BE558481A - - Google Patents

Description

       

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   The present invention relates to photography and more especially to a process for improving photographic polymer mordants for acid dyes used for printing elements by transfer or dye imbibition.



  It further relates to film elements containing improved polymer mordants for acid dyes and to elements bearing photographic silver halide emulsions containing the improved polymer mordants for acid dyes.



   It is well known that the mordants used in etched films for transfer or imbibition dye printing operations tend to diffuse out of the etched image receiving element and into the etch matrix.

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 gelatin bearing the image. This migration or diffusion of the bite is called return transfer and is very troublesome. Thus, after repeated transfers of successive applications of dyes of the same matrix in serial printing operations, the matrix becomes impregnated with the mordant accumulated by the pre-mixed image receiving element at each successive printing. and the efficiency and usefulness of this matrix are thus reduced.



    In addition, the mordant may spread in regions of the matrix which should not contain transfer dye and therefore ultimately determine a lack of sharpness and undesirable dye density in the light regions of the print. finally obtained.



     An object of the invention is to provide a method for improving the back transfer properties of an acidic dye mordant for photography and more especially to provide a method for treating a polymer mordant for inclusion in a mordant. dye impression receptor film element and especially in a light-sensitive silver halide photographic emulsion without causing any adverse effect to either the emulsion or the polymeric agent, i.e. without any effect detrimental to the photographic properties of the emulsion such as its gamma index, haze density and haze stability.

   '
Another object of the invention is to provide improved film elements, in particular gelatin plates, light sensitive silver halide emulsions and photographic films comprising light sensitive layers, these elements containing mordants. Polymers for acidic dyes which exhibit negligible back transfer when used in dye transfer or imbibition processes.



   It has been found that a decrease in mordant return transfer in mordant transfer processes is obtained.

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 when using a polymeric acid dye cord having recurrent extra-linear amino groups in the re-centering film of the image during the transfer dye printing operation, which miter has been processed by mixing the biting in solution with polyvalent metal ions, i.e. metal ions having a valence of at least two.

   The undesirable characteristics of the return transfer are further markedly reduced if the treated mordant undergoes a maturation or aging treatment as described below before introducing this mordant into the water-permeable colloid, for example gelatin, serving to force the layer which should ultimately receive the transfer dye.



   According to the present invention, in a process for the preparation of elements containing a polymeric acid dye-containing agent, a polymeric acid-dye mordant having repeating extra-linear amino groups is mixed, in solution, with polyvalent metal ions, in an amount of at least 0.006 g mole per 100 g of the mordant present.



   The invention also comprises a method of polishing reducing the tendencies to back transfer of a polymeric mordant for acid dyes of the type having recurrent extra linear amino groups in which the mordant is mixed, before including it in a receptor element of the acid dye. image, in solution with polyvalent metal ions, these ions being present in an amount of at least 0.006 g mole per 100 g of mordant present.



   The metal ions can be advantageously introduced by adding a corresponding metal salt to a solution already containing the mordant, or by adding the mordant to a solution of the metal salt, or by mixing two separate solutions, one of which contains the mordant and the other contains the metal ions which may have been introduced in the form of a metal salt.



  After mixing, the solution of metal ion and mordant can be added to a water-permeable colloid binder to form a

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 filmstrip element.



   The invention also comprises a method of the type indicated above in which the mixture obtained is subjected to an aging operation before including it in the image receiving element.



  The aging operation consists in subjecting the solution to certain conditions of time and. temperature which can vary between wide limits according to each particular case.



  It has been found that proper aging and the reduction in back transfer that it entails can even occur at refrigeration temperatures of about 45 F (8 C) if the aging period can occur for a sufficient time. long. Temperatures as low as 32 F (0 C) and up to 212 F (100 C) are considered satisfactory. In addition, there is no minimum or maximum time required for the aging of the solution of the mordant and the metal ion; the reduction in return transfer is all the more important as the aging period is longer.

   For example an approximately equal reduction in return transfer occurs when the aging process is performed for 264 hours at 45 F (8 C), 48 hours at 95 F (35 C), or 5/2 hours at 140 F (60 VS).



  A more or less thorough aging treatment at any given temperature, depending on the case, gives a greater or lesser degree of improvement in the reduction of the return transfer.



   The invention also includes emulsions of water permeable colloids and photographic emulsions containing the improved mordant described above and film elements prepared from such emulsions. Emulsions are made by simply mixing the polymers treated according to the method of the invention with a dispersion of a colloid, such as gelatin, which acts as a binder for the mordant.

   Such an emulsion, which may or may not be sensitive to. light can be applied to a suitable support or layer to form a film element which can be used as an image receptor element in a

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 dye imbibition transfer process.



   Thus, a photographic emulsion can be obtained by simply mixing the mordant treated according to the invention with an aqueous dispersion or an aqueous emulsion of a light sensitive silver halide in a permeable colloid. at. water, which may contain the usual emulsion builders such as sensitizing dyes, stabilizers, curing agents and anti-fog agents and in. 1''applying it on a suitable support or layer to obtain a photographic element. In general the. The amount used is about 25 to 55 g per mole of silver halide.

   The products obtained have excellent mordant properties against acid dyes and are particularly remarkable for the superior non-diffusing properties of the polymer mordant.



   Polymeric mordants used in the invention are polymeric mordants for acid dyes having repeating extra linear amino groups. By "amino group" is meant either an amino group proper or an acid salt or a quaternary salt of such a group. The polymers may or may not be substituted and may include polymers of amines, salts of amino acids and quaternary ammonium salts and copolymers of two or more of these amines, salts of amino acids and quaternary ammonium salts. , with each other or with other polymerizable ethylenically unsaturated compounds in an amount not exceeding about 50% thereof.

   Polymeric mordants suitable for the methods and products of the invention include the polymeric polyamine mordants described in U.S. Patent No. 2,753,263, the quaternary salts of polyvinylpyridine described in U.S. Patent No. 2,484,420, and the polymers of alkylamine described in U.S. Patent No. 2,675,316. The preferred mordants are the copolymeric esters of alpha-alkacrylic acids and amino alcohols having quaternary and tertiary salt groups in an amount of 35 to 75 moles:; of the former for 65 to 25 mole% of the latter,

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 Z1: -;

  , \, - Ic b1.'C'- "- .: c- '. ;; e n 543.03l. Les :: lOrG.cm, ts polr; cre ^ which have
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 molecular weights greater than 10,000 are preferred.



  Metal ions useful in the present invention
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 include those which are known from CO ::; Cnlcine curing agents. This hardening or crosslinking of gelatin or Q'aut: C'9s protein materials is well known.



  Appropriate metal ions which can be introduced are mentioned above as a suitable ionizable salt, inter alia, cilroeieue, cuprrique, aluainiuj.'ti and earth ions.



  Appropriate salts containing these% t2lliçues ions. co: ipre? nen'c the 'bromide chro.:içue, sulphate chror, 1ÍQue, chloride 6.' e.lu:1inivJQ, sulphate (-: "e, l1.12L1.2.l. ::,: et de) otCl.ssiD: ', chloru-re ferri4t? e, .le sulphate îerriçuc, 1' '' 2uli'c, te ('2 .. ::.:. OniU:, l and i'er r içue, the copper c? L7.orvre and the sul.'c.tc copper ctte.? Ami 1 es Useful salts those which contain ionizable trivalent 2'ta.llicve ions are preferred and in particular the metallic salt: ue) r6ff1.'6 is chrone alill1.



