JPH09106036A - Photoprint laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoprint laminate with high glossiness at a glance and high rigidity by setting the surface roughness of a coated layer to be a specified value or less. SOLUTION: For a resin coated sheet type photographic material support, a face on one silver halide photograph is constituting layer side of a basic sheet mainly containing natural pulp and a face on the opposite side of the basic sheet is coated with a resin layer containing resin with film forming capability. For a photoprint laminate, a photoprint already developed for silver halide photographic material with a silver halide photograph constituting layer and a sheet are pasted on the support via adhesive. The basic sheet has one face coated with the resin layer and coated with a coated layer formed of coating composition containing at least binder. The center surface average roughness of the coated layer in the sheet direction at a cutoff value of 0.8mm, when measured by a tracer type three-dimensional surface roughness meter, is 1.1μm or less. The basic sheet is a photoprint laminate containing inside sizing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin layer (A) containing a resin (a) capable of forming a film on one surface of a base paper mainly composed of natural pulp, on which a silver halide photographic constituent layer is provided.
Halogen in which a silver halide photographic constituent layer is provided on a resin-coated paper-type photographic support which is coated with a resin paper (B) containing a resin (b) capable of forming a film on the opposite side of the base paper surface. The present invention relates to a photographic print laminate in which a developed photographic print of a silver halide photographic material and a sheet are bonded together with an adhesive, and more specifically, an excellent photographic print laminate having a high-looking glossiness and a strong stiffness. The present invention relates to an excellent photographic print laminate having a high appearance glossiness, a high rigidity, and various recording performances on the back surface.

[0002]

2. Description of the Related Art Usually, a silver halide photographic material (hereinafter sometimes simply referred to as a photographic material) is composed of a photographic material support and a silver halide photographic constituent layer provided on the support. There is. Such silver halide photographic constituent layers include silver halide photographic emulsion layers, protective layers, subbing layers, intermediate layers or color mixing prevention layers, antihalation layers, or filter layers, ultraviolet absorbing layers and the like and combinations thereof. It is composed. For example, a single silver halide photographic material has a silver halide photographic emulsion layer and a protective layer provided on a photographic material support. Further, a multilayer silver halide color photographic material comprises an undercoat layer, a blue-sensitive silver halide photographic emulsion layer and an intermediate layer, a green-sensitive silver halide photographic emulsion layer and an ultraviolet absorbing layer, A silver halide photographic emulsion layer and a silver halide color photographic constituting layer such as a protective layer are provided in this order and are arranged in multiple layers.

Also, a resin-coated support for paper-type photographic materials, in which a base paper surface containing natural pulp as a main component is coated with a resin capable of forming a film, is well known. For example, Japanese Patent Publication Sho 55-1
Japanese Patent No. 2584 discloses a technique for a support for a photographic material, in which a base paper is coated with a resin capable of forming a film, preferably a polyolefin resin. U.S. Pat.No. 3,501,
Japanese Patent No. 298 discloses a technique for a photographic material support in which both sides of a base paper are coated with a polyolefin resin. Since the rapid photographic processing method for silver halide photographic light-sensitive materials was applied, a support for photographic materials in which both sides of a base paper were coated with a polyethylene resin was mainly put into practical use for photographic printing paper. However, if necessary, a titanium dioxide pigment is usually contained in the resin layer on the side on which one of the silver halide photographic constituent layers is provided in order to impart sharpness.

However, these resin-coated supports for paper-type photographic materials have serious problems, and in fact, satisfactory results have not yet been obtained.

First, the side of the base paper on which the silver halide photographic constituent layer is provided (hereinafter, the side on which the silver halide photographic constituent layer is provided is the front side, the resin layer coated on the front side is the front resin layer, and the opposite side is the opposite side). A resin for use as a support for photographic materials in which the back side and the resin layer coated on the back side are sometimes abbreviated as the back resin layer) are coated with a resin capable of forming at least a film, particularly a resin layer containing a polyethylene resin. Coated paper, using a melt-extruder polyethylene resin composition on the base paper that normally runs, coated by casting in a film form from its slit die, pressure-bonded between a pressure roll and a cooling roll, It is manufactured by a series of steps of peeling from the roll after cooling. At that time, in the case of producing resin-coated paper for photographic materials for glossy use, as a cooling roll, a cooling roll having a mirror surface or a glossy surface or a finely rough surface described in Japanese Patent Publication No. 62-19732 and having an extremely smooth surface. Is used. Thus, the surface resin layer of the resin-coated paper is processed into a surface having good smoothness because it is pressed against a cooling roll having extremely good smoothness in its molten state. Therefore, in a photographic material using the resin-coated paper as a support,
It should be possible to obtain a photographic print with a high-gloss appearance. However, it was not possible to obtain a photographic print having a sufficiently high glossy appearance with a photographic material having a resin-coated paper actually produced as a support.

Therefore, as a result of various examinations by the inventors of the factors of the appearance glossiness of photographic prints, the factors affecting the appearance glossiness of photographic prints include resin-coated paper as a support and silver halide photography. Although there are various factors such as constituent layers and development processing, it has been found that the appearance glossiness of the photographic print is greatly influenced by the factors of the resin-coated paper as the support. Therefore, as a result of various studies on the factors of the resin-coated paper that affect the appearance glossiness of the photographic print, the present inventors further found that the appearance glossiness of the photographic print depends on the factors of the resin layer and mainly the natural pulp. Factors such as the type and properties of the base paper used as a component, such as the type of natural pulp, fiber length, papermaking slurry conditions such as paper additives contained in papermaking slurry, papermaking speed, firmness press, machine calendering conditions It was found that it depends on various factors such as paper making conditions such as the above, post-processing conditions such as size press and tab size press, and eventually surface roughness of the base paper. Further, as the thickness of the surface resin layer of the resin-coated paper becomes thinner, particularly in the case of 31 μm or less, the appearance glossiness of the photographic print of the photographic material having the resin-coated paper as a support becomes remarkable. It turned out to drop. Originally, photographic materials for glossy use are required to have a high level of glossy appearance when used as photographic prints, and photographic materials with poor glossy appearance are not suitable for glossy use. There was a problem that it became something with no commercial value.

Secondly, there is a waist problem of photographic prints.
A photographic print is usually taken by a person for viewing, and if the photographic print, especially a horizontally long panoramic print, has a weak waist, it is difficult to view. Therefore, although the photographic print is required to be strong, the inventors of the present invention have found that the photographic print's stiffness depends largely on the stiffness of the resin-coated paper as the support, and It was found that the waist of the paper largely depends on the strength of the waist of the base paper.
However, the problem of stiffness of the base paper is often in conflict with the smoothness of the base paper.If the smoothness is good, the stiffness is weak, and if the stiffness is strong, the smoothness is poor, and thus the resin-coated paper is used as a support. It has been found that there is a contradictory problem that the glossiness of the photographic prints that appear to appear deteriorates.

By the way, in Japanese Patent Publication No. 5-55055, a base paper is adhered to one surface of a base paper (hereinafter, the paper before the coating layer is applied may be referred to as the base paper). Of a photographic resin-coated paper with improved sharpness using a coated paper which is provided with a coating layer containing an agent and which is pressed against a heated mirror surface drum or a gloss calender to give a highly smooth finish. The technology is disclosed. Further, JP-B-6-48365 discloses, as a base paper, one side of a base paper is coated with a coating composition containing a pigment and an adhesive as a main component, and then a gloss imparting machine, preferably a super calender. Discloses a technology of a photographic resin-coated paper having an excellent glossiness, which is used with a coated paper having gloss imparted thereto. However, when these techniques are used, although a support for a resin-coated paper type photographic material having a good appearance glossiness can be obtained, it has a drawback that it has a weak rigidity. Especially when the base paper is thin, 14
When it is less than 0 μm, it has a fatal defect that the waist is significantly lowered. On the other hand, when the base paper is thick, especially when it is 140 μm or more, the thicker the base paper, the more difficult it is to form the base paper. In order to improve the smoothness of the base paper by strengthening the calender conditions such as a calender, the density of the base paper becomes large and the thickness per unit mass becomes thin, making it extremely inefficient to secure the waist. There was a problem. In addition, the thicker the base paper, the slower the papermaking speed becomes, and if a new coating layer is provided on the base paper, the cost becomes extremely high, and there is also a problem that the cost competitiveness is lost. I was holding.

Further, Japanese Patent Laid-Open Nos. 63-70858 and 63-
Japanese Patent No. 316859 discloses a technique of a photographic print laminate for use in postcards. However, even if these techniques are used, there is only the disclosure of the technique using a conventionally known photographic print, and only a photographic print laminate having a considerably inferior appearance is obtained.

Thirdly, with the recent spread of personal computers and diversification for various uses of photographic prints, the back surface of photographic prints, that is, the surface opposite to the surface on which the silver halide photographic constituent layers are provided. In addition, there is an increasing demand for recording performance in various recording systems such as an inkjet recording system, a heat transfer type thermal transfer recording system, a thermal recording system, and a laser-sensitive thermal recording system. However, the current photographic prints have a problem that they do not essentially have recording performance in various recording systems.

For example, even if an ordinary ink jet recording system, a heat transfer type thermal transfer recording system or the like is used for recording on a photographic print, the recording system has little or no recording ability. In addition, the photographic print laminate for postcard applications disclosed in JP-A-63-70858, JP-A-63-316859, and the like has the ink bleeding even when recorded on the paper surface by an inkjet recording method. And the problem of uneven print density occurred, and the heat transfer type thermal transfer recording system had essentially no recording ability.

[0012]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to carry out silver halide photography using as a support a resin-coated paper in which both sides of a base paper mainly composed of natural pulp are coated with a resin layer. It is intended to provide a photographic print laminate in which a developed photographic print of a material and a sheet are bonded together via an adhesive, the photographic print laminate having a high appearance glossiness and a strong rigidity. A second object of the present invention is to provide a photographic print laminate having the above-mentioned structure, which has a high appearance glossiness, is strong, and has various recording performances on the back surface.

[0013]

As a result of intensive studies to solve the above-mentioned problems, the present inventors found that one surface of a base paper containing natural pulp as a main component was provided with a silver halide photographic constituent layer. Resin layer (A) containing resin (a) capable of forming a film
A silver halide photographic constituent layer was provided on a support for a resin-coated paper-type photographic material which was coated with a resin layer (B) containing a resin (b) capable of forming a film on the opposite side of the base paper surface. In a photographic print laminate in which a developed photographic print of a silver halide photographic material and a sheet are bonded together via an adhesive, the base paper has a surface on the side covered with one resin layer (A). A coating layer composed of a coating composition containing at least a binder, and having a cut-off value of 0.8 mm measured using a stylus type three-dimensional surface roughness meter on the surface of the coating layer. Center surface average roughness in the papermaking direction is 1.1 μm
It has been found that the first object of the invention is achieved by a photographic print laminate which is characterized in that the base paper contains an internal sizing agent: It has also been found that the second object of the present invention is achieved by a photographic print laminate in which the sheet has image recording performance.

