JP2001181544A - Aqueous ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous ink which shows an excellent water resistance, light resistance, clarity, shelf stability and OA performance and allows no drying of pen points. SOLUTION: The aqueous ink contains a resin particle which is dyed with a dye and comprises a copolymer containing a cyano group-containing vinyl monomer (A) and either or both of a vinyl monomer (B) of formula (I) and a vinyl monomer (C) of formula (II) wherein R is a hydrogen atom or a methyl group; Y is -CH2 or -CH2-CH(CH2X)-, wherein X is a halogen atom; and n is an integer of 1-5 as structural monomers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based ink, and more particularly, to an underline marker, a ball-point pen,
The present invention relates to a water-based ink for ink pens, ink jets, textile printing, and the like, and a water-based paint for paints, poster colors, and the like.

[0002]

2. Description of the Related Art Conventionally, dye-soluble water-based inks have a problem of insufficient light fastness and water fastness, whereas pigment-dispersed water-based inks have insufficient light fastness, There were problems such as drying and sedimentation of pigment particles. In addition, the water-based ink is required to have high clarity and excellent OA properties such that it does not discolor on thermal paper and does not erase characters on pressure-sensitive paper.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide excellent water resistance, light resistance, storage stability, and no drying of the pen tip.
An object of the present invention is to provide a water-based ink having excellent clarity and OA properties.

[0004]

The present invention relates to a cyano group-containing vinyl monomer (A) dyed with a dye, and one or both of a vinyl monomer (B) and a vinyl monomer (C) represented by the following general formula: An aqueous ink containing resin particles made of a copolymer containing both as constituent monomers.

[0005]

Embedded image In the formula, R represents a hydrogen atom or a methyl group, Y is -CH ₂ -
Or _{-CH 2 -CH (CH 2 X)} - (X represents a halogen atom), n represents an integer of 1 to 5. ]

The content of the vinyl monomer (A) is preferably 30 to 80% by weight, and the content of the vinyl monomer (B) is 0.1% by weight.
1 to 20% by weight, vinyl monomer (C) 0.1 to 0.4
% By weight and other vinyl monomers from 0 to 70% by weight, more preferably 50 to 55% by weight of the vinyl monomer (A), 1 to 10% by weight of the vinyl monomer (B), and 0.1 to 0% by weight of the vinyl monomer (C). 0.3% by weight and 35 to 50% by weight of other vinyl monomers.

The above-mentioned copolymer is obtained by radical polymerization in an aqueous dispersion system, and the resin particles comprising the copolymer preferably have a particle size of 0.05 to 0.50 μm.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The cyano group-containing vinyl monomer (A) may be any vinyl monomer containing a cyano group, and typical examples include acrylonitrile and methacrylonitrile. When the amount of the monomer (A) is less than 30% by weight, coloring with a dye tends to be insufficient, and the sharpness of color tone and the fastness to sunlight tend to decrease. When the amount exceeds 80% by weight, emulsion polymerization tends to be difficult. , Storage stability also tends to be poor.

The vinyl monomer (B) includes acid phosphooxyethyl methacrylate, acid phosphooxypropyl methacrylate, acid phosphooxyethyl acrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol monomethacrylate, -Chloro-2-acid phosphooxypropyl methacrylate and the like.

The vinyl monomer (C) is sodium styrenesulfonate and sodium α-methylstyrenesulfonate. When the use ratio of the monomer (C) exceeds 0.4% by weight, the polymer tends to increase in viscosity and tends to gel.

The vinyl monomers (B) and (C) have a function of improving dyeability and a dye receptivity (adsorption property).

The other vinyl monomers include (A),
A vinyl monomer other than the vinyl monomers (A), (B) and (C) copolymerized with (B) and (C).
Other vinyl monomers include styrene, α-methylstyrene, vinyl toluene, vinyl acetate, vinyl propionate, propyl vinyl ether, butyl vinyl ether, methyl acrylate, ethyl acrylate, n-
Propyl acrylate, isopropyl acrylate, n
Acrylates such as -butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, decyl acrylate, benzyl acrylate, and furfuryl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n- Methacrylates such as butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, decyl methacrylate, dodecyl methacrylate, benzyl methacrylate, furfuryl methacrylate, divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, The Chi glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, acrylic acid, a compound having a polymerizable unsaturated group of two or more as methacrylic acid and the like. Of these, preferred are compounds that give a hard polymer such as styrene, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid. If the use ratio of the other vinyl monomer exceeds 70% by weight, it is difficult to obtain a clear fluorescent ink having high light fastness.

The copolymer used in the present invention is obtained by radical polymerization in an aqueous dispersion system, and the resin particles comprising the copolymer preferably have a particle size of 0.05 to 0.50 μm. When the particle diameter of the resin particles is less than 0.05 μm, the appearance of the aqueous ink tends to be dark and the sharpness as the aqueous ink tends to be reduced, and the particle diameter is 0.50 μm
When the ratio exceeds the above range, the colored resin particles settle in the aqueous ink, and the ink tends to have poor storage stability, making it difficult for the ink to flow smoothly.

The emulsion polymerization method of the present invention is carried out by appropriately selecting the type and amount of the surfactant according to the purpose, and the polymerization temperature is preferably from 50 to 90 ° C.

Surfactants preferably used in the present invention include alkyl benzene sulfonate, alkyl phenol sulfonate, sulfonate having alkyl diphenyl ring, formalin condensate of alkyl allyl sulfonic acid, and alkyl allyl sulfonate Ketone compounds, sulfosuccinate salts, anionic surfactants such as polyoxyethylene alkyl sulfonate salts and fatty acids and esters such as glycerin, glycol, pentaerythritol, sorbitan, or mannitan,
Or nonionic surfactants such as condensates of polyethylene oxide with higher fatty acids, higher alcohols, higher alkylamines, or alkylphenol phosphoric acids, etc., when only anionic surfactants are used or when nonionic surfactants are used And so on. Preferably,
Nonionic polymerizable surfactants, specifically, "Adekaria Soap NE-10", "NE-20", "NE-30", and "NE-30" manufactured by Asahi Denka Kogyo Co., Ltd. 40 ",
“SE-10N”, “Latemul S-1” manufactured by Kao Corporation
80 "and" S-180A ", a higher alcohol ether type nonionic surfactant" Emulgen LS-106, 1 "
10, 114 ”,“ MS-110 ”,“ S-120 ”
A: “Eleminol JS-2” manufactured by Sanyo Chemical Industries, Ltd.
And the like, and one or more of them are used in combination.

The amount of the surfactant used is preferably 0.1 to 50% by weight based on the total amount of the vinyl monomer.

In the present invention, the light resistance is improved by using the above vinyl monomer (A), and the vinyl monomer (B) or (C) is further combined with an anionic surfactant and a nonionic polymerizable surfactant. Combination use improves the drying speed at the pen tip, improves long-term storage stability, and improves writability.

Examples of the polymerization initiator include ammonium persulfate, potassium persulfate, and hydrogen peroxide. If necessary, a reducing agent may be used in combination.

The copolymer used in the present invention is preferably
The above-mentioned vinyl monomer, polymerizable surfactant, ammonium persulfate, potassium persulfate, hydrogen peroxide or the like as a polymerization initiator, or, if necessary, an initiator in the form of using a reducing agent in combination, the usual emulsification It is synthesized by a polymerization method.

The fluorescent dye used in the present invention can be selected from various dyes such as a basic dye (including a catilone dye), a direct dye, and a fluorescent brightening dye. In particular, one or more daylight fluorescent dyes and daylight fluorescent dyes can be used. It is effective to use a combination of a light fluorescent dye and an ordinary dye (a dye having no fluorescence), but the present invention is not limited to this. Specifically, it is represented by a color index number (C · I), and BASIC YELLOW 1,
BASIC YELLOW 40, BASIC RED
1, BASIC RED 13, BASIC VIOL
ET 7, BASIC VIOLET 10, BASI
C ORANGE 22, BASIC BLUE 7,
BASIC GREEN 1, DIRECT YELL
OW 85, DIRECT ORANGE 8, DIR
ECTRED 9, DIRECT BLUE 22, D
IRECT GREEN 6, FLUORESCENT
BRIGTENING AGENT 55, FLU
ORESCENT BRIGHTENING WHIT
EX WS 52, FLUORESCENT 162,
FLUORESCENT 112 and the like, of which BASIC YELLOW 40, BA
SIC RED1, BASIC VIOLET 10,
FLUORESCENT BRIGHTTENING W
HITEX WS 52 is preferred.

The coloring with these dyes can be carried out either at the time of emulsion polymerization or after the polymerization. The conditions are as follows: 40-110 ° C. under atmospheric pressure or under pressure;
Preferably, the dye is used under stirring for 5 to 5 hours. The amount of the dye used is 0.01 to 100 parts by weight of the emulsion polymer (solid content).
10 parts by weight is preferable, and 0.1 to 5 parts by weight is more preferable.

The coloring with a dye can be carried out by a conventional method, but is preferably carried out by using a surfactant. When the emulsion polymer is anionic or nonionic, the color of the dye depends on the type of the dye. Regardless, the surfactant is preferably anionic or non-ionic.

The polarities of the emulsion polymer, the dye and the surfactant are appropriately selected according to the purpose.

The aqueous ink prepared from the above contains 10 to 40% by weight, preferably 20 to 3% by weight of the dyed resin particles.
0% by weight, 40 to 90% by weight of water and hydrophilic solvent as a solvent, preferably 50 to 80% by weight, and 0.2 to 0.2% of an additive.
A suitable amount is 5.0% by weight, preferably 0.5 to 3.0% by weight.

[0025]

(Example 1) A cooling tube, a thermometer, a 500 ml separatory funnel for charging monomers and a stirrer were attached to a 2 liter flask, and the flask was set in a hot water tank.

Next, 440 cc of water, 8.5 g of sodium dodecylbenzenesulfonate and a nonionic surfactant [Emulgen LS-11 manufactured by Kao Corporation] were added to the flask.
0 ″], and the internal temperature was raised to 80 ° C.

On the other hand, 140 g of acrylonitrile, 119 g of styrene and 14 g of 2-methacryloyloxyethyl acid phosphate were mixed and stirred, and then 2.1 g of potassium persulfate was charged into a flask heated to 80 ° C., and the mixed monomer was added to the above-mentioned monomer. The mixture was added from the separating funnel to the flask over 3 hours with stirring, and the polymerization was completed in 4 hours.

To the obtained polymer were added 200 g of water, 20 g of Kayacryl Brilliant Yellow F2G [Basic Yellow 40 manufactured by Nippon Kayaku Co., Ltd.], and a special polycarboxylic acid type polymer surfactant ["Demol" manufactured by Kao Corporation. EP "] 21
g was added at room temperature under stirring and mixed uniformly, then the temperature was gradually raised and dyed at 80 ° C. for 1 hour to give a particle size of 0.1 μm.
m yielded a clear yellow fine particle dispersion.

The ink prepared by using this exhibited excellent OA properties (no discoloration on heat-sensitive paper and no loss of characters on pressure-sensitive paper).

(Example 2) 200 g of water, 0.3 g of Rhodamine F3B [“Bathony Red 560” manufactured by BASF] and 0.3 g of Rhodamine F4G [BA
2.0 g of “Bassony Le Red 485” manufactured by SF Co., Ltd .; 17.5 g of a special polycarboxylic acid type polymer surfactant [ditto]
Was added at room temperature under stirring, mixed uniformly, then gradually heated, and dyed at 85 ° C. for 1 hour to obtain a particle diameter of 0.1 μm.
A clear pink fine particle dispersion was obtained.

[0031] The ink prepared by using this has excellent OA property.

Example 3 A cooling tube, a thermometer, a 1-liter separatory funnel for charging monomers and a stirrer were attached to a 2-liter flask, and the flask was set in a hot water tank.

Next, 150 cc of water was charged into the flask, and the internal temperature was raised to 80.degree.

On the other hand, a monomer mixture consisting of 140 g of acrylonitrile and 119 g of styrene was mixed with 267 g of water and Na styrene sulfonate ["Spinomer Na" manufactured by Tosoh Corporation.
ss "], 4.9 g of sodium dodecylbenzenesulfonate, 14 g of a nonionic surfactant [" Emulgen LS-110 "manufactured by Kao Corporation] was mixed, stirred and dispersed, and then potassium persulfate 2 0.1 g was charged into a flask heated to 80 ° C., and the mixed and stirred mixture was added to the flask from the separating funnel over 3 hours, and the polymerization was completed in 4 hours.

To the obtained polymer, 200 g of water, 20 g of Kayacryl Brilliant Yellow F2G [Basic Yellow 40 manufactured by Nippon Kayaku Co., Ltd.], and 21 g of a special polycarboxylic acid type polymer surfactant [same as above] were stirred at room temperature. And add
After uniform mixing, the temperature was gradually raised and dyed at 80 ° C. for 1 hour to obtain a clear yellow fine particle dispersion having a particle diameter of 0.1 μm.

[0036] The ink prepared using this exhibited excellent OA properties.

Example 4 200 g of water, 0.3 g of Rhodamine F3B (“Bassony Le Red 560” manufactured by BASF) and 0.3 g of Rhodamine F4G [BA were added to the polymer obtained in Example 3.
2.0 g of "Bassony Le Red 485" manufactured by S Company F], 17.5 g of a special polycarboxylic acid type polymer surfactant [the same as above]
Was added at room temperature under stirring, mixed uniformly, then gradually heated, and dyed at 85 ° C. for 1 hour to obtain a particle diameter of 0.1 μm.
A clear pink fine particle dispersion was obtained.

[0038] The ink prepared by using this had excellent OA properties.

(Comparative Example 1) A cooling tube, a thermometer, a 500 ml separating funnel for charging monomers and a stirring device were attached to a 2 liter flask, and the flask was set in a hot water tank.

Next, 440 g of water, 3 g of sodium dodecylbenzenesulfonate and 13 g of polyoxyethylene nonylphenyl ether were charged into the flask, and the internal temperature was adjusted to 8 g.
The temperature was raised to 0 ° C.

On the other hand, after 49 g of acrylonitrile, 196 g of styrene and 21 g of acrylic acid were mixed and stirred, 2.1 g of potassium persulfate was charged into a flask heated to 80 ° C., and the mixed monomers were stirred into the flask from the separating funnel. It was added over a period of 3 hours, and the polymerization was completed in 4 hours.

To the obtained polymer, 200 g of water, 20 g of Kayacryl Brilliant Yellow F2G [Basic Yellow 40 manufactured by Nippon Kayaku Co., Ltd.], and 21 g of a special polycarboxylic acid type polymer surfactant [the same as above] were stirred at room temperature. And add
After uniform mixing, the temperature was gradually raised and dyed at 80 ° C. for 1 hour to obtain a clear yellow fine particle dispersion having a particle diameter of 0.1 μm.

In the ink prepared using this, it was observed that the OA property was discolored on heat-sensitive paper and the tendency to erase characters on pressure-sensitive paper.

Comparative Example 2 The polymer obtained in Comparative Example 1 was added to 200 g of water, 0.3 g of Rhodamine F3B [“Bathony Red 560” manufactured by BASF], and Rhodamine F4G [BA
2.0 g of “Bassony Le Red 485” manufactured by SF Co., Ltd.] and 12 g of a special polycarboxylic acid type polymer surfactant [same as above] were added under stirring at room temperature, and the mixture was uniformly mixed. Dyeing was performed for 1 hour to obtain a fine pink particle dispersion having a particle diameter of 0.1 μm.

