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Publication numberUS3475174 A
Publication typeGrant
Publication dateOct 28, 1969
Filing dateMar 23, 1966
Priority dateMar 29, 1965
Also published asDE1572074A1
Publication numberUS 3475174 A, US 3475174A, US-A-3475174, US3475174 A, US3475174A
InventorsSakamoto Eiichi, Sakurai Setsuji, Sato Shui
Original AssigneeAjinomoto Kk, Konishiroku Photo Ind
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
N,n dialkyl n' acyl-diaminocarboxylic acid coating compositions
US 3475174 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,475,174 N,N DIALKYL N ACYL-DIAMINOCARBOXYLIC ACID COATING COMPOSITIONS Shui Sato, Hachioji-shi, Tokyo, Eiichi Sakamoto, Hannoshi, and Setsuji Sakurai, Fujisawa-shi, Japan, assignors to Konishiroku Photo Industry Co., Ltd., Tokyo, Japan, and Ajinomoto Co., Inc., Tokyo, Japan No Drawing. Filed Mar. 23, 1966, Ser. No. 536,628 Claims priority, application Japan, Mar. 29, 1965, 40/ 17,767 Int. Cl. G03c 1/02; C09d 3/04 US. C]. 96-94 7 Claims ABSTRACT OF THE DISCLOSURE Novel compounds and photographic coating compositions comprising same. The compounds are of the formula:

X-GH-OOOM wherein either X or Y is a lower dialkyl amino group of the formula wherein R and R are lower alkyl groups and the other of X and Y is an amide group of the formula NHR wherein R is an acyl group of 6 to 18 carbon atoms; M is hydrogen or a lower alkyl group and m is an integer from 2 to 4 inclusive.

This invention relates to N,Ndialkyl-N'-acyl-diaminocarboxylic acids, their lower alkyl esters and their acid addition salts. In the particular aspect, the present invention is directed to photographic layers containing the above-mentioned compounds as coating aids.

Photographic light-sensitive materials usually have a support and a plurality of layers coated thereon. ArnOng these layers there are included backing layer, subbing layer, light-sensitive emulsion layer, protective or antihalation layer, filter layer, etc. In the routine work of the art, these layers are formed on the film support by applying a coating liquid (solution, emulsion or dispersion) to the support and then drying the coating. In this case, it is very essential to apply a variety of coating liquids onto the entire surface of the support at uniform thickness. In the prior art, however, unevenness in the coating directions (frequently referred to as longitudinal unevenness or transverse unevenness) and local imperfection of coating (frequently referred to as comets) or unevenness at the peripheral zone are occasionally observed. In order to prevent such drawbacks, use of a coating aid, e.g. a surface tension depressant for coating liquids, is well known in the art.

Among the known coating aids, saponine is the most common. Because the saponine is a material of the natural origin, however, use of the saponine inavoidably causes an adverse effect on the photographic properties of the resulting film due to the varying quality of said saponine. Alternatively, use of certain synthetic surface active agents also has been proposed. However, the known surface active agents are not fully satisfactory, as they usually have an adverse influence on the photographic properties, e.g. storability under high humidity at high temperature, and show only poor ability to decrease surface tension and contact angle.

Another serious problem encountered in the prior art is undesired formation of static marks in an emulsion ICC layer as the result of static electricity induced on film base when dried photographic film is brought into frictional condition. Prevention of the formation of such static marks, as well as improvement in coating uniformity, is highly desirable in the art, but unfortunately it is to be said that such a compound which can provide both effects has never been known.

Now we have found that a compound of the general formula X-CH-COOM (CH2)n wherein one of X and Y is a group (wherein R and R individually mean lower alkyl) and the other is a group NHR (wherein R is acyl group having 6 to 18 carbon atoms); M is hydrogen or lower alkyl; and n is an integer of 2, 3 or 4, or the salt thereof, is useful as coating aid which permits us to be free from any disadvantages of the prior art coating techniques. Thus, if the above-indicated compound is used as a coating aid singly or in combination with any other known surface active agent, a film-coating liquid containing said coating aid shows an appreciable decrease in viscosity, thereby to facilitate high speed coating at about 40 m./ min, without formation of uneven coating or comets. Not only the formation of uniform coating but also the antistatic effect is provided by the present invention. A particular advantage of the present invention is that the compounds used therein has no little adverse influence on the photographic properties of the film produced. Thus, a coating aid of the present invention can be incorporated, without harmful effect, into not only photographic gelatinous emulsions but also various photographic dispersions which may contain a synthetic polymer (e.g. polyvinyl alcohol) as a binder.

Typical compounds which are usable in the present invention will be illustrated below. However, it should be noted that they are merely illustrative and do not limit the scope of the invention. Effectiveness of these compounds in the photographic application is entirely independent on the optical activity of the said compounds.

Compounds M.P.,

N 0. Chemical Name C.

I N gN -dimethyl-N -stearoyl-DL-ornithine. 154-156 II N",N -dimethyl-N -myristoyl-DL- -125 ornithine.

III N ,N -dimethyl-N -lauroyl-DL-ornithine. 159-161 IV. N,N -dimethyl-N -palmitoyl-DL-lysine 132-134 V N",N -dimethyl-N -lauroyl-DL-lysine 162-164 VI. N,N -dimethyl-N -caproyl-D L-lysine. 141-146 VII N -palmitoyl-N=,N -dimethyl-L-lysine 123-124. 5

VIII Npalm1toyl-N,N*-dimethyl-L-1ysine 86-88 methyl ester hydrochloride.

IX N,N -dimethyl-Nr-palmitoyl-DL- nr-diaminobutyric acid.

X N' ,N"-dimethyl-N -oleyl-DL-lysine 139-143 XI N ,N -diethyl-N -lauroyl-DL-ornithine XII N -lauroyl-N ,N -dimethyl-L-lysine methyl 65-67 ester hydrochloride.

XIII N,N -dimethyl-N -lauroyl-DL-ornithine methyl ester (syrup).

These compounds can be easily obtained by converting a diamino-carboxylic acid (eg, ornithine or lysine) having a di-lower alkyl substituent at either one of N- and N -positions into the copper salt or ester and then reacting the resulted compound, which carboxyl group has been blocked, with an acylating agent donating an acyl group of 6 to 18 carbon atoms, e.g. stearoyl chloride, palmitoyl chloride, etc. For information, typical procedures for the preparation of certain compounds will be described below:

N",N"-dimethyl-N"-lauroyl-DL-ornithine 34.2 g. of 3-aminopiperidone-(2) hydrochloride are dissolved in 130 ml. of an aqueous solution containing 34% formaldehyde. The resulting solution, together with 10 g. of 10% palladium-deposited carbon, is placed in a 300 ml. autoclave into which hydrogen is pressed at an initial pressure of 120 kg./cm. With stirring the resulting mixture is maintained at room temperatures for 2 hours. After completion of the reaction, the catalyst is filtered 01f from the reaction mixture which is concentrated under reduced pressure, added with toluene and concentrated again. The residue is subjected to fractional distillation under reduced pressure to recover the fraction boiling at 127 C./mm. Hg. It is dissolved in 67 ml. of 4.5 N-HCl methanolic solution, and the resulted solution is concentrated and added with acetone thereby to form 45.4 g. of crude crystalline 3,3-dimethylaminopiperidone-(2) hydrochloride. Yield 85%. The crude crystals are dissolved in 23 mil. of methanol and added with 68 ml. of acetone. After standing the resulting mixture overnight, crystals are separated. Additionally 90 ml. of acetone are added to obtain a further crop of separated crystals. Yield 37.7 g. M.P. 202-204 C. (decomp., uncorrected). Elementary analysis is as follows:

Calcd. for C H N OCl: C, 47.05%; H, 8.46%; N, 15.68%. Found: C, 47.22%; H, 8.67%; N, 15.43%.

The thus obtained 3,3-dimethylamino-piperidone-(2) hydrochloride (8.9 g.) is heated at reflux for 3 hours with 50 ml. of an aqueous solution containing 6 g. of sodium hydroxide. The resulting aqueous solution is neutralized with 8.3 ml. of 6 N hydrochloride acid and then poured into 35 m1. of an aqueous solution containing 6.3 g. of cupric sulfate pentahydrate. The insoluble matters formed are taken away by filtration and the mother liquor is concentrated to have 50 ml. of an aqueous solution containing the copper salt of N, -dimethyl-DL-ornithine. The aqueous solution is brought into reaction with lauroyl chloride and the resulted reaction mixture is treated with hydrogen sulfide for 60 minutes. The reaction mixture is filtered and the filtrate is concentrated under vacuum to obtain 10.3 g. of crude crystalline N,N-dimethyl-N- lauroyl-DL-ornithine. Yield 60% based on 3,3-dimethylamino-piperidone-(2) hydrochloride. The crude crystalline product is dissolved in 4 times volume of ethanol and treated with active carbon. On adding 1.5 times volume of ether to the resulted solution, 9.1 g. pure desired product are obtained, M.P. 159-161" C. (uncorrected). Elementary analysis is given below:

Calcd. for Owl 133N203: C, 66.62%; H, 11.18%; N, 8.18%. Found: C, 66.13%; H, 11.03%; N, 8.02%.

N, -dimethyl-N"-stearoyl-DL-ornithine 7.5 g. of N,N-dimethyl-DL-ornithine are dissolved in 100 ml. of an aqueous solution containing 10 g. of cupric acetate monohydrate. The resulting solution is concentrated and the separated crystalline mass is recrystallized from Water. The copper salt of N,N-dimethyl-DL-ornithine is dissolved in 100 ml. of water. To the resulting solution, 100 ml. of ethyl ether is poured to form an upper layer. To the mixture with stirring and ice-cooling (ll-5 C.) are added dropwise for 20 minutes 7 g. of stearoyl chloride dissolved in 50 ml. of ethyl ether and a normal sodium hydroxide solution sufficient to provide 1.1 moles of NaOH per mole of stearoyl chloride. Stirring is continued for additional two hours. The formed copper salt of N",N-dimethyl-N"-stearoyl-DL-ornithine precipitates as crystals which are collected by filtration. Yield 15 g. (70% on theoretical basis). The crude crystals are recrystallized from the small amount of ethanol to obtain 10 g. of the pure product.

5.0 grams of the pure copper salt are dissolved in 200 ml. of ethanol. Into the resulted solution, with stirring,

hydrogen sulfide gas is passed for 60 minutes. The reaction mixture is filtered and the filtrate is concentrated under reduced pressure to obtain 40 g. of crude crystalline N,N-dimethyl-N-stearoyl-DL-ornithine. Yield 87% The crude product is dissolved in 10 times amount by volume of ethanol and the resulted solution is treated with active carbon. After standing the filtrate overnight at 5 C., 2.0 g. of the pure product is obtained, which has a melting point of 154-l56 C. (uncorrected). Elementary analysis of the product is as follows:

Calcd. for C H N O C, 69.67%; H, 11.74%; N, 6.57%. Found: C, 70.37%; H, 11.81%; N, 6.37%.

N,N-dimethyl-N -myristoyl-DL-ornithine 7.5 g. of N,N-dimethyl-DL-ornithine are dissolved in ml. of an aqueous solution containing 10 g. of cupric acetate monohydrate. The resulting solution is concentrated to have separated crystals which are purified by repeated recrystallization from water. The formed copper salt of N",N -dimethyl-DL-ornithine is reacted with myristoyl chloride in amount of 1.1 moles per mole of said copper salt, and then the resulted reaction product is treated with hydrogen sulfide in the same manner as in the preceding example, thereby to remove the copper. 8.0 g. of crude crystalline N,N-dimethyl-N"-myristoyl- DL-ornithine are obtained. Yield 46%. The crude product is dissolved in ethanol and the resulting solution is concentrated in vacuo thereby to obtain 40 g. of the pure product having a melting point of -125 C. (uncorrected). Elementary analysis is given below:

Calcd. for C H N O C, 68.06%; H, 11.42%; N, 7.56%. Found: 67.50%; H, 11.61%; N, 6.89%.

N,N-dimethyI-N -IauroyI-DL-Iysine 5.0 g. of N ,N -dimethyl-DL-lysine are dissolved in methanol saturated with HCl. The resulting solution is heated under reflux and then concentrated under reduced pressure. The concentrated mass obtained is dissolved in chloroform and then added with 3.7 ml. of triethylamine and 5.7 g. of lauroyl chloride. After stirring, the resulted mixture is allowed to stand overnight at room temperature. The resulting reaction mixture is concentrated. The residue is dissolved in 75 ml. of methanol and added with 24 ml. of 2 N NaOH aq. The mixture is stirred at room temperature for one hour. The mixture is then neutralized with 12 ml. of 4 N HCl and concentrated under reduced pressure. The residual mass is added with a small quantity of ethanol and concentrated again under reduced pressure, thereby to remove water. The resulting waterfree residue is dissolved in 20 ml. of hot ethanol. Undissolved sodium chloride is separated by filtration. After standing the filtrate in an ice box overnight, 2.8 g. of crude crystalline N,N-dimethyl-N-lauroyl-DL-lysine are obtained. Yield 30.2% based on N,N-dimethyl-DL- lysine hydrochloride. The crude product is dissolved in 8.4 ml. of hot ethanol. The resulted solution is treated active carbon and then added with 10 ml. of ether. 6.6 g. of pure product as obtained, which has a melting point of -162 C. (uncorrected). Elementary anlysis of this product is as follows:

Calcd. for C H N O C, 67.37%; H, 11.31%; N, 7.86%. Found: C, 67.15%; H, 11.46%; N, 7.83%.

In carrying out the present invention in effect, a compound of the present invention is prepared as a solution (for example, 2% solution) dissolved in water or a watermiscible solvent, e.g. methanol, ethanol, acetone, etc., which solution is then added to a coating liquid. An amount of 1 to 50 ml. of 2% solution per 100 grams of the coating liquid usually is satisfactory. Any other known surface active agent may be used in combination with the coating aid of the present invention. In either case, the optimum amount of the coating aid used should be determined within the above-specified range, depending on the surfacial activity of the coating liquid, the contact angle against the support or the required mobility or antistatic activity.

In the typical embodiment of the present invention, incorporation of a coating aid of the invention into a photographic emulsion can be made in the manner heretofore 6 dimethyl N lauroyl-DL-ornithine and N,N-dimethyl N lauroyl-DL-lysine, are prepared as 3% aqueous solutions. The respective solutions are added at the amount of 6 ml. to each of three portions of the abovedivided emulsion. To the remaining 100 g.-portions, 6 ml.

known per se in the art. For example, the coating aid can 5 of an aqueous solution of 3% saponine is added for combe added to the emulsion at any time just before, during parison. The resulting mixtures are coated respectively or after the second ripening of the said emulsion. This to the subbed surfaces of cellulose triacetate film bases by photographic emulsion may be such that is sensitized by dipping method. way of gold-, sulfuror other chemical sensitization, for 10 On these cellulose triacetate films, the protective layers example, using polyalkylene oxide or optical sensitizaare provided by applying thereto 2% gelatine solution tion. Further it may contain an azaindene stabilizer, a to which the above-used coating aids have been added corhardener, or a color former, if color film is to be prerespondingly at the amount of 6 mL/lOO g. of the gelatine pared. solution. The results are set forth in the following tables.

TABLE 2 Notch Number at the of comperiphery ments per Relative Compound Coating of coating 1.0 m! speed Fog II Practicallyuniform... None 105 0.02 III do do 1 100 0. 03 V do .do 0 102 0.02 saponine (control) Unevenness appeared .do 2 100 0.02

at random.

The following examples describe certain ways in which TABLE 3 the principle of the invention has been applied, but are not to be construed as limiting its scope. 25255; s ifi EXAMPLE 1 by 3%??? re a 9:313: Surface Contact N,N-dimethyl-N -stearoyl-DL-ornithine (I), N,N-diand tats-1., 3l1s9% $33 at 5 methyl-N -palmitoyl-DL-lysine (IV) and N,N-dimethyl- RH (w) (am/m) -oleyl-DL-lysine (X) are prepared as 3% aqueous solu- H 67 9.4 10 36.2 32.6 tions, respectively. These aqueous solutions are individual- 5 I;I I gzgfig 22:2 2312 1y added in their respective amount of 6 ml. to 100 g. of a p 101 12. 5X10 43.4 45.4 high speed negative, photographic silver iodobrornide emulsion. Each of the thus obtained emulsions is coated The above data indicate that coating aids of the Present onto h bb d su fa of ll l triacetate fil b invention are comparable to saponine which is a relatively means of double rollers. 100 g. of 2% gelatine solution 40 satisfactory coating aid known in the It is found that are added with 6 ml. of each one of the above-named the coating aids the invention are Capable of Providing Compounds (I), (IV) and Thg gelatine solutions of uniform coating without an adverse effect on the photothe three kinds thus prepared are applied as protective graphic Properties of tha Tasultihg filmslayer onto the emulsion-coated surfaces of the above-said EXAMPLE 3 cellulose trlacetate film bases, respectively. 5

For comparison, 6 ml. of an aqueous slution contain- To 100 grams of a sllver chlorobromlde elhulslon for ing 2% sodium isoamyldecylsulfosuccinate (control) are phofogrflphlc Papers 1 aqueous Solutlon of 4 added to 100 of the ahovesaid photographic emulsion, sodium 1soamyldecylsulfosuccmate 1s added. The resulting which is then coated on the subbed surface of cellulose mlxture coated on a baryta Paper by dlPPmg alr'doctor triacetate film. 2% gelatine emulsion to which the aqueous method' Solution containing the control compound have been Separately, an aqueous solution conta1n1ng 2% gelatine added at the amount of 6 ml. per 100 gram is placed as 18 Prepare? dlvlded four eqPal P one of protective layer on the emhlsiomeoated Surface of the these portions 1s added with the said succmate aqueous ahovesaid cellulose triacetate film solutlon at the amount of 0.5 ml. per 100 grams of the The results are set forth in the following table gelatine solution. The other three 100 g.portions of the 2% gelatine solution are added with 3 ml. of an aqueous TABLE 1 solution containing the specified compound, i.e. N, N- Relatm dimethyl N palmitoyl-DL-lysine (IV), N-palmitoyl- Compound Coating property speed Fog Gamma NiN dimethyl-L-lysine (VII) 01' N-palmitoyl-N,N- I Neitherunevennesm, 111 M2 M4 dimethyl-L-lysine yl t hydrochloride UD- The repellency observed. thus prepared coating liquids are used to provide pro- 52'1331::::::::: it! 8:83 8:31 waive layers 0n the emlusion-ooated Surface of the above Control Unevenness in coating at 110 0.02 0.72 papers.

Places Without causing any adverse eifect on the quality of the photographic papers, uniform coating in double layers A shown i h ab d h compounds (1), (1V) 1s obtained as indicated in the following table: and (X) of the invention serves to provide uniform coating without an adverse effect on the photographic prop- TABLE 4 erties of the resulting film. Number $522; EXAMPLE 2 Coating 1.0 m.

400 grams of a high speed photographic silver iodo- Compou d: bromide emulsion is divided to four equal portions. The vff fffjff above-indicated compounds (II), (III) and (V), i.e. g

N,N dimethyl N myristoyl-DL-ornithine, N,N-

What is claimed is:

1. A photographic coating composition comprising a gelatine binder and, as a coating aid, an effective amount of a compound of the formula X-CfH-COOM wherein either X or Y is a lower dialkyl amino group of the formula wherein R and R are lower alkyl groups and the other is an amido group of the formula NHR wherein R is an acyl group of 6 to 18 carbon atoms; M is hydrogen or a lower alkyl group; and n is an integer from 2 to 4 inclusive.

2. A photographic coating composition as claimed in claim 1, wherein said compound is present in one or more layers selected from photo-sensitive layer, backing layer, protective layer, anti-halation layer and subbing layer.

3. A photographic coating compositon as claimed in claim 1, wherein said compound is used in combination with a surface active agent.

4. A light-sensitive photographic silver halide emulsion comprising a gelatine binder and, as a coating aid, an effective amount of a compound of the formula (HDn 8 wherein either X or Y is a lower dialkyl amino group of the formula References Cited UNITED STATES PATENTS 2,240,471 4/1941 Swan 96-94 3,133,816 5/1964 Ben-Ezra 9694 3,306,749 2/1967 Knox et al. 96-94 NORMAN G. TORCHIN, Primary Examiner M. F. KELLEY, Assistant Examiner US. Cl. X.R. 106-1 25

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2240471 *Mar 7, 1940Apr 29, 1941Eastman Kodak CoPhotographic gelatin layer containing a n-acylated amino acid
US3133816 *Jul 15, 1960May 19, 1964Gen Aniline & Film CorpPhotographic coating formulation
US3306749 *Mar 4, 1965Feb 28, 1967Eastman Kodak CoGelatin coating compositions
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US6071688 *Jul 29, 1998Jun 6, 2000Eastman Kodak CompanyContacting coating material on a support with uniform cloud of additive vaporized by flowing carrier gas through liquid phase additive
US7250202Jun 18, 1999Jul 31, 2007Ilford Imaging Ch GmbhSupport with image receiver sheet
WO2012035314A1Sep 7, 2011Mar 22, 2012Fujifilm Imaging Colorants LimitedPhotographic paper
U.S. Classification430/510, 430/570, 430/542, 430/635, 430/599, 106/155.21
International ClassificationG03C1/38
Cooperative ClassificationG03C1/38
European ClassificationG03C1/38