DD213074A1 - LIGHT-SENSITIVE PHOTOGRAPHIC MATERIAL WITH ANTISTATIC LAYER - Google Patents

Abstract

The invention relates to a photographic light-sensitive material having at least one silver halide emulsion layer comprising an antistatic layer of synthetic polymers. The object of the invention is to find synthetic polymers with antistatic properties for the antistatic layer of a silver halide material which can simultaneously be used as a binder for the layer without adversely affecting the photographic and mechanical properties. According to the invention, a maleic anhydride copolymer modified with polyethylene oxides and alkoxysilanes is used as antistatic agent.

Description

VEB Filmfabrik Wolfen. Wolfen, the .24.02.1982

PN 933 Wk / Mi

DC.Rittmeier Int. Cl,: G 03 C 1/82

DC. crinkly

Chem.Barrot

DC.Plaschnick

DC.Gragert

Prof. Dr. Bulldozing "fesch

Photosensitive photographic material with antistatic layer

Field of application of the invention

The invention relates to a photographic light-sensitive material having at least one silver halide emulsion layer comprising an antistatic layer of synthetic polymers.

Characterization of the known technical solutions

Photographic recording materials generally have a support which is electrically insulating. Friction during production and processing of the material causes the accumulation of electrostatic charges. These pose a variety of difficulties, as the discharge of the material is exposed. These so-called static markings reduce the quality of the photographic materials or do not permit their production. The accumulation of electrostatic charges can be prevented by reducing the electrical resistance of the carrier surface. Usually, this is done by applying an antistatic layer directly to a surface of the support or to the photographic layer. It is also possible to couple the antistatic function of this layer with the function of further auxiliary layers, z, 8. antiroll

- 2 - 19 HDD -iQfl9 * nO99 & n

_ 2 -

layer / antihalation layer, surface protective layer. For example, various compounds have been described to improve the conductivity of the surface of the support or coated layers, such as surfactants (U.S. Patent 3,552,972, U.S. Patent 3,655,387, U.S. Patent 3,786,002), zinc oxide, semiconductors, and the like colloidal silica (US Pat. No. 3,525,521) and various, mostly halogen-substituted polymers (US Pat. No. 3,615,531, US Pat. No. 3,753,716, DE-OS No. 2,717,998). However, the compounds described show different properties depending on the type of the vehicle or photographic layers. In addition, their effect is usually low, which means that sufficient antistatic equipment can not be achieved. Furthermore, these compounds often lead to disruption of the layer structure of the polymeric layers or there is only insufficient adhesion to the carrier material. In many cases, an increased downforce occurs or the layers have a higher adhesion to one another than the "layer on the carrier material, whereby a sticking of these layers occurs." This results in unusable materials.

Often, the photographic characteristics are influenced inadmissibly. In addition, these compounds are often not diffusion-resistant, thereby losing their effect or causing disturbances in the information recording material. In DE-OS 2,513,791 antistatic agents are presented which are not intended to show many of these disadvantages. These are copolymers based on maleic anhydride, which are esterified with polyethylene oxides. It turns out, however, that the antistatic activity of these polymers is not very good. The specific surface resistivity when using these compounds is higher than 10 ^ 5 cm. In addition, these polymers show only insufficient adhesion to the support materials, which is why their use can not be carried out. In gelatin layers, the oil levels are improperly increased, which makes their physico-mechanical properties inadequate. The conventional hardening agents can not be remedied because these polymers

Substances are chemically inaccessible. Object of the invention

The aim of the invention is to produce photographic light-sensitive materials having at least one silver halide emulsion layer with improved antistatic and mechanical properties,

Explanation of the essence of the invention

The invention is based on the object of finding a synthetic polymer with antistatic properties for photosensitive photographic silver halide materials which have an antistatic layer which can simultaneously be used as a binder and does not adversely affect the photographic and mechanical properties of the materials.

This object is achieved according to the invention in that a photosensitive photographic material having at least one silver halide emulsion layer has an antistatic layer comprising a copolymer of recurring structural units of the general formulas in the main chain

CH CH

RO C

Il

-OM

CH - CH

R - 0 - C

-b

, Ο -CH ₉ -CH ..

I 2 4L η

II and

0 0

CH C

U VV

III

wherein

R and M are identical or different and are hydrogen, alkali metal, alkaline earth metal, ammonium

T is the radical of an organic compound having an active hydrogen atom to which ethylene oxide can be added, preferably linear and branched alcohols, phenols having 4 to 25 carbon atoms,

U hydrogen, -C '

 ^ • 0 - R

V - hydrogen or methyl

OY OY

W -X- $ i-0Y, - / V "X-Si-OY

OY

OY OY

I S

-CZX-Si-OY, -CO-CH-CH ₀ CH ₀ -ZX-Si-OY

0 OY O OH - OY

X alkylene having 1 to 5 C atoms, -CH ₂ -CH-O-CH ₂ -CH ₂ -CH ₂ -,

OH

-CH ₀ -CH ₀ -I-NH-CH ₀ -CH ₀ A- CH ₀ -

^dd \ ^{d Δ} / m ^Z '

Y is alkyl, preferably having 1 to 2 C atoms

Z oxygen, -NH-

n 1 to 100 m 1 to 10

a, b and 'c the molar fractions of the monomers with

a 0.1 to 0.4 b 0.1 to 0.4 c O _S O5 to 0.8,

and other maleic anhydride copolymerizable monomer units.

Such copolymerizable monomers are e.g. Styrene, ethylene, propylene, methyl vinyl ether, methyl methacrylate, ethyl acrylate, vinyl acetate.

Surprisingly, it has been found that upon introduction of the structural unit III, the specific resistance of the polymers according to the invention drops by several orders of magnitude, whereby, when used as antistatic agent, substantial improvements are achieved compared with the previously known antistatic agents,

The polymers according to the invention also have excellent solubility in water and in organic solvents. In combination with gelatin, transparent films are obtained whose swelling values are significantly lower than those of gelatin.

The products further have excellent film-forming properties, so that there is no need for a further binder in the antistatic layer. Particularly noteworthy is the excellent adhesion to substrates of various kinds, such as glass, polyester and cellulose acetate. However, they are also very well compatible with the common binders of the photographic industry (e.g., gelatin, modified gelatin, cellulose derivatives), allowing their use in admixture with said binders. The copolymers of the invention may be cast alone or in admixture with other binders and excipients (for example coating aids, curing agents, plasticizers, filter dyes, antihalation dyes, other antistatic agents, lubricants, anti-adhesion agents, preservatives) by any conventional coating method.

According to the invention, copolymers having molecular weights of between 1,000 and 500,000, preferably between 5,000 and 100,000, are used.

Examples of typical copolymers which can be used according to the present invention are listed below;

Λ C ^ '* _ Λ

Connection 1

CH

NGO-C

- CH

-0.2 C-ON

Il ο

II

CH - CH

NaO-C 0

0.2

C-I-O-CH

CH ₀ 4- C ₅₃ H, _ L i g oil /

III

-0.1 NaO - C C - NH

j j

! ι '

0 0

OCH ₃

) CH

Si-OCH,

OCH,

Cbmonomer

Connection 2

.CH - CH 2

CH.

/ 0.5

CH - CH

NaO

0.35

C - ONa

ι -

CH - CH

NaO - C

, ι

IT -Γ "Τ

MaO

05 C-NH- f CH ₀ -V-Si

IT ² j 3 0

f2 ^H5 ,

OC ₂ H ₅

Comonoraer -hCH ₂ - CH

0.5

CH-

Method 3

CH - CH 0.35

NeO = - C C -ONa

O O

H-CH

NaO

_ C

0.1

C4 0CH _o --CH,

^C 10 ^H 21

CH - CH

NaO -

0.05 / C CO-CHa-CH-P - + - CH ₀

O O

OCH ₃ Si-OCH

OCH.

Comonoraer

CH

Γ. CH

0.5

Connection 4

I.

II

H-CH

0.2

HO-C C-OH

0 0

- CH - CH -

I i / ^Jo ' ²

HO - C C-

CH

O O

III

CH - CH

HO-C C -NHH-CH,

X '

O O

OCH

Si-OCH

OCH.

Comonorner connection

CH ₂ - CH

CH.

0.5

_] _ CH - CH -I-

m -

0.35

C-OH

Il

II

-4- CH - CH -

HO-C

CH - CH

0.05.

HO-C C-NH 4 CH

^Si - ^0C 2 ^H OC ₂ H ₅

comonomer

CH,

CH-

0.5

example 1

7 parts of MSA-styrene copolymer are dissolved in 70 parts of cyclohexanone and, after addition of 8 parts of pyridine and 37 parts of an ethoxylated octadecanol having an average molecular weight of 1500, stirred for two hours at 14O ° C. Subsequently, 9 parts of T'-aminopropyltrimethoxysilane are added and stirred at 20 ° C for 30 min. The product is precipitated in ether and refilled from acetone to ether. The yellowish-white powder obtained after drying can be dissolved in organic solvents such as acetone or methanol.

The aqueous solution is obtained by dissolving the powder in aqueous sodium hydroxide solution,

By analogous instructions, the other polymers according to the invention can also be prepared.

Example 2

A photographic emulsion for optical film, which has been treated with the usual hardeners and stabilizers, is applied to a polyethylene terephthalate base with an adhesive layer thereon. Then an antistatic layer according to the invention of the following composition is poured:

Gelatin; 2 parts

- ΊΟ -.

Compound 1: 5 parts water: 70 parts

The thickness of the antistatic layer is 1.4 μm. The same procedure is followed with the compounds 2 and 3 according to the invention.

After drying, test strips are cut and these at 20 ° C and 40% rel. Humidity conditioned for 20 hours. Subsequently, the surface resistivity is determined with a measuring arrangement consisting of a power supply unit, a resistance standard and a Schwingkondensatorvoltmeter »As a type (comparative sample) is poured onto the silver halide layer, a gelatin layer without antistatic agent. The results are summarized in Table 1.

Table 1: Specific surface resistance using different antistatics

F 1 serial no. Antistatic spec. Top

1 without (type) 2 · ΙΟ ¹⁵

2 connection 1 3 · 10

3 compound 2 3.5 · 10

4 connection 3 5 · 10 ⁷

The results of Table 1 show that in photographic materials equipped with antistatic layers containing compounds 1 to 3, the surface resistivity is several orders of magnitude better than that of the comparative material.

Example 3

A cyanogen triacetate film support is coated with a halothane layer (triphenylrhene dye - binder mixed codensate of formalin, p-hydroxybenzoic acid and p-cresol), a red-sensitive silver halide emulsion layer consisting of sensitizer, hardener, coating aid, color coupler and coupler solvent, and a silver salt-silver iodide.

bromide emulsion (osmid content: 2 mol%), an intermediate layer, a green-sensitive silver halide emulsion layer consisting of sensitizer, stabilizer, hardener, coating aid, color coupler and coupler solvent, and a gelatin silver iodobromide emulsion (oxyl content 3.3 % by mol ), a yellow filter film, a blue sensitive SiI emulsion. a halide emulsion layer consisting of sensitizer, hardener, coating aid, color coupler, coupler solvent and a gelatin silver iodobromide emulsion (do not content 3.3 mol %) and a protective layer successively applied.

Two samples are used as the surface protective layer, sample 1 contains 1.5 g gelatin per m ² and 0.5 g / 100 g binder of a curing agent (2-hydroxy-4,6-dichloro-5-triazine).

2 '

sodium salt) and "0.5 g per m of the compound 2 according to the invention as an antistatic agent,

Sample 2 contains 0.1 g pro.r sodium dodecylsulfonate instead of the compound 2 of the invention as a representative of a common antistatic agent.

After drying "test strips are cut and 20 hours at 20 ° C and 40 % rel. Humid conditioned. The determination of the surface resistance was carried out as in Example 2,

In the photographic film to which the compound of the present invention has been added to the surface protective layer, the surface resistivity is 4.5 * 10 Ω · cm. In contrast, the comparative film (Sample 2) has a surface resistivity of 3 "10 ¹ S cm,

*** _L «ΕΪ-

Claims (2)

invention claim A photosensitive photographic material comprising at least one silver halide emulsion layer having an antistatic layer, characterized in that the antistatic layer is a copolymer of recurring structural units of the general formulas in the main chain CH-CH - - RO-C Il a -O - M CH - CH RO-C C ₊ O-CH. 0 t η T II and I
CH-C III R and M are identical or different and are hydrogen, alkali metal, alkaline earth metal, ammonium T is the radical of an organic compound having an active hydrogen atom to which ethylene oxide can be added, preferably linear and branched alcohols, phenols having 4 to 25 carbon atoms, .0 hydrogen Hydrogen or methyl • Q-R DY OY W -X-Si-OY _ / 3 * r- X-Si-OY OY V = / _ογ ργ ηγ -CZX-Si-OY, -CO-CH-CH ₀ CH ₀ -ZX-Si-OY F ι Ii ² I ² ι 0 OY 0 OH OY X alkylene having 1 to 5 C atoms, -CH ₀ -CH-O-CH ₀ -CH ₀ -CH ₀ -, CH-O-CH ₂ -CH ₂ -CH ₂ - OH -CH ₀ -CH ₀ 4 NH-CH ₀ -CH ₀ J_ A CH ^ - ρ- υι ip -J ^ in ι-οι ip-i / ii _o _j_ υι ι_- Y is alkyl, preferably with 1 to 2 C atoms Σ oxygen, -NH- n 1 to 100 m 1 to 10 a, _b,; and c is the mole fractions of the monomers with a from 0.1 to 0.4 b 0.1 to 0.4 c 0.05 to 0.8 mean and other monomers copolymerizable with maleic anhydride. contains nomereneinheiten.