The center surface average roughness (SRa) at a cutoff value of 0.8 mm measured by using a stylus type three-dimensional surface roughness meter referred to in the present specification is defined by Formula 1. It is a thing.

[0015]

(Equation 1)

In Expression 1, Wx represents the length of the sample surface area in the X-axis direction (papermaking direction), Wy represents the length of the sample surface area in the Y-axis direction (direction perpendicular to the papermaking direction), and Sa Represents the area of the sample area.

Specifically, as a stylus type three-dimensional surface roughness meter and a three-dimensional roughness analyzer, SE manufactured by Kosaka Laboratory Ltd. is used.
-3AK type machine and SPA-11 type machine, cutoff value 0.8mm, Wx = 20mm, Wy = 8mm, therefore Sa
It can be calculated under the condition of = 160 mm ² . Note that 500 points of sampling are performed as data processing in the X-axis direction, and 17 lines or more are performed as scanning in the Y-axis direction.

An object of the present invention is to provide, as a base paper, a coated paper in which a coating layer is pressed against a heated mirror surface drum or a gloss calender to give a highly smooth finish, or a coating composition contains at least a binder and a pigment. It has been found that this can be effectively achieved by using a coated paper which contains and whose coating layer is calendered to a high smoothness. Another object of the present invention is to provide a base paper having a cut-off value of 0.8 mm measured by using a stylus type three-dimensional surface roughness meter on the surface of the coated layer, and a center surface average roughness in the paper making direction (hereinafter, referred to as touch). The term "center plane average roughness in the papermaking direction" at a cut-off value of 0.8 mm measured using a needle type three-dimensional surface roughness meter is simply referred to as "center plane average roughness". By using the paper,
I have found that it can be achieved significantly. Further, an object of the present invention is to provide a sheet for bonding, which has a specific flexural rigidity (“Handbook of Physicalland”).
Mechanical Testing of Pap
er and Paperboard ", Volume 1, R.S.
E. FIG. Edited by Mark (1983)) is 30 Nm ⁷ / kg ³
The inventors have found that the above can be achieved remarkably by using the above, and have reached the present invention.

Specifically, the specific bending rigidity Sb of the sheet
^* (Unit: Nm ⁷ / kg ³ ) is the flexural rigidity Sb (Unit: Nm)
Is determined according to JIS P 8125, and the basis weight w of the sheet is
(Unit: kg / m ² ) Calculated from Equation 2.

[0020]

[Formula 2] Sb ^* = Sb / w ³

The base paper used in the practice of the present invention is coated with a coating layer comprising a coating composition containing at least a binder on one side of the base paper on which the silver halide photographic constituent layer is provided. Yes, the coated layer is a highly smooth finish by press contact with a heated mirror drum or gloss calender, or the coating composition contains at least a binder and a pigment, and the coated layer is highly smooth on a calendar. Finished coated papers are preferred.

As a method for producing a coated paper in which a coating layer containing at least a binder is pressed against a heated mirror surface drum or a gloss calender and highly smooth finished, which is advantageously used in the practice of the present invention, a casting method or a There is a gross calendar method. As a manufacturing method of the casting method, a gelling casting method in which a wet coated paper is put into a gel state to be pressed against a heating drum surface to finish, and a wet coating layer is once dried or semi-dried and then re-wetted. A rewet casting method, etc., in which the material is plasticized and brought into pressure contact with the surface of the heating drum to achieve a highly smooth finish, etc. In the present invention, the cast finishing method itself is not particularly limited, but a rewet casting method that can relatively speed up is advantageously used.

As a manufacturing method by the gross calendering method, the heat calendering, which is generally known as the gross calendering, may be used for finishing. That is, for example, a method may be used in which the coated paper is pressed against the polishing finishing drum under the temperature condition that causes the coated surface to have a temporary plastic state, and the polishing is performed.

Further, it is advantageously used for carrying out the present invention.
As a method for producing a coated paper in which a coating layer containing at least a binder and a pigment is highly smooth finished with a calendar, a base paper is coated with a coating composition containing at least a binder and a pigment, dried, and then coated. A method in which the coating layer is finished with high smoothness by various calenders such as a super calender is advantageously used.

The binder to be contained in the coating layer in the practice of the present invention includes casein, soybean protein, other proteins, lime-processed gelatin, acid-processed gelatin, modified gelatin and other gelatins, and styrene-butadiene copolymer. , Conjugated methacrylate copolymer latex such as methyl methacrylate / butadiene copolymer, acrylic polymer latex such as polymer or copolymer of acrylic acid ester and / or methacrylic acid ester, vinyl such as ethylene / vinyl acetate copolymer -Based polymer latex, or an alkali-soluble or alkali-insoluble polymer latex or olefin modified with a functional group by copolymerizing or graft-copolymerizing various polymers with a functional group-containing monomer such as a carboxyl group・ Synthetic resin-based resin such as maleic anhydride resin and melamine resin Nda, cationic starch, phosphoric acid esterified starch, starches such as oxidized starch, carboxymethyl cellulose, cellulose derivatives such as hydroxyethyl cellulose, a general coated paper for binder may be used singly or in combination.

A pigment may be contained in the coating layer containing at least a binder used in the practice of the present invention. Further, a binder and a pigment may be used in combination in the coating layer of the glossy coated paper which is advantageously used in the practice of the present invention. As the various inorganic or organic pigments, for example, general coated paper pigments such as clay, kaolin, aluminum hydroxide, calcium carbonate, titanium dioxide, barium sulfate, zinc oxide, satin white and plastic pigments are used alone or in combination. Can be used.

Further, the coating layer of the base paper used in the practice of the present invention may appropriately contain, as necessary, a defoaming agent, a coloring agent, a release agent, a fluidity improving agent and the like as auxiliary agents. You can

In the present invention, the coating composition containing at least a binder is coated on a base paper by a blade coater, an air knife coater, a roll coater, a brush coater, a curtain coater, which is used in the production of general coated paper. An on-machine or off-machine coater provided with a coating device such as a Champlex coater, a bar coater, a gravure coater, and a size press coater is preferably used to coat the base paper in one or more layers.

The coating amount is 3 on a dry weight basis.
The range of from 45 g / m ² is useful, but the higher the coating amount, the higher the glossiness of the photographic print laminate, but the productivity and ease of production of the base paper and the photographic print laminate. From the viewpoint of curl physical properties, etc., the range of 5 to 30 g / m ² is preferable.

As the pulp constituting the base paper before the coating of the coating layer, which is used in the practice of the present invention, it is advantageous to use an appropriately selected natural pulp as described later. Natural pulp was subjected to usual bleaching treatment such as chlorine, hypochlorite, chlorine dioxide bleaching, alkali extraction or alkali treatment and, if necessary, oxidative bleaching treatment with hydrogen peroxide, oxygen, etc., and a combination thereof. Wood pulp such as softwood pulp, hardwood pulp and mixed hardwood hardwood pulp is used, and various types of recycled pulp (used paper pulp) as well as kraft pulp, sulfite pulp, soda pulp and the like can be used.

The base paper may contain various additives when preparing a stock slurry. As a sizing agent,
Fatty acid metal salt and / or fatty acid, Japanese Patent Publication No. 62-7534
Alkyl ketene dimer emulsions or epoxidized higher fatty acid amides, alkenyl or alkyl succinic anhydride emulsions, rosin derivatives, etc. described or exemplified in JP-A No. 1993-242, and anionic, cationic or amphoteric polyacrylamides as a dry paper strength enhancer. , Polyvinyl alcohol, cationized starch, vegetable galactomannan, etc., as a wet paper strength enhancer, polyamine polyamide epichlorohydrin resin, etc., as a filler, clay, kaolin, calcium carbonate, titanium oxide, etc. Water-soluble aluminum salts such as soil, pH adjusting agents such as caustic soda, sodium carbonate, sulfuric acid, etc., or other color pigments described or exemplified in JP-A-63-204251, JP-A 1-266537, etc. Contains dyes, optical brighteners, etc. in an appropriate combination. It is advantageous Mel.

In the base paper, a composition comprising various water-soluble polymers or hydrophilic colloids or latexes, antistatic agents, and additives is subjected to size press or tab size press or blade coating, air knife coating, etc. It can be contained by coating. As a water-soluble polymer or hydrophilic colloid, JP-A 1-266537
The starch-based polymer, the polyvinyl alcohol-based polymer, the gelatin-based polymer, the polyacrylamide-based polymer, the cellulose-based polymer, etc. described or exemplified in Japanese Patent Publication No. JP-A No. 55-4027, a petroleum resin emulsion as latexes. Emulsion or latex of a copolymer containing ethylene and acrylic acid (or methacrylic acid) at least as constituents described or disclosed in Kaihei 1-180538, styrene-butadiene type, styrene-acrylic type, vinyl acetate-acrylic type ,
Emulsion or latex of ethylene-vinyl acetate-based, butadiene-methyl methacrylate-based copolymers and their carboxy-modified copolymers, as antistatic agents, alkali metal salts such as sodium chloride and potassium chloride, calcium chloride, barium chloride, etc. Alkaline earth metal salts, colloidal metal oxides such as colloidal silica, organic antistatic agents such as polystyrene sulfonate, pigments such as clay, kaolin, calcium carbonate, talc, barium sulfate, titanium oxide, pH As a regulator, hydrochloric acid,
Advantageously, phosphoric acid, citric acid, caustic soda, and the like, as well as the above-mentioned color pigments, color dyes, optical brighteners, and other additives are appropriately combined and contained.

The thickness of the base paper is not particularly limited, but it is useful that the basis weight is in the range of ²⁰ to 200 g / m ² , and the basis weight of the present invention is 45 to 150 g / m ^2. A thin base paper in the range of is preferable.

The base paper used in the practice of the present invention is
The center surface average roughness SRa referred to in the present specification of the coated layer surface is 1.
The particle size is 1 μm or less, preferably 0.75 μm or less, more preferably 0.6 μm or less, and even less than 0.6 μm.
It is most preferably 45 μm or less. Center surface average roughness S
For the base paper having Ra of 1.1 μm or less, specifically, the following method is used, and preferably the following method is used.
It has been revealed by the study of the present inventors that one or more, and more preferably three or more are used in combination.

(1) As the natural pulp used, a large amount of sulfite pulp having smoothness, preferably hardwood sulfite pulp, is used. Specifically, JP 60
The hardwood sulfite pulp described or exemplified in JP-A-67940 is used in an amount of 30% by weight or more, preferably 50% by weight or more.

