CS239692B1 - Colour ink for marker - Google Patents

Abstract

Colored writing fluid is intended for those markers or markers that are determined for example, for writing on smooth, relatively did not beat the materials and the resulting lettering can be easily removed from these materials by wiping. Colored writing fluid consists of a mixture 0.5 to 20.0 wt. parts of a color pigment here, 2.0 to 25.0 wt. essential natural parts and / or synthetic acromolecular an average molecular weight of 2,000 up to 600,000, 5.0 to 20.0 wt. liquid parts organic compounds or mixtures of compounds boiling above 170 ° C, which is thermodynamically incompatible basic macromolecular preferably, oligomeric polymeric, polyaddition or polycondensation materials, 30.0 to 92.4 wt. part of the organic solvent or a mixture of solvents having a boiling point of 30 to 30 ° C 170 ° C, thermodynamically compatible all components of the writing fluid, 0.1 to 5.0 wt. and / or synthetic macromolecules! thermodynamically intolerant to basic macromolecules! substance, but compatible with the other ingredients writing fluids and optionally up to 2.0 wt. parts additives, preferably the use of nonionic agents surfactants.

Description

(54) Colored writing fluid for markers or markers

The colored writing fluid is intended for those markers or markers that are primarily intended for writing on smooth, relatively undisturbed materials, and the resulting ink can be easily wiped off from these materials.

The colored writing fluid consists of a mixture of 0.5 to 20.0 wt. 2.0 to 25.0 wt. parts by weight of the natural and / or synthetic acromolecular substance having an average molecular weight of 2,000 to 600,000, 5.0 to 20.0 wt. % of a liquid organic compound or a mixture of compounds having a boiling point above 170 DEG C. which is thermodynamically incompatible with the parent macromolecular substance, preferably using oligomeric polymeric, polyaddition or polycondensation materials, 30.0-92.4 wt. % of organic solvent or a mixture of solvents having a boiling point of 30 to 170 ° C, thermodynamically compatible with all components of the writing fluid, 0.1 to 5.0 wt. parts additional to natural and / or synthetic macromolecules! substances thermodynamically incompatible with basic macromolecules! however, compatible with the other components of the writing fluid and optionally up to 2.0 wt. parts of additives, preferably the use of non-ionic surfactants.

SUMMARY OF THE INVENTION The present invention provides a colored writing fluid for writing devices known under the name of a marker or marker. These are markers or markers which are primarily intended for writing on smooth, relatively non-porous materials, and the resulting font trace from said surfaces can be easily removed by wiping with a dry cloth, paper or the like.

As smooth, relatively non-porous materials, glass, enamels, polyethylene, polypropylene, polytetrafluoroethylene, polytrifluorochlorethylene and other fluoropolymers, cured urea-formaldehyde or melamine-formaldehyde resins, phenol-formaldehyde resins, polyamides, polyimides, polyurethane coatings, polyurethane coatings and polyurethane coatings are used. wherein the examples of materials do not exhaust all possibilities of the invention.

According to the prior art, white or colored chalks or markers filled with ink based on pigment dispersion in the solution of macromolecules are used for this purpose! substances in a mixture of at least two liquid substances which differ from each other in boiling points and in thermodynamic affinity for the macromo + ecular substance.

Precipitation of macromolecule particles! the substance together with the colored pigment in the wiping trace is ensured by the fact that the liquid substance with a higher boiling point is at the same time thermodynamically incompatible with the selected macromolecules! substance.

Said methods of wiping marking have a number of disadvantages. When working with chalk, fine dust is created from chalk particles, which pollutes the surroundings and significantly worsens the work hygiene. With the use of the known writing fluids, the deficiencies are mainly due to imperfections in the precipitation of the macromolecular substance. Writing fluids containing water are highly sensitive to relative air humidity: At lower relative humidity, traces get worse, while at high relative humidity, ink traces may run down from vertically laid substrates, (jap. Pat. 253/1972, 29666/1972 , U.S. Pat. No. 2,185,666, U.S. Pat.

