JP6821138B2 - Oil-based metallic color ink - Google Patents

Description

The present invention relates to an oil-based metallic color ink that is mainly used in a marking pen or the like and gives a writing line having a metallic luster.

Conventionally, ethanol-based inks for marking pens in which aluminum powder is dispersed in ethanol have been known, and for example, Patent Document 1 has been proposed. Aluminum powder, ethanol, and ethanol-soluble rosin-modified maleic acid resin are used as this ethanol-based ink. Therefore, it has little malodor and toxicity, has good writeability on many writing surfaces, and does not deteriorate due to gas generation even if ethanol reactive with aluminum or the like is used.

Japanese Unexamined Patent Publication No. 4-342775

However, Patent Document 1 has a drawback that the adhesion of the writing line is inferior to that of photographic paper and art paper. Poor adhesion of the writing line means that when the writing line is rubbed with a finger or the like, the writing line is displaced.

The oil-based metallic color ink of the first invention made to solve the above problems is an aluminum pigment and one or more alcohol-based organics selected from methanol, ethanol, propanol, butanol, pentanol, hexanol, and benzyl alcohol. A solvent, a resin soluble in the organic solvent, a solid content of 30% by mass, an acid value of the resin of 45 to 57 KOHmg / g, a glass transition point of 42 to 70 ° C., and an average particle diameter of 30 to 100 nm. It is characterized by containing at least a vinyl chloride acrylic emulsion having a property of not agglomerating even when mixed.

The second invention is the oil-based metallic color ink according to the first invention, wherein the aluminum pigment comprises a non-leaving type aluminum pigment and a leaving type aluminum pigment.

INDUSTRIAL APPLICABILITY The present invention can provide an oil-based metallic color ink having good adhesion to photo paper and art paper as well as having low malodor and toxicity.
Further, when the aluminum pigment is a mixture of a non-leaving type aluminum pigment and a leaving type aluminum pigment, the hiding property and brightness are high even though the aluminum content is suppressed, and the pen core (fiber core) Since clogging is unlikely to occur, it is possible to provide an oil-based metallic color ink in which the writing line is less likely to be blurred as a result.

(a) is a conceptual diagram of the present invention. (B) is a conceptual diagram of the prior art.

Next, the present invention will be described in detail.
As the aluminum pigment of the present invention, various aluminum pigments, particularly aluminum flake pigments, aluminum pastes and the like can be used.

Aluminum flake pigments include leafing type and non-leafing type. Here, the leafing type aluminum flake pigment uses a grinding device such as a ball mill having a steel ball and a spherical grinding medium such as a steel ball, and uses a saturated fatty acid such as stearic acid as a grinding aid to prepare a mineral spirit. It is obtained by wet grinding aluminum powder in an organic solvent such as solvent naphtha. Further, the non-leafing type aluminum flake pigment can be obtained by the same grinding using an unsaturated fatty acid such as oleic acid as a pulverizing aid instead of the saturated fatty acid described above.

Since the leafing type aluminum flake pigment has a low surface tension, it has a weak affinity with the solvent and binder contained in the paint. Therefore, it floats on the surface layer side of the coating film and is oriented substantially uniformly, thereby exhibiting an excellent metallic feeling and substrate hiding property. In addition, fatty acids used as pulverizing aids are adsorbed on the surface of the aluminum pigment, which imparts so-called leafing properties that are arranged in parallel with the surface of the coating film, and has a high reflectance represented by, for example, a chrome-plated finish. A coating film showing the above can be formed. As the leafing type aluminum flake pigment, a thickness of 0.1 to 1 μm and an average particle size of 5 to 15 μm can be used, and if the average particle size is 15 μm or more, it is difficult to pass through a thin tube such as a fiber core used for writing. In other words, so-called clogging is likely to occur, and if it is 5 μm or less, the brilliance (luminance) of the writing line is significantly reduced.

On the other hand, the non-leaving type aluminum flake pigment has a strong affinity with the solvent and binder contained in the paint because the surface tension is not so small. Therefore, it is distributed in a state of being substantially uniformly oriented inside the coating film, thereby giving the coating film a metallic feel and showing a so-called metallic design. As the non-leafing type aluminum flake pigment, a thickness of 0.5 to 1 μm and an average particle size of 5 to 15 μm can be used. If the average particle size is 15 μm or more, the pigment passes through a thin tube such as a fiber core used for writing. It is difficult, so-called clogging is likely to occur, and if it is 5 μm or less, the brilliance (luminance) of the writing line is remarkably lowered.

In addition, aluminum paste can also be used as the aluminum pigment.
The leafing type aluminum paste mainly contains unsaturated fatty acids (for example, stearic acid) as grease, and aluminum phosphorus pieces in the coating film float on the surface of the coating film.
Examples of such a leafing type aluminum flake pigment include EB651PA (manufactured by SILBERLINE).

On the other hand, the non-leaving type aluminum paste mainly contains saturated fatty acids (for example, oleic acid) as grease, and the phosphorus pieces of aluminum sink in the coating film.
Examples of such non-leafing type aluminum flake pigments include aluminum paste HIGH PRINT TD690PA (manufactured by Toyo Aluminum K.K.).

The aluminum pigment can be used alone, but it is more preferable to use a mixture of two or more. When two or more kinds of a mixture are prepared, it is preferable to use a mixture of a leaving type aluminum pigment and a non-leaving type aluminum pigment.
By mixing the leafing type and non-leaving type aluminum pigments, it is possible to impart an excellent metallic feeling and substrate hiding property.
In the present invention, the aluminum pigment can be used in an amount of 1 to 20% by weight, preferably 3 to 10% by weight, based on the total amount of the ink.

Organic solvents that can be used in the present invention include alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol and benzyl alcohol, alicyclic hydrocarbons such as methylcyclohexane, dimethylcyclohexane and ethylcyclohexane, and hexane. Aliper hydrocarbons such as octane, aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as methyl ethyl ketone, dimethyl ketone, diethyl ketone and 4-methoxy-4-methylpentanone, methyl acetate, ethyl acetate, etc. Esters such as propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 2-methoxypropanol, 3-methoxy-3-methylbutanol and other glycol ethers, etc. One or a mixture of two or more selected from the above is used.
Among them, lower fatty alcohols having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, 2-butanol, and tert-butyl alcohol are considered from the viewpoint of safety and quick-drying. Most preferred from.
In the present invention, the organic solvent can be used in an amount of 50 to 95% by weight, preferably 60 to 90% by weight, based on the total amount of the ink.
It is also possible to add water if necessary.

The resin that can be used in the present invention is used to disperse the aluminum pigment, and if it is stably soluble in the organic solvent, it is a maleic acid-modified rosin ester, gum rosin, rosin-modified phenol resin, phenol resin, ketone. Examples thereof include resins, alkyd resins, cellacs, xylene resins, kumaron resins, nitrocellulose, ethyl cellulose and the like. When ethanol is used as the organic solvent, it is preferable to use a maleic acid-modified rosin ester.
In the present invention, the resin can be used alone or in combination, and can be used in an amount of 1 to 20% by weight, preferably 10 to 15% by weight, based on the total amount of ink.

A vinyl chloride acrylic emulsion (vinyl chloride acrylic copolymer emulsion) is used in the present invention. The vinyl chloride acrylic emulsion is an aqueous emulsion of a copolymer resin of vinyl chloride and an acrylic acid ester, but has a property of not agglomerating even when mixed with the organic solvent. The copolymers of polyvinyl chloride and polyacrylic acid suspended in water exhibit high lipophilicity and low solubility in water, and thus exhibit high water resistance.
The vinyl chloride acrylic emulsion used in the present invention preferably has a solid content of 25 to 30% by mass, a resin acid value of 8 to 57 KOHmg / g, a glass transition point of 25 to 73 ° C., and an average particle diameter of 30 to 100 nm, and has a solid content of 30% by mass. %, The acid value of the resin is 45 to 57 KOHmg / g, the glass transition point is 42 to 70 ° C., and the average particle size is 30 to 100 nm.
Specifically, as the Viniblanc 700 series, grades 700, 701, 715S, 735, 745 (all manufactured by Nisshin Chemical Industry Co., Ltd.) and the like can be exemplified. Vinibran 700 has a solid content of 30% by mass, a resin acid value of 57 KOHmg / g, a glass transition point of 70 ° C., and an average particle diameter of 30 nm. Vinibran 701 has a solid content of 30% by mass, a resin acid value of 46 KOHmg / g, a glass transition point of 73 ° C., and an average particle diameter of 30 nm. Vinibran 715S has a solid content of 25% by mass, a resin acid value of 8 KOHmg / g, a glass transition point of 25 ° C., and an average particle size of 90 nm. Vinibran 735 has a solid content of 30% by mass, a resin acid value of 45 KOHmg / g, a glass transition point of 42 ° C., and an average particle size of 100 nm. Vinibran 745 has a solid content of 30% by mass, a resin acid value of 50 KOHmg / g, a glass transition point of 57 ° C., and an average particle diameter of 70 nm. Among them, Viniblanc 700 (solid content 30% by mass, resin acid value 57 KOHmg / g, glass transition temperature 70 ° C., average particle size 30 nm) and Viniblanc 735 (solid content 30% by mass, resin acid value 45 KOHmg / g, glass). A transition point of 42 ° C. and an average particle size of 100 nm) is preferable.
In the present invention, it can be used in an amount of 1 to 10% by weight, preferably 4 to 6% by weight, based on the total amount of ink.

In the present invention, by using the vinyl chloride acrylic emulsion, the adhesion of the writing line to the photographic paper or the art paper is improved. Good adhesion of the writing line means that the writing line does not shift even if the writing line is rubbed with a finger or the like. This is due to the fact that an ink absorbing layer is provided on the surface of photo paper or art paper.

As shown in FIG. 1, the photographic paper 3 is composed of an ink absorbing layer 31 and photographic printing paper (polyethylene resin layer 32 and paper layer 33) in this order from the front surface side. The ink absorbing layer 31 has a porous ceramic structure composed of inorganic ultrafine particles, and instantly and accurately absorbs innumerable droplets of several picolitres ejected by a printer head. The surface area of the A4 size ink absorbing layer 31 is about the same as that of a tennis court, and has a porous ceramic structure composed of innumerable pores of 20 nm.

As shown in FIG. 1 (b) conceptual diagram of the prior art, in the conventional oil-based metallic color ink that does not use a vinyl chloride acrylic emulsion, most of the vehicle content 4 in which the resin is dissolved in the organic solvent is said. It is considered that the ink is absorbed by the ink absorbing layer 31 and only the aluminum pigment 1 is left on the surface of the photographic paper. Therefore, when the writing line is rubbed with a finger or the like, the remaining aluminum pigment 1 is displaced. This is the phenomenon that the writing line is displaced, which was described in the above problem.

On the other hand, as shown in FIG. 1 (a) conceptual diagram of the present invention, it is considered that in the present invention, the vinyl chloride acrylic emulsion 2 is not absorbed by the ink absorbing layer 31 and remains on the surface of the photographic paper. Therefore, it is considered that the aluminum pigment 1 fixed by the resin component of the vinyl chloride acrylic emulsion 2 remains on the surface of the photographic paper, and the aluminum pigment does not shift even if the writing line is rubbed with a finger or the like. Therefore, it is considered that the phenomenon that the writing line is displaced does not occur and the adhesion is good.

In the present invention, known oil-soluble dyes and pigments can be used as coloring materials for color capture.
When the colorant is an oil-soluble dye, oil-soluble dyes such as monoazo, disazo, metal complex salt type monoazo, anthraquinone, phthalocyanine, and triallylmethane, which are generally available on the market, can be used alone or in combination. Salt-forming oil-soluble dyes in which the hydrophilic groups of acidic dyes are replaced with hydrophobic groups such as cationic activators, resin bases, amines, and basic dyes, and the hydrophilic groups of direct dyes are cationic activators, resin bases, amines, and basic dyes. Use salt-forming type oil-soluble dyes in which the hydrophilic groups of basic dyes are replaced with hydrophobic groups such as anionic activators, resin acids, acidic dyes, and direct dyes. be able to.
When the colorant is a pigment, conventionally known organic pigments and inorganic pigments can be used, for example, azo-based, phthalocyanine-based, anthraquinone-based, dioxazine-based, indigo-thioindigo-based, verinone-berylene-based, and isoindrenone. Organic pigments such as carbon black, mica, titanium white, pearl pigments, and inorganic pigments such as metal pigments such as iron oxide, aluminum powder, and brass can be used. These pigments are usually polyacrylic acid, polymethacrylic acid, styrene-acrylic acid copolymers, rosin esters, nitrocelluloses, ethylcelluloses, their metal salts, ammonium salts, amine salts, and other known resins. It is convenient to knead it into a processed pigment to make it easily dispersed when mixed with a solvent. Alternatively, a commercially available processed pigment in which the pigment has already been kneaded into the dispersant may be used.
As the coloring material, 0.5 to 20% by weight can be used with respect to the total amount of the ink, and preferably 1 to 6% by weight can be used.

Further, in the present invention, as a thickener, a hydrophobic silica having a hydrophobic surface, fine particle silica having a methylated surface, aluminum silicate, a swelling mica, and a clay-based thickener such as bentonite or montmorillonite having a hydrophobic treatment. Can be further added.
Further, a phosphoric acid-based wet dispersant can be further added as a dispersion aid, and examples thereof include DISPERBYK-103 (manufactured by Big Chemie Japan Co., Ltd.).
Further, as an anti-bleeding agent, polyether-modified polydimethylsiloxane (polyether-modified silicone oil) can be further added, and examples thereof include BYK-302 (manufactured by Big Chemie Japan Co., Ltd.).
In addition, additives usually used for inks such as preservatives, fungicides, dye dissolving aids such as amines and phosphate esters, and penetrants such as benzyl alcohol can be further added.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
The oil-based metallic color ink of the present invention is prepared by adding an aluminum pigment, a resin, a vinyl chloride acrylic emulsion, and various additives as necessary in an organic solvent and stirring the ink.
(Example)

表中のアルミニウムペーストＡは、リーフィングタイプのアルミニウムペーストであり、アルミニウム含有率７０重量％のペースト状物、アルミニウムの平均粒子径７μｍ、イソプロパノール分散体、商品名：ＥＢ６５１ＰＡ（ＳＩＬＢＥＲＬＩＮＥ社製）である。
アルミニウムペーストＢは、ノンリーフィングタイプのアルミニウムペーストであり、アルミニウム含有率６５重量％のペースト状物、アルミニウムの平均粒子径６μｍ、酢酸ｎ−プロピル分散体、商品名：アルミニウムペースト ＨＩＧＨ ＰＲＩＮＴ ＴＤ６９０ＰＡ（東洋アルミニウム株式会社製）である。
表中の塩化ビニルアクリル系エマルジョンＡは、ビニブラン７００（日信化学工業株式会社製）であり、塩化ビニルアクリル系エマルジョンＢは、ビニブラン７３５（日信化学工業株式会社製）である。 The formulations of Examples and Comparative Examples are shown in Table 1.

