JP2001011357A - Aqueous lustrous ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition forming no hard cake even after stored for a long period, to be used through filling writing or coating utensils such as marking pens therewith, and easy to redisperse the pigment by using aluminum powder as pigment. SOLUTION: This ink composition essentially comprises (A) a pigment essentially comprising aluminum powder pigment, (B) a dispersant essentially comprising a polyoxyethylene alkylphenyl ether phosphoric acid metal salt, (C) a resin, and (D) water; wherein it is recommended, for example, that the component A to be used is <=100 μm in particle size and flaky and accounts for 1.0-40 wt.% based on the total weight of the composition, the component B 0.1-5.0 wt.%, and the resin to be used is e.g. a water-insoluble resin such as an acrylic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a marking pen,
The present invention relates to a water-based glossy ink composition in which a pigment is easily redispersed, which is used by filling in a writing instrument such as a brush pen or an applicator.

[0002]

2. Description of the Related Art Conventionally, in an aqueous ink composition, at least an aluminum powder pigment is used as a pigment in an ink for obtaining glossy handwriting.

For example, Japanese Patent Publication No. 7-35491 discloses an aqueous metallic color ink containing aluminum powder pigment, an amphoteric compound, a resin emulsion and water as essential components.

When a water-based ink using an aluminum powder pigment is used by filling it into a writing implement, it is often used after applying an external force, such as shaking the writing implement a plurality of times immediately before writing. This is because the specific gravity of the pigment is higher than that of an organic pigment generally used for aqueous inks. That is, the aluminum powder pigment is easily separated and settled in the ink, and when stored, a supernatant liquid,
It is bisected into a solid containing a pigment. Therefore, unless an external force such as shaking is applied immediately before use, the pigment concentration in the ink will not be uniform, and handwriting with a uniform concentration cannot be obtained.

[0005]

However, aqueous inks using aluminum powder pigments, when left for a long time,
Even when the writing implement is shaken, the pigment concentration in the ink may not be uniform. This is because, after the aluminum powder pigment has settled and separated, the sediment containing the pigment is hardened to form a so-called hard cake, which makes it difficult to disperse the pigment again in the ink.

It is an object of the present invention to provide an aqueous gloss ink composition containing an aluminum powder pigment, which does not form a hard cake even when stored for a long period of time.

[0007] In the present invention, "redispersion" refers to a writing instrument or applicator which applies an external force such as shaking a writing instrument or applicator to a sediment containing a sedimented pigment to form an ink. It shows that it is dispersed again uniformly.

[0008]

According to the present invention, there is provided an aqueous glossy ink composition comprising at least a pigment, a dispersant, a resin and water, wherein the pigment is at least aluminum powder, and the dispersant is at least polyoxyethylene alkyl. A water-based glossy ink composition comprising a metal salt of phenyl ether phosphoric acid.

Hereinafter, the present invention will be described in detail. As the pigment used in the aqueous gloss ink composition of the present invention, at least an aluminum powder pigment is used. This aluminum powder is used for the purpose of imparting gloss to handwriting.

Aluminum powder pigments are prepared by stamping aluminum pieces with a lubricant such as stearic acid in a stamp mill, or by spraying aluminum powder obtained by spraying in a drum, a lubricant and an appropriate liquid onto a steel ball. It is obtained by a ball mill method of charging and pulverizing together, and a scaly one is preferable. Commercially available aluminum powder pigments include Super Fine No. 2200
0, the same No. 18000, Fine No. 900, 8
00 (above, manufactured by Daiwa Metal Powder Co., Ltd.), AA12, A
A8, No. 900, No. 1800 (all manufactured by Fukuda Metal Foil & Powder Co., Ltd.), aluminum powder 1000, 2700
(The above is manufactured by Nakatsuka Metal Foil & Powder Co., Ltd.). The aluminum paste is ground and polished in a ball mill containing a high boiling point petroleum solvent (mineral spirit) and a lubricant such as stearic acid.
Since it is made of very thin scale-like aluminum fine particles, there is little danger of ignition and explosion, storage stability is good, and it is easy to handle in use. As a commercially available aluminum paste, Super Fine No. 22
000WN, No. 1800WN (all manufactured by Daiwa Metal Powder Co., Ltd.), WB0230, WXM0630, WX
MU75C (all manufactured by Toyo Aluminum Co., Ltd.). The amount of the aluminum powder pigment used in the present invention can be in the range of 1.0 to 40% by weight, preferably 2.0 to 15% by weight, based on the total amount of the aqueous glossy ink composition.

