DE2164512B2 - Recording sheet and process for its manufacture - Google Patents

Description

to provide better recording material in which a deep color image is formed on the surface of the Recording sheet by ultrasonic vibration energy, which is applied directly and locally to the sheet surface is brought into action, is generated

According to the invention, this object is achieved by means of a recording sheet mentioned at the beginning from a base sheet and a layer of leuco dyes consisting of color-forming components and an acidic component containing at least one phenolic compound, dissolved thereby is characterized in that a combination of polymeric phenol-aldehyde condensates for the acidic component and monomeric substituted phenols of the general formula

15th

OH

3 _: 3-bis (p-dimethyiaminophen) 'l) -6-dimethyl-

aminophthalide,

(Crystal violet lactone),

S ^ -bisCp-DimethyiaminophenylJ ^ SjoJ-tetra-

chlorophthalide,

9- (p-nitroanilino) -3,6-bis (diethylamino) -

9-xanthenyl-o-benzoic acid lactam,

(Rhodamine-B-lactam),

3,3-bis (p-dibutylaminophenyl) phthalide

(Malachite green lactone),

3,3-bis (p-dipropylaminophenyl) phthalide,

3,3-bis (p-Dimethylaminophenyl) -6-aminophthalide ₃ 3,6-bis (diethylamino) -9-hydroxy-9-xanthenoyl-

benzenesulfonyl sultone,

2- (2 ', 4', 6'-trimethy] phenylamino) -8-diethyl-

ami.no-3,4-benzofluoran,

2,8-Di (n-ethyl-N-p-toluylamino) -fluorane,

S-diethylamino-o-methylchlorofluorane.

Typical examples of polymeric phenol aldeh} ^r d condensates are p-phenylphenol-formaldehyde condensates, p-tert-butylphenol-formaldehyde condensate, p-octylphenol-formaldehyde condensate, phenol-formaldehyde condensate, cresol-formaldehyde condensate , Phenol-acetaldehyde condensate, etc. Typical examples of monomeric substituted phenols are p-phenylphenol, p-tert-butylphenol, p-octylphenol, p-benzylphenol, 2,2-bis (4'-hydroxyphenyl) propane, p-benzyl -phenol, 2,2-bis- (4'-hydroxyphenyl) -sec-iso-

in which R is an alkyl group with 4 to 20 carbon atoms, an aralkyl group, a substituted aralkyl group, a phenyl group, a substituted phenyl group

or a cycloalkyl group is used, butane, p- (4'-chlorophenyl) phenol, cyclohexylphenol

where the weight ratio of polymeric phenol, etc.

aldehyde condensates to form monomeric substituted polyphenols which are preferably used in the invention ranges from 90:10 to 10:90. mere phenol-aldehyde condensate is a material that

While the ones mentioned in the introduction are generally referred to as »novolaks, which one

Publications disclosed recording material 35 has a free hydroxyl group, in the absence of one

materials are pressure-sensitive, the crosslinking agent becomes meltable and immersed in water.

the image is soluble in the system according to the invention.

Ultrasonic vibration energy generated. One of the basic features of the recording sheet has been shown to be that the substances mentioned in the publications mentioned according to the invention are that the polymeric phenol substances mentioned neither alone nor in combination aldehyde condensates and the monomeric substitution to dissolve the phenols produced according to the invention in the color-forming components could be used. An essential one
Finally, the difference is that the pressure-sensitive recording systems contain the dyes
have included in Mikrokapsel.i, so that 45
these only come into contact with the acidic components after the capsules have been destroyed by the action of pressure
can kick.

The recording system according to the invention brings
a number of advantages. It is free from the effect or advantage found in the foregoing influence of mechanical inertia; an over-specified recording system expedient application system, such as photoelectronic transmission, application; the recording system would not be required and, conversely, conventional recording sheets would not make it possible. Mono slight changes to the recording device, mere phenols or polymeric phenol-aldehyde condensers, the simplicity of construction and the high 55 sate ζ. For example, the system can be used alone, ie not in combination with sensitivity possible, in the case of fast-together, not with success in the running copier, facsimile system, etc., recording system,
apply. The color-forming components are preferred

The colorless color-forming compounds used in the form of a coating layer on a surface

Suitable for the invention include connections 60 attached to the base arch. For the invention

with Läctonringert, Lactamringeii and Sultonringen, suitable polymeric phenol-aldehyde conensates and

which are colorless or light in color, monomeric substituted phenols are those which are

but are solid at room temperature after contact with acidic materials, but become

Implement color. Such compounds will liquefy at temperatures between 90 and 200 ° C. It isl

I mean, however, as "leuco compounds" or "leuco color" 65 that the melting point is dei

substances «denotes; the phenols and phenol-aldehyde conensates listed below are no

Compounds or combinations thereof are considered an additional factor.

