CN1375528A - Photochromic ink compound and its application - Google Patents
Photochromic ink compound and its application Download PDFInfo
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- CN1375528A CN1375528A CN 01122606 CN01122606A CN1375528A CN 1375528 A CN1375528 A CN 1375528A CN 01122606 CN01122606 CN 01122606 CN 01122606 A CN01122606 A CN 01122606A CN 1375528 A CN1375528 A CN 1375528A
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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
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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
- 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
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Abstract
The composition of photochromic printing ink comprises (wt%) 1-60% of photochromic pigment, 1-95% of connecting material and 0-20% of printing ink adjuvant. At the same time said invention also relates to its application.
Description
The present invention relates to the printing-ink field, is photochromatic printing ink composition specifically.
The invention still further relates to the application of described photochromatic printing ink composition.
In history, forged banknote, bank money, car/ship/air ticket, various certificate, famous-brand and high-quality goods trade mark, raise a check etc. is offender's content the most deeply concerned.In recent years, people forge in order to prevent, have done a large amount of research work at high-technology field.As fluorescent material with the ultraviolet excitation of 365 nanometers and 254 nanometers; Thermo-sensitive material; Photochromic material; There is not the infrared printing ink of absorption composition; Safety ink composition etc.But As time goes on, the offender utilizes these anti-counterfeiting technologies successfully to forge various Valued Securities, famous-brand and high-quality goods trade mark etc.Especially the appearance of color copy machine and high-definition scanning instrument proposes a lot of new problems for the anti-counterfeiting technology worker.Photochromatic printing ink composition is exactly to forge in order to prevent, satisfies social needs and the product innovation studied.
The manufacturing of optically variable pigments and optic metachromatic principle thereof can be seen in following document, as USP 5279657; WO 00/22049; CN 1236795; CN 1152011; CN 1230577 etc.
At present, Switzerland slcpa company supply carved gravure photochromatic printing ink composition only on the market.Among the WO of Switzerland slcpa house journal 00/22049, introduced the optic metachromatic principle of photochromatic printing ink composition in more detail.In WO 00/22049, photochromatic printing ink composition contains polymer resin and connects material and two kinds of optically variable pigments, i.e. OVP A and OVP B, wherein, OVP A is phgsical Vapour deposition (PVD), and OVP B is chemical vapourdeposition (CVD).The commercial price of PVD is very expensive.And the commercial price of CVD is very cheap.In order to reduce the printing ink cost, to improve the quality of products and don't influence optic metachromatic, Switzerland slcpa company does not use PVD separately, but adds a part of CVD, and use instrumentation in ink composite, finds out the optimum ratio of PVD and CVD.In ink formulations, account for how much per-cent as for this optimum ratio, in WO 00/22049, do not describe.And polymer resin connects material and the printing ink auxiliary selects for use the manufacture method of what kind and photochromatic printing ink composition all less than describing.In WO 00/22049, mention photochromatic printing ink composition twice can be applied to banknote, check, credit card etc., how not use and application conditions but describe.
Photochromatic printing ink composition is not only to add optically variable pigments just can finish in polymer resin.The core of photochromatic printing ink composition is an optically variable pigments and be connected material.The printing ink auxiliary is identical with the effect in the common ink composition in photochromatic printing ink composition.But photochromatic printing ink composition has certain selectivity to connecting kind, the type of expecting with resin, printing ink auxiliary etc.In addition, in photochromatic printing ink composition, do not allow to add the stopping composition (as lime carbonate, titanium dioxide, zinc oxide, barium sulfate, kaolin etc.) that has strong opacifying power or influence the optic metachromatic effect of optically variable pigments, and these stopping composition, in the common ink composition, be the starting material of using always.Therefore, the composition of the composition of photochromatic printing ink composition and common ink composition is different.With ortho-water scraped without set-off intaglio ink composition is example, the alkyl aryl sulphonic acid ammonium that in the ink combination composition formula, adds some amount, or introduce water-soluble group (as sulfonic group etc.) in the part resin connecting material, then neutralize with ammonia, the liquid water-soluble resin that obtains does not all have influence to the use of ink composite, the physical and chemical performance and the aftertreatment technology of printing.The alkyl aryl sulphonic acid ammonium, or above-mentioned liquid water-soluble resin is acid very strong chemical substance.Wherein, the alkyl aryl sulphonic acid ammonium is to print the normal starting material that use in the paper money industry engraving intaglio printing ink composition at present.If it is joined in the photochromatic printing ink composition, (because the multi-layer colour-changing membrane structure of optically variable pigments is formed by stacking from level to level by metal, nonmetal, metal oxide, nonmetal oxide etc.) destroyed optically variable pigments to natural reflection of light, interference condition because the multi-layer colour-changing membrane structure of strongly-acid chemical substance corrosion optically variable pigments.Thereby influence the appearance color and the optic metachromatic effect of photochromatic printing ink composition.The optic metachromatic effect can be judged like this: printing goes respectively to observe from about an angle of 90 degrees and about 30 degree angles, can see two kinds of distinct colors with a kind of ink composite.
The manufacture method of photochromatic printing ink composition also is not only that conventional ink formulation method can realize.The manufacture method of common ink composition is: almost very close to each other between the forward and backward roller of three roller ink grinding mills and the central roll, by three rotating speeds that roller is different, the coarse particles porphyrize with in the ink composite that is to say, the fineness of printing ink is shut out.And photochromatic printing ink composition is different with the manufacture method of common ink composition.
The application facet of photochromatic printing ink composition is mainly used in banknote, check, credit card, various certificates etc.Is but what the application conditions of photochromatic printing ink composition? be suitable for which kind of printing process? especially the aftertreatment technology of various countries' carved gravure technology, engraving intaglio printing ink technology, carved gravure process and technology, dry offset technology etc. all belong to highly confidential state.Therefore, the present invention has formed characteristic from aspects such as the composition of photochromatic printing ink composition, manufacture method, application after having carried out a large amount of conscientious careful research work.
The object of the present invention is to provide photochromatic printing ink composition, wherein, volatile dry type photochromatic printing ink composition is mainly used in gravure printing, flexible letterpress, part screen printing; Oxypolymerization drying or light-cured type photochromatic printing ink composition are mainly used in lithography, relief printing plate (number printing, dry offset) printing, part screen printing, intaglio ink; This photochromatic printing ink composition is according to factors such as different mode of printings, printing type, print speed, ink transfer mode, a wiping version mode, aftertreatment technology requirement, environmental requirement, stock, environments for use, by different forming and proportioning.
Another object of the present invention provides the manufacture method of this photochromatic printing ink composition and the application of this photochromatic printing ink composition.
Photochromatic printing ink composition of the present invention is made up of optically variable pigments, connection material, printing ink auxiliary etc.In this composition, optically variable pigments accounts for the 1-60% of total weight; Connect the 1-95% that material accounts for total weight; The printing ink auxiliary accounts for the 0-20% of total weight.
The manufacture method of above-mentioned photochromatic printing ink composition is as follows:
Photochromatic printing ink composition of the present invention, other all raw material except that optically variable pigments should grind or other treatment process (as heat filtering etc.) in advance in advance, and fineness is reached below 15 microns.
For oxypolymerization drying and/or light-cured type photochromatic printing ink composition, can adopt following method manufacturing:
Manufacture method 1: whole starting material that photochromatic printing ink composition is required, pack in the stepless speed regulation high-speed stirring apparatus, start stirring, rotating speed is progressively upgraded to high speed by low speed.In low speed (the preferred 0-100 rev/min) stage, make solid materials fully wetting by liquid material, the height of rotating speed does not splash with material and is advisable.The rotating speed that then progressively raises preferably reaches 800-1200 rev/min and carries out high speed dispersion.Each optically variable pigments is wrapped up by ink adhesive.Then, adjust China ink, packing, standby.
The temperature of dispersion system is 0-100 ℃, and preferred temperature is controlled at 50 ± 5 ℃ or 60 ± 5 ℃.Improve dispersion temperature, help to improve dispersion efficiency, shorten jitter time.To non-volatile (as offset printing, or carved gravure, or number printing, or dry offset, or part silk-screen photochromatic printing ink composition) photochromatic printing ink composition, it also is feasible that the dispersion system temperature is controlled at 80 ± 5 ℃.
Manufacture method 2: low speed scatter stage in manufacture method 1, make solid materials by liquid material fully wetting after, also can disperse by three roller ink grinding mills.But it should be noted that the forward and backward roller of three roller ink grinding mills and the gap between the central roll can not be less than 15 microns.Generally be controlled at about 50 microns.Each optically variable pigments is wrapped up by ink adhesive.
To volatile dry type ink composite, can disperse with sand mill or ball mill.That is: after will all mixing of materials except that optically variable pigments, grind in advance.Fineness is reached below 20 microns, then optically variable pigments is added again and grind, each optically variable pigments is wrapped up by ink adhesive.Then, adjust China ink, packing, standby.
The temperature of dispersion system is controlled at 0-100 ℃, and preferred temperature is 25 ± 5 ℃, or 15 ± 5 ℃.The purpose that reduces dispersion temperature is to reduce the loss as far as possible, avoids topsoil.To the air drying ink composite, dispersion temperature can be brought up to 80 ± 5 ℃.
The optically variable pigments that is used for photochromatic printing ink composition of the present invention is the known all optically variable pigments of technical field of ink, and for example, USP 5279657; CN 1230577; CN 1152011; CN1236795; The optically variable pigments that production method described in WO 00/22049 document is produced or Guangdong Huizhou optical technology company limited produces, or be optical film fragment, or be multi-layer colour-changing film fragment, its fineness (here fineness is meant the mean diameter of optically variable pigments) is the 2-50 micron, wherein, the optically variable pigments that is used for volatile dry type photochromatic printing ink composition, its fineness are at the 2-30 micron, and preferred fineness is at the 10-20 micron; The optically variable pigments that is used for oxypolymerization drying and/or light-cured type photochromatic printing ink composition, its fineness are at the 2-50 micron, and preferred fineness is at the 2-25 micron.
Every pair of color of optically variable pigments determines that by the production technique of optically variable pigments for example: selecting different materials and film is that the number of plies can obtain by golden virescence; By the magenta virescence; Become magenta by green; Become blue look by green; Become optically variable pigments such as gold by magenta.
The thickness of optical film fragment is unit with the nanometer, and the trace thickness of printed matter is unit with the micron.Therefore, the thickness of optically variable pigments is not generally considered.In photochromatic printing ink composition, when considering the fineness of optically variable pigments, should note following some:
-offset printing or protruding seal photochromatic printing ink composition are the 2-15 micron to the fineness requirement of optically variable pigments.Preferred fineness is at the 5-10 micron.The photochromatic printing ink composition that fineness is made at the optically variable pigments of 2-5 micron is used for that trace is thin, the printing lines pattern of thin (line thickness is in 0.20 millimeter).The photochromatic printing ink composition that fineness is made at the optically variable pigments of 10-15 micron is used for that trace is thicker, the printing lines pattern of thick (line thickness is in 0.30 millimeter).Fineness does not almost have practical value less than 2 microns optically variable pigments.
The reticulate pattern density of version the line degree of depth and the silk screen version of-gravure should satisfy the fineness of optically variable pigments.Take pictures gravure and silk-screen photochromatic printing ink composition are the 2-30 micron to the fineness requirement of optically variable pigments, and preferred fineness is the 10-20 micron.The version line degree of depth that requires gravure is at the 30-70 micron.The reticulate pattern density of silk screen version can be selected half tone with reference to the version line degree of depth of gravure.
-intaglio ink photochromatic printing ink composition is the 2-50 micron to the fineness requirement of optically variable pigments, and preferred fineness is at the 5-25 micron.But during actually operating, the fineness of optically variable pigments should be too not thick.Because the proportion of optically variable pigments is bigger, fineness surpasses 50 microns, in printing process, is difficult to all fineness are transferred on the stock above 50 microns optically variable pigments by connecting material, and printing disadvantages such as scumming, heap roller appear in the result.
The connection material that the present invention uses, according to factors such as different mode of printings, printing type, print speed, ink transfer mode, a wiping version mode, aftertreatment technology requirement, environmental requirement, stock, environments for use, by different forming and proportioning, can be divided into two classes, that is:
The connection material that is used for oxypolymerization drying and/or light-cured type photochromatic printing ink composition by (A) resin, accounts for the 20-100% that connects the material gross weight; (B) solvent accounts for the 0-25% that connects the material gross weight; (C) vegetables oil accounts for the 1-80% that connects the material gross weight; (D) gummy oil accounts for the 0-35% that connects the material gross weight; (E) stand linseed oil accounts for the 0-20% that connects the material gross weight; (F) connect the material auxiliary, account for the 0-20% that connects the material gross weight and form.
The connection material that is used for volatile dry type photochromatic printing ink composition by (A) resin, accounts for the 5-60% that connects the material gross weight; (B) solvent accounts for the 40-95% that connects the material gross weight; (F) connect the material auxiliary, account for the 0-10% that connects the material gross weight and form.
As (A) resin in above-mentioned connection material (the connection material of oxypolymerization drying and/or light-cured type and the volatile dry type photochromatic printing ink composition) composition, can enumerate Synolac, unsaturated polyester resin, resol, rosin ester, polyamide resin, cellulose nitrate ester and fiber derivative, rubber resin, vinylformic acid and derivatives resin thereof, urethane resin, urea-formaldehyde resin, terpolycyantoamino-formaldehyde resin, Resins, epoxy and modified epoxy, polythylene resin etc., these resins can independent or multiple being used.
In above-mentioned (A) resin, concrete example as Synolac, can enumerate the Synolac of vegetables oil and/or rosin and derivative thereof and/or vinylbenzene and/or other synthetic resins and/or organosilicon and/or organic multiple isocyanate modification, further preferred, can enumerate the used polyvalent alcohol of these modified alkyd resins can be that dibasic alcohol is (as ethylene glycol, neopentyl glycol etc.), trivalent alcohol is (as glycerine, TriMethylolPropane(TMP) etc.), tetravalent alcohol (as tetramethylolmethane etc.) pentavalent alcohol (as Xylitol etc.) hexavalent alcohol is (as sorbyl alcohol, N.F,USP MANNITOL etc.), used acid can be phenylformic acid, p-tert-butyl benzoic acid, hexanodioic acid, sebacic acid, phthalic acid and acid anhydride thereof, m-phthalic acid, terephthalic acid, succsinic acid, maleic acid and acid anhydride thereof, FUMARIC ACID TECH GRADE, pyromellitic acid and acid anhydride thereof, tetrahydrochysene phthalic acid and acid anhydride thereof, hexahydrobenzene dioctyl phthalate and acid anhydride thereof, tower fatty acid oil etc.When these polyvalent alcohols and polyprotonic acid are used to produce modified alkyd resin, can independent or multiple being used.The Synolac of described modification for example has the product LV-800 of Tianjin Lao Te international corporation series Synolac, TERLON Synolac, DSM product URALAC S Synolac, PLUSS-STAUFER product P LUSOL L 72, ALFTALAT AR 680, HOECHST product A LFTALAT 707 D, the product WY-2600 of Beijing Wan Yang anti-counterfeiting technology limited liability company, WY-2700, WY-2800, WY-2900 Synolac etc.
Concrete example as unsaturated polyester resin, can enumerate commercially available epoxy acrylate, acrylic acid modified polyester resin, polyalcohol acrylate (as trimethylolpropane acrylates or pentaerythritol acrylate, EDIA etc.), vegetable oil acid and/or epoxy resin modification unsaturated polyester resin, liquid unsaturated polyester resin (as #143, #153, #154, #530 photosensitive resin etc.), these unsaturated polyester resins can be pieced together mixed the use separately or with various kinds of resin.
As the concrete example of resol, can enumerate rosin and derivative thereof and/or tung oil and/or eleostearic acid and/or C
6-C
17Fatty compounds modified phenolic resins, oil soluble pure phenolic resin with conjugated double bond are as the product WY-126 of Beijing Wan Yang anti-counterfeiting technology limited liability company, WY-132, WY-138, WY-216 modified phenolic resins, WY-111 pure phenolic resin etc.; The product ULTRA REZ of Tianjin Lao Te international corporation 10 series, 20 series, 30 series, 100 series, 210 series, 8000 series, 7000 series modified resol, KR-40.150, KR-40.081, KRUMBHAAR K-111 pure phenolic resin etc.
Above-mentioned modified phenolic resins can use separately, or multiple being used, and can also and use with various kinds of resin.
Object lesson as rosin ester, can enumerate commercially available rosin and derivative-glycerine thereof (or tetramethylolmethane) ester, maleic acid and anhydride modification rosin thereof and derivative-glycerine (or tetramethylolmethane) ester thereof, FUMARIC ACID TECH GRADE modified rosin and derivative-glycerine thereof (or tetramethylolmethane) ester, these rosin esters can independent or multiple being used, and also can and use with various kinds of resin.
As the concrete example of polyamide resin, can enumerate molecular weight less than 4000, select lower alcohol dissolvings such as ethanol for use; Molecular weight is greater than 4000, select the dissolving of mixed solvents such as toluene, dimethylbenzene, Virahol for use, as Tianjin the atropic 5320 ethanol-soluble type polyamide resins produced of Fine Chemical Co., Ltd, P-4512 ethanol-soluble type polyamide resin that Lao Te international corporation in Tianjin produces, P-1155 ethanol-soluble type polyamide resin, P-4584 ethanol-soluble type polyamide resin, the molten type polyamide resin of P-3370 benzene, P-1060 cosolvent lysotype polyamide resin, the molten type polyamide resin of P-1074 benzene etc. now.
After polyamide resin is dissolved in solvent, can be separately or piece together to mix with cellulose nitrate ester and fiber derivative, rosin ester, resol etc. and use.
As the concrete example of cellulose nitrate ester, can enumerate commercially available viscosity and be 1/16 second, 1/8 second, 1/4 second, 1/2 second, 1 second, the cellulose nitrate ester of 5-6 second etc., further preferred, can enumerate viscosity is cellulose nitrate ester of 1/4 second, 1/2 second etc.
Above-mentioned various cellulose nitrate esters generally do not use separately, but piece together mixed the use with Synolac, plant oil modified unsaturated polyester resin, resol, rosin ester, polyamide resin, vinylformic acid and derivatives resin, urethane resin etc.
Concrete example as fiber derivative, can enumerate the ethyl cellulose in the fiber derivative, further preferred, can enumerate oxyethyl group content in the ethyl cellulose in the product of 44-49% (the technical grade ethyl cellulose of producing as Shanghai reagent one factory etc.), it dissolves in most of organic solvents, or vegetables oil, or in the various kinds of resin, piece together mixed the use with long oil alkyd, plant oil modified unsaturated polyester resin, resol, rosin ester, polyamide resin, vinylformic acid and derivatives resin, urethane resin etc.
As the concrete example of rubber resin, can enumerate chlorinated rubber resin, further preferred, in the chlorinated rubber resin, viscosity is at the product below 25 seconds.Products C R-5, CR-20 as chlorinated rubber factory of Zhongyuan Oil Field chemical industry group, it is dissolved in aromatic hydrocarbons (as toluene, dimethylbenzene etc.), chlorinated hydrocarbon (as trieline etc.), ester class (as dioctyl sebacate etc.), ketone (as acetone etc.) solvent, or be dissolved in vegetables oil, or in the various kinds of resin, can use separately or also use with Synolac, resol, rosin ester, vinylformic acid and derivatives resin thereof, rosin and derivative thereof, terpine resin, clorafin, chlorodiphenyl, cumarone resin etc.
Also further preferred, cyclized rubber resin, it is dissolved in the aliphatic solvents, can also use separately or with various kinds of resin.