In the ink prepared using this, it was observed that the OA properties tended to cause discoloration on heat-sensitive paper and the disappearance of characters on pressure-sensitive paper.

Comparative Example 3 A cooling tube, a thermometer, a 1-liter separatory funnel for charging monomers and a stirrer were attached to a 2-liter flask, and the flask was set in a hot water tank.

Next, 150 cc of water was charged into the flask, and the internal temperature was raised to 80 ° C.

On the other hand, a monomer mixture comprising 140 g of acrylonitrile, 119 g of styrene and 4 g of acrylic acid was mixed with 267 g of water, 4 g of sodium styrenesulfonate ["Spinomer Nass" manufactured by Tosoh Corporation], 4.9 g of sodium dodecylbenzenesulfonate, After mixing, stirring and dispersing in a mixed solution of 14 g of a surfactant [“Emulgen LS-110” manufactured by Kao Corporation], 2.1 g of potassium persulfate was charged into a flask heated to 80 ° C. Was added from the separatory funnel into the flask over a period of 3 hours. Near the completion of the addition, the viscosity increased and gelation occurred. Therefore, the following performance test was not performed.

The fine particle dispersions of the above Examples and Comparative Examples were made into inks according to the following formulation, and the following performance tests were carried out using a marking pen.

[0050]

<Storage Stability> The marking pen was placed in a hot air circulating drier at 60 ° C., and the marking property was checked for 30 days.

<Drying resistance of pen tip (recovery of decapping)
> After removing the cap, the marking pen was placed in a hot air circulating drier at 50 ° C. and dried for 6 hours. After that, it was confirmed that the marking pen was faint or impossible to mark.

<Lightfastness> The marked paper is faded.
The meter was checked by irradiation for 10 hours.

<Waterfastness> The marked paper was immersed in water for 1 hour to check for discoloration.

[0055]

[Table 1]

[0056]

The aqueous ink of the present invention has water resistance, light resistance, storage stability, decap restorability, sharpness, OA properties,
In particular, it is excellent in light fastness and is useful for aqueous inks including writing instruments which are required to have such performance, and also for aqueous paints.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akiyuki Wada 2-19-12 Tailo, Kamakura-shi, Kanagawa Prefecture Shinloich Co., Ltd. (72) Inventor Seiji Nikura 2-19-12 Tailo, Kamakura-shi, Kanagawa Shinloich Co., Ltd. F Term (reference) 4J039 AD02 AD03 AD08 AD09 AD10 AD11 BE01 BE02 BE03 BE05 CA06 EA11 EA28 EA35 EA38 EA44 GA24 GA26 GA27

Claims (3)

[Claims] 1. A copolymer containing a cyano group-containing vinyl monomer (A) dyed with a dye and one or both of a vinyl monomer (B) and a vinyl monomer (C) represented by the following general formula as constituent monomers: A water-based ink containing resin particles composed of coalesced particles. Embedded image In the formula, R represents a hydrogen atom or a methyl group, Y is -CH ₂ -
Or _{-CH 2 -CH (CH 2 X)} - (X represents a halogen atom), n represents an integer of 1 to 5. ] 2. The copolymer is composed of 30 to 80% by weight of a vinyl monomer (A) and a vinyl monomer (B).
0.1-20% by weight and other vinyl monomers 0-7
The water-based ink according to claim 1, wherein 0% by weight, or 30 to 80% by weight of the vinyl monomer (A), 0.1 to 0.4% by weight of the vinyl monomer (C), and 0 to 70% by weight of another vinyl monomer. . 3. The aqueous ink according to claim 1, wherein the copolymer is obtained by radical polymerization in an aqueous dispersion system, and the particle size of the resin particles comprising the copolymer is 0.05 to 0.50 μm. .