The size of the aluminum powder pigment used is desirably one having a particle diameter of 100 μm or less. If the particle diameter is larger than 100 μm, the ink may be clogged at the pen tip made of a fiber of a marking pen or a brush pen or a sponge-like communicating porous body, and writing may not be performed.

The dispersant used in the aqueous gloss ink composition of the present invention must contain at least a metal salt of polyoxyethylene alkylphenyl ether phosphate.
The purpose is that the pigment contained in the ink does not form a hard cake even after settling during storage, and the settling pigment is easily redispersed by shaking the writing or applicator. This is to make it possible. Specific examples of polyoxyethylene alkylphenyl ether phosphoric acid include
Phosphanol RS-410 (carbon number of alkyl group:
12 to 15, polyoxyethylene addition mole number: 3), and RS-610 (carbon number of alkyl group: 12 to 15; polyoxyethylene addition mole number: 6), and RS-710 (carbon number of alkyl group: 12 to 15, polyoxyethylene addition mole number: 9), RE-410 (polyoxyethylene addition mole number: 4), RE-510 (polyoxyethylene addition mole number: 6), RE-610 (poly) The number of moles of oxyethylene added: 9) and the RA-600 (number of moles of added polyoxyethylene: 4) (all of which are manufactured by Toho Chemical Industry Co., Ltd.)
Manufactured). The metal salt of the above substance can be obtained by a method generally known as a reaction for forming a salt. The following is a description of a sodium salt as a specific example of the metal salt. While stirring the above 10% aqueous solution of phosphoric acid, while watching the pH meter, 20% sodium hydroxide is added little by little until the pH becomes about 7.3. The dispersant is preferably used in an amount of 0.1 to 5.0% by weight based on the total amount of the aqueous glossy ink composition.

The resin used in the present invention is used for fixing a solid substance in the aqueous glossy ink composition to a writing surface such as paper. Specific examples include water-insoluble resins such as acrylic resins, vinyl acetate resins, and styrene-acryl copolymers. The water-insoluble resin is used in the form of an aqueous emulsion.

Water is used as the main solvent.

In producing the 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 turbo mixer or a Henschel mixer.

In addition to the above components, various additives conventionally used in aqueous ink compositions can be used. For example, a water-soluble organic solvent can be used for the purpose of preventing the ink from drying at the pen tip and preventing the ink from freezing at low temperatures. Specifically, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, 1,3-butylene glycol, thiodiethylene glycol, 1,5-pentanediol, and glycerin; Monomethyl ether, diethylene glycol monomethyl ether,
2-pyrrolidone, N-methyl-2-pyrrolidone, triethanolamine and the like can be used alone or as a mixture. In addition, urea, ethylene urea, wetting agents and lubricants such as thiourea, benzothiazoline-based, omazine-based preservatives, rust-preventive agents such as benzotriazole, anionic-based,
Various additives such as nonionic surfactants and defoamers can be used.

Further, as viscosity modifiers, natural polymers such as guar gum and derivatives thereof, xanthan gum, locust bean gum, welan gum, ramzan gum, tragacanth gum, and cellulose-based polymers such as sodium carboxymethylcellulose, hydroxypropylcellulose and hydroxypropylmethylcellulose. Molecule, polyvinylpyrrolidone and the like can be used.

