JP3721243B2 - Water-based stamp stand ink - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to a water-based ink mainly used for a stamp stand.
[0002]
[Prior art]
Conventionally, metal pigments such as brass, brass, and aluminum have been used to obtain gold, silver, and other metallic inks.
However, these metal pigments are deteriorated with time, and particularly when used in water-based inks, they have the disadvantages that they oxidize and rust to discolor the ink or generate gas.
Therefore, pearl pigments obtained by attaching titanium oxide and / or iron oxide to the surface of mica instead of metal pigments are used in some inks, and Japanese Patent Publication No. 5-45633 and Japanese Patent Application Laid-Open No. 5-117469. JP-A-8-143808 and JP-A-8-143809 are disclosed.
However, since these conventional inks are marking pen inks, particularly raw ink type marking pen inks that are used while being redispersed using a stirring sphere, when used on a stamp stand, the ink drops, Problems such as ink drop and board drying occurred and could not be put to practical use.
In addition, the ink for conventional stamp bases, whether water-based or oil-based, is dyed and fixed on the surface of a stamp such as a rubber stamp, and cannot be completely removed even using water or an organic solvent. Therefore, when using a stamp stand having a color different from that used, there is a drawback that colors are mixed.
[0003]
[Problems to be solved by the invention]
Therefore, the present inventor has solved the above-mentioned problems and succeeded in developing an ink suitable for a stamp stand, although it is a water-based ink using a pearl pigment.
[0004]
[Means for Solving the Problems]
It contains a solvent comprising water and a water-soluble organic solvent, a pearl pigment, one or more resins selected from acrylic resin powder, water-dispersible acrylic resin colloidal dispersion, and water-dispersible acrylic resin emulsion. Water-based stamp stand ink. Furthermore, the viscosity at 0.5 rpm is 2000 mPa · s or more, and η1 / η2 = 0.2 to 0.5, η3 / η4 = 0.2 to 0.5, (η1: viscosity at 10 rpm, η2: 1 Aqueous stamp stand ink with a viscosity at 0.0 rpm, η3: viscosity at 5.0 rpm, and η4: viscosity at 0.5 rpm. The water-soluble organic solvent is 25% to 90% by weight based on the total amount of the ink, and one or more selected from the acrylic resin powder, water-dispersible acrylic resin colloidal dispersion, and water-dispersible acrylic resin emulsion A water-based stamp base ink in which the total amount of the resin is 0.01% by weight to 0.9% by weight with respect to the total amount of the ink.
[0005]
[Action]
Since the resin selected from the acrylic resin powder, water-dispersible acrylic resin colloidal dispersion, and water-dispersible acrylic resin emulsion blended in the present invention imparts appropriate thixotropy, the ink is impregnated in an ink tank such as felt. In the state, the ink is gelled, the pearl pigment does not settle, and the pearl pigment is prevented from becoming a lump, so-called hard cake. Moreover, since it has excellent wettability with respect to the pearl pigment, it can adhere to the entire pearl pigment and maintain a dispersed state for a long period of time.
[0006]
Hereinafter, the present invention will be described in detail.
The solvent used in the present invention contains at least water and a water-soluble organic solvent. The water may be tap water, but purified water is preferably used because of the presence of various bacteria. As the water-soluble organic solvent, one or more polyhydric alcohols selected from glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, butylene glycol and the like are used, and 25% by weight with respect to the total amount of the ink. ˜90% by weight is preferably used.
The water and the water-soluble organic solvent are preferably used in a ratio of water: water-soluble organic solvent = 10 to 50% by weight: 50 to 90% by weight. It is used in the range of -98% by weight.
[0007]
The colorant used in the present invention is a pearl pigment, and (1) natural mica is pulverized and then coated with titanium oxide, which is filtered and dried, such as Iriodin 111, 120, 121, etc. As described above, manufactured by Merck), MearlinMagnaPearl 3000-3100, etc. (hereinafter, manufactured by The Mearland Corporation), (2) After pulverizing natural mica, it is coated with iron oxide, filtered and dried, for example, Iriodin 504, 520, 522, 524, etc. (Merck, Inc.), Marylin LusterPigments MAJESTIC GOLD 9222X, MAYAN GOLD 9233X, AZTEC GOLD 9363C, INCA GOLD 9222GLDARD 02 ・ NU-ANTIQUE GOLD 9212GB, etc. (above, manufactured by The Mary Corporation), (3) After crushing natural mica, coat with titanium oxide, and then coat with iron oxide, and filter and dry it. For example, Iriodin 300/302/323 (Merck), Ms. Linlin Pigments SUPER RED-RUSSET 9550Z / SUPER BLUE-RUSSET 9650Z / SUPER RUSSET 9450Z / SUPER CUPSER 9 The Mear Corporation) can be used.
