DE2058472A1 - Light-sensitive silver halide photographic emulsion - Google Patents

Description

PATENTANWÄLTE _ _X _ _{β MÖNCHEN a} li ...... Oct., ... 117O

DR.-ING. WOLFF, H. BARTELS, thierschstrasse t

DR. BRANDES, DR.-ING. HELD phone, pm) »» 97

H / 77

Reg. No. 122 704

EASTMAN KODAK COMPANY, 3 ^ 3 State Street, Rochester, New York State, United States of America

Light-sensitive silver halide photographic emulsion

109824/1737

The present invention relates to a light-sensitive silver halide photographic emulsion having improved anti-fogging properties and improved stability.

It is known that sulfur compounds, for example mercaptans and simple thioethers, for sensitizing SiI overhalide emulsions can be used and give them improved photographic sensitivity (see e.g. U.S. Patent 3,046,134). There are already different ones Compounds containing sulfur and nitrogen have been proposed as antifoggants in silver halide emulsions (see. Glafkides "Photographic Chemistry", 1958, pages 37 ^ -378). However, as yet there are no silver halide photographic emulsions known that at the same time have good stability, good anti-fog properties and good sensitivity without impairing other properties.

The object of the invention is to provide a photosensitive photographic Indicate silver halide emulsion which has both improved stability and improved anti-fogging properties as well as an improved sensitivity or a combination of these properties without affecting the rest Properties of the emulsion are impaired.

It has now been found that this object can be achieved by determining photographic silver halide emulsions thio-substituted polycyclic compounds added.

The invention relates to a photosensitive photographic Silver halide emulsion, which is characterized in that it contains at least one monomeric or polymeric, polycyclic, Contains thio-substituted compound which has a radical of the formula:

109824/1737

Such a light-sensitive silver halide photographic emulsion w for improved photographic properties, particularly less fogging and improved te stability. This improvement in the photographic properties of the silver halide emulsion is extremely surprising, since the person skilled in the art previously assumed that the thio substitution on the ring provided with a /~2.2.1_7 bridge was completely is inactive and inert.

In those in the light-sensitive silver halide photographic emulsion the invention contained thio-substituted compounds with a residue with a /~2.2.1_7 bridge can are both macrocyclic compounds and simple compounds. Simple connections are preferred, which contain at least one such radical, or polymeric compounds which contain recurring units in where at least one of the recurring units contains the remainder mentioned above, is used.

According to a particularly preferred embodiment of the invention, the photographic silver halide emulsion contains a compound with a ring with bridging, which is a divalent Diels-Alder adduct of cyclopentadiene and a dienophile.

In another preferred embodiment, the invention relates to a silver halide photographic emulsion which a thio-substituted /~2.2*l_7-bicyclic compound holds.

109824/1737

According to a third preferred embodiment, the light-sensitive silver halide photographic emulsion of the invention a polymeric compound composed of repeating units the formula:

-f- D-S ~) ~

consists, in which D is a polycyclic group which has a ring connected to the sulfur atom with a /~2.2.1_7 bridge contains. The polycyclic group can of course also be formed by various groups, for example further cyclic groups ad-chain groups, which are preferably condensation groups, such as. B. ester, carbamide and urethane groups contain substituted be.

Those in light-sensitive photographic silver halide emulsions Thio-substituted compounds which can be used in the invention can generally be prepared by adding hydrogen sulfide, a monomer mercaptan or a bis mercaptan with an unsaturated one Implementing connection with a ring with a bridge. Of course, in the case of polymeric and macrocyclic compounds intralinear groups and in the case of simple compounds, polymeric compounds and macrocyclic compounds outer groups exist. A typical simple implementation is the reaction of cycloalkadiene with a dienophile, d. H. a compound with at least one double bond, according to the known Diels-Alder reaction, as described, for example, in "Organic Reactions", Volume IV, Chapters I and II, John Wiley and Sons, Inc., New York, 19 ^ 8, with a bicyclo- / ~ 2.2.1_7-5-hepten arises. This Diels-Alder adduct is then reacted with the sulfur compound to form a thio-substituted one Bicyclo / ~ 2.2.1__7-heptane.

In particular, Bind

Examples of in the silver halide photographic emulsion

especially, Thio-substituted compounds which can be used according to the invention are / those that contain a group of the general formula:

1Ö982W1737

Bl-I

in which A is a methylene radical, an oxygen atom, a sulfur atom or an -NH- group, preferably a methylene radical, and m is the number 1, 2, 3 or 4. These compounds can be polymeric compounds or simple compounds Act. When it comes to simple compounds, they have the general formula:

S-R-

"* m-l

12? l \

in which R, R, R ^ and R each hydrogen atoms, optionally substituted and branched Allaireste with 1 to about 8 carbon atoms, carboxy residues, alkoxycarbonyl residues, mercapto residues, cyano residues, acylthio residues in which the acyl residue is an alkanoyl group, alkanol radicals, e.g. B. a hydroxy methyl radical, mean, where at least one of the radicals R to R is a hydrogen atom, or in which R to R together with the carbon atoms to which they are linked, a cyclopentene or cyclopentane ring, or a radical of Form formula:

109824/1737

Il

C 1

in which X is -O- or -NH-; R ¹ and R can also represent a radical of the formula:

S-R-

and R- 'can represent a hydrogen atom, an optionally substituted one Alkyl radical or a heteroatoms, such as. B. Oxygen ;, Sulfur or nitrogen atoms, containing alkyl radical within the alkyl chain or attached to the alkyl chain, mean and the alkyl radicals can have an end group of the formula

R-

R ^J

m-1

1 4

in which m, A and R to R have the meanings given above, For example, a methyl, ethyl, propyl, butyl, carboxyraethyl, S ^ -Dicarboxynorborn-S-ylthioäthoxyäthoxyäthyl, Acetyl, proponyl, butyryl, 1,2-dicarboxyethyl, Carboxypropyl, ethoxycarbonylpropyl, methoxycarbonylethyl, 1,2-bis (ethoxycarbonyl) ethyl, 2- (norborn-2-yl) ethylthioethyl,

109824/173?

2- (5,6-dicarboxynorborn-2-yl) ethylthioethyl, hydroxypropyl, Hydroxyethyl, hydroxyraethyl, aryl group, for example one optionally substituted phenyl group, or a group of the formula:

ra-1

1 H.

in which m, A and R to R have the meanings given above.

When the compounds contained in the photographic silver halide emulsion of the invention are polymeric compounds, they contain repeating units of the formulas I, H ₃ III or IV given below:

-3-0-

ra-l

-R ¹

X-I

in which m “A and R ¹ and R individually have the meanings given above and R and R together with the carbon atom to which they are bonded form a radical of the formula:

1ÖÖ824 / 1737

R optionally substituted, optionally branched and optionally a hetero atom contained alkylene radical, for example an ethylene, propylene, trimethylene, tetramethylene, Äthylenoxyäthoxyäthyl-, Hydroxymethyläthylen- or Äthy lent a hioäthylrest;

G is a carboxymethylmethylene _{radical CH 2} -CH-, a carboxyethylene

remainder -CH-CH ₂ - COOH

COOH
or a residue of the formula

m-1

1 ii

in which m, A, R and R individually have the meanings given above own; and

R ^ is an alkylene, cycloalkylene or arylene radical which is the condensation radical of a diol or a diamine, ie a radical -0-R ⁸ -0-, -NH-R ⁸ -NH-, NH-Ar-NH- or a radical the formula represents:

-N

in which R ° denotes an optionally substituted, optionally branched and optionally heteroatom-containing alkylate radical and an alkylene radical containing cycloalkylene groups}, for example, R ⁷ can be a radical of the formula

100824/1737

-NH-CH

-CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ Ch ₂ -S

CH ₂ -NH-

or

HIGH

CH ₂ CH ₂ SCH ₂ CH ₂ S

CH ₂ OH

and Ar represents an aryl radical; and

χ means the number 1 or 2, with the proviso that χ = 1 if -G- the rest means:

Jm-I

in which R ¹ and R together with the carbon atoms to which they are bonded represent a radical of the formula:

109824/1737

II -Y-R

R ³ -YR ¹⁰ -

14 6

where m, A and R and R individually as well as R the above

q
have meanings, Br is an alkylene radical having 1 to 6 carbon atoms, preferably the methylene radical; Y is a -0- or -NH-Q group and R is the condensation radical of an aliphatic or aromatic dicarboxylic acid, ie a radical of the formula:

—C-R "C

ι H

0 0

in which R "is an aromatic or aliphatic radical, e.g. a phenylene, alkylene, phenylene bisalkylene, alkylene bisphenylene, Cycloalkylene, Cycloalkylenbisalkylenrest and an alkylene radical, the heteroatoms and cycloalkylene groups contains, for example the rest means:

HOOC

S-CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ -S-h \ j

^ sJs * COOH

III

¹² -

10S624 / 173?

1 it

wherein A and R and H individually have the meanings given above

12th

and R is an ester bridge (-C-0-) or a Araoro Bridge (-NH-C-) 0

0
containing alkylene radical or a substituted derivative thereof

means, for example, one

Carboxymethylmethyleneearbonyloxy radical (-OC-CH-),

ff

Ethylenoxy carbonyl radical (-CH ₂ CH ₂ OC-),

Methylenoxycarbonyl radical (-CH ₂ -OC-),

Methylenecarbonyloxymethyl residue (-CH ₂ CO-CH ₂ -),

CH ₂ OOOH

Carboxymethyliaethylenecarbonyloxymethyl radical (-CH-COOCH ₂ -),

CH ₂ -COOH

Ethylenecarbonyloxymethyl radical -CH ₂ CH ₂ COOCH ₂ -,

Trimethylene carbonyloxymethyl residue -

> Jm-I

109824/1737

where m, A and R and R individually have the abovementioned meaning

1 U

functions and R and R together with the carbon atoms, to which they are bound represent a residue of the formula:

Il s

C-

-N

13 12

and R ^{J is} one of the radicals mentioned for R or a radical of

Formula:

-R '

m-l

12 1 ^ l

in which m, A, R and R and R individually the | above

Have meanings

or an alkylene, arylene, arylenebisalkylene or alkylenebisarylene radical, e.g. B. a phenylenedlmethylene, phenylene, methylenediphenylene, ethylene or Tetramet hy lenrestPf, ^β ν $ 3ηΐί R and R together with the carbon atoms to which they are bonded form a radical of the formula:

-N

109824/1737

The light-sensitive silver halide photographic emulsions of the invention can also contain the respective sulfoxide and Contain sulfon compounds of the formulas given above, in which the sulfur atom becomes a sulfoxide or sulfon is oxidized.

The polymeric compounds which can be used according to the invention can be prepared by reacting sulfur compounds, for example hydrogen sulfide or mono- and / or polyfunctional mercaptans, with a polycyclic compound which contains an unsaturated, /~2.2.1_7- bicyclic radical. Reaction conditions which favor the reaction of free radicals are preferred. Reactions which run off only with difficulty are prevented by the use of catalysts which produce free radicals, for. B. from ascaridol, peroxides, or using ultraviolet light, optionally with photosensitizers, such as. B. acetone and benzophenone, and catalyzed by heat or combinations of these measures. The reaction generally proceeds in such a way that a mercaptan is added to the double bond of a /~2.2.1_ _r 7-bicyclic radical which contains an unsaturated group. In general, the mercaptan or the polycyclic compound has further functional groups, e.g. B. condensable groups, such as alcohol-j acid and amide groups, especially when polymeric or macrocyclic compounds are formed. The g-linear bridge formation can be obtained by a condensation reaction within these groups or simultaneously with the reaction of the mercaptan with the double bond at the /"2.2J. _7-bicyclic radical to be completed.

The thio-substituted compounds used in the present invention are added to the photographic superhalide emulsions added to the invention in general by known methods, such as those in the United States patent 3,046,134. The concentration of the added Connections depends on the desired improvement

108824/173?

the properties. Silver halide emulsions can do them for example in concentrations from about 0.010 mg to about 10 g, preferably from about 0.5 mg to about 1 g, per mole of silver halide can be added.

The silver halide emulsions of the invention can be silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide or Mixtures of these included. The emulsions can be coarse grained or fine grained and they can be prepared by any known method be prepared and, for example, single enema emulsions, Double enema emulsions, e.g. B. Lippmann emulsions, ammoniacal Emulsions or emulsions matured with thiocyanate or thloether, such as those from the USA patents 2 222 264, 3 320 069 and 3 271 157 are known. Surface emulsions or internal emulsions can also be used may be used, such as those in U.S. Patents 2,592,250, 3,206,313, and 3,367,778, as well as the Belgian Patent 704,255 are described. If desired, mixtures of surface and interior image emulsions can also be used (Deep emulsions) as disclosed in U.S. Patent 2,996,332 are known to be used. Furthermore, negative emulsions or direct positive emulsions can be used, such as, for example from US patents 2,184,013, 2,541,472, 3 367 778, 2 563 785, 2 456 953 and 2 86I 885 as well as from the British patent 723 019 and French patent 1,520,821 are known.

The silver halide photographic emulsions of the invention can be mixed with chemical sensitizers, for example with Reducing agents, with sulfur, selenium or tellurium compounds, with QoId, platinum or palladium compounds or Combinations of these compounds, be sensitized. Suitable methods are, for example, in the USA patents 1 623 499, 2 399 083, 3 297 447 and 3 297 446.

109Ö24 / 17S7

The silver halide emulsions of the invention can also contain developer compounds, for example hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and derivatives of which contain reductones and phenylenediamines. Combinations of these developer compounds can also be used will. The developing agents can either be in the silver halide emulsion itself and / or in another layer of one comprising the silver halide emulsion of the invention photographic recording material may be included. The developer connections can be added as solutions in suitable solvents or in the form of dispersions, as they are for example, U.S. Patent 2,592,368 and U.S. Patent No. 2,592,368 French Patent 1,505,778.

The emulsion layer and the other layers of one of the layers according to the invention Photographic material comprising silver halide emulsion can be represented by various organic or inorganic hardeners, which are used either alone or in combination, for example with aldehydes

Ketones, carboxylic acids and carboxylic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfones, reactive halogen compounds, epoxy compounds, aziridines, reactive olefins, isocyanates, carbodiimides, hardeners and polymer hardeners with mixed punctures, ζ. B. oxy- g dated polysaccharides such as dialdehyde starch and oxyguargumrai, hardened.

The silver halide solutions of the invention can be various Colloids either alone or in combination, such as auxiliaries and binders, contain and different layers exhibit. Suitable hydrophilic substances are, for. B. both naturally occurring substances such as proteins, z. B. gelatin, gelatin derivatives, cellulose derivatives, polysaccharides, e.g. B. dextran, gum arabic, as well as synthetic polymeric substances, such as. B. water soluble polyvinyl

109824/1737

compounds such as poly (vinylpyrrolidone) and acrylamide polymers.

The photographic emulsion layers and the other layers of photographic recording surfaces comprising the Silver halide emulsions of the invention may also contain, alone or in combination with hydrophilic, water-permeable Colloids, other synthetic polymeric compounds, e.g. B. dispersed vinyl compounds, for example in latex form, and in particular contain those compounds which improve the dimensional stability of the photographic recording materials. Examples of suitable synthetic Polymers are those as described, for example, in US Patents 3,142,568, 3,193,386, 3,062,674, 3,220,844, 3,287,289 and 3,411,911 are described. The water-insoluble polymers of alkyl acrylates are particularly effective and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, which have crosslinking points, which facilitate hardening, and which have recurring sulfobetaines as described in Canadian Patent 774.

The photographic layers and the remaining layers of a photographic material prepared using the photographic silver halide emulsion of the invention can be coated on a wide variety of supports. Examples of suitable supports are those made of cellulose nitrate, cellulose ester, poly (vinyl acetal), polystyrene, poly (ethylene terephthalate), polycarbonate and similar supports or those made of resinous materials, and supports made of glass, paper and metal. A flexible layer support, in particular a layer support made of paper, is preferably used, which is partially acetylated or with barium oxide and / or an α-olefin polymer, in particular a polymer of an α-olefin with 2 to 10 carbon atoms,

1 0Θ62Α / 1 737

for example polyethylene, polypropylene and ethylene butene copolymers, is coated.

The layers of the photographic material can Plasticizers and lubricants, for example polyalcohols, e.g. B. Glycerin and diols described in U.S. Patent 2,960,404 type, fatty acids or esters such as those described in U.S. Patents 2,588,765 and 3,121,060 and silicone resins such as those described in British Patent 955,061. You can also surface-active agents, for example saponin, anionic compounds, e.g. B. Alkylarylsulfonate, as described in the U.S. Patent 2,600,831 and amphoteric compounds as described in U.S. Patent 3,133,816 included.

The light-sensitive silver halide emulsion of the invention can be used in a multilayer photographic material expediently with epectral sensitizing dyes be ortho- or pan-sensitized. The emulsions of the invention can be prepared, for example, by treatment with a solution of a sensitizing dye in an organic Solvent or by adding the dye in the form of a dispersion, as in French patent 1,482,774 described, be spectrally sensitized. Sensitizing dye useful in sensitizing the emulsions of the invention e are described in U.S. Patents 2,526,632, 2,503,776, 2,493,748, and 3,384,486, for example. Examples suitable spectral sensitizing dyes are cyanines, merocyanines, complex (trinuclear) cyanines, complexes (trinuclear) merocyanines, styryls and hemicyanines. The cyanines can have basic nuclei, such as. B. thiazoles, oxazoles, selenazoles or imidazoles. These nuclei can be sulfoalkyl, Contain carboxyalkyl and alkylamino groups and they can optionally be replaced by halogen, phenyl, alkyl or alkoxy

109824/1737

Reate substituted benzene or naphthalene rings condensed on be. The dyes can be symmetrical or unsymmetrical and they can be alkyl, phenyl or heterocyclic on the polymethine chain Contain substituents. The merocyanine dyes can have the above-mentioned basic nuclei as well as acidic nuclei, for example thiohydantoin, rhodanines, oxazolidenedienes and barbituric acids. The acidic nuclei can be replaced by alkyl, Phenyl, carboxy, sulfo or amino groups may be substituted. The emulsions of the invention can also contain supersensitizing dye combinations such as those described in the United States patents 2 739 964, 2 688 545, 2 701 198 and 2 739 as well as in British patent specification 1 128 840, or the dyes can be mixed with ascorbic acid derivatives, Azaindenes, cadmium salts, and organic sulfonic acids such as those described in U.S. Patents 2,933,390 and 2,937,089 are described to be supersensitized.

The silver halide photographic emulsions of the invention can by known coating processes, for example by dip coating, by applying with an air brush, by paint coating or extrusion coating using coating hoppers of the type disclosed in the United States patent 2 681 294 of the type described. If so desired can have two or more layers at the same time according to the US Pat. No. 2,761,791 and US Pat British Patent 837 095 can be applied.

The super halide photographic emulsions of the invention can be used to make recording materials suitable for colloid transfer processes such as those described in US Pat U.S. Patent 2,716,059 for SJJ super salt diffusion transfer processes, as described in U.S. Patents 2,352,014, 2,543,181, 3,020,155, and 2,861,885 are for color image transfer processes like them U.S. Patents 3,087,817, 3,185,567, 2,983,606,

109824/1737

3 253 915, 3 227 550, 3 227 551, 3 227 552, 3 415 644, 3 415 645, and 3 4l5 646 are described, as well as for suction transfer methods, as described in U.S. Patent 2,882,156.

The photographic silver halide emulsions of the invention can also be used in color photographic recording materials are used which contain color couplers, as for example in US Patents 2,376,679, 2,322,027, 2 801 171, 2 698 794, 3 227 554 and 3 046 129, or they can be used in recording materials, the solutions containing color couplers are developed, as for example in US Patents 2,252,718, 2,592,243 and 2,950,970.

Examples of compounds for use in the photographic Silver halide emulsions are particularly suitable are listed below. If it is polymeric or

as the recurring macrocyclic compounds act, they contain / units of the formulas given below, in which η denotes a positive integer.

109824/1737

Connect
manure

formula

Ii

—C

HOOC

Il

₂ CH ₂ S NH- +

Il

™ - "-» C HOOC

CH ₀ CH

HOOC

MHCH ₂ CH ₂ MH-

COOH

109824/1737

Connection no.

-TT-

formula

Il

—C

HOOC

3-

CH ₀ CH ₀ S

^{ά ά}

Il

C-NHCH ₂ CH ₂ NH-COOH

Il

- c

HOOC

Il

, -C-NHCH ₀ CH ₀ NH-J- CH ₉ CH-SI- ^ά

HOOC

N N-

₀ CH ₀ S

COOH

CH ₀ CH ₀ S

C N N

Il

~ ^c }

HOOC-J

Ii

C N N -

COOH

109824/1737

Connection no.

formula

O
C-NH (CH ₀ )

COOH

COOH HOOC

O 0 CN ² 2 _{N c} COOH ^{2 2} HOOC

SCH ₂ Ch ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ - ^

0 0

Il Il

C-NH (CH ₂ ) ₆ NH-C COOH HOOC

CH) Jp CH

OH

0 0

I) H.

C-NH (CH ₂ ) ₆ NH-C COOH HOOC

109824/1737

Connection no.

33

Formula CH,

C-NH-CH,

COOH

SCH ₂ CH ₂ OCH ₂ CH ₂ OCh ₂ CH ₂ -

CH

3 Q

CH ₂ NH-HOOC

CH,

CH

11 4 p

-d

12 fs4- P

HOOC HOOC

SCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ Ch ₂ -S

COOH COOH

109824/1737

Connection no.

formula

HOOC-CH ₂ S

SCH ₂ COOH

SCH ₂ COOH

SCH ₂ COOH

Link

formula

HOOC-CH ₂ -S

HOOC-CH ₂ -S

HOOC-CH ₂ -S

SCH ₂ COOH

109824/1737

2058A72

Connection no.

formula

CH ₃ CS

SC-CH,

It CH ₃ CS

CH ₃ CS

HS

CH ₂ OH

108824/1737

Connection no.

formula

HS

SH

4OCH ₂ CH ₂ S ^ TN C ^

HOOC-CH-S HOOC-CH ₂

109 6 2 4/1737

Connect
manure
No.

- 38 »

38

formula

OCCHS

HOOC-CH,

CH

0 0

1! ϋ

C-O-C

OCH ₂ CH ₂ OC

108824/1737

Link

formula

OCH ₀ CH ₀ S-

2 2 L \ J-COOH

CH ₂ OH

CH ₂ COOH

CH ₂ OH

Il

-C- (CH ₂ ) ₂ S

CH-

CH ₂ O

CH ₂ OH

-C- (CH ₂ KS-H I >' ^{2 3} N ^ Hi CH ₂ ⁰ -

CH ₂ OH

109824/1737

Connect
manure
No.

formula

44 4OCH,

CH ₀ OC

² Il

CH-

C-OCH,

CH ₂ OC

109824/1737

Link

formula

ο p— S — 1 O Il ^. I I ι \ T " ^C C-Vv> O O

CH,

S-

109824/1737

Link

formula

Il

Il

Il

C C

Il ο NCH ₀ CH ₅ N ..

HOOC

II C-OCH, COOH

HOOC
HOOC

AJ ¹ U-

COOH COOH

HIGH,

CH ₂ OH

109824/1737 - 32a -

The table below gives some intrinsic viscosity values for the compounds 35 to 37, 44, 46 and 50-52 listed above. The measurement of the Eigenviskosltätswerte (n) was carried out in methylene chloride as solvent at a temperature of 25 ⁰ C and at a concentration of 0.25 g / dl according to the formula η = In η, / c. The different intrinsic viscosity values for compound 37 arise from the fact that different solvents were used to measure it, e.g. B. methylene chloride, benzene, ethyl acetate, cyclohexane, that various irradiations were carried out, for. B. using a 275 watt lamp with or without certain ™ sensitizing additives.

K ,.

35 0.07

36 0.29

37 0.06, 0.09, 0.11, 0.19, 0.21,

0.23, 0.24 and 0.46

44 0.08

46 0.29

50 0.04

51 0.13

52 0.27

The polymers used according to the invention have an inherent viscosity in methylene chloride of preferably about 0.01 to about 0.60, especially from about 0.04 to about 0.46.

- 33 -

109824/1737

3H 2058A72

Below are some manufacturing methods for some of the above described compounds. Further examples of manufacturing processes are the same in that of the applicant Days under the internal reg. No. 122,705 filed patent application described.

Establishing connection no. 9

Copoly {bicyclo / ~ 2.2.l_7-5-hepten-2,3-dicarboxylic acid anhydride bis (2-mercaptoethyl) sulfide-hexamethylenediamine}

32.8 g (o, 2 hol) ßicyclo - / "2.2.1_7-5-hepten-2,3-dicarboxylic anhydride were dissolved in 100 ml of benzene and 15.4 g (0.1 mol) of bis (2-mercaptoethyl ) mixed sulfide. After two days, v / urde half of the benzene solution with an aqueous solution of 5.3 g (0.05 mol) of distilled hexamethylene diamine and 0.1 mol of sodium hydroxide was stirred in 50 ml of water. the mixture was heated to 80 ⁰ C. The aqueous layer was acidified with dilute hydrochloric acid until a white, fibrous (viscous) polymer was formed, which was obtained by precipitating its sodium salt three times with acid from aqueous solutions and then washing was cleaned with water after each precipitation.

Analysis for C ^ H ^ N-O ^ -S,:

do jo c ο;> neutralization equivalent

Calc .: C 56.7 'H 6.1 N 4.7 S 16.2 (N.E.) 296

Found: C 53.0 H 7.2 N 4.1 S 15.3 % (NE) 284

Division of compound no.14

Copoly / ~ 1,2-bis (2-mercaptoethoxy) ethane-dodecahydro-1,4: 5,3-dlmethananthraquinonylene- ^, 6 (or 7) _7

109824/1737

12 g (0.05 mol) 1,4,4a, 5,8,8a, 9a _a 10a-0ctahydro-1,4: 5,8-dimethane-9,10-anthrachinone and 9.1 g (0.05 Mol) 1,2-Bls (2-mercaptoethoxy) -ethane were mixed with 4 drops of ascaridol, the temperature rising immediately from 24 to 32 ° C. within 2 minutes. The reaction mixture was then heated for 24 hours and precipitated from 3enzene with methanol.

Analysis (molecular weight 46Q):
Calc .: C 62.5 H 7.1 S 15.1
Found: C 61.0 H 7.1 S 14.9 %

Establishing connection no.19
5-carboxymethyl mercaptobicyclo / ^ 2.2.1 _> _7hepten-2,3-dicarboximide

8.7 g (0.053 moles) ^ J
and 19.5 g (0.21 mol) of mercaptoacetic acid were mixed with 4 drops of ascaridol and heated on the steam bath for one hour. Two more drops of ascaridol were added and heating continued for an additional 10 hours. The crystals formed were washed with benzene and recrystallized from ethyl acetate, mp 151-152 ° C.

analysis for ^c 11 ^H. H IO yyS: N 5 , 50 S. 12th , 5. Ber. : C 51 , 7 H 5 , 10 N 5 , 3 S. 12th , 2 Found : C 51 , 3 5 , 3

Establishing connection no.38

9.62 g (0.0265 mol) 5.5 * (or 5.6 «) - Thiobis (bicyclo / ~ 2.2.1_7-heptane-2,3-dicarboxylic anhydride) were dissolved in 500 ml of glacial acetic acid, and there were 6 ml of 32Jfiges aqueous hydrogen peroxide admitted. The reaction mixture was left for 48 hours Stand room temperature. Then the solution lasted for an hour

1098-24 / 1737

heated on a steam bath, the solvent removed and the residue taken up in hot ethyl acetate. Benzene was added until cloudiness appeared, and the mixture was then left to stand for a few weeks, 10 g of white crystals separating out, P.> 310.degree. Analysis showed that this product was the tetrabasic acid. After drying overnight in vacuo at 1P; 5 ^° C., the anhydride was obtained in quantitative yield.

Establishing connection no.

Equimolar amounts of mercaptosuccinic acid and bicyclo / ~ 2.2.1_7-2-methyl-3,3-dihydroxymethyl-5-heptene were mixed together at room temperature in an inert nitrogen atmosphere. To When the exothermic reaction which occurred at the beginning had subsided, a small amount of ascarldol (2-4 drops) was added. the Reaction mixture was in the presence for a few hours at <1 mm Hg an esterification catalyst heated. Formed on completion of the reaction and after cooling to room temperature a hard, glass-like solid.

Analysis for C, ^ H ₂₀ SO ₅ : Calc .: C 56.0 H 6.67 S 10.65 Qef .: C 55.2 H 6.7 S 10.7 %

Establishing connection no.

A mixture of 68 g (0.25 mol) 3-methylbicyclo / 2.2.1_7-5-hepten-2-ylmethyl-3-methylbicyclo / "2.2.1_7-5-hepten-2-carboxylate and 0.375 g (0.00206 mol) of benzophenone was dissolved in 375 ml of Cyclone xan In a 500 ml quartz flask equipped with a magnetic stirrer, a sintered glass inlet pipe and an outlet pipe was released. The reaction mixture was stirred

109824/1737

while hydrogen sulfide was bubbled into the solution. The bulb was irradiated with a 275 watt lamp placed 2.5 cm from the outer surface of the bulb. After 70 hours of reaction, the hot solution (68 ° G) was allowed to cool to room temperature and an insoluble oil separated out. The oil was dissolved in 100 ml of ethyl acetate, precipitated in 700 ml of ethyl alcohol, dissolved in 200 ml of methylene chloride and precipitated twice in 600 ml of acetone. The product obtained in this way was then ^{dried in a vacuum oven at 117 °} C. for one hour with formation of 50 g of a brittle, glass-like polymer (yield 65 %) .

Establishing connection no. 51

A mixture of 4.955 g (0.025 mol) of 4,4'-methylenedianiline and 94 ml of dry dimethylacetamide (distilled over phosphorus pentoxide) was placed in a 250 ml flask which was filled with a nitrogen inlet tube, a magnetic stirrer and a drying tube was provided. 9.06 g (0 ^ 025 mol) 5.5 '(or 5.6') -thiobis- (bicyclo / 2.2.1_7-heptane) were added to this mixture with stirring The reaction mixture was stirred under nitrogen for 17 hours and then stored in a refrigerator.

The reaction mixture was placed on a glass plate, heated under nitrogen for 20 minutes at 30 ° C, one hour at 400 microns Hg at 25 ° C and then held for 1 hour in nitrogen at 300 ⁰ C. The polymer obtained was a clear, hard resin.

The same connection could be made by unifying the half-ester (Dimethyl ester) of the above bisanhydride with 4,4'-methylenedianiline can be obtained.

109824/1737

Hers tellung of compound no. 56

5,5 '(or 5, ö ^f ) -Thlobls (bicycle / "2.2.1_7heptane-2,3-dicarboxylic acid anhydride) was hydrolyzed with four parts of sodium hydroxide in v / water and then acidified with dilute hydrochloric acid. The product obtained was the tetrabasic acid described above.

example 1

The compounds listed above were added to a coarse-grained silver brorajodide emulsion which contained 6, 25 Mo 1-35 iodide and was panchromatically sensitized with a cyan dye. The emulsion obtained in this way was used for the production of a photographic recording material , samples of this emulsion being applied to a cellulose peace film support, so that 49.0 mg of silver and 11,200 mg of gelatin accounted for 1 m of support. Samples of the photographic recording material obtained in this way were exposed to light with a conventional sensitometer (Eastman IB), developed for 5 minutes in a conventional developer (Kodak developer DK-50), fixed, washed and dried.

Del the examinations carried out on these samples the results given in Table I below are obtained:

109824/1 737

Table I.

Examination of the freshly produced recording material

Investigation of the at 49 ° C and 50% rel. humidity

Concentration 0.9 ReI. γ 22 veil ReI.
Rece -
findl materials • γ veil Incubation
time in
Weeks Probe tion in
No. g / mol Ag Receive
findl. 1, 25th 0.16 89 1.05 0.16 2 1 0.75
0.75
0.75 110 1, 07
05
05
23 0.15 44 0.75 0.72 2 Compare .-
material 0.15 100 1,
1,
1,
1, 25th
28 0.10
0.13
0.11
0.10 65
29
23
33 5 0.92
0.90
0.92
0.57 0.12
0.15
0.15
0.87 2
2
2
2 2
4th
Comp.-
material 0.3 67
68
59
100 1,
1, 30th
, 47 0.11
0.14 71
10, 2 1.13
0.53 0.15
1.29 2
2 5
Cf. -
material 0.9 94
100 I ₃
ι, , 43
, 58 0.11
0.11 69
20th 1.07
0.67 0.12
0.97 2
2 6th
Comp.-
material 0.3 89
100 I ₃ , 13
, 17th 0.17
0.16 48
12, , 3 0.87
0.70 0.14
0.77 2
2 7th
Compare -
material 87
100 I ₃
1 = 0.10
0.12 33
1: , 3 1.02
0.45 0.20
1.28 2
2 3
Comp.-
material 97
100

Table I (cont.)

Comp. Material

Comp. Material

Comp. - "I * material

SI ²
oo comp.-κ> material

^ 13
- ^ Comparative material

Comp. Material

Versl.-material

Comp. Material

0.3 0.15

0.3 0.3

7.2

0.3 0.6

1.5

76
100 1.32
1.55 0.15
0.17 63
12.6 1.07
0.60 0.11
1.15 2
2 Jt
C. 91
100 1.27
1.18 0.10
0.12 74
14th 1.07
0.62 0.14
1.11 2
2 80
100 1.23
1.42 0.10
0.11 46
12.6 0.87
0.62 0.20
1.01 2
2 107
100
82-
100 1.17
1.17
0.58
1.25 0.11
0.12
0.17
0.10 65
7.3
18th
13th 0.98
0.45
0.63
0.58 0.34
1.28
0.10
0.99 2
2
2
2 ro
CD
cn
co 74
100 1.12
1.24 0.11
0.10 63
46 0.90
0.61 0.10
0.82 2
2 87
100 1.13
1.02 0.10
0.14 74
22nd 1.03
0.52 0.14
1.12 2
2 83
100 1.42
1.42 0.08
0.11 42
12.6 0.98
0.62 0.35
1.01 2
2

Table I (Ports.)

16 0, 60 58 1, 0.07 63 0, 95 O, 18th 2 mm Comp.- 100 1. 0.10 32 0, 62 O, 69 2 JT material 17th 0, , 60 89 ! 0.14 67 1, 10 O. 29 1 Comp.- 100 1 0.15 50 O, 96 O, 65 1 materal 18th O ₃ , 60 97 1 0.13 57 O, 83 O, 56 2 _ » Comp.- 100 1 0.15 49 O, 67 O, 90 2 O material CD OO 19th 2; , 40 16 1 0.07 29 I ₃ , 23 O, 08 1 N> Comp.- 100 1 0.13 83 O. , 98 O ₃ , 49 1 ro material O 20th 0: , 90 73 1 0.12 57 0, , 93 O ₃ , 23 2 cn ω Comp.- 100 1 0.15 32 o _: , 55 O. , 96 2 OO material 21 0. , 90 80 1 0.12 62 1, , 07 0. , 36 1 ~ -3 Comp.- 100 1 0.13 54 0. , 95 0; , 53 1 NJ material 22nd 3 , 00 30th 1 0.08 52 1 , 02 0 , 26 2 Comp.- 100 1 0.12 17.5 0 , 68 1 , 08 2 material 23 0 , 03 69 0 0.13 59 0 , 80 0 , 20 1 25th 0 76 1 0.11 68 1 , 07 0 , 26 1 26th 0 Ιθ3 63 1 0.10 53 0 , 98 0 , 24 1 23 0 , 006 69 1 0.10 59 0 , 98 0 , 27 1 29 0 , 03 97 1 0.11 91 1 , 02 0 , 20 1 30th 0 , 03 97 1 0.13 83 1 , 00 0 1 Comp.- 100 1 0.13 74 0 , 90 0 ', 44 1 material , 27 »18th M. , 39 , 28 , 28 , 35 , 23 , 35 , 36 , 18 ., 24 ₅ 12 , 28 , 93 , 08 , 17th , 12 , 15 , 08 , 15

Table I (cont.)

24

27

31

Comp. Material

32

Ver-1.-material

0.30
0.03
0.15

0.30

0.9

ro
* »34
> - Compare, -
- * material 0 , 9 "35
36
37
Comp.-
material 0
0
0 , 75
, 75
, 75 39
Comp.-
material 0 , 06 40
Compare -
material 0 , 6

100

85 100

100

39 100

1.10
1.07
0.90
1.14

1.48
1.40

0 ,!

i ,:

1.47
1.68

1.47
1.13
1.48
1.28

1.32
1.32

1.23
1.25

0.09 0.15 0.12 0.13

0.09 0 10

0.07 0.10

0.14 0.13

0.11 0.12 0.12 0.15

0.19 0.16

0.13 0.10

39
71
55
21.5 0,
0,
0,
0, 87
93
65
53 36
12.3 0,
O ₃ 97
, 61 71
76 O ₃
O ₃ VO OO
MVJl 71
29 1.
O ₃ , 23
, 86 47
50
60
41 1
1
1
1 , 13
, 13
, 05
, 05 82
38 1
0 , 27
, 82 57
63 1
1 , 05
, 01

0.45 0.26

0.35 1.09

0 _a 4l 0.99

0 11 0.20

0.20 1.02

0.26

0.31 0.28

0.59

0.22 0.85

0.13 0.28

2 2 2

2 2

2 2

2 2 2 2

2 2

2 2

Table I (cont.)

0.3

0.9

0.3
Comp. Material

0.75

0.75

0.75
- * 47 0.15
ο 48 0.75
£ 52 .75
S comp.

^. material

Il 49 0.15
-J 50 0.15
°> 51 0.75

- ■ cf. - material

2.4
Comp. Material

0.75
1.5

Comp. Material

1.5

1.5

0.15
Comp. Material

87

73

100

100

100

100

76 100

1.55 1.52 1.47

1.68

1.22

1.40

r, i5

1.22 1.22

1.47 1.28

1.27 1.28 1.30

1.37 1.48

1.35 1.27 1.41

1.38 1.25 1.32 1.47

0.17 0.17 0.18

0.10 0.12 0.11 0.12 0.12 0.13 0.15

0.12 0.18 0.12 0.16

0.09 0.13

0.11 0.12 0.16

0.11 0.11 0.13 0.16

58 1.18 0.22 57 1 ₃ 3O 0.34 52 1.22 0.27 29 0.86 1.02 36 1.05 0.49 60 1.05 0.28 55 1.03 0.27 39 1.20 0.40 49 1.12 0.35 50 1.15 0.40 41 1.05 0.59 55 1.07 0.34 57 1.02 0.36 62 1.05 0.28 55 0.93 0.50 67 1.18 0.13 60 1.13 0.43 50 1.08 0.30 58 1.00 0.25 55 0.93 0.50 52 OK 0.40 63 1.07 0.27 67 1.07 0.31 44 0.99 0.64

2 2 2

2 2 2 2 2 2 2

2 2

2 2

2 2 2

2 2 2 2

2058Λ72

Example 2

Some of the recording materials prepared in Example 1 which contained the compounds listed above in the silver halide emulsion were subjected to "enhanced development", i.e. h # a 12-minute development in a standard developer (Kodak developer DK-50), ie subjected to a longer development than usual, in order to determine any tendencies towards obscuration of the compound contained therein. The sensitometric results given in Table II below
show that in the recording materials which contained the compounds used according to the invention in the silver halide emulsion layer, there was significantly less fogging.

Concentration
tion in
g / mol Ag Table II development veil 0.6 Reinforced "Χ 0.12
0.16 sample
No. 9.0 ReI.
Sensation
opportunity Ι, 30
1.21 0.16
0.23 16
Compare -
material 3.0 63
100 1.35
1.29 0.12
0.21 17th
Comp.-
material 0.3
0.03
0.006 67
100 1.42
1.28 0.14
0.14
0.16
0.24 22nd
Comp.-
material 1.5 83
100 1.33
1.23
1.23
1.23 0.14
0.28 24
26th
28
Comp.-
material 83
83
83
100 1.72
1.43 39
Comp.-
material 69
100

10 9 8 2 Λ / 1737

Table II (F orts.)

34 0.9 85 1.72 0.19

42 0 ^ 9 82 1.57 0.23

43 0.3 78 1.67 0.22 Comp. - 100 1.88 0.30 material

53 7.2 67 1.42 0.14 Comp. - 100 1.75 0.24 material

38 1.5 83 1.33 0.20

54 0.75 83 1.50 0.20 comp. - 100 1.38 0.26 material

109824/1737

Claims (1)

PATENT CLAIMS 1. Light-sensitive photographic silver halide emulsion, characterized in that it has at least one monomeric or polymeric, polycyclic, thio-substituted compound which has a radical of the formula: 2. The silver halide photographic emulsion of claim 1 characterized characterized j that the thio-substituted compound contains a compound of the general formula: m-1 where mean: A is a methylene radical, an oxygen or sulfur atom or an NH group, m is the number 1, 2, 3 or 4, 1 0 9 8 2 A / 1737 R ¹ , R ² , R ³ and optionally substituted individually in each case a hydrogen atom, a / Alkyl, carboxy, mercapto, cyano, acylthio or an alkanol radical or R ¹ , R ² , R ³ and R together with the carbon atoms to which they are attached form a cyclopentene ring, a cyclopentane ring or a radical of the formula: Il in which X is -0- or -NH-, or a radical of the formula: optionallyB substituted a hydrogen atom, an / alkyl or Aryl radical or a radical of the formula R ^J m-1 10982A / 1737 1 2 ~ "> 4 In the A, m, R, R, R- * and R the above Have meanings. 3. The silver halide photographic emulsion of claim 1 characterized characterized in that it is a thio-substituted compound polymeric compound with recurring units of the general formula contains: m-1 SR ⁶ -SG 4- CR ⁷ -C - - ü u O O x-1 in which m, A and R and R are individually as specified in claim 2 1 4 Have meanings or R and R together with the carbon atoms, to which they are bound form a residue of the formula: in which R is an alkylene radical, G is a carboxymethylmethylene radical, a carboxyethylene radical or a remainder of the formula: 109824/1737 Jm-I in which m, A and R and R are individually as specified in claim 2 Have meanings R 'is an alkylene, cycloalkylene or arylene radical which has the Represents the condensation radical of a diol or a diamine, and x denote the number 1 or 2, with the proviso that χ = 1 when G denotes a radical of the formula: m-1 1 U in which R and R together with the carbon atoms which they are bound form a residue of the formula: 109824/1737 A silver halide photographic emulsion according to Claim 1, characterized in that it is used as a thio-substituted compound has a polymeric compound with repeating units of the general formula: (ll) -Y-I R ^] R ⁹ -YR ¹⁰ - m-1 m-1 1 4 in which m, A and R and R are individually as specified in claim 2 Have meanings R is an alkylene radical with 1 to 6 carbon atoms, Y is the radical -0- or -NH- and R denotes the condensation residue of a dicarboxylic acid. 5. The silver halide photographic emulsion of claim 1 characterized characterized in that, as a thio-substituted compound, it is a polymeric compound with repeating units the general formula contains: (in) S R 12th in which A and R ¹ and R individually have the meanings given in claim 2 and 1 0 9 8 2 Λ / 1 737 2058Λ72 12th an alkylene radical containing an ester or amido bridge means. D. The silver halide photographic emulsion of claim 1 characterized characterized as being a thio-substituted compound contains a polymeric compound with repeating units of the general formula: (IV) A-J S h A m-1 m-1 in which m, A and R and R are individually as specified in claim 2 Have meanings or R and R together with the carbon atoms, to which they are bound form a residue of the formula: ■ ι -ζ to in which R ^ one of the radicals specified for R in claim 5 or a remainder of the formula: • R ¹² - R ^J m-1 109824/1 737 2058Λ72 12 3 k
in the m, A, R and R and R individually those in the claims 1 and 5 have given meanings, or an alkylene, arylene, arylenebisalkylene or alkylenebisarylene radical means, when R and R hold the carbon atoms together, to which they are bound are a residue of the formula: Il -N Il mean. 7. The silver halide photographic emulsion of claim 1 characterized characterized in that, as a thio-substituted compound, it is the sulfoxide or sulfonoxydation product of one of the in contains the claims 2 to 6 specified polymeric compounds. 8. A photographic silver halide emulsion according to claim 1, characterized characterized in that it contains a compound / of the general formula as a thio-substituted compound: with recurring units HOOCCH ₂ CH ₂ OH in which η £ 3 & Χ £ Χ £ Ϊ means a positive whole number. 10982 4/1737 - sy 9. Photographic silver halide _{emulsion according to claim I 3,} characterized in that it contains, as thio-substituted compound, a compound / of the general formula: with repeating units ΓΥ-Ν in which η has the meaning given in claim 8. 10. The silver halide photographic emulsion of claim 1 characterized characterized as being a thio-substituted compound contains a compound of the ^ general formula: with recurring units CH- S - in which η has the meaning given in claim 8. 11. The silver halide photographic emulsion of claim 1 characterized characterized in that it is the thio-substituted compound copoly {bicyclo / ~ 2.2.1_7-5-hepten-2,3-dicarboxylic anhydride-bis (2-mercaptoethyl) sulfide-hexamethylenediamine}, Copoly- / ~ 1,2-bis (2-mercaptoethoxy) ethandodecahydro-1,4: 5,3-dimethananthraquinonylene-2,6 (or 7) _7, 5-carboxymethylmercaptobicyclo / 22.2.1_7-hepten-2,3-dicarboximid, 5,5 '(or 5,6') - sulfonylbls (bicyclo / ~ 2.2.l_7-heptane-2,3-dicarboxylic acid anhydride) or 5,5 '(or 5,6') - Thiobis {bicyclo / "2.2.1_7-5-heptane-2,3-dicarboxylic acid} contains. 10982 Z _1/1737 2058Λ72 "12. Photographic silver halide emulsion according to claims 1 to 7, characterized in that it is the polymeric condensation product of 1,8-bis- (2 _} 3-oxydicarbonylnorborn-5-ylthio) -3jo-dioxaoctane, 1- / ~ as the thio-substituted compound 1,2-oxydicarbonylethylthio-8- (2,3-dicarboxynorborn-5-ylthio) 7-3,6-dioxaoctane, 1,8-BIs (I ₃ 2-oxydicarbonylethylthio) -3,6-dioxaoctane or 1,2- Contains bis (2,3-oxydicarbonylnorborn-5-ylthio) -2-hydroxymethylethane and 1,6-hexylenediamine, 1,2-ethylenediamine or piperazine. 13. Silver halide photographic emulsion according to the claims 1 to 7, characterized in that it is the polymeric condensation product of 1,8-bis- (2,3-oxydicarbonylnorborn-5-ylthio) -3 ₃ 6-dioxaoctane and 1,8-bis (2-aminomethy1- Contains 2-methylnorborn-5 (6) -ylthio) -3,6-dioxaoctane. 14. Silver halide photographic emulsion according to the claims 1 to 7, characterized in that it is the polymeric condensation product of 1,8-bis- (2,3-oxydicarbonyl-7-oxabicyclo / ~ 2.2.l_7hept-5-ylthio) -3,6-dloxaoctane as the thio-substituted compound and 1,6-hexylenediamine. 15. Photographic silver halide emulsion according to the claims 1 to 7, characterized in that it is a thio-substituted compound l, 8-bis (2,3-dicarboxynorborn-5-ylthio) -3,6-dioxaoctane, Copoly ΓΊ , 2-bis (2-mercaptoethoxy) ethanodecahydro-1, 4: 5,8-dimethananthraquinonylene-2,6 (7) J, 2-carboxymethylthionorbornane, 2,5 (6) -dimercaptonorbornane, 2,6 (7) -dimercapto-1, ¹ I • .5,8-dimethane perhydronaphthalene, 2-hydroxymethyl-5 (6) -mercaptonorbornane, poly / "2- (I, 2-dicarboxyäthylthio) -5 (6) -hydroxymethylnorbornane ^ ?, poly / ~ 2-carboxy-3-methyl-5 (6) - ( 2-hydroxymethyl-3-methylnorborn-5 (6) -ylthio) norbornane_7, poly - / "2,2-bis (hydroxymethyl) -3-methyl-5 (6) - (1 , 2-dicarboxyäthylthio) norbornane_7, 5- Acetylthionaic anhydride, 2,5 (6) bis (acetylthio) norbornane or 2,6 (7) bis (acetylthio) -1, 4: 5, B: 9, 10-trimethane perhydroanthracene. a 5-Acetylthio-bicyclo / "2.2.1 7heptane-2, 3-dicarboxylic anhydride 109824/1737 - £ Jr- 16. Photographic silver halide emulsion according to claims 1 to 7, characterized in that it is thio-substituted Compound a polymeric compound with one at 25 ° C in methylene chloride at a concentration of 0.25 g / dl according to the formula n = In η _--, / c contains measured inherent viscosity of about 0.01 to about 0.60. 17. A photographic silver halide emulsion according to claim 16, characterized in that it is thio-substituted Compound contains a polymeric compound having an inherent viscosity of about 0.04 to about 0.46. f 109824/1737