JPH03259970A - Water-based ink composition - Google Patents

Abstract

PURPOSE:To improve the resistance to drying at a pen point, the adhesion of written lines to a written surface, and water resistance by compounding water, a colorant dissolved or dispersed in water, a specific resin, and a lanolin deriv. CONSTITUTION:The title compsn. is prepd. by compounding 50-90wt.% water as a solvent; 0.5-40wt.% colorant, pref. a pigment, dissolved or dispersed, if necessary in the presence of a dispersant, in water; 0.1-30wt.% resin which forms a film at room temp. and is selected from the group consisting of an aq. emulsion, a hydrosol, and a solubilized resin (solubilized by salt-forming reaction with a base) of a water-insol. resin; 0.01-15wt.% lanolin deriv. selected from the group consisting of ethoxylated lanolin, polyoxyethylene lanolin alcohol ether, and polyoxyethylene lanolin fatty acid ester; and, if necessary, a lower aliph. alcohol, a surfactant, a pH modifier, an antiseptic agent, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous ink composition, and more particularly, to an aqueous ink composition, which is aqueous and has excellent quick-drying handwriting and water resistance, and particularly,
For example, the present invention relates to an aqueous ink composition that is difficult to dry at the nib of a writing instrument such as a marking pen even if the cap is removed and left for a long period of time, and thus has excellent drying resistance at the nib.

Conventionally, ink compositions for marking pens generally contain organic solvents, pigments, resins, etc., and ketones and alcohols are usually used as the solvents. However, ketones are highly toxic, and among alcohols, methanol is highly toxic and has a bad odor. On the other hand, ethanol, although less toxic, increases raw material costs.

Therefore, various aqueous ink compositions using water as the main solvent have been proposed. However, in general, when such water-based ink acids are left for a long time with the cap removed, the ink composition quickly dries at the pen tip.
It becomes difficult or impossible to write.

In order to improve the drying resistance of such water-based Mi acid ink at the nib, it is already known that urea can be added to the ink composition, as described in Japanese Patent Publication No. 4B-43301. It is also designated as Special Publication No. 53-43324
The publication describes that ethylene urea is blended into an ink composition. However, aqueous ink compositions containing a urea-based compound generally have poor adhesion of handwriting to a writing surface and water resistance of handwriting, and furthermore, have poor drying properties of handwriting on a non-absorbent writing surface.

On the other hand, Japanese Patent Application Laid-Open No. 55-84376 uses a water-soluble dye as a coloring agent and a lanolin derivative as a lubricant to make writing smooth and give a smooth writing feel.
An aqueous ballpoint pen ink composition has been proposed in which a water-soluble polyhydric alcohol such as ethylene glycol, diethylene glycol, or glycerin as a humectant is contained in water as a solvent. However, as is well known, in order for a water-based ballpoint pen to be able to write, there must be a minute gap between the ball and the pole holder, usually 0°01-0.
It is necessary that the ink composition always wets a minute gap of about 005 mn, and therefore, such a water-based ink M
The i-acid cannot be applied to marking pens with so-called felt-tip nibs or synthetic resin nibs, which are excellent in quick-drying handwriting.

Furthermore, water-based ink compositions containing a water-soluble polyhydric alcohol as a humectant have poor adhesion of handwriting to writing surfaces and water resistance of handwriting, as described above, and are particularly difficult to write on non-absorbent writing surfaces. Since the drying properties of handwriting are poor, from this point of view as well, it is difficult to apply it to marking pens.

As a result of intensive research to improve the drying resistance of felt pen nibs, synthetic resin pen nibs, etc. in conventional water-based ink compositions for marking pens, the present inventors have found that water as a solvent Water-based marking pens with lanolin derivatives and a resin that has film-forming properties at room temperature have excellent drying resistance at the pen tip, and the resulting handwriting has excellent adhesion to the writing surface and water resistance. The inventors have discovered that an ink composition can be obtained, leading to the present invention.

The aqueous ink composition according to the present invention for divination includes (a) water as a solvent, ~) a colorant dissolved or dispersed in water, and (c) an aqueous emulsion or hydrosol of a water-insoluble resin. and (d) a lanolin derivative.

In the marking pen ink composition according to the present invention,
Water is used as a solvent. The amount of water in the ink composition is usually 50 to 90% by weight, preferably 60 to 8% by weight.
It is in the range of 0% by weight. When the amount of water in the ink composition is too large, the dryness of handwriting on the writing surface is poor;
On the other hand, when the amount is too low, the ink composition has a high viscosity and has poor writing properties.

