US3291624A - Acetylated derivatives of dialdehydes and of their hemiacetals as gelatin hardeners - Google Patents

Description

United States Patent ACETYLATED DERIVATIVES 0F DIALDEHYDES AND OF TIER HEMIACETALS AS GELATIN HARDENERS Roy Arthur Jefireys, Harrow, and Donald M. Bnrness, Wealdstone, Middlesex, England, assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Aug. 21, 1963, Ser. No. 303,664

5 Claims. (Cl. 106-125) This invention relates to gelatin compositions containing therein as a hardener a diacyloxy compound of a certain type.

Various compounds have been suggested as gelatin hardeners. Some of these compounds have exhibited properties of one kind or another which limited their use in certain situations. For instance, formaldehyde has shown desensi-tizing characteristics in contact with certain highly sensitized photographic emulsions. eners have been so efiective that thickening of gelatin coating compositions occurs very shortly after the hardener addition, hence, the urgency of almost immediate coating. Some hardeners have had toxic effects and have been avoided where possible in manufacturing operations. Other hardeners have shown tendencies to fog and stain photographic elements with passage of time.

One object of our invention is to provide compositions which will give hardened gelatin layers but which do not exhibit thickening upon incorporating the hardener in the coating composition. Another object of our invention is to provide hardeners for gelatin-silver halide photographic emulsion which do not adversely aifect their sensitivity and do not fog or stain the emulsions. A further object of our invention is to provide gelatin coating compositions which provide layers which retain a high degree of flexibility upon storage or aging. Other objects of our invention will appear herein.

We have found that certain diacyloxy compounds added to gelatin compositions exert a hardening effect upon gelatin layers formed therefrom, particularly upon aging or the like of those layers. Almost any amount of these hardeners will exert hardening on the gelatin but to obtain a substantial hardening advantage it is desirable that at least 0.1% and preferably .55%, based on the weight of the gelatin, be incorporated in the gelatin coating composition.

The hardeners in accordance with our invention are represented by the following type formulas in which acetyl is used as the acyl group. If desired, other acyl groups may be employed but the acetoxy compounds are preferred having been found to be quite convenient for use as hardeners:

073.000 OOOGH;

CH(CHZ)nCH R0 OR in which R is an alkyl of 14 carbon atoms and n equals 0-5.

(IJH OH H-O CH OH3000 O OCOOH Other hard- "ice CH =CHZ O OGOCHQ The gelatin compositions such as photographic gelatinsilver halide photographic emulsions containing a hardener in accordance with the invention may be coated out onto a support such as paper, film base or the like, to form photographic elements.

The following examples illustrate the preparation of some hardeners useful in hardening gelatin in accordance with our invention.

Example 1 Mixed 1,1,2,2-diacetoxydiethoxyethane isomers were prepared by refluxing a mixture of 1,1,2,2-tetraethoxyethane and acetic anhydride plus a drop of methylsulphate as the catalyst. See the article by Fiesselmann and Horndler, Chem. Ber., 87, 911, (1954).

Example 2 Twenty-two ml. of 1,1,3,3-tetraethoxypropane was mixed with 20' ml. of acetic anhydride and one drop of methylsulphate was added thereto. The mixture was refluxed overnight. The product was then distilled yielding mixed 1,1,3,3-diacetoxydiethoxypropane isomers.

Example 3 Thirty grams of 1,1,2,2-tetramethoxyethane was reacted with 42 ml. of acetic anhydride with one drop of methyl sulphate by the method described in the preceding example. The product obtained after distillation of the reaction mixture was fractionally crystallized from petroleum distillate (B.P., 60-80 to give the isomers of 1,1,2,2-diacetoxydi methoxyethane, M.P. 77 and 51, described by Fiesselmann and Horndler, Chem. Ber., 87, 908, 911 (1954).

Example 4 2,5-diacetoxy-2,S-dihydrofuran was prepared by the method described by Clauson-Kaas, U.S. Patent No. 2,514,026.

Example5 2,3-diacetoxy-1,4-dioxane was prepared by the method of Boeseken, Tellegen and Henriquez, J. Amer. Chem. Soc, 55, 1284, (1933).

The above hardeners were added to portions of a fine grain negative gelatino-silver bromoiodide emulsion in the proportions specified, the properties obtained being indicated in the following table. The emulsion originally contained 67% gelatin and the final emulsion pH Was as designated.

Final emulsion pH 8.4

Fog Cont. Rel. M.P. M.P. Speed F.) F.)

Control 0. 31 0. 98 4. 30 92 93 Control+2,3-diaeetoxy-1,4-dioxan (O.3g./1.) 0. 23 0. 95 4. 38 90 93 Control +2,8-diacetoxy-1,4-dioxan(1.0g./1.) 0. 23 0. 96 4. 30 94 100 Control-{234iiaeetoxy-L4-clioxan (3.0g./l.) 0. 22 0.92 4.33 105 123 Contr01+2,5-diaeetoxy-2,5-dihydrofuran (03.g./1.) 0. 25 0. 98 4.30 92 155 Control+2,5-d1acet0xy-2,5-dihydrofuran (1.0g./1.) 0.21 0.02 4.30 92 200 Control+Example 1 product (O.3g./l.) 0.34 0.98 4. 93 190 Control-i-Exarnple 1 product (1.0g./1.) 0.28 0. 96 4. 2-0 94 197 Control-l-Exemple 1 product (3.0g./1.) 0. 24 0. 94 4. 20 94 200 Control+diacetoxydimethoxy ethane (m.p.

77") (0.3g. 0. 32 0. 98 4. 18 88 164 Control+diacetoxydimethoxy ethane (m.p.

77) (1. 1. 0. 27 0.94 4. 23 90 200 Control+diacetexydimethoxy ethane (m.p.

77) (3. ./1. 0.23 0. 94 4. 27 101 200 Contro1+diaoetoxydimethoxy ethane (m.p.

51) (0. ./1. 0.27 0.98 4. 28 90 180 Oontrol+diacetoxydimethoxy ethane (m.p.

51) .Og. 0.26 0.98 4.32 96 200 Control+diacetoxydirnethoxy ethane (m.p.

51) (2.0g./1.) 0. 24 0. 99 4. 26 96 200 Control+diacetox ample 2) (0.3g./l.) 0.29 0.98 4.20 96 200 (2.) Tested 7 days after coating. (b) Coatings tested alter incubation at 42% RH. and 120 F. for 2 weeks.

Final emulsion pH 8.5

Fog Rel. M.P. Speed F.)

ControL 0.36 4.12 96 30 Control+2,3-diacetoxy-1,4-dioxan (0.3g./1.) 0. 30 4. 21 100 Control+2,3-diacetoxy-1,4dioxa.n (1.0g./1.) 0.31 4. 16 120 Control+2,3-diaeetoxy-1,4-dioxan (3.0g./1.)- 0. 34 4. 05 160 (o) Coatings tested after 3 months. 35

Final emulsion pH 8.4

Fog Cont. Rel. M.P. M.P. Speed 0 F.) F.)

Control 0. 22 0.99 4. 20 94 105 Control+2,5-diaeetoxy-2,5-dihydrofuran (0 3g,/1 0. 20 0. 97 4. 22 96 1 Control+2.5-diacet0xy-2,5-dihydrofuran (1,0 /1) 96 200 Control+2,5-diaoetoxy-2,S-dihydroiuran (3 Og,/l. 0.17 o 93 4. 21 96 2 0 Control+diacetoxydimethoxy ethane (m.p.

77) (0.3g. O. 22 0.98 4. 25 Oontrol+diacetoxydimethoxy ethane (n1.p.

77) (1.0g./1.) 0.20 1.02 4.24 90 130 Control-i-diaeetoxydimethoxy ethane (m.p.

77 )(3.0g./1.) 0. 22 0.91 4. 22 90 180 Control+diaoetoxydietl1oxy propane (Example 2) (0.3g./1.) 0.22 0.97 4.26 96 200 (2.) Tested 7 days after coating.

(1)) Coatings tested after incubation at 42% RH. and F. or 2 weeks.

Final Emulsion pH Six Month Keeping Test pH 6.5 pH 8.5

Fog Rel. M.P. Fog Rel. M.P. Speed F.) Speed F.)

. Contr 0. 25 4. 32 0. 38 4. 26 Control+2,3-diacetoxy-1,4-dioxan (0.3 0. 24 4.26 150 0.39 4. 22 Oontrol+2,3-diaoetoxy-l,4-dioxan (1.0g 0. 25 4. 28 155 0. 32 4. 16 200 Control+2,3-diaeetoxy-1,4-dioxan (3.0g./l.) 0.21 4. 28 0.30 4.06 200 Melting points were determined by immersing the element containing the gelatin coating in water and increasing the temperature until disintegration of the coating occurred.

We claim: 1. A composition of matter composed of gelatin containing a hardener selected from the group consisting of omooo ooooH3 CH(CHz)nCH BO OR in which R is an alkyl of 1-4 carbon atoms and n=0-5;

OHQC OZCH=OHOH=CHO C O CH;

and

(EH 0 O2CH=CHCH2CH=CHO O OCH;

References Cited by the Examiner UNITED STATES PATENTS 2,585,596 2/1952 Stanton 96l11 2,870,013 1/1959 Harrow 96--100 3,241,972 3/1966 Wilson 96-111 MORRIS LIEBMAN, Primary Examiner.

D. I. ARNOLD, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 291, 624 December 13, 1966 Roy Arthur Jeffreys et a1 a It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, lines 53 to S7, for the right-hand portion of the formula reading OOOCH read OCOCH same column 1, lines 60 to 63, the formula should appear as shown below instead of as in the patent:

CH CH c CHSCOO/ \O/:\OCOCH3 column 2, lines 1 to S, the formula should appear as shown below instead of as in the patent:

H-2-CH2 columns 3 and 4, in the heading to the third table, first column for "804" read 605 ---n CH COO OCOCH Signed and sealed this 24th day of October 1967.

(SEAL) Attest:

EDWARD J., BRENNER EDWARD MGFLETCHERJRO Commissioner of Patents Attesting Officer

Claims (1)

1. A COMPOSITION OF MATTER COMPOSED OF GELATIN CONTAINING A HARDENER SELECTED FROM THE GROUP CONSISTING OF