CA1238187A - Solvent for the dye of pressure-sensitive recording paper - Google Patents
Solvent for the dye of pressure-sensitive recording paperInfo
- Publication number
- CA1238187A CA1238187A CA000487874A CA487874A CA1238187A CA 1238187 A CA1238187 A CA 1238187A CA 000487874 A CA000487874 A CA 000487874A CA 487874 A CA487874 A CA 487874A CA 1238187 A CA1238187 A CA 1238187A
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- CA
- Canada
- Prior art keywords
- solvent
- pressure
- sensitive recording
- recording material
- dye
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
- B41M5/1655—Solvents
Landscapes
- Color Printing (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A solvent for the dye of pressure-sensitive recording paper which solvent has no offensive odor and both the color developing rate and developed color density are excellent. The solvent is is characterized in that it comprises a fraction mainly containing triaryldialkanes having boiling points above 350°C but not higher than 450°C
that is prepared by disproportionating diarylalkane or a hydrocarbon mixture comprising the same at temperatures in the range of 20 to 500°C in the presence of a disproportio-nation catalyst, said diarylalkane having boiling points in the range of 260 to 320°C.
A solvent for the dye of pressure-sensitive recording paper which solvent has no offensive odor and both the color developing rate and developed color density are excellent. The solvent is is characterized in that it comprises a fraction mainly containing triaryldialkanes having boiling points above 350°C but not higher than 450°C
that is prepared by disproportionating diarylalkane or a hydrocarbon mixture comprising the same at temperatures in the range of 20 to 500°C in the presence of a disproportio-nation catalyst, said diarylalkane having boiling points in the range of 260 to 320°C.
Description
~L2~8~L8~
SOLVENT FOR THE DYE OF
PRESSURE-SENSITIVE RECORDING PAPER
BACKGROUND OF THE INVENTION
(1) Field of the Invention This invention relates to a solvent for the dye of pressur~-sensitive recording paper. More particularly, the invention relates to a solvent for the dye of pressure-sensitive recording paper which solvent comprises a heavier frocks that is prepared by disproportionating diary-alikeness or a mixture mainly containing diarylalkanes in the presence of a disproportionation catalyst.
SOLVENT FOR THE DYE OF
PRESSURE-SENSITIVE RECORDING PAPER
BACKGROUND OF THE INVENTION
(1) Field of the Invention This invention relates to a solvent for the dye of pressur~-sensitive recording paper. More particularly, the invention relates to a solvent for the dye of pressure-sensitive recording paper which solvent comprises a heavier frocks that is prepared by disproportionating diary-alikeness or a mixture mainly containing diarylalkanes in the presence of a disproportionation catalyst.
(2) Description of the Prior Art Various kinds of pressure-sensitive recording papers are hitherto well known. For example, a colorless dye, that is a dye-precursor, is dissolved in a solvent and the obtained solution is encapsulated into micro capsules.
One surface of a sheet of paper is applied with micro capsules and the surface of another sheet of paper is applied with clay or a polymeric material such as phenol resin (color developer) which produces a color upon reacting with the dye-precursor. When the recording paper is used, the treated surfaces of the above set of paper sheets are put together face to face and local pressure is applied to the paired sheets by handwriting or any other measure, thereby obtaining desired duplicate impressions.
The recording mechanism in the pressure-sensitive recording paper is such that the micro capsules on the surface of a sheet of paper are ruptured by the pressure of handwriting or else to release the dye solution from the micro capsules. The solution containing a dye comes into contact with clay or polymeric material (color developer) on the opposing surface of the other sheet of paper to produce a color.
The dyes for pressure-sensitive recording paper are exemplified by Crystal Violet Lactose, Malachite Green, bouncily Leucomethylene Blue, Radiomen B and 3-dialkylamino-7-dialkylamino fluorine.
As the solvents for pressure-sensitive recording paper, diarylalkanes such as diphenylmethane and phenol-xylylethane are conventionally used. Some of diarylalkanesare, however, have offensive odor due to their chemical structures, which are not suitable as the solvents for pressure-sensitive recording paper.
Meanwhile, it is known that diphenylethanes are contained in the by-product oil that is produced in a certain preparation process. However, the by-product oil usually contains many kinds of other compounds and it is impossible to separate them simply by distillation. For this reason, even though the diphenylethanes in the by-product oil is not expensive, they are not widely used due to their offensive odor and for other reasons. For example, as disclosed in Japanese Laid-Open Patent Publication No. 56-161195, it is necessary to treat them in order to remove offensive odor and to add some odor-masking agents.
Other aromatic hydrocarbons such as dibenzyltoluene that is heavier than diarylalkanes are also proposed as the solvents for pressure-sensitive recording paper. Due to their higher molecular weight, however, the pour points and viscosities of them are generally high and the color developing properties of them are not always satisfactory.
Accordingly, more heavier aromatic hydrocarbons are scarcely used as solvents for pressure-sensitive recording paper.
BRIEF SUMMARY OF THE INVENTION
It is, therefore, the primary object of the present invention to provide an improved solvent for the dye of pressure-sensitive recording paper which is free from the above-described disadvantages in the conventional art.
Another object of the present invention is to provide a solvent for the dye of pressure-sensitive recording paper which solvent has no offensive odor though it is prepared from diarylalkanes, be excellent in the color developing property and anti-fading property, and have sufficiently lower pour point and viscosity irrespective of its high boiling point.
A further object of the present invention is to provide a solvent for the dye of pressure-sensitive recording paper, which solvent is inexpensive, has desirable properties and can be prepared from a by-product oil fraction of a hydrocarbon mixture mainly containing diarylalkanes that is obtained from a specific production process.
According to the present invention, the solvent for the dye of pressure-sensitive recording paper is characterized in that the solvent comprises a fraction which is prepared by disproportionating diarylalkanes or a hydra-carbon mixture mainly containing the same at temperatures iII
the range of 20 to 500C in the presence of a disproportion nation catalyst to obtain a fraction mainly containing triaryldialkanes having boiling points above 350C but not higher than 450C converted to atmospheric pressure basis.
A preferable example of the above-mentioned hydrocarbon mixture mainly containing diarylalkanes is the by-product oil fraction that is obtained in the process to produce alkylated monocyclic aromatic hydrocarbons by alkylating monocyclic aromatic hydrocarbons such as Bunsen and Tulane with olefins such as ethylene in the presence of an alkylation catalyst. When the above by-product oil fraction is used as a starting material, it is inexpensive and a fraction containing triaryldialkanes can be obtained efficiently, in addition, it is desirable in that a solvent for the dye of pressure-sensitive recording paper which scarcely has offensive odor can be obtained.
DETAILED DESCRIPTION OF THE INVENTION
The diarylalkanes according to the present invention are represented by the following general formula (I) and the boiling points of the above diarylalkanes or the hydrocarbon mixture mainly containing the same are in the range of 2~Q to 320C and preferably 260 -to 310C.
Diarylal]canes or a hydrocarbon mixture having a boiling point higher than the above range is not desirable because the effect of below-described disproportionation cannot be expected.
`~¦ ' Rum Run wherein each of R1 and R2 is a hydrogen atom or a straight chain or branched chain alkyd group; R3 is a straight chain or branched chain alkaline group; and each of m and n is an integer from 0 to 3. The above diarylalkanes are used singly or in a mixture of two or more kinds.
Exemplified as the above diarylalkanes are diphenylmethane, ditolylmethane, diphenylethane, phenyltolylethane and ditolylethane.
The hydrocarbon mixture mainly containing diarylalkanes that is used as a preferable starting material is a by-product oil that is obtained from a specific preparation process. More particularly, it is a by-product oil fraction which is produced in a process to prepare alkylated monocyclic aromatic hydrocarbons such as alkyd-Bunsen by alkylating monocyclic aromatic hydrocarbons with olefins in the presence of an alkylation catalyst.
The monocyclic aromatic hydrocarbons are benzeneand lower alkylbenzenes such as Tulane and the olefins are ~3~87 lower olefins such as ethylene and propylene. As the alkylation catalysts mainly used industrially are Lewis acids such as aluminum chloride and boron fluoride, synthetic zealots that are typically represented by ZSM-5 type zealot such as ZSM-5 and ZSM-ll, and pro tonic acids such as phosphoric acid.
The above-mentioned alkylation is widely put into practice as preparation processes for lower alkylbenzenes such as ethylbenzene, ethyltoluene and cumin. Ethylbenzene and ethyltoluene that are produced by alkylating Bunsen and Tulane with ethylene, are dehydrogenated into styrenes and methylstyrene, respectively, and they are consumed in large quantities for producing polymers.
An example of ethylbenzene preparation process will be described, in which Bunsen is alkylated with ethylene in the presence of aluminum chloride catalyst.
The molar ratio of the feed of Bunsen to ethylene is, for example, about 10:1 to about 3:1. In liquid phase alkylation, 0.005 to 0.030 part of catalyst is added to one part of produced ethylbenzene. The reaction is carried out at temperatures of 90 to 150C, pressures of 0.5 to 15 kg/cm2 and duration of 20 minutes to 3 hours.
Through the above alkylation, unrequited Bunsen, aimed ethylbenzene, polyethylbenzenes such as diethylbenzene and triethylbenzene, and the by-product oil fraction containing diarylalkanes are obtained.
~38~7 After the alkylation, the catalyst is removed by a conventional method. For example, the catalyst is separated by sedimentation in a settler, which is followed by neutralization and repeated water rinsing.
Then the unrequited Bunsen by 80C), ethylbenzene by 136C) and polyethylbenzene by 176 to 250C) are recovered by distillation from the alkylation product to obtain the by-product oil, as the remainder, containing diarylalkanes.
The by-product oil fraction that is especially preferable in the present invention is those which are obtained from the process to produce ethylbenzene or ethyltoluene by alkylating Bunsen or Tulane with ethylene.
This by-product oil fraction substantially comprises diary-alikeness and can be obtained in large quantities at low cost.
Furthermore, the effect of disproportionation of the invention can be produced markedly. Accordingly, said by-product oil fraction is desirable as the starting material to be used in the present invention.
In the present invention, the above-described starting material is subjected to dispxoportionation in the presence of a disproportionation catalyst.
The disproportionation catalysts are exemplified by Lewis acids such as aluminum chloride and ferris chloride, solid acids such as silica-alumina, and synthetic zealots represented by ZSM-5 type zealots such as ZSM-5 and ZSM-ll, heteropoly acids such as silicotungstic acid, super strong ~:3~7 acids such as trifluoromethane sulfonic acid, and super strongly acidic cation exchange resin such as Nation (trademark, made by ELI. duo Pont de Numerous). However, sulfuric acid and natural clay such as activated clay are not preferable because the disproportionation is not proceeded substantially.
The temperatures for the disproportionation can be selected in a wide range of 20 to 500C with the kind of used catalyst. For example, the temperature range of 20 to 150C is suitable for aluminum chloride; 150 to 230C, for Nation; and 250 to 500C, for synthetic zealot.
The disproportionation does not occur at temperatures lower than the above range, while side reaction such as decompose-lion occurs at temperatures higher than the above range, neither of which is, accordingly, desirable.
With regard to the type of reaction, any of bushes and continuous types can be employed.
Preferable reaction times are 20 minutes to 10 hours in bushes reaction and 0.5 to 10 in LHSV in continuous reaction.
The pressures of disproportionation are not especially limited, however, they are generally in the range of atmospheric pressure to 10 kg/cm2.
In the disproportionation according to the invention, monocyclic aromatic hydrocarbons of Bunsen and alkylbenzene such as Tulane that are lighter than the starting hydrocarbons and triaryldialkanes that are heavier ill g than the starting hydrocarbons and are represented by the following general formula (II), are produced.
J
Rip (R2)q (R3)r wherein each of R1, R2 and R3 is a hydrogen atom or a straight chain or branched chain alkyd group; each of R4 and Us is a straight chain or branched chain alkaline group; and each of p, q and r is an integer from 0 to 3.
In the present invention, it is characterized in that the fraction mainly containing the foregoing triaryldialkanes is used as the solvent for the dye of pressure-sensitive recording paper. Accordingly, after the disproportionation, the catalyst is removed by settling or filtration and the above fraction mainly containing triaryldialkanes is obtained by distillation. The boiling temperature of the fraction that is suitable as the solvent for the dye of pressure-sensitive recording paper is above 350C but not higher than 450C, preferably below 420C as converted to atmospheric pressure basis. In the fraction containing triaryldialkanes having boiling points above 450C, the viscosity and pour point are too high which are not desirable.
As described above, as monocyclic aromatic hydrocarbons that are lighter than the starting material are produced in the disproportionation, lighter materials can be 1~3~
continuously removed outside the reaction system especially in a bushes system. This is desirable because the yield of the above triaryldialkanes can be improved.
The fraction mainly containing triaryldialkanes is preferable because it has no offensive odor. In addition, in spite of its higher boiling point, the viscosity and pour point are relatively low. Furthermore, the dissolving property (dissolving power) and color developing property relative to the conventional dyes are also excellent.
Accordingly, -the above fraction is most suitable for use as the solvent for the dye of pressure-sensitive recording paper. Still further, when the by-product oil fraction in alkylation process is used as a starting material, it is desirable because the solvent can be produced at lower cost.
