KR20110073810A - Method for preparing uv curing curing vehicle for the ink and uv curing intaglio ink - Google Patents

Abstract

PURPOSE: A method for preparing UV curable vehicles for ink is provided to ensure polymerization reaction of a binder compound by ultraviolet irradiation, and to appropriately wipe low concentration NaOH in a wiping solution. CONSTITUTION: An intaglio ink composition comprises: oligomers selected from water-soluble urethane acrylate oligomers or unsaturated ester oligomers; at least one kind of water-soluble monomers selected from 1,6-hexanediacrylate, tripropylene glycol diacrylate, trimethylopropane triacrylate, pentaerythritol triacrylate, pentaetriol tetraacrylate, dipentaerythriol pentaacrylate, and polyethylene glycol diacrylate; pigment; filler; photoinitiator; photostabilizer; emulsifier; and wax.

Description

Method for preparing UV curable colorant and intaglio ink {Method for preparing UV CURING curing vehicle for the ink and UV curing intaglio ink}

The present invention relates to an ultraviolet curable intaglio ink composition and a method of manufacturing the same.

More specifically, after printing properly wiped in the wiping solution of low concentration sodium hydroxide during printing, the liquid is separated from the liquid and ink during the coagulation process, infrared absorption, magnetic for the authenticity of various security products The present invention relates to an ink capable of printing by imparting color conversion characteristics, an ultraviolet curable intaglio ink colorant used in the preparation of such an ink, and a manufacturing method.

Rosin-modified maleized alkyd resin varnishes and linseed fatty acids synthesized using linseed oil, rosin, glycerin, etc. in the past intaglio printing of banknotes, various securities, gift certificates, and other security documents. And epoxy modified alkyd varnishes synthesized using an epoxy resin were used.

In addition, the conventional intaglio ink drying method had to be oxidatively polymerized by taking a drying method such as permeation, evaporation method or metal salt. There was a disadvantage of taking time. In addition, productivity is reduced due to a large amount of time and space area for backfilling or subsequent processing of printed matters, and solvents generated during the drying process are diffused in the air, and thus, there are many problems in working environment hygiene due to air pollution.

The present invention provides an intaglio printing composition which enables the ink film to harden rapidly when printed by the UV curing method in an intaglio high speed printing machine, and is capable of high depth intaglio printing with excellent wipeability and transferability. In addition, it is an object of the present invention to provide a UV-curable intaglio printing ink intaglio printing composition having excellent ink surface dryness, high ink coating flexibility, and excellent durability, including chemical resistance, alkali resistance and abrasion resistance of printed products. .

 The present invention relates to an intaglio ink composition comprising an oligomer selected from a water-soluble urethane acrylate oligomer or an unsaturated ester oligomer capable of curing by irradiation with ultraviolet rays and polymerized through a radical reaction. The oligomer is used for an ultraviolet curable developer. The intaglio ink composition according to the present invention is capable of instant drying without a separate drying process, and is capable of high depth intaglio printing due to its excellent wipeability and transferability. In addition, the ink surface is excellent in drying properties, and the ink film has high flexibility and excellent durability, including chemical resistance, alkali resistance, and abrasion resistance of printed products, thereby reducing workability of organic solvents, thereby improving workability.

The present invention provides an ink composition excellent in erosion resistance by reacting 2-hydroxyethyl acrylate (2-Hydroxy ethyl acrylate, HEA) in the process of preparing the water-soluble urethane acrylate oligomer, intaglio ink composition according to the present invention The unsaturated ester oligomer is produced by adjusting the acid value to 50 ~ 70 in the manufacturing process, and then produced by the final ink is effective to wash off the basic insoluble solution in the printing plate.

The intaglio ink composition is the ink waste dissolved in the wiping solution after the printing process is agglomerated sedimentation by an anionic polymer flocculant and the precipitate is easily filtered by a filter aid (volcanic stone) to separate the precipitated ink and the wiping solution recovered can do.

Hereinafter, the present invention will be described in more detail.

