JPH08151547A - Aqueous metallic luster color ink - Google Patents

Abstract

PURPOSE: To obtain the ink not affected by aluminum ions, and little in deterioration on storage for a long period because of causing the lowering of viscosity, gelation and precipitation. CONSTITUTION: The ink contains at least 1-30wt.% of aluminum powder, 0.2-2.0wt.% of welan gum and/or rhamsan gum, 5-40wt.% of a watersoluble organic solvent such as ethylene glycol or glycerol, and water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous metallic luster ink of metallic color such as gold, silver and copper, which uses aluminum powder as a coloring material, and has little deterioration of the ink even after long-term storage. Regarding color ink.

[0002]

2. Description of the Related Art Conventionally, metal powder pigments such as aluminum powder and bronze powder have been used as a metallic luster imparting agent for obtaining a metallic color tone such as gold or silver. Bronze powder has a specific gravity of 8.5 and a particle size of several μm is required to impart metallic luster to the handwriting, so problems such as sedimentation separation and clogging at the nib are likely to occur. It is very difficult to use for ink. On the other hand, aluminum powder has a specific gravity of 2.5.
It is easier to use than bronze powder, and there are many applications.

For example, Japanese Patent Publication No. 62-37678 discloses a dye consisting of a metal powder pigment such as aluminum powder, an oil-soluble dye, a resin, and a solvent. A dual color ink composition is disclosed which permeates and diffuses to produce a contour effect. Further, Japanese Patent Publication No. 1-56109 discloses a surface-treated fine metal powder such as aluminum powder, a resin, and a solvent.
There is disclosed a metallic gloss ink for a marking pen, which has a smooth ink outflow from the marking pen and is easily dispersible during use. Since the marking inks described in the above publications have low viscosities, the aluminum powder sediments and separates in a short period of time. Therefore, for these inks, a stirring member such as a metal ball is stored in the ink storage chamber,
The metal powder pigment settled by using the stirring member at the time of use is re-dispersed and used.

Unlike the above ink for marking pen,
A high-viscosity ink having metallic luster that does not use a stirring member such as a metal ball has also been proposed. For example, JP-A-60-1
Japanese Patent No. 86573 discloses that a solvent, a thickening resin soluble in the solvent, a metal powder pigment and a coloring pigment are each contained in at least a required amount, and that the resin has a high viscosity of a required value or more. Disclosed is an ink having a tonal color, which has a high viscosity and little sedimentation of a metal powder pigment, and is suitable for use in a pressure ballpoint pen. Japanese Examined Patent Publication No. 64-4551 discloses gelled ink.

The ink proposed as the above prior art is an oil-based ink which uses an organic solvent as a solvent.

On the other hand, as a water-based ink using aluminum powder, an acetylene alcohol derivative is added as an additive to the ink main component consisting of resin, aluminum paste and water as disclosed in JP-A-1-210478. Disclosed is a water-based metallic luster color ink which is characterized by preventing smearing of coating due to pinholes.

[0007]

When water is used as the solvent, the aluminum powder may react with water to generate gas (foam) or lose metallic luster over time and become white. . In order to prevent such a phenomenon, as the aluminum powder, one whose surface is treated with fatty acid, phosphoric acid or a salt thereof is usually used. However, since fatty acids, phosphoric acid and their salts are only physically adsorbed on the surface of the aluminum powder, they are desorbed from the surface of the aluminum powder due to the influence of surfactants and electrolytes used for the purpose of dispersion, resulting in , It tends to be foamed or lose its metallic luster over time to become white. That is, when designing a water-based metallic luster color ink using aluminum powder, it is necessary to prevent the aluminum powder from reacting.

Further, it is necessary for the ink to have appropriate physical property values set according to the purpose of use. For example, when it is used for a writing instrument that has a stirring member accommodated in the ink storage chamber, when it is used for a writing instrument that does not have a stirring member, and the physical properties such as surface tension and viscosity depend on the type of the pen tip such as a ballpoint pen tip or a fiber bundle. Is set appropriately. Among the physical properties, the viscosity is usually a water-soluble resin, but in that case, the viscosity is reduced by the influence of aluminum powder, or it gels, or it acts on the aluminum powder to generate gas. It needs to be something that does not.

However, JP-A 1-210478 describes that a water-soluble resin or an emulsion is simply used as the resin, and only a styrene-acrylic acid copolymer is disclosed as a specific example. When such a water-soluble resin such as a styrene-acrylic acid copolymer or a styrene-maleic acid resin is used, the aluminum powder is likely to react with each other to generate gas or lose the metallic luster.

An object of the present invention is to provide an aqueous metallic luster color ink which uses aluminum powder and has little deterioration of the ink even during long-term storage.

