WO1998034156A1

WO1998034156A1 - Image material supporter

Info

Publication number: WO1998034156A1
Application number: PCT/JP1998/000257
Authority: WO
Inventors: Touru Noda; Masayuki Tsubaki; Kengo Yamane
Original assignee: Mitsubishi Paper Mills Ltd.
Priority date: 1997-01-31
Filing date: 1998-01-23
Publication date: 1998-08-06
Also published as: DE19880298T1; JP3866296B2

Abstract

The surface of a paper substrate of an image material supporter on which an image forming layer is formed is covered with a multilayer resin sheet. The upper layer contains not less than 40 wt.% of thermoplastic resin (a) whose melting point is higher than 100 °C and the lower layer contains thermoplastic resin (b) whose melting point is not higher than 105 °C and lower than the melting point of the thermoplastic resin (a). After the substrate surface is covered with the multilayer resin sheet, the multilayer resin sheet and the substrate are joined to each other by compression while heat is not applied or heat is held in the multilayer resin sheet side. The image material supporter is highly glossy and can provide an image material and a print which do not have uneven gloss. Further, when the supporter is manufactured, the releasability of the supporter from a cooling roll is improved and uneven release is prevented. Moreover, the supporter has excellent curling properties and can be manufactured stably at a high speed, and hence the productivity and economy can be improved.

Description

Ichiichi Akira Itoda Sho Technical Support for Imaging Materials

The present invention relates to a support for image materials, and more particularly, to a paper substrate containing natural pulp as a main component, the surface of which is provided with an image forming layer, which is coated with a multilayer resin sheet. Image materials and their prints, especially silver halide photographic printing paper and its prints, which have a high sensation and have no gloss unevenness (the silver halide photographic printing papers are sometimes simply referred to as photographic prints hereinafter). The present invention relates to a support for an image material, which can be provided, has improved releasability from a cooling roll at the time of production of the support, does not cause uneven peeling, has good curl physical properties, and can be produced at high speed and stably. Background art

Usually, the image material is composed of an image material support and an image forming layer provided on the support. For example, silver halide photographic materials, ink jet recording materials, heat transfer type thermal transfer recording image-receiving materials, heat-sensitive recording materials, photosensitive heat-sensitive recording materials, etc. Layer, a heat transfer type thermal transfer recording image receiving layer, an image forming layer such as a thermosensitive coloring layer, a photosensitive thermosensitive coloring layer and the like, and an undercoat layer, a protective layer and the like as required. In particular, the silver halide photographic constituent layers include a silver halide photographic emulsion layer, a protective layer, an undercoat layer, an intermediate layer or a color mixing prevention layer, an antihalation layer, or a film layer, an ultraviolet absorbing layer, and the like. It is composed of a combination of 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. The 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 on a photographic material support. A silver halide photographic emulsion layer and a protective layer and other silver halide silver halide photographic constituent layers are provided in this order and arranged in multiple layers. --Conventionally, a resin-coated paper-type support in which a base paper surface for an image material support is coated with a thermoplastic resin is well known. As a photographic material support for silver halide photographic material applications, for example, there is known a technique for a photographic material support in which a base paper is coated with a resin having a film forming ability, preferably a polyolefin resin. I have. Also, there is known a technique for a photographic material support in which both sides of a base paper are coated with a polyolefin resin. In addition, since the rapid photographic processing method for silver halide photographic materials was applied, supports for photographic materials in which both sides of the base paper were coated with polyethylene resin have been mainly used for photographic printing paper. If necessary, the resin layer on the side where one of the image forming layers is provided usually contains a titanium dioxide pigment in order to impart sharpness.

In addition, a thermal transfer recording image receiving element having a support made of a resin-coated paper having a resin coating having a surface roughness of 7.5 microinch-AA or less, especially a polyethylene resin-coated paper in which the base paper is coated with a polyethylene resin, has been proposed. ing. Also, Japanese Patent Application Laid-Open No. 63-307979 discloses a technique relating to an ink jet recording sheet having a resin-coated paper as a support.

However, a resin-coated paper-type image material support in which the side on which the image forming layer is provided of a base paper, particularly a base paper mainly composed of natural pulp, is coated with a resin layer still has some serious problems. In fact, there are problems and no satisfactory results have yet been obtained.

