DE1934457C - Pressure sensitive recording material - Google Patents

Description

j.

I 934 457

1 2

The invention relates to pressure-sensitive recording a substituent with a Hammet's substituent separation materials, in which the formation of colored constants less than zero than electron donating to markings is seen by a reaction between basic.

chromogenic substance and acidic substance takes place. The invention relates to a pressure-sensitive recording material, consisting of one of those in which the chromogenic substance, for example, sheet-like material, on and / or within the crystal violet lactone and, as acid clay, for example, chromogenic substance, phenolic substance and a wise attapulgite was used. In the case of the main oily solvent for the substances mentioned, patent 12 75 550 were used in place of the whole or one of the polymers which are oil-soluble in the oily solution part of the clay in a common solution and which react in the medium to form a dye Desensitization by the Wi ^r Vung measured patent 12 75 550.

resistant to light and air during storage. The invention is characterized in that min are and due to their solubility in the chromogenic at least 70 percent by weight of the phenolic material Substances dissolving solvents a fast and from oil-soluble polycondensates of formaldehyde cause intense color formation. 15 and one or more p-substituted phenols Phenolic polymers are suitable for recording materials, of which at least 100 percent by weight close the type mentioned particularly well, since they ent an electron-attracting p-substituent of the geweder applied as a coating to a sheet or have named species, and that each molecule of the be contained as a solution in microcapsules or otherwise polycondensates at least three p-substituted Phewie can be isolated until their reaction contains mi * den * ole units.

chromogenic substances for the purpose of forming a marking The polycondensates according to the invention contain is desired on the recording material. It is generally known polymer chains of three or more with methylene that one or both of the re-groups connected phenolic units and participants in the action can be arranged in this way are referred to below as "tri and higher condensates" or that both are referred to as dry coating, the upper limit of the chain length arranges, for which a suitable solvent in the pre- is determined by the fact that the condensate is oil-soluble said manner is provided in isolation. Must be essential. Condensates with a chain length of up to The only thing here is that the two reaction participants have to have twelve phenolic units as more useful not allowed to mix in solution before proved bar. Preferably the chain length should be a response is desired. Furthermore, it is generally 30 but three to six phenolic units known that the two reactants to- The formaldehyde content of the condensates moves flavors on a single so-called "autogenic" range between about 0.65 to about 1.0 moles, preferably Sheets can be located, or they can be separated from about 0.8 to 1.0 moles of formaldehyde per mole of one Surfaces of leaves, creating a mixture of the p-substituted phonols, the »Multiple recording material system« receives. The mixture is between about 1 to 5 moles, preferably 2.0 Way as the chromogenic substance and the acidic to 3.5 mol, phenols with electron-attracting p-sub-substance are arranged is not essential to the invention. substituents per mole of phenols with electron donating Rather, the invention is directed to the dye containing p-substituents.

education system per se and in particular on systems that in the recording medium according to the invention

in which the named phenolic polymers are used as a 4 ° material phenolic substance is phenolic resin, the

come dung. 75 to 100 percent by weight tri- and higher p-substituted

The invention is based on the fact that one contains found phenol / formaldehyde polycondensates,

has that polycondensates of formaldehyde with one whereby the remaining 0 to 25 percent by weight does not

or more p-substituted phenols exist in the reaction of the monomer and dimer reacted. Preferential

in a joint solution with suitable chromogenic 45 ways, the phenolic substance contains more than 80 genes

Sfoff a fast and intensive color formation, weight percent of the tri- and higher condensates, because

call when a high proportion of phenolic substances are more soluble and give better results

p-substitutions electron withdrawing groups, e.g. B. result as dimer-p-substituted phenol / formaldehyde

Halopean groups, are. It has also been found that hyd condensates that are highly crystalline and not

j the presence of electron donating p-sub-5 "are easily oil-soluble.

substituents in the condensate, e.g. B. of alkyl groups, to the description of the invention

! a greater resistance of the color after its polycondensates, the term »oil-soluble« is used

! Formation and less yellowing of the background indicates that these condensates do not mix with water

'prurdes cVs absorbent material with aging miscible organic solvents under

! leads. On the basis of these discoveries it is possible to form clear stable solutions which are soluble

expensive pressure-sensitive recording material sys- the solvents mentioned also solvents for

sir me with which it is on the one hand possible to det the basic chromogenic substance to the extent

j to achieve rapid and intense color formation Formation of solutions represent the least

On the other hand, this means both the 0.25 percent by weight, preferably more than 1

Fäfhiwp »Is the background stable and 6% by weight of the basic chromogenic substance

7 «iir jiwcils according to the requirements of the he- included.

IrcffcriVn Syslrms. In all cases at least ts is essential to the invention that the aforementioned

LOCiWichlfrrrVrnt of the polycondensates forming the condensate are reactive hydroxyl groups

p-HihsliUik'Ncn phenols electron-attracting p-sub- sit to the color formation on reaction with the

slilucnltn wake up. ⁶ S basic chromogenic substance to facilitate.

I InliT lim m clcktroncnatizichcndcn p-substituent Vs must be guaranteed that one of the phenolic

vrrMihl nidii a Siihsliluenlcn with a collar fabric containing coating under normal Bc-

"Then Suhsliiucnlcn Konslunlc greater than zero, whereby conditions are not" sticky "and that the condensates

3 4

containing phenolic substance is so hard that it turns into n-amylphenol, p-U-dimethyl-n-amylphenol, p-n-Oc-

small particles can be ground without tylphenol, p-l, l, 3,3-tetram2thyIbutylphenol, p-iso-

these result from the grinding or similar octylpnenol, p-n-nonylphenol, p-isononylphenol,

Crushing process occurring heat together- p-l.l ^ -Tetramethylamylphenol, l-n-Dicylphenol,

menbaüen, 5 p-isodecylphenol, p-n-undecylphenol, p-isoundecyl-

Of the suitable condensates of phenols with phenol, pn-dodecylphenol and isorn ^ s any electron-withdrawing p-substituent, any of the aforementioned pC _r to C ^ -alkylphenols, p-halophenol condensates, which are each divided by two belisbip or r m5 ' ar djr aforementioned p-alkyl-reaction of p-Ha! ophenolen at temperatures phenols and mixtures comprising Isomjre between about -4 and about 100 ⁰ C using the same io. The addition of mUa substituents η can be produced by acids as catalysts. For the above p-substituted phenols, catalysis of the condensation can again be any conventional without any significant effect.
Acid can be used. In a preferred embodiment of the invention, the electron donating p-substituent is up to about 8 hours and is accompanied by the formation of an alkyl group with 4 to 12, preferably 8 to 9, water and volatile matter in a preferred embodiment of the invention fairly quickly in time spans between 30 minutes . It is convenient- carbon atoms, while the electron-attracting moderate, the water for example by vacuum- p-substituted phenol p-chlorophenol. Remove the distillation. This can happen in intervals, preferably tri- and higher polycondensate is the pro or practically uninterrupted during its formation with an acid as a catalyst or even after the condensation, ao condensation of p-chlorophenol and p-l, 3.3 -Te-Normally the condensation takes place with autogenous tramethylbutylphenol with formaldehyde in the pre-pressures and temperatures between about 15 and mentioned molar concentrations,
about 100 ° Cin time spans νοκ about 30 minutes to In the general discussion that now follows, about 4 hours. Suitable inorganic and organic phenols and phenol condensates with an electronic acid as catalysts for the condensation as attractive substituents in the para position are, for example, hydrochloric acid, bromine form of preferred p-halophenols and their hydrocarbons. Sulfuric acid, phosphoric acid, oxalic condensates are described. It is understood that, acid, p-toluenesulfonic acid. when p-halophenols are considered suitable for the invention

Further phenol condensers used according to the invention are mentioned, also other members of the group

Sates can be prepared analogously to the aforementioned p-halo-30 of electron-attracting p-substituted phenols

make phenols using maize to make p-halophenol,

replaced by the corresponding p-substituted phenol. A feature of the invention consists in the use

Examples of electron-attracting p-substituents of phenols which are particularly suitable for the specific purpose and which are suitable for the production of poly-pased polycondensate mixtures, the p-halophenol condensates for use in the tri- and higher condensates and p-alkyl compounds contained in the invention Suitable recording materials include tri- and higher condensates containing phenol, p-fluorophenol, p-chlorophenol, p-bromine. This gives recording materials, phenol, p-iodophenol, p-nitrophenol, p-carboxy- lien, on which an intensive color development phenol, p-carbalkoxyphenols, p-acylphenols and both the markings as p-aroylphenols. P-Chlorophenol is preferred, with 40 the background color is also permanent. This not only achieves good results, but also contains special polymer blends that are easily available and economical in advance. The previously described tri- and higher p-halogenated p-substituted phenols produce condensephenol / p-Cj- to Cjj-alkyl-substituted phenol- (and / sate, the rapidly intense color markings ent- or p-benzylphenol and / or low p-Alkoxy coils when they come into contact with a mixture of basic chromogenic substances such as phenol) -formaldehyde polycondensates. As already said, with at least one free hydroxyl group this is due to the fact that the condensates contain phenol-containing tri- and higher condensates of form units with electron-withdrawing p-substituents aldehyde with a substance selected from pC, - bis. Further substituents (electron-withdrawing C, ₂ -alkyl-substituted phenol, p-benzylphenol and / or electron-donating) in one or both meta-5 ° lower p-alkoxyphenol, whereby the p-halophenol positions to the phenolic hydroxyl group have no more condensates between 10 and 35 percent by weight Effect. So 3-methyl-4-nitro- make up this mixture, while the last phenol, for example, something like p-nitrophenol and called condensate between 65 and 90 weight effects of 3,4-dichlorophenol and 3-methyl-4-chloro percent of the specified special Mixture of triphenol both roughly like p-chlorophenol. SS and higher polycondensates.

Examples of electron-donating p-substituents The latter condensate is usually

containing phenols for the production of poly- also with acid as a catalyst in the same

condensates for use in the preferred embodiment and under the same general conditions

exemplary embodiments of the invention are as follows: 1. Never formed, as in the preceding with respect to the third p-alkoxyphenol; 2. p-benzylphenol; 3. Described every 60 p-halophenol condensates. To the

any pC, - to C, _a -alkylphenol, e.g. B. p-methyl production of this condensate suitable pC, - bis

phenol, p-ethylphenol, pn-propylphenol, p-isopropyl-C ₁₂ -alkyl-substituted phenols include any

phenol, pn-outylphenol, p-isobutylphenol, p-Tcr- of the above-mentioned pC, - to C ₁₃ -alkyl-

tiarbulylphenol, p-n-amylphenol, p-Isoatnylphenol, substituted phenols, which are related to the p-U-dimethyl-n-propylphenol, p-n-hexylphenol, 65 to form the aforementioned p-halophenol contained-

p-Isohexylphenol, p-1,1-dimethyl-n-butylphenol, which condensates have been appropriately named. In glci-

p-l, 2-dimethyl-n-butylphenol, p-cytlohexylplicnol, more likely can be used in place of p-benzylphenol or

1 -n-lkptylphnol, p-isoheptylphenol, p-5,5-Dinu: thyl- a single pC, - to C ,. _a -alkyl substituted phenol

4 4!