  It has been found that the concentration range of the ions r10te, llique to use; '-' 'in the iJl'ocÚ1és and products of the invention is limited to a çw w ='. I t -: lÍnL1u :: .. '1. 0.006 Dole per 100 g of
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 Darting present. Below this level the quantity of metal ion
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 that added is insufficient to determine a substantial improvement in the return transfer properties of the north. The superior 7¯irite is not critical but it has been found that large concentrations of l ': 1 ions (t :: c.1J.iç, ues cause embrittlement of a water-permeable colloid eruption. or the) elicle.

   The. upper limit is therefore due to:.: Ün'2 by the degree of freshness it / which can be attained for the skin and this fragility is "; :: <= ,, 1 (;, 'C: lt affected by other : cC tC.2 '! r ,, par', C '.: 1) 10 additives 0.' (', ulsiof1 lyt the eO (16iaOl:'; 'é' .1d.ê ", ttCE 'of temperature and humidity. jer ions: '.- tc.llic, tles en cy: r.n'.; it: 'can [ttcL1, cl1.'e 0.065 c -'010 and more by 100 ;;. (, O -ordant are considered eoi = 1.ie ra.tiiiéiir8iits.



  The preferred ZiLl.l0 of COl1Cc.ltrr ion is from 0.02 to 0.055 at 101L per 100 C of cord.

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 We have. found that it is essential to mix the ions
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 metallic at. Mordsnt polyrier before inserting it in the;. 1u1 sion plhotograahicue or client of film. Merely adding the metal ions to the photographic emulsion or to the water-permeable colloid as is done when the ions are used as colloid curing agents does not achieve the remarkable reduction in return transfer obtained following the process of the invention.
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  The colloids used as binders in the emulsions according to the invention can be any ordinary colloid used by manufacturers of photographic materials. They are generally 2. water permeable and can be natural or synthetic. thus, the colloid, which is preferably gelatin,
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 can also be ô agar, e; arc1, albuiiiine, zein, collol1., iJol3Tvinyl alcohol, ¯ partially hydrolyzed 901er acetals and hydrophilic copolymers of these compounds with non-acidic monomers. ethylenic saturation such as ethylene or vinyl chloride;

   polyvinyl acetals, for example
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 'acetals of polyvinyl alcohols with acctaldehyde or benzaldehyde; or water-soluble or hydrophilic cellulose derivatives. Suitable binders or water permeable colloids of these different types are described in the United States patents.
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 cains n s z.llo..91, 2.211.323, 2.276.322, 2.276.323, 2.286.215 and? .397.866.



   To form a film element the emulsion containing the mordant solution and metal ions according to the invention
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 is 2.l) JliquGe by any suitable means on a suitable support. These supports include paper, which can be covered with this barite, cardboard or paper waterproofed or made transparent or
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 any other film.

   The support? 7eu.'t, be composed of any hydrophilic sheet as a film, for example of cellulose derivatives, such as cellulose nitrate, cellulose triacetate,
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 cellulose pI09ionate, and cellulose acéto-hu'tyra.U; the

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 1> Olyviiyrl chloride, Ci1lOî'Ola. Polyvinyl acetate: i: '! û, acftalc h> - <ropliiles, for example of fomaldehyde and cC, ''. t8¯1C? CrilùrC'¯eSj fuper: JOlY2.itlÎnes, for example polypuids, polyesters correct the tre11hté :, polyethylene lint and polystyrene. The support of the. film may be linpid or contain yiv-¯ezt ;: or dyes.

   The base 1. # coated polyester film described in patent na 2.ex27.008 is particularly useful co 1 = e
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 support material.
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  For "J.Slf, :: l ::; er the polymer cord with. ::: rl ts 1ic ^ s ions in solution, the solvent must be a solvent co :. tn at Y, '. Or; 8.nt and at
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 metallic salt. When the colloids permeable to. usual water
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 C #: 1:, the binder the solvent is preferably water.



  The processes and products of the invention are illustrated by the examples which follow which t '-eòī <; cannot be considered as part of the invention.



  : 5JT "IPLE 1.On ap) licuG to a photographic citiulsion c '? Oco-bro-.ure c"' .. 'silver and gelatin sensitive to 11Xli8re .. of the washed positive type .. a second ordinary treatment of digestion and divide it into four equal parts. Has the. first part (1) an aqueous solution of 5 :: by weight u.l'J. copolymer of tertiary salt of ethyl -'lÍno (: tl1yl ;;: thacrylc, te and quaternary salt of di ± th> + 1- 8-: inos thylns thacryl, ::, te having an: olar ratio of 60; ;) tertiary salt for 0; . quaterm'.iro salt, prepared following the methods dccribs in the African patent application no. 574,593 j fi. ratio of 22.0 g of copoly.:çre per 100 g of gelatin at the ulsion.



  In the second part (2) a quantity of a solution of cordant c01) olY:, lore (it has been aged 1.140 F (b0 C) for 21 hours is added. . third part (3) of 1 '<'>. mlsion was added a quantity ([you were the solution of copoly-ior cordant to which we added 1 'mon of chr, o. = ie at the rate of 0.041 g Mole per 100 s of cord, the solution, 1 t of alum oe chrone and of 'cord po15f1èr:.: 7Rnt

 <Desc / Clms Page number 9>

 
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 5t :) aged for 24 hours at 75 F before incorporating it into the ii1úl 'sion. To the fourth part (4) of the emulsion is added an equal amount of a mixture of chromium alum and polymer mordant co "ple in part 3, but the mixture is aged at 140 F for 21 hours before using it.

   To parts of emulsion 1 and 2 are added a quantity of chromium alum equal to that contained in the mixtures of chromium alum and mordant used in parts 3 and 4. The usual post-digestion additives,
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 stabilization and coating aids are added to each portion and the emulsions are applied to a carrier rinse made of a cellulose acetate film and dried in the usual manner.



   Strips of each coating are then treated without.
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 exposure in a positive-type metol-hydroquinone developing solution and fixed in a hyposul- type fixation bath
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 fite, non-hardening, to remove silver halide.



   The film samples are then dried and subjected to an imbibition blot test to determine the degree of mordant migration which approximately corresponds to the degree. transfer of bite that normally occurs in the mouth.
 EMI9.5
 co; tuierciales operations when carrying out 20 successive transfers of dye by imbibition from the same matrix.

   The aqueous solution of the dye used is adjusted to a pH of
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 2L ,. to 3.0 and contains approximately per liter of water 1.6 g of Pontacyl Carmin 6B Extra Concentrate (Color Index n 57), magenta dye. 'The spectral density of the residual coloration obtained on the film used to determine the degree of
 EMI9.7
 return transfer is given by a color densitometer (described in J.S.II.P.T.E. 5.2, page 23, 1951) with a wavelength of 540 rilliiiaicrons. The spectral density of the residual coloration is a direct measure of the degree of back transfer. The density of the residual coloration is all the greater as the quantity of
 EMI9.8
 rit Qcsorb ':: e from the test etched during the test

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 transfer rate by imbibition is stronger.

   For example, if a control film containing no mordant is used instead of the etched film in the test method described above, the spectral density of the residual coloration determined for a wavelength of 540 millimicrons is zero. in measuring the accuracy of the density determination.



   Sensitometric testing of four layers of light-sensitive silver halide emulsion containing mordants; which have been treated differently as described above is carried out as follows: Samples from each layer are exposed in a sensitometer Ib and developed for 7/2 minutes in a developing agent of the positive type metol-hydroquinone at 68 F (190C). Fixing, washing, drying, and determining the speed of the gamma index and haze is carried out in the usual manner. A second sample from each layer is subjected to an incubation treatment at 120 F (48 C) and 65% relative humidity for 48 hours and treated with the unincubated samples. For the incubated samples only haze values are recorded.

   The results obtained are given in Table I.



   TABLE I
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<tb>
<tb> Layer <SEP> Treatment <SEP> of <SEP> Density <SEP> of <SEP> the <SEP> Test <SEP> on <SEP> layer <SEP> Test <SEP> on
<tb> n <SEP> nordant <SEP> coloring <SEP> fresh <SEP> layer <SEP> in-
<tb> ¯¯¯¯¯¯¯¯¯¯ <SEP> residual <SEP> Speed <SEP> Gamma <SEP> Sail <SEP> cubed <SEP> sail
<tb> 1 <SEP> None <SEP> 1.26 <SEP> 100 <SEP> 3.07 <SEP>, 01 <SEP>, 13
<tb> 2 <SEP> Aged <SEP> for
<tb> 21 <SEP> hours <SEP> to
<tb> 140 F <SEP> (60 C) <SEP> without
<tb> alum <SEP> from <SEP> chrome <SEP> 1.19 <SEP> 102 <SEP> 3.23 <SEP>, 01 <SEP>, 13
<tb> 3 <SEP> Aged <SEP> for
<tb> 21 <SEP> hours <SEP> to
<tb> 75 F <SEP> (25 C) <SEP> with
<tb> alum <SEP> from <SEP> chrome <SEP>, 77 <SEP> 100 <SEP> 3,18 <SEP>, 01 <SEP>, 10
<tb> 4 <SEP> Standby <SEP> for
<tb> 21 <SEP> hours <SEP> to <SEP> 140 F
<tb> (60 C)

   <SEP> with <SEP> alum <SEP> from
<tb> chrome <SEP>, 06 <SEP> 66 <SEP> 3,18 <SEP>, 01 <SEP>, 06
<tb>
 
The results of example i show that the metal ion treatment and retort aging in the layers n s3 and 4 determines a reduction in return transferrespec-

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 EMI11.1
 tiveaent of 3S, 9; and 95, 2: 'relative to the untreated mordant. No detrimental effect on the photographic properties of the emulsion is observed. The slight reduction in speed shown in the table is not critical in emulsions of the positive type and can be
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 cO :: l1Jée by means well known in the art.



  E r'.nI 1, I I. -
This example illustrates the reduction of the return transfer as a function of the variation and the aging time of
 EMI11.3
 mixtures I, Ord8.11.t-poly; .lere uetallicue ion at, elevated temperature.



  The copoly- mordent mordent is added to a 5% by weight aqueous solution.
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 mother of tertiary salt of diéthy18noéthylDÓthacrylate and quaternary salt of diethyl2n.inoethylmethacrylate of chromium alum as described in Example I. The mixture of nordant copolymer and chromium alum is divided into seven equal parts and each part is subjected to an aging treatment indicated in.
 EMI11.5
 table II.

   A washed positive-type light-sensitive gelatin C106, o-silver o-bromide photographic emulsion was divided into seven equal parts after the usual second digestion treatment. To each part of emulsion is added one of the pre-aged mixtures of chromium alum and of. The amounts of the various ingredients are calculated so that after combining
 EMI11.6
 naison each portion of the ulsion contains 22.0 g of copolymer per 100 g of gelatin emulsion and 0.041 g mole of chromium alum per 100 g of mordant. Equal amounts of the usual adjuvants
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 of post-digestion are added to each part of emulsion and the exhaustions are then applied and dried.

   The samples of each layer are then subjected to the back transfer test and.
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 of the sensitometric speed of the ganna and of the COI: 11: 1e veil described in Example I. The pre-sorting: tite-TLernt of the nelanse of silver alum and of mordant and the results of the tests are given in Table II .

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 EMI12.1
 '' 11'.¯'T <¯U II.
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 Layer Test Density Treatment [u: r layer f; Sé'.i cur
 EMI12.3
 
<tb>
<tb> n <SEP> alum <SEP> of <SEP> chro- <SEP> the <SEP> colora :;

   <SEP> ion <SEP> - <SEP> fresh <SEP> layer
<tb>: -, the <SEP> and <SEP> of the <SEP> ¯or- <SEP> residual <SEP> Speed <SEP> Gamma <SEP> Veil <SEP> incubated
<tb>
 
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 die ((lt ¯¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯ 1 21 hours at 75, 44 100 2.86, 02 , 09
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<tb>
<tb> 2 <SEP> 15 <SEP> minutes <SEP> to
<tb> 140 F <SEP> + <SEP> 20 <SEP> 3/4
<tb>
 
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 hours at 75? , 33 96 3, OG-, 02, 0
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<tb>
<tb> 3 <SEP> 1 <SEP> hour <SEP>?;

   <SEP> 140 F
<tb> + <SEP> 20 <SEP> hours <SEP> to
<tb>
 
 EMI12.8
 75 F, 15 75, 9 '02, 08
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<tb>
<tb> 4 <SEP> 5/2 <SEP> hours <SEP> to <SEP> 140 F
<tb> +37/2 <SEP> hours-to
<tb>
 
 EMI12.10
 75 F, 08 68 326, 02, 11
 EMI12.11
 
<tb>
<tb> 5 <SEP> 5 <SEP> hours <SEP> to <SEP> 140 F
<tb> + <SEP> 16 <SEP> hours <SEP> to
<tb>
 
 EMI12.12
 75 F 06 68 2.97, 02, 16
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<tb>
<tb> 6 <SEP> 10 <SEP> hours <SEP> to <SEP> 140 F
<tb> + <SEP> It <SEP> hours <SEP> to
<tb>
 
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 '5 F, 05 64 3.00, 02, lo
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<tb>
<tb> 7 <SEP> 21 <SEP> hours <SEP> to <SEP> 140 F <SEP>, 05 <SEP> 66 <SEP> 2.93 <SEP>, 02 <SEP>, 11
<tb>
 EXAMPLE III.-
This example serves to illustrate the effect of the variation
 EMI12.16
 siDu1: ta, born of ë.1.U0e and te =: miavure of the treatenent of aging.1ent of the solution of i on: Js te.l 1 i oue and e rt ordering CO:

  ,) 2 'the means of reducing the undesirable effects of the return transfer during the operation i # i1Jression by transfer by 1 == ibibition of dye.



  To seven equal Q1.11titGS of the compositions c¯e =; ndeaa of the tertiary quaternary COl101Y '-' lGreS previously described in the e :: e.unles 1 and II, equal 01.1anti ts of chromium alum are added at intervals suitable so that the different aging treatments written in Table III can be carried out: 1 <ii ià4ia.te: iJi-it before the preparation of ,,, ul ::. iol1., 'son ō'nli..c "1-.ion and its s {c!: <, Fe. We give 2 a 6" 11.118ion hotora -.;. iyuc ("ioc o-orO! luro d '[' r: ont and gelatin sensitive to lU, .i;:; rc .: of the positive type j J ,, ;;, v: c, a second usual digestion treatment and it is divided into seven equal parts.

 <Desc / Clms Page number 13>

 
 EMI13.1
 prc: -viei7¯li of chromium alum and polymer mordant is added to each part of the erlulsion.

   The amounts of the ingredients are such that each part of the final eluriision contains 22.0 g of mordant copolymer per 100 g of gelatin and 0.041 -9 moles of chrone alum per 100 g of mordant. After addition of the usual adjuvants for 'Jost-digestion, the seven emulsions are applied and dried as in Examples I and II. The samples of each layer are then tested for return transfer and sensitometric value as described in Example I. The details of aging of the biting chromium alum mixture used in each case and the results of the tests are shown in Table III.



   TABLE III.
 EMI13.2
 
<tb>
<tb>



  Layer <SEP> Treatment <SEP> of <SEP> Density <SEP> of <SEP> Test <SEP> on <SEP> fresh <SEP> layer
<tb> n <SEP> alum <SEP> from <SEP> chro- <SEP> the <SEP> coloring <SEP> Speed <SEP> Gamma <SEP> Veil
<tb> me <SEP> and <SEP> of the <SEP> mor- <SEP> residual
<tb>
 
 EMI13.3
 tooth ¯¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
 EMI13.4
 
<tb>
<tb> 1 <SEP> Fresh <SEP> solutions <SEP> 0.57 <SEP> 100 <SEP> 3.28 <SEP>, 02
<tb> 2 <SEP> 1 <SEP> day <SEP> to <SEP> 75 F <SEP> 0.58 <SEP> 105 <SEP> 3.37 <SEP>, 02
<tb> 3 <SEP> 4 <SEP> days <SEP> to <SEP> 75 F <SEP> 0.23 <SEP> 95 <SEP> 3.41 <SEP>, 01
<tb>
 
 EMI13.5
 /;

   '5 days at 75 F 0.22 90 z. , O1
 EMI13.6
 
<tb>
<tb> 5 <SEP> 6 <SEP> days <SEP> to <SEP> 75 F <SEP> 0.20 <SEP> 82 <SEP> 3.27 <SEP>, 01
<tb> 6 <SEP> 1 <SEP> day <SEP> to <SEP> 95 F <SEP> 0.27 <SEP> 85 <SEP> 3.25 <SEP>, 01
<tb> 7 <SEP> 4 <SEP> days <SEP> to <SEP> 95 F <SEP> 0.15 <SEP> 72 <SEP> 3.34 <SEP>, 01
<tb>
 
It appears from the indications in Table III that a one-day aging treatment of the alum mixture of chromium-mordant polymer at 95 F ensures the same reduction in return transfer that would produce approximately 3 days at 75 F. It also appears that a treatment 4-day aging treatment at 95 F is superior to a 6-day aging treatment at 75 F in reduced return transfer.
 EMI13.7
 



  Tf¯EtnL :. IV. In this example, it is clear that the reduction in transfer and return obtained thanks to the aging process of the combinations

 <Desc / Clms Page number 14>

 
 EMI14.1
  .'ion.:. 1 (; to..llicue and this: ïOrG.é: i1-G JOIYJÍ13re can be 2E ', lc:, e: 1t obtained by the use of temperatures appreciably lower ,? to tG: ï ¯îl'21? Res 0l'c -; 'i: ï.:. 8, ires, par t.'īe = .Iß7 the temperatures prevailing in the ordinary refrigerators as well as 7c.r e :: By using temperatures significantly higher than the normal temperatures, it is also shown that concentrations of metal ions other than these previous examples may be useful.



  We add e.l1n c? E chror: ie to seven equal cluailti t :: s solution of nordant co-ol r-lere tertiary quaternary coirie indicates c.2als 1 'e.¯c-¯ 31e l so that the c # îcentl2tio: î of the [', li..1l1 of chro -'. Te in the photographic'¯-171S.O¯1 finally Or) tGl'lUe corresponds to those indicated in the table .in either z041 gr # ole or 0.0615 g uole c 'c.l1.ll1. ci chromium per 100 g of 2: lOrda.nt, the quantity of nordant copolyricre being 220 g per 100 g of gelatin in emulsion.

   C5 1112ne of chromium alum and aordant are mixed so that aging at different
 EMI14.2
 time and temperature conditions as shown in the table
 EMI14.3
 IV is completed Immediately before the final preparation of the emulsion - One of the mixtures of chrone alum and pre-treated cordant is then added to part of the el '6 ::: 1UlsioD. photographic gelatin and C¯7.OC0-7r3ilüre silver sensitive to light in positive type, washed, which has undergone a second usual treatment digestion. The remaining operations c'addition der; adjuvants for post-digestion / e-, reaction, drying: 3e, transfer 'back test and (,' sensi to-: 1'tric test, carried out as described in the examples previous ones.

   The alum concentrations of C11i0 = '(. "' ¯; 105T.E. ';', 1. th conditions of the treatment of (: V1.C; 1.7¯l.; ':: CitOn t, the nature of the treatment ".cnt of: .l2.Yl; C '. alum of chro', lC-l, 10rc1, [':" lt and the results are given in Table IV.

 <Desc / Clms Page number 15>

 
 EMI15.1
 



  "'....'. # U T 4
 EMI15.2
 Layer, -: '<= :; .02.8 2ri :. :: - ¯L-L. t'c i ".J .." F: 1: tC 4S '^ - fur ¯'! = [:. i n C. a.1¯U1 of ll [1 This chromium;: r ;! the layer .¯; i;: S chromo) Ol? 1.-iori-1-.i cO} ¯OrL- '1: C'C'.ICrJ.G incu- 1 00 of 1 - J. V..L. balllo ï.i. é: 1: l É 1 1 S "- tes- ti011 ¯¯¯¯ ¯¯¯¯¯¯¯¯ <: c: ù? -11: e se i <: '=: 2c ^.

   Sail. o., 04i 2L (2 È br "ies C) .. '0:' 9l; .2 100 3 ,, '- 7, 02, la 006l5 24 hours soor 0.0615 (26 C) µ ± 0] 1 , 3? 93 3.30, O1 ', la 3 0.041? -4 hours at 95? V, V. 4.1 (35 C) Q5, 14 84 3.13, 01, 10 4 O, OO15 24 h2QeS 5 ?, 12 67 -, 0-7, 01, 0 7 5 or 041 43 1 e; 5 ¯, 09 67 3, Oû, 01, 09 6 0.0615 43 = 1'LliC.; ¯ 95?, 06 60 2 , 77, 01 'J03 7 0.0! .1 11 .days L5 F', 10 72 3.17, 01, 07 (GC)
 EMI15.3
 It emerges from the figures of the table, IV ru 'by varying the quantity.': (';;, h, l.l1. <' E cnr-o-ic = piii # c; ii; # (;: . "1 ;: le - ::: l ['. 1.ze LI-an de chro .'- e and' ..lord-an t poly.erc between the limits siiiiri =>. T the invention is noticeably affects' .- en t leefficactt ';' of the trF.ite.ient of agedispe- -.:cnt.

   We see, l,, 1 # ié: 1-e: ent <.. u <? <;:. = E reduction f'e = -1.fi) lG ëe trc.:.1sfert in return can be obtained 2 , GL;: - ::.: Ct.l18,1t the trc-ite: .ient <.c aging- '-..- snt of the mixed ion ..- :.' tllic¯ue - ;. 'Lordc' nt ¯; ol, y: éré c'c the invention. ; t i ± - these s t;> ii => i i? J.i; .az% e i. i; -z <.: i.l., l. i. ; .i i.t. -Lux conaitions hc '.' :; ituelleE Li. '. Ci <.¯.L;' é, <.cs te-Aj-'higher ratures co =: i.: Ie describes d.e'.ns s 1 c e ';: e;.? Le ¯r-: C! :(:' 8: 1.tS.



  0.1 = irf'p; oei <; and we iiiise in eight parts a solution: CU8use µ, # in ooid. ':'. îe .. = orr r :, il; eO :: 'lo1y,' - 'l?; l'C (0 tertiary salt of (j, <thyJ. ;;, - LlO' :: thyl \ ét'll1ac} ::: ll, cc and <'. e quaternary salt of é.ièhYlC. e 2: yl tc <J. -: <written r 'anr:' i: 1 'er: e ..: = i] ¯ e I. ¯i the portion na 1 on; .. joust ij, o /, 1; j drown "': .lll.V.'i; chrone by 100 éle' :: oro. [1nt ;, la) ol ': io--] 110 iJ, 041 jj! .L01e .: ce .--. '. Ulfate <:' a.Il¯uzi.niu..i and potassiru'i pe.t 100 de "oiÉll'ntj la '] OàÎ't'l .OÎÔ "1 0.041 ::; o" lol, e ce sulfate î. 'I:: i <J..15.u. I:>.' Ii, i, j. <. I.ia.; ¯> :.>. r 100 of oi, <".:.!. it and a portion n 7

 <Desc / Clms Page number 16>

 
 EMI16.1
 00.41 g of copper sulphate per 100 g of water. Portions 1, 3, 5 and 7 are then aged for 24 hours at 140 F.

