JPH0364052B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Field of Application) 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. When these polymeric substances are used as supports, it is necessary to firmly adhere a photographic layer made of hydrophilic colloid, mainly gelatin, onto these supports, as they all have hydrophobic surfaces. It is. Surface treatments of hydrophobic supports in conventional techniques attempted for this purpose include (1) chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, and activated plasma treatment. (2) After surface activation treatments such as laser treatment, mixed acid treatment, and ozone oxidation treatment, adhesive strength is obtained by directly applying photographic emulsion. There are two methods: first, and then coating a 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, in order to perform the undercoating method entirely in an aqueous system to obtain sufficient adhesion between a hydrophobic support and a hydrophilic silver halide emulsion for practical use, vinylidene chloride copolymers, diene copolymers, etc. A merger is currently 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 a gelatin derivative to the primed base surface in order to obtain adhesive strength with the photographic emulsion layer. By the way, when applying water as the main solvent for the undercoating liquid, if the coating liquid is left for a long time,
Microorganisms propagate and putrefy, resulting in floating matter in the undercoating solution, which can lead to failures on the coated surface such as repelling and foreign matter adhesion. On the other hand, the subbed support must have antistatic properties. The reason for this is that before a silver halide photographic emulsion layer is applied to a subbed support, handling may cause charging due to peeling from a roller, which may cause uneven coating of the emulsion layer. . Alternatively, if the undercoat base surface remains on the back side or end portion even after the emulsion layer is coated, a so-called static failure may occur due to discharge from there. We have arrived at the present invention as a result of intensive studies aimed at simultaneously solving the above two problems. (Object of the Invention) The first object of the present invention is to prevent spoilage of the undercoating liquid. The second purpose is to impart antistatic properties to the surface of the subbed support. The third objective is to provide an undercoat layer that does not have any adverse effect on the photographic emulsion layer. Fourthly, it is necessary to provide an undercoat layer that does not cause failure of the coated surface due to cissing, foreign matter, etc. (Means for Solving the Problems) These objects of the present invention are to provide a photographic material having an undercoat layer coated on a hydrophobic support with a water-soluble undercoat liquid or a water-dispersible undercoat liquid; This has been achieved by a photographic material characterized in that at least one of the following substances is added to the undercoating liquid. However, R in the above general formula is a hydrogen atom or
Represents C _o +H _2o+1 (n=1 to 20). 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. In the present invention, the undercoating solution provided on the hydrophobic support usually contains a synthetic or natural polymeric substance, although it is not absolutely necessary. The undercoat layer provided on the hydrophobic support may have one or more layers, and the additives (1) to (3) used in the present invention may be added to any of these layers. (1)～
(3) may be added during the synthesis and purification of the polymeric substance, or may be added during the preparation of the undercoating solution. As the synthetic polymer material, copolymers of diene monomers, vinylidene chloride copolymers, acrylic ester copolymers, maleic anhydride copolymers, etc. are preferably used. Synthetic polymer substances are
The structure of the polymeric substance is not particularly limited as long as it is used as a water-based latex emulsion or a water-soluble polymer and the solvent is water. Usually, such synthetic polymeric substances are used as the layer closest to the hydrophobic support, and a silver halide emulsion layer is coated directly on this layer, or a layer such as gelatin is applied on top of this layer. After providing a hydrophilic binder layer, a silver halide emulsion layer is provided. 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 glycidyl 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-hydroxy Ethyl acrylate, 2
-Hydroxypropyl methacrylate, 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. Carbon number selected from 2 to about 8 vinyl or vinylidene compounds. These are conveniently produced by emulsion polymerization methods and are also available commercially. The amount of diene component in this copolymer is about 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, diethylene glycol 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, vinylbenzoic acid, vinylbenzoic acid methyl ester, etc.): Crotonic acids, e.g., crotonic acid, crotonic acid Amides, crotonate esters (e.g. butyl crotonate, etc.) Vinyl kettles (e.g. methyl vinyl ketone, phenyl vinyl ketone, etc.) Olefins (e.g. dicyclopentadiene, ethylene, 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. Examples of water-soluble polymers include gelatin, acylated gelatin such as phthalated gelatin and maleated gelatin, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, grafted gelatin in which acrylic acid, methacrylic acid or amide is grafted onto gelatin, and polyvinyl Alcohol, polyhydroxyalkyl acrylate, polyvinylpyrrolidone, copolyvinylpyrrolidone-vinyl acetate, casein, agarose, albumin, sodium alginate, polysaccharide, agar, starch, grafted starch, polyacrylamide, polyethyleneimine acylate, or acrylic acid, Synthetic or natural hydrophilic polymer compounds such as methacrylic acid acrylamide, N-substituted acrylamide, N-substituted methacrylamide, etc. alone or copolymers, or partial hydrolysates thereof are used. These materials can be used alone or in combination. A preferred hydrophilic polymer is gelatin or a gelatin derivative. The additives (1) to (3) used in the present invention are commercially available products equivalent to Proxel CRL (1) from ICI, Somacide RS (2) + (3) from Somar Industries, and Takeda Pharmaceutical Co., Ltd. You can also use one equivalent to Suraoff 72N (2) from Permakem Asia Co., Ltd., or Topside 800 (2) from Permakem Asia. There is no particular restriction on the amount of these additives added, but they are used in the range of 0.0001% to 10%, preferably 0.001% to 1% in the undercoating liquid. To these, water, methanol, ethylenediamine, etc. can be added as a solvent. In order to apply an aqueous dispersion or solution of a copolymer or homopolymer as an undercoat, the aqueous dispersion is further diluted with water, and if necessary, a crosslinking agent,
Surfactants, swelling agents, matting agents, other antistatic agents, electrolytes, etc. can be added. 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. 3,642,486; 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'. [Test method for spoilability of undercoat liquid] After preparing the undercoat liquid, it was left in a culture cell at 23°C and 50% RH, and the presence or absence of microbial growth and odor were checked after one week. [Evaluation method of antistatic property] The surface electrical resistance of the primed base surface was measured at 23℃65
After standing for 21 hours at %RH, measure under the same conditions. Example 1 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 in an amount of approximately 6 c.c./m ² It was applied using a wire bar coater and dried at 140°C for 1 minute. Next, the first undercoat layer was applied to the opposite side in the same manner. These undercoating solutions were checked for the presence of microorganisms and odor in a culture cell. Next, a 1% gelatin solution was coated on both sides of the first undercoat layer using a wire bar coater at a density of about 10 c.c./m ² and dried at 140° C. for 1 minute.
The antistatic properties of this film were evaluated by measuring surface electrical resistance. Next, a silver halide emulsion layer having the following formulation (1) was coated on one side of each of the eight types of coated films so that the dry thickness was 6.0 μm and the coated silver amount was 5.0 g/m ² . Further, on the silver halide emulsion layer, a protective layer of the following formulation (2) was applied, and on the opposite side, a gelatin pack 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)-
4-methyl-2-tetrazoline-5-ylidene-ethylidene] rhodanine 6 mg/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-dodecylbenzenesulfonic acid sodium 40mg/m ² Prescription - (2) Protective layer formulation gelatin 1g/m m ² Matting agent Polymethyl methacrylate with an average particle size of 3.0 to 4.0 μm 0.05 g/m ² Surfactant Sodium p-dodecylbenzenesulfonate 0.03 g/m ² Gelatin hardening agent 2-Hydroxy-4.6-dichloro-S-triazine. Sodium salt 0.01g/m ² Formulation - (3) Back layer formulation gelatin 5g/m ² Gelatin hardener 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 the protective layer ** Same as the silver halide emulsion layer *** The following dyes (1): (2): (3) )=1:1:1 mixture The eight types of photographic materials obtained were evaluated for adhesion between the film support and the photographic emulsion layer. Composition 1 [] Butadiene-styrene copolymer latex (solid content 43%, butadiene/styrene weight ratio = 32/68) 13c.c. [] 2,4-dichloro-6hydroxy-S-
Triazine sodium salt 8% solution 7 c.c. [] Sodium laurylbenzenesulfonate 1% aqueous solution 1.6 cc [] Distilled water 80 c.c. Composition 2 [] to [] are the same as composition 1 1% methanol solution 1 c.c. [] Distilled water 79 c.c. Composition 3 [] to [] are the same as composition 1 1% methanol solution 0.5cc 1% methanol solution 0.5cc [] Distilled water 79cc. Composition 4 [] to [] are the same as composition 1 1% methanol solution 1 c.c. [] 79 c.c. Composition 5 [] to [] are the same as composition 1 1% methanol solution 1 c.c. [] Distilled water 79 c.c. Composition 6 [] to [] are the same as composition 1 Methanol dispersion 1 c.c. [] Distilled water 79 c.c. Composition 7 [] to [] are the same as composition 1 [] Distilled water 79c.c. Composition 8 [] ~ [] are the same as composition 1 [] Distilled water 79c.c.

[Table] The adhesion between the film support and the emulsion layer and back layer is determined by composition 1 after coating the emulsion, after processing, and in the processing solution.
All cases of 8 to 8 were A class. Example 2 A biaxially stretched polyethylene terephthalate film with a thickness of 100 μm was subjected to corona discharge treatment, and the undercoating liquid of composition 1 of Example 1 was applied in an amount of about 6
It was coated using a wire bar coater at a coating density of cc/m ² and dried at 140° C. for 1 minute. Next, the first undercoat layer was applied to the opposite side in the same manner. Next, a second undercoat liquid having the composition shown below was coated on both sides of the first undercoat layer using a wire bar coater at a coating density of approximately 10 c.c./m ² , and then coated at 140°C for 1 hour.
Dry for a minute. Regarding this second undercoating liquid, the presence or absence of microorganism generation and odor were confirmed in a culture cell. Furthermore, the antistatic properties of these films were evaluated. Next, as in Example 1, a silver halide emulsion layer and a protective layer were coated on one side, and a gelatin back layer was coated on the other side, and the adhesion between the film support and the photographic emulsion layer was evaluated. Composition 1 [] Gelatin 1g [] Distilled water 99c.c. Composition 2 [] Gelatin 1g 1% methanol solution 1c.c. [] Distilled water 98c.c. Composition 3 [] Gelatin 1g 1% methanol solution 0.5cc 1% methanol solution 0.5cc [] Distilled water 98cc. Composition 4 [] Gelatin 1g 1% methanol dispersion 1c.c. [] 98c.c. Composition 5 [] Gelatin 1g 1% methanol solution 1c.c. [] Distilled water 98c.c.

[Table] Note that the adhesion between the film support and the emulsion layer and back layer was A class in all cases of compositions 1 to 5 after coating the emulsion, after processing, and in the processing solution.

Claims (1)

[Scope of Claims] 1. In a photographic light-sensitive material having an undercoat layer coated on a hydrophobic support with a water-soluble undercoat liquid or a water-dispersible undercoat liquid, at least one of the following substances is contained in the undercoat liquid. A photographic material characterized by being added with. However, R in the above general formula is a hydrogen atom or
Represents C _o +H _2o+1 (n=1 to 20).