S 6

Reductions of any two or more such amines; Acylauramines, e.g. N-Benzoylaur 'and

Substances including a p-Cycloalky'iphenol with N-Acetylauramin; Arylauramines (e.g. N-phenylaur-

Formaldehyde are implemented. In addition, the amine); «-, ^ -unsaturated aryl ketones, z, B, dianisyli-

the latter condensate component of the special denacetone, dibenzylideneacetone and anisylidenacetone;

Mixture of a number of individual condensates of 5 basic monoazo dyes, e.g. B. p-dimethylamino

Formaldehyde with pC _r to C ^ -alkyl-substituted azobenzene-o-carboxylic acid (methyl red), 4-aminoazc

Phenol, p-benzylphenol and lower p-alkoxy- benzene (oil yellow AAB) and 4-phenylazo-l-naphthaH-

phenol. According to a preferred executor; Rhodamine B lactams, e.g. B. N- (p-nitrophenyl) -

Approximation example of the invention consists of the special Rhodamir.B-Lactam (hereinafter referred to as RBL);

Mixture of condensates from about 20 to about 10 polyarylcarbinols, e.g. B. bis (p-Dimethylaminophenyl) -

30 percent by weight of the aforementioned p-halophenol methanol, called Michler's Hydrol, Kristallviolctt-

containing condensate and about 70 to 80 weight carbinol u "d malachite green carbinol; and 8'-methoxy-

percent of the latter condensate together, benzoindiolinospiropyrans, e.g. B. 8'-methoxybenzoin

of which a part, preferably a large part (on dolinospiropyran, 4,7,8'-trimethoxybenzoindolinospi-

Molar basis) is p-t-butylphenol. This special Kon- 15 ropyran ,, and o'-chloro-e'-methoxybenzoindolinospi-

Densate mixture is used for recording materials as ropyran, as well as p-dimethylaminostyrylcliinoIin. When

preferred with paper backing. the basic chromogenic substance can also be two

In the following examples various arbitrary 0 or more of the vo "; jnannt.en basic chro-

Phenolic condensates and condensate mixtures as well as mixtures containing like color formers

the test results obtained with these are described. 30 should be turned.

A suitable method for creating recipe- For achieving optiimbr properties of the

guidelines is the titration of condensates in benzene - according to the recording material according to the invention, it is

solution with non-aqueous base, such as borrowed that the phenolic condensates and mixtures

Tetramethylguanidiiizumethyl bis (2,4-dinitrophenyl) - the same as well as the basic chromogenic substance

acetate endpoint. Mixtures of condensates can together be soluble in a solvent, preferably-

arbitrarily prepared in such a way that titration values are wisely obtained in the oil or in the solvents by which

obtained which are equivalent to the value obtained by the color formation reaction in the recording material

Titration of any standard phenol / formal is effected. A suitable and preferred way that

Dehydkondensats obtained, which is due to its recording material with the solvent or

chose appropriate color developing properties. 3 ° to provide oil consists in using a solvent or

An oil solution of at least one of the color formers, e.g. B.

Mixtures can be expected to have the same of the basic chromogenic substance, by means of the

Standard service in the development of color-encapsulating and microencapsulation technology

together with basic chromogenic substances on paper, the capsules on the paper or another carrier

provide. Such titrations can therefore be applied to or incorporated into this, so that at

Choice of a number of condensate mixtures for testing Release of the solvent (e.g. by the

according to the pressure applied in the examples.

iated test results are used. At least one of the color-forming components should be used as the titration standard

for the mixed resin condensates of the invention the solvent or oil is already practically dissolved,

was generally p-pheny! phenolformaldehyde resin (at 40, which accelerates color formation,

a Hammet's substituent constant of about when the other color formers are in the solution

Zero for a p-phenyl substituent). mixes. It is also in the mind of the invention,

The p-halophenol condensates and special solutions of the chromogenic substance and the mixtures of the condensates containing them are encapsulated with these reacting condensates and produce a visible strong color in the reaction. The separately encapsulated solutions in or on the contact in solution with basic chromogenic substance. To arrange recording material. Another, normally the chromogenic compound or, however, somewhat less expedient possibility of the chromogenic substance is colorless before the reaction until only encapsulating the solvent is so lightly tinted. The chromogenic substance should, however, dissolve both color formers when released be able to change color so that it shows a very distinct coloration when used in solution generally known in the art, numerous types of capsules for this purpose
Contact with the aforementioned p-halophenol ent- The solvent should be able to contain condensates and special condensates- at least 1.0 percent by weight of the basic chromium mixtures. These combinations of chromic substance and a corresponding concentration of homogeneous substance and the aforementioned condensates of the aforementioned p-halophenol-containing condensates and special condensate mixtures can be dissolved in sate or special mixtures of these, any of the known color-producing or preferred ones Systems can use the liquid solution marking-forming recording medium systems to dissolve more potycondensate than necessary, in which the chromogenic substance is basic in order to optimally utilize the basic chromogenic and the complementary color-generating component 60 genes and thus a maximum color intensity is lukewarm. Ensure examples of suitable basic chromogenic at the reaction sites. For educational connections with chromogenic groups, diarylation should give the best possible results the combination of phthalides, e.g. B. i, 3-bis (p-dimethylaminophenyl) -6-di- of the common solvent and the color former tnethylamine phthalide (crystal violet lactone, in the following be so that the solvent both inner color formers called KVL for short) and 3,3-bis ( p-Dimethylamino- 65 half about 15 seconds after the release of the solution rhenyO-phüialid (malachite green lactone, in the following dissolves by means of the capsule. Suitable solvents called MGL for short); Leukauramines, e.g. N-Halo- are among others the following: volatile and non-phenyl, especially N (2,5Dichlorophenyl) Leukaur- volatile hydrocarbons and halogenated carbons

Hydrogen including aryl hydrocarbons ^ ζ. Benzene, toluene and xylene; halogenated aliphatic hydrocarbons, e.g. B. perchlorethylene; chlorinated polyphenols, e.g. B. chlorinated diphenyls; and aromatic and / or halogenated aromatic petroleum distillates, for example those with a boiling point between about 135 and 260 ^° C., which mainly consist of aromatic and / or halogenated mono- or polycyclic aromatic components, but also smaller amounts of C ₄ - to Cjo-paraffins may contain.