Concrete example as vinylformic acid and derivatives resin thereof, can enumerate known all printing ink vinylformic acid and derivatives resin thereof in the commercially available printing ink industry, further preferred, can enumerate the esterification products of known vinylformic acid and polyethers or diphenylol propane or Resins, epoxy etc. in the printing ink industry, vinylformic acid and derivative-styrol copolymer thereof (as Co., Ltd's product in the ROHM AND HAAS), dissolve in aromatic hydrocarbons (as toluene, dimethylbenzene etc.), the ester class is (as vinyl acetic monomer, N-BUTYL ACETATE etc.), alcohols is (as ethanol, Virahols etc.) vinylformic acid in equal solvent or their mixed solvent and derivatives resin thereof are (as 5388 alcohol ester type acrylic resins of Tianjin atropic Fine Chemical Co., Ltd's production now, 5320 ethanol-soluble type acrylic resins, the molten type acrylic resin of 5386 benzene etc.), the acrylic acid modified polyurethane resin, acrylic acid modified alkyd resin, acrylic acid modified unsaturated polyester resin etc., these vinylformic acid and derivatives resin thereof or acrylic acid modified resin can use separately, or piece together mixed the use with other resin.
Concrete example as urethane resin, can enumerate known all printing ink single component and hypergolic polyurethane resin in the commercially available printing ink industry, further preferred, can enumerate Synolac or the unsaturated polyester resin of organic diisocyanate modification or the siccative oil and the semi-drying oil of organic diisocyanate modification of organic diisocyanate modification, all belong to single component blocked polyurethane resin.
Concrete example as urea-formaldehyde resin and terpolycyantoamino-formaldehyde resin, can enumerate the terpolycyantoamino-formaldehyde resin of low degree of etherification, the terpolycyantoamino-formaldehyde resin of high degree of etherification, butanols or octanol or other fatty alcohol modified urea-formaldehyde resin, these products are dissolved in aromatic hydrocarbons, in the alcoholic solvent, use separately or with above-mentioned Synolac, resol, urethane resin, unsaturated polyester resin, assembly such as Resins, epoxy and modified epoxy is used (as the WY-121 of Beijing Wan Yang anti-counterfeiting technology limited liability company production, the WY-122 terpolycyantoamino-formaldehyde resin, the WY-181 urea-formaldehyde resin).
As the concrete example of Resins, epoxy, can enumerate molecular-weight average such as commercially available E-51, E-44, E-42, E-35, E-31, E-20, E-12, E-06, E-03 at the epoxy resin product below 3750.These Resins, epoxy can be used separately or with various kinds of resin.
As the concrete example of modified epoxy, can enumerate the esterification products (as the product WY-3000 linolenic acid epoxy ester wet goods of Beijing Wan Yang anti-counterfeiting technology limited liability company) of drying oil fatty acid or semi-drying oil lipid acid and Resins, epoxy.
Concrete example as polythylene resin, can enumerate commercially available low molecular weight polyethylene wax (viscosity-average molecular weight 1500-2000), chlorosulfonated polyethylene (molecular-weight average is about 20000), polyvinyl chloride (PVC) RESINS and supervinyi chloride resin, polyvinylidene dichloride and vinylchlorid vinylidene chloride copolymer, Vinyl Acetate Copolymer and vinylchlorid acetate ethylene copolymer, polyvinyl butyral acetal, low molecule vinylbenzene homopolymer (molecular weight is at 10000-14000), styrene alkyd resin, phenylethene modified maleficent acid resin, styrene acrylic copolymer etc., these resins are dissolved in aromatic hydrocarbons (as benzene, toluene, dimethylbenzene) solvent, ketones solvent, esters solvent, alcoholic solvent, or in their mixed solvent, can use separately, or piece together usefulness with various kinds of resin.
As (B) solvent in above-mentioned connection material (the connection material of oxypolymerization drying and/or light-cured type and the volatile dry type photochromatic printing ink composition) composition, can enumerate ethanol, n-propyl alcohol, Virahol, phenylethyl alcohol, butanols, ethylene glycol, polyoxyethylene glycol, 1, the 2-propylene glycol, 1, the 2-butyleneglycol, glycol ether, diethylene glycol ether, ethyl acetate, n-propyl acetate, isopropyl acetate, butylacetate, phthalic acid dibutyl ester, dioctyl phthalate, tributyl phosphate, acetone, isopropyl acetone, hexone, pimelinketone, butanone, toluene, dimethylbenzene, silicone oil, aliphatic solvents, high-boiling point kerosene, the #200 solvent oil, the #210 Dormant oils, water etc.These solvents can independent or multiple being used.
(C) vegetables oil as in above-mentioned connection material (the connection material of oxypolymerization drying and/or light-cured type and the volatile dry type photochromatic printing ink composition) composition can exemplify commercially available oleum lini, tung oil, synourin oil, perilla oil, Chinese catalpa oil, OITICICA oil, soya-bean oil, Oleum Helianthi, wine stone oil, Viscotrol C, the tower fatty acid oil, the above-mentioned vegetables oil of modification such as vinylbenzene or maleic acid and acid anhydride or FUMARIC ACID TECH GRADE, the stand oil that above-mentioned vegetables oil obtains through high temperature refining is (as the #4 stand linseed oil, the #6 stand linseed oil, boiled wood oil etc.), in the above-mentioned vegetable oil acid one or more.
(D) gummy oil as in above-mentioned connection material (the connection material of oxypolymerization drying and/or light-cured type and the volatile dry type photochromatic printing ink composition) composition can exemplify commercially available WY-831 gummy oil (Beijing Wan Yang anti-counterfeiting technology limited liability company product).
As (E) stand linseed oil in above-mentioned connection material (the connection material of oxypolymerization drying and/or light-cured type and the volatile dry type photochromatic printing ink composition) composition, can enumerate high-boiling point kerosene, #210 Dormant oils, #200 solvent oil, glycol ether, diethylene glycol ether, phthalic acid two fourths (or two sufferings) ester, tributyl phosphate etc., these stand linseed oil, can independent or multiple being used, in connecting material, be mainly used to adjust the viscosity that connects material.
In the solventless ink composition, stand linseed oil can be selected #6 stand linseed oil in the vegetables oil, boiled wood oil, soya-bean oil etc. for use.
Connect the material auxiliary as (F) in above-mentioned connection material (the connection material of oxypolymerization drying and/or light-cured type and the volatile dry type photochromatic printing ink composition) composition, can enumerate UV light absorber (as st-yrax dme, michaelis ketone, benzophenone etc.), connect material or printing ink stablizer (as low-molecular-weight epoxy resin etc.), oxidation inhibitor (as BHT, Resorcinol etc.), wax, silicone oil, fatty amide (as amine hydroxybenzene, stearylamide etc.) etc., these connect material auxiliarys can independent or multiple being used.
Printing ink auxiliary as the present invention's use, siccative, slow dried agent be can enumerate, stick, wax, tensio-active agent, UV light absorber (as st-yrax dme, michaelis ketone, benzophenone etc.), thinner etc. removed, these printing ink auxiliarys can independent or multiple being used.
Concrete example as siccative, can enumerate the known organic acid metal-salt of printing ink industry, the organic acid cobalt that acid, naphthenic acid, sad, capric acid etc. are saturated as how, manganese, cerium, vanadium, lanthanum, iron, lithium, lead, zirconium, aluminium, calcium, zinc salt etc. also can be enumerated the known manganese borate of printing ink industry.
As preferably, can enumerate wherein how acid or sad cobalt, manganese, zirconium, cerium, lead salt, manganese borate.
Further preferred, can enumerate wherein sad cobalt, manganese, zirconates (as the product of Beijing Wan Yang anti-counterfeiting technology limited liability company).
As the slow concrete example of doing agent, can enumerate the known phenol of printing ink industry, oxime, amine, hydrazine, acid etc.
As preferably, can enumerate wherein phenol, oxime (as HBT, Diacetylmonoxime, butyraldehyde oxime etc.).
Concrete example as wax, can enumerate printing ink industry known natural wax (as carnauba wax, gama wax, esparto wax, ouricury wax, Japan tallow, fir wax, palm wax, beeswax, insect wax, wool wax, paraffin, Microcrystalline Wax, montanin wax, ore deposit ceresine etc.), synthetic wax (as stearic acid and derivative thereof or they and pure esterification products, stearyl alcohol, polyethylene wax etc.), modified waxes (as oxidized polyethlene wax, chlorinated wax, polymeric fatty family acid amides, aluminum foil stearate, Vaseline etc.).
Synthetic wax also comprise other molecular weight greater than the esterification products of 293 polymer fatty acid and alcohol and other molecular weight greater than 293 polymeric fatty alcohol.
Modified waxes also comprises other natural wax or synthetic wax, the wax that obtains after chemical treatment (as purification, oxidation, chlorination etc.).
Above-mentioned wax can independent or multiple being used.Two or more waxes are used, and also are blended wax.
As the concrete example of tensio-active agent, can enumerate the known commercially available various aniorfic surfactant of printing ink industry (as the pH value at the alkylaryl sulphonate of 7-8, sulfonated castor oil hydrochlorate etc.), various nonionic surface active agent (as alkylbenzene Soxylat A 25-7, polypropylene glycol etc.), various cationic surfactant (as long-chain fat amine etc.), various zwitterionics (as the sweet soda acid of quaternary ammonium, glycine derivative etc.).
Above-mentioned tensio-active agent when being used for carved gravure water and wiping not the set-off typography, also must satisfy the aftertreatment technology requirement.
Concrete example as thinner, can enumerate the known stand linseed oil of printing ink industry, high-boiling point kerosene, #200 solvent oil, #210 Dormant oils, no aromatic hydrocarbons Dormant oils, Diethylene Glycol ethers, gylcol ether, 1,2-propylene glycol, phthalic acid ester etc., these thinners can use separately also and can multiplely be used.
As the concrete example of removing stick, can enumerate commercially available 8043 and remove stick (Tianjin printing ink company product).
