CN108373787A - A kind of hydrophobic fast light UV-LED cured gloss oils of paper wrapper printed matter - Google Patents
A kind of hydrophobic fast light UV-LED cured gloss oils of paper wrapper printed matter Download PDFInfo
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- CN108373787A CN108373787A CN201610988793.1A CN201610988793A CN108373787A CN 108373787 A CN108373787 A CN 108373787A CN 201610988793 A CN201610988793 A CN 201610988793A CN 108373787 A CN108373787 A CN 108373787A
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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
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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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
- 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
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- 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
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- 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
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- 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 hydrophobic fast light UV LED cured gloss oils of paper wrapper printed matter, be added in gloss oil mass percent be 1 10%, improve by the plasma polymerization dispersion performance, ceria of 10 60nm of powder D50 diameters or zinc oxide or titanium dioxide.It is 3eV or so using nano-powder energy gap, can absorb the ultraviolet light in daylight or illumination light to improve the light resistance of printed matter.Using the synergistic effect of inorganic nanometer powder and levelling agent, inorganic nanometer powder forms random island in printed matter surface and is distributed rough surface, achievees the effect that surface hydrophobicity.By selecting the synergistic effect of the polyester acrylate of low viscosity, 9 functional groups, the monomer for selecting high reaction activity, photoinitiator and reactive amines, the reactivity of the oil polish of preparation is improved, quick-setting purpose the luminous illumination of LED is weak is reached.Properties meet cigarette paper wrapper to the various performance requirements of oil polish after oil polish solidification.
Description
Technical field
This application involves a kind of hydrophobic fast light UV-LED cured gloss oils of paper wrapper printed matter, belong to printing material and skill
Art field.
Background technology
Paper wrapper often needs to be coated with layer of transparent gloss oil in printing ink layer surface full version after printing, solid after coating
Change forms transparent coating, and protection printing layer of ink improves printed matter water resistance, wearability；And improve the table of package printed matter
The glossiness in face forms special apparent effect.Paper wrapper requires that oil polish transparency is high, tasteless, gloss after being cured with oil polish
Sense is strong, drying is rapid, chemical resistance is good, light resistance is good, cured film will have certain elasticity and flexibility, attached to ink
Put forth effort to be eager to excel, good leveling property, film surface is smooth, extensive post-press finishing adaptability and excellent wearability.
Paper wrapper uses paper as printing element, by offset printing or gravure on line glazing, if glazing oil meter face is excessively hydrophilic,
It is then easy to form water mist or moisture film on solidifying film layer surface, reduces the mechanical strength of paper packing material, further, water can penetrate
Paper packing material causes products to be packaged to become damp and rotten into products to be packaged.Therefore, if after oil polish solidification, hydrophobicity
It is good, then it is not easily formed water mist or moisture film.On the other hand, paper wrapper printing mostly uses greatly water-based ink at present, there is most
Using organic dyestuff or organic pigment, it can fade under solar ultraviolet effect serious, lead to the color of paper wrapper printing figure message
It is color to generate prodigious aberration because seriously fading over time.Since the colour fading of product external packaging color is thin out, consumer holds
The commodity that the resting period is grown easily are regarded as obsolete merchandise, or even regard counterfeit goods as.Based on this, this application discloses a kind of paper
Package printed matter has the hydrophobic and good oil polish of light resistance.
Oil polish is one of important foundation material of package printed matter, and by the difference of curing mode, oil polish can be divided into
Oiliness oil polish (solvent type oil polish), water lustering oil and UV (ultraviolet) oil polish three classes.Water lustering oil exist it is dry slow,
The shortcomings of being easy set-off.UV oil polishes because rapid curing, it is solvent-free volatilization, curing membrane performance is good due to be widely used.Closely
Nian Lai, in the UV-LED curing technologies that UV curing modes grow up using the light source of the LED 365-420nm sent out, substitution passes
The UV photocurings of system irradiate oil polish, gloss oil generally using light sources such as mercury lamp, metal halid lamp or Excimer lamps
Photopolymerization reaction is carried out under the action of light, is changed into solid-state from liquid, that is, solidification.
Basic, normal, high pressure mercury lamp is commonly used in traditional UV solidifications, and emission wavelength is all in 200-380nm wider ranges.And
The light approximate monochromatic light that UV-LED lamps are sent out, is usually described with centre wavelength, emission wavelength is in centre wavelength or so 20-30nm
Range, the relationship between luminous intensity and wavelength are in Gaussian Profile.Not according to LED wavelength convert fluorescent powders and packaged type
Together, it is referred to as UV-LED solidifications, but it is respectively the differences such as 365nm or 385nm or 395nm or 405nm or 420nm to have centre wavelength.
In addition, illumination and total energy density ratio tradition mercury lamp of the LED luminescence irradiations on gloss oil surface are weak.Therefore, it is required that gloss oil has
There is higher photopolymerization reaction activity.On the other hand, the prepolymer of photopolymerization, also referred to as resin, activated monomer and light-initiated
The raw material such as agent are still the cured raw material of traditional UV, without the raw material to match with UV-LED curing technologies.Photoinitiator is in light
Very crucial effect is played in solidification process, most basic requirement is emission wavelength range of the photoinitiator in solidification light source
Inside there is absorption that could generate active group, causes photopolymerization reaction.Most of photoinitiator absorbing wavelengths are all small currently on the market
In 365nm, since UV-LED solidifications are new technologies, there is a serious shortage of have the light absorbed by force to draw in 365-420 wave-length coverages at present
Agent is sent out, the photoinitiator of only a small number of tradition UV solidifications has weak absorbing in 365-420nm, and the efficiency of initiation of photoinitiator is not
It is high.Due to above-mentioned two, cause oil polish slow in UV-LED solidification rates, curing degree is low, the UV-LED solidifications of gloss oil
Rate is much smaller than printing rate.
To solve this problem, the application uses anti-with low viscosity, super multi-functional polyester acrylic prepolymer, height
Activated monomer, reactive amines and the suitable photoinitiator of matching is answered to be significantly improved by the synergistic effect of each component
The photopolymerization reaction activity of gloss oil, improves the solidification rate and curing degree of photopolymerization reaction, to make the UV-LED of oil polish
Solidification rate and tradition offset printing, flexo, the printing rate-matched of gravure.
Invention content
Used nano-TiO2, nano-ZnO and nano Ce O2The D50 diameters of powder are between 10nm between 60nm.
The first step, by the nano-TiO of synthesis2Or nano-ZnO or nano Ce O2Layer of transparent is formed with plasma polymerization
SiOx(x=0.3-2) thin layer, thickness of thin layer are less than 10 angstroms.
In a closed glass container, nano-powder moves under the action of mechanical agitation, is with frequency
13.56MHz, maximum power 1000W power supply plasma discharge system is formed in confined space, when vacuum degree reaches 20Pa
When left and right, it is passed through the reaction monomers hexamethyldisiloxane or dimethyl siloxane or tetramethyl siloxanes that Ar is carrier gas, in powder
Body surface aggregate forms the transparent SiO that thickness is less than 10 angstromsx(x=0.3-2) film improves dispersibility of the powder in activated monomer
Energy.
