US2374563A - Stabilized diazo-type sensitive material - Google Patents

Description

- component.

Patented Apr. 24, 1945 UNITED '-\STATES PATENT oFri-c STABILIZED DIAZO-TYPE SENSITIVE MATERIAL No Drawing. Application December 4, 1942, Serial No. 467,902

13 Claims.

This invention relates to the stabilization of light-sensitive layers which are produced by the incorporation of a diazo compound as the lightsensitive medium onto the surface of a suitable carrier base. 7 More particularly, it refers to the stabilization of so-called d'ry development diazotype light-sensitive layers wherein the diazo compound is a diazo compound derived from ortho or para aminonaphthol or from N-monoor di-substituted aromatic para-diamines, which diazo compound is incorporated into the light-sensitive' layer, together with an azo dyestuff coupling Various processes are known for the preparation of light-sensitive layers which depend upon the use of a diazo compound as the light-sensitive medium, and various materials have been employed for the carrier of the light-sensitive with the diazo compound, the development of the.

dyestufl forming the image is eilected by bringing the exposed light-sensitive layer into contact with.

ammonia gas. This is known as the ing process. v

The dyestuflf components, as applied on the carrier, are relatively unstable and cannot be stored for long periods prior -to use. The lightdry developsensitive layers which carry the coupling component as well as the diazo compound in the light-sensitive layer are subject to premature.

coupling of the said dyestufl components as well as decomposition of the diazo compound upon long storage. Many attempts have been made to obtain more stable coating solutions and to render the light-sensitive layers produced therefrom less sensitive todeterioration without imcompound upon which the production of 'aocu- The sensitized pairing the light-sensitive qualities of the diazo rate images from the original depends. These attempts have hitherto been relatively unsuccessful. It is therefore the object of this invention to provide coating solutions and light-sensitive layers, using diazo compounds as the lightsensitive medium which can be stored for long periods prior to use and will be stable during storage even under unfavorable conditions.

I have found that coating solutions and. the

10 light-sensitive layers prepared therefrom can be stabilized against decomposition of the lightsensitive materialand premature coupling of the dyestufl components by adding to the coating solution a compound of the following class: saturated and unsaturated gamma lactones of the following general formulae:

I g O X\ ZI Y o o-a Y l 0 H =o so X Y l n 40 o BIC- 0 H: C V a 11.

wherein X is a member of'the group consisting of H, OH, COOH and alkyl, Y is a member of the group consisting of H and alkyl, Z is a. member of the group consisting of H and OH, R is a lower alkyl radical, this a member of the group consisting of H and COOH, and All; means alkylene.

Examples of such compounds are: 1. Gamma-valero lactone Gamma-valero lactone -y -carbonic acid HaC- mo coon 3. 'y-Dihydroxy lactone of the gamma-hydroxy crotonic acid 4. 'y-Dihydroxy lactone of the gamma-hydroxy p-methyl crotonic acid OH. OH

. a-Angelica lactone 6. p-Angelica lactone Example! 2.1-diazo-hydroxy-naphthalenesulfonic acid "parts... 14.0 Concentrated hydrochloric acid parts by volume- 7.0 Nickel sulp j arts" 31.5 Phloroglucine do 4.9

Thiourea 'do' .200

The following are dissolvedin 1000 cc. of water. To this coat-' I ing solution there are added 10.2 grams of gamma valero lactone per liter. This solution is then spread on paper, fabric, film or the like by the v usual coating method for the production of diazo type light-sensitive layers, using a doctor blade to insure a thin even coating. After storage at room temperature for several months, the stability of the sensitized material containing the gamma valero lactone was tested by exposing a. test piece to light under a suitable diapositi've and developing the image by application of ammonia gas. The resulting image reproduced on the light-sensitive layer containing the gamma valero lactone was compared with the image reproduced under the same conditions on a light-sensitive layer made from the same coating composition but containing no gamma valero lactone which latter had been stored under the same conditions for the same length of time. The background and consequently the contrast of the image reproduced on thelight-sensitive layer made in accordance with this example is superior to that of the sample which doesnot contain the gamma valero lactone in the lightsensitive layer.