The solvents according to the present invention can be used singly or in a mixture with one or more kinds of known solvents, for example, kerosene, alkylbenzenes such as dodecylbenzene, diarylalkanes such as 1-phenyl-1-xylylethane and 1-phenyl-2-isopropylphenylethane, alkylbiphenyls such as isopropylbiphenyl, and alkylnaphthalenes such as diisopropylnaphthalene.
As the dyes (dye-precursors), there are typically triarylmethane type compounds, diphenylmethane type compounds, xanthene type compounds, thiamine type compounds, and spiropyran type compounds.
The dye-precursors of triarylmethane type compounds are exemplified by:
One surface of a sheet of paper is applied with micro capsules and the surface of another sheet of paper is applied with clay or a polymeric material such as phenol resin (color developer) which produces a color upon reacting with the dye-precursor. When the recording paper is used, the treated surfaces of the above set of paper sheets are put together face to face and local pressure is applied to the paired sheets by handwriting or any other measure, thereby obtaining desired duplicate impressions.
The recording mechanism in the pressure-sensitive recording paper is such that the micro capsules on the surface of a sheet of paper are ruptured by the pressure of handwriting or else to release the dye solution from the micro capsules. The solution containing a dye comes into contact with clay or polymeric material (color developer) on the opposing surface of the other sheet of paper to produce a color.
The dyes for pressure-sensitive recording paper are exemplified by Crystal Violet Lactose, Malachite Green, bouncily Leucomethylene Blue, Radiomen B and 3-dialkylamino-7-dialkylamino fluorine.
As the solvents for pressure-sensitive recording paper, diarylalkanes such as diphenylmethane and phenol-xylylethane are conventionally used. Some of diarylalkanesare, however, have offensive odor due to their chemical structures, which are not suitable as the solvents for pressure-sensitive recording paper.
Meanwhile, it is known that diphenylethanes are contained in the by-product oil that is produced in a certain preparation process. However, the by-product oil usually contains many kinds of other compounds and it is impossible to separate them simply by distillation. For this reason, even though the diphenylethanes in the by-product oil is not expensive, they are not widely used due to their offensive odor and for other reasons. For example, as disclosed in Japanese Laid-Open Patent Publication No. 56-161195, it is necessary to treat them in order to remove offensive odor and to add some odor-masking agents.
Other aromatic hydrocarbons such as dibenzyltoluene that is heavier than diarylalkanes are also proposed as the solvents for pressure-sensitive recording paper. Due to their higher molecular weight, however, the pour points and viscosities of them are generally high and the color developing properties of them are not always satisfactory.
Accordingly, more heavier aromatic hydrocarbons are scarcely used as solvents for pressure-sensitive recording paper.
BRIEF SUMMARY OF THE INVENTION
It is, therefore, the primary object of the present invention to provide an improved solvent for the dye of pressure-sensitive recording paper which is free from the above-described disadvantages in the conventional art.
Another object of the present invention is to provide a solvent for the dye of pressure-sensitive recording paper which solvent has no offensive odor though it is prepared from diarylalkanes, be excellent in the color developing property and anti-fading property, and have sufficiently lower pour point and viscosity irrespective of its high boiling point.
A further object of the present invention is to provide a solvent for the dye of pressure-sensitive recording paper, which solvent is inexpensive, has desirable properties and can be prepared from a by-product oil fraction of a hydrocarbon mixture mainly containing diarylalkanes that is obtained from a specific production process.
According to the present invention, the solvent for the dye of pressure-sensitive recording paper is characterized in that the solvent comprises a fraction which is prepared by disproportionating diarylalkanes or a hydra-carbon mixture mainly containing the same at temperatures iII
the range of 20 to 500C in the presence of a disproportion nation catalyst to obtain a fraction mainly containing triaryldialkanes having boiling points above 350C but not higher than 450C converted to atmospheric pressure basis.
A preferable example of the above-mentioned hydrocarbon mixture mainly containing diarylalkanes is the by-product oil fraction that is obtained in the process to produce alkylated monocyclic aromatic hydrocarbons by alkylating monocyclic aromatic hydrocarbons such as Bunsen and Tulane with olefins such as ethylene in the presence of an alkylation catalyst. When the above by-product oil fraction is used as a starting material, it is inexpensive and a fraction containing triaryldialkanes can be obtained efficiently, in addition, it is desirable in that a solvent for the dye of pressure-sensitive recording paper which scarcely has offensive odor can be obtained.
DETAILED DESCRIPTION OF THE INVENTION
The diarylalkanes according to the present invention are represented by the following general formula (I) and the boiling points of the above diarylalkanes or the hydrocarbon mixture mainly containing the same are in the range of 2~Q to 320C and preferably 260 -to 310C.
Diarylal]canes or a hydrocarbon mixture having a boiling point higher than the above range is not desirable because the effect of below-described disproportionation cannot be expected.
`~¦ ' Rum Run wherein each of R1 and R2 is a hydrogen atom or a straight chain or branched chain alkyd group; R3 is a straight chain or branched chain alkaline group; and each of m and n is an integer from 0 to 3. The above diarylalkanes are used singly or in a mixture of two or more kinds.
Exemplified as the above diarylalkanes are diphenylmethane, ditolylmethane, diphenylethane, phenyltolylethane and ditolylethane.
The hydrocarbon mixture mainly containing diarylalkanes that is used as a preferable starting material is a by-product oil that is obtained from a specific preparation process. More particularly, it is a by-product oil fraction which is produced in a process to prepare alkylated monocyclic aromatic hydrocarbons such as alkyd-Bunsen by alkylating monocyclic aromatic hydrocarbons with olefins in the presence of an alkylation catalyst.
The monocyclic aromatic hydrocarbons are benzeneand lower alkylbenzenes such as Tulane and the olefins are ~3~87 lower olefins such as ethylene and propylene. As the alkylation catalysts mainly used industrially are Lewis acids such as aluminum chloride and boron fluoride, synthetic zealots that are typically represented by ZSM-5 type zealot such as ZSM-5 and ZSM-ll, and pro tonic acids such as phosphoric acid.
The above-mentioned alkylation is widely put into practice as preparation processes for lower alkylbenzenes such as ethylbenzene, ethyltoluene and cumin. Ethylbenzene and ethyltoluene that are produced by alkylating Bunsen and Tulane with ethylene, are dehydrogenated into styrenes and methylstyrene, respectively, and they are consumed in large quantities for producing polymers.
An example of ethylbenzene preparation process will be described, in which Bunsen is alkylated with ethylene in the presence of aluminum chloride catalyst.
The molar ratio of the feed of Bunsen to ethylene is, for example, about 10:1 to about 3:1. In liquid phase alkylation, 0.005 to 0.030 part of catalyst is added to one part of produced ethylbenzene. The reaction is carried out at temperatures of 90 to 150C, pressures of 0.5 to 15 kg/cm2 and duration of 20 minutes to 3 hours.
Through the above alkylation, unrequited Bunsen, aimed ethylbenzene, polyethylbenzenes such as diethylbenzene and triethylbenzene, and the by-product oil fraction containing diarylalkanes are obtained.
~38~7 After the alkylation, the catalyst is removed by a conventional method. For example, the catalyst is separated by sedimentation in a settler, which is followed by neutralization and repeated water rinsing.
Then the unrequited Bunsen by 80C), ethylbenzene by 136C) and polyethylbenzene by 176 to 250C) are recovered by distillation from the alkylation product to obtain the by-product oil, as the remainder, containing diarylalkanes.
The by-product oil fraction that is especially preferable in the present invention is those which are obtained from the process to produce ethylbenzene or ethyltoluene by alkylating Bunsen or Tulane with ethylene.
This by-product oil fraction substantially comprises diary-alikeness and can be obtained in large quantities at low cost.
Furthermore, the effect of disproportionation of the invention can be produced markedly. Accordingly, said by-product oil fraction is desirable as the starting material to be used in the present invention.
In the present invention, the above-described starting material is subjected to dispxoportionation in the presence of a disproportionation catalyst.
The disproportionation catalysts are exemplified by Lewis acids such as aluminum chloride and ferris chloride, solid acids such as silica-alumina, and synthetic zealots represented by ZSM-5 type zealots such as ZSM-5 and ZSM-ll, heteropoly acids such as silicotungstic acid, super strong ~:3~7 acids such as trifluoromethane sulfonic acid, and super strongly acidic cation exchange resin such as Nation (trademark, made by ELI. duo Pont de Numerous). However, sulfuric acid and natural clay such as activated clay are not preferable because the disproportionation is not proceeded substantially.
The temperatures for the disproportionation can be selected in a wide range of 20 to 500C with the kind of used catalyst. For example, the temperature range of 20 to 150C is suitable for aluminum chloride; 150 to 230C, for Nation; and 250 to 500C, for synthetic zealot.
The disproportionation does not occur at temperatures lower than the above range, while side reaction such as decompose-lion occurs at temperatures higher than the above range, neither of which is, accordingly, desirable.
With regard to the type of reaction, any of bushes and continuous types can be employed.
Preferable reaction times are 20 minutes to 10 hours in bushes reaction and 0.5 to 10 in LHSV in continuous reaction.
The pressures of disproportionation are not especially limited, however, they are generally in the range of atmospheric pressure to 10 kg/cm2.
In the disproportionation according to the invention, monocyclic aromatic hydrocarbons of Bunsen and alkylbenzene such as Tulane that are lighter than the starting hydrocarbons and triaryldialkanes that are heavier ill g than the starting hydrocarbons and are represented by the following general formula (II), are produced.
J
Rip (R2)q (R3)r wherein each of R1, R2 and R3 is a hydrogen atom or a straight chain or branched chain alkyd group; each of R4 and Us is a straight chain or branched chain alkaline group; and each of p, q and r is an integer from 0 to 3.
In the present invention, it is characterized in that the fraction mainly containing the foregoing triaryldialkanes is used as the solvent for the dye of pressure-sensitive recording paper. Accordingly, after the disproportionation, the catalyst is removed by settling or filtration and the above fraction mainly containing triaryldialkanes is obtained by distillation. The boiling temperature of the fraction that is suitable as the solvent for the dye of pressure-sensitive recording paper is above 350C but not higher than 450C, preferably below 420C as converted to atmospheric pressure basis. In the fraction containing triaryldialkanes having boiling points above 450C, the viscosity and pour point are too high which are not desirable.
As described above, as monocyclic aromatic hydrocarbons that are lighter than the starting material are produced in the disproportionation, lighter materials can be 1~3~
continuously removed outside the reaction system especially in a bushes system. This is desirable because the yield of the above triaryldialkanes can be improved.
The fraction mainly containing triaryldialkanes is preferable because it has no offensive odor. In addition, in spite of its higher boiling point, the viscosity and pour point are relatively low. Furthermore, the dissolving property (dissolving power) and color developing property relative to the conventional dyes are also excellent.
Accordingly, -the above fraction is most suitable for use as the solvent for the dye of pressure-sensitive recording paper. Still further, when the by-product oil fraction in alkylation process is used as a starting material, it is desirable because the solvent can be produced at lower cost.
The solvents according to the present invention can be used singly or in a mixture with one or more kinds of known solvents, for example, kerosene, alkylbenzenes such as dodecylbenzene, diarylalkanes such as 1-phenyl-1-xylylethane and 1-phenyl-2-isopropylphenylethane, alkylbiphenyls such as isopropylbiphenyl, and alkylnaphthalenes such as diisopropylnaphthalene.
As the dyes (dye-precursors), there are typically triarylmethane type compounds, diphenylmethane type compounds, xanthene type compounds, thiamine type compounds, and spiropyran type compounds.
The dye-precursors of triarylmethane type compounds are exemplified by:
3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthhalide (Crystal Violet Lactose);
3,3-bis(p-dimethylaminophenyl)phthalide; 3-(p-dimethyl-aminophenyl)-3-(1,2-dimethylindole-3-yl)-phthalidee;
3-(p-dimethylaminophenyl)-3-(2-methylindole-3-yl)pphthalide;
3-(p-dimethylaminophenyl)-3-(2-phenylindole-3-yl)pphthalide;
3,3-bis(1,2-dimethylindole-3-yl)-5-dimethylaminophhthalide;
3,3-bis(1,2-dimethylindole-3-yl)-6-dimethylaminophhthalide;
3,3-bis(9-ethylcarbazole-3-yl)-5-dimethylaminophthhalide;
3,3-bis(2-phenylindole-3-yl)-5-dimethylaminophthaltide; and 3-p-dimethylaminophenyl-3-(1-methylpyrrole-2-yl)-66-dimethyl-aminophthalide.
The dye-precursors of diphenylmethane type compounds are exemplified by:
3,3-bis(p-dimethylaminophenyl)phthalide; 3-(p-dimethyl-aminophenyl)-3-(1,2-dimethylindole-3-yl)-phthalidee;
3-(p-dimethylaminophenyl)-3-(2-methylindole-3-yl)pphthalide;
3-(p-dimethylaminophenyl)-3-(2-phenylindole-3-yl)pphthalide;
3,3-bis(1,2-dimethylindole-3-yl)-5-dimethylaminophhthalide;
3,3-bis(1,2-dimethylindole-3-yl)-6-dimethylaminophhthalide;
3,3-bis(9-ethylcarbazole-3-yl)-5-dimethylaminophthhalide;
3,3-bis(2-phenylindole-3-yl)-5-dimethylaminophthaltide; and 3-p-dimethylaminophenyl-3-(1-methylpyrrole-2-yl)-66-dimethyl-aminophthalide.
