DE1447685C3 - Photographic film with improved electrostatic properties - Google Patents

Description

O - (CH ₂ - CH, O) ₁₁ -

P (OM) _y

contains, in which R _{1 is} an alkyl radical with 4 to 27 carbon atoms, R _{2 is} a hydrogen atom or an alkyl radical with 4 to 27 carbon atoms and M is a lithium, sodium, potassium or ammonium cation, the cation of N-methyltaurine , Means sarcosine or sodium N-methylsarcosinate, η is a number from 1 to 40 and .x and y are 1 or 2, where χ = 2 when y = 1 and vice versa.

2. Photographic film according to claim 1, characterized in that the salt of the phosphoric acid ester is contained in a layer that is the photosensitive halogen silver gelatin layer is adjacent.

3. Photographic film according to claim 1, characterized in that the salt of the phosphoric acid ester is contained in a gelatin layer.

US Pat. No. 2,420,610 discloses the production of photographic films which are in or on the film contain a dialkyl ester of a phosphoric acid as an antistatic compound. The DT-AS 1,047,615 relates to a photographic film coated on one of the outer surfaces with a layer is provided, which is a polyoxyethylene compound of the general formula

RO-C ₂ H ₁ - (OC ₂ Ht) ₁₁ -OH

contains as an antistatic compound in which R is an alkyl radical with 6 to 18 carbon atoms and η is a means an integer with a value of at least 4.

Experimental tests have shown that the dialkyl hydrogen phosphates according to US Pat. No. 2,420,610 and the ethylene oxide adducts according to DT-AS 1 047 615 do not yet produce a satisfactory increase in the conductivity of the photographic film. The photographic In the so-called finger rub test, the film was not yet free from electrostatic charge.

The object of the invention was therefore to provide a photographic film with a significantly reduced surface resistance and a correspondingly reduced tendency for static electricity to accumulate. This task is carried out by solved the invention.

The invention is thus a. photographic film with enhanced electrostatic Properties, consisting of a support on which at least one photographic emulsion layer, preferably a halogen silver emulsion layer, is applied and which in one of its Layers contains an antistatic compound which is characterized in that it is antistatic active compound is a salt of a phosphoric acid ester of the general formula

40

45

Electrical charges accumulate in the manufacture and use of photographic films which leads to considerable difficulties. These charges, known as electrostatic charges, cause exposure during production and handling of the film by so-called flashing, those after developing the film as black streaks or lines or as an irregular haze pattern become visible in the emulsion layer. An attempt was made to reduce the static electricity prevent or suppress by incorporating compounds into the photographic films, which are either electrolytes or have hygroscopic properties. These substances confer the films have improved electrical conductivity, thereby eliminating their electrostatic charge before it can accumulate and cause local discharges. Lots of for this purpose Recommended compounds are however with the materials used to make the photographic Films are used incompatible, which causes other difficulties. Others have one insufficient effect.

(CH ₂ -CH ₂ O) _n -

P (OML

contains, in which R _{1 is} an alkyl radical with 4 to 27 carbon atoms, R _{2 is} a hydrogen atom or an alkyl radical with 4 to 27 carbon atoms and M is a lithium, sodium, potassium or ammonium cation, the cation of N-methyltaurine, sarcosine or sodium N-methyl sarcosinate, η is a number from 1 to 40 and χ and y are 1 or 2, where χ = 2 when y = 1 and vice versa.

Examples of alkyl radicals R ₁ and R ₂ are butyl, hexyl, octyl, nonyl, decyl, hendeyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl -, eicosyl, heneicosyl, docosyl, tricosyl, tetrycosyl, pentacosyl, hexacosyl and heptacosyl groups.

The salts used according to the invention are made from known phosphoric acid esters of ethylene oxide addition products of the alkylphenols. Such acidic esters can be easily made, z. B. by esterification of a corresponding ethylene oxide addition product of an alkylphenol, such as nonylphenol, Dodecylphenol, octadecylphenol, dibutylphenol or dinonylphenol, with phosphorus pentoxide

(P ₂ O ₅ ) under practically anhydrous conditions at a temperature below about 115 ° C for 4 or more hours (see US Pat. Nos. 3,004,056 and 3,004,057).

The organic and inorganic salts can be formed in any known manner. A preferred one The manufacturing process is the neutralization of the acidic phosphoric acid diester to a pH value from about 7.0 to 7.5 as well as the subsequent purification and extraction of the salt.

The antistatic compounds can be various layers of a photographic film be incorporated. So you can z. B. Component of an emulsion layer, a protective layer, a Undercoat or a backing layer that has an anti-curling layer or an antihalation layer represents.

The antistatic compounds can be used in various types of photographic emulsions be used. They are not only suitable in orthochromatic and panchromatic emulsions, but can also be used in non-sensitized emulsions, X-ray emulsions, paper emulsions or paint emulsions can be used. They can be used in combination with known antifoggants and stabilizers, reduction and metal and noble metal sensitizers, or in combination can be used with other additives. The antistatic compounds can be found in gelatin or other colliodes can be used, e.g. B. water-soluble cellulose derivatives, such as. B. Oxyethyl cellulose, Methyl cellulose or cellulose acetate with a low acetyl value. They can continue to common substrates are applied, z. B. from an organic cellulose ester such as cellulose acetate or cellulose propionate, or from polymers such as polyvinyl chloride or vinyl chloride-vinyl acetate copolymers.

From US-PS 2,563,506 it is known that quaternary ammonium salts of phosphoric acid esters of the general formula

R - N®— R '

R.
O

O —P — OR '
OR '

in which R is a monovalent aliphatic hydrocarbon radical with 1 to 22 carbon atoms and R 'is a monovalent aliphatic, cycloaliphatic or aromatic hydrocarbon radical with 1 to 18 carbon atoms means, antistatic compounds are for superpolyamide and cellulose acetate yarns. FR-PS 1 135 486 discloses plasticized plastics based on vinyl polymers known to act as antistatic compounds either a tertiary amine of the general formula

RN [(RO) ₁₁₁ H] ₂
or its quaternary ammonium salt of the general formula

R "

N [(RO) _1n H] ₂

X = -

contain, in which R is an alkyl or alkenyl radical with at least 8 carbon atoms, R ' _{denotes the group (CH 2} J _{2 p} , in which ρ is at least 2, R "an alkyl, ίο alkenyl or aryl radical and X. means the remainder of an acid. Preferred compounds are

C ₁₇ H

17 ^ 33

• N

(CH ₂ - CH ₂ - O) _4-5 H

(CH ₂ - CH ₂ - O) ₄₅ H

and

(CH ₂ -CH ₂ -O) _{4, 5} H

Q ₇ H ₃₃ -N

®O-SO ₂ -OCH ₃

H ₃ C (CH ₂ -CH ₂ -O) ₄₅ H

Finally, it is known from DT-AS 1 084 231, polyethylene terephthalate textile with amine salts of Phosphoric acid esters - ethylene oxide adducts to make them antistatic and pleasing To give grip. These amine salts have the general formula

OR

H (O-CH ₂ - CH ₂ h5ö-O - Ρ— Ο ^Θ H ₃ N-R '

in which R is an alkyl radical and R 'is an alkyl or hydroxyalkyl radical.

In none of these publications addressed to the textile chemist is there any indication that the described antistatic compounds as an additive to gelatin-containing layers of a photographic Films are suitable. Photographic films containing any of the compounds described are also unknown. From the suitability of the compounds known in these publications No reliable methods can be used to reduce the electrostatic chargeability of textiles or threads Make predictions about whether such compounds will also be found in photographic films, d. H. a composite of several gelatin layers with a layer support made of a plastic are.

The examples illustrate the invention.

example 1

Samples of a highly photosensitive X-ray film of 70 mm wide were covered with a protective layer provided that in a 2% gelatin solution (1) 20 percent by weight sodium sarcosinate. (2) 20 percent by weight of the acidic phosphoric acid ester, prepared from an adduct of 1 mole of nonylphenol and 6 moles of ethylene oxide, (3) 20 percent by weight of the sodium sarcosinate salt and (4) 20 percent by weight, respectively of the sodium N-methyltaurine salt of the acidic phosphoric acid ester. Each protective layer

held an additive to ensure an even layer application and a second Hardening of the layer. The films were conditioned and soaked at 22 and 42% relative humidity The usual electrode method is examined for its electrical conductivity. As shown in Table I, the antistatic compound used according to the invention has a relative humidity of 22 and 42%, a more than 14-fold lower surface resistance.

Table I.

sample

Control*)... 1000+ 1 1000+ 2 130 3 60 4th 50 *) Without addition. B e i s ρ i e;

Surface resistance

22% / 22 ° C
in 10 ⁵ megohms / cm ²

42% / 23 "C in 10 ⁵ Megohm / cnr

50

35 7

3.5 2.5

The film samples prepared in Example 1 were used to determine their susceptibility to rubbing practically tested with the finger. The finger rub tests were performed on 8 pieces of each sample for static electricity Bodies examined. As can be seen from Table II, the control sample showed the sodium sarcosinate and the acidic phosphoric acid ester has a considerable static charge on most pieces. the However, antistatic compounds used according to the invention produced static charges free samples.

Table II

sample without low middle high**) Control*)...
1 2
1
0
8th
8th 3
7th
2
0
0 3
0
2
0
0 0
0
4th
0
0 2 3 4th

Conditioned moisture and then tested for its surface resistance. Next were samples these films were subjected to the finger rub test and also examined for their static charges. The conductivity tests show the clear superiority of the sodium sarcosinate salt used according to the invention compared to the known product.

IO sample 20th description Surface resistance 42% ΙΟ ⁵ megohms / cm ² relative humidity 23% 15th 170-109-1 Sodium sarcosi- relative natural salt humidity 200 270-2167-1 Lauryl alcohol 75 Ethylene oxide adduct 1000

The finger rub test was carried out on 8 pieces of each sample. It turned out that the film with the Sodium sarcosinate salt was essentially static free while using all samples the lauryl alcohol - ethylene oxide adduct contained static charges.

B. Comparison with those in the U.S. Patent
2 420 610 described antistatic effect
links

Samples of fine grain X-ray film were provided with a protective coating containing the sodium sarcosinate salt of the phosphoric acid ester or methyldodecyl hydrogen phosphate mentioned in Example 1. The samples were conditioned and on at room temperature of 50% relative humidity checked their surface resistance.

The conductivity tests show a considerable superiority of the photographic material according to the invention Movies.

55

*) Without addition.

**) Number of stripes without, with light, medium or heavy static electricity.

Example 3

A. Comparison with the antistatic compounds described in DT-AS 1 047 615

A highly sensitive X-ray photographic film was made with a protective layer of 2% Gelatin solution provided, which, in addition to the casting additive and the hardening agent, 10 percent by weight sodium sarcosinate salt of the phosphoric acid ester mentioned in Example 1 contained. On a second film a similar protective layer was produced, but as an antistatic compound that Addition product of lauryl alcohol with 8 to 15 mol Containing ethylene oxide. Samples of these films became more relative at room temperature and 22 and 42%, respectively

AJN sample description Surface resistance 45 10 ⁵ megohms / cm ² AJN 22 ⁰ C, 50% relative 1603 Sodium Sarcosi humidity natural salt 10 50 1601 Methyldodecyl hydrogen phosphate 150

Example 4

Samples of a highly photosensitive X-ray film of 70 mm wide were covered with a protective layer provided that in a 2% gelatin solution

1. 20 percent by weight of the sodium salt of N-methyltaurine,

2. 20 percent by weight of the acidic phosphoric acid ester, prepared from an adduct of 1 mol Nonylphenol and 6 moles of ethylene oxide,

3. 20 percent by weight of the sodium N-methyltaurine salt of the acidic phosphoric acid ester, prepared from an adduct of 1 mole of nonylphenol and 6 moles of ethylene oxide, or

4. a mixture according to DT-AS 1 047 615, namely 8 percent by weight of an adduct of 1 mol Lauryl alcohol and 8 to 15 moles of ethylene oxide and 0.8 percent by weight of tetradecyl sulfate

contained. Each protective layer contained an additive to ensure an even layer application and a second to harden the layer. The film samples were stored at 20 and 50% relative humidity conditioned and by standard electrode method examined for their electrical conductivity. The results are shown in Table III.

Table III

sample

Control*)...

1

2

3

4th

*) Without addition.

Surface resistance
in 10 ⁵ megohms / cm ²

20% R.F. '22, 2 ° C

1000+

1000+

130

1000+

50% R.F./22.2 ° C

50

35
5

3.5
200+

• 5

20th

In order to test the photosensitive film samples prepared in this way against static charging, The finger rub test was carried out on each sample at eight different locations. The results are in Table IV compiled.

Table IV

sample without small amount middle strong**) Control*)...
1 2
1
0
8th
0 3
7th
2
0
0 3
0
2
0
0 0
0
4th
0
8th 2 3 4th

*) Without addition.

**) Number of strips without, with low, with medium or high static charge.

From Tables III and IV it can be seen that with the antistatic used according to the invention active connection has the lowest surface resistance. At the Finger rub test proves this sample to be the only one free from electrostatic charge.

Example 5

Samples of a highly photosensitive X-ray film of 70 mm wide were covered with a protective layer provided that in a 2% gelatin solution

1. 20 percent by weight of the acidic phosphoric acid ester, prepared from an adduct of 1 mol Nonylphenol and 6 moles of ethylene oxide,

2. 20 percent by weight of the sodium salt of (1) or

3. a mixture according to DT-AS 1 047 615, namely 8 percent by weight of an adduct of 1 mol Lauryl alcohol and 8 to 15 moles of ethylene oxide and 0.8 percent by weight of tetradecyl sulfate

contained. Each protective layer contained an additive to ensure an even layer application and a second to harden the layer. The film samples became more relative at 44% and 53%, respectively Air humidity is conditioned and its electrical conductivity is checked using the usual electrode method tested. The results are shown in Table V.

Table V

sample

Control*)...

1..

2

3

*) Without addition.

Surface resistance in 10 ⁵ megohm / cm ²

44% R.H. / 22.2 ° C

1000+

120

1000+

53% R.F./22.2 ° C

50

12th

100

The film samples thus obtained were subjected to the finger rub test according to Example 4. The results are summarized in Table VI.

35

Table VI sample without small amount middle strong**) Control*)...
1 2
0 3
2 5
4 · ^: 4th 2 9
0 1
0 0
0 0
10 3

*) Without addition.

* ·) Number of strips without, with low, with medium or high static charge.

From Tables V and VI it can be seen that with the antistatic used according to the invention active compound produced film sample No. 2 at a relative humidity of 44 and 53% has a surface resistance that is more than a factor of 14 lower than that of the control sample and that only the film sample according to the invention is free from static charge.

When example 5 is repeated using the potassium instead of the sodium salt of the phosphoric acid ester essentially the same result as in example 5 is obtained.

Example 6

As in Example 4, samples of a highly photosensitive X-ray film with a protective layer were made provided that in a 2% gelatin solution 20 percent by weight sodium sarcosinate salt of an acidic Phosphoric acid ester made from an adduct of

1. 1 mole of nonylphenol and 4 moles of ethylene oxide

2. 1 mole of nonylphenol and 6 moles of ethylene oxide or

3. 1 mole of nonylphenol and 30 moles of ethylene oxide.

contained. Each protective layer also contained a casting additive and a hardening agent. The film rehearsals were conditioned for 24 hours at 50% relative humidity and 22.2 ° C. and checked for their surface resistance examined. The results are shown in Table VII.

509 634/247

Table VII sample Control*) 1 2 ... 3 Surface resistance
in tO ⁵ megohms / cm ²
50% RH / 22.2 ° C 10
5
5
5

*) Without addition.

It can be seen from the table that the antistatic effects of those used in accordance with the invention Compounds produced film samples have a significantly reduced surface resistance. The results of experiments according to Example 6 with

the sodium sarcosinate salts of acidic phosphoric acid esters, which are obtained from the adducts of 1 mole of dinonylphenol and 3 (sample 4) or 8 (sample 5) or 15 mol (sample 6) ethylene oxide were produced, are summarized in Table VIII.

Table VIII

sample

Control*)...

4th

5

6th

*) Without addition.

Surface resistance in 10 ⁵ megohm / cm ²

38% R.F./22.2 ° C

7.5 5.5 5 1

Claims (1)

Patent claims: 1. Photographic film with improved electrostatic properties, consisting of a Layer support on which at least one photographic emulsion layer, preferably one Halogen silver emulsion layer. is applied and which in one of its layers has an antistatic contains active compound, characterized in that it acts as an antistatic Compound is a salt of a phosphoric acid ester of the general formula