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Publication numberUS3291624 A
Publication typeGrant
Publication dateDec 13, 1966
Filing dateAug 21, 1963
Priority dateAug 21, 1963
Also published asDE1547752A1
Publication numberUS 3291624 A, US 3291624A, US-A-3291624, US3291624 A, US3291624A
InventorsArthur Jeffreys Roy, Burness Donald M
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Acetylated derivatives of dialdehydes and of their hemiacetals as gelatin hardeners
US 3291624 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

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

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2585596 *Dec 29, 1949Feb 12, 1952Du PontPhotographic emulsions containing 2, 5-dimethoxytetrahydrofuran
US2870013 *Nov 29, 1956Jan 20, 1959Eastman Kodak CoHardening of gelatin with 2,3 dihydroxy dioxane
US3241972 *May 28, 1963Mar 22, 1966Eastman Kodak CoGelatin compositions
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3471290 *Oct 1, 1965Oct 7, 1969Xerox CorpPhotochromic photoresist imaging
US3480440 *Jun 1, 1966Nov 25, 1969Agfa Gevaert AgHardening of photographic gelatin-containing layers
US3981857 *Mar 18, 1974Sep 21, 1976Konishiroku Photo Industry Co., Ltd.Gelatin hardening process
US4952332 *Aug 24, 1989Aug 28, 1990Basf AktiengesellschaftDetergents that contain acyl derivatives of dihydroxydioxane as bleach activators
US5851424 *Jul 25, 1996Dec 22, 1998Rolic AgPhoto cross-linkable liquid crystalline 1,4-dioxane-2,3 diyl derivatives
DE3518075A1 *May 20, 1985Jan 9, 1986Hoechst FranceGlyoxal derivatives and process for their preparation
EP0782045A1Dec 16, 1996Jul 2, 1997AGFA-GEVAERT naamloze vennootschapSilver halide colour photographic film element having a thermoplastic support capable of being marked by means of a laser
Classifications
U.S. Classification106/150.1, 430/624, 527/201, 530/354, 106/164.4
International ClassificationG03C1/30
Cooperative ClassificationG03C1/30, G03C1/301
European ClassificationG03C1/30, G03C1/30B