing and flexography, and a cured film formed on the surface of the paper printed matter after curing has good anti-fog and gold-stamping properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610988792.7A CN108373786B (en) | 2016-11-10 | 2016-11-10 | Anti-fog, gold-stamping and UV-LED (ultraviolet-light-emitting diode) curing varnish for cigarette paper packaging printed matter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610988792.7A CN108373786B (en) | 2016-11-10 | 2016-11-10 | Anti-fog, gold-stamping and UV-LED (ultraviolet-light-emitting diode) curing varnish for cigarette paper packaging printed matter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108373786A CN108373786A (en) | 2018-08-07 |
| CN108373786B true CN108373786B (en) | 2020-06-23 |
Family
ID=63015945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610988792.7A Active CN108373786B (en) | 2016-11-10 | 2016-11-10 | Anti-fog, gold-stamping and UV-LED (ultraviolet-light-emitting diode) curing varnish for cigarette paper packaging printed matter |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108373786B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110789244A (en) * | 2019-09-20 | 2020-02-14 | 湖北中烟工业有限责任公司 | Special 3D grating printed matter of waterproof fog |
| CN110539567A (en) * | 2019-09-20 | 2019-12-06 | 湖北中烟工业有限责任公司 | 3D grating printed matter for cigarette meeting YQ15 standard and preparation method thereof |
| CN111004567A (en) * | 2019-12-31 | 2020-04-14 | 义乌市齐彩印刷包装有限公司 | UV (ultraviolet) glazing oil and preparation method thereof |
| CN111205716B (en) * | 2020-02-28 | 2021-09-21 | 深圳市冠为科技股份有限公司 | UV gloss oil capable of gold stamping and preparation method and application thereof |
| CN111347737A (en) * | 2020-03-06 | 2020-06-30 | 乐美包装（昆山）有限公司 | Laminated material and manufacturing method thereof, packaging container and manufacturing method thereof |
| CN111334170A (en) * | 2020-05-06 | 2020-06-26 | 浙江银鹿新材料有限公司 | Formula of UVLED gloss oil |
| CN112239557A (en) * | 2020-10-16 | 2021-01-19 | 吉安市佳泓新材料有限公司 | UV (ultraviolet) curing type plastic-free scratch-resistant film and preparation method thereof |
| CN116004043A (en) * | 2022-12-28 | 2023-04-25 | 浙江美浓材料科技有限公司 | Pure transparent high-smoothness UV offset-printing hot-stamping gloss oil and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284968B (en) * | 2008-05-30 | 2010-06-16 | 深圳市通产丽星股份有限公司 | Weatherproof bronzing UV gloss oil |
| CN102031717B (en) * | 2009-09-29 | 2014-04-16 | 贵州若顿科技开发有限公司 | Water mist prevention UV (ultraviolet) gloss oil for gold card paper |
| CN103013295A (en) * | 2012-12-05 | 2013-04-03 | 北京化工大学常州先进材料研究院 | UV (ultraviolet) paper varnish and preparation method thereof |
| CN104179065B (en) * | 2014-07-31 | 2016-04-13 | 东莞宏石功能材料科技有限公司 | A kind of impermeable UV silk-screen paper gloss oil and preparation method thereof |
-
2016
- 2016-11-10 CN CN201610988792.7A patent/CN108373786B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108373786A (en) | 2018-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108373786B (en) | Anti-fog, gold-stamping and UV-LED (ultraviolet-light-emitting diode) curing varnish for cigarette paper packaging printed matter | |
| CN104334359B (en) | Radiation curable inkjet ink and industrial inkjet printing process | |
| CN100362062C (en) | Mineral-filled coatings having enhanced abrasion resistance and wear clarity and methods for using the same | |
| CN100526400C (en) | Ultraviolet cured printing ink composition and its uses | |
| CN101555365A (en) | Curable overcoat compositions | |
| JP2019094506A (en) | Ec primer coating for paper and paperboard | |
| CN108373782B (en) | Hydrophobic, scratch-resistant and wear-resistant UV-LED curing gloss oil for paper packaging printed matter | |
| TW201437294A (en) | Low migration energy curable inks | |
| JP5815913B1 (en) | Active energy ray-curable offset ink composition | |
| CN109263324A (en) | A kind of processing technology of reverse glazing | |
| JP2018083864A (en) | Active energy ray-curable off-set ink composition | |
| CN108373787B (en) | Hydrophobic light-resistant UV-LED curing glazing oil for paper packaging printed matter | |
| JP2020169251A (en) | Active energy ray-curable ink, method of producing ink-cured product, and printed matter | |
| CN108373842B (en) | High-transparency super-flexible UV-LED curing varnish for paper packaging printed matter | |
| JP4608620B2 (en) | Active energy ray curable composition for ink receiving layer formation | |
| JP2019001090A (en) | Method for manufacturing laminate | |
| JP7236262B2 (en) | Printed matter manufacturing method | |
| US20070126833A1 (en) | Digital printing using ultraviolet inks | |
| CN108467611A (en) | A kind of water-mist-proof gloss oil | |
| US9630395B2 (en) | Printing machine | |
| JP6926675B2 (en) | Active energy ray-curable paint composition for decorative board and decorative board using this | |
| KR102533020B1 (en) | Manufacturing method of packing film printed by flexographic printing using aqueous environment-friendly ink having water as solvent and the packing film manufactured by the same | |
| CN107418296B (en) | Ultraviolet-curing seamless holographic laser transfer gloss oil and preparation method thereof | |
| JP2012035437A (en) | Method for manufacturing ultraviolet-curable type printed matter and ultraviolet-curable type printed matter using the method | |
| TW202336175A (en) | Active energy ray curable water-based inkjet inks and printheads |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Huang Jiangwei Inventor after: Wu Changmao Inventor after: Mao Kelin Inventor after: Xiao Yong Inventor after: Cheng Zhuliang Inventor after: Meng Ruiqiang Inventor after: He Di Inventor after: Li Xiaoli Inventor after: Xu Wencai Inventor after: Luo Shiyong Inventor before: Huang Jiangwei Inventor before: Mao Kelin Inventor before: Xiao Yong Inventor before: Cheng Zhuliang Inventor before: Meng Ruiqiang Inventor before: He Di Inventor before: Li Xiaoli Inventor before: Xu Wencai Inventor before: Luo Shiyong |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |