CA1268629A - Solvent for chromogenic dye-precursor material for pressure-sensitive recording paper sheet and pressure-sensitive recording paper sheet prepared by using the solvent - Google Patents
Solvent for chromogenic dye-precursor material for pressure-sensitive recording paper sheet and pressure-sensitive recording paper sheet prepared by using the solventInfo
- Publication number
- CA1268629A CA1268629A CA000537162A CA537162A CA1268629A CA 1268629 A CA1268629 A CA 1268629A CA 000537162 A CA000537162 A CA 000537162A CA 537162 A CA537162 A CA 537162A CA 1268629 A CA1268629 A CA 1268629A
- Authority
- CA
- Canada
- Prior art keywords
- pressure
- solvent
- weight
- recording paper
- paper sheet
- 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.)
- Expired - Fee Related
Links
- 239000002904 solvent Substances 0.000 title claims abstract description 63
- 239000002243 precursor Substances 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000011161 development Methods 0.000 claims abstract description 20
- 230000009965 odorless effect Effects 0.000 claims abstract description 18
- KWSHGRJUSUJPQD-UHFFFAOYSA-N 1-phenyl-4-propan-2-ylbenzene Chemical group C1=CC(C(C)C)=CC=C1C1=CC=CC=C1 KWSHGRJUSUJPQD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003094 microcapsule Substances 0.000 claims abstract description 14
- LIWRTHVZRZXVFX-UHFFFAOYSA-N 1-phenyl-3-propan-2-ylbenzene Chemical group CC(C)C1=CC=CC(C=2C=CC=CC=2)=C1 LIWRTHVZRZXVFX-UHFFFAOYSA-N 0.000 claims abstract description 12
- AMBHHSBRXZAGDZ-UHFFFAOYSA-N 1-phenyl-2,3-di(propan-2-yl)benzene Chemical group CC(C)C1=CC=CC(C=2C=CC=CC=2)=C1C(C)C AMBHHSBRXZAGDZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 description 50
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 39
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 30
- 101000648997 Homo sapiens Tripartite motif-containing protein 44 Proteins 0.000 description 27
- 102100028017 Tripartite motif-containing protein 44 Human genes 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000003054 catalyst Substances 0.000 description 25
- 239000004305 biphenyl Substances 0.000 description 21
- 235000010290 biphenyl Nutrition 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 239000011541 reaction mixture Substances 0.000 description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 239000000126 substance Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 230000006207 propylation Effects 0.000 description 9
- HKTCLPBBJDIBGF-UHFFFAOYSA-N 1-phenyl-2-propan-2-ylbenzene Chemical group CC(C)C1=CC=CC=C1C1=CC=CC=C1 HKTCLPBBJDIBGF-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 229960004279 formaldehyde Drugs 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 235000019256 formaldehyde Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- -1 atapalgite Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000010555 transalkylation reaction Methods 0.000 description 2
- JLQFVGYYVXALAG-CFEVTAHFSA-N yasmin 28 Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1.C([C@]12[C@H]3C[C@H]3[C@H]3[C@H]4[C@@H]([C@]5(CCC(=O)C=C5[C@@H]5C[C@@H]54)C)CC[C@@]31C)CC(=O)O2 JLQFVGYYVXALAG-CFEVTAHFSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- YYKBFGMYHQMXIL-UHFFFAOYSA-N 1-phenyl-2,3,4-tri(propan-2-yl)benzene Chemical group CC(C)C1=C(C(C)C)C(C(C)C)=CC=C1C1=CC=CC=C1 YYKBFGMYHQMXIL-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000006268 biphenyl-3-yl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C1=C([H])C(*)=C([H])C([H])=C1[H] 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000006840 diphenylmethane group Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000001911 terphenyls Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 150000004897 thiazines Chemical class 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003732 xanthenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0083—Solutions of dyes
-
- 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
Abstract
ABSTRACT OF THE DISCLOSURE:
Disclosed herein are a substantially odorless solvent for a chromogenic dye-precursor material for a pressure-sensitive recording paper sheet, which comprises from 0 to 20% by weight of m-isopropylbiphenyl, from 40 to 75% by weight of p-isopropylbiphenyl and from 5 to 40% by weight of diisopropyldiphenyl, and a pressure-sensitive recording paper sheet comprising a colour-development sheet coated with microcapsules containing a dye solution which is composed of the chromogenic dye-precursor material and the substantially odorless solvent, and a colour-developer sheet.
Disclosed herein are a substantially odorless solvent for a chromogenic dye-precursor material for a pressure-sensitive recording paper sheet, which comprises from 0 to 20% by weight of m-isopropylbiphenyl, from 40 to 75% by weight of p-isopropylbiphenyl and from 5 to 40% by weight of diisopropyldiphenyl, and a pressure-sensitive recording paper sheet comprising a colour-development sheet coated with microcapsules containing a dye solution which is composed of the chromogenic dye-precursor material and the substantially odorless solvent, and a colour-developer sheet.
Description
BACKGROUND OF THE INVENTION:
~ . _ .
The present inventlon relates to a substantially odorless solvent for the chromogenic dye-precursor material for a pressure-sensitive recording paper sheet and a pressure-sensitive recording paper sheet prepared by using the solvent. More in detail, the present invention relates to a solvent ~or the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet, which com-prises from 0 to 20% by weight of m isopropylbiphenyl, from 40 to 75% by weight of p-isopropylbiphenyl and from 5 to 40%
by weight of diisopropylbiphenyl, and a pressure-sensitive recording paper sheet comprising a colour-development sheet coated with microcapsules containing a dye solution which is composed of the chromogenic dye-precursor material and the substantially odorless solvent, and a colour-de~eloper sheet.
A pressure-sensitive recording sheet comprises a colour-development sheet prepared by coating microcapsules, in which a solution of a colourless electron-donating chromogenic dye-precursor material having a colouring reactivity has been encapsulated, onto a supporting sheet and a colour-developer sheet prepared by coating a colour-developer which develops a colour on contacting to the chromogenic dye-precursor material onto the supporting sheet.
.
In recent years, the pressure-sensitive recording paper sheets have been broadly used instead of carbon copy-ing paper sheets and back-carbon copying paper sheets of pigment type.
As the pressure-sensitive recording paper sheets, it is necessary that they are excellent in colour-develop-ment, stability for long term preservation and light resistance and that they are low in toxicity not to cause environmental pollution.
As the solvent which dissolves the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet, it is demanded that the solvent ful~ills the following requirementsO
1) To dissolve the chromogenic dye-precursor material to a high concentration.
~ . _ .
The present inventlon relates to a substantially odorless solvent for the chromogenic dye-precursor material for a pressure-sensitive recording paper sheet and a pressure-sensitive recording paper sheet prepared by using the solvent. More in detail, the present invention relates to a solvent ~or the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet, which com-prises from 0 to 20% by weight of m isopropylbiphenyl, from 40 to 75% by weight of p-isopropylbiphenyl and from 5 to 40%
by weight of diisopropylbiphenyl, and a pressure-sensitive recording paper sheet comprising a colour-development sheet coated with microcapsules containing a dye solution which is composed of the chromogenic dye-precursor material and the substantially odorless solvent, and a colour-de~eloper sheet.
A pressure-sensitive recording sheet comprises a colour-development sheet prepared by coating microcapsules, in which a solution of a colourless electron-donating chromogenic dye-precursor material having a colouring reactivity has been encapsulated, onto a supporting sheet and a colour-developer sheet prepared by coating a colour-developer which develops a colour on contacting to the chromogenic dye-precursor material onto the supporting sheet.
.
In recent years, the pressure-sensitive recording paper sheets have been broadly used instead of carbon copy-ing paper sheets and back-carbon copying paper sheets of pigment type.
As the pressure-sensitive recording paper sheets, it is necessary that they are excellent in colour-develop-ment, stability for long term preservation and light resistance and that they are low in toxicity not to cause environmental pollution.
As the solvent which dissolves the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet, it is demanded that the solvent ful~ills the following requirementsO
1) To dissolve the chromogenic dye-precursor material to a high concentration.
2) Not to cause the decomposition and colour-development of the chromogenic dye-precursor material.
3) To show a considerably high boiling point, and not to evaporate in the thermal drying step and under a high atmospheric temperature.
4) Not to be educed to water on encapsulating.
5) To show a high speed of colour-development and a high concentration of the developed colour as well as the high colour stability after colour-developing.
6) To be stable to light, heat and chemicals.
~%~
~%~
7) To show a low viscosity so that its flow out from the broken capsules is freely carried out.
8) ~o be substantially odorless.
9) To show a low toxicity to human body and to be safe.
10) To show a favorable biodegradability and not to cause environmental pollution.
As the pressure-sensitive recording paper sheet prepared by using the solvent for the chromogenic dye-precursor material, which fulfills the above~mentioned requirements, the following examples have been proposed.
A pressure-sensitive recording paper sheet pre pared by using a solvent comprising at least one of alkylated biphenyls or alkylated terphenyls having alkyl group(s) of from 1 to 12 carbon atoms or the mixture with another solvent, wherein the number of the alkyl groups in the alkylated biphenyl is from 1 to 4 and the number of the alkyl groups in the alkylated terphenyl is from 1 to 6, with the proviso that not less than kwo alkyl groups are the same or different from each other [refer to Japanese Patent Publication No. 49-21608 (1974)].
~A material for a recording paper sheet coated with ; microcapsules encapsulating a solution of a chromogenic dye-precursor materia] in a solvent comprising not less than 65% by weight of isopropylbiphenyl represenked by the formula:
.
' , ~%~
~ CH(CH3)2 not more than 25% by weight of polyisopropylbiphenyl and not more than 10% by weight of biphenyl [refer to Japanese Patent Publication No. 54-37528 (1979)]~
Further, as the method for producing an alkyl-biphenyl, a method for producing an alkylbiphenyl rich in m- and p-substituted substances has been known, wherein from 0.5 to 5 mol of a lower olefin is brought into contact with 1 mol of biphenyl at a temperature of not less than 180C
in the presence of from 0.5 to 10~ by weight of a silica-alumina catalyst, a zeolite catalyst or a mixture thereof [refer to Japanese Patent Application Laid-Open No. 56-156222 (1981)].
Particularly, isopropylbiphenyl which is the main component constituti.ng the solvent for the chromogenic dye-precursor for the pressure-sensitive recording paper sheet discIosed in the Japanese Patent Publication No. 54-37528 (1979) is an isomeric mixture of the compound represented by the following structural formula:
r ~ _-CH(cH3)2 wherein ~he isopropyl group i.s bonded to the benzene ring at the position of ortho, meta or para thereof.
:
-- 5 ~
~2~
Further, in Japanese Patent Publication No. 54-37528 (1979), it has been shown that the suitable composition of the solvent for the chromogenic dye precursor material for a pressure~sensitive recordiny paper sheet comprises about 50~ by weight of m-isopropylbiphenyl, 30% by weight of p-isopropylbiphenyl, 25% by weight of polyisopropyl-biphenyl and 0.5% by weight of biphenyl.
Still more, the commerciallized "isopropylbiphenyl"
and the isopropylbiphenyl synthesized by Friedel-Crafts alkylation of biphenyl (refer to Industrial and Engineering Chemistry Product Research and Development Vol. 8, 239 -241, 1969) is a mixture of m-isomer and p-isomer (the weight ratio of m-isomer to p-isomer is about 2 :1) and contains a little amount of o-isomer.
With the propagation of the pressure-sensitive recording paper sheets, the case where the pressure-sensitive recording paper sheets are used in cold districts of not more than 0C in the ambient temperature or transported and preserved for a long time in the environment of about from 40 to 50C in the ambient temperature and of not less than ~about 80% in the relative humidity has increased.
Particularly, in the outdoor facilities such as gasoline service stands, the pressure-sensitive recording paper sheets are used under the environment of not more than 0C in winter.
` - 6~-: . .. ;:
~z~
Since in such an environment of low atmospheric temperatures, 1) the solvent for the chromogenic dye-precursor material used in the pressure-sensitive recording paper sheet crystallizes, 2) it takes a very long time for obtaining clear development of colour or 3) the colour-developed image is very light in colour, if developed, not to be deciphered, such a pressure-sensitive recording paper sheet is not to be put to practical use. Namely, it is demanded that an initial colour developing activity within about 30 sec from the recording is at least 40~.
Furthermore, from the viewpoint of the production and preservation of the pressure-sensitive recording paper sheet, an offer of a substantially odorless solvent for the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet has been earnestly desired.
The problem of offensive odor occurs in the process for preparing the pressure-sensitive recording paper sheet when the recording paper sheet material prepared by applying the microcapsules containing the solution of the chromogenic dye-precursor material onto the supporting paper sheet is cut after drying thereof. Namely, when the pressure-sensitive recording paper sheet is cut at a relatively high temperature of from ~0 to 50~C, the solvent ~lowing out from the thus borken microcapsules gives a disagreeable impression to the operators. In addition, in the cases when ~ - 7 :
~' .
.
the solvent adheres to clothes or hands of the operator in the cutting step of the pressure-sensitive recording paper sheet or in handling of the solvent, the odor still remains even after washing the clothes or the hands with a cleanser to give a disagreeable impression. Furthermore, the pressure-sensitive recording paper sheets which have been subjected to recording are assembled and presexved in a storehouse ~or a relatively long time. In such an occasion, the odor emitted from a large amount of the pressure-sensitive recording paper sheets which have been subjected to record-ing becomes the cause of disagreeable impression.
On examining the above-mentioned problem of odor of the pressure-sensitive recording paper sheet, the iso-propylbiphenyl which has been hitherto proposed as the solvent for the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet is not favorable as the solvent for such a purpose. Namely, the isopropyl-biphenyl is an isomeric mixture of o-isopropylbiphenyl, m-isopropylbiphenyl and p isopropylbiphenyl or an isomeric mixture of m-isopropylbiphenyl as the main component and p-isopropylbiphenyl. Ortho-isopropylbiphenyl shows a disagreeable odor, and also m-isopropylbiphenyl has an odor.
On the other hand, although p-isopropylbiphenyl is almost odorless and excellent in the property of dissolving the chromogenic dye-precursor material, since the melting point ~`' :
: ~:
of p-isopropylbiphenyl is relatively high, it has a defect that crystals thereof are apt to be educed at a low tem-perature~
Accordingly, it has been desired to provide with a solvent for the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet, which is almost odorless, from which cxystals thereof are scarcely educed at a low temperature (for instance, 0C) and which shows an excellent initial colour-developing propertyO
As a result of the present inventors' studies for providing with a solvent for the chromogenic dye-precursor material for a pressure-sensitive recording paper sheet, which has the specific character required as above, it has been found out by the present inventors that a solvent comprising from 0 to 20% by weight of m-isopropylbiphenyl, from 40 to 75~ by weight of p-isopropylbiphenyl and from 5 to ~0~ by weight of diisopropylbiphenyl is almost odorless, that tha crystals of such a solvent are scarcely educed at a low temperature and that such a solvent fulfills all the conaitions to be possessed by the solvent for the chromogenic dye-precursor material for a pressure-sensitive recording paper sheet, and on the basis of the findings, the present inventors have effected the present invention.
: ;
_ g _ ., ' ! .
SUMMARY OF THE INVENTION:
.
In a first aspect of the present invention, there is provided a substantially odorless solvent for the chromo-genic dye-precursor material for a pressure-sensitive recording paper sheet, which comprises from 0 to 20% by weight of m-isopropylbiphenyl, from 40 to 75% by weight of p-isopropylbiphenyl and from 5 to 40% by weight of diiso-propylbiphenyl.
In a second aspect of the present invention, there is provided a pressure-sensitive recording paper sheet comprising a colour-development sheet coated with micro-capsules containing a dye solution which is composed of a colourless chromogenic dye-precursor material and a sub-stantially odorless solvént comprising from 0 to 20% by weight of m-isopropylbiphenyl, from 40 to 75% by weight of p-isopropylbiphenyl and from 5 to 40% by weight of diiso-propylbiphenyl, and a colour-developer sheet.
BRIEF EXPLANATION OF DRAWING:
Of the attached drawing, Fig. 1 is a triangle showing the composition of the solvent according to the present invention, which contains m-MIPB, p-MIPB and DIPB.
DETAILED DESCRIPTION OF TEE INVENTION:
The solvent of the present invention is a mixed ~: .
.
solvent comprising from 0 to 20% by weight of m--isopropyl-biphenyl (hereinaf-ter referred to as m-MIPB), from 40 to 75% by weight of p-isopropylbiphenyl (hereinafter referred to as p-MIPB) and from 5 to 40% by weight of diisopropyl-biphenyl (hereinafter referred to as DIPB).
The mixing rates of m-MIPB, p-MIPB and DIPB which are the components constituting the solvent for the chromo-genic dye-precursor material for the pressure-sensitive recording paper sheet according to the present invention are in the range shown by the points A, B, C and D in the triangle shown in Fig. 1.
The composition of the point A in Fig. 1 is 20%
by weight of m-MIPB, 75% by weight of p-MIPB and 5% by weight of DIPB, composition of the point B is 0% by weight of m-MIPB, 75% by weight of p-MIPB and 25% by weight of DIPB, the composition of the point C is 0% by weight of m-MIPB, 60% by weight of p-MIPB and 40% by weight of DIPB and the composition of the point D is 20% by weight of m-MIPB, 40% by weight of p-MIPB and 40% by weight of DIPB.
The mixed solvent within the above-mentioned range is almost odorless, crystals thereof are scarcely educed therefrom at a low temperature, for instance, 0C
and the colour-developing property is excellentO Namely, the rate of initial colour-development after 30 sec of recording at -5C is larger than the practical value (40%) and accordingly, the mixed solvent according to the present invention is useful as the solvent for the chromogenic dye-precursor material for the pressure sensitive recording paper sheet.
The preferable mixing rate of the solvent according to the present invention is in the range shown by the points a, b, c and d. The composition of the point a is 20%
by weight of m-MIPB, 70% by weight of p-MIPB and 10% by weight of DIPB, the composition of the point b is 0% by weight of m-MIPB, 70% by weight of p-MIPB and 30% by weight of DIPB, the composition of the point _ is 0% by weight of m-MIPB, 65% by weight of p-MIPB and 35% by weight of DIPB
and the composition of the point d is 20% by weight of m-MIPB, 45% by weight of p-MIPB and 35~ by weight of DIPB.
In the case where the content of m-MIPB in the mixed solvent is more than 20% by weight, since the problem of odor occurs, such a situation is undesirable. In the case where the content of p-MIPB is more than 75% by weight, since the crystals thereof are apt to be educed at a low temperature, such a situation is also undesirable~ Further-more, in the case where the content of DIPB is more than 40% by weight,~since the colour-developing property at a .
low temperature becomes insufficient, such a situation is also undesirable.
Although DIPB which is one of the components :: ::
.
. : .
constituting the solvent according to the present invention is a mixture of isomers 2,2'-DIPB, 2,3'~DIPB, 2,4'-DIPB, 3,3'~DIPB, 3,4'-DIPB and 4,4'-DIPB, the effect of the present invention is not limited by the kinds of the isomers of DIPB.
So far as the above-mentioned specific properties of the solvent for the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet according to the present invention, namely the substantial odorless-ness, the excellent colour-developing property at a low temperature and the property of scarcely educing crystals thereof at a low temperature, are not damaged, any publicly known solvent for the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet, for instance, di-isopropylnaphthalene, hydrogenated terphenyl and butyl-biphenyl or any publicly known diluent Xor the solvent for the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet, for instance, dodecylbenzene and kerosene can be added to the solvent for the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet according to the present invention.
The solvent according to the present invention can be obtained by mixing m-MlPB, p-MIPB and DIPR a~ the mixing ratio in the above-mentioned range, and also can be produced according to the following methods.
(1) The method comprises the steps of reacting 1~
` ~:
.. . .
: ' ~6~36;~3 biphenyl with propylene at a temperature of from 120 to 260~C
in the presence of a silica-alumina catalyst, thereby carry-ing out the propylation of biphenyl, and subjecting the thus obtained reaction product to distillation, thereby obtaining the fraction having a mean boiling point of from 138 to 149C
under a reduced pressure of 5 mn~Ig.
(2) The method comprises the steps of reacting biphenyl with propylene at a temperature of from 50 to 110C
in the presence of a catalyst of aluminum chloride, thereby carrying out the propylation of biphenyl, subjecting the thus obtained reaction product to distillation under a reduced pressure, thereby rectifying p-MIPB, and mixing the thus rectified p-MIPB with DIPB which has been separately rectified, at a predetermined ratio.
As the catalyst used in the method of propylation of biphenyl, the silica-alumina catalyst which, in the reaction of transalkylation of a mixture of naphthalene and diisopropylnaphthalene at 280C, (i) shows the initial activity of not less than 0.1 kg of naphthalene/hour-kg of catalyst, preferably not less than 0.2 kg of naphthalene/
hour~kg of catalyst and (ii) retains the activity of not less than 90% even after treating the mixture of naphthalene and diisopropylnaphthalene in an amoun~ of 100 times by weight of the catalyst is desirable.
As the silica-alumina catalyst having the above-- :~
.
': ..... ; . ~
`~' '' ''' :' :
` "` : ;` ~ , mentioned specific properties, the catalysts made by NIKKI
Chemical Industries Co., Ltd. under the respective codes of X-632HN and N-632L may be exemplified.
The reaction temperature of propylation is from 120 to 260C, preferably from 150 to 240C. In the case where the reaction temperature is less than 120C, since the reaction velocity is low, such a reaction temperature is not practical, and on the other hand, in the case where the reaction temperature is more than 260C, since the decom-posit.ive r~action occurs as well as the alkylation reaction and the reaction product sh~ws a disagreeable odor, such a temperature is undesirable.
The heart of the present invention is characterized by using microcapsules containing a dye solution which is composed of the chromogenic dye-precursor materiai..and a substantially odorless solvent comprising from 0 to 20% by weight of m-MIPB, from 40 to 75~ by weight of p-MIPB and from 5 to 40% by weight of DIPB. A~cordingly, all the methods publicly known by the p2rsons skilled in the art can be applied to produce the pressure sensitive recording paper sheet without being limited to the chromogenic dye-precursor material, ~he colour-developer, the method of encapsulationj the method for preparing the slurry of the capsules, the method for applying the slurry, etc.
For instance, as the method of encapsulation, the .~
: .. ~ ~ .
.
~%6i~31ii;2~1 method of the coacervation disclosed in U.S. Patents Nos.
2,800,457 and 2,800,~158, the method of the interfacial poly-merization disclosed in British Patent No. 990,443 and U.S.
Patent No. 3,2g7,154, and several other methods can be utilized.
As the chromogenic dye-precursor material, tri-phenylmethanes, diphenylmethanes, xanthenes, thiazines, spiropyranes, etc. may be exemplified. Further as the acidic substance used as the colour-developer, active claysh substance such as Japanese acid clay, active clay, atapalgite, bentonite, zeolite and the like or organoacidic substance such as phenol resin, acid-reactive phenol-formaldehyde novolak resin, organoacidic substance such as metallic salt of an aromatic organic acid, etc. may be exemplified.
The solvent for the chromogenic dye-precursor mate~ial for the pressure-sensitive recording paper sheet according to the present invention is almost odorless and excellent in solubility of the chromogenic dye-precursor material, and fulfills the above-mentioned necessary conditions to be possessed by the solvent for the dye-precursor material for the pressure-sensitive recording paper sheet, and scarcely educes crystals of the solvent at a low temperature (0C).
Furthermore, the initial colour-development of the pressure-sensitive recording paper sheet after 30 sec ,~
'' '' '`''.
' ., ~
of recording at a low temperature of ~5C is not less than 40% and accordingly, the pressure-sensi-tive recording paper sheet of the present invention can be sufficiently put to practical use.
The present invention will be concretely explained while referring to the ~ollowing non-limitative examples.
[Method for measuring the catalytic activity]
Apparatus:
In the lower part of a stainless-steel reaction tube of an inner diameter of about 25 mm, 10 ml of glass beads of 2 mm in diameter are filled up for supporting tne catalyst, and 25 ml of the catalyst are filled up on the thus filled glass beads.
Furthermore, 20 ml of glass beads o 2 mm in diameter are filied up, as the preheating zone, on the layer of the catalyst.
Heating of the thus filled materials is conducted from outside by an electric heater, and the inner tempera-ture of the tube is measured by a thermocouple inserted in the reaction tube.
Method:
By heating an equimolar mixture of naphthalene and diisopropylnaphthalene (an isomeric mixture) to about 60C, naphthalene is dissolved in diisopropylnaphthalene.
. ., ` " ~ ;' z~
From the upper part of the reaction tube, the thus prepared mixture is supplied at a definite flow rate to reac~ con-tinuously naphthalene with diisopropylnaphthalene while maintaining the temperature of the catalyst layer at 280C.
The reaction liquid which flows out from the lower part of the reaction tube is cooled to a temperature of lower than 100C, and is put to sampling on occasion to be analyzed by gaschromatography. The flow rate of the reaction liquid from the reaction tube is set up so that the initial con-version rate of nap~thalene is from 10 to 20~. As the raw materials of the reaction, naphthalene and diisopropyl naphthalene containing scarcely the components such as sulfur, nitrogen compounds, etc., which deteriorate the catalytic activity, are used.
Evaluation of the ca ~ ty:
From the analytical results of the product obtained during the period from the commencement of ~he reaction to ; the time when the mixture of naphthalene and diisopropyl-naphthalene in amount of about 5 times by weight of the catalyst has been reacted, the conversion of naphthalene (Xo) is obtained, and the initial activity of the catalyst is obtained according to the following formula:
Initial activity (~0) = N _ 0 ( Wc ) ` 18 -: ::
.: ~ :: .
, :;:
.
~;1!3&;~
wherein Wc is the amount of the thus filled catalyst and WN
i5 the supplying speed of naphthalene (g/hour).
The reaction is continuously carried out, and at the time when the mixture of naphthalene and diisopropyl-naphthalene has been reacted in an amount of 100 times of the weight of the catalyst, the conversion of naphthalene (X100) is obtained from the analytical results of the product, and the retaining rate of the catalytic activity (~) is obtained according to the following formula:
Retaining rate of catalytic activity (Ap) = 100 x 100 (XO) TEST EXAMPLE OF CATALYTIC ACTIVITY:
~ _ . ~.
In a reaction tube, 25 g of a silica-alumina catalyst (pellets of 3 mm in diameter, made of NIKKI Chemical Industries Co., Ltd., Model: X-632HN) was filled up, and an equimolar mixture of naphthalene and diisopropylnaphthalene was supplied at ~the rate of 250 ml~hour (245 g/hour) to carry out transalkylation reaction.
After 30 min and 10 hours of the commencement of the reaction, the reaction liquid was sampled and analyzed by gaschromatograph~, the results being as follows:
X0 = 17.0~, X100 = 16.2~ and Ap = 95.3~.
Furthermore, since WN is 92.2 g/hour and Wc is . : . .
: ` ~
':
25 g, the initial catalytic activity was obtained as follows:
Ao = 92.~x 0 17 = 0.63 kg/hour-kg-catalyst c Into a stainless steel autoclave of a capacity of 1.5 litres, 1000 g of biphenyl and 100 g of the catalyst used in Test Example of Catalytic Activity were introduced, and the content was heated to a temperature of not less than 70C to melt biphenyl. The agitation was started and the content of the autoclave was further heated to bring the inner temperature of the autoclave to 240C.
Gaseous propylene was introduced into the auto-clave from a propylene gas bomb to carry out the propylation reaction while maintaining the pressure in the autoclave at about 2 kg/cm G.
During the reaction, ~he reaction mixture was sampled on occassion to analyze the composition of the reaction mixture, and at the time when the mean propylation degree became about 1.0, the supply of propylene gas was stopped and the autoclave was cooled to collect the reaction liquid. The composition of the thus collected reaction Iiquid is shown in Table 1 below.
-- ~0 --:~ , : . .
~, Table 1 Component Composition ~ ~ , . . ....
Biphenyl 2708 o-Isopropylbiphenyl(o-MIPB) 6.0 m-Isopropylbiphenyl(m-MIPB) 18.7 p-Isopropylbiphenyl(p-MIPB) 22.1 Diisopropylbiphenyl(DIPB) 23.9 Triisopropylbiphenyl(TIPB) and others 1.5 . . .
The thus obtained reaction mixture was carefully rectified at 140C under a reduced pressure of 5 mmHg, the composition of the thus obtained fraction being shown in Table 2.
Table 2 - . ~
Composition Co~ponent m-MIPB 15.0 p-MIPB 71.9 DIPB 13.1 COMPARATIVE EXAMPLE lo .
In the same manner as in Example 1, propylation 6~
of biphenyl was carried out, and the thus obtained reaction mixture was fractionally distilled under a reduced pressure of 5 mmHg, thereby collectiny the fraction distilled from 141 to 150C. The composition of the thus obtained fraction is shown in Table 3.
Table 3 Component (~ hy weight) m MIPB 0.8 p-MIPB 47.6 DIPB 51.6 EXAMPLES_2 to 4 and COMPARATIVE EXAMPLE 2:
By using the same silica-alumina catalyst, pro-pylation of biphenyl was carried out at a temperature shown in Table 4 and in same manner as in Example 1. By subjec-t-ing the thus obtained reaction mixture to the same method of distillation as in Example l, the fraction comprising p-MIPB as the main component was obtainedO
The composition of the reaction product and that of the fraction are shown in Table 4.
, ., , ~
8i~
E~AMPLE 5:
Into a glass autoclave of a capacity of 1 litre, 500 g of biphenyl were introduced, and the inner temperature of the autoclave was raised to 80C to melt the introduced biphenyl~ After adding 14 g of anhydrous aluminum chloride as the catalyst into the molten biphenyl, the autoclave was tightly closed and agitation was started. Propylene gas was introduced into the autoclave from a gas-bomb to carry out the alkylation reaction while maintaining the inner temperature of the autoclave at from 100 to 110C and maintaining the inner pressure of the autoclave at about 1 kg/cm2G, and the xeaction was continued until the mean alkylation degree became about 1.
