阅读说明：本技术 非酚系显色剂和热敏记录材料 (Non-phenolic color developer and thermosensitive recording material ) 是由 M·霍恩 T·斯塔灵 M·斯代帕特 于 2018-05-17 设计创作，主要内容包括：描述了式(I)的显色剂,(Ar<Sup>1</Sup>-SO<Sub>2</Sub>-NH-)<Sub>m</Sub>-Y-(-NH-C(O)-NH-SO<Sub>2</Sub>-Ar<Sup>2</Sup>)<Sub>n</Sub>(I),其中,Ar<Sup>1</Sup>为未取代的或被取代的芳族基团,Ar<Sup>2</Sup>为未取代的或被取代的苯基,Y为至少一个被取代(m+n)次的苯基团或萘基团,并且Y被这样取代,使得至少一个Ar<Sup>2</Sup>-SO<Sub>2</Sub>-NH-C(O)-NH-基团处于至少一个Ar<Sup>1</Sup>-SO<Sub>2</Sub>-NH基团的邻位；描述了热敏记录材料,其包括载体基材以及含有至少一种成色剂和至少一种不含酚的显色剂的热敏性成色层,其中至少一种显色剂为式(I)的化合物；和描述了用于制备该热敏记录材料的方法。(Color developers of formula (I), (Ar) 1 ‑SO 2 ‑NH‑) m ‑Y‑(‑NH‑C(O)‑NH‑SO 2 ‑Ar 2 ) n (I) Wherein Ar is 1 Is an unsubstituted or substituted aromatic radical, Ar 2 Is unsubstituted or substituted phenyl, Y is at least one phenyl or naphthyl group which is substituted (m + n) times, and Y is substituted in such a way that at least one Ar 2 ‑SO 2 ‑NH‑C(O)‑NH-groups at least one Ar 1 ‑SO 2 -ortho to the NH group; described are heat-sensitive recording materials comprising a carrier substrate and a heat-sensitive color-forming layer containing at least one color-former and at least one phenol-free developer, wherein at least one developer is a compound of formula (I); and a process for producing the thermosensitive recording material are described.)

1. A compound of formula (I)

(Ar¹-SO₂-NH-)_m-Y-(-NH-C(O)-NH-SO₂-Ar²)_n (I)，

Wherein Ar is¹Is an unsubstituted or substituted aromatic radical, Ar²Is unsubstituted or substituted phenyl, Y is at least one phenyl or naphthyl group which is substituted (m + n) times, and Y is substituted in such a way that at least one Ar²-SO₂-NH-C (O) -NH-at least one Ar group¹-SO₂Ortho to the NH group.

2. The compound of claim 1, wherein m-1 and n ≧ 1.

3. The compound of claim 1 or 2, wherein n is 1 or 2.

4. The compound of at least one of the preceding claims, wherein Ar¹Is unsubstituted or substituted phenyl or unsubstituted or substituted 2-naphthyl.

5. The compound of claim 4, wherein Ar¹Is unsubstituted phenyl or monosubstituted phenyl.

6. The compound of claim 5, wherein the mono-substituted phenyl is substituted with: c₁-C₅Alkyl, alkenyl, alkynyl, benzyl, RO-, halogen, formyl, ROC-, RO₂C-、CN-、NO₂-、R-SO₂O-、RO-SO₂-、R-NH-SO₂-、R-SO₂-NH-、R-NH-CO-NH-、R-SO₂-NH-CO-NH-、R-NH-CO-NH-SO₂-or R-CO-NH-group, wherein R is C₁-C₅Alkyl, alkenyl, alkynyl, phenyl, tolyl or benzyl, preferably phenyl or p-tolyl.

7. The compound of at least one of the preceding claims, wherein Ar²Is unsubstituted phenyl or monosubstituted phenyl, especially by C₁-C₄Alkyl-substituted phenyl, particularly preferably phenyl substituted by methyl.

8. The compound of at least one of the preceding claims, wherein Ar¹Is unsubstituted phenyl or monosubstituted phenyl, Ar²Is unsubstituted phenyl or monosubstituted phenyl, and Y is phenyl which is substituted (m + n) times.

9. Heat-sensitive recording material comprising a carrier substrate and a heat-sensitive color-forming layer containing at least one color-former and at least one phenol-free developer, wherein at least one developer is a compound of formula (I) according to at least one of claims 1 to 8.

10. The thermosensitive recording material according to claim 9, wherein the at least one color-former is a triphenylmethane-type, fluoran-type, azaphthalide-type and/or fluorene-type dye, preferably fluoran-type dye.

11. The thermosensitive recording material according to at least one of claims 9 and 10, wherein one or more additional non-phenolic color developers are present in addition to the compound of formula (I).

12. Thermosensitive recording material according to at least one of claims 9 to 11, wherein the compound of formula (I) according to at least one of claims 1 to 8 is present in an amount of from about 3 to about 35 wt. -%, preferably from about 10 to about 25 wt. -%, based on the total solid content of the thermosensitive layer.

13. The thermosensitive recording material according to at least one of claims 9 to 12, wherein the thermosensitive color-forming layer contains a urea-urethane compound of the general formula (II)

14. Process for the preparation of a heat-sensitive recording material according to at least one of claims 9 to 13, wherein an aqueous suspension of starting materials comprising a heat-sensitive color-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, preferably from about 30 to about 50% by weight, and is applied and dried using a curtain-film coating process at a speed of operation of the application device of at least about 400m/min, preferably at least about 1000m/min, very particularly preferably at least about 1500 m/min.

15. A thermosensitive recording material obtainable according to the process of claim 14.

Technical Field

The present invention relates to a color developer, a thermosensitive recording material including a support substrate and a thermosensitive color forming layer containing at least one color former and at least one phenol-free color developer, and a method for producing the same.

Background

Thermosensitive recording materials with a thermosensitive color-forming layer (thermoreactive layer) applied on a carrier substrate for direct thermal printing applications have been known for a long time. In the heat-sensitive color-forming layer, there are usually present a color former and a color developer which react with each other under the action of heat and cause color development. In this case, a (di) phenol-based color developer is often used. Also known is a thermosensitive recording material containing a non-phenolic color developer in a thermosensitive color-forming layer. These materials have been developed to improve the resistance of text images, especially even when printed heat-sensitive recording materials are stored for a long period of time or are in contact with hydrophobic substances such as plasticizer-containing materials or oils. In particular, interest in non-phenolic developers has increased greatly in the context of public discussions of the potential toxicity of (di) phenolic chemicals. The aim here is to avoid the toxic disadvantages of phenolic developers, but to at least maintain, preferably improve, the technical properties that can be achieved with phenolic developers.

The prior art on non-phenolic developers is able to identify common structural features despite the large chemical diversity of these substances.

The 1, 3-disubstituted ureido structure (Y-NH-CO-NH-Z) is therefore a feature common to a large number of non-phenolic developers. By appropriate selection of the groups Y and Z, functional properties relevant to suitability as developers can be adjusted.

Widely used is a compound having a sulfonyl-urea structure (-SO)₂-NH-CO-NH-) developers because of their relative ease of preparation and preparation using themThe prepared thermosensitive recording material has good application technical properties.

EP 0526072A 1 discloses developers from the class of aromatic sulfonyl (thio) urea compounds of the formula

Ar’-SO₂-NH-C(X)-NH-Ar，

Wherein X ═ O or S, and Ar' are aromatic groups.

With these developers, a thermosensitive recording material characterized by improved image durability can be obtained. Furthermore, thermosensitive recording materials based on these developers have a usable thermal print sensitivity with good surface whiteness, so that high print densities can be produced relatively easily using commercial thermal printers with a corresponding design of the formulation of the thermally sensitive color-forming layer.

WO 0035679 a1 aromatic and heteroaromatic sulfonyl (thio) urea compounds of the above formula (X ═ S or O) and/or sulfonylguanidines (X ═ NH), wherein Ar is linked to a further aromatic group via a divalent linking group. The non-phenolic developers from this category, 4-methyl-N- (((3- (((4-methylphenyl) sulfonyl) oxy) phenyl) amino) carbonyl) benzenesulfonamide (trade name Pergafast) widely used in practice

BASF) is characterized by a balance of application-technical properties of the thermosensitive recording material prepared with the developer. In particular, they have good dynamic response sensitivity and acceptable resistance of the prints to hydrophobic substances.

Sulfonylurea units linked via a divalent or polyvalent linker A, for example bissulfonylurea compounds of the formula have also been described many times as developers (cf. EP 0535887A 1, EP 0542556A 1, EP 0604832B 1, EP 0620122A 1 and EP 1044824A 2)

(Ar-SO₂-NH-C(O)-NH-)₂A，

Wherein Ar is an aromatic group.

In practice, N' - (methylenebis (4, 1-phenyleneiminocarbonyl)) bis (4-methyl-benzenesulfonamide) (B-TUM) inter alia gave the identity (a ═ CH)₂And Ar ═ 4-methylphenyl).

The combination of an N-sulfonyl (thio) carbamate group of formula with a sulfonylurea structure is the subject of JP H0664335,

(Ar-SO₂-NH-C(O)-NH-)_n(Ar-SO₂-NH-C(O)-X-)_mA，

wherein Ar is an aromatic group, A is an (m + n) -valent organic linking group and X ═ O or S.

For thermosensitive recording materials prepared with these developers, improved resistance of the glyphs to hydrophobic agents is described. However, the synthetic route to these developers is particularly problematic when chemically homogeneous substances are desired.

JP H0958242 combines a sulfonylurea structure with a primary sulfonamide group to obtain a developer of the formula

R-SO₂-NH-C(X)-NH-C₆H₄-SO₂-NH₂。

JP H11-263067 discloses a developer formed of a (thio) urea structure and a sulfonyl (thio) urea structure linked by an aromatic linker unit of the formula

Ar¹-NH-C(X)-NH-A-SO₂-NH-C(X)-NH-Ar²，

Wherein X ═ O or S, and Ar¹And Ar²Is an aromatic group.

The thermosensitive recording materials obtained with non-phenolic developers based on sulfonylurea chemistry have in common that they show good performance in many application-related aspects of properties, but otherwise disclose weaknesses.

The high durability of the text relative to hydrophobic substances is therefore often accompanied, for example, by a moderate response sensitivity (dynamic sensitivity) in thermal printers, which can only be effectively improved by means of a large number of partly very specific melting aids (in particular thermal solvents, in particular sensitizers).

On the other hand, relatively slightly higher dynamic sensitivity values are achieved with specific non-phenolic developers, among which the durability of the print is moderate. This drawback can be compensated by the aid of age resistors (stabilizers), but at the expense of a complex and expensive formulation of the recording layer.

Disclosure of Invention

The object of the present invention is therefore to eliminate the aforementioned disadvantages of the prior art. In particular, the object of the present invention is to provide a heat-sensitive recording material which has a high dynamic sensitivity (high response sensitivity in printers) and, with regard to other application techniques, relevant performance characteristics at least up to the level of heat-sensitive recording materials based on non-phenolic developers of the prior art, without relying on special formulation ingredients of the heat-sensitive functional layer, such as age resisters, or special melting aids with limited availability and/or high price. The main task of the present invention is to provide a developer that is capable of forming images of high print density without bringing together an undesirable effect on the onset temperature of the recording material (static sensitivity). At the same time, good durability of the thermal recording material, in particular with respect to hydrophobic agents, should be achieved compared to the prior art.

According to the invention, this object is achieved by the use of a compound according to claim 1 in a thermosensitive recording material according to claim 9.

It has surprisingly been found that it is possible to obtain a thermosensitive recording material with a developer of the specific substitution scheme of formula (I), which is characterized by a high dynamic sensitivity and cannot be produced with comparable formulations for thermosensitive recording materials with further substitution schemes of developers of the same compound class. The recording materials prepared with the developers according to the invention also have good resistance properties in the word to hydrophobic agents, which corresponds at least to the resistance properties of the prior art.

The compound according to claim 1 having formula (I),

Ar¹(SO₂-NH-)_m-Y-(-NH-C(O)-NH-SO₂-Ar²)_n (I),

wherein Ar is¹Is an unsubstituted or substituted aromatic radical, Ar²Is unsubstituted or substituted phenyl, Y represents at least one phenyl or naphthyl group which is substituted (m + n) times, and Y is so substitutedSo that at least one Ar is²-SO₂-NH-C (O) -NH-at least one Ar group¹-SO₂Ortho to the NH-group, i.e.in the 1, 2-position.

Preferably, m is equal to 1 and n is greater than or equal to 1.

Preferably, n is equal to 1 and m is 1 or 2.

Preferably, Ar¹Is unsubstituted or substituted phenyl or unsubstituted or substituted 2-naphthyl.

Particularly preferably, Ar¹Is unsubstituted phenyl or monosubstituted phenyl.

Preferably, the monosubstituted phenyl is substituted by: c₁-C₅Alkyl, alkenyl, alkynyl, benzyl, RO-, halogen, formyl, ROC-, RO₂C-、CN-、NO₂-、R-SO₂O-、RO-SO₂-、R-NH-SO₂-、R-SO₂NH-、R-NH-CO-NH-、R-SO₂-NH-CO-NH-、R-NH-CO-NH-SO₂-or R-CO-NH-group, wherein R is C₁-C₅Alkyl, alkenyl, alkynyl, phenyl, tolyl or benzyl, preferably phenyl or p-tolyl.

Preferred substituents are C₁-C₅Alkyl, RO-, halogen, RO₂C-、R-SO₂O-, R-NH-CO-NH-and R-SO₂-NH-CO-NH-groups.

Preferably, Ar²Is unsubstituted phenyl or monosubstituted phenyl, especially by C₁-C₄Alkyl-substituted phenyl, particularly preferably phenyl substituted by methyl.

In a particularly preferred embodiment, Ar¹Is unsubstituted phenyl or monosubstituted phenyl, Ar²Is unsubstituted phenyl or monosubstituted phenyl, and Y is a phenyl group which is substituted (m + n) times.

Particularly preferred compounds of formula (I) are shown in table 1 below.

Table 1: having Y groups, Ar¹Radical, Ar²Preferred compounds of formula (I) given the meanings of the radicals, m and n (R ═ as described above)

	Y	Ar1	Ar2	m	n
						I	Phenylene radical	Phenyl radical	Phenyl radical	1	1
II、XIV、XVII	Phenylene radical	Phenyl radical	C1-C4Alkyl substituted Phenyl radical	1	1
						III、XV、XVIII	Phenylene radical	C1-C5Alkyl substituted Phenyl radical	Phenyl radical	1	1
IV、V、VI、XVI、XIX	Phenylene radical	C1-C5Alkyl substituted Phenyl radical	C1-C4Alkyl substituted Phenyl radical	1	1
						VII	Phenylene radical	RO substituted phenyl	C1-C4Alkyl substituted Phenyl radical	1	1
VIII	Phenylene radical	Halogen substituted phenyl	C1-C4Alkyl substituted Phenyl radical	1	1
						IX	Phenylene radical	R-CO-NH substituted benzenes Base of	C1-C4Alkyl substituted Phenyl radical	1	1
X	Phenylene radical	Nitro substitutionPhenyl group of	C1-C4Alkyl substituted Phenyl radical	1	1
						XI	Phenylene radical	RO2C-substituted phenyl	C1-C4Alkyl substituted Phenyl radical	1	1
XII	Phenylene radical	Naphthyl radical	C1-C4Alkyl substituted Phenyl radical	1	1
						XIII	Phenylene radical	Benzyl radical	C1-C4Alkyl substituted Phenyl radical	1	1
XXI	Trisubstituted Benzene and its derivatives	C1-C5Alkyl substituted Phenyl radical	Phenyl radical	1	2
						XX、XXII、XXIII、XXIV	Trisubstituted Benzene and its derivatives	C1-C5Alkyl substituted Phenyl radical	C1-C4Alkyl substituted Phenyl radical	1	2

The preparation of the compounds of the formula (I) according to the invention can be carried out according to methods known per se.

Scheme 1 illustrates, as examples of compounds I to XIX (see table 2), possible synthetic routes to compounds of formula (I) according to the present invention.

Reaction scheme 1 (Ar)¹、Ar²: see Table 2)

Reaction scheme 2 illustrates possible synthetic routes for compounds of formula (I) according to the invention with examples of compounds XX to XXIV (see table 2).

Reaction scheme 2 (Ar)¹、Ar²: see Table 2)

Compounds XX (see table 2) which fall within the compounds of formula (I) according to the invention can be prepared: starting from 2, 6-dinitroaniline, it is first converted into 1, 2-diamino-3-nitrobenzene according to reaction scheme 3 below (v.milata, j.salo ň, org.prep.proceded.int., 31(3),347(1999)), and then into the end product according to the method described.

Reaction scheme 3

The preferred embodiments described for the compounds of the formula (I) apply equally to the process for their preparation.

As mentioned above, the present invention also relates to a heat-sensitive recording material comprising a support substrate and a heat-sensitive color-forming layer containing at least one color-former and at least one phenol-free developer, wherein the at least one phenol-free developer is a compound of formula (I) as described above.

The compound of formula (I) is preferably present in an amount of about 3 to about 35 wt.%, particularly preferably in an amount of about 10 to about 25 wt.%, based on the total solids content of the heat-sensitive layer.

The choice of carrier substrate is not critical. However, it is preferred to use paper, synthetic paper and/or plastic foil as the carrier substrate.

Optionally, at least one further intermediate layer is present between the carrier substrate and the heat-sensitive layer, wherein the purpose of the further intermediate layer is to improve the surface smoothness of the carrier substrate with respect to the heat-sensitive layer and to ensure a thermal barrier between the carrier substrate and the heat-sensitive layer. Preferably, organic hollow bead pigments and/or calcined kaolin are used in the intermediate layer. At least one protective layer and/or at least one layer which facilitates printability may also be present in the heat-sensitive recording material according to the invention, wherein these layers may be applied to the front or back of the substrate.

There is also no essential limitation of the present invention with respect to the choice of color former. Preferably, however, the colour former is a dye of the triphenylmethane type, fluoran type, azaphthalide type and/or fluorene type. A very particularly preferred color former is a fluoran type dye, since it is capable of providing recording materials with attractive cost performance due to availability and application-related balance of properties.

Particularly preferred fluoran-type dyes are:

3-diethylamino-6-methyl-7-anilinofluoran,

3- (N-ethyl-N-p-toluylamino) -6-methyl-7-anilinofluoran,

3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluoran,

3-diethylamino-6-methyl-7- (o, p-dimethylanilino) fluoran,

3-pyrrolidinyl-6-methyl-7-anilinofluoran,

3- (cyclohexyl-N-methylamino) -6-methyl-7-anilinofluoran,

3-diethylamino-7- (m-trifluoromethylanilino) fluoran,

3-N-di-N-butylamine-6-methyl-7-anilinofluoran,

3-diethylamino-6-methyl-7- (m-methylanilino) fluoran,

3-N-di-N-butylamine-7- (o-chloroanilino) fluorane,

3- (N-ethyl-N-tetrahydrofurfuryl amine) -6-methyl-7-anilino-fluoran,

3- (N-methyl-N-propylamine) -6-methyl-7-anilinofluoran,

3- (N-ethyl-N-ethoxypropylamine) -6-methyl-7-anilinofluoran,

3- (N-ethyl-N-isobutylamine) -6-methyl-7-anilinofluoran, and/or

3-dipentylamine-6-methyl-7-anilinofluoran.

The color formers can be used both as individual substances and as arbitrary mixtures of two or more color formers, provided that the desired application-technical properties of the recording materials according to the invention are not impaired.

The color former is preferably present in an amount of about 5 to about 30 wt%, and particularly preferably in an amount of about 8 to about 20 wt%, based on the total solid content of the heat-sensitive layer.

In order to control the specific application-technical properties, it may be advantageous for at least two compounds of the formula (I) to be present as developers in the heat-sensitive layer.

Also, in addition to the compound of formula (I), one or more additional (di) phenolic or non-phenolic developers may be present in the thermo-sensitive color-forming layer.

In addition to the at least one colour former and the at least one colour developer, one or more sensitizers (also referred to as thermal solvents) may be present in the heat-sensitive colour-forming layer, which sensitizers have the advantage that control of the thermal printing sensitivity is easier to achieve.

As sensitizers, crystalline substances are advantageously generally considered which have a melting point between about 90 and about 150 ℃ and dissolve the color-forming components (color former and developer) in the molten state without interfering with the formation of the colored complex.

Preferably, the sensitizer is a fatty acid amide such as stearamide, behenamide or palmitamide, an ethylene-bis-fatty acid amide such as N, N '-ethylene-bis-stearamide or N, N' -ethylene-bis-oleamide, a fatty acid alkanolamide such as N- (hydroxymethyl) stearamide, N-hydroxymethyl palmitamide or hydroxyethyl stearamide, a wax such as polyethylene wax or montan wax, a carboxylic acid ester such as dimethyl terephthalate, dibenzyl terephthalate, benzyl-4-benzyloxybenzoate, bis- (4-methylbenzyl) oxalate, bis- (4-chlorobenzyl) oxalate or bis- (4-benzyl) oxalate, an aromatic ether such as 1, 2-diphenoxyethane, 1, 2-bis- (3-methylphenoxy) ethane, a salt thereof, and a pharmaceutically acceptable carrier, 2-benzyloxynaphthalene or 1, 4-diethoxynaphthalene, aromatic sulfones such as diphenylsulfone and/or aromatic sulfonamides such as benzenesulphonanilide or N-benzyl-4-toluenesulphonamide or aromatic hydrocarbons such as 4-benzylbiphenyl.

The sensitizer is preferably present in an amount of about 10 to about 40 wt%, particularly preferably in an amount of about 15 to about 25 wt%, based on the total solids content of the heat-sensitive layer.

In another preferred embodiment, at least one stabilizer (anti-aging agent) is optionally present in the heat-sensitive colour forming layer in addition to the colour former, the phenol-free developer and the sensitizer.

The stabilizers are preferably sterically hindered phenols, particularly preferably 1,1, 3-tris- (2-methyl-4-hydroxy-5-cyclohexyl-phenyl) -butane, 1, 3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) -butane, 1-bis- (2-methyl-4-hydroxy-5-tert-butyl-phenyl) -butane.

As stabilizers in the recording materials according to the invention, it is also possible to use urea-urethane compounds of the general formula (II) (commercially available product UU) or ethers derived from 4,4 '-dihydroxydiphenylsulfone, such as 4-benzyloxy-4' - (2-methylglycidyloxy) -diphenylsulfone (trade name)Nippon Soda Co. Ltd.), or an oligoether of the formula (III) (trade name)

Nippon Soda Co.Ltd.)。

Particularly preferred are urea-urethane compounds of the general formula (II).

The stabilizer is preferably present in an amount of 0.2 to 0.5 parts by weight, based on 1 part by weight of developer of at least one phenol-free compound of the formula (I).

In another preferred embodiment, at least one binder is present in the thermo-sensitive color-forming layer. The binder is preferably water-soluble starch, starch derivatives,

Starch-based biological latexes of the type, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, partially or fully saponified polyvinyl alcohol, chemically modified polyvinyl alcohol or styrene maleic anhydride copolymers, styrene butadiene copolymers, acrylamide- (meth) acrylate copolymers, acrylamide-acrylate-methacrylate terpolymers, polyacrylates, poly (meth) acrylates, acrylate-butadiene copolymers, polyvinyl acetate and/or acrylonitrile-butadiene copolymers.

In a further preferred embodiment, at least one release agent (anti-adhesive agent) or lubricant is present in the heat-sensitive color-forming layer. These agents are preferably fatty acid metal salts, for example zinc stearate or calcium stearate, or also behenate, synthetic waxes, for example in the form of fatty acid amides, for example stearic acid amide and behenic acid amide, fatty acid alkanolamides, for example stearic acid methylolamide, paraffin waxes of different melting points, ester waxes of different molecular weights, propylene waxes of different hardness, ethylene waxes, and/or natural waxes, for example carnauba wax or montan wax.

The release agent is preferably present in an amount of about 1 to about 10 wt.%, particularly preferably in an amount of about 3 to about 6 wt.%, based on the total solids content of the heat-sensitive layer.

In another preferred embodiment, the heat-sensitive colour forming layer contains a pigment. The use of pigments is advantageous, inter alia, in that the pigments can fix, on their surface, chemical melts produced during thermal printing. The surface whiteness and opacity of the heat-sensitive color-forming layer and its printability with conventional printing inks can also be controlled by pigments. Finally, for example, for relatively expensive colored functional chemicals, the pigments have an "extender function".

Particularly suitable pigments are inorganic pigments of synthetic as well as natural origin, preferably clays, precipitated or natural calcium carbonate, aluminum oxide, aluminum hydroxide, silica, precipitated or fumed silica (e.g. silica fume

Type), diatomaceous earth, magnesium carbonate, talc, and organic pigments such as hollow pigments with styrene/acrylate copolymer walls or urea/formaldehyde condensation polymers. They may be used alone or in any mixture.

The pigment is preferably present in an amount of about 20 to about 50% by weight, particularly preferably in an amount of about 30 to about 40% by weight, based on the total solids content of the heat-sensitive layer.

In order to control the surface whiteness of the thermosensitive recording material according to the present invention, a brightener may be incorporated in the thermosensitive color-forming layer. The brightener is preferably stilbene.

In order to improve certain application-technical properties, it is in individual cases preferred to add further ingredients, in particular rheological auxiliaries, such as thickeners and/or surfactants, to the ingredients of the thermosensitive recording materials according to the invention.

The (dried) heat-sensitive layer preferably has an application weight per unit area of from about 1 to about 10g/m²More preferably from about 3 to about 6g/m²。

In a particularly preferred embodiment, the thermosensitive recording material is according to claim 9, wherein a fluoran type dye is used as a color former and a sensitizer selected from fatty acid amides, aromatic sulfones and/or aromatic ethers is additionally present. It is also advantageous in the preferred embodiment that the phenolic-free developer of claim 1 is present in an amount of from about 1.5 to about 4 parts by weight based on 1 part by weight of the color former.

The preferred embodiments described in connection with the compounds of formula (I) are also applicable to the thermosensitive recording material according to the present invention.

The thermosensitive recording material according to the present invention can be obtained by a known production method.

Preferably, however, the recording materials according to the invention are obtained by a process in which an aqueous suspension of the starting materials comprising the heat-sensitive color-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, preferably from about 30 to about 50% by weight, and the application and drying is carried out by the curtain-film coating process at a running speed of the application device of at least about 400 m/min.

The process is particularly advantageous from an economic point of view.

If the value of the solids content is below about 20% by weight, the economy is deteriorated, since a large amount of water must be removed from the spread in a short time by gentle drying, which adversely affects the spreading rate. On the other hand, if the value exceeds 75 wt.%, this ensures stability of the applied ink curtain film during the application process only with a resulting increased technical outlay.

A free-falling curtain film of the coating dispersion is formed in a curtain film coating method (curtain film coating method). The coating dispersion is applied to the substrate by "casting" the coating dispersion in the form of a thin film (curtain film) onto the substrate by free fall. DE10196052T1 discloses the preparation of information recording materials, especially heat-sensitive recording materials, using a curtain film coating process in which a multilayer recording layer (maximum speed 200m/min) is achieved by applying a curtain film consisting of a plurality of coating dispersion films onto a substrate.

Adjusting the application device operating speed to at least about 400m/min has not only economic advantages but also technical advantages. Preferably, the operating speed is at least about 750m/min, particularly preferably at least about 1000m/min, and very particularly preferably at least about 1500 m/min. It is particularly surprising that the thermosensitive recording material obtained is not affected in any way even at the last-mentioned rates and that the process proceeds in an optimum manner even at said high rates.

In a preferred embodiment of the process according to the invention, the degassed aqueous application suspension has a viscosity (Brookfield, 100 revolutions/min, 20 ℃) of from about 150 to about 800 mPas. If the value is below about 150mPas or the value exceeds about 800mPas, insufficient flow of the spread on the application equipment results. Particularly preferably, the viscosity of the degassed aqueous application suspension is from about 200 to about 500 mPas.

In a preferred embodiment, for optimizing the process, the surface tension of the aqueous application suspension can be adjusted to from about 25 to about 60mN/m, preferably to from about 35 to about 50mN/m (measured according to the static Ring method of Du No ü y, DIN 53914).

The formation of the heat-sensitive color-forming layer can be carried out in-line or under-line in a separate application process. The same is true of the later applied layers or intermediate layers which may be present.

Advantageously, the dried heat-sensitive colour-forming layer is subjected to a smoothing measure. It is advantageous here to adjust the smoothness of the Bekk, measured according to ISO 5627:1995-03, to about 100 to about 1000 seconds, preferably to about 250 to about 600 seconds.

The surface roughness (PPS) according to ISO 8791-4:2008-05 is preferably in the range from about 0.50 to about 2.50. mu.m, particularly preferably in the range from 1.00 to 2.00. mu.m.

The preferred embodiments carried out with respect to the compounds of formula (I) are equally applicable to the process according to the invention for preparing the thermosensitive recording material according to the invention.

The invention also relates to a thermosensitive recording material obtainable by the above process.

The above-described method is advantageous from an economic point of view and allows a high-speed process progress of the application device even at a rate of more than 1500m/min without affecting the process product, i.e. the heat-sensitive recording material according to the invention. The process can be performed either inline or offline, which results in the desired flexibility.

The thermosensitive recording material according to the present invention preferably contains no phenol and is well suited for POS (point of sale), labeling and/or ticketing applications. It is also suitable for the preparation of parking tickets, entrance tickets, lottery tickets and betting slips and the like, which can be printed directly using thermal processes and which require a high resistance to the images recorded thereon when the print is brought into contact with hydrophobic substances, such as plasticizers, binders, fatty or oily substances, etc.

It has been surprisingly shown that with the developer of formula (I) according to the invention it is possible to provide a thermosensitive recording material which is excellent in terms of excellent resistance of the print to hydrophobic agents and with which good print quality (high optical density of the printed image (o.D)) is achieved.

As the contrast color developer, a conventional non-phenolic color developer, i.e., sulfonylurea (Pergafast), was used

(PF201), BASF) and the urea derivative Z (N- (2- (3-phenylureido) phenyl) benzenesulfonamide).

The invention is explained in detail below with the aid of non-limiting examples.

Example (b):

preparation of the compounds of formula (I) according to the invention.

Compounds I-XXIV (Table 2) were prepared as follows:

step A1 preparation of sulfonamides

To a solution of 20mmol of aromatic diamine and 20mmol of pyridine in 125mL of dichloromethane is added dropwise a solution of 10mmol of the corresponding sulfonyl chloride in 75mL of dichloromethane at 0 ℃ with stirring. The reaction solution was stirred at room temperature for 16 hours, followed by the addition of 100mL of water. The organic phase was separated and incorporated into 250mL of 5% aqueous sodium hydroxide solution. The aqueous phase was washed with 100mL dichloromethane and adjusted to neutrality by addition of 25% hydrochloric acid. After multiple extractions with 100mL dichloromethane, the combined organic phases were washed with 200mL water and dried over magnesium sulfate. After removal of the solvent in vacuo, the sulfonamide remained in solid form. The sulfonamide was used in step B or C without further purification.

Simple filtration after the addition of water to the reaction solution is sufficient to obtain the precursor compounds of products IX and XII.

Step A2 preparation of sulfonamides

To a solution of 80mL of aromatic amine and 240mmol of potassium carbonate in 500mL of dichloroethane is added dropwise, with stirring at room temperature, a solution of 80mmol of the corresponding sulfonyl chloride in 150mL of dichloroethane. The reaction mixture was refluxed for 6 hours, then 300mL of ethyl acetate and 300mL of water were incorporated. The aqueous phase was made acidic by the addition of 25% hydrochloric acid. The phases were separated. After multiple extractions of the aqueous phase with 200mL ethyl acetate, the combined organic phases were washed with 200mL water and dried over magnesium sulfate. After removal of the solvent in vacuo, the sulfonamide remained in solid form. The sulfonamide was used in step B without further purification.

Step A3 preparation of sulfonamides

To a solution of 27.5mmol of sodium hydride (60% in oil) in 25mL of absolute THF at 0 ℃ under stirring and a protective gas atmosphere is added dropwise a solution of 25.0mmol of aromatic amine in 35mL of absolute THF. After stirring in two stages at room temperature for 2 hours, a solution of 25.0mmol of the corresponding sulfonyl chloride in 10mL of absolute THF is added dropwise at 0 ℃ with stirring. The reaction solution was stirred at room temperature for 40 hours, followed by the incorporation of 100mL of water and 100mL of dichloromethane. The aqueous phase was made alkaline by the addition of 5% aqueous sodium hydroxide. The phases were separated. The aqueous phase is washed with 100mL of dichloromethane and adjusted to neutrality by addition of 25% hydrochloric acid. After multiple extractions with 100mL dichloromethane, the combined organic phases were washed with 200mL water and dried over magnesium sulfate. After removal of the solvent in vacuo, the sulfonamide remained in solid form. The sulfonamides are used without further purification

And (B) performing the step (B).

Step B-reduction of the Nitro to Primary amine

To a solution of 8.0mmol of the product from step A1/A2/A3 in 140mL ethyl acetate at room temperature with stirring28.0mmol (product from step A1) or 56.0mmol (product from step A2/A3) SnCl was added₂·2H₂And O. The reaction solution was refluxed. The progress of the reaction is monitored by means of thin-layer chromatography (eluent: cyclohexane/ethyl acetate 1: 1). After the reaction was complete (about 2-3h), it was diluted with 70mL ethyl acetate, spiked with 10% aqueous potassium carbonate and stirred at room temperature for 30 min. The Sn compound is filtered off and the aqueous phase is separated from the organic phase in the filtrate. The organic phase was washed with 100ml (2 ×) of saturated aqueous sodium chloride solution and dried over magnesium sulfate. After removal of the solvent under vacuum, purification was carried out by recrystallization from dichloromethane and a few drops of n-hexane.

Step C1-preparation of sulfonylurea Compounds

To a solution of 7.0mmol of the product from step A1 in dichloromethane (20 to 40mL), in addition in 10mL of acetonitrile in the case of poor solubility, a solution of 7.0mmol of the corresponding sulfonyl isocyanate in 10mL of dichloromethane is added dropwise with stirring at room temperature. The reaction was monitored by means of thin layer chromatography (eluent: cyclohexane/ethyl acetate 1: 1). After the reaction was complete, the precipitated product was filtered off, washed with dichloromethane and dried in vacuo. In some cases, the reaction solution was concentrated in vacuo and crystallization was initiated by addition of a few drops of n-hexane.

Step C2-preparation of sulfonylurea Compounds

To a solution of 4.2mmol of the product from step B in DMF (16mL) was added dropwise, with stirring, a solution of 8.4mmol of the corresponding sulfonyl isocyanate in DMF (5 to 10 mL). The reaction was monitored by means of thin layer chromatography (eluent: cyclohexane/ethyl acetate 1: 1). After the reaction was complete, the reaction solution was diluted with 100mL of ethyl acetate, washed with 100mL (2X) of saturated aqueous sodium chloride solution, followed by 100mL of water. After removal of the solvent in vacuo, purification was performed by recrystallization from dichloromethane and a few drops of n-hexane.

Compounds I to XIX (table 2) were prepared following the general procedure of steps a1 and C1 starting from the corresponding phenylenediamine.

Compound XX (table 2) starts from 2, 6-dinitroaniline, which is first converted into 1, 2-diamino-3-nitrobenzene (reaction scheme 3, v.milata, j.salo ň, org.prep.proceed.int.,31(3),347(1999)), and finally into the final product following the general procedure of steps a1, B and C2.

Compounds XXI to XXIV (Table 2) are prepared from 2, 4-dinitroaniline (XXI and XXII), 4-nitro-1, 2-phenylenediamine (XXIII) and 2, 6-dinitroaniline (XXIV) according to the general procedure of Steps A1(XXIII), A2(XXI and XXII), A3(XXIV), B (XXI-XXIV) and C2 (XXI-XXIV).

The starting compounds are commercially available.

Table 2: a summary of selected compounds of formula (I)

	Y	Ar1	Ar2	m	n
						I	1, 2-phenylene radicals	C6H5	C6H5	1	1
II	1, 2-phenylene radicals	C6H5	4-CH3-C6H4	1	1
						III	1, 2-phenylene radicals	4-CH3-C6H4	C6H5	1	1
IV	1, 2-phenylene radicals	4-CH3-C6H4	4-CH3-C6H4	1	1
						V	1, 2-phenylene radicals	4-(tert-C4H9)-C6H4	4-CH3-C6H4	1	1
VI	1, 2-phenylene radicals	2,4,6-TriCH3-C6H4	4-CH3-C6H4	1	1
						VII	1, 2-phenylene radicals	4-OCH3-C6H4	4-CH3-C6H4	1	1
VIII	1, 2-phenylene radicals	4-Cl-C6H4	4-CH3-C6H4	1	1
						IX	1, 2-phenylene radicals	4-(NH-CO-CH3)-C6H4	4-CH3-C6H4	1	1
X	1, 2-phenylene radicals	4-NO2-C6H4	4-CH3-C6H4	1	1
						XI	1, 2-phenylene radicals	2-(CO2CH3)-C6H4	4-CH3-C6H4	1	1
XII	1, 2-phenylene radicals	2-naphthalene	4-CH3-C6H4	1	1
						XIII	1, 2-phenylene radicals	C6H5-CH2	4-CH3-C6H4	1	1
XIV	1, 3-phenylene	C6H5	4-CH3-C6H4	1	1
						XV	1, 3-phenylene	4-CH3-C6H4	C6H5	1	1
XVI	1, 3-phenylene	4-CH3-C6H4	4-CH3-C6H4	1	1
						XVII	1, 4-phenylene	C6H5	4-CH3-C6H4	1	1
XVIII	1, 4-phenylene	4-CH3-C6H4	C6H5	1	1
						XIX	1, 4-phenylene	4-CH3-C6H4	4-CH3-C6H4	1	1
XX	Benzene-1, 2, 3-triyl	4-CH3-C6H4	4-CH3-C6H4	1	2
						XXI	Benzene-1, 2, 4-triyl	4-CH3-C6H4	C6H5	1	2
XXII	Benzene-1, 2, 4-triyl	4-CH3-C6H4	4-CH3-C6H4	1	2
						XXIII	Benzene-1, 2, 5-triyl	4-CH3-C6H4	4-CH3-C6H4	1	2
XXIV	Benzene-1, 2, 6-triyl	4-CH3-C6H4	4-CH3-C6H4	1	2

*: comparative examples

Analyzing data:

I,C₁₉H₁₇N₃O₅S₂m ═ 431.5, N- ((2- (phenylsulfonylamino) phenyl) carbamoyl) benzenesulfonamide ms (esi): m/z (%) < 430.0(14) [ M-H ]]^-,273.0(100)[M-H-Ar²SO₂NH₂]^-,247.0(15)[M-H-Ar²SO₂NCO]^-。

*H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝11.66(1H,s),9.60(1H,s),8.57(1H,s),8.01-7.99(2H,m),7.86(1H,dd,J＝8.3,1.3Hz),7.73-7.69(1H,m),7.68-7.62(5H,m),7.56-7.53(2H,m),7.16-7.12(1H,m),6.80(1H,ddd,J＝8.9,7.9,1.4Hz),6.39(1H,dd,J＝7.9,1.1Hz)。

¹³C-NMR(126MHz,DMSO-d₆)：δ(ppm)＝149.12(NHCONH),139.78,138.87,135.56,133.39,133.01,129.10,129.03,127.82,127.27,127.23,127.08,125.28,123.15,120.75。

II,C₂₀H₁₉N₃O₅S₂M ═ 445.5, N- ((2- (phenylsulfonylamino) phenyl) carbamoyl) toluenesulfonamide

MS(ESI)：m/z(％)＝444.0(23)[M-H]^-,273.0(100)[M-H-Ar²SO₂NH₂]^-,247.1(21)[M-H-Ar²SO₂NCO]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝11.58(1H,s),9.60(1H,s),8.56(1H,s),7.89-7.86(3H,m),7.68-7.66(2H,m),7.65-7.62(1H,m),7.56-7.53(2H,m),7.44-7.43(2H,m),7.16-7.12(1H,m),6.79(1H,ddd,J＝8.9,7.7,1.4Hz),6.38(1H,dd,J＝7.9,1.3Hz),2.39(3H,s)。

¹³C-NMR(126MHz,DMSO-d6)：δ(ppm)＝149.16(NHCONH),143.93,138.90,136.95,135.67,133.02,129.52,129.05,127.84,127.37,127.25,127.10,125.22,123.08,120.68,21.00(CH₃)。

III,C₂₀H₁₉N₃O₅S₂M ═ 445.5, N- (2- (3- (phenylsulfonyl) ureido) phenyl) toluenesulfonamide

MS(ESI)：m/z(％)＝444.0(17)[M-H]^-,287.0(100)[M-H-Ar²SO₂NH₂]^-,261.1(7)[M-H-Ar²SO₂NCO]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝11.66(1H,s),9.51(1H,s),8.56(1H,s),8.01-7.99(2H,m),7.85(1H,dd,J＝8.3,1.4Hz),7.73-7.69(1H,m),7.66-7.63(2H,m),7.56-7.54(2H,m),7.35-7.33(2H,m),7.15-7.11(1H,m),6.81(1H,ddd,9.1,7.7,1.4Hz),6.43-6.42(1H,m),2.36(3H,s)。

¹³C-NMR(126MHz,DMSO-d₆)：δ(ppm)＝149.13(NHCONH),143.34,139.80,136.07,135.48,133.38,129.47,129.09,127.70,127.26,127.18,127.13,125.43,123.16,120.73,20.96(CH₃)。

IV,C₂₁H₂₁N₃O₅S₂M ═ 459.5, N- ((2- (toluenesulfonylamino) phenyl) carbamoyl) toluenesulfonamide

MS(ESI)：m/z(％)＝458.1(26)[M-H]^-,287.0(100)[M-H-Ar²SO₂NH₂]^-,261.0(10)[M-H-Ar²SO₂NCO]^-。

¹H-NMR(500MHz,DMS0-d₆)：δ(ppm)＝11.58(1H,s),9.50(1H,s),8.55(1H,s),7.89-7.85(3H,m),7.56-7.54(2H,m),7.44-7.42(2H,m),7.35-7.33(2H,m),7.15-7.11(1H,m),6.80(1H,ddd,J＝9.0,7.7,1.4Hz),6.43-6.41(1H,m),2.39(3H,s),2.36(3H,s)。

¹³C-NMR(126MHz,DMSO-d₆)：δ(ppm)＝149.15(NHCONH),143.88,143.33,136.98,136.11,135.59,129.49,129.45,127.70,127.36,127.19,127.15,125.37,123.07,120.65,20.98(CH₃),20.94(CH₃)。

V,C₂₄H₂₇N₃O₅S₂M ═ 501.6, N- (2- (3-toluenesulfonureido) phenyl) -4-tert-butylbenzenesulfonamide

MS(ESI)：m/z(％)＝500.1(56)[M-H]^-,329.1(100)[M-H-Ar²SO₂NH₂]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝11.57(1H,s),9.53(1H,s),8.55(1H,s),7.89-7.87(2H,m),7.86-7.85(1H,m),7.62-7.60(2H,m),7.58-7.56(2H,m),7.44-7.42(2H,m),7.14-7.11(1H,m),6.80-6.77(1H,m),6.42-6.40(1H,m),2.39(3H,s),1.28(9H,s)。

¹³C-NMR(126MHz,DMSO-d₆)：δ(ppm)＝156.10,149.16(NHCONH),143.89,136.96,136.15,135.48,129.51,127.66,127.35,127.03,127.03,125.84,125.44,123.05,120.68,34.83(C(CH₃)₃),30.71(C(CH₃)₃),21.00(CH₃)。

VI,C₂₃H₂₅N₃O₅S₂M ═ 487.6, N- (2- (3-toluenesulfonureido) phenyl) -2,4, 6-trimethylbenzenesulfonamide

MS(ESI)：m/z(％)＝486.1(37)[M-H]^-,315.1(100)[M-H-Ar²SO₂NH₂]^-,289.1(18)[M-H-Ar²SO₂NCO]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝11.66(1H,s),9.26(1H,s),8.62(1H,s),7.89-7.87(3H,m),7.44-7.42(2H,m),7.18-7.14(1H,m),6.98(2H,s),6.77(1H,ddd,J＝9.0,7.7,1.4Hz),6.26(1H,dd,J＝7.9,1.3Hz),2.39(3H,s),2.29(6H,s),2.24(3H,s)。

¹³C-NMR(126MHz,DMSO-d₆)：δ(ppm)＝149.26(NHCONH),143.87,142.02,138.89,136.96,136.06,133.30,131.54,129.48,127.99,127.83,127.35,124.76,123.09,120.55,22.42(2xCH₃),20.98(CH₃),20.36(CH₃)。

VII,C₂₁H₂₁N₃O₆S₂M ═ 475.5, N- (2- (3-toluenesulfonureido) phenyl) -4-methoxybenzenesulphonamide

MS(ESI)：m/z(％)＝474.1(28)[M-H]^-,303.0(100)[M-H-Ar²SO₂NH₂]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝11.59(1H,s),9.42(1H,s),8.56(1H,s),7.89-7.85(3H,m),7.60-7.58(2H,m),7.44-7.42(2H,m),7.15-7.12(1H,m),7.07-7.05(2H,m),6.82(1H,ddd,J＝8.7,7.7,1.0Hz),6.43(1H,dd,J＝7.9,1.1Hz),3.82(3H,s),2.39(3H,s)。

¹³C-NMR(126MHz,DMSO-d₆)：δ(ppm)＝162.53,149.16(NHCONH),143.90,136.96,135.64,130.47,129.50,129.34,127.70,127.34,127.30,125.46,123.07,120.58,114.17,55.60(OCH₃),20.99(CH₃)。

VIII,C₂₀H₁₈ClN₃O₅S₂M.480.0, N- (2- (3-toluenesulfonylureido) phenyl) -4-chlorobenzenesulfonamide

MS(ESI)：m/z(％)＝478.0(29)[M-H]^-,307.0(100)[M-H-Ar²SO₂NH₂]^-,281.0(49)[M-H-Ar²SO₂NCO]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝11.56(1H,s),9.70(1H,s),8.55(1H,s),7.88-7.86(3H,m),7.67-7.65(2H,m),7.63-7.61(2H,m),7.44-7.43(2H,m),7.18-7.14(1H,m),6.84(1H,ddd,J＝9.2,7.9,1.4Hz),6.44(1H,dd,J＝7.9,1.5Hz),2.39(3H,s)。

¹³C-NMR(126MHz,DMSO-₆)：δ(ppm)＝149.13(NHCONH),143.93,137.95,137.77,136.91,135.65,129.52,129.24,129.04,128.00,127.35,127.28,124.97,123.26,120.79,21.00(CH₃)。

IX,C₂₂H₂₂N₄O₆S₂M ═ 502.6, N- (4- (N- (2- (3-toluenesulfonylureido) phenyl) aminosulfonyl) phenyl) acetamide

MS(ESI)：m/z(％)＝501.0(32)[M-H]^-,330.1(100)[M-H-Ar²SO₂NH₂]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝11.60(1H,s),10.30(1H,s),9.45(1H,s),8.56(1H,s),7.89-7.86(3H,m),7.75-7.73(2H,m),7.60-7.57(2H,m),7.44-7.42(2H,m),7.15-7.12(1H,m),6.81(1H,ddd,J＝9.0,7.6,1.4Hz),6.40(1H,dd,J＝7.9,1.4Hz),2.39(3H,s),2.09(3H,s)。

¹³C-NMR(126MHz,DMSO-d₆)：δ(ppm)＝169.01(NHCOCH₃),149.19(NHCONH),143.91,143.26,136.96,135.69,132.36,129.51,128.38,127.73,127.35,127.28,125.41,123.08,120.59,118.34,24.11(CH₃),21.00(CH₃)。

X,C₂₀H₁₈N₄O₇S₂M ═ 490.5, N- ((2- (4-nitrophenylsulfonamido) phenyl) carbamoyl) toluenesulfonamide

MS(ESI)：m/z(％)＝489.0(31)[M-H]^-,318.0(55)[M-H-Ar²SO₂NH₂]^-,292.0(100)[M-H-Ar²SO₂NCO]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝11.51(1H,s),9.97(1H,s),8.52(1H,s),8.40-8.37(2H,m),7.92-7.89(2H,m),7.87-7.84(3H,m),7.44-7.42(2H,m),7.20-7.16(1H,m),6.85(1H,ddd,J＝8.9,7.7,1.4Hz),6.48(1H,dd,J＝7.9,1.3Hz),2.39(3H,s)。

¹³C-NMR(126MHz,DMSO-d₆)：δ(ppm)＝149.88,149.13(NHCONH),144.49,143.96,136.89,135.60,129.52,128.67,128.24,127.50,127.33,124.71,124.47,123.50,121.08,21.00(CH₃)。

XI,C₂₂H₂₁N₃O₇S₂M503.5, 2- (N- (2- (3-toluenesulfonylureido) phenyl) aminosulfonyl) benzoic acid methyl ester

MS(ESI)：m/z(％)＝5O2.1(32)[M-H]^-,331.0(100)[M-H-Ar²SO₂NH₂]^-,305.0(31)[M-H-Ar²SO₂NCO]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝11.53(1H,s),9.21(1H,s),8.53(1H,s),7.88-7.86(2H,m),7.82-7.81(1H,m),7.73-7.72(2H,m),7.67-7.65(2H,m),7.44-7.42(2H,m),7.18-7.15(1H,m),6.85-6.82(1H,m),6.55-6.54(1H,m),3.72(3H,s),2.39(3H,s)。

¹³C-NMR(126MHz,DMSO-₆)：δ(ppm)＝167.35(COOCH₃),149.29(NHCONH),143.90,136.93,136.57,135.40,133.17,132.03,130.94,129.49,129.13,129.11,127.91,127.42,127.34,125.39,123.43,121.21,52.87(COOCH₃),20.98(CH₃)。

XII,C₂₄H₂₁N₃O₅S₂M ═ 495.6, N- (2- (3-toluenesulfonureido) phenyl) naphthalene-2-sulfonamide

MS(ESI)：m/z(％)＝494.1(24)[M-H]^-,323.0(100)[M-H-Ar²SO₂NH₂]^-,297.0(26)[M-H-Ar²SO₂NCO]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝11.64(1H,s),9.73(1H,s),8.64(1H,s),8.27(1H,d,J＝1.4Hz),8.13-8.12(1H,m),8.08-8.06(1H,m),8.04-8.02(1H,m),7.90-7.89(2H,m),7.89(1H,dd,J＝8.3,1.3Hz),7.80(1H,dd,J＝8.7,1.9Hz),7.71-7.68(1H,m),7.65-7.61(1H,m),7.45-7.43(2H,m),7.12-7.09(1H,m),6.71-6.68(1H,m),6.37-6.36(1H,m),2.39(3H,s)。

¹³C-NMR(126MHz,DMSO-₆)：δ(ppm)＝149.19(NHCONH),143.92,136.96,135.95,135.74,134.29,131.43,129.52,129.26,129.19,128.94,128.34,127.84,127.81,127.61,127.37,127.22,125.21,123.09,122.45,120.67,20.99(CH₃)。

XIII,C₂₁H₂₁N₃O₅S₂M ═ 459.5, N- ((2- (benzylsulfonamido) phenyl) carbamoyl) toluenesulfonamide

MS(ESI)：m/z(％)＝458.0(16)[M-H]^-,287.0(100)[M-H-Ar²SO₂NH₂]^-,261.1(13)[M-H-Ar²SO₂NCO]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝11.47(1H,s),9.25(1H,s),8.40(1H,s),7.86-7.84(2H,m),7.81(1H,dd,J＝8.4,1.4Hz),7.39-7.34(8H,m),7.25-7.21(1H,m),7.10(1H,ddd,J＝9.0,7.6,1.5Hz),4.40(2H,s),2.36(3H,s)。

¹³C-NMR(126MHz,DMSO-₆)：δ(ppm)＝149.33(NHCONH),143.87,136.93,134.39,130.83,129.46,129.06,128.33,128.16,127.52,127.33,127.33,126.50,123.97,121.66,57.25(CH₂),20.98(CH₃)。

XIV,C₂₀H₁₉N₃O₅S₂M ═ 445.5, N- ((3- (phenylsulfonylamino) phenyl) carbamoyl) toluenesulfonamide

MS(ESI)：m/z(％)＝444.0(100)[M-H]^-,272.9(7)[M-H-Ar²SO₂NH₂]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝10.55(1H,s),10.24(1H,s),8.83(1H,s),7.86-7.84(2H,m),7.76-7.74(2H,m),7.59-7.56(1H,m),7.52-7.49(2H,m),7.43-7.41(2H,m),7.24-7.23(1H,m),7.10-7.07(1H,m),6.97(1H,ddd,J＝8.2,2.0,0.8Hz),6.76(1H,ddd,J＝8.1,2.1,0.9Hz),2.39(3H,s)。

¹³C-NMR(126MHz,DMSO-d₆)：δ(ppm)＝149.05(NHCONH),143.80,139.46,138.70,138.19,137.01,132.79,129.39,129.39,129.11,127.45,126.58,114.42,114.34,110.23,20.98(CH₃)。

XV,C₂₀H₁₉N₃O₅S₂M ═ 445.5, N- (3- (3- (phenylsulfonyl) ureido) phenyl) toluenesulfonamide

MS(ESI)：m/z(％)＝444.0(100)[M-H]^-,287.0(6)[M-H-Ar²SO₂NH₂]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝10.44(1H,s),10.17(1H,s),8.87(1H,s),7.99-7.97(2H,m),7.71-7.68(1H,m),7.64-7.61(4H,m),7.30-7.28(2H,m),7.24-7.23(1H,m),7.10-7.07(1H,m),6.97(1H,ddd,J＝8.2,2.1,0.9Hz),6.76(1H,ddd,J＝8.1,2.1,0.9Hz),2.30(3H,s)。

¹³C-NMR(126MHz,DMSO-d₆)：δ(ppm)＝149.03(NHCONH),143.16,139.90,138.64,138.34,136.61,133.28,129.54,129.36,128.97,127.37,126.66,114.27,114.22,110.04,20.87(CH₃)。

XVI,C₂₁H₂₁N₃O₅S₂M ═ 459.5, N- ((3- (toluenesulfonylamino) phenyl) carbamoyl) toluenesulfonamide

MS(ESI)：m/z(％)＝458.1(100)[M-H]^-,287.0(4)[M-H-Ar²SO₂NH₂]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝10.53(1H,s),10.17(1H,s),8.82(1H,s),7.86-7.85(2H,m),7.65-7.63(2H,m),7.42-7.41(2H,m),7.30-7.28(2H,m),7.24-7.24(1H,m),7.10-7.06(1H,m),6.97-6.95(1H,m),6.77-6.75(1H,m),2.38(3H,s),2.30(3H,s)。

¹³C-NMR(126MHz,DMSO-d₆)：δ(ppm)＝149.05(NHCONH),143.80,143.15,138.68,138.35,137.03,136.62,129.54,129.39,129.36,127.46,126.67,114.22,114.17,109.98,20.99(CH₃),20.87(CH₃)。

XVII,C₂₀H₁₉N₃O₅S₂M ═ 445.5, N- ((4- (phenylsulfonylamino) phenyl) carbamoyl) toluenesulfonamide

MS(ESI)：m/z(％)＝444.0(100)[M-H]^-,273.0(5)[M-H-Ar²SO₂NH₂]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝10.47(1H,s),10.05(1H,s),8.70(1H,s),7.84-7.82(2H,m),7.70-7.68(2H,m),7.58-7.55(1H,m),7.52-7.49(2H,m),7.40-7.39(2H,m),7.20-7.18(2H,m),6.99-6.97(2H,m),2.37(3H,s)。

¹³C-NMR(126MHz,DMSO-d₆)：δ(ppm)＝149.19(NHCONH),143.77,139.39,137.06,134.61,132.72,132.72,129.41,129.09,127.41,126.59,121.63,119.83,20.99(CH₃)。

XVIII,C₂₀H₁₉N₃O₅S₂M ═ 445.5, N- (4- (3- (phenylsulfonyl) ureido) phenyl) toluenesulfonamide

MS(ESI)：m/z(％)＝444.0(100)[M-H]^-,287.0(5)[M-H-Ar²SO₂NH₂]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝10.70(1H,s),9.98(1H,s),8.73(1H,s),7.96-7.95(2H,m),7.69-7.66(1H,m),7.62-7.57(4H,m),7.30-7.29(2H,m),7.20-7.18(2H,m),7.00-6.97(2H,m),2.30(3H,s)。

¹³C-NMR(126MHz,DMSO-d₆)：δ(ppm)＝149.16(NHCONH),143.04,139.94,136.56,134.40,133.25,132.96,129.51,128.98,127.31,126.64,121.41,119.91,20.87(CH₃)。

XIX,C₂₁H₂₁N₃O₅S₂M ═ 459.5, N- ((4- (toluenesulfonylamino) phenyl) carbamoyl) toluenesulfonamide

MS(ESI)：m/z(％)＝458.1(100)[M-H]^-,287.1(4)[M-H-Ar²SO₂NH₂]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝10.55(1H,s),9.97(1H,s),8.68(1H,s),7.84-7.82(2H,m),7.59-7.57(2H,m),7.40-7.39(2H,m),7.30-7.28(2H,m),7.20-7.17(2H,m),7.00-6.97(2H,m),2.37(3H,s),2.30(3H,s)。

¹³C-NMR(126MHz,DMSO-d₆)：δ(ppm)＝149.17(NHCONH),143.75,143.03,137.07,136.56,134.44,132.91,129.51,129.39,127.39,126.63,121.42,119.84,20.97(CH₃),20.86(CH₃)。

XX,C₂₉H₂₉N₅O₈S₃M ═ 671.8, N' - (((3-toluenesulfonylamino-l, 2-phenylene) bis (imino)) bis (carbonyl)) bis (toluenesulfonamide)

MS(ESI)：m/z(％)＝670.0(21)[M-H]^-,499.0(100)[M-H-Ar²SO₂NH₂]^-,302.0(70)[M-H-Ar²SO₂NCO-Ar²SO₂NH₂]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝11.38(1H,s),11.18(1H,s),9.47(1H,s),8.16(1H,s),7.91(1H,s),7.91-7.89(2H,m),7.80-7.78(2H,m),7.54-7.53(1H,m),7.49-7.47(2H,m),7.42-7.40(4H,m),7.29-7.28(2H,m),7.00-6.97(1H,m),6.42-6.40(1H,m),2.39(3H,s),2.38(3H,s),2.34(3H,s)。

¹³C-NMR(126MHz,DMSO-d₆)：δ(ppm)＝150.34(NHCONH),149.01(NHCONH),143.91,143.64,143.34,137.20,136.81,136.01,135.71,133.30,129.52,129.50,129.45,127.22,127.20,126.89,125.57,122.98,119.81,119.08,21.01(CH₃),21.01(CH₃),20.95(CH₃)。

XXI,C₂₇H₂₅N₅O₈S₃M ═ 643.7, N' - (((4-toluenesulfonylamino-l, 3-phenylene) bis (imino)) bis (carbonyl)) bis (benzenesulfonamide)

MS(ESI)：m/z(％)＝644.0(79)[M+H]⁺。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝11.69(1H,s),10.62(1H,s),9.36(1H,s),8.94(1H,s),8.53(1H,s),8.00-7.98(2H,m),7.95-7.93(2H,m),7.91(1H,d,J＝2.5Hz),7.74-7.59(6H,m),7.52-7.50(2H,m),7.33-7.32(2H,m),6.86(1H,dd,J＝8.7,2.5Hz),6.23(1H,d,J＝8.7Hz),2.35(3H,s)。

¹³C-NM R(126MHz,DMSO-d₆)：δ(ppm)＝149.05(NHCONH),148.98(NHCONH),143.35,139.85,139.72,137.58,136.32,135.91,133.45,133.30,129.47,129.13,129.01,127.95,127.35,127.21,125.84,119.89,113.18,110.52,20.98(CH₃)。

XXII,C₂₉H₂₉N₅O₈S₃M ═ 671.8, N' - (((4-toluenesulfonylamino-l, 3-phenylene) bis (imino)) bis (carbonyl)) bis (toluenesulfonamide)

MS(ESI)：m/z(％)＝670.0(15)[M-H]^-,499.0(100)[M-H-Ar²SO₂NH₂]^-,473.0(2)[M-H-Ar²SO₂NCO]^-,328.0(5)[M-H-2xAr²SO₂NH₂]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝11.60(1H,s),10.69(1H,s),9.34(1H,s),9.18(1H,s),8.55(1H,s),7.91(1H,d,J＝2.4Hz),7.87-7.85(2H,m),7.82-7.80(2H,m),7.51-7.50(2H,m),7.45-7.43(2H,m),7.40-7.39(2H,m),7.32-7.31(2H,m),6.82(1H,dd,J＝8.7,2.4Hz),6.24(1H,d,J＝8.7Hz),2.40(3H,s),2.38(3H,s),2.35(3H,s)。

¹³C-NM R(126MHz,DMSO-d₆)：δ(ppm)＝149.09(NHCONH),148.93(NHCONH),143.95,143.76,143.31,137.61,136.99,136.87,136.29,135.91,129.54,129.42,129.42,127.92,127.40,127.38,127.21,119.77,112.96,110.27,21.01(CH₃),21.00(CH₃),20.99(CH₃)。

XXIII,C₂₉H₂₉N₅O₈S₃M ═ 671.8, N' - (((2-toluenesulfonylamino-l, 4-phenylene) bis (imino)) bis (carbonyl)) bis (toluenesulfonamide)

MS(ESI)：m/z(％)＝670.0(60)[M-H]^-,499.0(100)[M-H-Ar²SO₂NH₂]^-.

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝11.38(1H,s),10.47(1H,s),9.47(1H,s),8.68(1H,s),8.33(1H,s),7.86-7.84(2H,m),7.82-7.81(2H,m),7.62(1H,d,J＝9.0Hz),7.54-7.52(2H,m),7.43-7.41(4H,m),7.28-7.26(2H,m),7.05(1H,dd,J＝9.0,2.5Hz),6.76(1H,d,J＝2.5Hz),2.39(3H,s),2.38(3H,s),2.32(3H,s)。

¹³C NM R(126MHz,DMSO-d₆)：δ(ppm)＝149.20(NHCONH),148.86(NHCONH),143.87,143.78,143.32,137.05,137.02,135.99,133.65,129.88,129.51,129.45,129.37,127.43,127.35,127.02,126.39,121.75,117.81,117.28,21.01(CH₃),21.01(CH₃),20.97(CH₃)。

XXIV,C₂₉H₂₉N₅O₈S₃M ═ 671.8, N' - (((2-toluenesulfonylamino-l, 3-phenylene) bis (imino)) bis (carbonyl)) bis (toluenesulfonamide)

MS(ESI)：m/z(％)＝670.1(100)[M-H]^-,499.0(33)[M-H-Ar²SO₂NH₂]^-,473.0(29)[M-H-Ar²SO₂NCO]^-,328.1(23)[M-H-2xAr²SO₂NH₂]^-,302.0(21)[M-H-Ar²SO₂NCO-Ar²SO₂NH₂]^-。

¹H-NMR(500MHz,DMSO-d₆)：δ(ppm)＝11.22(2H,s),8.91(1H,s),8.13(2H,s),7.84-7.82(4H,m),7.43-7.42(4H,m),7.40-7.38(2H,m),7.37-7.35(2H,m),7.19-7.17(2H,m),7.13-7.09(1H,m),2.39(6H,s),2.27(3H,s)。

¹³C NMR(126MHz,DMSO-d₆)：δ(ppm)＝148.89(NHCONH),143.85,143.78,136.95,136.62,135.51,129.44,129.22,128.40,127.28,126.87,116.40,115.44,20.97(CH₃),20.95(CH₃),20.95(CH₃)。

Application of an aqueous application suspension for the formation of a heat-sensitive color-forming layer of a heat-sensitive recording paper on a laboratory scale with the aid of a doctor blade at 63g/m²Synthetic base paper of (A), (B)

FP680) on one side. After drying a thermal recording web is obtained. The application amount of the thermosensitive color forming layer is between 3.8 and 4.2g/m²In the meantime.

The following formulation of the aqueous application suspension is used to form a composite structure on a carrier substrate, and then additional layers, in particular protective layers, are formed in a conventional manner, which are not separately described in detail here.

Preparation of the Dispersion for application of the suspension (1 part by weight each)

Aqueous dispersion A (coupler dispersion) was prepared by grinding 20 parts by weight of 3-N-di-N-butylamino-6-methyl-7-anilinofluoran (ODB-2) with 33 parts by weight of 15% Ghossenex in a bead mill^TML-3266 (sulfonated polyvinyl alcohol, Nippon Ghosei) in water.

Aqueous dispersion B (developer dispersion) was prepared by grinding 40 parts by weight of developer together with 66 parts by weight of 15% Ghosenex in a bead mill^TML-3266 in aqueous solution.

Aqueous dispersion C (sensitizer dispersion) was prepared by milling 40 parts by weight of sensitizer with 33 parts by weight of 15% Ghosenex in a bead mill^TML-3266 in aqueous solution.

All dispersions produced by milling have an average particle size D of from 0.80 to 1.20 μm_(4,3). The measurement of the particle size distribution of the dispersion was carried out by laser diffraction using a Coulter LS230 instrument from the Beckman Coulter company.

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^TML-3266 and 40 parts by weight of water.

Pigment P is a 72% coating kaolin suspension (

S，BASF)。

The binder consisted of a 10% aqueous solution of polyvinyl alcohol (Mowiol 28-99, Kuraray Europe).

The heat-sensitive application suspension was prepared as follows: mixing was carried out with stirring 1 part a, 1 part B, 1 part C, 56 parts D, 146 parts pigment P and 138 parts binder solution (all parts by weight) while considering the introduction sequence B, D, C, P, A, the binder, and bringing it to a solids content of about 25% with water.

The heat-sensitive coating suspension thus obtained is used for the production of a composite structure of a paper support and a heat-reactive layer.

The thermal recording materials were evaluated as described below (tables 3, 4 and 5).

(1) Dynamic color density:

an Atlantek 200 experimental printer (Atlantek corporation, usa) with a Kyocera printhead at 200dpi and 560Ohm was used on paper (6cm wide swath) to thermally print the checkerboard pattern at 10 energy levels with an applied voltage of 20.6V and a maximum pulse width of 0.8 ms. Image density (optical density, o.D.) was measured using a SpectroEye densitometer by X-Rite at energy levels of 0.25 and 0.45 mJ/point. The uncertainty in the measurement of the o.d. value is estimated to be less than or equal to 2%.

(2) Static color density (initial temperature):

at a rate of 0.2kg/cm²Extrusion force and contact time of 5 seconds recording paper web for a series of metal stamp prints heated to different temperatures and thermostatically controlled thermally (thermomechanical TP 3000QM, Maschinenfabrik HansRychiger ag, Steffisburg, switzerland). The image density (optical density) of the image thus produced was measured using a SpectroEye densitometer by X-Rite.

The static onset point is defined as the lowest temperature at which an optical density of 0.2 is reached. The accuracy of the measuring method is less than or equal to +/-0.5 ℃.

(3) Resistance test of printed images:

a) plasticizer resistance:

thermal recording paper samples dynamically recorded according to the method of (1) were contacted with plasticizer-containing cling film (PVC film with 20 to 25% dioctyl adipate) while avoiding wrinkles and air entrainment, wound into rolls and stored for 16 hours. One sample was stored at room temperature (20 to 22 ℃) and the second at 40 ℃. The image density (o.D.) was measured after the film was peeled off and correlated with respect to the corresponding image density value before plasticizer action according to equation (equation 1).

c) Adhesive resistance:

adhering a transparent Tesa self-adhesive tape to each of the thermal recording paper samples dynamically recorded according to the method of (1) (1)

A strip of kristar-klar, #57315) and a strip of Tesa packaging tape (#04204) separate therefrom while avoiding wrinkles and air entrainment. After storage at room temperature (20 to 22 ℃), the image density was measured after 24 hours and after 7 days through the respective adhesive tape (o.D.) and correlated according to equation (equation 1) for similarly determined image density values of freshly bonded samples.

The scatter in% values (Streuung) calculated according to (equation 1) is ≦ 2 percent points.

Tables 3 to 5 summarize the evaluations of the prepared recording materials.

Table 3: initial temperature of developer (onset) and image Density (optical Density at energy levels of 0.25 and 0.45 mJ/Point)

Color developing agent	o.D.(0.25mJ/dot)	o.D.(0.45mJ/dot)	Starting point (. degree. C.)
				I	1.16	1.22	81
II	1.20	1.24	76
				III	1.13	1.24	76
IV	1.19	1.20	71
				V	1.17	1.20	76
VII	1.15	1.23	86
				VIII	1.20	1.23	73
X	1.24	1.30	82
				XIII	1.14	1.20	79
XXIII	1.16	1.26	82
				XXIV	1.09	1.26	82
Z	1.19	1.24	86
				PF201	1.19	1.23	76

Table 4: image density depending on substitution pattern of developer (optical density at energy levels of 0.25 and 0.45 mJ/point)

*: comparative examples

Table 5: resistance of printed image of developer

Percentage of retained image density corresponding to equation 1

As can be seen from the foregoing examples, the thermosensitive recording material of the present invention particularly exhibits the following advantageous properties:

(1) the recorded images of the thermosensitive recording material based on the developer according to the present invention had print densities (optical densities) comparable to those of the comparative samples of the prior art (table 3).

(2) A thermosensitive recording material based on a developer having a substitution pattern (1, 2-position (ortho position) of the relevant functional group) according to the present invention has a significantly higher print density than a recording material based on a developer having an alternative substitution pattern (1, 3-position and 1, 4-position of the relevant functional group). See II and XIV and XVII, III and XV and XVIII, and IV and XVI and XIX (table 4).

(3) The temperature at which the recording material according to the invention starts to develop a visually perceptible greying (static onset) meets the requirements for marketable heat-sensitive recording materials (table 3).

(4) After the action of the hydrophobic agents (binders, plasticizers), the image resistance is better or comparable to the corresponding properties of the known non-phenolic developer substances of the prior art (table 5).

(5) With the color-developing agent according to the present invention, a thermosensitive recording material having high value in terms of key application technical relationship can be obtained. Recording materials based on known developers do not have comparable performance characteristics balanced across all properties tested.