JPH09157576A - Marking ink for warning against the presence of glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a marking ink for warning against the presence of glass, which can give a mark that is not peeled from the glass merely when it is exposed to wind and rain or when a man or a thing contacts with it softly, can be easily erased with, e.g. wet cloth even after a long time, and does not undergo sagging during the period from the transfer of the ink to its drying on the surface of the glass by using specified components as the essential components. SOLUTION: This marking ink essentially consists of a colorant (i), at least one member (ii) selected from among resin emulsions and alkali-soluble resins, a water-soluble resin (iii) in an amount to give a ratio to the solid content of component (ii) of 1/9 to 9/1 by weight, (iv) a thixotropic agent, and (v) water. Component (iv) comprises at least one member selected from among acidic heteropolysaccharides, swelling layered clay minerals and crosslinkable acrylic resin copolymers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention temporarily marks a glass surface to clarify the existence of transparent glass attached to doors, windows, etc. of a building under construction or extension, and erases it when not needed. The present invention relates to a marking ink for indicating the presence of glass.

[0002]

2. Description of the Related Art An ink of this kind proposed by the present inventor (Japanese Patent Laid-Open No. 82825/1995) has a glass surface coated with a roller type applicator equipped with a porous elastic roller having a plate formed on the surface thereof. The mark transferred to (1) is easily erased by rubbing with a wet cloth or the like even after a lapse of time, but there is a tendency that dripping occurs during the transfer until the ink dries. Here, dripping is a phenomenon in which the ink transferred onto a vertical glass surface does not resist the action of gravity until it dries, and hangs along the glass surface in an icicle, wavy, or semicircular shape. This is detrimental to the appearance, and in a remarkable case, the characters or symbols of the transferred ink become unreadable.

[0003]

DISCLOSURE OF THE INVENTION According to the present invention, the mark transferred to the glass surface does not peel off when exposed to wind and rain, or when a person or an object normally touches it, and the mark can be removed with a wet cloth even after a long period of time. It is an object of the present invention to provide a glass-presenting marking ink which does not cause a dripping phenomenon from the ink transfer to the drying, while maintaining the requirement that it can be easily wiped off by rubbing.

[0004]

The marking ink for presenting glass present of the present invention comprises (a) a colorant as an essential component,
(B) At least one selected from a resin emulsion and an alkali-soluble resin, (c) a water-soluble resin having a weight ratio of 1/9 to 9/1 with respect to the solid content of the component (b), (d)
It is a composition containing a thixotropic agent and (e) water.

Examples of the colorant include azo type, anthraquinone type, condensed polyazo type, thioindigo type, metal complex salt type,
Phthalocyanine-based, perinone-perylene-based, organic pigments such as dioxazine-based and quinacridone-based, carbon black, iron oxide, inorganic pigments such as titanium white, and fluorescent pigments composed of a polymer of a fluorescent dye and a vinyl-based monomer, etc. are used, It is used in the range of 3 to 40% by weight in the ink composition.

Examples of the resin emulsion of the component (b) include styrene / (meth) acrylic acid ester copolymer emulsion, (meth) acrylic acid ester / vinyl acetate copolymer emulsion, (meth) acrylic acid ester / vinylidene chloride copolymer A polymer emulsion or the like is used. Here, the notation of (meth) acrylic acid represents acrylic acid or methacrylic acid. As the alkali-soluble resin, styrene / acrylic acid copolymer ammonium salt, vinyl acetate / (meth) acrylic acid copolymer trimethylamine salt,
Ammonium polyacrylic acid salt or the like is used. These resin emulsions and alkali-soluble resins may be used alone or in 2
Used in combination of more than one species.

As the water-soluble resin of the component (c), partially saponified polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, vinyl acetate / vinyl alcohol / acrylic acid ester copolymer, vinyl acetate / vinyl alcohol / (meth) acrylic acid Vinyl acetate resins such as ester copolymers, cellulose resins such as methyl cellulose, ethyl hydroxypropyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose, and polysaccharides (Pullulan manufactured by Hayashibara Shoji Co., Ltd.) and the like are used.

The above components (b) and (c) are used in a weight ratio of solids in the range of 1/9 to 9/1. This range is a range that substantially satisfies the balance between the water resistance and abrasion resistance of the mark formed by the ink transferred to the glass surface and the ease of wiping with a wet cloth. The total amount of the components (B) and (C) is used in the ink composition in the range of 1 to 30% by weight as a solid content. With the composition of both resins out of the range of the weight ratio, for example, when the component (b) / (c) is smaller than the minimum value of the range, the mark transferred to the glass surface is light under high humidity or in a wet state. If the mark is larger than the above maximum value, the mark will not be erased even if it is rubbed strongly with a wet cloth or the like.

As the thixotropic agent of the component (d), an acidic heteropolysaccharide, a swellable layered clay mineral and a crosslinked acrylic resin copolymer are used. Specific examples of the acidic heteropolysaccharide include xanthan gum (Dainippon Pharmaceutical Co., Ltd. product Echo gum, Echo gum T, Echo gum BT, Echo gum GS,
Sansei Co., Ltd. product Kelzan, etc., succinoglycan (Sansei Co., Ltd. product Leosan), and others (Daiichi Kogyo Seiyaku Co., Ltd. product DK Ramdam, Sansan Co., Ltd. product K1A96) and the like. Specific examples of the swellable layered clay mineral include smectite structure clay (Smectite SWN, Smectite SWF manufactured by Cope Chemical Co., Ltd., Laponite XLG manufactured by Sansei Co., Ltd.). Specific examples of the cross-linking acrylic resin copolymer include Hibiswako 103, 104 and 105 manufactured by Wako Pure Chemical Industries, Ltd., Carbopol 934 and Carbopol 940 manufactured by Showa Denko KK. Addition of these thixotropic agents changes the physical properties of the ink to thixotropic (thixotropic) properties, which results in fluidity when shearing force is applied to the glass surface of the roller applicator during ink transfer. However, the ink that forms the mark without shearing force exhibits the effect of not exhibiting fluidity and causing the dripping phenomenon, and among them, xanthan gum is particularly excellent. Show the effect. The degree of thixotropy (thickness) is calculated from data measured by various test methods for rheology, but here the ratio of viscosity values measured at different rotor speeds by a rotational viscometer (low rotation) The degree of thixotropic change represented by (viscosity value in number / viscosity value at high rotation number) was calculated, and the relationship with the dripping inhibiting effect was investigated. At the room temperature (about 20 to 25 ° C.) in the experiment of the present inventor
In the EM type viscometer, the rotation speed of the rotor is 10 rotations /
The ink showing a value in the range of 2 to 5 in the thixotropic index, which is represented by the ratio of the viscosity value in minutes and the viscosity value in 50 rpm,
The ink transferability onto the glass surface by the roller-type applicator was good, and dripping of the transferred marks did not occur. When the acidic heteropolysaccharide, the cross-linked acrylic resin copolymer, or the above two are used in combination, they are used in the ink composition in an amount of 0.05 to 0.8% by weight, preferably 0.1 to 0.5% by weight. To be The swellable layered clay mineral is used in the ink composition in an amount of 0.5 to 5% by weight, preferably 1 to 3% by weight.

In addition, if necessary, a lower alcohol such as ethanol or propanol for accelerating the drying of the marks by the ink, ethylene glycol, propylene glycol, glycerin or the like as a wetting agent, a surfactant or a resin for improving the leveling property. A solubilizing agent, a preservative, an antifoaming agent, etc. may be added.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION While stirring a predetermined amount of water in a container with a disper, a thixotropic agent is gradually added and stirring is continued until a uniform viscous liquid is obtained (about 2 hours). Next, a resin, a pigment dispersion, and other additives were added, and the mixture was further stirred for 2 hours to obtain a sample ink. When a relatively large amount of alkali-soluble resin is used, a basic substance (triethanolamine) is added to the above-mentioned viscous liquid while being gradually stirred to prepare a basic liquid.

[0012]

EXAMPLES Table 1 shows the compositions of the example inks and the comparative example inks. The numerical values of the compositions are expressed in parts by weight.

