JPS60170848A - Silver salt diffusion transfer image receiving material - Google Patents

Abstract

PURPOSE:To enhance whiteness and to prevent deterioration of transfer density by incorporating a specified amt. of oil-soluble dye in a hydrophilic colloid layer, except the uppermost layer, of an image receiving material having at least two layers. CONSTITUTION:The hydrophilic colloid layer, except the uppermost layer, of a silver salt diffusion transfer image receiving material having at least two layers contains 0.05-5mg/m<2> of an oil-soluble dye, and said [at least two layers] are, preferably, hydrophilic colloid layers, and it is preferable from the view point of preventing the deterioration of transfer density that said hydrophilic colloid layer contg. said dye is one of the image receiving layers located nearer to a support, when the image receiving layers are composed of >=2 layers. As the oil-soluble dye, an anthraquinone type and an azo type are preferred, and visual whiteness can be enhanced without affecting transfer density by issolving them into an emulsion and incorporating the lower layer of the multilayer image receiving layers. This whiteness can be further enhanced by using it together with a fluorescent whitening agent, especially, watersoluble one.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to the treatment of an image receiving material for silver salt diffusion transfer method and/or to the improvement of the whiteness of a white background area after washing with water. More specifically, it relates to a method of improving whiteness by adding a blue tint with an oil-soluble dye.

(Prior Art) Visual whiteness varies depending on individual preference, but it is generally known that bluish white looks whiter than neutral white. The cause of undesirable light absorption on white backgrounds is the yellow tint of natural polymers such as gelatin used as binders, synthetic polymers such as polyvinylpyrrolidone, polyvinyl alcohol, carboxymethylcellulose, hydroxymethylcellulose, and sodium alginate, and the transfer from light-sensitive materials for diffusion transfer. Examples include coloring with sensitizing dyes and anti-irradiation dyes, and dyeing with coloring substances in processing solutions. In order to cancel out the appearance of these colors, inorganic coloring pigments are incorporated into the polyolefin of polyolefin-coated paper as seen in JP-A-33-021 as a means of adjusting the hue of the white background by adding blue tint. Means for adjusting the hue of the surface of a support and JP-A-Shojj-ta 3/! As shown in No. 0, a method is known in which an oil-soluble dye is used in the photographic layer to adjust the hue in the photographic layer. Hue adjustment on the surface of the support involves the complexity of creating different supports depending on the optical properties of the various photographic layers.
Also, extrusion coating of polyolefin is usually 3
The coloring agent must meet the requirements such as having a heat resistance of 30,000 or more, no bleed-out, no sublimation, and good dispersibility in polyolefin. This method has drawbacks such as a narrow range of colorant selection.

On the other hand, in order to avoid the above-mentioned drawbacks, a method of adding an oil-soluble dye to a silver halide photographic material to give it a blue tint is disclosed, for example, in JP-A No. 231JO. The inventors have found that when applied to an image-receiving layer, a decrease in transfer density becomes a problem. To explain this in detail, when putting an oil-soluble dye into the image-receiving layer, the binder of the image-receiving layer is a water-soluble polymer such as gelatin or carboxymethyl cellulose. It is necessary to do so. However, when such a dispersion is introduced into the image-receiving layer, the transfer density of silver decreases, probably because it poisons (inactivates) the physical development nuclei. In particular, when the processing solution becomes fatigued due to running, etc., the concentration decreases markedly.

Therefore, there has been a strong desire for a method of increasing whiteness by introducing an oil-soluble dye into the image-receiving layer of an image-receiving material without lowering the transfer density.

(Object of the Invention) An object of the present invention is to provide an image-receiving material with improved whiteness, and another object of the present invention is to provide an image-receiving material with improved whiteness, and another object of the present invention is to provide an image-receiving material with improved whiteness without reducing transfer density by containing a dye in the image-receiving layer. An object of the present invention is to provide an image-receiving material having the following properties. .

(Structure of the invention) This objective was achieved by the image-receiving material described below.

In an image-receiving material for silver salt diffusion transfer containing at least two layers, an oil-soluble dye is added to a hydrophilic colloid layer other than the top layer at θ, 0r.
An image-receiving material for silver salt diffusion transfer, characterized in that it contains −j■/m 2 .

The above-mentioned "at least two layers" are preferably hydrophilic colloid layers.

Among the above image-receiving materials, when the hydrophilic colloid layer containing an oil-soluble dye has an image-receiving layer of 1.2 or more layers, it is preferable that the image-receiving layer is close to the support.

The oil-soluble dyes of the present invention are anthraquinone-based, azo-based, phthalocyanine-based, oxanol-based, and benzylidene-based dyes, with anthraquinone-based, azo-based, and phthalocyanine-based dyes being particularly preferred.

