JP7151971B2 - Water-based metallic color ink - Google Patents

Description

Article 30, Paragraph 2 of the Patent Act applies Date of shipment October 16, 2018 (October 16, 2018) Destination LION STATIONERY CO., LTD. PTE LT (Location: 29 Kaki Bukit Road 2, Singapore 417852)

TECHNICAL FIELD The present invention relates to a water-based metallic color ink that is mainly used in marking pens and the like, and that gives writing lines with metallic luster.

Gold or silver water-based inks for marking pens, in which metal pigments are dispersed in water, have been known for some time. No. has been proposed. Aluminum pigments are mainly used in these water-based inks, and non-leafing type or leafing type aluminum pigments are used.
The non-leafing type has excellent adhesion (anti-peeling) because the scaly aluminum particles disperse in the ink film without floating on the surface of the ink film that makes up the writing line, and when complementary color pigments are added. Although it has the advantage that it is easy to obtain a coloring effect, it has the disadvantage that it is slightly inferior in terms of hiding power because it easily transmits light.
On the other hand, the leafing type has excellent luster and hiding properties because the scale-like aluminum particles float and are arranged on the surface of the ink coating film, but the adhesion (anti-peeling property) of the particles on the surface is poor. Even if a pigment is added, it is hidden by the aluminum particles aligned on the surface of the ink coating film, so there is a drawback that the coloring effect of the complementary color pigment is hardly obtained.
Patent Document 4 proposes a water-based metallic color ink in which the above-mentioned non-leafing type and leafing-type aluminum pigments are combined to improve color developability, luster and concealability.

JP-A-63-072771 JP-A-63-095277 JP-A-09-165545 Japanese Patent Application Laid-Open No. 2005-29730

However, the water-based ink described in Patent Document 4 has improved color development, luster, and hiding properties compared to the case where leafing and non-leafing aluminum pigments are blended alone. There is room for improvement, such as conspicuous show-through, color separation, etc. on the writing line when writing, and the color does not develop beautifully. Here, color separation means that the pigment settles on the paper surface before the aluminum pigment in the ink coating film when writing, and the aluminum pigment covers it from above, resulting in the loss of the color of the pigment and almost only the metallic color. It is a phenomenon that presents

The present invention is a water-based metallic color that can obtain beautiful writing lines with a metallic luster even when writing on paper, etc., especially black paper, etc., by reliably preventing the show-through, color separation, etc. of the writing line. provide ink.

The invention completed to solve the above problems is a water-based metallic color ink containing at least a non-leafing type aluminum pigment, a leafing type aluminum pigment, an ethylene-vinyl acetate emulsion, water, and a pigment.

Since the present invention is a water-based metallic color ink containing at least a non-leafing type aluminum pigment, a leafing type aluminum pigment, an ethylene-vinyl acetate emulsion, water, and a pigment, the ethylene-vinyl acetate emulsion forms a network structure. , it is possible to prevent the pigment from settling in the ink film when writing. Therefore, in the process in which the solvent permeates into the paper, the aluminum pigment settles on the surface of the paper before the pigment, and the pigment gets on top of it, so that the color of the pigment is not lost and the color developability is good. In addition, since the ethylene-vinyl acetate emulsion has the effect of orienting the aluminum pigment in the ink, the aluminum pigment settles on the surface of the paper in a regularly oriented state, forming a laminate with few gaps, which improves the brightness. , the concealability can be improved. In the present invention, "orientation" is defined as arranging in a certain direction.

The present invention will be described in detail below.
Non-leafing type aluminum pigments and leafing type aluminum pigments are known as aluminum pigments used in ordinary writing instruments. , the concealability can be improved.
The non-leafing type aluminum pigment and the leafing type aluminum pigment are mainly fine particles having an average particle size of less than 20 μm. A paste obtained by mixing and dispersing it in a medium comprising hydrogen or a glycol ether solvent such as polyoxyethylene alkyl ether using a ball mill or the like is preferably used from the viewpoint of safety. A dry method or a wet method as described in JP-A-55-99970 is usually used to form a paste. In particular, a non-leafing type aluminum pigment paste made by pasting a medium such as aluminum fine particles, oleic acid, mineral spirit, etc., and a surfactant, etc. is a paste of aluminum fine particles, a medium such as stearic acid, mineral spirit, etc., and a surfactant, etc. The resulting paste becomes a leafing type aluminum pigment paste, which is preferably used in the present invention.
The total amount of the non-leafing type aluminum pigment and the leafing type aluminum pigment is used in the range of 1.0 to 20.0% by weight, preferably 2.0 to 10.0% by weight, based on the total amount of the ink.
In the present invention, commercially available aluminum pigment pastes can be used, and as non-leafing types, specifically, ALPASTE EMR-D6390, ALPASTE 1500MA, ALPASTE WXM7640, ALPASTE WE7640, ALPASTE WJD7640, ALPASTE WJE7640 ( Above, product name: Toyo Aluminum Co., Ltd.), AW-600, AW-500B, AW-520B, AW-666C, AW-808C, AW-7000R (above, product name: Asahi Kasei Co., Ltd.) Specific examples of the leafing type include ALPASTE WXM0650, ALPASTE 0500M, WB0700, and WS0700 (trade names: manufactured by Toyo Aluminum Co., Ltd.).

In the present invention, an ethylene-vinyl acetate emulsion is used as the resin. The ethylene-vinyl acetate emulsion not only imparts adhesion to non-absorbing surfaces such as coated paper, but also has the effect of acting on both the pigment and the aluminum pigment in the ink to improve the color developability.
In the present invention, commercially available ethylene-vinyl acetate emulsions can be used, and specific examples include AQUACER526 and AQUATIX8421 (trade names: manufactured by BYK-Chemie Japan). The blending amount thereof is in the range of 5.0 to 30.0% by weight, preferably 10.0 to 20.0% by weight, based on the total amount of the ink.

The action of the ethylene-vinyl acetate emulsion on pigments and aluminum pigments will be described. In the ink film when writing, the ethylene vinyl acetate emulsion forms a network structure to prevent the pigment from settling. For this reason, in the process of the solvent penetrating into the paper, the aluminum pigment first settles on the paper surface, and the pigment is put on top of it. In addition, since the ethylene-vinyl acetate emulsion has the effect of orienting the aluminum pigment in the ink, the aluminum pigment settles on the surface of the paper in a regularly oriented state, forming a laminate with few gaps, which improves the brightness. , it is thought that the concealability can be improved.
By blending the ethylene vinyl acetate emulsion from the above, it is possible to make the most of the color of the pigment and the brightness of the aluminum pigment, and obtain writing lines with excellent coloring and hiding properties.

Water is used as the main solvent in the present invention. Tap water, distilled water, pure water, etc. may be used, but tap water is mainly used because it is the cheapest. used in the range of

A pigment is used as the colorant used in the present invention. As the pigment, conventionally known organic pigments and inorganic pigments can be used singly or in combination without any particular limitation. For example, azo-based, condensed azo-based, phthalocyanine-based, quinacridone-based, anthraquinone-based, dioxazine-based, indigo-thioindigo-based, berinone-berylene-based, isoindolenone-based, azomethyleneazo-based, diketopyrrolopyrrole-based organic pigments, etc. , carbon black, mica, titanium oxide, pearl pigments, and metal pigments such as iron oxide and brass.
These pigments are usually kneaded into known resins such as nitrocellulose, ethyl cellulose, terpene phenol, vinyl chloride/vinyl acetate copolymer, rosin ester, polyvinyl butyral, polyvinyl alcohol and the like to form processed pigments. It is convenient because it easily disperses into
Also, it is allowed to mix a dye as a coloring agent. As the dye, conventionally known oil-soluble dyes such as monoazo, disazo, metal complex monoazo, anthraquinone, phthalocyanine, and triallylmethane dyes can be used without particular limitation.
The above dyes and pigments may be used singly or in combination, and the blending amount thereof is preferably 1 to 30% by weight based on the total amount of the ink.

Although it is not essential for the present invention, a fixing agent can be added in order to adhere the ink coating film constituting the writing line to the material to be written. As the fixing agent that can be used in the present invention, a resin that dissolves or disperses in ink can be used. One or more of hydroxyethyl cellulose, hydroxypropyl cellulose and the like can be selected and used.
Examples of the acrylic resin include resins such as polyacrylic acid, polymethacrylic acid, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, and resins composed of alkali metal salts, ammonium salts, and amine salts thereof. Powder is used, Joncryl 683, 67, 586 (manufactured by Johnson Polymer Co., Ltd.), Jurimer AC-10P, AC-10NP, AC-103AP (manufactured by Nippon Junyaku Co., Ltd.) and the like are exemplified. As the water-soluble acrylic resin solution, an aqueous solution of an alkali metal salt, ammonium salt, or amine salt of polyacrylic acid, polymethacrylic acid, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, etc. Among them, those having a solid content of 20 to 60% are preferably used. Vinyl resins, vinyl acetate copolymer resins, acrylic copolymer resins, styrene-acrylic copolymer resins, styrene-butadiene copolymer resins, etc., and those having a solid content of 20 to 60% are preferably used. 1535, 537, 74J (manufactured by Johnson Polymer Co., Ltd.), Julimer ET-410, ET-510 (manufactured by Nippon Junyaku Co., Ltd.), Apletan 3410, Movinyl DM765, 771H, DM772, DM774 (manufactured by Nippon Junyaku Co., Ltd.) Clariant Polymer Co., Ltd.) and the like can be exemplified.
These fixing agents contribute to the adhesion of the ink coating to the writing material and the water resistance of the ink coating, and are 0.1 to 30.0% by weight, preferably 0.5 to 20% by weight of the total amount of the ink. It is used in the range of .0% by weight.

Various other substances can also be added in the present invention. For example, as preservatives, sodium benzoate, 1,2-benzisothiazol-3-one, 1,2-benzisothiazol-3-one sodium salt, 1,2-benzisothiazol-3-one alkylamine salt , Potassium sorbate, Sodium dehydroacetate, 2-Methoxycarbonylaminobenzimidazole-4'-N-dodecylbenzol sulfonic acid, Precipitable barium sulfate as a pigment anti-settling agent/anti-bleeding agent, Clay, Hydrophilic silica, Hydrophobic silica , Extender pigments such as ultrafine anhydrous silica, aluminum silicate, calcium carbonate, sorbitan trioleate, sorbitan monostearate, etc. as pigment dispersants, butylhydroxyanisole, 2,2'-methylenebis(4-methyl-6 -t-butylphenol), 2,2′-methylenebis(4-ethyl-6-t-butylphenol), 4,4′-thiobis(3-methyl-6-t-butylphenol), 4,4′-butylidenebis(3 -methyl-6-t-butylphenol), vitamin C, vitamin E, etc. may be added.

The ink of the present invention is prepared by selecting an appropriate amount of the above substances and mixing and dispersing the mixture with a stirrer at room temperature to 50° C. for about 3 hours.

表中の変性エチレン酢酸ビニルエマルジョンは、ＡＱＵＡＣＥＲ５２６（ビックケミー・ジャパン(株)社製）、アクリル酸エステルエマルジョンは、モビニールＤＭ７５８（日本合成化学工業(株)社製）、塩化ビニル系エマルジョンは、ビニブラン７００（日信化学工業(株)社製）、ポリメタクリル酸エステルエマルジョンは、ジュリマーＥＴ－３２５（日本純薬(株)社製）である。また、リーフィングアルミニウム顔料、ノンリーフィングアルミニウム顔料はそれぞれ、アルペーストＷＸＭ０６５０、アルペーストＥＭＲ－Ｄ６３９０（東洋アルミニウム（株）社製）である。
実施例及び比較例について、以下の条件で試験を行った。
（１）発色性試験：繊維芯を備えた生インキ式マーキングペンにインキを充填し、黒地の普通紙に筆記したインキ塗膜を評価した。
○：顔料の色彩を有している。
△：少し顔料の色彩を有している。
×：ほとんど金属色のみである。
（２）光輝性試験：繊維芯を備えた生インキ式マーキングペンにインキを充填し、黒地の普通紙に筆記したインキ塗膜を評価した。
○：金属光沢を有している。
△：少し金属光沢を有している。
×：金属光沢が無く、くすんでいる。
（３）隠蔽性試験：繊維芯を備えた生インキ式マーキングペンにインキを充填し、黒地の普通紙に筆記したインキ塗膜を評価した。
○：下地は全く見えない。
△：少し下地が見える。
×：下地が透けて見える。 Table 1 shows the ink formulations of Examples and Comparative Examples.

Modified ethylene-vinyl acetate emulsion in the table is AQUACER526 (manufactured by BYK-Chemie Japan Co., Ltd.), acrylic acid ester emulsion is Movinyl DM758 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and vinyl chloride emulsion is Vinyblan 700. (manufactured by Nissin Chemical Industry Co., Ltd.), and the polymethacrylate emulsion is Julimer ET-325 (manufactured by Nippon Junyaku Co., Ltd.). The leafing aluminum pigment and the non-leafing aluminum pigment are ALPASTE WXM0650 and ALPASTE EMR-D6390 (manufactured by Toyo Aluminum Co., Ltd.), respectively.
Examples and comparative examples were tested under the following conditions.
(1) Color developability test: A raw ink type marking pen having a fiber core was filled with ink, and the ink film was evaluated by writing on black plain paper.
◯: It has the color of a pigment.
Δ: It has a slight pigment color.
x: Almost metallic color only.
(2) Glitter test: A raw ink type marking pen having a fiber core was filled with ink, and the ink film was evaluated by writing on black plain paper.
○: It has metallic luster.
Δ: Slightly metallic luster.
x: No metallic luster, dull.
(3) Concealability test: A raw ink type marking pen having a fiber core was filled with ink, and the ink film was evaluated by writing on black plain paper.
◯: The base cannot be seen at all.
Δ: The base is slightly visible.
x: The base can be seen through.

Comparative Example 1 in Table 1 is a combination of modified ethylene vinyl acetate and leafing aluminum pigment, and Comparative Example 2 is a combination of modified ethylene vinyl acetate and non-leafing aluminum pigment. In Comparative Example 1, the writing line had no pigment color, and the coloring property was very poor compared to the glittering property and the hiding property. The reason for this is that the leafing type has excellent luster and hiding properties because the scale-like aluminum particles float and are arranged on the surface of the ink film. This is thought to be due to the drawback that almost no coloring effect can be obtained with complementary color pigments because they are hidden by the aluminum particles. In Comparative Example 2, the writing lines had no metallic luster, and the black background was seen through the writing lines, so that the brilliance and hiding properties were very poor. The reason for this is that in the non-leafing type, the scale-like aluminum particles disperse in the ink film without floating on the surface of the ink film that makes up the writing line, so it is easy to obtain the coloring effect when adding a complementary color pigment. Although it has an advantage, it is considered to have a disadvantage that it is slightly inferior in terms of concealability because it easily transmits light. Comparative Examples 3 to 5 are formulations in which leafing aluminum pigments and non-leafing aluminum pigments are used in combination with emulsions other than modified ethylene vinyl acetate. Compared with Comparative Examples 1 and 2, the color developability, brightness, and hiding properties are improved, but not good.
Example 1 is a combination of a leafing aluminum pigment and a non-leafing aluminum pigment combined with modified ethylene vinyl acetate. It is clear that the combined use of the three components improves the color developability, luster and concealability compared to Comparative Examples 1-5.

While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiments, the invention is not limited to the embodiments disclosed herein. However, it can be changed as appropriate within the range not contrary to the gist or idea of the invention that can be read from the scope of claims and the entire specification, and water-based metallic color inks with such changes are also understood to be included in the technical scope. There must be.

Claims (1)

A water-based metallic color ink comprising at least a non-leafing type aluminum pigment, a leafing type aluminum pigment, an ethylene-vinyl acetate emulsion, water and a pigment.