Suitable supports for the recording material according to the invention include paper sheets, woven or non-woven webs and fabrics, the paper fibers mixed with other materials (e.g. natural and / or synthetic textile fibers), as well as polymer matrices, films, sheets and -layers.

The capsules, which contain the liquid solvents in which one of the color reaction components is optionally dissolved, can be used as a coating applied to the support or web (e.g. paper) or during manufacture of the web or the Sheet to be incorporated into this or this.

As already stated, the solvent and both color formers can be in the same sheet of paper or the same path. This type of recording medium can then be referred to as "autogenic" because both color reaction components and the intimate mixture thereof causing agent (solvent) in the same sheet or sheet same train are included. It will be understood that the solvent will be held in capsules or otherwise to ensure that the essential Color reaction components cannot come into contact with one another until the mark formation is desired. In such recording materials, the chromogenic solution and the The aforesaid condensates containing p-halophenol (or special condensate mixtures) containing capsules evenly on the paper web or the Leaf are distributed so that a large number of evenly distributed microcapsules in intimate association to the aforementioned condensates is present on or within the paper carrier or the matrix. the The aforementioned special condensate mixtures can be produced using a variety of conventional coating or impregnation process applied to or impregnated with a paper web, z. B. by applying a solution, dispersion or suspension. It is also within the scope of the invention, inert fillers and / or fillers such as. B. to use acidic inorganic clays with the basic chromogenic substance react to form color. The aforementioned condensates by "dry" coating processes generally known to those skilled in the art of coating technology applied to the sheet of paper or web. When using dispersion or similar coating processes, the dispersant is usually water or predominantly aqueous, and the The aforementioned condensates and special condensate mixtures are ground to a particle size or crushed, suitable for application and even dispersion on and / or incorporation in the paper carrier or the matrix. Typically this particle size will be between about 0.1 and about 5 μπι, with most of the particles a Has a size of less than 2 μm. The preferred one Particle diameter is 2 μm and less. While the condensates are usually evenly distributed over the Paper carrier or the matrix are deposited or incorporated into these or these, it is also in the Within the scope of the invention, this coating or incorporation only in certain areas or parts to undertake, whereby the color reaction can then only take place in these.

ίο Even very small amounts of the two essentials Color formers produce colored markings when they are brought into contact with one another in the presence of an oil (solvent). To achieve adequate coloring in recording materials

However, the following amounts are used. The table below shows the concentrations of the essential color formers in g / m ^{1 of} the respective carrier.

ao Essential Useful Usual Preferred Color formers Conc Conc Conc tration tratton tration ^aJ A. Cap g / m « g / m « g / m « rarely chrom- 0.03 0.03 0.045 more mogenous until until until Material*) 0.12 0.11 0.09 B. At least ³⁰ 70 Ge 0.11 0.15 0.45 weight pro until until until cent tri- u. 3.7 1.5 1.2 higher Condensate ³⁵ te included tendes Phe nolharz

*) The stated concentrations apply to the encapsulated chromogenic stone * per se. The Gcwtchtskonzentration of the encapsulated solution of the active substance, including chromogenic solvent and kapselwandbildcndem substance may between ₁ IS O and 15 g / m * are. Usually it is between 1.5 and 7.5 g / m ·, preferably between 3 and 4.5 g / m *. 45

The arrangement and condition of the color formers are the same as in known recording materials.

The invention is illustrated in the following examples explained in more detail. Unless otherwise specified, all parts and concentrations are understood to be Parts and concentrations by weight.

example 1

This example describes the preparation of typical p-halophenol and PC ₁ - to C ₁₄ -alkyl-substituted phenol-formaldehyde condensate for use formation in the recording material according to the invention.

196 g of p-chlorophenol, 104 g of p-l, l, 3.3-tetramethylbulylphenol, 130 g of a commercially available 37 g weight percent aqueous solution of formalin (formalin) and 10 cm of concentrated hydrochloric acid as a catalyst. The reaction participants are at reflux temperature for 4 hours in

209619/295

1 93 ^ 457

the plastic bottle is condensed at autogenous pressures. Then the resulting condensate is cooled and the upper aqueous layer is removed. The condensate or water-containing reaction is vakuumdestllliert at temperatures between room temperature and 200 ⁰ C with a signal generated by a water jet pump Teilvafcuum, remove most of the water and the volatile substances to. The condensate is then heated to about 200 ° C. and kept at this temperature for 15 minutes, after which it is poured into a suitable container in which it is allowed to harden with the gradual decrease in temperature to room temperature.

10

An analysis to detect the elements C, H, Cl and O resulted in the following values: carbon 66.5%, hydrogen 5.8%, chlorine 16.2% and oxygen 11.5% compared to the theoretically determined values for the tetramer condensate : Carbon 67.5%, hydrogen 5.9%, chlorine 16.9% and oxygen 10.0%. When the infrared adsorption pattern was determined, this condensate showed adsorption in the range from 3200 to 2500 cm- ¹ (which is the free Indicates hydroxyl groups) and no adsorption in the range of 1600 to 1700 cm- ¹ (if there were any adsorption, this would indicate the desensitization of the hydroxyl groups).

Example 1 (Various p-halophenol and pC, - to Cjj-alkyl substituents.)

Execute Components Color intensity foresight the example p-chlorophenol Mark*) A. p-1,1,3,3-tetramethylbutylphenol 38 37 weight percent aqueous Solution of formaldehyde p-fluorophenol B. p-1,1,3,3-tetramethylbutylphenol 42 37 weight percent aqueous Solution of formaldehyde p-bromophenol C. p-1,1,3,3-tetramethylbutylphenol 43 37 weight promising watery ones Solution of formaldehyde p-iodophenol D. p-1,1,3,3-tetramethylbutylphenol 43 37 weight percent aqueous Solution of formaldehyde p-chlorophenol E. p-methylphenol 38 37 weight percent aqueous Solution of formaldehyde p-chlorophenol F. r> tertiary betylphenol 41 37 weight percent aqueous Solution of formaldehyde p-chlorophenol G p-dodecylphenol 41 37 weight percent aqueous Solution of formaldehyde

·) The color intensity test is a comparative evaluation of the ability of the respective condensate to generate a blue color on contact with a benzene solution containing 0.5% by weight crystal violet lactone (KVL). This Test is carried out as follows:

A 0.5 weight percent solution of the resin to be tested is prepared using reagent benzene as the solvent. If necessary, it can be filtered to obtain a clear solution. A comparable 0.5 weight percent solution of KVL in benzene is prepared, of which 5 ecm pt 100 ecm of the condensate solution are added. The solutions are thoroughly shaken so that the color formers come into good contact with one another. Using a pipette, 3 drops of this solution are applied to a round white filter paper (brand “Blue Ribbon No. 589”, diameter 15 cm manufactured by Schleicher & Schüll). It imagines colored spot about 3.2 to about 3.8 cm in diameter. There are five of these on each filter paper Creates spots. After allowing 10 minutes for solvent evaporation and further development of the color patch, the reflectance of the color patch and white background is read in a conventional manner using a Bausch & Lomb opacimeter. the Color intensity (percentage of the reflection ratio) is then calculated according to the following equation:

Reflectivity of the color patch Reflectivity of the background

The stated values are average values for the five color spots. The lower color intensity values indicate the creation of a more intense blue color,

2d85

_{Numerous water-insoluble p-halophenol- and pC r} to Cij-alkyl-substituted phenol-aldehyde condensates, which are soluble in a solvent, have been prepared with the components mentioned above. A two-part plastic glass container with a capacity of 200 ecm was used, the lid of which had four openings, one for the reflux condenser, one for the stirrer, one for the addition of reagents and one for a thermometer. Heat was supplied by means of a heating mantle adapted to the lower part of the vessel. The condensates were prepared and recovered using the following typical procedure for each embodiment: The p-halophenol (0.3 mol) and the p-alkylphenol (0.1 mol) were added to the reaction vessel in a molar ratio of 3: 1 and heated so that they melted. Then so much 27% by weight aqueous solution of formaldehyde was added that 0.32 mol of formaldehyde resulted, the acid serving as catalyst (from 2.5 to 4 ecm concentrated hydrochloric acid) and water (about 10 ecm) were added to the molten phenols (molar ratio of formaldehyde to the total amount of substituted phenols, ie p-halo plus alkylphenols, 0.8: 1). The temperature in the vessel was increased until the vapor line ran at the bottom of the reflux condenser. The reaction mixture was stirred and refluxed for 3 to 4 hours. Then the stirring was stopped so that she could sit and separate into two layers. The upper aqueous layer was then decanted. The reflux condenser was removed and the reaction vessel was fitted with a distillation device to remove water and other volatiles from the condensate. After this was done, the temperature in the vessel was gradually increased from 120 150 ⁰ C and higher, until no more water could be observed. Then, the condensate in suitable containers (for. Example, aluminum trays) for cooling to room temperature was gegössen (about 18 to 24 ⁰ C). A hard and brittle thermoplastic material was obtained.

In the production and isolation of the condensate in embodiment C, an additional cleaning step was carried out. After doing that

ίο Condensate from the reaction vessel into the suitable After pouring into a container, it was allowed to harden and then ground up using a mortar and Pestle to a fine powder. The ground condensate was dispersed in 500 ecm of water and with 100 ecm of benzene extracted from the water. The benzene layer was then in turn coated twice with 200 extracted up to 300 ecm of water. Eventually it did Verify benzene by drying at room temperature under reduced pressure in a vacuum separator evaporated, so that a solid condensate remained.

The condensates of embodiments A to G produced an instant blue color when exposed to a benzene solution of KCL. These condensates also immediately deliver a blue one

as mark when normal mark pressure is on a pair of sheets of paper is applied, one of which is called the receiving sheet on top of it The top is coated with the condensate and this side is another sheet of paper immediately is underlaid, the back or underside with a benzene solution of KVL containing Gelatinekapnein The marking print is coated on the upper side of the latter sheet for example by a pen, a pen, a pencil, the Type of typewriter or other similar pressure-generating marking device exercised

Example 3

Execution
example Substituted)
Phenol constituents) Molar ratio
Halo-to-Alkyi-
phenol Molar ratio
formaldehyde
zn PhenoKe) Color intensity
the
mark Colourfast A.
B.
C.
D.
E. p-chlorophenol
p-chlorophenol plus p-l, l, 3,3-Te-
tramethylbutylphenol
p-chlorophenol plus p-l, l, 3,3-Te-
trametbylbutylphenol
p-chlorophenol plus p-l, l, 3,3-Te-
tramethylbutylphenol
p-chlorophenol plus p-l, l, 3,3-Te-
tramethylbutylphenol 5: 1
3: 1
2: 1
1: 1 0.8: 1
0.8: 1
0.8: 1
0.8: 1
0.8: 1 38
37
38
37
42 Yes
Yes
Yes
Yes
Yes

Numerous tri- and higher p-halophenol-containing condensates with formaldehyde were prepared using the procedure described in Example 2 using hydrochloric acid as a catalyst, a 36 weight percent aqueous solution of formaldehyde and the p-substituted phenols listed above. In Examples A. to E, the molar ratio of p-halophenol to DC was ₁ to Cu-alkyl-substituted phenol between only p-halophenol in Example A and equal amounts of both substituted phenol components in Example E, while the molar ratio of formaldehyde to the total amount ar substituted Phenol was kept constant.

The condensates were then tested for color intensity (as in Example 2) and durability of the marking tested from the point of view of their practical usability in recording media! made of paper that you use for 2 weeks temperatures, humidity and oxydauons (Air) exposed. Color intensity values between 33 µm 43 are considered useful.

