DE1547817A1 - Light-sensitive photographic material with an addition of morpholine alkyl alkenoyl amide polymers - Google Patents

Description

"000 FRANKFURT (MAIN)

ANNASTRASSE 19 PATENTANIWXLTE DR. LOTTERHOS - DR.-ING * LOTTERHOS

TELEGRAMS · LOMOSAPATENT LANDESZENTRALBANK 4/951 DRESDNER BANK FFM., No. 5247 « POSTSCHECK ACCOUNT FFM. 1067

FRANKFURT

HI / Kl

Bhashin i'ilm Eabushiki Kuisha, ifo. 21 ο, Iraqis ma, Llinamiashigaxo-machi, Äshif-iarakami-gun, Kanagawa-ken, Japan.

Photosensitive photographic material with an additive on corpholinalkylalkenoylamide-j ^ olymerisaten.

The Ji / 'rxinäunfc relates to a light-sensitive material which contains -iaio ₀ önsilbei', u-elatine and a polymer and / or copolymer of iuorpholinalkylalkenoylaaiicis.

aiei lichteüipfindliehen photographic Jialo _E, Gnsill3eremulsionen can 'imilsion the opacity of the o /, ie the value of the optical density, divided by the number of grams of developed per ^ uadratdezimeter oirbers increase, Indians one of iümulsion natural or synthetic high molecular substances, such as i ^ ol ^ -ii-vinylactam, dextrin, laminarin, Mannon, hydroxyäthylierte .yellulose like. admits (see ₀ USA i ^j atentschriften 3 O58 826 3 00 ^ 878, fxaiizöslGche Patentnc.'trift 1,261,846, Belgian Pat o1i 622, 611 623).

The curves in the accompanying drawing can now be seen

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BAD OfWGfNAL

that the sensitivity is in the lower part of the loirve B, ■ „■ Characterizing the x'ür emulsions xn with the additives mentioned above is hardly different from the values of the Curve Δ, that for -umulsions without these high molecular weight additives 'ilt.

The iieiincuriö bezv / eckt dia making a ^ r ^ miljion with better ώ'ηιρίinolichkeit, maximum density and maximum Contrast.

JSs ™ has been found that at a Haloes η silver bromoiodide gelatin emulsion, which, by means of conventional chemical tteduktionsmitteln Jensibilisatomen as unstable sulfur compounds unci G-oldverüindunven in the best i ^l m -; wciaen is brought <finclliciikeit, cie ~ inpjL'inulichk; - it can still be learned if one admits rpolymerisate and / or oopol ;; merisste von Lorpholinalkylalkenojlamiuen ontrast and maxiiagle density, but you the environment, especially at the lower ends of the uxve, largely improved.

jj 'for the to be used ^ orphclinalkylalkenoylamio-JrOlymerisat the following formula applies

CD

GH ₂ 909847/0810

0 ^/

BATH ORIGINAL

in IL a hydrogen atom or GrU, λ a positive whole number and η equals 1, 2 or 3.

The following general formula applies to * the copolymer

f '

HII

(σΐΐ ₂ ) _η

, Λ

² \ ι ²

H ₃ O approx.,

V "

in the .B ^ and ίϊ _ρ a hydrogen atom or CL _; , x, -y positive integers, η equals 1, 2 or 3 ^ nc Z CjU ¹ JH ₂ , .OCOClI ,, COOGH ,.

GC

or

GH

R, G

el

mean.

Such Polyiaei'isa u'-e ooer Copolymeri: .ute can z..5., .Vie Poly-K -. ^ Ox-'lrolinLi. thylacrylamide by i-olymination of by reaction ν: η / icry: .aiaid, formalin and luor-pLplin iveXi si ^ elltem. .- ¹ J-Lci.'p.holi.i: ^ :; thyläciylamld gev / onncn be. Co-

9098A7 / 081Q

BATH ORIGINAL

polymers of morpholine methyl acrylamide can be prepared by polymerizing a mixture of N-morpholine methyl acrylamide and vinyl acetate, ethyl acrylate, acrylamide, vinyl pyrrolidone or acryloyl morpholine. It is desirable here for the copolymer to contain more than 1 mol% of N-morpholine methylaerylamide. If the degree of polymerization is too high, the compatibility of the polymer or copolymer with the gelatin is poor. The intrinsic molar viscosity should therefore be Ail ^ 2, ο (55 ⁰ G).