834 823 etc.).

In writing fluids containing organic solvents, imperfect precipitation of the macromolecular substance causes the formation of very fine precipitate particles, which often cannot adsorb all the color pigment in the ink. The pigment or pigment particles of the precipitate then penetrate into the described material, and the anchored trace is usually no longer removed. Solvent writing fluids are described, for example, in Japan. patents 17616/1969, 4807/1970, 40290/1971, 14630/1973, and in German Patent 2,365,171.

These drawbacks are overcome by the writing fluid of the present invention. The essence of the invention is that the writing fluid consists of a mixture of 0.5 to 20.0% by weight. 2.0 to 25.0 wt. parts by weight of the natural and / or synthetic macromolecular substance having an average molecular weight of 2,000 to 600,000, 5.0 to 20.0 wt. 30.0-92.4 parts by weight of a liquid organic compound or a mixture of compounds having a boiling point above 170 ° C which is thermodynamically incompatible with the parent macromolecular substance; % of the organic solvent or solvent mixture boiling at 30 to 170 ° C, thermodynamically compatible with all components of the writing fluid, and 0.1 to 5% by weight. parts of an additive natural and / or synthetic macromolecular substance having an average molecular weight of 2,000 to 400,000, thermodynamically incompatible with the basic macromolecular substance, but compatible with the other components of the writing fluid.

An advantage of the present invention of wipable colored writing fluids is the presence of at least two pairs of incompatible components that remain permanently in the written ink trace. Since one of the intolerable pairs is a system of two macromolecular substances, one of which is soluble in the liquid component of the other intolerable pair, the separation effect is enhanced, thereby macroscopically separating the base macromolecular substance with the adsorbed color pigment. High boiling organic liquid in which additional macromolecules are dissolved! substance, on the surface of the substrate forms a vertical layer on whose surface precipitated particles of basic macromolecules! substances with pigment.

This layer prevents the penetration of colored particles into the substrate material, which makes it possible to easily wipe off traces of writing fluid from materials other than the non-polar, absolutely non-porous surface, with a dry wiper. Excluded particles of macromolecules! the substances concentrate in themselves large pigments, so that even if a colorless protective liquid penetrates into the surface gaps of the substrate, the substrate will not be permanently discolored. This fluid continues to function until it evaporates or completely migrates to the substrate. Evaporation of this liquid is prevented by a prescribed boiling temperature above 170 ° C, which is further increased by the presence of an additional macromolecular substance.

The migration of this liquid into the substrate can be prevented by selecting the substrate materials, which must also be as thermodynamically compatible as possible with the liquid forming the protective layer.

The criterion of thermodynamic intolerance for the selection of the essential components of the writing fluid according to the invention is in the first stage tabulated values of solubility parameters of macromolecular substances and liquid organic compounds (Brandrup J., Immergut EH, Polymer Handbook, Intersci. Publ. J. Viley and Sons, New York, 1966;

J. Paint Technol. J2, 104, 505 (1967); Hansen C. H., The Three Dimensional Solubility Parameter, Copenhagen, 1968; Teas J.P., J. Paint Technol. 40. 19 (1968); Mandík L., Kašpar F., Selection of solvents for film-forming substances, DT ČVTS, Pardubice, 1972, etc.), which however serve only for preliminary estimation and it is necessary to verify their validity experimentally. A practical test of the mutual compatibility of the macromolecular substance and the organic liquid is the visual method consisting in the preparation of a mixture consisting of 20 wt. % macromolecules! and 80 wt. % organic liquid, and visual assessment of the homogeneity of the mixture.

Clear mixtures contain tolerant pairs, cloudy mixtures contain intolerant pairs. The intolerance of a pair of macromolecular substances is also practically assessed by a visual method consisting in mixing solutions of individual evaluated macromolecular substances in a common solvent in a ratio of 1: 1 by volume and visual assessment of the homogeneity of the resulting mixture.

the clear mixtures contain a pair of mutually compatible macromolecular substances, and a cloudy mixture of a pair of incompatible macromolecular substances. (The test is described in Mandík L., Kašpar F .: Solvent Selection for Film-forming Substances, DT ČVTS, Pardubice, 1972).

Like basic macromolecules! The writing fluid substance of the present invention may be selected from any natural and / or synthetic macromolecules. a substance having an average molecular weight of 2,000 to 600,000 for which a thermodynamically suitable volatile solvent and a high-boiling thermodynamically intolerable liquid organic compound can be determined. Like basic macromolecules! the substance can be used, for example, shellac, ketoproteins, phenol-formaldehyde resins, coumarone resins, polyindene resins, aa-resins, rosin-modified synthetic resins, cellulose acetobutyrate, cellulose triacetate, nitrocellulose, cellulose acetopropionate, homopolymers and copolymers such as polymers of copolymers such as polymers and copolymers vinyltoluene, dichlorostyrene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic or methacrylic acid and their alkyl esters, acrylonitrile, methacrylonitrile, maleic anhydride, crotonic acid, vinyl methyl ether, butadiene, as well as polyvinyl acetals such as polyvinylformal, polyvinyl butyral. Preferably, a vinyl chloride-vinyl acetate copolymer is used. These macromolecules! the substances can be added to the colored writing fluid system both alone and in combination with the pigment.

A variety of liquid organic compounds having a boiling point above the boiling point of the present invention may be used as the 3 component thermodynamically incompatible with the parent macromolecular substance.

170 ° C preferably of oligomeric moieties of up to 6,000 molecular weight, such as polyethylene glycols and polypropylene glycols, liquid polyisobutylenes, oligomeric polyacrylates based on acrylic or methacrylic esters with aliphatic alcohols having 1 to 14 carbon atoms, further aliphatic alcohols having 7 to 7 carbon atoms 20 carbon atoms, monoesters and diesters of aliphatic alcohols, dlols and polyols with mono- or bifunctional carboxylic acids, such as phthalic, tetrahydrophthalic, adipic, azelaic, sebacic, lauric, myristic, palmitic, stearic, oleic, ricinoolic, and some boiling C 4 -C 12 carbon atoms such as di-, tri- and tetraethylene glycol, butylene glycol, glycerin and the like, optionally C 3 -C 20 glycol ethers such as dlethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether.

As an additional macromolecular component of the writing fluid of the present invention, any macromolecular substance having an average molecular weight of 2,000 to 250,000 listed in the list of basic macromolecular substances of the invention that is thermodynamically incompatible with the selected macromolecular substance may be used. According to this rule, for example, a suitable macromolecular substance is cellulose acetopropionate for polyvinylbutyral, nitrocellulose for polyvinylbutyral, cellulose triacetate for acrylate copolymers, polyvinylbutyral for polyvinylbutyral, and the like. Advantageously, various cellulose derivatives, homopolymers and copolymers of vinyl monomers having 2 to 16 carbon atoms and / or resin materials such as ketone resins, phenol-formaldehyde resins, coumarone resins, polyindene resins, ammonium resins, rosin-modified synthetic resins and the like.

The volatile organic solvent according to the invention is an organic liquid substance or a mixture of these substances, which is a thermodynamically coarse solvent of the basic and additional macromolecules! and allows homogenization of the entire system of wiping writing fluid. They must also be thermodynamically compatible with a liquid boiling above 170 ° C. The organic solvent must furthermore allow good dispersion of the color pigment used, or other modifying components.

Organic solvents with a boiling point of 50-170 ° C, preferably 60-120 ° C, can be used. Ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-methoxy ethanol, 2-ethoxyethanol, methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, acetone, methyl ethyl ketone, methyl-isobutyl ketone, cyclo-hexanone, xylene, toluene, ethylbenzene and the like.

As regards the color pigment, any organic or inorganic pigment may be used, or a combination of both may be used. Preference is given to using pigments incorporated in a carrier of natural or synthetic macromolecular material. Pigments with a carrier based on vinyl chloride-vinyl acetate copolymer, polyvinylbutyral and the like have proved to be suitable.

Further, the properties of the writing fluid of the present invention can be favorably influenced by substances which allow perfect pigment dispersion or improve the flow properties of the writing fluid.

For example, nonionic surfactants may be used for this purpose, in particular polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers in which the alkyl chain contains 6 to 18 carbon atoms and the number of ethylene oxide units ranges from 6 to 20 and the like.

The writing fluid of the present invention then exhibits a number of advantages. The presence of other macromolecules! A substance which is thermodynamically intolerant to the base macromolecular substance but compatible with all other components of the writing fluid greatly increases the effect of the intolerance of the base macromolecular substance to the high-boiling liquid organic compound, thereby significantly precipitating the base macromolecular substance in the high-boiling liquid organic compound. The particles of the precipitated parent macromolecular substance are substantially larger than the particles that precipitate in previously known writing fluids, thereby completely eliminating the possibility of their migration into the described material.

Since the precipitated particles of the parent macromolecular substance in the writing fluid of the present invention adsorbs all the color pigment contained in the writing fluid, migration of the pigment to the writing pad is excluded, both migration of the pigment itself and its migration together with the precipitated macromolecular substance. The resulting writing can then be removed very easily and without dirt, even for a very long time, up to several months.

SĚíaLadzjBCOKgaení ^{.Pflaaí-lfilltmARy,:}

A yellow-white diazopigment vinyl chloride-vinyl acetate mole copolymer mol. weight of 50,000 cellulose acetopropionate; mol. wt. 20,000 polyethylene glycol 300 butyl acetate polyoxyethylene ethylether

20.0 wt. parts

25.0 wt. parts

5.0 wt. 20.0 wt. 28.0 wt. parts

2.0 wt. parts 100.0 wt. parts

EXAMPLE 2 Beta-1-Isopropyl and Beta Modification of Phthalocyanine Polyvinylbutyral;

mol. wt. 180,000 nitrocellulose;

mol. weight 30,000 dioctyl phthalate methyl isobutyl ketone pigment methyl ketone 0.5 wt. part

2.0 wt. parts

0.1 wt. part

16.2 wt. part

36.2 wt. 40.0 wt. part

100.0 wt. parts

Example 3 is shown in FIG

nitropigment . 4.0 wt. parts butyl acrylate-hydroxyethyl- methacrylate; mol. weight 5 000 10.0 wt. parts nitroeelulose; mol. wt. 60 000 1.0 wt. parts dibutyl phthalate 10.0 wt. parts cyclohexanone 40.0 wt. parts acetone IFQ-U-tU

100.0 wt. parts

239692 6 Example 4 žsrxgtá. R? A <? I? azo condensation pigment ethyl acrylate-methyl methacrylate copolymer; 10.5 wt. part mol. weight of 20,000 triacetes of cellulose; 15.0 wt. parts mol. wt. 40 000 3.5 wt. part polyethylene glycol 300 15.0 wt. parts butyl acetate 40.0 wt. parts n-butanol 16.0 wt. parts

100.0 wt. parts

Example 5 copper phthalocyanine pigment 3.8 wt. part styrene-butyl acrylate copolymer mol. weight 520 000 5.7 wt. part polyvinylbutyral; mol. wt. 30 000 0.8 wt. part polyethylene glycol 600 12.0 wt. parts methylethylketone 50.0 wt. parts xylene 27.7 masses, parts 100.0 wt. parts

Example 6 fonts .paarí-tefaiUaa soot 6.0 wt. parts cellulose triacetet; mol. wt. 40 000 18.0 wt. parts ethyl acrylate-methyl methacrylate copolymer mol. weight 20 000 3.7 wt. part polylsobutylene oil 9.5 wt. part methylbutylketone 40.0 wt. parts ethanol 10.0 wt. parts isopropyl acetate 12.8 wt. parts

100.0 wt. Parts t

Example 7 Black-Daacl fluid soot vinyl chloride-vinyl acetate copolymer; 4.25 wt. part mol. weight of 150,000 cellulose acetopropionate; 4.25 wt. part mol. wt. 20 000 0.10 wt. part isobutyl stearate 8.00 wt. parts methylethylketone 18.00 wt. parts methylisobutylketone 65.40 100.00 wt. part wt. part

Example 8 soot 6.00 wt. parts cellulose acetobutyrate; mol. wt. 30 000 6.00 wt. parts styrene-butyl acrylate copolymer; mol. weight 240 000 1.50 wt. part isobutyl stearate 16.50 wt. part ethyl acetate 30,00 wt. parts isobutyl acetate 40.00 wt. parts

100.00 wt. parts

Example 9

Black seed fluid

soot 3.0 wt. parts nitrocellulose; mol. weight 30 000 15.0 wt. parts polyvinylbutyral; mol. wt. 90 000 1.0 wt. parts polyisobutylene oil 14.0 wt. parts n-propyl acetate 40.0 wt. parts methylisobutylketone 27.0 wt. parts 100.0 wt. parts

The examples are not exhaustive of the invention.

The writing fluid of the present invention can also be used for writing on conventional types of porous materials, such as paper, wood or textiles, and the resulting writing is permanent, water and light-resistant on these materials.

Thus, when writing on said materials, the writing fluid of the present invention can be used for writing even in those cases where the resulting print trace is exposed to the weather.

Claims (3)

object of the invention CLAIMS 1. A colored writing liquid for markers or markers, characterized in that it consists of a mixture of 0.5 to 20.0% by weight. 2.0 to 25.0 wt. parts essential natural and / or synthetic macromolecules! 2,000 to 600,000, 5.0 to 20.0 wt. 30.0 to 92.4 parts by weight of a liquid organic compound or a mixture of compounds having a boiling point above 170 DEG C. which is thermodynamically incompatible with the parent macromolecular substance; a part of the organic solvent or solvent mixture boiling at 30 to 70 ° C, thermodynamically compatible with all components of the writing fluid, 0.1 to 5.0 wt. parts additional to natural and / or synthetic macromolecules! substances with an average molecular weight of 2,000 to 250,000, thermodynamically incompatible with the other components of the writing fluid and possibly up to 2.0 wt. parts of additives, preferably non-ionic surfactants. 2. The color writing liquid of claim 1, wherein the liquid organic compound or mixture of compounds boiling above 170 [deg.] C. comprises oligomeric substances having a molecular weight of up to 6,000, preferably polyethylene glycol and polypropylene glycol, liquid polyisobutylene, oligomeric polyacrylate. esters of acrylic and / or methacrylic acid with aliphatic alcohols having 1 to 14 carbon atoms, and / or aliphatic alcohols having 7 to 20 carbon atoms and / or monoesters and diesters of aliphatic alcohols, diols and polyols with mono- or di-functional carboxylic acids and / or glycols C 4 -C 12 carbon atoms, optionally also C 3 -C 20 glycol ethers. 3. The color writing liquid of claim 1, wherein said composition comprises, as an additional natural and / or synthetic macromolecular substance having an average molecular weight of 2,000 to 250,000, cellulose derivatives, homopolymers and / or copolymers of vinyl monomers having 2 to 16 carbon atoms, and and / or resinous substances, preferably ketone resins, phenol formaldehyde resins, coumarone resins, polyindene resins, amino resins, and rosin-modified synthetic resins.