(2) A pressure press is used during the drying of the wet paper. Specifically, for example, a multi-stage tension press described or exemplified in JP-A-3-29945 is performed on the wet paper.

(3) After making the base paper, at least two or more series of calender treatments are applied to the base paper using a machine calendar, a super calendar, a thermal calendar or the like. Specifically, for example, the base paper is subjected to a machine calendering treatment and / or a thermal machine calendering treatment as a first series calendering treatment, and then a machine calendering treatment is further performed as a second series calendering treatment and thereafter. It is preferable to perform the thermal soft calender treatment described or exemplified in JP-A-4-110939.

(4) The coating amount of the coating layer is 5 to 30 g
And optimize the conditions of cast or thermal calendering of the coated layer. High temperature and high pressure are effective in reducing the surface roughness, but since problems such as surface roughness occur separately, it is preferable to optimize them in consideration of them in advance. In the case of casting, it is desirable that the coating liquid has a high affinity for the cast roll.

The base paper used in the practice of the present invention has a thickness unevenness index Rpy in the paper making direction defined below.
Is preferably 250 mV or less, more preferably 200 mV or less, most preferably 150 mV or less. The film thickness nonuniformity index Rpy referred to here is an electronic micrometer using a film thickness measuring instrument that measures the thickness variation of the sample as an electric signal through an electronic micrometer by running the sample between two spherical stylus. Under the condition that the sensitivity range is ± 15 μm / ± 3 V, the thickness variation in the papermaking direction of the sample was measured by scanning the sample in the papermaking direction after adjusting the zero point at a constant speed of 1.5 m / min. Signal value is FF
Using a T analyzer, using a Hanning window for the time window, a fast Fourier transform is performed to obtain a power spectrum (unit: mV ² ) based on the arithmetic mean of 128 integrations,
2/3 by summing the power values in the frequency range of 2 Hz to 25 Hz
It is a value (unit: mV) obtained by multiplying the value multiplied by.

As a method for producing a base paper having a thickness unevenness index Rpy of 250 mV or less, which is preferably used in the practice of the present invention, specifically, 30% by weight or more of hardwood pulp, which is short fiber and easy to smooth, is preferable. Is used in an amount of 50% by weight or more and beaten with a beater so that the long fiber content is reduced as much as possible. For example, beating of pulp is such that the weight average fiber length of the pulp after beating is preferably 0.4 to 0.75 mm, particularly preferably 0.45 to 0.65 mm. Next, it is preferable to use a fourdrinier paper machine that employs an appropriate paper making method for a stock slurry to which internal additives have been added to make a base paper so that a uniform formation can be obtained. Specifically, for example, using a Fourdrinier paper machine having an appropriate upper dewatering mechanism as described or exemplified in JP-A-61-284762, which gives an appropriate turbulence to a stock slurry, wet part As a press, a multi-stage wet press, preferably 3 or more stages of wet press, and a smoothing crawl at the final stage of the press part are combined so that a uniform texture can be obtained by combining appropriate papermaking methods. After the papermaking, and after the papermaking, calendering is performed using a machine calender, a super calender, a thermal calender, or the like to produce a base paper having a thickness unevenness index Rpy of 250 mV or less.

Both sides of the base paper of the photographic material support used in the practice of the present invention are coated with a resin layer containing a resin capable of forming a film. As the resin capable of forming a film, a thermoplastic resin such as a polyolefin resin, a polyester resin, a polycarbonate resin, a polyamide resin or a mixture thereof is preferable, and among them, a polyolefin resin, a polyester resin or a mixture thereof from the viewpoint of melt extrusion coating property. Is more preferable. Further, it may be coated with an electron beam curable resin layer described or exemplified in JP-B-60-17104.

As the polyolefin resin for coating the base paper, which is preferably used in the practice of the present invention, polyethylene,
Homopolymers such as polypropylene, polybutene, and polypentene, copolymers composed of two or more α-olefins such as ethylene-butylene copolymer, and mixtures thereof, particularly, melt extrusion coating property and adhesiveness to base paper From the viewpoint of, polyethylene resin is particularly preferable.
Examples of such polyethylene resins include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, copolymers of ethylene and α-olefin such as propylene and butylene, carboxy modified polyethylene and the like. A mixture having various densities, melt flow rates (hereinafter abbreviated as MFR), molecular weights and molecular weight distributions can be used, but usually, the density is in the range of 0.90 to 0.97 g / cm ³ , and the MFR is 0.1 g. /10 minutes~
50g / 10min, preferably MFR 0.3g / 10min-40g / 1
Those in the range of 0 minutes can be advantageously used alone or as a mixture. When the resin has a multi-layered structure, the outermost layer resin is, for example, MFR 5 g / 10 min to 20 g / 10 min, and the lower layer resin is, for example, MFR 2 g / 10 min to 10 g / 10 min. It is also possible to use a resin having the above-mentioned properties and constitution.

The coating thickness of the resin layer on the front side of the photographic material support used in the practice of the present invention is from 4 μm to 70 μm.
A range of m is useful, but a range of 6 μm to 45 μm is preferred, and a range of 9 μm to 35 μm is particularly preferred. The back side of the base paper of the support for photographic materials is coated with a resin layer containing a resin capable of forming a film, and the resin is preferably the same resin as the front side resin, and the coating thickness is the front side. It is preferable to appropriately set the resin layer and the resin layer in a range in which the curl balance is obtained. Generally, the range of 4 μm to 70 μm is useful, but the range of 6 μm to 45 μm is preferable.

As a method of coating the resin layer on the surface of the base paper of the support for photographic material, when the resin is a thermoplastic resin, preferably a polyolefin resin, and particularly preferably a polyethylene resin, it is coated on a running base paper. The resin layer is preferably coated by a so-called melt extrusion coating method, in which the resin layer is cast into a film form from the slit die using a melt extrusion machine and coated. At that time, the temperature of the molten film is preferably 270 to 330 ° C. In the case of a polyester resin layer, the temperature is preferably 220 to 300 ° C. As a slit die, a T-type die,
Flat dies such as L-type dies and fishtail dies are preferable, and the slit opening diameter is preferably 0.1 to 2 mm. Also, before coating the resin layer on the base paper,
The base paper is preferably subjected to activation treatment such as corona discharge treatment or flame treatment. Further, as described in JP-B-61-42254, a resin layer may be coated on the running base paper after the ozone-containing gas is blown onto the surface of the molten resin which is in contact with the base paper.
Further, the front and back resin layers are sequentially and preferably continuously extrusion-coated, preferably the base paper is coated by a so-called tandem extrusion coating method, and the front and back resin layers are, if necessary, It has a multilayer structure of two or more layers,
It is preferably coated by a multi-layer extrusion coating method. Further, the resin layer surface can be processed into a glossy surface, a finely rough surface described in JP-B-62-19732, a matte surface or a silk surface. In particular, the effect of the present invention is remarkable in a photographic print laminate comprising a support for photographic materials in which the resin layer on the side where the silver halide photographic constituent layer is provided has a glossy surface or a slightly rough surface.

Further, various additives can be incorporated into the front resin layer of the support for photographic materials and, if necessary, the back resin layer. Japanese Patent Publication No. 60-3430, 63-11655
White pigments such as titanium oxide, zinc oxide, talc, calcium carbonate, etc., stearic acid amide, arachidin Fatty acid amides such as acid amides, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, zinc palmitate, zinc myristate, fatty acid metal salts such as calcium palmitate, described or exemplified in JP-A-1-105245. Various hindered phenols, hindered amines, phosphorus-based, sulfur-based antioxidants, cobalt blue, ultramarine blue, cerian blue, phthalocyanine blue and other blue pigments and dyes, cobalt violet, fast violet, manganese violet and other magenta Pigments and dyes described in JP-A-2-254440. Or illustrative of the fluorescent whitening agent, various additives as appropriate combination can be incorporated such as an ultraviolet absorber. Those additives are
It is preferably contained as a resin masterbatch or compound.

The surface of the surface resin layer of the support for photographic materials used in the practice of the present invention is subjected to activation treatment such as corona discharge treatment and flame treatment, and then, JP-A-61-84643 and JP-A-61-84643.
1-92740, JP 1-102551, JP 1-16603
An undercoat layer as described or exemplified in Japanese Patent Publication No. 5 can be provided by coating. Further, various back coat layers can be coated on the surface of the backing resin layer of the support for photographic materials after activation treatment such as corona discharge treatment and flame treatment to prevent static electricity. Further, the back coat layer has a Japanese Patent Publication No. 52-18020, Japanese Patent Publication No. 57-9059, and Japanese Patent Publication No. 57-53.
940, Japanese Patent Publication No. 58-56859, Japanese Patent Laid-Open No. 59-214849
JP, JP-A-58-184144 or the like, or an inorganic antistatic agent, an organic antistatic agent, a hydrophilic binder, a latex, a curing agent, a pigment, a surfactant or the like may be contained in appropriate combination. it can. In particular, when forming a photographic print laminate, the photographic print and the sheet are bonded together via an adhesive, and at this time, the backcoat suitability is that the adhesive can be easily applied to the backcoat layer, that is, the so-called adhesiveness suitability. Is preferable, and from that point of view, a backcoat layer containing a hydrophilic binder, preferably gelatin, which has a good wettability of the backcoat layer is preferable.

The silver halide photographic material used in the practice of the present invention is one in which various silver halide photographic constituent layers are provided on the photographic material support of the present invention, for color photographic printing paper, Various materials such as black and white photographic printing paper, reversal photographic material, silver salt diffusion transfer method positive, dye diffusion transfer method positive can be used. For example, silver chloride,
A silver bromide, silver chlorobromide, silver iodobromide, or silver chloroiodobromide emulsion layer can be used. A silver halide color photographic material containing a color coupler in the silver halide photographic emulsion layer can be used. Further, those provided with a photographic constituent layer for silver salt diffusion transfer method can be used. A silver halide photographic material which is particularly useful in the practice of the present invention is an undercoat layer, a blue-sensitive silver halide photographic emulsion layer containing a yellow coupler and an intermediate layer on a support for a photographic material, and a green-sensitive halide containing a magenta coupler. A multilayer silver halide color photographic material in which a silver photographic emulsion layer, an ultraviolet absorbing layer, a red-sensitive silver halide photographic emulsion layer containing a cyan coupler, and a silver halide color photographic constituent layer such as a protective layer are sequentially provided in a multilayer arrangement. Is. As a binder for those photographic constituent layers, in addition to ordinary gelatin, polyvinylpyrrolidone, polyvinyl alcohol,
A hydrophilic polymer substance such as a sulfate ester compound of a polysaccharide can be used. Further, the photographic image forming layer may contain various additives. For example, sensitizing dyes, cyanine dyes, merocyanine dyes, etc., chemical sensitizers, water-soluble gold compounds, sulfur compounds, etc., antifoggants or stabilizers, hydroxy-triazolopyrimidine compounds, mercapto-heterocyclic compounds, etc. , Hardener, formalin, vinyl sulfone compound, aziridine compound, etc., coating aid, alkylbenzene sulfonate, sulfosuccinic acid ester salt, etc., anti-fouling agent, dialkyl hydroquinone compound, etc., fluorescent brightening agent, sharpness improvement A dye, an antistatic agent, a pH adjusting agent, a fogging agent, and a water-soluble iridium, a water-soluble rhodium compound, or the like can be contained in an appropriate combination during the production and dispersion of silver halide.

In the practice of the present invention, the silver halide photographic material is as described in "Photosensitive Material and Handling Method" (Kyoritsu Shuppan, Goro Miyamoto, Photographic Engineering Course 2) according to the photographic material. Photographic prints can be created by processing such as exposure, development, stopping, fixing, bleaching, and stabilizing.
Further, the silver halide color photographic material, preferably the multilayer silver halide color photographic material may be treated with a developer containing a development accelerator such as benzyl alcohol, thallium salt and phenidone, or benzyl alcohol may be substantially used. Color photographic prints may be prepared by processing with a developer that does not contain it.

In carrying out the present invention, the method for producing a photographic print laminate by laminating a developed photographic print and a sheet with an adhesive can be roughly classified into two methods. The first method is to supply a solution containing an adhesive (hereinafter, may be simply referred to as an adhesive solution) to the back surface of a photographic print, preferably the backcoat layer surface or the laminating sheet surface or both surfaces thereof. The second method is a bonding method, and the second method is to prepare a bonding sheet in which an adhesive is applied in advance, and water is preferably applied to the back surface of the photographic print, preferably the backcoat layer surface or the adhesive layer surface or both surfaces thereof. Is a method in which an aqueous solution containing an appropriate additive such as a surfactant or water-soluble alcohol for improving wettability is supplied and then bonded. You may stick together by any method. In order to apply the adhesive layer to the sheet in advance, it is possible to use the coating apparatus used in the general coated paper production as described above.

Based on the drawing (FIG. 2), a method for producing a photographic print laminate in the present invention by laminating a photographic print and a sheet with an adhesive, and first of all, a concrete example of the first laminating method. I will describe. From the liquid supply device (24) to the back coat surface (21a) of the developed photographic paper fed from the developed photographic paper roll (21),
The adhesive liquid (25) is a liquid supply brush (or head) (2
6). Thus, the back coat surface (21
a) and the adhesive surface (22a) of the sheet fed out from the laminating sheet roll (22) are pressure-contacted and laminated between the press roll (27) and the backup roll (28) via an adhesive, If necessary, dry zone (2
After being dried in 9), it is wound up as a photographic print laminate (23) and then cut into a desired size to prepare a photographic print laminate. The drying device is preferably a device such as a hot air drying system or an infrared drying system having an appropriate capacity, and may be cut before being wound as a photographic print laminate. Next, a specific example of the second bonding method will be described. Back coated surface (21a) of the developed photographic paper fed from the developed photographic paper roll (21)
From the liquid supply (or water supply) device (24), an aqueous solution (or water) (25) containing an appropriate additive is supplied from a liquid supply (or water supply) brush (or head) (26).
Thus, the back coat surface (21a) and the adhesive layer surface (22a) of the sheet unwound from the laminating sheet roll (22) having the adhesive layer have the press roll (2).
7) and the backup roll (28) are pressed and bonded together, and then a photographic print laminate is prepared in the same manner as in the first bonding method.

Various adhesives can be used as the adhesive used in the adhesive liquid for bonding in the practice of the present invention. For example, glue, gelatin, casein,
Starch, dextrin, carboxymethyl cellulose, hydroxyethyl cellulose and the like and mixtures thereof can be used. In the adhesive liquid, urea, oxalic acid and other organic acids or salts thereof, sodium silicate, turpentine oil, glycerin, ethylene, for the purpose of adhesive dissolution promoters, viscosity modifiers, adhesion strength promoters, etc. Various additives such as glycol monobutyl ether, ricinoleic acid ester, borax, caustic soda, sodium bisulfite, funnel oil, acetamide, carbamic acid ester, N-acetyl-ethanolamine and the like can be contained.

Examples of the laminating sheet used in the practice of the present invention include natural pulp paper containing normal natural pulp as a main component, mixed paper containing natural pulp and synthetic fiber, and synthetic fiber containing synthetic fiber as a main component. Paper, so-called synthetic paper that is made of synthetic resin film such as polyethylene, polypropylene, and the like, resin-coated paper or cellulose acetate in which one or both sides of the paper is coated with a resin capable of forming a film,
Although any film such as polyethylene terephthalate or polycarbonate may be used, natural pulp paper is preferably used because it can provide a strong photographic print laminate economically and advantageously.

As the laminating sheet used in the practice of the present invention, from the viewpoint of providing a photographic print laminate having a strong rigidity, the specific bending rigidity of the sheet is 0.30 Nm ⁷ / kg ³ or more,
It is preferably 0.35 Nm ⁷ / kg ³ or more. Further, as a natural pulp paper for a sheet, the total thickness is generally 150 to 500 μ when it is formed into a photographic print laminate.
It may be about m, and is appropriately selected according to the user's request and the purpose of the photographic print laminate.
Those having a thickness of up to 400 μm can be advantageously used. Further, the density is generally a useful those 0.8~1.2g / cm ^3, those 0.85~1.1g / cm ³ is in close contact at the time of bonding properties and photographic print stack It is preferable in terms of strength of the waist of the body.

The pulp constituting the natural pulp paper for the laminated sheet, which is advantageously used in the practice of the present invention, includes
In addition to the various pulps used for the base paper of the support for photographic materials, mechanical pulp, groundwood pulp and the like can be widely used. In addition, in the natural pulp paper for laminated sheets, the same size, dry paper strength enhancer, and wet paper strength enhancer as those contained in the base paper of the support for photographic materials at the time of preparing the paper slurry are prepared. , Filler, fixing agent,
Various additives such as a pH adjusting agent, a colorant, and a fluorescent whitening agent can be appropriately contained. Further, in natural pulp paper, the same water-soluble polymer or hydrophilic colloid or latex as that contained in the base paper of the support for photographic materials, antistatic agent, pigment, pH adjuster, colorant, fluorescent whitening agent A composition comprising various additives such as an agent can be contained or applied by size press or tab size press, or coating such as blade coating or air knife coating. Also, by using a coated paper having a coating layer having the same composition as that used in the practice of the present invention on the surface opposite to the surface to be bonded, as a laminating sheet, a photograph that is suitable for a special application A printed laminate can be provided.

As a laminating sheet used in the practice of the present invention, a heat transfer type thermal transfer recording image receiving layer, an ink jet recording image receiving layer, and A photographic print laminate having various recording performances on the back surface can be provided by using a recording medium provided with a heat-sensitive recording layer, a heat-melt ink recording layer, a laser-sensitive heat-sensitive recording layer and the like. From the viewpoint of image recording convenience, gradation, sharpness, and color vividness,
Those having heat transfer type thermal transfer recording performance or ink jet recording performance are preferable. In this case, as the base material for the sheet on which various recording layers or image receiving layers or receiving layers are provided, those having a smooth back surface are preferable, and coated paper, resin-coated paper, synthetic paper, or a coating obtained by laminating a resin layer on paper is used. Paper, film and the like are preferable.

As the laminating sheet used in the practice of the present invention, various kinds of heat transfer type thermal transfer recording image-receiving layers are used to provide a photographic print laminate having heat transfer type thermal transfer recording performance. can do.
Examples of the synthetic resin used for the heat transfer type thermal transfer recording image receiving layer include polyester resin, polyacrylic acid ester resin, polycarbonate resin, polyvinyl acetate resin,
Polyvinyl butyral resin, styrene acrylate resin, resin having ester bond such as vinyltoluene acrylate resin, resin having urethane bond such as polyurethane resin, resin having amide bond such as polyamide resin, resin having urea bond such as urea resin, Other examples include polycaprolactam resin, styrene resin, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, polyacrylonitrile resin and the like. In addition to these resins,
Mixtures or copolymers of these can also be used.

In the heat transfer type thermal transfer recording image receiving layer, a releasing agent, a pigment or the like may be added in addition to the above synthetic resin. Examples of the release agent include polyethylene wax, amide wax,
Examples thereof include solid waxes such as Teflon powder, fluorine-based surfactants, phosphoric acid ester-based surfactants, and silicone oils. Among these release agents, silicone oil is most preferred. As the silicone oil, oily ones can be used, but curable ones are preferable. Examples of the curable silicone oil include a reaction curable type, a photocurable type, and a catalyst curable type, and a reaction curable type silicone oil is particularly preferable. As a reaction-curable silicone oil,
Examples thereof include amino-modified silicone oil and epoxy-modified silicone oil. The amount of the reactive silicone oil added is preferably 0.1 to 20 wt% in the image receiving layer. As the pigment, extender pigments such as silica, calcium carbonate, titanium oxide and zinc oxide are preferable. Further, the thickness of the image receiving layer is preferably 0.5 to 20 μm, and 2 to 10
μm is more preferred.