2485

457

Example 4

Embodiment

Substituted. Phenol component (s)

Molar ratio Halo to alkyl

phenol

Molar ratio formaldehyde to phenol (s)

Color intensity

the mark

A.
B.
C.
D.
E.

p-Chloropfienol plus p-l, l, 3,3-tetramethylbutyl-

phenol

p-chlorophenol plus p-l, l, 3,3-tetramethylbutyl-

phenol

p-chlorophenol plus p-l, l, 3,3-tetramethylbutyl-

phenol

p-chlorophenol plus p-l, l, 3,3-tetramethylbutyl-

phenol

p-chlorophenol plus p-l, l, 3,3-tetramethylbutyl-

phenol

3: 1 3: 1 3: 1 3: 1 3: 1

0.65: 1 0.7: 1 0.8: 1 1: 1 1.2: 1

34 41 38 40 45

Analogously to Example 2, a number of tri- and higher p-Haiophenol-p-octylphenol / formaldehyde condensates manufactured. The molar ratio of p-halophenol to p-alkylphenol was kept constant, while the molar ratio of formaldehyde to the total amount of p-substituted phenols was varied by the To determine the effect on the color intensity of the marking. As can be seen from the table above, leads to the use of condensates with a molar ratio of formaldehyde to the total amount of the p-substituted phenol greater than 1: 1 (e.g. in exemplary embodiment E) leads to insufficient color intensity in the case of recording media made of paper.

It has also been found that using too little formaldehyde (e.g. less than about 0.65 mole Formaldehyde per mole of total amount of p-substituted Phenol) also leads to insufficient color production (e.g. reduced reactivity of the condensates obtained with the basic chromogenic compounds). The use of too little Formaldehyde also causes difficulties in the production of coatings from the condensates, when applied by conventional coating processes in the form of aqueous dispersions especially with regard to the grinding of the condensate and the loss of condensate due to its water solubility.

Example 5

The following are the results of color intensity tests that show the effectiveness of tri- and higher phenol / Show formaldehyde condensates with various electron-withdrawing p-substituted phenol units. p-halophenol resins (m-unsubstituted), the are also representative of this group are treated as in the other examples.

The molar ratio of formaldehyde to p-substituted (n) Phenol (s) in all of the aforementioned resins was 0.8: 1.

Comparatively, formaldehyde and various electron-donating p-substituted phenols resulted produced tri- and higher condensates (with the same molar ratio of formaldehyde to phenol from 0.8: 1) the following color intensities of the marking: p-nonylphenol resin 65.9; p-amylphenol resin 67.5; p-octylphenol resin 58.7 and p-cyclohexane phenol resin 64.9. The standard n-phenylphenolic resin made in the same way gave a color inlensibility of the marking of 45.1.

Substituted Color intensity Phenol constituents) the marking 3,4-dichlorophenol 35.4 3,4-dichlorophenol plus p-octylphe- nol (molar ratio 1: 1) 41.5 Propyl p-hydroxybenzoate plus p-Oc- tylphenol (molar ratio 3: 1) 50.7 p-hydroxybenzophenone 55.4 p-hydroxybenzophenone plus r> Oc- tylphenol (molar ratio 1: 1) .. 54.3 3-methyl-4-nitrophenol plus p-Oc- tylphenol (molar ratio 2: 1) .. 39.9 3-methyl-4-nitrophenol plus p-Oc- tylphenol (molar ratio 1: 2) 45.9 p-hydroxypropiophenone plus p-Oc- tylphenol (molar ratio 2: 1) 53.1

Example 6

This example covers the typical production of recording material using a Carrier sheet made of paper and various p-halophenols containing tri- and higher condensates and special mixtures thereof.

The color-forming condensates and mixtures condensate mentioned later in the example were prepared with the indicated ingredients in the indicated molar ratios, by the F ^r 'ah condensation process described 1piel 1 with an acid catalyst. In all cases the other constituent of the condensate was formaldehyde in 37 weight percent aqueous solution. Mixers of condensates were produced by separately condensing the respective condensates and then mixing them before grinding and further steps for producing the coating. The overall process comprised four main stages: the production of the condensate (and possibly mixing of the condensates); grinding the condensates; du production of the aqueous dispersion, which is applied as a coating; the application of the coating. The typical processes given below for grinding, producing the coating and applying the coating relate to the production of a coating containing 17 percent by weight of condensate (s). It is understood, however, that coatings. which contain few condensate, which have concentrations of substances mentioned in the table.

2 * 85

934,457

To grind the condensate, add 1700 g Condensate and 1700 g of water and 204 g of a 25 weight percent aqueous solution of a dispersant, that is a commercially available sodium salt of a condensed, sulfonated organic acid is, in a grinding device with a capacity of about 7.5 1, about two thirds with Stainless steel balls with a diameter of about 3 mm is filled. The grinding process takes about 180 rpm 75 to 90 minutes.

Then the coating mass is prepared by adding 550Og kaolin, 900 to 1200g calcium carbonate and optionally, 300 grams of commercially available silica gel in about 600 grams of water with a dissolver or another suitable high speed stirrer. Dispersants, z. B. tetrasodium phosphate, can in conventional Quantities used to ensure the formation of the desired smooth, lump-free dispersion for easier coating. As soon as the aforementioned components are sufficiently dispersed are, 4240 g of the ground condensate are added. Then the addition of takes place with stirring 4750 g of an aqueous dispersion of commercially available hydroxyethyl corn starch containing 20% solids medium viscosity together with 13COg of a 50% solids containing im Commercially available carboxylated styrene butadiene latex. The coating composition is left in place before use pass through a 100-mesh sieve.

The coating compounds described above and passed through a sieve are then applied to conventional white fine paper (made for example of 80 percent by weight Kraft fibers and 20 percent by weight sulfite fibers) with a basis weight of about 50 g / m ² in an amount of about 6 g / m * . This can be done by any of the conventional methods, e.g. B. by rolling on, brushing on or by means of an air brush, the aqueous dispersion of the coating having the following solids content:

In the case of roller application or brushing, 48 to 55 percent by weight;

when applied with an air brush, 28 to 32 percent by weight.