Further, as a method of obtaining glossy handwriting of another color, it can be obtained by combining an aluminum powder pigment and a coloring agent. As the coloring agent used at this time, conventionally known water-soluble dyes and pigments such as acid dyes, basic dyes and direct dyes can be used. Acid dyes include C.I. I. Acid Blue 1, basic dyes include:
C. I. Basic Blue 7, direct dyes such as C.I.
I. Direct Blue 86, C.I. I. Direct Green 6, C.I. I. Direct Orange 8 and the like.
As the pigment, orange pigment C.I. I. 12055, C.I. I.
12075, C.I. I. 12125, C.I. I. 1230
5, C.I. I. 21165, C.I. I. 1248
0, C.I. I. 12071, C.I. I. 4253
5, C.I. I. 60010, blue pigment C.I. I. 7410
0, C.I. I. 74160, C.I. I. 74180, green pigment C.I. I. 74260 and the like. When a pigment is used, a commercially available water-dispersed pigment is preferably used because the handleability and productivity are enhanced. As a specific example of the water dispersion type, EM YELLOWSCARRET 2
Y, EM YELLOW PINK 2B, EM YE
LLOW GREEN G, EM YELLOW BL
UE 2G (above, manufactured by Toyo Ink Co., Ltd.), Sandy
e Super, Yellow 1608, D21
5. Sandy Super Carmine F
B, Sandye Super Blue GLL (manufactured by Sanyo Dyeing Co., Ltd.) and the like. The weight ratio of the aluminum powder pigment to the colorant is preferably 3.0 or less for the pigment 1 with respect to the colorant. Further, since aluminum powder pigments previously colored with a coloring agent are commercially available as colored aluminum powder pigments, they can also be used.

Incidentally, the aluminum powder pigment reacts with water and loses its luster. This is because the aluminum powder pigment is corroded by the reaction with water to produce rust. For this reason,
The aluminum powder pigment is surface-treated with a fatty acid, phosphoric acid, a salt thereof, or the like in order to impart a rust-preventive effect.
However, when an aluminum powder pigment is used in an aqueous ink, it is immersed in water for a long period of time, so the surface treatment alone is not sufficient. Then, many inventions which suppress the reaction between the aluminum powder pigment and water have been proposed. For example, in the case of aluminum powder pigments, see JP-A-6-192.
No. 610 discloses that a perfluoroalkylphosphate ester and / or a perfluoroalkyltrimethylammonium salt is used in combination. Also, Japanese Patent Application Laid-Open
JP-209053 discloses the addition of N-fatty acyl-L-glutamate. Further, a method of subjecting an aluminum powder to a plasma treatment is disclosed in JP-A-59-138280. The aqueous luster ink composition of the present invention can employ the invention described in the above publication in order to prevent the aluminum powder pigment used from reacting with water to lose the luster of the metal powder pigment.

[0020]

The aluminum powder pigment used in the water-based glossy ink composition of the present invention has a plate-like shape having a small thickness and a large planar area. When the aluminum powder pigment settles, it is expected that the aluminum powder pigment will form a layered structure in which the planes of the aluminum powder pigment face each other and are stacked. In this layered structure, since the area of the portion where the aluminum powder pigments are in contact with each other is large, it is considered that the resulting contact resistance is also large. Therefore, this structure is in a stable state, and it is considered that it is difficult to break the structure by applying a small external force. However, the dispersant used in the aqueous gloss ink composition of the present invention reduces the contact resistance between aluminum powder pigments caused by the layered structure by adhering to the surface of the aluminum powder pigment used. That is, the presence of the dispersant used in the aqueous glossy ink composition of the present invention between the layered structures formed by the aluminum powder pigments reduces the contact resistance between the aluminum powder pigments, so that a small external force is applied. With this, the layered structure is easily broken. Therefore, since the aluminum powder pigment to which the dispersant of the present invention is attached has an effect of imparting fluidity, even after the aluminum powder pigment settles in the ink, an external force such as shaking is applied to the writing implement or the coating implement filled with the ink. It is thought that the re-dispersion of the aluminum powder pigment becomes possible by giving.

[0021]

EXAMPLES Example 1 Aluminum paste (WXM 0630, manufactured by Toyo Aluminum Co., Ltd.) 10.0 parts by weight Dispersant (10% aqueous solution of sodium salt of phosphanol RE-610, manufactured by Toho Chemical Industry Co., Ltd.) 20.0 parts by weight Resin (Johncryl 450, styrene-acrylic acid copolymer, manufactured by Johnson Polymer Co., Ltd.) 10.0 parts by weight Water 42.7 parts by weight Ethylene glycol 7.0 parts by weight Defoamer (TSA739) , Silicone oil emulsion, manufactured by Toshiba Silicone Co., Ltd.) 0.1 parts by weight Preservatives (Proxel GXL, 1,2-benzoisothiazolin-3-one, manufactured by ICI Japan KK) 0.2 parts by weight Was mixed with a propeller stirrer for 30 minutes to obtain a glossy silver ink.

