WO2002074871A1 - Composition d'encre optiquement variable et utilisation correspondante - Google Patents

Composition d'encre optiquement variable et utilisation correspondante Download PDF

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Publication number
WO2002074871A1
WO2002074871A1 PCT/CN2002/000177 CN0200177W WO02074871A1 WO 2002074871 A1 WO2002074871 A1 WO 2002074871A1 CN 0200177 W CN0200177 W CN 0200177W WO 02074871 A1 WO02074871 A1 WO 02074871A1
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Prior art keywords
ink composition
light
changeable
oil
resin
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PCT/CN2002/000177
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English (en)
Chinese (zh)
Inventor
Guanbao Fan
Peng Fan
Wei Zhang
Chunhua Zhou
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Guanbao Fan
Peng Fan
Wei Zhang
Chunhua Zhou
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Application filed by Guanbao Fan, Peng Fan, Wei Zhang, Chunhua Zhou filed Critical Guanbao Fan
Publication of WO2002074871A1 publication Critical patent/WO2002074871A1/fr

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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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings

Definitions

  • the invention relates to the field of printing inks, in particular to a light-varying ink composition.
  • the invention also relates to a preparation method and application of the light-varying ink composition.
  • optically variable pigments and the principle of their optical discoloration can be seen in the following documents, such as USP 5279657; W0 00/22049; CN 1152011; CN 1230577 and so on.
  • the Swiss SICPA company patent WO 00/22049 describes in more detail the optical discoloration principle of the photovariable ink composition and two photovariable pigments used in the photovariable ink composition, namely OVP A and OVP B.
  • Light-changeable ink compositions can be accomplished by adding light-changeable pigments to a polymeric resin.
  • the core part of the light-changeable ink composition is a light-changeable pigment and a binder.
  • the ink adjuvant has the same effect in the optical variable ink composition as in the ordinary ink composition.
  • the optically variable ink composition has a certain selectivity to the types and types of the binder resin, the ink auxiliary, and the like.
  • fillers such as carbonic acid, titanium dioxide, zinc oxide, barium sulfate, kaolin, etc.
  • these fillers Agents are common raw materials in common ink compositions. Therefore, the composition of the light-changeable ink composition is the same as that of the ordinary ink composition. Success is different.
  • the engraving gravure ink composition can be added to the ink composition formula, or a water-soluble group (such as Etc.), and then neutralized with ammonia gas, the liquid water-soluble resin obtained has no effect on the use of the ink composition, the physical and chemical properties of the printed product, and the post-treatment process.
  • Alkyl aryl sulfonates, or the liquid-soluble resins mentioned above, are highly acidic chemicals. Among them, ammonium alkylarylsulfonate is a normal raw material currently used in engraving gravure ink compositions.
  • the multilayer film structure of the photo-changeable pigment is corroded by strong acidic chemicals (because the multilayer color-changeable film structure of the photo-changeable pigment is composed of metal, non-metal, metal oxide, and non-metal oxide Layer by layer), destroying the reflection and interference conditions of light-varying pigments on natural light.
  • the optical discoloration effect can be judged as follows: The printed product is observed from an angle of about 90 degrees and an angle of about 30 degrees, respectively, and two completely different colors can be seen in the same ink composition.
  • the manufacturing method of the light-varying ink composition is not realized by the conventional ink preparation method.
  • the inventors of the present invention have carried out a lot of careful and careful research work, and have solved the urgent problems in the field from the aspects of the components, manufacturing methods, applications, etc. of the light-changeable ink composition. Summary of the Invention
  • An object of the present invention is to provide a light-varying ink composition. Another object of the present invention is to provide a method and application of the optically variable ink composition.
  • the light-changeable ink composition of the present invention includes a volatile-drying light-changeable ink composition, an oxidative polymerization drying, and a photo-curable light-changeable ink-change ink composition.
  • the volatile-drying light-changeable ink composition is mainly used for gravure printing and flexible letterpress printing Partial screen printing;
  • the oxidative polymerization drying or photo-curing light-changeable ink composition is mainly used for lithography, letterpress printing, partial screen printing, and engraving gravure printing.
  • the light-changeable ink composition of the present invention is composed of a light-changeable pigment, a binder, an ink auxiliary, and the like, wherein the light-changeable pigment accounts for 1-60% of the total weight of the light-changeable ink composition; the linker accounts for the light-changeable ink composition.
  • the total weight is 1-95%; the ink auxiliary agent accounts for 0-45% of the total weight of the light-varying ink composition.
  • Preparation method 1 All the raw materials required for the photo-changeable ink composition are loaded into a stepless speed-adjusting high-speed stirring device, and the stirring is started, and the rotation speed is gradually upgraded from a low speed to a high speed. At a low speed (preferably 0-100 revolutions per minute), the solid material is sufficiently wetted by the liquid material. Then gradually increase the rotation speed to 800-12000 rpm, preferably 2000-4000 rpm, for high-speed dispersion, so that the light-varying pigment is wrapped by the ink binder. Finally, adjust the ink properties, pack, and set aside.
  • the temperature of the system is 0-100 * ⁇ , preferably 50 ⁇ 5 or 60 ⁇ 5 "C.