Second step, the nano-TiO that will be modified by surface2Or nano-ZnO or nano Ce O2It is dispersed in tripropylene glycol two
Acrylate (TPGDA) or hexanediyl ester (HDDA) or trifunctional trimethylolpropane trimethacrylate (TMPTA)
Or in N- acryloyl morpholines (acmo) activated monomer.It is not added under conditions of wetting dispersing agent, powder is added in activated monomer, warp
High speed dispersion is crossed, is then sanded with sand mill, the zirconium oxide bead of a diameter of 0.05mm of sand mill is lasting to be sanded until in Electronic Speculum
Lower observation powder is at nano-dispersed state.Because wetting dispersing agent currently on the market cannot participate in photopolymerization reaction mostly, it is
The solidification rate and curing degree for making the gloss oil of preparation are not influenced by the wetting dispersing agent that cannot occur photopolymerization reaction, this
Application using plasma is aggregated in powder surface and forms the transparent SiO that thickness is less than 10 angstromsx(x=0.3-2) film improves powder
Dispersion performance in activated monomer.On the other hand, it using unique sand milling technique, ensure that before being not added with wetting dispersing agent
It puts, can also accomplish that single nanoparticle disperses.
Third walks, rational formula, prepares UV-LED gloss oil.
Usual oil polish resin, also referred to as prepolymer, reactive functional group number are 2, more than namely 4,5
A or 6 functional groups.Number of functional groups is more, and photopolymerization reaction activity is bigger, but prepolymer viscosity is bigger simultaneously.The print of preparation
For brush product oil polish according to glazing mode and upper light quantity difference, viscosity requirement is different.For paper surface anilox roll glazing,
Coating dry measure is normally controlled in 4-12 grams/m2.It is required that viscosity is 60-120 seconds with No. 4 cup tests of Cai's grace.In this way, the more officials of prepolymer
Viscosity can be rolled into a ball to be disadvantageous in that greatly, it is necessary to the activated monomer of mating low viscosity, also referred to as reactive diluent.Activated monomer
Viscosity is still directly proportional to functional group's number of photopolymerization reaction can occur.That is, the photopolymerization that improve oil polish is anti-
The rate answered leads to common polyfunctional group prepolymer by selection, since it must be equipped with the activated monomer of low functional group, reaction
Rate is difficult to increase significantly.The application uses the polyester acrylic prepolymer with 9 functional groups, the ratio of viscosities of feature
Common prepolymer is much smaller, and 25 DEG C of viscosity is 300cps, suitable with the viscosity of reactive diluent, and it is big to overcome aforementioned viscosity
Defect, the photopolymerization reaction rate of prepared gloss oil can be increased substantially.
Another prepolymer that the application uses, bifunctional based epoxy acrylate prepolymer, low cost have very high
Chemical reactivity assigns cured film very high chemical stability, hardness and Scratch Resistance energy.
Photoinitiator is one of key component in oil polish.After the completion of oil polish solidification, wherein remaining ultraviolet light draws
It sends out agent under certain conditions, chemical transport can also equally occur or by physical contact, pollutes the food in packaging, from
And potential hazard is caused to the health of human body.According to《Low migration UV photoinitiators license uses list》.《Smoking material license makes
Use substance list》(YQ 15.4-2012),《Frame paper, cigarette wrapping paper (item and box) and seal paper》：Formal license 33+face
When license 8 initiators in select.
Photoinitiator absorbs light energy under the illumination that LED is sent out, and causes photopolymerization reaction, must be sent out in LED
There is absorption in narrow optical wavelength range (20-30nm).
The application has the photoinitiator of absorption using absorbing wavelength in the narrow centre wavelengths of LED, coordinates suitable activity
Amine improves the UV-LED solidification rates of oil polish.According to applicant test common photoinitiator absorption spectrum, only 2,
4,6- trimethylbenzoy-dipheny phosphine oxides (TPO), camphorquinone, N- [2- (dimethylamino) ethyl ester] -1,8- naphthalenes, two formyl
Bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides (819) of imines, phenyl, 4- second propyl thioxanthone, 2- second propyl thioxanthenes
Ketone has weak absorbing within the scope of 360-420nm, and therefore, the application selects 2,4,6- trimethylbenzoy-dipheny phosphine oxides
(TPO), camphorquinone, N- [2- (dimethylamino) ethyl ester] -1,8-naphthalimide, bis- (2,4, the 6- trimethylbenzoyls of phenyl
Base) phosphine oxide (819), 4- second propyl thioxanthones or 2- second propyl thioxanthones as photoinitiator, drawn by these types of light
The compounding collaboration for sending out agent, takes into account the deep cure and surface cure rate of oil polish.
Using acroleic acid esterification reactive amines as reactive amine aided initiating, with activated monomer, urethane acrylate
Deng dissolving each other completely, it is a kind of crosslinkable amine aided initiating of low viscosity, is mixed with suitable photoinitiator to carry as synergist
High laser curing velocity is especially to speed up the speed of surface cure.Acroleic acid esterification reactive amines will not move to surface to avoid
Surface floating, the active amine polymer with double bond group have good compatibility, high oil/water balance, low volatilization, resist
Migration, resistance to the oxygen inhibiting polymerization function, smell are low.
Activated monomer, also referred to as reactive diluent have the functional group for participating in photopolymerization reaction.It is molten to solid photoinitiator
Xie Du is big.By the solidification rate contrast experiment to commonly using reactive diluent, the application selects trifunctional trimethylolpropane
Triacrylate (TMPTA), difunctional 1,6- hexanediyl esters (HDDA) and simple function group N- acryloyl morpholines
(acmo) it is applied in combination as activated monomer.There are three functional groups for TMPTA tools, have solidification rate quickly, in addition also assign
Give the good water resistant of cured film, chemical resistance corrosion, anti-friction and high flexibility.HDDA is typical low viscosity, quickly consolidates
Change the activated monomer often selected, can be used for adjusting the viscosity of oil polish in wide range, meanwhile, HDDA also assigns cured film
Higher hydrophobic performance.N- acryloyl morpholines (acmo) nitrogen containing monomer has stronger adhesive force to paper substrates, ultra-low-smell,
Shrinking percentage is low, solidification rate is fast.
Levelling agent can reduce the surface tension of oil polish strongly, select polyester modification, be grafted with acrylic-functional
Dimethyl silicone polymer, acrylic-functional can photoinitiator effect under cross linking reaction and solidification occur.And usually UV is solid
The reactionless active group of levelling agent that the oil polish of change uses, is not involved in photopolymerization reaction.Exactly using reaction can be crosslinked
Levelling agent, adjust the surface tension of oil polish in certain range, that is, control the levelling rate of gloss oil coating rear surface, regulation and control
Cure the geometrical morphology of film surface, i.e. roughness.Surface roughness is different, the coefficient of kinetic friction and confficient of static friction of cured film
It differs, meets requirement of the automatic packaging machine to the coefficient of kinetic friction and confficient of static friction.
By experiment test repeatedly, a kind of cigarette paper package printed matter that present patent application proposes is with fast light, hydrophobic, UV-
The optimization formula of LED cured gloss oils is expressed as (Wt%) with mass percent：
Nano-powder (TiO2Or ZnO or CeO2)：1-10；
Prepolymer, also referred to as resin：Bifunctional base bisphenol A epoxy acrylate 10-40, nine functional group's polyester acrylates
10-30；
Activated monomer, also referred to as reactive diluent：Trifunctional trimethylolpropane trimethacrylate (TMPTA) 5-15；Double officials
1,6- hexanediyl esters (HDDA) 10-50 can be rolled into a ball；N- acryloyl morpholines (acmo) 0-30.
Reactive amines：Acroleic acid esterification reactive amines 3-10；
Levelling agent：Polyester modification, the dimethyl silicone polymer 0.1-0.5 that is grafted with acrylic-functional；
Photoinitiator：2,4,6- trimethylbenzoy-dipheny phosphine oxide (TPO) 1-6, camphorquinone 0.5-5, N- [2-
(dimethylamino) ethyl ester] -1,8-naphthalimide 0.5-4, bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides (819) of phenyl
0-4,4 (2)-second propyl thioxanthone 0-4.
By each component according to component design precise, stainless steel cauldron is added at room temperature, stirs 12 hours, rotating speed
800-1000r/min makes solid initiator be completely dissolved, no visible solid particle, and viscosity and levelling are adjusted with a small amount of HDDA
Agent adjusts surface tension, and viscosity and surface tension are examined in filtering.The 4# glasss of detections of Cai's grace of glazing oil viscosity, the time is in 60-120
In second, levelling agent controls the surface tension of gloss oil between 20 to 30Dynes/cm.It is packed with metal drum.As herein described production
Product.All operations preferably carry out under yellow illuminant light.
Prepared gloss oil is uniformly coated on 80 grams/m2Transfer paper on, solidification is LED light source with light source, middle cardiac wave
Long is respectively 365nm, 385nm, 395nm and 405nm, and illumination is each about 0.5-15W/cm2, chart drive speed be 120-180 meters/
Min cures front and back examination of infrared spectrum by gloss oil, and gloss oil is in 810cm-1Absorption band disappear after LED illumination cures card
Bright C=C conversions are complete, completion of cure.Solidification film surface is pressed with finger, noresidue fingerprint is also demonstrated from another angle
Completion of cure.
4th step, after gloss oil coating solidification, inorganic nanometer powder ceria, zinc oxide and titanium dioxide in gloss oil,
Dimethyl silicone polymer using polyester modification, being grafted with acrylic-functional is cooperateed with, coarse shape is constructed in printed matter surface
Looks, gloss oil cured film form the random rough surfaces structure as shown in Figure of description.Surface hydrophobicity is obtained using rough surface
Performance, control water contact angle achieve the effect that surface hydrophobicity within the scope of 120-145 °.By be using nano-powder size
10-60nm has substantially no effect on the visible transparent of the cured film formed after gloss oil solidification.
Prepared oil polish uses K100 type surface tension instrument test surfaces tension.
Cured film crocking resistance is tested：Prepared gloss oil is uniformly coated on 80 grams/m2Transfer paper on, coating weight
About 4-6 grams/m2, after being cured with LED light source, press《The decoration printed matter detection of 7705-2008 lithographic plates》It is existing without scratching, falling the effect of ink etc.
As.
Cured film water contact angle is tested：Prepared gloss oil is uniformly coated on 80 grams/m2Transfer paper on, coating weight is about
For 4-6 grams/m2, after being cured with LED light source, water contact angle is tested using DSA100 type video contact angle instrument.
According to ISO 12040-1997, " printing technology-printed matter and stamp-pad ink-use optical filtering xenon arc lamp to the light resistance of cured film
Evaluation " test.
Static and dynamic friction coefficient is tested：Prepared gloss oil is uniformly coated on 80 grams/m2Transfer paper on, coating weight is about
4-6 grams/m2, after being cured with LED light source, sample is cut into 65 × 90mm of specification, by plastic film cut into specification 150 ×
400mm, as ground, for being attached on sliding block and ground friction.Reference《GB/T10006-1988 plastic films and thin slice friction
Coefficient determination method》Detection.
Water-mist-proof is tested：Prepared gloss oil is uniformly coated on 80 grams/m2Transfer paper on, coating weight is about 4-6 grams/
m2, after being cured with LED light source, test by the following method.
A, the cigarette peduncle paper major part for coating oil polish is cut into fritter with scissors；
B, the sample being cut into is attached to drum surface, printing faces outwardly；
C, with plastic film tightly it is attached on the surface of the samples, cling fixation with adhesive tape；
D, Blowing drum alignment sample blowout hot wind is exported to heat sample 1 minute or so；
E, whether observation sample surfaces have water mist phenomenon after cooling.
Cured film flexible test：Prepared gloss oil is uniformly coated on 80 grams/m2Transfer paper on, coating weight is about 4-
6 grams/m2, after being cured with LED light source, printed matter folds 5 times or more, the disadvantages such as no quick-fried color, explosion.
Surface waterproofing mist and automatic packaging machine have gloss oil solidification rear surface flatness, smoothness and surface energy
It is required that.Surface energy is described with surface water contact angle, and the water contact angle before the uncoated gloss oil of cigarette package transfer paper is 55-
60°.By testing repeatedly, meet cigarette packaging material requirement in other performances such as guarantee cured film flexibility, light resistance, wearabilities
Under the premise of, if the surface tension of control oil polish between 20-30Dynes/cm, by coating, after LED light source solidification, table
Face water contact angle is 120-145 °.Dynamic rub of control solidification film surface examines coefficient as 0.050-0.200, confficient of static friction 0.100-
0.300.The cured film of printed matter surface has good light resistance and hydrophobicity.
The advantageous effect of the application is：The nano ceric oxide or oxidation that mass percent is 1-10% are added in gloss oil
Zinc or titanium dioxide.The energy gap of these three powders is 3eV or so, utilizes ceria or zinc oxide or Titanium dioxide absorption
Ultraviolet light in daylight or illumination light achievees the purpose that protect printed matter fast light.Utilize inorganic nanometer powder ceria or oxygen
Change zinc or titanium dioxide, cooperates with levelling agent, form random rough pattern in printed matter surface, achieve the effect that surface hydrophobicity.