The dye-precursors of diphenylmethane type compounds are exemplified by:
4,4-bis-dimethylaminobenzhydrine bouncily ether;
N-halophenyl Luke Armenia; and N-2,4,5-trichlorophenyl Luke Armenia.
The xanthene type dye-precursors are exemplified by: Radiomen B-anilinolactam;
Radiomen B-(p-nitroanilino)lactam;
Radiomen B-(p-chloroanilino)lactam;
3-dimethylamino-6-methoxyfluoran;
3-diethylamino-7-methoxyfluoran;
3-diethylamino-7-chloro-6-methylfluoran;
3-diethylamino-7-(acetylmethylamino)fluoran;
~23~
3-diethylamino-7-(dibenzylamino)fluoran;
3-diethylamino-7-(methylbenzylamino)fluoran;
3-diethylamino-7-(chloroethylmethylamino)fluoran;
3-diethylamino-7-(diethylamino)fluoran; and 3-diethylamino-6-methyl-7-anilinofluoran.
The thiamine type dye-precursors are exemplified by: bouncily Luke ethylene blue and p-nitrobenzoyl Luke ethylene blue.
The Spiro type dye-precursors are exemplified by:
3-methyl-spiro-dinaphthopyran; 3-ethyl-spiro-dinaphthopyran;
3,3'-dichloro-spiro-dinaphthopyran;
3-benzyl-spiro-dinaphthopyran;
3-methylnaphtho-(3-methoxybenzo)spiropyran; and 3-propyl-spiro-dibenzodipyran.
The dye-precursors can be dissolved into the solvent of the invention in the manner likewise the use of conventional solvents.
As the color developer, there are clay, polymers, and aromatic carboxylic acids or their metal salts.
The polymers are exemplified by phenol-aldehyde polymer, phenol-acetylene polymer, malefic acid-rosin polymer, partially or completely hydrolyzed styrene-maleic android copolymer, partially or completely hydrolyzed ethylene-maleic android copolymer, car boxy polyethylene, and partially or completely hydrolyzed vinyl methyl ether-maleic android copolymer.
~',23~
The aromatic carboxylic acids and their derivatives are exemplified by: 3,5-di(a-methylbenzyl)salicylic acid;
3-(a-methylbenzyl)-5- (a ,a-dimethylbenzyl)salicylic acid;
3-(4' -a' ,a~-dimethylbenzyl)phenyl-5-(a~a-dimethylbenzyl) salicylic acid; 3,5-di-tert-butyl salicylic acid;
3,5-di-tert-octyl salicylic acid;
3-cyclohexyl-5- (a, a-dimethylbenzyl)salicylic acid;
3-phenyl-5-~a,a-dimethylbenzyl)salicylic acid; and Dow (a,a-dimethylbenzyl)salicylic acid. Furthermore, their salts of polyvalent metals such as zinc, aluminum, barium, tin, iron, calcium and lead can also be used.
As the method to prepare the micro capsules of the dye-precursor solution, which is obtained by dissolving a dye-precursor into the solvent, there is a coacervation method in which the fine particles of the dye-precursor solution that are dispersed in water are coated by a protective colloidal material such as gelatin or gum Arabic thereby obtaining the micro capsules which contain therein the dye-precursor solution. Another method is the inter-facial polymerization method or a in situ polymerization method in which a monomer or a partially condensed polymerizable product is employed and a polymerization initiator, an accelerator or a catalyst is added to cause polymerization on the surfaces of fine particles of the dye-precursor solution, thereby preparing the micro capsules containing therein the dye-precursor solution. The specific solvent of the present invention can be used in any one of ~LJfZ~3~ 7 the above methods.
In the practical process for preparing micro-capsules in the conventional art, an auxiliary solvent has been used in dissolving a dye-precursor in order to control the viscosity and volatility of the dye-precursor solution, the particle size of the fine dispersion in micro capsule formation, the dissolving property to the polymeric material that is coated onto the surface to be recorded, and the rate of color development. However, the specific solvent of the 10 present invention can satisfactorily be used without employing such an auxiliary solvent. Nevertheless, any solvent which does not degrade the characteristics of the solvent of the present invention may be used as an auxiliary solvent.
It should be noted also that the specific solvent of the 15 present invention can be used together with conventional solvents.
The present invention will be described in more detail with reference to the following examples.
Example 1 Using aluminum chloride catalyst, alkylation was carried out by reacting bushes Bunsen with ethylene in a molar ratio (benzene:ethylene) of 5:1 at 130 DC and 4.9 kg/cm2 for 1 hour.
Unrequited Bunsen, ethylbenzene and polyethyl-Bunsen were distilled off from the above obtained reaction mixture to recover a by-product oil fraction of boiling points 260 to 310C (converted to atmospheric pressure) that I
contained the following diarylalkanes.
Composition % by weight C14 - C16 diarylethane 71 O t h e r s 29 T o t a l 100 (Triaryldialkane was scarcely contained.) The above by-product oil fraction had strong offensive odor and could not be used as a solvent.
Then, 30 g of aluminum chloride was added to 2000 ml of the above by-product oil fraction and it was dispropor-shunted at 80C for 5 hours with stirring.
After the disproportionation, the catalyst was deactivated and the disproportionation product was rinsed with water and dried. It was followed by distillation to obtain a C6 - Cog monocyclic aromatic hydrocarbon fraction of 80 to 160C in boiling points (yield: 5.0%), unrequited by-product oil fraction and heavier fraction of 351 to 400C
in boiling points (yield: 14.8%).
It was confirmed that the above heavier fraction mainly contained triaryldialkanes by GC-mass spectrum analysis. Furthermore, even though the fraction has high boiling points, the pour point and viscosity of the fraction were low as follows:
Pour point -27.5C
Viscosity 18.5 cyst (at 40C) This fraction had almost no odor.
Then, 5.0 g of crystal Violet was added to 100 g of the above fraction and it was emulsified by adding 100 g of gelatin, and water was added to make up 600 g as the whole. The pi of the above was adjusted to 4.5 with adding an aqueous solution of CMC and the capsule membranes were cured by glutaraldehyde to prepare micro capsule slurry.
A paste (CMC aqueous solution) and a blocking agent were added to the above obtained micro capsule slurry and they were mixed well. The above mixture was applied uniformly to sheets of quality paper using a wire bar and they were dried. The coated paper sheets were used as test papers where the the quantity of coated micro capsules was determined by weighing the test paper that was maintained at 1C and 60% humidity.
This test paper was combined with another sheet of paper that was coated with acid clay to obtain a set of pressure-sensitive recording paper. This pressure-sensitive recording paper was applied with a load of 675 kg/cm2 for 1 minute and color densities at 1 minute and 60 minutes after removing the load were obtained by determining the absorbances at 610 no. The results are shown in the following Table 1.
