DE1813161A1 - Photographic layers containing ultraviolet light absorbing compounds - Google Patents

Description

A Gi rvV- Gi in "'ν'Ά L \ r ·. Ι

LCV! RKUSf.N 1 81 3 ID I

i'iio tofji-iiphicclie ^ :; hin: il.on r.it .irc: i Heh.J. t of ultraviolet Ll ^ ht i'r.u'jrb-i erosion VovM ::, inr: _:: <\

'.uiα invention relates to UV-r; b;: i; ri.:.: rhaJ ti ^ ca ochiohteri for {.photo ^ raphische Materialier ..

Numerous compounds are burned, which then absorb the UV portion of the light and are therefore suitable for the production of UV piIter and UV protective coverings. Such lies lie; are used in the photographic industry to increase the lightfastness of color images. The UV absorbers should be stored in the highest possible concentration in a separate protective layer in order to achieve the highest possible effect. It is generally not possible to use the UV absorbers with the image dyes together in a homogeneous or heterogeneous distribution in one layer, since mutual influence can very often be observed here, which leads to the increased coloration of the image. If possible, the UV absorbers should not be colored, have a high extinction in the UV range and must be as stable as possible .

The UV absorbers can be used in the most varied of ways, for example in water-insoluble binders. The finished color image is produced in a special process

A-G 4--8

009826/1752

ORIGINAL

LMt, ei.;. Er sole;.; =. Ι „.ο; · ¹ ·; υ · "->-;■;".'. j civ ^: ',:. i ,. "^ E.": ·. '\ -Γ ^: ιϊ :.; ίυΐ _-je de: oh only with grp. · ,.: c ν;:;:.;,! ^ ··; · -; .:.!.!.:. ... ·., V; iri ^; ·>: Ι: · ._ 'ί.α: c ^ u ·: α J.3ü- ■ half not all, -jor. iein. aj-./erjüüğ.r. Also the ■ i.1 .'fuyicnoochid storage of v / acöerlöülich.? ::,. uriu water-insoluble ;! UY absorbers in a heat; chi ;; ht eats note :. -! has just been .. Here I -:. special requirements must be placed on the chemical and physical surface of a UV absorber, e.g. 3. It must be in a long, concentrated form in real sizes with a thickness of 1 to 2 μm Can be used without the UV absorber crystallizing out or separating out as oil and leaking out of the layer. A wide variety of UV absorbers have already been used for the present purpose, but none of these compounds satisfies the requirements of practice to a sufficient extent UV absorbers, especially aromatic azines, have been recommended, among other things. However, these generally have a high melting point, so that they are difficult to use because of the associated crystallization tendency. Derivatives of this type, which can be easily incorporated into photographic layers, as described in German Patent 1,182,066, have a slight yellowish intrinsic color, so that they deteriorate the whites of color images. The reason for this lies in the low absorption of light from the visible range of the spectrum.

The invention is based on the object of photographic To develop layers with a content of UV light absorbing substances, whereby the UV absorbers must be easy to incorporate and, if possible, only in the UV range of the spectrum should absorb.

It now became a single layer photographic material found, which contains ultraviolet light absorbing compounds, with compounds of the fol- lowing as UV absorbers

009826/1752

where mean:

E and K ^ = V / b.c ..- 3 er substance, alkyl or alkoxy bin au 13 carbon atoms preferably with bio au 4 C axons, in particular

expanded alkyl or alkoxy groups, in which each

1 ? but at least one of the substituents 2Γ and R "

represents an alkoxy group ';

The following compounds have proven to be particularly suitable

O,

Pp .: 69-71 C

Pp .:

- 89 ° C

rG 438

Pp .: 73-75 C.

- 3 -009826/17 6 2

η P ^υ -Π

^{η υ} 4 "9

Fp.-: 72-74 ⁰ C

Pp .: 71-73

ο ,.

C?

R ₇ ; = Hydrogen or alkyl with up to 5 carbon atoms, especially methyl.

The compounds to be used in the inventive method are produced in a known manner. In the case of compound 1, for example, 4-nitro-1,2-diisopropoxybenaol can be used start out in a known V / ice from 1,2-di-isopropoxy-benzene can be obtained by nitration. The nitro compound is hydrogenated with Eaney nickel and then with diazotized Implemented o-aminophenol in a known manner. You get 4,5-Di-isopropoxy-2-amine-phenylazo-2 (2'-hydroxyphenyl) - 'benzotriazole (Compound 1) takes place in a known manner, e.g. treatment with copper sulfate in methanolic solution in the presence of ammonia. Compound 1 can be recrystallized from propanol.

A-G 438

009 8 26/1752

Mo ti b rl ^ t, η compounds can be enteprocnencei · V / eise yut L er / res * .; e J i t weriif / i. ■

The UV absorbers to be used in the invention have higher than similar known compounds Advantages. The extraordinarily favorable absorption behavior is particularly surprising. The absorption flank drops steeply towards the long-wave area and is down Approximately 10 nm shifted to a short distance compared e.g. with 2 ~ o-hydroxyphenyl ~ benzotriazole UV absorbers, which only contain alkyl groups as substituents.

The UV absorbers are just in the solvents that are used in used as so-called oil formers in the production of photographic materials, particularly soluble. the solution can be easily in the casting solutions for emulsify the layers.

The UV absorbers to be used in the method according to the invention can also be used in combination with other UV absorbers, especially the 2-hydroxyphenylbenztriazo.l series will.

The UV absorbers do not affect the photographic properties of adjacent layers, in particular the Color coupling reaction not slowed down in the case of dissolved color derivatives. Many of the known UV absorbers are disadvantageous in this regard. The molar absorption is extraordinary high, so that the amount of UV absorbers used can be kept relatively low.

The UV absorbers are preferably in the form of their solutions in high-boiling solvents with the aid of a suitable Dispersing device in the goat solutions for the concerned Emulsified layer.

0098267 ^ 7 * 52

The .HisCiiUn:; 3verhali; ilB of. V; V-absorbers to Iciouu- ^ iit ·;,; ,,]. can range between 1: 1 and 1: 0.1 gaits. 'Lnoei kor.n <".·' R.:i ^;. Rigsiedende auxiliary solvent c _o 3." üssigecter, i- ^ e ühylenchlorid alcohols, and mixtures dieaer LosungcMittel ar ^ ov / are completed. The low-boiling lo; - ' ^v mg; -. R.ittel are pergated after the li s with thin-film evaporators. removed in vacuo. Suitable high-boiling compounds which are insoluble in the chemical are, for example, libutyl phosphate, tricresyl phosphate, but preferably higher fatty acids, in particular branched ones with about 10-20 carbon atoms.

The UV absorbers can be the color coupler-containing overhalide] 5 emulsions directly or a gelatin-containing Schutachicht solution be suspended.

The gelatin layers containing UV absorber can be inside of the layer structure of the photographic material Any place, preferably above the dye-containing layers.

The UV absorbers are particularly suitable as the top layer for photographic multilayer materials usual structure.

The concentration of the UV absorber in the layers can fluctuate within wide limits. As a sufficient addition of 10-50 wt. -I "has been found based on the binder of the layer.

When using multilayer color photographic materials, the concentration is chosen so that when exposed to light the stability of the image dyes in the 3 layers is equally good.

The layer thickness of the protective layers containing UV absorbers, is 2-5 nm.

AG 438 - 6- -

009826/1752

BAB ORIGINAL

Υιί.; ΝΛ: I (-I ' uiylicl'iftn i''\ vbr.} ^ If.o: <r ^r : r ■. "Chcj. Yo? ·. · ..Vt-tiv.; *. ^ ·) Ϊ́Λ fru ·· i'ung (xes re; ju ".!.! .Irrcmion rarnbii.:; ■■■; -atf üfiuo Li cm.bojjtandigkeit derhalt rum cine- V orb es ■; <;: · ι . dieoe not Schuta-Bcliichten onthäJt u: :: · .- .; "ver ^ liohön nit dej :: same farnph ;; t; orrr; u j}} aco ior; ^·.!. rial, u , im den Ξ ■;,} ·: gate 4 - TO.

The determination of the SchthuiteverVcaij-erur: ^ is carried out in such a way that the parts are t'clieiltet v. 'With the same color density up to the same bleaching ^ forrad. Saa ratio of required lux hours gives the improvement factor. In addition to the concentration of the UV absorber, the protection rate depends on the thickness of the protective layer. M.

The layers containing UV absorbers are in a dry place Condition completely clear and practically not colored. They survive the photographic processing operation, e.g. Color development process, and are not destroyed. One "No yellowing after prolonged exposure to light is noticeable.

example 1

TO .

1 1 of a 10 gelatin solution used as a wetting agent

50 ml of a 10bigen saponin contains at 5O ⁰ C, a solution

30 g of compound 1

3 g of sulfosuccinic acid bis (2-ethyl) hexyl ester and

15g of a mixture of highly branched aliphatic sheaf acids with 15-19 carbon atoms in

30 g of ethanol and

30 g of methylene chloride
emulsified.

AG 438 - 7 -

009826/1752

löiito CV-Al; ; ^: ; or her is through :: a J-.chr dense a "; IIuto7 'dor

. ". '.. LrcKc'lrcne arictLranhu,!» Rich Jer addition v / ird another 15 i.iru

after ^ orukrt. ■.

The quality of the color photographic images is over eggs? JTjü-rTor -10 "larger than when testing without a UV absorber Protective layer.

1 1 G G 50 ml G 30th a G 3 15th 60 15th

GjL_e BJg now, ^ for UV absorber contained layer:

At 50 ° C., a solution of
the connection 6

Sulphobernsteinsäiire-bis- (2-ethyl) -hexylester and a mixture of highly branched aliphatic carboxylic acids with 15 g - 19 carbon atoms in dimethylformamide and
Methylene chloride
emulsified.

A multilayer color photographic material available on the market is as described in Example 1, coated with the above casting solution. The finished picture is around the pactor 10 more lightfast than untreated photographic material.

Example 3

The procedure is as described in Example 1, however In the casting solution for the layer containing UV absorbers, the genic of branched fatty acids is replaced by the same Amount of dibutyl phthalate replaced.

In this way, equally good results are obtained with appropriate processing.

A-G; 4ÜB - 8 -

—— .. 009826/1752

Claims (1)

1 * rhotographisci-.es material with a layer that ult2 * a ~ Contains violet light absorbing compounds, characterized in that this rail UV absorber of the following Formula contains: where mean: 1 2
R and R = hydrogen, alkyl or alkoxy up to 18 carbon atoms, but at least one of the substituents 1 2
R and R represent an alkoxy group; R = hydrogen or alkyl with up to 5 carbon atoms 2 »Photographic material according to claim 1, characterized in that R and
Represents butoxy group. 1 2 indicates that R and R is a branched propoxy or 3. Photographic material according to claims 1 and 2, characterized in that the UV absorbers are contained in an amount of 10-50 wt .- ^, based on the binder of the layer. 4. Photographic material according to claims 1 - A _t, characterized in that the UV absorbers are contained in the layer as a solution in a higher-boiling solvent in emulsified form. A-G 438. - 9 - 009826/1752