   The remaining portions of north-an t nos 2, 4j 6 and 8 are maintained at 75 F without further addition or treatment. After the second usual digestion, a photographic elution of silver iodine-sensitive silver sensitive to the positive type, washed, is divided into eight equal portions and one of the ejection portions is combined with one of the eight. Dordant compositions of the different slowly treated eoine described above. In the nejemge: '10rd, ant-enulsion n 2 we add the amount of chromium alum previously used in the treatment of pr 5-aged # 1ent of chromium alum and ::. 1orë .ant for the portion of cord No. 1.

   From r: .ê!. '1e, we add to: 1818.J. "1.i: c uordant enulsion ns 4" 6 and 8 respectively similar molar quantities of sulsate alu :: ¯iniun and potassiwi, of sulphate C'2!. 'lr.:oni11l.'1. and ferricue and cupric sulfate. Addition of yost-6 adjuvants, igestiü: '1, enc1uctiol1, drying, back transfer test and back-flow test are performed as described. in the previous examples. The results drawn up are shown in Table V.



     TABLE V
 EMI16.2
 Metallic Salt Layer Salt Treatment ::! tall.? - Density of test on n added to the: slow of that added to the aged mordant fresh color, - the ermlsion tion. resi- Vites- Gamma. rcL.
 EMI16.3
 
<tb>
<tb> semont <SEP> after <SEP> the dual <SEP> <SEP> is <SEP> on
<tb> of the <SEP> mor- <SEP> was biting
<tb>
 
 EMI16.4
 dan'L ¯¯¯¯¯¯¯¯¯¯ - ¯¯¯¯¯¯¯¯¯¯¯ 1 24 hour alum ---, 10 44 2, .30, yes
 EMI16.5
 
<tb>
<tb> to <SEP> 140 F
<tb> 2 <SEP> -.- <SEP> 24 <SEP> hours <SEP> Alum <SEP> of
<tb>
 
 EMI16.6
 at 5 chrome, 57 100 3.29, 02
 EMI16.7
 
<tb>
<tb> 3 <SEP> Sulfate <SEP> of <SEP> po- <SEP> 24 <SEP> hours <SEP> - <SEP>, 43 <SEP> 119 <SEP> 3.04 <SEP>, 01
<tb> tassium <SEP> and <SEP> from <SEP> to <SEP> 140 F
<tb>
 
 EMI16.8
 x.iuà, iiniuui 4 - 24 hbtires ir2ulfate de po-, 72 133 3.51, 01 to 75 .L, tas.sÎ1.1l:

  1 and bzz a7.1.7., L1? LJ.uTi1
 EMI16.9
 
<tb>
<tb> 5 <SEP> Sulfate <SEP> am- <SEP> 24 <SEP> hours <SEP> - <SEP>, 39 <SEP> 95 <SEP> 2.91 <SEP>, 01
<tb> monium <SEP> and <SEP> fer- <SEP> to <SEP> 140 F
<tb> risk <SEP> '<SEP>
<tb>
 
 EMI16.10
 6 - 24 hours SiMo- sulphate, 52 They 3.34, Ol to 7 5 niml and ferric 7 Sulfate cuivri- z, hours #, 48 26 3.42 eOI
 EMI16.11
 
<tb>
<tb> than <SEP> to <SEP> 140 F
<tb> 8 <SEP> - <SEP> 24 <SEP> hours <SEP> Sulfate <SEP> copper <SEP>, 62 <SEP> 30 <SEP> 3,52 <SEP>, 0 <SEP>
<tb> to <SEP> 75 F <SEP> that
<tb>
 

 <Desc / Clms Page number 17>

 
The figures in Table V indicate substantial reduction * and return transfer due to the use of any of the metal ions by the cord treatment process according to the invention.
 EMI17.1
 tion.

   It also appears that chronic ions are more effective in treating polymeric biting metal ion pre-aging to minimize back transfer than the other metal ions illustrated and are therefore preferred.
 EMI17.2
 



  ': -¯:: L VI. Aqueous solutions containing 5) to by weight of mordant copolYJ'1ère of tertiary salt of diethylsminoethyl methacrylate are prepared. and quaternary salt of diethylar.1inoethylnethacrylate, poly-1-acthyl-2-vinylpyridiniwn cyclohexane tallow wadding foil, and poly- nethyl-5-vinyliJyria.ine hydrochloride.

   Chromium alum, chromium ferric sulphate or aluminum potassium sulphate are added to the extent of 0.041 g of metal ion per 100 g of polymer material. selected portions of this solution and then the mixture of metal ion and mordant is aged for 24 hours at 140 F. The polymer solutions are kept as controls without adding metal ion thereto, and they are maintained at 75 F during the test. 24 hour aging process for treated polymer materials. Details of the spawning
 EMI17.3
 ber-ient applied to. each case are shown in Table VI.



  The treated and untreated polymer cord solutions are then added to equal amounts of a photographic gelatin and light-sensitive silver ioda-bromide gel.
 EMI17.4
 positive who received a second usual digestion treatment.



  To raordaxzt-ê: zulsion mixtures which contain the tenoin solutions. of untreated nordant, a quantity of alum of chromium sulphate c3 'ai-toniuxl and ferric or of sulphate el' at "moni '# Jl and of potash" t!: l "respectively, which is equal to the amount of metal ion previously present in each of the mordant compositions poLrnère timaitc = s Gt aged.

   additions of post-digestion adjuvants and usual operations of cnd.uctiol1 and of

 <Desc / Clms Page number 18>

 
 EMI18.1
 drying we perform return transfer tests and determinations of sensitouetric values co: we described above 'The type of -' twisting used for each case, the treatment of aging of the cord and type of hardening agent used, thus cue the result of the return transfer and seiisitor: i3trie es <wi are given in the t; blue 'I. The sail values indicated
 EMI18.2
 
 EMI18.3
 for the esse-1 after incubation are determined 2.prés having sou-lis layers at 120 / and 65; Ï to i'h7: .iià.itµ relative for 48 hours.

 <Desc / Clms Page number 19>

 
 EMI19.1
 
<tb>



  Layer <SEP> n <SEP> Mordant <SEP> Metal <SEP> salt <SEP> Treatment <SEP> of <SEP> Metal <SEP> salt <SEP> Density <SEP> of <SEP> Test <SEP> on < SEP> layer <SEP> Test <SEP> after
<tb> of the <SEP> biting <SEP> sion <SEP> after <SEP> the <SEP> tion <SEP> resi- <SEP> Vites- <SEP> Gamma <SEP> Sail
<tb> biting <SEP> dual <SEP> se
<tb>
 
 EMI19.2
 1 Chromium Alum Copolymer 24 hours at -, 08 48 3,21, 01, 05
 EMI19.3
 
<tb> (I) <SEP> 140 F
<tb> 2 <SEP> "<SEP> 24 <SEP> hours <SEP> to <SEP> Alum <SEP> from <SEP> chrome <SEP>, <SEP> 83 <SEP> 100 <SEP> 3.18 <SEP>, 03 <SEP>, 13
<tb> 3 <SEP> PMe2VP <SEP> (II) <SEP> Alum <SEP> from <SEP> chrome <SEP> 24 <SEP> herues <SEP> to <SEP>, <SEP> 58 <SEP> 97 <SEP> 3.32 <SEP>, 01 <SEP>, 03
<tb> 140 F
<tb>
 
 EMI19.4
 4 il 24 heures à Chromium Alum, 79 110 3el5, 03,

  01
 EMI19.5
 
<tb> 75 F
<tb>
 
 EMI19.6
 5 P2Ke5VP (III) Chromium alum 24 hours at -, 06 13 1.76, Ol, 02 140 F Il - 2, hours at Chromium alum, 18 11 1.76, 01, 02 75 F P2Me5VP (III ) Aramo sulfate 2., hours at -, 43 10 1.77, 01, 01 '
 EMI19.7
 
<tb> and <SEP> ferric <SEP> 140 F
<tb>
 
 EMI19.8
 8 il - 24 hours at Ammonium sulphate, 92 6 1.5 $, 01, 01 75 F and ferric 9 Pile2vp (here) Sulfate of potassium- 24 hours at, 56 138 3.33, 03, 04 siùm and alumi11i # l 140 F
 EMI19.9
 
<tb> 10 <SEP> 24 <SEP> heres <SEP> to <SEP> Aluminum <SEP> sulphate <SEP> 1.48 <SEP> 130 <SEP> 3.24 <SEP>, <SEP> 04 <SEP>, 04
<tb> 75 F <SEP> and <SEP> of <SEP> potassium
<tb>
 
 EMI19.10
 (I) Copolymer of tertiary salt of diethylaminoethyl methacrylate and quaternary salt of (II) Poly-1-mehyl-2-vinylpyridinium cyClohexanesulfonate.



  (III) Poly-2-methYl-5-vinylpyridine hydrochloride.
 EMI19.11
 diethylaminoethylinethacrylate,

 <Desc / Clms Page number 20>

 
 EMI20.1
 El <11 TLE VI l. An aqueous solution a 5) b toe moly-1-¯aethyl-2vinylpyrid.iniw-1 cyclohexane sulfonate is prepared and divided into six equal portions. To portions n s 2, 3, 4 and 5 are added respectively 0.0068, 0.0205, 0.041 and 0.082 - g sole of brown alum per 100 g
 EMI20.2
 of a vinylpyridine polynere. Nothing is added to the portions numbered 1 and 6. ' The five first portions of Nordant are then aged for 24 hours at 140 F and the sixth which serves as a control is aged for 24 hours at the ordinary temperature of
 EMI20.3
 75 .F.

   At the end of the aging process, the six solutions obtained are added in identical quantities separated from a digested ulsion of the positive type similar to the enulsioh described in the preceding examples. Additional quantities of chromium alum are then added to the mixtures of: .¯orcamt and ¯¯ul Si021 containing the first-r, -ibres three portions and the sixth portion of bites so to bring the total of chromium alum 8. 0, OL1 g: 101st JOUI 100 g of polynere vinyipyridine.

   The portions of: 1TI11sion iiu2, iérot, es 4 and 5 already contain in #. = Oins this quantity of chromium alum introduced by the treatment of the cord. After the usual additions
 EMI20.4
 post-diestion adjuvants, applied, dried and evening-iet 2. test the six exhaustions as described in the previous examples.

   The results of the tests are shown in Table VII.

 <Desc / Clms Page number 21>

   TABLE VII
 EMI21.1
 
<tb>
<tb> Layer <SEP> g / nole <SEP> Treats- <SEP> g / mole <SEP> Density <SEP> Test <SEP> of <SEP> layer <SEP> Test
<tb>
 
 EMI21.2
 n dalun xnent of c1'2, lu, n of de'la Vîtes- fresh after aged chrone- chrome by color- Gamna veil incuba. per 100 g s e - 2 'L;

  -q 100 g of your ratio of 1i1or- de.? or- Sidual elordaiit veil datzt before c.4n t in s 1 'the tra i- ul = ion dull ¯¯¯¯¯ ¯¯¯¯ ¯¯¯¯ ¯¯¯¯¯¯ ¯¯¯¯ ¯¯¯¯¯¯¯¯ ¯¯¯¯¯
 EMI21.3
 
<tb>
<tb> 1 <SEP> - <SEP> 24 <SEP> hours
<tb> to <SEP> 140 F <SEP> 0.041 <SEP> 0.98 <SEP> 98 <SEP> 3.27 <SEP>, 01 <SEP>, 04
<tb> 2 <SEP> 0.0068 <SEP> 24 <SEP> hours
<tb> to <SEP> 140 F <SEP> 0.0342 <SEP> 0.73 <SEP> "97 <SEP> 3.23 <SEP>, 01 <SEP>, 03
<tb> 3 <SEP> 0.0205 <SEP> 24 <SEP> hours
<tb> to <SEP> 140 F <SEP> 0.0205 <SEP> 0.79 <SEP> 103 <SEP> 3.21 <SEP>, 01 <SEP>, 03
<tb> 4 <SEP> 0.041 <SEP> 24 <SEP> hours <SEP> - <SEP> 0.74 <SEP> 106 <SEP> 3.35 <SEP>, 01 <SEP>, 04
<tb> to <SEP> 140 F
<tb> 5 <SEP> 0.082 <SEP> 24 <SEP> HOURS
<tb> to <SEP> 140 F <SEP> - <SEP> 0.72 <SEP> 104 <SEP> 3.29 <SEP>, 04 <SEP>, 04
<tb> 6 <SEP> - <SEP> 24 <SEP> hours
<tb> to <SEP> 75 F <SEP> 0.041 <SEP> 1,

  39 <SEP> 100 <SEP> 3.01 <SEP>, 03 <SEP>. <SEP>, 04
<tb>
 EXAMPLE VIII. -
To five equal parts of an aqueous solution is added
 EMI21.4
 5% by weight of mordant copolymer of tertiary salt of d1ethyla..lll0lO-ethyl methacrylate and quaternary salt of diethylaminoethylmethacrylate respectively 0.041 g mole of chromium alum, 0.0273 g mole of aluminum potassium sulfate , 0.082 mole of aluminum sulphate
 EMI21.5
 minium and potassium, 0.0273 g mole of sulphate of nonilu and ferric effi #, and 0.082 g mole of sulphate of xmniniLnn and ferric: These five solutions of mordant thus treated are then aged at 140 F for 24 hours. A sixth control mordant solution receives no addition and is stored at 75 ° F for 24 hours.

   Once the aging process is complete, the five solutions of treated mordant and the sixth untreated are added in equal portions.
 EMI21.6
 of a silver halide emulsion of the positive type, digested, described in the preceding examples. To the sixth control emulsion containing the untreated mordant, chromium alum at 0.041 g mole per 100 g of mordant copolymer is added. The remaining operations of adding post-digestion adjuvants, coating and

 <Desc / Clms Page number 22>

 drying are carried out and the usual tests are applied to the films thus prepared. The test results are given in Table VIII.



   TABLE VIII
 EMI22.1
 Layer Salt == 1tal - Treated- Salt -eié ûal - Density Test nical test added nsnt liciue added to the layer e-near per 100 g mordaiW ted at 1-1 colora- fresh incu-
 EMI22.2
 
<tb>
<tb> of <SEP> biting <SEP> sion <SEP> by <SEP> tion <SEP> d- <SEP> Vites- <SEP> Gam- <SEP> Sail <SEP> bation
<tb> before <SEP> the <SEP> 100 <SEP> g <SEP> of <SEP> siduel- <SEP> se <SEP> my <SEP> Sail
<tb>
 
 EMI22.3
 ¯¯¯¯ slow spawning siordant 1 0.0l1 g Elole 24 hours of alum from 1 to zoos - 0.0 $ 95 3.12 z01, 12
 EMI22.4
 
<tb>
<tb> chrome
<tb>
 
 EMI22.5
 2 0.0273 g:.: J.o1e z hours Qe sulfate at 110 .F - 0.2 $ 102 3.40 ', 01, 20 c' a1'tz ':

  ZinitL ..
 EMI22.6
 
<tb>
<tb> e <SEP> t <SEP> of <SEP> potassium
<tb> 3 <SEP> $ 0.0 2 <SEP> g <SEP> mole <SEP> 24 <SEP> hours
<tb> from <SEP> sulfate <SEP> to <SEP> 140 F <SEP> - <SEP> 0.19 <SEP> 105 <SEP> 3.46 <SEP>, 01 <SEP>, 17
<tb>
 
 EMI22.7
 al wl1ini U '.' l
 EMI22.8
 
<tb>
<tb> and <SEP> of <SEP> potassium
<tb> 4 <SEP> 0 <SEP> Il <SEP> 0 <SEP> 27 <SEP> g <SEP> mole <SEP> 24 <SEP> hours
<tb> from <SEP> sulfate <SEP> to <SEP> 140 F <SEP> - <SEP> 0.22 <SEP> 98 <SEP> 3.29 <SEP>, 01 <SEP>, 13
<tb>
 
 EMI22.9
 d-1 ammonium and ferric 5 $ 0.0 2 gIJ1.Ole 24 hours sulfate at 140 F - 0.13 94 3.28 z01 ;, 14
 EMI22.10
 
<tb>
<tb> ferric <SEP> and
<tb>
 
 EMI22.11
 from a: c:

  r.lonÍUi.l1
 EMI22.12
 
<tb>
<tb> 6 <SEP> - <SEP> 24 <SEP> hours <SEP> 0.041 <SEP> g
<tb> to <SEP> 75 F <SEP> mole <SEP> d '
<tb> alum <SEP> from
<tb>
 
 EMI22.13
 chromium 0.42 lido 3, l.l, Ol, 19
 EMI22.14
 EZ:;:;: iPL: C IX. A 5 by weight aqueous solution of ol y -? -. Ethyl-5-vüzyl-9yriGine hydrochloride was prepared and divided into five equal parts. To these portions are added respectively 0.041 g Mole of ehrō alum: Le, 0.0273 g, .1010 of aluminum and potassium sulphate 0032 g, 401 of alurzinilam and y7ot sulphate, .ssiu? a, 0.0273 g mole of :: ¯rL.on: iua and ferric sulphate, 0.082 g mole of sulphate, c1'auLloniuu and ferric :.

   After the treaty''icnt of vicillissei: ie t one of the solu. tions of; .ior6: zit treated est. "when ['jOl1túe to each of CL1Ç1 claies portions C'un.0 ±. iv, 1-ri% n of ïta'¯OÉ11111C. d'arsont 1.igôi', 1 . of the positive type

 <Desc / Clms Page number 23>

 described in the previous examples. The steps necessary to complete the emulsification and film testing operations are carried out analogously to that of Example '
 EMI23.1
 VIII. The results of the seiisitori, -tr4-Ques and return transfer tests are shown in Table IX. TABLE IX ..
 EMI23.2
 
<tb>
<tb>



  Layer <SEP> Metal <SEP> salt <SEP> Treatment <SEP> Density <SEP> of <SEP> Test <SEP> on <SEP> layer <SEP> Test
<tb> n <SEP> added <SEP> by <SEP> 100g <SEP> dù <SEP> biting <SEP> of <SEP> colora- <SEP> fresh <SEP> after
<tb>
 
 EMI23.3
 of bite before tion revites- Garera Va7e incule treats: nent siete, uel'le se bation,
 EMI23.4
 
<tb>
<tb>
<tb>
 
 EMI23.5
 1 0.041 mole 24 hours C, 21,100 1.95.01, 01 alum. from chroue to 1400F
 EMI23.6
 
<tb>
<tb> 2 <SEP> 0.273 <SEP> g <SEP> mole <SEP> of <SEP> 24 <SEP> hours
<tb> sulfate <SEP> from alu- <SEP> to <SEP> 140 F
<tb> minimum <SEP> and <SEP> of
<tb>
 
 EMI23.7
 potassium 0.36 111 1.96 z01 z01
 EMI23.8
 
<tb>
<tb> 3 <SEP> 0.082 <SEP> g <SEP> mole <SEP> of <SEP> 24 <SEP> hours
<tb> sulfate <SEP> from alu- <SEP> to <SEP> 140 F
<tb>
 
 EMI23.9
 i7.11¯L11;

  1 and potassiura. 0.13 III 2.01 01 ', O1
 EMI23.10
 
<tb>
<tb> 4 <SEP> 0.0273 <SEP> g <SEP> mole <SEP> of <SEP> 24 <SEP> hours
<tb>
 
 EMI23.11
 sulfate c1'a ::, HlO- at 140 F nil'1 and ferric 0.19 78 1.76 z01.01
 EMI23.12
 
<tb>
<tb> 5 <SEP> 0, <SEP> 0 $ 2 <SEP> g <SEP> mole <SEP> of <SEP> 24 <SEP> hour's
<tb>
 
 EMI23.13
 ¯sulfate c'a: 2no- at 140 F niu'tR'et ferric '0.05 78 le66 z01, O1
 EMI23.14
 litlT '.

   X. -
A 5% aqueous solution of diethylamino tertiary salt copolymer mordant was prepared and divided into six equal portions.
 EMI23.15
 ethylenethacrylate and quaternary salt of diethylaminoethylmethacrylate. ilux nwmérot6es portions 3, 4, 5 and 6 are respectively added OOO6t5, 0.0205, 0.041 and 0.0615 g flask of alum. chromium per 100 g of mordant copolymer. Portion # 1 serves as an untreated old control at room temperature (75F) and Portions z to 6 are old! . 140 F for 24 hours.

   At the end of the treatment of vici-llise., Eiient the six solutions of aordro'lt 'are added' ai; .e J 't, a.queuse of' 1 t, '5 5 of fuue each' 1 a aqueous solution of salts-tine 55 ,. ' so that each nclaneue of uordant and gelatin solution contains 22.0 d0 mordant per 100 g 100 gelatin. To each of the gniatin solutions

 <Desc / Clms Page number 24>

 
 EMI24.1
 conti1.é: .nt c: es portions due ::: orèa1.t 3.J -? '1¯'O t'E.'. ^ -. S 1 2, 3 and 4 we add enough aluii of chromium to obtain a concentration of 0.04.1 ': lolo Ci'E..1u21 due chromium per 100 g of nordant.



  The usual coating auxiliaries are added to each of the gelatin nordant compositions and the coating is carried out and the films are dried oïat.lufs.- 0; 1 using the ".t '. (. :: rocéc. 1. :: => orc the back transfer test that in the previous examples but the samples bearing a silver halide undergo appropriate development and fixing before the actual back transfer test. table had X.
 EMI24.2
 



  TicBL21 ':. U X.
 EMI24.3
 



  Layer g / noles of alum Treatment of g-, oleS d3elu-n C.e Density of the chromium by aging chromium per 100 g coloring.



  100 - de i: ior- de nordant de cordant added residual d2nt before au: é2.2.Ilge de ti'2 '' n'- eI: '¯uO.i # C.¯c "¯'.1 y - Zc. Tl ¯¯¯¯¯¯¯¯¯
 EMI24.4
 
<tb>
<tb> 1 <SEP> - <SEP> 24 <SEP> hours <SEP> to
<tb> 75 F <SEP> 0.041 <SEP>, 45
<tb> 2 <SEP> - <SEP> 24 <SEP> hours <SEP> to
<tb> 140 F <SEP> 0.041 <SEP>, 50
<tb> 3 <SEP> 0.0068 <SEP> 24 <SEP> hours <SEP> to
<tb> 140 F <SEP> 0.0342 <SEP>, 24
<tb> 4 <SEP> 0.0205 <SEP> 24 <SEP> hours <SEP> to
<tb> 140 F <SEP> 0.0205 <SEP>, 08
<tb> 5 <SEP> 0.041 <SEP> 24 <SEP> hours <SEP> to
<tb> 140 F <SEP>, 06
<tb> 6 <SEP> 0.0615 <SEP> 24 <SEP> hours <SEP> to
<tb> 140 F <SEP> - <SEP>, 10
<tb>
 EXAMPLE yI. -
 EMI24.5
 We take back. the re ipl.e X But the: - .: orc.n - used is cyclohexane ::: uli '# 1.é te de iJoly-1-ìfthyi -2 - *. inyliJyridiniin; i.Lcs results fi; 3Urc! Lt nu tabler .:

   XI.

 <Desc / Clms Page number 25>

   TABLE XI.
 EMI25.1
 Alum school layer Treatment of g / moles of alum of., Of 1.1
 EMI25.2
 
<tb>
<tb> n <SEP> of <SEP> chrome <SEP> by <SEP> aged <SEP> s <SEP> sow <SEP> chrome <SEP> by <SEP> 100 <SEP> g <SEP> coloring
<tb>
 
 EMI25.3
 100 g of mordant mordant add residual-Ile before to the treatment mix ¯. , 1 2. ',. hours at 75 F 0.0.1, 38 ''.



  21 ,. hours at 140 F 0.0.1 36. "" 3 0.700 (D8 24 hours at 140QF 0.0342, 1.
 EMI25.4
 
<tb>
<tb>



  0.0205 <SEP> 24 <SEP> hours <SEP> to <SEP> 140 F <SEP> 0.0205 <SEP>, 11
<tb> 5 <SEP> 0.041 <SEP> 24 <SEP> hours <SEP> to <SEP> 140 F <SEP> - <SEP>, 15
<tb> 0.0615 <SEP> 24 <SEP> hours <SEP> to <SEP> 140 F <SEP>, 06
<tb>
 Among the acid dyes which can be etched with
 EMI25.5
 using ¯xord ^ azts? olyyneres exhibiting the diffusion properties. improved according to the invention there are: the Axlthra.cene yellow GR (purity, 00; 4, Schultz n 177) The solid red S Cone. (Color Index no 176) Pontacyl Green SN Ex. (Color Index no 7 (37), - Acid black blue (ColourIndex no 246) 0 acid magenta (Color Index no 692) Naphthol green B. Cone ( Color Index n 5) Glossy paper yellow Ex. 125% cone (Color Index n 364) Tartrazine (Color Index n 640) ¯ Metanil yellow Cone.

   (Color Index No. 138)
 EMI25.6
 The ca.mùi, n Pontacy-1 6B Ex. Cone. (Color Index no 57) L-1c'cqrlate Pontacyl R Cone. (Color Index n .87) The ifiubin Pontacyl R Ex. Cone. (Color Index n. 179) 1'invcotioiz ta. cures therefore a simple and new process to reduce the tendencies to the diffusion of polymer mordants
 EMI25.7
 for dye.- '', acids useful in the operations Ci'ir.sbibition, d.e dye and ct ': ī yrerai orz by transfer of dye. Dandruff. ï ': -slOl' <¯J: 1.CLC? â Containing the improved polymeric additives at the same hold no halo'iurc sonsiblo in the light can be "

 <Desc / Clms Page number 26>

 exposed and treated before transfer of the dye in a
 EMI26.1
 that the film carries 1 .- # a, õs c'e.rent, by e: er7¯e, an optical soundtrack.



  The improved cords of the invention do not disturb the silver halide layers and can therefore be directly incorporated therein ..: .. J.1. In addition, these cords fr "ls1iorÓ: used in the receiving layer of dye imbibing image produces sharper color images and allows a satisfactory number of prints from a single die in serial transfer printing operations and ensures
 EMI26.2
 a reduction in the dye density., "C; ¯W ', = 1 iC: 0CS the brightly lit connections of the final print. \
 EMI26.3
 R E V F. li T Ci Il T 1 0 jj 8.



  1 .- Preparation process C, '1LYJ. Polyr-iere mordant improves for aciô dyes, characterized in that a #ordant "9 1Y: .. ler is used for acid dyes having amino groups: tre.linear recurring in solution, with the poly- velent netallik ions.


    

Claims (1)

2. - Method according to claim 1, characterized in EMI26.4 that the cord and the r-ietallic ions are in aqueous solution. 3. - Method according to claim 1 or 2, characterized EMI26.5 in that the metallic ions are present in an amount of at least 0.006 g drowned per 100 g of mordant. 4.- A method according to claim 3, characterized in that the metal ions are present in an amount of 0.006 to 0.085 EMI26.6 ,,! ole per 100 g of: iorôcnt. 5.- Process according to one or the other of the rcve1l.clici ', tions 1 il! R the solution thus obtained by, 1 (lcJ'lCc is f01..DlÍse 2i. A treatment of: .ature: U; ioiz or aging. G.- Process according to rcvcl1.cli, cction 5, characterized in that the solution is aged 3: '- ;; 12 I (0-10Ô C). <Desc / Clms Page number 27> 7. - A method according to claim 5, characterized in that the solution is aged at 45-140 F (8-60 F) 8.- A method according to claim 7, characterized in that the solution is aged for at least 5 / 2 hours. 9. A method curing one or the other of claims 1 to 8, characterized in that mixing a solution of the mordant and a solution of a salt of a polyvalent metal. 10. A method according to claim 9, characterized in that the .metallic salt is chromium alum. 11. A method according to either of claims 1 to 10, characterized in that the mordant is a copolymeric ester of alpha-alkacyclic acid of an amino-alcohol having tertiary and quaternary salt groups in proportion. from 35 to 75 mole percent of the former to 65 to 25 mole percent of the latter. 12. A method according to claim 11, characterized in that the mordant is a copolymer of the tertiary salt of diethylaminoethyl methacrylate and of the quaternary salt of diethylaminoethyl methacrylate. 13. - Improved polymer mordant for acid dyes, characterized in that it comprises, in aqueous solution, a polymer mordant for acid dyes having recurring extraline amino groups and polyvalent metal ions. 14.- An emulsion of a water-permeable colloid containing, in amounts suitable for mordanting, a polymeric mordant for acid dyes having recurrent extralinear amino groups, and, mixed in solution with this mordant, polyvalent metal ions. 15.- Emulsion according to claim 14, characterized in that au.- 'it contains a light-sensitive silver halide. 16. - Emulsion according to claim 14, characterized in that the colloid is gelatin. 17. - Photographic element characterized in that it comprises a layer of an emulsion according to claim 15. <Desc / Clms Page number 28> 18.- Process of -preparation of an element for transfer by dye imbibition characterized in that one adds to an aqueous solution of a water-permeable colloid a solution EMI28.1 obtained in:,:, 18 ... '1.:;e8nt au) r38.1 & .blO, in solution, -a. 10 day mordant for acid dyes having; r0117eS 'c ^ ,.'.? 1 = 10 recurrent extraline and a salt of a polyvalent remover and the resulting solution is aged, then applies a layer of the solution obtained on a support. EMI28.2 19. An element for transfer by inhibition of dye obtained by the process of claim 18