The present invention is an oligomer selected from a water-soluble urethane acrylate oligomer or unsaturated ester oligomer; 1,6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), trimethylpropane triacrylate (TMPTA), pentaerytriol triacrylate (PETA), pentaerytriol tetraacrylic Water-soluble monomers selected from at least one of acrylate (PETTA) and dipentaerythritol pentaacrylate (DPPA) and polyethylene glycol diacrylate (PEGDA); Pigments; Fillers; Photoinitiators; Light stabilizers; Emulsifiers; And it relates to an intaglio ink composition comprising a wax.

The water-soluble monomer of the present invention is to use the intaglio ink composition so that the water solubility is increased, the viscosity and curing rate is improved, containing 30 to 85 parts by weight based on 100 parts by weight of the oligomer can further improve the viscosity and curing rate have.

The 1,6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), trimethyl propane triacrylate (TMPTA), pentaerytriol triacrylate (PETA), pentaerytriol tetra Water-soluble monomers selected from acrylate (PETTA) and dipentaerythritol penta acrylate (DPPA) and polyethylene glycol diacrylate (PEGDA) are polyfunctional diluents that control flexibility and improve viscosity and cure rate. When included in the above range, it is possible to improve the printability and flexibility, viscosity, erosion properties, and improve the curing performance, characterized in that the photoinitiator has a maximum absorbance at a wavelength of 200 ~ 450nm.

The photoinitiator is for initiating the polymerization reaction of the oligomer. The photoinitiator is isopropyl thioxanthone (maximum absorption wavelength 258-383 nm), α-amino ketones (maximum absorption wavelength 280-340 nm), α-hydroxyketone (maximum absorption). Wavelength 220-270 nm), and phosphine osides (maximum absorption wavelength 220-380 nm) can be selected, and can be used.

In the present invention, the filler is characterized in that selected from the group comprising sieving pigment having a low oil absorption grade, CaCO ₃ (heavy, hard), TiO ₂ , BaSO ₄ , Talc (Talc).

More preferably, the catalyst is a zirconium chelate-based catalyst.

The intaglio ink composition of the present invention comprises an infrared absorbing pigment, and the infrared absorbing pigment has a strong durability and chemical resistance, good ink manufacturing ability, and an ink coating film is insoluble in various solvents even after printing. The phthalocyanine-based compound is used, and the polycrosslinked phthalocyanine-based compound used is prepared by the method disclosed in Korean Patent No. 0528155, and has an infrared absorption wavelength range (λmax) of 800 to 900 nm and a pH of 5.5 ± 1.5. As a compound having an average particle of 0.4 to 4 µm and an ignition residue of 8.9%, a commercially available representative product may be added with the trade name CMS Blue 2A-905 (CMS Technology Co., Ltd.).

The addition amount of the infrared absorbing pigment is preferably further included so as to be 1 to 4% by weight based on the total intaglio ink composition.

The intaglio ink composition of the present invention includes a magnetic material, and the yellow-based magnetic pigment has a coercive force (Hc) of 385 ± 10 (Oe), a saturation magnetic flux density (σs) of 71 to 73 (emu / g), and a pH of 2.7 to 3.6, oil absorption (OA) is preferably 6.5 ~ 8.0 (mL / 20g), surface area (BET) of 24.5 ± 1.5 (㎡ / g) characteristics, is a representative commercially available product of Magnetic Iron Oxide Brown EP -060, gray magnetic pigment has a surface area (BET) of 0.4 (㎡ / g), average particle of 4-6 (㎛), specific gravity of 7.7 (g / cm 3), oil absorption of 7.5 (g oil / 100g pigment ), The maximum residual magnetic flux density (δm) is 200 (A ㎡ / kg), it is preferred that the iron has a characteristic of Fe> 97%, a representative commercially available product may be added BASF Co. Magnetic Pigment 025 BASF.

The amount of the magnetic material may be further included so as to be 10 to 20% by weight based on the total ink composition.