The coated paper sheets were then air dried and subjected to several tests for determination their usefulness as record transfer materials subjected. The final coatings contain the following on a solid basis:

a typewriter and on the other hand with regard to its color fastness) and evaluated comparatively, with the worst product receiving the rating "7" and the best product receiving the rating "1" for each of the tests. To test the chromaticity of the typewriter writing, the sheet of paper coated with the condensate was placed with the coated side facing up under a sheet of paper, the underside of which was coated with capsules containing a solution of basic chromogenic substance. Two uncoated sheets of fine paper were placed under the sheet coated with the condensate as a base. The record set was placed in a typewriter and printed with six rows of characters approximately 7.5 cm long. The color intensity of the marked part (/) and that of the unmarked background (Z ₀ ) were then read off by means of an opacimeter. The specific color intensity of the

ao typewriter writing was obtained by dividing / by I ₀ .

For the color fastness test, leaves were used in which the capsules had been broken open and colored markings distinguished by typewriter

As were called, normal ambient conditions for three weeks with the test samples attached to a wall. The aforementioned measurements of »/« and »/« «with the opacimeter were before and after the three weeks mentioned. Reducing the color intensity of the markings within the period of three weeks shows the extent of the fading or the color fastness on.

The corresponding results can be found in the table below:

component

Condensate (s) Calcium carbonate

Dispergens

Silica gel

kaolin

Styrene butadiene latex Starch ether

Weight parts (in grams)

1700

900 to 1200 51 300

(if used)

5450

650

950

Weight percent

The sheets each containing different phenolic resins in their coating become two each Tests (once regarding the color intensity of the

17.0 9.0 to 12.0

0.5
0.0 to 3.0 «ο

54.5
6.5
9.5

Condensate (s) Color ink Color be Execute sity of constant foresight Write- speed example p-chlorophenol / machine formaldehyde pressure cs A. Condensate of formal 1 dehyd and a wed 1 B. quenching of p-chloro- phenol or p-1,1,3,3- Tetramethylbutylphenol in a molar ratio from 3: 1 Condensate of formal 2 dehyd and a wed 2 C. the p-substitute ated phenols des management example B im Molar ratio 2: 1 .... Condensate of formal 3 dehyd and a wed 3 D. education of the p subs ated phenols des management example B im Molar ratio 1: 1 .... p4-Buiylphend / 4th formaldehyde 4th E. p-1, l, 3,3-tetramethyl 5 butylphenol / form * 5 F. aldehyde, 6th 6th

934 457

The goal of making a recording material high quality with a balanced combination of beneficial properties consists in an optimal intensity of typewriter pressure and color fastness without serious impairment the yellowing resistance and the printing speed. True, the measurements seem the color intensity of the typewriter print and color resistance to the use of p-halophenol furinaldehyde condensates alone require, but will, by p-alkyl-substituted phenolaldehyde condensates achieved increased resistance to yellowing and the printing speed, d. H. the speed at which the pressure is after when the capsules are broken, no matter how long the recording material was previously stored was not slowed down. Also are p-alkylphenols more economical than p-halophenols as they are cheaper.

Example 7

This example deals with the preparation of a coating for color-former transfer-based paper using a tri- and higher condensate of formaldehyde and p-chlorophenol in admixture with a tri- and higher condensate of formaldehyde and a pC ₈ -alkyl-substituted phenol. This condensation mixture can of course also be used for so-called autogenous recording materials.

& '»Indicated 340 g of a tri and higher condensate of formaldehyde and p-chlorophenol, 1360 g of one Tri- and higher condensate of formaldehyde and p-l, l, 4,4-tetramethylbutylphenol, 1700 g of water and 204 g of a 25 weight percent aqueous solution of the dispersant used in Example 6 in a Grinding device with a capacity of about 7.5 l, which is about:? U two-thirds with stainless steel balls was filled with a diameter of about 3 mm. The aqueous mixture was 75 to 90 minutes long at a speed of 180 rpm.

Then 550Og of kaolin, 900 to 1200 g of calcium carbonate and 300 grams of silica gel in about 6000 grams of water with a dissolver or other suitable high speed stirrer. Dispersants, e.g. B. tetrasodium phosphate, can be used, if desired, to provide a smooth, lump-free coating jr. to obtain.

After good dispersion, 4240 g of the ground tri and higher condensate mixture together with 4750 g of a 20 percent strength by weight aqueous solution of corn starch and 13COg of styrene butadiene latex (solids content HO ⁰ I ₀ ), as used in Example 6, were added to the dispersion containing alumina, with constant stirring. The coating compound was then applied to paper in the manner described in Example 6,

Example 8

Here the typical production of so-called autogenous recording materials from paper is described, in which both the basic chromogenic substance and the tri- and higher p-substituted phenol-formaldehyde condensate (s) reacting with it are on the same side of the same sheet are arranged. In principle, in this process a coating containing the solution of the basic chromogenic substance previously enclosed in microcapsules is deposited on the paper, after which a further coating containing the condensate or condensates is applied. Suitable longitudinal encapsulation processes are generally known in the art and are not explained in more detail here.

Lower class

Weight Components share 17.5 percent by weight of encapsulated KVL Solution (as known in the art) ent holding aqueous dispersion 296 Calcined kaolin 25th Purified wood cellulose fibers (microfine) 8.8 Medium particle size talc (100% passes through 375 mesh sieve) 3.7 Ethylated corn starch of medium viscosity 38.5 water 28

The ingredients listed above are mixed in a mixer or colloid mill at high speed for 5 minutes. A coating compound with a solids content of 25 percent by weight is obtained, which is applied to the paper carrier ^{in an amount of 7.2 to 7.5 g / m a by means of an air brush or a Meyer rod.}

-, ο top layer

Components

condensate

water

Gum arabic

kaolin

Calcined kaolin

Aqueous etherized corn starch

(Solids content 20%)

Carboxylated styrene butadiene latex

Parts by weight

140
703
10
590
120

400
120

This upper layer is produced by adding 140 g of resin condensate (s), 10 g of water and 10 g Gum arabic in a grinding device of a suitable size two-thirds filled with stainless steel balls Milled for 1 hour or so long until an average particle size of less than 3 μm, ζ. B. between 1 and 3 μηι, depending on the conventional Light transmission measurements.