The aluminum paste A in the table is a leafing type aluminum paste, which is a paste-like product having an aluminum content of 70% by weight, an average particle diameter of aluminum of 7 μm, an isopropanol dispersion, and a trade name: EB651PA (manufactured by SILBERLINE).
Aluminum paste B is a non-leaving type aluminum paste, which is a paste with an aluminum content of 65% by weight, an average particle size of aluminum of 6 μm, an n-propyl acetate dispersion, and a trade name: aluminum paste HIGH PRINT TD690PA (Toyo Aluminum). (Made by Co., Ltd.).
The vinyl chloride acrylic emulsion A in the table is Vinibran 700 (manufactured by Nisshin Chemical Industry Co., Ltd.), and the vinyl chloride acrylic emulsion B is Vinibran 735 (manufactured by Nisshin Chemical Industry Co., Ltd.).

In addition, the results of the tests conducted under the following conditions for Examples and Comparative Examples are shown.
Written aptitude test (test method)
Hand-write a 4 cm straight line on PPC paper, photo paper, art paper, or glass plate, and after 1 minute, touch the midpoint of the writing line.
(Result confirmation method)
◯: No line deviation occurs. X: Line deviation occurred.
Preservation test over time (test method)
The test sample is stored in an environment of 20 ° C., 65% (room temperature) and 50 ° C. for a period of 30 days with the pen core facing down, and the writeability after storage is confirmed.
(Result confirmation method)
⊚: There is no blur on the writing line. ◯: There is no significant blurring on the writing line. X: The writing line is blurred.

As is clear from Table 1, the inclusion of the vinyl chloride acrylic emulsion significantly improves the writing suitability of photo paper and art paper.
This is because, as described above, it is considered that the vinyl chloride acrylic emulsion is not absorbed by the ink absorbing layer and remains on the surface of the photographic paper (FIG. 1 (a)). Therefore, it is considered that the aluminum pigment fixed by the resin component of the vinyl chloride acrylic emulsion remains on the surface of the photographic paper, and the aluminum pigment does not shift even if the writing line is rubbed with a finger or the like.
Further, although the leafing type aluminum pigment has good storage stability over time, it has low hiding power and brightness, so that the aluminum content must be increased (Examples 1 and 5). Further, although the non-leaving type aluminum pigment has high hiding power and brightness, the pen core is liable to be clogged after storage over time, and as a result, the writing line is liable to be blurred (Examples 3 and 7).
Therefore, when a leaving type and a non-leafing type aluminum pigment are mixed as in Example 2, Example 4, Example 6, and Example 8, concealing property and brightness are suppressed even though the aluminum content is suppressed. As a result, it was possible to produce an oil-based metallic color ink in which the writing line is less likely to be blurred because the pen core is less likely to be clogged.

As described above, the present invention has been described in relation to the most practical and preferable embodiments at present, but the present invention is not limited to the embodiments disclosed in the present specification. It is understood that oil-based metallic color inks accompanied by such changes are also included in the technical scope, as they can be changed as appropriate within the scope of the claims and the scope of the invention that can be read from the entire specification without contradicting the gist or idea of the invention. There must be.

1 Aluminum pigment 2 Vinyl chloride acrylic emulsion 3 Photo paper 31 Ink absorption layer 32 Polyethylene resin layer 33 Paper layer 4 Vehicle content

Claims (2)

With aluminum pigment
One or more alcohol-based organic solvents selected from methanol, ethanol, propanol, butanol, pentanol, hexanol, and benzyl alcohol , and
The resin soluble in the organic solvent and
A vinyl chloride acrylic chloride having a solid content of 30% by mass, a resin acid value of 45 to 57 KOHmg / g, a glass transition point of 42 to 70 ° C., an average particle size of 30 to 100 nm, and a property of not agglomerating even when mixed with the organic solvent. Emulsion and
An oil-based metallic color ink characterized by containing at least. The oil-based metallic color ink according to claim 1, wherein the aluminum pigment comprises a non-leaving type aluminum pigment and a leaving type aluminum pigment.

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