For comparison purpose, 10% by weight of activated clay powder was added to the foregoing by-product oil fraction and it was treated at 180C for 1 hour. Meanwhile, to the by-product oil fraction was added 5% by volume of 97 wt.% sulfuric acid and it was shaken at room temperature for 30 minutes. The two of treated by-product oil fractions aye were analyzed by GC-mass spectrum where the formation of triaryldialkane was hardly observed. Furthermore, the odor was hardly changed after the above treatments.
Example 2 Using synthetic zealot ZSM-5, Tulane was alkylated with ethylene under the following conditions:
Reaction -temperature 500C
Tolu.ene/ethylene 5 (molar ratio) After the alkylation, unrequited Tulane, ethyltoluene and polyethyltoluene were distilled off from the reaction mixture to obtain a heavier fraction, which had the following property and composition:
By-Product Oil Fraction Boiling Point 2~0 - 300C
Composition by weight C14 - C1s diarylmethane 59.1 C16 diarylethane25.9 O t h e r s 15.0 T o t a l 100.0 (Triaryldialkane was scarcely contained) The odor of the by-product oil fraction obtained here was better than the by-product oil fraction obtained in Example 1, however, it had considerable offensive odor yet.
The above by-product oil fraction (2000 ml) was disproportionate at 200C for 3 hours under atmospheric pressure by using 50 g of strongly acidic cation exchange ~L23~ 7 resin trademark: Nation made by duo Pont de Numerous).
During the disproportionation, the produced lighter fractions of Bunsen and C7 - Cog alkylbenzenes such as Tulane were removed continuously from the reaction system.
After the disproportionation, the catalyst was filtered off and 1550 ml of the filtrate was distilled to recover Fraction 2 containing diarylalkanes corresponding to unrequited fraction and Fraction 3 containing heavier triaryl-dial Kane. Incidentally, as the lighter fraction that were removed during the disproportionation was also collected, it is also shown in the following:
Fraction Boiling Point Recovery Lighter fraction 80 - 160C 9.9%
Fraction 3 351 - 400C 29.5%
It was confirmed that the above Fraction 3 mainly contained triaryldialkanes by GC-mass spectrum analysis.
This fraction had almost no odor and the properties of the fraction were low as follows:
Pour point -35~C
Viscosity 16.8 cyst (at 40C) Using the above Fraction 3, pressure-sensitive recording papers were prepared in the like manner as Example 1 and color densities and rates of color development were determined. The results are shown in the following Table 1.
For comparison purpose, other pressure-sensitive recording papers were prepared in the like manner as Example 1 by using, as solvents, diisopropylnaphthalene (trademark:
~'3~7 KMC made by Query Chemical Industry) and partially hydrogenated terphenyl (trademark: HB-40 made by Huts), and similar tests were carried out. The results of them are also shown in Table 1.
T a b l e ~~--__ Time 1 minute 60 minutes Example ~~~~~--.
Example 1 39.7 40.9 Example 2 39.6 40.8 " (K M C) 34.5 38.8 ' (HB-40) 30.7 38.0 _
N-halophenyl Luke Armenia; and N-2,4,5-trichlorophenyl Luke Armenia.
The xanthene type dye-precursors are exemplified by: Radiomen B-anilinolactam;
Radiomen B-(p-nitroanilino)lactam;
Radiomen B-(p-chloroanilino)lactam;
3-dimethylamino-6-methoxyfluoran;
3-diethylamino-7-methoxyfluoran;
3-diethylamino-7-chloro-6-methylfluoran;
3-diethylamino-7-(acetylmethylamino)fluoran;
~23~
3-diethylamino-7-(dibenzylamino)fluoran;
3-diethylamino-7-(methylbenzylamino)fluoran;
3-diethylamino-7-(chloroethylmethylamino)fluoran;
3-diethylamino-7-(diethylamino)fluoran; and 3-diethylamino-6-methyl-7-anilinofluoran.
The thiamine type dye-precursors are exemplified by: bouncily Luke ethylene blue and p-nitrobenzoyl Luke ethylene blue.
The Spiro type dye-precursors are exemplified by:
3-methyl-spiro-dinaphthopyran; 3-ethyl-spiro-dinaphthopyran;
3,3'-dichloro-spiro-dinaphthopyran;
3-benzyl-spiro-dinaphthopyran;
3-methylnaphtho-(3-methoxybenzo)spiropyran; and 3-propyl-spiro-dibenzodipyran.
The dye-precursors can be dissolved into the solvent of the invention in the manner likewise the use of conventional solvents.
As the color developer, there are clay, polymers, and aromatic carboxylic acids or their metal salts.
The polymers are exemplified by phenol-aldehyde polymer, phenol-acetylene polymer, malefic acid-rosin polymer, partially or completely hydrolyzed styrene-maleic android copolymer, partially or completely hydrolyzed ethylene-maleic android copolymer, car boxy polyethylene, and partially or completely hydrolyzed vinyl methyl ether-maleic android copolymer.
~',23~
The aromatic carboxylic acids and their derivatives are exemplified by: 3,5-di(a-methylbenzyl)salicylic acid;
3-(a-methylbenzyl)-5- (a ,a-dimethylbenzyl)salicylic acid;
3-(4' -a' ,a~-dimethylbenzyl)phenyl-5-(a~a-dimethylbenzyl) salicylic acid; 3,5-di-tert-butyl salicylic acid;
3,5-di-tert-octyl salicylic acid;
3-cyclohexyl-5- (a, a-dimethylbenzyl)salicylic acid;
3-phenyl-5-~a,a-dimethylbenzyl)salicylic acid; and Dow (a,a-dimethylbenzyl)salicylic acid. Furthermore, their salts of polyvalent metals such as zinc, aluminum, barium, tin, iron, calcium and lead can also be used.
As the method to prepare the micro capsules of the dye-precursor solution, which is obtained by dissolving a dye-precursor into the solvent, there is a coacervation method in which the fine particles of the dye-precursor solution that are dispersed in water are coated by a protective colloidal material such as gelatin or gum Arabic thereby obtaining the micro capsules which contain therein the dye-precursor solution. Another method is the inter-facial polymerization method or a in situ polymerization method in which a monomer or a partially condensed polymerizable product is employed and a polymerization initiator, an accelerator or a catalyst is added to cause polymerization on the surfaces of fine particles of the dye-precursor solution, thereby preparing the micro capsules containing therein the dye-precursor solution. The specific solvent of the present invention can be used in any one of ~LJfZ~3~ 7 the above methods.
