DE1547721A1 - Use of sulfobetaines as coating aids in the production of photographic layers - Google Patents

Description

• PATENT LAWYERS
Dr.-Imj. Wolff, Bartels, Dr. BrarrV,! Y! Ng. hero
MUNICH 22. Thierschstrasse 8 / III

TELEPHONE 293297 Ree.Nr. 120 366

Eastman Kodak Company, 343 State Street, Rochester, New York State, United States of America

Use of sulfobetaines as coating auxiliaries in the production of photographic layers

In the manufacture of photographic materials, it is known that liquid aqueous coating solutions and Coating compounds applied to a carrier material. For the production of light-sensitive photographic materials, for example, silver halide dispersions, containing gelatin or another polymer as a binder, applied to a film support or paper. Often several layers are applied to a carrier at the same time or one after the other. For example, on a support, apart from a silver halide emulsion layer , for example layers with reflecting pigments, layers with anti-light dye or fiber dyes or sent x to improve the Abrasion resistance and the like are applied «

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Including the application of hydrophilic colloidal binders To facilitate coating aassen on a carrier, it has become known and customary to use the Beschichtuhgsmasscn add surface-active compounds as coating aids. It has been shown that when using such Coating aids the quality and uniformity of the layers applied to the substrate can be significantly improved. With the help of a coating aid Furthermore, the surface hardness, the permeability of the generated Affect layers for aqueous solutions and the like.

A well-known and particularly preferred coating aid is saponin, which is known from the Quillaia bark is won. The naturally occurring saponin, however, has the disadvantage that its composition depends on the batch to batch, for example due to a different extraction process carried out, can be different. Of Furthermore, the saponin obtained from natural products often has the disadvantage that it contains impurities, which the sensitometric properties of the photographic * Adversely affect materials.

In view of the disadvantages described, saponin 909851/1480 is sufficient

especially today, it is not fully compliant with the requirements of high-speed coating processes be placed on a coating aid. So did the use of For example, saponin as an aid to gelling such recently developed coating process problese raised in which several layers at the same time can be applied to a support or layers are applied to an underlayer before the latter has dried up.

The invention was therefore based on the object of providing new coating aids find out which do not have the disadvantages of saponin.

The invention was based on the knowledge that tostinte Sulfobetaines, namely aaaoniuasulfonslurebetaine, excellent Coating aids in the manufacture of photographic products Represent layers.

Accordingly, the invention relates to use of sulfobetaines of Fenia1:

ft

I. R'-N ^§ (CHR ¹ ··), SO, ^θ

R ^H

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where mean:

R is an alkyl or anidoalkyl radical «it I bis

20 carbon atoms;

Rf and R "alkyl, alkenol or polyalkylene glycol

radicals up to 20 carbon atoms, the radicals R, R * and R ″ together not exceeding Have 40 carbon atoms and not more than 6 oxygen atoms;

R " ^{f is} a hydrogen atom, a hydroxyl radical or a

Alkoxy, alkyl or hydroxyalkyl radical with in each case 1 to 4 carbon atoms and

x ■ 2, 3 or 4,

as a layering aid in the manufacture of photographic products Layers"

It has been found that the sulfobetaines used in the invention not only enable the production of particularly uniform layers on photographic supports, but also the coefficient of friction of the surface of the produced Considerably reduce photographic material · It has also been found that those used in the present invention Sulphobetaines old coating aid ·! in advantageous

i,

Use it wherever saponin was previously used could be.

Particularly advantageous sulfobetaines have proven to be those of the following structural formula:

II. R

CH

wherein R is an n-alkyl radical having 8 to 20 carbon atoms or is an amidoalkyl radical having 4 to 20 carbon atoms. as Such compounds have proven particularly advantageous of the specified Poreel II, in which R is the meaning a lauryl, myristyl, cetyl, stearyl or aaidoalkyl radical owns,

According to the invention, sulfobetaines are commercially available, _for example under the names “Sulfobetaines DLH, DMH, OP ₉ DST and CA”, manufacturer Textlien Corporation, USA.

As a particularly distributable layer, I have *

the compounds listed in the following table -909851/1480

proven The compounds all had the formula I,

where R, R ¹ , R '*, and R' * 'and X had the meanings given,

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Tabel link

R »

H I Jf

^C 12 ^H 25 " ^C 12 ^H 2S"

^C M ^H Z9 ~

CHj- CHj- twice hydrogen
atoms and one
CHj group 3 CHj- CHj- ^M. 3 CHj- CHj- Il 3 CHjCH ₂ - CHjCH ₂ - It 3 CHj- CHj- Hydrogen atoms 4th CHj- CHjCH ₂ - What are atomic atoms 4th CHjCHjCHj- CHjCH ₂ CH ₂ - twice hydrogen atoms
and once a CH, group 3 CHj- CHj- Hydrogen atoms 3 CHj- CHj Hydrogen atoms 2 CHjCHj- CH CH ₂ Hydrogen atoms 2

-CH ₂ CH ₂ OCH ₂ CH ₂ OH CHj

two hydrogen atoms one hydroxyl group

0m 7 " ¹ TeCNHCHwCH» - —GH. »CH ^ O (JH-CH-OH CH_

two hydrogen atoms 3 and one hydroxyl group

The sulfobetaines used according to the invention can easily be obtained by reacting a tertiary amine with a Sulton or by quaternizing a tertiary aminoalkylene sulfonate produce according to the following reaction equation:

R ϊ

R »-N + CH, CH,» R'-N®- (

Y 2 Y 2

R ¹¹ CH, SO ₉ R "

RR «-N-CH ₂ CH ₂ SO ₃ Na ♦ CH ₃ - / V-SO ₃ R"-> R · -NScH ₂ CH ₂ SO ₃ ⁸

It has been found that those used in the present invention Sulfobetaines are photographically extremely inert compounds, which is why they are used as coating aids for a variety of photographic emulsions or photographic coating compositions can be used. the Photographic materials prepared using the sulfobetaines used in the present invention are notable due to excellent wettability by developers *

* ■■ · ■■ · .- ,,. 909851/14 80

solutions and other aqueous solutions as well as excellent low coefficients of friction.

By the property, excellent, by aqueous solutions To provide wettable photographic materials, the sulfobetaines used according to the invention differ even

in particular of known anion-active compounds,

such as Natriuanaleopimarat, which in itself also can be used as a coating aid. Although, for example, sodium opiaate as a coating aid zua applying hydrophilic colloid layers to photographic support material at high speeds is very suitable, it has been shown that only layers are obtained when using sodium aleopiaate that are poorly rewettable, d. H. which are poor, for example, in photographic developer solutions let wet »

It has now been found "that" to, if necessary, the inven- '. · dungsgeatfi used sulfobetaines also geaeinsaa ait J anion-active compounds, such as sodium) aaleopiaarat can use «When used at the same time of Natriuaaaleopiaarat and a sulfobetaine after de? invention For example, there is a high surface roughness ait simultaneously achieve excellent wettability «

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The sulfobetaines used according to the invention are suitable as coating auxiliaries not only for applying gelatin-containing coating compositions to photographic substrates, but also as coating auxiliaries for applying coating compositions whose colloidal binder consists of polymers other than gelatine. For example, the sulfobetaines used according to the invention are also suitable as coating auxiliaries for mixtures containing gelatin and another hydrophilic colloid, for example zub application of coating materials that contain copolymers of ethyl acrylate and acrylic acid, e.g. B. ia ratio 4: 1 or mixed polymers of butyl acrylate and acrylic acid, z. B. in a ratio of 9: 1, these copolymers can be used together with gelatin or alone. Such mixed polymers can, for example, also be added to gelatin emulsions to reduce the modulus of elasticity. Further suitable colloidal binders, for the processing of which into photographic layers, a sulfobetaine according to the invention is suitable as a coating aid, are, for example, mixed polymers of acrylic acid and N-substituted acrylic _s ^ aides, as they are, for example, in the French patent,

(o scripture 1 328 889 are described and which are particularly

u " ¹ to increase the opacity of photographic layers

are suitable.

It has been shown that they used the invention Coating Aid «! equally good to apply photo-

graphic silver halide emulsion layers as well such layers are suitable that do not contain silver halide, special top layers, anti-halation layers, Are filter layers, reflective pigment layers, and the like. Due to the excellent wettability that using a coating aid layers produced according to the invention, the layers have excellent permeability for developing solutions.

The sulfobetaines are suitable as coating aids especially with coating processes that operate at high speeds work and according to which multilayer photographic materials are made. Such procedures are for example in British patents 855 849 and 929 905 and in the USA patent 2 751 791.

example 1

"Several photographic materials were produced, by placing a silver halide gelatin emulsion on baryta paper backing and over it a pure gelatin layer was applied * The two layers were applied simultaneously

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applied to the paper carrier.

From the photographic papers obtained, the developer spread, the coefficient of friction and the number uncoated areas (flaws) recorded. The "developer spread" was determined by applying one cm of developer solution onto the photographic paper and measuring the surface area developed over a period of 30 seconds. The results obtained are a measure of the wettability of the material surface. A developer spread of

2 at least 4.0 cm.

A betaine with the following structural formula was used as the sulfobetaine used:

CiI-

t "9

t CIi

From the results compiled in the table below the advantageous properties of the sulfobetaine used according to the invention clearly result.

ORK51NAL INSPECTED

9 0 9 8 5 1 / U 8 n

Concentration of the coating aid in the

wet emulsion in g / kg emulsion

wet top layer in g / kg layer weight

Developer spread

ⁱⁿ cm ²

Coefficient of friction

Coating error per 7000 cni support surface

uncoated areas

Inhomogeneities

co
ο
co

0.0

0.28

0.55

1.1

1.1 1.1 1.1 1.1

16.60 16.60 16.60 16.60

0.25 0.24 0.25 0.26

ο comparison test
without additives

0.0

0.0

3.80

0.47

Comparative experiment
Bit sodium maleopimarate / saponin

dl 7)

0.0

11.0

5.72

0.52

Example 2

The procedure described in Example 1 was followed using of the following sulfobetaines, which consisted of technical products:

A * laurylammonium sulfonic acid betaine;

B ■ myristylamine sulfonic acid betaine;

C «stearylammonium sulfonic acid betaine;

D ■ cetylanmonium sulfonic acid betaine.

The following results were achieved:

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COPY

SuIfο- concentration of the betain coating aid in the

wet emulsion in g / kg top coat emulsion layer in g / kg layer

- 15 -

Develop- ment friction coefficient propagation is efficient
in cn

Viewing errors per 7000 cm support area

unevenly layered places

0.0 Dimensions - ■ · ..'- .: '■■. 0.38 - - A. 0.28 1.1 6.16 0.38 1 1 A. 0.55 1.1 6.16 0.35 1 . 1 A. 0.1 1.1 16.60 0.32 - - A. 0.0 1.1 16.60 0.28 - - B. 0.28 1.1 9.62 0.25 - - B. 0.55 1.1 16.60 0.26 - - B. 1.1 1.1 16.60 0.23 - _ B. 0.0 1.1 16.60 0.19 - C. 0.28 1.1 16.60 0.19 - - C. 0.55 1.1 16.60 0.16 - - C. 1.1 1.1 16.60 0.17 _ C. 0.0 1.1 16.60 0.19 - - D. 0.28 "1.1 16.60 0.18 - - D. 0.55 1.1 H, 60 0.19 1 D. 1.1 1.1 16.60 0.18 D. 1.1 16.60

9 0 9 8 5 1/1 / - * 3 L.

COPY

Two other photographic materials were prepared for comparison, but none in one case Coating aids used and in the other case a mixture of sodium maleopimarate and saponin was used as the coating agent. The results obtained are compiled in the following table:

Concentration of the iintwick friction coating defect Coating aid- efficacy- per 7000 cm carrier-

means in the spread cient

in 2

area

wet lmul-wet
sion in g / kg coating emulsion layer
in g / kg
Layer-

cm

uncoated areas

Inhomogeneities

Dimensions

Comparative sample

Sodium Maleopiraarate /
Saponin
(Ratio: 1: 7)

0.0

4.52

11.1

10.70

0.45

0.48

Example 3

The procedure described in Example 1 was repeated,

90985Ί / £ 80

ORIGINAL INSPECTED

however, this time it was used as a coating finish AcylaraidoaKBonium sulfonic acid betaine used. There were get the following results:

