CH638627A5 - REPROGRAPHY MATERIALS CONTAINING SILICIA AND PHOSPHORUS DERIVATIVES OF 2,3-NAPHTHALENE DIHYDROXY. - Google Patents

Description

The invention relates to information recording or document reproduction materials. It relates more particularly to recording or reproduction materials comprising a sensitive layer containing a chromogenic compound capable of reacting with a phenolic derivative, as well as a phenolic derivative in the form of a complex product capable of being decomposed into a phenolic derivative capable of reacting with said chromogenic compound and forming a colored image.

In the Belgian patent N ° 849049 are described reprographic materials comprising a chromogenic compound and a phenyl-urethane, and methods of implementation of said materials. Under the action of an energy supply (heat or contact with a liquid or a gas), the phenylurethane is broken down and releases a phenol which reacts with the chromogenic compound to give rise to a colored trace.

If photosensitive chromogenic compounds are used, it is then possible to make reproductions of documents by exposure to light through an original of a material containing the photosensitive chromogen and phenylurethane, then development by energy supply allowing release the phenol which then reacts locally with the chromogen which is not destroyed during the exposure.

It is also known, from French patents Nos 2368736 and 2368737, diazo sensitive layers comprising a diazonium compound, a precursor of a coupler capable of being transformed in the presence of an acid into an active coupler, and a progenitor of photosensitive acid. The implementation of such sensitive layers is done using ultraviolet radiation which generates the acid (but which also destroys the diazonium compound), which makes the coupler active. By passing through ammonia vapors, the coupler then reacts with the undecomposed diazonium compound.

Such a process and such a sensitive layer have numerous drawbacks: this diazotypy material must be stored completely protected from daylight (which includes ultraviolet rays) to avoid making the coupler active which will then react immediately with the neighboring diazonium salt, since the medium which surrounds it is alkaline. Therefore, the problem of prolonged storage of such material is not resolved. Furthermore, such a method cannot give satisfactory results, since exposure to ultraviolet light also decomposes the diazonium salt.

Consequently, either the time of exposure to ultraviolet light is very short, to avoid destroying too much diazonium salt, in which case little coupler becomes active and the image can only be very pale, or else the time exposure is longer and a lot of diazonium salt is destroyed, there is almost no more left to react with the coupler, which also gives a very pale image. Furthermore, it is obvious that, when the photosensitive acid progenitor is the diazonium salt itself, there can be generation of acid only insofar as there is destruction of the diazonium salt. Consequently, it is immediately clear that this process is very limited and cannot give rise to very colorful images. In addition, it is specified in these patents that the background of the image is stabilized by complete ultraviolet exposure of the material. It is difficult to understand why in one case the ultraviolet exposure would make it possible to obtain a colored image (without destroying the diazonium salt) while, in the other case, the same ultraviolet exposure would make it possible to obtain a decomposition of the diazonium salt without generate an active coupler. This is all the less likely since said complete UV exposure, to stabilize the background, takes place after passing through ammonia vapors of image development. However, we know from experience that ammonia penetrates all the material during this operation. Therefore, during total UV exposure, the bottom areas will be in a favorable reaction medium for coloring to occur. All this is moreover confirmed by the exemplary embodiments given in French patent N ° 2368737, in which the control sample (without acid anhydride) is that which corresponds to the teaching of French patent N ° 2368736. We then notes that, in this case, the image areas and the background areas have practically the same optical density. In other words, the image on the control sample is practically not visible.

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It has now been found that certain derivatives of dihydroxy-2,3-naphthalene are capable of reacting with certain chromogenic compounds to give rise to colored images. The recording or reproduction materials according to the invention are characterized in that the complex product is chosen from dihydroxy-2,3-naphthalene derivatives of formula:

0 - Z 0 - X

(I)

1

In formula I, G represents a hydrogen atom, a sulfonic group, an ammonium sulfonate group or an amine sulfonate group designated by Gj and having the overall formula:

-so.

eh

-If-A I

r2

O-T

I

-P = 0

I

Yi

When Z represents a radical of formula IIa, X! and A have one of the following meanings:

A constitutes a radical R3, the latter being either a hydrogen atom or a hydrocarbon radical, the meaning of which will be given below. When A represents a radical R3 as defined above, Xj constitutes a triorganosilyl radical having the formula:

/ Rl

-If — R2

r3

The X symbols! and A together constitute either a valential bond or a divalent radical of the following formula:

* 1

Yes \

0 0

if r 4>

* 2

-o I

—If — Rj

I

r2

~ (çh2) n - Si-R! r,

In these formulas, the silicon atom of this radical is linked to the oxygen atom placed in position 3 of the naphthyl group; if there are several radicals G in the molecule, they are identical to each other, G then representing either a hydrogen atom or a sulfonic or sulfonate group, the meaning of which has been given previously. The radicals R1; R2, R3, identical or different, represent a hydrogen atom, a straight or branched alkyl or alkenyl group having at most 6 carbon atoms (optionally substituted by a chlorine atom or a nitrile group), a phenyl or alkylphenyl group, the alkyl part contains at most 4 carbon atoms.

Preferably, these radicals Rx, R2, R3 represent a hydrogen atom, a methyl, vinyl, chloromethyl, cyano-ethyl, phenyl and tolyl radical. Preferably, G represents a hydrogen atom; n represents an integer equal to 1, 2 or 3, Z also represents a radical of formula:

E denoting ammonia or an aromatic or aliphatic primary, secondary or tertiary amine. Preferably, E represents ammonia, a tertiary aliphatic monoamine or a tertiary aliphatic polyamine. The groups carried by the nitrogen atom are alkyl, hydroxyalkyl or alkylene groups having at most 6 carbon atoms. By way of illustration, there will be mentioned, in addition to ammonia, trimethylamine, triethylamine, triethylenediamine, hexamethylene tetramine, etc.

When G represents a sulphonic or sulphonate group, the latter is preferably placed in position 6 of the naphthalene ring.

In formula I, Z represents a radical having one of the following formulas:

Ri

O-T

-P = 0

(IIb)

Section I:

In this formula, Yj constitutes an OR radical, R representing a straight or branched alkyl radical having at most 8 carbon atoms. The radical OR, in addition to the preceding meaning, represents a group of formula - [- O-, X + -J- with X representing EH, Na, K, Li and E having the meaning previously given. When Yj represents an OR radical as defined above, the other 30 radicals have the following meaning:

T represents a radical R,

X! then represents the radical of formula:

(lia)

35

vfTi?

(Hb)

GOLD

Lp /

K

0

p)

(Ubi)

GOLD

p being an integer equal to 0,1,2 or 3.

If there are several radicals G, they are identical and represent either a hydrogen atom or a sulfonic or sulfonate group. The OR radicals are necessarily identical when one of them represents a group -f-0 ~, X +]. In this situation, G represents a hydrogen atom or a sulfonate group as defined above.

Section II:

50 The radical T also represents a radical R '", R"' being a hydrogen atom or a radical R. Yx and Xt then represent the divalent radical of formula:

Cp)

1 L_

r I

0 \

1

GOLD'

(Hb2)

(q)

p being a number equal to 0, 1, 2 or 3, q being a number equal to 0 or 1. When q is equal to 1, the phosphorus atoms are linked by an oxygen atom. When p and q are both zero, X, and Y1 constitute the valence bond.

If there are several G radicals, these are identical to each other. They represent either a hydrogen atom or a sulfonic or sulfonate group.

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The radicals OR 'are necessarily identical when one of them represents a group -f O-, X +]. In this situation, G represents a hydrogen atom or a sulfonate group as defined above.

Section III:

T also represents a radical of formula:

H

> if <

R1

R2

(Ib)

in which the different symbols are linked together in one of the following ways:

X2 and Y2 together constitute a valential link,

when X2 and Y2 together constitute a valential link, X! and Y! together constitute a value bond;

Yt and Y2 together constitute the radical:

- Wo (Hb4)

Ml <4

o -

o -

<CVn

(the)

If there are two G radicals in the same molecule, these are identical.

As already said, the preferred compounds according to the invention are those in which G is equal to H and where the symbols Rt, R2, R3 represent a hydrogen atom, a methyl, vinyl, chloromethyl, cyanoethyl group , phenyl and tolyl and where n is an integer equal to 1 or 2. Among the latter, particular mention will be made of the compounds in which Rj, R2 and R3 all represent a methyl group.

^ Phosphorus derivatives of the invention

The various phosphorus compounds can be classified into three groups depending on whether they are prepared from simple phosphorus compounds having 1,2 or 3 reactive groups.

45

in which the symbols Wt and W2 represent a valence bond respectively with the symbols Xt and X2, G represents either a hydrogen atom or a sulfonic or sulfonate group, and p is an integer equal to 0.1,2 or 3 .

Preferably, for all the phosphorus derivatives, G is a hydrogen atom and R is a straight or branched alkyl radical having from 1 to 4 carbon atoms or a radical -f O-, X +] which, when it is an oxyammonium radical, is derived from ammonia or from tertiary aliphatic mono- or polyamine. The numbers p and q are variable depending on the conditions for obtaining the different products.

Silicon derivatives of the invention

When the compounds I are silicon derivatives, they have the formula one of the following formulas:

tion then have the following formula:

50

Section I:

The first group is obtained from phosphorus-containing compounds having a reactive group. The phosphorus compounds of the invention

0

He OR

0 P

^ OR

55

60

(If)

GOLD

(the)

NOT

GOLD

(P)

R having the meaning previously given (straight or branched alkyl radical having at most 8 carbon atoms, or ammo- radical

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nium), p being an integer equal to 0, 1,2 or 3, G having the meaning previously given.

If there are several G radicals in the same molecule, they are identical. When OR is a group -f-O-, X +], all the groups R are identical and the groups G are hydrogen atoms or sulphonate radicals.

The compounds of formula If generally exist in the form of a mixture of products differing only in the value of p and in their distribution. They can be separated by crystallization. Preferably, R is a straight or branched alkyl radical having from 1 to 4 carbon atoms or a radical -f O-, X +],

Section II:

The second group of phosphorus derivatives is that obtained from difunctional phosphorus derivatives. The phosphorus compounds according to the invention then have one of the following formulas:

In this group, preference is given to the compounds in which R represents a hydrogen atom, a straight or branched alkyl group having from 1 to 4 carbon atoms, or a group -f-O-, X +] as defined above.

Section III:

The third group of phosphorus derivatives is that obtained from trifunctional phosphorus derivatives. These compounds then have one of the formulas:

p being equal to 0.1, 2 or 3, R 'being a hydrogen atom or having the same meaning as the radical R, G having the meaning previously given. When there are several G radicauuxes in the same molecule, these are identical. When one of the groups OR 'is a group -f-O-, X +], all the radicals R' are identical. The radicals G are then hydrogen atoms or sulphonate radicals. In these formulas, p and R 'have the meaning already given.

When p is zero, the organophosphorus compound of formula Ih has the formula:

(Ig)

The compounds Ig, Ih and Ii generally exist in the form of a mixture in variable proportions. These compounds can be separated by crystallization.

G being a hydrogen atom, a sulfonic or sulfonate group; the preferred compounds are those which correspond to G = H and 50 p = 0.

It has in fact been found that said derivatives of dihydroxy-2,3-naphthalene are capable of decomposing under the action of a contribution of thermal energy, or by bringing into contact with certain liquid or gaseous fluids, and thus releasing a phenol capable of reacting with the chromogenic compound.

The chromogenic compounds which can be used in the sensitive layers according to the invention are all the chromogenic products capable of reacting with phenols.

By way of preference and without limitation, mention may be made of the 60 indolinic or benzothiazolic spiropyrans, tri-phenylmethane derivatives, ferric salts, diazonium salts, non-photosensitive silver salts, etc.

Generally, the weight ratio between the chromogenic compound and the dihydroxy-2,3-naphthalene derivative can be between 65 and 0.01 and 10, but preferably between 0.05 and 3.

The sensitive layers according to the invention can also contain, in a manner known per se, binders such as polyvinyl alcohols, polyvinyl esters, acrylic esters, homo-

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or copolymers based on polyvinyl chloride, or any other binder well known to those skilled in the art.

The sensitive layers according to the invention can be deposited on any suitable support such as paper, transparent or opaque plastic films, glass, metals, etc. The implementation of the sensitive layers according to the invention can be carried out in different ways.

A first method consists in decomposing the derivative of dihydroxy-2,3-naphthalene by adding thermal energy so as to generate dihydroxy-2,3-naphthalene which reacts with the chromogenic compound used to form a colored trace.

If the chromogenic compound is photosensitive (for example a diazo compound), it is possible to reproduce a document: after exposure through a transparent original, the exposed areas are modified (the diazo compound is destroyed); by passing through a thermal development machine, the dihydroxy-2,3-naphthalene is unblocked and reacts locally with the chromogenic compound which is not destroyed.

If the chromogenic compound is not photosensitive, it can either be sensitized with photosensitizers and thus carry out the reproduction of documents, or carry out a thermal recording using a heated tip which releases 2,3-dihydroxy-naphthalene which reacts locally with the chromogenic compound to form a colored trace (it is quite obvious that the thermal recording can also be carried out with photosensitive chromogenic compounds, such as the diazo compounds).

In this thermal development process, it may be advantageous to lower the release temperature of the dihydroxy-2,3-naphthalene derivative by incorporating into the sensitive layer a catalyst for the decomposition of said derivative.

Among these catalysts, there may be mentioned, without limitation:

- ammonia,

- bases such as soda, potash, etc.,

- the aliphatic amines and preferably the aliphatic tertiary amines of general formula:

/ Rl

(with Ri, R2, R3 comprising

S. 2 from 1 to 10 carbon atoms)

R3

- cyclic aliphatic tertiary polyamines, such as hexamethylenetetramine, triethylenediamine, etc.,

- hydroxylated amines (or amino alcohols) such as, for example, mono-, di- or triethanolamines, 2-amino-1-butanol, tri (hydroxymethyl) aminomethane, etc.

- organic or mineral ammonium salts such as carbonates, acetates, hydrocarbonates, formates, Oxalates, benzoates, etc.,

- morpholine derivatives such as morpholine, N-methylmorpholine, 2,6-dimethylmorpholine, N-aminoethyl-morpholine, etc.

- products or pairs of products producing ammonia by heat and in particular urea, thiourea and their derivatives, ammonium salts decomposable by heat such as for example ammonium carbonate, ammonium benzoate, etc., the pairs of products which by reaction to heat produce ammonia, such as the pairs of products described in French patent No. 1403004 (ammonium salt of strong acid + metallic compound ) or such as the product pairs described in French patent No. 1418156 (strong acid and weak base salt + weak acid and strong base salt).

In general, the purpose of the above thermal decomposition catalysts is to produce, on heat, an alkaline base or medium which promotes the decomposition of the 2,3-dihydroxynaphthalene derivatives used in the invention.

To the list of products mentioned above we can add, in general, the products which by reaction between them to heat generate a base, the products which by the action of heat decompose and give rise to a base, as well as mixtures of products consisting of a base and an excess volatile acid which, by the action of heat, release the volatile acid and leave the base in the photosensitive layer.

Without limitation, mention may in particular be made of sodium, potassium or amine trichloroacetates (-iperidine, tertiary amine, ethanolamine), sodium and amine formates, etc.

As volatile acids, mention may in particular be made of trichloroacetic, formic, glycolic, malonic, lactic acids, etc.

For more details on these products and their implementation, reference may be made to French patent N ° 1249913 or to addition 78.619 of said patent.

In the case of thermal recording, this can be done using a heating head or any other means well known to those skilled in the art; the colored trace appears alos where the material has been heated.

Another process for using the materials according to the invention, to allow the reaction of the chromogenic compound with the derivative of 2,3-dihydroxy-naphthalene, consists in bringing a fluid into contact with the sensitive layer according to the invention, this liquid or gaseous fluid allowing a colored trace to appear.

Among the fluids likely to generate such a reaction, there may be mentioned in particular, without limitation:

- ammonia (gas) or ammonia (liquid),

- bases such as soda, potash, etc.,

- the aliphatic amines and preferably the aliphatic tertiary amines of general formula:

/ Rl

(with Rls R2, R3 containing \ 2 from 1 to 10 carbon atoms)

rs

- cyclic aliphatic tertiary polyamines such as for example hexamethyltetramine, triethylenediamine, etc.

- hydroxylated amines (or amino alcohols) such as, for example, mono-, di- or tri ethanolamines, 2-amino-1-butanol, tri (hydroxymethyl) aminomethane, etc.,

- organic or mineral ammonium salts such as carbonates, hydrocarbonates, formates, Oxalates, benzoates, etc.,

- morpholine derivatives such as morpholine, N-methylmorpholine, 2,6-dimethylmorpholine, N-aminoethyl-morpholine, etc.

It is obvious that fluids in gaseous form can only be used in reproduction, in order to develop the material previously exposed according to the known methods which are outside the scope of the invention. When the fluid is in liquid form, it is possible to make recordings on a material according to the invention using a point or an ink style of a well known type, the ink being replaced by the Phenolic derivative release liquid.

The making of reproductions using a material according to the invention can also be carried out by liquid development. In order to speed up the reaction and dry the material, it may be useful to slightly heat the material to a temperature above 40 ° C but below the phenol release temperature.

A particularly important application of the invention is diazotypy in all its forms. It is known, in fact, that the diazo products react in particular with phenolic couplers to generate colored traces. The reaction of the diazo compound and of the coupler can be brought about either by heat, or by semi-wet route, or by gaseous route using ammonia. Diazotypy materials all have the disadvantage of being unstable over time; it is indeed difficult to keep diazotypie materials for more than three months under the usual storage conditions. The invention provides a considerable improvement in diazotypy materials. The diazotypie materials according to the invention can undergo a very prolonged storage which can reach several years.

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In the particular case of diazotypy, it is not necessary to use a binder to associate the diazo compound and the coupler.

The derivatives of dihydroxy-2,3-naphthalene can be prepared in the following manner.

Process for the preparation of silyl ethers

The organosilicon compounds of naphthalenediol-2,3 corresponding to formulas I and Ha can be obtained according to the conventional methods used in organosilicon chemistry.

G

this H2)

(the)

Silylated derivatives by which G = H or G = S03H The silylated ethers of formula la:

) If can be obtained by reaction in an inert solvent between dihydroxy-2,3-naphthalene with respectively a dichlorosiloxane of formula:

i? 1 ut

Yes

Ri r2

Rs Ri

112 Ra

ClSi-

o-

R] R2 R, or a dichlorodisilylalkane of formula:

Yes

/ \

-Cl r,

C1 can be obtained by reacting, in a substantially stoichiometric proportion, in an anhydrous inert solvent, dihydroxy-2,3-naphthalene with an organosilicon compound bringing a triorganosilyl group:

,. / Rl

Sik rt

\

r,

A chlorosilane with the formula:

/ Rl

ClSi ^ -R2 r3

The silyl ethers of formulas Ib and the

- o-

35

l ^ îX-0

Yes

Cl Si (CH2) n Si -

/ \ / \

Rf NR2 Ri R2

Silylated derivatives for which G is a sulfonate group

These derivatives are obtained by reaction of the compounds la with with the appropriate amine, in aqueous solution or suspension, or alternatively in solution in an inert organic solvent and under moderate temperature conditions (generally at 100 ° C.).

It is advantageously operated at ordinary temperature.

Process for the preparation of phosphorus compounds

The phosphoric esters of dihydroxy-2,3-naphthalene can be obtained by reacting dihydroxy-2,3-naphthalene on mono-, di- or trifunctional phosphoric derivatives such as polyphosphoric acid, phosphoric anhydride, or compounds of formula POCl3, PC13, POCl2 (OR), PC12 (0R), or POCl (OR) 2.

Preparation of phosphorus-containing compounds of formula If in which G is a hydrogen atom or an SO 3 H radical and in which R represents an alkyl group

Such phosphoric esters of formula If can be obtained by reacting the dihydroxy-2,3-naphthalene of formula:

sfm year)

can be obtained by reaction in an anhydrous solvent between dihydroxy-2,3-naphthalene and a dichlorosilane of formula: 50

Cl, Si

./ \

Ri

R2

The two compounds Ib and are in equilibrium with one another. The compound Ib can be distilled, but it transforms at room temperature into the compound.

The silylated compounds of formulas Id and the

R, R,

£ 0 =

(Id)

with the monofunctional phosphorus compound of formula C1P0 (0R) 2, R then being an alkyl group.

Depending on the proportions of the reagents used, a mixture of compounds corresponding to the formula If is obtained, but differing by the value of p. By recrystallization treatments, it is possible to isolate compounds If corresponding to a single p value.

Preparation of phosphorus-containing compounds of formula If in which G is a hydrogen atom or a sulfonate group and where OR represents a group -fO ~, X +]

The corresponding compounds are obtained by reaction of a compound If defined above (with G representing a hydrogen atom or a sulfonic group) with ammonia, sodium hydroxide, potassium hydroxide, etc., or an appropriate amine, by working either in solution or in aqueous suspension, or in solution in an inert organic solvent and under moderate temperature conditions (generally less than 100 ° C.). It is advantageous to operate at ordinary temperature.

Preparation of phosphorus-containing compounds of formula Ig, Ih or Ii in which G is a hydrogen atom or an SO 3 H radical and in which R represents an alkyl group

The various esters Ig, Ih, Ii can be obtained by reaction of the

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2,3-naphthalenediol of formula III with the di-functional phosphorus-containing compounds of formula:

Cl \

> -OR

c / 11 Cl o

R representing an alkyl group.

The compounds Ig, Ih, Ii are obtained in varying proportions according to the proportion of the reagents and according to the mode of introduction of these reagents.

Preparation of phosphorus-containing compounds of formula Ig, Ih or Ii in which G represents a hydrogen atom or a sulfonate group and where OR represents a group {-0 ~, X +]

These compounds are obtained by reacting a compound Ig, Ih or Ii as defined above (G being a hydrogen atom or a sulphonic group, R being an alkyl group) with ammonia, sodium hydroxide, potassium hydroxide, or an appropriate amine, by working either in solution or in aqueous suspension, or in solution in an inert organic solvent and under moderate temperature conditions (in general lower than 100 ° C). It is advantageous to operate at ordinary temperature.

Such organophosphorus compounds can also be obtained by reacting 2,3-naphthalenediol with phosphorus oxychloride POCl3. In a first stage, compounds similar to those of formula Ig, Ih or Ii are thus prepared, but the formula of which comprises a chlorine atom in place of the OR radical.

In a second stage, the base or the amine is reacted and the expected organophosphorus compounds are obtained.

Preparation of phosphorus compounds of formula Ig, Ih or lì in which G represents a hydrogen atom or a sulphonic group and where OR is a hydroxyl group

These compounds are obtained by hydrolysis of an ester of formula IG, Ih or Ii in which G is a hydrogen atom or a sulfonic group and where R is an alkyl group. After hydrolysis, the compounds Ig, Ih, Ii can be isolated from their mixture by suitable recrystallization treatments. These phosphorus compounds can also be obtained by reacting 2,3-naphthalenediol with phosphorus oxychloride POCl3. In a first stage, compounds similar to those of formula Ig, Ih or Ii are thus prepared, but the formula of which comprises a chlorine atom in place of the OR radical.

In a second stage, the phosphorus compounds obtained in the first stage are hydrolyzed cold and the compounds of formula Ig, Ih or Ii are obtained in which OR is a hydroxyl group.

