DE2149746C3 - Diazotype material - Google Patents

Description

CF ₃

N ₁ X

OR

diazonium salts, which in the 6-position a Trilluormeihyl- or have methyl group, known, however are not sufficiently photosensitive and reactive, as shown in a comparative example.

The invention is based on the object of an improved light-sensitive diazotype material to produce the novel, highly photosensitive diazonium compounds that are opposite to azo coupling components are very reactive and provide a high density color image.

This object is achieved by a diazotype material of the type described above, which thereby is characterized in that the trifluoromethylbenzenediazonium salt the general formula

where R is an alkyl radical with 1 to 5 carbon atoms, the radicals R ₁ and R ₂ , which can be the same or different, are alkyl and / or aralkyl radicals and the alkyl radicals contain 1 to 5 carbon atoms or the radicals R ₁ and R ₂ together form a 5- or 6-membered saturated heterocyclic ring consisting of nitrogen, carbon and oxygen atoms, and X -Cl- 1/2 ZnCl ,, -Cl ■ 1 / 2CdCl ₂ , - Cl · 1 / 2SnCl ₄ , -BF ₄ odc'r - SOjH.

The invention relates to a diazotype material which is used in its photosensitive layer as a diazonium compound a trifluoromethyl benzene diazonium salt contains.

The coupling of a diazonium compound is advantageous in a wet development process with an azo coupling component in a weakly alkaline or weakly acidic aqueous solution Solution stirred and with a dry development process or with a thermal development process worked with dilute ammonia vapor or at low temperatures.

Benzene diazonium salts are known to be used as highly photosensitive and reactive diazonium compounds with a halogen substituent in the ortho position to the diazo group in the light-sensitive Diazotype material used.

For example, 2-chloro-4-N, N-dibenzylamino-5-butoxybenzenediazonium chloride (ZnCl ₂ double salt) couples with azo coupling components such as 1-naphthol-4-sulfonic acid, sodium 2,3-dihydroxynaphthalenesulfonate and 2-hydroxy-3 - (hydroxyethylamino ) - naphthoic acid in an alkaline aqueous solution or in ammonia vapor and forms a purple azo dye. To form a black color, this diazonium compound must be coupled with phloroglucinol in an alkaline aqueous solution with heating. Under these conditions, however, no deep black azo dye is obtained, but a bluish black color Itoff which has only a low density.

2 - chloro - 4 - N, N - diethylamino - 5 - methoxybenzenediazonium chloride couples with the above-mentioned coupling components in an alkaline aqueous solution or in ammonia vapor, but the azo dye obtained is reddish. This diazonium compound cannot be coupled with phloroglucinol under acidic conditions.

From the German Offenlcgschrift 1 572 106 and the USA patent 3 290 150 are benzene

where R is an alkyl radical having 1 to 5 carbon atoms. the radicals R ₁ and R ₂ , which can be identical or different. Are alkyl and / or aralkyl radicals and the alkyl radicals contain 1 to 5 carbon atoms or the radicals R ₁ and R ₂ together form a 5- or 6-membered saturated heterocyclic ring consisting of nitrogen, carbon and oxygen atoms, and X is an anion such as Cl -I Z ZnCl _2. -Cl ■ 1 2 CdCl ₂ , -Cl · 1/2 SnCl ₄ . --BF ₄ or - SO _{1 is} H.

To the particularly valuable trifluoromethylbenzol · diazonium salts. which are present, for example, as double salts with ZnCl, include the following compounds, in which the decomposition temperature is given in degrees Celsius and the absorption maxima in mu.

Diazonium compounds

Formula No. 1

3-Methoxy-4-N, N-dimethylamino-6-trifluoromethylbenzenediazonium chloride · 1/2 ZnCl ₂

N-

CF,

Y N Cl · I 2ZnCK

CH,

OCH.,

Formula No. 2

(146 to 147 C

(415 nij.