Example 2 Aluminum paste (WB0230, manufactured by Toyo Aluminum Co., Ltd.) 10.0 parts by weight Dispersant (20% aqueous solution of sodium salt of phosphanol RS-410, manufactured by Toho Chemical Co., Ltd.) 15.0 Parts by weight Resin (Movinyl DM772, acrylic copolymer resin emulsion, manufactured by Hoechst Co., Ltd.) 5.0 parts by weight Water 62.8 parts by weight Glycerin 6.0 parts by weight Polyvinylpyrrolidone K-15 (polyvinylpyrrolidone, USA, General * Aniline & Film Co., Ltd.) 1.0 parts by weight Preservative (Proxel GXL, described above) 0.2 parts by weight The above components were stirred and mixed for 30 minutes with a propeller stirrer to obtain a glossy silver ink.

Example 3 Aluminum paste (WXM0630, manufactured by Toyo Aluminum Co., Ltd.) 8.0 parts by weight Dispersed pigment (Sandye Super Blue GLL, manufactured by Sanyo Pigment Co., Ltd.) 25.0 parts by weight Dispersant (Phosphanol RS) 15.0 parts by weight of resin (Primal MV-23LO, acrylic emulsion, manufactured by Rohm and Haas Japan K.K.) 10.0 parts by weight Water 36.7 parts by weight 1,3-butylene glycol 5.0 parts by weight Xanthan gum 0.1 parts by weight Preservatives (Proxel GXL, as described above) 0.2 parts by weight The above components are stirred and mixed with a propeller stirrer for 30 minutes, and are glossy. Was obtained.

Example 4 Aluminum paste (WXM0630, described above) 10.0 parts by weight Dispersed pigment (EM YELLOW FX3024, manufactured by Toyo Ink Co., Ltd.) 20.0 parts by weight Dispersant (sodium salt of Phosphanol RE-610 10) % Aqueous solution, described above) 20.0 parts by weight Resin (Movinyl DM772, described above) 5.0 parts by weight Water 37.8 parts by weight Ethylene glycol 7.0 parts by weight Preservative (Proxel GXL, described above) 0.2 parts by weight Defoaming 0.1 parts by weight of an agent (YMA6509, emulsion of silicone oil, manufactured by Toshiba Silicon Co., Ltd.) The above components were stirred for 30 minutes with a propeller stirrer to obtain a glossy gold ink.

Comparative Example 1 A glossy silver ink was obtained in the same manner as in Example 1 except that the amount of water was increased except for the dispersant of Example 1.

Comparative Example 2 A glossy silver ink was obtained in the same manner as in Example 1 except that the dispersant used in Example 1 was not changed to a sodium salt.

Comparative Example 3 In place of the dispersant of Example 1, 10 parts by weight of an ammonium salt of a styrene-acrylic copolymer (John Krill 62 (manufactured by Johnson Polymer Co., Ltd.)) was added to increase the amount of remaining water. A silver ink was obtained in the same manner as in Example 1 except for the above.

The aqueous gloss ink compositions obtained from Examples 1 to 4 and Comparative Examples 1 to 3 were subjected to a redispersibility test. The test method is as follows. Table 1 shows the test results.

(Redispersibility Test: Conditions) An aqueous gloss ink composition was placed in a screw vial (a bottle with a screw-type lid) for 10 minutes.
g, put φ5.0mm stainless steel ball,
After being left in a constant temperature layer at 50 ° C. for one month, it was taken out and cooled at room temperature.

(Redispersibility Test) The screw vial after standing at room temperature was shaken up and down by about 30 cm by hand, and the number of times of shaking until the ink separated into two layers was uniformly redispersed (one up and down).
Once). (Confirmation of redispersion) Take out the shaken ink, and
Apply to fine paper with a mill applicator. It is assumed that redispersion is performed at a point where uniform application was possible without any transparent portion on the application mark.

[0031]

[Table 1]

[0032]

As described above in detail, the water-based glossy ink composition according to the present invention can easily redisperse a pigment.
It is an excellent ink composition that can obtain gloss.

Claims (1)

[Claims] 1. A water-based glossy ink composition comprising at least a pigment, a dispersant, a resin and water, wherein the pigment is at least an aluminum powder pigment and the dispersant is at least a metal salt of polyoxyethylene alkylphenyl ether phosphate. A water-based glossy ink composition comprising: