JPH0364051B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a photographic material, and more particularly to a photographic material having a photographic layer comprising a hydrophilic colloid on a support having a hydrophobic surface. (Prior Art) Conventionally, polyethylene terephthalate, cellulose triacetate, polystyrene, polycarbonate, polyolefin laminated paper, and the like have been widely used as photographic supports due to their excellent transparency and flexibility. However, when these polymeric substances are used as supports, since all of the supports have hydrophobic surfaces, it is difficult to firmly adhere a photographic layer made of hydrophilic colloids, mainly gelatin, onto these supports. is extremely difficult. Surface treatments of hydrophobic supports in conventional techniques attempted to overcome these difficulties include (1) chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, and glow treatment. (2) After surface activation treatment such as electrical discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc., a photographic emulsion is directly applied to obtain adhesive strength. There are two methods, one is to provide an undercoat layer and then coat the photographic emulsion layer thereon. (For example, U.S. Patent Nos. 2,698,241, 2,764,520,
No. 2864755, No. 3143421, No. 3462335, No. 3475193,
No. 3615556, British Patent No. 788365, No. 804005,
No. 891469, etc.). Among these methods, method (2) is more effective and widely used. All of these surface treatments treat the originally hydrophobic surface of the support.
To some extent, surface adhesion is increased by creating polar groups, removing thin layers that are a negative factor for adhesion on the extreme surface, and increasing the crosslinking density on the surface to increase adhesion strength. It seems like something,
This is due to an increase in affinity with the polar groups of the components contained in the undercoat liquid, or
This may be due to an increase in the fastness of the adhesive surface. Various methods have also been used to apply the undercoat layer, such as providing a layer that adheres well to the support as the first layer, and coating a hydrophilic resin layer on top of it as the second layer. There is a gravimetric method and a single layer method in which only one resin layer containing both a hydrophobic group and a hydrophilic group is applied. All of these methods are well researched;
Examples include copolymers starting from monomers selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc., as well as polyethyleneimine and epoxy resin grafts. The suitability of many resins such as gelatin and nitrocellulose has been investigated. In particular, vinylidene chloride copolymers, diene copolymers, are being considered. We have found that a copolymer containing a diene monomer as one component is effective as an undercoat component, either alone or in combination with an appropriate crosslinking agent, as a method for adhering the base and the emulsion layer. I came. (For example, JP-A-51-114120, JP-A No. 54-94025,
(No. 55-65949) It is well known to apply a hydrophilic substance such as gelatin or gelatin derivatives to the primed base surface in order to obtain adhesive strength with the photographic emulsion layer. However, with these methods, if the emulsion layer is left under high temperature and high humidity after coating (e.g. 40℃ or higher),
It has been impossible to obtain sufficient adhesion strength for practical use between a hydrophobic support and a hydrophilic silver halide emulsion (at a humidity of 60% or higher). (Object of the Invention) The first object of the present invention is to improve the adhesion between a hydrophobic support and a photographic emulsion layer even under harsh conditions such as being left under high temperature and high humidity for a long time. . The second is that it forms a uniform film and does not adversely affect the transparency of the film. Third, it provides an undercoat surface with good coating properties for photographic emulsion coating solutions. The fourth objective is to provide an undercoat layer that does not have any adverse effect on the photographic emulsion layer. (Means for solving the problems) These objects of the present invention include an undercoat layer made of a copolymer of engine monomers on a hydrophobic support, and in the undercoat layer, iron is added. , cobalt, nickel, manganese, cerium, copper, and at least one of these ions. Hereinafter, the constituent elements used in the present invention will be explained in detail. In the present invention, hydrophobic supports include, for example, cellulose esters (especially cellulose triacetate, cellulose diacetate, cellulose propionate), polyamides, polycarbonates, polyesters (especially polyethylene terephthalate,
Films made of poly(1,4-cyclohexane dimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate), polystyrene, polypropylene, polyethylene, etc., and these films can be used in other materials such as paper. A composite film formed by coating or laminating on a support. Among them, polyethylene terephthalate film is most preferably used, especially biaxially stretched and heat-set polyethylene terephthalate film.