By selecting the polyester acrylate of low viscosity, 9 functional groups, the monomer for selecting high reaction activity, photoinitiator and reactive amines
Synergistic effect, improves the reactivity of the oil polish of preparation, reaches quick-setting mesh the luminous illumination of LED is weak
's.4# glasss of Cai's grace detection of glazing oil viscosity, the time in 60-120 second, the surface tension of levelling agent control gloss oil between 20 to
30Dynes/cm；By the synergistic effect of each component in formula, dynamic rub of control examines coefficient between 0.050-0.200, quiet to rub
Coefficient is wiped between 0.100-0.300, it is anti-zoned to friction coefficient and surface to cigarette packing carton to meet cigarette automatic packaging machine
Hinder performance.Photoinitiator residual meets cigarette package with volatile organic matter after the application has taken into account the solidification of printed matter oil polish
Material requirements can be used for the surface glazing of cigarette package printed matter, improve printed matter hydrophobicity and printing color it is resistance to
Photosensitiveness.
Description of the drawings
Attached drawing is the electron scanning micrograph of gloss oil solidification rear surface, and the bead in figure is nano-scale titanium dioxide
Cerium, zinc oxide or titanium dioxide powder form coarse structure in printed matter surface, improve the hydrophobic performance of printed matter surface.
Specific implementation mode
Present patent application is described further with specific embodiment below.
Embodiment 1
The formula of UV-LED cured gloss oils is expressed as (Wt%) with mass percent：
The first step, by the nano-TiO of the D50 diameters 30nm of synthesis2The SiOx of layer of transparent is formed with plasma polymerization
(x=0.3-2) thin layer.
In a closed glass container, powder moves under the action of mechanical agitation, is 13.56MHz, most with frequency
The power supply of high-power 1000W forms plasma discharge system in confined space, when vacuum degree reaches 20Pa or so, is passed through
Ar is the reaction monomers hexamethyldisiloxane of carrier gas, and the transparent SiO of about several angstroms of thickness is formed in powder surfacex(x=0.3-2)
Film improves dispersion performance of the powder in activated monomer.
Second step, the nano-TiO that will be modified by surface2It is living to be dispersed in tripropylene glycol diacrylate (TPGDA)
In property monomer.It is not added under conditions of wetting dispersing agent, powder is added in activated monomer, by high speed dispersion, then with sand milling
Machine is sanded, the zirconium oxide bead of a diameter of 0.05mm of sand mill, lasting to be sanded until observing powder under Electronic Speculum into nano-dispersed
State.The mass ratio of nano particle and activated monomer is 25: 75.
Prepolymer：Bifunctional base bisphenol A epoxy acrylate 20, nine functional group's polyester acrylates 28；
Activated monomer：Trifunctional trimethylolpropane trimethacrylate (TMPTA) 5；Difunctional 1,6- hexylene glycol dipropyls
Olefin(e) acid ester (HDDA) 5, is dispersed with nano-TiO2Tripropylene glycol diacrylate (TPGDA) monomer 21, N- acryloyl morpholines
(acmo)6；
Reactive amines：Acroleic acid esterification reactive amines 8；
Levelling agent：Polyester modification, the dimethyl silicone polymer 0.1 that is grafted with acrylic-functional；
Photoinitiator：2,4,6- trimethylbenzoy-dipheny phosphine oxides (TPO) 3, camphorquinone 0.5, N- [2- (diformazans
Amido) ethyl ester] -1,8-naphthalimide 2.5,4- second propyl thioxanthone 1.
By each component according to component design precise, stainless steel cauldron is added at room temperature, stirs 12 hours, rotating speed
800r/min makes solid initiator be completely dissolved, no visible solid particle, adjusts viscosity with a small amount of HDDA and levelling agent is adjusted
Surface tension, filtering are examined viscosity and surface tension qualified, are packed with metal drum.
Oil polish 4# glasss of Cai's grace detection viscosity, the time at 78 seconds, surface tension 28Dynes/cm.
Prepared gloss oil is uniformly coated on 80 grams/m2Transfer paper on, coating dry measure be about 4-6 grams/m2, use center
Wavelength is 395nm, illumination 0.5W/cm2LED light solidification.Chart drive speed is 150m/min.It after solidification, is tested, is tested
As a result as follows：
Cured film water contact angle is tested：130°.The coefficient of kinetic friction is 0.154, confficient of static friction 0.210.Cured film
Light resistance is tested according to ISO 12040-1997 " printing technology-printed matter and stamp-pad ink-are evaluated using optical filtering xenon arc lamp ", light resistance
It is 6 grades.
Other performance meets《YQ15.4-2012 cigarettes license substance list Part IV：Frame paper, cigarette wrapping paper (item
With box) and seal paper》It is required that after prepared oil polish can be used for the printing of cigarette package printed matter, cured with LED light source on
Light.
Embodiment 2
The formula of UV-LED cured gloss oils is expressed as (Wt%) with mass percent：
The nano-ZnO of the D50 diameters 40nm of synthesis is formed the SiO of layer of transparent by the first step with plasma polymerizationxIt is thin
Layer.
In a closed glass container, powder moves under the action of mechanical agitation, is 13.56MHz, most with frequency
The power supply of high-power 1000W forms plasma discharge system in confined space, when vacuum degree reaches 20Pa or so, is passed through
Ar is the reaction monomers dimethyldisiloxane of carrier gas, and the transparent SiO of about several angstroms of thickness is formed in powder surfacex(x 0.3-
2.0) film, improve dispersion performance of the powder in activated monomer.
The nano-ZnO being modified by surface is dispersed in trifunctional trimethylolpropane trimethacrylate by second step
(TMPTA) in activated monomer.It is not added under conditions of wetting dispersing agent, powder is added in activated monomer, by high speed dispersion, so
Be sanded afterwards with sand mill, the zirconium oxide bead of a diameter of 0.05mm of sand mill, it is lasting be sanded until observed under Electronic Speculum powder at
Nano-dispersed state.The mass ratio of nano particle and activated monomer is 30: 70.
Prepolymer：Bifunctional base bisphenol A epoxy acrylate 22, nine functional group's polyester acrylates 25；
Activated monomer：It is dispersed with the trifunctional trimethylolpropane trimethacrylate (TMPTA) 23 of nano zine oxide；Double officials
1,6- hexanediyl esters (HDDA) 18 can be rolled into a ball；
Reactive amines：Acroleic acid esterification reactive amines 6；
Levelling agent：Polyester modification, the dimethyl silicone polymer 0.2 that is grafted with acrylic-functional；
Photoinitiator：2,4,6- trimethylbenzoy-dipheny phosphine oxides (TPO) 2, camphorquinone 1, N- [2- (dimethylamine
Base) ethyl ester] -1,8-naphthalimide 1.5,2- second propyl thioxanthone 1.
By each component according to component design precise, stainless steel cauldron is added at room temperature, stirs 12 hours, rotating speed
900r/min makes solid initiator be completely dissolved, no visible solid particle, adjusts viscosity with a small amount of HDDA and levelling agent is adjusted
Surface tension, filtering are examined viscosity and surface tension qualified, are packed with metal drum.
Oil polish 4# glasss of Cai's grace detection viscosity, the time at 85 seconds, surface tension 27Dynes/cm.
Prepared gloss oil is uniformly coated on 80 grams/m2Transfer paper on, coating dry measure be about 4-6 grams/m2, use center
Wavelength is 385nm, illumination 15W/cm2LED light solidification.Chart drive speed is 160m/min.It after solidification, is tested, is tested
As a result as follows：
Cured film water contact angle is tested：135°.The coefficient of kinetic friction is 0.081, confficient of static friction 0.158.Cured film
Light resistance is tested according to ISO 12040-1997 " printing technology-printed matter and stamp-pad ink-are evaluated using optical filtering xenon arc lamp ", light resistance
It is 7 grades.
Other performance meets《YQ15.4-2012 cigarettes license substance list Part IV：Frame paper, cigarette wrapping paper (item
With box) and seal paper》It is required that after prepared oil polish can be used for the printing of cigarette package printed matter, cured with LED light source on
Light.
Embodiment 3
The nano-cerium oxide of the D50 diameters 10nm of synthesis plasma polymerization is formed layer of transparent by the first step
SiOxThin layer.
In a closed glass container, powder moves under the action of mechanical agitation, is 13.56MHz, most with frequency
The power supply of high-power 1000W forms plasma discharge system in confined space, when vacuum degree reaches 20Pa or so, is passed through
Ar is the reaction monomers tetramethyl disiloxane of carrier gas, and the transparent SiO of about several angstroms of thickness is formed in powder surfacex(x 0.3-
2.0) film improves dispersion performance of the powder in activated monomer.
The nano-cerium oxide being modified by surface is dispersed in N- acryloyl morpholines (acmo) activated monomer by second step
In.It is not added under conditions of wetting dispersing agent, powder is added in activated monomer, by high speed dispersion, is then sanded with sand mill,
The zirconium oxide bead of a diameter of 0.05mm of sand mill, it is lasting to be sanded until observing powder under Electronic Speculum into nano-dispersed state.It receives
The mass ratio of rice grain and activated monomer is 20: 80.
The formula of UV-LED cured gloss oils is expressed as (Wt%) with mass percent：
Prepolymer：Bifunctional base bisphenol A epoxy acrylate 10, nine functional group's polyester acrylates 24；
Activated monomer：Trifunctional trimethylolpropane trimethacrylate (TMPTA) 8；It is dispersed with the N- third of nano-cerium oxide
Dimethomorph (acmo) activated monomer 37；
Reactive amines：Acroleic acid esterification reactive amines 4；
Levelling agent：Polyester modification, the dimethyl silicone polymer 0.2 that is grafted with acrylic-functional；
Photoinitiator：2,4,6- trimethylbenzoy-dipheny phosphine oxides (TPO) 3, camphorquinone 1, N- [2- (dimethylamine
Base) ethyl ester] -1,8-naphthalimide 1, bis- (2,4,6- trimethylbenzoyl) phosphine oxides 1.5.
By each component according to component design precise, stainless steel cauldron is added at room temperature, stirs 12 hours, rotating speed
1000r/min makes solid initiator be completely dissolved, no visible solid particle, and viscosity and levelling agent tune are adjusted with a small amount of HDDA
Surface tension, filtering are saved, as herein described product is examined viscosity and surface tension qualified, packed with metal drum.
Oil polish 4# glasss of Cai's grace detection viscosity, the time at 68 seconds, surface tension 25Dynes/cm.
Prepared gloss oil is uniformly coated on 80 grams/m2Transfer paper on, coating dry measure be about 4-6 grams/m2, use center
Wavelength is 405nm, illumination 0.95W/cm2LED light solidification.Chart drive speed is 150m/min.It after solidification, is tested, is surveyed
Test result is as follows：
Cured film water contact angle is tested：137°.The coefficient of kinetic friction is 0.077, confficient of static friction 0.112.Cured film
Light resistance is tested according to ISO 12040-1997 " printing technology-printed matter and stamp-pad ink-are evaluated using optical filtering xenon arc lamp ", light resistance
It is 6 grades.
Other performance meets《YQ15.4-2012 cigarettes license substance list Part IV：Frame paper, cigarette wrapping paper (item
With box) and seal paper》It is required that after prepared oil polish can be used for the printing of cigarette package printed matter, cured with LED light source on
Light.
Embodiment 4
The formula of UV-LED cured gloss oils is expressed as (Wt%) with mass percent：
The nano-cerium oxide of the D50 diameters 50nm of synthesis plasma polymerization is formed layer of transparent by the first step
SiOxThin layer.
In a closed glass container, powder moves under the action of mechanical agitation, is 13.56MHz, most with frequency
The power supply of high-power 1000W forms plasma discharge system in confined space, when vacuum degree reaches 20Pa or so, is passed through
Ar is the reaction monomers tetramethyl disiloxane of carrier gas, and the transparent SiO of about several angstroms of thickness is formed in powder surfacex(x=0.3-
2.0) film improves dispersion performance of the powder in activated monomer.
The nano-cerium oxide being modified by surface is dispersed in N- acryloyl morpholines (acmo) activated monomer by second step
In.It is not added under conditions of wetting dispersing agent, powder is added in activated monomer, by high speed dispersion, is then sanded with sand mill,
The zirconium oxide bead of a diameter of 0.05mm of sand mill, it is lasting to be sanded until observing powder under Electronic Speculum into nano-dispersed state.It receives
The mass ratio of rice grain and activated monomer is 35: 65.
Prepolymer：Bifunctional base bisphenol A epoxy acrylate 22, nine functional group's polyester acrylates 24；
Activated monomer：Trifunctional trimethylolpropane trimethacrylate (TMPTA) 5；Difunctional 1,6- hexylene glycol dipropyls
Olefin(e) acid ester (HDDA) 15；It is dispersed with N- acryloyl morpholines (acmo) activated monomer 20 of nano-cerium oxide；
Reactive amines：Acroleic acid esterification reactive amines 6；
Levelling agent：Polyester modification, the dimethyl silicone polymer 0.3 that is grafted with acrylic-functional；
Photoinitiator：2,4,6- trimethylbenzoy-dipheny phosphine oxides (TPO) 4, camphorquinone 0.5, N- [2- (diformazans
Amido) ethyl ester] -1,8-naphthalimide 1, bis- (2,4,6- trimethylbenzoyl) phosphine oxides 1.
By each component according to component design precise, stainless steel cauldron is added at room temperature, stirs 12 hours, rotating speed
1000r/min makes solid initiator be completely dissolved, no visible solid particle, and viscosity and levelling agent tune are adjusted with a small amount of HDDA
Surface tension is saved, filtering is examined viscosity and surface tension qualified, packed with metal drum.
Oil polish 4# glasss of Cai's grace detection viscosity, the time at 77 seconds, surface tension 20Dynes/cm.
Prepared gloss oil is uniformly coated on 80 grams/m2Transfer paper on, coating dry measure be about 4-6 grams/m2, use center
Wavelength is 365nm, illumination 1.7W/cm2LED light solidification.Chart drive speed is 160m/min.It after solidification, is tested, is tested
As a result as follows：
Cured film water contact angle is tested：140°.The coefficient of kinetic friction is 0.058, confficient of static friction 0.183.Cured film
Light resistance is tested according to ISO 12040-1997 " printing technology-printed matter and stamp-pad ink-are evaluated using optical filtering xenon arc lamp ", light resistance
It is 6 grades.