After the reaction was over, the reaction mixture was washed with hydrochloric acid and then with water to rémove the catalyst from the reaction mixture. The thus obtained reaction mixture was distilled in a rectifying tower of reduced pressure to separate about 120 g of p-MIPB
of a purity of 926.
The thus obtained crude p-MIPB was cooled in a jacketed glass vessel to 12C to a slurry-like substance.
The slurry-like substance was subjected to centrifugal separation thereby obtaining p-MIPB of a purity of 996.
On the other hand, 26 g of a mixture of 86 by weight of p MIPB and 92% by weight of DIPB were separated = 23 -' ' ,.. .
: ' by the distillation of the reaction mixture.
By combining the thus separated mixture of p-M¢PB
and DIPB with p-MIPB of a purity of 99%, a mixture of 73.2%
by weight of p-MIPB and 26.8% by weight of DIPB was obtained.
COMPAR~TIVE EXAMPLE 3:
In the same manner as in Example 5, propylation of biphenyl was carried out and the thus obtained reaction mixture was carefully distilled under a reduced pressure of 5 mmHg, thereby collecting the fraction distilled from 138 to 149C. The composition of the reaction mixture and the thus obtained fraction is shown in Table 5.
Table 4 Example and Com- Example Example Example Comparative parative Example 2 _ _ 3_ _4 Example 2 ture (C) P 150 200 255 300 . .
Reaction mixture (mol %) Biphenyl 27.8 28.4 28.527.5 o-MIPB 21.3 14~3 2.4 1.8 m-MIPB 5.8 10.0 22.926.5 p-MIPB 15.7 18.3 20.818.2 DIPB 27.3 27.0 23.623.0 TIPB and others 2.1 2.0 1.8 3.0 - ~4 ~æ~za Fraction (_y weight) m-MIPB 7.5 1106 16~2 15.8 p-MIPB 56.3 6306 7407 80.3 DIPB 36.2 24.8 9.1 3.9 Table 5 Reaction mixture Fraction Component (mol %) (% by weight) Biphenyl 28.6 o-MIPB 0.2 m-MIPB 26.4 703 p-MIPB 17.2 92.2 DIPB 24.1 0.5 TIPB and others 3.5 EXAMPLE 6: (Preparation of the solvent for the chromogenic dye-precursor material for ~he pressure-sensitive paper sheet):
One hundred millilitres of the solvent obtained : in Example 1 were warmed to 150C, and 30 g of Crystal Violet Lactone (a blue dyestuff made by HODOGAYA Chemical Industries Co., Ltd.) (hereinafter rèferred to as CVL) were dissolved in the thus warmed solvent under agitation.
:
.:
~z~
The thus prepared solution was introduced into a thermostat at ~0C and left therein, and the concentration of CVL was measured in course of the timeO The results are shown in Table 6. As are clearly seen in Table 6, the state of the extremely high concentration was maintained for a long time period.
Table 6 , Time passed (day) 1 7 14 Concentration of CVL
in the solution 1906 13.9 10.8 (g/100 ml) EXAMPLE 7:
~9L~ ' Microcapsules were prepared by using the solvent for the dye~precursor material for the pressure-sensitive recording paper sheet obtained in Example 6 according to the following method.
Six hundred and thirty grams of melamine and 1620 g of formalin (an aqueous 37% solution of formaldehyde) adjusted to pH of 9.0 by an aqueous 2~ solution of sodium hydroxide were mlxed, and the thus obtained mixture was heated to 70C. Just after the dissolution of melamine, 2250 g of water were added to the thus obtained solution .
.., ;.
.
, ~6~
and the whole mixture was stirred for 3 min to obtain an aqueous solution of melamine ~ formaldehyde prepolymer.
Separately, 1460 g of formalin adjusted to pH of 8.5 by triethanolamine and 600 g of urea were mixed together and the thus obtained mixture was reacted for 1 hour at 70C
to obtain an aqueous solution of urea - formaldehyde pre-polymer.
Furthermore, 1620 g of formalin and 600 g of urea were mixed and the thus formed mixture was stirred. To the thus prepared mixture, triethanolamine was added to adjust the pH of the mixture to 8.8 and the thus treated mixture was reacted for 30 min at 70C. To 400 g of the thus pre-pared reaction mixture, 24 g of water and 30 g of tetra-ethylenepentamine were added and the pH of the thus formed mixture was adjusted to 3 by adding an aqueous 15% solution of hydrochlorlc acid while stirring the mixture at 70Co Since the pH of the mixture was reduced with the progress of the. reaction, the pH was re-adjusted to 3 by the addition of an aqueous 10% solution of sodium hydroxide, and the reaction was continued while lowering the temperature of the reaction mixture to 55C.
: At the time when the viscosity of the reaction mixture became 200 cps, the reaction mixture was neutralized with an aqueous 10~ solution of sodium hydroxide and then r 4000 g of water were added to the thus neutralized reaction ~%61~6~
mixture to obtain an aqueous solution of a water~soluble cationic urea resin.
After adjusting the pH of the liquid mixture of 1000 g of the aqueous solution of melamine - formaldehyde prepolymer, 500 g of the aqueous solution of urea - formal-dehyde prepolymer, 1580 g of the aqueous solution of a water-soluble cationic urea resin, 620 g of water and 10 g of triethanolamine to 5.2 by the addition of an aqueous 10 %
solution of citric acid, 30 g of an aqueous 10% solution of NEOPELEX ~ (a surfactant made by KAO-ATLAS Co., Ltd.) were added to the liquid mixture to obtain "A" liquid.
Separately, 500 g of CVL were dissolved in 9500 g of the solvent obtained in Example 1 to prepare "B" liquid, and 1000 ml of "B" liquid were emulsified in "A" liquid in a homogenizer so that the diameter of the droplets of "B"
liquid becomes from 2 to 8 ~m. Thereafter, the thus formed emulsion was kept at 30C while gently stirring thereof and the pH of the emulsion was adjusted -to 3~6 by the addition of an aqueous 1% solution of citric acid. After further stirring the emulsion for 1 hour, 2000 ml of water were added to the thus treated emulsion. After leaving the emulsion for 3 hours, an aqueous 20% solution of citric acid was added to the emulsion to adjust the pH thereof to 3.0 and the agitation was continued for 20 hours to obtain a slurry of microcapsules.
, .. ..
Preparation of the pressure-sensitive xecordin~ paper sheet:
To 600 ml of an aqueous 10~ solution of polyvinyl alcohol (made by KVRARE Co., Ltd.) (hereinafter referred to as PVA), which had been prepared separately, 300 g of the thus obtained microcapsules were added, and by stirring the thus ~ormed mixture well, a liquid dispersion of the micro-capsules was obtained.
Onto a paper sheet of 45 g/m2, the liquid dis-persion was applied so that the applied amount of the microcapsules was 22 g/m2. By superposing the thus treated paper sheet with a colour-developing paper sheet on which a colour-developing substance having a polycondensate of p-phenylphenol and formaldehyde as the main colour-developer has been applied according to a conventional method, the pressure-sensitive recording paper sheet according to the present invention was obtained.
After subjecting the thus obtained pressure-sensitive recording paper sheet to colour-development by a typewriter made by OLIVETTI Co. under an ordinary environ-ment and preserving the thus treated pressure-sensitive recording paper sheet in a dark place ~or 24 hours, ~he concentration o~ the thus developed colour was measured by a refraction chromaticity meter made by MACBETH Co.
On the other hand, a pressure-sensitive recording paper sheet prepared by the same procedures as above was - ' ` .. ~. :~
: :
.. . : ,: .
~Z~ 2~
subjected to colour-development in the same manner as above, however, under an environment of -5C, and the change of the colour density was measured from just after the colour-development by the same refraction chromaticity meter.
Thereafter, the relative rate of colour-development at each time in course of the time from the time of the beginning of colour development was obtained, in the case where the colour density of the thus-treated pressure-sensitive recording paper sheet after preserving thereof for 24 hours at room temperature was appointed as 100. The results are shown in Table 7. As seen in Table 7, the thus formed pressure-sensitive recording paper sheet showed a sufficient colour-developing ability even at the initial time such as 30 sec after typewriting.
Tab Time passed30 sec 1 min 1 hour Rate of colour-70 % 77 ~ 88 development EXAMPLE 7:
By using each of the solvents obtained in Examples 2 to 5 and Comparative Example 1, each of the pressure-sensitive recording paper sheets was prepared according to ~8~g the method in Example 6.
The initial colour-development of each of the thus obtained pressure-sensitive recording paper sheets (colour-development after 30 sec of the recording at a temperature of -5C) is shown in Table 8.
Table No of Example Example Example Example Example Comparative 2 3 4 5Example 1 Rate of colour-development (~) 57 62 72 59 25 _ _ _ _ _ On each of the solvents obtained in Examples 1 to 5 and Comparative Examples 2 and 3, the pane~ test , concerning the odor of the solvent was carried out by 20 : men and 20 women (total 40 persons) unintentionally : selected. The results are shown in Table ~.
:' ' .
-~31 -:.: .
, ,. ~ :
'' ; ": ' " ' ~
. ,,~ ~
Table 9 Number of evaluating person No. of Example or Comparative Example ~ B C - ------ Evaluatlon ~ ~ _ ~
Example 1 6 26 8 O B
Example 2 7 28 5 0 Example 3 7 24 9 0 B
Example 4 4 25 11 0 B
Example 5 3 26 10 1 B
Comparative Example 3 0 913 1~ D
(Note) Evaluation A: odorless B: almost odorless C: odor was present D: disagreeable odor was present As the solvent for the chromogenic dye-precursor material for the pressure~sensitive recording paper sheet which can be put to practical use, it is necessary that the solvent is evaluated to be A or B.
TEST EXAMPLE 2:
Each of the solvents obtained in Examples 1 to 5 and Comparative Examples 2 and 3 was kept for 24 hours in a thermostat of 5C and in a thermostat of 0C, and the presence or absence of eduction of crystals from the A
. . .
~Læ~
solvent was observed. The results are shown in Table 10.
Tab No. of Example Example Example Example Example Comparative Comparative Example 1 2 3 4 5Example 2Example 3 _ _ _ . . . . _ . _ Notes: A: no crystal was educed.
B: cxystals were scarcely educed.
C: a large amount of crystals was educed.
As the solvent for the chromogenic dye-precursor material for the pressure-xesistent recording paper sheet, it is necessary that the result of the evaluation is A or B.
~' .
- -,, ~ '~ , : : ~ : , .
: . . .
' ~
As the pressure-sensitive recording paper sheet prepared by using the solvent for the chromogenic dye-precursor material, which fulfills the above~mentioned requirements, the following examples have been proposed.
A pressure-sensitive recording paper sheet pre pared by using a solvent comprising at least one of alkylated biphenyls or alkylated terphenyls having alkyl group(s) of from 1 to 12 carbon atoms or the mixture with another solvent, wherein the number of the alkyl groups in the alkylated biphenyl is from 1 to 4 and the number of the alkyl groups in the alkylated terphenyl is from 1 to 6, with the proviso that not less than kwo alkyl groups are the same or different from each other [refer to Japanese Patent Publication No. 49-21608 (1974)].
~A material for a recording paper sheet coated with ; microcapsules encapsulating a solution of a chromogenic dye-precursor materia] in a solvent comprising not less than 65% by weight of isopropylbiphenyl represenked by the formula:
.
' , ~%~
~ CH(CH3)2 not more than 25% by weight of polyisopropylbiphenyl and not more than 10% by weight of biphenyl [refer to Japanese Patent Publication No. 54-37528 (1979)]~
Further, as the method for producing an alkyl-biphenyl, a method for producing an alkylbiphenyl rich in m- and p-substituted substances has been known, wherein from 0.5 to 5 mol of a lower olefin is brought into contact with 1 mol of biphenyl at a temperature of not less than 180C
in the presence of from 0.5 to 10~ by weight of a silica-alumina catalyst, a zeolite catalyst or a mixture thereof [refer to Japanese Patent Application Laid-Open No. 56-156222 (1981)].
Particularly, isopropylbiphenyl which is the main component constituti.ng the solvent for the chromogenic dye-precursor for the pressure-sensitive recording paper sheet discIosed in the Japanese Patent Publication No. 54-37528 (1979) is an isomeric mixture of the compound represented by the following structural formula:
r ~ _-CH(cH3)2 wherein ~he isopropyl group i.s bonded to the benzene ring at the position of ortho, meta or para thereof.
:
-- 5 ~
~2~
Further, in Japanese Patent Publication No. 54-37528 (1979), it has been shown that the suitable composition of the solvent for the chromogenic dye precursor material for a pressure~sensitive recordiny paper sheet comprises about 50~ by weight of m-isopropylbiphenyl, 30% by weight of p-isopropylbiphenyl, 25% by weight of polyisopropyl-biphenyl and 0.5% by weight of biphenyl.
Still more, the commerciallized "isopropylbiphenyl"
and the isopropylbiphenyl synthesized by Friedel-Crafts alkylation of biphenyl (refer to Industrial and Engineering Chemistry Product Research and Development Vol. 8, 239 -241, 1969) is a mixture of m-isomer and p-isomer (the weight ratio of m-isomer to p-isomer is about 2 :1) and contains a little amount of o-isomer.
With the propagation of the pressure-sensitive recording paper sheets, the case where the pressure-sensitive recording paper sheets are used in cold districts of not more than 0C in the ambient temperature or transported and preserved for a long time in the environment of about from 40 to 50C in the ambient temperature and of not less than ~about 80% in the relative humidity has increased.
Particularly, in the outdoor facilities such as gasoline service stands, the pressure-sensitive recording paper sheets are used under the environment of not more than 0C in winter.
` - 6~-: . .. ;:
~z~
Since in such an environment of low atmospheric temperatures, 1) the solvent for the chromogenic dye-precursor material used in the pressure-sensitive recording paper sheet crystallizes, 2) it takes a very long time for obtaining clear development of colour or 3) the colour-developed image is very light in colour, if developed, not to be deciphered, such a pressure-sensitive recording paper sheet is not to be put to practical use. Namely, it is demanded that an initial colour developing activity within about 30 sec from the recording is at least 40~.
Furthermore, from the viewpoint of the production and preservation of the pressure-sensitive recording paper sheet, an offer of a substantially odorless solvent for the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet has been earnestly desired.
The problem of offensive odor occurs in the process for preparing the pressure-sensitive recording paper sheet when the recording paper sheet material prepared by applying the microcapsules containing the solution of the chromogenic dye-precursor material onto the supporting paper sheet is cut after drying thereof. Namely, when the pressure-sensitive recording paper sheet is cut at a relatively high temperature of from ~0 to 50~C, the solvent ~lowing out from the thus borken microcapsules gives a disagreeable impression to the operators. In addition, in the cases when ~ - 7 :
~' .
.
the solvent adheres to clothes or hands of the operator in the cutting step of the pressure-sensitive recording paper sheet or in handling of the solvent, the odor still remains even after washing the clothes or the hands with a cleanser to give a disagreeable impression. Furthermore, the pressure-sensitive recording paper sheets which have been subjected to recording are assembled and presexved in a storehouse ~or a relatively long time. In such an occasion, the odor emitted from a large amount of the pressure-sensitive recording paper sheets which have been subjected to record-ing becomes the cause of disagreeable impression.
On examining the above-mentioned problem of odor of the pressure-sensitive recording paper sheet, the iso-propylbiphenyl which has been hitherto proposed as the solvent for the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet is not favorable as the solvent for such a purpose. Namely, the isopropyl-biphenyl is an isomeric mixture of o-isopropylbiphenyl, m-isopropylbiphenyl and p isopropylbiphenyl or an isomeric mixture of m-isopropylbiphenyl as the main component and p-isopropylbiphenyl. Ortho-isopropylbiphenyl shows a disagreeable odor, and also m-isopropylbiphenyl has an odor.
On the other hand, although p-isopropylbiphenyl is almost odorless and excellent in the property of dissolving the chromogenic dye-precursor material, since the melting point ~`' :
: ~:
of p-isopropylbiphenyl is relatively high, it has a defect that crystals thereof are apt to be educed at a low tem-perature~
Accordingly, it has been desired to provide with a solvent for the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet, which is almost odorless, from which cxystals thereof are scarcely educed at a low temperature (for instance, 0C) and which shows an excellent initial colour-developing propertyO
As a result of the present inventors' studies for providing with a solvent for the chromogenic dye-precursor material for a pressure-sensitive recording paper sheet, which has the specific character required as above, it has been found out by the present inventors that a solvent comprising from 0 to 20% by weight of m-isopropylbiphenyl, from 40 to 75~ by weight of p-isopropylbiphenyl and from 5 to ~0~ by weight of diisopropylbiphenyl is almost odorless, that tha crystals of such a solvent are scarcely educed at a low temperature and that such a solvent fulfills all the conaitions to be possessed by the solvent for the chromogenic dye-precursor material for a pressure-sensitive recording paper sheet, and on the basis of the findings, the present inventors have effected the present invention.
: ;
_ g _ ., ' ! .
SUMMARY OF THE INVENTION:
.
In a first aspect of the present invention, there is provided a substantially odorless solvent for the chromo-genic dye-precursor material for a pressure-sensitive recording paper sheet, which comprises from 0 to 20% by weight of m-isopropylbiphenyl, from 40 to 75% by weight of p-isopropylbiphenyl and from 5 to 40% by weight of diiso-propylbiphenyl.
In a second aspect of the present invention, there is provided a pressure-sensitive recording paper sheet comprising a colour-development sheet coated with micro-capsules containing a dye solution which is composed of a colourless chromogenic dye-precursor material and a sub-stantially odorless solvént comprising from 0 to 20% by weight of m-isopropylbiphenyl, from 40 to 75% by weight of p-isopropylbiphenyl and from 5 to 40% by weight of diiso-propylbiphenyl, and a colour-developer sheet.
BRIEF EXPLANATION OF DRAWING:
Of the attached drawing, Fig. 1 is a triangle showing the composition of the solvent according to the present invention, which contains m-MIPB, p-MIPB and DIPB.
DETAILED DESCRIPTION OF TEE INVENTION:
The solvent of the present invention is a mixed ~: .
.
solvent comprising from 0 to 20% by weight of m--isopropyl-biphenyl (hereinaf-ter referred to as m-MIPB), from 40 to 75% by weight of p-isopropylbiphenyl (hereinafter referred to as p-MIPB) and from 5 to 40% by weight of diisopropyl-biphenyl (hereinafter referred to as DIPB).
The mixing rates of m-MIPB, p-MIPB and DIPB which are the components constituting the solvent for the chromo-genic dye-precursor material for the pressure-sensitive recording paper sheet according to the present invention are in the range shown by the points A, B, C and D in the triangle shown in Fig. 1.
The composition of the point A in Fig. 1 is 20%
by weight of m-MIPB, 75% by weight of p-MIPB and 5% by weight of DIPB, composition of the point B is 0% by weight of m-MIPB, 75% by weight of p-MIPB and 25% by weight of DIPB, the composition of the point C is 0% by weight of m-MIPB, 60% by weight of p-MIPB and 40% by weight of DIPB and the composition of the point D is 20% by weight of m-MIPB, 40% by weight of p-MIPB and 40% by weight of DIPB.
The mixed solvent within the above-mentioned range is almost odorless, crystals thereof are scarcely educed therefrom at a low temperature, for instance, 0C
and the colour-developing property is excellentO Namely, the rate of initial colour-development after 30 sec of recording at -5C is larger than the practical value (40%) and accordingly, the mixed solvent according to the present invention is useful as the solvent for the chromogenic dye-precursor material for the pressure sensitive recording paper sheet.
The preferable mixing rate of the solvent according to the present invention is in the range shown by the points a, b, c and d. The composition of the point a is 20%
by weight of m-MIPB, 70% by weight of p-MIPB and 10% by weight of DIPB, the composition of the point b is 0% by weight of m-MIPB, 70% by weight of p-MIPB and 30% by weight of DIPB, the composition of the point _ is 0% by weight of m-MIPB, 65% by weight of p-MIPB and 35% by weight of DIPB
and the composition of the point d is 20% by weight of m-MIPB, 45% by weight of p-MIPB and 35~ by weight of DIPB.
In the case where the content of m-MIPB in the mixed solvent is more than 20% by weight, since the problem of odor occurs, such a situation is undesirable. In the case where the content of p-MIPB is more than 75% by weight, since the crystals thereof are apt to be educed at a low temperature, such a situation is also undesirable~ Further-more, in the case where the content of DIPB is more than 40% by weight,~since the colour-developing property at a .
low temperature becomes insufficient, such a situation is also undesirable.
Although DIPB which is one of the components :: ::
.
. : .
constituting the solvent according to the present invention is a mixture of isomers 2,2'-DIPB, 2,3'~DIPB, 2,4'-DIPB, 3,3'~DIPB, 3,4'-DIPB and 4,4'-DIPB, the effect of the present invention is not limited by the kinds of the isomers of DIPB.
So far as the above-mentioned specific properties of the solvent for the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet according to the present invention, namely the substantial odorless-ness, the excellent colour-developing property at a low temperature and the property of scarcely educing crystals thereof at a low temperature, are not damaged, any publicly known solvent for the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet, for instance, di-isopropylnaphthalene, hydrogenated terphenyl and butyl-biphenyl or any publicly known diluent Xor the solvent for the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet, for instance, dodecylbenzene and kerosene can be added to the solvent for the chromogenic dye-precursor material for the pressure-sensitive recording paper sheet according to the present invention.
The solvent according to the present invention can be obtained by mixing m-MlPB, p-MIPB and DIPR a~ the mixing ratio in the above-mentioned range, and also can be produced according to the following methods.
(1) The method comprises the steps of reacting 1~
` ~:
.. . .
: ' ~6~36;~3 biphenyl with propylene at a temperature of from 120 to 260~C
in the presence of a silica-alumina catalyst, thereby carry-ing out the propylation of biphenyl, and subjecting the thus obtained reaction product to distillation, thereby obtaining the fraction having a mean boiling point of from 138 to 149C
under a reduced pressure of 5 mn~Ig.
(2) The method comprises the steps of reacting biphenyl with propylene at a temperature of from 50 to 110C
in the presence of a catalyst of aluminum chloride, thereby carrying out the propylation of biphenyl, subjecting the thus obtained reaction product to distillation under a reduced pressure, thereby rectifying p-MIPB, and mixing the thus rectified p-MIPB with DIPB which has been separately rectified, at a predetermined ratio.
As the catalyst used in the method of propylation of biphenyl, the silica-alumina catalyst which, in the reaction of transalkylation of a mixture of naphthalene and diisopropylnaphthalene at 280C, (i) shows the initial activity of not less than 0.1 kg of naphthalene/hour-kg of catalyst, preferably not less than 0.2 kg of naphthalene/
hour~kg of catalyst and (ii) retains the activity of not less than 90% even after treating the mixture of naphthalene and diisopropylnaphthalene in an amoun~ of 100 times by weight of the catalyst is desirable.
As the silica-alumina catalyst having the above-- :~
.
': ..... ; . ~
`~' '' ''' :' :
` "` : ;` ~ , mentioned specific properties, the catalysts made by NIKKI
Chemical Industries Co., Ltd. under the respective codes of X-632HN and N-632L may be exemplified.
The reaction temperature of propylation is from 120 to 260C, preferably from 150 to 240C. In the case where the reaction temperature is less than 120C, since the reaction velocity is low, such a reaction temperature is not practical, and on the other hand, in the case where the reaction temperature is more than 260C, since the decom-posit.ive r~action occurs as well as the alkylation reaction and the reaction product sh~ws a disagreeable odor, such a temperature is undesirable.
The heart of the present invention is characterized by using microcapsules containing a dye solution which is composed of the chromogenic dye-precursor materiai..and a substantially odorless solvent comprising from 0 to 20% by weight of m-MIPB, from 40 to 75~ by weight of p-MIPB and from 5 to 40% by weight of DIPB. A~cordingly, all the methods publicly known by the p2rsons skilled in the art can be applied to produce the pressure sensitive recording paper sheet without being limited to the chromogenic dye-precursor material, ~he colour-developer, the method of encapsulationj the method for preparing the slurry of the capsules, the method for applying the slurry, etc.
For instance, as the method of encapsulation, the .~
: .. ~ ~ .
.
~%6i~31ii;2~1 method of the coacervation disclosed in U.S. Patents Nos.
2,800,457 and 2,800,~158, the method of the interfacial poly-merization disclosed in British Patent No. 990,443 and U.S.
Patent No. 3,2g7,154, and several other methods can be utilized.
As the chromogenic dye-precursor material, tri-phenylmethanes, diphenylmethanes, xanthenes, thiazines, spiropyranes, etc. may be exemplified. Further as the acidic substance used as the colour-developer, active claysh substance such as Japanese acid clay, active clay, atapalgite, bentonite, zeolite and the like or organoacidic substance such as phenol resin, acid-reactive phenol-formaldehyde novolak resin, organoacidic substance such as metallic salt of an aromatic organic acid, etc. may be exemplified.
The solvent for the chromogenic dye-precursor mate~ial for the pressure-sensitive recording paper sheet according to the present invention is almost odorless and excellent in solubility of the chromogenic dye-precursor material, and fulfills the above-mentioned necessary conditions to be possessed by the solvent for the dye-precursor material for the pressure-sensitive recording paper sheet, and scarcely educes crystals of the solvent at a low temperature (0C).
Furthermore, the initial colour-development of the pressure-sensitive recording paper sheet after 30 sec ,~
'' '' '`''.
' ., ~
of recording at a low temperature of ~5C is not less than 40% and accordingly, the pressure-sensi-tive recording paper sheet of the present invention can be sufficiently put to practical use.
The present invention will be concretely explained while referring to the ~ollowing non-limitative examples.
[Method for measuring the catalytic activity]
Apparatus:
In the lower part of a stainless-steel reaction tube of an inner diameter of about 25 mm, 10 ml of glass beads of 2 mm in diameter are filled up for supporting tne catalyst, and 25 ml of the catalyst are filled up on the thus filled glass beads.
Furthermore, 20 ml of glass beads o 2 mm in diameter are filied up, as the preheating zone, on the layer of the catalyst.
Heating of the thus filled materials is conducted from outside by an electric heater, and the inner tempera-ture of the tube is measured by a thermocouple inserted in the reaction tube.
Method:
By heating an equimolar mixture of naphthalene and diisopropylnaphthalene (an isomeric mixture) to about 60C, naphthalene is dissolved in diisopropylnaphthalene.
. ., ` " ~ ;' z~
From the upper part of the reaction tube, the thus prepared mixture is supplied at a definite flow rate to reac~ con-tinuously naphthalene with diisopropylnaphthalene while maintaining the temperature of the catalyst layer at 280C.
The reaction liquid which flows out from the lower part of the reaction tube is cooled to a temperature of lower than 100C, and is put to sampling on occasion to be analyzed by gaschromatography. The flow rate of the reaction liquid from the reaction tube is set up so that the initial con-version rate of nap~thalene is from 10 to 20~. As the raw materials of the reaction, naphthalene and diisopropyl naphthalene containing scarcely the components such as sulfur, nitrogen compounds, etc., which deteriorate the catalytic activity, are used.
Evaluation of the ca ~ ty:
From the analytical results of the product obtained during the period from the commencement of ~he reaction to ; the time when the mixture of naphthalene and diisopropyl-naphthalene in amount of about 5 times by weight of the catalyst has been reacted, the conversion of naphthalene (Xo) is obtained, and the initial activity of the catalyst is obtained according to the following formula:
Initial activity (~0) = N _ 0 ( Wc ) ` 18 -: ::
.: ~ :: .
, :;:
.
~;1!3&;~
wherein Wc is the amount of the thus filled catalyst and WN
i5 the supplying speed of naphthalene (g/hour).
The reaction is continuously carried out, and at the time when the mixture of naphthalene and diisopropyl-naphthalene has been reacted in an amount of 100 times of the weight of the catalyst, the conversion of naphthalene (X100) is obtained from the analytical results of the product, and the retaining rate of the catalytic activity (~) is obtained according to the following formula:
Retaining rate of catalytic activity (Ap) = 100 x 100 (XO) TEST EXAMPLE OF CATALYTIC ACTIVITY:
~ _ . ~.
In a reaction tube, 25 g of a silica-alumina catalyst (pellets of 3 mm in diameter, made of NIKKI Chemical Industries Co., Ltd., Model: X-632HN) was filled up, and an equimolar mixture of naphthalene and diisopropylnaphthalene was supplied at ~the rate of 250 ml~hour (245 g/hour) to carry out transalkylation reaction.
After 30 min and 10 hours of the commencement of the reaction, the reaction liquid was sampled and analyzed by gaschromatograph~, the results being as follows:
X0 = 17.0~, X100 = 16.2~ and Ap = 95.3~.
Furthermore, since WN is 92.2 g/hour and Wc is . : . .
: ` ~
':
25 g, the initial catalytic activity was obtained as follows:
Ao = 92.~x 0 17 = 0.63 kg/hour-kg-catalyst c Into a stainless steel autoclave of a capacity of 1.5 litres, 1000 g of biphenyl and 100 g of the catalyst used in Test Example of Catalytic Activity were introduced, and the content was heated to a temperature of not less than 70C to melt biphenyl. The agitation was started and the content of the autoclave was further heated to bring the inner temperature of the autoclave to 240C.
Gaseous propylene was introduced into the auto-clave from a propylene gas bomb to carry out the propylation reaction while maintaining the pressure in the autoclave at about 2 kg/cm G.
During the reaction, ~he reaction mixture was sampled on occassion to analyze the composition of the reaction mixture, and at the time when the mean propylation degree became about 1.0, the supply of propylene gas was stopped and the autoclave was cooled to collect the reaction liquid. The composition of the thus collected reaction Iiquid is shown in Table 1 below.
-- ~0 --:~ , : . .
~, Table 1 Component Composition ~ ~ , . . ....
Biphenyl 2708 o-Isopropylbiphenyl(o-MIPB) 6.0 m-Isopropylbiphenyl(m-MIPB) 18.7 p-Isopropylbiphenyl(p-MIPB) 22.1 Diisopropylbiphenyl(DIPB) 23.9 Triisopropylbiphenyl(TIPB) and others 1.5 . . .
The thus obtained reaction mixture was carefully rectified at 140C under a reduced pressure of 5 mmHg, the composition of the thus obtained fraction being shown in Table 2.
Table 2 - . ~
Composition Co~ponent m-MIPB 15.0 p-MIPB 71.9 DIPB 13.1 COMPARATIVE EXAMPLE lo .
In the same manner as in Example 1, propylation 6~
of biphenyl was carried out, and the thus obtained reaction mixture was fractionally distilled under a reduced pressure of 5 mmHg, thereby collectiny the fraction distilled from 141 to 150C. The composition of the thus obtained fraction is shown in Table 3.
Table 3 Component (~ hy weight) m MIPB 0.8 p-MIPB 47.6 DIPB 51.6 EXAMPLES_2 to 4 and COMPARATIVE EXAMPLE 2:
By using the same silica-alumina catalyst, pro-pylation of biphenyl was carried out at a temperature shown in Table 4 and in same manner as in Example 1. By subjec-t-ing the thus obtained reaction mixture to the same method of distillation as in Example l, the fraction comprising p-MIPB as the main component was obtainedO
The composition of the reaction product and that of the fraction are shown in Table 4.
, ., , ~
8i~
E~AMPLE 5:
Into a glass autoclave of a capacity of 1 litre, 500 g of biphenyl were introduced, and the inner temperature of the autoclave was raised to 80C to melt the introduced biphenyl~ After adding 14 g of anhydrous aluminum chloride as the catalyst into the molten biphenyl, the autoclave was tightly closed and agitation was started. Propylene gas was introduced into the autoclave from a gas-bomb to carry out the alkylation reaction while maintaining the inner temperature of the autoclave at from 100 to 110C and maintaining the inner pressure of the autoclave at about 1 kg/cm2G, and the xeaction was continued until the mean alkylation degree became about 1.
After the reaction was over, the reaction mixture was washed with hydrochloric acid and then with water to rémove the catalyst from the reaction mixture. The thus obtained reaction mixture was distilled in a rectifying tower of reduced pressure to separate about 120 g of p-MIPB
of a purity of 926.
The thus obtained crude p-MIPB was cooled in a jacketed glass vessel to 12C to a slurry-like substance.
The slurry-like substance was subjected to centrifugal separation thereby obtaining p-MIPB of a purity of 996.
On the other hand, 26 g of a mixture of 86 by weight of p MIPB and 92% by weight of DIPB were separated = 23 -' ' ,.. .
: ' by the distillation of the reaction mixture.
By combining the thus separated mixture of p-M¢PB
and DIPB with p-MIPB of a purity of 99%, a mixture of 73.2%
by weight of p-MIPB and 26.8% by weight of DIPB was obtained.
COMPAR~TIVE EXAMPLE 3:
In the same manner as in Example 5, propylation of biphenyl was carried out and the thus obtained reaction mixture was carefully distilled under a reduced pressure of 5 mmHg, thereby collecting the fraction distilled from 138 to 149C. The composition of the reaction mixture and the thus obtained fraction is shown in Table 5.
Table 4 Example and Com- Example Example Example Comparative parative Example 2 _ _ 3_ _4 Example 2 ture (C) P 150 200 255 300 . .
Reaction mixture (mol %) Biphenyl 27.8 28.4 28.527.5 o-MIPB 21.3 14~3 2.4 1.8 m-MIPB 5.8 10.0 22.926.5 p-MIPB 15.7 18.3 20.818.2 DIPB 27.3 27.0 23.623.0 TIPB and others 2.1 2.0 1.8 3.0 - ~4 ~æ~za Fraction (_y weight) m-MIPB 7.5 1106 16~2 15.8 p-MIPB 56.3 6306 7407 80.3 DIPB 36.2 24.8 9.1 3.9 Table 5 Reaction mixture Fraction Component (mol %) (% by weight) Biphenyl 28.6 o-MIPB 0.2 m-MIPB 26.4 703 p-MIPB 17.2 92.2 DIPB 24.1 0.5 TIPB and others 3.5 EXAMPLE 6: (Preparation of the solvent for the chromogenic dye-precursor material for ~he pressure-sensitive paper sheet):
One hundred millilitres of the solvent obtained : in Example 1 were warmed to 150C, and 30 g of Crystal Violet Lactone (a blue dyestuff made by HODOGAYA Chemical Industries Co., Ltd.) (hereinafter rèferred to as CVL) were dissolved in the thus warmed solvent under agitation.
:
.:
~z~
The thus prepared solution was introduced into a thermostat at ~0C and left therein, and the concentration of CVL was measured in course of the timeO The results are shown in Table 6. As are clearly seen in Table 6, the state of the extremely high concentration was maintained for a long time period.
Table 6 , Time passed (day) 1 7 14 Concentration of CVL
in the solution 1906 13.9 10.8 (g/100 ml) EXAMPLE 7:
~9L~ ' Microcapsules were prepared by using the solvent for the dye~precursor material for the pressure-sensitive recording paper sheet obtained in Example 6 according to the following method.
Six hundred and thirty grams of melamine and 1620 g of formalin (an aqueous 37% solution of formaldehyde) adjusted to pH of 9.0 by an aqueous 2~ solution of sodium hydroxide were mlxed, and the thus obtained mixture was heated to 70C. Just after the dissolution of melamine, 2250 g of water were added to the thus obtained solution .
.., ;.
.
, ~6~
and the whole mixture was stirred for 3 min to obtain an aqueous solution of melamine ~ formaldehyde prepolymer.
Separately, 1460 g of formalin adjusted to pH of 8.5 by triethanolamine and 600 g of urea were mixed together and the thus obtained mixture was reacted for 1 hour at 70C
to obtain an aqueous solution of urea - formaldehyde pre-polymer.
Furthermore, 1620 g of formalin and 600 g of urea were mixed and the thus formed mixture was stirred. To the thus prepared mixture, triethanolamine was added to adjust the pH of the mixture to 8.8 and the thus treated mixture was reacted for 30 min at 70C. To 400 g of the thus pre-pared reaction mixture, 24 g of water and 30 g of tetra-ethylenepentamine were added and the pH of the thus formed mixture was adjusted to 3 by adding an aqueous 15% solution of hydrochlorlc acid while stirring the mixture at 70Co Since the pH of the mixture was reduced with the progress of the. reaction, the pH was re-adjusted to 3 by the addition of an aqueous 10% solution of sodium hydroxide, and the reaction was continued while lowering the temperature of the reaction mixture to 55C.
: At the time when the viscosity of the reaction mixture became 200 cps, the reaction mixture was neutralized with an aqueous 10~ solution of sodium hydroxide and then r 4000 g of water were added to the thus neutralized reaction ~%61~6~
mixture to obtain an aqueous solution of a water~soluble cationic urea resin.
After adjusting the pH of the liquid mixture of 1000 g of the aqueous solution of melamine - formaldehyde prepolymer, 500 g of the aqueous solution of urea - formal-dehyde prepolymer, 1580 g of the aqueous solution of a water-soluble cationic urea resin, 620 g of water and 10 g of triethanolamine to 5.2 by the addition of an aqueous 10 %
solution of citric acid, 30 g of an aqueous 10% solution of NEOPELEX ~ (a surfactant made by KAO-ATLAS Co., Ltd.) were added to the liquid mixture to obtain "A" liquid.
Separately, 500 g of CVL were dissolved in 9500 g of the solvent obtained in Example 1 to prepare "B" liquid, and 1000 ml of "B" liquid were emulsified in "A" liquid in a homogenizer so that the diameter of the droplets of "B"
liquid becomes from 2 to 8 ~m. Thereafter, the thus formed emulsion was kept at 30C while gently stirring thereof and the pH of the emulsion was adjusted -to 3~6 by the addition of an aqueous 1% solution of citric acid. After further stirring the emulsion for 1 hour, 2000 ml of water were added to the thus treated emulsion. After leaving the emulsion for 3 hours, an aqueous 20% solution of citric acid was added to the emulsion to adjust the pH thereof to 3.0 and the agitation was continued for 20 hours to obtain a slurry of microcapsules.
, .. ..
Preparation of the pressure-sensitive xecordin~ paper sheet:
To 600 ml of an aqueous 10~ solution of polyvinyl alcohol (made by KVRARE Co., Ltd.) (hereinafter referred to as PVA), which had been prepared separately, 300 g of the thus obtained microcapsules were added, and by stirring the thus ~ormed mixture well, a liquid dispersion of the micro-capsules was obtained.
Onto a paper sheet of 45 g/m2, the liquid dis-persion was applied so that the applied amount of the microcapsules was 22 g/m2. By superposing the thus treated paper sheet with a colour-developing paper sheet on which a colour-developing substance having a polycondensate of p-phenylphenol and formaldehyde as the main colour-developer has been applied according to a conventional method, the pressure-sensitive recording paper sheet according to the present invention was obtained.
After subjecting the thus obtained pressure-sensitive recording paper sheet to colour-development by a typewriter made by OLIVETTI Co. under an ordinary environ-ment and preserving the thus treated pressure-sensitive recording paper sheet in a dark place ~or 24 hours, ~he concentration o~ the thus developed colour was measured by a refraction chromaticity meter made by MACBETH Co.
On the other hand, a pressure-sensitive recording paper sheet prepared by the same procedures as above was - ' ` .. ~. :~
: :
.. . : ,: .
~Z~ 2~
subjected to colour-development in the same manner as above, however, under an environment of -5C, and the change of the colour density was measured from just after the colour-development by the same refraction chromaticity meter.
Thereafter, the relative rate of colour-development at each time in course of the time from the time of the beginning of colour development was obtained, in the case where the colour density of the thus-treated pressure-sensitive recording paper sheet after preserving thereof for 24 hours at room temperature was appointed as 100. The results are shown in Table 7. As seen in Table 7, the thus formed pressure-sensitive recording paper sheet showed a sufficient colour-developing ability even at the initial time such as 30 sec after typewriting.
Tab Time passed30 sec 1 min 1 hour Rate of colour-70 % 77 ~ 88 development EXAMPLE 7:
By using each of the solvents obtained in Examples 2 to 5 and Comparative Example 1, each of the pressure-sensitive recording paper sheets was prepared according to ~8~g the method in Example 6.
The initial colour-development of each of the thus obtained pressure-sensitive recording paper sheets (colour-development after 30 sec of the recording at a temperature of -5C) is shown in Table 8.
Table No of Example Example Example Example Example Comparative 2 3 4 5Example 1 Rate of colour-development (~) 57 62 72 59 25 _ _ _ _ _ On each of the solvents obtained in Examples 1 to 5 and Comparative Examples 2 and 3, the pane~ test , concerning the odor of the solvent was carried out by 20 : men and 20 women (total 40 persons) unintentionally : selected. The results are shown in Table ~.
:' ' .
-~31 -:.: .
, ,. ~ :
'' ; ": ' " ' ~
. ,,~ ~
Table 9 Number of evaluating person No. of Example or Comparative Example ~ B C - ------ Evaluatlon ~ ~ _ ~
Example 1 6 26 8 O B
Example 2 7 28 5 0 Example 3 7 24 9 0 B
Example 4 4 25 11 0 B
Example 5 3 26 10 1 B
Comparative Example 3 0 913 1~ D
(Note) Evaluation A: odorless B: almost odorless C: odor was present D: disagreeable odor was present As the solvent for the chromogenic dye-precursor material for the pressure~sensitive recording paper sheet which can be put to practical use, it is necessary that the solvent is evaluated to be A or B.
TEST EXAMPLE 2:
Each of the solvents obtained in Examples 1 to 5 and Comparative Examples 2 and 3 was kept for 24 hours in a thermostat of 5C and in a thermostat of 0C, and the presence or absence of eduction of crystals from the A
. . .
~Læ~
solvent was observed. The results are shown in Table 10.
Tab No. of Example Example Example Example Example Comparative Comparative Example 1 2 3 4 5Example 2Example 3 _ _ _ . . . . _ . _ Notes: A: no crystal was educed.
B: cxystals were scarcely educed.
C: a large amount of crystals was educed.
As the solvent for the chromogenic dye-precursor material for the pressure-xesistent recording paper sheet, it is necessary that the result of the evaluation is A or B.
~' .
- -,, ~ '~ , : : ~ : , .
: . . .
' ~
Claims (3)
1. A solvent for the chromogenic dye-precursor material for a pressure-sensitive recording paper sheet, which comprises from 0 to 20% by weight of m-isopropylbiphenyl, from 40 to 75% by weight of p-isopropylbiphenyl and from 5 to 40% by weight of diisopropylbiphenyl.
2. A pressure-sensitive recording paper sheet comprising a colour-development sheet coated with microcapsules containing a dye solution which is com-posed of a colourless chomogenic dye-precursor material and a substantially odorless solvent comprising from 0 to 20% by weight of m-isopropylbiphenyl, from 40 to 75%
by weight of p-isopropylbiphenyl and from 5 to 40% by weight of diisopropylbiphenyl, and a colour-developer sheet.
by weight of p-isopropylbiphenyl and from 5 to 40% by weight of diisopropylbiphenyl, and a colour-developer sheet.
3. A substantially odorless solvent for a chromogenic dye-precursor material for a pressure-sensitive recording paper sheet, the solvent consisting essentially of:
from 0 to 20% by weight of m-isopropylbiphenyl, from 40 to 75% by weight of p-isopropylbiphenyl, and from 5 to 40% by weight of diisopropylbiphenyl.
from 0 to 20% by weight of m-isopropylbiphenyl, from 40 to 75% by weight of p-isopropylbiphenyl, and from 5 to 40% by weight of diisopropylbiphenyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62036686A JPS63203376A (en) | 1987-02-19 | 1987-02-19 | Dye solvent for pressure-sensitive recording paper and pressure-sensitive recording paper using said solvent |
| JP36686/87 | 1987-02-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1268629A true CA1268629A (en) | 1990-05-08 |
Family
ID=12476714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000537162A Expired - Fee Related CA1268629A (en) | 1987-02-19 | 1987-05-14 | Solvent for chromogenic dye-precursor material for pressure-sensitive recording paper sheet and pressure-sensitive recording paper sheet prepared by using the solvent |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS63203376A (en) |
| CA (1) | CA1268629A (en) |
| CH (1) | CH671369A5 (en) |
| DE (1) | DE3715649A1 (en) |
| ES (1) | ES2004286A6 (en) |
| FR (1) | FR2611211B1 (en) |
| GB (1) | GB2201697B (en) |
| IT (1) | IT1204604B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4902422A (en) * | 1988-12-06 | 1990-02-20 | Board Regents The University Of Texas System | Defect-free ultrahigh flux asymmetric membranes |
| JPH0741738B2 (en) * | 1989-03-27 | 1995-05-10 | 日本製紙株式会社 | Coloring material |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4921608B1 (en) * | 1970-08-24 | 1974-06-03 | ||
| US3627581A (en) * | 1970-10-19 | 1971-12-14 | Ncr Co | Pressure-sensitive record material |
| FR2226283A1 (en) * | 1973-04-23 | 1974-11-15 | Champion Paper Co Ltd | |
| DE2537982A1 (en) * | 1974-08-26 | 1976-03-11 | Champion Paper Co Ltd | PRESSURE SENSITIVE RECORDING MATERIAL USING ALKYLNAPHTHALINE SOLVENTS FOR DYE PRECURSORS |
| CH645306A5 (en) * | 1980-04-16 | 1984-09-28 | Ciba Geigy Ag | METHOD FOR PRODUCING CONCENTRATED SOLUTIONS OF COLOR IMAGES. |
| JPS57116686A (en) * | 1981-01-13 | 1982-07-20 | Kureha Chem Ind Co Ltd | Pressure-sensitive recording paper |
| GB2106529B (en) * | 1981-08-05 | 1985-06-12 | Monsanto Co | Solvent systems containing a high proportion of diluent for pressure-sensitive copying systems |
| JPS62257880A (en) * | 1986-05-02 | 1987-11-10 | Kureha Chem Ind Co Ltd | Dye solvent for pressure-sensitive recording paper and pressure sensitive recording paper using said solvent |
| JPS62257879A (en) * | 1986-05-02 | 1987-11-10 | Kureha Chem Ind Co Ltd | Dye solvent for pressure-sensitive recording paper and pressure-sensitive recording paper using said solvent |
-
1987
- 1987-02-19 JP JP62036686A patent/JPS63203376A/en active Granted
- 1987-05-07 CH CH1764/87A patent/CH671369A5/de not_active IP Right Cessation
- 1987-05-07 GB GB8710770A patent/GB2201697B/en not_active Expired - Fee Related
- 1987-05-11 DE DE19873715649 patent/DE3715649A1/en active Granted
- 1987-05-12 ES ES8701422A patent/ES2004286A6/en not_active Expired
- 1987-05-13 FR FR878706725A patent/FR2611211B1/en not_active Expired - Fee Related
- 1987-05-13 IT IT20503/87A patent/IT1204604B/en active
- 1987-05-14 CA CA000537162A patent/CA1268629A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| FR2611211B1 (en) | 1992-03-13 |
| DE3715649C2 (en) | 1989-06-08 |
| GB8710770D0 (en) | 1987-06-10 |
| FR2611211A1 (en) | 1988-08-26 |
| CH671369A5 (en) | 1989-08-31 |
| GB2201697A (en) | 1988-09-07 |
| IT8720503A0 (en) | 1987-05-13 |
| ES2004286A6 (en) | 1988-12-16 |
| DE3715649A1 (en) | 1988-09-01 |
| IT1204604B (en) | 1989-03-10 |
| JPH0441912B2 (en) | 1992-07-09 |
| JPS63203376A (en) | 1988-08-23 |
| GB2201697B (en) | 1991-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4352855A (en) | Transfer-onto-plain paper type pressure-sensitive copying paper | |
| CA1107501A (en) | Low-odor dye solvents for pressure-sensitive copying systems | |
| CA1268629A (en) | Solvent for chromogenic dye-precursor material for pressure-sensitive recording paper sheet and pressure-sensitive recording paper sheet prepared by using the solvent | |
| CA1255500A (en) | Solvent for chromogenic dye-precursor material for pressure-sensitive recording paper sheet and pressure-sensitive recording paper sheet prepared by using the solvent | |
| US4699658A (en) | Solvent for chromogenic dye-precursor material for pressure-sensitive recording paper sheet and pressure-sensitive recording paper sheet prepared by using the solvent | |
| CA1049709A (en) | Pressure-sensitive record material employing alkyl naphthalene dye-precursor solvent | |
| US4795493A (en) | Solvent for chromogenic dye-precursor material for pressure-sensitive recording paper sheet and pressure-sensitive recording paper sheet prepared by using the solvent | |
| GB2042014A (en) | Pressure-sensitive recording material | |
| US4774136A (en) | Solvent for the chromogenic dye-precursor material for a pressure-sensitive recording paper sheet and a pressure-sensitive recording paper sheet prepared by using the solvent | |
| KR900004790B1 (en) | Solvent ink and coated paper for carbonless copying system | |
| EP1132362B1 (en) | Hydrocarbon solvent and pressure-sensitive copying material made with the same | |
| US3968301A (en) | Pressure-sensitive record material and dye solvents therefor | |
| US5458974A (en) | Microencapsulated composition containing solvent including triisopropyylbiphenyl | |
| CA1339248C (en) | Heat-sensitive record material and microcapsule | |
| JPS6050155B2 (en) | Microcapsules for carbon-free copy paper | |
| CA2148694C (en) | Method of printing onto pressure-sensitive record materials | |
| US4774223A (en) | Solvent, ink and coated paper for carbonless copying system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |