JP3716545B2 - Highly concealed metallic glossy water-based ink - Google Patents

Description

上記各成分を、実施例１と同様になして金色のインキを得た。
【００２０】
実施例３

上記成分中の顔料は、フタロシアニンブルー３０重量部、エチレングリコール２０重量部、水４５重量部、ＮＰ−１０（ＰＯＥ（１０）ノニルフェニルエーテル、日光ケミカルズ（株）製）５重量部を媒体分散機にて分散したものである。
上記各成分を実施例１と同様になして、金属光沢のある青色インキを得た。
【００２１】
実施例４

上記各成分を実施例１と同様になして、金属光沢のある緑色のインキを得た。
【００２２】
実施例５
アルミニウムペースト（ＷＸＭ０６３０、東洋アルミニウム（株）製、アルミ
ニウム粉末含有量６０．０重量％） １．６重量部
酸化チタン（チタニックスＪＲ８００、テイカ（株）製） １０．０重量部
エチレングリコール １５．０重量部
グリセリン １０．０重量部
水 ６１．２重量部
スチレン−アクリル共重合物エマルジョン（ジョンクリルＪ７７５、固形分４
５重量％、ジョンソンポリマー（株）製） ２．０重量部
防腐剤（プロクセルＧＸＬ、ＩＣＩジャパン（株）製、１，２−ベンゾイソチ
アゾリン−３−オン） ０．２重量部
上記各成分を実施例１と同様になして、銀色のインキを得た。
【００２３】
実施例６

上記各成分を、実施例１と同様になして金色のインキを得た。
【００２４】
実施例７

上記各成分を、実施例１と同様になして金色のインキを得た。
【００２５】
比較例１
実施例１において、アルミニウムペーストを８．０重量部から３５．０重量部にし、さらに酸化チタンを１０．０重量部から０にし、その分水を減らした以外は、実施例１と同様になして、銀色のインキを得た。
【００２６】
比較例２
実施例２において、アルミニウムペーストを８．０重量部から３５．０重量部にし、さらに酸化チタンを１０．０重量部から０にし、その分水を減らした以外は、実施例２と同様になして、金色のインキを得た。
【００２７】
隠蔽力試験
以上、実施例１〜７、比較例１〜２で得た高隠蔽性金属光沢色水性インキを、白の上質紙、黒の上質紙に各々５０μｍのアプリケーターで塗布し、その塗布面を３時間乾燥させる。所定時間後、塗布面のＹ値を測定し、次式により隠蔽率を算出した。
隠蔽率（％）＝（黒上質紙上の塗布面のＹ値）／（白上質紙上の塗布面のＹ値）×１００
この隠蔽力試験は、インキ作成直後のインキと、同インキをサンプル瓶に入れ、５０℃恒温槽中に１ヶ月放置した後のインキとで行った。
【００２８】
筆記試験
実施例１、５及び比較例１のインキは繊維収束体のペン先を有し、インキ収容室内にインキ撹拌用撹拌部材を内在させたマーキングペンに充填して試験用筆記具となし、実施例２〜４、６及び比較例２のインキはステンレス製のボールペンチップ（ボール材質；超硬合金）を一端に連接したポリプロピレン製の中空軸筒よりなる透明なインキ収容管に充填して試験用筆記具となして、各々、黒画用紙に「♀」を連続で１００回筆記した。結果を表１に示す。
【００２９】
【表１】