The intaglio ink composition of the present invention includes a pigment having a color conversion effect, and the color when viewed from the front and the color when viewed from the side may be different from each other. Pearl pigments, copper powders with golden luster, aluminum powders with golden luster, encapsulated pigments, metal evaporated powders, acicular pigments and the like can be mixed and used.

The addition amount of the color conversion pigment is preferably further included so as to be 30 to 40% by weight based on the total intaglio ink composition.

The intaglio ink composition of the present invention is 10 to 50 parts by weight of the pigment, 30 to 85 parts by weight of the filler, 1 to 25 parts by weight of the photoinitiator, 0.1 to 15 parts by weight of the light stabilizer, emulsifier 3 with respect to 100 parts by weight of the oligomer It is characterized in that the intaglio ink composition comprising ˜15 parts by weight, 3 to 15 parts by weight of wax and the physical properties of the intaglio ink composition in the above range can be achieved to achieve the object of the present invention. Hydroquinone is mentioned as said light stabilizer.

The intaglio ink composition according to the present invention has a characteristic of having a fast curing speed when printed on a substrate having an ink film thickness of about 10 to 150 μm, and excellent in-corrosiveness from a wiping solution, specifically, 0 to 0.3% of hydroxide The composition is completely dispersed in a wiping solution having a sodium concentration and has a viscosity of 3 to 30 Pas.

In the present invention, when the water-soluble urethane acrylate oligomer is irradiated with strong energy including ultraviolet rays, it is characterized in that it is cured by the reaction of the acrylic group, thus, when preparing the water-soluble urethane acrylate oligomer, the molecular weight of the starting material, the final composition According to the compound structure, urethane bonds can adjust the flexibility of the cured product after UV curing.

In particular, 2-hydroxyethyl acrylate (2-Hydroxy ethyl acrylate, HEA), which is introduced during the preparation of the water-soluble urethane acrylate oligomer, is a water-soluble acryl-based compound, and the water-soluble urethane acrylate can be prepared while giving an acrylic group to the final oligomer.

The present invention is characterized in that the unsaturated ester oligomer is characterized in that the acid value is adjusted to 50 to 70 in the manufacturing process, by adjusting the acid value as described above, when the composition according to the present invention is inkized to control the erosion properties to the optimal state And, it contains a carboxyl group has an effect that can be easily given water solubility.

Hereinafter will be described in more detail the manufacturing process of the water-soluble urethane acrylate oligomer, unsaturated ester oligomer.

In the present invention, the water-soluble urethane acrylate oligomer is polyethylene glycol having a molecular weight of 400 ~ 600 in an inert atmosphere; 2-hydroxyethyl acrylate (2-Hydroxy ethyl acrylate, HEA); Polyethylene glycol diacrylate having a molecular weight of 400 to 500; After mixing hydroquinone as a catalyst and a light stabilizer, isophorone diisocyanate (IPDI) is prepared by reacting.

More specifically, the water-soluble urethane acrylate oligomer is polyethylene glycol having a molecular weight of 400 ~ 600 in an inert atmosphere, more preferably in a nitrogen atmosphere; 2-hydroxyethyl acrylate (2-Hydroxy ethyl acrylate, HEA); Polyethylene glycol diacrylate having a molecular weight of 400 to 500; Mix catalyst and hydroquinone,

The content is based on 100 parts by weight of polyethylene glycol having a molecular weight of 400 ~ 600, the 2-hydroxyethyl acrylate (2-Hydroxy ethyl acrylate, HEA) is a water-soluble urethane acrylate oligomer comprises 10 to 40 parts by weight, The polyethylene glycol diacrylate having a molecular weight of 400 to 500 is 20 to 70 parts by weight, the catalyst is 0.03 to 0.2 parts by weight, the hydroquinone is preferably mixed 0.1 to 5 parts by weight.

 The polyethylene glycol diacrylate having a molecular weight of 400 to 500 may be properly prepared when the viscosity is mixed in the above range, hydroquinone may be included in the above range to increase the storage stability of the final product.

Reacting isophorone diisocyanate (IPDI) to the mixture, but mixing 20 to 95 parts by weight with respect to 100 parts by weight of polyethylene glycol having a molecular weight of 400 to 600, effective in controlling the viscosity of the final product, It is good to slowly add dropwise at a rate of 3-6ml per 10 minutes. At this time, the temperature of the reactants is checked and adjusted so that it does not exceed 50 ~ 60 ℃, and the dropping can effectively react. After the dropping, the isocyanate group content test method of KS M 5969 is used to terminate the synthesis when the urethane group is formed and the isocyanate group is fully reacted. The resulting composites should be stored in a container where light cannot pass through.

In the present invention, the unsaturated ester oligomer is an inert atmosphere, more preferably, a polyethylene glycol having a molecular weight of 400 to 600; maleic acid; a catalyst; After the reaction at 100 ~ 150 ℃ and cooled isophorone diisocyanate (Isophorone diisocyanate, IPDI) is characterized in that it is prepared by the reaction.

More specifically, the content is based on 100 parts by weight of polyethylene glycol having a molecular weight of 400 to 600, 15 to 40 parts by weight of the maleic acid, 0.05 to 0.6 parts by weight of the catalyst, 0.1 to 3.5 parts by weight of the hydroquinone by mixing the storage stability After impregnating, the acid number (Acid number) is maintained after cooling at 100 ~ 150 ℃ until 50 ~ 70, and then cooled to 100 parts by weight of polyethylene glycol having a molecular weight of 400 ~ 600, the isophorone diisocyanate (Isophorone diisocyanate, IPDI) is good to react 5 to 40 parts by weight.

The heating is more preferably using a heating mantle to heat the reaction tank, in order to remove the water generated during the reaction, a Dean-stark trap (Dean-stark trap) is installed and heated using a heat insulating material. When the maleic acid disappeared from the product through structural analysis and the acid value reached 50 to 70, the heating tape and mantle were stopped and slowly cooled, and then cooled to 40 to 60 ° C. Isophorone diisocyanate (IPDI) ) Is slowly added dropwise in the above range, and the synthesis is terminated when the isocyanate group is completely extinguished by the method for testing the content of isocyanate group of KS M 5969. The resulting compound is stored in a light-permeable container.

More specifically, the water-soluble urethane acrylate oligomer or unsaturated ester oligomer is characterized in that the viscosity is 3 ~ 30Pas at 40 ℃ independently of each other. In the present invention, the water-soluble urethane acrylate oligomer has a weight average molecular weight of 500 to 2000, preferably 1000 to 1500, and the unsaturated ester oligomer has a weight average molecular weight of 500 to 2000, preferably 1000 to 1500 It features.

The viscosity range is more than 6,000 sheets per hour, printing line pressure of about 50 tons at the time of high-speed high-pressure printing imparts good printability characteristics on the printing press, scattering, etc., the molecular weight of the water-soluble urethane acrylate oligomer and unsaturated ester oligomer The range of is a range that can give a moderate improvement in curing suitability during printing, and durability and flexibility of the printed matter after printing.

The present invention uses a water-soluble urethane acrylate oligomer or an unsaturated ester oligomer which can be polymerized through a radical reaction by irradiation with ultraviolet rays, and is used as a raw material for the intaglio inks. In addition, it provides infrared absorption, magnetic, color conversion characteristics for authenticity of various security products, and the intaglio ink composition according to the present invention is used to prevent forgery and alteration of printed intaglio printing of banknotes, various securities, gift certificates, and other security documents. Can be.

The intaglio ink composition of the present invention has a polymerization reaction of a binder compound by ultraviolet irradiation, and has an effect of being properly wiped in a wiping solution of a low concentration of sodium hydroxide during printing, and the cured coating of the ink has chemical resistance and alkali resistance. It may have excellent quality characteristics such as wear resistance and durability.

Intaglio ink composition according to the present invention can be instantaneous drying without a separate drying process, excellent in wipeability, transferability, high depth intaglio printing as well as excellent ink surface dryness, flexibility of ink coating This is high and has the effect of infrared absorption, magnetic, color conversion characteristics.

