KR830001754B1 - Manufacturing method of pressure-sensitive copy paper - Google Patents

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Description

Manufacturing method of pressure-sensitive copy paper

Figure is a change in color density at -5 ℃ low temperature of the pressure-sensitive radiation paper produced by the method of Example 1.

The present invention relates to a novel pressure sensitive copy paper manufacturing method, and in particular to a novel pressure sensitive copy paper manufacturing method having excellent properties even under bad environmental conditions such as ambient high temperature and high humidity or ambient low temperature.

In general, pressure-sensitive radiation paper (1) a colorless electron donor material having a color-forming activity in a solvent on the back of the paper (hereinafter referred to as a color-forming body). Paper coated with Micro Gapsules formed from a solution (hereinafter referred to as CB paper) is coated with a coloring material (hereinafter referred to as a colorant) capable of forming a coloring material by reacting the entire surface of the paper with the above-described color-forming material. One sheet of paper (hereinafter referred to as CF paper) may be manufactured by overlapping, or (2) both sides of the paper may be coated with the above-mentioned microcapsules and coloring agents (hereinafter referred to as CFB paper) in the form of a combination of the above-mentioned CB paper and CF paper. Or (3) only one side of the paper is coated with the above-described microcapsules and colorant to produce a form. All of these pressure sensitive copy papers are broken by the artificial pressure applied to the paper, and thus the color capsules are broken and thus the color-forming agent comes into contact with the colorant.

In the pressure sensitive copy paper produced as described above, the material which has an important influence on the quality is a wall material forming the microcapsules with the color forming agent solvent contained in the microcapsules.

To this end, the properties required by the solvent described above are as follows.

(1) Be able to dissolve color forming agent in high concentration.

(2) When used for pressure sensitive copy paper, the coloring speed, color density after coloring and color stability should be high.

(3) Recognize light, heat and chemicals.

(4) Almost odorless.

(5) No harm to human body.

(6) It is possible to dissolve colorigraphy and not cause environmental pollution.

On the other hand, the wall material of the microcapsules requires uniformity and excellent mechanical strength, and the microcapsules are generally manufactured by a so-called coacervate method.

Although several kinds of polymer materials have been used as wall materials that meet the above requirements and can easily achieve microcapsulation, gelatin is now commonly used as the most suitable wall material. In recent years, however, the use of pressure sensitive radiant paper has spread worldwide, and even in high temperature, high humidity and very cold climates.

This increases the chances of exposing pressure sensitive copy paper to extreme environmental conditions or the use of such materials under extreme environmental conditions during transportation or during the storage of paper in warehouses in the aforementioned special climate areas when exporting pressure sensitive copy paper. do.

As used herein, the term "extreme environmental conditions" refers to the so-called high temperature and high humidity environment conditions of about 40 to 50 ℃ and relative humidity of about 80% or more and cold conditions of about 0 ℃ or less.

Examples of exposure of the pressure sensitive copy paper to the above-mentioned extreme environmental conditions include when the pressure sensitive copy paper stays in a hot and humid region with an end-time shipment to the cargo ship during the transport period following exports, and when the climate is stored for a long time in the original hot and humid warehouse. Can be raised. An example of the use of pressure sensitive radiant paper under acute environmental conditions is the use of pressure sensitive radiant paper at atmospheric temperatures, such as in gasoline stations.

When the pressure sensitive copy paper is kept for a long time under high temperature and high humidity environment, the color forming agent solution contained in the microcapsules of the pressure sensitive copy paper flows out of the capsule to develop unnecessary color before use of the paper and satisfactory color at the appropriate point of use. This will cause the paper to be damaged as it will become dirty from copying. Such damage causes a fatal problem that the damaged pressure sensitive recording paper can no longer actually be used.

On the other hand, when the pressure-sensitive copy paper is commonly used in the above-mentioned very cold areas, it takes a long time to develop a color that is sufficiently visible, and thus there is a problem in that the paper can no longer be actually used because the recording cannot be read for a considerable time.

However, until now pressure sensitive copy papers are often exposed to the extreme environmental conditions described above or are not advanced enough to be used under the above mentioned extreme environmental conditions, so the pressure sensitive copy papers have excellent characteristics for important requirements up to the above mentioned extreme environmental conditions. There is no recognition that it must be maintained. Therefore, there was no pressure sensitive copy paper capable of maintaining excellent characteristics even in the above-mentioned extreme environmental conditions.

In view of the above conditions, the present invention pays special attention to the fact that the selection of solvents among the microcapsules contained in the pressure sensitive copy paper is very important to provide a pressure sensitive copy paper which can maintain excellent characteristics even in the above-mentioned extreme environmental conditions. Tilting and running the experiment. However, it has been found that the linearity of the solvent which can satisfy the above requirements (1) to (6) up to the extreme environmental conditions described above is very difficult. This difficult black contrasts between the properties that must be met by solvents in hot and humid climate areas and those that must be filled by the same solvent in very cold areas.

Test results of well-known solvents used in prior pressure sensitive radiation papers so far indicate that under these conditions, solvents that meet the requirements of (1) to (6) at the same time cannot be found.

However, experiments with several compounds that have never been known as solvents in pressure sensitive radiant paper have shown that surprisingly, 1-isopropylphenyl-2-phenylethane has been described in the above extreme environmental conditions, ie high temperature and humidity climate conditions and below 0 ° C. It has been found that under cold environmental conditions, all have the characteristics satisfying the above-mentioned requirements.

Representative solvents satisfying the above requirements (1) to (6) actually used so far are as follows.

(a) diisopropylnaphthalene

(b) isopropylbiphenyl

(c) hydrogenated thiphenyl

(d) 1-dimethylphenyl-1-phenylethane and

(e) ethylphenyl-phenylmethane

Among these solvents, (b), (d) and (e) are unstable when used in pressure sensitive radiation paper under high temperature and high humidity conditions, while (a) and (c) have poor color development at temperatures below 0 ° C. Pressure sensitive radiant paper is not suitable as a solvent when used under the extreme environmental conditions mentioned so far.

In fact, US Pat. No. 3,836,383 describes a solvent of the following structural formula resembling the 1-isopropylphenyl-2-phenylethane used above as a solvent for pressure sensitive copy paper.

However, pressure sensitive radiant papers using such solvents are unstable under high temperature and high humidity conditions, and the compounds described in particular are not sufficiently decomposed biologically.

U. S. Patent No. 3,936, 566 also describes a solvent of the following structure resembling 1-isopropylphenyl-2-phenylethanol used in pressure sensitive copy paper.

However, the compounds described are also not very stable under high temperature and high humidity conditions and are not sufficiently decomposed biologically and therefore not sufficiently as solvents of pressure sensitive copy paper.

And Japanese Patent Publication No. 499830/1971 also describes a solvent for pressure sensitive copy paper of the following structural formula.

However, the described compounds dissolve only small amounts of color formers, and the coloring properties of pressure sensitive copy papers produced using this solvent are poor in very cold areas.

As described above, the solvents generally known so far under the conditions of extreme climate cannot satisfy the above requirements (1) to (6), so that the pressure-sensitive radiant paper prepared as such a solvent is known as the above-mentioned extreme environmental conditions. You can't actually use it under

Accordingly, an object of the present invention is to select and use a compound that satisfies the above requirements (1) to (6) as a solvent, even under extreme environmental conditions, even under high temperature and high humidity climate conditions and very cold climate environment conditions. To produce a stable and practically usable pressure sensitive copy paper.

Another object of the present invention can be extracted from the following technique. A feature of the present invention is to produce a pressure sensitive copy paper containing a microcapsule containing a color former solution obtained by dissolving a color former in 1-isopropylphenyl-2-phenylethane or a solution containing the same. It is applied to a sheet of paper to make it.

The structural formula and physical properties of 1-isopropylphenyl-2-phenylethane used as the color former solvent in the present invention are described below with reference to.

constitutional formula

Boiling Point: 313-315 ℃ / 760mmHg

Specific gravity: 0.963

Equivalent viscosity (100 ℉): 4.5 Cst

In addition, the above-mentioned compound can be actually manufactured as follows.

(a) benzene and 1,2-dichloroethanol catalysts were polymerized in the presence of aluminum chloride to obtain 1,2-diphenylethanol, and the 1,2-diphenylethane thus prepared was subjected to propyl addition reaction to give 1-isopropyl Phenyl-2-phenylethanol is prepared or (b) 1-isopropylphenyl-2-phenylethane is prepared by reacting benzene and cumene with 1,2-dichloroethane in the presence of aluminum chloride as catalyst. The 1-isopropylphenyl-2-phenylethane thus obtained is an almost odorless and colorless liquid.

As described in the following examples, the 1-isopropylphenyl-2-phenylethane used in the present invention has the above requirements (1) to 1, which are required as solvents of pressure sensitive copy paper under high temperature and high humidity conditions and under very cold environmental conditions. Although (6) is sufficiently satisfied, it is considered that the above-described compound has such characteristics in view of scientific common sense.

According to the prior art, the chemical structure of the solvent which is stably applied to the pressure sensitive copy paper under high temperature and high humidity environment is high molecular weight aliphatic material and on the contrary, the pressure sensitive copy paper shows excellent coloring property under very cold environmental conditions. The chemical structural characteristics of the solvents produced are known to be low molecular weight aromatic rich materials.

This is in contrast to the solvents for producing stable pressure sensitive copy paper under high temperature and high humidity environment and the courageous chemical structural features of pressure sensitive copy paper with good coloration under very cold climatic conditions.

Therefore, it was considered practically impossible to obtain a compound that can be used for the production of pressure-sensitive radiation paper that retains its excellent properties under these two conditions in terms of its chemical structure.

In the present invention, it is most preferable to use 1-isopropylphenyl-2-phenylethanol alone as a solvent, but it may be used in combination with other solvents if the intrinsic properties do not change.

In addition, since 1-isopropylphenyl-2-phenylethane is excellent in dissolving various color forming agents used in pressure sensitive copying paper, examples of color forming agents that can be used in the present invention include benzoyl leucomethylene methylene (BLMB) and crystal bioel. Diaminofluorane derivatives such as lactone (CVL), malachite green lactone and 3-dialkylamino-7-dialkylamino fluorane and the like.

Moreover, examples of the colorant in the present invention include acidic clays, phenol resins, salicylate derivatives and the like which have been used so far.

The following examples illustrate the production of pressure sensitive copy paper according to the present invention and the improvement effect of the pressure sensitive copy paper described above. Therefore, it will be appreciated that the inventive concept is not limited to this embodiment.

Example 1

Synthesis of 1-isopropylphenyl-2-phenylethane

5 mole benzene, 5 mole cumene and 0.5 mole aluminum chloride as a catalyst were added to the detachable flask, and the flask was heated to 70 ° C. in the aqueous phase, and then 2 mole of 1, 2- was added to the mixture while removing gaseous hydrogen chloride generated while stirring. Dichloroethanol is added dropwise. After completion of the reaction, the reaction product is separated from the catalyst and the product is washed with water and evaporated in vacuo to give a colorless 1-isopropylphenyl-2-feethane. The properties of the product thus obtained are as follows.

Boiling Point: 313-315 ℃ / 760mmHg

와Specific gravity: 0.963

Wow

Kinematic Viscosity: 4.5cst / 100 ℉

Preparation of Microcapsules

Thus obtained 1-isopropylphenyl-2-phenylethane was dissolved in 2.7 g of crystallized purple lactone and 1.8 g of leucomethylene bulen, and this solution was added to an aqueous solution of 30 g gelatin dissolved in 270 g of water, followed by emulsification. An aqueous solution in which the gum arabic is dissolved is added to the emulsion described above while stirring the resulting mixture and maintaining the temperature at 50 ° C. Next, the pH of the mixture was gradually lowered to 4.4 using a 50% aqueous solution of vinegar acetic acid (Coacervate), and the mixture was cooled to 10 ° C. to solidify the membrane of the microcapsules thus formed, and then to 20 ml of 25%. An aqueous solution of gurtaraldehyde is added to the liquid containing the microcapsules. The membrane of the microcapsules is further solidified by adding 10% aqueous sodium hydroxide solution to the mixture to maintain the pH at 9 to terminate the encapsulation.

Preparation of Pressure Sensitive Copy Paper

45 g / m ^{2 of the} microcapsule weight thus obtained was coated on one side with a dry material at a rate of 5 g / m ² to prepare CB paper, and combined with CF paper prepared according to the previous method to produce pressure sensitive copy paper.

Example 2

This example provides experimental results under high temperature and high humidity conditions for pressure sensitive radiation paper according to the present invention. After removing the pressure sensitive recording paper prepared by the method described in Example 1 for 16 hours in a box kept at a constant temperature of 40 ° C. and a relative humidity of 90 ° C., the paper was hung on calender-rolls and stained. The color density is measured with a red color density densitometer (Refraction Color densitometer manufactured by Macbeth).

In parallel with this, other pressure sensitive copy papers prepared according to the same method as described in Example 1 and stored for 16 hours in an air at a temperature of 15 ° C. and a relative humidity of 65% were colored in the same manner as described above. Measure Subsequently, the color density of the pressure sensitive copy paper (as a standard value) of the pressure sensitive copy paper, which was left under the high temperature and high humidity conditions described above, was obtained by calculating the color density of the latter pressure sensitive copy paper which was left for 16 hours in an atmosphere having a temperature of 15 ° C and a relative humidity of 65%. Can be. This value is 70. From this value, it turns out that the pressure sensitive copy paper produced in Example 1 is sufficiently stable if the characteristic examination is not remarkable even under the above-mentioned extreme environmental conditions.

Example 3

This example provides the coloring speed of pressure sensitive copy paper produced according to the present invention under very cold climatic environmental conditions. Pressure sensitive copy paper prepared according to the method described in Example 1 The color of the pressure sensitive copy paper was processed by the roller roll at a normal temperature and the color density of the treated pressure sensitive copy paper was measured with a refractive color density meter (manufactured by Macbeth) Used as.

On the other hand, the color density measured by carrying out the same operation mentioned above with another sheet of paper mentioned above in the room which maintained temperature -5 degreeC is set to B. % Of B relative to A, i.e. (B / A) x 100, is used to describe the chromaticity at -5 ° C. The results are recorded in the accompanying drawings.

As shown in the figure, the coloring speed of the pressure sensitive copy paper produced according to the preparation of Example 1 at -5 ° C as an example is 70% after 30 seconds and is not affected by the low temperature of -5 ° C. The results are contained in the accompanying drawings. As shown in the results, the pressure sensitive copy paper of the present invention has a clear color and is stable even at low temperatures.

Example 4

This example provides test results for the biological degradation of 1-isopropylphenyl-2-phenylethane used in the present invention. In a 300 ml conical flask, 1-isopropylphenyl-2-phenylethane and activating sludge prepared according to the method described in Example 1 were added together with the culture medium so that the concentrations of the two substances in the medium were 200 ppm and 100 ppm, respectively. The sludge is incubated for two weeks with shaking. After incubation, the culture extract is analyzed by gas chromatograph with solvent to measure the biodegradation rate of 1-isopropylphenyl-2-phenylethane. The results indicate that 1-isopropylphenyl-2-phenylethane remains about 15% of the initial dose, which means that the compound has a high biodegradation of 85%.

Example 5

This example provides stability test results of pressure sensitive radiation paper produced according to the present invention under environmental conditions of high temperature and high humidity climate.

Pressure sensitive copy paper prepared according to the method described in Example 1 was stored for 16 hours in a drying furnace maintained at a constant temperature of 105 ° C. The pressure sensitive copy paper thus treated was subsequently colored according to the manufacturing method described in Example 2, and its color density was compared with the standard color density measured using another input sensitive copy paper produced by the same method as described above. Color is stored for the same period at room temperature under normal environmental conditions. The former color density is 97% of the latter. The test results indicate that the pressure sensitive radiation paper according to the present invention is stable even under extreme environmental conditions of high temperature and low humidity.

Next, the results of the stability tests of existing solvents used in pressure sensitive radiation paper under extreme environmental conditions are described in the following comparative examples.

Comparative Example 1

A pressure sensitive copy paper was prepared according to the same method as described in Example 1 except that isopropyl biphenyl was used instead of 1-isopropenyl-2-phenylethane. In addition, the stability of the pressure sensitive copy paper thus produced under high temperature and high humidity conditions is measured by the same operation as described in Example 2. The test results show that the color density of the paper produced according to Comparative Example 1 is only 11% of the standard color density. From the experimental results, it was found that the pressure sensitive copy paper produced using isopropyl biphenyl almost lost the coloring properties under the high temperature and high humidity environment, and the used paper was not practically used.

Comparative Example 2

A pressure sensitive copy paper was produced according to the same method as described in Example 1 except that 1-diethylphenyl-1-phenylethanol was used instead of 1-isopropylphenyl-2-phenylethane. The stability under the high temperature and high humidity climatic conditions of the pressure sensitive radiation paper thus produced is measured according to the operation described in Example 2. The experimental results showed that the color density of the pressure sensitive copy paper of this Comparative Example 2 was only 16% of the standard color density.

This means that pressure sensitive radiant paper prepared using 1-diethylphenyl-1-phenylethane is unstable and practically unusable under environmental conditions of high temperature and high humidity.

Comparative Example 3

In addition to using ethylphenyl-phenyl methane instead of 1-isopropylphenyl-2phenylethane, pressure sensitive copy paper was prepared according to the same method as in Example 1. The stability under the environmental conditions of the high temperature and high humidity climate of the pressure sensitive radiation paper thus produced is measured according to the method described in Example 2. The test results indicated that the color density of the pressure sensitive copy paper thus prepared was only 11% of the standard color density. This means that pressure sensitive sensitizers prepared using ethylphenyl-phenylmethane are unstable under high temperature and humidity environmental conditions and cannot be used in practice.

Comparative Example 4

A pressure sensitive copy paper was prepared according to the same method as described in Example 1 except that hydrogenated thiphenyl was used instead of 1-isopropylphenyl-2-phenylethane. The coloring properties of the pressure sensitive copy paper thus prepared under very cold environmental conditions were measured according to the method described in Example 3. As a result, it was observed that the described coloring did not occur even after 30 seconds of the coloring process of the pressure-sensitive copy paper thus produced, and thus, it was found that such copy paper could not be actually used under very cold environmental conditions.

Comparative Example 5

The preparation was carried out according to the same method as described in Example 1 except for using di-isopropylnaphthalene instead of 1-isopropylphenyl-2-phenylethane. The coloring characteristics under very cold environmental conditions of the pressure sensitive copy paper thus produced were prepared according to the manufacturing method described in Example 3. As a result, it was found that the color density after 30 seconds of the coloring process of the pressure-sensitive copy paper thus produced was only 12% of the standard color density, and such paper was not practically used under very cold environmental conditions.

Comparative Example 6

A pressure sensitive copy paper was prepared according to the same method as described in Example 1 except that 21, 2-ditolylethanol was used instead of 1-isopropylphenyl-2-phenylethane. The stability under the high temperature and high humidity environmental conditions of the pressure sensitive radiation paper thus produced was measured by the method described in Example 2. As a result, the pressure sensitive copy paper thus produced has a color density of only 11% of the standard color density, and this means that the pressure sensitive copy paper produced is very poor in stability.

In other experiments, the biological decay of 1,2-ditolylethane was determined according to the same method as described in Example 4. As a result, the biological decay rate of 1,2-ditolylethane is only 28%.

Comparative Example 7

A pressure sensitive copy paper was prepared according to the same method as described in Example 1 except that 1, 2-dicumyl ethane was used instead of 1-isopropylphenyl-2-phenylethane. The coloring properties under the very cold environmental conditions of the pressure sensitive copy paper thus produced were determined by the preparation described in Example 3. As a result, the color density of the pressure sensitive copy paper thus obtained was only 10% of the standard color density 30 seconds after the coloring treatment.

In other experiments, the biological decay of 1, 2-dicumylethane was measured by the method described in Example 4. The results showed that the biological decay of 1, 2-dicumyl ethane was only 12%.

Comparative Example 8

Pressure sensitive copy paper was prepared according to the same method as described in Example 1 except that 1-isopropylphenyl-1-phenylethane was used instead of 1-isopropylphenyl-2-phenylethane as a solvent. The stability in the high temperature and high humidity environmental conditions of the pressure sensitive radiation paper thus produced was measured by the method described in Example 2. The color density of the pressure sensitive copy paper thus prepared was found to be 48% of the standard color density. The color paper density of the copy paper was only 50% of the standard color density in another stability test by the method described in Example 5 under the high temperature and high humidity environmental conditions, and thus the stability under the above-described environmental conditions was poor.

In a separate experiment where the biological decay of 1-isopropylphenyl-1-phenylethane was measured by the method described in Example 4, the biological decay of this solvent was only 16%. As can be easily understood from the above results, the pressure sensitive copy paper according to Comparative Example 8 has poor practicality under extreme environmental conditions.

Claims (1)

Paper coated with microcapsules comprising at least one solution characterized by containing 1-isopropylphenyl-2-phenylethane as a solvent in the solution and a solution containing a color-former therein. Method for producing pressure-sensitive copy paper produced by.

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