POLYMORPHIC FORMS OF N-(4-((4-(3-PHENYLUREIDO)PHENYL)SULFONYL)PHENYL)BENZOLSULFONAMIDE
20220363629 · 2022-11-17
Inventors
Cpc classification
B41M5/3336
PERFORMING OPERATIONS; TRANSPORTING
International classification
Abstract
The present invention relates to an N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl)benzenesulfonamide in the polymorphic form ω.sup.18.9, characterised by an x-ray powder diffractogram having the Bragg angles (2θ/CuK.sub.α) 10.9, 11.7, 14.6, 15.0, 15.8, 16.6, 17.6, 18.9, 19.4, 20.9, 21.2, 22.0, 23.3, 24.4, 24.7, 26.1, 27.4, 29.4, 34.2,
or in the polymorphic form α.sup.21.2, characterised by an x-ray powder diffractogram having the Bragg angles (2θ/CuK.sub.α) 8.7, 9.8, 10.8, 13.2, 13.9, 14.9, 15.2, 16.0, 17.4, 17.7, 18.7, 20.4, 21.2, 21.6, 22.3, 23.0, 23.3, 23.9, 24.4, 25.0, 25.8, 26.6, 28.1, 28.9, 29.4, 30.1, 30.6, 31.8, 34.5, 35.3, 35.6, 36.9, a method for production thereof, use thereof as a colour developer in a heat-sensitive recording material, and a heat-sensitive recording material comprising N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl)benzenesulfonamide in the polymorphic form ω.sup.18.9 or in the polymorphic form α.sup.21.2.
Claims
1. An N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl) benzenesulfonamide in the polymorphic form ω.sup.18.9, characterised by an x-ray powder diffractogram having the Bragg angles (2θ/CuK.sub.α) 10.9, 11.7, 14.6, 15.0, 15.8, 16.6, 17.6, 18.9, 19.4, 20.9, 21.2, 22.0, 23.3, 24.4, 24.7, 26.1, 27.4, 29.4, 34.2, or in the polymorphic form α.sup.21.2, characterised by an x-ray powder diffractogram having the Bragg angles (2θ/CuK.sub.α) 8.7, 9.8, 10.8, 13.2, 13.9, 14.9, 15.2, 16.0, 17.4, 17.7, 18.7, 20.4, 21.2, 21.6, 22.3, 23.0, 23.3, 23.9, 24.4, 25.0, 25.8, 26.6, 28.1, 28.9, 29.4, 30.1, 30.6, 31.8, 34.5, 35.3, 35.6, 36.9.
2. The N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl) benzenesulfonamide in the polymorphic form ω.sup.18.9 or in the polymorphic form α.sup.21.2 according to claim 1, characterised in that the polymorphic form ω.sup.18.9 has characteristic absorption bands according to Fourier transformation infrared spectroscopy at the wavelengths 1092 cm.sup.−1, 1105 cm.sup.−1, 1145 cm.sup.−1, 1233 cm.sup.−1, 1319 cm.sup.−1, 1495 cm.sup.−1, 1548 cm.sup.−1, 1598 cm.sup.−1, 1655 cm.sup.−1 and 3239 cm.sup.−1 and the polymorphic form α.sup.21.2 has characteristic absorption bands according to Fourier transformation infrared spectroscopy at the wavelengths 1089 cm.sup.−1, 1110 cm.sup.−1, 1149 cm.sup.−1, 1237 cm.sup.−1, 1311 cm.sup.−1, 1321 cm.sup.−1, 1500 cm.sup.−1, 1556 cm.sup.−1, 1597 cm.sup.−1, 1697 cm.sup.−1, 3365 cm.sup.−1 and 3408 cm.sup.−1.
3. The N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl) benzenesulfonamide in the polymorphic form ω.sup.18.9 or in the polymorphic form α.sup.21.2 according to claim 1, characterised in that the polymorphic form ω.sup.18.9 has a melting range of 232 to 233° C. and the polymorphic form α.sup.21.2 has a melting range of 219 to 221° C.
4. A method for producing N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl)benzenesulfonamide in the polymorphic form ω.sup.18.9, characterised in that monophase N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl) benzenesulfonamide in the polymorphic form α.sup.21.2 is heated.
5. A method for producing N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl) benzenesulfonamide in the polymorphous form α.sup.21.2, characterised in that non-monophase N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl)benzenesulfonamide is obtained by recrystallisation from a mixture of ethyl acetate and n-hexane, or in that monophase N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl)benzenesulfonamide in the polymorphic form ω.sup.18.9 is recrystallised from acetonitrile.
6. An N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl) benzenesulfonamide in the polymorphic form ω.sup.18.9, obtained by the method according to claim 4.
7. An N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl) benzenesulfonamide in the polymorphic form α.sup.21.2, obtained by the method according to claim 5.
8. A heat-sensitive recording material, comprising a carrier substrate and a heat-sensitive colour-forming layer containing at least one colour former and at least one phenol-free colour developer, wherein the at least one phenol-free colour developer is N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl)benzenesulfonamide in the polymorphic form ω.sup.18.9 and/or in the polymorphic form α.sup.21.2, according to claim 1.
9. The heat-sensitive recording material according to claim 8, wherein the colour developer is present in an amount of from about 3 to about 35% by weight in relation to the total solids content of the heat-sensitive layer.
10. The heat-sensitive recording material according to claim 8, wherein the at least one colour former is a dye of the triphenylmethane type, of the fluoran type, of the azaphthalide type and/or of the fluorene type.
11. The heat-sensitive recording material according to claim 8, wherein, besides the phenol-free colour developer, at least one colour developer of general formula
Ar.sup.1—SO.sub.2—NH—C.sub.6H.sub.4—SO.sub.2—C.sub.6H.sub.4—NH—CO—NH—Ar.sup.2, wherein Ar.sup.1 and Ar.sup.2 are an unsubstituted or substituted phenyl group, is also present.
12. The heat-sensitive recording material according to claim 11, characterised in that Ar.sup.1 is a phenyl group, and/or in that Ar.sup.2 is a phenyl group.
13. The heat-sensitive recording material according to claim 11, characterised in that Ar.sup.1 is substituted with at least one C.sub.1-C.sub.5 alkyl group, an alkenyl group, an alkynyl group, a benzyl group, a formyl group, a CN group, a halogen group, an NO.sub.2 group, an RO group, an R—CO group, an RO.sub.2C group, an R—OCO group, an R—SO.sub.2O group, an R—O—SO.sub.2 group, an R—SO.sub.2—NH group, an R—NH—SO.sub.2 group, an R—NH—CO group or an R—CO—NH group, wherein R is a C.sub.1-C.sub.5 alkyl group, an alkenyl group, an alkynyl group, a phenyl group, a tolyl group, or a benzyl group.
14. A method for producing a heat-sensitive recording material according to claim 8, wherein an aqueous suspension containing the starting materials of the heat-sensitive colour-forming layer is applied to a carrier substrate and dried, wherein the aqueous application suspension has a solids content of from about 20 to about 75% by weight and is applied and dried by the curtain coating process at an operating speed of the coating plant of at least about 400 m/min.
15. Heat-sensitive recording material obtained by the process according to claim 14.
16. The method of claim 4 wherein the monophase N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl) benzenesulfonamide in the polymorphic form α.sup.21.2 is refluxed in an organic solvent.
17. The method of claim 16 wherein the organic solvent is ethyl acetate.
18. The heat-sensitive recording material according to claim 8, wherein the colour developer is present in an amount of from about 10 to about 25% by weight in relation to the total solids content of the heat-sensitive layer.
19. The heat-sensitive recording material according to claim 8, wherein the at least one colour former is a dye of the fluoran type.
20. A method for producing a heat-sensitive recording material according to claim 8, wherein the aqueous application suspension has a solids content of from about 30 to about 50% by weight and is applied and dried by the curtain coating process at an operating speed of the coating plant of at least about 1000 m/min.
Description
EXAMPLES
Example 1
[0095] The non-monophase compound N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl)benzenesulfonamide was produced as follows:
[0096] A solution of 7.5 mmol of phenylisocyanate in 20 ml dichloromethane was added dropwise at 0° C. with stirring to a mixture of 7.5 mmol of 4,4′-diaminodiphenylsulfone and 7.5 mmol pyridine in 80 mL dichloromethane. The reaction solution was stirred for 16 hours at room temperature. A solution of 7.5 mmol of benzenesulfonyl chloride in 15 ml dichloromethane was then added dropwise at 0° C. with stirring. The reaction mixture was refluxed and the progress of the reaction was monitored by means of HPLC. Once the reaction was complete, the product was filtered off, washed with dichloromethane, and dried in a vacuum.
Example 2
[0097] 6.84 g of N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl)benzenesulfonamide, produced according to Example 1, was recrystallised from EtOAc/n-hexane. N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl)benzenesulfonamide was obtained, characterised by an x-ray powder diffractogram with the following Bragg angles (2θ/CuK.sub.α): 8.7, 9.8, 10.8, 13.2, 13.9, 14.9, 15.2, 16.0, 17.4, 17.7, 18.7, 20.4, 21.2, 21.6, 22.3, 23.0, 23.3, 23.9, 24.4, 25.0, 25.8, 26.6, 28.1, 28.9, 29.4, 30.1, 30.6, 31.8, 34.5, 35.3, 35.6, 36.9 (see
Example 3
[0098] N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl)benzenesulfonamid, characterised by an x-ray powder diffractogram with the following Bragg angles (2θ/CuK.sub.α): 10.9, 11.7, 14.6, 15.0, 15.8, 16.6, 17.6, 18.9, 19.4, 20.9, 21.2, 22.0, 23.3, 24.4, 24.7, 26.1, 27.4, 29.4, 34.2 (see
Example 4
[0099] A heat-sensitive recording material or thermal paper was produced, with the following formulations of aqueous application suspensions being used to form a composite structure on a carrier substrate, and then the other layers, especially a protective layer, being formed in the usual manner, which will not be discussed separately here.
[0100] An aqueous coating suspension was applied to one side of a 63 g/m.sup.2 synthetic base paper (Yupo® FP680) using a doctor bar on a laboratory scale to form the heat-sensitive colour-forming layer of a heat-sensitive recording paper. After drying, a thermal recording sheet was obtained. The application rate of the heat-sensitive colour-forming layer was between 3.8 and 4.2 g/m.sup.2.
[0101] Production of the dispersions (in each case for 1 part by weight) for the application suspensions:
[0102] The aqueous dispersion A (colour former dispersion) was produced by grinding 20 parts by weight of 3-N-n-dibutylamino-6-methyl-7-anilinofluoran (ODB-2) with 33 parts by weight of a 15% aqueous solution of Ghosenex™ L-3266 (sulfonated polyvinyl alcohol, Nippon Ghosei) in a bead mill.
[0103] The aqueous dispersion B (colour developer dispersion) was produced by grinding 40 parts by weight of the colour developer (N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl)benzenesulfonamide, form ω.sup.18,9 or form α.sup.21,2 together with 66 parts by weight of a 15% aqueous solution of Ghosenex™ L-3266 in a bead mill.
[0104] The aqueous dispersion C (sensitising dispersion) is produced by grinding 40 parts by weight of the sensitiser with 33 parts by weight of a 15% aqueous solution of Ghosenex™ L-3266 in a bead mill.
[0105] The following sensitising agents were used: 1,2-diphenoxyethane (DPE), stearamide (SA), diphenylsulfone (DPS), di-(4-methylbenzyl)oxalate (HS3520), benzyloxynaphthalene (BON), 1,2-di(3-methylphenoxy)ethane (EGTE).
[0106] All dispersions produced by grinding had an average particle size D.sub.(4.3) of 0.80 to 1.20 μm. The particle size distribution of the dispersions was measured by laser diffraction with a Coulter LS230 apparatus from Beckman Coulter.
[0107] Dispersion D (lubricant dispersion) is a 20% zinc stearate dispersion consisting of 9 parts by weight of Zn-stearate, 1 part by weight of Ghosenex™ L-3266, and 40 parts by weight of water.
[0108] Pigment P is a 72% coating kaolin suspension (Lustra® S, BASF).
[0109] The binder consists of a 10% aqueous polyvinyl alcohol solution (Mowiol 28-99, Kuraray Europe).
[0110] The heat-sensitive application suspension is produced by mixing, with stirring, 1 part of A, 1 part of B, 1 part of C, 56 parts of D, 146 parts of pigment P and 138 parts of binder solution (all parts by weight), taking into account the order of introduction B, D, C, P, A, binder, and bringing the mixture to a solids content of about 25% with water.
[0111] The heat-sensitive coating suspensions obtained in this way were used to produce composite structures consisting of paper carrier and thermal reaction layer.
[0112] The thermal recording materials were evaluated as described below (see Table 2).
[0113] (1) Dynamic Colour Density:
[0114] The papers (6 cm wide strips) were thermally printed with a chessboard pattern with 10 energy levels using an Atlantek 200 test printer (Atlantek, USA) with a Kyocera print bar of 200 dpi and 560 ohms at an applied voltage of 20.6 V and a maximum pulse width of 0.8 ms. The image density (optical density, o.d.) was measured with a SpectroEye densitometer from X-Rite at an energy level of 0.45 mJ/dot. In each case, the highest o.d. Value of the chessboard pattern was taken into consideration for the evaluation (Table 2). The measurement uncertainty of the o.d. values was estimated at ≤2%.
[0115] (2) Static Colour Density (Starting Temperature):
[0116] The recording sheet was pressed against a series of thermostatically controlled metallic stamps heated to different temperatures with a contact pressure of 0.2 kg/cm.sup.2 and a contact time of 5 seconds (thermal tester TP 3000QM, Maschinenfabrik Hans Rychiger AG, Steffisburg, Switzerland). The image density (opt. density) of the images thus produced was measured with a SpectroEye densitometer from X-Rite.
[0117] The static starting point was, by definition, the lowest temperature in ° C. at which an optical density of 0.2 was achieved. The accuracy of the measuring method was ≤±0.5° C.
[0118] Table 2 summarises the evaluation of the recording materials produced.
TABLE-US-00002 TABLE 2 Polymorphic form of the Sensitising o.d. Starting point CD agent max. (° C.) ω.sup.18.9 EGTE 1.29 93 a.sup.21.2 1.27 91 ω.sup.18.9 DPE 1.30 85 a.sup.21.2 1.29 84 ω.sup.18.9 SA 1.19 92 a.sup.21.2 1.18 89 ω.sup.18.9 BON 1.24 91 a.sup.21.2 1.24 88 ω.sup.18.9 DPS 1.22 91 a.sup.21.2 1.22 87 ω.sup.18.9 HS 3520 1.28 90 a.sup.21.2 1.27 89
[0119] It can be deduced from the above examples that the heat-sensitive recording material of the present invention shows the following advantageous properties especially:
[0120] (1) Both the use of the α.sup.21.2 form and the use of the ω.sup.18.9 form as colour developer lead to high maximum print densities of the heat-sensitive recording materials according to the invention and to high temperatures at which a visually discernible greying of the heat-sensitive recording materials according to the invention (starting point ° C.) occurs.
[0121] (2) The temperature from which a visually discernible greying of the recording materials according to the invention occurs (static starting point) is higher with use of the polymorph ω.sup.18.9 than in the examples with the α.sup.21.2 form of the colour developer. On the one hand, this gives rise to the possibility for use of the heat-sensitive recording materials manufactured with the ω.sup.18.9 form also at higher ambient temperatures, and on the other hand a thermally less sensitive coating benefits the process when drying the aqueous coating (Table 2).
[0122] (3) The recorded image of the heat-sensitive recording materials obtained with the ω.sup.18.9 form of the colour developer has practically the same maximum print density (optical density) as that of the α.sup.21.2 form (Table 2).
[0123] (4) Both the starting point and the print density generated dynamically during the printing process can be influenced to a significant extent by the sensitising agent. The data from Table 2 reveal that the advantageous properties according to (2) and (3) are valid for a representative selection of sensitising agents.