【００３０】
【発明の効果】
以上、詳細に説明したように、本発明に係る高隠蔽性金属光沢色水性インキは、隠蔽力のある鮮明な金属光沢色の筆跡を与え、経時後も変質のない所期の目的が充分に達成できる有用なものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a highly concealed metallic luster color water-based ink using aluminum powder and titanium oxide as coloring materials, and provides a high concealable metallic luster that gives a highly concealed metallic gloss color even when written on a dark colored writing surface. The present invention relates to a color water-based ink.
[0002]
[Prior art]
Conventionally, as inks for writing instruments for dark colored writing surfaces such as black paper and colored rubber sheets, metallic inks are mainly used by using aluminum powder as the coloring material, and titanium oxide is used as the coloring material. Some of them are used to obtain white handwriting.
[0003]
For example, as a low-viscosity marking pen ink using aluminum powder, there are inks described in Japanese Patent Publication No. 62-37678 and Japanese Patent Publication No. 1-56109.
Japanese Patent Publication No. 62-37678 discloses a metal powder pigment such as aluminum powder, an oil-soluble dye, a resin, and a solvent, and the dye penetrates and spreads around the handwriting formed by the metal powder pigment. A dual color ink composition that produces a line effect is disclosed.
Japanese Examined Patent Publication No. 1-56109 includes a surface-treated fine metal powder such as aluminum powder, a resin, and a solvent, and has a smooth ink outflow property from a marking pen, and easy dispersibility during use. A metallic gloss ink for a marking pen is disclosed.
Moreover, as an ink using titanium oxide as a coloring material, there is an ink described in JP-A-4-258877.
This ink comprises at least a concealing material such as titanium oxide, a binder such as a resin emulsion, and water, and is used for a correction liquid and a marking pen.
[0004]
The ink described in the above Japanese Patent Publication No. 62-37678, Japanese Patent Publication No. 1-56109, and Japanese Patent Application Laid-Open No. 4-258679 uses aluminum powder or titanium oxide having a large specific gravity as a colorant. The colorant settles in a short period of time. Therefore, this ink is used by redispersing the coloring material settled before use.
As a redispersion method of the coloring material, a generally known method can be adopted. For example, when ink is incorporated in a writing instrument, a stirring member such as a metal sphere may be accommodated in the writing instrument together with the ink and re-dispersed by an operation such as swinging the writing instrument.
[0005]
On the other hand, unlike the above-described marking pen ink, an ink has been proposed in which the viscosity of the ink is increased and redispersion is unnecessary while using aluminum powder and titanium oxide.
For example, JP-A-60-186573 contains at least a required amount of a solvent, a thickening resin soluble in the solvent, a metal powder pigment and a color pigment, and has a high viscosity exceeding the required value. An ink having a metallic color, which is characterized by having the following, is disclosed. Since this ink has a high viscosity, the metal pigment is less precipitated, but a pressure ballpoint pen is suitable as a writing instrument.
Further, as an example of an ink used for a normal ballpoint pen which is not pressurized, Japanese Patent Publication No. 64-4551 discloses a non-flowable ink which has been gelled.
As an example of an ink using a white pigment such as titanium oxide, Japanese Patent Application Laid-Open No. 59-217776 discloses an ink having an ink viscosity of 10,000 CPS using sodium polyacrylate.
[0006]
The ink using the aluminum powder proposed as the above prior art is a so-called oil-based ink using an organic solvent as a solvent.
[0007]
On the other hand, as a water-based ink using an aluminum powder, Japanese Patent Application Laid-Open No. 1-210478 discloses a water-based metallic glossy ink that prevents stains due to pinholes.
[0008]
[Problems to be solved by the invention]
By the way, the water-based metallic glossy color ink in which the handwriting has a metallic luster uses aluminum powder as one component of the ink. The aluminum powder used in the water-based ink is one whose surface is treated with a fatty acid or inorganic phosphoric acid for the purpose of preventing reaction with water. However, even though it has been treated with the above substances, when stored for a long period of time, the aluminum powder and water undergo a chemical reaction, and the quality of the ink is generated such that gas is generated.
This deterioration of ink tends to occur when the amount of aluminum powder in the ink is large. Therefore, the amount of aluminum powder added is limited in aqueous ink. Therefore, it is difficult to say that the handwriting obtained using the water-based metallic glossy ink has a sufficient hiding power.
[0009]
It is an object of the present invention to provide a highly concealing metallic luster color water-based ink that gives a handwriting having a high concealing metallic luster on a dark writing surface such as black paper or a colored rubber sheet, in various colors. Is to provide.
[0010]
[Means for Solving the Problems]
The gist of the present invention is a highly concealing metallic luster color water-based ink comprising at least aluminum powder, titanium oxide, a water-soluble organic solvent, and water.
[0011]
Hereinafter, the present invention will be described in detail.
The aluminum powder used in the present invention is used as a coloring material that imparts brightness to the handwriting and causes the handwriting to have a metallic luster. A scale-like one is particularly preferred because the brightness appears more clearly.