  • Preparation method 2 In the middle and low speed stage of preparation method 1, after the solid materials are sufficiently wetted with the liquid materials, they are dispersed by a three-roll ink mill. However, the gap between the front and rear rollers and the middle roller of the three-roller ink rolling machine cannot be less than 15 microns, preferably about 50 microns, so that the light-varying pigment is wrapped by the ink binder. Finally, adjust the ink properties, pack, and set aside.
  • the preparation of the volatile dry type light-varying ink composition is performed by the following method, namely: Preparation method 3: a sand mill or a ball mill can be used for dispersion. After mixing all materials except light-varying pigments, pre-milling is performed. The fineness is reduced to less than 20 microns, and then the light-variable pigment is added for re-grinding, so that each particle of the light-variable pigment is wrapped by the ink binder. Finally, adjust the ink properties, pack, and set aside.
  • Preparation method 3 a sand mill or a ball mill can be used for dispersion. After mixing all materials except light-varying pigments, pre-milling is performed. The fineness is reduced to less than 20 microns, and then the light-variable pigment is added for re-grinding, so that each particle of the light-variable pigment is wrapped by the ink binder. Finally, adjust the ink properties, pack, and set aside.
  • the temperature of the system is controlled at 0-100 ° C, preferably 25 ⁇ or 15 ⁇ 5.
  • the light-changeable pigment used in the light-changeable ink composition of the present invention is well known in the technical field of inks. All of the light-variable pigments, for example, USP 5279657; CN 1230577; CN 1152011; CN 1236795; W0 00/22049 light-variable pigments produced by the production methods described in the literature or Guangdong Huizhou Optical Technology Co., Ltd., or optical Thin film fragments, or multilayer color-changing film fragments, have a fineness (here, the fineness refers to the average diameter of the light-changing pigment) of 2-50 microns.
  • the light-changing pigment used to volatilize the dry light-changing ink composition Its fineness is 2-30 micrometers, preferably 10-20 micrometers;
  • the light-variable pigments used for oxidative polymerization drying and / or photo-curable light-changeable ink composition have a fineness of 2-50 micrometers, preferably 2-25 Microns.
  • the color of each pair of light-variable pigments is mainly determined by the production process of light-variable pigments, for example: Choose different materials and the number of layers of the film system to get from gold to green; from magenta to green; from green to magenta; from green to Blue; light-varying pigments such as magenta to gold.
  • optical variable ink composition for offset printing or relief printing.
  • the fineness of the optical variable pigment is 2-15 microns, preferably 5-15 microns.
  • Photographic gravure plate depth and stencil screen density should meet the fineness of light variable pigment.
  • the optically variable ink composition for gravure and screen printing requires the fineness of the optically variable pigment to be 2-30 microns, preferably 10-20 microns.
  • the gravure is required to have a depth of 30-70 microns.
  • the screen pattern is dense and dense. You can select the screen pattern by referring to the depth of the pattern on the photo gravure.
  • the light-variable ink composition for engraving gravure printing requires the fineness of the light-variable pigment to be 2-50 microns, preferably 5-25 microns. However, in practice, the fineness of the light-varying pigment should not be too coarse. Because the specific gravity of the optically variable pigment is larger, the fineness exceeds 50 microns. In the printing process, it is difficult to transfer all the optically variable pigments with a fineness exceeding 50 microns to the substrate by the connecting material. As a result, scumming and stacking rollers appear. And other printing ills.
  • the light-changeable pigment used for the oxidative polymerization drying and / or light-curable light-changeable ink composition accounts for 10 to 60%, preferably 20 to 47% of the total weight of the light-changeable ink composition; for the volatile dry light-changeable ink composition
  • the light-changeable pigments comprise 1-40%, preferably 10-25% of the total weight of the light-changeable ink composition.
  • the binder used in the present invention can be divided into two categories, namely: used for oxidative polymerization drying and / Or a binder for a light-curable light-changeable ink composition and a binder for volatilizing and drying the light-changeable ink composition.
  • the binder for oxidative polymerization drying and / or light-curing light-changeable ink composition (A) resin accounts for 20-99% of the total weight of the binder, and (B) solvent accounts for 0-25% of the total weight of the binder.
  • (C) Vegetable oil accounts for 1-79% of the total weight of the connection material
  • (D) Gum oil accounts for 0-35% of the total weight of the connection material
  • (E) Adjusting ink accounts for 0-20% of the total weight of the connection material
  • the binder for the volatile and dry type light-changeable ink composition is composed of 5-60% of the total weight of the binder
  • the binder for oxidative polymerization drying and / or light-curing light-changeable ink composition comprises 20-80%, preferably 45-60% of the total weight of the light-changeable ink composition;
  • the binder comprises 50-95% of the total weight of the light-varying ink composition; preferably 70-90%.
  • Examples of the (A) resin in the composition of the binder include alkyd resins, unsaturated polyester resins, and phenolic resins. , Rosin ester, polyamide resin, nitrocellulose and fiber derivatives, rubber resin, acrylic and its derivative resin, polyurethane resin, urea resin, melamine formaldehyde resin, epoxy resin and modified epoxy resin, polyethylene These resins can be used alone or in combination.
  • alkyd resin examples include vegetable oil and / or rosin and its derivatives and / or styrene and / or other synthetic resins and / or silicones and / or organic polyisocyanates.
  • Alkyd resins preferably the polyols used in these modified alkyd resins are glycols (such as ethylene glycol, neopentyl glycol, etc.), triols (such as glycerol, trihydroxymethylpropane, etc.), quaternary Alcohols (such as pentaerythritol, etc.) Pentavalent alcohols (such as xylitol, etc.) Hexavalent alcohols (such as sorbitol, mannitol, etc.).
  • the acids used are benzoic acid, p-tert-butylphenylarsinic acid, adipic acid, sebacic acid.
  • modified alkyd resin is, for example, a product of Tianjin Lauter International Co., Ltd.
  • LV-800 series alkyd resin TERL0N alkyd resin, DSM product URALAC S alkyd resin, PLUSS-STAUFER product PLUSOL L72, ALFTALAT AR 680, H0ECHST product ALFTALAT 707 D, Beijing Wanyang anti-counterfeiting technology limited liability company product WY-2600 , WY-2700, WY-2800, WY-2900 alkyd resin, etc.
  • the unsaturated polyester resin examples include epoxy acrylate, acrylic modified polyester resin, and polyol acrylate (such as trimethylolpropane acrylate, pentaerythritol acrylate, and ethylene glycol propionate). ), Vegetable oleic acid and / or epoxy resin modified unsaturated polyester resin, liquid unsaturated polyester resin (such as # 143, # 153, # 154, # 530 photosensitive resin, etc.), these unsaturated polyester resins can be separately Use or mix with multiple resins.
  • the phenol resin include rosin and its derivatives and / or tung oil and / or tung oil and / or C6-C17 aliphatic compound modified phenolic casein resin having a conjugated double bond, and oil-soluble pure phenol resin, Such as Beijing Wanyang Anti-counterfeiting Technology Co., Ltd. products WY-126, WY-132, WY-138, WY-216 modified phenol casein resin, WY-111 pure phenol casein resin, etc .; Tianjin Laute International Co., Ltd. products ULTRA REZ 10 Series, 20 series, 30 series, 100 series, 210 series, 8000 series, 7000 series modified phenolic resin, R-40. 150, KR-40. 081, KRUMBHAAR K-111 pure phenol resin, etc.
  • the above-mentioned modified phenols can be used alone or in combination with a variety of resins, or can be used in combination with various resins.
  • rosin ester examples include rosin and its derivative-glycerol (or pentaerythritol) ester, maleic acid and its anhydride-modified rosin and its derivative-glycerol (or pentaerythritol) ester, and fumaric acid Modified rosin and its derivatives-glycerol (or pentaerythritol) esters.
  • rosin esters can be used singly or in combination, and can also be used in combination with various resins.
  • polyamide resin those with a molecular weight of less than 4000 are dissolved with a lower alcohol such as ethanol; If the amount is greater than 4000, dissolve it in a mixed solvent such as xylene, xylene, and isopropyl alcohol.
  • a mixed solvent such as xylene, xylene, and isopropyl alcohol.
  • polyamide resins are: 5320 alcohol-soluble polyamide resin produced by Tianjin Atos Fine Chemical Co., Ltd., P-4512 alcohol-soluble polyamide resin produced by Tianjin Laute International Co., Ltd., and P-1155 alcohol-soluble polymer Amide resin, P-4584 alcohol-soluble polyamide resin, P-3370 benzene-soluble polyamide resin, P-1060 cosolvent-soluble polyamide resin, P-1074 benzene-soluble polyamide resin, etc. After the polyamide resin is dissolved in the solvent, it can be used alone or mixed with nitrocellulose and fiber derivatives, rosin ester, phenolic resin, and the like
  • nitrocellulose examples include nitrocellulose having a viscosity of 1/16 second, 1/8 second, 1/4 second, 1/2 second, 1 second, 5-6 seconds, and the like, and the viscosity is preferably 1/16. 4 second, 1/2 second nitrocellulose.
  • various nitrocellulose esters are generally not used alone, but are combined with alkyd resins, vegetable oil-modified unsaturated polyester resins, aldehyde resins, rosin esters, polyamide resins, acrylic acid and its derivative resins, and polyurethane resins. Mixed use
  • ethyl cellulose in the fiber derivative may be mentioned, and a product having an ethoxy group content in ethyl cellulose of 44-49% (such as an industrial-grade ethyl ester produced by Shanghai Reagent No. 1 Factory) is preferred.
  • Cellulose, etc. it is soluble in most organic solvents or vegetable oils or various resins, with long oil alkyd resins, vegetable oil-modified unsaturated polyester resins, phenolic resins, rosin esters, polyamide resins, acrylic and Derivative resin, polyurethane resin, etc.
  • the rubber resin include a chlorinated rubber resin, and a chlorinated rubber resin having a viscosity of 25 seconds or less is preferred.
  • a chlorinated rubber resin having a viscosity of 25 seconds or less is preferred.
  • products CR-5 and CR-20 of Zhongyuan Oilfield Chemical Group Chlorinated Rubber Factory which are soluble in aromatic hydrocarbons (such as toluene, xylene, etc.), chlorinated hydrocarbons (such as trichloroacetamidine, etc.), esters (such as decyl Dioctyl diacid, etc.), ketones (such as acetone, etc.) in solvents or soluble in vegetable oils or in various resins, can be used alone or with alkyd resins, phenolic resins, rosin esters, acrylic resins and derivatives resins , Rosin and its derivatives, terpene resin, chlorinated paraffin, chlorinated biphenyl, indene resin, etc. Cyclic rubber
  • acrylic and its derivative resins include all acrylics for inks. Acid and its derivative resin, preferably esterified products of acrylic acid with polyether or diphenol-based propane or epoxy resin, acrylic acid and its derivative-acetophenone copolymer (such as products of Rohm and Haas China Co., Ltd.), Soluble acrylic acid in aromatic hydrocarbons (such as toluene, xylene, etc.), esters (such as ethyl acetate, butyl acetate, etc.), alcohols (such as ethanol, isopropyl alcohol, etc.) or their mixed solvents
  • Derivative resins such as 5388 alcohol ester acrylic resin, 5320 alcohol soluble acrylic resin, 5386 benzene soluble acrylic resin, etc.
  • acrylic modified polyurethane resin acrylic modified alkyd resin
  • Acrylic modified unsaturated polyester resin etc.
  • urethane resin examples include all one-component and two-component urethane resins for inks, and organic diisocyanate-modified alkyd resins, or organic diisocyanate-modified unsaturated polyester resins, or organic diisocyanate resins are preferred.
  • Isocyanate-modified dry oils and semi-dry oils are both single-component closed-type polyurethane resins.
  • urea-formaldehyde resin and melamine formamidine resin include melamine formaldehyde resin with a low degree of etherification, melamine casein resin with a high degree of etherification, butanol or octanol, or other fatty alcohol-modified urea resins.
  • epoxy resin examples include E-51, E-44, E-42, E-35, E-31, E-20, E-12, E-06, and E-03 with an average molecular weight of 3750.
  • the following epoxy products. These epoxy resins can be used alone or in combination with multiple resins.
  • an esterified product of a dry oil fatty acid or a semi-dry oil fatty acid and an epoxy resin such as a product of Beijing Wanyang Anti-Counterfeiting Technology Co., Ltd. WY-3000 linoleic acid epoxy Ester oil, etc.
  • polyethylene resin ⁇ f molecular weight polyethylene wax (viscosity average) 1500-2000), chlorosulfonated polyethylene (average molecular weight is about 20,000), polyvinyl chloride resin and perchloroethylene resin, polyvinylidene chloride and vinylidene chloride copolymer, polyvinyl acetate and chlorine Ethylene acetate copolymer, polyvinyl butyral, low-molecular-weight styrene homopolymer (molecular weight 10000-14000), styrene-modified alkyd resin, styrene-modified dehydrated malic acid resin, styrene-acrylic copolymer
  • resins are soluble in axe hydrocarbon (such as benzene, toluene, xylene) solvents, ketone solvents, ester solvents, alcohol solvents, or mixed solvents thereof, and can be used alone or in combination with various resins.
  • Examples of the (B) solvent in the composition of the binder (oxidative polymerization drying and / or photocuring and volatile-drying photovariable ink composition binder) composition include ethanol, n-propanol, isopropanol, and phenylethanol , Butanol, ethylene glycol, polyethylene glycol, 1, 2-propanediol, 1, 2-butanediol, glycol ether, diethylene glycol ether, ethyl acetate, n-propyl acetate, isopropyl acetate Ester, butyl acetate, dibutyl phthalate, dioctyl phthalate, tributyl phosphate, acetone, isoacetone, methyl isobutyl ketone, cyclohexanone, methyl ethyl ketone, toluene, xylene, silicone oil, Aliphatic hydrocarbon solvents, high boiling point kerosene, # 200 solvent
  • Examples of the (C) vegetable oil in the composition of the above-mentioned binder include linseed oil, tung oil, dehydrated castor oil, perilla oil, azalea oil, 0ITICICA oil, soybean oil, sunflower oil, grape seed oil, castor oil, tower oil fatty acid, styrene or maleic acid and its anhydride or fumaric acid, etc.
  • the obtained polymer oil (such as # 4 tune oil, # 6 tune oil, cooked tung oil, etc.), one or more of the above-mentioned vegetable oleic acid.
  • (D) gum oil in the composition of the above-mentioned binder (oxidative polymerization drying and / or light-curing light-changeable ink composition binder) composition WY-831 gum oil (Beijing Wanyang Anti-counterfeiting Technology Co., Ltd.) company's product) .
  • Examples of the (E) varnish in the composition of the above-mentioned binder include high boiling point kerosene, # 210 mineral oil, # 200 Solvent oil, glycol ether, diethylene glycol ether, dibutyl phthalate, dioctyl phthalate, tributyl phosphate, etc. These inks can be used alone or in combination.
  • the varnish can be selected from # 6 varnish, cooked tung oil, soybean oil and the like in vegetable oil.
  • Examples of the (F) linker auxiliary in the composition of the linker include ultraviolet absorbers (such as benzoin methyl ether, Michler's ketone, xylone, etc.), binders or ink stabilizers (such as low molecular weight epoxy resin, etc.), antioxidants (such as BHT, hydroquinone, butanone oxime, butanone oxime, etc.), waxes, Silicone oil, fatty amide (such as oleic acid amide, stearamide, etc.), etc.