In the marking pen ink composition according to the invention, pigments are preferably used as colorants. Pigments include carbon black, phthalocyanine series such as copper phthalocyanine blue, azo series, quinacridone series, anthraquinone series, dioxane series, indigo series, thioindigo series, perinone series, perylene series, indorenone series, azo-azomethine series, etc. Any one can be used.

Dispersions made by dispersing various pigments in water are already commercially available, and such commercially available products can be preferably used in the present invention as well. Since the pigment dispersion described above may contain various resin dispersants, surfactants, etc. as pigment dispersants, the ink composition according to the present invention also contains such resins, surfactants, etc. It may be contained.

Pigment dispersants are known per se and are usually used for pigment 1.
1 to 300 parts by weight, preferably 5 to 1O
It is used in a range of 0 parts by weight.

In the present invention, dyes can also be used as colorants. In this case, water-soluble dyes are preferably used as the dyes.

The colorant in the ink composition is usually 0.5 to 40
Contained in a range of 1 to 35% by weight, preferably 1 to 35% by weight.
Contained within the range of When too much colorant is contained, the ink [parabolic viscosity is too high, resulting in poor writing properties; on the other hand, when too little colorant is contained, the density of the handwriting is too thin, making it impractical. .

Furthermore, in the ink composition according to the present invention, hollow resin particles may be used as the white pigment in the form of an emulsion together with other colorants.

Emulsions of such hollow resin particles are known as plastic pigments, and are disclosed in Japanese Patent Application Laid-open No. 63-14.
As described in JP-A-5382 and JP-A-63-145383, it is known that it can be used as a white pigment in, for example, aqueous ink compositions.

Plastic pigments are hollow particles of polystyrene, acrylic-styrene copolymer, polymethyl methacrylate, polyvinyl chloride resin, etc. obtained by emulsion (co)polymerization, and have a specific gravity of about 1 or less and a particle size of 0. 3
It is an emulsion of resin particles of about 1.0 μm. For example, "Bonco" J (manufactured by Dainippon Ink and Chemicals)
acrylic-styrene copolymer) and “gerandole” (
Acrylic styrene copolymer), etc., ``Opaque Polymer'' (acrylic-styrene copolymer) manufactured by Rohm and Haas, ``Latex 5BL880'' manufactured by Asahi Kaei Kogyo ■
1J (polystyrene), etc., and such commercial products can be suitably used in the present invention.

In the present invention, from the viewpoint of the stability of the ink composition and the adhesion of handwriting to the writing surface, the solid content of such hollow resin particles is usually 50% by weight or less, particularly 40% by weight. % or less.

The ink composition according to the present invention improves the dispersibility of the colorant in the ink composition, has excellent adhesion to the writing surface, and provides handwriting with excellent water resistance.
At least one resin that has film-forming properties at room temperature (hereinafter referred to as "room-temperature film-forming resin") selected from aqueous emulsions and hydrosols of resins that are originally water-insoluble, and resins that have been water-solubilized by salt formation with bases. ).

The emulsion or hydrosol of the water-insoluble resin is not particularly limited, but includes, for example, an emulsion of polyvinyl acetate, vinyl acetate copolymer, styrene-maleic acid copolymer, alkyd resin, urethane resin, etc. Hydrosols are used.

Further, as the resin made water-solubilized or water-dispersible by salt formation with a base, for example, water-solubilized vinyl acetate copolymer, alkyd resin, urethane resin, etc. are preferably used.

The comonomer of vinyl acetate in the emulsion, hydrosol or water-solubilized vinyl acetate copolymer may be a vinyl ester compound other than vinyl acetate, such as vinyl propionate or vinyl versatate, or an unsaturated carboxylic acid, e.g. , acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, citraconic acid, etc., or vinyl hydrocarbons, e.g.
Ethylene, propylene, styrene, α-methylstyrene, etc. can be mentioned. These may be mixed and used as a comonomer. Furthermore, in addition to the above, esters of the aforementioned unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, methyl methacrylate, and dimethyl maleate can also be used as comonomers. Moreover, the vinyl acetate copolymer may be a graft copolymer to polyvinyl acetate.

In particular, specific examples of preferable vinyl acetate copolymers include vinyl acetate-acrylic acid copolymers, vinyl acetate-acrylic acid copolymers,
Methacrylic acid copolymer, vinyl acetate-styrene-acrylic acid copolymer, vinyl acetate-styrene-maleic anhydride copolymer, vinyl acetate acrylic acid-methyl acrylate copolymer, vinyl acetate-methacrylic acid-methyl acrylate Examples include copolymers, vinyl acetate-acrylic acid-ethyl acrylate copolymers, vinyl acetate-methacrylic acid-methyl methacrylate copolymers, vinyl acetate-maleic anhydride copolymers, and the like.

Emulsions and hydrosols of polyvinyl acetate and the above-mentioned vinyl acetate copolymers can be easily prepared manually as commercial products.

Water-solubilized vinyl acetate copolymer is water-solubilized vinyl acetate copolymer as described above by salt formation with an inorganic or organic base, and is a water-solubilized vinyl acetate copolymer with an alkali metal salt such as sodium or potassium. , organic salts such as ammonium salts and organic amine salts. Such water-solubilized vinyl acetate copolymers are also available as commercial products.

Similarly, for water-solubilized alkyd resins, alkyd resins containing free carboxyl groups obtained from excess amounts of polybasic acids and polyhydric alcohols are neutralized with alkali metal bases, ammonium bases, organic alkynes, etc. They are made by making salt and making them solubilized in water, and these are also available as commercial products.

Water-solubilized urethane resin is also made by, for example, having a carboxyl group in the main chain of the polymer, and neutralizing the carboxyl group with an alkali metal base, ammonium base, organic amine, etc. to form a salt. These can also be made manually as commercially available products.

Furthermore, emulsions and hydrosols of alkyd resins and urethane resins can also be prepared manually as commercial products.

The room-temperature film-forming resin described above is contained in the ink composition according to the present invention in an amount of 0.1 to 30% by weight, preferably 0.5 to 20% by weight. When too much resin is contained, the viscosity of the ink composition is too high, resulting in poor writability.On the other hand, when too little resin is contained, adhesion of handwriting to the writing surface is poor, and Water resistance is also not sufficient.

The ink composition according to the present invention thus contains an emulsion or hydrosol of a resin that is originally water-insoluble, or a water-solubilized resin, and as described below, when written, the resin contains a colorant. Then, a film is formed as a carrier for these. Therefore, the water-based ink set Ffc according to the present invention provides handwriting with excellent water resistance.

The aqueous ink composition according to the present invention contains a lanolin derivative to improve drying resistance at the nib. Examples of such lanolin derivatives include ethoxylated lanolin, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin fatty acid ester, lanolin alcohol phosphate ester, lanolin fatty acid polyhydric alcohol ester, lanolin fatty acid sorbitan ester,
Examples include lanolin fatty acid adenoids, lanolin fatty acid alkanolamine salts, and mixtures of two or more thereof. Among these, ethoxylated lanolin is particularly preferably used in the present invention.

The ink composition according to the present invention contains 0.01 to 15% by weight, preferably 0.1 to 5% by weight of such lanolin derivatives.
Contain within the range of 15% by weight based on ink composition
If the amount exceeds 0.01% by weight, the viscosity of the ink composition will be too high, resulting in poor writing properties, while if it is less than 0.01% by weight, the drying resistance at the intended pen tip will be affected. Unable to improve sex.

Furthermore, when the ink composition contains a resin emulsion as a drying accelerator for improving the drying properties of handwriting formed on the writing surface, the ink composition according to the present invention may contain a lower fat to the extent that the emulsion is not destroyed. In particular, ethanol, isopropanol or butanol, which may contain group alcohols, are preferably used. The amount of such lower aliphatic alcohol blended is usually 15% by weight or less, preferably 1 to 1% by weight based on the ink Mi acid.
It is in the range of 0% by weight.

Further, in addition to the above, the ink composition may contain various surfactants, arbitrary pH adjusters, preservatives, etc. that are usually added to aqueous ink compositions, if necessary.

For example, the surfactant is not particularly limited, and any of anionic, nonionic, cationic, and amphoteric surfactants can be used.

However, in particular, nonionic surfactants and anionic surfactants such as carboxylic acid type, sulfonic acid type, sulfuric acid ester type, phosphoric acid ester type, etc. having polyoxyethylene chains, amphoteric surfactants of alkyl betaine type, fluorine type surfactants, etc. Activators and the like are preferably used. Such surfactants are generally 10% by weight or less, preferably 0.2 to 511% by weight.
Contained within the range of When blended in excess, writability is reduced.

The water-based ink product for marking pens according to the present invention is made by using water as a solvent and blending a lanolin derivative with a film-forming resin at room temperature. When water evaporates and evaporates from the ink composition on the nib after being left for a period of time, the lanolin derivative quickly precipitates on the surface of the nib, forms a thin film, and covers the surface of the nib. This further prevents water from evaporating and transpiring. However, when writing again, the film is easily and immediately destroyed, so even if you start writing after exposing the nib to the atmosphere for a long time, the ink composition will not flow out from the nib. , not hindered in any way.