In the present invention, particles having a particle size of 100 μm or less are preferably used. The pearl pigment can be used in the range of 1 to 40% by weight based on the total amount of ink.
Further, in the present invention, conventionally known organic pigments and inorganic pigments can be used alone or in combination as pearl pigments, for example, azo, phthalocyanine, quinacridone, anthraquinone, dioxazine, indigo. Organic pigments such as thioindigo, berylone / berylene, isoindolenone, and azomethyleneazo, and inorganic pigments such as carbon black and titanium white can be used. These pigments are usually kneaded into polyacrylic acid, polymethacrylic acid, styrene-acrylic acid copolymers, and their metal salts, ammonium salts, amine salts, and other known resins as processed pigments. It is convenient because it is easily dispersed when mixed with a solvent. Moreover, you may use the commercially available processed pigment which has already kneaded the pigment in the dispersing agent. These pigments can be used alone or as a mixture in consideration of the desired color.
[0008]
As the resin used in the present invention, one or more selected from an acrylic resin powder, a water-dispersible acrylic resin colloidal dispersion, and a water-dispersible acrylic resin emulsion are used as a pigment dispersant / thixotropic agent.
The acrylic resin powder that can be used in the present invention is a resin such as polyacrylic acid, polymethacrylic acid, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, and alkali metal salts / ammonium salts thereof. A resin powder made of an amine salt is used. Among them, a crosslinked branched acrylic resin powder is particularly preferable because a small amount exhibits a sufficient effect.
The water-dispersible acrylic resin colloidal dispersion that can be used in the present invention includes alkali metal salts, ammonium salts, amines such as polyacrylic acid, polymethacrylic acid, styrene-acrylic acid copolymer, and styrene-methacrylic acid copolymer. A colloidal solution obtained by dispersing and stabilizing a salt in an aqueous solution and having a solid content of 20 to 60% is preferably used.
The water-dispersible acrylic resin emulsion that can be used in the present invention is water-soluble by alkali metals such as polyacrylic acid, polymethacrylic acid, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, ammonium amine, etc. A self-emulsifying acrylic resin prepared by dispersing and stabilizing in an aqueous solution is preferably an emulsion having a solid content of 20 to 60%.
The acrylic resin powders used in the present invention are specifically listed as “Jonkrill J-683, Jonkrill J-68, Jonkrill J-586 (manufactured by Johnson Co., Ltd.), Ultra Hold 8, Ultra Hold Strong, Rubymer 100P, Rubymer 30E (above, manufactured by BASF Japan Co., Ltd.), Leogic 250H, Leogic 252L, Leogic 835H, Leogic 830L, Leogic 305H, Leogic 306L, Junron PW-110, Junron PW-111, Junron PW-150, Jurimer AC-10P / Julimer AC-10NP / Jurimer AC-103AP / Aronbis S / Aronbis SS / Aronbis GL / Aronbis M / Aronbis MS / Aronbis S (FB) / Aronbis AH / Aronbis A -105 (Nippon Pure Chemicals Co., Ltd.), Glass Coal HA2, Glass Coal HA4, Glass Coal PA6, Glass Coal GH, Glass Coal 616W (Made by Hoechst Co., Ltd.), Heimer TBH-1500, Heimer TBH -2500 · UNI-3000 · UNI-3500 · TB-1800 · TB-180 (manufactured by Sanyo Chemical Co., Ltd.) ”and the like, and the water-dispersible acrylic resin colloidal dispersion used in the present invention Specific examples include “John Crill J-61J, John Crill 354, John Crill 501 (manufactured by Johnson Co., Ltd.)” and the like. Specific examples of the water-dispersible acrylic resin emulsion used in the present invention Enumerated in "Jonkrill J-61, Jonkrill J-62, Jonkrill J-68 Jonkrill J-537 (above, manufactured by Johnson Co., Ltd.), Rubymer 36D, Rubymer LOW VOC (above, manufactured by BASF Japan), Carboset XL-30 (manufactured by BF Goodrich Co., Ltd.), Jurimer ET-410 Julimer ET-510 (above, manufactured by Nippon Pure Chemical Co., Ltd.), APPRETAN3700, MOBILOL 771H, MOBILE DM772, MOVINYL DM774, VISCALEX HV30, VISCALEX VM, VISCALEX VS, VISCALEX VG2, VISCALEX HV1000, VISCALEX L030 Leobis CR, Leobis CRX, Leobis DP6-3902, Versicol E5, Versicol E7 (above, manufactured by Hoechst Co., Ltd.), Primal (manufactured by ROHM Co., Ltd.) and the like.