[0011]

DISCLOSURE OF THE INVENTION The gist of the present invention is an aqueous metallic luster color ink characterized by containing at least aluminum powder, welan gum and / or rhamsan gum, a water-soluble organic solvent, and water. Is.

Aluminum powder is a metallic gloss imparting agent for handwriting. The scale-like material is particularly preferable because the metallic luster appears more clearly. Aluminum powder is produced by a stamping method in which aluminum pieces are crushed with a friction reducing agent such as stearic acid or inorganic phosphoric acid in a stamping mill, or aluminum powder obtained by an injection method, a lubricant and a suitable liquid in a drum together with a hard ball. It is obtained by a ball mill method or the like in which the aluminum pieces are crushed by rotating the drum by rotating the drum. As a commercial product, it is usually available as an aluminum paste.
Aluminum paste is made by grinding and polishing aluminum powder in a ball mill containing a high boiling point petroleum solvent (mineral spirits) and a reducing agent such as stearic acid or inorganic phosphoric acid, and forming a very thin scale of aluminum. Since it is made into fine particles, there is little danger of ignition and explosion, storage stability is good, and it is easy to handle in use.

The amount of the aluminum powder used is preferably 1 to 30% by weight based on the total amount of the ink. If the amount used is less than 1% by weight, the metallic luster of the handwriting tends to be insufficient,
When the amount used exceeds 30% by weight, the solid content increases and the fluidity decreases, so that it becomes difficult to apply, and when it is used as an ink for an ink-incorporated writing instrument, ink ejection tends to deteriorate.

The average particle diameter of the aluminum powder is 5 μm
It is preferable to use the above. This is because if the average particle size is less than 5 μm, the metallic luster of the handwriting is reduced, and unclear handwriting is likely to occur. Especially when used as an ink for ballpoint pens, the average particle size is 30μ.
m or less is preferable. This is because if the average particle diameter exceeds 30 μm, the ink discharge tends to be reduced with a pen tip having a size conventionally used as a ball-point pen, and it tends to be difficult to apply.

Commercially available aluminum powders include AA12, No. 900, No. 18000 (above, manufactured by Fukuda Metal Foil & Powder Co., Ltd.). Further, as the aluminum paste, Super Fine No.
22000 WN, the same No. 18000WN (above, Daiwa Metal Powder Co., Ltd.), WB0230, WXM0630
(Manufactured by Toyo Aluminum Co., Ltd.).

Both welan gum and rhamsan gum are polysaccharides produced by microbial fermentation. Although welan gum and / or rhamzan gum are used as a viscosity modifier, they maintain the initial quality after long-term storage even when used in combination with aluminum powder. Moreover, welan gum and / or ramzan gum are excellent in preventing the precipitation of aluminum powder, and when used as ink for a ballpoint pen, the ink attached to the ball surface as the ball at the tip of the ballpoint pen tip rotates It has an excellent property that it is easy to set a physical property value such that an appropriate amount is transferred when it is transferred onto a writing surface. Examples of commercially available products include K1A96 (welan gum, manufactured by Sansho Co., Ltd.), K1A112, and K7C233 (above, lamsan gum, manufactured by Sansho Co., Ltd.). The amount used is appropriately set depending on the application, but in the case of ink for a ballpoint pen, it is preferably 0.2 to 2.0% by weight. This is because when the amount used is less than 0.2% by weight, precipitation of the aluminum powder is likely to occur, and when it exceeds 2.0% by weight, there is a problem with ink viscosity physical properties. It tends to be worse.

The water-soluble organic solvent is used for various qualities as an ink, for example, for the purpose of preventing the ink from freezing at low temperatures and for preventing the ink from drying at the pen tip when used for a writing instrument. . Specifically, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol,
Glycols such as 1,3-butylene glycol, thiodiethylene glycol and glycerin, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, 2-pyrrolidone, triethanolamine and the like can be used alone or in combination. The amount used is preferably 5 to 40% by weight with respect to the total amount of ink.

Water is used as the main solvent.

Further, wetting agents such as urea, ethylene urea and thiourea, preservatives such as benzothiazoline and omadine, rust inhibitors such as benzotriazole, surfactants as dispersants for aluminum powder, and handwriting If necessary, various additives such as pigments and dyes for forming a colored metallic luster can be added.

In producing the water-based metallic luster color ink of the present invention, various conventionally known methods can be adopted. 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 pulverizing with a disperser such as a ball mill.

[0021]

[Function] In an aqueous ink using aluminum powder, the aluminum powder is surface-treated with stearic acid, phosphoric acid, or salts thereof for the purpose of preventing reaction with water. Elute. The welan gum and the rhamsan gum used in the present invention do not undergo deterioration such as viscosity decrease, gelation, or precipitation even in the presence of aluminum ions, and therefore the initial quality can be maintained even when stored for a long period of time.

