DE1805697A1 - A color forming paper for pressure sensitive copier papers - Google Patents

Description

MUKTANWXLTl DR. E. WIEGAND DIPL-ING. W. NIEMANN 1805697. DR. M. KÖHLER DIPUNG. C. GERNHARDT MONCHlN HAMIURO KAMATINT 8000 MONKS 15.28. October 1968 KAIPATINT NUISIAUMITiAtSS 1

W. 13 969/68 13 / Loe

Fuji Shashin Film Kabushiki Kaieha Kanagawa (Japan)

and

Hodogaya Kagaku Kogyo Kabushiki Kaisha Tokyo (Japan)

Color former paper for pressure-sensitive copier papers.

The invention relates to pressure-sensitive copier papers in which a color reaction between a colorless; organic electron donating compound (hereinafter referred to as "color former") and a solid electron acceptor acid (hereinafter referred to as "developer" ' designated) is used.

■ ■ f ' >

In general, pressure-sensitive copier papers consist of a color former paper with one layer

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the color former and a developer paper or construction paper with a layer of the developer, e.g. a clay. For the production of the color former paper an oil solution of the color former emulsified in water to to form microscopic oil particles. A rupturable capsule is formed around each oil particle to protect the oily material from air, thereby endowing the oily material with sufficient durability and then the oily materials enclosed in capsules are placed on a sheet of paper. The construction paper is made by applying the developer to a sheet of paper together with a suitable binder manufactured. ·

The invention relates to an improved Color former paper with a layer of a special color former used alone or for such a purpose has never been used together with known color formers

As color formers for pressure-sensitive copier papers, crystal violet lactone, malachite green lactone, Hhodaminlacton and Benz oy lleükomethy lenbiau in general known and were used for this.

The above-mentioned color formers are used in pressure-sensitive copier papers which are blue to be colored. ι

You orangegelb _v according to the invention FarbbildneyWerden used, colored red or purple.

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■ ■■ '"flüil'f · ¹ '! ¹ ;: ·. '! ¹ " ■ ""■■' Wfyi '! . '■

' ^! '"' ^lll! "'WlllH ¹ ! '' ■ ϊ " ^Ι! :: 'P *»! "I" ¹ ! ¹ ! ¹ "! ■ ϊ ^{| ι:} τ ^{!! |} "'■» τ ?! wf ^ ^M ■: "■ ' ■■■: ι;: w> » ■ ?

The object of the invention is thus the creation of a pressure-sensitive paper produced by the use of the color former according to the invention together with a conventional blue coloring color former can be colored black. Another purpose of the invention is to provide of pressure-sensitive copier papers that can be colored with beautiful red color by using the above specified color former used alone or together with another red coloring color former.

The color formers used according to the invention can * nen are colored very quickly and the material colored by the color former on the developer paper or construction paper has a high idfastness

Have the color formers used according to the invention the skeleton of silamine (3-substituted-amino-6-chlorofluorane) the general formula

BBH

where E is a hydrogen atom, a lower alkyl group, a Represents aryl or an aralkyl group

By changing the group R in the formula above the color formed by the color formers can be varied in a wide range from yellow-orange to purple

Typical examples of color formers of the general formula given above are as follows.

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F ( ⁰ O)

Chemical name

3-amino-6-chlorofluorane
3-methylamino-6-chlorofluorane, 3-ethylamineb-6-chlorofluorane
3-propylamino-6-chlorofluorane

3-phenylamino-6-chlorofluorane

// V-GH ₂ - 3-Benzylamino-6-chlorofluorane 84-lo3 - ^ 3-m-Toluylamino-6-chlorofluorane 184

3-m-xylylamino-6-chlorofluorane 199

Colour·

215-223 yellow-brown 198 orange 2o9 orange 179-180 ' orange 217 Orange red 84-lo3 orange . 184 ' purple colored

purple colored

They have a high color formers shown above Dyeing Extent and Excellent Liohfastness. if In addition, the color formers specified above together with customary color formers, for example a malachite green lactone, Crystal Violet Lactone, Michler's Hydrol, Rhodamine Lactone and leucomethylene blue, are used, the coloring power becomes of the color former according to the invention is not reduced. In addition, the color formers according to the invention have no adverse influence on the color formers used. Further have the color formers used according to the invention satisfactory properties for pressure-sensitive Copy papers are required, e.g. coloring behavior, extent of coloring, Lightfastness, durability, oil-solubility. And Water insolubility.

The 3-substituted-amino-e-chlorofluorane compound, represented by the general formula given above can, in general, by implementing fluo: - ■

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^{11 1} I HPW HMH RMIII Hl Hill HH ι ill nil "ι

rescein with phosphorus pentachloride to form 3,6-dichlorofluorane and condensation of this 3,6-dichlorofluorane with an amine in the presence of zinc chloride as Condensation agents are produced.

The preparation of the compounds is explained in practice using the following examples:

Manufacturing Production of 3-A * thylamino-6-chlorofluorani

A 300 cm flask was charged with 60 g of ethanol, 68 g of zinc chloride and 10 g of monoethylamine, whereupon 36.9 g 3,6-dichlorofluorane were added to the mixture

The flask was heated in an oil bath. The mixture began to dissolve at 130 to 14O ⁰ C and the flowability of the mixture was increased at ISO ⁰ G. The reaction liquid gradually turned yellow. After 3 hours * the mixture was colored orange-red · 'The mixture was cooled, solidified and crushed ·

The solid obtained in this way was mixed with water, to dissolve a large amount of zinc chloride, which was then removed by filtration. The remaining solid Toluene was added, after which a 3% aqueous solution of sodium hydroxide was added, making the solution alkaline set, whereby the product was extracted into toluene. After separation of the aqueous layer, the toluene was

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The first layer was filtered with the addition of activated charcoal and the filtrate was concentrated under reduced pressure and allowed to cool, whereby 25 g of colorless or black-yellow crystals of the desired chlorofluorane with a melting point of 209 ° C. were obtained.

Manufacturing 2

H ₅ O ₆ H ₂ CHM,

Production of 3-benzylamino-6-chlorofluorane:

In a mixture of 9ο g ethanol and Ho g zinc chloride 39 g of benzylamide was added to form a salt, and after adding 60 g of 3,6-diohlorofluorane, the obtained was obtained Mixture reacted at 140 ° C. for 4 hours, the reaction mixture changing from yellow to red-brown in color became. The mixture was allowed to cool, solidified, and crushed.

The solid thus obtained was mixed with water to dissolve a large amount of zinc chloride, which was removed by filtration. By treatment of the filtrate as bed Herat "Uiaqg X rüokstandee 45 g of colorless or pale organgen crystals of the desired compound nit a Sohmelspunkt 114-11 $ ⁰ O · obtain

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Manufacturing 3

. Manufacture of Jm-Xylylamino-o-ohlorfluorani

25 g of m-xylidine were introduced into a mixture of 60 g of ethanol and 68 g of zinc chloride to form a salt and, after addition of 36.9 g of 3f6-dichlorofluorane, the mixture obtained was reacted at 150 ° for 4 hours. The mixture was allowed to cool, solidified and crushed. The pesticide was mixed with water to dissolve a large amount of zinc chloride, which was removed by filtration. By treating the filtrate residue as in preparation 1, 32 g of colorless or pale purple-colored crystals of the desired compound with a melting point of 196 to 199 ^° C. were obtained · * · 5 ·.

j

The preparation of the color formers used according to the invention was explained with the aid of a few examples. however, it can be seen that the other color formers can be prepared in a similar manner.

The invention is illustrated below by means of examples explains in more detail in which the specified parts refer to Ge ν '., based on weight, unless otherwise stated

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example 1

2 parts of a color former, namely J-aniino-δ-chlorofluorane, were dissolved in 100 parts of trichlorodiphenyl. 2o parts GummiarabiciM and 2o parts of acid behände It he gelatin were dissolved in 2oo parts of water at 45 ⁰ O and the above-mentioned Farbbildneröl was added to the obtained solution under stirring to emulsify the solution. When the size of the oil droplets in the emulsion was reduced to 4-6 microns, 100 parts of water at 40 ° G became. was added to the emulsion, and acetic acid was added thereto with stirring to adjust the pH to 5. Thereafter, coacervation was caused by adding 400 g of water to form concentrated liquid films of gelatin and gum arabic around the oil droplets, whereupon 3.8 parts of 37 # formalin were added to form the above liquid films at pH Harden value of 4.4. The system was then ^{cooled to Io 0} O to gelate the liquid films, and an aqueous sodium hydroxide solution was added to the system to adjust the pH to 9. The system was then allowed to stand for 5 to 6 hours to complete the hardening of the capsules. The microcapsules were applied to a sheet of paper using a roller application method or a slot nozzle applicator and then dried. When the paper thus treated has been brought into close contact with a construction paper and; When the assembly was pressed locally with a pencil or typewriter, a deep yellow-orange color was instantly formed on the pressed area of the construction paper. If the colored construction paper is