These acrylic resin powders, water-dispersible acrylic resin colloidal dispersions, and water-dispersible acrylic resin emulsions are extremely excellent in compatibility with the solvent. For example, both of them are mixed and stirred and left at 80 ° C. for 5 days. In some cases and when left at 5O 0 C for 5 days, the resin does not precipitate at all.
Further, the viscosity of the ink at 2000 rpm is 2000 mPa · s or more, and η1 / η2 = 0.2 to 0.5, η3 / η4 = 0.2 to 0.5, (η1: viscosity at 10 rpm) Η2: Viscosity at 1.0 rpm, η3: Viscosity at 5.0 rpm, η4: Viscosity at 0.5 rpm), and when thixotropy is imparted, the ink in a state where no shear stress is applied The viscosity becomes 30000 mPa · s or more, and the ink is gelled, the pearl pigment does not settle, and the pearl pigment can be prevented from forming a lump, so-called hard cake. Further, since the resin has excellent wettability with respect to the pearl pigment, it can adhere to the entire pearl pigment and maintain a dispersed state in the ink for a long period of time.
When using a stamp stand, by applying a force (shear stress) to press the stamp, etc., the viscosity of the ink will decrease moderately, so that the ink has an ideal viscosity enough to adhere to the stamp surface. It becomes.
Further, the resin acts as a fixing agent that adheres to the entire pearl pigment and strongly fixes the pearl pigment to the paper surface or the like, and the pearl pigment does not peel off even if the imprint after printing is rubbed with a finger.
The acrylic resin powder, the water-dispersible acrylic resin colloidal dispersion, and the water-dispersible acrylic resin emulsion may be used in at least one kind, and of course, a plurality of kinds may be mixed and used. In particular, the viscosity at 0.5 rpm is 2000 mPa. S or more, η1 / η2 = 0.2 to 0.5, η3 / η4 = 0.2 to 0.5, (η1: viscosity at 10 rpm, η2: viscosity at 1.0 rpm, η3: viscosity at 5.0 rpm Η4: Viscosity at 0.5 rpm) is preferable. Further, in the present invention, the acrylic resin powder and the like can be used in a range where the total amount of the resin is 0.001 to 50% by weight with respect to the total amount of the ink, but 0.01 to 0.9% by weight. In this case, the ink is most stable, and the most preferable change in viscosity is given without excessive thickening.
[0009]
In the present invention, polyacrylic acid, polymethacrylic acid, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer ester, polyvinylpyrrolidone, and the like can be blended as an auxiliary fixing agent in addition to the above substances. Further, in order to slightly accelerate the penetrating and drying of the imprint after stamping, a small amount of glycol ether such as diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, or triethylene glycol monobutyl ether may be blended as a penetration aid.
[0010]
In addition to the above additives, 1,3,5-hexahydrotriazine, 2-methoxycarbonylaminobenzimidazole-4′-N dodecylbenzol sulfonate, 1,2-benzisothiazolin-3-one, benzothiazole, Antiseptics and fungicides such as dimethylbenzylalkylammonium chloride, antioxidants such as dibutylhydroxytoluene, and pH adjusters such as diethanolamine, triethanolamine, and ammonia can be used, but they are not used or used if possible. However, it is preferable to use a very small amount.