Preparation of organophosphorus compounds of formula Ij or If in which G is a hydrogen atom or a sulfonic group

The phosphoric esters of formulas Ij and Ij 'can be obtained by reaction of phosphoric anhydride with 2,3-naphthalenediol of formula:

moderate temperatures (generally less than 100 ° C). It is advantageous to operate at ordinary temperature.

The invention will be better understood with the aid of the following exemplary embodiments, given without implied limitation.

In all of these examples, the identification of the various compounds was confirmed by microanalysis, infrared analysis, spectral analysis by nuclear magnetic resonance and mass spectrography.

Example 1:

10 The naphthalenedioxo-2,3-dimethylsilane of formula:

I "i

° \

^ If

\

EYELASH

in balance with its dimer of formula:

ClL CH_

X ./3

--Yes -

If —0 ——

/ \

25

CH3 CH3

In a solution of 64.1 g of 2,3-dihydroxy-naphthalene in 500 ml of toluene, 1 g of triethylamine is added and poured under reflux (110 ° C) in 2 h 56.8 g of dichlorodimethylsilane. Heating is then maintained for 2 h until the evolution of hydrochloric acid is complete, the mixture is cooled, filtered by triethylamine hydrochloride and the solvent is distilled off, and a white precipitate of 80 g corresponding to the dimer (PF: 190 ° C). By distillation of the dimer, the monomer is obtained which is in liquid form at ordinary temperature. This turns very slowly into a dimer. The following recording material is then produced. On a paper support, a first layer of the following composition (3 g / m2) is deposited:

crystal violet lactone 0.5 g

40 carboxylated styrene / butadiene resin (Dow Latex 241

from Dow Chemical) 30 g

After drying, a second layer (2 g / m2) consisting of:

O CH-,

0 / \

CH,

50 15% polystyrene in methyl ethyl ketone

3g

50g

55

Information is recorded on this material using a tip heated to about 120 ° C; we get a blue trace on a white background.

Example 2:

The synthesis of naphthalenedioxo-2,2-diphenylsilane of formula:

G representing a hydrogen atom or a sulfonic group.

Preparation of organophosphorus compounds of formula Ij or Ij 'in which G is a sulfonate group

These compounds are obtained by reaction of a compound of formula Ij or Ij ', having at least one sulfonic group, with ammonia or an amine by working either in aqueous solution, or in solution in an inert organic solvent and in condi-

0T0

O

in balance with its dimer:

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3g r-isopropyl-3 ', 3'-dimethyl-6-nitro-8-methoxyspiro-

(2H-1-benzopyran-2,2'-indoline) 1 g polyvinyl alcohol (Rhodoviol 4/125 from the company

Rhône-Poulenc, 10% in water) 50 g

This sensitive layer is deposited on a paper support at a rate of approximately 6 g / m2. A thermal recording is carried out as in the previous example; the trace obtained is blue-black on a white background.

Example 3:

We synthesize the compound of formula:

^ ^ / ° \ ch,

i ° x ° 0 <

ch,

The following homogeneous mixture is then produced:

0 \

^ If

O o

0

\vs

5g

■ h,

3

64.1 g of dihydroxy-2,3-naphthalene, 500 ml of toluene and 1 ml of triethylamine are introduced into a flask, the mixture is heated to reflux and 111.4 g of dichlorodiphenylsilane are poured over 2 hours. It is then maintained at reflux for 6 h to ensure the end of the release of hydrochloric acid, it is cooled, the precipitate of triethylamine hydrochloride is filtered, the solvent is distilled, the precipitate is rinsed with acetonitrile (2 times 50 g). After recrystallization from propionitrile, 135 g of a compound corresponding to the dimer are obtained (m.p .: 169-170 ° C). By distillation, the liquid monomer is obtained at room temperature and slowly transforming into a dimer.

The following products are dispersed in a Dangoummeau crusher:

polyvinyl acetate

(Rhodopas H 45 AE from the company Rhône-Poulenc) 50 g silver behenate 5 g ferric stearate 10 g hexamethylenetetramine 0.05 g ethyl acetate 100 cm3

After coating at a rate of approximately 4 g / m2 on a paper support, a thermal recording is carried out as in Example I; the trace obtained is brown on a light background.

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Example 4:

The synthesis of the trimethylsilylated diether of 2,3-dihydroxy-naphthalene of formula:

25

30

cn3

sx ^ cej x ch3

according to the method described in example 1.

200 ml of bis-trimethyl-silylacetamide are poured into a suspension in 64.1 g of dihydroxy-2,3-naphthalene in 150 ml of dichloromethane. It is brought to a boil for 6 h, then the reaction mixture is distilled. 118 g of diethersilyl are obtained (Ebl: 124 ° C). The following composition is then prepared:

trimethysilyl diether of 2,3-dihydroxy-naphthalene 40 citric acid thiourea

4-Diazo-2,5-dibutoxyphenylmorphoiineborofluoride methylethyl ketone This composition is coated at a rate of 20 cm3 / m2 on a support paper. After drying, the paper is exposed through an original, the image being revealed under the conditions summarized in Table I.

2g 1g 2g 3g

200g

Table I

Example No.

Disclosure process

obtained result

4

Heating at 150 ° C for 10 s

Light blue image

5

Passage through an ammonia pulling machine

Navy image

6

Development using the following solution: triethylenediamine 7 g water 100 g

Light blue image

7

Same development conditions as in Example 6, then heating to 80 ° C.

Dark blue image

8

Development using the following solution: thiourea 1 g sodium metaborate 1 g potassium metaborate 5 g water 1 1

Light blue image

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Table I (continued)

Example No.

Disclosure process

obtained result

9

Development identical to Example 8, then heating at 80 ° C for 4 s

Blue picture

10

Development using the following solution: monoethanolamine 10 ml water 90 ml

Navy image

11

Development in a thermal machine at 100 ° C for 10 s, the paper being impregnated with a backing layer comprising a mixture of% ammonium sulphate and Zz of sodium bicarbonate by weight

Navy image

Example 12:

We realize the following solution:

20 Example 14:

The synthesis of naphthalenedioxy-2,3-bis- (dimethylsilyl) -1,2-ethane of formula: çjj qjj is carried out

\ 3/3

13 g

O

30

(prepared in Example 2)

citric acid 5 g thiourea 10 g methyl ethyl ketone 1 1

paradimethylaminobenzenediazoniumborofluoride 12 g This solution is deposited at the rate of 15 cm3 / m2 on a polyester support coated with a layer of a varnish based on cellulose acetate. Insolation of the support is carried out through an original and the same modes of development are carried out successively as in Examples 4 to 11 (the backing layer of Example 11 is, in this case, coated as an undercoat on the 'cellulose acetate). The results obtained are identical, the image being in each case a little more purple than in the corresponding examples 4 to 11.

Example 13:

In formula 12, the naphthalene-dioxy-2,3-diphenylsilane is replaced by a stoichiometrically equivalent amount of naphthalene-dioxy-2,3-dimethylsilane, prepared according to example 3, of formula:

.0

45

The same results are obtained as in Example 12 (same coloration for the same development modes).

ch3 ch3

64.1 g of dihydroxy-2,3-naphthalene, 500 ml of toluene and 2 ml of triethylamine, heated to reflux are introduced into a flask and poured in 2 h 94.7 g of bis- (chlorodimethylsilyl) ethane in solution 50 ml of toluene. It is then maintained at reflux for 3 hours to ensure complete release of hydrochloric acid. Cooled, filtered the triethylamine hydrochloride, distilled toluene and obtained by vacuum distillation a fraction of 93.5 g of naphthalenedioxy-2,3-bis- (dimethylsilyl) -1,2-ethane (Eb 0.9: 140 ° C).

The following solution is then prepared: naphthalenedioxy-2,3-bis- (dimethylsilyl) -1,2-ethane 11.5 g citric acid 5 g thiourea 10 g methyl ethyl ketone 1 1

paradiethylaminobenzenediazoniumborofluoride 12 g

This solution is deposited at a rate of 15 cm3 / m2 on a paper support. After exposure through an original, the image is developed according to the methods described in Examples 4 to 11 respectively. The same colors are obtained respectively as in Example 12. It is noted, however, that the development of the image with ammonia (as in Example 5) is much faster than in the previous examples. The sensitivity of such a diazotypy material is substantially the same as that of the corresponding material in which the coupler would not have been blocked.

Examples 15 to 17:

The synthesis of the following phosphorus product, of formula:

13

638,627

64.1 g of dihydroxy-2,3-naphthalene are loaded into 500 ml of benzene with 81 g of triethylamine. 68 g of phosphorus oxychloride (POCl3) are poured into the boiling solution over 2 hours and the mixture is kept under reflux for 1 hour until the release of hydrochloric acid. Cool on ice, add 20 ml of water and filter. The precipitate is washed with 4 times 100 ml of ice water, then with 3 times 100 ml of acetonitrile. 74 g of white solid are obtained which are recrystallized from DMF, corresponding to the expected formula.

The following solution is then prepared:

(phosphorus product above) 16 g dimethylformamide 1 1

citric acid 5 g thiourea 10 g s 4-diazo-2,5-diethoxyphenylmorpholineborofluoride 20 g

This solution is coated on a paper support at a rate of 15 cm3 / m2. After exposure through an original, the material is developed according to different processes. The results are collated in Table II.

Table II

Example No.

Development process

Color obtained

15

Ammonia

Green

16

Triethanolamine solution

Light blue

17

Development at 120 ° C. by contacting for 10 s with a paper coated with a solution of Ys of ammonium sulphate and Vi of solium bicarbonate by weight

Green

Example 18:

The synthesis of 2,3-naphthyl hydrogen phosphate having the formula:

80.1 g of dihydroxy-2,3-naphthalene, 2 ml of triethylamine and 250 ml of freshly distilled phosphorus oxychloride (POCl3) are loaded into a flask. It is slowly heated to reflux, which ensures dissolution, and maintained at reflux for 4 h to ensure complete release of hydrochloric acid.

The mixture is cooled, the triethylamine hydrochloride is filtered and distilled; a white solid is obtained corresponding to the formula:

0.

© 3M

Cl

This compound is cooled to 0 ° C, then hydrolyses very slowly at this temperature with 220 ml of water. The aqueous phase is extracted with ethyl acetate (4 times 100 ml). The solvent is distilled and the expected compound is obtained (it melts, decomposing at 160 ° C).

On a paper support, the following solution is deposited at a rate of 3 g / m2:

polyethylene dispersion (Epotal 181 D from BASF) 25 g triethylenediamine 2.5 g water 25 g

After drying, the following overcoat is coated, at a rate of 15 cm 3 / m2, with the solution consisting of:

O o oh

1 g oh citric acid 0.6 g thiourea 1.3 g

4-diazo-2,5-diethyoxyphenylmorpholinechlorozincate 2.5 g water 60 g alcohol 60 g

After exposure through an original, the diazotypie material 30 is developed in a thermal development machine (120 ° C for 8 s). The image obtained is blue-violet in color and there is no unpleasant odor during development. The same material is also developed in a dry and semi-wet drawing machine. The same results are obtained. It should be noted that the sublayer used makes it possible both to catalyze the release of the coupler and to ensure an alkaline medium favorable to the reaction.

Example 19:

40 A paper backing is coated at 5 g / m2 with the following undercoat:

Rhodopas S 051 (company polystyrene emulsion

Rhône-Poulenc) 70 g

Diofan 207 D (polyvinylidene chloride 45 from BASF) 30 g hexamethylenetetramine 5 g

This sublayer is then coated with the same overlay as in Example 18. Under the same conditions, the same results are obtained.

50

Example 20:

The following undercoat is coated with a paper support, at a rate of 5 g / m2:

Dow Latex 241 (styrene / butadiene carboxylated resin 55 from Dow Chemical) 12.5 g

Neocryl A 291 (acrylic resin / polyvinyl styrene Chemie) 12.5 g water

The following overcoat (20 cm 3 / m2) is then deposited: water citric acid thiourea

25g

0.6g

50 g 0.5 g 1 g

638,627

14

paradiethyleneaminobenzenediazoniumchlorozinate 0.75 g dabco WT (triethylenediamine-based compound from Air Products and Chemicals Inc. 1 g

After exposure through an original, the material is developed at 100 ° C for 8 s. A dark blue-violet coloration is obtained.

Example 21:

The following composition is dispersed in a ball mill: sodium bicarbonate 50 g ammonium sulfate 200 g polyvinyl acetate (Rhodopas H from the company

Rhône-Poulenc) 35 g toluene 250 g

This dispersion is coated on the back with a paper support at a rate of 10 g / m2.

The following layer is then deposited on the front of the support:

lg

Example 23:

The following composition is mixed in a Dangoumeau mill

\ / °

boasts:

N) hr, 3 ', 3'-trimethyl-6-nitro-8-methoxy spiro (2H-1 -benzopyran-2,2'-indoline) polyvinyl alcohol (Rhodoviol 4/20 from the company Rhône-Poulenc) at 10 % in water

10g

5g 120g

This composition is coated on a paper support at a rate of 6 g / m2. By recording with a point heated to 140 ° C., a trace of navy blue color on a light background is obtained.

Example 24:

The following mixture is produced: silver behenate

20

citric acid 0.6 g thiourea 1.3 g

4 diazo-2,5-diethoxyphenylmorpholinechlorozincate 2.5 g water 60 g alcohol 60 g

After insolation, the development is carried out in a heat drawing machine, for 8 s at 120 ° C. There is the appearance of a blue-violet image.

Example 22:

The following composition is produced:

7g crystal lactone violet 0.5 g styrene / butadiene resin carboxylated

emulsion (Dow Latex 241) 65 g

This mixture is homogenized and then coated on a paper support at the rate of 3 g / m2.

This produces a thermal recording paper developpable at about 130 ° C, having very good storage stability.

oTo

K

.0 0E

5g

8g

25 triethylenediamine 0.3 g 15% polystyrene in methyl ethyl ketone 50 g methyl ethyl ketone 30 g

5 g / m2 of this solution are deposited on a paper support. By recording with a point heated to 140 ° C, a 3rd colored trace of dark brown color is obtained.

Examples 25 and 26:

The ammonium salt of 2,3-naphthyl hydrogen phosphate of formula:

Nile,

40 On 2.22 g of 2,3-naphthyl hydrogen phosphate (prepared in Example 18) dissolved in 10 ml of water, 1 ml of ammonia is poured slowly while cooling to 0 ° C (d = 0 , 92) diluted in 10 ml of water; the ammonium salt precipitates, it is filtered, washed with water, dried. 2.2 g of a white solid are thus obtained corresponding to the expected formula 45.

Also prepared triethylenediamine 2,3-naphthylphosphate of formula:

, r / CR2, HN CH2-

CH2-

-CH0

-CII0— ~ H

Ch

Poured onto 1.34 g of triethylenediamine in solution in 15 ml of isopro-panol, a solution of 2.22 g of 2,3-naphthyl hydrogen phosphate in 15 ml of isopro- panol; the amine salt precipitates, it is filtered, washed with cold isopropanol and dried. 3.3 g of white solid are thus obtained corresponding to the expected formula.

We then carry out the following solution:

2,3 triethylenediamine naphthylphosphate 12 g water I 1

This solution is deposited on a paper support at a rate of 20 cm3 / m2.

The following overcoat is then deposited, at a rate of 20 cm3 / m2: citric acid 5 g

60 thiourea 10 g paradiethylaminobenzene diazonium chlorozincate 15 g ammonium acetate 10 g water 1 1

After exposure through an original, the material is developed 65 in a thermal machine at 120 ° C for 10 s. We get a blue-purple copy.

The same result is obtained by development in the presence of ammonia.

15

638,627

The same solution is made as above, replacing, in the first layer, the triethylenediamine 2,3-naphthylphosphate by the ammonium salt of 2,3-naphthyl hydrogen phosphate and replacing the ammonium acetate , in the second layer, with urea (the respective weights of the new constituents remain the same as those of the previous constituents).

By operating under the same conditions as above, the same results are obtained.

In the present description, the terms naphthalenediol-2,3 and dihydroxy-2,3-naphthalene have been used alternately and have the same meaning.

Example 27:

The following solution is prepared:

0.25 g

We have

0.5 g

4-diazo-2,5-diethoxy-l- (4'-tolyl) mercapto 0.5 g benzenechlorozincate 0.5 g

After exposure through an original to be reproduced, the image is developed by passing through water vapor at 100 ° C. We get a faded purple image. In general, the development of the materials according to the invention with water vapor is possible when using rapidly coupling diazonium salts well known to those skilled in the art.

Example 29:

The following solution is prepared:

sodium trichloroacetate 0.2 g water 25 cm3

This solution is deposited on a paper support at the rate of 0.5 g / m2. After drying, a second layer (1 g / m2) of the following solution is deposited:

paradiethylaminobenzenediazoniumchlorozincate 0.3 g citric acid 0.12 g thiourea 0.25 g water 25 cm3

After exposure through an original, the image is developed by heating to 100 ° C. We get a blue-violet image.

Example 28:

On a support of polyethylene terephthalate sold under the brand Terphane, coated with a mounting layer, the following solution is deposited at the rate of 0.5 g / m2:

methanol 25 g tartaric acid 0.12 g thiourea 0.25 g

(NH3CH2CH2OH) + 0.4 g water 25 cm3

ammonium acetate 0.3 g

This solution is deposited on a paper support at the rate of 0.5 g / m2. After drying, the following overlay is deposited, at a rate of 1 g / m2:

4-diazo-2,5-dibutoxyphenylmorpholine chlorozincate 0.35 g lactic acid 0.75 g thiourea 0.5 g water 25 cm3

After exposure through an original to be reproduced, development is carried out at 120 ° C. We get a blue image.

R

Claims (16)

638,627 1. Recording or reproducing material comprising a sensitive layer containing a chromogenic compound capable of reacting with a phenolic derivative, as well as a phenolic derivative in the form of a complex product capable of being decomposed into a phenolic derivative capable of reacting with said chromogenic compound and form a colored image, characterized in that the complex product is chosen from derivatives of 2,3-naphthalenediol of formula: ~ -z (I) Li, E having the meaning previously given, T then also represents a radical R, and X, represents a radical of formula: 0 X-, in which G represents a hydrogen atom, one or more sulfonic groups, ammonium sulfonate or amine designated by G [and having the overall formula: fS03 ", EH +] E denoting ammonia or an aromatic or aliphatic primary, secondary or tertiary amine, Z represents one of the groupings: r. I -If-A I R2 (Ha) O-T I —P = o I y, (IIb) a) when Z represents a radical of formula (Ha), Xi and A have one of the following meanings: A constitutes a radical R3 representing a hydrogen atom, a straight or branched alkyl or alkenyl group having at most 6 carbon atoms and optionally substituted by a chlorine atom, a nitrile group, a phenyl or alkylphenyl group, the part of which alkyl contains at most 4 carbon atoms, and Xj represents a triorganosilyl radical of formula: / Rl -If ^ -R2 in which R! and R2, identical or different, have the same meaning as the radical R3, or else Xj and A together constitute a valential bond or one of the radi- in which the silicon atom is linked to the oxygen atom placed in position 3 of the naphthyl group, n represents an integer equal to 1,2 or 3, G has the meaning previously given and, when there are several radicals G, these are identical; b) when Z represents a radical of formula (IIb), Y! and T have one of the following meanings: Y i constitutes an OR radical, R representing a straight or branched alkyl radical having at most 8 carbon atoms or the OR group of formula -f 0 ~, X +], with X representing EH, Na, K, p being an integer equal to 0.1, 2 or 3, G has the meaning given above and, when there are several radicals G, they are identical, the radicals OR are identical when one of them represents a group -fO-, X + -J- and when OR represents a group of formula (O-, X +), G is a hydrogen atom or a sulfonate group (SO3 ~, EH +), the symbols E representing identical radicals , or T represents a radical R '", R'" being a hydrogen atom or a radical R as defined above, Y! and Xj then represent a di valent radical of formula: "I Ó I r o -GOLD' U) 30 p being a number equal to 0.1,2 or 3, q being a number equal to 0 or 1, when q is equal to 1, the phosphorus atoms are linked by an oxygen atom, when p and q are both null, Xx and Yt constitute a valential bond, G has the meaning previously given and, when there are several radicals G, they are identical to each other, 35 the radicals OR 'are necessarily identical when one of them represents a group -f O-, X + -f, G then represents a hydrogen atom or a sulfonate group, and the groups E are then identical, or else T represents a radical of formula: in which the different symbols X2 and Y2 are linked together in one of the following ways: X2 and Y2 constitute a valential link; when X2 and Y2 consti-55 kill a valential bond, Xt and Yt also constitute a valential bond, or Yj and Y2 together constitute the radical of formula: é d 0 — p v70 2. Recording or reproduction material according to claim 1, characterized in that the complex product is an organosilicon compound having one of the following formulas: (the) Ri Rz (Ib) (the) 25 30 (Id) 35 CCHjjyie) / 2 (Hb4) O .0 in which the groups Wi - X, and W2 - X2 each represent a valential link, G has the meaning previously given and p is an integer equal to 0.1, 2 or 3. 2 3. Recording or reproduction material according to claim 2, characterized in that G represents a hydrogen atom or a sulphonic radical. 4 0 0. 4. Recording or reproduction material according to claim 2, characterized in that G represents a sulfonate group. 5. Material according to one of claims 2, 3 or 4, characterized in that the radicals R1; R2, R3 are the same or different and represent a hydrogen atom, a methyl, vinyl, chloromethyl, cyanoethyl, phenyl and tolyl radical. 6. Material according to claim 1, characterized in that the complex product is an organophosphorus compound having one of the following formulas: 45 (If) 638,627 7. Material according to claim 6 and having the formula (10, characterized in that G is a hydrogen atom or a sulfonic group and where R is an alkyl radical. 8. Material according to claim 6 and having the formula If, characterized in that G is a hydrogen atom or a sulfonate group and where OR is a radical -fO ", X + -f. 9. Material according to claim 6 and having one of the formulas (Ih), (Li) or (Ig), characterized in that G represents a hydrogen atom or a sulphonic radical and where R 'represents an alkyl group. 10. Material according to claim 6 and having one of the formulas (Ih), (Li) or (Ig), characterized in that G represents a hydrogen atom or a sulfonate group and where OR represents a group - [" O-, X +]. 11. Material according to claim 6 and having one of the formulas (Ih), (Ii) or (Ig), characterized in that G represents a hydrogen atom or a sulphonic radical and where OR 'represents a hydroxyl group. 12. Material according to claim 6 and having one of the formulas (Ij) or (Ij '), characterized in that G is a hydrogen atom or a sulfonic group. 13. Material according to claim 6 and having the formula (Ij) or (Ij '), characterized in that G is a sulfonate group. 14. Material according to 1 to 13, characterized in that the chromogenic compound is chosen from triphenylmethane derivatives, iron salts, indolinic or benzothiazolic spiropyrans, non-photosensitive silver salts or diazo compounds. 15. Material according to one of claims 1 to 14, characterized in that the weight ratio between the chromogenic compound and the derivative of 2,3-dihydroxy-naphthalene is between 0.05 and 3. 16. Thermal recording or reproduction material according to one of claims 1 to 15, characterized in that it also comprises a catalyst for decomposition of the derivative of 2,3-dihydroxy-naphthalene.