In the practical process for preparing micro-capsules in the conventional art, an auxiliary solvent has been used in dissolving a dye-precursor in order to control the viscosity and volatility of the dye-precursor solution, the particle size of the fine dispersion in micro capsule formation, the dissolving property to the polymeric material that is coated onto the surface to be recorded, and the rate of color development. However, the specific solvent of the 10 present invention can satisfactorily be used without employing such an auxiliary solvent. Nevertheless, any solvent which does not degrade the characteristics of the solvent of the present invention may be used as an auxiliary solvent.
It should be noted also that the specific solvent of the 15 present invention can be used together with conventional solvents.
The present invention will be described in more detail with reference to the following examples.
Example 1 Using aluminum chloride catalyst, alkylation was carried out by reacting bushes Bunsen with ethylene in a molar ratio (benzene:ethylene) of 5:1 at 130 DC and 4.9 kg/cm2 for 1 hour.
Unrequited Bunsen, ethylbenzene and polyethyl-Bunsen were distilled off from the above obtained reaction mixture to recover a by-product oil fraction of boiling points 260 to 310C (converted to atmospheric pressure) that I
contained the following diarylalkanes.
Composition % by weight C14 - C16 diarylethane 71 O t h e r s 29 T o t a l 100 (Triaryldialkane was scarcely contained.) The above by-product oil fraction had strong offensive odor and could not be used as a solvent.
Then, 30 g of aluminum chloride was added to 2000 ml of the above by-product oil fraction and it was dispropor-shunted at 80C for 5 hours with stirring.
After the disproportionation, the catalyst was deactivated and the disproportionation product was rinsed with water and dried. It was followed by distillation to obtain a C6 - Cog monocyclic aromatic hydrocarbon fraction of 80 to 160C in boiling points (yield: 5.0%), unrequited by-product oil fraction and heavier fraction of 351 to 400C
in boiling points (yield: 14.8%).
It was confirmed that the above heavier fraction mainly contained triaryldialkanes by GC-mass spectrum analysis. Furthermore, even though the fraction has high boiling points, the pour point and viscosity of the fraction were low as follows:
Pour point -27.5C
Viscosity 18.5 cyst (at 40C) This fraction had almost no odor.
Then, 5.0 g of crystal Violet was added to 100 g of the above fraction and it was emulsified by adding 100 g of gelatin, and water was added to make up 600 g as the whole. The pi of the above was adjusted to 4.5 with adding an aqueous solution of CMC and the capsule membranes were cured by glutaraldehyde to prepare micro capsule slurry.
A paste (CMC aqueous solution) and a blocking agent were added to the above obtained micro capsule slurry and they were mixed well. The above mixture was applied uniformly to sheets of quality paper using a wire bar and they were dried. The coated paper sheets were used as test papers where the the quantity of coated micro capsules was determined by weighing the test paper that was maintained at 1C and 60% humidity.
This test paper was combined with another sheet of paper that was coated with acid clay to obtain a set of pressure-sensitive recording paper. This pressure-sensitive recording paper was applied with a load of 675 kg/cm2 for 1 minute and color densities at 1 minute and 60 minutes after removing the load were obtained by determining the absorbances at 610 no. The results are shown in the following Table 1.
For comparison purpose, 10% by weight of activated clay powder was added to the foregoing by-product oil fraction and it was treated at 180C for 1 hour. Meanwhile, to the by-product oil fraction was added 5% by volume of 97 wt.% sulfuric acid and it was shaken at room temperature for 30 minutes. The two of treated by-product oil fractions aye were analyzed by GC-mass spectrum where the formation of triaryldialkane was hardly observed. Furthermore, the odor was hardly changed after the above treatments.
Example 2 Using synthetic zealot ZSM-5, Tulane was alkylated with ethylene under the following conditions:
Reaction -temperature 500C
Tolu.ene/ethylene 5 (molar ratio) After the alkylation, unrequited Tulane, ethyltoluene and polyethyltoluene were distilled off from the reaction mixture to obtain a heavier fraction, which had the following property and composition:
By-Product Oil Fraction Boiling Point 2~0 - 300C
Composition by weight C14 - C1s diarylmethane 59.1 C16 diarylethane25.9 O t h e r s 15.0 T o t a l 100.0 (Triaryldialkane was scarcely contained) The odor of the by-product oil fraction obtained here was better than the by-product oil fraction obtained in Example 1, however, it had considerable offensive odor yet.
The above by-product oil fraction (2000 ml) was disproportionate at 200C for 3 hours under atmospheric pressure by using 50 g of strongly acidic cation exchange ~L23~ 7 resin trademark: Nation made by duo Pont de Numerous).
During the disproportionation, the produced lighter fractions of Bunsen and C7 - Cog alkylbenzenes such as Tulane were removed continuously from the reaction system.
After the disproportionation, the catalyst was filtered off and 1550 ml of the filtrate was distilled to recover Fraction 2 containing diarylalkanes corresponding to unrequited fraction and Fraction 3 containing heavier triaryl-dial Kane. Incidentally, as the lighter fraction that were removed during the disproportionation was also collected, it is also shown in the following:
Fraction Boiling Point Recovery Lighter fraction 80 - 160C 9.9%
Fraction 3 351 - 400C 29.5%
It was confirmed that the above Fraction 3 mainly contained triaryldialkanes by GC-mass spectrum analysis.
This fraction had almost no odor and the properties of the fraction were low as follows:
Pour point -35~C
Viscosity 16.8 cyst (at 40C) Using the above Fraction 3, pressure-sensitive recording papers were prepared in the like manner as Example 1 and color densities and rates of color development were determined. The results are shown in the following Table 1.
For comparison purpose, other pressure-sensitive recording papers were prepared in the like manner as Example 1 by using, as solvents, diisopropylnaphthalene (trademark:
~'3~7 KMC made by Query Chemical Industry) and partially hydrogenated terphenyl (trademark: HB-40 made by Huts), and similar tests were carried out. The results of them are also shown in Table 1.
T a b l e ~~--__ Time 1 minute 60 minutes Example ~~~~~--.
Example 1 39.7 40.9 Example 2 39.6 40.8 " (K M C) 34.5 38.8 ' (HB-40) 30.7 38.0 _
Claims (24)
1. A solvent for the dye of pressure-sensitive recording paper which comprises a fraction mainly containing triaryldialkanes having boiling points above 350°C but not higher than 450°C, which fraction is prepared by dispropor-tionating diarylalkane or a hydrocarbon mixture comprising the same at temperatures in the range of 20 to 500°C in the presence of a disproportionation catalyst, said diarylalkane having boiling points in the range of 260 to 320°C.
2. The solvent in claim 1, wherein said disproportionation catalyst is a Lewis acid.
3. The solvent in claim 2, wherein said Lewis acid is aluminum chloride.
4. The solvent in claim 1, wherein said disproportionation catalyst is a solid acid.
5. The solvent in claim 4, wherein said solid acid is a synthetic zeolite.
6. The solvent in claim 1, wherein said hydrocarbon mixture is the by-product oil fraction mainly containing diarylalkanes and being obtained in the process to prepare an alkylated monocyclic aromatic hydrocarbon by alkylating a monocyclic aromatic hydrocarbon with an olefin in the presence of an alkylation catalyst.