Other performance meets《YQ15.4-2012 cigarettes license substance list Part IV：Frame paper, cigarette wrapping paper (item
With box) and seal paper》It is required that after prepared oil polish can be used for the printing of cigarette package printed matter, cured with LED light source on
Light.
Embodiment 5
The formula of UV-LED cured gloss oils is expressed as (Wt%) with mass percent：
The first step, by the nano-TiO of the D50 diameters 60nm of synthesis2The SiO of layer of transparent is formed with plasma polymerizationxIt is thin
Layer.
In a closed glass container, powder moves under the action of mechanical agitation, is 13.56MHz, most with frequency
The power supply of high-power 1000W forms plasma discharge system in confined space, when vacuum degree reaches 20Pa or so, is passed through
Ar is the reaction monomers hexamethyldisiloxane of carrier gas, and the transparent SiO of about several angstroms of thickness is formed in powder surfacex(x 0.3-2)
Film improves dispersion performance of the powder in activated monomer.
Second step, the nano-TiO that will be modified by surface2It is dispersed in trifunctional trimethylolpropane trimethacrylate
(TMPTA) in activated monomer.It is not added under conditions of wetting dispersing agent, powder is added in activated monomer, by high speed dispersion, so
Be sanded afterwards with sand mill, the zirconium oxide bead of a diameter of 0.05mm of sand mill, it is lasting be sanded until observed under Electronic Speculum powder at
Nano-dispersed state.The mass ratio of nano particle and activated monomer is 25: 75.
Prepolymer：Bifunctional base bisphenol A epoxy acrylate 19, nine functional group's polyester acrylates 25；
Activated monomer：It is dispersed with nano-TiO2Trifunctional trimethylolpropane trimethacrylate (TMPTA) 29；Difunctionality
Group's 1,6- hexanediyl esters (HDDA) 9.5；
Reactive amines：Acroleic acid esterification reactive amines 9；
Levelling agent：Polyester modification, the dimethyl silicone polymer 0.2 that is grafted with acrylic-functional；
Photoinitiator：2,4,6- trimethylbenzoy-dipheny phosphine oxides (TPO) 5, camphorquinone 0.8, N- [2- (diformazans
Amido) ethyl ester] -1,8-naphthalimide 0.5, bis- (2,4,6- trimethylbenzoyl) phosphine oxides 1.
By each component according to component design precise, stainless steel cauldron is added at room temperature, stirs 12 hours, rotating speed
1000r/min makes solid initiator be completely dissolved, no visible solid particle, and viscosity and levelling agent tune are adjusted with a small amount of HDDA
Surface tension is saved, filtering is examined viscosity and surface tension qualified, packed with metal drum.
Oil polish 4# glasss of Cai's grace detection viscosity, the time at 99 seconds, surface tension 28Dynes/cm.
Prepared gloss oil is uniformly coated on 80 grams/m2Transfer paper on, coating dry measure be about 4-6 grams/m2, use center
Wavelength is 405nm, illumination 1.25W/cm2LED light solidification.Chart drive speed is 160m/min.It after solidification, is tested, is surveyed
Test result is as follows：
Cured film water contact angle is tested：120°.The coefficient of kinetic friction is 0.068, confficient of static friction 0.158.Cured film
Light resistance is tested according to ISO 12040-1997 " printing technology-printed matter and stamp-pad ink-are evaluated using optical filtering xenon arc lamp ", light resistance
It is 6 grades.
Other performance meets《YQ15.4-2012 cigarettes license substance list Part IV：Frame paper, cigarette wrapping paper (item
With box) and seal paper》It is required that after prepared oil polish can be used for the printing of cigarette package printed matter, cured with LED light source on
Light.
Embodiment 6
The formula of UV-LED cured gloss oils is expressed as (Wt%) with mass percent：
The nano-ZnO of the D50 diameters 20nm of synthesis is formed the SiO of layer of transparent by the first step with plasma polymerizationxIt is thin
Layer.
In a closed glass container, powder moves under the action of mechanical agitation, is 13.56MHz, most with frequency
The power supply of high-power 1000W forms plasma discharge system in confined space, when vacuum degree reaches 20Pa or so, is passed through
Ar is the reaction monomers tetramethyl disiloxane of carrier gas, and the transparent SiO of about several angstroms of thickness is formed in powder surfacex(x 0.3-
2.0) film improves dispersion performance of the powder in activated monomer.
The nano-ZnO being modified by surface is dispersed in difunctional 1,6- hexanediyl esters by second step
(HDDA) in activated monomer.It is not added under conditions of wetting dispersing agent, powder is added in activated monomer, by high speed dispersion, so
Be sanded afterwards with sand mill, the zirconium oxide bead of a diameter of 0.05mm of sand mill, it is lasting be sanded until observed under Electronic Speculum powder at
Nano-dispersed state.The mass ratio of nano particle and activated monomer is 30: 70.
Prepolymer：Bifunctional base bisphenol A epoxy acrylate 22, nine functional group's polyester acrylates 25；
Activated monomer：Trifunctional trimethylolpropane trimethacrylate (TMPTA) 10；It is dispersed with double officials of nano zine oxide
1,6- hexanediyl esters (HDDA) 21 can be rolled into a ball；N- acryloyl morpholines (acmo) 10；
Reactive amines：Acroleic acid esterification reactive amines 6；
Levelling agent：Polyester modification, the dimethyl silicone polymer 0.2 that is grafted with acrylic-functional；
Photoinitiator：2,4,6- trimethylbenzoy-dipheny phosphine oxides (TPO) 2, camphorquinone 1, N- [2- (dimethylamine
Base) ethyl ester] -1,8-naphthalimide 1.5,4- second propyl thioxanthone 1.
By each component according to component design precise, stainless steel cauldron is added at room temperature, stirs 12 hours, rotating speed
900r/min makes solid initiator be completely dissolved, no visible solid particle, adjusts viscosity with a small amount of HDDA and levelling agent is adjusted
Surface tension, filtering are examined viscosity and surface tension qualified, are packed with metal drum.
Oil polish 4# glasss of Cai's grace detection viscosity, the time at 85 seconds, surface tension 23Dynes/cm.
Prepared gloss oil is uniformly coated on 80 grams/m2Transfer paper on, coating dry measure be about 4-6 grams/m2, use center
Wavelength is 385nm, illumination 15W/cm2LED light solidification.Chart drive speed is 160m/min.It after solidification, is tested, is tested
As a result as follows：
Cured film water contact angle is tested：142°.
Static and dynamic friction coefficient is tested：The coefficient of kinetic friction is 0.075, confficient of static friction 0.138.
According to ISO 12040-1997, " printing technology-printed matter and stamp-pad ink-use optical filtering xenon arc lamp to the light resistance of cured film
Evaluation " test, light resistance are 6 grades.
Other performance meets《YQ15.4-2012 cigarettes license substance list Part IV：Frame paper, cigarette wrapping paper (item
With box) and seal paper》It is required that after prepared oil polish can be used for the printing of cigarette package printed matter, cured with LED light source on
Light.
Embodiment 7
The formula of UV-LED cured gloss oils is expressed as (Wt%) with mass percent：
The first step, by the nano-TiO of the D50 diameters 20nm of synthesis2The SiO of layer of transparent is formed with plasma polymerizationxIt is thin
Layer.
In a closed glass container, powder moves under the action of mechanical agitation, is 13.56MHz, most with frequency
The power supply of high-power 1000W forms plasma discharge system in confined space, when vacuum degree reaches 20Pa or so, is passed through
Ar is the reaction monomers dimethyldisiloxane of carrier gas, and the transparent SiO of about several angstroms of thickness is formed in powder surfacex(x=0.3-2)
Film improves dispersion performance of the powder in activated monomer.
Second step, the nano-TiO that will be modified by surface2It is dispersed in N- acryloyl morpholine activated monomers.It is not added with
Under conditions of wetting dispersing agent, powder is added in activated monomer, by high speed dispersion, is then sanded with sand mill, sand mill
It is lasting to be sanded until observing powder under Electronic Speculum into nano-dispersed state with the zirconium oxide bead of a diameter of 0.05mm.Nano particle
Mass ratio with activated monomer is 25: 75.
Prepolymer：Bifunctional base bisphenol A epoxy acrylate 24, nine functional group's polyester acrylates 23；
Activated monomer：Trifunctional trimethylolpropane trimethacrylate (TMPTA) 13；It is dispersed with nano-TiO2Monomer N-
Acryloyl morpholine (acmo) 18, difunctional 1,6- hexanediyl esters (HDDA) 8；
Reactive amines：Acroleic acid esterification reactive amines 8；Levelling agent：Polyester modification, the poly- diformazan that is grafted with acrylic-functional
Radical siloxane 0.1；
Photoinitiator：2,4,6- trimethylbenzoy-dipheny phosphine oxides (TPO) 1.5, camphorquinone 1.5, N- [2- (two
Methylamino) ethyl ester] -1,8-naphthalimide 1.5,4- second propyl thioxanthone 1.5.
By each component according to component design precise, stainless steel cauldron is added at room temperature, stirs 12 hours, rotating speed
900r/min makes solid initiator be completely dissolved, no visible solid particle, adjusts viscosity with a small amount of HDDA and levelling agent is adjusted
Surface tension, filtering, as herein described product are examined viscosity and surface tension qualified, are packed with metal drum.
Oil polish 4# glasss of Cai's grace detection viscosity, the time at 88 seconds, surface tension 25Dynes/cm.
Prepared gloss oil is uniformly coated on 80 grams/m2Transfer paper on, coating dry measure be about 4-6 grams/m2, use center
Wavelength is 385nm, illumination 12W/cm2LED light solidification.Chart drive speed is 160m/min.It after solidification, is tested, is tested
As a result as follows：
Cured film water contact angle is tested：138°.The coefficient of kinetic friction is 0.075, confficient of static friction 0.138.Cured film
Light resistance is tested according to ISO 12040-1997 " printing technology-printed matter and stamp-pad ink-are evaluated using optical filtering xenon arc lamp ", light resistance
It is 6 grades.
Other performance meets《YQ15.4-2012 cigarettes license substance list Part IV：Frame paper, cigarette wrapping paper (item
With box) and seal paper》It is required that after prepared oil polish can be used for the printing of cigarette package printed matter, cured with LED light source on
Light.
In summary embodiment, the application propose by using low viscosity, 9 functional groups polyester acrylate, choosing
With the synergistic effect of the activated monomer of high reaction activity, photoinitiator and reactive amines, the reactivity of the oil polish of preparation is improved,
Reach quick-setting purpose the luminous illumination of LED is weak.Oil polish can respectively centre wavelength be 365nm,
385nm, 395nm, 405nm, illumination are about 0.5-15W/cm2, irradiation distance is rapid curing under the LED illumination of 5mm.By
It is 1-10%, ceria, zinc oxide and the titanium dioxide of a diameter of 10-60nm of D50 that mass percent is added in gloss oil；It utilizes
Ultraviolet light in ceria, zinc oxide and Titanium dioxide absorption daylight or illumination light reaches the fast light mesh of protection printed matter
's；Rough morphology is constructed in printed matter surface using inorganic nanometer powder ceria, zinc oxide and titanium dioxide, reaches surface
Hydrophobic effect.The 4# glasss of detections of Cai's grace of glazing oil viscosity, the time, levelling agent controlled the surface tension of gloss oil in 60-120 seconds
Between 20 to 30Dynes/cm；By the synergistic effect of each component in formula, dynamic rub of control cured film examines coefficient between 0.050-
Between 0.200, confficient of static friction is between 0.100-0.300.The application improves light resistance after the solidification of printed matter oil polish
And hydrophobic performance, photoinitiator residual and volatile organic matter meet cigarette packaging material requirement, are printed for cigarette package
The Surface L ED glazings of product, it is numerous to list herein.Above example is merely to illustrate and the technical side of unrestricted present patent application
Case, it will be understood by those skilled in the art that the technical solution to present patent application carries out various variations and equivalence replacement, without carrying on the back
Principle from present patent application technical solution and range should all cover among present patent application the scope of the claims.
Claims (9)
1. a kind of hydrophobic fast light UV-LED cured gloss oils of paper wrapper printed matter, are expressed as (Wt%) with mass percent：It receives
Rice flour body (TiO2Or ZnO or CeO2)：1-10；Prepolymer, also referred to as resin：Bifunctional base bisphenol A epoxy acrylate 10-40, nine
Functional group polyester acrylate 10-30；Activated monomer：Trifunctional trimethylolpropane trimethacrylate (TMPTA) 5-15；Double officials
1,6- hexanediyl esters (HDDA) 10-50 can be rolled into a ball；N- acryloyl morpholines (acmo) 0-30；Reactive amines：Acroleic acid esterification
Reactive amines 3-10；Levelling agent：Polyester modification, the dimethyl silicone polymer 0.1-0.5 that is grafted with acrylic-functional；It is light-initiated
Agent：2,4,6- trimethylbenzoy-dipheny phosphine oxide (TPO) 1-6, camphorquinone 0.5-5, N- [2- (dimethylamino) second
Ester] -1,8-naphthalimide 0.5-4, phenyl bis- (2,4,6- trimethylbenzoyls) phosphine oxide (819) 0-4,4 (2)-second
Propyl thioxanthone 0-4；
Preparation method is：
The first step, in a closed glass container, the nano-TiO of synthesis2Or ZnO or CeO2Powder is in churned mechanically work
With lower movement, with frequency be 13.56MHz, the power supply of maximum power 1000W forms plasma discharge system in confined space
System is passed through the reaction monomers hexamethyldisiloxane or dimethyl siloxane that Ar is carrier gas when vacuum degree reaches 20Pa or so
Or tetramethyl siloxanes, it polymerize the transparent SiO to form thickness and be less than 10 angstroms in powder surfacex(x=0.3-2) film improves powder
Dispersion performance in activated monomer；
Second step, the nano-TiO that will be modified by surface2Or ZnO or CeO2It is dispersed in tripropylene glycol diacrylate
(TPGDA) or hexanediyl ester (HDDA) or trifunctional trimethylolpropane trimethacrylate (TMPTA) or N- propylene
In morpholide (acmo) activated monomer；It is not added under conditions of wetting dispersing agent, powder is added in activated monomer, by high speed point
It dissipates, is then sanded with sand mill, the zirconium oxide bead of a diameter of 0.05mm of sand mill, it is lasting to be sanded until observing powder under Electronic Speculum
Body is at nano-dispersed state；Because wetting dispersing agent currently on the market cannot participate in photopolymerization reaction mostly, in order to make preparation
Gloss oil solidification rate and curing degree do not influenced by the wetting dispersing agent that cannot occur photopolymerization reaction, using plasma
Body is aggregated in powder surface and forms the transparent SiO that thickness is less than 10 angstromsx(x=0.3-2) film improves powder in activated monomer
Dispersion performance；Meanwhile using unique sand milling technique, ensure that under the premise of being not added with wetting dispersing agent, can also it accomplish single
Nano particle disperses；
Third walks, and according to the accurate metering of formula, is stirred 12 hours in stainless steel cauldron at room temperature, is changed into no visible solid
Solution, filtering, viscosity adjusts with activated monomer, detects viscosity with No. 4 cups of Cai's grace, the time in 60-120 seconds, uses levelling agent
The surface tension of adjustment gloss oil is between 20 between 30Dynes/cm.
2. a kind of hydrophobic fast light UV-LED cured gloss oils of paper wrapper printed matter according to claim 1, characterized in that
Used nano-TiO2Or ZnO or CeO2The D50 diameters of powder between 10nm between 60nm, to cured film gloss, color,
Transparent and other physical properties, which not will produce, to be significantly affected.
3. a kind of hydrophobic fast light UV-LED cured gloss oils of paper wrapper printed matter according to claim 1, characterized in that
By the nano-TiO of synthesis2Or ZnO or CeO2The SiO of layer of transparent is formed in powder surface with plasma polymerizationx(x=0.3-
2) thin layer, thickness of thin layer are less than 10 angstroms, improve the dispersion performance of powder.
4. a kind of hydrophobic fast light UV-LED cured gloss oils of paper wrapper printed matter according to claim 1, characterized in that
By surface treated nano-TiO2Or ZnO or CeO2Powder is pre-dispersed in the activated monomer of oil polish, is not added with wetting
It under conditions of dispersant, by high speed dispersion, is then sanded with sand mill, the zirconium oxide bead of a diameter of 0.05mm of sand mill,
It is lasting to be sanded until observing powder under Electronic Speculum into nano-dispersed state.
5. a kind of hydrophobic fast light UV-LED cured gloss oils of paper wrapper printed matter according to claim 1, characterized in that
On the basis of rational formula forms, in high reaction activity resin, high activity monomer, photoinitiator and reactive amines and with anti-
Under the synergistic effect for answering the levelling agent of group, the photopolymerization reaction activity of prepared oil polish is significantly improved；In centre wavelength
For 365 or 385 or 395 or 405nm, illumination 0.5-15W/cm2, can cure rapidly under the LED illumination of distance 5mm.
6. a kind of hydrophobic fast light UV-LED cured gloss oils of paper wrapper printed matter according to claim 1, characterized in that
It is formed according to rational formula, prepared gloss oil is uniformly coated on 80 grams/m2Transfer paper on, coating weight is about 4-6 grams/m2,
After being cured with LED light source, inorganic nanometer powder ceria, zinc oxide and titanium dioxide are under the synergistic effect of levelling agent, powder
Body forms random island in printed matter surface and is distributed rough surface, cured film surface water contact angle between 120 ° -145 °,
Dynamic rub examines coefficient between 0.050-0.200, and confficient of static friction is between 0.100-0.300, the cured film of paper surface
With good hydrophobic performance；Using the energy gap of nano-powder ceria or zinc oxide or titanium dioxide, it can absorb day
Ultraviolet light in light or illumination light improves the light fastness of printed matter.
7. a kind of hydrophobic fast light UV-LED cured gloss oils of paper wrapper printed matter according to claim 1, characterized in that
Used photoinitiator is 2,4,6- trimethylbenzoy-dipheny phosphine oxides (TPO), camphorquinone, N- [2- (dimethylamine
Base) ethyl ester] -1,8-naphthalimide, bis- (2,4,6- trimethylbenzoyl) phosphine oxides, 4- second propyl thioxanthone, 2-
A variety of photoinitiators such as second propyl thioxanthone are applied in combination, and have both met that cigarette packaging material is remaining to photoinitiator to be wanted
It asks, and has relatively stronger absorption in the LED emission wavelength ranges that centre wavelength is 365nm or 385nm or 395nm or 405nm.
8. a kind of hydrophobic fast light UV-LED cured gloss oils of paper wrapper printed matter according to claim 1, characterized in that
Glazing oil viscosity is suitble to 120 line anilox roll glazings, and being coated on cigarette wrapping paper with common offset printing, gravure and flexo on line makes
With the cured film formed in paper printed matter surface after solidification has outstanding hydrophobic and light fastness.
9. a kind of hydrophobic fast light UV-LED cured gloss oils of paper wrapper printed matter according to claim 1, characterized in that
Its properties meets《YQ15.4-2012 cigarettes license substance list Part IV：Frame paper, cigarette wrapping paper (item and box)
With seal paper》It is required that meeting requirement of the cigarette package to oil polish.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108956486A (en) * | 2018-08-21 | 2018-12-07 | 海南金海浆纸业有限公司 | A kind of dyestuff appraisal procedure |
| CN113072835A (en) * | 2021-03-30 | 2021-07-06 | 中山市中益油墨涂料有限公司 | Ultraviolet light curing glass printing ink and preparation method thereof |
| EP4159799A1 (en) * | 2021-09-30 | 2023-04-05 | Rapollo Resins ApS | Photo initiator compositions |
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| CN108956486A (en) * | 2018-08-21 | 2018-12-07 | 海南金海浆纸业有限公司 | A kind of dyestuff appraisal procedure |
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| CN113072835A (en) * | 2021-03-30 | 2021-07-06 | 中山市中益油墨涂料有限公司 | Ultraviolet light curing glass printing ink and preparation method thereof |
| CN113072835B (en) * | 2021-03-30 | 2023-09-01 | 中山市中益油墨涂料有限公司 | Ultraviolet light curing glass printing ink and preparation method thereof |
| EP4159799A1 (en) * | 2021-09-30 | 2023-04-05 | Rapollo Resins ApS | Photo initiator compositions |
| WO2023052634A1 (en) * | 2021-09-30 | 2023-04-06 | Rapollo Resins Aps | Photo initiator compositions |
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