DE1547969A1 - Heat developable photosensitive compositions and materials - Google Patents

Description

Armonk, N = Y. 10 504, USA

_{Heat developable 9} light-sensitive Zueaaunena amazed

and materials

The present invention relates to photosensitive, heat »developable a photosensitive Diaaoniumverbindung and a thermolabile _s containing compositions by the action of heat capable of coupling expectant compound.

Heat developable photosensitive diazo type compositions and »materials of various types are known * Some contain acid stabilizers, which are broken down by heat and also change the pH of the system. Others contain compounds that change when heated

decompose with the formation of a base and thus also change the pH value of the system up to a value at which the color formation reaction between the light-sensitive

90 984 7/0817

BATH ORIGINAL

bj & ue documents (α <?. ? £ ι Paragraph 2 No. ι sau, 3

lascivious

union salt and a coupling component present in the Zueanmeneetzung can take place. Other systems capable of developing more heat contain compounds which decompose in situ on heating to form coupling components which react with the light-sensitive diazonium salt.

According to the invention, the diazotype compositions contain and materials at least one compound of the general formula

? 5
R ₁ - CH ₉ - C - CH »R ₉

• ί s _c . d.

R ₃ R ₄

O O

in which R ₁ and R ₂ radicals -CN, -C-NHRg or -C-ΟΗγ and R ^, R ,, Rc, Rg and R ~ each a hydrogen atom, an optionally substituted alkyl radical with 1 to 8 carbon atoms in the chain or may represent an optionally substituted aryl radical.

The invention creates a new class of diachotype material-usable connections created through which the image quality and shelf life is improved, some of these compounds being advantageous can serve both as a pH modifier and as a coupler former

■ 9-0984 77 0817

These compounds work under the following conditions In advantageous catfish both as a coupler and partner as a pH modifier:

0 T) if both radicals R ₁ and Rg groups -C-OR «and Ry a

Are hydrogen atom; and

2) if one of the radicals R ₁ and Rg is a group -C-OH and

0 0

ti η

the other is a group -CN »-C-NHRg or -C-ORo.

When R ^ * R ₊ * H and R _{5 is} an alkyl chain from 1 to 8 carbon atoms in the chain, the compounds are predominant. pH modifiers when the other substituents are as follows:

R ₁ = R ₂ = 0 a) R- = O -C-OH -C-OH b) 0
-C-OH and c) and

O = -C-NHRg and

= -CN

909847 / OS 17

The 'temperature at which the present compounds react' to act via pH modifiers and / or coupler formers, soh varies depending on the nature of the substituents, but lies in the generally in the range between about 75 and about 200 ° C.

The essential components of the compositions according to the invention consist of a light-sensitive diazonium salt W or an Oemisoh such salts and a compound or an Oeffliaoh of compounds of the general formula

R ₁ -CH ₀ -C-CH-R ₀

• 2 ι ι 2

^R 3 ^R 4

In which the radicals R ₁ to Rr have the meanings given above.

The essential ingredients are usually in a solution of a filling resin in a volatile solvent and applied as a coating on a suitable substrate upset. Self-supporting materials can also be made by applying the composition as a layer to a temporary base, drying it and then peel off the filrc.

909847/0817

BATH ORIGINAL

The exact proportions of the ingredients are not critical, yet good results will be achieved by combining the Ingredients in the following general proportions aims:

Component wt Photosensitive diazonium

salt Q, 2-6.0

? ^R 5

R ₁ -CH ₂ -C-CH-R ₂ 1.0-20.0

Film-forming natural or

synthetic resin 5 * 0 - 40.0

Volatile solvent for

the resin rest

For best results, the composition can also be given quantities Up to a few percent of various other additives can be added, such as a stabilizing acid, cyanoguanidine, zinc chloride, thiourea and other base or Coupler builders.

A preferred recipe for satisfactory photosensitivity The composition borrowed according to the invention is the following:

9098 47/0817

BATH ORIGINAL

Component Qew .- $ t Photosensitive diazonium salt 0.5 - 5 %

OR ₅

R ₁ - CH ₂ ~ C - CH - R ₂ 5 - 20 %

R ₅ R ₄

Zinc chloride 0 - 1 % Thiourea 0 - 2 # Cyanoguanidine 0 5 % Stabilizing acid 0 - 5% Filra-making natural or

synthetic resin 5 - 15 %

Volatile solvent for that

Resin rest

Among coupler formers and / or pH modifiers, the are suitable for use in the present invention, the following are typical:

O OH O

1. HO-C-CH ₀ -C-CR-Cw OH

H H O OCH, C

2. HO - C - CH _n - C - CH - O - Ori

2 ι »

ριΐ «ι» ΟΠ, On,

ff ^OC 8 ^H 1 ₇ S

3. CoH ₄ "0 - C - CH ₀ - C - CH - C - OH

O 17 egg ι

C ₈ H ₁₇ CH ^

909847/0 817

BATH ORIGINAL

O OH

4. C ₆ H ₅ -0-C-CH ₂ -C- CH -C- OC ₆ H ₅

CHj CH ₅

0 OH 0

5. HgN -C-CH ₂ -C-CH-C-NHg

H H

HO OH OH

6. C ₄ H ₉ -NC-CHg-C-CH-CN- C ₄ H ₉

HH

7th ^C 6 ^H 5 H
t
- N 0
-C-CHg- OCH ₅
C CH
I f 0
π
- C ) H
r N CH ₅ CH, OH 8th. NC - CH ₂ -C-CH-
ft
HH CN 9. NC - CH ₂ OC ₈ H ₁₇
- C CH
I f - CN C ₈ H ₁₇ CH 10. NC - CH ₂ . C CH
ι ι - CN

O OH

11. HO - C - CH ₀ - C - CH - CN

CtI

H H

O OCH,

12. CH, 0 - C - CH ₉ - C - CH - CN

H H

O OH

13. C ₆ H ₅ -OC-CH ₂ -C -CH-CN

HH

909847/0117

O OCH,

14. H ₂ NC-CH ₂ -C-CH-CN

H H

HO OH

15. CGH ₁₇ -NC- CH ₂ - C - CH - CN

CH, CH,

HO OH

16 C _Ä Hc -HC- CH ₉ - C - CH - CN

O 5 2 ι ι

^ ₅

O OH O

17.HO - C - CH ₂ - C - CH - C - NH ₂ *

HH

O OCH ₅ OH

18. C ₂ H 1 O -C -CH ₂ -C-CH-CN

H H

O OH O H

19. C ₆ H 1 O -C -CH ₂ -C-CH-CN

0 OH 0

20. HOC - CH ₀ - C - CH ₀ - C - OH

CH ₅

O OH O

21. HOC-CH ₂ -C -CH-C-OH

H CH ₅

O OH O

22. HO - C - CH ₀ - C - CH - C - O - C (CH,)

2 ι ι J

H H

O OH

23. (CH ₅ ) ₅ C -OC-CHg-C-CH-CO

H H

9098Α7 / 0Ι17

24. CVl O
It
- C 2 OH
r
C -
t CH -
CH, 0
Il
C * ~ OH 25th NC - CH ₂ OH
I.
-C- CH - 0
η
. C - OH CH ^ CH ₃ 26th NH ₂ O
η
- C - CH ₂ OH
t
- C -
t
H • CH
I.
H 0
Il
-C- OH 27 NC - CH ₂ OH
- C -
CH, CH -
ι
H 0
I »
. C - OH

0 OH 0

28. NH ₀ - C - CH ₀ - C - CH - C - OH

H H

CH 0

29.NC-CH ₂ -C-CH-C-NHR (RH or alkyl)

CH,

Under the influence of heat, certain of the present compounds form a component which is capable of coupling with a light-sensitive diazonium salt. It is assumed that the coupling component is generated by splitting off water, an alcohol or a phenol, formed by the radical RjO and a hydrogen of fat (ob) from the carbon atom to which Rj is bonded, when R _{2 is} hydrogen atom, the dehydration can occur in the direction, depending on the type of R ₁ and

909847/0817

- ίο -

R, take place. If R- is a hydrogen atom, the minor is

2 ^p

product water, and, when R, - is an alkyl or aryl radical, is the by-product is an alcohol or a phenol. The elimination of water is accompanied by the formation of a double bond between the carbon atoms to which the groups R- * and R ^ are bound. This in turn leads to the formation of an active methylene group on the carbon atom adjacent to _{R 1.} When R ^ is hydrogen, the active methylene group R <or Rg may be adjacent.

It should be noted that the invention is not intended to depend on the correctness of the reaction theory established is only an attempt to explain the mechanism by which couplers are produced by heating the instant compounds can be.

Conventional photosensitive diazonium salts which are stable at exothermic temperatures and which couple with the couplers produced by the present compounds can be used in the compositions of the present invention. To such Diazonium salts include, for example, p-Dlazodimethylaniline zinc chloride (full salt) [p-diazodimethylaniline full zinc chlorides], p-diazodiethylaniline zinc chloride (full salt) and - 1/2 zinc chloride, p-diazo ~ N-ethyl-N-hydroxyethylaniline

909847/0817

BATH ORIGINAL

1 / S zinc chloride, p-diazo-N-methyl-N-hydroxylthylaniline 1/2 zinc chloride, p-dlazodiphenylamine sulfate, p-diazo-2,5-diethoxy-benzoyl aniline 1/2 zinc chloride, p-dlazo -1-morpholnobenzol · 1/2 zinc ohlorld, p-diazo-2,5-dinethoxy-1-p-toluylHnercaptobenzol · 1 / 2ZInIcOhXOrId, 2,4,5-trlethoxy-diphenyl ~ 4-diazonium oxalate and

The following examples explain the invention without inferring it. .

example 1

100 ml solution of the following composition are prepared:

Beatand part

p-Diazodieethylanilln zinc chloride (full salt)

Weight ~

OH

HO - C - CH ₀ - C - CH - C - OH 2 ι t

H H

Polyynyl butyral resin methanol

10 %

ίο α

Rest for 100 ml of solution

The solution is applied as a layer to a transparent polyethylene terephthalate base and left in the air for 24 hours

909847/0817

BATH ORIGINAL

dried. The resulting material is tielichtet durv.h a negative and then developed by heating with infrared radiation while seconds at a temperature of 150 ⁰ C.

Example 2

Be prepared 100 ml of solution of the following composition:

Component Qew .- <

p-diasodiethylaniline

Zinc chloride (full salt) 6.0 %

0 OH 0 H ₂ NC-CH ₂ -C-CH-C-NH ₂ 20.0 %

HH thiourea 2.0 %

Citric acid 3.0 % Tin carbide 1.0 % Cellulose acetate butyrate 13.0 % Aoetone, methyl ethyl ketone and Methanol (1 t 1 % 1) remainder for

■ 1 line

The solution is applied to the Arbeltswelse of Example 1 as a layer, dried, exposed and developed old except that the Bntwioklungetemperatur is 18O ⁰ C.

909847/0 * 17

ORIGlNAL BATHROOM

Example 3

Ea 100 ml of solution of the following composition are prepared:

Ingredient wt .- #

p-diazo-2,5-diethoxybenzoyl-

aniline. 1/2 zinc chloride 3.0

? ^C 6 ^H 5 NC - CH ₀ - C CH - CN 10.0

Tartaric acid 1.5 %

Thiourea 0.5 % Zinc chloride 0.5 S ^ Cyanguanidine 2.0 # Polyvinyl butyral resin 20.0 % Methanol remainder for

ml of solution

The solution is applied as a layer as in Example 1, dried, exposed and developed.

Example fr

100 ml of solution of the following composition are obtained represents:

909847/0817

BATH ORIGINAL

«. 14 -

Part of Gcw.-g

p-Diaxo-1-norpholinobenzene

. 1/2 zinc chloride 5.0 %

0 OH

H f

CaHr-OC - CH ₀ - C - CH - CN 15.0 #

H H

Thiourea 1.0 %

Tartaric acid. 2.5 %

Zinc chloride 0.2 % Cellulose acetate 20.0 % Acetone, methyl ethyl ketone and Methanol (1: 1: 1) balance for

ml of solution

The solution is applied as a layer as in Example 1, ge dries, exposed and developed.

Example 5

5s 100 ml of the following composition are made:

Component Qew .- #

p-Diazodiphenylaaine sulfate 4.0 %

HO OH - M - C - CH ₂ - C-CH-CN 13.0 %

Thiourea 1.0 %

Tartaric acid 3.0 %

90984 7/0817 baq original

Component part üew.-ff

Zlnkohlorld 0.5 %

Polyvinyl butyral 15.0 %

Methanol remainder for

ml of solution

As in Example 1, the solution is applied as a layer, dried, dried and developed.

Example 6

■! Solution of the following additions are made

Component Pew .- *

p-Diasodiaethylanllln-

Zlnkohlorld (full salt) 3.0 %

0 OH 0

HO - C ■ - CH ₂ - C - CH - C - HH ₂ 10.0% HH

Thiourea 1.0 % CltraoonsMure 5.0 % Zinc chloride 0.4 %

Polyvinyl butyral 15.0 %

Methanol remainder for

ml of solution

The ventilation is applied as a layer as in Example 1, dried, exposed and developed.

909847/0817 _woWW t

When the particular compound of the invention is above all a coupler, it is necessary to add a base builder to the composition. In Examples 3 and 5, for example, cyanguanidine and thiourea fulfill this puncture.

The compositions of the invention are for manufacture all kinds of photosensitive heat-developable materials " such as copy papers, films and the like «through ) Heat development can be developed alone, extremely valuable. The main advantage of the compounds used in the invention is that they result in exceptionally stable dlazo compositions and thus those with them Materials obtained from compositions have a long shelf life. In the case of those connections «which both Coupler formers as well as pH modifiers are “if the preparation of the preparations is also simplified” there only a substance is needed to fulfill both punctures.

909847/0117 bathroom ORIGINAL

Claims (1)

- 17 claims U photosensitive, heat developable ^ a photosensitive Diazonium compound and a thermolabll @ »by action Compound that becomes capable of coupling by heat Composition »characterized by a content of at least a compound of the general formula R ₁ - CH ₂ - C - CH - ■ h Ä O O- in which R ₁ and R ₂ radicals -GN, -C-NHRg or -C-OR, and R, _s R ₁ ^, Rc »Rg and Ry Wasserst of i'afcenia, substituted or unsubstituted alkyl radicals with 1- 8 carbon atoms in the chain or substituted or unsubstituted aryl radicals mean « 2 «Composition according to claim 1« characterized in that that they 0.2 to 6 wt ° - $ £ photosensitive diazonium compound, 1-20 weight ₀ - # compound of formula I 5-40 Gewo ~ $ film-forming resin and the remainder contains a volatile solvent for the resin 3. Composition according to claim 1 or 2, characterized in that that it contains a compound of the formula Σ for 0 ft which both R ,, and Rg represent a group -C-OH ο , 909847/0817 Documents (Art. 7 § j Abs. 2 Ur l Sau α , _w Anderungsges. V. 4, S. JUg ^ BATH 4 «Light-sensitive, heat-developable diazotype material with an underlay and a cover on at least one part of at least one surface of the base »characterized in that the coating is after evaporation of the volatile Solvent-obtained residue of a composition according to any one of claims 1 to 3 5ο Light-sensitive, heat-developable diazotype material, characterized by a self-supporting film containing the residue obtained after evaporation of the volatile solvent a composition according to claim 2 or 3 contains « 909847/0 817