It is also advantageously used in terms of stability, toughness, etc. There is no particular limit to the thickness of the plastic film support, but a thickness of about 15 to 500 microns, especially about 40 to 200 microns, is advantageous in terms of ease of handling and versatility. Further, the support may be transparent, may contain a dye, may contain a pigment such as titanium dioxide, and may further include silicon dioxide, alumina sol,
It may contain chromium salt, zirconium salt, etc. Copolymers of diene monomers include butadiene,
A copolymer containing a diene monomer having 4 to about 8 carbon atoms, such as isoprene, as one component of the polymer. Copolymerization partners include, for example, styrene, acrylonitrile, acrylic esters, methacrylic esters (methyl, ethyl, butyl, propyl, etc.), vinyl ethers (methyl, ethyl, chloroethyl, butyl, etc.), vinyl esters (such as vinyl acetate, propion). vinyl acid, etc.), glycidyl acrylate, glycidyl methacrylate, allyl glycyl ether, dimethylaminoethyl methacrylate, vinylpyridine, tert-butylaminoethyl methacrylate, acrylic acid,
Methacrylic acid, crotonic acid, itaconic acid, itaconic acid half ester, maleic acid, maleic acid half ester, itaconic anhydride, maleic anhydride, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate Acrylate, 2-hydroxypropyl acrylate, monoallyl ether of polyhydric alcohol, acrylamide, methacrylamide, maleamide, N-methylol acrylamide, N-methylol methacrylamide and its ether, vinyl isocyanate, allyl isocyanate, etc. having 2 to about 8 carbon atoms. vinyl or vinylidene compounds. These are conveniently produced by emulsion polymerization methods and are also available commercially. Also, the amount of diene component in this copolymer is approximately
30 to 60% by weight, preferably 32 to 40% by weight. In addition, the copolymer contains amide, hydroxy,
0.1 monomer with hydrophilic moiety such as carboxy
It can be contained in an amount of about 20% by weight. In addition, examples of the polymeric substance used in the present invention include copolymers or homopolymers having a glass transition temperature in the range of -20°C to 40°C. Examples of monomers used in the synthesis of such copolymers or homopolymers include acrylic esters, acrylamides, methacrylic esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, Examples include vinyl heterocyclic compounds, N-vinyl compounds, styrenes, crotonic acids, itaconic acids, olefins, olefins, maleic anhydride, and the like. Specific examples of these include acrylic acids, such as acrylic acid, acrylates (e.g. ethyl acrylate, butyl acrylate, amyl acrylate, octyl acrylate, 2-butoxyethyl acrylate, chloroethyl acrylate, hydroxyethyl acrylate, cyanoethyl acrylate) , dimethylaminoethyl acrylate, diethylene glycol monoacrylate, trimethylolpropane monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, etc.): Methacrylic acids, such as methacrylic acid, methacrylates (such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, cyanoacetoxyethyl methacrylate, chlorobenzyl methacrylate, ethylene glycol monomethacrylate, 3-hydroxypropyl methacrylate,
2,2-dimethyl-3-hydroxypropyl methacrylate, diethylene glycol monomethacrylate, glycidyl methacrylate, dimethylaminophenoxyethyl methacrylate, phenyl methacrylate, etc.): Acrylamides, such as acrylamide, N
-Substituted acrylamide (e.g., methylacrylamide, ethylacrylamide, butylacrylamide, t-octylacrylamide, benzylacrylamide, dimethylaminoethylacrylamide, phenyl acrylamide, hydroxyphenylacrylamide, dimethylacrylamide, dibutylacrylamide, etc.): methacrylamides, For example, methacrylamide, N-substituted methacrylamide (e.g., methyl methacrylamide, t-butyl methacrylamide, t-octyl methacrylamide, benzyl methacrylamide, cyclohexyl methacrylamide, etc.); Allyl compounds, such as allyl esters (e.g., allyl acetate). , allyl caproate, allyl caprylate, allyl laurate, etc.), allyl exciethanol, allyl butyl ether, allyl glycidyl ether, allyl phenyl ether, etc. Vinyl ethers, (for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, (ethylhexyl vinyl ether, methoxyethyl vinyl ether, chloroethyl vinyl ether, 2-ethyl butyl ether, hydroxyethyl vinyl ether, etc.): Vinyl esters, such as vinyl acetate,
Vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl dimethyl propionate, vinyl ethyl butyrate, vinyl valerate, vinyl caproate, vinyl chloroacetate, etc. Vinyl heterocyclic compounds, such as N-vinyl Oxazolidone, vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, N-vinylcarbazole, N-vinylethylacetamide, etc.: Styrenes (e.g. styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene) , hexylstyrene, cyclohexylstyrene, benzylstyrene, chloromethylstyrene, acetoxymethylstyrene, methoxystyrene, chlorstyrene, dichlorostyrene, 2-bromo-4-trifluoromethylstyrene, vinylbenzoic acid, vinylbenzoic acid methyl ester, etc.) : Crotonic acids, such as crotonic acid, crotonic acid amide, crotonic acid esters (such as butyl crotonate, etc.) Vinyl kettles (such as methyl vinyl ketone, phenyl vinyl ketone, etc.) Olefins (such as dicyclopentadiene, ethylene, etc.) propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, etc.), itaconic acids (e.g. itaconic acid,
itaconic anhydride, methyl itaconate), crotonic acids (e.g. crotonic acid, methyl crotonate),
Sorbic acid, cinnamic acid, methyl sorbate, glycidyl sorbate, citraconic acid, chloroacrylic acid, mesaconic acid, maleic acid, fumaric acid, ethacrylic acid, halogenated olefins (such as vinyl chloride, vinylidene chloride, isoprene, etc.),
Unsaturated nitriles (e.g. acrylonitrile,
(methacrylonitrile, etc.). The copolymer may be a copolymer made of two or more types of monomers. Examples of such copolymers include styrene/n-butyl acrylate/acrylic acid copolymers, styrene/n-butyl acrylate/glycidyl acrylate copolymers, and the like. Next, iron, cobalt, nickel, cerium, manganese, copper and/or ions thereof, which are the main constituents of the present invention, will be described. These substances are preferably added in the form of water-soluble salts. Examples of substances include FeO, Fe(OH) ₂ , FeCl ₂ ,
_FeSO4 , _Fe2O3 , _FeCl3 , _Fe2 ( _SO4 ) ₃ , _NiO , Ni
(OH) ₂ , NiCl ₂ , NiSO ₄ .nH ₂ O (n=0, 6,
7), _Ce2O3 , Ce ₍ OH) ₃ , _CeCl3 , _CeBr3 , _Ce2
(SO ₄ ) ₃・nH ₂ O (n=0, 4, 5, 8, 9, 12),
CeO ₂ , Ce(SO ₄ ) ₂・4H ₂ O, CoO, CoS, CoCl ₂ ,
CoNO ₃ , CoSO ₄ , MnO ₂ , MnSO ₄ , CuO,
Examples include CuSO ₄ and Cu(NO ₂ ) ₂ . There is no particular limit to the amount of these additions, but in the case of FeSO ₄ , the weight ratio is usually 0.01 to the polymeric material.
% to 5%, more preferably 0.16% to 1.6%, and for other substances, the preferable addition amount is such that the weight ratio is equivalent to that of Fe ions. In order to apply the aqueous dispersion of the copolymer thus obtained as an undercoat, the aqueous dispersion is further diluted with water, and if necessary, a crosslinking agent, a surfactant, a swelling agent, a hydrophilic polymer, and a matting agent are added. , antistatic agents, electrolytes, etc. can be added. The content of the copolymer according to the present invention in the undercoating liquid is 1
-20% by weight, especially 2-13% by weight is preferred. Examples of crosslinking agents include U.S. Pat. No. 3,325,287;
No. 3288775, No. 3549377, Belgian patent no.
Triazine compounds described in US Pat. No. 3,291,624, US Pat. No. 3,232,764, French Patent No.
1543694, dialdehyde compounds described in British Patent No. 1270578; US Patent No. 3091537,
Epoxy compounds described in US Pat. No. 49-26580, etc.; Vinyl compounds described in US Pat. No. 3,642,786; Aziline compounds described in US Pat. No. 3,392,024;
Examples include ethyleneimine compounds described in US Pat. No. 3,549,378 and the like; and methylol compounds. Among these compounds, examples of dichlorotriazine derivatives include the following formula:

[Method for evaluating adhesion between film support and emulsion layer]

After emulsion coating and processing (development, fixing, washing)
For the subsequent adhesion test, use a knife to make 6 vertical and horizontal cuts at 3-5 mm intervals, making 5 x 5 squares.
Apply tape to this area, peel it off, and count the number of squares in the peeled emulsion layer. Those with 0 squares are classified as A class, those with 1 to 2 squares are classified as A' class, those with 3 to 4 squares are classified as B class, and those below this are classified as C class. For adhesion test in processing solution, the end of the emulsion coating base was rubbed strongly with fingers 15 times, and the length of peeled from the end was 0 mm was classified as A class, and 1 to 2 mm was classified as A class.
A' class, 2-4mm is B class, below this is C
class. The test was carried out using a plate development method using LDS-715 (manufactured by Fuji Photo Film Co., Ltd.) as a developing solution and LF-308 (manufactured by Fuji Photo Film Co., Ltd.) as a fixing solution. In these evaluation methods, materials that can be used as photographic materials are in classes A to A'. Example A biaxially stretched polyethylene terephthalate film with a thickness of 100 μm was subjected to a corona discharge treatment, and a first undercoating liquid having the composition shown below was applied using a wire bar so that the coating amount was approximately 6 c.c./m ² . It was applied using a coater and dried at 140°C for 1 minute. Next, a first undercoat layer was provided on the opposite side in the same manner. Composition 1 [] Butadiene-styrene copolymer latex (solid content 43%, butadiene/styrene weight ratio = 32/68) 13 c.c. [] 2,4-dichloro-6-hydroxy-s
-Triazine sodium salt 8% solution 7c.c. [] Sodium laurylbenzine sulfonate 1% aqueous solution 1.6cc Distilled water 80c.c. Composition 2 [] to [] are the same as composition 1 FeSO ₄ 1% solution 4.4cc Distilled water 76c.c. Composition 3 [] to [] are the same as composition 1 FeSO ₄ 1% solution 0.8cc Distilled water 80c.c. Composition 4 [] to [] are the same as composition 1 CoSO ₄ 0.044g Distilled water 80c.c Composition 5 [] to [] are the same as composition 1 Ce ₂ (SO ₄ ) ₃ 0.044g Distilled water 80c.c. Composition 6 [] to [] are the same as composition 1 MnSO ₄ 0.044g Distilled water 80c.c. Composition 7 [] to [] are the same as composition 1 CuSO ₄ 0.044g Distilled water 80c.c. On top of the first undercoat layer on both sides above, apply a second undercoat layer with the following composition in a coating amount of approximately 9c.c. The coated film (primed support) was prepared by coating one side and both sides at a coating thickness of .c./m ² and drying. Composition of second undercoat gelatin 1g Acetic acid 0.3cc Distilled water 99c.c. Next, a silver halide emulsion layer of the following formulation (1) was coated on one side of the seven types of coated films to a dry thickness of 6.0μ, coating amount of silver 5.0 It was applied so that it became g/ ^m2 . Further, on the silver halide emulsion layer, a protective layer of the following formulation (2) was applied, and on the opposite side, a gelatin back layer was applied according to the following formulation (3) to a dry thickness of 5 μm.
Various types of photographic materials were produced. Prescription - (1) Silver halide emulsion layer prescription Gelatin 5 g/m ² Silver chloroiodobromide (Cl: 80 mol% Br: 19.5 mol%
I: 0.5 mol%) Chloroauric acid 0.1 mg/m ² Polyethyl acrylate latex (U.S. Patent No.
3525620 Specification Example 3)
1.5g/m ² Sensitizing dye 3-allyl-5-[2-(1-ethyl)-4methyl-2tetrazolin-5ylidene-ethylidene] rhodanine 6mg/m ² Antifoggant 4-hydroxy-6-methyl- 1, 3, 3a-
7-Sotrazaindene 30mg/m ² Polyoxyethylene compound 20mg/m ² Gelatin hardening agent 2-hydroxy-4,6-dichloro-S-triazine sodium salt 60mg/m ² Surfactant p-dodecylbenzenesulfonate sodium
40mg/m ² Prescription - (2) Protective layer formulation Gelatin 1g/m ² Matting agent Polymethyl methacrylate with average particle size of 3.0 to 4.0μ 0.05g/m ² Surfactant Sodium p-dodecylbenzenesulfonate
0.03g/m ² Gelatin hardening agent 2-Hydroxy-4,6-dichloro-S-triazine sodium salt 0.01g/m ² Prescription-(3) Back layer prescription gelatin 5g/m ² Gelatin hardening agent 2-Hydroxy-4 , 6-dichloro-S-triazine sodium salt 0.1g/m ² Matting agent ^* 0.03g/m ² Polymer latex ^** 50g/100g Gelatin dye ^*** 0.3g/m ² * Same as protective layer ** Same as silver halide emulsion layer *** Mixture of the following dyes (1):(2):(3)=1:1:1 The seven types of photographic materials obtained were evaluated for adhesion between the film support and the photographic emulsion layer. The results are shown in Table 1.

[Table] Further, photographic materials 1 to 7 were left for 5 days at 50° C. and 65% RH, and then the adhesion between the film support and the photographic emulsion layer was evaluated. The results are shown in Table 2.

[Table] As is clear from Tables 1 and 2, the photosensitive materials 2 to 7 according to the present invention show good bonding between the support and the emulsion layer even immediately after being prepared and after being exposed to high temperature and high humidity for a long time. It can be seen that the adhesion is extremely good. Further, all of the photosensitive materials according to the present invention had good photographic properties and haze.

Claims (1)

[Claims] 1. An undercoat layer made of a copolymer of a diene monomer is provided on a hydrophobic support, and at least one of nickel, cobalt, manganese, cerium, iron, copper, and their ions is added to the layer. A photographic material comprising: