DE1013166B - Process for the production of photographic layers from synthetic polymeric hydrosols - Google Patents

Description

The invention relates to photography and, more particularly, to photographic storage Materials such as color couplers in polymeric hydrosols. Polymeric hydrosols and suspensions or emulsions of a polymeric material in water are usually obtained by emulsion polymerization, i.e. H. by Polymerizing a polymerizable material in water or in other aqueous medium. These polymeric hydrosols have been used in photographic emulsions. For example, Fowler describes in U.S. Patent 2,739,137 the preparation and photographic use of esters of the Acrylic acid or methacrylic acid, amides such as acrylamide, and styrene-made hydrosols. Tong in U.S. Patent 2,772,163 describes the use of these hydrosols in containing color couplers Emulsions. Gates et al. describe in Belgian patents 534059 and 534060 protein or Hydrosols containing protein derivatives. According to a proposal that is not yet part of the state of the art For example, such hydrosols can be used in photographic coupler-containing emulsions.

It has been found to be advantageous to polymerize into one of the hydrosol components prior to emulsion polymerization a photographically active agent, particularly an aromatic photographic material having a or to incorporate several mononuclear aromatic rings. Photographically active media based on this Ways that can be built in are, for example, color couplers, ultraviolet light absorbents, stain removers and other additions of photographic inks or emulsions.

The invention further relates to hydrosols of the Belgian patents 534059 and 534060 type described, which according to the invention by emulsion polymerization of a mixture of

1. 5 to 60% protein material, which is proteins, proteins with an organic acid radical or unsaturated contains acidic protein derivatives;

2. a bend-resistant component, the alkyl acrylates containing 2 to 10 carbon atoms Alkyl groups, acrylic methacrylates with 4 to 10 carbon atoms containing acrylic groups, butadiene, isoprene or chloroprene; and

3. a reinforcing component, the styrene, acrylonitrile, substituted styrenes, substituted acrylonitriles, Vinyl acetate, vinylidene chloride or isopropenyl acetate. The bendable one The component and the reinforcing component can be called "self-polymerizable" components.

Other useful hydrosols have been emulsion polymerized a mixture of an ester of acrylic or methacrylic acid and an aliphatic, Alcohol containing not more than 10 carbon atoms, method of preparation

photographic layers

from synthetic polymeric hydrosols

Applicant:

Eastman Kodak Company,
Rochester, NY (V. St. A.)

Representative: Dr.-Ing. W. Wolff, patent attorney,
Stuttgart-N, Lange Str. 51

Claimed priority:
V. St. v. America December 20, 1954

Bernard David Illingsworth,

John Robert Dann, Scheuring Session Fierke,

and John Warburton Gates Jr.,

Rochester, NY (V. St. A.),
have been named as inventors

e.g., methyl acrylate, methyl methacrylate, n-butyl acrylate etc., made with nitriles, e.g., acrylonitrile, or with styrene or substituted styrenes, as in the U.S. Patent 2,739,137. Butadiene-styrene type liquids can also be used will.

Photographically active agents that can be incorporated into the hydrosol include couplers such as e.g. the couplers described in U.S. Patent 2,322,027 to Jelley and Vittum and elsewhere. the the following couplers are particularly suitable:

1. 1-Oxy-2- [<5- (2 ', 4'-di-tert-amylphenoxy) -n-butyl] -naphthamide (U.S. Patent 2,474,293),

2.1- Oxy - 4 - phenylazo - 4 '- (p - tert-butylphenoxy) 2-naphthanilide (U.S. Patent 2,521,908),

3. 2 - (2,4-Di-tert. Amylphenoxyacetamino) -4, 6-dichloro-5-methylphenol (Graham, U.S. Patent 2,725,291),

4. 2- (a-Di-tert. Amylphenoxy-n-butyrylamino) -4, 6-dichloro-5-methylphenol,

5. 6-α-4- [α- (2,4-Di-tert. Amylphenoxy) -butyramido] -phenoxyacetamido-2, 4-dichloro-3-methylphenol,

6.2- [3 '- (2 ", 4" - diamylphenoxy) - acetamido] - benz amido ^ -chloro-S-methylphenol,

709 509/304

3 4

7. l- (2 ', 4', 6'-trichlorophenyl) -3- [3 "- (2 '", 4 "' - di-tert. 5% strength suceinyl glue (see Example 1) were dissolved, and * ■ amylphenoxyacetaimdo) -benzamido] -5-pyrazolone (USA-8.4 g gelatin, which contained 13.4 g of the coupler No. 9 ',. Patent 2,600,788). The addition of the mixture and the solution «ιδ. 1- (2 ', 4', 6'-tricruorophenyl) -3- [3 "- (2 '", 4 "' - di-tert. was complete in 17 minutes; the mixture then became J: amylphenoxyacetamido) benzamido ] - 4 - (p - methoxy -. 5 kept 2 hours at 85 ⁰ C. The hydrochloride oil "i obtained phenylazo) -5-pyrazolone, was compatible with gelatin solutions. ν

9. N- (4-Benzoylacetaminobenzolsuh ^c onyl) -N- (y-phenyl;..? Propyl) -p-toluidine (USA. Patent 2,298,443), Example ό

10. α - o-Methoxybenzoyl-a-chloro-4- [a- (2,4-di-tert. To a solution of 0.37 g of potassium persulfate in 442 cm ⁸ : ί amylphenoxy) -n-butyramido] -acetanilide (McCrossen, ¹⁰ distilled water were stirred at 85 ° C #? USA. Patent Application 295 806), 36 g of n-butyl acrylate, 15 g of styrene and a solution of |

11. α- {3- [α- (2, 4-Di-tert. Amylphenoxy) acetamido] - 11 g glue and 11 g gelatin added, in which 200 cm ^{3 of} benzoyl-2-methoxyacetanilide, 20.5 g distilled water containing coupler No. 1 |;

12. 3-Benzoylacetamino - 4-methoxy - 2 ', 4'-di-tert. was dispersed. These materials were made within Sf amylphenoxyacetanilide, J-5 was added over a period of 9 minutes. The f;

13. 4-Benzoylacetamido -3-methoxy-2 ', 4'-di-tert. The reaction mixture was thereupon for 1 hour at i ;: amylphenoxyacetanilide. Stirred at 85 ° C, then cooled and filtered. The obtained f ||

The preparation of Coupler Nos. 4, 5, 6, 8, 11, 12 and Hydro Oil was dried to a clear film and the ¹ N 13 is described in Belgian patent 543,745. Color developed in a known way. "f = i

Ent- 2 ° used in color photographic processes. ί ||;

teasing agents, like ζ. B. 2,5-Di-iso-octyl-hydroquinone, Example 4 _; _;. '| p

2, S-Di-n-octyl-hydroquinone and others in the USA.- To a solution of 1.21 g of potassium persulfate and 2äi, g, :: i *

Patents 2,728,659, 2,735,765 and 2,732,300 be-Duponol ME (sodium lauryl sulfate) in 360 cm ^{3 of} water | j compounds can be added to the hydrosol with stirring at 85 ° C within 10 Mj-. ., Ji,!, Be built. ² 5 grooves from a dropping funnel a solution of 0.5 g '*

Substances absorbing ultraviolet light can also be incorporated into the hydrosoil with 63 g of n-butyl acrylate and 27 g of acrylo- ^: S " ^{: coupler no} -3-phenyl-2-phenylirnino-4-thiazolidone, 5-benzylidene through another dropping funnel, a solution of 38lg _|: cm added S-ethyl ^ ^ -phenylimino -thiazolidon, 5-o-Carboxybutoxy- glue in 180 ³ water The hydrosol,?; Benzal-3-phenyl-2-phenyhinino-4-thiazolidone (USA.- 3 ° was stirred for another 45 minutes in patent specification 2739888), S-benzylidene-Sn-ketyl ^ -phenyl- 85 ° C and then dried to a clear flexible film | imino-4-thiazolidone (U.S. Patent 2,739,971). W / ^ ¹

The poly examples 5 · 5 to be used with particular advantage

meren hydrosols are made up of hydrophobic components, ''' ^: -' \ ^: '%'

e.g. n-butyl acrylate, styrene and a protein material, 35 To a solution of 0.57 g of potassium persulfate and 2.22 g || such as glue, gelatin or a saturated or Duponol ME in 930 cm ^{3 of} water, while stirring _: |. Unsaturated derivative of glue or gelatin put together at 85 ° C dropwise a solution of 0.5 g coupler No. 9 % . The coupler or other photographic in 65 g of n-butyl acrylate and 28 g of acrylonitrile are added. l || Material may be either prior to polymerization in the same time to another solution of 17.8 g was ΐ hydrophobic monomer can be dissolved or F in the 5 40 ° / ₀ hydrochloric Maleylleim (Yutzy and frame, USA.-PateiLt- hydrophilic gelatin - or protein component, written 2 525 753) in 84 cm ^{3 of} water also drop by drop, j || be spitted. After the coupler is added on one of. The addition took place over 10 _micro: is dissolved or dispersed i these types, the manufacturer is utes, the reaction mixture was then 25 Miau- ä »position of the hydrosol in the usual manner performed th to 85 ° C. · '| I

as illustrated in the following examples. 45 _......, ijjl

Example 6 *;

Example 1 _{To a solution of} 64 g of potassium persulfate and 2.5 g of .

^{While stirring, Duponol ME in 455 cm 3 of} water was added to a hot solution at 85 ° C. with stirring.

of 0.535 g of potassium persulfate in 373 cm ^{3 of} water through a solution of 5 g of coupler Ns. 9 · | · dropwise at 85 ° C.

Add a dropping funnel to a mixture of 27.2 g of n- ^ butyl · 50 in 80 g of n-butyl acrylate and 35 g of acrylonitrile. ,, |,

acrylate and 11.7g styrene added dropwise. At the same time a solution of 12.7 g i |

A solution of the 5% maleyl glue in 58 cm ^{3 of} water was added dropwise through another funnel.

the following substances were added dropwise: 8.4 g of given. The addition took place within 7 minutes, || "

5 ° / ₀ sodium Suceinylleim (glue that 5 percent by weight of the reaction mixture was was then reacted for 15 micro ¹ V succinic anhydride [YutziundFrame, 55 utes stirred at 85 ° C. The hydrochloride obtained oil was USA. Patent 2,525,753]) and 8.4 g of gelatin in which dried to a pliable, clear film and the 13.4 g of Coupler No. 7 dispersed, both materials having developed color in a known manner, were dissolved in 135 cm ^{3 of} water. The material was. added over a period of 10 minutes; Example/

then the mixture was stirred at 85 ° C. for 1 hour. ⁶ ° This example differs from the example 6 '"

The hydro oil obtained was dried to a film only in that instead of coupler no. 9 in this _{| (}

and develop the color in a familiar way. Example 5 g of Coupler No. 7 was used. '

Example 2 Example 8

To a solution of 0.282 g potassium persulfate in 65 To a solution of 1.27 g of potassium persulfate in 856 "a ⁸ 370 cm ³ of water was stirring at 85 ⁰ C droplet of distilled water with stirring at 85PC, a mixture of 27.2 g n-butyl acrylate and 40 g of 5 ° / ₀ hydrochloric Suceinylleim dissolved in 144 cm ³ of water and 11.7 g styrene added. a solution of 10 grams of Coupler No. 9 in 150 grams of n-butyl acrylate

A solution and 64 g of styrene were added over the course of 10 minutes through a different dropping funnel, and the solution was added, which consisted of 138.4 cm ^{3 of} water, in which 8.4 g of 7 ° C. The reaction mixture was then added for a further 1 hour

5 6

85 ° C stirred. The hydrosol obtained was cooled. At the same time, 20 g of 5% strength succinyl glue were added to 72 cm ³

filtered and dried to a clear film. Added water. After adding this material

. . The reaction mixture was still stirred while stirring

Example _{held at 85} ° _{C for 9 t} hours, then cooled and cooled

To a solution of 1.27 g of potassium persulfate in 850 cm ³ 5 filters.

Water was passed through an example 14 ^{at 85 ° C. with stirring}
Dropping funnel, a mixture of 150 g of n-butyl acrylate

and 64 g of styrene were added, in which 15 g of ultraviolet to a solution of 1.089 g of potassium persulfate in 400 cm ³

Light absorbing 5-benzylidene-3-ethyl-2-phenyl-water with stirring at 85 ⁰ C was added dropwise

imino-4-thiazolidone were dissolved; and by an anio a solution of 15 g of ultraviolet light absorbing

their dropping funnel was 40 g of 5% succinyl glue in 5-benzylidene-3-n-ketyl-2-phenylimino-4-thiazolidone in

191 cm ^{3 of} water were added. The additions were made 126.25 g of n-butyl acrylate and 54 g of styrene were added,

within 13 minutes; the reaction mixture was from another dropping funnel at the same time became one

^{then held at 85 °} C. for a further 1 hour. The resulting solution of 34.25 g of 5% succinyl glue in 100 cm ³

Hydrosol, which was compatible with gelatin solutions, added water. The addition took place within

was dried to a clear film. The absorption 8 minutes; the reaction mixture was then

this material of ultraviolet light was ^{stirred in a 2 hours at 85 0} C, and was long 20 minutes

a stream of vapor is passed through the reaction mixture in a manner known in this field of technology,

proven. The hydrosol obtained was filtered and checked.

Example 10 ²⁰ Example 15

This example differs from example 9 to a solution of 2.54 g of potassium persulfate in 1700 cm ³

only in that to the original solution, water was stirred under stirring at 85 ⁰ C a mixture of 2 g Duponol ME as a surfactant hinzu- of 300 g n-butyl acrylate and 128 g styrene added dropwise

were given. 25 added, in which 14 g of 2, 5-di-n-octyl-hydroquinone-

■ D: - 111 stain removal agent was dissolved. By someone else

Dropping funnel was a solution of 80 g of 5% suc-

Added to a solution of 10.74 g of potassium persulfate in cinyl glue in 384 cm ^{3 of} water. The additions of 4413 cm ^{3 of} distilled water were made at 85 ^° C. within 15 minutes; Then the reaction mixture was stirred continuously from two dropping funnels at 85 ° C. for 30 minutes, 333 g of 5% succinyl glue in 820 cm ^{3 of} distilled then a stream of steam through the water and a solution of 135 g of the Ultraviolet light reaction mixture passed through to remove the volatile, absorbent substance of Example 9 in a mixture of unreacted monomers. The obtained of 1244 g of n-butyl acrylate and 533 g of styrene were added. Hydrosol turned into a clear, pliable film. After everything was added, the solution was dried for 1 hour and its stain-preventing effect was kept at 85 ° C. The solution demonstrated 20 microns of species,
utes long steam passed through it to remove the excess. ,

Remove monomer. The hydrosol was by an .oeispie

Layer of cellulose paper pulp with a high content of To a solution of 2.54 g of potassium persulfate in 1700 cm ³

α-Cellulose filtered and then through a flannel layer 40 water was stirred at 85 ° C, a solution of sifted. 300 g of n-butyl acrylate and 128 g of styrene are added dropwise

The hydrosol obtained was given a clear, bendable, in which 14g of the stain removal agent 2, 5-di-isosame film was dried; its ability to dissolve ultraviolet octyl hydroquinone. To absorb light by another has been proven in a known manner. Dropping funnel a solution of 80 g of 5 ° / _o sodium -Suc was. 45 cinyl glue in 392 cm ^{3 of} water was added. The encores

Example 12 took place within 13 minutes, the reaction

To a solution of 2.178 g of potassium persulfate in 859 cm ^{3 of} mixture, distilled water was then stirred at 85 ° C. for a further 2 hours at 85 ° C., and 68.5 g were simultaneously stirred by introducing steam from two dropping funnels for half an hour one the liquid, unreacted monomers were removed. Derivative of the 5% succinyl glue in 141 cm ^{3 of} water at 5 ° The hydrosol obtained was absorbed by gelatin solutions and a solution of 60 g of ultraviolet light was absorbed.

biting substance of example 9 in a mixture of example 17

252.5 g of n-butyl acrylate and 108 g of styrene were added.

After the addition, the solution was made into a solution of 1.27 g of potassium persulfate and 5 g for 1 hour

Held at 85 ° C. ^{Duponol ME in 857 cm 3 of} distilled water was passed through the solution for 20 minutes under steam to remove excess monomer. Stirring at 85 ^° C. a mixture of 150 g of n-butyl-20 g of dry paper pulp (alpha stock) was added acrylate and 64 g of styrene, in which 3 g of 2, 5-dir and the solution sieved through a flannel layer. η-octyl hydroquinone stain remover was dissolved. The hydrosol obtained became a clear, pliable one. At the same time, 40 g of 5% succinyl glue was ^{dried in 143 cm 3 of} film, and its ultraviolet absorption in water was added to the reaction mixture. The known way demonstrated. Materials were added within 10 minutes, and the reaction mixture was then _{kept at g5} o _{C for 1 hour. Example 13 The} hydrosol obtained was

To a solution of 0.63 g of potassium persulfate and 2.5 g, cool, filter and dry to a clear film.

Duponol ME in 428 cm ^{3 of} distilled water was under 65 -R- ¹ IiS

Stirring a mixture of 75 g of Example 18 dropwise at 85 ° C

n-Butyl acrylate and 32 g of styrene were added, in the To a solution of 1.27 g of potassium persulfate in 856 cm ³

5 g of ultraviolet light absorbing 5-o-carboxybut-distilled water were added at 85 ° C. with stirring

oxybenzal-3-phenyl-2-phenylimino-4-thiazolidone solved ^e r Succinylleim dissolved 40 g of 5% strength in 144 cm ³ of water

was. 70, together with a mixture of 150 g of n-butyl

acrylate and 64 g of styrene, in which 10 g of laurylphenol had been dissolved, were added within 10 minutes. The reaction mixture was then stirred ^{at 85 ° C. for 1 hour.} Then it was cooled and filtered.

Claims (11)

Patent claims: 1. Process for the production of photographic layers from synthetic, polymeric hydrosols, the aromatic compounds involved in the photographic process such as color couplers, fogging preventive compounds, ultraviolet light absorbing compounds or the like. Contain thereby characterized in that the aromatic compound in * 5 an organic component is dispersed, which together with at least one organic Component - at least one component being self-polymerizing - an emulsion polymerization is subjected, whereupon the hydrosol obtained is cast into a photographic layer will. 2. The method according to claim 1, characterized in that an acrylic ester with a polymerizable Vinyl compound in the presence of proteinaceous material such as gelatin, glue or the like. Polymerized in which an aromatic compound involved in the photographic process is dispersed, and that thereupon the hydrosol obtained is cast to form a photographic layer. 3. The method according to claim 1 and 2, characterized in that in a synthetic polymer Hydrosol, which is made by polymerizing in water or an aqueous solution of three organic components (1, 2, 3), two of which are self-polymerizable, one of which is color-forming in the photographic Develop with a developer containing a primary aromatic amino compound reactive Compounds is incorporated by adding a mixture of the three components (1, 2, 3) after incorporating the color-forming Compound into one of the three components (1, 2, 3) and / or in the presence of the color-forming compound is polymerized, the three components (1, 2, 3) containing: Component 1: proteinaceous material from the class of proteins that has an organic acid radical tagged proteins and the unsaturated acidic derivatives of proteins; Component 2: a bending-resistant component selected from the class of alkyl acrylates, the alkyl groups containing 2 to 10 carbon atoms have, the alkyl methacrylates, which have alkyl groups with 4 to 10 carbon atoms, of butadiene, isoprene and chloroprene; Component 3: a reinforcing component selected from the class of styrene, the substituted one Styrene, acrylonitrile, substituted acrylonitrile, vinyl acetate, vinylidene chloride and of isopropenyl acetate and wherein the proportion of the protein material is 5 to 60% of this mixture. 4. The method according to claim 3, characterized in that as the three organic components (1, 2, 3) (1) glue provided with an organic acid radical, (2) n-butyl acrylate and (3) styrene are used will. 5. The method according to claim 3, characterized in that that as the three organic components (1,2,3) (1) an unsaturated, acidic glue derivative, (2) n-butyl acrylate and (3) acrylonitrile can be used. 6. The method according to claim 4, characterized in that than with an organic acid radical provided glue succinyl glue is used. 7. The method according to claim 4, characterized in that the unsaturated, acidic glue derivative Maleyl glue is used. 8. The method according to claim 3, characterized in that the color-forming compound is dispersed in gelatin, the dispersion obtained is mixed with proteinaceous material (1) and that this mixture together with 95 to 40 ° / ₀ (based on the entire mixture) a Mixture of styrene and n-butyl acrylate is polymerized. 9. The method according to claim 8, characterized in that succinyl glue is used as the proteinaceous material will. 10. The method according to claim 3, characterized in that the color-forming compound is dissolved in a mixture of n-butyl acrylate (2) and acrylonitrile (3), the solution with 5 to 60 ° / ₀ (based on the entire mixture) proteinaceous material mixed and the mixture is polymerized. 11. The method according to claim 10, characterized in that maleyl glue is used as the proteinaceous material will. © 709 590/304 7.57