DE2149746B2 - - Google Patents

Description

N-

-N ₁ X

OR

-Cl · 1/2 CdCl ₁ .
-SO ₃ H is.

diazonium salts, which in the 6-position are a TriBuormeihyl- or methyl group are known, but they 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 having 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 ₁ together form a 5- or 6-membered saturated heterocyclic ring consisting of nitrogen, carbon and oxygen atoms, and X - Cl -1'2ZnCU.

■ -C1 · 1-2 SnCl., -BF, or

The invention relates to a diazotype material which is used in its photosensitive layer as a diazonium compound cm Trinuormeihyi-btrizoldiazoniumsal /. contains.

Usually this is done in a wet development process the coupling of a diazonium compound with an azo coupling component in one carried out weakly alkaline or weakly acidic aqueous solution and in a dry development process or in a thermal development process with dilute ammonia vapor or worked at low temperatures.

As is known, the highly photosensitive and reactive diazonium compounds are benzene / .onium salts 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 -dibcnzyU couples amino - 5 - buloxybenzene diazonium chloride (ZnCL double salt) with azo coupling components such as 1-naphthol-4-sulfonic acid. Sodium 2,3-dihydroxynaphthalene sulfonate and 2 - hydroxy - 3 - (hydroxyäthylamino) naphthoic acid in an alkaline one aqueous solution or in ammonia vapor and forms a purple azo dye. This diazonium compound must also be used to form a black color Phloroglucinol can be coupled in an alkaline aqueous solution with heating. Linier these terms However, one does not get a black azo dye, but a bluish-black dye, which has only a low density.

2-ChIOr - ^ - N.N-diethylamino-5-methoxybcnzoldiazoniumchlorid couples with the above-mentioned coupling components in alkaline aqueous soldering 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 Official Journal 1 572 106 and U.S. Patent 3,290,150 are Bcnzol-

35

• 10

45 has. where R is an alkyl radical having 1 to 5 carbon atoms, the radicals R ₁ and R ₁ . can be the same or different from you. Alkyl and / or Aralkylres'.e are and the alkylresie 1 to 5 carbon atoms. Or the radicals R ₁ and R ₂ together form a 5- or 6-g-sized saturated heterocyclic ring made of nitrogen. Consists of carbon and oxygen atoms, and X is an anion such as - -Cl-I 2 ZnCl ,. -Cl · 1/2 CdCU.-Cl · 1.2 SnCl _4. -BF ₄ or - SO ₃ H.

The following compounds belong to the particularly valuable trifluoromethylbenzene diazonium salts, which _{are present, for example, as double salts with ZnCl 2, where;} into the decay temperature in Gnu! Celsius and the absorption maxima in ηΐμ are given.

Diazonium compounds
Formula No. 1

3-Methoxy-4-NN-dimethylamino-6-irifluoromethylbenzene diazonium chloride ■ 1 2 ZnCl ₂

CH,

CF ₁

'Ν - f

-N ₁ Cl · LIZnCU

CH ₃

OCHj

Formula No. 2

(146 to 147 Ci (415 m; i.)

; ^ Buloxy-4-NN-dipropylamino-6-triniiorrnethvlben / oldia7oniumchlorid ■ 1 2 ZnCl ₂

6O C ₃ H-

VN ₂ Cl ■ 1 2ZnCl ₂

(132 to 134 C) (4IS mO

Formula No. 3

Formula No. 7

3-Methoxy-4- (N-methyl-N-benzy!) - amino-6-trifluoromethylbenzene-jazonium chloride 1 / 2ZnCU 3-penioxy-4- (N-pentyI-N-hydroxyethyI) -amino-6-trifluoromethylbenzenediazonium chloride 1 / 2 ZnCI ₂

CH ₃

CF ₃

N-

-N ₂ C! -1 / 2ZnCl _{2 I0}

OCH ₃

(114 to 115 C)

(424 πΐμ) ' ⁵

OC ₅ H

5 ¹ ml

: i 1/2 ZnCl ₂

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

Formula No. 4

Formula No.

J-Methoxy ^ -N.N -benzylamino-o-trifluoimethylbenzenediazonium chloride 1 / 2ZnCK 3-ethoxy-4- (N-methyl-N-pentyl) -amino-6-trifluoromethylbenzenediazonium chloride · 1 / 2ZnCK

(' VCH,

- NXl ■! 2ZnCl ₂

OCH,, ο

(95 C) (428 to 430 mu)

Formula No. 5

3-Butoxy-4- (N-methyl-N-benzyl) -amino-6-trifluorinethylbenzenediazonium chloride 12 ZnCK

CH,

CF ₁

N- f SN ₁ Cl ■ 1 / 2ZnCl ₁

35

40

45

/ V

CH ₂

OC ₄ H _n

(101 to 102 C)

(425 m.J so

Formula No. 6

3-Phenoxy-4-N, N-dibenzylamino-6-tri) 1uormethylbenzene diazonium chloride 1/2 ZnCK

55

N- ^ f \ -N, CI · 1 / 2ZnCK

(105 C) (430 to 432 mu) CH ₃

N—
/
C ₅ H ₁₁

^ 'SN ^ Cl ■ 1 / 2ZnCl ₁

OC ₁ H,

(112 to 115 C) (416 in · ;.)

Shape! No. 9

3-butoxy-4-morpholino-6-trifh] ormelethylbenzenediazonium chloride · 1/2 ZnCl ₁

CF,

TT'n - / S-- N ₂ Cl ■ 1 / 2ZnCl ₁

!
OC ₄ H ₉

! 125 C (413 to 415 mu

Formula No. 10

3-Methoxy-4-rnorpholino-6-trifluorimelhvlbenzenediazonium chloride ■ 1/2 ZnCK

OHN-

₂ Cl · 1 / 2ZnCl ₂

OCH,

(135 C

Shape! No. Il

S-ethoxy - ^ - pyrrolidinyl-o-trifluoromethylbenzenediazonium chloride 1/2 ZnCU

-N, CI 1 / 2ZnCl,

(128 C) (420 to 423 ηΐμ)

OCH ₅

The trifluoromethylbenzene diazonium salts listed 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 type of wet, dry or thermal process and they can be any desired by selecting suitable azo coupling components Form a color image, for example a black 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

13 - Methoxy - 4 - N.N - dibenzylamino - 6 - irifluoromethylbenzenediazonium chloride ■ 1 2 ZnC '! -.)

45 g of 3-nitro-4-chlorotrifluoromethylbenzene are dissolved in 200 ml of methanoi and added to this solution dropwise a solution of 11 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 Dcstilla! is 3-nitro-4-methoxy-trifluoromethylbenzene with a boiling point of 152 to 153 ° C / 28 Torr. Yield 41g. This distillate is dissolved in 150 ml of dioxane and catalytically using gaseous hydrogen in the presence a Raney nickel catalyst to form a / \ mino connection reduced. After removal of the catalyst, 75 g of benzyl bromide are uirJ then an aqueous solution of 35 g of sodium triacetate in 120 ml of water added dropwise at a temperature of 90 ° C. The reaction will Continued for 8 hours. The obtained oily material is distilled under reduced pressure. The distillate is 3 "N, N-dibenzylamino-4-mclhoxylrinuomethylbenzene 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 nitrated by dropping 6 g of 91% strength nitric acid into the solution at a temperature below 30 ^{° C.} The crystals that form are filtered off. After recrystallization from ethanol, 2-nitro-4-methoxy-5-N, N-dibenzy laminotrifluoromethylben-ol with a melting point of 1.2 ° C. is obtained in a yield of 20 g.

These crystals are dissolved in 200 ml of dioxane and treated with hydrogen gas in the presence of a Raney nickel catalyst reduced. After removing the catalyst and the dioxane, the residue is

The oily amino compound obtained in an aqueous solution of 200 ml of hydrochloric acid in 1000 ml of water and dissolved by adding a solution of 3.5 g Sodium nitrite in 15 ml of water to the solution at a temperature between 0 and 5 ° C diazciier.

ίο After stirring for a little while, the solution becomes with Purified activated carbon, and 10 g of zinc chloride are added to the resulting reddish solution. In this way, 15 g of orange crystals of 3-methoxy-4-N, N-dibenzylamino-6-trifluoromethyl-

benzene diazonium chloride ■ 1/2 ZnCl ₂ with a decomposition temperature of 95 ° C and an absorption peak of the UV spectrum at 428 ηΐμ.

2. The preparation of the diazonium compound
of formula no. 5

(3-Butoxy-4- (N-methy 'N-benzy!) -Amino-6-trifluoromethylbenzene diazonium chloride ■ 1/2 ZnCK)

45 g of 3-NittO-4-chlorotrifluoromethylbenzene are dissolved in 100 ml of butanol, and slowly a solution of sodium butoxide (prepared from 5 g of metallic sodium in 300 ml of butanol) with stirring at room temperature admitted. It is stirred for 1 hour at 50 C, the butanol is distilled off and the residue

, ο distilled under reduced pressure. One receives on in this way 3-nitro-4-butoxytrifluoromethylbenzene with a boiling point of 145 to 146 C 10 Torr in a yield of 47 g.

This distillate is dissolved in 150 ml of dioxane and treated with hydrogen gas in the presence of a Rane \ - Niekel catalyst reduced to an amino compound. After removing the catalyst, 100 ml of formic acid are added to the solution and the Mixture cooked. 3-Fori; iamido-4-but-

. ₄ o oxytrifluoromelhylbenzene in the form of white crystals with a melting point of 103C. (Yield 43 g.) 100 in! Methanol and 25 g of dimethyl sulfate are added, and a solution of 14 g of potassium hydroxide in 100 ml of methanol at a temperature of 30 ° C. is added dropwise to this mixture. It is stirred for 3 hours at 30 ° C. and then the mixture is poured into 500 ml of water. An oil separates out. that solidifies. This solid is separated and 2 hours

cooked in 200 ml of 10% hydrochloric acid. This Mixture is made alkaline by adding sodium carbonate while cooling. The severed Oi is extracted with ether and dried. After removing the ether, the residue is distilled It becomes 3-N-Mci'nylamino-4-butoxylrirluormethy! - 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 are added to the distillate dissolved in 100 ml of dioxane, followed by one dropwise

to solution of 13 g of sodium acetate in 50 ml of water at a temperature of 90 ⁰ C given. After 5 hours, the separated oil is distilled. 3- (N-methyl-N-benzyl) -amino-4-butoxytriftuormethylbenzene 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 'M'Oigc nitric acid are added dropwise to this solution at a temperature below 30 ° C.

• 7-les
nd
en
he
G

rt.
lit
• 1-n.

■ I- r-

2

The crystals obtained are filtered off and removed Recrystallized ethanol. You get 2 - nitro-

4-butoxy -5- (N-methyl-N-benzyl) -aminotrifluoromethylbenzene, Melting point 115 "C, in one yield from 26 g. These crystals are dissolved in 200 ml of dioxane and with hydrogen gas in the presence a Raney nickel catalyst to an amino compound reduced. After the remover, the catalyst and the dioxane, the residue is in a Solution of HK) ml of concentrated hydrochloric acid dissolved in 5 (K) ml of water and by adding a 1 solution of 5 g Sodium nitrite in 20 ml of water at a temperature of 0 to 5 C diazotized. After getting 20 g of zinc chloride added to this solution. 3-butoxy -4- (N -methyl-N -benzyl) -amino-6-tritium- ι ς is obtained methylben / oldia / .onium chloride 1'2Ζη (I, with a Decomposition temperature from 101 to 102 C and an absorption peak in the I 'V spectrum at 420 ηΐμ in a yield of 25 g.

3. The preparation of the diazonium compound
of formula No. 10

(.VMethoxy ^ -inorphulino-ft-trifluoromethyl-

hcnzoldiazonium chloride 1 2 ZnCl ₂ )

38.2 g of 3-amino-4-methoxytrifluoromcthyibenzene are boiled in 100 ml of acetic anhydride for 1 hour and this solution is poured into 300 ml of water. 3 - Acetylamino - 4 - methoxytrifluoromethylbenzene with _{a melting point of 133 °} C. is crystalline in a yield of 40 g. These crystals are dissolved in 150 ml of acetic acid and nitrated by adding 15 ml of SH'Oigc nitric acid at a temperature of less than 30 ° C. The crystals obtained are filtered off and boiled in 500 ml of 10% hydrochloric acid for 2 hours. This solution is cooled and neutralized by adding sodium carbonate. 2-Nitro-4-methoxy-5-aminotrifluoromethylhenzene with a melting point of 132 ° C. is obtained in a yield of 34 g. This compound is diazotized according to a conventional method, and the resulting solution is poured dropwise into a boiling solution of 20 g of copper (I) chloride in 50 ml of 20% hydrochloric acid. The brownish crystals obtained are recrystallized from ethanol. 2-Nitro- 4-methoxy-5-chlorotrifiuormethy ^ benzene with a melting point of 84 to 85 ° C. is obtained in a yield of 23 g .

This compound is boiled in 40 g of morpholine for 8 hours and then poured into 300 ml of water. In this way, 2-nitro-4-methoxy-

5 - morpholinotrifluoromethylbenzene with a melting point of 128 to 129 C as crystals in a yield of 21 g. These crystals are dissolved in 200 ml of ethanol and reduced to the amino compound with hydrogen gas in the presence of a Raney nickel catalyst. After the catalyst and the solvent have been removed, the residual oily material is diazotized with 5.5 g of sodium nitrite in a solution of 50 ml of concentrated hydrochloric acid in 250 ml of water at a temperature of 0 to 5 ° C. 10 g of zinc chloride are then added to this reaction mixture 3-Methoxy-4-morpholmo- 6-trifluoromethylbenzenediazonium chloride - 1/2 ZnCl _{2 is obtained} with a decomposition temperature of 135 ² C and an absorption peak of the UV spectrum of 418 μm in a yield of 25 g.

746

The invention is explained in more detail below using examples:

example 1

A photosensitive solution is prepared by mixing the following ingredients.

. ^ - Melhoxy ^ -morpholino-trifluoroniethylben / okliazonium-

chloride ■ 1 2 Zn (I ₂ (Formula No. 10) 1.0 g

Kon /. Sulfuric acid 0.4 ml

Acetic acid 4.0 12

Boric acid 1.0 u

Kofi in 0.5 g

Isopropyl alcohol 2.0 ml

Sodium 2,3-dihydroxynaphthalene

6-sulfonal '2.0 g

Water KX) ml

The surface of a white paper is coated with the photosensitive solution. On that is dried. The photosensitive material thus obtained is exposed to a fluorescent lamp imagewise exposed and then cn ^ Aickclt with ammonia vapor. A blue color image is obtained with a high Density.

This light-sensitive material also gives a high-density blue color image upon wet development Place of dry development. provided that a weakly alkaline aqueous solution is used, the is made from the following ingredients.

Potassium metaborate 3 g

Potassium carbonate 1.5 g

Water 100 ml

Example 2

A photosensitive solution is prepared by mixing the following ingredients.

3-Melhoxy-4-N.N-dibcnzyUiniino-6-trifluoromethylbenzoldiazonium-

chloride · 1 2 ZnCl _: (Formula No. 4) 1.2 g

Sulfuric acid (con /.) 0.3 ml

Acetic acid 5.0 g

Caffeine 0.5 2

Water 100 ml

The surface of a white paper is coated with the photosensitive solution. This is followed by drying. The light-sensitive material thus obtained is exposed to light in the same manner as in Example i and then subjected to development in a liquid developer which is prepared from the following ingredients and has a pH of about 6.5. In this way, a high-density black color image is obtained at a high developing speed.

Thiourea 1.0 g

Phloroglucine 0.7 g

Sodium formate 1.4 g

Sodium benzoate 2.0 g

Sodium citrate 4.0 g

Citric acid 0.1 g

Water 100ml

Example 3

White paper will
100 ml water,

2

Solids content) 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.

S-butoxy ^ -N.N-dipropylamino-

6-trifluoromethylbenzenediazonium

Chloride · 1/2 ZnCl ₂ (Formula No. 2) 1.0 g

Thiourea 1.0 µ

Sodium-1,3.6-naphlhalintri-

sulfonate 1.5 g

Acetic acid 0.K g

2,4,6-trihydroxy-3,5-dibromo-

benzoic acid 1.3 g

Water H) OmI ' ^s

The light-sensitive material obtained is exposed to light in the same manner as in Example 1 and (LiIiti a thermal development at a Teni temperature Subjected from 120 to 130 C where / u man it runs through hot rollers. Ice turns blue-purple High density color image obtained.

B c i s ρ i c 1 4

For comparison, diazotype materials are produced, exposed and developed which contain diazonium compounds, which are known from German publication 1 572 106 and US Pat. It can be seen that the -> ₀

746

10

Benzoldiazoniumchloridc according to the invention are far more light-sensitive and reactive than the known compounds, as can be seen from the following table.

ι .. 'tested Vcrbiiuluiit!

3-Methoxy-4- (N-methyl-N -benzyl) -amino-6-hydroxyl alcohol / oldia / .onium chloride · 1 / 2SnCl ₄ (according to the linkage). . .

4- (N-methyl-N-benzyl) amino-6-trifluoromethyl] benzene / oldiazonium chloride I 2 SnCl ₄ (according to German publication 1 572 106) ". .." .....

3-Methoxy-4- (N-methyl-N-benzyl) -amino-6-diethylbenzyl / .oldia / .onium chloride · 1 2 SnCl ₄ (according to US Pat. No. 3 290 150)

Density of Λ / ofLirbstofTcs *) ISSek.-

l ^: .nt «iekling

1.05

O.KS

Finishing

0.83

0.70

0.52

0.16

*) The density of the a / of; irbslofTcs (of the l-arbbildcsl is with a commercially available densitometer.

-P-

Claims (1)

Claim: Diazotype material which has a trifluoromethyl in its photosensitive layer as a diazonium compound - Contains benzene diazonium salt, characterized in that the trifluoromethylbenzene diazonium salt the general formula R, CF ₃