  • ultraviolet absorbers such as benzoin methyl ether, Michler's ketone, xylone, etc.
  • binders or ink stabilizers such as low molecular weight epoxy resin, etc.
  • antioxidants such as BHT, hydroquinone, butanone oxime, butanone oxime, etc.
  • waxes such as BHT, hydroquinone, butanone oxime, butanone oxime, etc.
  • Silicone oil such
  • ink auxiliary agent examples include desiccant, retarder, tack remover, wax, surfactant, ultraviolet absorber (such as benzoin diethyl ether, Michler's ketone, benzophenone, etc.), dilution
  • desiccant desiccant, retarder, tack remover, wax, surfactant, ultraviolet absorber (such as benzoin diethyl ether, Michler's ketone, benzophenone, etc.), dilution
  • ultraviolet absorber such as benzoin diethyl ether, Michler's ketone, benzophenone, etc.
  • the desiccant include metal salts of organic acids, such as cobalt, manganese, zirconium, cerium, vanadium, lanthanum, iron, lithium, lead, and saturated organic acids such as naphthalic acid, naphthenic acid, octanoic acid, and capric acid.
  • organic acids such as cobalt, manganese, zirconium, cerium, vanadium, lanthanum, iron, lithium, lead, and saturated organic acids such as naphthalic acid, naphthenic acid, octanoic acid, and capric acid.
  • Aluminum, calcium, zinc salts and manganese borate are preferred.
  • cobalt, manganese, zirconium, cerium salts and manganese borate are preferred.
  • the retarder examples include phenol, oxime, amine, hydrazine, and acid.
  • phenols and oximes BHT, butanone oxime, butoxime, etc. are preferred.
  • natural waxes such as Brazilian palm wax, candelilla wax, spanish wax, small crown coconut wax, Japanese wax, fir wax, palm wax, beeswax, insect wax, wool wax, paraffin wax) , Microcrystalline wax, montan wax, mineral wax, etc.
  • synthetic wax such as stearic acid and its derivatives or their esterification products with alcohol, stearyl alcohol, polyethylene wax, etc.
  • modified wax such as Oxidized polyethylene wax, chlorinated wax, macromolecular fatty amide, aluminum stearate, vaseline, etc.
  • Synthetic wax also includes other natural waxes or synthetic waxes, waxes obtained after chemical treatment (such as purification, oxidation, chlorination, etc.) . These waxes can be used alone or in combination. The combination of two or more waxes is also called mixed wax.
  • anionic surfactants such as
  • the above-mentioned surfactant is used for engraving gravure, the water rubbing does not stain the printing process, it must also meet the requirements of the post-treatment process.
  • diluents include inking oil, high boiling point kerosene, # 200 solvent oil, # 210 mineral oil, aromatic-free mineral oil, glycol ethers, diethylene glycol ethers, and 1,2-propanediol. , Formate, etc. These diluents can be used alone or in combination.
  • 8043 release agent product of Tianjin Ink Co., Ltd.
  • the following examples further describe the optically variable ink composition of the present invention:
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6
  • Example 7 Code Material name wt% wtX fft3 ⁇ 4 wt3 ⁇ 4 wt3 ⁇ 4 t3 ⁇ 4 wt3 ⁇ 4 wt3 ⁇ 4 wt3 ⁇ 4 wt3 ⁇ 4 wt3 ⁇ 4 wt3 ⁇ 4
  • Example 1-8 the raw materials used are as follows:
  • Light-varying pigment RGN 10 magenta turns green, product of Guangdong Huizhou Optical Technology Co., Ltd.
  • Alkyd resin a WY-2600 alkyd resin, viscosity 14-16pa.
  • S OOHAAKE acid value less than 15mgK0H / g;
  • alkyd resin b WY-2700 alkyd resin, viscosity 3-5pa.
  • S / 40 C HAAKE Acid value less than l OmgKOH / g;
  • alkyd resin c WY-2800 alkyd resin, viscosity 14-16pa.
  • S / 40iC HAAKE acid value less than 15mgK0H / g
  • polyurethane resin WY-2900 polyurethane resin, viscosity 14-16pa s / 40 * CHAAKE, acid value less than 15mgK0H / g
  • unsaturated polyester resin WY-4000 epoxy acrylic linker, viscosity 15-17pa.
  • sy O HAAKE acid value less than 15mgK0H / g; trimethylolpropane Triacrylate
  • Modified epoxy resin WY- 3000 linoleic acid epoxy ester oil binder, viscosity 2-3pa.
  • S / 40t HAAKE acid value less than 15mgK0H / g; modified unsaturated polyester resin: WY- 5000 modified unsaturated polyester resin, viscosity 14-16pa.
  • S / 40 "HAAKE acid value less than 15mgK0H / g; phenolic resin connecting material a: WY-1380 phenolic resin oil connecting material, viscosity 3- 4pa.