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p mm ^{! "!} ■" P s ι ■ '! ι! ■ * - ■ ■■■■■■

exposed to light for a long period of time in a tent or was wetted with water, no fading was observed. Further, when the above-mentioned color-forming Paper has been heated to 100 ° C for 20 hours or exposed to sunlight for several hours there was hardly any decrease in coloring power of the color-forming paper observed

Example 2

The procedure described in Example 1 was repeated with the modification that two parts of a B • color former, namely J-methylamino-δ-chlorofluorane, were used in place of the color former used in Example 1, whereby a color former paper was produced * When the color former in close contact was brought with a construction paper and this assembly was locally pressed, an orange color was instantly formed on the construction paper. When the colored construction paper was exposed to sunlight or wetted with water for a long period of time, almost no fading was observed. In addition, when the thus prepared color-forming paper was heated to 100 ° C. for 20 hours or exposed to sunlight for several hours, a decrease in the coloring property was hardly observed. * *

Example 3 «

The same procedure as described in Example 1 was repeated old the modification that 2 parts of

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- Io -

J-phenylamino-ö-chlorofluorane as a color former instead of the color former used in Example 1 were used to prepare a color former paper. When the color former paper was brought into close contact with a construction paper and these papers were locally pressed, it instantly became a deep one Orange-red paint formed on the construction paper. The light fastness and the water resistance behavior of the coloring material formed from the color former were also good excellent and so were the lightfastness and the heat resistance of the color-forming paper before color formation is very high.

Example 4

Repeating the same procedure as described in Example 1, but using 3-m-toluylamino-6-chlorofluorane as the color former instead of that in Example 1 When the color former used was used, a color former paper was prepared. When the color former paper is in Brought tight contact with a construction paper and the papers were locally pressed on the construction paper a deep purple color quickly formed. The thus formed coloring material showed good lightness and water resistance, and also showed the color-former paper good lightfastness and heat resistance prior to color formation.

Example 5

The same procedure as described in Example 1 was repeated with the modification that a part

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"———- iemeueeiiiiiip" T- up> ΐι, ρ, ι,

Crystal violet lac ton, o, 5 parts 3-Plienylain ± no-6-chlorofluorane, 0.5 parts of 3-m-xylylamino-6-ohlorfluoran and 0.4 parts of benzoylleucomethylene blue instead of the example 1 were used to produce a color former paper. If that Color former paper was brought into tight contact with a construction paper and the assembly was locally pressed a deep blue-black color was instantly formed on the construction paper. The coloring material thus formed showed good lightfastness and the color former paper showed sufficient lightfastness and Heat resistance.

Example 6

The same procedure as described in Example 1 was repeated with the modification that as a color former 0.3 parts benzoylleuoomethylene blue, 0.6 parts malachite green lactone, 0.6 parts crystal violet laotone and 0.4 parts of 3-m-toluylamino-6-chlorofluorane were used instead of the color former used in Example 1, with a color former paper was produced. When the color former is in close contact with a construction paper and the assembly was pressed in place, the construction paper instantly became a deep black color educated. The coloring material thus formed showed good lightfastness, and also showed the color former paper sufficient lightfastness and heat resistance.

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BAD ORlGiNAL

Claims (4)

- 12 claims 1. Color former paper for pressure-sensitive copier papers with a carrier, characterized in that
the carrier carries a layer of microcapsules containing at least one 3-amino-6-chlorofluorane compound, wherein
the amino group may be substituted, of the general formula below HHN contain, in which R is a hydrogen atom, a lower alkyl group, represents an aryl or aralkyl group. 2. color former paper according to claim 1, characterized in that the microcapsules as color former
3-amino-6-chlorofluorane, 3-methylamino-6-chlorofluorane,
3-ethylamino-6-chlorofluorane, 3-propylamino-6-chlorofluorane, 3-phenylamino-6-chlorofluorane, 3-benzylamino-6-chlorofluorane, 3-m-toluylamino-6-chlorofluorane or 3-m-xylylamino-6- contain chlorofluorane 3. color former paper according to claim 1 or 2, characterized in that the microcapsules also at least contain a common color former which produces a blue color. • 909831/1173 1805R97 4. color former paper according to claim 3 _f, characterized in that the microcapsules contain as common, a blue color resulting color former crystal violet lactone, benzoylleuoomethylene blue or malachite green laoton. 909831/1173