JPS59140273A - Water ink - Google Patents

Abstract

PURPOSE:To provide water ink which is excellent in wate resistance, density, oozing and dryness, runs smoothly on paper and gives clear handwriting, consisting of an emulsion of a specified high-molecular dye and a water-soluble viscosity modifier. CONSTITUTION:An anionic dye and/or a reactive dye are/is added to an emulsion contg. 5-45wt% water-insoluble amino group-contg. polymer selected from among a polymer obtd. by polymerizing a vinyl monomer having a primary to tertiary amino group, such as dimethylaminoethylstyrene, a copolymer of a vinyl monomer having a primary to quaternary amino group, such as acrylamide, with a vinyl monomer having no amino group, such as styrene, or a diene monomer, and a polymer having amino groups (e.g. polyurethane) obtd. by addition polymn. or polycondensation to bond the dye to the polymer, whereby an emulsion of a high-molecular dye having a particle size of 5mu or below can be obtd. A water-soluble viscosity modifier such as CMC is added to the emulsion to adjust the viscosity to 50-3,000cP.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-based ink, and more particularly to a water-based ink for ballpoint pens that uses a polymer pigment in which a dye is bonded to a polymer having an amino group.

When water-based ink is used in a ballpoint pen, it has the advantage of being less likely to bleed or show through handwriting, and has no odor or toxicity. Also,
It has a good writing quality and has the advantage of not causing smudges or broken lines. On the other hand, when oil-based ink is used in ballpoint pens, it has advantages such as good water resistance of handwriting.

Generally, water-based ink is a solution-type ink in which dye is dissolved in water, but when this ink is used to record on paper, the characters easily dissolve when water or a damp object comes into contact with them. As a result, there was a problem that the characters were blurred and smudged or unclear, resulting in poor water resistance. Furthermore, in order to obtain clear, dark-colored characters, for example, when basic dyes are used, there is a problem that light resistance deteriorates. Furthermore, since the dye is dissolved in water, there is a limit to the solubility of the dye, and in order to obtain dark handwriting, it is necessary to supply an extra amount of ink to the paper, which prevents the handwriting from drying on the paper. It was slow and had problems with smudging.

Furthermore, since such water-based ink has a low viscosity, the ink storage tube (2) filled with the porous body (1) and the ink guide core (3) as shown in FIG.
4), and if this is used as a ballpoint pen for oil-based ink, that is, an ink storage tube (5) as shown in Fig.
When filling the structure consisting of the writing tip (5) containing the ball (4) and the writing tip (2), the ink viscosity is low, so when the writing tip (5) is left facing downward, the pressure of the ink column (H) There is a problem that the ink drips from the writing tip, and it has not been possible to directly fill the ink storage tube with such water-based ink to create the ballpoint pen of FIG. 2, which has a simple structure.

Up until now, attempts have been made to mix pigments into polymer emulsions, but since pigments with high specific gravity are used, there are problems with dispersion stability, and pigments alone cannot provide vivid colors, and complementary colors with dyes have been used. It has the disadvantage of poor water resistance, and fully satisfactory results have not yet been obtained.

In view of the current situation, the present inventor has conducted intensive research to solve the above-mentioned problems of water-based inks and obtain a new water-based ink that has both the advantages of conventional water-based inks and the advantages of oil-based inks. The inventors have discovered that a water-based ink using a polymeric dye and a viscosity modifier can solve the above-mentioned problems and can be used in a ballpoint pen with a simple structure, and have thus arrived at the present invention.

That is, the present invention consists of an emulsion of a polymer dye formed by combining a water-insoluble polymer having an amino group and a dye selected from anionic dyes and reactive dyes, and a water-soluble viscosity modifier as main components. This is a distinctive water-based ink.

The polymers forming the polymer dye used in the present invention are the first to
It has a quaternary amino group and is insoluble in water, and the amine group is oriented on the surface of the polymer particle during the process of creating a single emulsion. Further, the anionic dye and reactive dye that form a polymeric dye together with this polymer have a hydrophilic group in the dye molecule. Therefore, the polymer dye in which the above polymer and the above dye are combined has extremely excellent dispersion stability in water. Also, since this polymeric dye is insoluble in water,
It forms a water-insoluble film when writing, giving water resistance to handwriting.

