DE1949212A1 - Projection system - Google Patents

Description

Dr. rer. nat. Horst Schüler oFrankfurt / Main ^ Sept. 26, 1969

PATENT ADVERTISER Niddastraße 52 Dr. Sat / Tue / Hö

Telephone (0611) 237220 Postscheck-Account: 282420 Frankfurt / M. 1 Q λ Q O 1 O Bank account: 523/3168

( \ J * t ν? L I L Deutsche Bank AG, Frankfurt / M.

1276-38-AE-18O

GENERAL ELECTRIC COMPANY

1 River Road Schenectady, N.Y./U.S.A.

Prοj ect ion sys tem

The present invention relates to projection systems of the electronic type. In particular, it relates to projection systems that have an internally conductive piston and an inside piston Have deformable medium, the resistance of which decreases with decreasing thickness in the medium, the medium being the polymeric Is the reaction product of benzyl alcohol and aromatic hydrocarbons.

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In commonly assigned US Pat. No. 2,943,147, a projection system of the above type using a deformable medium having a high resistance and on responds to a velocity modulated electron beam. In general terms, the projection system shown in Figure 1 of the drawing has an evacuated glass jacket 10, which contains a cathode ray generator 11 for generating an electron beam 13 and it in a right-angled Deflects grid over the surface of a translucent deformable medium 15 which is within a part 17 of the transparent piston is located. Figure 2 shows an enlarged View of this part of the arrangement. The beam 13 is preferably speed controlled with the aid of a television signal, that to the deflection device, not shown in the cathode ray generator 11 is applied. The deformable medium 15 has a central part 19 of reduced Thickness equal to that by the electrons of a conductive coating 21 on the inner surface of the piston part 17 attracted electron beam 13 caused grid surface coincides. These same electrons are calling deformations emerge in the surface of the deformable medium 15, the extent of these deformations being a function is the number of electrons deposited by the beam 13 at the various points on the surface of the medium 15. The extent of these deformations is therefore a function of the modulated electron beam 13.

The deformations on the surface of the medium 15 are for. Deflection of light from a source 23 in an optical System used which contains a lens 24, which an image of the light source 23 via a line and slit system 25 on the Surface of the medium 15 maps. Another lens 29 forms the slots of the system 25 on the lines of another Line and slot system 31 from when there are no deformations on the surface of the deformable medium 15 are. However, any deformations on such a surface refract the light passing through, so that

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it passes through the slots in the system 31 with an intensity that corresponds to the extent of the deformations and thus the The size of the applied modulating signal, for example a television signal, corresponds. That through the system 29 light passing through is made through a projection lens 23 imaged on the screen 35 with the aid of a mirror 37.

In the system shown, it becomes a conventional deformable at 15 Medium used, then the average charge density on the medium 15 causes a force that the surface tension of the excess medium outside the grid area overcomes and the part 19 of the medium 15 on Reduces zero thickness. Under such conditions, no deformations can be formed and the system becomes inoperable until the medium is replaced. The aforementioned patent shows that when the medium has the property has to decrease in its resistance with decreasing thickness, the part 19 does not change under the pressure of the charges is reduced to zero thickness, but maintains a thickness which is a function of the size of the charge density on the surface of the medium 15 is. As the resistance decreases, the time constant for the passage of leakage current becomes of the surface of the deformable medium 15 is reduced to the underlying conductive coating. This leads to a Increase in leakage current, reducing the charge density on the Surface of the medium 15 is reduced and the pressure is weakened somewhat. Eventually it becomes a state of equilibrium achieved in which the pressure of the charges on the surface of the medium equals the pressure from the surface tension on the excess medium in the vicinity of the grid and the thickness is maintained at this equilibrium state. The charge density on the The surface of the medium never decreases to zero because of such a leakage process, since it is continuously through Electrons from the beam 13 is replaced.

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The compositions described in the above-mentioned US Pat. No. 2,943,147 as being suitable for the medium must be transparent, withstand electron bombardment without noticeable decomposition, and have a viscosity of about 100 to 50,000 ^{at the operating temperature (between about 25 and 150 ° C.)} cSt, the deformable mass must not decompose the conductive coating. The medium must also have a specific resistance which varies within a range of about 10 to 10 ohms / cm, the average resistance at the stable thickness being about 10 ohms / cm.