[0022]

【Example】

Example 1 Aluminum paste 8.0 parts by weight (WB0230, manufactured by Toyo Aluminum Co., Ltd., aluminum powder content 68.4%) Welan gum 0.5 parts by weight Ethylene glycol 10.0 parts by weight Glycerin 10.0 parts by weight Water 71 .3 parts by weight Preservative 0.2 parts by weight (Proxel GXL, ICI Japan Co., Ltd., 1,2-benzisothiazolin-3-one) The above components were stirred and mixed with a Henschel mixer for 30 minutes. Viscosity 180 poise (E type viscometer, 1 rpm, 25 ° C)
I got the ink.

Example 2 Aluminum paste 8.0 parts by weight (WXM0630, manufactured by Toyo Aluminum Co., Ltd., aluminum powder content 60%) Welan gum 0.2 parts by weight Ethylene glycol 10.0 parts by weight Glycerin 10.0 parts by weight Water 61.6 parts by weight Water-dispersed pigment 10.0 parts by weight (EM YELLOW FX3024, manufactured by Toyo Ink Co., Ltd.) Preservative (Proxel GXL, mentioned above) 0.2 parts by weight The above components are mixed and stirred for 1 hour with a stirrer. And viscosity 100
Poise (E type viscometer, 1 rpm, 25 ° C.) ink was obtained.

Example 3 Aluminum paste 10.0 parts by weight (WXM0630, mentioned above) Welan gum 2.0 parts by weight Ethylene glycol 10.0 parts by weight Glycerin 15.0 parts by weight Water 52.8 parts by weight Pigment (1) 10.0 Parts by weight Preservative (Proxel GXL, described above) 0.2 parts by weight The above components were mixed by stirring with a lab mixer for 1 hour to obtain an ink having a viscosity of 1500 poise (E type viscometer, 1 rpm, 25 ° C.). In addition, in the above components, the pigment (1) is 30 parts of phthalocyanine blue and 20 parts of ethylene glycol.
Part, water 45 parts, NP-10 (polyoxyethylene (1
0) Nonyl phenyl ether, Nikko Chemicals Co., Ltd.
(Manufactured) are dispersed by a medium disperser.

Example 4 10.0 parts by weight of aluminum paste (Super Fine No. 22000 WN, manufactured by Daiwa Metal Powder Co., Ltd., aluminum powder content 70%) Welan gum 0.8 parts by weight Ethylene glycol 10.0 parts by weight Glycerin 5.0 parts by weight Water 67.0 parts by weight Surfactant 1.0 parts by weight (N-coconut oil fatty acid acyl-L-potassium glutamate) Water-soluble dye (CI Direct Green 6) 5.0 parts by weight Parts Jonkuryl 537 1.0 parts by weight (fixing agent, styrene-acrylic acid copolymer, Johnson Polymer Co., Ltd.) preservative (Proxel GXL, mentioned above) 0.2 parts by weight Each of the above components in a lab mixer for 1 hour By stirring and mixing, an ink having a viscosity of 450 poise (E type viscometer, 1 rpm, 25 ° C.) was obtained.

Example 5 Aluminum paste 8.0 parts by weight (Super Fine No. 18000 WN, manufactured by Daiwa Metal Powder Co., Ltd., aluminum powder content 70%) Welan gum 1.5 parts by weight Propylene glycol 10.0 parts by weight Water 72.4 parts by weight Surfactant 1.5 parts by weight (polyoxyethylene (15) oleylamine) Dye (CI Food Yellow 3) 6.0 parts by weight Preservative (Proxel GXL, mentioned above) 0.1 parts by weight Parts The above components were stirred and mixed with a lab mixer for 1 hour to obtain an ink having a viscosity of 700 poise (E type viscometer, 1 rpm, 25 ° C.).

Example 6 Aluminum paste (WB0230, mentioned above) 8.0 parts by weight Rumzan gum 0.5 parts by weight Ethylene glycol 15.0 parts by weight Glycerin 15.0 parts by weight Water 71.3 parts by weight Preservative (Proxel GXL, mentioned above) ) 0.2 parts by weight The above components are stirred and mixed in a Henschel mixer for 30 minutes to give a viscosity of 160 poise (E type viscometer, 1 rpm, 25 ° C).
I got the ink.

Example 7 Aluminum paste (WXM0630, previously described) 5.0 parts by weight Ramzan gum 0.2 parts by weight Ethylene glycol 10.0 parts by weight Glycerin 10.0 parts by weight Water 66.6 parts by weight Water dispersion pigment 8.0 parts by weight Parts (EM YELLOW FX3024, above) Preservative (Proxel GXL, above) 0.2 parts by weight The above components are mixed and stirred for 1 hour with a stirrer to give a viscosity of 100.
Poise (E type viscometer, 1 rpm, 25 ° C.) ink was obtained.

Example 8 Aluminum paste (WXM0630, previously described) 10.0 parts by weight Ramzan gum 2.0 parts by weight Ethylene glycol 10.0 parts by weight Glycerin 5.0 parts by weight Pigment (1) 10.0 parts by weight Water 62.8 Parts by weight Preservative (Proxel GXL) 0.2 parts by weight The above components were stirred and mixed in a lab mixer for 1 hour to obtain an ink having a viscosity of 1450 poise (E type viscometer, 1 rpm, 25 ° C.). In the above components, the pigment (1) is the same as the pigment (1) used in Example 3.

Example 9 Aluminum paste 10.0 parts by weight (Superfine No. 22000WN, mentioned above) Ramzan gum 0.8 parts by weight Ethylene glycol 10.0 parts by weight Glycerin 5.0 parts by weight Water 67.0 parts by weight Surfactant 1.0 parts by weight (N-coconut oil fatty acid acyl-L-potassium glutamate) Colorant (CI Direct Green 6) 5.0 parts by weight Johncryl 537 (previously described) 1.0 parts by weight Preservative (Proxel GXL, above) 0.2 parts by weight The above components were stirred and mixed in a lab mixer for 1 hour to obtain an ink having a viscosity of 300 poise (E type viscometer, 1 rpm, 25 ° C.).

Example 10 Aluminum paste 8.0 parts by weight (Superfine No. 18000 WN, mentioned above) Rhamzan gum 1.5 parts by weight Propylene glycol 15.0 parts by weight Water 68.0 parts by weight Surfactant 1.4 parts by weight ( Polyoxyethylene (15) oleylamine) Dye (CI Food Yellow 3) 6.0 parts by weight Preservative (Proxel GXL, described above) 0.1 parts by weight The above components are stirred and mixed for 1 hour with a lab mixer. An ink having a viscosity of 760 poise (E type viscometer, 1 rpm, 25 ° C.) was obtained.

Example 11 Aluminum paste (WXM0630, previously described) 8.0 parts by weight Welan gum 0.5% by weight Ramzan gum 0.3 parts by weight Ethylene glycol 10.0 parts by weight Glycerin 10.0 parts by weight Water 71.0 parts by weight Preservative Agent (Proxel GXL, described above) 0.2 parts by weight The above components are mixed by stirring with a Henschel mixer for 30 minutes to give a viscosity of 400 poise (E type viscometer, 1 rpm, 25
(° C) ink was obtained.

Comparative Example 1 The procedure of Example 1 was repeated except that 1.0 part by weight of hydroxyethyl cellulose was added instead of welan gum and the amount of water was increased by 0.5 part by weight.
An ink of 0 poise (E type viscometer, 1 rpm, 25 ° C.) was obtained.

Comparative Example 2 An ink having a viscosity of 1000 poise was obtained in the same manner as in Example 3 except that carboxymethyl cellulose was used instead of the welan gum of Example 3.

Comparative Example 3 The amount of carboxymethyl cellulose added in Comparative Example 2 was 1.
A viscosity of 220 poises (E type viscometer, 1
An ink of rpm, 25 ° C.) was obtained.

As described above, the aqueous metallic luster color inks obtained in Examples 1 to 11 and Comparative Examples 1 to 3 were subjected to a viscosity change test and a writing test. The results are shown in Table 1.

Viscosity change test: The inks obtained in Examples and Comparative Examples are filled in a bottle with a cap and stored at a temperature of 50 ° C. for one month. The ink viscosity was measured before and after storage. E type viscometer, 1 rpm, 25 ° C., unit is poise. In addition, in the viscosity change test, the ink was foamed in the comparative example after the passage of time, and the viscosity could not be measured.

Writing test: A writing test sample was prepared using the inks obtained in the examples and comparative examples, and the writing test sample was attached to a cap at a temperature of 50 ° C. and a humidity of 3
Leave it in a 0% room for 1 month. JI before and after leaving
Writing was performed on the high-quality paper A specified in SP 3201 and the handwriting before and after standing was observed. Sample for writing test: 0.8 g of ink is directly filled in a transparent ink storage tube consisting of a polypropylene hollow shaft cylinder with a stainless steel ball-point pen tip (ball material; cemented carbide) connected at one end, and backflow is prevented above it. Agent 0.1
After filling with g, the pen tip was capped and air bubbles were centrifugally degassed.

[0039]

[Table 1]

[0040]

As described above in detail, the water-based metallic luster color ink according to the present invention is excellent in that there is little change in viscosity even after being left for a long time and there is no change in handwriting.

Claims (1)

[Claims] 1. A water-based metallic luster color ink comprising at least aluminum powder, welan gum and / or rhamsan gum, a water-soluble organic solvent, and water.