[Table 1] The contents of the raw materials and physical properties in the table will be described along with the note numbers. Hereinafter, all% represent% by weight. (1) Aqueous dispersion comprising 50% titanium white pigment, 1.3% anionic surfactant, 0.5% ethylene glycol and water (2) Aqueous dispersion containing 42% pink fluorescent pigment (Shin Loihi Co., Ltd. ) Product SW-17) (3) Aqueous dispersion consisting of 8% azo red pigment, 3% nonionic surfactant and water (4) Acrylic acid resin ammonia neutralized product (active ingredient 3
0.5%, John Polymer 61J manufactured by Johnson Polymer Co., Ltd. (5) Acrylic ester / styrene copolymer resin emulsion (active ingredient 50%, Movinyl DM60 manufactured by Hoechst Synthesis Co., Ltd.) (6) 10% polyvinyl alcohol (Nippon Gosei Chemical Co., Ltd. product Gohsenol GL-05) aqueous solution (7) 5% hydroxypropyl cellulose (Nippon Soda Co., Ltd. product HPC-L) aqueous solution (8) Dainippon Pharmaceutical Co., Ltd. product echo gum (9) Crosslinking type Acrylic resin copolymer (Hibiswako 105, Wako Pure Chemical Industries, Ltd.) (10) Smectite SWN, Cope Chemical Co., Ltd. (11) Surflon S-141, Asahi Glass Co., Ltd. (12) All viscosities are at room temperature (approx. 20-25 ° C.) under measurement in BM type viscometer, the value (13) viscosity eta ₅₀ of the viscosity eta ₁₀ at a rotor rotation speed 10 rotations / minute b Tar rotation speed 50 values in rev / min

The comparative ink is an example of an ink having a composition in which only the component (d) thixotropic agent in the above essential components is not added. Each sample ink prepared by the above ink preparation method was subjected to the following tests.

The roller portion of an applicator equipped with a rubber sponge roller having a concave surface of "glass" mirror image characters was dipped in the sample ink to be contained therein and fixed in a vertical state. The roller was pressed against the surface of the glass and rotated to transfer the solid mark containing the characters without "glass". Two sample glass plates were prepared for each sample ink, one plate was left as it was, and the other plate was left in a thermo-hygrostat controlled at about 20 ° C. and 90% relative humidity (RH). . After 1 hour, the state of marks (presence or absence of dripping) was visually observed on the glass plate left at room temperature. Next, place the glass plate of the same sample horizontally and put it on a wet cloth for 500
The mark was rubbed 10 times under a load of g, and the degree of erasing the mark was visually observed. Further, with respect to the sample glass plate left in the constant temperature and humidity chamber, the mark on the plate surface was rubbed once with a load of 500 g on a dry cloth in the same tank, and the dry cloth abrasion resistance of the mark was visually observed. Table 2 shows the test results.

[Table 2] The contents of the evaluation symbols in the table are as follows. Mark status (presence or absence of dripping) ○: No dripping phenomenon is observed ×: Liquid dripping occurs Mark erasability with wet cloth ○: Completely erasing Dry cloth abrasion resistance in high humidity atmosphere ○: Mark does not change after scratching

[0015]

As can be seen from the test results, when the marking ink for indicating the presence of glass of the present invention is transferred to the glass surface in the vertical state, the mark formed by the ink does not cause a dripping phenomenon, and It maintains the erasability by rubbing with a wet cloth, which is a necessary condition for this kind of ink, and the basic performance that it is not erased by the normal touch of a person or object under high humidity.

Claims (2)

[Claims] 1. An essential component, (a) a colorant, and (b)
At least one selected from a resin emulsion and an alkali-soluble resin, (c) a water-soluble resin in a weight ratio of 1/9 to 9/1 with respect to the solid content of the component (b), (d) a thixotropic agent, and (E) A marking ink for glass presence indication, which is a composition containing water, wherein the component (D) is at least one selected from acidic heteropolysaccharides, swellable layered clay minerals and crosslinked acrylic resin copolymers. 2. The glass-presenting marking ink according to claim 1, wherein the composition ratio of each of the components in the ink composition is 3 to 40% by weight of component (a) and components (b) and (c). Total solid content 1 to 30% by weight, component (d)
When the acidic heteropolysaccharide and / or the cross-linking acrylic resin copolymer is used as 0.05 to 0.8% by weight, and when the swelling layered clay mineral is used, the range is 0.5 to 5% by weight. is there.