Furthermore, according to the water-based ink composition of the present invention, the room-temperature film-forming resin, which is originally water-insoluble, forms a film on the writing surface as a carrier for the colorant, so the resulting handwriting quickly becomes water resistant. It will be done. Furthermore, the aqueous ink composition according to the present invention can be used on both absorbent writing surfaces such as paper and non-absorbent writing surfaces made of glass, metal, resin, and the like.

The present invention will be described below with reference to examples for one ship group, but the present invention is not limited to these examples in any way.

An aqueous marking pen ink composition as an example of the present invention was prepared comprising the components shown below.

In the following, the amount of the component indicates the amount by weight as an effective amount in the ink m acid, and the remainder is water containing an effective amount of preservative.

Uncertified top colorant Carbon black dispersant Joncryl J-682” Resin Hylos , Pigment Red 17 Dispersant Sodium Polyacrylate Resin Aloron 585゜Lanolin Derivative Belbol C-24'ゝ7 % 3% 8% 0.5% Technique 41 Colorant Copper Phthalocyanine Blue Dispersant Niracol D OP - 8" Resin Movinyl DMIH') Lanolin derivative Belball L-30"" Soil Colorant Carbon Black 5 Gerandol PP-1100"170 Dispersant Niracol TLP-410' 1 Resin Polysol HR-C,"' 5 Lanolin derivative Bellball A-20" 1 Otsu2m Rainbow Coloring agent Titanium oxide dispersant Emulgen A 9QIZl Resin Hylos AW-36"' Lanolin derivative Bellball 1, 75141% 1. Red 51 Carbon Black Dispersant Nyracol DLP-10Is) Resin Polytron A-6516 Lanolin Derivative Belbol C-24' Handwriting Drying Agent Isopropanol 0.9% 12% 2% 4% 1% 10% % 33% 2 % % Otsumv1 coloring agent Copper phthalocyanine blue dispersant Styrene-acrylic acid copolymer ammonium salt resin Vinizol DV-230"' Lanolin derivative Bellball L-30" 4% 2% 6% 0.5% Otsuno m % Colorant C, 1, Direct Black 38 resin Polysol AT2040"' Lanolin derivative Bellball L 5QI91 8.5% 8% 1.5% Ink 11 Colorant Carbon black dispersant Joncryl J-68 Resin Hylos X-201 4% 2% 5% Otsugami IJ Hohong 1 Colorant C,1, Acid Blue 90 Resin Movinyl 770!6) Lanolin derivative Bellball L 75141 6% 6% 0,5% Ink 12 Colorant Carbon black dispersion Agent: Joncryl J-682 Resin Hylos Agent isopropanol 10% 5% Ink 13 Colorant Copper phthalocyanine blue dispersant Niracol DOP-8 Resin Movinyl DMIH 4% 1% 6% 2% 10% Ink 14 Colorant Copper phthalocyanine blue dispersant Niracol DOP-8 % 1 % Ink compositions as comparative examples are listed below.