  • optically variable ink composition obtained from Example 1-8 should meet the following requirements for printing:
  • A. Graphic design 1 The light-varying ink composition is applied to areas that do not interfere with the effect of optical discoloration; 2 Avoid areas that are folded and held;
  • Pattern production 1 The area of the pattern is subject to clear identification of the optical discoloration effect; 2 The width of the pattern is 0. 20 mm or more; 3 The area where the light-varying ink composition is applied in the pattern is not less than 80%;
  • the optically variable ink composition for offset printing is first printed on the substrate with an ink composition that does not interfere with the optical discoloration effect, and then overprint the optically variable ink composition.
  • the obtained printed product from an angle of about 90 degrees and an angle of about 30 degrees, respectively, you can see two very different colors, namely: magenta turns green.
  • the pattern is clear, the overprint is accurate, and the physical and chemical fastnesses are better than the engraving gravure light variable ink composition.
  • the area where the light-varying ink composition is applied in the pattern is not less than 80%.
  • the coverage of light-variable pigments in the actual printing area is more than 40%.
  • the printing cost is lower than the cost of engraving gravure.
  • the obtained printed product has a relatively poor optical discoloration effect.
  • the optical discoloration effect printed on the coated paper is better than that printed on the offset paper.
  • the optical discoloration effect is good. This is due to the uneven surface of the offset paper.
  • optically variable ink compositions for offset printing given in Examples 1-8 are only representative.
  • the connecting material can be replaced with other resin connecting materials as described above.
  • One or more of the above-mentioned resin binders can be selected for use in combination with the ink adjuvant.
  • the optically variable ink composition given in Example 1-8 is used for stock printing, and the print is very thin. Therefore, in the formulation design, while ensuring the printability of the optically variable ink composition, it should be improved as much as possible. Light-variable pigment ratio.
  • the optically variable ink compositions given in Examples 1-8 are also suitable for dry offset (plano relief) printing. Photovariable ink composition for gravure
  • Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Number Material name wt1 ⁇ 4 wt3 ⁇ 4 wtX wtX wtX wt%
  • Ink index fineness is less than 20 «; viscosity is 30-80 seconds / 25 (coated with 4 viscosity cup).
  • the raw material families used are as follows:
  • Light-varying pigment RGB 20 magenta turns green, product of Guangdong Huizhou Optical Technology Co., Ltd.
  • Phenolic casein resin WY-138 modified phenolic resin; Rosin ester: WY-108 spearm ester, the above are products of Beijing Wanyang Anti-Counterfeiting Technology Co., Ltd.
  • Nitrocellulose Viscosity 1/2 second. Product of Hengshui Dongfang Chemical Co., Ltd.
  • Fiber Derivatives Industrial grade ethyl cellulose with 44-49% ethoxy group content, a product of Guangzhou Chemical Reagent Factory.
  • Rubber resin CR-20 chlorinated rubber resin, product of chlorinated rubber factory of Zhongyuan Oilfield Chemical Group.
  • Polyamide resin AZ-2420 alcohol-soluble polyamide resin; acrylic acid and its derivative resin a: AZ-5388 alcohol-ester compatible acrylic resin solution; acrylic acid and its derivative resin b: AZ-5388 benzene-soluble acrylic acid Resin solution, the above is the product of Tianjin Atoz Fine Chemical Co., Ltd.
  • Polyethylene wax Low-molecular-weight polyethylene wax LPE-3 (F), a fine chemical plant product of Beijing University of Chemical Technology.
  • Aliphatic hydrocarbon solvent # 200 solvent oil, product of Beijing Yanshan Petrochemical Company.
  • Fatty amide stearamide, product of Wuhan Ammonia Soda Plant.
  • the photovariable ink composition for photogravure obtained in Example 9-14 should meet the following conditions:
  • Pattern design same as light-varying ink composition for offset printing
  • Pattern production 1 The pattern area is subject to clear identification of the optical discoloration effect; 2 the depth of the pattern is 30-70 microns; 3 the width of the pattern is 0. 2-3 mm; 4 the pattern is applied with a light-varying ink composition The area is not less than 80%; 5 The pattern is as perpendicular to the erasing direction as possible.
  • Printing conditions The same as the ink composition for ordinary gravure printing.
  • the optically variable ink composition for gravure printing is In the printing process, printing is performed directly on the substrate, and the obtained printed product is observed from an angle of about 90 degrees and an angle of about 30 degrees, respectively. You can see two completely different colors, namely: magenta turns green.
  • the pattern is clear and the physical and chemical fastnesses are better than the engraving gravure light variable ink composition.
  • the area where the light-varying ink composition is applied in the pattern is not less than 80%.
  • the coverage of the light-variable pigment in the actual printing area is more than 40%.
  • the printing cost is lower than the cost of engraving gravure.
  • the photovariable ink composition for photogravure given in Example 9-14, or the photovariable ink composition for flexible relief printing obtained on the basis of Examples 9-14, are representative examples.
  • binders including various resins and solvents
  • aromatics such as toluene and xylene
  • solvents have good solubility for most resins, but they have a strong odor and are highly toxic.
  • Alcohols, esters, water, etc. as solvents have low toxicity and are widely used.
  • alcohol-soluble polyamide resins benzene-soluble polyamide resins, mixed solvent-soluble polyamide resins, nitrocellulose, cellulose and its derivatives, and alcohol-soluble Type acrylic resin, alcohol ester type acrylic resin, and ethanol, isopropanol, n-propanol, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, toluene, xylene and the like.
