JPH0222652A - Photographic element and production of same - Google Patents

Abstract

PURPOSE:To improve adhesion and water resistance of an image forming layer and the like by irradiating a composition hardenable with activated energy beams containing a prepolymer and a polymerization initiator with said beams at 30-100 deg.C to harden it and to form a protective coating layer. CONSTITUTION:The protective coating layer is formed by irradiating the composition hardenable with activated energy beams containing the prepolymer having at least 2 epoxy groups in the molecule and the polymerization initiator, preferably, such as complex onium salts capable of releasing a polymerization initiative Lewis acid upon irradiation, and hardening it with said beams at 30-100 deg.C. As the prepolymer, a combination of each one kind of aromatic epoxy resin, alicyclic epoxy resin, and aliphatic epoxy resin is used, thus permitting the obtained photographic element to be improved in each of adhesion, moisture resistance, and photographic imaging performance.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to photographic elements having a small number of image-bearing layers on a support and a protective coating, and to a method for manufacturing the same. It relates to a method. More particularly, it relates to a photographic element that is easy to manufacture, has good adhesion to an imaging layer, and has good water resistance. The photographic elements of the present invention find particular use, for example, in authentication identification cards. I can do it.

[Background of the invention]

Traditionally, authentication identification cards, such as employee ID cards, credit cards, driver's licenses, and traffic permits, are so-called ID cards, which are printed with predetermined information such as address, name, and number on the surface of a support plate made of paper, plastic, etc. Generally, bibliographic items (information) are filled in by printing, etc., and confirmation information such as a photograph is pasted to confirm the person, and a tally mark is attached to this. However, conventional devices of this type have a problem in that they are easily tampered with, such as forgery or alteration. In addition, these materials have poor durability against friction (and were often contaminated or damaged while being carried around all the time.In order to improve these defects, recently, silver halide emulsions, etc., are used on supports. A photosensitive material coated with a light-sensitive emulsion is now used, and bibliographic information is printed onto the photosensitive material, as well as a photograph of a person's face printed onto the photosensitive material.Furthermore, the surface of such cards is covered with a resin film. Various methods are known to prevent tampering, such as those that are heat-sealed and those that have both sides of the card laminated with a resin film.However, these cards also require the emulsion side of the photosensitive material and the resin film to be peeled off and tampered with. However, it was not completely tamper-proof, and there was also a risk of discoloration, which caused problems with durability.Furthermore, products that adhere or laminate resin films require the use of thermal welding equipment or laminating equipment. This method requires a complicated device and a complicated process, and as a result, there is a problem that a low-quality ID card cannot be obtained.

As a method for solving these problems, a technique is known in which an active energy ray-curable composition is applied onto the image forming layer and then the composition is cured with active energy rays to form a protective coating layer.

As a method of obtaining a protective coating layer by curing with active energy rays, for example, in order to impart scratch resistance, abrasion resistance, bloom resistance, etc. to the photographic material after image formation, ultraviolet curable protection is applied to the surface of the photographic material. It is known to provide a covering layer.

For example, Japanese Patent Application Laid-open No. 53-57023, U.S. Patent No. 4171
No. 979, No. 4049861, No. 4333998,
JP-A-53-121100, JP-A No. 56-91233,
Publication No. 159-501642, etc. describes a method of coating a composition containing an acrylic prepolymer having an unsaturated group and a polymerization initiator that generates photoradicals and curing it by radical polymerization, and an epoxy resin. A technique for curing using a combination of an acrylic prepolymer, a cationic polymerization initiator, and a radical polymerization initiator has been disclosed. However, although these protective coating layers have sufficient performance in improving the abrasion resistance of projection films and in normal handling of print films, they are completely insufficient when this technology is applied to ID cards. However, the properties required for ID cards, especially water resistance and adhesiveness, cannot be sufficiently obtained.

That is, when trying to use an active energy ray-curable resin as a protective layer on a silver halide photographic emulsion, acrylic polymers generally have problems with adhesion to the emulsion layer, and in some cases an intermediate layer is required. It may become. As a technique to improve this adhesive property, Japanese Patent Application Laid-Open No. 61-20124
No. 8, No. 61-201250, No. 61-201249
No. 61-201251 discloses a method of using an acrylate oligomer in combination with a compound that is reactive or has an affinity for gelatin, but although it is effective in improving adhesion, it is still insufficient. In addition, the photographic performance was not necessarily satisfactory, such as insufficient light resistance. On the other hand, in the case of epoxy polymers, it has been found that sodium sulfite may cause problems in their curing properties.

Examples of using a curable coating layer coated with a composition containing an epoxy resin and a cationic polymerization initiator for ID cards include JP-A-57-90489, JP-A 62-21150, JP-A 62-23042, JP-A No. 62-23042; No. 62-23043, 6
No. 2-24256, No. 62-25758, No. 62-2
No. 29133, but under the various conditions in which ID cards are used, it is not possible to satisfy all of the required adhesive properties, water resistance, pinhole resistance, and stain resistance in the case of scratches.
In order to satisfy all of these requirements using the above technology, a very large curing device is required, and it is difficult to easily produce inexpensive cards.

In addition, as a technology for improving adhesion using acrylate oligomers and epoxy polymers, JP-A-62-2
No. 29133 discloses a technique in which a specific hardening agent is used in a layer adjacent to an ultraviolet-cured layer, and this effect is greater as the amount of hardening agent used increases, but in that case, photographic sensitivity decreases. There is a problem.

[Purpose of the invention]

The present invention was made in view of the above-mentioned problems, and an object of the present invention is to provide a photographic element in which a protective coating layer is formed by curing with active energy rays. Second, the objective is to provide a photographic element that has good adhesion and water resistance, and that provides a satisfactory image without impairing light fastness. The goal is to provide the following. Another object of the present invention is to provide a manufacturing method that allows such photographic elements to be formed easily and inexpensively by irradiation with low-energy active energy rays.

[Means for solving problems]

The object of the present invention is to provide a photographic element having a small number of image-bearing layers on a support and a protective coating layer cured with active energy rays, and a method for producing the same, the protective coating layer comprising: An active energy ray-curable composition containing a prepolymer containing at least two epoxy groups in the molecule and a polymerization initiator activated by active energy rays is cured by irradiating active energy rays at a temperature of 30 to 100°C. This was achieved by taking technical measures.

By the above means, it was possible to obtain a photographic element that has both good adhesiveness and water resistance, and good photographic performance (image), which were difficult to achieve in the past.

The present invention will be explained in more detail below.

Photographic elements according to the present invention have on a support at least one image-bearing layer and a protective coating layer cured with active energy radiation.

Such photographic elements have a small number of image-bearing layers on a support (herein referred to as "image members"). It can be obtained by forming a protective coating layer cured with active energy rays on a photographic material, etc.

The protective coating layer formed on the image member is preferably formed as the layer furthest from the support.

However, an overcoat, another protective layer, a laminate layer, etc. may be formed on the side further away from the support than the protective coating layer, that is, on the outer side.

In the present invention, the protective coating layer of the photographic element is made of an active energy ray-curable composition containing a prepolymer containing at least two epoxy groups in the molecule and a polymerization initiator activated by active energy rays at a temperature of 30 to It is cured and formed by irradiation with active energy rays at 100°C.

As the active energy ray-curable composition for forming the protective coating layer that can be used in the present invention, various active energy ray (for example, ultraviolet rays and other radiation) curable resin compositions can be used. can. Explanation and examples of specific compositions will be given later.

In the present invention, the active energy ray-curable composition is cured at a temperature of 30 to 100°C (indicates a temperature of 30°C to 100°C; the same applies throughout the present specification).

The temperature of the composition at the time of irradiation with active energy rays only needs to be 30 to 100°C, but such temperature control of the composition can be performed, for example, as follows.

(A) The image member is heated prior to applying the curable composition to the image member. For example, an imaging member, such as a developed photographic film comprising a photographic element, is heated prior to applying the curable composition.

As a heating method, for example, the image member may be heated with a heater or the like on a conveyor that conveys the image member to a coater or the like that applies the curable composition, and the temperature may be measured and controlled with an infrared thermometer. can.

(B) Heating the curable composition. For example, it is possible to use means for heating the curable composition in a vat attached to the coater using a heater or the like.

(C) After applying the curable composition, the whole is heated before and/or during irradiation with active energy rays. For example, before the image member coated with the composition is transported to, for example, a UV lamp for irradiation with energy rays, the image member is heated with a heater or the like on the transport conveyor, and measured and controlled with an infrared thermometer or the like. You can take measures.

The active energy ray-curable composition is more preferably cured at a temperature of 40 to 80°C.

The means for temperature control is arbitrary, for example, the above-mentioned (A) to
Although any of (C) may be used, it is preferable that some kind of temperature control (heating) is performed prior to curing with active energy rays, and in particular, temperature control means including the above-mentioned (A) means are preferably used. It is preferable to use for example,(
It is preferable to use means A), a combination of means (A), (B), or (A) and (C), and a combination of means (A), (B), and (C).

In addition, even if the temperature of the composition may fall outside the range of 30 to 100°C during irradiation with energy rays (for example, when the temperature is raised from a state of 30°C or lower while irradiating ultraviolet rays). The invention encompasses any material that can be cured by energy ray irradiation within the temperature range of the invention.

When controlling the temperature by heating, any means that can be used for heating is not particularly limited.

It is desirable to have an apparatus that can uniformly heat the surface of an image member, such as a card, from which a desired photographic element is to be obtained.

For example, the one shown in FIG. 3(a) can be called a convection type, and for example, a space formed around a conveyor 31 serving as a conveying means is partitioned and used as a heating chamber 32. This type uses a heater H provided inside to maintain the indoor atmospheric temperature to a predetermined temperature. In the figure, 33
3 is a conveyance entrance into the heating chamber 32, and 34 is a conveyance exit.

In this configuration, the chamber (heating chamber 32) formed at the location of the conveyor 31 is controlled to the required temperature, and the card-shaped image member C, which is the object to be heated, is heated to the required temperature during the passage time on the conveyor 31. It turns out.