As described above, the polymeric dye used in the present invention provides dispersion stability and water resistance, which are one of the important features of the present invention. Even if the above-mentioned dye is bonded to a water-soluble polymer having an amino group to form an ink, the water resistance is poor because the polymer dye is water-soluble, and the drying of handwriting is slow, making it difficult to obtain a good ink. Addition of other polymer emulsions cannot improve these properties. Further, dispersion stability cannot be obtained in polymer emulsions using pigments. Even if a water-soluble dye is added to a polymer emulsion without functional groups, a water-based ink with good water resistance of handwriting cannot be obtained.

In the present invention, an emulsion-type water-based ink is produced using the above-mentioned polymeric dye, but in this case, the polymeric dye itself has a particle shape that is smaller than that of the normal dissolved water-soluble dye or water-soluble polymeric dye molecules. big. Therefore, the degree of infiltration into the fibers of the paper is much smaller, and it is concentrated on the surface of the paper to form handwriting, improving the density and blurring.

Furthermore, with ordinary water-based inks, the ink itself becomes dry when it is completely absorbed into the paper fibers, so it takes a considerable amount of time to dry. For this reason, additives have been added to speed up absorption at the expense of bleeding and Ib bleed-through, but with the present invention, even if the water in the emulsion is not completely absorbed into the paper fibers, the polymer dye can be absorbed quickly. Particle fusion occurs, forming an apparently dry film. Therefore, good handwriting drying properties can be imparted to the water-based ink.

Next, the reason why a water-soluble viscosity modifier is added to the water-based ink of the present invention will be explained.

The present inventor has determined that the viscosity of the ink of the present invention is 50 to 3000.
It has been found that by adjusting the ink within the cps range, even if the ink is directly filled into the ink storage tube, it is possible to improve the writing quality and prevent the ink from dripping without causing any smearing or line breakage. That is, when an ink which is a polymer emulsion and whose viscosity is further adjusted to an appropriate range is manufactured, the A-A-plane (ball holding part (5) shown in FIG. 3) is produced.
), the ball (4) and the outside air (circumferential area)
At this point, water, which is a component of the dispersed phase of the water-based ink, evaporates and the ink becomes highly viscous at the curved part along the △-8 plane. Furthermore, it forms a dry polymer film, and the ink column itself becomes viscous. In other words, the pressure of the ink column must be sufficient to support the gravity and prevent sagging.In other words, the polymer, which has become non-fluid due to water evaporation, is plugged along the A-A plane. I found it to be tolerable. Conventional dissolving ink requires at least 10% to prevent sagging. It is necessary to have a viscosity of 1,000 cps or more, and there is no effective means to prevent ink from dripping other than using a ballpoint pen with a complicated mechanism. By using an emulsion and adjusting the viscosity appropriately, the problem of dripping was solved. In order to eliminate the drawback of having to fill a conventional water-based ink into a ballpoint pen with a complicated structure, the viscosity of the polymer dye emulsion itself used in the present invention is set to 50 to 300.
It is thought that if the ink is adjusted to 0 cps and directly filled into the ink storage tube, ink dripping can be prevented in the same way, but in this case, the amount of polymer used in the total amount of ink may be excessive (4
5% or more), making it difficult to prepare ink, and the stability of the ink may be poor, making it impossible to obtain a satisfactory ink. That is why in the present invention, a viscosity modifier is blended, and this viscosity modifier must be water-soluble in order to stabilize the ink and ensure smooth outflow of the ink from the writing tip.

Therefore, the present invention can improve water resistance, density, bleeding, and drying speed, which could not be achieved with conventional water-based inks.
Furthermore, it is possible to obtain a water-based ink that achieves the dispersion stability of an emulsion ink, has the good writing feel and clarity of handwriting that conventional water-based inks have, and can be filled into a ballpoint pen with a simple structure.

Examples of polymers used in producing the polymer dye emulsion of the present invention are as follows.

(1) Polymer obtained by polymerizing the vinyl monomers in Table 1-(a) (2) The vinyl monomers in Table 1-(a) and Table 1-3\
) copolymer (31 Table 1-(0) vinyl monomer and Table 1'-r\
4) Polymers having amino groups obtained by polyaddition, polycondensation, etc., such as polyurethane and polyamide.

A polymer emulsion such as that obtained by emulsion polymerization of the monomers shown in Table 1-1 may be added to such a polymer emulsion.

In addition, in the polymers (2) and (3), copolymers made using diene monomers or fluorine-containing vinyl monomers have the ability to form films with low adhesion and cohesiveness, so they can be used as adhesives such as erasers. It has the property of giving handwriting that can be erased by mechanical abrasion.

Table 1 Dimethylaminoethylstyrene, dimethylaminoethylstyrene, propylaminoethylstyrene, butylaminoedylstyrene, cyclohexylaminoethylstyrene, N,N-1 diethylethylenediaminoethylstyrene, aminoethylmethylaminoethylstyrene, diethylaminoethyl Methacrylate, N-vinylcarbazole, N-vinyl phthalimide. Acrylamide, methacrylamide, N-methylolacrylamide, dimethylaminoethyl methacrylate, vinylpyridine, N-vinyldimethylamine, N- Vinylimidazole, N-vinylpyrrolidone, vinylpiperazine, aminostyrene, vinylsulfonamide, dimethylaminoethyl methacrylate methyl chloride salt, vinylphenethyltriethylammonium bromide.
Vinyl acetate, acrylic esters, methacrylic esters, acrylonitrile, vinyl chloride, vinylidene chloride (these are the seven commonly used vinyls), isoprene, butadiene, chloroprene, fluoroprene, phenylbutadiene (the above are seven dienes), vinylidene fluoride , trifluorochloroethylene (the above fluorine-containing vinyl monomers) These monomers can be used alone or in combination of two or more.

Specifically, examples of polymers include poly(2-diethylaminostyrene), poly(dimethylaminoethyl methacrylate/2-ethylhexyl methacrylate), poly(2-isopropylaminoethylstyrene/butadiene/2- Ethylhexyl methacrylate), diethylaminoethyl methacrylate from graph 1 to
Examples include polymerized styrene and butadiene rubber.

The above polymers are usually obtained by emulsion polymerization. Emulsion polymerization is carried out in an aqueous medium using an emulsifier, a polymerization initiator, an electrolyte, etc. according to a known method. In addition, as a method that does not involve emulsion polymerization, there is also a method in which a polymer solution is emulsified in an aqueous medium using an emulsifier to obtain a polymer emulsion.

In the ink of the present invention, it is necessary that the amount of the polymer having an amine group is in the range of 5 to 45% by weight, preferably 10 to 30% by weight based on the total amount of the ink. If it is less than 5% by weight, the amount of dye that can be used will be too small, making it impossible to satisfy both water resistance and the density of handwriting. If it exceeds 45% by weight, the ink will be difficult to prepare as described above, and the stability of the ink will deteriorate.

Examples of dyes to be bonded to polymers having amine groups include the following, all of which have a sulfonic acid group, a carboxyl group, or a hydroxyl group in the dye molecule, or are of an anionic complex type.

O anion type acidic dye: c, i, acid black 2°26, 1
09. 110 C, 1, Acid Blue'9, 22° 23, 40 C, R, Acid Red 18° 27, 87. ．． 92.94 Direct dye: C,1, Direct black 19°54 C,1, Direct blue 106°158, 200 C,1, Direct red 79°83 C,1, Dyref 1 to Violet 48 Mordant dye: C,1 , Mordant Black 7C, 1, Mordant Blue 13° 47, 48 C, 1, Mordant Red 3° 7.27 Metal complex dye: C, “J, Acid Black 51.52
．． 118.119.155.158 °C, 1, Acid Blue 61 C, 1, Acid Red 186, 265 0 Reactive dyes Dichlorotriazinyl group as reactive group 4 Monochlorotriazinyl group, chlorpyrimidyl group, vinyl sulfone group, Dyes containing alkyl sulfate groups, bromoacrylamide groups, etc. For example, C,1, Reactive Black 9,10°4 C,1, Reactive Blue They are bonded by van der Waalska bonds, hydrogen bonds, ionic bonds, or covalent bonds. Binding of the dye is usually carried out by mixing the dye into an emulsion of a polymer having amino groups, or by mixing and heating the mixture.

The ratio of dye used is 5 to 100 per 100 moles of amine group.
A molar range gives suitable results. It is also possible to use an anionic dye and a reactive dye in combination.

A final particle size of the polymeric dye in the emulsion thus prepared is less than 5 microns to give favorable results.

Used in the present invention, the viscosity is 50 to 3000 cp
Water-soluble viscosity modifiers for adjusting the viscosity to s include alkali salts of polyacrylic acid or polymethacrylic acid, alkali salts of copolymers containing acrylic acid or methacrylic acid, alkali salts of styrene-maleic acid copolymers, and acetic acid. Alkali salts of vinyl-crotonic acid copolymers, polyvinyl alcohol (including modified polyvinyl alcohol), methyl vinyl ether male, alkali salts of phosphoric acid copolymers, polyalkylene oxide derivatives, methyllerulose, hydroxyethyl cellulose, carboxymethyl cellulose Na Synthetic or natural water-soluble polymers such as alkaline salts of salt, gum arabic, and shellac may be mentioned. In addition, polyethylene oxide,
Alginate TiNa salt, tragacanth gum, guar gum, karaya gum, ■Fulsion thickening additives, such as San Nopco's SN-thickener (water-soluble oligomer), loam
Thickener QR-708 manufactured by And Haas Co., Ltd. can also be used. The viscosity modifier is used in an amount of 0.01 to 15% by weight based on the total amount of the ink.

In addition to the emulsion of the above-mentioned polymeric dye, the water-based ink of the present invention may optionally contain a moisture absorbent, a plasticizer or solvent, an antibacterial agent,
Lubricants, rust preventives, surfactants, etc. can be added. Hygroscopic agents include polyhydric alcohols and their derivatives such as glycerin, propylene glycol, diethylene glycol, polyethylene glycol, and triethanolamine, as well as pyrrolidone carboxylic acid sodium salt, pyrrolidone carboxylic acid triethanolamine salt, dimethyl sulfoxide, 1.3- Dimethyl-2-imidazolidinone and the like can be used. As a plasticizer or solvent,
In addition to esters such as dibutyl phthalate, dioctyl phthalate, dioctyl adipate, dibdermaleate, and trimethyl phosphonoate, plasticizers such as epoxidized soybean oil, epoxidized triglyleride, and chlorinated fatty acid esters, butyl cellosolve acetate, and phenyl carbide 1. Polar solvents such as cellosolves and carbitols, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, 1,3-dimethyl-2-imidazolidinone, and N-methyl-2-pyrrolidone can be used. Adding these plasticizers and solvents to the emulsion softens and dissolves the polymer particles and polymeric dyes, making it possible to control properties such as adhesion to paper surfaces. As antibacterial agents, methyl P-oxybenzoate, 1,2-benzisothiazoline-
Water-soluble or water-friendly fungicides such as 3-one can be used. Various lubricants,
For example, polyalkylene glycols, alkali salts of fatty acids, fluorine surfactants, phosphate ester surfactants, polar a additives, and the like can be used. Various types of rust inhibitors effective for iron and copper alloys are commercially available, and these can be used as appropriate, and pigments can also be used to adjust the color tone. Adjusting the surface tension of ink,
In order to improve the stability of the ink, various nonionic or anionic surfactants can be used as appropriate.

In addition to the above additives, natural rubber latex, polyisoprene, polybutadiene, polychloroprene, poly(
Synthetic rubber latexes such as styrene/butadiene), poly(acrylonitrile/butadiene), poly(methyl methacrylate/butadiene), and poly(trifluorochloroethylene/vinylidene fluoride) can also be used.

These additions can provide water-based inks with handwriting that can be erased by mechanical rubbing, such as with an eraser.

The water-based ink of the present invention produced in this way has excellent water resistance and sharpness, has little bleeding, and can be filled into a ballpoint pen with a simple structure, giving satisfactory results.

Next, an example of preparing an emulsion used in the present invention will be explained in detail. Parts are parts by weight.

Preparation Example 1 A, Water 435 parts Lauryl sulfate ester Na salt 4.1 parts Polyoxyethylene nonylphenol ether 18.9 parts
Part Trisodium Phosphate 2.4 Part 2.2
'-Azobis(2-amidinopropane) hydrochloride
0.6 parts 3, 2-ethylhexyl methacrylate-82 parts 0 parts dimethylaminoethyl methacrylate-1 to 45 parts C,2,2'''-azobis(2-amidinopropane) hydrochloride 0.6 parts water
Pour the entire amount of A and 90 parts of B into a container equipped with a reflux device, flow nitrogen gas, start polymerization at 65°C, and continue polymerization while dropping the remaining amount of B and C. The polymerization was completed by raising the temperature to 10°C.The time required for the polymerization was 5 hours, and 2-
An emulsion of a copolymer of ethylhexyl methacrylate and dimethylamino]nidyl methacrylate was obtained. The solid content (measured as solid content minus polymer content) was 39%.

Preparation Example 2 A/Water 99 parts Lauryl sulfate ester Na salt 1.08 parts Polyoxyethylene nonylphenol ether
4.3 parts trisodium phosphate 0.
54 parts 2.2'-azobis(2-amidinopropane) hydrochloride 0.14 parts B, n-butyl acrylate 60 parts dimethylaminoethyl methacrylate 12 parts C12,2''-azobis(2-amidinopropane) hydrochloride 0. 28 parts water
5 parts Put the entire amount of A and 18 parts of 8 into a container with a reflux device, flow nitrogen gas, start polymerization at 60°C, continue polymerization while dropping the remaining amount of B, and then raise the temperature to 70°C. , C were added dropwise to complete the polymerization. The time required for polymerization was 4 hours and 30 minutes, and n
An emulsion of a copolymer of -butyl acrylate and diethylaminoethyl methacrylate was obtained. Solid content was 38%.

Preparation Example 3 A, water 300 parts lauryl sulfate ester Na salt 3.6 parts polyoxyethylene, nonylphenol ether 14.4
Part 2.2-Azobis(2-amidinopropane) hydrochloride 0.5 parts Trisodium phosphate 3 parts 8, 200 parts 2-ethylhexyl methacrylate 40 parts 2-isopropylamine ethylstyrene C, 2,2'-azobis( 2-amidinopropane) hydrochloride 1 part water
30 parts A in a container with a reflux device! : Pour the entire amount of B, flow nitrogen gas, and heat to 75°C.
The polymerization was started by adding C dropwise to continue the polymerization, and the polymerization was completed in 6 hours, and 2-ethylhexyl methacrylate and 2-
An emulsion of a copolymer of isopropylaminoethylstyrene was obtained. Solid content was 39%.

Preparation Example 4 A, Water 300 parts Lauryl sulfate ester Na salt 3 parts Polyoxyethylene nonylphenol ether 1
2 parts 2.2'-azobis(2-amidinopropane) hydrochloride 0.4 part trisodium phosphate 1.3 parts B, 200 parts 2-diethylaminoedylstyrene C, 2,2-azobis(2-amidinopropane) Propane) hydrochloride 0.4 parts water
10 parts Pour the entire amount of A and B into a container with a reflux device, flush with nitrogen gas, and boil for 75 minutes.
Polymerization was started at 0.degree. C., C was added dropwise to continue the polymerization, and the polymerization was completed in 6 hours to obtain an emulsion of poly(2-diethylaminoethylstyrene). Solid content was 32%.

Preparation Example 5 △, Water 600 parts Lauryl sulfate ester Na salt 5.7 parts Polyoxyethylene nonylphenol ether 23 parts Trisodium phosphate 2.7 parts 2.2-
Mono-azobis(2-amidinopropane) hydrochloride
0.77 parts B, 51 parts C, 2-isopropylaminoethylstyrene, 370 parts Imbrene,
2.2'-azobis(2-ami, dinopropane) hydrochloride 0.77 parts water
15 parts A in a pressure container
After replacing with nitrogen gas, the entire amount of C was injected, and polymerization was started at 75°C. D was added dropwise to continue polymerization. The polymerization was completed in 6 hours, and the isoprene and 2- An emulsion of a copolymer of isopropylaminoethylstyrene was obtained. Solid content was 25%.

Preparation Example 6 A, Water 60 parts Lauryl sulfate ester Na salt 0.58 parts Polyoxyethylene nonylphenol ether
2.3 parts trisodium phosphate 0.3
Part 2.2-Azobis(2-amidinopropane) hydrochloride 0.077 part 8,
2-Impropylaminoethylstyrene 3.5 parts Styrene 35 parts C,2,2=
-Azobis(2-amizip[1pan) hydrochloride
0.077 parts water
2 Polymerization was carried out in the same manner as in Rhine Preparation Example 4 to obtain an emulsion of a copolymer of 2-isopropylaminoethylstyrene and styrene. Solid content was 33%.

Next, Examples 1 to 8 will be shown. Parts are parts by weight.

In each example, after dissolving a hygroscopic agent, an antibacterial agent, and a dye in water, this was added to a polymer emulsion, mixed under heating, and then a water-soluble viscosity modifier was added, followed by filtration if necessary. The particles exceeding 5 microns were removed and used as ink.

In Example 8, the plasticizer was pre-emulsified in the polymer emulsion using a surfactant.

Example 1 C,1, Direct Black 19 9 parts (manufactured by Daiwa Kasei Co., Ltd., Daiwa Black 300H) Moisture absorbent (diethylene glycol) 16 parts Antibacterial agent (manufactured by IC1, trade name, Proxel XL-2) 1 part water
18 parts Emulsion of Preparation Example 1 56
1 part water-soluble viscosity modifier [Joncryl 142 (trademark, Alkali-soluble 39 manufactured by Johnson Company)
% acrylic polymer emulsion) 5 parts, 10% caustic soda aqueous solution 2 parts] Example 2 C, 1, Direct Black 19 9 parts Diethylene glycol 16 parts Proxel XL-2
1 part water
18 parts Emulsion of Preparation Example 1 56 parts Water-soluble viscosity modifier [Aron A S-7,180 (trademark, manufactured by Toagosei Kagaku Kogyo Co., Ltd., 18% acrylic copolymer-Na salt aqueous solution)] 11 parts Example 3 C , 1, Acid Black 2 5 parts (Nigrosine NBC manufactured by Sumitomo Chemical Co., Ltd.) Diethylene glycol
15 parts Proxel XL-21 parts water
19 parts Emulsion of Preparation Example 2 60 parts Water-soluble viscosity modifier [Aron ΔS-7601 (30% polymer aqueous solution manufactured by Toagosei Chemical Industry Co., Ltd.)
7 parts Example 4 Lanazol Black 5095 6 parts (trademark, reactive dye manufactured by Ciba Geigy) Moisture absorbent (glycerin)
15 parts Proxel XL-21 parts water
28 parts Emulsion of Preparation Example 4 50 parts Water-soluble viscosity modifier (carboxymethyl cellulose Na salt) 0.25 parts Example 5 C,1, acid black 2 5 parts Glycerin
20 parts Proxel XL=2
1 part water
24 parts 1 part Emulsion of Preparation Example 3 50 parts Water-soluble viscosity modifier (50% aqueous solution of vinyl acetate/crotonic acid copolymer NH3 salt F)
ARBWERKE HOECH8TAG ・Made by
, MOW ■ L I T 1cT5A>12
Part Example 6 C,1, Acid Black 1195 parts (manufactured by Odogaya Chemical Industry Co., Ltd., trademark, Eisen Opal Black New Conc) Glycerin 20 parts Proxel XL-21 part Water
24 parts polyurethane emulsion 50 parts
Department (manufactured by Sanyo Chemical Industries, Ltd., trademark, Sunbren UX-3
500, 40% as evaporation residue) Water-soluble viscosity modifier (polyvinyl alcohol) 0.8 parts Example 7 Lanazol Black 5095 4 parts Glycerin 20 parts Proxel XL
-21 parts water
25 parts Emulsion of Preparation Example 5 50
Part styrene/butane latex (40% solids)
20 parts Water-soluble viscosity modifier (carboxymethylcellulose Na salt>0.25 parts Example 8 C,1, Acid Black 26 4 parts (manufactured by Nippon Kayaku Co., Ltd., trademark, Kayanol Milling Black VLG) Glycerin 15 parts Proxel XL- 21 parts water
30 parts emulsion 52.0
2 parts [To 50 parts of the emulsion of Preparation Example 6, add 2 parts of plasticizer (dibutyl maleate) and 0.02 part of surfactant (polyoxyethylene nonylphenol derivative)] Water-soluble viscosity modifier (carboxymethylcellulose Na salt) ) 0.3 copies, Example 1
Group 2 shows the viscosity of the ink obtained in steps 8 to 8 and the results of testing by filling it into a ballpoint pen.

Table 2 (1) Viscosity = Using a B-type viscometer, 20°C, 60r, p
, the value measured in m.

(2) Ballpoint pen type 1: The ballpoint pen shown in Fig. 2, in which the writing tip (5) is attached to the ink storage tube (2) and the ball (4) is attached to the writing tip (5).

Type 2: Outside air induction pipe (6) Ink storage tube with The writing tip (5) is installed in (2). Place the ball on the writing tip (5). (4) Attach the C board as shown in Figure 4. Le Pen.

(3) Ink dripping test: The ballpoint pen was held vertically with the writing tip facing downward, and the presence or absence of ink dripping was observed and evaluated after holding at 20° C. for 24 hours.

(4) Water resistance test: After 10 minutes had elapsed after writing on the writing paper, the writing paper was immersed in water for 30 minutes, and the stains on the box marks were observed and evaluated.

(5) Smearing, smearing, and line breakage test: The handwriting was written on paper and observed for smearing and line breakage, and the state of smearing of the handwriting was observed with a magnifying glass and evaluated.

As is clear from the above results, the water-based ink of the present invention was extremely excellent.

[Brief explanation of drawings]

1, 2, and 4 are cross-sectional views of various types of ballpoint pens, and FIG. 3 is a cross-sectional view of the writing tip. (1) Porous body (2) Ink storage chamber (3) Ink guide core (4) Ball (5) ...Writing tip patent applicant Pilot Mannen Pen Co., Ltd. agent Patent attorney Hide Komatsu Commissioner of the Japan Patent Office Kazuo Wakasugi Indication of the Tonoichi case Name of the invention of Patent Application No. 14/100/1980 Water nature In Who makes the main amendment What is the relationship between the case and the person making the main amendment? 107
(Telephone number 58 (38854) Date of amendment order: Voluntary) 6. Circular of the specification to be amended, column for detailed explanation of the invention (1) The following text between page 9, line 16 and line 17 for specification: Insert. 1 The amino group referred to in the present invention is a group of nitrogen compounds thought to be derived from ammonia, and includes a primary amine group (-NH2) in which two hydrogen atoms are bonded to a nitrogen atom, and a primary amino group. A secondary amine group in which one hydrogen of a primary amine group is replaced with another group, a tertiary amino group in which two hydrogens of a primary amine group are replaced with another group, an alkyl halide or alkyl sulfate in the tertiary amino group There is a quaternary amino group (also called quaternary ammonium salt) bound to. Substituents include hydrocarbons, carbonyl, and others, and specific examples of amino groups include:
There are groups of nitrogen compounds as described in the examples of polymers and examples of monomers for synthesizing polymers. These amino groups may be attached to the side chains of the polymer or may be included in the main chain of the polymer (eg polyurethane, polyamide). ” (2) “…Aminostyrene” on page 13, line 2
wo "...aminoethylstyrene" is corrected. (3) Page 14, line 6 to line 911, 1... exists, and all of them are... great. " is corrected to "...there is." U] Insert the following sentence between page 14, line 10 and line 11. "Anionic dyes have sulfonic acid groups, carboxyl groups, or hydroxyl groups, or are of the anionic button type."

Claims (1)

[Claims] 1.1 A polymer dye emulsion formed by combining a water-insoluble polymer having a mino group and a dye selected from anionic dyes and reactive dyes, and a water-soluble viscosity modifier as the main components. water-based ink. 2. The water-insoluble polymer is (a) a polymer obtained by polymerizing a vinyl monomer having primary to tertiary amino groups, (0)
A copolymer of a vinyl monomer having a primary to quaternary amino group and a vinyl monomer or diene monomer that does not have an amine group that can be copolymerized with the hexamer, (iii) obtained by polyaddition or polycondensation. The water-based ink according to claim 1, which is one or more polymers selected from polymers having amine groups.
% by weight of the water-based ink according to claim 1. 4. The aqueous ink according to claim 1, wherein the particle size of the polymeric dye is 5 microns or less. 5. The water-soluble viscosity modifier is 0.01% of the total amount of ink.
The water-based ink according to claim 1, wherein the amount is 15% by weight. 6. The water-based ink according to claim 1, wherein the ink has a viscosity of 50 to 3000 cps at 20°C.