The aluminum powder is put into a drum with a rigid ball and a stamping method in which an aluminum piece is pulverized with a lubricant such as stearic acid by a stamping mill, or an aluminum powder obtained by a spraying method and a suitable liquid. Is obtained by, for example, a ball mill method in which an aluminum piece is crushed by rotating.
Usually, it can be obtained as an aluminum paste as a commercial product. The aluminum paste was crushed and polished in a ball mill containing a high-boiling petroleum solvent (mineral spirit) and an anti-friction agent such as stearic acid to produce very thin scaly aluminum particles. However, since the scaly aluminum fine particles are wet with a petroleum solvent, there is little risk of ignition and explosion, good storage stability, and easy handling.
Commercially available aluminum powders include AA12, No. 900, no. 18000 (manufactured by Fukuda Metal Foil Powder Co., Ltd.). As the aluminum paste, Super Fine No. 22000WN, ibid. 18000WN (above, manufactured by Daiwa Metal Powder Industry Co., Ltd.), WB0230 (manufactured by Toyo Aluminum Co., Ltd.), WXM0630 (manufactured by Toyo Aluminum Co., Ltd.), and the like.
The amount of aluminum powder used is preferably 1 to 20% by weight based on the total amount of ink. When the amount used is less than 1% by weight, the metallic luster of the handwriting decreases, and when the amount used exceeds 20% by weight, the solid content increases and the fluidity becomes low, so that the ink discharge tends to deteriorate.
The average particle diameter of the aluminum powder is preferably 5 to 60 μm. This is because when the average particle size is less than 5 μm, the metallic luster of the handwriting is reduced, and it becomes easy to produce unsharp handwriting without a feeling of brightness, and when it is 60 μm or more, ink discharge tends to be reduced at the pen tip and difficult to apply. Because there is. When applied to a ballpoint pen, 30 μm or less is preferable in consideration of dischargeability from the pen tip.
[0012]
Titanium oxide is used as a coloring material that imparts concealment to the handwriting. In particular, in order to improve dispersibility and light resistance, those subjected to surface treatment with alumina and / or silica or the like are preferable.
Commercially available titanium oxides include Tytone SR-1, R-650, R-3L, R-5N (manufactured by Sakai Chemical Industry Co., Ltd.), Typek R-580, R-550, R-930, A-100, A-220, CR-58 (above, manufactured by Ishihara Sangyo Co., Ltd.), Kronos KR-310, KR-380, KR-480 (above, Titanium Industry ( Co., Ltd.), Taipure R-900, same R-902 (above, manufactured by DuPont Japan Limited), Titanic JR-300, same JR-600A, same JR-701 (above, manufactured by Teika Co., Ltd.) and so on.
The amount of titanium oxide used is preferably 5 to 20% by weight based on the total amount of ink. When the amount used is less than 5% by weight, the hiding power of the handwriting becomes weak, and when the amount used exceeds 20% by weight, the solid content tends to increase and ink ejection tends to be poor.
[0013]
The water-soluble organic solvent is used for the purpose of various qualities as ink, for example, prevention of ink freezing at low temperatures, and prevention of ink drying at the pen tip when used for writing instruments.
Specifically, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol 1, 3-butylene glycol, thiodiethylene glycol, glycerin, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, 2-pyrrolidone, tri Examples include ethanolamine.
The above water-soluble organic solvents can be used alone or in combination. The amount used is preferably 5 to 40% by weight based on the total amount of ink.
[0014]
Water is used as the main solvent.
[0015]
In addition, wetting agents such as urea, ethylene urea and thiourea, antiseptics such as benzothiazoline and omadin, rust preventives such as benzotriazole, dispersants and fixing agents for aluminum powder and titanium oxide, and ballpoint pens When used, various additives such as thickeners and colored pigments and dyes for making the handwriting a colored and highly concealed metallic luster can be added as necessary.
[0016]
In producing the highly concealing metallic luster color aqueous ink of the present invention, various conventionally known methods can be employed. For example, it can be easily obtained by blending the above components and stirring and mixing with a stirrer such as a Henschel mixer, or by mixing and grinding with a disperser such as a ball mill.
[0017]
[Action]
The aluminum powder needs to have a particle size of 5 μm or more in order to bring about a metallic luster. On the other hand, it is necessary to increase the amount of addition in order to increase the handwriting density and to provide high concealment. However, when the concentration is increased, the deterioration of the aluminum powder over time is further promoted, and as a result, the metallic luster is lost. Titanium oxide used in the present invention does not transmit light even if the particle size is 1 μm or less, has high hiding power, and does not deteriorate over time. Highly concealed metallic glossy handwriting is obtained.
[0018]
【Example】
Hereinafter, it demonstrates still in detail based on an Example.
Example 1
Aluminum paste (WXM0630, manufactured by Toyo Aluminum Co., Ltd., aluminum powder content 60% by weight) 8.0 parts by weight Titanium oxide (Titanics JR800, manufactured by Teika Co., Ltd.) 10.0 parts by weight Ethylene glycol 15.0 parts by weight Glycerin 10.0 parts by weight Water 54.8 parts by weight Styrene-acrylic copolymer emulsion (Johncrill J775, solid content 4
5% by weight, manufactured by Johnson Polymer Co., Ltd.) 2.0 parts by weight preservative (Proxel GXL, manufactured by ICI Japan Co., Ltd., 1,2-benzisothiazolin-3-one) 0.2 parts by weight Among the above components, The components excluding the aluminum paste were mixed and dispersed with a ball mill for 24 hours, then the aluminum paste was added, and the mixture was stirred with a stirrer for 1 hour to obtain a silver ink.
[0019]
Example 2