Examples of leuco dyes: The polymeric phenol-aldehyde condensates and the

used within a certain weight ratio, namely in the ratio of 90:10 to 10:90 will.

This relationship is critical, as will emerge from the examples given later. It is found that the components used according to the invention have a very high chemical activity in the color formation reaction. This ge

monomeric substituted phenols are preferably present in the coating layer as individual small solid particles before, which are premixed according to a particularly preferred embodiment.

The coating layer is preferably a calendered smooth surface. The present invention also relates to a method of making a recording sheet which is characterized is that the color-forming components on one side of the base sheet in the form of an aqueous suspension a pH in the range from 6.0 to 11.0 is applied ».. The polymeric phenol-aldehyde condensates and the monomeric substituted phenols, preferably as premixed small solids suspended particles.

The above-identified aspects of this invention will become even clearer from the examples and drawings given below.

The recording sheet according to the invention can be produced by adding a base sheet to a aqueous or non-aqueous suspension, in which the color-forming components as small solid particles 'are dispersed, is applied in these In some cases, it is advisable that the color components are placed closely next to one another on the base sheet are applied so that the dye components a locally limited applied energy easily pick up. In order to meet these requirements, the base sheet is covered on one side with a suspension, which contains the solid particles from color-forming components, applied. The above specified method is particularly suitable for the production of a recording sheet for the above-mentioned Aufzeir ^ "Mrigssysteiii. Since * solvents, that in the not wäl. '«·'" "· !! Suspension is used, a :: ™ must be selected from such solvents, which do not dissolve the color-forming components. Examples of such solvents are aliphatic Hydrocarbons with 5 to 12 carbon atoms, such as n-paraffin hydrocarbons, isoparaffin hydrocarbons and cycloparaffinic hydrocarbons. However, ordinary aqueous systems are more preferred than non-aqueous systems because they are more economical and easier to use, safer with them too work is and the like

If necessary, an adhesive can be added to the suspension or a binder can be added, such as. B. polyvinyl alcohol, carboxymethyl cellulose. Hydroxyethyl cellulose. Casein. Starch, synthetic latices and the like, through which the solid particles Farbbüdenden components are glued to the base sheet. The base sheet can be paper or synthetic polymers that form sheets can be used, but paper is preferred because it is most commonly used is most economical and can be easily deformed.

One of the improvements of the production process according to the invention is the adjustment of the pH value of the aqueous suspension containing the dye compositions to a value between 6.0 and 11.0 by adding basic materials or buffers such as sodium hydroxide, potassium hydroxide, ammonia, lower amines and basic salts thereof and urea and thiourea. Adjusting the pH helps prevent the substrate from becoming greasy, which often occurs during storage or recording. A further improvement of the method according to the invention is that the coated and dried sheet of a Kaläriderbehandlurig, ζ. Β with a supercalender, is subjected. When the surface of the recording sheet is smoothed by this treatment, it can evenly receive energy from a recording pen or a needle. This treatment also makes the coating layer stronger because the coating layer can be mechanically densified. This saves the amount of adhesive in the suspension, and the mutual contact of the dye components is facilitated. Another improvement is the production of solid particles of phenolic material by uniformly mixing the polymeric phenol-aldehyde condensates and the monomeric substituted phenols in the molten state and the like -.d Cooling to the solidification point, after which it is pulverized. The phenolic solid particles obtained in this way become more active in the color formation reaction. The particle size of the phenolic materials of the invention should be between 1 and 5 microns. However, the size is not limited to this area, but can be set as desired according to the required screen fineness.

Reference is now made to the figures, of which show

F i g. 1 and 2 illustrate exemplary apparatus using the improved recording system of the present invention reproduces,

F i g. 3 those in the examples used below obtained results.