7. The solvent in claim 6, wherein said monocyclic aromatic hydrocarbon is benzene or toluene.
8. The solvent in claim 6, wherein said olefin is ethylene.
9. The solvent in claim 6, wherein said alkylation catalyst is a Lewis acid.
10. The solvent in claim 9, wherein said Lewis acid is aluminum chloride.
11. The solvent in claim 6, wherein said alkylation catalyst is a solid acid.
12. The solvent in claim 11, wherein said solid acid is a synthetic zeolite.
13. In a pressure-sensitive recording material prepared by using a dye-precursor which produces a color when said dye-precursor is brought into contact with a color developer, the pressure-sensitive recording material which is characterized in that the solvent for said dye-precursor comprises a fraction mainly containing triaryldialkanes having boiling points above 350°C but not higher than 450°C, which fraction is prepared by disproportionating diarylalkane or a hydrocarbon mixture comprising the same at temperatures in the range of 20 to 500°C in the presence of a dispropor-tionation catalyst, said diarylalkane having boiling points in the range of 260 to 320°C.
14. The pressure-sensitive recording material in claim 13, wherein said disproportionation catalyst is a Lewis acid.
15. The pressure-sensitive recording material in claim 14, wherein said Lewis acid is aluminum chloride.
16. The pressure-sensitive recording material in claim 13, wherein said disproportionation catalyst is a solid acid catalyst.
17. The pressure-sensitive recording material in claim 16, wherein said solid acid is a synthetic zeolite.
18. The pressure-sensitive recording material in claim 13, wherein said hydrocarbon mixture is the by-product oil fraction mainly containing diarylalkanes and being obtained in the process to prepare an alkylated monocyclic aromatic hydrocarbon by alkylating a monocyclic aromatic hydrocarbon with an olefin in the presence of an alkylation catalyst.
19. The pressure-sensitive recording material in claim 18, wherein said monocyclic aromatic hydrocarbon is benzene or toluene.
20. The pressure-sensitive recording material in claim 18, wherein said olefin is ethylene.
21. The pressure-sensitive recording material in claim 18, wherein said alkylation catalyst is a Lewis acid.
22. The pressure-sensitive recording material in claim 21, wherein said Lewis acid is aluminum chloride.
23. The pressure-sensitive recording material in claim 18, wherein said alkylation catalyst is a solid acid.
24. The pressure-sensitive recording material in claim 23, wherein said solid acid is a synthetic zeolite.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59-164533 | 1984-08-06 | ||
| JP16453384A JPS6141593A (en) | 1984-08-06 | 1984-08-06 | Solvent for dye of pressure-sensitive paper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1238187A true CA1238187A (en) | 1988-06-21 |
Family
ID=15794967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000487874A Expired CA1238187A (en) | 1984-08-06 | 1985-07-31 | Solvent for the dye of pressure-sensitive recording paper |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0171039B1 (en) |
| JP (1) | JPS6141593A (en) |
| CA (1) | CA1238187A (en) |
| DE (1) | DE3588130T2 (en) |
| ES (1) | ES8801152A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH074986B2 (en) * | 1986-05-26 | 1995-01-25 | 富士写真フイルム株式会社 | Thermal recording material |
| EP0273752B1 (en) * | 1986-12-25 | 1992-08-19 | Fuji Photo Film Co., Ltd. | Method of manufacturing heat sensitive recording material |
| JPH02106387A (en) * | 1988-10-14 | 1990-04-18 | Kanzaki Paper Mfg Co Ltd | Pressure sensitive copying sheet |
| JPH0761387B2 (en) * | 1989-04-05 | 1995-07-05 | ペガサスミシン製造株式会社 | Overlock sewing machine for matsuri sewing with a chain stitching device |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5016967B1 (en) * | 1971-08-04 | 1975-06-17 | ||
| GB1361638A (en) * | 1971-09-23 | 1974-07-30 | Wiggins Teape Res Dev | Pressure-sensitive copying systems |
| BE790321A (en) * | 1971-10-20 | 1973-04-19 | Monsanto Co | SOLVENTS FOR COLORANTS OF PRESSURE SENSITIVE RECORDING MATERIALS |
| JPS5321328B2 (en) * | 1973-10-31 | 1978-07-01 | ||
| US4130299A (en) * | 1977-09-12 | 1978-12-19 | Monsanto Company | Low-odor dye solvents for pressure-sensitive copying systems |
| JPS5571589A (en) * | 1978-11-24 | 1980-05-29 | Mitsubishi Petrochem Co Ltd | Solvent for pressure-sensitive duplicating paper dye |
| JPS5738878A (en) * | 1980-08-21 | 1982-03-03 | Nippon Mining Co Ltd | Preparation of electrical insulating oil, solvent for pressure-sensitive paper and heat medium oil |
| IT1136651B (en) * | 1981-06-04 | 1986-09-03 | Caffaro Spa Ind Chim | SOLVENT FOR DYES IN SELF-COPYING PAPER |
| US4365103A (en) * | 1981-12-04 | 1982-12-21 | The Dow Chemical Company | Process for the preparation of bis(1-phenylethenyl) compounds |
| JPS615982A (en) * | 1984-06-21 | 1986-01-11 | Nippon Petrochem Co Ltd | Pressure-sensitive copying material |
| JPS6112389A (en) * | 1984-06-29 | 1986-01-20 | Nippon Petrochem Co Ltd | Solvent for pressure-sensitive paper dyes |
| JPS6143129A (en) * | 1984-08-03 | 1986-03-01 | Nippon Petrochem Co Ltd | Treatment of by-product oil |
-
1984
- 1984-08-06 JP JP16453384A patent/JPS6141593A/en active Granted
-
1985
- 1985-07-31 CA CA000487874A patent/CA1238187A/en not_active Expired
- 1985-08-02 DE DE19853588130 patent/DE3588130T2/en not_active Expired - Lifetime
- 1985-08-02 EP EP85109696A patent/EP0171039B1/en not_active Expired - Lifetime
-
1986
- 1986-04-01 ES ES553588A patent/ES8801152A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3588130D1 (en) | 1997-01-23 |
| EP0171039A3 (en) | 1987-05-13 |
| EP0171039B1 (en) | 1996-12-11 |
| ES8801152A1 (en) | 1988-01-01 |
| ES553588A0 (en) | 1988-01-01 |
| JPS6141593A (en) | 1986-02-27 |
| DE3588130T2 (en) | 1997-07-03 |
| EP0171039A2 (en) | 1986-02-12 |
| JPH0441664B2 (en) | 1992-07-09 |
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