The above components were made in the same manner as in Example 1 to obtain a golden ink.
[0020]
Example 3

The pigment in the above components is 30 parts by weight of phthalocyanine blue, 20 parts by weight of ethylene glycol, 45 parts by weight of water, and 5 parts by weight of NP-10 (POE (10) nonylphenyl ether, manufactured by Nikko Chemicals). Dispersed in
The above components were made in the same manner as in Example 1 to obtain a blue ink with metallic luster.
[0021]
Example 4

The above components were made in the same manner as in Example 1 to obtain a green ink with metallic luster.
[0022]
Example 5
Aluminum paste (WXM0630, manufactured by Toyo Aluminum Co., Ltd., aluminum powder content 60.0% by weight) 1.6 parts by weight Titanium oxide (Titanics JR800, manufactured by Teika Co., Ltd.) 10.0 parts by weight Ethylene glycol 15.0 Parts by weight glycerin 10.0 parts by weight water 61.2 parts by weight styrene-acrylic copolymer emulsion (Johncrill J775, solid content 4
5% by weight, manufactured by Johnson Polymer Co., Ltd.) 2.0 parts by weight preservative (Proxel GXL, manufactured by ICI Japan Co., Ltd., 1,2-benzisothiazolin-3-one) 0.2 parts by weight In the same manner as in Example 1, a silver ink was obtained.
[0023]
Example 6

The above components were made in the same manner as in Example 1 to obtain a golden ink.
[0024]
Example 7

The above components were made in the same manner as in Example 1 to obtain a golden ink.
[0025]
Comparative Example 1
In Example 1, the same as in Example 1 except that the aluminum paste was changed from 8.0 parts by weight to 35.0 parts by weight, titanium oxide was changed from 10.0 parts by weight to 0, and water was reduced by that amount. Thus, a silver ink was obtained.
[0026]
Comparative Example 2
In Example 2, it was the same as Example 2 except that the aluminum paste was changed from 8.0 parts by weight to 35.0 parts by weight, titanium oxide was changed from 10.0 parts by weight to 0, and water was reduced accordingly. As a result, a golden ink was obtained.
[0027]
Over the hiding power test, the high hiding metal glossy color aqueous inks obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were applied to white high quality paper and black high quality paper with an applicator of 50 μm, respectively. Is dried for 3 hours. After a predetermined time, the Y value of the coated surface was measured, and the concealment rate was calculated by the following formula.
Concealment rate (%) = (Y value of coated surface on black fine paper) / (Y value of coated surface on white fine paper) × 100
This hiding power test was performed with the ink immediately after ink preparation and the ink after placing the ink in a sample bottle and leaving it in a thermostatic bath at 50 ° C. for one month.
[0028]
The inks of the writing test examples 1 and 5 and the comparative example 1 have a fiber converging nib, and are filled in a marking pen in which an ink stirring stirring member is contained in an ink containing chamber to form a writing instrument for testing. The inks of Examples 2 to 4, 6 and Comparative Example 2 were used for testing by filling a transparent ink containing tube made of a polypropylene hollow shaft cylinder with a ballpoint pen tip made of stainless steel (ball material: cemented carbide) at one end. As a writing instrument, “黒” was continuously written 100 times on black drawing paper. The results are shown in Table 1.
[0029]
[Table 1]

[0030]
【The invention's effect】
As described above in detail, the highly concealing metallic luster color water-based ink according to the present invention provides a clear metallic luster color handwriting with a concealing power, and has an intended purpose with no deterioration after time. It is a useful thing that can be achieved.

Claims (1)

A highly concealing metallic luster aqueous ink comprising at least aluminum powder, titanium oxide, a water-soluble organic solvent, and water.