JPS6266985A - Solvent for pressure-sensitive copy paper - Google Patents

Abstract

PURPOSE:To obtain excellent dye dissolvability, biodegradability and low temp. flowability, by using a diphenylbutane isomer mixture comprising a specific composition or the hydrocarbon solvent containing said isomer mixture. CONSTITUTION:A solvent for pressure-sensitive copy paper is constituted of a diphenylbutane isomer mixture consisting of 10-40wt% of 1, 1-diphenylbutane and 60-90wt% of 1, 2-diphenylbutane and/or 1, 3-diphenylbutane or the hydrocarbon solvent containing said isomer mixture. The solvent can be used alone and can be also used by mixing with other inert solvent not damaging the characteristics of said solvent such as indane, for example, 1-methyl-3- phenylindane or aromatic ether. As a method for obtaining the diphenylbutane mixture, a method for reacting benzene and 1-phenyl-2-butene in the presence of a aluminum halide catalyst is designated as a suitable enbodiment.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a solvent for pressure-sensitive copying, particularly a solvent for pressure-sensitive copying paper comprising diphenylbutane.

BACKGROUND OF THE INVENTION The use of diphenylbutane isomers in solvents for pressure-sensitive copying paper is already known.

1. An example of using 1-diphenylbutane is JP-A-413-86615, an example of using 1,2-diphenylbutane is JP-A-49-21217, and 1,6-diphenylbutane is used. An example is Japanese Patent Application Laid-Open No. 55-27225.

Problems to be Solved by the Invention Characteristics required of a solvent for pressure-sensitive copying paper include (1)
High boiling point, non-volatility (2) Low flammability (3) No odor (4) Low temperature fluidity (5) Solubility of pressure-sensitive dyes (6) Stable in air (7)
It is non-toxic and biodegradable (8) it is cheap and easily available (9) it does not inhibit the color reaction.

However, each isomer of diphenylbutane did not satisfy all of these properties. For example, 1,
Although 1-diphenylbutane has good solubility in the color former crystal violet lactone (CVL), it has relatively poor biodegradability. The pour point is also high. On the other hand, 1,2-
and 1,5-diphenylbutane μ have good biodegradability but relatively poor CVL solubility.

Further, although there are examples of using each of the five isomers of diphenylbutane as a single product, there has been no study as to what composition is most suitable for this purpose when used as a mixture.

The reason why the inventors of the present invention considered all of these technical issues is that diphenylbutane is generally synthesized as a mixture of isomers, and the boiling points of the three isomers are in an extremely narrow range of 292 to 302°C. Extracting it industrially as a single product requires a large amount of money and is not practical. This is because we thought that if these mixed golds were used as they were for this purpose, they would be industrially significant.

Means for Solving the Problem Summary of the Invention In order to solve the above problem, the present inventors conducted a test with various combinations and found that the results showed that the properties were superior to those of each different type of diphenylbutane alone. It was possible to find a mixed composition having the following properties.

That is, the present invention uses 1,1-diphenylbutane 10 to 40M
The present invention relates to a solvent for pressure-sensitive copying paper comprising a diphenylbutane isomer mixture consisting of 1,2-diphenylbutane and/or 1,3-diphenylbutane in an amount of 60 to 90 g, or a hydrocarbon solvent containing the isomer mixture.

The solvent of the present invention can be used alone or in combination with other inert solvents (indanes such as 1-methyl-5-phenylindane, aromatic ethers, etc.) that do not impair properties. be able to. ``In addition, pressure-sensitive copying paper can be manufactured by methods known in the art. That is, microcapsule manufacturing methods such as coacervation, interfacial polymerization, internal polymerization, and external polymerization can be used. The coloring agent is crystal violet lactone (OVL).
), benzoylleucomethylene blue (BLMB)
, diaminofluorane derivatives, etc. Examples of color developers include bentonite, zinc oxide, kaolin, clay, activated clay, acid clay, zeolite, Merck, inorganic substances such as colloidal silica, phenol aldehyde polymers, Maleic acid-rosin m JI! , acidic polymers such as styrene-maleic anhydride copolymer hydrolyzate, ethylene-maleic anhydride copolymer hydrolyzate, carboxypolyethylene, vinyl methyl ether-maleic anhydride copolymer hydrolyzate, succinic acid, tannic acid, gallic acid,
Examples include carboxylic acids such as zinc salicylate or their gold maple salts.

The method for obtaining the diphenylbutane mixture of the present invention is as follows in the presence of an aluminum halide catalyst.
A preferred example is a method in which benzene and 1-phenyl-2-butene are reacted.

Preferred backing method example catalyst is aluminum halide, AZCZseA
Although t"r3 e At"3 and AlF2 can be used, AtCt is preferred.

Aluminum halide may be used by itself, but is preferably used in the form of a complex.

The complexing agent used for complexation is referred to herein as a cocatalyst.

Cocatalysts include organic nitro compounds such as tromethane, nitrohenzene, etc.) esters (methyl acetate, ethyl acetate, ethylene glycol diacetate, etc.), ethers (diethyl ether, glyme, etc.), ketones (acetone, methyl ethyl ketone, etc.), methylbenzene (mesitylene, durene, etc.). , indulene, pentamethylbenzene, hexamethylbenzene, etc.). In particular, methylbenzene is preferred because it improves the yield. As methylbenzene, those without adjacent aromatic nuclear hydrogen are substantially non-reactive. The function of methylbenzene is preferable.
and liquid σ complex (ArH2+AtC1m-, ArH2”
A4Ct7-3 is considered to be a co-catalyst that is formed entirely. (Published by Interscience Publishers Friedel-Craft & Related Reactions
1, Part I, p. 5, 1964) The complex can be prepared before the aralkylation, or it can be removed during the reaction.

The co-catalyst is used in the range of co-catalyst/aluminum halide (molar ratio) α3 to 10, preferably (L5 to 5).Also, the amount of aluminum halide used is not particularly limited; More preferably, the molar ratio to 1-aryl-2-butene is 1/100 to 1/2.

The reaction operation can be carried out in a batch, semi-batch or continuous manner, and the reaction temperature can be from 0 to 60°C, preferably from 5 to 50°C.

In addition, the raw material ratio (aromatic hydrocarbon/1-aryl-2-
butene) is 5 to 40, preferably 5 to 50; if it is lower than this, the sequential reaction of the target product will proceed and the yield will decrease.

Effects of the Invention The solvent Fi for pressure-sensitive copying paper with the composition of the present invention has excellent properties, especially dye solubility, biodegradability, and low-temperature fluidity, and is comprehensively superior to the properties of diphenylbutane isomers alone for this purpose. .

Example Hereinafter, the present invention will be explained in more detail with reference to Examples.

Biodegradation rate, CVL bath dissolution, and fluidity were measured by the following method.

These results are summarized in Table-1.

Biodegradability Test Add 100 ml of basal culture medium to a 500-volume shake flask.
and 9, the test compound was added at a concentration of 200 ppm. Next, activated sludge was added so that the suspended solids concentration was 100 ppm.

Each flask was plugged with cotton and placed in a shaking culture machine (manufactured by Mitamura Riken) for 25 minutes.
The cells were cultured for 2 weeks while being maintained at ±1°C.

After culturing, all test compounds were extracted from the shaker flask and the biodegradation IEk of each compound was determined using a gas chromatograph.

Crystal violet) (OvL)r8]iik for CvL solubility test sample
% and heated to dissolve. Thereafter, it was left to stand at 25°C for 5 days, and the presence or absence of precipitation of the dye was examined.

Pour point was measured by J-Tech 5K2269 (Petroleum Products Pour Point Test Method).

Table-1 Comparative example-100100A BBL-2010
00A B B#-55095A
BB l-455045A B AJ
-55950A BB 5NMAJ-1154045A A
A1-220 10 70 A
A A1-520
40 40 A A
AJ-4207010A A
AJ-530070A AAl-65
02050A A A1-75
0 50 20 A
A AJ-830700A
A AJ-9555530A
A AJ Yopu Station Father 1 Series-650050
B A B#-750252
5B A B#-850500
B AB#-91000QCA
0 tatami 1 Living minute jIJv rate (%): A near 5% or more B: 5
0-74%C: 49% or less Tatami 2CVL solubility; A: No precipitation B: No precipitation
Pour point: A below 45℃ B: -45℃~-
50℃C knee 29℃ or higher Example-10 (11 Production of microcapsules) 10 parts of gelatin and 1 part of gum arabic were added to 4 parts by weight.
Example 3
1 part of 40iii of the diphenylbutane obtained in step 1 was added and emulsified and dispersed. Emulsification was stopped when the size of the oil droplets reached an average of 5 microns, and water at 40'C was added to make a total of 9001 parts by stirring. Next, 10% by weight of acetic acid was added to adjust the pH of the solution to 4.0 to 4.2 to cause coacervation. The mixture was further stirred for 20 minutes and cooled with ice water to gel the coacervate film deposited around the oil droplets. At the time when this liquid temperature reaches 20℃, it is 3
7 parts by weight of 7% formalin were added. More armpits @
Gold after cooling to 10'C, 15'! lt% aqueous sodium hydroxide solution was added to bring the pH to 9.0. Subsequently, the mixture was heated for 20 minutes while stirring to bring the liquid temperature to 50° C. to complete the curing of the capsules.

(2) Production of pressure-sensitive copying paper One of the pressure-sensitive copying papers, Paper A, was obtained by coating the microcapsule gold paper obtained by the above method. Paper B fully coated with clay is the paper opposite to this pressure-sensitive copy paper A.
and paper C fully coated with phenol-aldehyde copolymer.
When the microcapsule-coated surface of paper A and the coated surfaces of papers B and C face each other, and pressure is applied to the non-coated surface of paper A, paper B is created.

A blue image immediately appeared on C. It was observed that the obtained copied image was clear and free from bleeding, and the coloring speed was sufficiently fast.

Example-11 Production of fi+ microcapsules (a) Part of gelatin 800MLi and gum arabic 960
(b) 87 parts by weight of crystal violet lactone and 57 parts by weight of benzoyl leucomethylene blue were added to an aqueous solution prepared by dissolving 1 part of Japanese cypress in 8000 parts by weight of warm water, and 2.2 parts of the diphenylbutane obtained in Example-9. ooog Dobe and commercially available mineral oil [boiling point 180-270°C, specific gravity [1L796 (15°/4°C)
)) A pigment-containing oil dissolved in a mixed oil with 400 parts by weight was added and emulsified with stirring to form an oil droplet dispersion system of 2 to 6 microns. Add warm water to this thread to make a total of 32,000 tons.
parts by weight, and then, with stirring, 101i% acetic acid was added to adjust the pH to 4.2. To this, 800 parts by weight of 37% formalin was added for the purpose of hardening, and after holding at 40°C for 60 minutes, gelation resistant to cooling up to 5°C, and further 10% by weight.
An aqueous sodium hydroxide solution was added to adjust the pH to 9.0 to complete curing of the microcapsules.

(2) Production of pressure-sensitive copying paper Pressure-sensitive copying paper was produced in the same manner as in Example 10 using the microcapsules obtained by the above method. When the obtained copy paper was subjected to pressure writing, it gave a clear blue copy image without bleeding.

Example-12 (Production of @ agent) 10 moles (781f) of benzene and pulverized anhydrous aluminum chloride [L1
mol (IA5f)') inside while stirring.
! It was kept at 1-10°C. Here, 1-phenyl-2-butene (synthesized from benzene and butadiene in the presence of a phosphoric acid catalyst. A mixture of 15 moles of butadiene g (D yield 67%) and 2 moles of benzene was subjected to a glass reaction continuously for 4 hours. The mixture was dropped into a container for reaction. Even after the mixture was dropped, the temperature was maintained at a total temperature of 10° C. for 20 minutes with stirring.

Thereafter, stirring was stopped, and the raw reaction product was separated and recovered, washed and neutralized with an aqueous solution of caustic soda, dried over sodium sulfate, and then distilled under reduced pressure to produce colorless and transparent diphenylbutane (hereinafter referred to as DPB).
) (boiling point: normal pressure conversion 1'j: 2 9 0
〜300℃）368mm
I got (77,4?). The isomer composition of DPB is 1,
1 piece was 24, 1,2 piece was 25%, and 1,5 piece was 51%.

In addition, the viscosity is 4.5708t, 040℃, and the pour point is 14.
The temperature was below 7°C. The conversion rate of 1-phenyl-2-butene was 100%. The yield based on 1-phenyl-2-butene was 7i6%.

Example 13 As a catalyst, anhydrous aluminum chloride α1 mole <1!
An experiment similar to Example 12 was conducted except that a complex obtained by mixing 112 moles of mesitylene (24,01) with b5f) was used. Clear and colorless due to vacuum distillation
B a 40 m+) mol (92.5F) was obtained. The isomer composition of this DPB is 1.1 22%, 1,2 5
9%, 1.5 unit 59%, i. 1-phenyl-2
-Butene conversion was 99%. Moreover, the yield based on 1-phenyl-2-butene was 8 aO%.

Claims (1)

[Claims] 10-40% by weight of 1,1-diphenylbutane and 1,2-
A solvent for pressure-sensitive copying paper comprising a diphenylbutane isomer mixture comprising 60 to 90% by weight of diphenylbutane and/or 1,3-diphenylbutane, or a hydrocarbon solvent containing the isomer mixture.