The deformable media or liquids mentioned in the aforementioned US patent include beeswax, methyl silicone oils, methyl silicone oils containing up to 5% phenyl silicone, methyl phenyl silicone which have an average of about 2 methyl and phenyl radicals per silicon atom, in which the molar ratio of the methyl groups to the Silicon atoms larger than zero and smaller than 2 is among other things. However, it has been found that these deformable liquids are not as stable as would be desired, since under the influence of an electron beam the deformable medium or the deformable liquids tend to increase in their viscosity and the viscosity increases with prolonged use in the projection system, as described above, to a point at which gel particles form, and the deformable medium finally gels. Obviously, the apparatus can no longer be operated with a gelled medium that does not decrease in thickness.

This partially addressed the disadvantages of the above media fixed that typically very specific Friedel-Crafts reaction products from benzyl chloride and aromatic substances, such as. B. biphenyl, naphthalene, toluene and benzene =, including substituted compounds of this type. In a typical way

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such projection systems are for example in the US U.S. Patent 3,317,664 relating to media which is the reaction product of benzyl chloride and naphthalene in U.S. Patent No. 3,317,664 U.S. Patent 3,317,665, the Friedel-Crafts reaction products from benzyl chloride and biphenyl relates, and in US Pat. No. 3,288,927 which consists of such reaction products Benzyl chloride and benzene, toluene, etc. are described.

Although the materials obtained by the disclosures of the aforementioned patents, a desirable one and exhibited long lasting useful viscosity, it was found to be under continuous electron bombardment at operating conditions there was a tendency for a substrate to form in the medium which reproduced the sharpness of the Font diminished. With continued. use the substrate will develop to the point where the system's ability to reproduce images is limited.

From the above it follows that there is a need for materials which are used as medium 15 can and which are subject to the radiation effects of the electrons of the beam 13 not only by a long-lasting and useful Characterize viscosity, but at the same time against substrate formation or the formation of materials within the medium are resistant, which reduce the writing ability of the medium or even the medium in this respect completely to make something useless. The present invention therefore primarily has materials which can be used as media, the objects under Irradiation show the desired and long-lasting viscosity and those under such irradiation against formation of substrates or products are resistant, which reduce their usefulness for the production of images.

It was surprisingly found that certain polymeric reaction products from benzyl alcohol with aromatic hydrocarbons using acidic material as a catalyst.

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meet the properties mentioned above and a deformable Medium result in a long service life and other advantageous properties together under the operating conditions with a resistance to the formation of substrates or inclusions, which shows its ability to Decrease picture reproduction. -

The following is a preferred embodiment of the present Invention described in detail with reference to the drawing, in which:

Figure 1 is a schematic representation of the present projection system including medium 15 and

FIG. 2 shows a detailed reproduction of the medium 15 in its immediate vicinity.

Although benzyl alcohol, preferred as a hydroxyl-containing material, Is used, other related materials, including alkyl and aromatic substituted benzyl alcohol, such as. B. methyl and benzyl, phenyl and naphthyl substituted Materials i.a. Find use.

The useful substituted or unsubstituted aromatic hydrocarbons include benzene, toluene, xylene, naphthalene, Tetralin, dihydroanthracene, phenanthrene, biphenyl, terphenyl, Cyclohexylbenzene, ethylbenzene, propylbenzene, t-butylbenzene, Benzyltoluene, diphenylmethane and others. as known to those skilled in the art are. Mixtures of the aforementioned materials can also be used.

A preferred one used in the context of the present invention The condensation catalyst is polypuonphoric acid. Others useful acidic materials are sulfuric acid, p-toluene, sulfonic acid, Phosphoric acid, phosphorus pentoxide, hydrogen fluoride, alkane sulfuric acids, such as. B. methyl, ethylsulphuric acid etc., acidic cation exchange resins, such as. B. Dowex 50

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sulfonated styrene divinylbenzene and Amberlite IR-100 or sulfonated phenol-formaldehyde, etc. Also useful is a synthetic fuller's earth known as Celkate and the adsorbed sulfuric or phosphoric acid contains. Celkate is a synthetic magnesium silicate that manufactured by the Johns-Manville Corporation.

In general terms, for the production of the media according to the invention preferably about 1.0 to 4.0 moles of benzyl alcohol are used per mole of aromatic hydrocarbons. Generally, from about 0.1 to about 10 moles of benzyl alcohol or related materials per mole become more aromatic Used hydrocarbon.

Although the amount of condensation catalyst required for the desired reaction between benzyl alcohol and toluene, depending on the activity of the particular catalyst system, there is a useful mole percentage range for polyphosphoric and sulfuric acids, the preferred catalysts of the present invention, between 0.1 to 10 mol% per mol of benzyl alcohol, with a preferred range between 0.8 to 1.2 mol% of benzyl alcohol lies. For those skilled in the art, the determination of the effective amounts for other catalysts is the same as that described here Type possible.

The invention is illustrated in more detail below with the aid of the examples described.

example 1

One with a stirrer, thermometer, gas inlet tube, and one Constant volume dropping funnels of equipped flasks were purged with nitrogen with 4,360 g of polyphosphoric acid charged and heated to 100 ° C. A mix of 3260 ecm Benzyl alcohol (32 moles) and 1060 ecm (10 moles) of toluene were added dropwise to the heated polyphosphoric acid with stirring admitted. The temperature showed the tendency during this

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To increase the addition, so that the rate of addition and the heating or cooling required was such that a temperature of about 140 to 145 ° C. was maintained, the addition being complete after 4 hours. The mixture was further stirred for another hour at 140 to 145 ° C heated, then cooled to about 115 ⁰ C, followed by 3 1 of water were added. After separating the layers, the oil layer was washed with a further 3 liters of water, and the water was separated off and discarded. 1 l of toluene was added to the oil layer and the solution was washed out with 500 ml of aqueous sodium hydroxide solution (20% by weight). The oil layer was further washed neutral with water, then dried with anhydrous potassium carbonate, stirred with Celkate and potassium carbonate, the filter cake rinsed with toluene, the rinsing water added to the oil, which was then treated with charcoal and then with Celite, a finely divided silicon dioxide. The Celite-charcoal mixture was then filtered off, washed out with toluene and the oily liquid was distilled to remove the toluene. The remaining oily liquid was then distilled and gave the fractions listed below in Table I:

Vessel temp.
PcJ Table I. fraction
Cg] pressure
. in Hg] fraction 133-138
170-244
227-287 Steam temp.
L ° c] 389.0
142.9
250, 8 60 to 1
<1
2.7 2
3
4th 104 (max.)
51-178
160-185

The residue remaining in the vessel was about 2070 g. This material was placed in a short path still transferred and at a temperature of about 164 to 404 ° C

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distilled. This distillation yielded about 1070 grams of crude distillate, which continued to be based on that summarized in Table II below Way was distilled.

Vessel temp.
L ° d Tabel II Viscosity of the
Materials in
Vessel passing
fraction 100-195
140-182 pressure
[μ Hg ^ distillate
W. 490 cSt (50 ° C)
639 cSt (50 ° C) 1
2 14th
10 "" ⁵ 69.8
75.7

The material remaining in the distillation vessel was divided into two Shares divided and treated as follows:

A 323 g aliquot was poured into a 1 liter short-path still entered and 9 g of substance at 118 to 148 ° C and

- *> -7

distilled off in a vacuum of 1.2x10 * to 2.2x10 Torr. The material remaining in the still had a weight of 220 g and was then with adsorption materials that / percent by weight Norit contained and activated carbon or charcoal, and 0.5 wt.% Celite treated, after each addition for one hour at 50 ° C or one was stirred for half an hour. After the liquid had been filtered off, 2% by weight of Celkate were added to the filtrate, whereupon was stirred at 50 ° C for one hour. The filtrate was treated with 1 wt.% Celite, with one hour at Stirred 50 ° C and the liquid obtained was filtered off through a filter of 0.45 μ permeability. The remaining Liquid weighed about 200 g and had a viscosity of 813 cSt at 50 ° C. The material was suitable as Recording material and, as will be shown later herein, was particularly resistant to formation of harmful substrate material.

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The after separation of the above-mentioned aliquot portion From 323 g of remaining liquid, as listed in Table III below, was distilled:

Tabel III distillate
Cg] viscosity
CcStJ [Temp3 Passing
fraction Vessel temp.
[ ⁰ C] pressure
Gt HgI 80.2
17.0
504 997 (50 ° C)
Resin, high
viscosity 1
2
3 159-206
135-175
178-322 ΙΟ " ⁵
ίο " ⁶
ίο " ⁶

The product of 504 g had a viscosity of 1048 cSt at 50 ° C. and was suitable as a recording material.

Example 2

Example 1 was repeated with the modification that a 20% strength potassium hydroxide solution was used as the alkaline wash water with a 20% solution of sodium sulfate to remove the alkali. The remaining liquid was distilled according to Table IV:

^ Vessel temp. Table IV pressure Weight of fraction Steam temp. Distillate L ° c] Qi Hg] [G] until 209 [° c] . Atm. not Gewoj 1 up to 200 up to max 10-15 mm 0 2 106-198 42-10 412 3 183-248 68-91 4-10 192 4th 240-288 61-174 10-28 150 5 156-185

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The remaining 1820 g of material were in a short path still at 175 to 379 ° C and a vacuum of 1 to 290 μ distilled and gave 876 g of a crude product which had a viscosity of 390 cSt at 50 ° C. This material was further distilled as shown in Table V below:

Table V pressure Passing Temp, im fraction Vessel [μ Hg] C ° c] 30-9 1 120-195 ~ 10 ~ ⁷ 2 172-173

Distillate remarks

Lg]

91 viscose. 541 cSt at 51.1 ° C

93 Visc. = 911 cSt at FO ⁰ C Quantity = 660 g Refractive index = 1.6323 at 25 ° C

The residue of 660 g remaining after the above-mentioned distillation had a vapor pressure of 3.5 × 10 Torr at 50 ° C as measured by the effluent method. After a treatment with an adsorbent similar to that in Example 1, the remaining liquid had a liquid Weight of 600 g with a viscosity of 911 cSt at 50 ° C.

Example 3

Example 2 was repeated and gave 768 g of an end product which had a viscosity of 868 cSt at 50 ° C., a vapor pressure of 2.3 × 10 " ¹¹ torr at 50 ° C. and 9.0 × 10" ⁴ torr at 25 ° C., the Refractive index was 1.6320 (25 ° C). This material was useful as an imaging medium.

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Example 4

Example 2 was used in every respect with the exception of short path distillation repeated. In the present case, only about 60-70% of the amount normally used was Distillates are used for the production of the final liquid. The equivalent vessel residue, that of the five more volatile after distillation, was correspondingly Fractions of Example 2 remained, subjected to a short path distillation and gave 603.8 g of material such as it is listed in Table VI below:

Table VI

fraction Vessel temp. Steam temp. pressure weight C ° c] C ° c] Tu Hg] C * I 1 up to 200 110 Atm. 664 2 131-200 4P 10-15 66 3 130-196 95-100 about 80 382.3 4th 199-228 81-192 approx. 14 325.4 IT. 153-271 4 ~ 3 603.8

Stripping and slurrying fraction 5 in a manner similar to the preceding examples gave a final product which weighed 347 g, had a refractive index of 1.6281, a viscosity of 1065 cSt at 40 ° C., a vapor pressure of 3.5 × 10 " ¹² Torr at 50 ° C and Ι, Ο-ΙΟ" ¹⁵ Torr at 25 ° C. This material was useful as a recording liquid.

Example 5

This example demonstrates the practice of the present invention using a mole ratio of 1.6 moles Benzyl alcohol to 1 mole of toluene. It was based on the example 1

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described manner using 1415 g (15.4 mol) of toluene, 2657 g (24.8 mol) of benzyl alcohol and 1120 g of polyphosphoric acid made a material. After removing the acidic impurities according to the previous examples the distillation resulted in the following products:

Table VII

fraction Boiling range 6th Refractive viscosity weight 9 invention index 4th [° c] Gnm Hg] [25 ° C] IcSt at 50 ° g1 ω 1 1 40-200 (10) 1.5491 798, 1 2 129-200 (0.1) 1.5857 - 153 6th 3 200-250 (0.1) 1.5996 - 127 0 4th 250-290 (0.1) 1.6067 _ 459, 4th -Jl 98-160 (10 ~ ⁵ ) 1.6158 45 136 6th 6th 150-250 (10 ~ ⁵ ) 1.6275 305 514, 6 and 7 usable 7th 250 (10 ~ ⁵ ) 1.6373 6305 204 in the context of the present Residue in the vessel - - 660, It showed Factions ; that the show fluids was. example

This example demonstrates the preparation of a toluene-derived useful recording liquid using a ratio of about 4 moles of benzyl alcohol to 1 mole of toluene. The procedure of Example 5 was repeated using 335 g (3.9 mole) of toluene, 1660 g (15.4 mol) benzyl alcohol and 2337 g Polyphosphorsäur e. After removing the acidic impurities, the material was distilled in the manner listed in Table VIII below:

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- 14 Table VIII

fraction Boiling range Hg] Refractive viscosity 43 _ weight (30) index FS [° C] Gnm (0.1) [25 ° C] [cSt at 50 ° c] 395 [G] 1 - 42-200 (0.1) 1.5626 67.7 2 100-200 (0.1) 1.5731 - 142.6 3 200-250 (IO " ⁵ ) 1.5992 - 64.0 4th 250-290 UO " ⁵ ) 1.6026 - 101.7 5 110-125 (ΙΟ ' ⁵ ) 1.6185 26.1 6th 115-125 in the vessel 1.6173 25.4 7th ~ 125 1.6288 356.0 Residue __ 825.8

It was found that fraction 7 of the table above was useful as a recording liquid.

Example 7

This example shows the preparation of one derived from toluene Material using a ratio of about 3.2 hol of benzyl alcohol per mole of toluene, with the reaction at a temperature of 115 ° C compared to a temperature of 140 to 145 ° C in Examples 5 and 6 was carried out. The reactants used were 449 grams (4.88 moles) of toluene, 1660 grams (15.35 moles) of benzyl alcohol, and 2133 grams of polyphosphoric acid. After removal of the acidic impurities a distillation was carried out according to the following Table IX:

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Boiling range Table IX viscosity weight fraction Refractive C ⁰ C] (jam Hg] index CcSt at 50 ° qJ ω 37-200 (15) [25 ° Cj 225.6 1 130-200 (0.04) 1.5693 - 48.0 2 200-250 '(0.04) 1.6002 - 15.0 3 250-290 (0.04) 1.6017 - 124.0 4th 109-115 (IO " ⁷ ) 1.6031 - 28.9 5 129-133 (IO " ⁷ ) (fixed) 55 16.6 6th > 133 (10 ~ ⁷ ) 1.6170 317 414.0 7th in the vessel 1.6278 _ 732.0 Residue

It was found that fraction 7 of the table above was particularly useful as a recording liquid.

Example 8

This example is similar to example 7 with the modification that the original reaction takes place at a temperature of 175 ° C was carried out. After removing the acidic impurities, the material became as shown in Table below X is listed, distilled:

Table X

Fraction boiling range

[° CJ [mm Hgj

1 189-200 (15) 1.5685 2 154-200 (0.01) 1.5733 3 200-250 (0.01) 1.5930 4th 250-290 (0.01) 1.6031 If. 97-133 do " ⁵ ) (fixed)

Refractive viscous. weight

index ^
[25 ^o c] [cSt at 50 ° c] [gl

1.0 177.0

37.0 143.5

32.4

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fraction Boiling range Refractive viscosity weight index LQjljnm HgJ & 5 ° C | CcSt at 50 ° c] [G] 6th 94-118 (1O ~ ⁵ ) 1.6179 56 21.6 7th 125-130 (10 ~ ⁵ ) 1.6174 60 21.1 8th > 130 (10 ~ ⁵ ) 1.6295 395 370.0 Residue in the vessel __ _ 741.5

It was found that fraction 8 was particularly useful as a recording liquid.

Example 9

This example shows the production according to the invention of a material derived from naphthalene. A three-necked flask filled with nitrogen and equipped with a stirrer, gas inlet tube, thermometer and dropping funnel was charged with 1652 g of polyphosphoric acid which was heated to a temperature of 125 ° C. ^E ine solution of 1031,6g (8.06 mol) of naphthalene (1237 cc), 1298 g (12 mol) of benzyl alcohol were at a temperature of about. 120 ° C. to the polyphosphoric acid was slowly added over about 2 hours. The temperature of the contents of the flask rose to about 155 ° C. at the end of the addition, was kept at a temperature of about 150 ° C. for one hour, then cooled to about 50 ° C. and mixed with 1 liter of water. The acidic layer was separated and the organic phase treated in a manner similar to that described in Example 1. The material was distilled in the manner listed in Table XI below, the third and subsequent fractional distillations being carried out with a short path still. The finished product was suitable as a recording liquid.

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Vessel temp.
C ° c] Tabel Vapor pressure XI Dimensions
CgI fraction 215-352 90-221 pressure - 1 233-319 194-275 Atm. 409 2 184-320 water
beam 560 3 37-75 ιιΗε

Overflow 1 120-160

Bulk 148-270 distillation

6.5x10 ";!
1.5x10 torr

4xlO " ⁶ ₆ 494
2.2x10 "Torr

Remarks

Mainly unreacted naphthalene and toluene solvents .

Crude product, viscosity 973.4 cSt at 50 ° C

52.5 Means the removal of volatile components from the crude product

Viscosity of the product = 743 cSt (50 ° C) ₈ Vapor pressure = 7.5x10 Torr (50 ⁵ C)

Example 10

This example shows the preparation of a recording liquid using xylene as a precursor. At 3525 g Polyphosphoric acid was converted from separate dropping funnels at 90 ° C. under dry nitrogen to 1388 g (12.85 moles) of benzyl alcohol and 425.5 g (4 mol) of p-xylene are added with the proviso that about 2 drops of alcohol per drop of p-xylene were added. The addition was made over a period of 5 hours carried out at a temperature of about 110 ° C. The cooled reaction mixture was hydrolyzed with water and the organic layer twice with water, with 10% sodium hydroxide solution and again washed out with water until the aqueous extracts were neutral. During the washing process 1 l of benzene were added to reduce the viscosity of the organic phase. The separation of the solvents and the light fractions as well as the isolation of the liquid obtained from the organic phase was carried out by distillation carried out according to the following table XII:

Tabel Boiling range XII pressure lot Fraction = /] = 85-155 ° C ~ 20 mm Hg 10 g 187-50-1 150-235 ° C 0.4 mm 171.7 g 187-50-2 150-2OO ° C 2x10 mm 241.3 g 187-51-1 262-276 ° C —4
4x10 mm 246.5 g 187-51-2
(Raw product) —_ 611.5 g
(Residue) 187-51-3

The product from the above distillation was again distilled according to the information in Table XIII below, The residue was suitable as a recording liquid and had a viscosity of 1000 cSt at 46 ° C and a refractive index of 1.6237 at 25 ° C.

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Table XIII pressure lot fraction Boiling range 1.8x10 ~ ^B mm 35 g 187-55 126 ⁰ C 8x10 "mm 138.62 g 187-56-1 217-21 ° C ——— 31.44 g
(Residue) product
187-56-2 ——— Example 11

This example shows the use of sulfuric acid as a condensing agent for material based on naphthalene. To a rapidly stirred slurry of 1025 g (8 mol) of naphthalene, 1300 g (12 mol) of benzyl alcohol and 1500 ecm of cyclohexane, which had cooled to 10 ° C., 1000 ecm of concentrated sulfuric acid were slowly added over a period of 1.1 hours added, the temperature being kept between 5 and 75 ° C. The stirring was continued for a further half an hour at 5 ^° C. and then the organic layer was separated off. The fluffy organic phase was first stirred with Celkate and filtered off, diluted with one liter of benzene, again stirred with Celkate and filtered off, giving a clear filtrate. Benzene, cyclohexane, naphthalene and the light fractions were separated off by distillation as above and 797 g of crude products were isolated by distillation over a range from 147 to 300 ° C, this material having a viscosity of 587.6 cSt at 49.8 ° C and a Had a refractive index of 1.6532. This material was drawn off and distilled to give a final product weighing 331 g, boiling range from about 133 to 232 ° C at 2 μHg, a refractive index of 1.6545 at 24 ° C and a viscosity of 1200 cSt at 50, 2 ° C. This material was useful as a recording liquid.

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Example 12

Example 11 was used on a larger scale of 2050 g (16 mol) of naphthalene, 2600 g (24 mol) of benzyl alcohol, 4 liters of cyclohexane and 2000 ecm of concentrated sulfuric acid. 1694 g of a final liquid were obtained which had a Boiling range from 134 ° C to 245 ° C at 4 μHg, one viscosity

ο -9

of 1215 cSt at 49.8 C and a vapor pressure of 2.5x10 Torr at 50 ° C. This material was used as a recording liquid useful.