[0011]
In the present invention, at 25 ° C., the viscosity at 0.5 rpm is 2000 mPa · s or more, η1 / η2 = 0.2 to 0.5, η3 / η4 = 0.2 to 0.5, (η1: viscosity at 10 rpm, η2 : The viscosity at 1.0 rpm, η3: the viscosity at 5.0 rpm, η4: the viscosity at 0.5 rpm), the most preferable effect was obtained, and 0 <η1 deviated from this range. /Η2<0.2, 0.5 <η1 / η2 ≦ 1.0, 0 <η3 / η4 <0.2, 0.5 <η3 / η4 ≦ 1.0 I can't. In the present invention, all viscosities including those at 10 rpm, 1.0 rpm, 5.0 rpm, and 0.5 rpm are values measured with an E-type viscometer (ST rotor, 25 ° C.).
[0012]
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples.
As comparative examples, a stamp base ink based on a marking pen ink (Comparative Example 1) and a conventional oil-based stamp base gold ink (Comparative Example 2) were given.
Note that “part” simply means “part by weight”.
[0013]
(Example 1)
Water 20 parts Glycerin 40 parts Iriodin 300 Gold Pearl 18 parts (Pearl pigment: manufactured by Merck)
Carbon black 15 parts Crosslinked branched polyacrylic resin powder 0.3 part Polyvinylpyrrolidone 4 parts Diethylene glycol monobutyl ether 2 parts Diethanolamine 0.3 part 1,2-benzisothiazol-3-one 0.4 part Carbon black and crosslinked branched polyacrylic resin powder were put into a three roll and mixed, and then mixed with the remaining substance with a propeller stirrer and measured with an E-type viscometer (ST rotor, 25 ° C.) However, 10 rpm: 2500 mPa * s, 1.0 rpm: 8000 mPa * s, 5.0 rpm: 3000 mPa * s, 0.5 rpm: 9000 mPa * s of golden ink was obtained.
When this ink was impregnated into a stamp stand made of urethane foam, ink leakage did not occur and the board surface was not dried even after 3 months.
[0014]
(Example 2)
Water 20 parts Glycerin 35 parts
Mearlin MagnaPearl 3000 20 parts (Pearl pigment: The Mearl Corporation)
CI Solvent Black27 18 parts Cross-linked branched polyacrylic resin emulsion (solid content 60%) 1 part Polyvinylpyrrolidone 4 parts Diethylene glycol monobutyl ether 1.5 parts Diethanolamine 0.1 part Dimethylbenzylalkylammonium chloride 0.4 part The pearl pigment and CI Solvent Black 27 were put into a three roll and mixed, and then mixed with the remaining substance with a propeller stirrer, and the value measured with an E-type viscometer (ST rotor, 25 ° C.) Silver inks of 10 rpm: 4500 mPa · s, 1.0 rpm: 12000 mPa · s, 5.0 rpm: 5000 mPa · s, 0.5 rpm: 14000 mPa · s were obtained.
When this ink was impregnated into a stamp stand made of urethane foam, ink leakage did not occur and the board surface was not dried after 3 months.
[0015]
(Example 3)
Water 20 parts Glycerin 40 parts Iriodin 504 Red 18 parts (Pearl pigment: manufactured by Merck)
CI Solvent Red124 15 parts Crosslinked branched polyacrylic resin powder 0.3 parts Styrene-acrylic acid copolymer 4 parts Diethylene glycol monobutyl ether 2 parts Triethanolamine 0.3 part 1,2-benzisothiazole-3- ON 0.4 part The above-mentioned pearl pigment, CI Solvent Red124, and a crosslinked branched polyacrylic resin powder are put into a three roll and mixed, and then this is mixed with the remaining substance with a propeller stirrer. Values measured with an E-type viscometer (ST rotor, 25 ° C.) have a gloss of 10 rpm: 5000 mPa · s, 1.0 rpm: 14000 mPa · s, 5.0 rpm: 8000 mPa · s, 0.5 rpm: 21000 mPa · s. A red ink was obtained.
When this ink was impregnated into a stamp stand made of urethane foam, ink leakage did not occur and the board surface was not dried after 3 months.
[0016]
(Comparative Example 1)
Water 60 parts Glycerin 5 parts Ethylene glycol 5 parts
20 parts of Mearlin Luster Pigments SUPER BLUE-RUSSENT 9650Z (Pearl pigment: manufactured by The Mearl Corporation)
C.I. Solvent BLUE5 15 parts Polyvinylpyrrolidone 5 parts 1,2-benzisothiazol-3-one 0.4 parts After the above pearl pigment and C.I. Solvent BLUE5 were put into three rolls and mixed, This was mixed with polyvinylpyrrolidone and the remaining substance with a propeller stirrer, and values measured with an E-type viscometer (ST rotor, 25 ° C.) were 10 rpm: 100 mPa · s, 1.0 rpm: 140 mPa · s, and 5. A blue ink of 0 rpm: 110 mPa · s and 0.5 rpm: 180 mPa · s was obtained.
When this ink was impregnated into a stamp stand made of urethane foam, ink drop occurred after 2 days at room temperature, and the board surface was hardened and could not be printed.
[0017]
(Comparative Example 2)
Polypropylene glycol dibutyl ether 60 parts Rosin modified ester 20 parts Brass powder 20 parts The above materials were mixed with a propeller stirrer and the value measured with an E-type viscometer (ST rotor, 25 ° C) was 10 rpm: 5000 mPa · s, 1 Gold ink of 0.0 rpm: 8000 mPa · s, 5.0 rpm: 6500 mPa · s, 0.5 rpm: 12000 mPa · s was obtained.
When this ink was impregnated into a stamp stand made of urethane foam, ink leakage did not occur even after 3 months, and the board surface was not dry. It exuded.
Since this ink is hydrophobic, ethanol was used for washing the marking surface.
[0018]
(Test method and evaluation criteria)
(1) Ink drop test on ink occlusion body * Stamps made of urethane foam were impregnated with each ink and allowed to stand at room temperature for 1 month, and then imprinted on fine paper, and the imprint was observed.
○: Vivid △: Smudged ×: Cannot be stamped (2) Board surface drying test * Stamps made of urethane foam are impregnated with each ink and left on the board surface for 1 month at room temperature. Then, the impression was observed.
○: Vivid △: Faint ×: Not stamped (3) Test of cleaning of marking surface * After marking, the stamp surface of the stamp was washed with tap water and the marking surface was observed.
(However, Comparative Example 2 was washed with ethanol.)
○: Completely removed △: A little removed ×: Unremovable [0019]
[Table 1]
┌────┬──────┬──────┬──────┐
│ │ Ink drop │ Board surface drying │ Print surface cleaning │
├────┼──────┼──────┼──────┤
│Example 1│ ○ │ ○ │ ○ │
├────┼──────┼──────┼──────┤
│Example 2│ ○ │ ○ │ ○ │
├────┼──────┼──────┼──────┤
│Example 3│ ○ │ ○ │ ○ │
├────┼──────┼──────┼──────┤
│Comparative Example 1│ × │ × │ △ │
├────┼──────┼──────┼──────┤
│Comparative Example 2│ ○ │ ○ │ △ │
└────┴──────┴──────┴──────┘
[0020]
【effect】
In the present invention, when the stamp stand is not used, the ink is gelled with the pearl pigment dispersed therein, so that the ink does not fall off or drop. Further, since the ink does not evaporate and the board surface does not dry, an appropriate amount of ink can always be provided on the printing surface.
Furthermore, since the ink adhering to the stamp surface of the stamp can be easily and completely removed with water, color mixing does not occur even when different color inks are used.
Further, since the pearl pigment is entangled in paper fibers and hardly diffuses, it functions as a bleed-proofing agent, and a sharp impression can be obtained.

Claims (3)

It contains a solvent comprising water and a water-soluble organic solvent, a pearl pigment, one or more resins selected from acrylic resin powder, water-dispersible acrylic resin colloidal dispersion, and water-dispersible acrylic resin emulsion. Water-based stamp stand ink.   The viscosity at 0.5 rpm is 2000 mPa · s or more, and η1 / η2 = 0.2 to 0.5, η3 / η4 = 0.2 to 0.5, (η1: viscosity at 10 rpm, η2: 1.0 rpm The water-based stamp base ink according to claim 1, wherein: η3: viscosity at 5.0 rpm, η4: viscosity at 0.5 rpm). The total amount of one or more resins selected from acrylic resin powder, water-dispersible acrylic resin colloidal dispersion, and water-dispersible acrylic resin emulsion, wherein the water- soluble organic solvent is 25% to 90% by weight with respect to the total amount of ink. The water-based stamp base ink according to claim 1 or 2, wherein is from 0.01% by weight to 0.9% by weight based on the total amount of the ink.