Then the above-mentioned 590 g of kaolin, 120 g of calcined kaolin and 52Og of water in one Mixers or other suitable high-speed stirring device and such mixed long until the clays are well dispersed. Then 333 g of that in the above are added described manner prepared, ground resin dispersion, which intimately with the alumina dispersion

is mixed. Then 400 g of the OK percent

etherized corn starch added with constant stirring, after which the addition of 120 g of the carboxy

lated styrene butadiene latex takes place.

The upper layer, which has a solids content of 30%, is then applied to the paper already provided with the lower layer in an amount of 6.2 ± 0.3 g / m ¹ by means of an air brush or a suitable applicator stick. After Trock-

The autogenous paper sheets are then subjected to a test for the color intensity of typewriter printing and rated from 1 to 4, with rating 1 indicating the best and rating 4 indicating the worst quality. S.

This test is carried out as follows: two uncoated paper sheets (22 g / m ^s ) are placed under an autogenous paper sheet and a paper sheet of this type is overlaid. Using a typewriter, the autogenous sheet is printed with colored characters by breaking the capsule coating, and the color intensity of the print on the autogenous sheet is then determined as in Example 6.

The results of the test shown below show the effect of using different ones Condensates in the upper layer of the autogenous recording paper.

Execution
ruiigs-
example Condensates) Color inks
sity of
write
machinery
pressure A.
B.
C.
D. pl, l, 3,3-tetramethylbutyl
phenol / formaldehyde
pt-butylphenol / formaldehyde
KoLdensat
Formaldehyde and condensate
a mixture of p-chlorine
phenol and p-1,1,3,3 tetram-
thylbutylphenol in Molver
ratio 3: 1
Mixture containing 80
percent condensate of form
aldehyde and pt-butylphenol
and 20 percent by weight of con
formaldehyde and densate
a mixture of p-chloro-
phenol or a mixture
of p-chlorophenol and
p-1,1,3,3-tetramethylbutyl-
phenol in a molar ratio of 3: 1 4th
3
1
2

35

Claims (15)

Claims: 45 1. Pressure-sensitive recording material, consisting of a sheet-like material on and / or within which there is a chromogenic substance, a phenolic substance and an oily solution medium for the substances mentioned, which react in common solution in the oily solvent to form a dye, according to the patent 12 75 550, characterized in that at least 70 percent by weight of the phenolic substance consists of oil-soluble polycondensates of formaldehyde and one or more p-substituted phenols, of which at least 10 percent by weight have an electron-attracting p-substitute, and that each molecule of the polycondensates at least contains three p-substituted phenol units. 2. Pressure-sensitive »recording material according to claim 1, characterized in that the phenols containing electron-attracting p-substituents are p-halophenols. 3. Pressure-sensitive recording material according to claim 2, characterized in that the p-halophenol is essentially p-chlorophenol. 4. Pressure-sensitive recording material according to claim 2 or 3, characterized in that that the p-substituted phenols have at least one phenol from the group of p-alkylphenols which the p-alkyl group contains 1 to 12 carbon atoms, and which contain p-benzylphenol. 5. Pressure sensitive recording material according to claim 4, characterized in that the molar ratio of the p-halophenol to the uus of The phenol selected from the group of p-alkylphenols and p-benzylphemols is 1: 1 to 5: 1. 6. Pressure-sensitive recording material according to claim 4 or 5, characterized in that that at least one p-alkylphenol having 8 or 9 carbon atoms is used in the alkyl group. 7. Pressure-sensitive recording material according to claim 6, characterized in that practically all of the p-alkylphenol p-l, l, 3,3-tetramethylbutylphenol is. 8. Pressure-sensitive recording material according to one or more of claims 2 to 7, characterized in that the condensates from 0.65 to 1.0 mol of formaldehyde per condensate Moles are p-substituted phenol. 9. Pressure-sensitive recording material according to claim 1, characterized in that the having an electron-attracting p-substituent Phenols at least one from the group of p-nitrophenols, p-carboxyphenols, p-C'arbalkoxyphenols, p-Acylphenols and p-Aryoi- ' contain phenols. 10. Pressure-sensitive recording material according to claim 1 or 9, characterized in that the p-substituted phenols contain one or more phenols with an electron-terminating p-sub- / S substituent. 11. Pressure-sensitive recording material according to claim 10, characterized in that the phenols containing at least one phenol from the Group of p-alkylphenols in which the alkyl group contains 1 to 12 carbon atoms, the Contain p-benzylphenols and the p-alkoxyphenols. 12. Pressure-sensitive recording material according to claim 11, characterized in that the molar ratio of the phenol or phenols with electron-withdrawing p-substituents to the or the phenols from the group of p-alkylphenols, p-benzylphenols and p-alkoxyphenols 1: 1 to 5: 1 amounts to. 13. Pressure-sensitive recording material according to claim 11 or 12, characterized in that at least one p-alkylphenol having 8 or 9 carbon atoms in the alkyl group is used. 14. Pressure-sensitive recording material according to claim 13, characterized in that practically the whole of p-alkylphenol is p-l, l, 3,3-tetramethylbutylphenol. 15. Pressure-sensitive recording material according to claim 1 or claims 9 to 14, characterized in that the condensates of 0.65 to 1.0 mol of formaldehyde per mol of p-substituted phenol! or composed of phenols are.