Example 13

This example shows the preparation of the inventive Materials using benzene as a precursor. A mixture was added to 1308 g (3.9 mol) of polyphosphoric acid at 80 ° C of 234.3 g (3 mol) of benzene and 810.8 g (7.5 mol) of benzyl alcohol were added over a period of 1.7 hours, the Reaction temperature was maintained at about 90 to 95 ° C. That The resulting mixture was cooled to 80.degree. C. and one liter of water was slowly added in order to keep the temperature below 95.degree. After cooling to below ^ -half 80 ° C, one liter of benzene was added Stir added over a period of several minutes. The organic material was separated from the acid and with 500 ecm of an aqueous sodium sulfate-potassium hydroxide solution washed out. The weakly basic material was then washed with 500 ecm of a saturated aqueous sodium sulfate solution until it was neutral and then filtered off. The organic layer was collected, filtered slurried with Celkate, benzene and the light ones Portions distilled off at atmospheric pressure and in vacuo as above. That taken up in the vacuum distillation Product of 123.5 g was made at a temperature of 220 to

ο -5 -4

Distilled at 350 C and a pressure of 10 'to 10 Torr. The final product had a refractive index of 1.6402 at 25 ° C and a viscosity of 2563.6 cSt at 50.2 ° C. This Material was. useful as a recording medium.

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Example 14

This example shows the production of the inventive geniuses Materials using tetralin as a precursor material.

810.8 g (7.5 mol) of benzyl alcohol were added to a mixture of 396.6 g (3.0 mol) of tetralin and 1308 g of polyphosphoric acid at a temperature of 80 ° C admitted. The addition took 2.0 hours and was regulated so that a reaction temperature of 85 to 90 ° C was maintained. After another 30 minutes Stirring was added to 1500 ml of water and stirring was continued for a further 20 minutes.

The acidic layer was stripped off and the organic layer diluted with about 2 liters of benzene. The organic layer was washed twice with 600 ml each time of Na _n SO. * _{Washed out H 0} O solutions. It was then washed out with aqueous KOH until it was weakly basic and finally extracted four times with 600 ml of Na ₀ SO ₄ · HgO solutions each time.

The organic material was then taken up, slurried with Celkate for about half an hour and then filtered off. The benzene, the remaining tetralin and the light portions were reduced by distillation Separated at atmospheric pressure and in vacuo. The crude product, 345.8 g, was also collected by distillation.

An end product, 186-3-5B, was isolated from this crude product by stripping and distillation. Sample 186-3-5B was Slurried with Celkate and through Whatmaη paper and microporous Filter filtered off. The filtered material gave a satisfactory recording liquid.

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Example 15

A 2 1 flask fitted with a mechanical stirrer, nitrogen inlet tube, Thermometer, dropping funnel and reflux condenser was fitted with 460 g of polyphosphoric acid and 180 g (1 mole) "9,10-dihydroanthracene was charged. The mixture was heated to 110 ° C to melt the dihydroanthracene.

To this mixture, 324 g (3 mol) of benzyl alcohol was added dropwise with stirring. During this addition the temperature rose and the rate of addition and / or the heating and cooling was regulated so that a temperature between 120 and 130 ° C. was maintained. The addition was complete after 45 minutes. The mixture was heated and heated to 120-130 ° C for an additional 3 hours before cooling. When the mixture had cooled to room temperature, 200 ml of methanol were added with stirring, the temperature rising to about 55 ° C. Then
stirred for half an hour.

55 ° C rise. Then the mixture was during a

The solvents benzene and methanol were at atmospheric pressure and a vessel temperature of 123 ° C distilled off. That residual solvent was distilled off with the aid of a water jet pump and a vessel temperature of 177 ° C.

The liquid was then pumped using a mechanical vacuum pump and a diffusion pump, as shown in Table XIV is listed, distilled:

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Table XIV pressure
[Torr] weight fraction Vessel temp.
C ° c] 2.7 x 10 " ²
1, OxIO " ²
2xl0 " ⁶ -3xl0" ⁵ 58.3
59.2
98.0 1
2
3 189-193
176-214
168-240

Fractions 2 and 3 were recombined and distilled as listed in Table XV below:

Table XV pressure
t / Torr] weight fraction Vessel temp.
L ° c] · ΙΟ " ⁶
XO " ⁵ 37.4
66.5 I ¹
2 «" 111-167
167-205

Fraction 2 'had a refractive index of 1.6482 at 25 ° C and a viscosity of 970 cSt at 50 ° C. This material had a vapor pressure of 5.5 x 10 " ¹ Torr at 50 ° C, 1x10" Torr at 25 ° C, and made a good recording medium.

Example 16

The representation was carried out in a manner similar to that in Example 15 with following modifications:

1. There was 2 moles (360 g) of 9,10-dihydroanthracene, 920 g Polyphosphoric acid and 4 mol (432 g) benzyl alcohol

. turns.

2. The addition of the benzyl alcohol took place during one Period of 5 hours.

3. About 500 ml of methanol were added to the vessel

temperature was 80 ° C

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and the temperature was 80 ° C.

4. The mixture was diluted with 500 ml of benzene.

5. The product was washed out three times with 500 ml of methanol each time and once with 1 l of methanol.

The washing fractions 1 to 3 were taken up. They contained the acid and the methanol fractions.

The orange oil was transferred to a still and the solvent is distilled off at atmospheric pressure and a vessel temperature of 125 ° C. The remaining solvent was drawn off with the aid of a water jet pump at a temperature of 125 ° C. The remaining 9,10-dihydroanthracene (Fraction 4) was made on the cold end by sublimation

—2 —2

under a vacuum of 5x10 to 3x10 Torr and a ge

barrel temperature of 118 ° C added.

The liquid was then with the help of a mechanical vacuum pump and a diffusion pump on the distilled in Table XVI below:

Table XVI pressure
CTorr] weight
Cg] fraction Vessel temp.
C ° c] 4xlO " ³
io- ³ -io- ⁴ 90.3
190 5
6th 120-169
176-293

Fraction 6 was again distilled and drawn off and yielded 80 g of a material with a viscosity of 1280 cSt at 50 ° C and a refractive index of 1.6434 at 25 ° C. It it was found that this liquid was extremely resistant to substrate formation.

0 09816/1294

The samples of certain materials from the previous examples as listed in Table XVII below were tested for their resistance to substrate formation, by placing them on a disc divided into segments and irradiating them with radiation from an 8 kV source became. In the same way, a sample of a typical material according to US Pat. No. 3,288,927 issued by Reaction of benzyl chloride and toluene in the presence of aluminum chloride was established, examined. After irradiation for a period of about 100 hours, the segments became oil-free washed, the substrate, if any, determined and the loss of light transmission measured, this Value was expressed as a percentage of blue loss. The results of these experiments are detailed below in Table XVII listed:

Table XVII Blue loss, example material BTL C%] description 0.41 1 WM 323 0.52 3 WM 625 0.78 4th WM 685 0.70 5 WM 834 1.01 6th WM 1086 0.78 7th WM 974 0.59 8th WM 908 0.38 10 WM 1109 0.44 16 WM 1117 2.22 according to US patent
3,288,927 WM 526

It is easy to see from the table above that the blue loss of the materials according to the invention is significantly less than that of a typical material as is known from the prior art.

009816/1294

The advantages of the present invention are an improved electronic projection system with a deformable recording medium that can operate for long periods of time allowed if there is a slight decrease in the ability to record.

009816/1234

Claims (9)

EXPECTATIONS 1. Projection system from an internally conductive piston, a deformable medium in this piston, a device for generating an electron beam, which is an electrical Creates charge on the surface of the deformable medium as a function of an applied electrical signal and cooperates with the conductive interior so that the medium is subjected to a deforming force and deformations can be generated on the surface of the medium as well as a light and optical system for projecting Light as a function of the deformations on the surface of the medium, characterized in that the deformable medium is the reaction product (A) a material from the group of substituted and unsubstituted benzyl alcohol and their mixtures and (b) is an aromatic hydrocarbon. 2. Projection system according to claim 1, characterized in that that the reaction product is the reaction product of benzyl alcohol and toluene. 3. Projection system according to claim 1, characterized in that the reaction product is the Reaction product of benzyl alcohol and naphthalene is. 4. PiOjection system according to claim 1, characterized that the reaction product is the reaction product of benzyl alcohol and xylene. 5. Projection system according to claim 1, characterized that the reaction product is the reaction product of benzyl alcohol and benzene. 009816/1294 6. Projection system according to claim 1, characterized in that the reaction product is the reaction product of benzyl alcohol and tetralin. 7. Projection system according to claim 1, characterized in that the reaction product is the Reaction product of benzyl alcohol and dihydroanthracene is. 8. Projection system according to claim 1, characterized in that the molar ratio of Benzyl alcohol to aromatic hydrocarbon between about 0.1 to 10 moles of benzyl alcohol per mole of aromatic Hydrocarbon. 9. Projection system according to claim 1, characterized in that the molar ratio of Benzyl alcohol to aromatic hydrocarbon is between about 1 to 4 moles of benzyl alcohol per mole of aromatic hydrocarbon. 009816/1294