By using, as the laminating sheet used in the practice of the present invention, those coated with various ink jet receiving layers, it is possible to provide a photographic print laminate having ink jet recording performance. Various binders may be contained in the inkjet receiving layer for the purpose of improving the drying property of the ink, the sharpness of the image and the like. Specific examples of these binders include lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives, and various gelatins such as gelatin reacted with an anhydride of a dibasic acid such as phthalic acid, maleic acid or fumaric acid. Derivatives, ordinary polyvinyl alcohols with various degrees of saponification, carboxy-modified, cation-modified and amphoteric polyvinyl alcohols and their derivatives,
Starch such as oxidized starch, cationized starch, etherified starch, carboxymethyl cellulose, cellulose derivative such as hydroxyethyl cellulose, polyvinylpyrrolidone, polyvinylpyridinium halide, sodium polyacrylate, acrylic acid methacrylic acid copolymer salt, polyethylene glycol, Polypropylene glycol, polyvinyl ether, alkyl vinyl ether / maleic anhydride copolymer, styrene / maleic anhydride copolymer and salts thereof, synthetic polymers such as polyethyleneimine, styrene / butadiene copolymer, methyl methacrylate / butadiene copolymer Conjugated diene-based copolymer latex such as
Vinyl acetate polymer latex such as polyvinyl acetate, vinyl acetate / maleic acid ester copolymer, vinyl acetate / acrylic acid ester copolymer, ethylene / vinyl acetate copolymer, acrylic acid ester polymer, methacrylic acid ester copolymer Coalesced, ethylene / acrylic acid ester copolymer,
Acrylic polymer or copolymer latex such as styrene / acrylic acid ester copolymer, vinylidene chloride copolymer latex, etc., or functional groups of monomers containing functional groups such as carboxyl groups of these various polymers Water-based adhesives such as modified polymer latex, thermosetting synthetic resin such as melamine resin, urea resin and polymethylmethacrylate,
Polyurethane resin, unsaturated polyester resin, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral,
Synthetic resin adhesive such as alkyd resin, Japanese Patent Publication No. 3-24906
Inorganic binders such as alumina sol and silica sol described or exemplified in Japanese Patent Application Laid-Open No. 3-281383 and Japanese Patent Application No. 4-240725 can be mentioned, and these may be contained alone or in combination. You can

In addition to the binder, the ink jet receiving layer may contain various additives. For example, as the surfactant, an anionic surfactant such as a long-chain alkylbenzene sulfonate, a long-chain, preferably a branched alkylsulfosuccinate ester salt, a long-chain, preferably a polyalkylene oxide of a branched alkyl group-containing phenol. Nonionic surfactants such as ethers and polyalkylene oxide ethers of long-chain alkyl alcohols, fluorinated surfactants described in Japanese Patent Publication No. 47-9303, U.S. Pat. Silane coupling agents such as ethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and hardeners for polymers, such as active halogen compounds, vinyl sulfone compounds, aziridine compounds, epoxy compounds, acryloyl compounds, isocyanate compounds. Hardener such as JP-A-1-102551
P-hydroxybenzoic acid ester compounds, benzisothiazolone compounds, isothiazolone compounds, etc. described or exemplified in JP-A-63-204251 and JP-A-1-266.
Coloring pigments, coloring dyes, fluorescent whitening agents, etc. described or exemplified in JP 537, etc., sodium hydroxide methanesulfonate, sodium P-toluenesulfinate, etc. as an anti-yellowing agent, and hydroxy-di-alkyl as an ultraviolet absorber. Benzotriazole compounds having a phenyl group at the 2-position, such as antioxidants, hindered phenol compounds described or exemplified in JP-A-1-105245, pencil writing agents such as starch granules, barium sulfate, and silicon dioxide. Fine particles of organic or inorganic particle size of 0.2-5 μm
Organopolysiloxane compounds described or exemplified in 1337, etc., as pH adjusting agents, various additives such as caustic soda, sodium carbonate, sulfuric acid, hydrochloric acid, phosphoric acid, citric acid, etc., octyl alcohol, silicon antifoaming agents, etc. It may be contained in an appropriate combination.

[0060]

EXAMPLES Examples will now be described in order to more specifically describe the present invention.

Examples 1 to 10 and Comparative Examples 1 to 4 Base papers (P1) to (P4) were made into paper. (Base paper P1) Fiber length of pulp after beating hardwood bleached kraft pulp (JAPAN TAPPI paper pulp test method No. 52-89 "paper and pulp fiber length test method")
Was beaten so that the length-weighted average fiber length (measured in accordance with the above) was 0.62 mm, and then 100 parts by weight of pulp, 3 parts by weight of cationized starch and 0.2 parts of anionized polyacrylamide were used. Parts by weight, alkyl ketene dimer emulsion (as ketene dimer content) 0.4 parts by weight, polyamide epichlorohydrin resin 0.4 parts by weight and a suitable amount of optical brightener, blue dye and red dye, and stock slurry Was prepared. Then, the stock slurry is placed on a Fourdrinier paper machine running at 360 m / min to form a web while giving an appropriate turbulence, and a wet part of 15 kg / cm ~
After performing the three-stage wet press in which the linear pressure is adjusted in the range of 100 kg / cm, the wet press is treated with a smoothing roll, and the two-stage in which the linear pressure is adjusted in the range of 30 kg / cm to 70 kg / cm in the subsequent drying part. It was dried after being pressed. Then, in the course of drying, 0.5 part by weight of carboxy-modified polyvinyl alcohol, 0.05 part by weight of optical brightener, 0.002 part by weight of blue dye, 4 parts by weight of sodium chloride and 9 parts by weight of water.
A size press liquid consisting of 5.5 parts by weight is pressed at 25 g / m ² size, dried so that the moisture content of the base paper finally obtained is 8% by weight of absolute dry water, and a machine calender at a linear pressure of 30 kg / cm. After the treatment, the basis weight is 70 g / m ² , the density is 0.90 g / cm ³ , the film thickness unevenness index Rpy is 135 mV, and the center surface average roughness S is
A base paper (P1) having an Ra of 2.01 μm was produced.

(Base paper P2) Hardwood bleached kraft pulp 5
Fiber length of pulp after beating a mixed pulp consisting of 0% by weight and 500% by weight of hardwood bleached sulfite pulp (J
APAN TAPPI Paper Pulp Test Method No. 52-8
After beating so that the length-weighted average fiber length (measured in accordance with 9 "Paper and pulp fiber length test method") was 0.62 mm, 100 parts by weight of pulp was used to give 3 parts of cationized starch. Parts by weight, anionized polyacrylamide 0.
2 parts by weight, alkyl ketene dimer emulsion (as ketene dimer content) 0.4 part by weight, polyamide epichlorohydrin resin 0.4 part by weight and a suitable amount of optical brightener, blue dye, red dye and paper stock. A slurry was prepared.
After that, the stock slurry is placed on a Fourdrinier paper machine running at 360 m / min to form a web while giving an appropriate turbulence, and a linear pressure is applied in the range of 15 kg / cm to 100 kg / cm in the wet part. After performing the adjusted three-stage wet press, it is treated with a smoothing roll, and in the subsequent drying part, after performing the two-stage tightness press in which the linear pressure is adjusted in the range of 30 kg / cm to 70 kg / cm, Dried. Then, in the middle of drying, a size consisting of 0.5 parts by weight of carboxy-modified polyvinyl alcohol, 0.05 parts by weight of optical brightener, 0.002 parts by weight of blue dye, 4 parts by weight of sodium chloride and 95.5 parts by weight of water. The press liquid is pressed with a size of 25 g / m ² and dried so that the moisture content of the base paper finally obtained is 8% by weight of absolutely dry water, and machine calendering is performed at a linear pressure of 70 kg / cm to obtain a basis weight of 82 g / m ² , density 1.05 g / cm ³ , film thickness unevenness index R
py is 130 mV and center surface average roughness S Ra is 1.40.
A base paper (P2) having a size of μm was produced.

(Base papers P3 to P4) 30% by weight of hardwood bleached kraft pulp and 7% of hardwood bleached sulfite pulp
Fiber length of pulp after beating a mixed pulp consisting of 0% by weight (JAPAN TAPPI paper pulp test method No. 52
-89 "Paper and pulp fiber length test method"
Measured length (displayed as weighted average fiber length) is 0.58 mm
Beating to 100 parts by weight of pulp,
3 parts by weight of cationized starch, 0.2 part by weight of anionized polyacrylamide, 0.4 part by weight of emulsion of alkyl ketene dimer (as ketene dimer content), 0.4 part by weight of polyamide epichlorohydrin resin and a suitable amount of optical brightener. A blue slurry and a red dye were added to prepare a stock slurry. After that, the stock slurry is placed on a Fourdrinier paper machine running at 200 m / min to form a web while giving an appropriate turbulence, and a wet part of 15 kg / cm to 100 kg /
After performing the three-stage wet press in which the linear pressure is adjusted in the range of cm, the strip is treated with a smoothing roll, and in the subsequent drying part, the linear pressure is adjusted in the range of 30 kg / cm to 70 kg / cm. After press pressing, it was dried. Then, in the middle of drying, 25 g of a size press liquid comprising 4 parts by weight of carboxy-modified polyvinyl alcohol, 0.05 part by weight of optical brightening agent, 0.002 part by weight of blue dye, 4 parts by weight of sodium chloride and 92 parts by weight of water. Press the m ² size press, dry so that the moisture content of the base paper finally obtained is 8% by weight, and machine calender at a linear pressure of 70 kg / cm to obtain a basis weight of 170 g / m ² (base paper P3 ) Or 140 g / m ² (base paper P
4), the density is 1.05 g / cm ³ , the film thickness unevenness index Rpy is 130 mV, and the center surface average roughness SRa is 1.20 μ.
m base paper (P3 or P4) was produced.

Next, coating liquids (liquids A to C) were prepared. (Coating liquid A) 70 parts by weight of kaolin, 30 parts by weight of light calcium carbonate and 0.5 parts by weight of sodium polyacrylate were dispersed in water using a Choles disperser to obtain a solid content concentration of 6
A 0% pigment slurry was prepared. To this, 10 parts (solid content) of styrene / butadiene copolymer latex and 5 parts (solid content) of oxidized starch starting from corn starch were added and sufficiently stirred to obtain a coating liquid (Liquid A).

(Coating liquid B) Separately, kaolin 10
0 parts by weight and 0.2 parts by weight of sodium pyrophosphate were dispersed in water using a core disperser to prepare a pigment slurry having a solid content concentration of 70%. Acrylic acid, butadiene,
12 parts (solid content) of methylmethacrylate copolymerized latex and 1 part (solid content) of phosphoric acid esterified starch made from corn starch were added, and the mixture was sufficiently stirred to obtain a coating liquid (B
Liquid).

(Coating liquid C) Further, 50 parts by weight of kaolin, 50 parts by weight of light calcium carbonate and 0.5 parts by weight of sodium polyacrylate were dispersed in water using a Corres disperser to obtain a solid content concentration of 60%. A pigment slurry of was prepared. To this, 7 parts (solid content) of styrene / butadiene copolymer latex and 4 parts (solid content) of oxidized starch made from corn starch as raw material were added and sufficiently stirred to obtain a coating liquid (C liquid).

Next, these coating solutions were combined as shown in Table 1, and the solution A was applied to the base paper with an air knife coater.
Further, the liquid C is coated on the base paper with a blade coater, and the liquid B is coated thereon with an air knife coater.
Highly smooth finish with super calendar. In addition,
The coating amount ratios of the liquid C and the liquid B were each set to 1: 1. Table 1 shows the results of measuring the surface roughness (SRa) on the coated layer surface side of these base papers.

Then, after the base paper surface (back surface) opposite to the side on which the silver halide photographic constituent layer is provided is subjected to corona discharge treatment,
Low density polyethylene resin (density 0.924 g / c
m ^3, MFR = 1g / 10 min) 30 parts by weight of a high density polyethylene resin (density ^{0.967g / cm 3, MFR = 15g} / 10 min) 70
The compound resin composition consisting of parts by weight is added to a resin temperature of 32
Melt extrusion coating was performed at 0 ° C. to a resin thickness of 20 μm at a running speed of the base paper of 200 m / min. At this time, the cooling roll used had a center line average roughness Ra of 1.0 μm defined by JIS K 0601 on the back resin layer surface. The cooling roll used was a cooling roll roughened by the liquid honing method, and the cooling water temperature was 12 ° C.
Operated in.

Subsequently, the base paper surface (surface) on which the silver halide photographic constituent layer is provided is subjected to corona discharge treatment, and then 30 parts by weight of a master batch of the following titanium dioxide pigment and a high-density polyethylene resin (density: 0. 967 g / cm ³ , M
FR = 6.8 g / 10 min) 20 parts by weight and low-density polyethylene resin (density 0.924 g / cm ³ , MFR = 3.0 g / 10
Min) A resin composition having a composition of 50 parts by weight is applied at a resin temperature of 315 ° C. to a thickness of 25 μm at a running speed of the base paper of 200 m / min and an effective press pressure of a cooling roll and a press roll using a melt extrusion coating machine. Melt extrusion coating was performed at 30 kg / cm ² . At this time, as the cooling roll, a chrome-plated, slightly rough surface was used, and the cooling water was operated at a temperature of 12 ° C. Further, the melt extrusion coating of the front and back resin compositions, sequential extrusion coating is performed,
It was conducted in the so-called tandem system.

(Preparation of Titanium Dioxide Pigment Masterbatch) The surface of titanium dioxide particles was surface-treated with hydrous aluminum oxide (0.5% by weight as Al ₂ O ₃ content per titanium dioxide) and steam-milled. Anatase type titanium dioxide pigment with a number average diameter of 0.118 μm 50% by weight, low density polyethylene resin (density 0.923 g / cm ³ , MFR = 8.5 g / 10 minutes) 47.5% by weight
And 2.5% by weight of zinc stearate, 240 ppm of 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethyl-benzyl) as an antioxidant.
A master batch of titanium dioxide pigment was produced by thoroughly kneading in a Banbury mixer at 150 ° C. in the presence of cyanurate, cooling and pelletizing.

Subsequently, after processing the front and back resins and before winding up, the resin layer surface on the back side of the resin-coated paper was subjected to corona discharge treatment, and then the following back coating liquid was applied on-machine.
It consists of gelatin: silicon dioxide matting agent (average particle size 2 μm) = 3: 1 as dry weight, and contains an appropriate amount of a coating aid and an inorganic antistatic agent in addition to an epoxy hardener with 15% by weight of gelatin. The backcoat coating solution was uniformly applied on-machine at a coating amount of 0.5 g / m ² for gelatin.

Further, after applying the back coat coating liquid and before winding the resin-coated paper, corona discharge treatment was applied to the resin surface on the front side, 0.75 g of lime-treated gelatin, low molecular weight gelatin (Nitta gelatin Manufactured by P-3226)
0.75 g, 0.3 g of a 10% by weight methanol solution of butyl paraoxybenzoate and 5% by weight of methanol and water of 2-ethylhexyl sulfosuccinate ester salt
A subbing coating solution containing 0.45 g of a mixed solution, the total amount of which was adjusted to 100 g with water, was uniformly applied on-machine to a gelatin coating amount of 0.06 g / m ² to obtain a support for photographic materials. It was

Then, the following multilayer silver halide color photographic constituent layers were coated on the undercoat layer on the front side of the photographic material support to obtain a color photographic printing paper. The multilayer silver halide color photographic constituent layer is composed of a blue-sensitive silver halide emulsion layer, an intermediate layer, a green-sensitive silver halide emulsion layer, an ultraviolet absorber layer, and a red-sensitive layer, which are adjacent to the undercoat layer of a support for photographic materials. Six layers were simultaneously coated from a multilayer coating E-bar so that the silver halide emulsion layer and the protective layer were located.

The blue-sensitive silver halide photographic emulsion layer was prepared by first thermoforming in the presence of an appropriate amount of potassium hexachloroiridium (III), and had an average grain size of 0, which had a halogen composition of AgBr / AgCl = 95/5. A neutral silver halide emulsion comprising a mixed crystal of [1, 0, 0] and [1, 1, 1] planes, which was sulfur-sensitized to an optimum sensitivity of 0.8 μm, was added in an amount of silver nitrate of 0.8.
6 g / m ² in addition to 1.5 g / m ² gelatin and a yellow color coupler, an appropriate amount of stabilizer, blue sensitizing dye,
It includes coating aids, hardeners, thickeners and the like. The intermediate layer contains an appropriate amount of a color mixing inhibitor, a coating aid, a thickener, a hardener, etc. in addition to 1.5 g / m ² of gelatin.

The green-sensitive silver halide emulsion layer was AgBr / AgCl = 95/5, which was produced by the first thermal formation in the presence of appropriate amounts of potassium hexachlororhodium (III) and potassium hexachloroiridium (III). An acid-processed silver halide emulsion essentially consisting of [1,0,0] faces, which has a halogen composition and has an average grain size of 0.4 μm and which is sulfur-sensitized to an optimum sensitivity, is contained in an amount of silver nitrate of 0.6 g / m ² . In addition to 1.5 g / m ^{2 of} gelatin and a magenta color forming coupler, an appropriate amount of a stabilizer, a sensitizing dye for green sensation, a sharpness improving dye, a coating aid, a hardener, a thickener and the like are contained. The ultraviolet absorbing layer contains 1.5 g / m ² of gelatin and an appropriate amount of an ultraviolet absorbent, a coating aid, a thickener, a hardener and the like.

The red-sensitive silver halide emulsion layer contains a silver halide emulsion prepared in exactly the same manner as the green-sensitive silver halide emulsion in an amount of silver nitrate of 0.6 g / m ² , and further contains gelatin of 1.5 g / m ^2.
In addition to the cyan color coupler, a proper amount of a stabilizer, a red sensitizing dye, a sharpness improving dye, a coating aid, a hardener, a thickener and the like are contained. The protective layer contains an appropriate amount of a coating aid, a thickener, a hardener and the like in addition to 1.5 g / m ² of gelatin.

The coated / dried sample was cut into rolls by a slitter, wound up, packaged, and stored at 40 ° C. under normal humidity for 4 days, and then a group photograph was printed, developed and bleached.
After fixing, washing and development, the film was dried and rolled into a roll of photographic print. Separately, white solid (unexposed) and black solid (black colored) print samples were also prepared. In addition,
A series of processes of exposure, development and drying was performed by an automatic printer and an automatic developing machine. The color development processing is carried out by a CP-31 type automatic development processor manufactured by Lucky Co., and color development (1 minute 30 seconds) → bleach-fixing (1 minute 30 seconds) → stable (1 minute 30 seconds) → drying Made in steps.

Subsequently, water containing an appropriate amount of anionic surfactant and amphoteric surfactant for improving the wettability was uniformly supplied to the back layer surface of the photographic print, and then the following rewetting adhesive layer was carried. The sheet to be coated and the photographic print were attached using the attaching apparatus shown in FIG. 2, the back surface was dried, and then cut with a cutter to prepare a photographic print laminate.

The basis weight is 71 g / m ² , the density is 0.85 g / m ³ ,
In addition, a neutral type high-quality paper having a Steckigt sizing degree of 40 seconds is used as a base material by internal addition of an alkyl ketene dimer sizing agent, and one side thereof is subjected to corona discharge treatment. 30 g of 10 wt% gelatin aqueous solution, 37.5 g of 8 wt% aqueous solution of sodium carboxymethyl cellulose (etherification degree is 0.7 to 0.8, viscosity of 2 wt% aqueous solution with B type viscometer is 5 cp or less) Including other suitable amount of surfactant, wetting aid, etc.,
The total amount of the coating liquid was adjusted to 100 g with a solid content of 2 g / m ²
Separate coating was performed to prepare a bonding sheet having a specific bending rigidity of 0.41 Nm ⁷ / kg ³ .

With respect to the obtained group photograph, white solid and black solid photographic print laminates or non-laminated photographic prints, the visual glossiness of the photographic prints was comprehensively evaluated visually by 10 monitors. Also, 10
Hold the edge of the sample by a human monitor and shake it up and down.
The strength of the lower back was evaluated by the feeling of touch.

The evaluation criteria for the apparent glossiness of a photographic print are as follows. ⊚: The glossy appearance is quite high. ◯: The glossy appearance is high. □: The glossy appearance is slightly high. Δ: Appearance of gloss is slightly low, but practical use is possible. X: The appearance has a low glossiness, and there is a practical problem.

The evaluation criteria of the waist strength based on the feeling of touch are as follows. ◎: The waist is quite strong. ：: The waist is strong. Δ: The waist is slightly weak, but it is practical. X: The waist is weak and there is a problem in practical use.

The results obtained are shown in Table 1.

[0084]

[Table 1]

As is clear from Table 1, the surface on the side of which the silver halide photographic constituent layer is provided as the base paper is coated with a coating layer comprising a coating composition containing at least a binder, and the coating layer surface Having a center plane average roughness of 1.1 μm or less and containing an internal sizing agent, a silver halide photographic in which a silver halide photographic constituent layer is provided on a resin-coated support for paper-type photographic materials Photographic print laminate according to the present invention (Examples 1 to 10) in which a developed photographic print of a material and a sheet are bonded together via an adhesive.
Is an excellent photographic print laminate having a high glossiness and a strong rigidity. Further, from the viewpoint of the effect of improving the glossy appearance, the base paper preferably has a center surface average roughness of the coated layer surface of 0.75 μm or less,
It is well understood that those of 60 μm or less are more preferable, and those of 0.45 μm or less are particularly preferable.

On the other hand, the center surface average roughness of the coated layer surface is 1.1.
When a base paper having a size larger than μm is used (Comparative Example 1), when no coating layer is applied on the surface of the base paper (Comparative Examples 2 to 4), or when no sheet is attached (Comparative Examples 3 to 4). ) A photographic print laminate or photographic print outside the invention of
It's easy to see that there is a problem with a low glossiness and a weak waist.

Examples 11 to 16 and Comparative Example 5 Instead of the base paper (P1) used in Example 3, the addition amount was changed so that the content of the alkyl ketene dimer emulsion was as shown in Table 2. Example 3 was carried out in the same manner as in Example 3 except that the base paper produced by changing the method was used.

Table 2 shows the obtained results.

[0089]

[Table 2]

[Note 1] to [Note 3] in Table 2 are as follows.

(Note 1) The content (wt%) is expressed as a weight% per absolutely dry pulp as an alkyl ketene dimer content.

(Note 2) Regarding the evaluation of the edge colorability,
A sample of the developed photographic print before being laminated with the sheet was thermo-treated at 50 ° C. for 3 days, and then the coloring degree of the edge of the photographic paper was visually evaluated by 10 people's monitors.
The evaluation criteria of the edge colorability are as follows. A: Almost no coloring is observed. ◯: Slight coloring is observed. □: Some coloring is observed. Δ: There is coloring, but there is no problem in practical use. Δ to ×: A large amount of coloring, which is a problem in practical use. X: Remarkable coloring is recognized.

As is clear from Table 2, as the base paper, the surface on the side where the silver halide photographic constituent layer is provided is coated with a coating layer comprising a coating composition containing at least a binder, and The photographic print laminate of the present invention (Examples 11 to 11) having a center surface average roughness of the layer surfaces of 1.1 μm or less and a resin-coated paper having a base paper containing an internal sizing agent as a support. It can be clearly seen that 16) is an excellent photographic print laminate having a high-gloss appearance, a strong elasticity, and no edge coloring. The content of the internal sizing agent in the base paper is preferably 0.1% by weight or more, and more preferably 0.2% by weight, based on the pulp, from the viewpoints of the effect of improving the colorability of the edge and the appearance glossiness. Above, even more preferably,
It can be clearly seen that it is 3% by weight or more, particularly preferably 0.4% by weight or more. On the other hand, when the base paper does not contain the internal sizing agent (Comparative Example 5), the edges are markedly colored, and the apparent glossiness is lowered, which is a problem.

Examples 17 to 19 and Comparative Example 6 20 parts by weight (solid content) of a styrene / butadiene copolymer latex having a glass transition temperature of 40 ° C. was added to 25 parts by weight of a 10% by weight lime-treated gelatin aqueous solution, and a binder-containing coating was applied. A liquid was obtained. Using a roll coater while appropriately adjusting the concentration of this coating liquid, the coating amount shown in Table 3 was obtained in Example 3
After coating on the base paper (P1) used in 1., it was dried in a dryer so that the water content of the paper became 6% by weight, and then the same method as the rewet casting method disclosed in JP-A-61-28097 was used to increase the water content. A smooth coated paper was obtained. The same procedure as in Example 3 was carried out except that these coated papers were used instead of the base paper used in Example 3.

The results obtained are shown in Table 3.

[0096]

[Table 3]

As is clear from Table 3, the use of cast paper satisfying the requirements of the present invention as the base paper provides a particularly excellent photographic print laminate having a high appearance glossiness and a strong elasticity (Example 17). It is well understood that the above results are obtained. On the other hand, the photographic print laminate other than the present invention (Comparative Example 6) has a low apparent glossiness, which clearly shows a problem.

Examples 20 to 22 and Comparative Example 7 The base paper (P1) used in Example 3 had a glass transition temperature of 40.
Styrene / butadiene copolymer latex (solid content 4
(0% by weight) while appropriately adjusting the concentration so that the coating amount (dry weight) shown in Table 4 is obtained using an air knife coater, and then the moisture content of the paper is adjusted to 7% by weight with a drier. Dry and then heat calender treatment (temperature 150 ℃, linear pressure 50
(kg / cm) to obtain a highly smooth coated paper. The same procedure as in Example 3 was carried out except that these coated papers were used instead of the base paper used in Example 3.

The results obtained are shown in Table 4.

[0100]

[Table 4]

As is clear from Table 4, the use of gloss-calendered coated paper which satisfies the requirements of the present invention as the base paper provides a particularly excellent photographic print having a high glossy appearance and strong elasticity. Laminate (Examples 20 to 2)
It is clear that 2) is obtained. On the other hand, the photographic print laminate other than the present invention (Comparative Example 7) has a low apparent glossiness, which is a problem.

Examples 23 to 25 The same operation as in Example 3 was carried out except that the following sheets were used as the laminating sheets used in Example 3.

(Sheet S1) Basis weight 71 g / m ² , density 0.8
The same adhesive layer as in Example 3 was coated on a high-quality paper of neutral type having a Steckigt sizing degree of 40 seconds by internal addition of an alkyl ketene dimer sizing agent of 5 g / cm ³ and the same adhesive layer as in Example 3, A sheet with a bending rigidity of 0.41 Nm ⁷ / Kg ³ .

(Sheet S2) Basis weight 71 g / m ² , density 0.9
The same adhesive layer as in Example 3 was coated on a high-quality neutral type paper having a Steckigt sizing degree of 45 seconds by internal addition of an alkylketene dimer sizing agent of 5 g / cm ³ and the same adhesive layer as in Example 3, A sheet with a bending rigidity of 0.35 Nm ⁷ / kg ³ .

(Sheet S3) Basis weight 71 g / m ² , density 1.0
The same adhesive layer as in Example 3 was coated on a high-quality neutral type paper having a Steckigt sizing degree of 50 seconds by internal addition of an alkyl ketene dimer sizing agent as a base material, the ratio of which was 2 g / cm ^3. A sheet with a bending rigidity of 0.31 Nm ⁷ / kg ³ .

(Sheet S4) Basis weight 71 g / m ² , density 1.0
The same adhesive layer as in Example 3 was coated on a high-quality neutral type paper having a Steckigt sizing degree of 55 seconds by internal addition of an alkylketene dimer sizing agent of 6 g / cm ³ and the same adhesive layer as in Example 3, A sheet with a bending rigidity of 0.28 Nm ⁷ / kg ³ .

The results obtained are shown in Table 5.

[0108]

[Table 5]

As is clear from Table 5, the photographic print laminates of the present invention (Examples 23 to 26) are excellent in that they have a high gloss appearance and a strong stiffness. In addition, the laminating sheet used for carrying out the present invention has a specific flexural rigidity of 0.30 Nm ⁷ / kg ³ or more, preferably 0.35 Nm ⁷ / kg ³ from the viewpoint of improving the strength of the waist.
It can be seen that the above is preferable.

Example 27 In Example 27, bonding was performed by a method different from the bonding method used in Example 3. In FIG. 2, 21 is a developed printing paper roll, 22 is a laminating sheet having no adhesive layer (the same as the high-quality paper base material used in Example 3, specific flexural rigidity 0.42 Nm ⁷ / Kg ³ )roll,
Therefore, 21a is the backside of the developed photographic paper, 22a
In the arrangement where is the bonding surface of the bonding sheet, 2
Same as Example 3 except that the adhesive liquid is uniformly supplied to the back coat surface from the liquid supply device No. 4 (adhesive liquid is supplied to the inside of both ears 0.5 to 1 mm of the developed photographic paper) and then bonded. Was carried out. The adhesive solution used was a commercially available one for making photo postcards.

As a result, an excellent photographic print laminate (Example 27) having a high appearance gloss (grade: ◯) and a strong elasticity (grade: ◯) was obtained.

Example 28 Instead of the laminating sheet used in Example 27, a sheet having the following inkjet image-receiving layer pre-coated on the surface opposite to the laminating surface of the sheet used in Example 27 was used. Example 27 was carried out in the same manner as in Example 27 except that it was used as a laminating sheet (specific bending rigidity 0.41 Nm ⁷ / Kg ³ ).

The ink jet image receiving layer is composed of a 10% by weight aqueous gelatin solution of alkali-processed gelatin having a molecular weight of 70,000.
25 g of 8 wt% aqueous solution of sodium carboxymethyl cellulose (degree of etherification 0.7-0.8, viscosity of 2 wt% aqueous solution with a B-type viscometer is 5 cp or less), average particle size by sedimentation method 4 μm 10% aqueous solution of porous silica (manufactured by Fuji Devison Chemical Co., Ltd., Cyloid 79)
g, an epoxy compound (NER-01 manufactured by Nagase & Co., Ltd.
0) 5% by weight methanol solution 0.3 g, sulfosuccinic acid-2-ethylhexyl ester salt 0.5% by weight methanol / water mixture 0.5 g, and pure water 14.2 g of a coating solution having a solid content of 6 g / cm 3. ^{It was applied for 2} minutes and formed.

As a result, an excellent photographic print laminate (Example 28) having a high apparent glossiness (grade: ◯) and a strong elasticity (grade: ◯) and having good ink jet recording performance was obtained. It was

Example 29 Instead of the laminating sheet used in Example 27, a foamed polypropylene film (manufactured by Toyobo Co., Ltd., Toyopearl SS) was formed on the surface opposite to the laminating surface of the sheet used in Example 27. ) Is laminated with an adhesive composed of polyester polyol and polyurethane polyisocyanate, and then the foamed polypropylene film surface is subjected to corona discharge treatment, and a sheet on which the following heat transfer type thermal transfer recording image-receiving layer is applied is applied to the treated surface. Example 27 was carried out in the same manner as in Example 27 except that it was used as a laminating sheet (specific bending rigidity: 0.39 Nm ⁷ / Kg ³ ).

The heat transfer type thermal transfer recording image receiving layer is composed of a saturated polyester resin (manufactured by Nippon Gosei Co., Ltd., TP-220) 10
Parts by weight, amino-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd.,
KF-393) 0.75 parts by weight and solvent (xylene /
An image receiving composition consisting of 30 parts by weight of methyl ethyl ketone (1/1) was applied by a wire bar at a solid content of 5 g / m ² for 5 minutes and dried.

As a result, an excellent photographic print laminate having a high appearance gloss (grade: ◯) and a strong elasticity (grade: ◯), and having a good heat transfer type thermal transfer recording performance (Example 29). ) Got.

[0118]

According to the present invention, the apparent glossiness is high.
Further, it is possible to provide a photographic print laminated body which is strong and has various recording performances on the back surface.

[Brief description of the drawings]

FIG. 1 is an enlarged sectional view of a photographic print laminate.

FIG. 2 is a schematic view of a conveyance traveling path of the bonding device.

[Brief description of reference numerals]

1 Photographic Print Laminate 2 Developed Printing Paper 3 Support for Photographic Materials 4 Base Paper 5 Base Paper 6 Coating Layer 7 Back Resin Layer 8 Front Resin Layer 9 Backcoat Layer 10 Undercoat Layer 11 Silver Halide Photographic Constituent Layer 12 Adhesion Agent layer 13 Sheet 21 Developed photographic paper roll 21a Developed photographic paper back coat surface 22 Sheet roll for bonding or sheet roll having adhesive layer 22a Adhesive surface or adhesive layer surface 23 Photographic print laminate roll 24 Liquid supply ( Or water supply device 25 adhesive liquid or aqueous solution (or water) containing appropriate additive 26 liquid supply (or water supply) brush (or head) 27 press roll 28 backup roll 29 drying zone R roll

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 10, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0001

[Correction method] Change

[Correction contents]

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin layer (A) containing a resin (a) capable of forming a film on one surface of a base paper mainly composed of natural pulp, on which a silver halide photographic constituent layer is provided.
A silver halide photographic constituent layer was provided on a support coated with a resin-coated paper type photographic material , the base paper surface of which was opposite to The present invention relates to a photographic print laminate in which a developed photographic print of a silver halide photographic material and a sheet are bonded together with an adhesive, and more specifically, an excellent photographic print that has a high appearance glossiness and is strong. Regarding the laminated body,
The present invention also relates to an excellent photographic print laminate having a high appearance glossiness, a high rigidity, and various recording performances on the back surface.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction contents]

An object of the present invention is to provide, as a base paper, a coated paper in which a coating layer is pressed against a heated mirror surface drum or a gloss calender to give a highly smooth finish, or a coating composition contains at least a binder and a pigment. It has been found that this can be effectively achieved by using a coated paper which contains and whose coating layer is calendered to a high smoothness. Another object of the present invention is to provide a base paper having a cut-off value of 0.8 mm measured by using a stylus type three-dimensional surface roughness meter on the surface of the coated layer, and a center surface average roughness in the paper making direction (hereinafter, referred to as touch). (The term "center plane average roughness in the paper-making direction" at a cutoff value of 0.8 mm measured using a needle type three-dimensional surface roughness meter is simply abbreviated as "center plane average roughness".)
It was found that it was remarkably achieved by using a coated paper having a thickness of 0.75 μm or less. The object of the present invention is
As a sheet for bonding, its specific bending rigidity (“Ha
ndbook of Physical and Mech
animal Testing of Paper a
ndPaperboard ", Volume 1, R.S. E. FIG. Mar
The present invention has been found to be remarkably achieved by using k.ed. (1983)) of 0.30 Nm ⁷ / kg ³ or more, and the present invention has been completed.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction contents]

The base paper used in the practice of the present invention is
The center surface average roughness SRa referred to in the present specification of the coated layer surface is 1.
The particle size is 1 μm or less, preferably 0.75 μm or less, more preferably 0.6 μm or less, and even less than 0.6 μm.
It is most preferably 45 μm or less. Center surface average roughness S
The base paper having Ra of 1.1 μm or less can be obtained by specifically using the following methods, preferably two or more, and more preferably three or more of the following methods in combination. It became clear by the study of the inventors.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0054

[Correction method] Change

[Correction contents]

The pulp constituting the natural pulp paper for the laminated sheet, which is advantageously used in the practice of the present invention, includes
In addition to the various pulps used for the base paper of the support for photographic materials, mechanical pulp, groundwood pulp and the like can be widely used. In addition, in the natural pulp paper for laminated sheets, the same size, dry paper strength enhancer, and wet paper strength enhancer as those contained in the base paper of the support for photographic materials at the time of preparing the paper slurry are prepared. , Filler, fixing agent,
Various additives such as a pH adjusting agent, a colorant, and a fluorescent whitening agent can be appropriately contained. In natural pulp paper, the same water-soluble polymer or hydrophilic colloid or latex as that contained in the base paper of the support for photographic materials, antistatic agent, pigment, pH adjuster, colorant,
A composition comprising various additives such as an optical brightening agent can be contained or applied by size press or tab size press, or coating such as blade coating or air knife coating. Also, as a bonding sheet,
By using a coated paper having a coating layer having the same composition as that used in the practice of the present invention on the side opposite to the laminating side, it is possible to provide a photographic print laminate that matches a particular application. I can.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction contents]

Examples 1 to 10 and Comparative Examples 1 to 4 Base papers (P1) to (P4) were made into paper. (Base paper P1) Fiber length of pulp after beating hardwood bleached kraft pulp (length-weighted average fiber length measured according to JAPAN TAPPI paper pulp test method No. 52-89 "paper and pulp fiber length test method") After beating to 0.62 mm, cationized starch 3 parts by weight, anionized polyacrylamide 0.2 parts by weight, alkyl ketene dimer emulsion (as ketene dimer content) per 100 parts by weight of pulp. ) 0.4 parts by weight, 0.4 parts by weight of polyamide epichlorohydrin resin and an appropriate amount of optical brightener, blue dye and red dye were added to prepare a stock slurry. Then, the stock slurry is placed on a Fourdrinier paper machine running at 360 m / min to form a web while giving an appropriate turbulence, and a wet part of 15 kg / cm ~
After performing the three-stage wet press in which the linear pressure is adjusted in the range of 100 kg / cm, the wet press is treated with a smoothing roll, and the two-stage in which the linear pressure is adjusted in the range of 30 kg / cm to 70 kg / cm in the subsequent drying part. It was dried after being pressed. Thereafter, in the course of drying, 0.5 part by weight of carboxy-modified polyvinyl alcohol, 0.05 part by weight of optical brightener, 0.002 part by weight of blue dye, 4 parts by weight of sodium chloride and 9 parts of water.
A size press liquid consisting of 5.5 parts by weight is pressed at 25 g / m ² size, dried so that the moisture content of the base paper finally obtained is 8% by weight of absolute dry water, and a machine calender at a linear pressure of 30 kg / cm. Treated to have a basis weight of 70 g / m ² , a density of 0.90 g / cm ³ , a thickness unevenness index Rpy of 135 mV, and a center surface average roughness SR.
A base paper (a) having an a of 2.01 μm was produced.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0062

[Correction method] Change

[Correction contents]

(Base paper P2) Hardwood bleached kraft pulp 5
Fiber length of pulp after beating mixed pulp consisting of 0% by weight and 50 % by weight of hardwood bleached sulfite pulp (JA
PAN TAPPI Paper Pulp Test Method No. 52-89
After beating so that the length-weighted average fiber length measured according to the “paper and pulp fiber length test method” is 0.62 mm, 3 parts by weight of cationized starch are added to 100 parts by weight of pulp. Parts, anionic polyacrylamide 0.2 parts by weight, alkyl ketene dimer emulsion (as ketene dimer content) 0.4 parts by weight, polyamide epichlorohydrin resin 0.4 parts by weight and appropriate amount of optical brightener, blue dye, red A dyestuff was added to prepare a stock slurry. After that, the stock slurry was placed on a Fourdrinier running at 360 m / min to form a web while giving an appropriate turbulence, and the linear pressure in the wet part ranged from 15 kg / cm to 100 kg / cm. After a controlled 3-stage wet press, smoothing rolls are applied, followed by a drying part for 30
After performing a two-stage tightness press in which the linear pressure was adjusted in the range of kg / cm to 70 kg / cm, it was dried. Then, in the middle of drying, a size press consisting of 0.5 part by weight of carboxy-modified polyvinyl alcohol, 0.05 part by weight of optical brightener, 0.002 part by weight of blue dye, 4 parts by weight of sodium chloride and 95.5 parts by weight of water. The liquid is pressed at 25 g / m ² size, dried so that the moisture content of the base paper finally obtained is 8% by weight in absolute dryness, and machine calendered at a linear pressure of 70 kg / cm to obtain a basis weight of 82 g / m 2. ² , density 1.05 g / cm ³ , film thickness unevenness index Rpy is 1
A base paper (P2) having a center surface average roughness SRa of 30 mV of 1.40 μm was manufactured.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0079

[Correction method] Change

[Correction contents]

Basis weight 71 g / m ² or 90 g / m ² , density 0.8
After the corona discharge treatment on one surface of a neutral type high-quality paper having 5 g / m ³ and having a Steckigt sizing degree of 40 seconds by internal addition of an alkyl ketene dimer sizing agent,
As the adhesive layer, 30 g of a 10% by weight aqueous solution of an alkali-processed gelatin having a molecular weight of 70,000, sodium carboxymethyl cellulose (etherification degree: 0.7 to 0.8, viscosity of a 2% by weight aqueous solution by a B type viscometer is 5 cp). 8)
A coating solution containing 37.5 g of an aqueous solution of 3% by weight and an appropriate amount of a surfactant, a wetting aid and the like, which is adjusted to 100 g with water, is applied at a solid content of 2 g / m ² for a specific bending rigidity of 0. .41 Nm ⁷ / kg ³
A bonding sheet was prepared.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0089

[Correction method] Change

[Correction contents]

[0089]

[Table 2]

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0090

[Correction method] Change

[Correction contents]

[0090] It should be noted that, in Table 2 (Note 1) through (Note 2) are as follows.

[Procedure amendment 10]

[Document name to be amended] Statement

[Name of item to be corrected] 0113

[Correction method] Change

[Correction contents]

The ink jet image receiving layer is composed of a 10% by weight aqueous gelatin solution of alkali-processed gelatin having a molecular weight of 70,000.
g, sodium carboxymethyl cellulose (etherification degree: 0.7 to 0.8, viscosity of a 2 wt% aqueous solution with a B type viscometer is 5 cp or less) 25 g of 8 wt% aqueous solution, sedimentation method average particle diameter 4 μm 30 g of a 10% aqueous solution of porous silica (manufactured by Fuji Devison Chemical Co., Ltd., Cyloid 79),
Epoxy compound (NER-010 manufactured by Nagase & Co., Ltd.)
5% by weight methanol solution of 0.3 g, sulfosuccinic acid-2-ethylhexyl ester salt methanol and water 5
A coating liquid consisting of 0.5 g of a weight% mixed liquid and 14.2 g of pure water was applied at a solid content of 6 g / m ² to form a coating liquid.

Claims (9)

[Claims] 1. A surface of one side of a base paper mainly composed of natural pulp on which a silver halide photographic constituent layer is provided is coated with a resin layer (A) containing a resin (a) capable of forming a film, and vice versa. Of a silver halide photographic material in which a silver halide photographic constituent layer is provided on a resin-coated support for a paper-type photographic material, the base paper side of which is coated with a resin layer (B) containing a resin (b) capable of forming a film. In a photographic print laminate in which a developed photographic print and a sheet are bonded together via an adhesive, the base paper has a coating on at least a binder side surface of one side of which is coated with the resin layer (A). An average of the center plane in the paper-making direction at a cut-off value of 0.8 mm measured by using a stylus type three-dimensional surface roughness meter of the coating layer surface, which is coated with a coating layer made of the composition The roughness is less than 1.1 μm, and the base paper is A photographic print laminate comprising a partial sizing agent. 2. The photographic print laminate according to claim 1, wherein the base paper is a coated paper having a highly smooth finish by pressing the coated layer against a heated mirror drum or a gloss calender. 3. The photographic print laminate according to claim 1, wherein the base paper is a coated paper in which the coating composition contains at least a binder and a pigment, and the coating layer is highly smooth finished by a calendar. 4. The photographic print laminate according to claim 3, wherein the calendar is a super calendar. 5. The photographic print laminate according to claim 1, wherein the content of the internal sizing agent is 0.1% by weight or more based on the dry pulp. 6. The sheet has a specific flexural rigidity of 0.30 Nm ⁷
The photographic print laminate according to claim 1, 2, 3, 4 or 5, which has a / Kg ³ or more. 7. The photographic print laminate according to claim 1, wherein the sheet has image recording performance. 8. The photographic print laminate according to claim 7, wherein the image record is a non-silver salt image record. 9. The photographic print laminate according to claim 8, wherein the non-silver salt image recording is of an inkjet type or a heat transfer type thermal transfer type.