In Fig. 1 electrodes II are attached to the opposite sides of a ceramic piezoelectric substance 12, at the end of which a pen 13 is connected. This pen can consist of piano drums with a width of 700 microns, a thickness of 15 microns and a length of 3 mm. Its edges come into slight contact with the surface of the moving recording sheet 14, / .. B. under a pressure of 1 to 6 g When currency exchange will omsignale applied to the ceramic piezoelectric substance 1 1 of a Wechselstroinquclle 16! :. this causes a continued expansion up.! contraction of the substance 12, which the stylus!. ' is vibrated according to the frequency of the alternating current signal, and the vibration energy is transmitted to the surface of the recording sheet H. Although the vibration frequency νorzus:
is wisely between 10 and 100 kHz, it is not limited to this range, but can correspond .; the resonance frequency of the ceramic electrical substance that is used can be determined. Ow optimal frequency can be selected at will depending on the size and shape of the pen, the recording speed, the running speed and the sensitivity of the ·. Recording sheet, pen line density, etc. The vibrational energy causes actual contact between the ink components and, as a result, a visible image is formed on the surface of the recording sheet in accordance with the pattern of alternating electrical signals applied. The device shown in FIG. 2 has a multiple writing pen 15. consisting of a number of writing pens 15 ', each of which has a line density of 3 to 5 lines per mm and is practically applicable for producing any type pattern.

The invention will now be based on the following

4 ^r 6

2 1ß Ml 2:

Examples that are not, limitation, .show are described in more detail. In Λόχϊ: »Examples * the quantities are given in parts by weight.

B e i sp'ie 1 1

13.5 parts of p-phenylphenol (melting point 169 ° G) were uniformly mixed with 1.5 parts of polymer! p-Phenylphenol-formaldehyde condensate (50:50, ^{melting point 140 °} C.) mixed under melting conditions. At this point the weight ratio of the two materials was 90:10. This mixture was then solidified by cooling and pulverized. The pulverized mixture was then mixed in a ball mill for 3 hours with 0.4 part of an anionic wetting agent (as a dispersant), 0.3 part of hydroxyprnpylcellulose (as a viscosity regulator) and 59.8 parts of water. The particle size of the phenolic materials so premixed was about 3 to 5 microns after ball mill treatment.

8th : 5 p-phenyl
phenol:
(Weight
parts) ■ polymer,.:
₅ p-ehenyl-:
⁵ / phenol- ■
formaldehyde-
Kohdensat
(Weight
'stupid) Weight
ratio io EXAMPLE 2 ....
Example 3.,; .-.
Example 4 ....
Example 5 ....
Example 6 ....
₁₅ Example 7 ....
Control
example A ..
Control
example B .. 12th
9
7.5
6th
j
1.5 . 3
6th
7.5
9
12th
13.5 80:20
, ■ 60:40
'50: 50
40:60
20:80
I 10:90 15th 15th 100: 0
0: 100

Component B parts by weight

2- (2 ', 4', 6'-trimethylphenylamino) -

8-diethylamino-3,4-benzofluorane 0.7

2,8-Di (N-ethyl-N-p-toluylamino) -fluorane 0.5

Rhodamine B anilide 0.7

^ -Diethylamino-ö-methylchlorofluorane .. 0.5

anionic wetting agent 0.1

Water 15.2

The mixture of the above composition was milled in a ball mill for 2 hours. The particle size of the dyes was about 3 to 5 microns after ball mill treatment.

75.5 parts of the resulting component A and 17.7 parts of component B were uniformly mixed with 2.7 parts Slyrol-ButadienKopolymerisat latex to a solid content of 50% and 2.8 parts of a 10 ° _o aqueous potassium hydroxide solution. The pH of the final suspension was about 11.0. Then r .: - e »; i« ίίηρς basic paper

- οι -ι— "

Sheets were then supercalendered with a 12.5 kg / cm ^2.

B e i s ρ i e 1 e 2, 3, 4, 5, 6, 7 Control Example A and Control Example B.