Resin Movinyl DMIH Moisturizer Propylene glycol 6% 20% Ink 15 Colorant Titanium oxide dispersant Emulgen A-90 Resin Hylos AW-36 33% 2% 5% Ink 16 Colorant Titanium oxide dispersant Emulgen A-90 Resin Hylos AW -36 Moisturizer Propylene Glycol 30 Ink 17 ・ Colorant c, i, Acid Red 51 Carbon Black Dispersant Niracol DLP-10 Resin Polytron A-65 0.9% 12% 2% 4% Ink 18 ・ Colorant C,1, Acid Red 51 Carbon Black Dispersant Niracol DLP-10 Resin Polytron A-65 Humectant Propylene Glycol Ink 19 ・Colorant C,1, Acid Blue 90 Resin Movinyl 770 Ink 20 ・Colorant C,1, Acid Blue 90 Resin Movinyl 770 Humectant Propylene Glycol 0.9% 12% 2% 4% 20% % 6% 6% 6% 20% Ink 21 ・Colorant C, 1, Acid Red 87c, r, Acid Yellow 23 Moisturizer Thiodiethylene glycol 4% 2% 15% Ethylene glycol 5% Lanolin derivative Lanolin fatty acid jetanolamine salt 0.2% (Note) 1) Acrylic resin manufactured by Johnson Polymer 2) Styrene-maleic acid copolymer manufactured by Seiko Kagaku Combination 3) Ethoxylated lanolin alcohol manufactured by Yoshikawa Oil 4) Water-solubilized alkyd resin manufactured by Nippon Shokubai 5) Ethoxylated lanolin cholesterol manufactured by Yoshikawa Oil 6) Polyoxyethylene oleyl ether sodium phosphate manufactured by Nikko Chemicals 7) Vinyl acetate manufactured by Hoechst Synthesis Maleic acid copolymer emulsion 8) Ethoxylated lanolin manufactured by Yoshikawa Oil Co., Ltd. 9) Hollow resin sphere manufactured by Dainippon Ink & Chemicals 10) Polyoxyethylene lauryl ether sodium phosphate manufactured by Nikko Chemicals Polyvinyl acetate emulsion manufactured by Showa Kobunshi Polyvinyl acetate emulsion manufactured by Kao Nonionic Surfactant Acrylic resin manufactured by Seiko Chemicals Ethoxylated lanolin manufactured by Yoshikawa Oil Co., Ltd. Polyoxyethylene lauryl ether Sodium phosphate manufactured by Nikko Chemicals Styrene-acrylic copolymer manufactured by Daido Chemical Industries Polyurethane emulsion manufactured by Daido Chemical Industries Styrene manufactured by Showa Kobunshi −
Acrylic emulsion 19) Ethoxylated lanolin manufactured by Yoshikawa Oil Co., Ltd. 20) Vinyl acetate-acrylic copolymer manufactured by Hoechst Synthesis 21) Acrylic resin emulsion manufactured by Johnson Polymer These respective ink compositions were filled into a marking pen equipped with a felt-tip pen, With the cap removed,
The pen was left for a predetermined period of time at a temperature of 2°C and t = 65%, and the drying resistance was evaluated as the time until the pen tip became dry and writing became impossible.

In addition, each ink composition was written on ordinary paper, and the time required for drying the handwriting was evaluated as the handwriting drying property under conditions of a temperature of 20''C and a humidity of 65%.

Furthermore, each ink composition was written on a glass plate, the handwriting was dried, and then the handwriting was rubbed with a dry cloth.
The adhesion of the handwriting to the glass surface was evaluated.

The above results are shown in Table 1.

In particular, the water-based ink m-acid of Comparative Example 21 is for water-based ballpoint pens containing a water-soluble polyhydric alcohol as a humectant, and from the results shown in Table 1, the dryness and adhesion of handwriting are poor. , it has been shown that it is difficult to apply it to marking pens.

Next, the ink compositions of Example 10 and Comparative Example 21 were filled into core ballpoint pens, and the writing speed was 7 cm/
Seconds, before writing! A written test was conducted at 100 g and a writing angle of 60°. As a result, in all cases, the ink flow amount was 180 square meters or more up to 100 meters of handwriting.

However, when the ink compositions of Example 1o and Comparative Example 21 were respectively filled into core ballpoint pens and stored at 50°C for one month, the ink composition of Example 1° was
Although it was not possible to write, the ink composition of Comparative Example 21
I was able to write it down immediately. That is, it is shown that the ink composition of Example 10 cannot be applied to ballpoint pens.

Claims (6)

[Claims] (1) (a) Water as a solvent; (b) Colorants dissolved or dispersed in water; (c) Water-soluble resins made water-soluble by aqueous emulsions, hydrosols, and salt formation with bases. 1. A water-based ink composition comprising at least one resin having film-forming properties at room temperature selected from the resins listed above, and (d) a lanolin derivative. (2) (a) Water as a solvent; (b) 0.5 to 40% of a colorant dissolved or dispersed in water;
(c) at least one resin having film-forming properties at room temperature selected from aqueous emulsions of water-insoluble resins, hydrosols, and resins made water-soluble by salt formation with bases, 0.1 to 10% by weight; 30% by weight, and (d) 0.01 to 15% by weight of a lanolin derivative. (3) Lanolin derivatives include ethoxylated lanolin, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin fatty acid ester, lanolin alcohol phosphate ester, lanolin fatty acid polyhydric alcohol ester, lanolin fatty acid sorbitan ester, lanolin fatty acid amide, lanolin fatty acid alkanolamine 3. The water-based ink composition according to claim 1, which is a salt or a mixture of two or more thereof. (4) The aqueous ink composition according to claim 1, which contains a lower aliphatic alcohol as a drying agent for handwriting on a writing surface. (5) Claim 1, characterized in that the coloring agent is a pigment.
The aqueous ink composition described in . (6) The water-based ink composition according to claim 1, wherein the water-based ink composition is used for marking pens.