DE2164512C3 - Recording sheet and process for its manufacture - Google Patents

Description

OH

Condensates and the monomeric substituted phenols as premixed small solid particles Be probed and applied.

in which R is an alkyl group with 4 to 20 C- " Atoms, an aralkyl group, a substituted aralkyl group, a phenyl group, a substituted one Phenyl group or a cycloalkyl group means, used w.rd, where the weight ratio from polymeric phenol-aldehyde condensates to monomeric substituting phenols in the The range is from 90:10 to 10: W.

2. Recording sheet according A.ispruch 1, characterized in that the color-forming components in the form of a coating layer applied on Ciner ^P surface of the base sheet

"'S" recording sheet according to claim 2, characterized characterized in that the polymeric phenol-aldehyde condensates and the monomeric substituted phenols are solid at room temperature, but at e.ner temperature / between 90 and

^2Q T record sheet according to one of the preceding claims, characterized in that you polymer !; Pheno.-a.dehyde condensates and the monomeric substituted phenols in the _1S individucHc kicinc KtT Frlinduna relates to a recording sheet,

Uie «nnuui's of _the action of a reactive

in the case of the m ^ ^ _{color-matching} components

"" "JJ" ^ Ultrasonic vibration energy a

^ver . ^u. ^ i, J55 _ents trht and a method for visible BJD entstem,

'S at which one

^ / JSÖr.A ^ eptorReaion between base Dyes and monomeric phenols is used for color formation, z. B. heat sensitive «; or pressure sensitive recording systems smd known. In these systems there are the Farbbüdenden Components from basic dyes unu mononie.cn phenols, which on reactive contact react with each other to form a visible color, contact being made by the application of Warmer pressure with or without A — J ™ Center of solution * "re ^ molecular distance

reakt.ve Kon ^ means _{Eliklronenakzeplür}

^ ™ Πο that a color-forming reaction

¹ J ¹ h F-ktronenaboabe and -absorption take place by ^ tronenabgaDe _{like bckanntcs}

can Eη Be.sP ^ ^ur _austra metallic patent

^ ÄJfTSieln: it is about step 4UJ / JJ dc scm nuncsmal eri al loading

em w ^ mesensitive recording mau

standing from a 'J ^ gcrbU -J ^ S _c Ha ", ^^ ί ^" ^ i normal

Λ5JSSShO _1n , ,,, C, one that "™ -g = hciKlcnAn _S priirfic.dadun.-l, _s ek = nn" ichnc ₁ .dal) Si = polymeric phen "l-, ddel, _y dK,> ™ de " _SM e _u " d Thermograph temperature f

steam, ^ ufgebrac sL ^^^^^ Butylphenol 4-Phcn> IpI ₁ 1 I. NP "J ^ ^ propylidcn-diphcnol etc. as ρΙκηοΙ.,. Ικ" SSsensitive record, sma.criaU is also in the al ^ ren ' ^Λΐ ^ " ^π ^ ^""j; ■ V ^ battered which
wickU.rsthicni.uit. ^ll iv deten I-irb-

™ dor

acidic ^K " ^m l"'«"»"
jertadu, * V b

"!""The claims, dadurd, ₈ ckn, n _{Ä |} cl, ", dali die Ob ^ u ₈ SSd ₁ M ₁₁ cnc knh.ndr, =" = gU ... = upper, ech = "d ™ U4 lindid.c""->". _{As sa} " _rc Κ ,,,,, ρ ,,

dc _s

, U _; v, approx

Components «ι.Γ one side of the base arch in

α »έτι ^ = _honorable

liesserles recording material / u schnfTcn. in which a deeply colored image is generated on the surface of the recording sheet by ultrasonic vibrational energy which is applied directly and locally to the surface of the image.

According to the invention, this object is achieved by means of a recording sheet mentioned at the beginning tfus 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

OH

in which R is an alkyl group with 4 to 20 carbon atoms, an aralkyl group, a substituted aralkyl group, denotes a phenyl group, a substituted phenyl group or a cycloalkyl group, is used, wherein the weight ratio of polymeric phenol aldehyde condensates to monomeric substituted Phenols in the range of 90:10 to 10:90.

Whereas the reference painting disclosed in the publications mentioned at the beginning If the material is pressure-sensitive, the image is transmitted through the system according to the invention Ultrasonic vibration energy generated. I have shown that in the publications mentioned mentioned substances neither alone nor in combination to solve the task set according to the invention can be used. Ultimately, the main difference is that the pressure-sensitive Recording systems which have dyes enclosed in microcapsules so that 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 has a number of advantages. Fs is free mechanical from F.influß inertia: a C'bertragungssystem as phoioelektronischc (transmission is not required, and vice versa, there make small changes to the recording apparatus, the Finfachheit in the design and the high Fmplindlichkeit possible to Syslem in ^{high-speed!..} Copy machine !!. I use acsimilc-ssstem etc.

The colorless color-forming compounds used for the Frfinduni! suitable si ml, close compounds with l.aetonrings. l.actamringen and Sultonringen. which are colorless in themselves or of a light color, themselves but after contact with acidic materials / u a Implement color. Such connections are common as »l.cuko-Vecbinduiigen« or · Ι eukn-Farhstoffe « denotes: the compounds listed below or their nominal ions are not referred to as Examples for l.euko-f arbsloftV uehrachl:

3,3-bis (p-DimethylaminophenylW> -dimethyl-

aminophthalide,

(Kristalhioletilacton),

3,3-bis (p-dimethylaminophenyl) -4,5,6,7-tetra-

chlorophthalide,

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

y-xanlhenyl-o-benzoic acid lactam,

(Rhodamine-B-Iaclam),

3,3-bis (p-dibutylaminophenyl) phthalide

I malachite green lactone),

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

3,3-bis (p-dimethylaminophenyl) -6-aminophthalide,

3,6-bis (diethylamino) -9-hydroxy-9-xanthenoyl-

benzenesulfonyl sultone,

2- (2 ', 4 \ 6'-trimethylphenylamino) -8-diethyl-

amino-3,4-benzofluoran,

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

3-diethylamino-6-methylchloronuorane.

Typical examples of polymeric phenol-aldehyde condensates are p-phenylphenofformaldehyde condensates, p-terL-butylphenol-L-naldehyde condensate, p-octylphenol-formaldehyde condensate, phenol-formaldehyde condensate, Cresol-formal-hydrogen condensate,

Phenoi-acetaldehyde condensate etc. Typical examples for monomeric substituted phenols are p-phenylphenol, p-tert.-butylphenol, p-octylphenol, p-Benzylphenol, 2,2-bis (4'-l hydroxyphenyDpropane, p-Benzyl-phenol, 2,2-bis- (4'-hydroxyphenyl) -sec-iso-

butane, p- (4'-chlorophenyl) phenol, cyclohexylphenol, etc.

The preferred polymer used in the invention Phenol-aldehyde condensate is a material commonly referred to as "novolak," which is a

has free hydroxyl group, fusible in the absence of a crosslinking agent and insoluble in water is.

One of the main features of the drawing sheet according to the invention is that the polymeric phenolaldehyde condensates and the monomeric substituted phenols are used in the color-forming components within a certain (weight ratio, namely in the ratio of ¹ K): 10 hi -H): 90 will.

This relationship is critical, as will emerge from the examples given later. F.s is found been that the crtindungsgcmäl.l used Components have a very high chemical activity in the color formation reaction. This one found FfTckt or Advantage is appropriately used in the above-mentioned recording system: the recording server would not be possible with the usual recording sheets. Monomers Phenology «uler polymer l'heiiol-aldchyd condensate

ΓιΓ) sale ζ. B. can do everything, i. not in combination together.! ie> elzt. not with failure in that Logging system must be applied

Preferably, the farhhildenden Koniponcnlen in I orm a (iber / ugscliicht on a Oberlliulic ties (iiiindbogens appropriate. For the \ rlinduni! Üeeii'nele polymeric phenol aldrhyd-Koncns.He and monomeric substituted phenols are those in st L-Raumlempeialiir are, but at a temperature between ¹ K) and 200 (liquefy Fs is, however , note that the melting point of the phenols and f'hcnol-aldi.hyd-koneusale is not an insoluble substance.

The polymeric phenol-aldehyde condensals and the

monomeric substituted phenols are preferred in the Oberzugschiehl as individual small I eslstolT -partikcln before, which are mixed according to a particularly preferred embodiment.

The cover layer is preferably a calendered one smooth surface. The present invention also relates to a method of manufacture of a recording sheet, which is characterized in that the color image components one side of the base sheet in a standard aqueous suspension a pH in the range of 6.0 to 11.0 can be applied. The polymeric phenol-aldehyde condensates are thereby and the monomeric substituted phenols, preferably as premixed small solid particles suspended.

The above-noted advantages of this invention will be apparent from the examples given below and the drawings even more clearly.

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 cases it is useful that the color-forming Components are applied to the base sheet closely together so that the color-forming components easily absorb a locally applied energy. To meet these requirements, the base sheet is on one side with a suspension, which the Fcststoffparlikcln from color-forming Contains components, broken up .. The method given above is particularly suitable for Manufacture of a recording sheet for the above-mentioned recording system. The solvent, which is used in the non-aqueous suspension 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, isoparaffinic hydrocarbons and cycloparaffinic hydrocarbons. However, ordinary aqueous systems are more preferable 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 or a binding agent can be added to the suspension, such as e.g. B. Polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose. Casein, starch, synthetic latices and the like, through which the solid particles color-forming components are glued to the base sheet. Paper or synthetic polymers forming arcs can be used. However, paper is preferred because it is on is most economical and can be easily deformed.

One of the improvements in the manufacturing process of the invention is the adjustment of the pH the aqueous suspension containing the color-forming components 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 as well Urea and thiourea. Adjusting the pH helps keep the Avoid subsoil, which is common during storage «; or recording occurs. One A further improvement of the process according to the invention is that the coated and dried sheets of a calender treatment, ζ. Β with a Supcrkalatulcr, is subjected. if the surface read the recording sheet through this Treatment is smoothed, it can get energy from one Pick up the recording pen or a needle evenly This treatment also makes the top layer stronger because the top layer is mechanical \ can be forged. This saves the amount of glue in the suspension, and

ίο the mutual contact of the color-forming components is made easier. Line further improvement is the production of solid phenolic particles Material by uniformly mixing the polymeric phenol-aldehyde condensates and the monomeric substituted phenols in the molten state and cooling to the solidification point, whereafter is pulverized. The phenolic parallels obtained in this way are used in the color-forming reaction more activated. The particle size of the phenolic

ao materials according to the invention should be between 1 and 5 microns. The size is not limited to this area, but can be adjusted according to the required screen resolution can be set arbitrarily.

In the following, reference is made to the figures

a5 nonimcn, \ on which show

F i t. 1 and 2 an exemplary device, which reproduces the recording system improved according to the invention,

F i g. 3 shows the results obtained in the examples given below.

In Fig. 1, electrodes 11 are on the opposite sides a ceramic piezoelectric substance 12 attached, at the end of which a pen 13 is connected is. This pen can be made from piano wire 700 microns wide and 15 microns thick and a length of 3 mm. Its edges come into light contact with the surface of the current recording sheet 14, e.g. B. under a pressure of 1 to 6 g. When AC signals are applied to the ceramic piezoelectric substance 12 from an alternating current source 16, this causes a continuous expansion and contraction of the substance 12, which the pen 13 vibrated according to the frequency of the AC signal, and the vibration energy is transferred to the surface of the recording sheet 14. Although the oscillation frequency is preferable is between 10 and 100 kHz, it is not restricted to this range, but can accordingly the resonance frequency of the ceramic electrical substance that is used can be determined. the 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, the line density of the pen, etc. The vibration energy causes the actual contact between the color-forming components and. as a result of this, eir visible image on the surface of the recording sheet generated according to the pattern of applied alternating electrical signals. The ir F i g. The device shown in FIG. 2 has a multiple writing pen 15. consisting of a number of writing eyelets donate 15 '. each of which has a line density of 3 to 5 lines per mm and for producing each; Tvpenmusters is practically applicable.

The invention should now be based on the following

Examples that do not represent a restriction: eschriebeii become. In the examples, the Quantities given in parts by weight.

example 1

13.5 parts of p-phenylphenol (melting point 169 ^° C.) 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 hydroxypropyl chloride (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.

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

S-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 of styrene-butadiene copolymer latex having a solids content of 50% and 2.8 parts of a 10% strength potassium hydroxide solution. The pH of the final suspension was about 11.0. This suspension was then applied to one side of a base paper weighing 50 g / m² in a thickness of 5 g / m² dry weight. The coated sheet was then supercalendered with a roller pressure of 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

Each of these examples were the same as Example 1 except that the p-phenylphenol and the polymeric p-phenol-formaldehyde condensate in the following weight ratios were used

8th 5 p-phenyl
phenol Polymer Weight
relationship (Weight P-phenyl
phenol-
formaldehytl
condensate parts) (Weight ο Example 2 .... 12th parts) 80:20 Example 3 .... 9 3 60:40 Example 4 .... 7.5 6th 50:50 Example 5 .... 6th 7.5 40:60 Example 6 .... 3 9 20:80 , ₅ Example 7 .... 1.5 12th 10:90 Control 13.5 example A .. 15th 100: 0 Control - example B .. - 0: 100 15th

Control Examples A and B given above were the same as Example 1 except that the p-Phenylphenol (melting point 169 ° C) and the polymeric p-Phe-

a5 nylphenol-formaldehyde condensate (50:50, melting point 140 ° C) were used individually, namely in the preparation of these control examples, each of the Materials given above are used on their own as small particles and with the other components mixed in the ball mill.

The products obtained from the examples given above and the control examples, i.e. H. the Recording sheets were checked using the apparatus shown in FIG.

Any recording sheet obtained according to any of the examples and control examples given above was subjected to a recording test and using the device of FIG. I subjected: Ultrasonic energy generated according to the alternating electrical signals of 100 volts (effective), a frequency of 30 kHz was applied locally by the pen on the surface of the recording sheet, running at a speed of 50 mm / minute. In addition, the The surface of the recording sheet was scanned with a hot pen at a temperature of 200 "C The results of the tests are shown in FIG. 3 given again. The dashed lines in FIG. 3 pointers the colored image created by ultrasonic vibration * energy, and the two lines on the de on the right side are the colored pictures that were created by the hot pen.

The in F i g. The results given in 3 clearly show that the use of p-phenylphenol (Kon troH example A) and polymeric p-phenylphenol formaldehyde condensate (control example B) respectively is not applicable to the recording system described.

B e i s ρ i e I 8

This example was the same as Example 1, except that 7.5 parts of small solid particles vo p-Phenylphenol and 7.5 parts of small solid particles of polymeric p-phenylphenol-formaldehyde condensation sat without premixing with 0.4 parts of anionic net by means of, 0.5 part of hydroxypropyl cellulose and 59.8 T < len water in the ball mill to produce component A were mixed. The receive

Recording sheet was tested in the same manner as in Example 1 and the same results were obtained obtained as shown in fig. 3 for example 1 shows.

Example 9
Component A

8 parts of polymeric p-tert-butylphenol-formaldehyde condensate (50:50, melting point 128 to 13TC) were evenly mixed with one another in the molten state with 1.2 parts of p-phenylphol (melting point 169 ° C.). At this point the weight ratio of the two materials was 87:13; this mixture was then solidified by cooling and pulverized. Further, the pulverized mixture in a ball mill for 3 hours with 10 parts of a 20 ° / ₀ solution with phosphoric acid esterified starch and 70 parts of water was treated.

Component B

10 parts of crystal violet lactone and 10 parts of benzoyl leucomethylene blue were 20 ° / ₀ by weight solution with phosphoric acid esterified starch and 70 parts of water, mixed for 2 hours with 10 parts.

75 parts of component A and 15 parts of component B were evenly mixed with 2.7 parts of styrene-butadiene copolymer latex having a solids content of 50%. The finished suspension was then applied to one side of a base paper weighing 50 g / m ² in a thickness of 5 g / m ² , dry basis. The coated sheet was then supercalendered under a nip pressure of 12.5 kg / cm ^2.

The recording sheet obtained was then tested in the same way as described in Example 1, and the same results were obtained.

Example 10
5

Component A

25 parts of p-Phenyiphenol and 25 parts of polymeric p-phenylphenol-formaldehyde condensate (m.p. 169 ⁰ C.) (50: 50, mp 140 ⁰ C.) Were thoroughly mixed together in a molten state. This mixture was then solidified by cooling and pulverized. The pulverized mixture was mixed with 100 parts of white spirit and 3 parts of cyclized rubber in the ball mill for 2 hours. The particle size of the premixed phenolic material after ball mill treatment was approximately 3 to 5 microns.

Component B

ao 10 parts of crystal violet lactone were cyclized with 20 parts of white spirit and 0.5 parts for 3 hours Ball milled rubber. The particle size of the dye after the treatment was in the ball mill about 3 to 5 microns.

100 parts of component A and 20 parts of component B were evenly mixed with one another. This suspension was then applied to one side of a glassine paper of 40 g / m ² in a layer thickness of 5 g / m ² , based on dry weight. The coated sheet was then supercalendered under a nip pressure of 12.5 kg / cm ^: .

The obtained recording sheet was tested in the same manner as in Example 1, and di < the same results as in Example 1 were obtained.

1 sheet of drawings

Claims (1)

Patent claims: 1. Recording sheet in which as a result of the action of a reactive contact between the color-forming components, ultrasonic vibrational energy causing a visible image is created, consisting of a base arch and one consisting of color-forming components Layer of leuco dyes and an acidic component, which is at least one phenol compound contains, characterized in that a combination for the acidic component of polymeric phenol-aldehyde condensates and monomeric substituted phenols of the general formula