It is necessary that these dyes substantially exist in the layer to which they are added, and that they do not migrate to other layers or dissolve out during processing or washing with water. The most desirable means for adding such an oil-soluble dye into the image-receiving layer is to dissolve the dye in a high-boiling organic solvent and use it as an emulsified dispersion.

Furthermore, dye dispersions can also be made by latex dispersion or polymer dispersion.

The present invention is to include this emulsified dispersion in a layer other than the top layer of the image-receiving material. When an emulsified dispersion is used in the uppermost layer, the transfer density decreases significantly, but when it is contained in the F layer, the transfer density decreases almost completely. In this way, by making the image-receiving layer multilayer and containing the emulsified dispersion in the lower layer, which is not the uppermost layer, it was possible to visually improve the whiteness without substantially affecting the transfer density.

Furthermore, it is preferable to use a fluorescent brightener in combination as a means to improve whiteness.

Fluorescent brighteners include oil-soluble brighteners and water-soluble brighteners. These brighteners must have the property of not being washed out during processing or washing with water, similar to oil-soluble dyes.

In the case of an oil-soluble brightener, the preferred method for incorporating it into the image-receiving layer is to dissolve it in a high-boiling organic solvent and use it as an emulsified dispersion, as in the case of dyes; Addition to the top layer results in a decrease in transfer density. Therefore, it is preferable to put it in the lower layer. In the case of water-soluble brighteners,
Although it can be incorporated into the image-receiving layer in the form of an aqueous solution, it may be eluted during processing or washing with water, resulting in changes in whiteness and reduction in transfer density. For this reason, it is preferable to use it in combination with polyvinylpyrrolidone. The average molecular weight of polyvinylpyrrolidone is 10,000 or more, particularly preferably 10,000 or more. If the average molecular weight is lower than this, the water-soluble brightener may flow out during processing or washing, or the water-soluble brightener may not interact with polyvinylpyrrolidone and exist in a free state, poisoning the physical development nuclei. This is because the transfer density may be lowered.

At least two image-receiving layers may be used in the present invention.

The type, amount and density of physical development nuclei per unit area may be changed for each layer. Furthermore, the type and combination of binders may be changed for each layer.

Typical examples of oil-soluble dyes used in the present invention are shown below.

D-≠ S U a Na S Oa Na -j 2H5 -7 -1r The mixture of the j and 2 -10 803N a 1Ill! , Z Q ρ - Handle 1 ρ ρ - Sheep/tsuko ○ Kokotsu σ Mouth rope ,. Shameda cp% 5 \ 1 1 ρ p The purpose of the dye used in the present invention is to adjust the hue of the white background of the image-receiving material, and it should be selected so that it looks the whitest visually, depending on the hue of the white background. Even if a blue dye or the like is used alone, the absorption characteristics can be adjusted by using two or more of ζ such as a red dye, a green dye, or a blue dye, if necessary. The dye content is actually determined by the type of photographic layer and the type of processing, and is not particularly limited, but is usually 0.03η to 3m9/m.
It is preferable that it is 2.

The method for preparing emulsions of these oil-soluble dyes is covered by the British patent io7.
There is a method in which a fluorescent brightener is dissolved in a high boiling point organic solvent such as λli No. 13, and this is emulsified and dispersed in a hydrophilic colloid such as gelatin together with a surfactant.

As a high boiling point organic solvent, US Patent λ, 3 here, 017
No., J, J7A, No. 137, J, 77? .

No. 7tj, West German patent 1. /32. A10, British Patent 1
．． Phthalate esters and phosphate esters such as those described in JP-A No. 27, ZTI, JP-A No. 53-732θ, JP-A No. 11017, JP-A-J-37376, etc. are generally used. It can be used, but is not limited to these, for example, U.S. patents j, 4'/j, and ri2.
Amide compounds and benzoic acid esters disclosed in No. 3,
Substituted graphenes can also be used advantageously.

Any water-soluble fluorescent brightener used in the present invention can be used as long as it has the property of emitting purple to blue fluorescence when it absorbs ultraviolet light.

Direct dyeing fluorescent brighteners such as stilbene derivatives, diphenyl derivatives, henzidine derivatives, induoxazole derivatives, and benzimidazole derivatives are known, and these known fluorescent brighteners are preferably used in the present invention. In particular, compounds represented by the following general formulas CI) to (l[[) are preferably used.

General formula CI) 1A2 [wherein A□ and A2 each represent a hydrogen atom, a lower alkyl group, a hydroxyl group, a carboxyl group or a salt thereof, or a sulfonyl group or a salt thereof, and Bo
and B2 are each a hydrogen atom, 4 (B3 and B4 are each a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted lower alkoxy group, an aryloxy group, a heterocyclic group, a lower alkylthio group, an arylthio group, a thiohetero cyclic group, amino group), =NHCOBs group (B5 represents a substituted or unsubstituted lower alkoxy group, aryl group, aryloxy group, heterocyclic group, lower alkylthio group, thioheterocyclic group, or amino group, respectively. ), B6 (Y and Y2 each represent a group of nonmetallic atoms necessary to form a substituted or unsubstituted aromatic ring, and B6
represents a hydrogen atom or a substituted or unsubstituted lower alkyl group. ). ] General formula (11) [wherein C0 and C2 each represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a sulfonyl group or a salt thereof, or a carboxyl group or a salt thereof, and Dl and D2 each represent Substituted or unsubstituted diphenyl group, α-naphthyl group, β-naphthyl group, a group or a salt thereof, or a carboxyl group or a salt thereof, D4 is a hydrogen atom, ), a rogen atom, a lower alkyl group, or a lower alkoxy group , D5 represents a hydrogen atom or a lower alkyl group. ). ] General formula ([[l) [In the formula, Eo, E2, E3 and E4 are each a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group or a salt thereof, a sulfonyl group or a salt thereof, or each is substituted or unsubstituted represents a lower alkyl group or a lower alkyl group #7, and Z□ and Z2 each represent a group of nonmetallic atoms necessary to form a substituted or unsubstituted aromatic ring. ) Among the compounds of general formula (1), compounds represented by the following formulas (IV) to (V) are preferred.

:C! C) 0 1 111 11 As the water-soluble fluorescent brightener, a compound represented by the general formula (IV) is particularly preferred.

Specific examples of the water-soluble fluorescent brightener used in the present invention are listed below, but the invention is not limited thereto.

Sails too ＼　） Be 1 fart ) '1.

Technique Sword Pi"1 枳もI'l1v1 < 1 1 Csu(- 呵 Ball fT1 ~ 4'l dan~ Do-fri r咋も＼ 1 ＄ ＄ 呵 vine84＄ ＄ $ ＄ ＼2/ These Water-soluble fluorescent brighteners are well-known compounds in the dyeing industry, and their synthesis can also be found in, for example, Hiroshi Horiguchi's "Line Theory Synthetic Dyes" (Sankyo Publishing), Special Publication No. 4 Zj-/yirr, No. 11.
6-2091! No. uA-, No. 222Ot and No. ≠
This can be easily carried out according to the method described in Japanese Patent No. 8'-3,2943.

Also, some of these compounds are commercially available,
For example, Whitex PA Conc manufactured by Sumitomo Chemical Co., Ltd.
Same BF conch, same BO conch, same BK, same BB, same BR
F, 3B, BN Conch, SF Conch, BWB,
The same FLG, the same RP, etc., the Nippon Kayaku ■Kayahole B Conk, the same FB Conk, the same jB8. Same As conch, same A conch, same CR conch, same PAS conch, same SN, same BR, same PS.

Mika White ATN Conch, ACR Liquid, KT
N Conc, etc., Keikoru BB made by Nisso Kako ■.

1i'i] BI, BU1 BZ, BA, 11iQ
BX, same B A1 same J] 3L, same PAN, etc., Mitsui Toatsu Chemical ■ Mikehoar BS Conch, same BA Conch, 4 B X
% Same BP Conch, Same BI Conch, Same BM Conch, Same B
E Conch, same BN, same MX Conk, same I also FA Conk, etc., Showa Kagaku Hatsukor BX Conk, same H1 same sp, same SN, same A, E, same AF, same WG, etc., Ciba Geigy Chino Pearl M8P, 8'lL'P and the like can be used as the water-soluble fluorescent brightener of the present invention.

The water-soluble fluorescent whitening agent is preferably 2η~200~/rn2
It is particularly preferably used in the range of IO■ to 300■/
Used in m.

Preferred oil-soluble fluorescent brighteners for use in the present invention include substituted stilbenes, substituted coumarins, and those described in British Patent No. 7Ji, No. 234; Substituted thiophenes such as those described in Japanese Patent Publication No. 4TJ-37376, Japanese Patent Application Laid-open No. 30-1988, and No. 2J77 are particularly advantageously used. can.

If the amount of fluorescent brightener used is too small, the effect of improving white embryos will not be sufficient, and if it is too large, so-called blooming will occur in areas of high image density, resulting in a decrease in the apparent image density.

The luminous efficiency of fluorescent light varies depending on the type of fluorescent brightener, the type and concentration of oil used for emulsification, the coexistence of various quenching substances, and the coexistence of other ultraviolet absorbing substances, so it cannot be expressed uniformly. The fluorescent whitening agent used in the invention is 2■~200~
/m2 is preferably used in the range of ioη~3
It is most preferable to use a range of 00 μm/m 2 .

The ratio of emulsifying oil to fluorescent brightener is selected and used at an optimal value from the viewpoint of solubility and concentration quenching of the fluorescent brightener.

(Operations and Effects of the Invention) By employing the structure of the present invention, that is, by containing a relatively small amount of oil-soluble dye in the hydrophilic colloid layer that is not the uppermost layer, the transfer density can be effectively maintained without lowering the transfer density. Visual whiteness is obtained. This whiteness is further improved when a fluorescent brightener, especially a water-soluble fluorescent brightener, is used in combination with the above-mentioned oil-soluble dye.

(Example) Example 1 A coating solution consisting of gelatin containing metal palladium cores and carboxymethyl cellulose (1A:/) was divided into 7 parts.
One was used as a coating solution for the lower layer, and three types were prepared by adding an emulsion prepared as described below.

The other seven coating solutions were used as they were for the upper layer.

On one side of a /109/m2 paper support coated on both sides with polyethylene, the above coating solutions for the lower layer and upper layer were applied so that the dry weight of gelatin was 117 m2, respectively, to obtain an image receiving material having two image receiving layers. were produced and designated as AXB and C.

For comparison, the coating liquid for the upper layer and the coating liquid for the lower layer (sample A
(for the lower layer) was coated on the paper support in a single layer so that the dry weight of gelatin was 22/m 2 to prepare two types of image-receiving materials, designated as D and E, respectively.

On the other hand, on a paper support of the same type as the image-receiving material, 0.2197 m of car 8-bone black and 0.197 m of hydroquinone and 0.2 f/m were used to prevent nolation.
Then, a gelatin layer (gelatin≠, θf/m2) containing Kudimethyl-7-phenyl-3-pyrazolidone was placed on top of the gelatin layer, and 6 tablespoons of 0.3 μ of average p6 was added on top of the gelatin layer (gelatin≠, θf/m2). A light-sensitive material was prepared by providing an ortho-sensitized gelatin silver chlorobromide emulsion layer containing 2.097 m2 of phosphoric acid (2 moles).

[Method for preparing dye emulsion]

Dye compounds shown in specific examples D-4, CO V, cresyl phosphate 100 stomach 1 and ethyl acetate! 100 g of an aqueous cotigelatin solution containing 7 y of dodecylbenzenesulfonic acid as a solid content dissolved in Oml and about 6 oz.
The mixture was mixed at 0C, and an emulsified dispersion was prepared using a homogenizer, which was designated as emulsion X. Dye compound D-1. D-
Similarly, emulsions were prepared for Y and Z respectively.

〔process〕

This light-sensitive material was exposed to light using a continuous tone wedge for sensitometry, and the image-receiving surface of the image-receiving material and the emulsion surface of the light-sensitive material were brought into contact with each other, and a processing composition for silver salt diffusion transfer having the following composition (
After passing through a squeezing roller (liquid temperature -13°C),
Peel off both materials in seconds, wash the image-receiving material with water for 1 minute,
Transmission density of sample after drying (l of transferred image excluding support) m
From the measurement table, it can be seen that if the dye emulsion is included in the sensitive material, the transfer density will not decrease if it is placed in the lower layer.

Diffusion transfer treatment composition H2Q l' 00 m1 Na PO-iko H207zy 4 Na 2so3 tAOf KBr O9! V Na2s203 202 /-phenyl-j-mercabutotetrazole 70m9 N-methylamine ethanol 1Oy at H20 /l Patent applicant Fuji Photo Film Co., Ltd. Procedural amendments Commissioner of the Patent Office 1, Indication of case Showa J. Application No. 27, 41 No. 2, Title of the invention: Receiver for salt-recording diffusion transfer 1 House material 3, Relationship with the person making the amendment Case Patent applicant Location: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52)
0) Tomijugo Shin Film Co., Ltd. 4, Subject of amendment The description in the "Detailed Description of the Invention" column 5 of the specification and the "Detailed Description of the Invention" section of the description are amended as follows: do.

(1) In the structural formula of page 2 1)-7 " and correct it.

(2) Place the first line on the third line of the page. "Sulfonyl group" "Sulfonic acid group" and correct it.

(3) ≠ line from the first artist "Sulfonyl group" "Sulfonic acid group" and correct it.

(4) 3rd line from the bottom of page 120 "Sulfonyl group" "Sulfonic acid group" and correct it.

(5) Refer to page μ, in the structural formula of 7. and correct it.

that's all

Claims (1)

[Claims] In an image-receiving material for silver salt diffusion transfer containing at least two layers, an oil-soluble dye of 0.03% is added to a hydrophilic colloid layer that is not the top layer.
An image-receiving material for silver salt diffusion transfer, characterized in that it contains -j■7 m2.