DE2445782B2 - Photographic recording material with an image-receiving or antihalation layer - Google Patents

Description

25th

to

j5

is

20th

CH ₂ R ⁵ -N * -R ^J

R ⁴

in which:

R ¹ and R ² each represent a hydrogen atom or

an alkyl radical with 1 to 6 carbon atoms, R ³ . R ⁴ and R ⁵ each represent an alkyl radical with 1 to

20 carbon atoms and Χ ^θ one anion,

and its insolubility in water is due to the fact that

a) the total number of carbon atoms in the radicals R ³ , R ⁴ and R ^{5 is} at least 12 and / or that

b) the polymeric compound other than vinylbenzyl units of the given formula units contains from hydrophobic monomers.

2. Photographic material according to claim I, characterized in that it contains a mordant having units of the formula given in which - »ί the total number of carbon atoms in the radicals R ³ , R ⁴ and R ⁵ is 12-30.

3. Photographic material according to claim 1, characterized in that it contains a mordant Units of the formula given and styrene or so Contains methyl methacrylate units.

4. Photographic material according to one of claims 1 to 3, characterized in that it contains a mordant having units of the formula given in which R ³ , R ⁴ and R ^{5 represent} hexyl radicals v>.

To use mordants consisting of polymeric image receiving layers and antihalation layers of photographic recording materials for the mordanting of dyes. For pickling acidic dyes it is known, for example from US-PS 36 25 694 and 37 09 690, polymers with basic units with Use ammonium residues obtained by quaternizing polymers with tertiary nitrogen atoms can be produced. The polymers can be homopolymers or copolymers act, and the basic units can e.g. B. consist of vinylbenzyl units.

Disadvantageous in the use of the known pickling agents with basic units of the one described The type is that the pickling effect of the pickling agent is still unsatisfactory, i.e. h that the pickled dyes, have a tendency to wander, which z. B. can lead to pickled image dyes from Bildbedrken in Non-image areas migrate, as a result of which the quality of the images obtained is reduced. Dyes stained in antihalation layers can also be extracted from the Layers migrate and contaminate neighboring layers.

The object of the invention is to find suitable layers for the production of image receiving and antihalation layers To find polymers which the image dyes transferred to the image receiving layers and in the Antihalation layers are able to hold stained dyes in such a way that no migration of the More dyes can be made.

The invention is based on the knowledge that insoluble in water to solve the problem Polymers are suitable whose units are at least 1/3 of vinylbenzyl units of a certain structure exist.

The recording material according to the invention, which is in at least one colloidal image receiving layer or Antihalation layer as a mordant a polymeric compound with polyvinylbenzyl units, which are attached to the Methylene group of the benzyl radical are substituted with a quaternary ammonium group, contains characterized in that at least 'Λ of the units of the polymeric mordant consist of vinylbenzyl units of the following formula:

R ¹

- CH- -C-

CH ₂ X <

R ⁵ - N> - R ¹ R ⁴

The invention relates to a photographic recording material in at least one colloidal Image-receiving layer or antihalation layer as a mordant a polymeric compound with vinylbenzyl units attached to the methylene group of the benzyl radical are substituted with a quaternary ammonium group contains.

It is well known for the production of

fi5 which means:

R ¹ and R ² each represent a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms,

R ³ , R ⁴ and R ⁵ each represent an alkyl radical having 1 to 20 carbon atoms and

Χ ^θ an anion,

and its insolubility in water is due to the fact that

a) the total number of carbon atoms in the radicals R ³ , R ⁴ and R ^{s is} at least 12 and / or that

b) the polymeric compound consists of units other than vinylbenzyl units of the formula given contains hydrophobic monomers.

In the formula given, R ¹ and R ^{2 can be,} for example, methyl, ethyl, propyl, butyl, pentyl or hexyl radicals.

R ³ , R ⁴ and R ⁵ can be, for example, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, benzyl, octyl and decyl radicals.

Χ ^Θ is, for example, a halogen ion, for example a bromine or chlorine ion or an alkyl sulfate ion, an alkane or arene sulfonate ion, for example in p-toluenesulfonate ion or a dialkyl phosphate ion.

The polymers which can be used according to the invention can consist of homopolymers or copolymers, where it applies that in the case of copolymers at least 1/3 of the repeating units of the copolymers Units of the given formula I are.

In the case of homopolymers, the total number of carbon atoms of the radicals R ³ , R ⁴ and R ^{5 is} greater than 15, since z. B. the homopolymer poly (N, N, N-tripentyl-N-vinylbenzylammonium chloride) is soluble in water

In the case of copolymers, the units make up the comonomer or comonomers, preferably at least 30 mol%, so that insolubility in water is achieved will.

The minimum amount of comonomer or comonomers required to make the copolymer insoluble in water depends on the total number of carbon atoms in the radicals R ³ , R ⁴ and R ⁵ . It has proven to be particularly advantageous if the total number of carbon atoms <* τ radicals R ³ , R ⁴ and R ^{5 is} at least 12: and between 12 and 30

The cationic part of the polymeric mordant preferably has no free carboxyl groups, since the presence of carboxyl groups in the polymer could interfere with the mordant action of the mordant.

Typical ethylenically unsaturated hydrophobic monomers used for the production of the invention usable copolymers (including those of 2, 3 or more different repeating Monomer units) are suitable are, for example, ethylene; Propylene; 1-butene; Isobutene; 2-methylpentene; 2-methylbutene, 1,1,1,4,4-tetramethylbutadiene; Styrene, α-methylstyrene; monoethylenically unsaturated esters of aliphatic acids such as vinyl acetate, isopropenyl acetate and allyl acetate; Esters of ethylenically unsaturated mono- or dicarboxylic acids, e.g. B. Methyl acrylate, methyl methacrylate, ethyl acrylate and diethyl methylene malonate; monoethylenically unsaturated compounds such as acrylonitrile, allyl cyanide and dienes, such as butadiene and isoprene. A preferred class of ethylenically unsaturated hydrophobic monomers used to make the Athenian polymers consists of short-chain 1-alkenes with 1 to 6 Carbon atoms, styrene and tetramethylbutadiene and methyl methacrylate.

The water-insoluble polymers used according to the invention are those of which less than 1g dissolve in 100ml of room temperature (25 ° C) water.

A homopolymer of repeating units of the formula given, in which the total number of

Carbon atoms R ³ , R ⁴ and R ^{5 is} a total of 12, can be soluble in water and thus not a polymer which can be used according to the invention. In contrast, a corresponding polymer with 10 to 40% by weight of styrene units, for example, has the required insolubility in water, so that the special mordant properties are achieved when such a copolymer is used.

The polymers which can be used as mordants according to the invention can be prepared in that a Polymer that consists of at least 1/3 of repeating units of the following formula:

(il)

with a tertiary amine of the following formula:

R ³ N-R ⁴

(III)

R ⁵

with the proviso that R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the meanings already given and X is a halogen atom is quaternized.

Polymers with repeating units of the formula II are, for example, poly (vinylbenzyl chloride) and Copolymers of vinylbenzyl chloride and other ethylenically unsaturated monomers, e.g. B. styrene and Methyl methacrylate. typical suitable tertiary amines which are used for quaternization are, for example, tributylamine. Trihexylamine. Tripentylamine, trioctylamine, diethyldodecylamine, dimethyltetradecylamine, dimethyloctadecylamine, dimethyl

"Λ thyldodecylamine and triisopentylamine.

The vinyl polymer and the tertiary amine can be prepared by heating in the presence of a solvent, e.g. B. an alcohol with a boiling point of over 100 ⁰ C, especially with oxyethanol, ethoxyethanol and

Benzyl alcohol, are reacted with one another. the

The reaction can be carried out at various temperatures, but is preferably carried out at a temperature of 70 to 110 ° C.

Virtually equimolar amounts can be used for the reaction

fco of polymer, e.g. B. poly (vinylbenzyl halide) and tertiary amine can be used. An anion exchange by reaction of a Polymers with a salt, e.g. B. silver acetate or silver p-toluenesulfonate with the preferred anion

(" be performed.

The polymers which can be used according to the invention and which are prepared in the manner described can be used possibly a certain percentage of re-

have recurring units of the following formula IV:

2) Homopolymer from Ν, Ν, Ν-Trihexyl-N-vinylbenzylammonium chloride:

(IV)

IO

15th

in the R ^! and R ^{2 have} the meaning given and R ^{6 is} the remainder of an alcoholic solvent that was used in the reaction mixture. This means that R ^{6 is,} for example, an alkyl, alkaryl or Aryiresi or an Aikoxyatkyirest z. B. a methyl, ethyl, phenyl, benzyl, Methoxyäthyc "- or Äthoxyäthylrest can be.

Optionally, a vinyl polymer can only be incomplete by reacting with less than the stoichiometric amount of the tertiary amine are quaternized. The preferred quaternization in mol% in the case of incomplete quaternization is 80 to 973%. The excess Haloalkyl radicals of the polymer chain can then optionally be reacted further, namely with a compound with more than one amine residue, e.g. B. a polyamine. Examples of suitable polyamines are gelatin, 1,4-butanediamine, imidazole and pyrazine. r> The amount of polyamines usable as crosslinking agents can be 0 to 20% by weight based on the polymer.

If the polyamine, e.g. B. gelatin, used as a binder at the same time, more than 20 wt .-% can be zuese.zt -to. Crosslinking with such polyamines can be carried out in a solvent, e.g. B. in water, acetone, benzene, dimethylformamide, dimethyl sulfoxide, dimethylacetamide and alcohols, such as methanol, ethanol, isopropanol or 2-ethoxy · τ> ethanol. Temperatures are suitably applied from 20 to 8O ⁰ C.

Typical polymers which can be used according to the invention are those with repeating units of the following formulas, in which χ is a numerical value corresponding to 0 to C6 ¹ Ii percent and y is 100 -x .

1) Mixed polymer of styrene and N.N.N-Trihexyl-N-vinylbenzylammonium chloride: ■> *>

-ff CH ₂ - CH), - fCH ₂ - CH)

Cl

Cl ^

QH ₁₃

3) Stype mixed polymer; and Ν, Ν, Ν-tributyl-N-vinyibenzyiammoniumth ' 'riu:

-E (CH ₂ -CH fc-f CH ₂ - CHtl · -

C ₄ H ₉ -N 1 -C ₄ H ₉ Cl C ₄ H ₉

4) Homopolymer from Ν, Ν, Ν-tripentyl-N-vinylbenzvlammoniumchlorici:

-f CH ₂ -

Q, H, CH,

I "

C ₅ H ₁₁ - N - C ₅ H ₁₁ Cl "C ₅ H ₁₁

The polymerization of the monomers can be carried out by customary known methods using the customary known polymerization catalysts take place, for example using peroxides. Azo compounds, gen. for example 2,2'-azobis (2-methylpropiconitrile) and ultraviolet light.

The polymers which can be used according to the invention can be used alone or together with organic binders can be used to produce image receiving layers and antihalation layers, e.g. B. to Production of image-receiving layers, so-called dye-absorbent copy sheets and color absorbent printing plates and image receiving layers of recording materials

for the color transfer process such as from US-PS 33 62 819, 29 83 606, 32 27 552 and 32 27 550 are known, and for the production of LichtholV'hutzschiehten, as shown, for example, from the US-PS 32 82 699 are known. Typical suitable binders for this purpose are the known ones hydrophilic binders which are used for the production of photographic materials, for example Polyvinyl acetate, cellulose acetate butyrate, gelatin and polyvinyl alcohol. The optimal amount of in each individual case Polymers used as mordants depend on the amount of dye to be etched, the polymer itself as well as the chemistry on which the pickling process is based.

The mordant layers are preferably 20 to 80% by weight of one of those which can be used according to the invention Polymers built up.