For example, photochromatic printing ink composition of the present invention is further described below:
---the offset printing photochromatic printing ink composition:
Prescription:
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | ||
| Numbering | Title material | wt％ | wt％ | wt％ | wt％ | wt％ | wt％ | wt％ | wt％ |
| 1 | Optically variable pigments | 42.50 | 30.00 | 42.50 | 18.10 | 33.50 | 43.00 | 45.00 | 45.00 |
| 2 | Synolac a | 30.00 | - | - | 52.30 | - | - | - | - |
| Synolac b | 5.00 | - | 5.00 | 7.30 | 3.50 | - | - | - | |
| Synolac c | - | - | - | - | 40.56 | - | - | - | |
| 3 | Urethane resin | - | - | 30.00 | - | - | - | - | - |
| 4 | Unsaturated polyester resin | - | - | - | - | - | 35.00 | 35.00 | - |
| Viscoat 295 | - | - | - | - | - | 15.00 | 13.00 | - | |
| 5 | Modified epoxy | - | - | - | - | - | - | - | 10.00 |
| 6 | Modified unsaturated polyester resin | - | - | - | - | - | - | - | 21.00 |
| 7 | Phenolic resin connection material a | 5.00 | 7.70 | 5.00 | - | - | - | - | - |
| Phenolic resin connection material b | - | 42.70 | - | - | 3.50 | - | - | - | |
| Phenolic resin connection material c | - | - | - | - | - | - | - | 8.50 | |
| 8 | Gummy oil | 15.00 | 15.40 | 14.00 | 18.20 | 10.49 | - | - | 10.00 |
| 9 | Micro mist wax | 1.00 | 1.50 | 1.00 | 2.30 | 0.70 | 1.00 | 1.00 | 1.00 |
| 10 | 404 siccative | 1.50 | - | - | - | - | - | - | - |
| 11 | Composite drying agent | - | 2.00 | 2.00 | 1.80 | 1.40 | - | - | 2.00 |
| 12 | Phthalic acid dibutyl ester | - | - | 0.50 | - | 0.70 | - | - | 2.00 |
| 13 | Oxidation inhibitor | - | 0.70 | - | - | - | - | - | - |
| 14 | Diacetylmonoxime | - | - | - | - | - | - | - | 0.50 |
| 15 | Benzophenone | - | - | - | - | - | 4.00 | 4.00 | - |
| 16 | Michaelis ketone | - | - | - | - | - | 2.00 | 2.00 | - |
| 17 | The #6 stand linseed oil | - | - | - | - | 5.60 | - | - | - |
| Add up to | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
Manufacturing process: above-mentioned photochromatic printing ink composition, other all raw material except that optically variable pigments should grind or other treatment process (as heat filtering etc.) in advance in advance, and fineness is reached below 15 microns.Then disperse with following method:
(1). whole starting material that photochromatic printing ink composition is required, pack in the stepless speed regulation high-speed stirring apparatus, start stirring, rotating speed progressively is elevated to 60 rev/mins by 0 rev/min, makes solid materials fully wetting by liquid material; Also can adopt other ordinary method, make solid materials fully wetting by liquid material;
(2). disperse by three roller ink grinding mills, the forward and backward roller and the gap between the central roll of three roller ink grinding mills can not preferably be controlled at about 50 microns less than 15 microns, and each optically variable pigments is wrapped up by ink adhesive;
Then adjust China ink.
The manufacturing process of oxypolymerization drying and/or light-cured type photochromatic printing ink composition can also be disperseed with following method: promptly
Whole starting material that photochromatic printing ink composition is required are packed in the stepless speed regulation high-speed stirring apparatus in proportion, start stirring, and rotating speed progressively is elevated to 60 rev/mins by 0 rev/min, improve the speed of rotating speed, do not splash with material and exceed.After treating that solid materials is fully moistened temperature by liquid material, progressively raise turn up 1000-1100 rev/min and carry out high speed dispersion, temperature is controlled at 60 ± 5 ℃, and each optically variable pigments is wrapped up by ink adhesive, then, adjusts China ink.
The printing ink index:
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | |
| Degree of mobilization mm/25 ℃ | ??35.5 | ??32.5 | ??29.5 | ??35.5 | ??34.5 | ???31.5 | ??34.0 | ??34.0 |
| Fineness≤ | ??15 | ??15 | ??15 | ??15 | ??15 | ???15 | ??15 | ??15 |
| Viscosity pa.s/40 ℃ of HAAKE | ??11.0 | ??11.6 | ??13.0 | ??11.0 | ??11.0 | ???12.0 | ??13.0 | ??11.5 |
In routine 1-8, used starting material are as follows:
Optically variable pigments: RGN 10 product red stains are green, Guangdong Huizhou optical technology company limited product.
Synolac a:WY-2600 Synolac, viscosity 14-16pa.s/40 ℃ of HAAKE, acid number be less than 15mgKOH/g, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Alkyd resin b:WY-2700 Synolac, viscosity 3-5pa.s/40 ℃ of HAAKE, acid number be less than 10mgKOH/g, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Synolac c:WY-2800 Synolac, viscosity 14-16pa.s/40 ℃ of HAAKE, acid number be less than 15mgKOH/g, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Urethane resin: WY-2900 urethane resin, viscosity 14-16pa.s/40 ℃ of HAAKE, acid number be less than 15mgKOH/g, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Unsaturated polyester resin: the WY-4000 epoxy acrylic connects material, and viscosity 15-17pa.s/40 ℃ of HAAKE, acid number be less than 15mgKOH/g, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Viscoat 295: Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Modified epoxy: WY-3000 linolenic acid epoxy ester oil connects material, and viscosity 2-3pa.s/40 ℃ of HAAKE, acid number be less than 15mgKOH/g, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Modified unsaturated polyester resin: WY-5000 modified unsaturated polyester resin, viscosity 14-16pa.s/40 ℃ of HAAKE, acid number be less than 15mgKOH/g, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Phenolic resin connection material a:WY-1380 resol oil connects material, viscosity 3-4pa.s/40 ℃ of HAAKE, WY-1380 resol oil connects material by WY-138 modified phenolic resins (160.5 ℃ of softening temperatures, viscosity 2 ± 0.5pa.s/40 ℃ HAAKE, acid number is not more than 25mgKOH/g, Beijing Wan Yang anti-counterfeiting technology limited liability company product) and oleum lini in 35: 65 mixing forming of ratio, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Phenolic resin connection material b:WY-1381 resol oil connects material, viscosity 14-16pa.s/40 ℃ of HAAKE, WY-1381 resol oil connects material, by the WY-138 modified phenolic resins (with phenolic resin connection material a), tung oil, oleum lini is in 40: 40: 20 mixing forming of ratio, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Phenolic resin connection material c:WY-1382 resol oil connects material, viscosity 14-16pa.s/40 ℃ of HAAKE, WY-1382 resol oil connects material, by the WY-138 modified phenolic resins (with phenolic resin connection material a), tung oil, boiled wood oil is in 40: 40: 20 mixing forming of ratio, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Gummy oil: WY-831 gummy oil, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Micro mist wax: AMWAX-12, Tianjin Lao Te international corporation product.
404 siccative: the emerging printing ink of Tianjin cloud company limited product.
Composite drying agent: wherein used cobalt octoate (cobalt contents 10-11.5%) accounts for 15.20% of composite drying agent gross weight; Manganese octoate (manganese content 9.5-10.5%) accounts for 20.00% of composite drying agent gross weight; Zirconium caprylate (zirconium content 30-32%) accounts for 31.70% of composite drying agent gross weight; Wax accounts for 4.30% of composite drying agent gross weight; Lime carbonate accounts for 28.80% of composite drying agent gross weight.Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Slow agent, Beijing Wan Yang anti-counterfeiting technology limited liability company product done of oxidation inhibitor: WY-1001.
By the photochromatic printing ink composition that routine 1-8 obtains, printing should meet the following conditions:
A. figure line design :-photochromatic printing ink composition is applied to not disturb the zone of optics color changeable effect;
-avoid the zone that folds, hold;
B. the figure line is made :-pattern area is as the criterion clearly to recognize the optic metachromatic effect;
-version line width is more than 0.20 millimeter;
In-the pattern, the area of using photochromatic printing ink composition is not less than 80%;
C. printing condition: common flexographic ink composition is identical with using.
After satisfying above-mentioned primary condition, the offset printing photochromatic printing ink composition is by normal typography, on stock, print a kind of ink composite that does not disturb the optics color changeable effect earlier, chromatography photochromatic printing ink composition more then, the printing that obtains is from about 90 ° of angles and about 30 ° of angles, observe respectively, can see distinct two kinds of colors, that is: the product red stain is green, and clear patterns, accurate, the every materialization fastness of chromatography all are better than the carved gravure photochromatic printing ink composition.In the pattern, the area of using photochromatic printing ink composition is not less than 80%, and the fraction of coverage of optically variable pigments in the actual print area is more than 40%, and printing cost is lower than the cost of carved gravure.
Example 3 so need the chromatography both sides, just can be seen tangible optic metachromatic effect because optically variable pigments content is low.
If the offset printing photochromatic printing ink composition, by normal typography, directly (as paper product) print on stock, the printing that obtains, and the optic metachromatic effect is poor.The optic metachromatic effect of undertaking the printing of on White Board is more effective than the optic metachromatic of undertaking the printing of on offset paper.This is because due to the offset paper air spots.
Represent with photochromatic printing ink composition is just typical by the offset printing that routine 1-8 provides.Connection material wherein can be replaced by other above-mentioned resin binder as required.Aspect the resin binder selection, each ink technology worker's custom has nothing in common with each other.Can select one or more above-mentioned resin binders and printing ink auxiliary to be used.This is because print the type difference, and the environment for use difference is also different with the requirement of photochromatic printing ink composition to offset printing.In order to adapt to high speed printing, generally speaking, guaranteeing under the situation that printing is carried out smoothly, offset printing with photochromatic printing ink composition do as far as possible thick, it is bigger that viscosity is done as far as possible, increasing value of tack is smaller as far as possible.Because optically variable pigments proportion is bigger, printing ink is thick and viscosity is big, helps the transmission of photochromatic printing ink composition in printing process.
