JPH01255856A - Photographic base - Google Patents

Abstract

PURPOSE:To obviate the film exfoliation of a photosensitive material layer by development processing by incorporating a copolymer of vinylidene chloride, vinyl chloride, vinyl acetate, and maleic anhydride and a polyurethane urea resin into an adhesive layer. CONSTITUTION:The adhesive agent is prepd. by using 40-95wt.% copolymer contg. the vinylidene chloride, vinyl chloride, vinyl acetate, and maleic anhydride, and 5-60wt.% polyurethane urea resin. The copolymer of the vinylidene chloride, vinyl chloride, vinyl acetate and maleic anhyride is preferably the copolymer of 29-80mol% vinylidene chloride, 20-80mol% vinyl chloride, 5-20mol% vinyl acetate, and 0.1-5mol% maleic anhydride. The generation of the film exfoliation of the silver halide photosensitive layer, fogging and spots by development processing is thereby obviated and the image having the good reproducibility of hues, gradations, etc., and excellent sharpness is obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a photographic support that provides excellent images, and in particular, it relates to a photographic support that provides excellent images, and in particular, prevents peeling of the silver halide photosensitive layer, fog, spots, etc. during development processing. Hue, without occurring
This invention relates to a photographic support that provides images with good reproducibility of gradations and excellent sharpness.

(Prior art) Conventionally, transparent plates and films such as TAC, PET, and polycarbonate, which are known as photographic supports, paper,
Synthetic paper, baryta paper or white pigment-containing films, plates and metal plates, such as aluminum plates with anodized surfaces, have a metallic reflective or type 2 diffuse reflective surface. When photographic supports are used, photographs and recording media with excellent gradation reproducibility, hue reproducibility in the case of color photographs, and image sharpness can be obtained.

For example, JP-A/-2103≠6, JP-A-A/-2103≠6, JP-A-A/-2103≠6, patent application Sho+1-it
rroo issue, +/-1trr.

No. 1, Kaikai 67-itrro, No. 2, Kaikai A1-/1r
ro3, opening +/-16rrou, opening +1-it
It is described in No. rroj, JP-A No. 4/-2175973, etc.

Inorganic materials such as natural mica, fish scales, and pearls can be used to provide specular reflection or type 2 diffuse reflection, but in most cases metals such as aluminum, silver, gold, copper, chromium, nickel, platinum, etc. Generally speaking, aluminum is used as the alloy.

However, if a metal less noble than silver is used as a support for a photographic or recording light-sensitive material using a silver halide photographic emulsion, it tends to cause spots if it overlaps before and after development. For this reason, it is known to provide an adhesive layer of thermoplastic resin. However, peeling of the film is likely to occur during the acid treatment or after drying, and when thermoplastic resin is used, it is thin, for example, 0.1 to 100 ml. There is a difficulty in providing a μm layer.

Furthermore, due to long-term aging after development, there is a risk of deterioration of parallel or type 2 diffuse reflection or unevenness of reflection.

(Objective of the Invention) The object of the present invention is to provide a photographic support that does not cause defects such as peeling of the light-sensitive material layer during the development process or before and after the development process, and also to improve the storage stability of the obtained image. The objective is to provide an excellent photographic support.

(Structure of the Invention) An object of the present invention is to provide a photographic support in which an adhesive layer is provided on a metal surface having specular reflection property or type 2 diffuse reflection property. Copolymer containing maleic anhydride ≠ 0 to 1% by weight and polyurethane urea resin! Achieved by using ~boM lid%9.

The copolymer of vinylidene chloride, vinyl chloride, vinyl acetate, and maleic anhydride according to the present invention includes (a) 20 to 10 mol % vinylidene chloride, rb) xo-to mol % vinyl chloride, (C) jN 20 mol % % vinyl acetate, (d)Q,
/~! It is preferable to use a copolymer of mol% maleic anhydride.

If the vinylidene chloride content is less than 20% by weight, the hydrophobicity decreases and the film strength of the adhesive layer when wet becomes weak, which is not preferable.

Furthermore, if the amount of vinyl chloride is less than 1% by weight or more than 10% by weight, the solubility in organic solvents decreases, which is not preferable.

Moreover, if the vinyl acetate content is 20% by weight or more, blocking with the back surface of the support may occur, which is not preferable.

If it is less than 5%, the adhesive layer will not be colored by the developer.

If the amount of maleic anhydride is less than 0.01% by weight, the adhesion and strength to the silver halide emulsion layer will be weakened, which is not preferable.

In addition, the polyurethane urea resin of the present invention has a urethane bond (-N-C-0)> and a urea bond, and a polyvalent incyanate or a prepolymer thereof reacts with a polyvalent hydroxy compound or a polar liquid forming a continuous phase. Insert the resulting resin.

Examples of the polyvalent incyanate or polyvalent incyanate prepolymer used in the present invention include m-phenylene diisocyanate, b-phenylene diisocyanate, 2,1. -tolylene diisocyanate, u, 1
LL-) lylene diisocyanate, naphthalene-/, ≠
-diincyanate, diphenylmethane-≠, ≠'-diisocyanate, 3.3' -dimethoxy-≠, ≠'-
biphenyl diisocyanate, 3. ! '-dimethyldiphenylmethane-Hiro, ≠'-diisocyanate, xylylene-/, Hiro-diincyanate, xylylene-1,
J-Diisocyanate% Hiro, ≠′-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-/, J-
Diisocyanate, butylene/2-diisocyanate, ethyridine diisocyanate, cyclohexylene
/, diisocyanate such as 2-diisocyanate, cyclohexylene-7, Hiro-diisocyanate, p, l.

Triisocyanates such as ≠“-triphenylmethane triisocyanate, toluene-2,≠, 6-dolyisocyanate, polymethylene polyphenylinocyanate,
≠, Hiro'-dimethyldiphenylmethane, 2. λ',j
Tetraisocyanate monomers such as , j'-tetraisocyanate or these polyvalent incyanates are attached to compounds such as polyvalent amines, polyvalent carboxylic acids, polyvalent thiols, polyvalent hydroxy compounds, epoxy compounds, etc. Examples include isocyanate groups -i/one or more remaining in the molecule.

Examples of polyhydric hydroxy compounds include aliphatic or aromatic polyhydric alcohols, hydroxy polyesters, hydroxy polyalkylene ethers, alkylene oxide adducts of polyhydric amines, and the like. For example, catechol, resorcinol, hydroquinone, 7.2-dihydroxy-Hiro-methylbenzene, /, J-dihydroxy-Yo-methylbenzene, 3. ≠-dihydroxy-/-methylbenzene, J, r-dihydroxy-7-methylbenzene, λ, ≠-dihydroxyethylbenzene%/,
3-naphthalenediol, l,! -naphthalenediol, co, 7-naphthalenediol, 3-naphthalenediol, o, o'-biphenol, p, p'-biphenol, /, l'-bi-2-naphthol, bisphenol A% co, co'-bis =(e-hydroxyphenyl]phthane, 2゜2' -bis-[≠-hydroxyphenyl]-isopentane, /, /' -bis-(≠-hydroxyphenyl)-cyclopentane, /, /' -bis-( ≠-hydroxyphenyl)-cyclohexane, 2,
λ′-bis-(Hiro-hydroxy-3-methylphenyl)-propane, bis-(2-hydroxyphenyl)-methane, xylylene diol, ethylene glycol, /,
J-Flopylene glycol, /, Hiro-butylene glycol, l,! -bentanediol, /, A-hebutanediol, l,7-hebetanediol, /, ? -Octanediol, /, /, /-trimethylolpro/cene, hexanetriol, pentanerythritol, glycerin and sorbitol, aromatic or aliphatic polyhydric alcohols, etc. are used.

The hydroxy polyester used is Pit, which is obtained from a polycarboxylic acid and a polyhydric alcohol.

Examples of polycarboxylic acids for hydroxypolyester insect repellents include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, isophthalic acid, terephthalic acid, gluconic acid, and the like. As the polyhydric alcohol, those mentioned above can be used.

Hydroxy polyalkylene ethers are, for example, condensation products of alkylene oxides and polyhydric alcohols. As the alkylene oxide, butylene oxide or allene oxide used to produce the hydroxy polyalkylene ether, and as the polyhydric alcohol, the compounds mentioned above are used.

The alkylene oxide adduct of a polyvalent amine refers to a compound in which seven or more hydrogen atoms in the amine group of a polyvalent amine are replaced with alkylene oxide. Examples of polyvalent amines for producing alkylene oxide adducts of polyvalent amines include aromatic polyvalent amines such as 0-phenyl diamine, b-phenyl diamine, and diamino naphthalene; ethylene diamine; There are aliphatic polyvalent amines such as J--/ropylene diamine, diethylene triamine, and 1,6-hexamethylene diamine. Examples of alkylene oxide adducts include ethylene oxide, propylene oxide, and butylene oxide.

The most typical polar liquid that forms the continuous phase is water, but equivalents thereof, such as ethylene glycol, glycerin, butyl alcohol, octyl alcohol, etc., can also be used.

The ratio of vinylidene chloride, vinyl chloride, vinyl acetate, maleic anhydride copolymer and polyurethane urea resin is a weight ratio of j/J-10/lO, preferably 0/10.
! 0/jO. The ratio of polyurethane urea resin is j
If Ml is less than 1%, the adhesion to the metal reflective surface will be insufficient, and if it is more than 1021%, the adhesion between the adhesive layer and the silver halide emulsion layer will be insufficient.

After the adhesive layer is applied and dried, it is effective to perform pretreatment such as corona discharge, glow discharge, flame treatment, etc. in order to strengthen the adhesion with the silver halide emulsion. Further, a gelatin undercoat layer may be provided before the silver halide emulsion layer.

The adhesive layer of the present invention is in contact with the metal reflective layer on the narrow side of the support base material. It is necessary to apply it extremely thinly and uniformly with a thickness of 1 to 70 μm. If the thickness is less than 0.1 .mu.m, poor adhesion between the metal reflective layer and the silver halide photosensitive layer occurs, and if it is 70 .mu.m or more, it is disadvantageous in terms of cost, and the reproducibility of hue, gradation, etc. decreases.

In addition, as a diluting solvent for the adhesive layer of the present invention, any of ketone-based baths such as MEK and acetone, chlorides such as trichloride, ester-based baths such as ethyl acetate and butyl acetate, and aromatic organic baths such as triol can be used. Particularly preferred is ethyl acetate.

Furthermore, the adhesive layer of the present invention is significantly different from the metallic reflective layer in that it is provided on the upper surface of the metallic thin layer having type 2 diffuse reflective properties, but it is similar to that of JP-A No. 3l-41) O2j
No. Kaikai IA? -/I//I can be applied using the method shown in No.-/I//I.

Specifically, it can be applied by dip coating, air knife coating, curtain coating, -roller coating, doctor coating, wire barcoding, slide coating, gravure coating, reverse coating, etc. .

A support with a specularly reflective or type 2 diffusely reflective surface according to the invention can be found with a thin layer of material that provides a specular reflector when the surface is sufficiently smooth on the support substrate. . For example, the method described in JP-A-67-2103171, No. 1) 00, JP-A 27-/Otsu-r♂01, JP-A-27-2-2 Hiro-r72, etc. is used. Preferably, the metal is F1 Benfurt (F,
Benford) et al. J, Opt, Soc, Amer,
j Volume 2/74L ~/Page IIA (/9 Ko2) Metals such as silver, aluminum, gold, copper, chromium,
Nickel, platinum, etc. and their alloys, such as aluminum/magnesium, aluminum, etc. Further, it is also possible to use a layer filled with the above-mentioned metal powder, natural mica, scale powder, etc., which provide specular reflection among inorganic substances.

The substrate of the support may be one conventionally used as a support, such as plastic film, paper, FLC-paper, synthetic paper, metal plate, etc., or polycarbonate, polystyrene, polyacrylate, polycarbonate, etc., which have excellent dimensional stability. These are plates made of polymers and copolymers such as methacrylate and PET.

Particularly preferably, paper, RC- is good, RC
It can be obtained easily and at a low cost level by laminating the pre-textured aluminum foil of the present invention by using a polyethylene layer of -Beno ξ- in combination with low density polyethylene. Polycarbonate, polystyrene, polyimide resin, and ceramic materials, which have particularly excellent dimensional stability and physical strength, are used for the disk-like recording medium described in Japanese Patent Application Sho t/-2≠R J'73. It will be done.

The support of the present invention can be widely used as a reflective support for photography, and can also be provided with a silver halide emulsion layer for black and white photographic paper and a protective layer thereon. Similarly, a color photographic paper photosensitive material can be prepared by providing two or more light-sensitive silver halide emulsion layers, each of which has a different spectral sensitivity and each contains a different color coupler, for ordinary color photographic paper. I can do it. It is also possible to make color reversal material, direct positive color photographic paper, or direct positive color copy material using the optical fogging method. Further, on this support, red, green, and evening halide containing dyes used in the silver dye bleaching (SDB) method are added to the silver halide grains, which change the molecule t and sensitivity, respectively. A silver emulsion layer can also be provided to produce an SDB type printed photosensitive material. It can also be applied to reflective disk plates, disk films, and recording materials that use silver halide. For more details, please see Tokuhan Shoj/-/41♂02
No., Kaikai A/-161) No. 03, Kaikai j/-1 Arto
p issue and opening 4/-/61) 0! No., Special Application Showa A/-2 Hirori No. 73, Showa 1. /-2! Ri7 Rihiro No., Showa A/-2
7! It can be widely used in photosensitive materials such as those described in No. 72.

It is also possible to provide a mordant layer on the support according to the present invention and to diffuse and transfer the color-developing dye to use it as a material for forming a Buddhist pattern. It can also be used as a material for forming a silver diffusion transfer type silver image by providing a physical development layer as an undercoat layer on the support of the present invention. Also % special public Akira! Tar 3737 and Tokukai Sho! 0-6
! It is also possible to provide an adsorption layer ADL of substances such as No. 230 that have anti-silvering properties or suppress the desilvering action, such as Ooku ions, bromine ions, heterocyclic compounds having a mercapto group, and heterocyclic compounds that have the possibility of producing iminosilver. can.

Further, the photographic support of the present invention is disclosed in U.S. Patent No. ≠.

300.421. Thermal developable photosensitive materials and/or dye-fixing materials (image-receiving material).

(Effects of the Invention) By providing the adhesive layer of the present invention on a metal surface having specular reflection property or type 2 diffuse reflection property, film peeling, fogging, spots, etc. of the silver halide photosensitive layer during development processing can be avoided. The next image can be obtained with no occurrence of image generation, excellent reproducibility of hue and gradation, and excellent sharpness.

(Examples of the Invention) The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.

Examples 7-6 Comparative examples! - Filled with 2% silica with an average particle size of 3 μm as a Hiro base *2! A polyethylene terephthalate film having a thickness of 60 Q angstroms was placed in a vacuum deposition apparatus, and vacuum deposition was performed at a vacuum degree of 1 O-5 torr to form an aluminum deposited film having a thickness of 60Q angstroms on the surface of the substrate.

An adhesive layer having the composition shown in Table 1 was diluted with ethyl acetate and coated on the surface of this vapor-deposited film so that it would have a coating density of 31/m2 after drying, and then dried in an oven at 100° C. for 2 minutes.

Next, the wood made from LBSPxo part and LBKPrOM was refined using a disc refiner to a Canadian freeness of 300CX, and sodium stearate i and o parts, anionic polyacrylamide 005 parts, and aluminum sulfate 1.5 parts. , polyamide polyamine epichlorohydrin Q,! Part, alkyl ketene dimer 〇, and J part were added in the bone dry weight ratio to the wood pulp, and weighed using a Fourdrinier paper machine @/60? /m2 paper was made.

The density is determined by the machine calender F) / , 0? /
It was set to crrt3. After corona discharge treatment of this base paper, low density polyethylene (M'1.=7t/10 minutes, density 0.
A polyethylene resin layer was formed by extrusion coating 239/CX:, ) to a thickness of 30 μm. Next, after corona discharge treatment was applied to the other surface (back surface) of the substrate, high-density polyethylene (MI=lrt/
10 minutes, density 0. ? jOf/CX: , ) was extrusion coated to form a 30 μm thick polyethylene resin layer to produce double-sided polyethylene laminated paper.

Next, apply a two-component polyurethane adhesive with the following composition to the back side (opposite side to the vapor deposition side) of the aluminum vapor-deposited film mentioned above after drying. /m,'' and dried at 10 o 0 c for 2 minutes. The coated surface was combined with the low-density polyethylene side of double-sided polyethylene laminated paper, and heat and pressure bonding was performed at ro 0 c and a pressure of 201 cl/α.

Example of patent application Sho TL-ITRRO 1 on the above-mentioned support
A silver halide emulsion was coated according to the method described in 1. Color photographic paper was obtained.

Silver halide emulsion (1) used in the present invention was prepared as follows.

(1 liquid) (, 2 liquids) Sulfuric acid (/N) ≠ mark (
3 liquid) The following silver halide bath agent (7%) Mikuni H3 H3 (Hori liquid) (J liquid) (6 liquid) Add LH20 tooa:.

(Liquid 7) (Liquid L) was heated to t+', and (Liquid 2) and (Liquid 3) were added. After that, % (Liquid) and (Liquid J) were added simultaneously for 30 minutes. After another 70 minutes, (liquid) and (liquid 7)
were simultaneously added for λθ minutes. After 10 minutes of addition, the temperature was lowered and desilvering was performed. Add water and dispersed gelatin and adjust the pH to 6.
2, the average particle size is 0.41 μm 1 coefficient of variation (standard deviation divided by average particle size: s/d) O
, Ot1 A monodispersed cubic silver chlorobromide emulsion containing 70 mol % of silver bromide was obtained. To this emulsion, add thiosulfuric acid (IJ),
Optimal chemical sensitization was performed.

Next, silver halide emulsion (2) f3 with different silver chloride contents
) (41 was prepared in the same manner by changing the weighting times of the v solution, KBr, NaQ!! of the 6 solutions, and the ≠ solution and j solution as shown in Table 2.

Average grain size of silver halide emulsions (1) to (4),
The coefficient of variation and halogen composition are shown in Table 3.

Table 3 Layers 1 to 7 shown in Table μ were overlaid on each support to obtain a color photosensitive material.

7th layer: silver halide emulsion (4)! Sensitizing dye (a
) was spectrally sensitized by adding F)7 and OxI O-4 mok per mole of AfX. Further, yellow coupler (b) and color image stabilizer (e) were dissolved in a mixed bath with solvent (f), dispersed, and added in predetermined amounts. This was applied as the first layer.

Third layer: silver halide emulsion (3) with green-sensitive sensitizing dye (b)
) as A g X / a per mole, oxio mo,
Spectral sensitization was performed by adding I+/. Furthermore, magenta coupler (h) and color image stabilizer (i) were mixed and dissolved in bath agent (j), dispersed, and added in predetermined amounts. This was applied as the third layer.

5th layer: Silver halide emulsion (2) with red-sensitive sensitizing dye (C
) was spectrally sensitized by adding OxI0 mok per mole of Ag. Further, a cyan coupler (n) and a color image stabilizer (o) were mixed and dissolved in a solvent (f) and dispersed to obtain a predetermined amount of 7 JD. This was applied to form the fifth layer.

Coating liquids were obtained in the same manner for the second layer, the μth layer, the sixth layer, and the seventh layer.

On top of the undercoat layer of the support, the first layer, second layer, 3Ni, ≠ layer, J layer, 6th layer and 7th layer are applied to the predetermined amounts shown in Table 1 by a conventional method. Sample shop/Naishi/fL6
and comparative samples were obtained. (See Table 5) The above sample was
! Using a light source at ≠0, gradation exposure for centometric exposure was performed through three-color analysis filters of blue, green, and red, or exposure was performed for enlargement printing through negative film (1! exposure).

Thereafter, a photographic image was obtained through the steps of color development, bleach-fixing, and rinsing.

Development Prescription A 33a (: Hiro! seconds bleach fixing Prescription A jj'c Hiro! seconds Prescription A 2r ~ 3! r0c / minute 30 seconds color developer human water roo
cc diethylenetriaminepentaacetic acid /, 01 sodium sulfite 0021N, N-diethylhydroxylamine, ≠, 2fI potassium bromide o, ty sodium chloride
/ ,! f-triethanolamine
g', or potassium carbonate
307N-ethyl-N-(β-methanesulfonamidoethylamino)-3-methyl-≠-aminoaniline sulfur 1! l! Hiroshi Shio, Hiroshi Sy, 4”-diaminostilbene-based fluorescent whitening agent (Sumitomo Chemical Whitex4j) 2,0
? Add water 1oooccKO
At H pi(10,,2j bleaching fixer formulation A thiosulfuric ammonium /!0rtd(!
Hiroshiwt%) Na2SO3/ jf NH4(Fe(II[)(EDTA))
! ! ? EDTA-JNa
4′? Glacial acetic acid r, tip
Add water and bring the total volume to 100% (pHj
, ≠) Rinse solution formulation A EDTA-uNa-,2H200, 4tf/add water to make a total of 1000tnl (pHj,
Hiroshi) (a) Night-sensitizing dye! 803H-N(C2H5) 3 (b) Green-sensitive sensitizing dye 80aH-N(C2Hs)a (c) Red-sensitive sensitizing dye (d) Yellow coupler α (e) Color image stabilizer Obtained as above The adhesiveness of the photographic paper was evaluated using the adhesion test method shown below.

Adhesion test method/) Adhesion test during drying before processing After drying the photographic emulsion, attach Toto Mylar tape &31) to the polyester adhesive tape and peel it off instantly.

e) Adhesion test when processing is wet In a wet state, make a square-like scratch with an iron brush on the emulsion surface of the sample after fixing, fixing, and washing with water. Rub it 10 times with a rubber with a load of .

3) Adhesion test when drying after processing: After cutting, fixing, washing with water, and drying, scratches are made on the emulsion surface of the sample with a pen in the form of a square, knit-mylar tape, %3/
Paste 2! 0C! After being left for 2≠ hours under the condition of j%⇠H, the tape was instantly peeled off.

In the above tests /) to 3), those in which the emulsion layer does not peel off at all are grade A, those in which the emulsion layer peels off slightly are grade B, and those in which the emulsion layer peels off but are at the upper and lower limits of practical use are grade 6, which poses a practical problem. Items that peel to a certain degree - are classified as iD class.

Check out the results of the adhesion test! Shown in the table.

As is clear from the results shown in Table 5, it is clear that the adhesion of the silver halide emulsion layer is improved by providing the adhesive layer of the present invention.

Claims (1)

[Claims] In a photographic support in which an adhesive layer is provided on a metal surface having specular reflection property or type 2 diffuse reflection property, the adhesive layer is (1
1.) A photographic support comprising 40 to 95% by weight of a copolymer of vinylidene chloride, vinyl chloride, vinyl acetate, and maleic anhydride; and (2) 5 to 60% by weight of a polyurethane urea resin.