Recording materials according to the invention can

7. B. IiIiS eir! S! Ti layer backing ⁽⁷ ' ⁱ r with a mordant layer applied with a pinprickraiif with or from one of the polymers usable according to the invention and optionally further layers, / .. B. a so-called polymeric acid layer, ie a layer made of an acidic polymer and / or a so-called delay or timer layer (see, for example, US Pat. No. 3,362,819) and / or a light-reflecting intermediate layer with a light-reflecting white pigment, e.g. TiO; and a polymeric binder (cf. . For example, US-PS 34 45 228).

The polymers which can be used according to the invention are particularly advantageously suitable for production of photographic image recording materials with an integral image-receiving layer, such as, for example from BE PS 7 57 959 and 7 57 965 and US-PS 34 15 644 are known. Such recording materials consist of a layer support and a layer applied to it with an or several of the polymers which can be used according to the invention and at least one light-sensitive silver halo genide emulsion layer. their silver halide in contact with an image dye-forming compound stands.

The polymers which can be used as mordants according to the invention can be applied to customary photographic Supports are applied, for example flexible supports, e.g. B. from films made of cellulose acetate, Polyesters and vinyl polymers or on paper or glass substrates.

If necessary, several of the polymers which can be used according to the invention can also be used together Production of one layer or used in two or more different layers. the seed dressings which can be used according to the invention can furthermore also be mixed with other known ones Mordants can be used in the same layer or in different layers of a material.

Regardless of whether the polymers are used in one layer or in two layers, concentrations of 5 to 55 mg / dm ² are preferably used.

The polymers which can be used according to the invention are suitable for pickling a wide variety of acidic ones Dyes.

In the following, the preparation of some of the polymers which can be used according to the invention will first be described are described in more detail.

1) 15 g of a Copolymcrcn were in a reactor of styrene and vinylbenzyl chloride in a molar ratio of 1: 1, with 60% of the for

Manufacture of the Cupulyineren used vinylbenzyl chloride consisted of the mcta isomer and 40% of the para isomer. Furthermore, in the Reactor 150 ml of benzyl alcohol and 16 g of tris (n-pentyl) amine given. The mixture was heated on a steam bath for 16 hours, then cooled and added to diethyl ether to precipitate the reaction product. The solid precipitated mass became filtered off, washed with ether and dried in vacuo. There were 18.5 g of a polymer from Stvrol and Ν, Ν.Ν-TriDentyl-N-vinylbenzylaminemonium chloride units obtain.

II) In a nitrogen atmosphere, a mixture of 40 g of methyl methacrylate, 61 g of vinylbenzyl chloride, 500 mg potassium persulfate, 200 mg sodium bisulfite, 4 ml of the sodium salt of an alkylaryl poly (ether sulfate) and 200 ml of water heated to 60 "C for 3 hours. The mixture was then heated to a Tpmppriitiir brought from - 20 "C and then warmed back to room temperature. The solid mass which has precipitated out is filtered off and washed with water and Methanol washed. The resulting white powdery mass was in vacuo at room temperature dried. The polymer obtained had an inherent viscosity, measured in acetone, of 0.87.

A mixture of 12.5 g of the polymer prepared in the manner described and composed of Metp-'l methacrylate and vinylbenzyl chloride units was placed in a reactor. 21g trihexylamine and 200 ml of ethoxyethanol introduced, and the mixture was heated 3 days in a nitrogen atmosphere to a temperature of 80 to 90 C ^r. The resulting polymer was then precipitated from the resulting viscous solution in hexane. The precipitated material was filtered off, washed and dried ^{at 40 ° C. in a vacuum oven.} The polymer obtained was then dissolved in methanol and precipitated in a mixture of hexane and ether in a volume ratio of I: t. The resulting copolymer of methyl methacrylate units and NNN-tri-n-hexyl-N-phenylbenzylammonium chloride units had an inherent viscosity, measured in methanol at 25 ° C. and a concentration of 0.25 g / dl, of 8.56.

III) The procedure described under II) was repeated, with the exception, however, that instead of Tri-n-hexylamine was used this time. Thus became a copolymer of methyl methacrylate units and Ν, Ν, Ν-tri-n-butyl-N-vinylbenzylammonium chloride units obtain.

IV) The procedure described under II) was repeated, with the exception, however, that instead of "on Tri-n-hexylamine this time tri-isopentylamine was used. In this way, a copolymer was made Methyl methacrylate units and Ν, Ν, Ν-triisopentylamine-N-vinylbenzylammonium chloride units obtain.

V) to X) The compounds V) to X) given in the table below were prepared by the process described under I) using the solvents and trialkylamines given. The polymers obtained had the alkyl substituents R ³ , R ⁴ and R ⁵ indicated in Table I on the nitrogen atom. The table also shows the results of the elemental analyzes for C, H, N and Cl. The corresponding calculated values are also given. The inherent viscosities of the compounds produced are also given.

24 45 782 9 Table I. analysis 10 Cl I. Standard pickling agent _ _ Inherent Example R 'R ⁴ R ⁵ Used 8.0 viscosity and solvents (Calculated 7.8 binding C. Found) 7.4 . No. 78.8 6.1 Dye! ösunf! ΐ Look at 1.6 V -C ₄ H, -C ₄ H, -C ₄ H, benzyl alcohol 78.5 H N 6.7 79.4 10.0 3.2 5.0 TiC) ₂ 0.82 Vl -C ₅ H _n -C ₅ H ₁₁ -CH ₁₁ benzyl alcohol 77.9 10.0 3.2 6.2 79.9 10.3 2.9 5.6 0.81 VII -CJI ₁₁ -CJI ₁₁ -CJI ₁ , 2-methoxyethanol 76.9 9.7 2.2 5.9 81.4 10.7 2.7 5.1 1.78 VIII -C ₇ H ₁₅ -C ₇ H ₁₅ -C ₇ H ₁ , benzyl alcohol 78.1 10.9 2.0 η ι
7, I. 82.1 10.9 2.5 7.3 1.78 IX C "H, τ -C _U H ₁₇ -CsHi ₇ benzyl alcohol 81.2 11.1 2.1 76.6 9.7 2.3 r \ S. ι
U, UI X -CH ₁ -CH ₁ -Ciiiin N, N-DimciMyifornianiiu 78.0 11.1 1.8 and benzyl alcohol 10.7 3.6 10.5 2.9 The inherent viscosities were determined in benzene I look at it at 25 C and a concentration of 0.25 g / dl solution. -> "> Xl) A reactor was filled with 50 g of a copolymer Test at / middle from styrene and vinylbenzyl chloride, 0.16 moles of tri-n-he- - xylamine and 900 ml of 2-ethoxyethanol charged, whereupon TiO, the mixture in the reactor for 24 hours at 95 ° C was stirred. The resulting solution then became i <> cooled, whereupon 15 ml of concentrated chlorinated water chemical acid were added. The mixture was then Poured into water with stirring to form the polymer to fail. The polymer was then washed with water washed and dried in vacuo. In this way η

80 g of a copolymer of styrene units and N.N.N-tri-n-hexyl-N-vinylbenzylammonium chloride units were obtained obtained, with a degree of quaternization of 80%.

The following examples are intended to illustrate the invention in more detail.

Examples
(Comparative examples)

According to the invention usable polymers were on their mordant properties compared to a Comparative mordant tested, which consists of a copolymer of styrene units and N-benzyl-N, N-dimethyl-N- (3-maleimidopropyl) ammonium chloride units was built. The mordant used for comparison purposes is the mordant of Example XIV of U.S. Patent 37 09 690.

The comparative constant K, which is explained in more detail below, was determined in the tests carried out. The tests were carried out with a test material of the structure described below, for the preparation of which a yellow dye and a purple dye were dissolved in a liquid containing 40 g of hydroxyethyl cellulose per liter of 1 molar KOH solution at a pH of 14, whereupon the solution between a layer of pickling agent with the matching stain! and a layer with a mordant according to the invention was applied. The test material had the following structure:

At certain time intervals, the reflection densities were measured on both surfaces of the sandwich formed in order to determine the occurrence of the dyes in to trace each of the mordant layers. The density measurements were carried out over a period of 24 hours it was determined to which mordant the dyes diffused to a greater extent.

The comparison constant K was determined by dividing the reflection density of the test mordant by the reflection density of the comparison mordant. This created a ratio of pickling ability! of the pickling agent to be tested versus the pickling ability of the comparative pickling agent.

The following table II gives the various values of the comparative constants for homopolymers and copolymers having repeating units of the following Formei again:

-CH ₂ -CH-

(V)

both for the purple dye (K _m )

and the yellow dye (K,).

In the case of comparative experiments A to E and the Examples 1 to IU and 12 passed the pickling agents Copolymers of styrene and the specified comonomer. In the case of Example 11 and the

Comparative ^{example p} were homopolymers. Examples 13 to 15 were copolymers with comonomer units of the following structure:

CH,

CH ₂ -C-

C = O

CH,

(IV)

Table 11

Examples R ' R ⁴ R ' K, K- Mole percent comonomer Compare example A CH, CH, 1.0 1.0 50 "ο styrene Compare example B CH, CH, CH, 2.9 3.1 50 "η styrene Compare example C C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ 2.8 2.9 50 "ο styrene Compare example D C ₁ H ₁ CJI ₇ C ₁ IU 3.1 3.5 50 "ο styrene Compare example E C ₄ H ₉ C ₄ H, C ₄ H, 3.6 3.7 50 "ο styrene 1 C ₅ H ₁₁ C -, ^ η CJI ₁₁ 6.4 15.4 50 "ο Slyrol 2 Cf ₁ H, ι; "» CJI ₁ , 15.5 14.2 50 ",. Slyrol 3 C ₈ H ₁₇ C _H I Ip CsIIp 14.0 11.3 50 "ο styrene 4th C ₂ H ₅ C ₂ H ₅ C ₁₂ IU 12.1 12.7 50% styrene 5 CH, cn, C ₁₄ H :, 11.3 11.9 50% styrene 6th C ₅ H ₁₁ CJI ₁ , C ₅ H ₁ , 17.1 16.1 60% styrene 7th C ₅ H ₁₁ CJI ₁₁ C ₅ H ₁₁ 15.6 15.8 33% Stvrol S. Wu CJI ₁ , CJI ₁ , 14.6 15.3 33% styrene 9 CH, CH, C, s H, - 5.2 4.8 50% styrene IO CH, CH, C ₁₂ H ₂₅ 14.7 14.9 50% styrene 11 CJI ₁₁ CJI _1. , CJI ₁₁ 15.6 14.3 Homopolymer Compare example F C ₄ IL, C ₄ II., C ₄ Il, 0.88 1.10 Homopolymer 12th C ₄ H, C ₄ II ₄ C ₄ K, 8.6 11.9 67% styrene 13th CJI ₁ , CJI ₁ , CJI ₁ , 13.5 14.3 50% Formula VI 14th C ₄ H, C ₄ H, C ₄ Il, 8.5 9.7 50% Formula VI 15th ISO-C ₅ H ₁₁ ISO-C ₅ H ₁ I. JSO-C ₅ H ₁₁ 13.2 14.5 50% Formula VI

In the case of Examples 1 to 15, all of the cases in which the mordant properties achieved were superior to polymers which were insoluble in water. In the case of will. The comparative examples also show that comparative examples A to F were water-soluble that it is not sufficient for the carbon polymer content to be present. From the data obtained, μ atoms of the substituents R ³ , R ⁴ and R ^{5 are} at least such that in the case of water-insoluble 12, but that the mordant must also be polymers of the specified structure and recurring-insoluble in water. The insolubility can be achieved by generating units of the formula given, in which the size of the radicals R ^J , R ⁴ and / or R ⁵ results in the total carbon content of R ³ , R ⁴ and R ⁵ in and / or the amount of hydrophobic comonomers. at least 12 carbon atoms is surprising- b5

Claims (1)

Patent claims: 1. Photographic recording material which is contained in at least one colloidal image-receiving layer or antihalation layer as a mordant a polymeric compound with vinylbenzyl units which are substituted on the methylene group of the benzyl radical with a quaternary ammonium group, contains, characterized in that the units of the polymeric mordant at least '/ 3 a'is vinylbenzyl units of the following formula exist: ίο