WO1990012782A1 - Non-ionic surface active compounds - Google Patents

Non-ionic surface active compounds Download PDF

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Publication number
WO1990012782A1
WO1990012782A1 PCT/EP1990/000606 EP9000606W WO9012782A1 WO 1990012782 A1 WO1990012782 A1 WO 1990012782A1 EP 9000606 W EP9000606 W EP 9000606W WO 9012782 A1 WO9012782 A1 WO 9012782A1
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WIPO (PCT)
Prior art keywords
surface active
group
compound
formula
compound according
Prior art date
Application number
PCT/EP1990/000606
Other languages
French (fr)
Inventor
Alan Robert Pitt
Ian Martin Newington
Original Assignee
Kodak Limited
Eastman Kodak Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kodak Limited, Eastman Kodak Company filed Critical Kodak Limited
Priority to EP90906162A priority Critical patent/EP0470101B1/en
Priority to DE69009469T priority patent/DE69009469T2/en
Publication of WO1990012782A1 publication Critical patent/WO1990012782A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/28—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines
    • C07C217/30—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines having the oxygen atom of at least one of the etherified hydroxy groups further bound to a carbon atom of a six-membered aromatic ring
    • C07C217/32—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines having the oxygen atom of at least one of the etherified hydroxy groups further bound to a carbon atom of a six-membered aromatic ring the six-membered aromatic ring or condensed ring system containing that ring being further substituted
    • C07C217/34—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines having the oxygen atom of at least one of the etherified hydroxy groups further bound to a carbon atom of a six-membered aromatic ring the six-membered aromatic ring or condensed ring system containing that ring being further substituted by halogen atoms, by trihalomethyl, nitro or nitroso groups, or by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/28—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/08—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/38—Dispersants; Agents facilitating spreading

Definitions

  • the invention relates to non-ionic surface active compounds.
  • Japanese Patent Application No. 54/163829 describes low toxicity cosmetic compositions which contain a compound having the formula
  • R 1 is an alkyl or alkenyl group having from 10 to 22 carbon atoms and R 2 is a polyhydroxyalkyi group.
  • the compounds can be dissolved or dispersed in water and oily cosmetic bases for the preparation of products such as milky lotions, face lotions, hair conditioners, shampoos and rinses.
  • non-ionic surface active compounds which are more water-soluble than the compounds described above. Solubility affects the appearance of the surfactant solution e.g a surfactant which is
  • the solubility of the surfactant can affect its use e.g. for use as an effective coating aid in a hydrophilic colloid solution the surfactant must be soluble.
  • the invention provides such surface active compounds.
  • the surface active compounds of the invention may be used as dispersants, emulsifiers, wetting agents and coating aids.
  • the compounds may be used in the manufacture of photographic materials
  • the invention provides a water-soluble, non-ionic surface active compound having the formula
  • R 1 and R 2 are each independently hydrogen or an alkyl group having from 1 to 4 carbon atoms;
  • X is a hydrophobic substituted
  • Y 1 and Y 2 are each independently a
  • n is an integer from 1 to 6;
  • R 3 is as defined for R 1 and R 2 ; and, Z 1 and Z 2 are each independently a
  • X is an arylene group it is preferably an alkyl substituted phenylene group.
  • the alkyl substituent or substituents preferably have a total of from 6 to 18 carbon atoms.
  • a particularly preferred substituted arylene group is represented by the formula
  • R 4 is an alkyl group having from 6 to 18 carbon atoms.
  • suitable alkyl substituents include 4-C 6 H 13 , 4-C 12 H 25 and
  • X is an alkylene group it preferably contains a total of from 6 to 23 carbon atoms.
  • a particularly preferred alkylene group is represented by the formula
  • R 5 is an alkyl group having from 3 to 20
  • substituents include -C 6 H 13 , -C 10 H 21 ,
  • Z 1 and Z 2 may be selected include groups derived
  • the polyhydroxyalkyi group may have the formula -(CH 2 ) n (CHOH) p CH 2 OH
  • n 0 or 1 and p is an integer from 3 to 6.
  • Another example of a preferred polyhydroxyalkyi group is represented by the formula -C(CH 2 OH) 3 .
  • the compounds do not contain polyether linkages.
  • the compounds of the invention may be any organic compound having the same properties as the compounds of the invention.
  • the bisepoxide intermediate compound may be reacted with an amine having the formula Z 1 -NR 1 H or Z 1 -CONH(CH 2 ) m NR 1 H wherein Z 1 , R 1 and m
  • the bisepoxide may be converted to the corresponding bisamine either by reaction with ammonia or by reaction with sodium azide with subsequent reduction.
  • the resulting bisepoxide may be converted to the corresponding bisamine either by reaction with ammonia or by reaction with sodium azide with subsequent reduction.
  • bisamine can be reacted with a polyhydroxyalkyi ester e.g. a sugar lactone, to provide a compound of the invention having amide links between the
  • the compounds of the invention may be used as emulsifying agents.
  • stable oil-in-water emulsions can be prepared by mixing the oil and water together in the presence of a compound of the
  • oils which can be emulsified in this way include hydrocarbons such as dodecane and pentadecane.
  • the compounds of the invention may be used as coating aids in aqueous hydrophilic colloid
  • compositions e.g. a gelatin solution.
  • the compounds may be used in the
  • Such a material comprises a support having thereon at least one layer comprising a hydrophilic colloid and a compound of the invention.
  • a support In the preparation of a photographic material, it is usual to coat a support with one or more layers comprising an aqueous solution of a hydrophilic colloid binder e.g. gelatin.
  • a hydrophilic colloid binder e.g. gelatin.
  • Such layers include, for example, silver halide emulsion layers, intermediate layers, antihalation layers, filter layers, antistatic layers and protective layers.
  • the layers may be coated
  • repellencies are a round, oval-shaped or comet-shaped indentation or crater in the layer or one or more of the layers coated and is usually produced by the presence of small particles or droplets of insoluble materials in the form of addenda, impurities or contaminants which are in contact with the uppermost liquid-air interface of the coated layer(s) and have surface activity (i.e. are capable of reducing the surface tension of the liquid-air interface during the coating process).
  • Solutions coated in the preparation of photographic materials often contain dispersed, insoluble photographic addenda, which might include organic solvents, or addenda to alter certain physical properties, which might include lubricants, each of which may be capable of imparting repellencies to the coated layer(s).
  • photographic gelatin may contain insoluble residues of naturally-occuring animal fats and fatty acids which are capable of imparting repellencies to the coated layer(s).
  • surface active contaminants may originate from
  • the layer(s) being coated, or immediately after coating may be unintentionally showered by droplets of
  • a surface active compound of the invention is used as a coating aid in the formation of a hydrophilic colloid layer.
  • the coating aid is used in an amount from 0.01 to 0.30, more preferably from 0.05 to 0.20, weight % based on the weight of the hydrophilic colloid coating composition. The range of
  • concentration within which the coating aid is used depends on the source of repellency. It also depends on whether other surface active agents are present.
  • the preferred hydrophilic colloid is gelatin e.g. alkali-treated gelatin (cattle bone or hide gelatin) and acid-treated gelatin (pigskin gelatin) or a gelatin derivative e.g. acetylated gelatin and phthalated gelatin.
  • suitable hydrophilic colloids include naturally occurring substances such as proteins, protein derivatives, cellulose
  • cellulose esters e.g. cellulose esters, polysaccharides e.g. dextran, gum arable, zein, casein and pectin, collagen derivatives, agar-agar, arrowroot and albumin.
  • suitable synthetic hydrophilic colloids include polyvinyl alcohol, acrylamide polymers, maleic acid copolymers, acrylic acid copolymers, methacrylic acid copolymers and
  • the photographic material may comprise a negative-working or positive-working silver halide emulsion layer. Suitable emulsions and their
  • the photographic materials or individual layers thereof can contain brighteners (see Research Disclosure Section V), antifoggants and stabilizers (see Research Disclosure Section VI), antistain agents and image dye stabilizer (see Research Disclosure Section VII, paragraphs I and J), light absorbing and scattering materials (see Research Disclosure Section VIII), hardener's (see Research Disclosure Section XI), plasticizers and lubricants (see Research Disclosure Section XII), antistatic agents (see Research Disclosure Section V), antifoggants and stabilizers (see Research Disclosure Section VI), antistain agents and image dye stabilizer (see Research Disclosure Section VII, paragraphs I and J), light absorbing and scattering materials (see Research Disclosure Section VIII), hardener's (see Research Disclosure Section XI), plasticizers and lubricants (see Research Disclosure Section XII), antistatic agents (see Research Disclosure Section V), antifoggants and stabilizers (see Research Disclosure Section VI), antistain agents and image dye stabilizer (see Research Disclosure Section VII, paragraphs I and J), light absorbing and scattering materials (see
  • the photographic materials can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image as described in Research Disclosure Section XVIII and then processed to form a visible dye image as described in Research Disclosure Section XIX.
  • Processing to form a visible dye image includes the step of contacting the element with a colour developing agent to reduce developable silver halide and oxidize the colour developing agent. Oxidized colour developing agent in turn reacts with the coupler to yield a dye. With negative working silver halide emulsions this processing step leads to a negative image.
  • this step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and then uniform fogging of the element to render unexposed silver halide developable.
  • a direct positive emulsion can be employed to obtain a positive image.
  • 2-Decyl-1,3-propanediol (14.0g, 65mmol) was dissolved in diethyl ether-hexane (200ml:600ml) and treated with epibromohydrin (12.3 ml, 144mmol), tetrabutylammonium hydrogen sulphate (2.0g) and a solution of sodium hydroxide (140g) in water (150 ml). The mixture was stirred vigorously for 72 hours, the organic layer separated, dried over magnesium sulphate and evaporated. The product was purified by chromatography on silica gel (63-200 ⁇ m grade) in a diethyl ether petrol gradient to give the bisepoxide as a colourless oil (5.4g, 26%).
  • the bisepoxide (1.0g 3.0mmol) was dissolved in t-butanol (30 ml) with N-methyl-D-glucamine (1.2g, 6.0mmol) and heated under reflux for 24 hours, cooled, and the solvent evaporated under reduced pressure to give the product surfactant as a viscous gum.
  • N-Methylethylenediamine (5.0g, 68mmol) with D-gluconolactone (12.0g, 68mmol) were dissolved in methanol (200 ml) and heated under reflux for 20 hours. The solvent was reduced to half volume and the solution stored at 4°C for 48 hours. The solid product was filtered off, washed with a little methanol, and dried at 45°C under vacuum to give a white solid (10.35g, 61%) m.p. 116-120°C.
  • R 4 4-C 6 H 13 , 4-C 12 H 25 and 5-C 15 H 31 ;
  • R 4 4-C 6 H 13 , 4-C 12 H 25 and 5-C 15 H 31 ;
  • the prior art compounds were either dispersible in water and formed cloudy dispersions, or formed crystals.
  • the top layer consisted of a 7% by weight solution of lime-processed bone gelatin in water containing a coloured dye marker, lppm oleic acid emulsified in small droplet form to induce repellency, and surfactant at one of the concentrations indicated in Table 1.
  • the top layer was applied at a coverage of 14.2 ml/m 2 .
  • Compound (1) was made into a 1% by weight aqueous solution and the solution was mixed with various amounts of dodecane and, independently, pentadecane.
  • the surfactant was used in amounts to provide oil: surfactant ratios (by weight) of 1:2, 1:1 and 5:1. Emulsions were prepared by thorough mixing with an ultrasonic mixer for 5 minutes.

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Abstract

Water-soluble, non-ionic surface active compounds are provided having formula (I), wherein R?1 and R2¿ are each independently hydrogen or an alkyl group having from 1 to 4 carbon atoms; X is a hydrophobic substituted or unsubstituted arylene group or a hydrophobic substituted or unsubstituted alkylene group; Y?1 and Y2¿ are each independently a chemical bond, -CO- or -(CH¿2)mNR?3CO-; m is an integer from 1 to 6; R3 is as defined for R?1 and R2¿; and, Z?1 and Z2¿ are each independently a hydrophilic polyhydroxyalkyl group. The compounds are particularly useful as coating aids for the coating of hydrophilic colloid layers in the preparation of photographic materials.

Description

NON-IONIC SURFACE ACTIVE COMPOUNDS
The invention relates to non-ionic surface active compounds.
Japanese Patent Application No. 54/163829 describes low toxicity cosmetic compositions which contain a compound having the formula
R1OCH2CHCH2N-R2
I I
Figure imgf000003_0001
wherein R1 is an alkyl or alkenyl group having from 10 to 22 carbon atoms and R2 is a polyhydroxyalkyi group. The compounds can be dissolved or dispersed in water and oily cosmetic bases for the preparation of products such as milky lotions, face lotions, hair conditioners, shampoos and rinses.
It is desirable for a number of applications to use non-ionic surface active compounds which are more water-soluble than the compounds described above. Solubility affects the appearance of the surfactant solution e.g a surfactant which is
dispersible rather than soluble will result in a cloudy rather than a clear solution. Also, the solubility of the surfactant can affect its use e.g. for use as an effective coating aid in a hydrophilic colloid solution the surfactant must be soluble. The invention provides such surface active compounds.
The surface active compounds of the invention may be used as dispersants, emulsifiers, wetting agents and coating aids. In particular, the compounds may be used in the manufacture of photographic
materials.
The invention provides a water-soluble, non-ionic surface active compound having the formula
Figure imgf000004_0002
wherein
R1 and R2 are each independently hydrogen or an alkyl group having from 1 to 4 carbon atoms;
X is a hydrophobic substituted or
unsubstituted arylene group or a hydrophobic
substituted or unsubstituted alkylene group;
Y1 and Y2 are each independently a
chemical bond, -CO- or -(CH2)mNR3CO-;
m is an integer from 1 to 6;
R3 is as defined for R1 and R2; and, Z1 and Z2 are each independently a
hydrophilic polyhydroxyalkyi group.
When X is an arylene group it is preferably an alkyl substituted phenylene group. The alkyl substituent or substituents preferably have a total of from 6 to 18 carbon atoms. A particularly preferred substituted arylene group is represented by the formula
Figure imgf000004_0001
wherein R4 is an alkyl group having from 6 to 18 carbon atoms. Specific examples of suitable alkyl substituents include 4-C6H13, 4-C12H25 and
5-C15H31.
When X is an alkylene group it preferably contains a total of from 6 to 23 carbon atoms. A particularly preferred alkylene group is represented by the formula
Figure imgf000005_0001
wherein R5 is an alkyl group having from 3 to 20
carbon atoms. Specific examples of suitable alkyl
substituents include -C6H13, -C10H21,
-C12H25 and -C15H31.
Preferred polyhydroxyalkyi groups from which
Z 1 and Z2 may be selected include groups derived
from sugars. For example, the polyhydroxyalkyi group may have the formula -(CH2)n(CHOH)pCH2OH
wherein n is 0 or 1 and p is an integer from 3 to 6.
Another example of a preferred polyhydroxyalkyi group is represented by the formula -C(CH2OH)3.
Preferably, the compounds do not contain polyether linkages.
Specific examples of compounds of the
invention are as follows
Figure imgf000005_0003
I I
OCH2CHCH2NCH2(CHOH)4CH2OH
(1)
Figure imgf000005_0002
OCH2CHCH2NCH2(CHOH)4CH2OH
Figure imgf000005_0004
Figure imgf000005_0005
OCH2CHCH2NHC(CHOH)4CH2OH > ( 2) OCH2CHCH2NHC(CHOH)4CH2OH
Figure imgf000005_0007
Figure imgf000005_0006
Figure imgf000006_0003
OCH2CHCH2NHC(CH2OH)3
(3)
Figure imgf000006_0002
X OCH2CHCH2NHC(CH2OH)3
Figure imgf000006_0004
Figure imgf000006_0005
I I
CH2OCH2CHCH2NCH2(CHOH)4CH2OH
(4) CH2OCH2CHCH2NCH2(CHOH)4CH2OH
Figure imgf000006_0006
OH CH3
Figure imgf000006_0008
CH2OCH2CHCH2NCH2(CHOH)4CH2OH
' (5) OCH2CHCH2N(CH2)2NHC(CHOH)4CH2OH
Figure imgf000006_0007
ι ι
Figure imgf000006_0009
The compounds of the invention may be
prepared from known dihydroxy compounds having the formula HO-X-OH wherein X is as defined above.
Reaction of the dihydroxy compound with epibromohydrin provides a bisepoxide intermediate compound as follows:
Figure imgf000006_0001
From the bisepoxide intermediate compound, various routes may be taken to produce the compounds of the invention. For example, the bisepoxide may be reacted with an amine having the formula Z 1-NR1H or Z1-CONH(CH2)mNR1H wherein Z1, R1 and m
are as defined above. Alternatively, the bisepoxide may be converted to the corresponding bisamine either by reaction with ammonia or by reaction with sodium azide with subsequent reduction. The resulting
bisamine can be reacted with a polyhydroxyalkyi ester e.g. a sugar lactone, to provide a compound of the invention having amide links between the
polyhydroxyalkyi groups and the bisamine residue.
Details of the reaction conditions used for making the compounds of the invention are to be found in the specific examples given later in the
specification.
The compounds of the invention may be used as emulsifying agents. For example, stable oil-in-water emulsions can be prepared by mixing the oil and water together in the presence of a compound of the
invention. Examples of oils which can be emulsified in this way include hydrocarbons such as dodecane and pentadecane.
The compounds of the invention may be used as coating aids in aqueous hydrophilic colloid
compositions e.g. a gelatin solution. In a particular application, the compounds may be used in the
preparation of light sensitive photographic
materials. Such a material comprises a support having thereon at least one layer comprising a hydrophilic colloid and a compound of the invention.
In the preparation of a photographic material, it is usual to coat a support with one or more layers comprising an aqueous solution of a hydrophilic colloid binder e.g. gelatin. Such layers include, for example, silver halide emulsion layers, intermediate layers, antihalation layers, filter layers, antistatic layers and protective layers. For multilayer materials, the layers may be coated
simultaneously on conventional photographic supports as described in U.S. Patents 2,761,791 and 3,508,947.
In producing the thin hydrophilic colloid layers of such photographic materials, it is required that coating solutions are coated uniformly without the formation of repellency spots or craters,
hereinafter referred to as repellencies. A repellency is a round, oval-shaped or comet-shaped indentation or crater in the layer or one or more of the layers coated and is usually produced by the presence of small particles or droplets of insoluble materials in the form of addenda, impurities or contaminants which are in contact with the uppermost liquid-air interface of the coated layer(s) and have surface activity (i.e. are capable of reducing the surface tension of the liquid-air interface during the coating process).
Solutions coated in the preparation of photographic materials often contain dispersed, insoluble photographic addenda, which might include organic solvents, or addenda to alter certain physical properties, which might include lubricants, each of which may be capable of imparting repellencies to the coated layer(s). Even photographic gelatin may contain insoluble residues of naturally-occuring animal fats and fatty acids which are capable of imparting repellencies to the coated layer(s). Also, surface active contaminants may originate from
external sources during the preparation of the coating composition or during coating. For example, the layer(s) being coated, or immediately after coating, may be unintentionally showered by droplets of
lubricating oils used in the apparatus.
In one aspect of the invention, a surface active compound of the invention is used as a coating aid in the formation of a hydrophilic colloid layer. Preferably, the coating aid is used in an amount from 0.01 to 0.30, more preferably from 0.05 to 0.20, weight % based on the weight of the hydrophilic colloid coating composition. The range of
concentration within which the coating aid is used depends on the source of repellency. It also depends on whether other surface active agents are present.
The preferred hydrophilic colloid is gelatin e.g. alkali-treated gelatin (cattle bone or hide gelatin) and acid-treated gelatin (pigskin gelatin) or a gelatin derivative e.g. acetylated gelatin and phthalated gelatin. Other suitable hydrophilic colloids include naturally occurring substances such as proteins, protein derivatives, cellulose
derivatives e.g. cellulose esters, polysaccharides e.g. dextran, gum arable, zein, casein and pectin, collagen derivatives, agar-agar, arrowroot and albumin. Examples of suitable synthetic hydrophilic colloids include polyvinyl alcohol, acrylamide polymers, maleic acid copolymers, acrylic acid copolymers, methacrylic acid copolymers and
polyalkylene oxides.
In the following discussion concerning the nature of photographic materials, reference will be made to Research Disclosure, December 1978, Item 17643, published by Industrial Opportunities Ltd., The Old Harbourmaster's, 8 North Street, Emsworth, Hants P010 7DD, U.K. This publication will be identified hereafter as "Research Disclosure".
The photographic material may comprise a negative-working or positive-working silver halide emulsion layer. Suitable emulsions and their
preparation are described in Research Disclosure Sections I and II and the publications cited therein. Suitable vehicles for the emulsion layers and other layers of elements of this invention are described in Research Disclosure Section IX and the publications cited therein.
For colour photographic materials, references giving information on couplers and on methods for their dispersions are given in Sections VII and XIV, respectively, of Research Disclosure. An account of dye-forming development is given in 'Modern
Photographic Processing', Vol. 2, Grant Haist, Wiley, New York, 1978, Chapter 9.
The photographic materials or individual layers thereof, can contain brighteners (see Research Disclosure Section V), antifoggants and stabilizers (see Research Disclosure Section VI), antistain agents and image dye stabilizer (see Research Disclosure Section VII, paragraphs I and J), light absorbing and scattering materials (see Research Disclosure Section VIII), hardener's (see Research Disclosure Section XI), plasticizers and lubricants (see Research Disclosure Section XII), antistatic agents (see Research
Disclosure Section XIII), matting agents (see Research Disclosure Section XVI) and development modifiers (see Research Disclosure Section XXI).
The photographic materials can be coated on a variety of supports as described in Research
Disclosure Section XVII and the references described therein.
The photographic materials can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image as described in Research Disclosure Section XVIII and then processed to form a visible dye image as described in Research Disclosure Section XIX. Processing to form a visible dye image includes the step of contacting the element with a colour developing agent to reduce developable silver halide and oxidize the colour developing agent. Oxidized colour developing agent in turn reacts with the coupler to yield a dye. With negative working silver halide emulsions this processing step leads to a negative image. To obtain a positive (or reversal) image, this step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and then uniform fogging of the element to render unexposed silver halide developable.
Alternatively, a direct positive emulsion can be employed to obtain a positive image.
Development is followed by the conventional steps of bleaching, fixing, or bleach-fixing, to remove silver and silver halide, washing and drying.
Specific examples of the preparation of compounds of the invention are as follows.
Preparation of Compound (1)
4-Dodecylresorcinol (36.0mmol) was added to a suspension of sodium hydride (79.0mmol) in dry
dimethylformamide (250 ml). After stirring at 20°C for 45 minutes, epibromohydrin (79.0mmol) was added and the mixture stirred for a further 18 hours. Water (700 ml) was added and the product extracted into ethyl acetate. The solution was washed with water, dried over magnesium sulphate, filtered and
concentrated at reduced pressure. The bisepoxide was isolated after purification by chromatography on silica gel (diethyl ether-petrol gradient) as a white solid (86% yield).
Found: C, 73.89; H, 10.03.
C24H38O4 requires: C, 73.81; H, 9.81.
The bisepoxide (5.0mmol) was dissolved in t-butanol (75 ml) with N-methyl-D-glucamine
(10.0mmol). The solution was heated under reflux for 24 hours, cooled and the solvent removed under reduced pressure to give Compound (1) as a hygroscopic white solid foam. Found : C , 57 . 74 ; H , 9 . 23 ; N , 3. 57 .
C38H72N2O14 · 1/ 2H2O req uires : C , 57 . 77 ;
H , 9 . 31 ; N , 3. 55 Preparation of Compound (3)
The same bisepoxide (5.0mmol) used in the preparation of Compound (1) was dissolved in t-butanol (75 ml) with tris(hydroxymethyl)aminomethane
(10.0mmol). The solution was heated under reflux for 24 hours, cooled and the solvent removed under reduced pressure to give the product surfactant as a
hygroscopic solid foam.
Found: C, 59.89; H, 9.57; N, 4.32.
C32H60N2O10·1/2H2O requires: C, 59.88;
H, 9.58; N, 4.36
Preparation of Compound (4)
A solution of diethyl malonate (28 ml,
186mmol) in ethanol (20 ml) was added slowly to a solution of sodium (4.2g. 180mmol) in ethanol (175 ml) under reflux. This was followed by addition of
1-bromodecane (38.0g, 155mmol) after which reflux was continued for a further 3 hours before cooling. The suspension was filtered and the filtrate evaporated under reduced pressure. The crude product was
partitioned between ethyl acetate (300 ml) and water (200 ml) and the organic layer dried over magnesium sulphate and evaporated. The product was purified by vacuum distillation to give 2-decyldiethylmalonate as a colourless liquid (37.5g, 67%) b.p. 127-130°C at 0.05mbar.
2-Decyldiethylmalonate (20.0g, 67mmol) in diethyl ether (30 ml) was added dropwise to a
suspension of lithium aluminium hydride (10.1g,
268mmol) in diethyl ether (800 ml) and the mixture stirred for 24 hours at 20°C. The reaction was quenched with 2N hydrochloric acid and the organic layer separated, dried over magnesium sulphate and evaporated to give 2-decyl-1,3-propanediol as a white solid (14.1g, 98%).
2-Decyl-1,3-propanediol (14.0g, 65mmol) was dissolved in diethyl ether-hexane (200ml:600ml) and treated with epibromohydrin (12.3 ml, 144mmol), tetrabutylammonium hydrogen sulphate (2.0g) and a solution of sodium hydroxide (140g) in water (150 ml). The mixture was stirred vigorously for 72 hours, the organic layer separated, dried over magnesium sulphate and evaporated. The product was purified by chromatography on silica gel (63-200μm grade) in a diethyl ether petrol gradient to give the bisepoxide as a colourless oil (5.4g, 26%).
Found: C, 69.39; H, 11.01.
C19H36O4 requires: C, 69.47; H, 11.05.
The bisepoxide (1.0g 3.0mmol) was dissolved in t-butanol (30 ml) with N-methyl-D-glucamine (1.2g, 6.0mmol) and heated under reflux for 24 hours, cooled, and the solvent evaporated under reduced pressure to give the product surfactant as a viscous gum.
Found: C, 54.29; H, 9.68; N, 3.71.
C33H70N2O14·1/2H2O requires: C , 54.45;
H, 9.83; N, 3.85.
Preparation of Compound (5)
N-Methylethylenediamine (5.0g, 68mmol) with D-gluconolactone (12.0g, 68mmol) were dissolved in methanol (200 ml) and heated under reflux for 20 hours. The solvent was reduced to half volume and the solution stored at 4°C for 48 hours. The solid product was filtered off, washed with a little methanol, and dried at 45°C under vacuum to give a white solid (10.35g, 61%) m.p. 116-120°C.
This material (1.3g, 5.2mmol) was added to a solution of the same bisepoxide used in the
preparation of Compound (1) (1.0g. 2.6mmol) in t-butanol (30 ml) and the solution heated under reflux for 18 hours. The solvent was evaporated to give a white solid foam.
Found: C, 55.45; H, 8.63; N, 6.01.
C44H78N4O16·1/2H2O requires: C, 55.80;
H, 8.81; N, 6.20.
The invention is further illustrated having regard to the following examples.
Example 1
The solubility of the compounds of the invention was demonstrated by preparing 1% by weight solutions of the following compounds:
Figure imgf000014_0001
OCH2CHCH2NCH2(CHOH-)4CH2OH
Figure imgf000014_0002
OCH2CHCH2NCH2(CHOH)4CH2OH
Figure imgf000014_0006
wherein R4 = 4-C6H13, 4-C12H25 and 5-C15H31;
Figure imgf000014_0005
OCH2CHCH2NHC(CH2OH)3 OCH2CHCH2NHC(CH2OH)3
Figure imgf000014_0003
Figure imgf000014_0004
wherein R4 = 4-C6H13, 4-C12H25 and 5-C15H31;
Compound (2), Compound (4) and Compound (5).
All the compounds listed above dissolved in water to give clear solutions.
By way of comparison, the solubility of prior art compounds was demonstrated by attempting to dissolve 1% by weight of the following compounds in water:
Figure imgf000015_0001
R6-OCH2CHCH2NCH2(CHOH)4CH2OH wherein R = C12H25, C16H33 and C18H37;
Figure imgf000015_0002
and C12H25OCH2CCH2NHC(CHOH)4CH2OH
The prior art compounds were either dispersible in water and formed cloudy dispersions, or formed crystals.
Example 2
The ability of a compound of the invention to control repellencies caused by an impurity often found in hydrophilic colloid coating compositions was tested as follows.
Two gelatin layers, the uppermost of which contained, one of the surfactants listed below in Table
1 as a coating aid, were coated onto a polyethylene terephthalate film base subbed to give good adhesion to gelatin. The bottom layer consisted of a 4% by weight solution of lime-processed bone gelatin in water coated at 85.4 ml/m2. The top layer consisted of a 7% by weight solution of lime-processed bone gelatin in water containing a coloured dye marker, lppm oleic acid emulsified in small droplet form to induce repellency, and surfactant at one of the concentrations indicated in Table 1. The top layer was applied at a coverage of 14.2 ml/m2. Both
layers were applied simultaneously at a temperature of
40°C using a conventional double slide hopper with applied suction and a linear coating speed of 15.25 m/min.
Figure imgf000016_0001
Each coating was free from repellencies in the tests whereas in the absence of surfactant the coating contained many repellencies.
Example 3
The suitability of compounds of the invention as emulsifying agents was demonstrated by the
preparation of, oil-in-water emulsions.
Compound (1) was made into a 1% by weight aqueous solution and the solution was mixed with various amounts of dodecane and, independently, pentadecane. The surfactant was used in amounts to provide oil: surfactant ratios (by weight) of 1:2, 1:1 and 5:1. Emulsions were prepared by thorough mixing with an ultrasonic mixer for 5 minutes.
In each instance, emulsions were formed which were stable without creaming over a period of hours.

Claims

CLAIMS :
1. A water-soluble, non-ionic surface active compound having the formula
Figure imgf000017_0002
wherein
R1 and R2 are each independently hydrogen or an alkyl group having from 1 to 4 carbon atoms;
X is a hydrophobic substituted or
unsubstituted arylene group or a hydrophobic
substituted or unsubstituted alkylene group;
Y1 and Y2 are each independently a
3
chemical bond, -CO- or -(CH2)mNR3CO-;
m is an integer from 1 to 6;
R3 is as defined for R1 and R2; and, Z1 and Z2 are each independently a hydrophilic polyhydroxyalkyi group .
2. A compound according to claim 1 wherein X is an alkyl substituted phenylene group.
3. A compound according to claim 2 wherein X is represented by the formula
V \
\
Figure imgf000017_0001
wherein R4 is an alkyl group having from 6 to 18 carbon atoms.
4. A compound according to claim 1 wherein X is an alkylene group having a total of 6 to 23 carbon atoms.
5. A compound according to claim 4 wherein X is represented by the formula
X
Figure imgf000018_0001
wherein R5 is an alkyl group having from 3 to 20 carbon atoms.
6. A compound according to any one of the preceding claims wherein each of Z 1 and Z2,
independently, is represented by the formula
-(CH2)n(CHOH)pCH2OH wherein n is 0 or 1 and p
is an integer from 3 to 6, or is represented by the formula -C(CH2OH)3.
7. A coating composition comprising a hydrophilic colloid and a surface active compound characterised in that the surface active compound is a compound according to any one of the preceding claims.
8. A composition according to claim 7 wherein the hydrophilic colloid is gelatin.
9. A photographic material comprising a support having thereon at least one layer comprising a hydrophilic colloid and a surface active compound characterised in that the surface active compound is a compound according to any one of claims 1 to 6.
10. A photographic material according to claim 9 comprising at least one photosensitive silver halide emulsion layer.
11. Use of a compound according to any one of claims 1 to 6 as a surfactant.
PCT/EP1990/000606 1989-04-26 1990-04-13 Non-ionic surface active compounds WO1990012782A1 (en)

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FR2731010A1 (en) * 1995-02-24 1996-08-30 Renault Multifunctional additive for petrol or diesel motor fuels
WO2011084273A1 (en) * 2009-12-17 2011-07-14 Dow Global Technologies Llc Aminoalcohol compounds, precursors, and methods of preparation and use
CN104557791A (en) * 2014-12-01 2015-04-29 苏州保力瑞生物材料科技开发有限公司 Method for preparing plant bisphenol glycidyl ether

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CA2723509C (en) * 2009-12-22 2016-01-12 Dow Global Technologies, Inc. Diamino-alcohol compounds, their manufacture and use in coatings applications
WO2019087666A1 (en) * 2017-11-02 2019-05-09 三栄源エフ・エフ・アイ株式会社 Method for producing water-soluble or water-dispersible microparticles, use or usage thereof as substitute having emulsifying function, method for producing emulsion, method for producing food and food containing emulsion

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EP0688781A1 (en) * 1994-06-17 1995-12-27 Kodak Limited Non-ionic surface active compounds
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CN104557791A (en) * 2014-12-01 2015-04-29 苏州保力瑞生物材料科技开发有限公司 Method for preparing plant bisphenol glycidyl ether
CN104557791B (en) * 2014-12-01 2017-05-03 苏州保力瑞生物材料科技开发有限公司 Method for preparing plant bisphenol glycidyl ether

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DE69009469T2 (en) 1995-01-26
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US5270161A (en) 1993-12-14
GB8909576D0 (en) 1989-06-14
EP0470101B1 (en) 1994-06-01
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US5391476A (en) 1995-02-21
DE69009469D1 (en) 1994-07-07

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