' Example II v The composition of the coating solution is the same as in Example I but as a stabilizer 13.4 grams of gamma valero lactone 'y carbonic acid per liter are used instead of the gamma valero the above class show greatly improved solution not containing a gamma lactone stabil- 'coating made from a solution gamma lactone stabilizer.

v ing, storage lactone. The coating, storage and testing procedures are the same as in Example I. The stability of the coating made according to this example was found to be superior to that of a Example III The composition of the coating solution is the same as in Example I but as a stabilizer 10.4

grams of the 'y di-hydroxy lactone of gamma-.

hydroxy crotonic acid per liter are used instead of the gamma valero lactone. The coating, storage and testing procedures are the same as in Example I. The stability of the coating made according to this example was found to be superior to that of a coating made from a solution notcontaining a gamma lactone stabilizer.

Example IV The composition of the coating solution is the same as in Example I but as a stabilizer 11.8 grams of the 'ydi-hydroxy lactone of gammahydroxy betamethyl crotonic acid per liter are used instead of the gamma valero lactone. The coating, storage and testing procedures are the same as in Example I. The stability of the coating made according to this example was found to be superior to thatof a coating made from a izer.

Example V I The composition of the coating solution is the same as in Example I but as a stabilizer 8.7 grams of alpha-beta-angelica lactone are used instead of the gamma valero lactone. The coatand testing procedures are the same as in Example I. The stability of the coating made according to this example was found to be superior to that of a coating made from a solution not containing a gamma lactone stabilizer.

not containing a- Example v1 I Parts Zinc chloride double salt of the diazo-compound obtained from N-ethanol-ethyl are dissolved in 1000 cc. water. To this solution there are added 10.2 grams of. gamma valero of the gamma valero lactone. The coating, storage and. testing procedures are the same as in Example VI. The stability of the coating made according to this example was found to be superlor to that of a coating made from a solution not containing a Eamma lactone stabilizer.

amino-i-aminobenzene 10.5 Citric acid I i l I 50.0 2.3-dihydroxy-naphthalene 5.9

Thiourea 45.0 The sodium salt of the naphthalene-1.3.6

trisulfonic acid 32.5 Aluminum sulphate 6.9

Example X The composition of the coating solution is the same as in Example VI but as a stabilizer 8.7 grams of alpha-beta-angelica lactone per liter are used instead of the gamma valero lactone.

lactone per liter. The solution is then spread on a suitable base, such as paper, fabric, fllm or the like by the usual coating method in the same manner as described in Example I. The lightsensitive layer thus produced is then stored at room temperature for several months and its stability is then tested by observing the appearance of color in the light-sensitive layer due to premature coupling of the dye components and by comparison of its light-sensitive qualities with those of a test sample prepared and treated in the same manner as the light-sensitivelayer of this example but omitting the gamma valero lactone stabilizer. When so tested, it was found that the light-sensitive layers made in accordance with this example show a negligible amount of coloring due to premature coupling of the dye components after the storage period, whereas,

light-sensitive layers made from the same solu-. tion but not having the gamma valero lactone stabilizing agent, under the same conditions, show a considerable amount of coloring due to premature coupling. It also was found that upon ex osure to light under a suitable diapositive and The coating, storage and testing procedures are the same as in Example VI. The stability of the coating made according to this example was found to be superiorto that of a coating made from a solution not-containing a gamma lactone stabilizer.

Various changes may be made in the details 0 of my invention as described in the foregoing development of the image by application of a'mmonia gas, the light-sensitive layers of this example produce images having better definition and less background color than do light-sensitive layers not having the gammavalero lactone staspeciflcation within the, scope of the claims appended hereto without sacrificing the advantages of my invention.

. Example XI Parts Zinc chloride double salt of the diazo-compound obtained from N-mono-ethyl- To this solution there are added 10.2 grams of gamma valero lactone per *liter. The coating. storage and testing procedures are the same as in. Example I. The stability of the coating, made 40 according to this example was found to be superior to that of a coating made from a solution bilizlng agent, but'otherwise having been made and treated the same as thelight-sensitive layer of this example.

Eeample VII The composition of the coating solution is the same asin Example VI but as a stabilizer 13.4 grams of gamma valero lactone 'y carbonic acid per liter are used instead of the gamma valero lactone. The coating. storage and testing pro cedures arethe same as in Example VI. The

stability of the coating made'according to this example was found to be superior to that of a gamma lactone stabilizer.

, Example v11: v The coating composition is the same as in Example VI but as a stabilizer 10.4 grams of the coating made from a solution notcontaining a di-hydroxy' lactone of Bamma-hydroxy crotonic acid per liter are used instead of-the gamma valero lactone. The coating, storage and testing procedures are the same as in Example VI.

not containing a gamma lactone stabilizer.

Example XII Zinc chloride double salt of the diazo-compound obtained from N-ethanol-ethylamino-4-aminobenzene 10.5 Citric acid .j 5 Thiourea 45 The sodium salt of the naphthalene 1,3.6-- 32.5

, trisulfonic acid The aluminum sulfate are dissolved in 1000 cc. of-water 8.9

To this solution there areadded 10.2 of

gamma valero lactone per liter. The solution is then spread on a suitable base, such as paper, fabric, film or the like by the usual coating method in the same manner as described in Example I. The light-sensitive layer thus produced is then stored at room temperature. for

' several months and its stability is then tested by,

4 The stability of the coating" made according to this example was found to-be superior to that 4 of a. coating made from a solution not containing a gamma lactone stabilizer. a

Example IX The coating compositionis the same as Example VI but as a stabilizer 11.8 grams of the I di-hydroxy lactone of gamma-hydroxy betamethyl crotonic acid per liter are used instead observing the appearanceof color in the light-.- sensitive layer due to decomposition of the diazo-.

compound and by comparison with that of atest j sample prepared and treated in the same manner as the light-sensitive layer of this example but omitting the gamma valero lactone. The test pieces are then exposed to light under a suitable diapositive and the images developed by appli-'' cation of an alkali solution of a suitable azo-' component such as phloro-glucine resorclne, or 2 3 dihydroxy naphthalene. The resulting image reproduced on the light-sensitive layer,

containing the gamma valero lactone showed a 4 r higher color contrast of the image indicatingthe prevention of the decomposition and the consequent discoloration of at storage. v

I claim:

1. The process oi increasing the stability of a diazo-type light-sensitive layer containing a suitthe diam-compound while able'diazo compound which comprises adding to the coating solution a member the class consisting of saturated and unsaturated gamma lactones of the following formulae: I

and

wherein X is a member of the group consisting of H, OH, COOH and alkyl, Y is a member of the group consisting of H and alkyl, Z is a member of the group consisting of H and OH, R is a lower alkyl radical. R1 is a member of the. group which comprises adding to thecoating solution a member of the group consisting of saturated and unsaturated gamma lactones of the following formulae:

wherein X is a member of the group consisting of H, OH, COOH and alkyl, Y is a member of the group consisting of H and alkyl, Z is a member of the groupconsisting of H and 0H,"R is a lower alkyl radical, R1 is a member of the group consisting of H and COOH, and Alk means alkylene; and coating a suitable base with said solution.

3. The process of increasing the stability of a dlazo-type light-sensitive layer containing a diazo compound derived from a para amino aniline compound and an azo dye coupling component and produced by applying to a suitable base a coating solution containing said diazo compound and said azo dye component, which comprises adding to the coating solution a member of the group consisting of saturated and unsaturated gamma lactones of the following formulae:

wherein X is a member of the group consisting of H, OH, COOH and alkyl, Y is a member of the group consisting of H and alkyl, Z is a member of the group consisting of H and OH, R is a lower alkyl radical, R1 is a member of the group consisting of H and COOH, and Alk means alkylene; and coating a suitable base with said solution.

4. The process of increasing the stability of a diazo-type light-sensitive layer containing a diazo compound derived from an ortho amino naphthol compound and an azo dye coupling component and produced by applying to a suitable base a coating solution containing said diazo compound and said azo dye component, which comprises 2,374,563 l adding to the coating solution a member of the the group consisting of saturated and unsaturgroup consisting oi saturated and unsaturated ated gamma lactones of the following formulae:

gamma lactonesof the following furmulae: 0 y

0 Y-C-C v y-c-ik p o Y 70/ Y- -c Y a i z a at z 1 Y\ E .Y o (ic- Y/ o Y i o n H 1':

x Y 0 Y\ a Y):- Y-C---C- l Y 0 a Y Aik iiik and a and o ,0 I i Bic-( 1 v 0 11, -0 80 a R, R

wherein x is a member of the group consisting wherein X is a member of the group onsistin or H, OH, COOH and alkyl, Y is a member of the of H, OH, 000K, and alkyl, Y is a membe of group consisting of H and alkyl Z is a member of .the group consisting f E n l. Z i a .1 the group consisting of H and OH, R is a lower be 0! thegmllp consisting of H a d OH R 15 11 alkyl radical R1 is a member of the grou 4 p conlower alkyl radical, R1 s 8 member of the 8 sisting of H and COOI-l, and Alk means alkylene.

consisting of H and COOH, and means a y- 9. Light-sensitive layers on a suitable base gene; and coating a suitable base withsaid solu- -comprjsing a diam compound t i from a on. i I

5.The process or increasing he s il of a pling component and a member or the grou diamyp fight-Sensitive lay r aining a diam consisting of saturated and unsaturated gamma compound obtained from an ortho amin naphlactones of the following formulae: Y

' ponent and produced by applying a coating soluthol compound and an azo dye coupling com- 0 tion containing said diazo compound and mo dye component on a suitable base, which comprises adding gamma valero lactone to the coat- Y ing solution-and coating a suitable base with said solution. h I X Z 6. The process of increasing the stability of a 0 dlazo-type light-sensitive layer containing a diazo a compound obtained from a para aminoaniline a, compound and an azo dye coupling component Y 0 and produced by applying a coating solution coni taining said diazo compound and azo dye comi l ponent toa. suitable base, which comprises addin! Eamma'valero lactone '7 carbonic acid tothe Y c coating solution'and coating a suitable base with and produced by applying acoating solution V prises adding the gamma-di-hydroxy lactone of a 'T said solutiona Y 60 'l. The process of increasing the stability of a diam-type light-sensitive layer containing a diazo Y compound obtained from a para amino aniline. compound and an azo dye couplingcomponent H containingsaid diazo compound and said azo and dye component to a suitable base, which comthe gamma-hydroxy crotonic acid to the coating solution and coating a suitable base with said solution.

8. light-sensitive layers as a suitable base R1 i i comprising a diazo compound suitable for formwherein X is a member of the group consisting ing a stable two component diazo-type layer, an of H; OH, COOH and alkyl, Y is a member of the azo dye coupling component and a member of 76 group consisting of Hand alkyl, Z is a inember of para amino aniline compound, an azo dye couthe group consisting of H and OH, R is a lower alkyl radical, R1 is a member of the group con-. sisting of H and COOH, and All: means alkylene.

10. Light-sensitive layers on a suitable base and 0 H inc-0 '/O m '-c wherein X is a member of the group consisting of H, OH, COOH and alkyl, Y is a member of the group consisting of H and alkyl, Z is a member of the group consisting of H and OH, R is a lower alkyl radical, R1 is a member of the group consistingv of H and COOH, and Alk means alkylene. v a

11, Light-sensitive layers on a suitable base comprising a diazo compound obtained from an ortho amino naphthol compound, an azo dye coupling component and gamma valero lac ne.

12. Light-sensitive layers on a suitable ase comprising a, diazo compound obtained from a para amino aniline compound, an azo dye coupling component, and gamma valero lactone 'y carbonic acid.

13. Light-sensitive layers on a suitable base comprising a diazo compound obtained from a para amino aniline compound, an azo dye coupling component and the 'y di-hydroxy lactone of gamma-hydroxy crotonic acid.

MAXmm-IAN K. REICHEL.