DD219304A1 - PHOTOGRAPHER, GELATINE-BASED SILVER HALOGENIDE MATERIAL WITH PLASTICATORS - Google Patents

Abstract

The invention relates to a gelatin-containing photographic material containing novel plasticizers. The aim of the invention is to improve the physico-mechanical properties, such as flatness and poor Bruechigkeitsverhalten of gelatin-containing photographic materials, without causing damage to the photograph, Truebungserscheinungen are recorded in the dry and wet state and without deterioration in tensile strength, with the lowest possible amount. The materials comprise, according to the invention, spherical hydrophobic particles obtained by dispersing one or more high boilers and one or more polymers whose molecular weight is 100,000 and whose glass transition temperature is 40 C, using surfactants, auxiliary solvents and protective colloids. These plasticizer mixtures have glass transition temperatures of 40 C and show excellent effects even at levels of 1-5%, which are retained even in extreme material and climatic conditions.

Description

Photographic, gelatinous silver halide material with plasticizers

Field of application of the invention

The invention relates to photographic, gelatin-containing material based on silver halide emulsions containing plasticizers.

Characteristic of the known technical solutions

The physical-mechanical properties of the photographic materials are decisively determined by the binders used. Since gelatine has hitherto found its widest application as a layer former and will retain this supremacy in the future, it is above all the properties of this protein that influence the physical properties such as flatness, brittleness and swelling. Gelatin crosslinking agents (curing agents) are most commonly used to control the swelling of the gelatin. This hardening and the forming three-dimensional networks of gelatin significantly increase the brittleness and worsen the flatness.

ηκΐ 1933 * 12347 8

Gelatine itself only shows sufficient plasticity if its innewoh ing water content causes a sufficiently low glass transition temperature. Thus, at a water content of about 15 - 20 % results in a sufficiently low glass transition temperature of about 2O ⁰ C. Already a water content of about 10 % , the glass transition temperature can rise to about 80 ⁰ C, which brittle due to the lack of molecular mobility brittle materials result. It is known that the gelatin layers also change their water content as a function of the relative humidity. The above-mentioned water content of 15 - 20 % is usually only achieved at relative humidities of about 40 ~ 60 % . Lower relative humidities, which are not uncommon in experience, lead to brittle materials. Hardeners, hydrophilic color couplers and hydrophilic polymers in addition to gelatin cause even bad the favorable relative humid brittle materials. The reasons lie in the networking, the associative and Polyekktrolytkomplexbildung. Intensive drying processes in the preparation of the photographic materials can also cause brittle materials through increased formation of globular structural segments of the gelatin. Crack formation takes place in the gelatin layers on the basis of microcracks, as a result of which the substrate also breaks. This is particularly evident in the case of low-humidity and extreme temperatures in kite and amateur materials. Another disadvantage of brittle materials is their poor flatness, which can lead to, for example, a trouble-free transport in the development machine is not given. These disadvantages described result in unusable or degraded photographic materials. On the other hand, since the advantages of gelatin predominate, research has been carried out for decades to impart sufficient plasticity to the gelatin layers by suitable additives to prevent breakage and poor flatness.

First, the water content of the gelatin layers was tried by addition of polyhydroxy compounds, e.g. Glycols and glycerol, and thus exploit the plasticizing effect of water (US Patent 2376 005, US Patent 2,960,404, US Patent 3,042,524, US Patent 3,271,178, DE-AS 1,154,717). These compounds are effective only at high humidities and must be added in excessive amounts to achieve a satisfactory effect. Their small molecular size also allows no specific use in photographic single layers, as a diffusion-resistant storage is not given. Disadvantageously, the layer strength is also reduced, as a result of which bonding of the photographic materials results. Often also turbidity phenomena of the layers are noted. Other research has been carried out with the aim of achieving an external softness of the gelatin by low molecular weight plasticizers which have a surfactant-like structure. These compounds cause no significant change in the Grenzflächeneigenschaf th. Rather, a strong attenuated interaction mechanism similar to the hydrophilic color couplers is observed. Compounds are described in SU-PS 108 677, SU-PS 129 939, SU-PS 207 013, SU-PS 210 657, BE-PS 658 592, BE-PS 605 378, US-PS 2 904 434, DE-PS 1 146 362 and FR-PS 1,114,721 called. However, the amounts of these plasticizers are often in ranges that do not allow a practical application. In most cases, an unacceptable photographic activity is observed, and the loss of layer strength results in increased adhesion.

Other patents describe polymer grafting reactions on gelatin as a suitable route (SU-PS 159 725, Vysokomolek, Soed, A 12 (1970) 8). Although this procedure leads to the plasticization by the incorporation of polymer sequences of lower glass transition temperatures into the gelatin, but the disadvantages outweigh, so that a wide application does not occur.

Thus, the grafting reaction always produces considerable proportions of homopolymer of the monomer to be grafted, which can not or only with difficulty be separated off. The fluctuating composition of gelatin also leaves different

Reaction products arise. In most cases, there is an additional reaction step before the grafting which is supposed to create active sites for the grafting in the gelatin molecule. For sufficient plasticization, high polymer grafting levels, typically 20-40 % , based on the gelatin dry weight, are necessary. However, such a high gelatin substitute is not possible with many photographic materials. The main disadvantage is the loss of advantageous properties of gelatin, such as gel strength and sufficiently high sol-gel conversion point. Thus, this method has acquired only minor importance for the practice.

The drawbacks of the types of plastification described in the last few years have led to increasingly disperse systems and here above all polymer dispersions becoming the focus of research work.

Polymer dispersions retain their disperse character in gelatin layers up to 90 % gelatin substitute. Dispersions with a glass transition temperature ^. the processing temperature are useful plasticizers. Numerous studies have been carried out on their conditions of use (3rd Signal AM 8 (1980) 4,229-241). Their ease of preparation in the emulsion polymerization process and the breadth of variation by the choice of monomers contribute to the broad application (US Pat. No. 2,376,005, US Pat. No. 2,772,166, US Pat. No. 2,865,753, DE-AS 1,146,749, DE-AS 1,154,717, BE -PS 661 697, DO-PS 137 284). ,

However, sufficient plasticization requires about 15-40 % of the gelatin dry weight of polymer. An often unrealizable quantity of thin-layered materials. Further disadvantages are the turbidity of the moist materials due to the refractive index divergence,

Thus, the use is e.g. Limited in photographic materials. The molecular weights are usually around 500,000 at 2,000,000 and their glass transition temperature ^. the processing temperature. Another significant disadvantage when using polymer dispersions is the significant loss of tear resistance of the layer.

Object of the invention

The aim of the invention is to improve photographic materials in their physico-mechanical properties.

Explanation of the essence of the invention

It is an object of the invention to provide photographic materials which have improved physico-mechanical properties in terms of brittleness and flatness, without detriment to the photographic parameters and without clouding of the dry and wet layers, and without loss of tensile strength of the layers.

According to the invention the object is achieved in that in a photographic gelatin-containing silver halide material with plasticizers, as plasticizers spherical hydrophobic particles consisting of one or more high-boiling solvents having a boiling point greater than 150 ⁰ C and one or more polymers having a molecular weight average less than 100 000 and a Glass transition temperature greater than 40 ⁰ C, the mixture causes a glass transition temperature of the polymer is less than 40 ⁰ C, optionally with the use of low-boiling auxiliary solvents, dispersed in water, with protective colloids and surfactants.

The plasticizers contain high boiling solvent and polymers in a ratio of 1: 5 to 5: 1. The plasticizers are prepared by dispersion using known technological techniques, e.g. by ultrasound, by Druckverdüsssung, but preferably using apparatuses that operate on the rotor-stator principle.

A mixture of high boilers, polymers and auxiliary solvents is dispersed. The co-solvents are water-immiscible or only slightly miscible low-boiling organic liquids which dissolve the polymer and cause solubilization in the high boiler. Ethyl acetate is advantageously used. These solvents are removed from the dispersion after dispersion by washing or distillation, usually under reduced pressure. Remaining residual solvent contents are below 0.5 %. In addition to solubilizing these solvents also serve better dispersibility, since they advantageously reduce the viscosity of the organic phase. High boilers are liquids whose boiling point is> 150 ^° C. Examples include the esters of phthalic and phosphoric acid. To stabilize the disperse phase surfactants are advantageously used. It has been found that especially anionic surfactants are suitable * An Obersicht'bekannte surfactants is given for example by Gawallek in "surfactants" (Akademie Verlag Berlin 1975). It has also been shown that protective colloids are advantageously used to obtain storage stable dispersants in the aqueous phase. In general, amounts of protective colloid of 5 to 40 %, based on parts by weight of the organic phase, sufficient. Gelatine showed the best properties in the investigations.

The Plastifjkatordispersionen prepared by the described methods and tools show grain diameter of 0.06 to 0.4 .um'bei very narrow distribution. Their storage stability is several months, without loss of effect, or caused by coalescence turbidity. The plasticizers are universally applicable without damaging photographic properties. Already at use levels of 1 to 5 % , significant plastification effects occur, which are only observed at amounts of 15 to 40 % when using polymer dispersions prepared according to the emulsion polymerization principle, or are not achieved.

A deterioration of the quality of the casting, as it can be caused by changes in the surface tension, is also not recorded. A particular advantage is that both the use of static and dynamic test methods, the plasticizing effect of the plasticizers occurs, which is often not the case with the known. Particularly advantageous is the retention

or increase the tensile strength while excellent plasticizing. All previous plasticizers cause significant losses of tensile strength with a satisfactory plasticizing effect.

Another advantage is the lack of turbidity of the dry and swollen layer. Thus, a universal use in all photographic materials is possible. Damage to the operation of other photographic components can not be determined. The use can also be done in different Gelatinesorten without the plasticizing effect is lost. Even in the critical extreme areas in which the known plasticizers fail, the plasticizers of the invention show a good effect.

embodiments

In the examples, the following compounds are used:

high boiler

dibutyl phthalate (DBP) tricresyl (CPM) wetting agent alkylnaphthalenesulfonate (ANS) sodium lauryl sulfate (NaLS)

polymers

Oligomers of the general formula

CH-CH ^ -x

X ₁ X ₁ = -H _f -OH, -COOH η = 3 - 20

<C-Methyloligostyrene of the general formula

CH,

I ³

C-CH,

• X-

- η

-H, -OH, -COOH 3 - 20

Ethylene vinyl acetate copolymers of the general formula

H έ-CH

I o

i-0

ing χ

CH-CH,

C = O

CH,

η -

X = -H ₁ -Cl η = 40 - 3000 S ₁ = 1 - 500 m ₂ = 1 - 500 The total out

+ nu does not exceed 500 «

polymer dispersions

1) 73 wt.% Of ethyl acrylate 17 wt.% Of styrene

5 wt.% Of acrylic acid

2) 50 wt.% Styrene 47 wt.% Butadiene

3 wt.% Acrylic acid

Both polyrader dispersions are prepared by the known emulsion polymerization techniques (e.g., DD-PS 80,546).

3) 60 wt.% Oligostyrene 1)

, dg "wt 0,1IyUm 40 with η = 4, Xe-H.% dibutyl phthalate.,

4) 60 wt.% Oligostyrene 1)

with η = 4, X = -OH, dg a 0.09 to 40 wt.% of dibutyl phthalate

5) 60 wt.% Oligostyrene 1)

with η »4, X = -COOH ₁ dg = 0.08 / around 40% by weight of dibutyl phthalate

6) 60 wt.% £ / -Methyloligostyrene 2)

to 40 wt η = 4, X a -COOH, dg = 0.12.% dibutyl phthalate

7) 60 wt.% Ethylene vinyl acetate copolymers 3)

with η = 200, m ^ = 2, m ₂ = 8, X = -Cl, dg = 0.12, Um 40 wt.% of dibutyl phthalate

8) 60% by weight of ethylene vinyl acetate copolymers 3)

with η = 180, n ^ + n ^ = 20, X = -H, dg = 0.11, um

H '

40% by weight of dibutyl phthalate

Polymers and high boilers of dispersions 3-8 are dissolved in ethyl acetate and dispersed in an aqueous, gelatin-containing gelatin solution. After dispersion, the ethyl acetate is stripped off in a thin-film evaporator.

- 10 -

Be i s ρ i e 1 1

On a pad of cellulose acetate having an acetylation degree of 61.2% and a thickness of 120 μm, which is provided with a gelatin adhesive layer having a thickness of 0.5 μm, a multilayer color material for positive purposes is built up. On the reverse side, an alkali-soluble binder-middle layer containing a decolorizable green triphenylmethane dye and, as a binder, a methyl-styrene oligomer of the following structure is used to inhibit the reflection of light. >

COOH

0OH

contains, offered.

In addition, a wax protection layer is applied.

On the emulsion side, an unsensitized bromoiodine silver emulsion containing 80 g of gelatin per kg of crude emulsion, 35 g of silver in the form of the halides and 50 g of a yellow coupler F 535 (Bios Final Rep. 721, 22, 1946) was added. As a curing agent Triacryloylhexahydros-triazine is used. The base is separated from the center casting by a 1.5 to thick gelatin interlayer. The medium casting contains 80 g of gelatin per kg of chlorobromic silver emulsion, 3.5 g of silver in the form of halides, 45 g of cyan coupler KÖ 686 (Bios Final Rep. 721, 18 1946) and 30 mg of the red sensitizer Rr 1953 (Bios Final Rep. 721, 10 1946 ). For interlayer and medium casting, triacryloylhexahydro-s-triazine is used as the curing agent

On a renewed intermediate layer of Oberguß, is offered. It contains 80 g of gelatine per kg of chlorobromic silver emulsions.

      - ii -

30 g of silver in the form of the halides, 40 g of magenta coupler Z 169 (Bios Final Rep. 721, 21, 1946) and 60 mg of green sensitizer Rr 340 (Bios Final Rep. 721, 7, 1946). The curing agent is again triacryloylhexahydro-s-triazine. The coating is a gelatin layer which contains a silicone oil to improve the sliding properties. In addition to the compounds described, the known additives, such as filter dyes, stabilizers, clear coaters, preservatives and wetting agents are used. The total layer thickness of the material is 18.5 μm. Color development takes place in a known manner at 27 ^° C. The color developer used is p-diethylaminoaniline. The properties of the material are summarized in Table 1 (Material A). It can be seen that unsatisfactory physico-mechanical properties are present.

Example 2

In all 3 Eraulsionsschichten the material of Example 1, different amounts of plasticizers are added, based on the gelatin dry weight.

Material B: Material C: Material D: Material E: Material F: Material G: Material H: Material I: Material G: Material K: Material L: Material M: Material N: Material O: Material P: Material Q:

1 % aqueous polyether dispersant 1)

20 % aqueous polymer dispersion 1)

5 % aqueous polymer dispersion 1)

1 % aqueous polymer dispersion 2)

20 % aqueous polymer dispersion 2)

5 % aqueous polyraper dispersion 2)

1 % aqueous polymer dispersion 3)

aqueous polymer dispersion 3)

aqueous polymer dispersion 4)

1 % aqueous polymer dispersion 5)

1 % aqueous polymer dispersion 6)

5 % aqueous polymer dispersion 6)

1 % aqueous polymer dispersion 7)

5 % aqueous polymer dispersion 7)

1 % aqueous polymer dispersion 8)

5% aqueous polymer dispersion 8)

- 12 -

In table! the physical-mechanical and photographic properties of materials A to Q are set forth

 It can be seen that the physico-mechanical properties are most advantageously improved by the compounds according to the invention or that with low concentrations and under extreme conditions a sufficient improvement can be achieved only with the new plasticizers.

Meaning of the reference signs:

Q a. Swelling (gH ₂ 0 / g gelatin) R = Elongation at break {%) FH a Drop hammer (cm) tf aReißfestigkeit (MPa) P = Flatness

Egg »emulsion inside ^ bad flatness, -« good flatness

1 inflow

E. Rel. Sensitivity j 2 a medium

Γ --Gradation J ₃ , _overcast

D. a minima density

% Values in columns R-P relate to relative humidity.

B e i s ρ i e 1 3

To the photographic material of Example 1 are added plasticizers corresponding to the material J of Example 2 but with sodium lauryl sulfate as wetting agent and varying amounts of dibutyl phthalate.

At the same time, the glass transition temperatures of the differential scanning calorimeter DSC-18 of the company are determined by the plasticizers

 Perkin-Elmer determines.

 '. - 13 -

6.2 8.2 5.8 5.7 10.8 8.2 35.1 > 27 36.4 > 27 32.2 > 27 31.1 24.6 29.2 18.4

Table 2 illustrates that only with the lowering of the glass transition temperature, the good plasticizing effect is achieved.

Table 2

Material % DBP Tg ( ⁰ C) R ^X 'F _u ^X '

A -

D without 68

10 34

20 20

25 13

"30 5

40 1

60 -21

Tg = glass transition temperature of the plasticizer mixture

Measurements at 55 % relative humidity

Example 4

To a high sensitivity silver halide emulsion for radiological use, having more than 2 mole % silver iodide and a gelatin content of 80 grams per kilogram of emulsion, the plasticizers described in Table 3 are added. The emulsion is ripened with the known sulfur compounds, a triazaindolizine is used for stabilization, and the curing agent used is the sodium salt of 2-hydroxy-4,6-dichloro-s-triazine. The emulsion is cast on both sides on a blue-dyed cellulose acetate pad with a thickness of 180 μm. The processing of the exposed material takes place in the following developer:

- 14 -

0.6 G l-Phenylpyrazolidon- (3) 10.0 G hydroquinone 55.0 G sodium sulphate 0.15 G T- diethylamino-O-hydroxypropyl hydrazindioxalat 55.0 G sodium 10.0 potassium 0,008 G 1-phenylmercaptotetrazole with water fill up to 1.

The results in Table 3 confirm the good plasticizing effect of the compounds of the invention and their photographic safety.

Table 1

Material Q R 30% FH 5.2 30% Ö 50% e 1 2 3 0 1 2 3 ^D min 50 % 1.7 50% 5.2 1.? 50% egg 100 100 100 > 3.0 > 3.0 > 3.0 A 2.35 6.2 1.7 5.2 13.4 1.9 102.4 egg 100 100 100 > 3.0 > 3.0 > 3.0 0.08 B 2.35 6.2 5.2 5.1 5.4 102.0 -. 96 94 94 2.7 2.6 2.4 0.08 C 2.10 16.0 8,40.2,8 1.6,5 1.9 76.0 egg 98 98 96 > 3 0 2.9 2.8 0.06 D 2.40 6.1 1.7 > 27.0 1.9 83.1 egg 100 100 100 > 3.0 > 3.0 > 3.0 0.07 l Tim 2.35 6.2 1.8 18.4 6.2 102.2 - 98 98 96 > 3.0 > 3.0 > 3.0 0.08 F 2.05 17.2 10.0 18.0 1.9 78.4 egg 100 100 100 > 3.0 > 3.0 > 3.0 0.09 2.30 6.1 1.8 14.8 9.1 85.0 - 100 100 100 > 9.0 > 3.0 > 3.0 0.08 H 2.35 22.5 18.9 24.6 14.8 107.3 - 100 100 100 > 3.0 > 3.0 > 3.0 0.03 I 2.30 35.1 24.8 14.4 LO 2 111.1 em 100 100 100 > 3.0 > 3.0 > 3.0 0.07 3 2.35 28.4 22.6 9.8 112.4 - 100 100 100 > 3.0 } 3.0 > 3.0 0.08 K 2.35 27.0 21.9 8.5 108.4 100 100 100 > 3.0 > 3.0 > 3.0 0.08 L 2.35 24.1 19.5 L3, l 106.0 - 100 100 100 > 3.0 > 3.0 > 3.0 0.08 M 2.30 38.6 24.7 8.1 110.2 - 100 100 100 > 3.0 > 3.0 > 3..Ο 0.07 N 1.35 21.2 16.9 105.7 0.07

Table 1

Material Q R 30 % FH 30 % 50 % P e .. '. \ - 3 1 2 3 min 50 % 21.4 50 % 12.4 109.4 50 % 1 2 100 > 3.0 > 3.0 > 3.0 O 2.35 28.7 15.6 22.8 8.0 105.6 mm 100 100 100 > 3.0 > 3, 0 > 3.0 0.08 P 2.35 20.7 ^ 21.2 14.1 12.0 109.1 mm ' 100 100 100 > 3.0 ".0 > 3.0 0.08 Q. 2.30 27.9 22.7 - 100 100 0.08

Table 3

Plastifikatordispension Polymer Mas.% High boiler Ma s. % surfactant photography e T min physico-mechanical. properties & FH Q No. amount used - - '. - 100 2.8 0.06 R 50 % 50 % 1 % Gelatin dry weight 60 vonl) with n = 10 X = COOH 40 DBP ANS 100 2.9 0.06 50 % 115.2 8.5 2.30 2 - It M NaLS 100 2.8 0.05 11.1 118.1 2.21 3 3 Il 40 CPM NaLS 100 2.8 0.05 35.4 117.6 2.12 4 3 Il 40 CPM ANS 100 2.9 0.06 36.0 118.4 (> 27 2.24 5 3 60 of 2) nit n = 4 X = COOH 20 DBP ANS 100 2.9 0.07 35.6 117.4 2.24 6 3 Il 20 CPM ANS 100 2.8 0.06 35.4 117.9 2.16 7 3 36.1 118.6 2.14 3 37.0

1) Type without plasticizer

Claims (2)

invention claim 1. Photographic, gelatin-containing silver halide material with plasticizers, marked thereby . in that it comprises spherical hydrophobic particles consisting of one or more plasticizers
high-boiling solvents having a boiling point greater than 150 ° C and one or more polymers having a molecular weight of less than 100 000 and a glass transition temperature greater than 40 ⁰ C, the mixture causes a glass transition temperature of the polymer below 40 ° C, optionally using low-boiling auxiliary solvents, in water with protective colloids and surfactants dispersed. 2, Photographic, gelatin-containing silver halide material according to item 1, characterized in that the plasticizers contain high-boiling solvents and
Polymers in a ratio of 1: 5 to 5: 1
enthalten.ι