The amount of polymer to be incorporated into the emulsion is not critical in itself. However, the best effect in terms of sensitivity, gamma and maximum density is to some extent depending on the type of halogen silver emulsion and the purpose of use. The appropriate additional amount is generally 3 to 4o, preferably 6 to 2o% by weight of the total emulsion.

Instead of directly interfering with the photographic According to the invention, silver halide gelatin emulsion can be used. called polymer and / or copolymer also one of the Watchable layers in an amount of 1o to 4-o % By weight are added.

The additive according to the invention can be used during any Production stage of the emulsion are added. Preferably mixing takes place after the second soaping and before application to the carrier underlay. The addition can in powder form, but preferably as 1o to -2o> & ige aqueous

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solution. Since hydrolysis is to be feared, as soon as the pH-iivert of the aqueous solution is higher than 7, it is preferably adjusted to a pH of 4 to 6.

The invention is applicable to any types of halide emulsions applicable, e.g. for üromgoasilbereinulsionen or Chlorobromosirber emulsions. "Lan can use emulsions, sensitized with sulfur and / or gold compounds and the light sensitizers, polyalkylene oxide sensitizers, stabilizers, hardeners, coating aids, color coupler etc. included

Conventional materials, such as glass plates, elm made of 'friacetyl cellulose, polyethylene terephthalate, Polycarbonate, polystyrene, polypropylene or baryta paper be used.

In order to further explain the invention, the following Examples of synthesis of the polymers to be used and practical examples given. ■

jynthe s e be is pi e - ■ "] _ .. ■

An aqueous solution of 71 S acrylamide in 2oo ecm of water vmrde with 1 g of hydroquinone and then with 1.2σ ecm Jo / ^ igem formalin offset. Under lead were 8? g morpholine added dropwise, after the addition is complete the temperature increased to 70 ° G and to complete it the action still another 3 otd. touched. Then it was

• 9098 k 7/0810 BAD ORIGINAL

filtered, the water was distilled off under reduced pressure and finally distilled in vacuo. N-ivloropholine methyl acrylamide was obtained with a boiling point of 136 to 158 ° 0.6 mm · Hg. After recrystallization from benzene, was the melting point 92 to 93 ° C

Analysis for G ₈ H ₁₄ O ₂ N ₂ :

G: calculated 5'5.45 / <>, found 56.57% II: calculated '8.29 % ·> found 8, o4 % IT: calculated 16.46; 6, found 16.62%.

Synthesis example 2

In 4oo ocm of a 2oyo aqueous isopropanol solution were 100 g of the N-iviorpholinmethrylacrylamide obtained according to Example 1 solved. This solution is mixed with 0.5 g of L-ascorbic acid and 0.6 ecm of an aqueous hydrogen peroxide solution added and in a stream of nitrogen 5 ötd. held at 40 ° C. The product is produced using a for one day Gellojnandiaphragmas dialyzed and then the 'free' cool drying subjected, lvian received 80 g of a water-soluble Polymer of IV-korpholinmethylacrylamids with the basal molar Viscosity number o, 2.

a yntheses example 3

In 600 ecm of absolute -! Ethanol, 129 g of acetyleneimine, 500 g of morpholine and 3 g of concentrated sulfuric acid mixed in. The mixture was 12 btd. boiled under fi reflux. After first the ^ ethyl alcohol and the excess

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Morpholine has been distilled at reduced pressure who were "vacuum distillation" 2oo g of morpholine ethylamine obtained with a boiling point of 69 to 73 ° 0/5 mm Hg.

r ^ ch]

90.5% acrylic chloride were added to 5% of toluene. Then a mixture of Ί-Jo g of the above Morpholine ethyl amine and 1o1 g of triethyl amine obtained according to the instructions added drop by drop while stirring and cooling. Haoh filter off the precipitated triethylamine hydrochloride a small amount of hydroquinone was added and then the toluene was distilled off. After vacuum distillation crystalline li-morpholine ethyl acrylamide was obtained with a melting point of 160 ° C and a boiling point of 1.31 to 14o ° C / o, o6 mm Hg.

Analysis for CqH _-16 N ₂ O ₂ :

H: calculated 15.22% _t found -15.25; ».

S. synthsebei pie I 4

In 76 ecm of dimethylformamide, 24 g of the according to Example 5 prepared ii-I.iorpholinäthylacrylamids dissolved. Then were 0.05 g of azobisisobutyronitrile were added and the mixture was added for 4 hours. stirred at 70 ° C in a stream of nitrogen. The dimethylformamide was concentrated and the product dissolved in water, dialyzed and deeply refrigerated. 11 g of Poly-JK-Morpholinäthyl2crylamid were obtained.

Synthesis example 5

To a mixture of 91 g (1 i-iol) Acrylc-lchlorid and 3oo ecm

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Toluene wuide ßühien and cooling dropwise a mixture of 144 g (1 mol) N-Äminopiopylmoipholin and ToI g (1 mol) Tiiäthylamin at a temperature below 10 ° G was added. After three hours of charging at room temperature, the Tiiäthylaminhydiochloiid formed was filtered off and the soluble mixture dried with kölnigem sodium hydroxide. After distilling off the toluene Wuide in a nitrogen stream while adding Einei succeed amount of hydroquinone in VakuumizfestilXiert h. 73 g of N-morpholine propyl

acrylamide. Yield 37%, boiling point 149 to 152 ° C./0.5 mm

Ed.; ■■■■

Analysis füi ^g i _o ^h iq ^N 2 ° 2 ^:

N: calculated 14.13 #, found 14.08 ⁰ A

Synthesis Example 6 ,:.

0.03 g of azobisisobutyronitrile were added to a solution of 30 g of morpholine propyl acrylamide in 10 ° of dimethylformamide and polymerization was carried out for 8 hours at 7 ° C. in a stream of nitrogen. After the polymerization, most of the dimethylformamide was removed. The product was then dissolved in water and dialyzed using a gellophane diaphragm. After deep-freeze drying, 20 g of polymorpholine propyl acrylamide were obtained. The intrinsic molar viscosity number in dimethylformamide at 35 ⁰ was o.125.

Synthetic example 7

A solution of 85 g of methyl amide in 2oo ecm of water

90984 7./0810

was with 1 g hydroquinone and 12ο ctfm 30 / & Lgem formalin offset. Then was carried out dropwise under 87 g of morpholine added, the temperature increased to 5o to 6o ° C became. To complete the reaction, another 3 hours. stirred at 70 ° C. Bach was filtering the water under distilled off under reduced pressure. In the subsequent Vacuum distillation gave N-morpholine methyl methacrylamide from boiling point 134 to 158 ° C / 0.5 mm Hg. After recrystallization from benzene, the melting point was 82 bis

Analysis for OqII ₁₆ O ₂ H ₂ :

0: calculated 58j67 %> found 59 »35 ^z / ° ■ ■ H: calculated 8.75%, found 8.72% N-: calculated 15.21 %, found 15.19%.

Synthesis example 8 "

Jo g of the iT morpholine methyl methacrylamide obtained according to Example 7 were dissolved in 7 ° ecm Vi / ater. With the addition of The solution was dissolved for 4 hours at 0.09 g of potassium peroxide 7o ° C in a stream of nitrogen. The product was dialyzed and frozen dried. 11 g of a water-soluble polymer with an intrinsic molar viscosity of 0.47 are increased. ; · * ..-. .; ■;. ■.

synthesis example 9

71 g of N-morpholine methyl acrylamide were added to 3oo ecm 50 / g isopxyl alcohol and 29 g of acrylamide dissolved. Then with the addition of 0.5 g of L-ascorbic acid and 6 'ecm of a 3

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-1ο-

Hydrogen peroxide solution was stirred for 4 hours at 40 ° C. in a stream of nitrogen. The solution was dialyzed for one day using a cellophane diaphragm and the product was deep-freeze-dried. 65 g of a water-soluble polymer with an intrinsic viscosity of 0.2 were obtained.

Synthesis example 1o

In 3oo ecm of a 30 / oi @ en aqueous Isopror.anollösung were 9o g of N-morpholine methyl acrylamide and 10 g of acrylamide dissolved. The solution was with the addition of a 3o / £ aqueous water. substance peroxide solution 4 ütd. stirred at 40 ° C in a stream of nitrogen. Then the solution was a day with a cellophane diaphragm dialyzed. After deep-freeze drying, 76 g of a water-soluble polymer with the basal molar were obtained Viscosity number 0.26.

Synthesis Example 11

51 g of ri-iviorpholine methyl acrylamide and 49 g of acrylamide were dissolved in 300 cc of a 50% aqueous isopropanol solution. ψ with the addition of 0.5 g L ~ ascorbic acid and 6 ecm one

30% aqueous hydrogen peroxide solution was added for 4 hours. stirred at 40 ° C in a stream of nitrogen. Then came a day dialyzed with a cellophane junction. After the sieve cool drying 57 g of a water-soluble polymer with an intrinsic molecular viscosity of 0.5 are obtained

Synthesis example 12

In 3oo ecm of water were. 85 g of H-morpholine methyl acrylamide.

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BATH ORIGINAL

and 56 g of vinyl pyrrolidone dissolved. The solution was stirred with the addition of 0.75 g of L-ascorbic acid and 3 ecm of a 30% aqueous hydrogen peroxide solution for 4 hours at 40 ° C. in a stream of nitrogen. It was then dialyzed with a Cellophandiaphragma a "day. Liach the freezing drying to obtain 118 g of a water soluble polymer having the intrinsic viscosity o _≤ 65.

Synthesis Example 15 .

Ecm 3oo in a 25 # ^s is aqueous isopropanol were dissolved 54 g of N-Morphorinmethylacrylamid and 54 g of acryloyl morpholine * The solution was the addition of 1.5 g of L-Ascortinaäure and 5 "3 cc of a 30 / 'öigen aqueous hydrogen peroxide solution 6 3td. stirred at 40 ° C in a stream of nitrogen. Dialyzed with a cellophane diaphragm was then carried out for one day. After deep-freeze drying, 60 g of a water-soluble polymer with an intrinsic viscosity of 0.1 were obtained.

Example 1 .

A halogen silver gelatin emulsion for highly sensitive \ Negative material containing 1.8 moles of shark silver (5 Mo1 *% silver acid, - 95 mol% silver bromide) and 25ο g Gelatin was made using sulfur and gold sensitizers to the. best sensitivity. The emulsion is de in divided three equal parts and each part were 10 g of the the following substances added:

a) inactive gelatin

BAD ORlÖINAi

h) polyvinylpyrrolidone, molecular weight 4,000 ej. Polyr-N'-morpholine methyl acrylamia

The emulsion was then still with a sensitizing dye, a stabilizer, a coating aid and a hardener added. With the emulsions triacetyl cellulose films were coated. The exposure took place for 1/2 second in a sensitometer at 54-oo ° E. Development took place for 150 minutes at 20 ° C in a solution following the composition

1-phenyl-3-pyrazolid one ITodium sulfite, anhydrous Hydroquinone Borax

Boric acid potassium bromide water to fill up

Table 1 shows the results of measurements of the photo- graphic _t density of the developed films B _x b and o.

Table 1 . -

Belative Sensitivity Relative Sensitivity Gamma Veil sweetness with density

o, 1 about tench! ° »5 About solstice

I00 1 »17 ö» 1o

1o3 1.26 * M °

"I5I".'- ■ 1 | ^ · ■ '■''''■ $$ &"._:■■' ■.

O , 2 g 100 6th 7th S. 1o S. 5 G 1 δ 1 Liter"

a I00 b 97 0 .131

15478 Π

Table 1 shows that by adding poly-N-morpholine methyl acrylamide the gamma value and the sensitivity increases will. It also increases the sensitivity for the lower Improved the area of the characteristic curve, which is what a Addition of polyvinylpyrrolidone is not the ITaIl.

Example 2 \ ~

A halogen silver emulsion for highly sensitive negative material containing. 1o59 g gelatine and ^ o mole of halosilver (5> - mole-% silver dodide and 95 mole-% silver bromide) was matured with sulfur and gold sensitizers to the best sensitivity and then divided into 10 parts. oigen aqueous solution of the following substances added; _v

d) inactive gelatin

e) Poly-Sr-morpholine methyl acrylamide /, - 'HJ = 0.12 "

f) Pol'j'-H-moxpholine methyl methacrylamide

g) Gopolyiaerisat from li-morpholine methyl acrylamide (vol. mol%) and acrylamide (3σ. Ιο1 -? 'ό)

h) Copolymer of H-iviorpholinmethylacrylamid (5o

and lcxylamide (50 Iviol- / 0
i) Copolymer of i ^ l-Liorpholinmethylacrylamid (3o

and acrylamide (7o Mo1-; ü)
j) Copolymer of τί-morpholine methyl acrylamide (5o

and vinyl acetate (5o Μ0Ι- / 0)
k) Copolymer of ii-iVIorpholinmethylacrylamid (50 Μ0Ι- / Ο)

and methyl acrylate (.50. mol%) ". ■. ■ ■

909847/0810 BADORfGiNAt.

1) Copolymer of li-morpholine methyl acrylamide (5o mol%)

and vinyl pyrrolidone (5o mol-76)
m) Copolymer of IT morpholine methyl acrylamide (5o mol- / ») and acryloylmorpholine (5o mol- ^ ö)

To impart panchromatic properties, each emulsion was given a sensitizing dye and, in addition, 2o ecm of a 1% strength aqueous solution of 4-hydroxy-6-methyl-1,3 »3a, 7-tetrazaindene as a stabilizer, 1.5 * ecm of a 10% aqueous solution Chrome alum solution as hardening agent and 1.5 ecm of a 4% aqueous saponin solution added as a coating agent. Iriacetyl cellulose films were coated with the same thickness with the emulsions. The films were wetted in a sensitivity parameter of 5 ^ PO ⁰ E 1 / 2o Selpinde. The development took place for 7 minutes at 20 ° C in a solution of the following composition:

H-methyl-p-aminophenol sulfate 2 g

IT triunsulfite, anhydrous - 100 g

Hydroquinone "5 g

Borax 2g

Water to make up to 1 liter.

The values for the photographic density of the developed Films are shown in Table 2.

Table 2

He la ti ve sensation .Relative sensation- Gamma Schlei Liability with density Liability with density o, 1 above veil ο, 5 above veil

1oo 9Q984 7? E§> §t0 o _t 81 o, o6

e 115 f 12o β ■■ -. 125 H 135 i 12p 4th 112 k Ho 1 112 m, Example 3

I3H / Olf

-15-

12o

129 148 155

1 , 00 O 1 O 1 _t 14 ■ - « 1 , p8 0 1 O 1 Qf) O 8th ,oil O, 1 ,Pi @ 1

126

a Bromjodsilberemulsion for highly sensitive Ilöntgenfilme _t chemically to the best sensitivity was ge ^ matures, were η with the following substances, ο, p _t in einef Ifienge of 5 g each per o, 6 mol HaIpgensilber added.

Π / inactive gelatin

o) Poly ^ W-morpholeinäthylaorylamid

p) poly-N-mqrpholinpropylacrylamid.

Kaoh addition of stabilizer | hardening agent and coating |

Processing aids were undercoated poly-ethylterephthalate films coated. The films were exposed for 1/2 a second in a sensitometer with blue filex " and high in a Metol hydroquinone developer developed. When determining the photographic duty, eich showed that the film with the additions ο and ρ a had higher sensitivity.

Example 4

BATH ORIGINAL

A solution of 26 g of potassium chloride, 7 ½ of potassium bromide and 8 g of gelatin in 23o ecm t drum was brought to 55 ⁰ O and while maintaining this temperature a solution of 50 g of silver nitrate in 92o was carried out. ecm of water added. After further addition of 100 g of gelatin, the mixture was stirred for 15 minutes and then allowed to solidify while cooling with ice. The mass was divided into fine particles and washed with water until the conductivity of the emulsion was 1500 microohms / cm.

The emulsion was dissolved while heating and, after adding 24 g of sensitizing gelatine and 80 g of inactive gelatine, was kept at 55 ° C. for 100 minutes. 20 g of poly-N-morpholine methyl acrylamide were dissolved in this emulsion and then Ao ocm of a 0.05% methanol solution of 3-aryl-3'-ethyl-5- (2- (i-ethyl-4-quinolini <3ene) ethylidene ) -5 ', 6'-dimethyl - ^ - 0x0thiazoIinooxyoyaniniοdid and 300 oom of a 5% aqueous alkaline solution of Nn-Ootadeayl-1-hydroxy-A-aul £ o ~ 2-naphthamide was added. This mixture was applied to an undercoated Txiaoetyloellulosefilm in a Ψ Schiohtdioke of about 5 microns applied.

The sensitometric measurement showed that this emulsion layer provided with blue-green coupler shows a higher coupling density than an otherwise identical emulsion which instead of of the poly-N-morpholine methyl aylamide an equivalent amount Contains gelatin.

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Example 5

A triacetyl cellulose film was made with that described in Example 1 -Emulsion in a layer thickness of about 1o Micron coated and cut in two. One part received another coating of about 2 microns, with a solution of 13 g of gelatin and 8 g of poly-N-morpholine methyl acrylamide was made in 1 liter of water. The second part received another also 2 microns thick coating by means of a solution of 25 g of gelatin in 1 Idter water. After exposure and development according to Example 1 showed the first-mentioned part to be higher maximum density.

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Claims (6)

Claims 1) Liohtsensitliohea photographic material, labeled by a Halogenailberemulaionasohioht and / or one to the adjacent auxiliary layer with a content of at least a polymer of the general formula I 00 I HH H ₂ C VJ where E _x , a hydrogen atom or CH ₃ ,, χ is a positive integer and η is 1, 2 or 3 and / or a copolymer of the general formula t \ "" d - j x V -ü j / y ? 2 909847/0818 ORiaiNAL INSPECTlD 15 A 7 81 / (I in the JL · and Hp a hydrogen atom or CH, χ and y posi- I I tive integers, η equals 1, 2 or 3 and Z COM ₂ , OCOCH ₅ , COOCH,, 7 I. CO I ί \ ■ A CH ₀ . "Ii ₀ G CO 2 or 2 2 or 2 CH ₂ H ₂ G mean. 2) J ¹ OtOgEafiaches material nsoh claim 1, characterized duroh an addition of poly-K-morpbolinmethylacrylsmid or poly-N-morpholinraethylmethaexylaniid. 4 ^f 3) Photographic material according to claim 1 or 2, _t E ^ ichaet by an addition of copolymers the N-morpho- Iinmethyl8orylamida with aouyl8mid _t ¥ lnylaoetat ₄ methyl ¹ - * »Orylate, vi ^ ipyrrolidon, aaryloylmorpholine. ^rt 4) Photographic material according to claim 1 to t> _% thereby characterized in that the polymer of halosilver emuletlonaeohicht in an amount of 5 - 4 ° preferably 6 - 2o wt .-% is added. 5) Photographic material according to claim 1 to 4, characterized in that the polymer has been added to the emulsion after the second ripening and before the coating of the carrier substrate. 909847/0810 BATH ORIGINAL · ,, IO4 / O I / ι ao 6) Photographic material according to claim 1 to 5, characterized in that the polymer is in the form of a 1o Ms 2o # strength aqueous solution with a pH of 4 to 6 "ugttet" orden . 909847/0810