DE1267975B - Photographic recording material composed of a polyethylene terephthalate support, an adhesive layer and at least one halogen silver emulsion layer - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

German

G03c

Number:
File number:
Registration date:
Display day:

Class: 57b-l /.

P 12 67 975.3-51
February 14, 1962
May 9, 1968

A problem in the production of photographic films is the adhesion of the hydrophilic To achieve gelatin halide silver emulsion layers on the hydrophobic support. One uses for this purpose, depending on the nature of the support, a specific adhesive layer.

It is, among other things, from the USA patent specification 2,698,239 known that polyethylene terephthalate film advantageously consists of the usual substrate Can replace cellulose esters and polystyrene. The polyethylene terephthalate carrier requires a special one Adhesive layer, because the usual adhesive layers for layers made of cellulose ester or polystyrene here not satisfy.

However, it is difficult to find one which is completely satisfactory for polyethylene terephthalate supports To find adhesive layer. From the Belgian patent specification 604 869 there is an effective adhesive layer known, but this is because of the existing cellulose nitrate layer in the course of the photographic Treatment by some sensitizers strongly stained.

From the German patent specification 971 996 it is known to use a polyester as an adhesive layer Use glycol and terephthalic acid which is soluble in trichlorethylene while in the process the German Patent 941 764 the same adhesive layer an organic polyisocyanate or a organic polyisothiocyanate is incorporated.

The adhesion of the photosensitive emulsion layer to the support, which is useful for photographic Materials obtained according to these patents is, however, available in both wet and wet totally inadequate when dry.

In the German Auslegeschrift 1 019 909 the polyester carrier is superficially treated with chlorosulfonic acid and, if desired, subsequently treated with a primary or secondary amine. This creates however, an undesired cloudiness on the support, and that on top by means of a gelatin intermediate layer The attached emulsion layer is easily detached from the carrier in the baths.

Furthermore, according to the German Auslegeschrift 1 083 121, an adhesive layer made of chlorosulfonated Polyethylene used. With this material, gluing in the wet state is sufficient, there will be but after drying large pieces of emulsion layer from the carrier in the adhesive tape test torn loose.

The invention is based on the object of eliminating these disadvantages and of specifying a pholographic recording material whose analogue photographic recording material consists of
a polyethylene terephthalate support,
an adhesive layer and at least one
Halogen silver emulsion layer

Applicant:

Gevaert Photo-Products N.V.,

Mortsel-Antwerp (Belgium)

Representative:

Dr. W. Muller-Bore

and Dipl.-Ing. H. Gralfs, patent attorneys,

3300 Braunschweig, Am Bürgerpark 8

Named as inventor:

Dr. Lodewijk Felix de Keyser, Mortsel;

Dr. Andre Jan Conix, Antwerp;

Lodewijk August van Dessel, Edegem (Belgium)

Claimed priority:

Belgium 7 December 1961 (41190)

silver emulsion layer, both in dry and in wet state, firmly on a layer support Polyethylene terephthalate adheres.

This object is achieved according to the invention by a photographic recording material, that of a polyethylene terephthalate substrate, an adhesive layer and at least one halogen silver emulsion layer consists and is characterized in that between the support and the emulsion layer one of the following layers composite adhesive layer arranged in the specified order starting from the substrate is:

a) a layer of a polyester soluble in chlorinated hydrocarbons of at least a phthalic acid and at least one aliphatic diol;

b) a layer of a copolymer of styrene and one or more with styrene copolymerizable unsaturated compounds containing at least one carboxylic acid group or a functional group derived therefrom that can easily be converted into a carboxylic acid group

809 548/397

Carry group, it being possible for the mixed polymer of styrene to be present in the polyester-containing layer a) instead of in a separate layer;
c) a gelatin layer.

The polyesters of at least one phthalic acid and at least one aliphatic diol can contain various diols in various proportions. However, it becomes a mixed polyester preferred, which to promote solubility in addition to ethylene glycol units at least 5% neopentyl

contains glycol or 1,6-hexanediol units. Man preferably uses polyester whose molecular weight is at least 45 (X) and whose solubility in 1,2-dichloroethane is up to 10 percent by weight, because the layer is used to achieve good adhesion must be poured from an approximately 10 weight percent solution. To illustrate the influence, the incorporation of neopentyl glycol or 1,6-hexanediol units into the structure of the

ίο polyethylene isophthalate affects solubility, Comparative solubility values are given in the following table:

O
Il
c - Mole percent Viscosity number (i;)
at 25 C in
sym-trachloroethane Solubility in
1,2-dichloroethane
(Weight percent) O
- O - CH, - CH, - O - C - / V- C -
■ "" \ /
O ^v 100 0.15 dl / g 14th CH ₃
- O - CH ₂ - C - CH, - O - C - / V-
ι ■ Ii Λ Γ
CH ₃ O \ /
O
/ \ ii '
- O - CH, - CH, - O - C - / VC-
ii \ J
ο \ / O
ν I!
VC 10
90 0.26 dig 30th O
- O - (CH ₂ ), - O - C- / V- C -
ο \ /
O
-0- (CH ₂ J ₆ -OC-ZV-C-
ON / 90
I.
H) 0.30 dl g ^l
I.
I. ± 20 CH ₃
- O - CH, - C - CH, - O - C - /
- ι ■ ii Λ
CH ₃ O ^ 100 0.26 dl g 25th

The polyesters or mixed polyesters which are suitable for an adhesive layer according to the invention can can be produced in the melt using the classic transesterification and polycondensation methods.

Some manufacturing examples of these polyesters and mixed polyesters follow, although the manufacturing processes the polyester are not the subject of the invention. The viscosity number (>,) is in all cases measured in sym-tetrachloroethane at 25 ° C.

Preparation 1: polyneopentyl glycol isophthalate

A mixture of 128 g of dimethyl isophthalate and 156 g of neopentyl glycol is heated. 21mg zinc acetate, 42 mg of antimony trioxide and 20 mg of butyl orthotitanate to 255 C. The rapidly released Methanol is distilled over through a fractionator and the transesterification is after 2 hours completed. The polycondensation is then carried out

3 hours under a vacuum of 0.5 to 5 mm Hg while one through the melt Passing a stream of pure nitrogen through it. The melt becomes very viscous. (</) = 0.26 dl / g.

The polyester consists of structural units of the following formula:

Production 2: mixed polyester

of isophthalic acid, ethylene glycol (90 mol percent) and 1,6-hexanediol (10 mol percent)

A mixture of 50 g of isophthalic acid and 41 g of ethylene glycol is heated. 2.54 g 1,6-hexanediol, 10 mg zinc acetate and 20 mg antimony trioxide while passing through a moderate stream of nitrogen for 1 hour to 255 C. The melt becomes completely clear.

The water released is then slowly distilled off for a further hour. whereupon '·.> Hour the ethylene glycol excess distillierl. Then you bet the polycondensation continued for 3 hours under a vacuum of 1 to 10 mm Hg. (,,) = 0.30 dl g.

The mixed polyester consists of structural units of the following formulas:

90 ",

O O -O - (CH ₂ I ₂ -O- I. - C- O O -0- (CH ₂ I ₁₁ -O- -c-

10 ""

IO

20th

35

Production 3: mixed polyester

of isophthalic acid. Ethylene glycol (95 mol percent and neon pentyl glycol (5 mol percent)

A mixture of 50 g of isophthulic acid is heated. 41g ethylene glycol. 1.56 grams of neopentyl glycol. 10 mg of zinc acetate and 20 mg of antimony trioxide for 1 hour at 255 ° C. with the water formed in the reaction being distilled over through a fractionation attachment. A very clear solution is obtained after one hour. - ^So The excess ethylene glycol is then distilled off without a fractionation attachment. The condensation of the melt is then continued for a further 3 hours under a vacuum of 1 to 10 mm Hg at 255 ° C.

The mixed polyester consists of structural units of the following formulas: *

55

95 ""

6o Preparation 4: Polyester of isophthalic acid
and neopentyl glycol

A mixture of 29.1 g of dimethyl isophthalate and 41.6 g of neopentyl glycol is heated. 3 mg zinc acetate, 6 mg of antimony trioxide and 6 mg of methyl orthotitanate under a nitrogen atmosphere for 2 hours to 282 ° C., the methanol split off being distilled over through a fractionation attachment. The mixture is then condensed for 4 hours at 282 ° C. under a vacuum of 0.5 to 20 mm Hg. (/, J = OJOdIg.

The polyester consists of structural units of the following formula:

OO CH ₁

Il / \ Il! '

CH,

Preparation 5: polyester of isophthalic acid
and ethylene glycol

A mixture of 50 g of isophthalic acid is heated. 50 g of ethylene glycol, 10 mg of zinc acetate and 20 mg of antimony trioxide for 1 hour at 255 ° C. At the end of the reaction, the solution becomes completely clear. The water formed during the reaction is distilled off for a further hour at 255 ° C. through a fractionation attachment. Then '■> hour distills the Athylenglykolüberschuß from without fractionating. The reaction mixture is then condensed at 255 ° C. for 3 hours under a vacuum of 2 to 10 mm Hg while a stream of nitrogen is passed through. (<_; ) = 0.26 dl g.

The polyester consists of structural units
following formula:

—C — o-

Preparation 6: Mixed polyester and isophthalic acid. Sebacic acid and ethylene glycol

A mixture of 39.8 g of isophthalic acid is heated. 13.8 g dimethyl sebacate. 41 g of ethylene glycol, 10 mg of zinc acetate and 20 mg of antimony trioxide to 255 ° C. After one hour a very clear solution is obtained. The water and methanol released during the reaction are then distilled off for a further 1 hour through a fractionation attachment, and the excess ethylene glycol is distilled off for a further half hour without a fractionation attachment. The condensation reaction in the melt is continued for a further 2 hours under a vacuum of 1 to 10 mm Hg at 255 ° C. (,,) = 0.38dig.

The mixed polyester consists of structural units of the following formulas:

C — O — CH, —C — CH, -

O O

Ii / χ I!

- 5 ° o --C- / VCO- (CH ₂ J ₂ -O--

-C- (CH ₂ J ₈ -CO- (CH ₂ J ₂ -O-

Production 7: Mixed polyester of isophthalic acid, terephthalic acid and ethylene glycol

A mixture of 40 g of isophthalic acid, 11.75 g of dimethyl terephthalate, 60 g of ethylene glycol, 10 mg of zinc acetate and 20 mg of antimony trioxide is heated to 255 ° C. After ¹ 1/2 hours of reaction, the solution is completely clear. Then more are distilled

2 hours at 255 C released water and methanol and then polycondensed under Reduced pressure the reaction mixture further

3 hours at 255 C while passing through a slow stream of nitrogen, the mass always becomes more viscous. (//) = 0.28 dl / g.

The mixed polyester consists of structural units of the following formulas:

for the sensitization of halogen silver emulsion layers which are cast on such adhesive layers were suitable.

20 ",) Examples of such cyanine dyes are below

others mentioned in

a) U.S. Patent 2,231,658; more characteristic Hetero nitrogen substituent:

Il / \ Il
--C- / VCO-CH ₂ -Ch ₂

-0

25th

il

CO-CH ₁ -CH ₁ -O-

-V ο

Production 8: Mixed polyesters of isophthalic acid, terephthalic acid and adipic acid and ethylene glycol

The procedure is as in preparation 7. but the reaction products used are 40 g of isophthalic acid, 5.8 g of dimethyl terephthalate, 4.4 g of adipic acid and 60 g of ethylene glycol. ( _(/ ) = 0.2 dfg.

The mixed polyester consists of structural units of the following formulas:

O O

Il / \ Il

--CY YC - O-CH ₂ -CH ₂ -Of 80 ¹¹ O

C-O-CH, -CH ₁ -O

O O

Ii Il

-C- (CH ₂ J ₊ -CO-CH ₂ -CH ₂ -O-

10 °

50

55

10%

To produce the adhesive layer, a second layer consisting of a styrene copolymer is cast on this first layer. Compared to the cellulose nitrate layer of the abovementioned Belgian patent, the second layer according to the invention shows less resin coloration after treatment in the photographic baths due to the sensitizers present in the photographic silver halide emulsion. Cyanine dyes with hydrophilic nitrogen substitutes are particularly good ^ N- (CH ₂ J _n -COOH

or
^ N- (CH ₂ J ₁₁ -COO

b) German patent specification 929 080; characteristic helero nitrogen substituent:

(CH ₂ J ₁₁ -SO ₃ H] X

₃ H]

or

c) the German Auslegeschrift 1072 476; more characteristic Helero nitrogen substituent:

N - (CH ₂ J ₁₁ - COO (CH ₂ J ₁₁₁ - SO ₃ h] X

^ N- (CH ₂ J ₁₁ - COO - (CH ₂ J ₁₁₁ SO., -

z. B. a dye of the formula

CH ₁ -COO-CH ₁

d) German patent specification 1028 718; more characteristic Hetero nitrogen substituent:

/ N- (CH ₂ J ₁ , - OSO ₃ HJ X
or

^ N- (CH ₁ J ₁₁ -OSO ₃ -u lid

elder German Auslegeschrift 1081311; more characteristic Helero nitrogen substituent:

N - (CH ₂ I ₁₁ - SO ₂ NH - R

ίο

wherein R, a hydrogen atom or an alkyl group means,

j, N - (CH ₂ ) ,, - CO - NH - SO ₂ - R ₁
and
> N - (CH ₂ ) ,, - NH-SO ₂

R ₁

wherein R _{1 is} an alkyl group,
generally:

IO

or) n- SO ₂ N -

or ^ N-NHSO ₂ -

or ^ N- NSO ₂ -

e.g. the dyes of the following formulas:

CH

(CH ₂ J ₄ - SO ₂ - NH - C ₂ H ₅

NS,

H, C

Br

(CH ₂ J ₄ - SO ₂ - NH - CO - CH ₃ C ₂ H

₂ H ₅

Some styrene preparations now follow. The reaction mass is cooled and obtained copolymers that contribute to the formation of this second 40 a precipitate. This precipitate is isolated Layer come into consideration. and dried at 40 to 50 C.

Production 9: mixed poly-styrene / acrylic acid]
(Molar ratio 85/15)

^{192 g of acrylic acid, 111 g of styrene, 1160 cm 3 of} acetone and 4.5 g of azo-bis-isobutyronitrile are placed in a flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet. This solution is heated to 70 ° C. while a stream of nitrogen is passed through it.

The reaction is then continued at 75 ° C. for 6 hours.

Then another 4.5 g of azo-bis-isobutyronitrile are added and the reaction continues 20 hours away.

After the reaction mass has been diluted with acetone, the polymer is precipitated by pour the solution into water. The polymer is isolated at 50.degree. C. and dried.

60

Manufacture 10:
Mixed poly-styrene / maleic anhydride]

In one with a stirrer. Thermometer, reflux condenser and nitrogen inlet is added 850 ^{cm; i} toluene, 42 g styrene, 44 g maleic anhydride and 0.420 g azo-bis-isobulyronitril. The polymerization is carried out for 4 hours at 90 ° C. Preparation 11:
Mixed poly-styrene / acrylic acid / ethyl acrylate]

Into a flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet 238 g of acrylic acid, 1030 g of styrene, 330 g of ethyl acrylate, 1.6 l of acetone and 8 g of azo-bis-isobutyronitrile are added. The polymerization is carried out at 60 ° C. for 24 hours. Then you pour the syrupy mass in about 41% acetone and add about 2 l of water to the mixture while stirring thoroughly. The precipitated polymer is isolated and dried at 30.degree.

Manufacture 12:
Mixed poly-styrene / itaconic acid / acrylic acid]

The procedure is as in preparation 9, but the reaction products used are 32.3 g of acrylic acid, 19.4 g of itaconic acid, 248.2 g of styrene and 3 g of azo-bis-isobutyronitrile, dissolved in 200 cm ^{3 of} butanone.

Production 13:
Mixed poly [styrene / itaconic acid]

The procedure is as in Preparation 9, but 23.8 g of itaconic acid are used as reaction products, 76.2 g of styrene and 0.5 g of azo-bis-isobutyronitrile, dissolved in 1 l of acetone.

801 548 397

The third layer for forming an adhesive layer is that of one of the above-described ones Mixed polymers of styrene layer consisting of a gelatin layer.

The following examples serve to illustrate the invention.

example 1

One wears on a polyethylene terephthalate film a first layer from an 8 percent by weight solution of polyethylene isophthalate in dichloroethane on.

Then a second layer of a solution of the following composition is poured onto it:

Mixed poly [styrene / acrylic acid] " ⁵

(Molar ratio 85/15) 60 g

Acetone 9 (K) cm ³

Methylene glycol KX) cm ³

A third layer of a solution of the following composition is poured onto this layer:

Gelatin 10 g

Water 490 cm ³

Chrome alum 0.8 g

Ammonia 10 cm ³

Ethanol 500 cm ³

A conventional gelatin halide silver emulsion layer is applied to the dry adhesive layer.

The scratch test of the adhesive layer obtained shows both in the dry and in the wet State after wetting in the photographic baths a firm adhesion between the Polyethylene terephthalate support and the gelatin halide silver emulsion layer.

Example 2

A solution of the following composition is applied to a support made of polyethylene terephthalate a first layer on:

Polyethylene isophthalate 10 g

Mixed poly [styrene acrylic acid]

(Molar ratio 85 15) 60 g

Acetone 200 cm ³

1,2-dichloroethane 700 cm ³

Ethylene chlorohydrin 100 cm ³

Then one carries out of the solution that in Example 1 as the starting solution for potting the third Layer was used, put a second layer on top.

A silver halide emulsion containing a cyanine dye is poured onto this second layer contains the following formula:

(CH ₂ I ₄ - SO ₂ ~ NH - CO - CH,

After developing such a photosensitive film, in contrast to that in FIG Belgian patent specification 604 869 no staining observed.

Furthermore, this adhesive layer has the same properties as the material described in Example 1 on.

Example 3

On a polyethylene terephthalate carrier. the first layer, as described in example 1, contains, pour a second layer of the following solution:

Mixed poly [acrylic acid styrene ethyl acrylate] (molar ratio 60 20 20) 60 g

Acetone 500 cm ³

Ethylene chlorohydrin 100 cm ³

Butanol. ' 100 cm ³

Isopropanol 300 cm ³

A third layer is then applied from a solution of the following composition:

Gelatin 10 g

Water 480 cm ³

Ammonia 20 cm ³

Chrome alum Ig

Methanol 500 cm ³

Example 4

In the same way as in Example 1, a first is carried on a polyethylene terephthalate support Layer on. This is covered with a second layer of a solution of the following composition.

Mixed poly-styrene itaconic acid acrylic acid]

(Molar ratio 80 10 10) 60 g

Acetone 900 g

Ethylene chlorohydrin 100 cm ³

The layer described in Example 1 is worn as the third layer, and one on top of it Halogen silver emulsion layer on.

Such a photosensitive material has the same properties as that described in Example 1 Material on.

Example 5

Similar to Example 4, a first layer is applied to a polyethylene terephthalate support. This is covered with a second layer of a solution of the following composition.

The carrier thus substituted is treated in the same manner as in Example 1 and has the same properties as the material according to example 2.

Mixed poly [styrc4 itaconic acid]

(Molar ratio 80-20) 60 a

Acetone 900 cm ³

Ethylene chlorohydrin 100 cm ³

A third layer of a solution of the following composition is then poured onto it:

Gelatin 10 g

Water 497.5 cm ^:!

Chrome alum Ig

Ammonia 2.5 cm ^:!

Ethanol 500 cnr ¹

A silver halide emulsion layer is applied to this layer.

Such a subbed photosensitive material has the same properties as that in Example 1 described material.

15th

Example 6

A first layer of a solution of the following is poured onto a polyethylene terephthalate support Composition:

Poly (ethylene isophthalate) 6 g

Mixed poly [styrene maleic anhydride] 2 g

Dioxane 70 cnv ¹

Acetone 20 cm ³

Ethylene chlorohydrin H) cnv ¹

Methacrylate chromium chloride Ig

Then apply a second layer of the following solution:

Gelatin Ig

Water 49 g

Chrome alum 0.0S g

Ammonia 1 cnv ¹

Ethanol 500 cnv ¹

A silver halide emulsion layer is then applied. Such a substituted photosensitive Material has the same properties as the material described in Example 1.

Claims (3)

Patent claims: 1. photographic recording material, that of a polyethylene terephthalate support, an adhesive layer and at least one Halogen silver emulsion layer consists. through this marked that between the substrate and the emulsion layer a composite of the following layers 35 40 applied adhesive layer is arranged in the specified order starting from the substrate: a) a layer of a polyester soluble in chlorinated hydrocarbons of at least a phthalic acid and at least one aliphatic diol; b) a layer of a copolymer of styrene and one or more with Styrene copolymerizable, unsaturated compounds that contain at least one carboxylic acid group or carry a functional group which is derived therefrom and which is easily convertible into a carboxylic acid group, the Styrene copolymer also in the polyester instead of in a separate layer containing layer a) may be present: c) a gelatin layer. 2. Photographic recording material according to claim 1, characterized in that the polyester soluble in chlorinated hydrocarbons is a polyester of isophthalic acid and one or more aliphatic diols, from isophthalic acid. Terephthalic acid and one or several aliphatic diols, from isophthalic acid, one or more aliphatic saturated Dicarboxylic acids in a maximum amount of 20 mol percent, based on the total amount of acid, and one or more aliphatic diols, or of isophthalic acid. Terephthalic acid, one or more aliphatic saturated dicarboxylic acids in a maximum amount of 20 mole percent, based on the total amount of acid, and one or more aliphatic diols. 3. Photographic recording material according to claim 1, characterized in that the second adhesive layer b) consists of one or more of the following styrene copolymers: Mixed poly [styrene acrylic acid], Mixed poly-styrene maleic anhydride]. Mixed poly [styrene acrylic acid äthylacrviat], Mixed poly [styrene itaconic acid acrylic acid] or Mixed poly [styrene itaconic acid]. In consideration of iiezouene publications:
German Patent Nos. 941 764,971,996;
German Auslegeschriften No. 1019909. 1083 121. 809 548/397 4.6 “O Bundesdruckerei Berlin