The photochromatic printing ink composition that is provided by routine 1-8 is used for offset printing, and trace is very thin, so in formulating of recipe, under the situation of the printability that guarantees photochromatic printing ink composition, answer the ratio of raising optically variable pigments as much as possible.
Add micro mist wax among the example 1-8 and help to improve the toughness of ink film, smooth property, rub resistance.
The photochromatic printing ink composition that is provided by routine 1-8 also is fit to dry offset (plano-convex version) machine printing.
---the gravure photochromatic printing ink composition of taking pictures
Prescription:
| Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 | ||
| Numbering | Title material | wt％ | wt％ | wt％ | wt％ | wt％ | wt％ |
| ??1 | Optically variable pigments | 15.00 | 15.00 | 10.00 | 10.00 | 15.00 | 12.50 |
| ??2 | Resol | 31.00 | - | - | - | - | 10.00 |
| ??3 | Rosin ester | - | 35.00 | - | - | - | - |
| ??4 | Polyamide resin | - | - | 10.00 | - | - | - |
| ??5 | The cellulose nitrate ester | - | - | 8.00 | 10.00 | 8.00 | - |
| ??6 | Fiber derivative | - | - | - | - | - | 1.50 |
| ??7 | Rubber resin | - | - | - | - | - | 10.50 |
| ??8 | Vinylformic acid and derivatives resin a thereof | - | - | - | 59.00 | - | - |
| ??9 | Vinylformic acid and derivatives resin b thereof | - | - | - | - | 57.00 | - |
| ??10 | Ethanol | - | - | - | 5.00 | - | - |
| ??11 | Virahol | - | - | 25.00 | 5.00 | - | - |
| ??12 | Ethyl acetate | - | - | - | 5.00 | - | - |
| ??13 | Butylacetate | - | - | - | 5.00 | - | - |
| ??14 | Toluene | - | - | 10.00 | - | - | - |
| ??15 | Dimethylbenzene | - | - | - | - | 19.000 | 42.30 |
| ??16 | Aliphatic solvents | 51.40 | 47.50 | - | - | - | - |
| ??17 | N-propyl alcohol | - | - | 25.00 | - | - | - |
| ??18 | Isopropyl acetate | - | - | 10.00 | - | - | - |
| ??19 | The #200 solvent oil | - | - | - | - | - | 20.00 |
| ??20 | Polyethylene wax | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 3.00 |
| ??21 | Fatty amide | - | - | 1.00 | - | - | - |
| ??22 | Resins, epoxy | - | - | - | - | - | 0.20 |
| ??23 | Aluminum stearate | 1.00 | 1.00 | - | - | - | - |
| Add up to | 100.00 | 100.0 | 100.00 | 100.00 | 100.00 | 100.00 |
Manufacturing process:
(solvent stays 10% to all materials that will be except that optically variable pigments, adjust viscosity with) pack into sand mill or ball mill, grind in advance, the temperature of dispersion system is controlled at 25 ± 5 ℃, after making fineness reach below 20 microns, optically variable pigments is added grinding again, each optically variable pigments is wrapped up by ink adhesive.Before discharging, viscosimetric is adjusted according to the viscosity size, makes viscosity at acceptability limit, and packing is standby.
The printing ink index: fineness is less than 20 microns; Viscosity is ℃ (being coated with 4 flow cups) in 30-80 second/25.
In routine 9-14, used starting material are as follows:
Optically variable pigments: RGB 20 product red stains are green, Guangdong Huizhou optical technology company limited product.
Resol: the WY-138 modified phenolic resins, 160.5 ℃ of softening temperatures, viscosity 2 ± 0.5pa.s/40 ℃ HAAKE, acid number is not more than 25mgKOH/g, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Rosin ester: the WY-108 rosin ester, 165 ℃ of softening temperatures, acid number is not more than 25mgKOH/g, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Polyamide resin: AZ-2420 ethanol-soluble type polyamide resin, the Tianjin atropic is Fine Chemical Co., Ltd's product now.
Cellulose nitrate ester: viscosity 1/2 second, Hengshui orient chemical company limited product.
Fiber derivative: oxyethyl group content is at the technical grade ethyl cellulose of 44-49%, Guangzhou Chemical Reagent Factory product.
Rubber resin: CR-20 chlorinated rubber resin, chlorinated rubber factory of Zhongyuan Oil Field chemical industry group product.
Vinylformic acid and derivatives resin a:AZ-5388 alcohol-ester thereof the molten type acrylic resin soln of holding concurrently, the Tianjin atropic is Fine Chemical Co., Ltd's product now.
The molten type acrylic resin soln of vinylformic acid and derivatives resin b:AZ-5386 benzene thereof, the Tianjin atropic is Fine Chemical Co., Ltd's product now.
Polyethylene wax: low molecular weight polyethylene wax LPE-3 (F), Fine Chemical Factory of Beijing University of Chemical Technology's product.
Aliphatic solvents: #120 solvent oil, Beijing Yanshan Petrochemical Company's product.
Fatty amide: stearylamide, Wuhan ammonia alkali factory product.
The resulting gravure photochromatic printing ink composition of taking pictures of example 9-14, printing should meet the following conditions:
A. figure line design :-photochromatic printing ink composition is applied to not disturb the zone of optics color changeable effect;
-avoid the zone that folds, hold;
B. the figure line is made :-pattern area is as the criterion clearly to recognize the optic metachromatic effect;
-version line degree of depth 30-70 micron;
-version line width 0.20-0.3 millimeter;
In-the pattern, the area of using photochromatic printing ink composition is not less than 80%;
-version line is as far as possible perpendicular to wiping the version direction.
C. printing condition: the common gravure of taking pictures is identical with ink composite with using.
After satisfying above-mentioned primary condition, the gravure photochromatic printing ink composition of taking pictures, by normal typography, directly print on stock, the printing that obtains is from about 90 ° of angles and about 30 ° of angles, observe respectively, can see distinct two kinds of colors, that is: the product red stain is green, and clear patterns, every materialization fastness all are better than the carved gravure photochromatic printing ink composition.In the pattern, the area of using photochromatic printing ink composition is not less than 80%, and the fraction of coverage of optically variable pigments in the actual print area is more than 40%, and printing cost is lower than the cost of carved gravure.
With in the photochromatic printing ink composition, add aluminum stearate at the gravure of taking pictures, can improve the stability of photochromatic printing ink composition, can prevent precipitation.The add-on of aluminum stearate in prescription can not be too many, and printing ink can thickening when too many.
Based on routine 9-14, adjust the rheological of printing ink, just can obtain flexible relief printing plate light sensitive ink composition.Because these two kinds of printing ink all belong to liquid ink.Aspect complete processing, the specification of quality aspect is more approaching, so no longer discuss here.
The gravure photochromatic printing ink composition of taking pictures that provides by routine 9-14, or on the basis of routine 9-14, the flexible convex seal photochromatic printing ink composition that obtains, all be typical example, the gravure that can be used for taking pictures has a large amount in variety with the material (comprising various resins and solvent) that is connected of flexible convex seal with photochromatic printing ink composition.In real work, should formulate the concrete prescription of photochromatic printing ink composition according to different printing types, print speed, different stocks, different environments for use.That is to say and select different connection material resin and solvent.Solvent is good to most of dissolving resin for aromatic hydrocarbons (as toluene, dimethylbenzene), but smell is big, and toxicity is big.Alcohols, ester class, water etc. are made solvent, and toxicity is little, use wide.At present, senior printed matter major part such as tobacco package, wine lebal is all used ethanol-soluble type polyamide resin, the molten type polyamide resin of benzene, mixed solvent lysotype polyamide resin, cellulose nitrate ester, Mierocrystalline cellulose and derivative, ethanol-soluble type acrylic resin, alcohol ester type acrylic resin and ethanol, Virahol, n-propyl alcohol, ethyl acetate, isopropyl acetate, n-propyl acetate, butylacetate, toluene, dimethylbenzene etc.When making these two kinds of photochromatic printing ink compositions, the gravure photochromatic printing ink composition viscosity controller of taking pictures is in 30-80 second/25 ℃, flexible convex seal photochromatic printing ink composition viscosity controller in 80-150 second/25 ℃ (being coated with 4 flow cups) scope better, reserve the leeway of adjusting photochromatic printing ink composition viscosity for the printing board.But the use viscosity of the common ink composition that should use a little more than these two kinds of mode of printings of the use viscosity of the photochromatic printing ink composition used of these two kinds of mode of printings in actual use.Help improving the optic metachromatic effect of photochromatic printing ink composition like this.
---the number photochromatic printing ink composition
Prescription:
| Example 15 | Example 16 | Example 17 | ||
| Numbering | Title material | ????wt％ | ????wt％ | ????wt％ |
| ????1 | Optically variable pigments | ????40.00 | ????40.00 | ????35.00 |
| ????2 | Synolac a | ????20.00 | ????- | ????20.00 |
| ????3 | Synolac b | ????20.00 | ????24.00 | ????25.00 |
| ????4 | Resol oil connects material a | ????15.00 | ????- | ????- |
| ????5 | Resol oil connects material b | ????- | ????20.00 | ????- |
| ????6 | Modified epoxy | ????- | ????10.50 | ????14.50 |
| ????7 | 404 siccative | ????0.50 | ????- | ????- |
| ????8 | Composite drying agent | ????- | ????1.00 | ????1.00 |
| ????9 | Oxidation inhibitor | ????0.50 | ????- | ????- |
| ???10 | Diacetylmonoxime | ????- | ????0.50 | ????0.50 |
| ???11 | Wax mixture | ????4.00 | ????3.00 | ????3.00 |
| ???12 | Phthalic acid dibutyl ester | ????- | ????1.00 | ????1.00 |
| Add up to | ????100.00 | ????100.00 | ????100.00 |
Manufacturing process:
With the offset printing photochromatic printing ink composition.
The printing ink index:
| Example 15 | Example 16 | Example 17 | |
| Viscosity pa.s/40 ℃ of HAAKE | ????7.7 | ????9.0 | ????7.2 |
| Degree of mobilization mm/25 ℃ | ????25 | ????24.5 | ????26.0 |
In routine 15-17, used starting material are as follows:
Optically variable pigments: YSB 30 gold medals turn green, Guangdong Huizhou optical technology company limited product.
Synolac a: with the offset printing photochromatic printing ink composition.
Synolac b: with the offset printing photochromatic printing ink composition.
Resol oil connects material a: with the offset printing photochromatic printing ink composition.
Resol oil connects material b: with the offset printing photochromatic printing ink composition.
Modified epoxy: with the offset printing photochromatic printing ink composition.
404 siccative, composite drying agent, oxidation inhibitor: with the offset printing photochromatic printing ink composition.
Wax mixture: WY-1203 number wax mixture, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
By the photochromatic printing ink composition that routine 15-17 obtains, printing should meet the following conditions:
A. figure line design :-photochromatic printing ink composition is applied to not disturb the zone of optics color changeable effect;
-avoid the zone that folds, hold;
B. the figure line is made :-pattern area is as the criterion clearly to recognize the optic metachromatic effect;
-version line width is more than 0.20 millimeter;
In-the pattern, the area of using photochromatic printing ink composition is not less than 80%;
C. printing condition: common letterpress printing ink composition is identical with using.
After satisfying above-mentioned primary condition, protruding seal photochromatic printing ink composition, by normal typography, directly on stock, print, though can obtain optic metachromatic printing to a certain degree, but not as before the printing photochromatic printing ink composition, earlier the concentration of the solid colour of a kind of appearance color of seal and photochromatic printing ink composition is than the common ink at the end or print a kind of colourless printing ink (being used to remedy the defective of paper surface injustice), chromatography photochromatic printing ink composition more then, the printing that obtains, from about 90 ° of angles and about 30 ° of angles, observe respectively, can see distinct two kinds of colors, that is: gold turns green, clear patterns, chromatography is accurate, every materialization fastness all is better than the carved gravure photochromatic printing ink composition.In the pattern, the area of using photochromatic printing ink composition is not less than 80%, and the fraction of coverage of optically variable pigments in the actual print area is more than 40%, and printing cost is lower than the cost of carved gravure.More effective in printing on the White Board than the optic metachromatic that on offset paper, prints the printing that obtains.
The number photochromatic printing ink composition is typical case's representative of protruding seal.According to conditions such as number type, print speeds, the resin among the routine 15-17 is replaceable to be other above-mentioned resin.
---the silk-screen photochromatic printing ink composition
Prescription:
| Example 18 | Example 19 | Example 20 | Example 21 | Example 22 | ||
| Numbering | Title material | wt％ | wt％ | wt％ | wt％ | wt％ |
| ??1 | Optically variable pigments | 12.50 | 20.00 | 25.00 | 15.00 | 20.00 |
| ??2 | Polyamide resin | 28.00 | - | - | - | - |
| ??3 | The E-42 epoxy resin solution | - | 40.00 | - | - | - |
| ??4 | Viscoat 295 | - | - | 12.00 | - | - |
| ??5 | Unsaturated polyester resin | - | - | 56.90 | - | - |
| ??6 | Acrylic resin (1) | - | - | - | 60.00 | - |
| ??7 | Acrylic resin (2) | - | - | - | - | 60.00 |
| ??8 | Virahol | 26.00 | - | - | - | 10.00 |
| ??9 | Butanols | 9.50 | - | - | - | - |
| ?10 | Ethyl acetate | - | - | - | - | 10.00 |
| ?11 | Dimethylbenzene | 20.00 | - | - | 25.00 | - |
| ?12 | Butylacetate | 4.00 | - | - | - | - |
| ?13 | Mixed solvent | - | 40.00 | - | - | - |
| ?14 | Benzophenone | - | - | 4.00 | - | - |
| ?15 | Michaelis ketone | - | - | 2.00 | - | - |
| ?16 | Resorcinol | - | - | 0.10 | - | - |
| Add up to | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
Manufacturing process:
To oxypolymerization drying or light-cured type silk-screen with the manufacturing process of photochromatic printing ink composition with the offset printing photochromatic printing ink composition.
To volatile dry type silk-screen with the manufacturing process of photochromatic printing ink composition with taking pictures the gravure photochromatic printing ink composition.
The printing ink index: viscosity is at 50-100cp/25 ℃, and preferred viscosities is at 80 ± 5cp/25 ℃ (Emila viscometer).
In routine 18-22, used starting material are as follows:
Optically variable pigments: RGB 20 product red stains are green, Guangdong Huizhou optical technology company limited product.
Polyamide resin: with taking pictures the gravure photochromatic printing ink composition.
E-42 epoxy resin solution: WY-6000 E-42 epoxy resin solution, the supply of Beijing Wan Yang anti-counterfeiting technology limited liability company.
Viscoat 295: with the offset printing photochromatic printing ink composition.
Unsaturated polyester resin: with the offset printing photochromatic printing ink composition.
Acrylic resin (1): the molten type acrylic resin soln of AZ-5386 benzene, the Tianjin atropic is Fine Chemical Co., Ltd's product now.
Acrylic resin (2): AZ-5388 alcohol-ester molten type acrylic resin soln of holding concurrently, the Tianjin atropic is Fine Chemical Co., Ltd's product now.
Mixed solvent: toluene: ethanol=1: 1.
The silk-screen photochromatic printing ink composition that example 18-22 provides, printing should meet the following conditions:
A. figure line design :-photochromatic printing ink composition is applied to not disturb the zone of optics color changeable effect;
-avoid the zone that folds, hold;
B. the figure line is made :-pattern area is as the criterion clearly to recognize the optic metachromatic effect;
-version line width is more than 0.20 millimeter;
In-the pattern, the area of using photochromatic printing ink composition is not less than 80%;
C. printing condition: common ink for screen printing composition is identical with using.
After satisfying above-mentioned primary condition, the silk-screen photochromatic printing ink composition, by normal typography, directly print on stock, the printing that obtains is from about 90 ° of angles and about 30 ° of angles, observe respectively, can see distinct two kinds of colors, that is: the product red stain is green, and clear patterns, every materialization fastness all are better than the carved gravure photochromatic printing ink composition.In the pattern, the area of using photochromatic printing ink composition is not less than 80%, and the fraction of coverage of optically variable pigments in the actual print area is more than 40%, and printing cost is lower than the cost of carved gravure.
Example 18 is applicable to silk-screen plastics film printing; Example 19 is applicable to silk-screen glass printing; Example 20 is applicable to the demanding printing of silk-screen sticking power; Example 21-22 is applicable to the wider of silk-screen.Ink for screen printing composition various in style, purposes is different.Example 18-22 is a typical example.Can be in real work according to purposes, printed substrates etc. are selected different resins and solvent for use.
Consider silk-screen with the China ink of photochromatic printing ink composition, the same with the China ink of common ink for screen printing composition should have thick, pine and lack, do not glue, be the cheese shape.In case of necessity, add an amount of aerosil at silk-screen in photochromatic printing ink composition and adjust China ink.The printing board can add proper amount of solvent as required or stand linseed oil carries out the viscosity adjustment.In a word, with the printing clear patterns, operation is as the criterion smoothly.
---the carved gravure photochromatic printing ink composition
Prescription:
| Example 23 | Example 24 | Example 25 | Example 26 | Example 27 | Example 28 | Example 29 | Example 30 | ||
| Numbering | Title material | wt％ | wt％ | wt％ | wt％ | wt％ | wt％ | wt％ | wt％ |
| ??1 | Optically variable pigments | 35.00 | 20.00 | 35.00 | 35.00 | 35.00 | 35.00 | 35.00 | 35.00 |
| ??2 | Resol (1) | 7.00 | 7.00 | 7.00 | 7.00 | - | - | 7.00 | 7.00 |
| Resol (2) | 30.00 | - | - | - | - | - | 30.00 | 13.00 | |
| Resol (3) | - | 30.00 | - | - | - | - | - | - | |
| Resol (4) | - | - | 30.00 | - | - | - | - | - | |
| Resol (5) | - | - | - | 30.00 | - | - | - | - | |
| Resol (6) | - | - | - | - | 30.00 | 20.00 | - | 30.00 | |
| Resol (7) | - | - | - | - | - | 30.00 | - | - | |
| ??3 | Synolac | 13.00 | - | 13.00 | 13.00 | 13.00 | - | 4.00 | - |
| ??4 | Urethane resin | - | 18.00 | - | - | 6.50 | - | 9.00 | - |
| ??5 | Blended wax | 5.00 | 5.00 | 5.00 | 5.00 | 5.00 | 5.00 | 5.00 | 5.00 |
| ??6 | Tensio-active agent | 6.00 | 7.00 | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 |
| ??7 | Composite drying agent | 2.00 | 1.50 | 2.00 | 2.00 | 1.50 | 1.50 | 1.50 | 1.50 |
| ??8 | Solvent | 2.00 | 11.50 | 2.00 | 2.00 | - | - | 1.00 | - |
| ??9 | Oxidation inhibitor | - | - | - | - | - | 0.50 | - | - |
| ??10 | Soya-bean oil | - | - | - | - | 3.00 | 2.00 | 1.50 | 2.50 |
| Add up to | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
Manufacturing process: with the offset printing photochromatic printing ink composition.
The printing ink index:
| Example 23 | Example 24 | Example 25 | Example 26 | Example 27 | Example 28 | Example 29 | Example 30 | |
| Degree of mobilization 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 |
| Viscosity pa.s/40 ℃ of HAAKE | ??4.2 | ??4.3 | ??3.8 | ?4.0 | ??4.5 | ??4.3 | ??4.0 | ??4.1 |
In routine 23-30, used starting material are as follows:
Optically variable pigments: YSB 30 gold medals turn green, Guangdong Huizhou optical technology company limited product.
Resol (1): WY-1111 pure phenolic resin oil connects material, viscosity 9-10pa.s/40 ℃ of HAAKE, WY-1111 pure phenolic resin oil connects material, by WY-111 oil soluble pure phenolic resin (Beijing Wan Yang anti-counterfeiting technology limited liability company product), tung oil, oleum lini in 40: 40: 20 mixing forming of ratio, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Resol (2): WY-2161 modified phenolic resin fatty oil connects material, viscosity 4-6pa.s/40 ℃ of HAAKE, WY-2161 modified phenolic resin fatty oil connects material, by (softening temperature: 130-140 ℃/ring and ball method of WY-216 modified phenolic resins, acid number: 145-155mgKOH/g, Beijing Wan Yang anti-counterfeiting technology limited liability company product), tung oil, oleum lini is in 40: 40: 20 mixing forming of ratio, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Resol (3): WY-2162 modified phenolic resin fatty oil connects material, 4-6pa.s/40 ℃ HAAKE, WY-2162 modified phenolic resin fatty oil connects material, by WY-216 modified phenolic resins (the same), tung oil, boiled wood oil in 40: 40: 20 mixing forming of ratio, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Resol (4): WY-2281 modified phenolic resin fatty oil connects material, 4-6pa.s/40 ℃ HAAKE, WY-2281 modified phenolic resin fatty oil connects material, by (softening temperature: 125-140 ℃/ring and ball method of WY-228 modified phenolic resins, acid number: 130-145mgKOH/g, Beijing Wan Yang anti-counterfeiting technology limited liability company product), tung oil, oleum lini is in 40: 40: 20 mixing forming of ratio, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
The shortcoming of WY-228 modified phenolic resins is: when softening temperature surpassed 140 ℃ (ring and ball method), oil soluble was bad, cleaned bad during printing.In the engraving intaglio printing ink composition, use the WY-216 modified phenolic resins as far as possible.The oil soluble of WY-216 modified phenolic resins is good, and is cleaned during printing, and the stability in storage of engraving intaglio printing ink composition is good.
Resol (5): WY-2221 modified phenolic resin fatty oil connects material, 4-6pa.s/40 ℃ HAAKE, WY-2221 modified phenolic resin fatty oil connects material, by (softening temperature: 100-110 ℃/ring and ball method of WY-222 modified phenolic resins, acid number: 140-150mgKOH/g, Beijing Wan Yang anti-counterfeiting technology limited liability company product), tung oil, oleum lini is in 60: 40: 20 mixing forming of ratio, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
The shortcoming of WY-222 modified phenolic resins is: in connecting the material composition, content surpasses at 50% o'clock, and in ink composite, consumption surpasses at 20% o'clock, and ink film is more crisp, and printing is in use fallen China ink easily.
Resol (6): WY-2101 modified phenolic resin fatty oil connects material, be rosin, eleostearic acid, tung oil modified phenolic resin connection material, it is liquid resin, wherein contain a certain amount of ethyl cellulose, viscosity is 4.3pa.s/40 ℃ (HAAKE), acid number is 75mgKOH/g, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Resol (7): WY-2341 modified phenolic resin fatty oil connects material, 4-6pa.s/40 ℃ HAAKE, WY-2341 modified phenolic resin fatty oil connects material, by WY-234 modified phenolic resins (softening temperature: 147 ℃/ring and ball method, acid number: 130mgKOH/g, Beijing Wan Yang anti-counterfeiting technology limited liability company product), tung oil, oleum lini is in 40: 40: 20 mixing forming of ratio, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
The shortcoming of WY-234 modified phenolic resins is: in connecting the material composition, content surpasses at 50% o'clock, and in ink composite, consumption surpasses at 20% o'clock, in printing process, cleans not so good.Under the assurance product quality premise, can improve dosage of surfactant and satisfy cleaning requirement.
Synolac: benzene Synolac between WY-2801, viscosity are 4-6pa.s/40 ℃ (HAAKE), and acid number is less than 25mgKOH/g, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Urethane resin: WY-2901 urethane resin, viscosity are 4-6pa.s/40 ℃ (HAAKE), and acid number is less than 15mgKOH/g, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Blended wax: WY-1201 blended wax, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Tensio-active agent: Viscotrol C sodium sulfonate, Beijing Wan Yang anti-counterfeiting technology limited liability company product.
Composite drying agent: with the offset printing photochromatic printing ink composition.
Solvent: the only methyl ether of Diethylene Glycol.
Oxidation inhibitor: with the offset printing photochromatic printing ink composition.
The carved gravure photochromatic printing ink composition that example 23-30 provides, printing should meet the following conditions:
A. figure line design :-photochromatic printing ink composition is applied to not disturb the zone of optics color changeable effect;
-avoid the zone that folds, hold;
-should avoid when wiping version, dirty by other engraving intaglio printing ink.
B. the figure line is carved :-pattern area is as the criterion clearly to recognize the optic metachromatic effect;
-version line degree of depth 60-70 micron;
-version line width 0.25-0.3 millimeter;
In-the pattern, the area of using photochromatic printing ink composition is not less than 80%;
-version line is as far as possible perpendicular to wiping the version direction.
C. printing condition: warm 65-85 ℃ of-version, preferred temperature 75-80 ℃;
45-50 ℃ of-wiping version liquid temp;
19-21 ℃ of the ink fountain temperature of-photochromatic printing ink composition;
20-25 ℃ of-other ink fountain temperature.
After satisfying above-mentioned primary condition, the carved gravure photochromatic printing ink composition is wiped not set-off typography by water, can directly be imprinted on the stock in printing on the stock or cover, obtains satisfied optic metachromatic printing.
The carved gravure that example 23-30 provides is represented with photochromatic printing ink composition is just typical, resin wherein, tensio-active agent, printing ink auxiliary etc. according to different printing types, print speed, ink transfer mode, wipe a version mode, aftertreatment technology requirement, environmental requirement etc., adjust or be replaced by the resin or the material of above-mentioned other.No matter but change which kind of resin or material, the optic metachromatic effect that the color that all can not contain in these materials has the chemical substance (as sulfide, alkyl aryl sulphonic acid ammonium, clorox etc.) of redoxomorphism, destruction or these materials to multi-layer colour-changing film fragment all can not the stray light variable pigments.
Above-mentioned various photochromatic printing ink compositions can directly print on stock, also can overlap to be imprinted on the stock.For carved gravure, the gravure of taking pictures (the version line degree of depth is at the 30-70 micron), silk-screen photochromatic printing ink composition, directly be imprinted on the stock in printing on the stock or cover, all can obtain satisfied optic metachromatic printing, but the printing cost height of carved gravure, waste is big.Use photochromatic printing ink composition for offset printing, protruding seal (number printing, dry offset), directly print on stock, the printing optic metachromatic effect that obtains is not so good.If on same stock, first a kind of ink composite that does not disturb the optics color changeable effect of seal, chromatography photochromatic printing ink composition more then, its optic metachromatic effect is better, and printing cost is lower.The optic metachromatic effect of undertaking the printing of on White Board is more effective than the optic metachromatic of undertaking the printing of on offset paper.This is because due to the offset paper air spots.So on offset paper, print photochromatic printing ink composition (except carved gravure, silk-screen, the gravure of taking pictures) before, print a kind of ink composite that does not disturb the optics color changeable effect earlier, can remedy the defective of paper surface injustice.
The printing of above-mentioned various photochromatic printing ink compositions, the materialization fastness in aqueous sodium hydroxide solution, aqueous sodium hypochlorite solution, saturated sodium sulfide solution is as follows:
| The offset printing printing | Protruding seal printing | The carved gravure printing | The silk-screen printing | The gravure printing of taking pictures | |
| 2% aqueous sodium hydroxide solution | ????3 | ????3 | ????1 | ????5 | ????5 |
| Clorox: the solution of water=1: 6 | ????4 | ????4 | ????4 | ????5 | ????5 |
| Saturated sodium sulfide solution | ????4 | ????4 | ????4 | ????5 | ????5 |
Illustrate: 1 grade for poor; 2 grades is relatively poor; 3 grades for well; 4 grades is good; 5 grades is good.
Materialization fastness pull source: offset printing printing/example 1, protruding seal printing/example 15, carved gravure printing/example 23, silk-screen printing/example 18, the gravure printing/example 11 of taking pictures.
The materialization fastness method of inspection: the printing sample is put into three kinds of above-mentioned solution,, under 25 ℃, left standstill 30 minutes, take out rinsing three times, compare with former state behind the airing by solution soaking.
HAAKE viscometer condition: Substance:803, Sensor:PK2-1.0, Meas.system:M5, Temperature:40 ℃.
Photochromatic printing ink composition can be used for printing of bank note and Valued Securities, bank money, credit card, car/ship/air ticket, stamp, invoice, various certificate, the required false proof products of people such as various product brands and/or packing and/or label, artwork, book, picture, propaganda material.
The advantage of photochromatic printing ink composition:
-strong to the antifalsification of high-definition scanning instrument, color copy machine;
-using method is simple, and is applied widely, with known printing equipment, prints at various stocks;
-photochromatic printing ink is nontoxic, radiationless, printability is good;
-offset printing, protruding seal, the gravure of taking pictures are better than the carved gravure photochromatic printing ink composition with photochromatic printing ink composition aspect following, namely
* ink consumption is low; * printability is good;
* wide application; * without the three wastes, pollution-free;
* printing cost low (almost not waste).
Claims (27)
1. photochromatic printing ink composition is characterized in that it is made up of the optically variable pigments that accounts for total weight 1-60%, the connection material that accounts for total weight 1-95%, the printing ink auxiliary that accounts for total weight 0-20%.
2. photochromatic printing ink composition as claimed in claim 1, optically variable pigments fineness wherein is the 2-50 micron.
3. photochromatic printing ink composition as claimed in claim 1 or 2, wherein, the printing ink auxiliary is selected from siccative, slow do agent, remove in stick, wax, tensio-active agent, uv-absorbing agent, the thinner one or more.
4. as each described photochromatic printing ink composition of claim 1-3, wherein, be used for the connection material of oxypolymerization drying and/or light-cured type photochromatic printing ink composition,, account for the 20-99% that connects the material gross weight by (A) resin; (B) solvent accounts for the 0-25% that connects the material gross weight; (C) vegetables oil accounts for the 1-80% that connects the material gross weight; (D) gummy oil accounts for the 0-35% that connects the material gross weight; (E) stand linseed oil accounts for the 0-20% that connects the material gross weight; (F) connect the material auxiliary, account for the 0-20% that connects the material gross weight and form.
5. photochromatic printing ink composition as claimed in claim 4 wherein, is used for the connection material of oxypolymerization drying and/or light-cured type photochromatic printing ink composition, by (A) resin, accounts for the 25-65% that connects the material gross weight; (B) solvent accounts for the 0-15% that connects the material gross weight; (C) vegetables oil accounts for the 35-75% that connects the material gross weight; (D) gummy oil accounts for the 0-25% that connects the material gross weight; (E) stand linseed oil accounts for the 0-15% that connects the material gross weight; (F) connect the material auxiliary, account for the 0-10% that connects the material gross weight and form.
6. as each described photochromatic printing ink composition of claim 1-3, wherein, be used for the connection material of volatile dry type photochromatic printing ink composition,, account for the 5-60% that connects the material gross weight by (A) resin; (B) solvent accounts for the 40-95% that connects the material gross weight; (F) connect the material auxiliary, account for the 0-10% that connects the material gross weight and form.
7. photochromatic printing ink composition as claimed in claim 6 wherein, is used for the connection material of volatile dry type photochromatic printing ink composition, accounts for the 50-95% of photochromatic printing ink composition gross weight, and preferred content accounts for the 70-90% of photochromatic printing ink composition gross weight.
8. as claim 6 or 7 described photochromatic printing ink compositions, wherein, be used for (A) resin that the connection material of volatile dry type photochromatic printing ink composition forms and be selected from unsaturated polyester resin, resol, rosin ester, polyamide resin, cellulose nitrate ester and fiber derivative, rubber resin, vinylformic acid and derivatives resin thereof, urea-formaldehyde resin, terpolycyantoamino-formaldehyde resin, Resins, epoxy, the polythylene resin one or more.
9. as each described photochromatic printing ink composition of claim 6-8, wherein, (B) solvent that is used for the connection material composition of volatile dry type photochromatic printing ink composition is selected from ethanol, n-propyl alcohol, Virahol, phenylethyl alcohol, butanols, ethylene glycol, polyoxyethylene glycol, 1, the 2-propylene glycol, 1, the 2-butyleneglycol, glycol ether, diethylene glycol ether, ethyl acetate, n-propyl acetate, isopropyl acetate, butylacetate, acetone, isopropyl acetone, hexone, pimelinketone, butanone, toluene, dimethylbenzene, aliphatic solvents, water, in the #200 solvent oil one or more.
10. as each described photochromatic printing ink composition of claim 6-9, wherein, (F) connection that is used for the connection material composition of volatile dry type photochromatic printing ink composition expects that auxiliary is selected from one or more in UV light absorber, connection material and/or printing ink stablizer, oxidation inhibitor, silicone oil, fatty amide, the Resins, epoxy.
11. each the described photochromatic printing ink composition as claim 6-10 wherein, is used for the optically variable pigments of volatile dry type photochromatic printing ink composition, its fineness is at the 2-30 micron, and preferred fineness is at the 10-20 micron.
12. each described photochromatic printing ink composition as claim 6-11, wherein, the optically variable pigments that is used for volatile dry type photochromatic printing ink composition accounts for the 1-40% of photochromatic printing ink composition gross weight, and preferred content accounts for the 10-25% of photochromatic printing ink composition gross weight.
13. as claim 4 or 5 described photochromatic printing ink compositions, wherein, the connection material that is used for oxypolymerization drying and/or light-cured type photochromatic printing ink composition accounts for the 20-80% of photochromatic printing ink composition gross weight, and preferred content accounts for the 45-60% of photochromatic printing ink composition gross weight.
14. as claim 4,5, each described photochromatic printing ink composition of 13, wherein, be used for (A) resin that the connection material of oxypolymerization drying and/or light-cured type photochromatic printing ink composition forms and be selected from Synolac, unsaturated polyester resin, resol, rosin ester, rubber resin, vinylformic acid and derivatives resin thereof, urethane resin, Resins, epoxy and modified epoxy, the polythylene resin one or more.
15. each described photochromatic printing ink composition as claim 4,5,13-14, wherein, (B) solvent that is used for the connection material composition of oxypolymerization drying and/or light-cured type photochromatic printing ink composition is selected from polyoxyethylene glycol, 1,2-propylene glycol, 1, one or more in 2-butyleneglycol, glycol ether, diethylene glycol ether, phthalic acid dibutyl ester, dioctyl phthalate, tributyl phosphate, silicone oil, aliphatic solvents, water, high-boiling point kerosene, #200 solvent oil, the #210 Dormant oils.
16. each described photochromatic printing ink composition as claim 4,5,13-15, wherein, be used for (C) vegetables oil that the connection material of oxypolymerization drying and/or light-cured type photochromatic printing ink composition forms and be selected from oleum lini, tung oil, synourin oil, perilla oil, Chinese catalpa oil, OITICICA oil, soya-bean oil, Oleum Helianthi, wine stone oil, vegetable oil acid, tower fatty acid oil, in the polymeric vegetable oil of high temperature refining one or more.
17. each described photochromatic printing ink composition as claim 4,5,13-16, wherein, be used for (D) gummy oil that the connection material of oxypolymerization drying and/or light-cured type photochromatic printing ink composition is formed, the colloidalmaterial of forming by resol or rosin ester, vegetables oil, organic acid aluminium etc.
18. each described photochromatic printing ink composition as claim 4,5,13-17, wherein, be used for (E) stand linseed oil that the connection material of oxypolymerization drying and/or light-cured type photochromatic printing ink composition forms and be selected from high-boiling point kerosene, #210 Dormant oils, #200 solvent oil, glycol ether, diethylene glycol ether, phthalic acid dibutyl ester, dioctyl phthalate, the tributyl phosphate one or more.
19. each described photochromatic printing ink composition as claim 4,5,13-18, wherein, (F) connection that is used for the connection material composition of oxypolymerization drying and/or light-cured type photochromatic printing ink composition expects that auxiliary is selected from one or more in UV light absorber, connection material and/or printing ink stablizer, the oxidation inhibitor.
20. each the described photochromatic printing ink composition as claim 4,5,13-19 wherein, is used for the optically variable pigments of oxypolymerization drying and/or light-cured type photochromatic printing ink composition, its fineness is at the 2-50 micron, and preferred fineness is at the 2-25 micron.
21. each described photochromatic printing ink composition as claim 4,5,13-20, wherein, the optically variable pigments that is used for oxypolymerization drying and/or light-cured type photochromatic printing ink composition, account for the 10-60% of photochromatic printing ink composition gross weight, preferred content accounts for the 20-50% of photochromatic printing ink composition gross weight.
22. as each described photochromatic printing ink composition of claim 4,5,13-21, wherein, for oxypolymerization drying and/or light-cured type photochromatic printing ink composition, used printing ink auxiliary accounts for the 3-15% of ink composite gross weight.
23. as the application of the described photochromatic printing ink composition of claim 1-22, it is characterized in that directly being imprinted on the stock printing on the stock or overlap, obtain printing.
24. application as claimed in claim 23, wherein, photochromatic printing ink composition is that cover is imprinted on the stock offscreen the time, obtains printing.
25. application as claimed in claim 24, wherein, photochromatic printing ink composition is before chromatography, and in advance the color of the ink composite of printing is consistent with the color palpus of photochromatic printing ink composition or do not disturb the color of photochromatic printing ink composition.
26. each the described application as claim 23-25 is used for printing of bank note and Valued Securities, bank money, credit card, car/ship/air ticket, stamp, invoice, various certificate, various product brand and/or packing and/or label, artwork, book, picture, propaganda material.
27. as each described application of claim 23-26, wherein the fraction of coverage of optically variable pigments in the actual print area is more than 20%, preferred fraction of coverage is at 40-80%.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
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| CN 01122606 CN1375528A (en) | 2001-03-19 | 2001-06-26 | Photochromic ink compound and its application |
| CN 02806457 CN1229450C (en) | 2001-03-19 | 2002-03-19 | Photochromatic printing ink composition and its application |
| PCT/CN2002/000177 WO2002074871A1 (en) | 2001-03-19 | 2002-03-19 | Optically-variable ink composition and the use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01103886 | 2001-03-19 | ||
| CN01103886.1 | 2001-03-19 | ||
| CN 01122606 CN1375528A (en) | 2001-03-19 | 2001-06-26 | Photochromic ink compound and its application |
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| CN1375528A true CN1375528A (en) | 2002-10-23 |
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| CN 02806457 Expired - Fee Related CN1229450C (en) | 2001-03-19 | 2002-03-19 | Photochromatic printing ink composition and its application |
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| CN 02806457 Expired - Fee Related CN1229450C (en) | 2001-03-19 | 2002-03-19 | Photochromatic printing ink composition and its application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5171363A (en) * | 1979-12-28 | 1992-12-15 | Flex Products, Inc. | Optically variable printing ink |
| CN1052994C (en) * | 1996-10-04 | 2000-05-31 | 中国科学院上海技术物理研究所 | Prepn of allochronic ink capable of resulting in high productivity |
| CN1230577A (en) * | 1998-11-02 | 1999-10-06 | 谭满清 | Anti-fake optical-film ink and its preparation |
-
2001
- 2001-06-26 CN CN 01122606 patent/CN1375528A/en active Pending
-
2002
- 2002-03-19 CN CN 02806457 patent/CN1229450C/en not_active Expired - Fee Related
- 2002-03-19 WO PCT/CN2002/000177 patent/WO2002074871A1/en not_active Application Discontinuation
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1229450C (en) | 2005-11-30 |
| WO2002074871A1 (en) | 2002-09-26 |
| CN1496393A (en) | 2004-05-12 |
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