Writing, marking and/or drawing liquid for writing implements, especially for capillary pens, and writing implement

Abstract

A writing, marking and/or drawing liquid for writing implements, especially for capillary pens, which has a viscosity of less than 50 mPas (Brookfield, 20 C., CPE-40 plate-cone), contains a resin mixture dissolved in a solvent matrix having at least one solvent. Wherein the resin mixture contains a first resin in the form of a modified resin ester and/or a dissolved polyester resin and a second resin in the form of a maleate resin and/or a rosin, especially a phenol-modified rosin. Additives are present in the form of at least one fluorosurfactant as wetter and at least one polyethersiloxane copolymer as glidant.

Claims

1. A writing, marking and/or drawing liquid for writing implements, comprising: a viscosity of less than 50 mPas (Brookfield, 20 C., CPE-40 plate-cone); and a resin mixture dissolved in a solvent matrix having at least one solvent, said resin mixture having a first resin in a form of a modified resin ester and/or a dissolved polyester resin, said modified resin ester having properties of: viscosity efflux time 80% in ethyl acetate at 20 C of between 20 to 40 s; dynamic viscosity 100% at 40 C.; rotational viscosity according to DIN 53214 4000-8000 mPas; acid number being less than or equal to 20 mg KOH/g; color number tested by Gardner Color Standard 50% in ethyl acetate ASTM D 1544 being less than or equal to 8; said modified resin ester being liquid 80% in ethyl acetate; and a second resin in a form of a maleate resin and/or a rosin, and additives in a form of at least one fluorosurfactant as wetter and at least one polyethersiloxane copolymer as glidant.

2. The writing, marking and/or drawing liquid according to claim 1, wherein said resin mixture is present from 3 to 30 wt %.

3. The writing, marking and/or drawing liquid according to claim 1, wherein said first resin is in a proportion of 1 to 25 wt % and/or the second resin is in a proportion of 2 to 25 wt %.

4. The writing, marking and/or drawing liquid according to claim 1, wherein a ratio of said first resin to said second resin is between 1:1 and 1:5.

5. The writing, marking and/or drawing liquid according to claim 1, wherein said solvent matrix is present in a form of 50 to 80 wt % of said at least one solvent.

6. The writing, marking and/or drawing liquid according to claim 1, wherein said solvent matrix includes an alcohol and a ketone or an alcohol, a ketone and an ester.

7. The writing, marking and/or drawing liquid according to claim 1, wherein said at least one solvent is selected from the group consisting of methyl ethyl ketone, 1-methoxy-2-propanol, ethanol, 1-propanol, 2-propanol, ethyl acetate and any combination of these solvents.

8. The writing, marking and/or drawing liquid according to claim 1, wherein said additives are present in a proportion of 0.1 to 8 wt %.

9. The writing, marking and/or drawing liquid according to claim 1, wherein: said wetter is present in a proportion of 0.3 to 2.0 wt %; and/or said at least one glidant is present in a proportion of 0.3 to 2.0 wt %.

10. The writing, marking and/or drawing liquid according to claim 1, further comprising at least one colorant in a proportion of 5 to 20 wt %.

11. The writing, marking and/or drawing liquid according to claim 10, wherein said colorant is a dye.

12. The writing, marking and/or drawing liquid according to claim 1, wherein said viscosity is less than 20 mPas (Brookfield, 20 C., CPE-40 plate-cone).

13. The writing, marking and/or drawing liquid according to claim 1, wherein said first resin is present in a proportion of 1 to 20 wt % and/or said second resin is present in a proportion of 2 to 20 wt %.

14. The writing, marking and/or drawing liquid according to claim 1, wherein a ratio of said first resin to said second resin is between 1:1 and 1:3.

15. The writing, marking and/or drawing liquid according to claim 1, wherein said at least one solvent is an organic solvent.

16. The writing, marking and/or drawing liquid according to claim 1, wherein said rosin is phenol-modified rosin.

17. The writing, marking and/or drawing liquid according to claim 1, wherein said additives are present in a proportion of 0.1 to 5 wt %.

18. The writing, marking and/or drawing liquid according to claim 10, wherein said dye is a metal complex dye and/or a color pigment.

19. The writing, marking and/or drawing liquid according to claim 1, wherein said viscosity is less than 10 mPas (Brookfield, 20 C., CPE-40 plate-cone).

20. A writing implement, comprising: a writing tip made of a capillary material; and a reservoir made of a further capillary material and containing a writing, marking and/or drawing liquid, said writing, marking and/or drawing liquid having: a viscosity of less than 50 mPas (Brookfield, 20 C., CPE-40 plate-cone); and a resin mixture dissolved in a solvent matrix having at least one solvent, said resin mixture having a first resin in a form of a modified resin ester and/or a dissolved polyester resin, said modified resin ester having properties of: viscosity efflux time 80% in ethyl acetate at 20 C of between 20 to 40 s; dynamic viscosity 100% at 40 C.; rotational viscosity according to DIN 53214 4000-8000 mPas; Acid number being less than or equal to 20 mg KOH/g; color number tested by Gardner Color Standard 50% in ethyl acetate ASTM D 1544 being less than or equal to 8; said modified resin ester being liquid 80% in ethyl acetate; and a second resin in a form of a maleate resin and/or a rosin, and additives are present in a form of at least one fluorosurfactant as wetter and at least one polyethersiloxane copolymer as glidant.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) The single FIGURE of the drawing is a diagrammatic, longitudinal sectional view of a capillary pen according to the invention.

DETAILED DESCRIPTION OF THE INVENTION

(2) Referring now to the single FIGURE of the drawing in detail, there is shown a writing implement, for example a marker, which is substantially pen-shaped and has a shaft 1 wherein is present a reservoir 2 made of a capillary material or a fiber reservoir of low density, for example a polyester fiber reservoir. The front end of the pen bears a writing tip 3 made of a capillary material or a fiber tip which at its rear end is in communication with the fiber reservoir 2 and/or projects thereinto.

(3) The manufacture of the writing, marking and/or drawing liquid takes place predominantly in mixing tanks in which the solvent is gradually admixed with the resin constituents, i.e., the hard resin and the tie resin, and also with the further components, for example colorants or additives. All the while a stirrer is working homogenizingly in order that the components may be intensively commixed and distributed in a sufficiently uniform manner. During manufacture, moreover, the temperature rises slightly to about 40 to 45 C. Evaporated fractions of solvent are replenished at the end of the homogenizing process. Thereafter, the writing, marking and/or drawing liquid thus obtained is filled into the reservoir 2 of capillary material in the writing implement described above.

(4) Tests were carried out by using the writing implement to draw lines on various surfaces, inter alia on paper, on smooth surfaces such as glass or plastics and also on surfaces contaminated with fat or oil. The drawn line was subsequently assessed against various criteria. Firstly, the color of the line was evaluated as regards its intensity after a delay time of a few seconds, as was the light-fastness of the line following irradiation with UV light. Secondly, wipe tests were carried out in order to analyze the adherence and rub-fastness of the line.

(5) Four example formulations of writing, marking and/or drawing liquids are adduced hereinafter:

EXAMPLE 1

(6) Example formulation for a red marking liquid having a viscosity of 4.0 mPas (Brookfield, 20 C., CPE-40 plate-cone):

(7) TABLE-US-00001 modified maleate resin.sup.1) 12.0 wt % modified resin ester 80% in ethyl acetate.sup.1) 5.0 wt % methyl ethyl ketone 27.5 wt % 1-methoxy-2-propanol 23.0 wt % ethanol 21.0 wt % fluorosurfactant: perfluoroalkyl- 0.5 wt % substituted polyether, CAS 52550-44-4.sup.6) C.I. Solvent Yellow 82.sup.3) 1.0 wt % Solvent Red 160.sup.2) 9.0 wt % polyethersiloxane copolymer.sup.7) 1.0 wt %

(8) The resin mixture is very readily soluble in the solvent matrix used in Example 1: a mixture of methyl ethyl ketone, 1-methoxy-2-propanol and ethanol. Lines drawn with a marking liquid according to Example 1 exhibit good water-fastness, especially on glass or ceramic surfaces, by comparison with commercially available alcoholic permanent marker inks, by virtue of the resin ester used as tie resin.

EXAMPLE 2

(9) Example formulation for a blue marking liquid having a viscosity of 4.3 mPas (Brookfield, 20 C., CPE-40 plate-cone):

(10) TABLE-US-00002 phenol-modified rosin.sup.1) 14.0 wt % modified resin ester 80% in ethyl acetate.sup.1) 6.0 wt % methyl ethyl ketone 25.0 wt % 2-propanol 22.0 wt % ethanol 20.0 wt % polyethersiloxane copolymer.sup.7) 1.8 wt % FC-4430.sup.5) fluorosurfactant 1.2 wt % C.I. Solvent Blue 44.sup.4) 10.0 wt %

(11) Example 2 has the highest proportion of additives, namely 1.2 wt % of fluorosurfactant and 1.8 wt % of polyethersiloxane copolymer. As a result, the drawn line has particularly good adherence, even to oil-containing or fat-containing surfaces. The line further exhibited uniform film formation. A further difference from the marking liquid of Example 1 is that a phenol-modified rosin is used as hard resin, making the marking liquid more universally useful. As a result, the marking liquid exhibits water-fastness and wipe- and rub-fastness on different substrates. It is further possible to also wet still trickier substrates, e.g., slightly greasy polypropylene.

EXAMPLE 3

(12) Example formulation for a green marking liquid having a viscosity of 10.0 mPas (Brookfield, 20 C., CPE-40 plate-cone):

(13) TABLE-US-00003 modified maleate resin.sup.1) 8.0 wt % tie resin solution for solvent-containing formulations (polyester resin styrene-free, as-supplied form liquid, solids content about 60 wt % in n-butyl acetate).sup.7) 8.0 wt % methyl ethyl ketone 26.0 wt % 2-propanol 22.0 wt % ethanol 20.0 wt % FC-4430.sup.5) fluorosurfactant 1.0 wt % polyethersiloxane copolymer.sup.7) 1.0 wt % C.I. Solvent Yellow 82.sup.3) 6.0 wt % C.I. Solvent Blue 44.sup.4) 8.0 wt %

(14) The formulation of Example 3 contains the first and second resins in equal proportions, i.e., in a ratio of 1:1, so overall, compared with the other examples, the marking liquid has a higher viscosity at 10.0 mPas but nonetheless low enough for capillary pens. Furthermore, lines drawn with marking liquids containing tie resin and hard resin in approximately equal concentrations exhibited good water-fastness on glass or ceramic surfaces in particular.

EXAMPLE 4

(15) Example formulation for a black marking liquid having a viscosity of 6.0 mPas (Brookfield, 20 C., CPE-40 plate-cone):

(16) TABLE-US-00004 phenol-modified rosin.sup.1) 10.0 wt % modified resin ester 80% in ethyl acetate.sup.1) 8.0 wt % ethyl acetate 10.0 wt % methyl ethyl ketone 20.0 wt % 1-propanol 20.0 wt % Ethanol 19.0 wt % TividaFL2500.sup.8) fluorosurfactant 0.5 wt % polyethersiloxane copolymer.sup.7) 0.5 wt % Pigment Black 7 (Hostatint-Schwarz A-N 100).sup.9) 12.0 wt %

(17) The colorant referred to here is a carbon black pigment in a solventborne aldehyde resin formulation. The universality is further improved as a result. Adherence, abrasion resistance, water-fastness of a line drawn with a marking liquid of Example 4 on various substrates improve. The use of the carbon black pigment further results in excellent resistance to light.

(18) The reported weight percentages are each based on the total mass of the writing, marking and/or drawing liquid.

(19) Product Designations/Manufacturers: 1) Robert Kraemer GmbH & Co. KG, 26180 Rastede, Germany 2) Reinhard Neuscheler Handelsvertretungen CDH, 72766 Reutlingen, Germany 3) Ming-Zu Europe GmbH, D-79576 Weil am Rhein, Germany 4) Clariant Iberica Produccion, S.A., 08970 Sant Joan Despi, Spain 5) 3M Osterreich GmbH, 2380 Perchtoldsdorf, Austria 6) Sintal Chemie GmbH, 22605 Hamburg, Germany 7) Evonik Resource Efficiency GmbH, 45127 Essen, Germany 8) Merck KgaA, 64271 Darmstadt, Germany 9) Clariant AG, D-65929 Frankfurt am Main)