The one shown in FIG. 3(b) can be called a conduction type, in which a material 35 with good thermal conductivity is placed on the heater H before the conveyor is conveyed by a conveyor 31 or the like as a conveying means. The material 35 is controlled to a required temperature, and the image member C, which is an object to be heated, is placed on the material and heated. In this configuration, the material 35 with good thermal conductivity is controlled at a necessary temperature, and the card-shaped image member C is stopped on the heater H for a certain period of time (necessary heating time), and then conveyed to the conveyor 31. become.

The one shown in FIG. 3(c) can be called a radiant type, in which the radiant heat of the heater H is used for heating. For example, as shown in the figure, a heated image member C is placed on a conveyor 31 for conveyance.
When the is located, heat with heater H. In this configuration, as in the case of FIG. 3(a), the necessary temperature of the image member C is controlled by the passage time on the conveyor 31.

In the present invention, when an ultraviolet curable composition is used as the active energy ray curable composition, the light source for the irradiation light in the ultraviolet region (hereinafter also simply referred to as ultraviolet rays) used may include sunlight, a low pressure mercury lamp, a high pressure mercury lamp, ultra-high pressure mercury lamp,
There are carbon arc lamps, metal halide lamps, xenon lamps, etc.

Further, the atmosphere during irradiation with ultraviolet rays may be air or an inert gas such as nitrogen gas or carbon dioxide gas.

The irradiation time of ultraviolet rays to the ultraviolet curable composition that can be used in the present invention varies depending on the type of irradiation light source in the above ultraviolet range, but is approximately 0.5 seconds to 5 minutes, preferably 3 minutes.
It is from seconds to 2 minutes.

Normally, when the irradiation time is short, a large light source with high irradiation intensity is required, and when the irradiation time is long, a light source with low irradiation intensity can be used, but the curing action time becomes longer, which is disadvantageous in terms of the manufacturing process. . However, according to the present invention, 200
Advantageously, the purpose can be achieved with irradiation for 3 seconds to 2 minutes using an ultraviolet generating lamp of W or less.

The above explanation was given using an ultraviolet curable resin composition as an example, but
Other active energy ray-curable resin compositions can also be used in the same manner as above, depending on the properties of each active energy ray and composition.

Such a resin composition can be applied as a liquid resin material onto the outermost layer (for example, an image forming layer) on a support, for example, a strip-shaped support. , the material liquid is applied to a double roll coater, a gravure offset coater, a slit coater, an air knife coater, a wire percoater, a slide hopper,
Conventional methods such as spray coating can be used and can be easily applied to the surface of an image member, for example in the form of a card. Although the coating thickness at this time is arbitrary,
Approximately 0.1μ to 30μ is suitable. Preferably 1 μ to 1
It is 5μ.

A prepolymer containing at least two epoxy groups in its molecule, which is a component of the energy ray-curable composition used in the present invention, is a prepolymer that is irradiated with energy rays in the presence of a polymerization initiator that is activated by active energy rays. It is an epoxy resin that undergoes molecularization or crosslinking reactions. Examples of such resins include conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins, which may be used alone or in combination. In a preferred embodiment of the present invention, one or more of each of an aromatic epoxy resin, an alicyclic epoxy resin, and an aliphatic epoxy resin are used in combination.

Preferred aromatic epoxy resins include polyglycidyl ethers of polyhydric phenols or their alkylene oxide adducts, such as glycidyl ethers produced by reacting bisphenols or alkylene oxide adducts with epichlorohydrin, and epoxy nobodies. Examples include rank resins.

In addition, preferable alicyclic epoxy resins include:
Containing cyclohexene oxide or cyclopentene oxide obtained by epoxidizing a polyglycidyl ether of a polyhydric alcohol having at least two aliphatic rings or a cyclohexene or cyclopentene ring-containing compound with a suitable oxidizing agent such as hydrogen peroxide or peracid. Examples include compounds.

Typical examples of alicyclic epoxy resins include hydrogenated bisphenol A diglycidyl ether, 3゜4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5, 5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene dioxide, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate , 3. 4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-
Methyl cyclohexane carboxylate, methylene bis(3,4-epoxycyclohexane) dicyclopentadiene dieboxide, ethylene glycol di(3,4
-epoxycyclohexylmethyl) ether, ethylene bis(3,4-epoxycyclohexane carboxylate), dicyclopentadiene dieboxide, and the like.

Preferred aliphatic epoxy resins include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts, polyglycidyl esters of aliphatic long-chain polybasic acids, and homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate. Typical examples include glycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, polyglycidyl ether of sorbitol, and polyethylene glycol. Diglycidyl ether of polypropylene glycol, diglycidyl ether of polyether polyol obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohol such as ethylene glycol, propylene glycol, glycerin, etc. , diglycidyl esters of aliphatic long chain dibasic acids, and epoxidized polybutadiene.

The prepolymer containing at least two epoxy groups in the molecule, which is a component of the energy ray-curable composition used in the present invention, may contain monoepoxide or a cationically polymerizable organic substance other than the epoxy resin depending on the desired performance. Can be used in combination.

For example, monoglycidyl ethers of aliphatic higher alcohols, phenol, cresol, butylphenol, or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide to these monoepoxides,
Glycidyl esters of higher fatty acids, epoxidized soybean oil,
Examples include butyl epoxy stearate, octyl epoxy stearate, epoxidized linseed oil, and the like.

Examples of cationically polymerizable organic substances that can be blended include oxetane compounds such as trimethylene oxide, 3,3-dimethyloxetane, and 3,3-dichloromethyloxetane; oxolanes such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran; Compound; cyclic acetal compound such as trioxane, 1°3-dioxolane, 1,3,6-drioxanecyclooctane; β
- Cyclic lactone compounds such as proviolactone, ε-caprolactone; thiirane compounds such as ethylene sulfide, 1°2-propylene sulfide, thioevils chlorohydrin; 1,3-prohylene sulfide, 3.3-
Thiecune compounds such as dimethyl ethane; ethylene glycol divinyl ether, polyalkylene glycol divinyl ether, alkyl vinyl ether, 3,4-dihydropyran-2-methyl (3,4-dihydropyran-
2-carboxylate); spiroorthoester compounds obtained by reaction of epoxy compounds with lactones; vinylcyclohexane,
Ethylenically unsaturated compounds such as isobutylene, polybutadiene and derivatives of the above compounds may be mentioned.

As the polymerization initiator activated by active energy rays, a compound capable of releasing a substance that initiates cationic polymerization upon irradiation with energy rays can be used, and particularly preferred is a compound capable of initiating polymerization upon irradiation. It is a member of the group of double salts, which are onium salts that release Lewis acids.

Typical such compounds have the general formula %) [wherein the cation is onium, Z is S, Se,
Te.

PtAstSb+Bi, O+/'10 gen (e.g. J
, Br, CI), N=N, and R1, R1, R3, R
4 is an organic group which may be the same or different. a,
b, c, d are each integers of 0 to 3, and a
+b+c+d is equal to the valence of 2. The gate is a metal or metalloid (metal 1) that is the central atom of the halide complex.
oid), B, P, As, Sb, Fe+Sn+B
i+AI+Ca, In, Tt+Zn, Sc+
V+ Cr, Mn, Co, etc. X is a halogen, n is the net charge of the halide complex ion, and n is the number of halogen atoms in the halide complex ion. ].

Anion MXfi of the above general formula. As a specific example of 7,
Tetrafluoroborate (BF4-), hexafluorophosphate (PF6-), hexafluorophosphate
(SbF6-), hexafluoroarsenate (AS
F&-) hexachloroantimonate (SbC1&-)
etc.

Furthermore, an anion of the general formula MX, (OH)- can also be used. Other anions include perchlorate ion (C104-), trifluoromethyl sulfite ion (CF3SO3-), and fluorosulfonate ion (FS
Oi-), toluenesulfonate anion, trinitrobenzesulfonate anion, and the like.

Among such onium salts, it is particularly effective to use aromatic onium salts as cationic polymerization initiators, and among them, JP-A-50-151996 and JP-A-50-15
Aromatic halonium salts described in JP-A-8680, etc., JP-A-50-151997, JP-A-52-30899, JP-A-56
-55420, VIA group aromatic onium salts described in Publications No. 55-125105, etc., JP-A-50-15869
VA group aromatic onium salts described in Publication No. 8, etc., JP-A-1989-5
No. 6-8428, No. 56-149402, No. 57-1
Preferred are oxosulfoxonium salts described in Japanese Patent Publication No. 92429, aromatic diazonium salts described in Japanese Patent Publication No. 17040/1983, thiopyrylium salts described in US Pat. No. 4,139,655, and the like. Also included are aluminum complex/photodegradable silicon compound-based initiators.

Such a cationic polymerization initiator can also be used in combination with a photosensitizer such as benzophenone, benzoin isopropyl ether, or thioxanthone.

In the active energy ray curable composition used in the present invention, the polymerization initiator is preferably 0.1 to 15 parts by weight per 100 parts by weight of the energy ray curable prepolymer for boat fishing.
The content is preferably in the range of 1 to 10 parts by weight, more preferably 1 to 10 parts by weight.

The active energy ray-curable composition that can be used in the present invention may optionally include:
Radical polymerizable organic substances other than the prepolymers described above, heat-sensitive polymerization initiators, colorants such as pigments and dyes, antifoaming agents, thickeners, leveling agents, flame retardants, ultraviolet absorbers, antioxidants, etc. Appropriate amounts of various resin additives, fillers, modifying resins, etc. can be mixed and used. Examples of the radically polymerizable organic substance include acrylate resins such as epoxy acrylate, urethane acrylate, polyester acrylate, and polyether acrylate. As a heat-sensitive polymerization initiator, for example, JP-A-57
Examples include aliphatic onium salts described in JP-A-49613 and JP-A-58-37004.

According to the present invention, in order to supplement adhesion, a new undercoat layer is provided between the layer furthest from the support (for example, image forming N) and the protective coating layer that is curable with active energy rays such as ultraviolet rays. There is no need to process the surface of the image forming layer, etc.

The support for the photographic element according to the present invention can be either opaque or transparent, such as paper, laminated paper made by laminating polyethylene on paper, or an electron beam curable composition containing a white pigment on the surface of the paper. A photographic support, a synthetic resin sheet, etc. obtained by coating and curing with an electron beam can be used.

In particular, from the viewpoint of image preservation, the oxygen permeability of the support is 2.0.
ml/rrf-hr-atm or less, more preferably 1. Omj! /m-hr-atm or less is desired. In addition, suitable supports that have appropriate hardness and handleability include plastic films, such as homopolymers and copolymers such as polyester, vinyl alcohol, vinyl chloride, vinyl fluoride, vinyl acetate, etc.
Homopolymers and copolymers such as cellulose acetate, acrylonitrile, acrylic acid alkyl esters, methacrylic acid alkyl esters, methacrylonitrile, alkyl vinyl esters, alkyl vinyl ethers, and polyamides, and films formed by laminating these polymers can be mentioned.

Particularly preferred among these films are polyester, polyester/polyethylene laminated films, and laminated paper. Further, since the oxygen permeability of the polyester film has no humidity dependence, the polyester film has the same oxygen permeability even in humid conditions as in dry conditions, which is preferable.

Further, the support may contain a white pigment to provide reflective properties, or a hydrophilic colloid layer containing a white pigment may be coated on the transparent support.

The white pigment is an inorganic and/or organic white pigment, preferably an inorganic white pigment, such as an alkali metal sulfate such as barium sulfate,
Alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, synthetic silicates, calcium silicate, alumina,
Examples include alumina hydrate, titanium oxide, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate, calcium carbonate, or titanium oxide, and more preferably barium sulfate.

The content of the opacifying pigment varies depending on the type of base resin to be mixed, film forming conditions, properties of the mixed pigment, and particle size, but is preferably 3 to 30 wt%.

It should be noted that embossing or coloring the transparent resin sheet on the surface of the opaque resin sheet, or forming a multi-layer structure, is necessary when embodying the photographic element of the present invention as a card such as ■D card. It can be used to prevent card forgery and tampering, and as a means of discrimination.

When configured as a card, the card may be provided with a magnetic recording layer.

FIG. 1 shows an example of a support structure particularly suitable for ID cards. In the figure, 11 is a white polyethylene terephthalate sheet, 12 is polyethylene with adhesiveness i, 13 is a white polyethylene terephthalate film, 1
4 is a polypropylene synthetic paper, which constitutes a support. In a more preferred embodiment,
As the polypropylene synthetic paper 14, it is preferable to use YUPO (trade name, manufactured by Tamago Oil Synthetic Paper), which is a synthetic paper containing voids. In FIG. 1, 3 is a photographic emulsion layer forming an image forming surface;
4 is a writing layer. In the illustrated example, the polypropylene synthetic paper 14 has a thickness of 80 μm, and a writing layer 4 containing clay is provided on one side of the paper as a writing layer 4 for improving writing and printing properties. In forming the illustrated support, melted polyethylene 12 containing 8% titanium oxide was extruded onto such synthetic paper 14 (Yubo), and a white polyethylene terephthalate film 11 with a transmission density of 1.35 and a diameter of 175 μm was pasted. Combined. A pattern 2 is printed on the surface opposite to the bonded surface of the white polyethylene terephthalate film 11, and a transmission density 1
．． 35, a 175 μm white polyethylene terephthalate film 13 that has been subjected to undercoating is extruded and laminated with molten polyethylene 12 containing 8% titanium oxide between them.

Note that the writing layer 4 may be processed to include supplementary information by printing, handwriting, or the like.

As mentioned above, a preferred embodiment of the photographic element of the present invention is an ID card, in which the acid card is formed by applying a protective coating layer according to the present invention to an image member bearing desired information as an image. It is preferable that the opaque resin sheet has a certain degree of hardness against physical pressure from the outside and will not be damaged by bending or the like when being carried. In particular, it is preferable that the opaque resin sheet has the desired hardness.

In the photographic element according to the present invention, the image member having a photographic image layer carrying an image can be constructed by forming an image on any photographic light-sensitive material. For example, it can be formed by subjecting a black and white or color silver halide photosensitive material, various types of diffusion transfer photosensitive materials, diazo photosensitive materials, electrophotographic image recording materials, etc. to predetermined processing steps.

In the photographic element according to the present invention, the photographic image layer is a layer containing a hydrophilic polymer compound, and the active energy ray-curable composition according to the present invention is added to the photographic image layer containing the hydrophilic polymer compound. Preferably, it forms a protective coating layer.

In the present invention, hydrophilic polymer compounds used in the photographic image layer that carries images include gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, l! Derivatives, cellulose derivatives can be used, and hydrophilic colloids such as synthetic hydrophilic polymer substances such as single or copolymers can also be used. Among these, the effect of the present invention is remarkable at least when gelatin is used.

As the gelatin, for example, lime-treated gelatin can be used, and in addition, acid-treated gelatin, Bull, Soc.
, Sci, Phot, Japan, + tlh16+
Oxygen-treated gelatin such as that described on page 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. As a gelatin derivative,
Gelatin is obtained by reacting various compounds such as acid halides, acid anhydrides, isocyanates II, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene onoxides, and epoxy compounds. You can use whatever is available. Specific examples thereof include U.S. Patent Nos. 2,614.928 and 3.132.
．． No. 945, No. 3.186.846, No. 3.312,
553, British Patent No. 861.414, British Patent No. 1,033,
No. 189, No. 1,005,784, Special Publication No. 1972-26
It is described in No. 845, etc.

Examples of proteins that can be used as hydrophilic polymeric compounds in place of gelatin or in combination with gelatin include albumin and casein. Examples of cellulose derivatives include hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters. As sugar derivatives, sodium alginate and starch derivatives can be preferably used.

Graft polymers of gelatin and other polymers can also be used, such as gelatin with acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, and monomers of vinyl monomers such as acrylonitrile and styrene. One (homo) or one grafted with a copolymer can be used. Particularly preferred are graft polymers with polymers which are compatible with gelatin to some extent, such as acrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates, and the like. Examples of these are described in U.S. Pat. No. 2,763,625, U.S. Pat.

Synthetic hydrophilic polymer substances can be used in place of gelatin or in combination with gelatin. Typical synthetic hydrophilic polymer substances include polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, and polyvinyl alcohol. Single or copolymers of acrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., such as West German Patent Application (QLS) No. 2.312.708, U.S. Patent No. 3
, No. 620.751, No. 3,879,205, and Japanese Patent Publication No. 43-7561.

When using gelatin as a hydrophilic polymer compound,
The jelly strength of gelatin is not limited, but jelly strength 2
It is preferably 50 g or more (value measured by baggy method).

The photographic image layer constituting the photographic element of this invention, or any other hydrophilic colloid layer formed as desired, is coated with one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. By using two or more types, hardening can be achieved. The hardener can be added in an amount such that hardening is achieved to the extent that it is not necessary to add a hardener to the processing solution, but it is also possible to add a hardener to the processing solution.

Furthermore, a plasticizer can be added to the photographic image layer or other hydrophilic colloid layer for the purpose of increasing flexibility.

The photographic image layer is a light-sensitive layer or an image-receiving layer of a photosensitive material, and is formed on a support such as the above-mentioned supports, such as a waterproof evaporator, a white opaque resin sheet support, a support with a black and white light-shielding layer coated on the back surface thereof, or a transparent support. It is obtained by applying a predetermined treatment to a support such as a resin sheet.

As the image forming layer of the photographic element according to the invention, for example, a positive silver halide color photographic light-sensitive material is suitably used; in this case too, the support may be opaque or transparent.

In carrying out the present invention, when a direct positive image forming silver halide emulsion is employed as the emulsion used in the light-sensitive material constituting the image-bearing layer, for example, an internal latent image type silver halide emulsion may be used. In that case, the emulsion, additives, dye-forming coupler, fog treatment, development process, etc. are as described in JP-A-62-229133, page 37, line 15 to page 62, line 1. It can be implemented in a similar manner.

〔Example〕

Examples of the present invention will be described in detail below, but the present invention is not limited to these embodiments.

As explained above, as shown in FIG. 1, the 80 μm polyester layer is made of two 175 μm polyester layers 11.13 that have been surface-treated and have a writable coating on the back side.
On a support to which a polypropylene synthetic paper 14 of
A color print sample was prepared by coating and drying nine layers from the red-sensitive emulsion layer to the protective layer shown below using a simultaneous coating method.

Red-sensitive emulsion layer (first layer) A 2.0% inert gelatin solution was maintained at 50° C., and the following solutions A and B were simultaneously added and poured over 3 minutes while stirring.

After 10 minutes, the following solution C was added by injection over 3 minutes. After aging for 40 minutes, excess salt was removed by precipitation and water washing, and the following solution and solution E were added to give 8g C7!95 mol%, AgBr3.
Silver chlorobromide consisting of mol% was laminated on the back side. Excess water-soluble salts were removed again by the precipitation washing method, and a small amount of gelatin was added and dispersed.

Thereafter, a solution containing a sensitizing dye (D-1), an aggravating dye (D-4), 2,5-dioctylhydroquinone protected and dispersed with dibutyl phthalate, and a cyan coupler (CC-1) in this silver halide emulsion; -Hydroxy-6
-Methyl-1,3゜3a, 7-chitrazaindene, 1-
Phenyl-5-mercaptotetrazole, gelatin, and coating aid (S-1) are added as appropriate. Coated silver amount 0.4
The coating was carried out so that the coating was carried out in an amount of g/m'.

First intermediate layer (second layer) A gelatin solution containing 2,5-dioctylhydroquinone dispersed in dioctyl phthalate, an ultraviolet absorber Tinuvin 328 (manufactured by Ciba Geigy), and a coating aid (Sl) is prepared. It was coated at a coating weight of 15 g/rd.

Green-sensitive emulsion layer (third layer) Silver halide grains were prepared in the same manner as the red-sensitive emulsion.

A liquid containing a sensitizing dye (D-2), 2,5-dioctylhydroquinone protected and dispersed with dibutyl phthalate, and a magenta coupler (MC-1), 4-hydroxy-6-methyl-1,3,3a, 7-chitrazaindene, 1-phenyl-5-mercaptotetrazole, gelatin, and coating aid (S-2) are added as appropriate. The amount of silver coated was 0.4 g/rrf.

Second intermediate layer (fourth layer) The same formulation as the first intermediate layer was used, except that the coating amount of Tinuvin 328 was 0.2 g/rd.

