DE2927005A1 - Removable print-forming stamping compsn. - contg. flexible thermoplastics, pref. soft PVC, reducible water-soluble dye and opt. cellulose fibres - Google Patents

Abstract

Permanent stamping compsns., forming prints removable with water or with reducing agents, contain flexible thermoplastics, pref. PVC opt. combined with polyvinyl acetate, and reducible, water-soluble dyes. The stamps can be used as learning toys and as hobby articles for decorating surfaces. The prints are easily removed, e.g. by wiping or with ink removers contg. sulphite solns.

Description

Kreuzer-Werk GmbH
5300 Bonn

Permanent stamp mass

The invention relates to a permanent stamp compound / which is suitable, inter alia, for colored stamp impressions with color effects.

So far known permanent stamp materials have the disadvantage / that they are made up of porous materials / those with stamp inks are formed on the basis of oil-soluble, indelible dyes. If the pressure on the stamp compound is too strong, it will give a lot of color so that the stamp imprint no longer shows sharp lines. Other permanent stamps with oil-soluble indelible marks Dyes have the disadvantage / that a strong pressure must be applied to achieve a good stamp impression.

Another disadvantage of the permanent stamp materials known up to now is the poor removability of unwanted impressions on a wide variety of surfaces and materials.

New permanent stamps have now been found in which reducible It contains dyes and thermoplastics, for example soft polyvinyl chloride, which do not have these disadvantages exhibit.

The invention therefore relates to what is described in the claims Object.

The permanent stamping materials according to the invention can be free of fibers be. However, it is possible to incorporate fibers. The incorporation of fibers increases the ability of the stamping ink to be released

O30062 / O45Ä

-A-

vastly improved. The cut length of the fibers is generally from 0.1 to 2 mm, in particular from 0.1 to 1 mm. The fiber material is not critical. Cotton linters and pure oC cellulose are suitable .

With the addition of fiber materials, light pressure on the permanent stamp material results in perfect impressions that the Have the advantage of being easy to remove: from smooth surfaces by wiping with a damp cloth and from porous materials such as B. paper, stone, textiles by using reducing agents such. B. in commercially available ink erase pens are common; for example, sulfite solutions can be used as reducing agents.

These advantages are particularly useful when using permanent stamps for children's stamps as well as for educational games and as a hobby item for decoration of objects of all kinds interesting.

By combining reducible and non-reducible dyes and the gelation of different stamp color combinations, multicolored stamps can be produced, their Imprints can be transformed into countless different stamp imprints by using reducing agents.

In order to achieve these effects in the permanent stamp materials, it is advantageous to use stabilizers when they are produced by a gelling process and use solubilizers. Inorganic stabilizers (for example for the reducible dyes) can be used and organic acids and salts are used.

Long-chain, polyhydric alcohols can be used as solubilizers 4-10 carbon atoms and polymeric compounds such as starch, Dextrins, polyvinyl alcohol and cellulose derivatives can be used.

In order to achieve rapid discoloration or color conversion in the stamp imprint To achieve this, it is also possible to use inorganic salts as further additives.

030062/0454

In the production of the permanent stamping materials according to the invention, Proceed as follows: Introduce a plasticizer with the usual stabilizers for PVC (polyvinyl chloride), add the PVC powder at low speed of the agitator. Let it swell overnight and then add the dye solution at a high number of revolutions. the Dye solution can be made from polyethylene glycols, glycerine and water-soluble, reducible dyes exist. After a few minutes of stirring, possible additives are added. For pH stabilization organic acids (1-2%) are added during the gelling process. As a stabilizer against premature separation Additions of starch, dextrins, polyvinyl alcohols can be added to the mixture or polyvinylpyrrolidones. After a deaeration process in a vacuum or after standing, the mass becomes bubble-free in an engraved mold and cast at temperatures of 160 - 180 C gelled for 10-20 minutes. After cooling, the stamp blanks are removed from the mold.

The following is a general example of a recipe for production permanent stamp masses according to the invention indicated:

Plasticizer 15-30% by weight

PVC powder 20 - 40% by weight

Fiber materials
(Short cut fibers 0.5 - 2 mm) 1 - 2% by weight

Stabilizers, e.g. B. organic

or inorganic acids or

Salts 1 - 2% by weight

Solubilizer, e.g. starch,

Dextrins, polyvinyl alcohol,

Cellulose 2-10% by weight

reducible dyes 1 - 4% by weight

non-reducible dyes 1 - 2% by weight glycerine and polyethylene glycols 30 - 50% by weight Reduction accelerators, e.g. B.

common inorganic salts 2 - 8% by weight

The following examples are intended to illustrate the invention. Unless otherwise stated, "parts" refer to the Weight.

Q30062 / CH54

- Ό ~

example 1 Blue permanent stamp mass

25 parts plasticizer, Palatinol AH (BASF)

2 parts stabilizer z. B. Nuostab (BASF) 35 parts of polyvinyl chloride, e.g. B. Vinoflex KR 3364 (BASF)

2 parts of cotton linters O ₇ 5 mm length of cut 37 parts of stamping ink, consisting of 55 parts of polyethylene glycol, molecular weight 35 parts of 85% glycerol, 2 parts of tartaric acid, 4 parts of magnesium sulfate crystallize

4 parts reducible, water-soluble, blue dye, e.g. B. Ink Blue JTN Hoechst C.J. acid Blue 93, 4 2780) Duasynic acid blue VF-UF Hoechst, CJ. Acid Blue 1, 42045)

Gelling temperature is 180 ° C., 10-20 minutes. The stamp impression can be made by suIfit solutions, as they are in the usual ink erase pens.

Example 2 Red permanent stamp mass

As described in example 1.

Basacryl Brillant Red X4G conc (BASF, c.J. Basic-Red 14), or Astrarot 3G 125% (Bayer, CJ. Acid-Red 28), or Sandozyl Brilliant Red BL4G for use. The stamp imprint is discolored with sulfite solutions.

Example 3 Green permanent stamp mass

As described in example 1.

030062/0454

Malachite green BXN (BAS ¹ ) or Astr ama lach it green (Bayer, CJ. Basic Green 4) or Remacryl green 3B (Hoechst, Basic-Green 4, 42000) are used as dyes. The stamp imprint is discolored with sulfite solutions

Example 4 Black permanent stamp material

As in example A mixture comes out as dyes 1 part Basacryl Brilliant Red X4R (BASF), 4 parts Remacryl Green 3B (Hoechst), 1.8 parts of Basycryl Yellow X-RL (BASF, CJ. Basic Yello 49) and 1 part of Basacryl Blue X-3GL (BASF, CJ. Basic Blue 41) for use.

With sulphite solutions, the stamp imprint is discolored,

Example 5

Permanent stamp mass, their imprints after the application of sulfite solutions show a color change from blue to turquoise.

As for example Duasyn acid blue VF-UF resp. Ink blue BJTN and special violet S4BNS (Bayer) as a non-reducible dye.

Example 6

Permanent stamp mass, their imprints after the application of sulfite solutions show a color change from red to yellow.

As in example 1. Special crocein MOSS (Bayer) is used as the dye

030062/0454

and special orange GX (Bayer used. Example 7

Permanent stamping material, the imprints of which after the application of sulphite solutions show a color change from black to green.

Same as example 1.

There is a dye mixture of special violet S4BNS (Bayer) Duasyn acid blue VF-UF (Hoechst) Spezialcorcein MOOS (Bayer)

Special yellow S (Bayer) is used.

A solution is used as the bleaching liquid

80 parts of water
20 parts glycol

1 part of 400 mg polyethylene glycol, 3 parts of 3% sodium hydroxide solution, 8 parts of sodium pyrosulfite 5 parts Na / K tartrate.

Q30062 / 04S4

Claims (6)

Claims 1. Dauerstempe! Masse whose stamp imprints with water or Reducing agents are removable, containing elastic, thermoplastic plastics and reducible, water-soluble Dyes. 2. Permanent stamp material according to claim 1, containing polyvinyl chloride as elastic thermoplastics, optionally in connection with polyvinyl acetates. 3. Permanent stamp material according to claim 1 or 2, the stamp imprint of which results in a color change when treated with reducing agents, Containing, in addition to the reducible dyes, also non-reducible dyes. 4. Permanent stamp compound according to one of the preceding claims, which can be decolorized on porous materials and removed with water on smooth surfaces and textiles can, consisting of embedded in soft polyvinyl chloride Stamp ink that is water-soluble and contains reducible dyes. 5. Permanent stamp compound according to one of the preceding claims, which contains fibers to derive the stamp color from the stamp material. 6. Permanent stamp compound according to one of the preceding claims, the absorbent and refillable with stamping ink, characterized in that it contains fibers. 030062 / (K-B * ORIGINAL INSPECTED Permanent stamping compound according to one of the preceding claims , the stamp impressions of which result in different color combinations through the use of reducing agents , in which compounds of different color combinations of reducible and non-reducible dyes are gelled to one another. 030062/045;