Concentration of the coating aid ■ in the

wet emulsion in g / kg top coat emulsion layer in g / kg layer ■ asse

Develop- Friction Coating defects leraus- coefficient per 7000 cn carrier width cient area ^ln c » ²

uncoated areas

Inhomogeneities

0 1 .1 16.60 0 .19 0 1 "1 16.60 0 , 28 O ₁ 1 "1 16.60 0 »27 1, 1 "1 16.60 0 , 30 Comparative
p death « - 4.15 0 , 58 Natriua-
■ aleopiaa-
rat / saponin
(Relationship
1: 7) O, 11 "O 8.55 0 , 56 .0 , 28 »55 "1 • , 0

A technical product was used in which the acyl residue consisted of fatty acid residues like those in coconut oil occur, i.e. the acyl residue mainly consisted of lauric acid residues.

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Example 4

The process described in Example 1 was repeated, except that mixtures were used as coating aids in this case of sodium maleopimarate and an acylaaidoaanoniuiasulfonsäurebetaine used. The following results were obtained:

* A technical product was used in which the Acyl residue consisted of fatty acid residues as they occur in coconut oil, i.e. the acyl residue mainly consisted of Lauric acid residues.

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Weight ratio
from sodium maleopimarate to acylamido
ammonium sulfonic acid betaine

Concentration of
Coating aid raittels in the

wet emul- wet oversion in g / kg traction layer emulsion in g / kg

Coating layer

Develops frictional coating errors leraus- coefficient per 7,000 cm of support surface

spread cient in cm

uncoated areas

Inhomogeneities

CD
O
CD
OO

10/0
10/0
10/0
10/0

0.0
0.28
0.55
1.1

1.1 1.1 1.1 1.1 4.90

5.72
5.72

0.54 0.56 0.55 0.54

9/1
9/1
9/1
9/1

0.0
0.28
0.55
1.1

1.1 1.1 1.1 1.1 8.55

5.72

8.04

13.90

0.51 0.48 0.42 0.44

4/1
4/1
4/1
4/1

ο, ο

0.28
0.55

1.1

1.1 1.1 1.1 1.1 16.60
13.20
13.90
16.60

0.46 0.41 0.37 0.41

CO I

«M

OO
K) 00
K) O)
K) K) K)
K) K) K) O K) K) K) K)
If) K)
M. O O O O O O* O O
νΟ O O O O O O O O O O
O) O
O) O
Ό O O
Ό 2 O
O) O

Ό LO ΙΛ \ O <OvO <OvO * O

OO LO O ΙΛ w a m * O O O -

to 00 Ld

r «iu)» - o «MLn ^ - O

oo * - ο ο ο · - ο

fs. l ^. t>. is. τ— »- τ— * - KJKJKJK)

CO 1
■ Η O

M «C ♦ *« I C

SSg.

W 3 M

O * OJ

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© -H · Η

> β CX

The results obtained clearly show the advantages of using a sulfobetaine according to the invention with Natriuanaleo at the same time pimarat can be achieved.

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Claims (3)

Claims 1. Use of sulfobetaines from the Foraelt R ^f -N ^§ - (CHR ^Mt ) SO. I X Λ R " where mean: R is an alkyl or aaidoalkyl radical ait I bis 20 C atoa; R 'and R "alkyl, alkenol or polyalkylene glycol radicals ■ it 1 to 20 carbon atoms, where the radicals R, R * and R "do not add up to more than 40 carbon atoms and have no more than 6 oxygen atoms; R "'is a hydrogen atom, a hydroxyl radical or a Alkoxy, alkyl or hydroxyalkyl radical with in each case 1 to 4 C atoms and χ ■ 2, 3 or 4 " as a coating aid in the manufacture of photographic products Layers· 909851 / U80 2. Use of sulfobetaines according to claim 1, characterized characterized in that they correspond to the following formula: CH- • ³ t R - N * - CH ₂ - CH ₂ - CH ₂ - SO ₃ CH ₃ where R has the meaning of a lauryl, myristyl, cetyl » Has stearyl or amidoalkyl radicals, 3. Use of sulfobetaines according to claims 1 and 2 _t characterized in that they are used together with an anionic surface-active compound. 0 9 8 5 1/14 8