Yellow filter layer (5th layer) 2,5-dioctylhydroquinone dispersed in yellow colloidal silver and dioctyl phthalate made by oxidation under an alkaline weak reducing agent (the weak reducing agent was removed by the noodle water washing method after neutralization) Add liquid, coating aid (S-2) and hardener (H-1) (add immediately before coating) to coat silver i.
It was applied at a weight of 15 g/rd.

Third intermediate layer N (6th Ff) Same formulation as the first intermediate layer, but Tinuvin 328 coating amount is 0.15g/r+? It was applied so that

Blue Sensitive Emulsion Layer (7th Layer) A 1.5% inert gelatin solution was kept at 60 DEG C., and while stirring, the following solutions A' and E' were simultaneously added and injected over 15 minutes. After 15 minutes, the following solution C was injected over 2 minutes, and after 1 minute, Hypo was added in an amount equivalent to 3 mg/Ag, and the mixture was further aged for 40 minutes. In addition, when I sampled and analyzed the composition ^gc1
Silver chlorobromide consisted of 4 mol %, AgBr 96 mol %, and 8gl 2 mol %.

After removing excess salt by precipitation and washing with water, the following solutions and E
' solution was added to form a surface layer containing 197 mol % of AgC and 3 mol % of 8 g Br, excess salt was removed again by precipitation and water washing, and gelatin for dispersion was added.

This silver halide emulsion contains a sensitizing dye (D-3) and a yellow coupler (YC-1) dispersed with dioctyl phthalate.
), 2-mercaptobenzothiazole, 4-hydroxy-6-methyl-1°3.3a, 7-titrazaindene, gelatin, coating aid (S-3) and hardener (H
-1) (added immediately before coating) using a solution containing 0 coating silver
．． It was applied at a rate of 5 g/n.

Fourth intermediate layer (eighth layer) The same formulation as the first intermediate layer was used, except that the coating amount of Tinuvin 328 was 0.3 g/rrl. However, a hardener (H-1) was added immediately before coating.

Protection N (9th layer) Amorphous silica with an average particle size of 3 μm, coating aid (S-3)
Using a gelatin solution containing a hardener (H-1) (added immediately before coating), the gelatin coating amount was 1.9 g/m.

Cyan coupler (CC) Magenta coupler (MC) Yellow coupler (YC ■) Sensitizing dye (D-1) Coating aid (S-1) Sensitizing dye (D-2) (D (D Coating aid) (S-2) Cz Hs CHz Coo CHz CH(CHI)3
C1hCHCOOCHt CH(CJ>z CHz
So, Na C, H.

Coating aid (S-3) CHz C00C)lz(CPzCFz)zHCH-
coocnzccpzcpz)z.

03Na 1°3°5-triglycidyl isocyanurate The specific photographic processing conditions in this example are as follows.

Processing process (processing temperature and processing time) [1] Immersion (color developer) 38°C [3] Color development [4] Bleach-fixing [5] Stabilization treatment [6] Drying Processing liquid composition (color developer) Benzyl Alcohol Ethylene glycol Potassium sulfite Potassium bromide Sodium chloride Potassium carbonate Hydroxylamine sulfate Polyphosphoric acid (TPPS) 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 38°C 35 ℃ 25-30℃ 75-80℃ 8 seconds 2 minutes 60 seconds 1 minute 30 seconds 1 minute 0mf 5 ml 2.0g 1.5g 0.2g 30.0g 3.0g 2.5g 5.5g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) ゛1. Add 2.0 g of Og potassium hydroxide water to bring the total amount to 11, and adjust the pH to 10.20.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100nl Ammonium sulfite
(40% solution) Adjust the pH to 7.1 with 27.5 ml potassium carbonate or glacial acetic acid, and add water to bring the total volume to 12.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 10 g l-hydroxyethylidene-1°1'-diphosphonic acid 2.5 g bismuth chloride 0.2 g magnesium chloride 0. 1g ammonium hydroxide (
28% aqueous solution) 2.0g sodium nitrilotriacetate Add 1.0g water to bring the total amount to 11,
Adjust pH to 7.0 with ammonium hydroxide or sulfuric acid.

The stabilization treatment was carried out using the same method with a two-tank configuration.

Coating compositions (1) to (6) according to the present invention shown below or an acrylic composition as a comparative composition are applied to the color print subjected to the above development treatment at a coating amount of 10 g/rd, Under 60W/cnl high pressure mercury lamp, ioa
The composition at the temperature shown in Table 1 was irradiated with ultraviolet rays for 4 seconds from a distance of m to cure the coating composition. In this way, Samples 1 to 21 were obtained using the compositions shown in Table 1 and the composition temperatures during irradiation shown in Table 1.

The temperature of the composition during UV irradiation using a high-pressure mercury lamp is controlled as shown in Table 1: (A) Heating the film before 2 cloths (B) Heating the coating solution (C) After application and before UV irradiation Three types of heating methods were used, and each was specifically performed as follows.

That is, the energy ray curable composition was heated to a temperature of 30°C to 1
As a heating means for raising the temperature to 00°C, an apparatus as shown in FIG. 2 was used in the embodiment of the present invention. In Figure 2, Hl, H2
, H3 each indicate a heater. L is a UV lamp which is the energy ray irradiation means in this example. 31 a+
3 lb is a conveyor that conveys a card-shaped image member C, which is an object to be heated. CO is a coating coater, and T is an infrared thermometer.

For example, a heater H1 is used to heat the image member C before applying the energy ray curable composition using the apparatus shown in FIG. That is, it is heated with a heater H1 and measured with an infrared thermometer T. In addition, to heat the composition coating solution,
Using the heater H3, the composition coating liquid in the container B can be heated. Further, in order to heat the coating after application and before irradiation with energy rays (UV light in this example), a heater H2 can be used, and the heater H2 can heat the coating and the infrared & 1 degree meter T can measure the temperature.

Note that among the heaters H1 to H3, any one of the heaters H1 to H3 is actually used.
The heaters H1 to H3 are shown in one apparatus for the sake of simplicity.

(Comparative composition) Acrylic resin composition: Epoxy composition (UV curable composition) Epoxy composition (1) Epoxy composition Epoxy composition Epoxy composition Epoxy composition (Sample evaluation) The sample obtained as above was evaluated by the following method.

1. Adhesion with photographic image layer Adhesive properties (1) to (4) were examined as follows.

(1) Cellotape (manufactured by Chiban Co., Ltd.) was firmly attached to the surface of the cured protective coating layer, and the cellotape was rapidly peeled off from the surface, and the state of peeling was observed.

(2) The protective coating layer was scratched at an angle of 90° with a cutter, and the adhesion to the photographic image layer was examined in the same manner as in (1).

(3) A sample having a cured protective coating layer was immersed in tap water at 20'C for one day and night, and its adhesion to the photographic image layer was examined in the same manner as in section (1).

(4) A sample having a cured protective coating layer was immersed in tap water at 20° C. for one day and night, and its adhesion to the photographic image layer was examined in the same manner as in section (2).

The evaluation results of adhesiveness are expressed as the remaining percentage of the area of adhesive cellophane tape, and are shown in Table 1. If this is 80% or more, it is acceptable in practice.

As is clear from Table 1, all the samples according to the present invention showed excellent results in each of the adhesiveness tests (1) to (4). In particular, it provides more than 80% of the remaining area even under the harsh conditions of making scratches with the cutter in (2),
Further, in the water resistance test (4) and (3), the adhesive gave a value of almost 100%, or at worst 90%, indicating that the adhesiveness was extremely excellent even under poor conditions.

Among the samples according to this example, samples 3 to 6 and 13 to 17 were temperature controlled by means (A), and samples 8 and 9 were temperature controlled by means (A) (
Sample 10.11 used means (A) and (C) together, and sample 18.19 used means <A), (B), and (C) together, but in this way, before applying the composition, Favorable results are obtained by using means (A) for heating the image member;
Furthermore, it will be understood that more favorable results are obtained by using means (B) and (C) in combination.

Further, the above-mentioned 11th to 9th layers were separately coated on a support made of photographic base paper laminated with polyethylene to prepare an image member. However, as a hardening agent for the protective layer (ninth layer), the following compound was used in place of the above (H-1).

(8 hours equivalent to Exemplified Compound (41) described in JP-A No. 62-229133) The obtained image member was subjected to the above-mentioned photographic processing, coated with epoxy composition (1), and irradiated with UV light. and hardened. However, heating was not performed, and curing was performed at 18° C. (room temperature).

When evaluating the photographic elements obtained through this method,
Although the adhesion was similar to the sample according to the present invention, the sensitivity was significantly lower than that of the sample according to the present invention.

It can be seen that even if a specific hardening agent is used to improve adhesion, sufficient effects in terms of photographic performance cannot be obtained if temperature control during curing is outside the scope of the present invention.

〔Effect of the invention〕

As described above, the present invention provides a photographic element in which a protective coating layer is formed by curing with active energy rays, which has good adhesion to the image forming layer, etc., and has good water resistance. be able to. Furthermore, it is possible to provide a manufacturing method that allows such photographic elements to be formed easily and inexpensively by irradiation with low-energy active energy rays.

[Brief explanation of the drawing]

FIG. 1 shows a cross-sectional view of an example of a photographic element prepared in an example. FIG. 2 is a configuration diagram of an apparatus used for heating and coating in the examples. Third
Figures (a) to (c) are schematic diagrams each showing a heating method. 1...Support, 3...Image forming layer.

Claims (1)

[Claims] 1. At least one image-bearing layer on a support;
A photographic element having a protective coating layer cured with active energy radiation, said protective coating layer comprising a prepolymer containing in the molecule at least two epoxy groups and a polymerization initiator activated by active energy radiation. 1. A photographic element obtained by curing an active energy ray-curable composition by irradiating it with active energy rays at a temperature of 30 to 100°C. 2. at least one image-bearing layer on the support;
A method for producing a photographic element having a protective coating layer cured with active energy radiation, the protective coating layer comprising a prepolymer containing in the molecule at least two epoxy groups and a polymerization initiator activated by active energy radiation. 1. A method for producing a photographic element, comprising curing an active energy ray-curable composition containing an active energy ray at a temperature of 30 to 100°C.