JPS6141593A - Solvent for dye of pressure-sensitive paper - Google Patents

Abstract

PURPOSE:To obtain excellent color phase and fading resistance and good physical properties without generating an unpleasant odor, by applying disproportionation treatment to diarylalkane or a hydrocarbon containing the same. CONSTITUTION:Diarylalkane to be used is represented by formula I or a stock hydrocarbon mixture mainly containing the same has b.p. ranging from 260 deg.C- 320 deg.C and is byproduct oil fraction formed in preparing alkylated monocyclic aromatic hydrocarbon such as alkylbenzene by alkylating monocyclic aromatic hydrocarbon with olefin. The especially pref. byproduct oil fraction is one obtained from a process for preparing ethylbenzene or ethyltoluene by alkylating benzene or toluene with ethylene and, for example, when disproportionation treatment is applied to said oil fraction by using an aluminum chloride catalyst and the catalyst is subsequently deactivated or separated by filtering and distillation is performed, a fraction containing triaryldialkane represented by formula II is obtained. This fraction is suitable as the solvent for the dye of pressure sensitive paper and the b.p. range thereof is 350-450 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a solvent for pressure-sensitive paper dyes. More specifically, the present invention relates to a solvent for pressure-sensitive paper dyes consisting of a heavier fraction obtained by disproportionating diarylalkane or a hydrocarbon mixture mainly containing diarylalkane using a disproportionation catalyst.

[Prior art and problems to be solved] Conventionally, a colorless dye is incorporated in the form of a solution in microcapsules and applied to one side of paper, and the dye and the other paper are coated on the opposite side of the paper. A method in which a polymeric material such as clay or phenolic resin that has the property of reacting to develop a color is applied, and when used, these coated layers are stacked facing each other, and copies are made by applying pen pressure. Pressure-sensitive (copying) paper of this or similar types is known.

The color development mechanism of the pressure-sensitive paper described above is that the microcapsule coating is torn due to pen pressure, the dye solution inside the capsule is released, and the dye in the solution is mixed with the clay or polymeric material applied to the opposing paper surface. It colors when it comes into contact with it.

Dyes used in pressure sensitive paper include crystal violet lactone, malachite green, benzoylleucomethylene blue, rhodamine B, and 3-dialkylamino-7-dialkylaminofluoranes.

Diarylalkane such as diphenylmethane and phenylxylylethane are widely used as solvents for pressure-sensitive paper dyes. However, some of these diarylalkanes have a strong odor depending on their structure, making them unsuitable as solvents for pressure-sensitive paper dyes.

On the other hand, it is known that by-product oils produced from certain manufacturing processes contain diarylalkane. However, the diaryl alkanes in the by-product oil are usually extremely diverse and also contain other compounds, which cannot be separated by simple distillation. Therefore, although the diarylalkane in the by-product oil is inexpensive, its use as a solvent is limited due to its unpleasant odor and other reasons. For example, as described in Japanese Patent Application Laid-Open No. 56-161195, after being treated to remove bad odor,
The reality is that it is unusable unless an odor masking agent is added.

Accordingly, an object of the present invention is to provide a solvent for pressure-sensitive paper dyes that uses diarylalkane as a raw material and is not only free from unpleasant odors but also has excellent hue and anti-fading properties. Still another object is to use a by-product oil fraction, which is a hydrocarbon mixture mainly containing diaryl alkanes, obtained from a specific manufacturing process, as diaryl alkanes, thereby producing pressure-sensitive paper dyes that are inexpensive and have favorable physical properties. The purpose is to provide a solvent.

[Means for Solving the Problems] The present invention involves subjecting a diaryl alkane or a hydrocarbon mixture containing the diaryl alkane having a boiling point in the range of 260 to 320°C to a disproportionation treatment in the presence of a disproportionation catalyst. This invention relates to a solvent for pressure-sensitive paper dye, characterized in that it consists of a fraction obtained by the above method and having a boiling point in the range of 350 to 450°C.

The invention will be further explained below.

The diarylalkane of the present invention is represented by the following general formula (I), and the boiling point of the hydrocarbon mixture mainly containing it is 260 to 320°C, preferably 260 to 310°C.
within the range of Hydrocarbon mixtures with boiling points higher than this are
This is not preferable because the effects of the disproportionation treatment described below cannot be expected.

Here, R and R2 are hydrogen, a straight chain or branched alkyl group, R3 is a straight chain or branched alkylene group, and m
and n is an integer from 0 to 3.

The diarylalkane mentioned above includes, for example, diphenylmethane, ditolylmethane, diphenylethane and ditolylethane.

In the present invention, the hydrocarbon mixture containing primarily diarylalkanes used as a preferred feedstock is a by-product oil obtained from a particular manufacturing process. That is,
It is a by-product oil fraction produced when monocyclic aromatic hydrocarbons are alkylated with olefins to produce alkylated monocyclic aromatic hydrocarbons such as alkylbenzenes.

Monocyclic aromatic hydrocarbons are lower alkylbenzenes such as benzene and toluene, and olefins are lower olefins such as ethylene and propylene. Alkylation catalysts are industrially mainly aluminum chloride, boron fluoride, silica/alumina, ZSM-5 and ZSM-1.
Synthetic zeolite represented by ZSM-5 type such as 1, phosphoric acid, etc. are used.

The above alkylation is widely practiced industrially as a process for producing lower alkylbenzenes such as ethylbenzene, ethyltoluene, and cumene.

The above production process produces polyalkylated products and diaryl compounds in addition to monoalkylated products. Therefore,
By-product oil distillate containing diaryl alkanes from heavy by-product oil after distillation separation of unreacted monocyclic aromatic hydrocarbons and mono- and polyalkylated monocyclic aromatic hydrocarbons from the alkylation reaction mixture. You can get minutes.

A particularly preferred by-product oil fraction in the present invention is a by-product oil fraction obtained from a process in which benzene or toluene is alkylated with ethylene to produce ethylbenzene or ethyltoluene.

In this by-product oil fraction, the effect of the disproportionation treatment is particularly noticeable.

Disproportionation catalysts include Lewis acids such as aluminum chloride and ferric chloride, silica/alumina, solid acids such as synthetic zeolite represented by ZSM-5, heteropolyacids such as silicotungstic acid, and trifluoromethane. Super strong acids such as sulfonic acid, strong acid type cation exchange resins such as Nafion (trade name, manufactured by DuPont), etc. are used.

The temperature of the disproportionation treatment ranges from 20 to 5, depending on the type of catalyst used.
Can be selected from a wide temperature range of 00℃ - For example, 20 to 150℃ for aluminum chloride, 150℃ for Nafion
~z3o0c,,250-50 for Ata synthetic zeolite
It is 0°C.

The reaction format can be either a batch type or a flow type.

The reaction time is preferably in the range of 20 minutes to 10 hours in the case of a batch type, and in the range of LH3V of 0.5 to 10 in the flow type.

The pressure during the disproportionation treatment is not particularly limited, but is usually from normal pressure to about 10 kg/Crr12.

By the disproportionation treatment of the present invention, in addition to producing monocyclic aromatic hydrocarbons that are lighter than the feedstock hydrocarbons made of alkylbenzenes such as benzene and toluene, the following general formula (H), which is heavier than the feedstock hydrocarbons, is produced. A fraction containing triarylsialkane represented by is also obtained.

Here, R1, R2 and R3 are hydrogen, straight chain or branched alkyl groups, R and R5 are straight chain or branched alkylene groups, and p, q and r are integers from O to 3.

In the present invention, the above-mentioned triarylsialkane-containing fraction is used as a solvent for pressure-sensitive paper dyes. Therefore, after the disproportionation treatment, the catalyst is separated by deactivation or filtration, and then distilled to obtain the above-mentioned fraction containing triarylsialkane. The boiling point of the fraction suitable as a solvent for pressure-sensitive paper dyes is 350-450" C1, preferably 350-42"
It is in the range of 0°C. A fraction with a boiling point higher than 450°C is undesirable because it increases the viscosity and pour point.

As mentioned above, the disproportionation process produces monocyclic aromatic hydrocarbons that are lighter than the raw material, but especially when processing in a batch process, the light components are continuously removed from the system during the process. It is preferable to remove the triarylsialkane at the same time because the yield of the above-mentioned triarylsialkane is improved.

In addition to being used alone, the solvent of the present invention may be used as a solvent for conventional pressure-sensitive paper dyes, such as kerosene, alkylbenzene such as dodecylbenzene, 1-phenyl-1-xylylethane, 1-phenyl-2-inpropylphenylethane, etc. It can be used by mixing with one or more types of diarylalkane, alkyl biphenyl such as isopropylbiphenyl, and alkylnaphthalene such as diisopropylnaphthalene in an appropriate ratio.

[Operations and Effects] The triarylsialkane-containing fraction of the present invention is free of unpleasant odor, has a good quality, has a relatively low viscosity despite its high boiling point, and has a low pour point. It also has excellent solubility and coloring properties for conventional pressure-sensitive paper dyes. Therefore, it is most suitable as a solvent for pressure-sensitive paper dyes.

[Example] The present invention will be explained in more detail below using examples.

Example 1 Using an aluminum chloride catalyst, benzene and ethylene were reacted at a molar ratio of 5:1 at 130° C. in a batchwise manner under normal pressure for 1 hour to perform alkylation.

From this reaction mixture, unreacted benzene, ethylbenzene, and polyethylbenzene were distilled off, and a by-product oil fraction with a boiling point of 260 to 310°C containing the following diarylalkane was recovered.

Composition Weight %C
-C diarylethane 71 Others
29 total 100 (Almost no triarylsialkane is included) Next, 30 g of aluminum chloride was added to 2000 ml of the above by-product oil fraction, and the mixture was stirred at 80° C. for 5 hours to carry out disproportionation treatment. .

After the disproportionation treatment, the catalyst is deactivated, washed with water and dried, and distilled to produce benzene and alkylbenzene with a boiling point of 8.
0-160°C 06-C-ring aromatic hydrocarbon fraction (recovery rate 5.0%), unreacted by-product oil fraction and boiling point 350-4
A heavy fraction (recovery rate: 14.8%) at 00°C was obtained.

The above heavy fraction was analyzed by GC-mass spectrum analysis.
It was confirmed that triarylsialkane was the main component. Moreover, its physical properties were as follows.

Pour point -27.5℃ Viscosity 18.5 cst (@4
0°C) Next, 5.0g of crystal violet) was dissolved in 100g of the above heavy fraction, and 100g of gelatin was added to this.
g was added to emulsify, and water was further added to make the total amount 600 g. After adding a CMC aqueous solution to adjust the pH to 4.5, the capsule membrane was hardened with glutaraldehyde to form microcapsules.

Glue (CMC aqueous solution) and blocking agent were added to the obtained microcapsule slurry, mixed well, and then coated uniformly on high-quality paper using a wire bar. After drying, 25 ± 1
The mass was measured at 60% humidity and the amount of capsule applied was determined, which was used as a test paper.

This test paper was combined with another paper coated with acid clay to form a pressure-sensitive copying paper. A load of 675 kg/am2 was applied to this for 1 minute, and after the load was removed, the color density after 1 minute and 60 minutes was determined by measuring the absorbance at 610 nm. The results are shown in Table 1.

Example 2 Using synthetic zeolite ZSM-5, toluene was alkylated with ethylene under the following conditions.

Reaction temperature = 500°C Toluene/ethylene = 5 (mole ratio) WH3V:
t.

After alkylation, unreacted toluene, ethyltoluene, and polyethyltoluene are distilled off from the reaction solution to obtain heavy components,
Next, a by-product oil fraction containing a diaryl alkane having the composition and physical properties shown below was recovered.

By-product oil fraction boiling point 260-300℃
Composition Weight % C14-C15 diarylmethane 59.1C16
Diarylethane 25.9 Others
15.0 total 100 (contains almost no triarylsialkane) 2000 ml of the above by-product oil fraction was treated with 50 g of a strong acid type cation exchange resin (trade name: Nafion, manufactured by DuPont), Disproportionation was carried out by stirring for 3 hours at 200° C. under pressure. During the disproportionation, the produced light fraction consisting of 07 to C9 alkylbenzenes such as benzene and toluene was continuously distilled out of the reaction system.

After the disproportionation treatment, the catalyst was filtered, and the resulting 1550 ml of liquid was further distilled to obtain a fraction (fraction 2) containing diaryl alkanes corresponding to the unreacted fraction shown below, and a fraction heavier than □ A fraction (fraction 3) containing rear, -, shear) and force was collected. In addition, the heavy components extracted outside the disproportionation system were also recovered and are also shown below.

Distillate Boiling point Recovery rate Heavy fraction
80-160℃ 9.9% fraction 3 350-400
C. 29.5% Furthermore, it was confirmed by GC-mass spectrometry that the main component of fraction 3 was triarylsialkane. Its physical properties are as follows.

Pour point -35°C Viscosity 16.8 cSt (@
(40°C) Using the above fraction 3 as a solvent, a pressure-sensitive copying paper was prepared in the same manner as in Example 1, and the color density and color development rate were determined. The results are also shown in Table 1.

For comparison, diisopropylnaphthalene (trade name: KMC1, manufactured by Kureha Chemical Industry ■) and partially hydrogenated terphenyl (trade name: HB-40, manufactured by Hikarusu Co., Ltd.) were used as solvents, and the same procedure as in Example 1 was carried out. Pressure-sensitive copying paper was made to
I conducted a test. The results are also shown in Table 1.

Table 1

Claims (4)

[Claims] (1) Diarylalkane with a boiling point in the range of 260 to 320°C or a hydrocarbon mixture mainly containing it,
A solvent for pressure-sensitive paper dyes, comprising a fraction having a boiling point in the range of 350 to 450°C obtained by disproportionation treatment in the presence of a disproportionation catalyst. (2) A patent in which the hydrocarbon mixture is a by-product oil fraction containing diarylalkane obtained when alkylating a monocyclic aromatic hydrocarbon with an olefin to produce an alkylated monocyclic aromatic hydrocarbon. A solvent for pressure-sensitive paper dyes according to claim 1. (3) The solvent for pressure-sensitive paper dyes according to claim 2, wherein the monocyclic aromatic hydrocarbon is benzene or toluene. (4) The solvent for pressure-sensitive paper dyes according to claim 2, wherein the olefin is ethylene.