3-Butoxy-4-N, N-dipropylamino-6-trifluoromethylbenzene diazonium chloride 1/2 ZnCl ₂

(132 to 134 ((418 m

Formula No. 3

Formula No. 7

3-melhoxy-4- (N-methyl-N-benzyl) -aminü- 3-pentoxy-4- (N-pentyl-N-hydroxyüthyl) -annno-

6-trinuomethylbenzenediazonium chloride · 1/2 ZnCl ₂ 6-trinuomethylbenzenediazonium chloride · 1 / 2ZnCl

CH ₃

-ο- N ₂ Cl (1 1/2 ZnCl ₂ 10 Γ
OCH ₃ 14th up to 115 C) (424 ηΐμ) "5 Formula No. 4th

CF ₃

N- / V ^N 2 ^CI ■ 1 / 2ZnCl,

C ₂ H ₄ OH

(90 to 93 C) (418 to 420nvi)

Formula No. 8

Nlethoxy ^ -N.N -benzylamino-o-trifluoromethylbenzenium chloride 1/2 ZnCK 3-ethoxy-4- | N-methyl-N-peniyl) -amino-6-trifluoromethylbenzenediazonium chloride 1 2 ZnC

^ -CH-,

-CH ₁

CF,

N- / V NiCl · 12ZnCl ₂ OCH ₃

(428 to 430

C) CH,

N - <f ~ ' y- NiCl · 1 2 ZnCK

C ₅ H ₁₁ OC ₂ H ₅

(112 bi: 115 Ci (416 in A

35

Formula No. 5

Formula No.

3-Butoxy-4- (N-methyl-N-benzyl) -amino-6-irilluomethylbenzenediazonium chloride · 1 '2 ZnCl ₂

CH ₃

CF ₃

-N ₂ Cl 1 2ZnCl ₂

40

45

OC ₄ Ho

(101 to 102 C)

(425 HVa) 50 3-butoxy-4-morpholino-6-tr ^; fluoromethylbenzene diazonium chloride · I / 2 ZnCK

O H N

CF,

- / \ N, C1 · 1,2ZnCK

OC ₄ H _q

(125 Cl (413 to 415 πιί)

Formula No. 6

3-Phenoxy-4-N, N-dibenzylamino-6-trifluoromethylbenzene diazonium chloride · 1/2 ZnCl ₂

55 Formula No.

3-methyloxy-4-rnorpholino-6-trifluorine-methylbenzene diazonium chloride 1/2 ZnCK

CH,

CF ₃

60

1 / 2ZnCI ₂

(105 C) (430 to 432 mn) CH ₃ O ^ ^X N - /> - N ₂ CI · 1 / 2ZnCl ₂

OCH ₃

(135 C) (418 ma)

Formula No. I.

3-Ethoxy-4-pyrrolidinyI-6-trinuormei h> lbenzenediazonium chloride · 1/2 ZnCl ₂

CT ₃

H N- <

N ₂ CI 1.2ZnCl ₂

OC ₂ H ₅

(128 C) (420 to 423 in) These crystals are geUM in 200 ml of dioxane erstoffgas in the presence of a Rane \ - Niid-ÄSTo «reduced. After removing the Kilafyilon. and the dioxane is used as the residue

i 1 PnV. Oil aminocompound in a half g of 2 (5 ml of hydrochloric acid in 1000 ml of water and by adding a solution of 3 ml of water in 15 ml of water to the solution at between 0 and 5 ° C. After stirring for one hour, the solution is purified with activated charcoal, and 10 g of zinc chloride are added to the resulting mt-solution.

The trifluoromethylbenzene / .onium salts mentioned above can be used with any azo coupling component as used in diazotype photosensitive materials can be used to be coupled to form an azo dye.

The diazonium salts can be used in any wet, dry or thermal process and they can go through. Selection of suitable A / .ocoupling components any desired Form a color image, for example a black-2CS or blue color image.

The diazonium compounds listed above can be prepared in the following ways:

1. Preparation of the diazonium compound of formula No. 4

(3 - Methoxv - 4 - N, N - dibenzylamino 6 - irilluomethylbenzoldiazonium chloride 1 2 ZnCl _2. )

45 g of 3-nitro-4-chloro-trifluoromethylbenzene are dissolved in 200 ml of methanol and added to this solution a solution of i i g of sodium methylate in 100 ml of methanol at room temperature with stirring given. After half an hour, the reaction mixture is poured into 1000 ml of water, the deposited orange-colored, oily material separated and reduced by distillation Pressure cleaned. The distillate is 3-nitro-4-methoxytrifluoromethylbenzene with a boiling point of 152 to 153 C / 28 Torr. Yield 41g. This distillate is dissolved in 150 ml of dioxane and catalytically under Use of gaseous water in the presence of a Raney-NickCI catalyst with formation an amino compound reduced. After removal of the catalyst, 75 g of benzyl bromide and then an aqueous solution of 35 g of sodium acetate in 120 ml of water dropwise at a Temperature of 90 "C. The reaction is continued for 8 hours. The oily material obtained is distilled under reduced pressure. The distillate is 3-N.N-Dibcnzylamino-4-meth (\\ ytrilluormethylbenzol having a boiling point of 172 to 174 ° C / 1 Torr; Yield 28g.

This material is dissolved in 150 ml of acetic acid and then 6 g of 91% nitric acid are added dropwise nitrated into the solution at a temperature below 30 ° C. The crystals that form will filtered off. After recrystallization from ethanol, 2-nitro-4-methoxy-5-N, N-dibenzylaminotrifluoromethylbenzene is obtained with a melting point of 112 ° C in an expansion of 20 g.

üonsspitze des

428

2. The preparation of the diazonium bonds; of formula no. 5

(H-Butoxy-4- (N-methyl-N-benzyl) -amino-6-trifluoromelhyibenzoldiazoniu; .. ehlcrid · 1 2 / n;! ■,

45 g of 3-nitro-4-chlorotrifluoromethylbenzene become dissolved in 100 ml of butanol, and slowly emc solution of sodium butoxide (prepared from 5 g of metallic sodium in 300 ml of butanol) with stirring at room temperature admitted. Fs becomes 1 hour at 50 < The mixture is stirred, the butanol is distilled off and the residue , ο desti'licrt under reduced pressure. You get au! this way 3-nitro-4-butoxylrifiuormeth \ lben / o! with a boiling point of 145 to 146 C 10 "hu ι in a bulge of 47 g.

This distillate is dissolved in 150 ml of dioxane and treated with hydrogen gas in the presence of a rough nickel catalyst reduced to an amino compound. After removal of the catalyst, 100 ml of formic acid are added to the solution and the Mixture cooked. 3-Formanido-4-nitrooxytrium methylbenzene is obtained in the form of white crystals that have a melting point of 103 C. (Yield 43 g.) IUO ml of methanol and 25 g of dimethyl sulfate are added to these crystals and / u add dropwise to this mixture a solution of 14; j 4 <; Potassium hydroxide in 100ml methanol at a lemperaiur of 30 "C. Fs is stirred for 3 hours at 30 C and then the mixture in 50U ml Poured water. An oil separates out. that I solidified. This solid is separated and 2 hours Boiled in 200 ml of IO% hydrochloric acid. These*. Mixture is made alkaline by adding sodium carbonate while cooling. The severed ö! is extracted with ether and dried. After removing the ether, the residue is distilled This becomes 3-N-methylamino-4-butoxy-trifluoromethyl-benzene obtained with a boiling point of 150 to 152 C 8 torr in a yield of 28 g.

25.6 g of benzyl bromide and then a solution of 13 g of sodium acetate in 50 ml of water at a temperature of 90 ^° C. were added dropwise to the distillate dissolved in 100 ml of dioxane. After 5 hours the separated oil is distilled. 3- (N-methyl N -benzyl) -amino-4-butoxytrifluoromethylbenzene with a boiling point of 185 to 187 C / 2 Torr is obtained in a yield of 33 g. This distillate is dissolved in 150 ml of acetic acid, and 9 ml of 91% nitric acid is added dropwise to this solution at a temperature below 30 ° C.

7 y 8

The crystals obtained are filtered off and the invention is subsequently recrystallized using ethanol. To give 2 - nitro examples explained in more detail: 4-butoxy-5- (N -methyl -N - benzyl) -aminotrifluor- Example I methylbcnzol, melting point 115 C ^n, g in a yield of 26th These crystals are dissolved in 200 ml of 5 '-' ^nc photosensitive solution by mixing dioxane and prepared with hydrogen gas in the presence of the following ingredients, a Raney nickel catalyst is reduced to an amino. After removal of the catalysis mcthylbcnzoldia / .oniumsators and the dioxane, the residue of a m _{chlorj (J., Ss z,} solution of 100 ml concentrated hydrochloric acid in 500 ml to ii ",""uJ.n ·· _(l \ is

Dissolved water and by adding a solution of 5 g * on / sulfuric acid 0.4 ml

Sodium nitrite in 20 ml of water at a temperature », £ ·. , ' ^g

diazotized from 0 to 5 ° C. After 20 g of zinc- »ors.iurc I .U g

chloride has been added to this solution, one obtains ° ^cm · '"'',"."■!« ι

3-Butox _y -4- (N-mcthyl-N-bcnzyl) amino-6-trinuor- "Uopropylalkohol ■■ ··. ···· ^{2 <ml} °

methylbcnzoldiazoniumchlorid 1 / 2ZnCl ₂ with a "N _a tr.um-2,3-d.hydroxynaphthal.n-

Decomposition temperature from 101 to 102 C and a --sullonate 2.0 g

Absorption peak in the UV spectrum at 420 ηΐμ in water iuu ml

a yield of 25 g. With the light-sensitive solution, the upper

20 surface of a white paper coated. On that

3. The preparation of the diazonium compound is dried. The photosensitive

The formula # 10 material comes with a fluorescent lamp

imagewise exposed and then with ammonia vapor

p-Mcthoxy ^ -morpholino-o-trifluormclhyl- developed. A blue color image is obtained with a high

bcnzoldiazonium chloride ■ 1/2 ZnCl ₂ ) 25 density.

Dkscs photosensitive material also gives a

38.2 g of 3-amino-4-methoxytrifluoromethylbenzene give a high-density blue color image on wet development are in 100 ml of E. acetic acid anhydride for 1 hour gc- point of dry development, provided that one boils and this solution is poured into 300 ml of water. weakly alkaline aqueous solution used that 3-Acctylamino-4-mclhoxytrifluormcthylbenzol with 30 is prepared from the following ingredients.

a melting point of 133 "C becomes crystalline in potassium metaborate 3 b

obtained in a yield of 40 g. These crystals of potassium carbonate 1.5 _a

are dissolved in 150 ml of acetic acid and nitrated. Water 100 ml

by adding 15 ml of 91% igc nitric acid at a

Temperature below 30 C admits. The obtained Kri- 35 B c i s ρ i c 1 2

Stalls are filtered off and in 500 ml of 10% igcr

Hydrochloric acid boiled for 2 hours. This solution becomes a photosensitive solution by mixing

cooled and by adding sodium carbonate. of the following ingredients.

neutralized. One obtains i-nitro ^ -mcthoxy-S-amino- .VMcthoxy ^ -N.N-dibcnzylamino-

trifluoromethylbenzene with a melting point of ₄₀ 6-trifluoromethylbenzene diazonium

132 C in a yield of 34 g. This compound _chloride . , _{/ 2 ZnCU (Formc} , _{No. 4)} , -, "

is after a conventional method d.azoi.crl sulfuric acid (concT) 0 3 ml

and the resulting solution drop by drop in a boiling l-sic acid Vn »

- -.v -ti— : a ; "fflml W / niocr w in ^:"

UNU ".ν v." - "-""KÜnferiD chloride in 50 ml iüVoigcr _Kof f _cin 0.5 u

SäuVc ^ g ^ erί The brownish Kri- _{45 water} , 00 ml

stalls are made from ethanol "^" ^ "ΐ'Γ ^;",. ^ With the light-sensitive solution, the obcr-

4-methoxy-5-, hlortr, nuormcthy1benzol with unem ^. ^ ^ ^^. _H ,

Melting point of 84 to 85 "C is _dried in c.ncr yield ^. _The light-sensitive

obtained from 23 g. . w _nrnho i _in 8 hours 50 material is made in the same way as in example 1

This compound is in 40 g of morpholine »μ 5 ^^ _{and then developing in} a liquid

the cooked and then 111> 300 ml water gt ■ ^ _{ick, he unterwor} n f _e. the following from the Be

In this way 2 "™" ^ ™ ^ components are produced and a pH value before 5 - morpholinotrinuormethy benzene with _ an _{& 5} ^^ _{You get tfd VVeis (}

Melting point from 128 to 129 C as KnstaHe ^^^ _{Farbbüd with higher} density be, emc,

a yield of 21 g.

^m _t ^ jssä ^^^^^^ ™ o— ^ofT i? ^G

with ^Was 7 \ ^to _r X ₇ crt After removing the cataly- phloroglucine ⁿ ·? G

Red catalyst. mc ^ _residual sodium formate -4 ^g

^S m ^r M ^Un , ttTriir ^ "g sodium nitrite in a solution 60 _Natriu mbcnzoat JO g

ÄmnSSikrtcr hydrochloric acid in 250 ml of water _Natri u _m citr.t jog

_Diazo acid 0.1 g

Water. ^1OOml

o-trinuormcthylbenzoldiazoniumcmona -: '■ - - ⁶ ^ B c. s ρ 1 c I 3

with a decomposition temperature of I3> e un _{r wjfd mjt cjner Suspcns) on} ai

one ^ οφΐΐοη ^ ρη ^^ υν ^^ η ^ ν ^^, τίμ ^ ^ ^ ^ _{JQ g} p _{olyvinylacetatC} mul _S .on (40 «

in a yield of 25 g. 409 684/3

Keststoffgchalt) and 5 g of finely powdered silicon dioxide precoated and dried.

A photosensitive solution containing the following components is applied to this pre-layer, applied and dried.

3-liutoxy-4-N, N-dipropylamino-6-trifluoromethylbenzene diazonium chloride · 1/2 ZnCl ₂ (Formula No. 2) 1.0 g

Thiourea 1.0 g

Sodium 1,3,6-naphlhalin trisulfonate 1.5 g

Acetic acid 0.8 g

2.4.6- trihydroxy-3,5-dibromo-

benzocic acid 1.3 g

Water 100 ml

The light-sensitive material obtained is exposed to light in the same manner as in Example I and then subjected to thermal development at a temperature of 120 to 130 "C, for which purpose it is runs through hot rollers. It becomes a blue-violet cs High density color image obtained.

Example 4

For comparison, Diazotypicmatcrialicn are produced, exposed and developed containing diazonium compounds from the German publication 1 572 106 and the USA. Patents (document 3 290 150 are known. This shows that the

According to the invention, benzene diazonium chloride are far more sensitive to light and more reactive than dii known compounds, as can be seen from the following table.

Tested connection

3-Methoxy-4- (N-methyl-N-benzyl) -amino-6-trifluoromethylbenzene diazonium chloride 1/2 SnCl ₄ (according to the invention) ...

4- (N-methyl-N-benzyl) -amino-6-; rifluoromethyl-benzene diazonium chloride 1/2 SnCl ₄ (according to German Offenlcgschrift 1 572 106)

3-Methoxy-4- (N-methyl-N-benzyl) -amino-6-methyl-benzene diazonium chloride 1/2 SnCl ₄ (according to USA patent 3 290 150)

Density of the a / ofarbsto (Tes * l

full development

1.05

0.88

0.52

15 sec development

0.83

0.70

0.16

♦) The density of the azo-fuel (of the color picture) becomes less than one commercially available densitometer.

Claims (1)

Claim: Diazotype material which, in its light-sensitive layer, is a trifluoromethyl as a diazonium compound - contains benzo'diazonium salt, characterized in that the trifluoromethyl - benzene diazonium salt the general formula