Any of these examples
except that the

the following weight
the:

The control samples A and B given above corresponded to Example 1, except that the p-Phenylphenol (melting point 169 ° C) and the polymeric p-phenylphenol-formaldehyde condensate (50:50, melting point 140 ° C) were each used for themselves, namely in the To make these controls, each of the materials listed above was identified as small on its own Particles used and mixed with the other components in the ball mill.

The products obtained from the above examples and the control examples, that is, the recording sheets, were prepared using the methods shown in FIG. 1 tested device. Each recording sheet obtained by any of the above Examples and Control Examples was subjected to a recording test using the apparatus shown in FIG. Subjected to 1: Ultrasonic energy caused in accordance with the alternating electrical signals of 100 volts (effective) at a frequency of 30 kHz was locally applied by the pen to the surface of the recording sheet running at a speed of 50 mm / minute. Moreover, the surface of the recording sheet has been scanned with a hot pen a temperature of 200 ⁰ C. The results of the experiments are shown in FIG. 3 reproduced. The dashed lines in FIG. 3 show the colored image created by the ultrasonic vibration energy, and the two lines on the right are the colored images created by the hot pen.

The in F i g. 3 reproduced results clearly show that the use of p-phenylphenol (control example A) as well as polymeric! p-phenylphenol-formaldehyde condensate (Control example B) is not applicable to this described recording system.

Example 8

This example was the same as Example 1 except that 7.5 parts of small solid particles of p-phenylphenol and 7.5 parts of small solid particles of polymeric p-phenylphenolformaldehyde condensate and the 5s sat without premixing with 0.4 parts of anionic wetting agent -Condensate in means, 0.5 parts of hydroxypropyl cellulose and 59.8 parts of water in the ball mill for the preparation of the Component A were mixed. The received

409 521/240

t matched the example!

; "" ~ _C "t7i where was used

ίο

Recording sheet was tested in the same manner as in the same manner as described in Example 1 : Example 1 tested, and the same results and the same results were obtained as in FIG. 3 for example 1 shows.

Example 10

Example9 5 _T,.

Component A

Component A 25 parts of p-phenylphenol (melting point 169 ^° C.) and 25 parts

polymeric p-phenylphenol formaldehyde condensate

8 parts of polymeric p-tert-butylphenol-formaldehyde (50. 50, mp 14O ⁰ C) were carefully in geschmolzefcondensat (50: 50, mp 128-131 ⁰ C.) Were at the same no io state mixed together. This mixture Üäßig with 1.2 parts of p-Phenylphol (mp. 169 ⁰ C) in was then solidified by cooling and pulverized, mixed molten state with each other. The powdered mixture was in the ball mill at this point, the weight ratio of the 2 hours with 100 parts of white spirit and 3 parts of both materials was 87:13; this mixture was blended with cyclized rubber. The particle size then solidifies and pulverizes by cooling. 15 of the pre-mixed material was phenolic Further, the pulverized mixture in an ig after the treatment in the ball mill for about 3 to ball mill for 3 hours with 10 parts of a 20% ^er * 5 microns.
Solution with phosphoric acid esterified starch and _T ,

Treated 70 parts of water. Component B

20 10 parts of crystal violet lactone were component B _{with 20} parts of white spirit and 0.5 parts of cyclized for 3 hours

Treated 10 parts of crystal violet lactone and 10 parts of benzoyl rubber in the ball mill. The partial leukomethylene blue were 2 hours with 10 parts size of the dye was after treatment in 20% solution with phosphoric acid esterified starch of the ball mill about 3 to 5 microns,
and 70 parts of water mixed. 25 100 parts of component A and 20 parts of

75 parts of component A and 15 parts of component B were mixed evenly with one another. Component B was mixed evenly with 2.7 parts. This suspension was then mixed on one side of styrene-butadiene copolymer latex of a solid paper of glassine paper of 40 g / m ² in a layer content of 50%. Then the finished thickness of 5 g / m ² , based on dry weight, suspension was applied to one side of a base ^^ pier of a 3 °. The coated sheet was then applied at a weight of 50 g / m ² at a thickness of 5 g / m ^s , under a nip pressure of 12.5 kg / cm ² dry basis. The coated sheet is supercalendered.

was then under a nip pressure. The recording sheet obtained became the same

of 12.5 kg / cm ² supercalendered. Way, as tested in Example 1, and the

The obtained recording sheet was then obtained in the same results as in Example 1.

1 sheet of drawings

Claims (8)

Condensates and the monomeric substituted claims: Phenols are suspended and applied as premixed small solid particles. 1. Record sheet. in which as a result of the
Applying reactive contact between the 5th color-forming components causing ul- ultrasonic vibration energy a visible image
arises, consisting of a basic arch and a consisting of color-forming components The invention relates to a recording sheet, Layer of leuco dyes and an acidic io in the case of which as a result of the action of a reactive Component that has at least one phenol compound contact between the color-forming components fertilization contains, characterized thereby, causing ultrasonic oscillation energy net that a combination visible image is created for the acidic component, as well as a method for nation of polymeric phenol-aldehyde conds- making the bow. seeded and monomeric substituted phenols 15 label-forming systems in which a of the general formula ~ electron donor-acceptor reaction between ba sic dyes and monomeric phenols OH color formation is exploited, e.g. B. heat sensitive I or pressure sensitive recording systems 20 bekanni. In these systems the color-forming I- the components from basic dyes and V monomeric phenols, which on reactive contact ^ _R together to form a visible color react, making contact by applying in which R is an alkyl group with 4 to 20 C-25 heat or pressure with or without the presence of one Atoms, an aralkyl group, a substituted solvent is achieved. The one described here Aralkyl group, a phenyl group, a substi-reactive contact means that the molecular distance tuated phenyl group or a cycloalkyl group between electron donor and electron acceptor means, is used, the weight being small enough that a fawning reaction The ratio of polymeric phenol-aldehyde condensates takes place through the release and acceptance of electrons Aten to monomeric substituted phenols in the can. An example of such a known one The range is from 90:10 to 10:90. Recording system is in the Australian patent 2. Recording sheet according to claim 1, written in 403 733; it's about characterized in that the color-forming a heat-sensitive recording material, beKomponenten in the form of a coating layer on top of a carrier sheet which is lined with crystals Surface of the base sheet applied violet lactone and a phenolic material that are. is solid at room temperature, but at normal 3. Recording sheet according to claim 2, since the thermograph temperature is liquid and / or through characterized in that the polymeric phenol vapor is applied. They are experiments under aldthyd condensates and the monomeric substitutes have been taken to monomeric pnenols such as 4-tertiary ituates Phenols are solid at room temperature, butylplu-nol, 4-phenylphenol, \ -naphthol, 4,4'-isosich abpr at a temperature between 90 and nropylidene-diphenol etc. as phenolic materials Liquefy at 200 C. to use. 4. Recording sheet according to one of the prior A pressure-sensitive recording material going claims, characterized in that 45 is also in the earlier application P 21 27 852.4 the polymeric phenol-aldehyde condensates and proposed which one Entdie on a carrier monomeric substituted phenols in the winding layer. the clay and at least one phenolic coating layer contains as an individual small solid compound. The paint particles used are present. substances are enclosed in microcapsules on the 5. Recording sheet applied to one of the front 50 carrier surface and not with the going claims, characterized in that acidic components, d. H. Clay and the phenolic polymeric phenol-aldehyde condensates and compounds, in conjunction. Only after destroying the the monomeric substituted phenols as pre-capsules by the action of pressure becomes the contact mixed small solid particles in the upper layer between the dyes and the acidic component layer are present. 55 th manufactured. 6. Recording sheet according to one of the preceding Also from German patent specification 855 406, the going claims, characterized in that the German Auslegeschrift 1 247 348 and the German the coating layer is a calendered smooth upper laid-open specification 1 934 457 go pressure-sensitive has area. Recording materials. As an acidic compo- 7. Method of making the recording component is given in the publications either clay A bow according to any one of the preceding claims, alone or in conjunction with a polymeric clay characterized in that the color-forming phenolic component proposed or, as in the Components on one side of the base sheet in German Offenlegungsschrift 1 934 457, polycondensation an aqueous suspension containing a sate of formaldehyde with one or more pH in the range 6.0 to 11.0 applied 65 p-substituted phenols, with a high proportion of the Will. phenolic p-substituents attract electrons 8. Method according to, V * «p'iicli 7, thereby identified groups, z. B. are halogen groups. teichnet that the polymeric phenol-aldehyde- The invention is based on the object of providing a