  • the viscosity of the photogravure light-variable ink composition is controlled at 30-80 seconds / 25 ⁇ (coated with a 4 viscosity cup), and the viscosity of the flexible letterpress light-variable ink composition is controlled at 80- The range of 150 seconds / 25 V (coated with 4 viscosity cups) is good, leaving room for the printer to adjust the viscosity of the light variable ink composition.
  • the use viscosity of the photovariable ink composition for the two printing methods should be slightly higher than the use viscosity of the ordinary ink composition for the two printing methods. This is beneficial to improve the optical discoloration effect of the photo-changeable ink composition.
  • Light-varying pigment YSB 30 gold to green, product of Guangdong Huizhou Optical Technology Co., Ltd. Alkyd resin &, alkyd resin! ), Phenol resin oil connection material a, phenol resin oil connection Material 1), modified epoxy resin, 404 desiccant, composite desiccant, antioxidant, the same as the optical variable ink composition for offset printing; wax mixture: WY-1203 wax mixture.
  • Phenol resin oil connection material a Phenol resin oil connection material 1
  • modified epoxy resin 404 desiccant, composite desiccant, antioxidant, the same as the optical variable ink composition for offset printing
  • wax mixture WY-1203 wax mixture.
  • the above are the products of Beijing Wanyang Anti-counterfeiting Technology Co., Ltd.
  • optically variable ink composition obtained from Examples 15-17 should meet the following requirements for printing:
  • Pattern design same as light-varying ink composition for offset printing
  • Pattern production same as light-varying ink composition for offset printing
  • the photovariable ink composition for letterpress printing is printed directly on the substrate according to the normal printing process.
  • optical discoloration prints can be obtained, it is better to print enough before printing the photovariable ink composition.
  • An ordinary ink whose appearance color is consistent with the color of the light-varying ink composition is relatively low, or is printed with a colorless ink (used to compensate for the unevenness of the surface of the paper), and then the light-varying ink composition is overprinted.
  • the printed product can be seen from an angle of about 90 degrees and an angle of about 30 degrees, respectively. You can see two very different colors, namely: gold turns green.
  • the pattern is clear, the overprint is accurate, and all the physical and chemical fastnesses are better than the engraving gravure light variable ink composition.
  • the area where the light-varying ink composition is applied in the pattern is not less than 80%.
  • the coverage of light-variable pigments in the actual printing area is more than 40%.
  • the printing cost is lower than the cost of engraving gravure. Printing on coated paper produces better optical discoloration than printing on offset paper.
  • optically variable ink composition for number is a typical representative of embossing.
  • the resins in Examples 15-17 can be replaced with other resins as described above.
  • Example 20 Except that the above-mentioned preparation method 1 is adopted in Example 20, the above-mentioned preparation method 3 is adopted.
  • the raw materials used are as follows:
  • Light-varying pigment RGB 20 magenta turns green, product of Guangdong Huizhou Optical Technology Co., Ltd.
  • Polyamide resin AZ-2420 alcohol-soluble polyamide resin; acrylic resin (1): AZ-5386
  • Benzene-soluble acrylic resin solution acrylic resin (2): AZ-5388 alcohol-ester-compatible acrylic resin solution.
  • acrylic resin (2) AZ-5388 alcohol-ester-compatible acrylic resin solution.
  • E-42 epoxy resin solution WY-6000 E-42 epoxy resin solution; trimethylol propylene
  • Alkane triacrylate Alkane triacrylate
  • Unsaturated polyester resin WY-4000 epoxy acrylic linker, viscosity 15-17 Pa.
  • S / 40X HAAKE acid value less than 15mgK0H / g e above is Beijing Wanyang anti-counterfeiting technology ⁇ f limited liability company products .
  • optically variable ink composition for screen printing given in Examples 18-22, the printing should meet the following conditions:
  • Pattern design same as light-varying ink composition for offset printing
  • Pattern production same as light-varying ink composition for offset printing
  • Printing conditions The same as using ordinary screen printing ink composition.
  • the optically variable ink composition for screen printing is directly printed on the substrate according to a normal printing process, and the obtained printed product is observed from an angle of about 90 degrees and an angle of about 30 degrees, respectively.
  • Two different colors, namely: Magenta turns green.
  • the pattern is clear and the physical and chemical fastness is better than the engraving gravure light variable ink composition.
  • the area to which the optically variable ink composition is applied in the pattern is not less than 80%.
  • the coverage of light-variable pigments in the actual printing area is more than 40%.
  • the printing cost is lower than the cost of engraving gravure.
  • Examples 18-22 are only representative examples, and the other resins and solvents mentioned above can also be used.
  • Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Fluidity mm / 25 32. 7 35. 5 33. 5 33. 0 31. 5 33. 0 32. 5 33. 0 Fineness ⁇ 20 20 20 20 20 20 20 20 20 Viscosity pa.s / 40X 4. 2 4. 3 3. 8 4. 0 4. 5 4. 3 4. 0 4. 1 HAAKB Technical index of optical variable ink composition for engraving gravure:
  • Phenolic resin (1) WY-1111 pure phenolic resin oil binder, viscosity 9-10 pa.
  • s / 4 HAAKE acid value is less than 25 mgKOH / g
  • Polyurethane resin WY-2901 polyurethane resin, viscosity is 4-6 pa.
  • S / 40tIHAAKE acid value less than 15 mgKOH / g
  • mixed wax WY-1201 mixed wax
  • surfactant castor oil sodium sulfonate
  • composite desiccant same as light-varying ink composition for offset printing
  • Oxygen same glue Optical variable ink composition for printing.
  • the above are the products of Beijing Wanyang Anti-counterfeiting Technology Co., Ltd.
  • Solvent Diethylene glycol monomethyl ether.
  • optically variable ink composition for engraving gravure given in Example 23-30, the printing should meet the following conditions:
  • Pattern design 1
  • the light-varying ink composition should be used in areas that do not interfere with the effect of optical discoloration; 2 Avoid areas that are folded and held by hands; 3 Avoid being stained by other engraving gravure inks when printing plates.
  • Pattern engraving 1 The pattern area is subject to clear identification of the optical discoloration effect; 2 the depth of the pattern is 60-70 microns; 3 the width of the pattern is 0. 25-3 ⁇ m; 4 the application of light-varying oil in the pattern The area of the ink composition is not less than 80%; 5 The pattern is perpendicular to the erasing direction as much as possible.
  • the optically variable ink composition for engraving gravure can be printed directly on the substrate or overprinted on the substrate according to the water-washing without staining printing process to obtain a satisfactory optical discoloration print.
  • optically variable ink composition for engraving gravure given in Examples 23-30 is only a typical representative, in which the resin, surfactant, ink auxiliary, etc. can be adjusted or replaced with other resins or materials mentioned above.
  • these substances must not contain chemical substances (such as sulfide, ammonium alkylarylsulfonate, sodium hypochlorite, etc.) that have redox and destructive effects on the light-changeable pigment, or the color of these substances. Neither can interfere with the optical discoloration effect of the light-varying pigment.
  • Level 1 is poor; Level 2 is poor; Level 3 is good; Level 4 is good; Level 5 is excellent.
  • Sources of physical fastness printing samples Offset printing samples / Case 1, convex printing samples / Case 15, engraving printing samples / Case 23, silk screen printing samples / Case 18, photogravure printing samples / Case 11.
  • Physical and chemical fastness test method Put the printed samples into the above three solutions, soak them in the solution, leave them below 25, let them stand for 30 minutes, take them out and rinse them three times, and compare them with the original samples after drying.
  • Light variable ink compositions can be used to print banknotes and marketable securities, bank notes, credit cards, tickets, ferry tickets, air tickets, stamps, invoices, various documents, various product trademarks and / or packaging and / or labels, crafts,
  • the anti-counterfeiting products that people need such as books, pictures, publicity materials, and the like, according to the present invention, can provide various optically variable ink compositions having good printability and a method for producing the same.
  • the direct print on the printing overprint on a substrate material can be satisfied with respect to the ⁇ optically variable intaglio prints, photographic gravure, screen printing, embossing with
  • the light-changing ink composition can be printed directly on the substrate or overprinted on the substrate, and can obtain satisfactory optical discoloration ⁇ .
  • the photochromic ink composition for stock printing if a sufficient amount of an ink composition that does not interfere with the optical discoloration effect is printed on the substrate, and then the photochromic ink composition is overprinted, a satisfactory optical discoloration print can be obtained. And printing costs are low.
  • the optical discoloration effect printed on coated paper is better than the optical discoloration effect printed on offset paper.

Abstract

La présente invention se rapporte à une composition d'encre optiquement variable constituée d'un pigment optiquement variable, d'un liant, d'additifs pour encre, etc. Cette composition se caractérise en ce que la proportion du pigment optiquement variable représente 1 à 60 % du poids total de ladite composition d'encre optiquement variable, la proportion du liant représente 1 à 95 % du poids total de la composition d'encre optiquement variable et la proportion des additifs pour encre représente 0 à 45 % du poids total de la composition d'encre optiquement variable. L'invention se rapporte également au procédé de préparation de cette composition d'encre optiquement variable et à son utilisation. La composition d'encre optiquement variable de la présente invention est facile à utiliser et elle peut servir à l'impression sur des imprimantes de types connus. Elle est utilisée pour une large gamme d'impression et permet d'imprimer sur divers substrats d'impression. Elle se caractérise par une forte résistance à la contrefaçon au moyen d'un scanner haute définition ou d'une machine à photocopier couleur ainsi que par une bonne caractéristique de mise au point de l'impression.
PCT/CN2002/000177 2001-03-19 2002-03-19 Composition d'encre optiquement variable et utilisation correspondante WO2002074871A1 (fr)

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CN01103886.1 2001-03-19
CN 01122606 CN1375528A (zh) 2001-03-19 2001-06-26 光变油墨组合物及其应用
CN01122606.4 2001-06-26

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CN115259668A (zh) * 2020-12-08 2022-11-01 福建省德化云水窑陶瓷有限公司 荧光釉上花纸及其荧光底墨层的制备方法
CN115259668B (zh) * 2020-12-08 2023-06-27 福建省德化云水窑陶瓷有限公司 荧光釉上花纸及其荧光底墨层的制备方法
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