In the intaglio ink composition according to the present invention, the ink waste dissolved in the wiping solution after the printing process is coagulated and precipitated by an anionic polymer flocculant, and the precipitate is easily filtered by a filtration aid (volcanic stone) to precipitate the ink and the wiping solution. It can be separated and recovered.

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the present invention is not limited to the following examples.

Preparation Example 1 Preparation of Urethane Acrylate Oligomer

50 g of polyethylene glycol (Aldrich 202401) having a molecular weight of 600 was added to the flask, followed by 10 g of 2-hydroxyethyl acrylate (HEA), 20 g of polyethylene glycol diacrylate having a molecular weight of 400, and zirconium chelate. ) 0.05 g of catalyst and 0.5 g of hydroquinone were added together, and the mixture was sufficiently stirred in a nitrogen atmosphere. 25 g of isophorone diisocyanate (IPDI) was slowly added dropwise at a rate of 5 ml per 10 minutes. At this time, the temperature of the reactants is properly adjusted so as not to exceed 60 ° C. After completion of the dropwise addition, the synthesis was terminated when the urethane group was formed through the isocyanate group content test method of KS M 5969 and the isocyanate group was completely reacted. The resulting composite was stored in a container that does not transmit light.

Preparation Example 2 Preparation of Water-soluble Ester Oligomer

15 g of maleic acid 60 g of polyethylene glycol (Aldrich 202401) having a molecular weight of 600, 0.1 g of zirconium chelate catalyst, and 0.5 g of hydroquinone were added to the flask, followed by stirring in a nitrogen atmosphere. After stirring, a Dean-stark trap is installed in order to remove the water generated by the condensation reaction, and is insulated using a heat insulating material, while heating the reactor at 150 ° C. using a heating mantle. Water was removed. While the water was removed, maleic acid remaining in the product disappeared through structural analysis, and the heating of the heating mantle was stopped and gradually cooled when the acid number became 60. After cooling to 40 ° C, 6 g of isophorone diisocyanate (IPDI) was slowly added dropwise, and the reaction was terminated when the isocyanate group disappeared completely by the isocyanate group content test method of KS M 5969. The product produced through the reaction was stored in a light-permeable container.

Example 1

Urethane acrylate oligomer prepared in Preparation Example 1 30g, 1, 6- hexanediol diacrylate (HDDA) 15g, coloring pigment 5g, extender pigment 15g, isopropyl thioxanthone 2g, emulsifier (Zephrym3300B, Croda Chemicals) 5g, wax An intaglio ink composition was prepared by mixing 3 g of hydroquinone as a 5 g light stabilizer.

Example 2

In the same manner as in Example 1, but using a water-soluble ester oligomer prepared in Preparation Example 2 instead of using the urethane acrylate oligomer prepared in Preparation Example 1, the rest is carried out as in Example 1 It was.

Example 3

The same procedure as in Example 1 was performed except that CMS Blue 2A-905 and CMS Technology Co., Ltd. 3g were further added as infrared absorbing pigments, and the rest was performed in the same manner as in Example 1.

Example 4

In the same manner as in Example 2 except that the addition of CMS Blue 2A-905, CMS Technology Co., Ltd. 3g as an infrared absorbing pigment, the difference was the same as in Example 2.

Examples 3 and 4 can identify forgery and alteration banknotes and securities from those having excellent solvent resistance, maintaining the intrinsic color of the printed matter, and exhibiting a maximum absorbance (λ max) in the wavelength range of 800 to 900 nm.

[Example 5]

In the same manner as in Example 1 except that magnetic iron oxide brown EP-060 (magnetic iron oxide brown EP-060, Saehan Media) 15g is the difference between the addition, the rest is the same as in Example 1 Was carried out.

[Example 6]

In the same manner as in Example 2 except that 15g of magnetic iron oxide brown EP-060 (magnetic iron oxide brown EP-060, Saehan Media) as a magnetic material is different, the rest is the same as in Example 2 Was carried out.

Embodiments 5 and 6 may facilitate authenticity identification in the automated teller machine.

Example 7

In the same manner as in Example 1, except that 35g of a pigment (Iriodin 233,225, Merck) having a color conversion effect is further added, the rest was performed in the same manner as in Example 1.

The ink composition according to the seventh embodiment is characterized in that the color when viewed from the front and the color when viewed from the side.

Claims (12)

Oligomers selected from water soluble urethane acrylate oligomers or unsaturated ester oligomers; 1,6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), trimethylpropane triacrylate (TMPTA), pentaerytriol triacrylate (PETA), pentaerytriol tetraacrylic Water-soluble monomers selected from at least one of acrylate (PETTA) and dipentaerythritol pentaacrylate (DPPA) and polyethylene glycol diacrylate (PEGDA); Pigments; Fillers; Photoinitiators; Light stabilizers; Emulsifiers; And a wax; intaglio ink composition comprising. The method of claim 1, Intaglio ink composition comprising the water-soluble monomer 30 to 85 parts by weight based on 100 parts by weight of oligomer. The method of claim 2, The intaglio ink composition is based on 100 parts by weight of the oligomer, 10 to 50 parts by weight of the pigment, 30 to 85 parts by weight of the filler, 1 to 25 parts by weight of the photoinitiator, 0.1 to 15 parts by weight of the light stabilizer, and 3 to 15 parts by weight of the emulsifier. Part, Intaglio ink composition comprising 3 to 15 parts by weight of wax. The method of claim 1, The water-soluble urethane acrylate oligomer is polyethylene glycol having a molecular weight of 400 ~ 600 in an inert atmosphere; 2-hydroxyethyl acrylate (2-Hydroxy ethyl acrylate, HEA); Polyethylene glycol diacrylate having a molecular weight of 400 to 500; An intaglio ink composition, which is prepared by mixing a catalyst and hydroquinone and then reacting isophorone diisocyanate (IPDI). 5. The method of claim 4, To 100 parts by weight of polyethylene glycol having a molecular weight of 400 to 600, The 2-hydroxyethyl acrylate (HEA) is 10 to 40 parts by weight, the polyethylene glycol diacrylate having a molecular weight of 400 to 500 20 to 70 parts by weight, the catalyst is 0.03 to 0.2 parts by weight The intaglio ink composition wherein the hydroquinone is 0.1 to 5 parts by weight and the isophorone diisocyanate (IPDI) is 20 to 95 parts by weight. The method of claim 1, The unsaturated ester oligomer is mixed with polyethylene glycol having a molecular weight of 400 to 600; maleic acid; catalyst; hydroquinone in an inert atmosphere, and then reacted and cooled at 100 to 150 ° C. until the acid number is 50 to 70. Intaglio ink composition, which is prepared by reacting poron diisocyanate (Isophorone diisocyanate, IPDI). The method of claim 6, To 100 parts by weight of polyethylene glycol having a molecular weight of 400 to 600, Intaglio ink composition wherein the maleic acid is 15 to 40 parts by weight, the catalyst is 0.05 to 0.6 parts by weight, the hydroquinone is 0.1 to 3.5 parts by weight, and the isophorone diisocyanate (IPDI) is 5 to 40 parts by weight. . The method of claim 1, Intaglio ink composition wherein the water-soluble urethane acrylate oligomer or unsaturated ester oligomer is 3 to 30 Pas at 40 ° C. independently of each other. The method of claim 1, The water-soluble urethane acrylate oligomer has a molecular weight of 500 ~ 2000, the unsaturated ester oligomer has a molecular weight of 500 ~ 2000 intaglio ink composition. The method of claim 1, The intaglio ink composition is an intaglio ink composition further comprising an infrared absorbing pigment to 1 to 4% by weight based on the total intaglio ink composition. The method of claim 1, The intaglio ink composition is intaglio ink composition further comprises a magnetic material to 10 to 20% by weight relative to the total intaglio ink composition. The method of claim 1, The intaglio ink composition further comprises a color conversion pigment 30 to 40% by weight relative to the total intaglio ink composition.