First, the side of the base paper on which the image forming layer is provided (hereinafter, the side on which the image forming layer is provided is the front side, the resin layer coated on the front side is the front resin layer, the opposite side is the back side, and the resin layer coated on the back side is Is sometimes referred to as a backing resin layer.) A resin-coated paper for use as a support for image materials, in which at least the surface is covered with a resin layer containing a thermoplastic resin, particularly a polyethylene-based resin, is usually placed on a running base paper. Using a melt extruder, the polyethylene resin composition is cast from the slit die into a film and coated, pressed between a pressure roll and a cooling roll, and separated from the opening after cooling. It is manufactured in a series of steps. At that time, when producing resin-coated paper for image material for glossy use, a cooling roll having an extremely smooth surface having a mirror surface or a glossy surface or a fine rough surface is used as the cooling roll. Thus, the surface resin layer of the resin-coated paper is extremely smooth in its molten state. --Because it is pressed against a good cooling roll, it is processed to a surface with good smoothness. Therefore, an image material and its print using the resin-coated paper as a support should be able to obtain a highly visible glossy material. is there. However, it was not possible to obtain a sufficiently high glossy appearance with an image material and a print thereof using a resin-coated paper actually produced as a support. In particular, with photographic printing paper using resin-coated paper as a support, it was not possible to obtain a photographic printing paper or a photographic print with a sufficiently high glossiness.

Therefore, the present inventors have conducted various studies on the factors of the apparent glossiness of the image material and its print, and found that factors affecting the apparent glossiness include resin-coated paper as a support, an image forming layer, and a developing agent. Although there are various factors such as image forming methods such as processing, it has been found that the apparent glossiness of the image material and its print is greatly affected by the factors of the resin-coated paper as the support. Then, the present inventors further examined various factors of the resin-coated paper on the apparent glossiness, and as a result, the apparent glossiness of the image material and its print depended on the factors of the resin layer and the natural pulp was used. Factors such as the type and properties of the base paper used as the main component, such as the type of natural pulp, fiber length, stock slurry conditions such as paper additives contained in the stock slurry, papermaking speed, strain pressing, and machine calender conditions It depends on various factors such as papermaking conditions such as the size press, post-processing conditions such as the size press and tab size press, and the surface roughness of the base paper. In addition, as the thickness of the surface resin layer of the resin-coated paper becomes thinner, particularly when the thickness is 31 / zm or less, the apparent glossiness of an image material using the resin-coated paper as a support and the appearance of the print thereof are reduced. It turned out to be significantly lower. In particular, photographic materials for single-use glossy require a high degree of glossiness in photographic prints, and photographic materials with poor glossiness in photographic prints are completely unsuitable for glossy use. There was a problem that the product value was lost.

Second, resin coated paper for image materials for glossy applications requires a high degree of smoothness, but the thicker the surface resin layer becomes, especially when extruding and coating the molten resin on the base paper In particular, when the production speed of the resin-coated paper is higher than 20 zm or more, especially at 20 Om / min or more, the releasability of the resin-coated paper from the cooling rolls deteriorates, This is the occurrence of horizontal width-wise unevenness called peeling unevenness on the coated paper surface. When the peeling unevenness occurs, an image material using the resin-coated paper as a support There was also a problem that gloss and unevenness occurred in the materials and prints, and the glossiness of the appearance was further reduced, and the commercial value was significantly reduced.

Heretofore, there have been several technical proposals for eliminating and improving the above-mentioned problems and other disadvantages of the resin-coated paper-type image material support. For example, the two-layer extrusion coating method of coextrusion coating method and sequential extrusion coating method prevents clay-like pores that tend to occur on the surface resin layer surface of coated paper type photographic supports Although there is known a technique for providing a photographic support which is improved and has no surface defects and has excellent smoothness, it is insufficient to solve the above-mentioned problems, and in particular, resin-coated paper is used as the support. It was extremely inadequate to improve and improve the apparent glossiness of the image material and its print.

After the laminated structure is formed, the resin-coated paper is pressed between two or more rolls including a metal roll in contact with the resin-coated surface, which is kept at a specific temperature and pressure, to improve surface smoothness. Techniques for obtaining good resin-coated paper are known. However, even when using this technique, the resin-coated surface loses heat and blocks, resulting in poor surface smoothness. In addition, there is no effect when trying to avoid heat loss. It was extremely insufficient to improve and improve the apparent glossiness of an image material having a paper support and its print.

The first coating layer is formed mainly of a low-density polyethylene resin, and the second coating layer is formed of a polymer having a high rigidity modulus. The technology for providing coated paper type photographic supports is known, and polymers having high rigidity modulus include high-density polyethylene (HDPE), polypropylene (PP), polycarbonate (PC), and linear low-density polyethylene. Polyamides such as (LLDPE), nylon 11, nylon 6, and nylon 66, and polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) are exemplified. However, even if this technique is used, it is not enough to solve the above-mentioned problems. In particular, it is extremely difficult to improve or improve the apparent glossiness of an image material having a resin-coated paper as a support and its print. It was enough. Further, the resin-coated paper using the technique and the image material using the resin-coated paper as a support are curled toward the image forming layer side and the handling thereof becomes extremely inconvenient. There was a problem that the so-called curl physical properties deteriorated. In other words, when a polymer having a high density is used as the polymer in the second coating layer, the higher the density, the higher the content of the polymer in the coating layer, the more the resin The coated paper and the image material using the resin-coated paper as a support have a problem that the physical properties of the polyester are deteriorated. Furthermore, JP-A-7-120868 discloses that at least two water-resistant resin coating layers are provided, and the density of the water-resistant resin in the layer farthest from the base paper is made higher than the density of the water-resistant resin in the other layers. In addition, Japanese Patent Application Laid-Open No. 7-168308 discloses that a water-resistant resin coating layer has at least two layers and that the outermost water-resistant resin has a specific flexural modulus, thereby A technology for a resin-coated paper-type photographic printing paper support in which the adhesiveness between paper and a water-resistant resin layer and the releasability from a cooling roll are improved has been disclosed. It was also extremely insufficient to improve and improve the apparent glossiness of an image material having a paper support and its print. In addition, a resin-coated paper using these techniques and an image material using the resin-coated paper as a support have a problem that the physical properties of force are deteriorated. That is, when a high-density water-resistant resin is used as the water-resistant resin in the coating layer, the higher the density is, the higher the content of the water-resistant resin in the coating layer is, the more the resin becomes. The coated paper and the image material using the resin-coated paper as a support have a problem that the physical properties of the polyester are deteriorated. Disclosure of the invention

Under the above circumstances, the present invention provides a support for an image material in which the front side of a paper substrate mainly composed of natural pulp is coated with a resin layer, which has a high apparent gloss and In addition to being able to provide image materials and prints without unevenness, the peelability from the cooling roll during the production of the support has been improved, and no uneven peeling has occurred, and the curl physical properties are good, and high-speed and stable production can be achieved. It is an object of the present invention to provide a support for an image material which is excellent in productivity and economy.

Accordingly, the present inventors have conducted intensive studies to develop a support for image materials having the above-mentioned preferable properties, and as a result, the front side of a paper substrate mainly composed of natural pulp was coated with a multilayer resin sheet. (1) When the upper layer of the multilayer resin sheet contains a certain percentage or more of a thermoplastic resin (a) having a specific melting point, In any case, the lower layer contains a thermoplastic resin (b) having a specific melting point, and in some cases, contains the thermoplastic resin (a) in a smaller amount than the upper layer, and the multilayer sheet is placed on a paper substrate. (2) The upper layer and the lower layer in the multilayer resin sheet have the same configuration as above, and after the multilayer resin sheet is covered on a paper substrate, the multilayer resin sheet is (3) The upper layer of the multi-layer sheet contains more thermoplastic resin (c) than the lower layer, and the lower layer contains thermoplastic resin (d) than the upper layer. Highly contained, the melting point of the thermoplastic resin (c) is higher than the melting point of the thermoplastic resin (d), and after coating the multilayer resin sheet on a paper substrate, pressing the multilayer resin sheet while holding the heat Is suitable for the purpose The inventors have found that the present invention can be performed, and have completed the present invention based on this finding. That is, the present invention

(1) A support for an image material comprising a paper mainly composed of natural pulp as a substrate, and a surface of the paper substrate on which an image forming layer is provided, covered with a multilayer resin sheet. The upper layer [surface layer] (A) contains at least 40% by weight of a thermoplastic resin (a) having a melting point higher than 100 ° C and the lower layer [one or more layers below the surface layer] (B ) Contains a thermoplastic resin (b) having a lower melting point than the above-mentioned thermoplastic resin (a) at 105 ° C or lower, and optionally contains the thermoplastic resin (a) and the thermoplastic resin in the upper layer (A). A support for an image material (hereinafter referred to as an image material support) characterized in that it is contained in an amount smaller than the content of the resin (a) and that the multilayer resin sheet is coated on a paper substrate and then pressed in a non-heated state. It may be referred to as support 1.)

(2) An image material support comprising a paper mainly composed of natural pulp as a substrate, and a surface of the paper substrate on which an image forming layer is provided, covered with a multilayer resin sheet. The upper layer [surface layer] (A) contains not less than 40% by weight of a thermoplastic resin (a) having a melting point higher than 100 ° C and the lower layer [surface layer]

One or more layers] (B) contains a thermoplastic resin (b) having a melting point lower than that of the above-mentioned thermoplastic resin (a) at 105 ° C or lower, and optionally contains a thermoplastic resin (a), Containing the thermoplastic resin (a) in the upper layer (A) in an amount smaller than that of the thermoplastic resin (a), and coating the multilayer resin sheet on a paper substrate, and then holding the heat on the multilayer resin sheet side. The image material support characterized in that it has been pressed against (hereinafter referred to as the image material support 2). -Sometimes referred to as-. ) , and

(3) A support for an image material, wherein a paper mainly composed of natural pulp is used as a substrate, and a surface of the paper substrate on which an image forming layer is provided is coated with a multilayer resin sheet. The upper layer [surface layer] (C) contains more thermoplastic resin (c) than the lower layer [one or more layers below the surface layer] (D), and the lower layer (D) contains thermoplastic resin (C). d) is contained more than the upper layer (C), the melting point of the thermoplastic resin (c) is higher than the melting point of the thermoplastic resin (d), and the multilayer resin sheet is placed on a paper substrate. After being covered, the multilayer resin sheet is pressed against the side of the multilayer resin sheet in a state of retaining heat (hereinafter, may be referred to as image material support 3).

Is provided. BEST MODE FOR CARRYING OUT THE INVENTION

The support for image material of the present invention (hereinafter, may be simply referred to as support) 1, 2 and 3 each have a front surface of a paper substrate covered with a multilayer resin sheet. The configuration of the multilayer resin sheet of the second and the second is the same.

First, the image material supports 1 and 2 will be described.

The multilayer resin sheets in the supports 1 and 2 can be divided into an upper layer, that is, a surface layer (A), and a lower layer, that is, one or more layers (B) below the surface layer. In the upper layer (A), as the thermoplastic resin (a) used as an essential component, various thermoplastic resins can be used as long as the melting point is higher than 100 ° C. Meltov's monolate, molecular weight and molecular weight distribution can be used alone or in combination. In addition, the melting point referred to in the present specification refers to a so-called DSC method melting point of a thermoplastic resin before being processed into a support for an image material, measured by a differential scanning calorimeter.

The thermoplastic resin ( _a ) used in the practice of the present invention may be any resin as long as its melting point is higher than 100 ° C. In view of this, the melting point is preferably higher than 105 ° C, more preferably 110 ° C or higher, still more preferably 115 ° C or higher. One-

Those having a temperature of 0 ° C or higher are particularly preferred. That is, if the melting point of the thermoplastic resin (a) used in the practice of the present invention is 100 ° C. or less, a highly visible glossy product aimed at by the present invention cannot be obtained, and uneven peeling may occur. It is easy to occur.

As such a thermoplastic resin (a), a polyethylene resin is preferably used. Examples of such polyethylene resins include a polyethylene resin polymerized and produced by a high-pressure method, a polyethylene resin polymerized and produced using a methyl alcohol polymerization catalyst, and a polyethylene resin produced by polymerization using a metal catalyst other than a metallocene polymerization catalyst. Examples thereof include resins and mixtures thereof.

As the thermoplastic resin (a), polyethylene resins polymerized and produced by a high-pressure method preferably used in the practice of the present invention include long chains produced by a high-pressure production method using an autoclave reactor, a tubular reactor, or the like. Various types of polyethylene resins having a branch. Examples of the polyethylene resins polymerized and produced by these high-pressure methods include low-density polyethylene resins, medium-density polyethylene resins, copolymers of ethylene with propylene, butylene, and other monoolefins, and carboxy-modified polyethylene resins. and the like and mixtures thereof, various density of a melt Furore one preparative molecular weight, can be used those having a molecular weight distribution, typically, density 0. 9 0~0. 9 5 g / cm 3 , preferably in the range density 0 · 9 2 4~0 9 5 g / cm 3 range, the melt flow rate is 0:..!. ~ 5 0 g / 10 min, preferably a melt flow rate 0 4~ 5 0 g / 10 Can be used alone or in combination of two or more. In addition, the melt flatness of the polyethylene resin is specified in accordance with JISK 670 “Polyethylene test method”.

As the thermoplastic resin (a), polyethylene resins polymerized and produced using a meta-mouth polymer catalyst preferably used in the practice of the present invention include JP-A-3-502710, JP-A-60-35006. As disclosed in JP-A-63-501369, JP-A-3-234717, JP-A-3-234718, and the like, a zirconium-based or hafnium-based meta-opening, It is produced by polymerization using a combination of methylaluminoxane and the like with enhanced catalytic activity as a polymerization catalyst. Examples of polyethylene resins produced by polymerization using these meta-opening polymerization catalysts include low-density polyethylene resin, medium-density polyethylene resin, high-density polyethylene resin, 1-1 Linear low-density polyethylene resin, ethylene-based copolymers with olefins such as propylene and butylene, carboxy-modified polyethylene resins, etc. and mixtures thereof, with various densities and melt flow rates , molecular weight, can be used those having a molecular weight distribution, typically in the range of density of 0.9 10~0.97g / cm ^3, preferably in the range of 0.9 1 5~0.97g / cm ^3, particularly preferably density 0.920~0.97g / cm ³ , and a melt flow rate in the range of 0.05 to 50 Og / 10 min, preferably 0.08 to 30 Og / 10 min, can be used alone or as a mixture of two or more.

As the thermoplastic resin (a), examples of the polyethylene resin produced by polymerization using a metal polymerization catalyst other than the meta-opening polymerization catalyst preferably used in the practice of the present invention include a zigzag method, a Philips method and the like. Various types of polyethylene-based resins polymerized and produced by using them can be exemplified. Examples of polyethylene resins polymerized and produced using metal polymerization catalysts other than those metal metacene catalysts include ultra-low-density polyethylene resin, low-density polyethylene resin, medium-density polyethylene resin, high-density polyethylene resin, and linear Low-density polyethylene resin, ethylene-based copolymers with propylene, butylene, etc., and carboxy-modified polyethylene resins, and mixtures thereof, with various densities, melt flow rates, molecular weight, can be used those having a molecular weight distribution, typically in the range of density 0.87~0.97g / cm ^3, preferably in the range density of 0.905 ~ 0.97 g / cm ^3, more preferably the density is 0.9. 10 to 0.97 g / cm ³ range, even more preferably in the range density of 0.9 from 15 to 0.97 g / cm ^3, more preferably in the range density of from 0.920 to 0.97 g / cm ^3, even more preferred Range properly a density of from .925 to .97 g / cm ^3, particularly preferably a density of 0.9 30 to 0.97 / 0! 1 ³ range, melt flow rate 0.05 ~ 50 Og / 10 min, it is preferable properly 0.08 to 30 Og / 10 minutes can be used alone or in combination of two or more.

In the practice of the present invention, a polyester resin, a polycarbonate resin, or a mixture thereof can be used as the thermoplastic resin (a). In the present invention, a polycarbonate-based resin has a softening point and is equivalent to the melting point of another resin.

Polyester resins used in the practice of the present invention include poly It is a polyester resin, a polybutylene terephthalate resin, a polyester-based biodegradable resin, a mixture thereof or a mixture thereof with a polyethylene resin, and various densities and intrinsic viscosities [] can be used. As a typical representative example, mention may be made of a polyester resin manufactured by Mitsubishi Kasei Corporation (trade name: NO VAPEX HS004, melting point 235 ° C, density 1.33 g / cm ³ , intrinsic viscosity [77] 0.73 dl / g). Can be. Further, a mixture of a polyester resin and a polyethylene resin can be advantageously used. For example, a mixture of a copolymerized polyethylene terephthalate resin and a copolymerized polyethylene resin (melting point: 74 ° C) graft-modified with maleic acid (melting point: 224 ° C, manufactured by Mitsubishi Chemical Corporation) can be given.

As the polycarbonate resin used in the practice of the present invention, various grades can be used. As a specific representative example, a polycarbonate resin (trade name: manufactured by Mitsubishi Chemical Corporation) NOVAREX 7022A, density 1.2 Og / cm ³ , melt flow rate 12-16 g / 10 min, softening point 160 ° C-190 ° C).

In the present invention, from the viewpoint of further improving the apparent glossiness and peeling unevenness of the image material and its print, and further from the viewpoint of improving the moldability of the resin composition, the thermoplastic resin used in the practice of the present invention. As (a), a resin composition comprising a low-density polyethylene resin and a high-density polyethylene resin is more preferable. As the low-density polyethylene resin, those having the above-mentioned various production methods, density, melt flatness, molecular weight, and molecular weight distribution can be used, and low-density polyethylene resin polymerized and produced by a high-pressure method is preferable. As the low density polyethylene resin, density, 0 is .90~0.95g / cm ³ in the range of what is advantageous, preferably in the range density of .918-.930 g / cm ^3, the density Is more preferably in the range of 0.924 to 0.93 Og / cm ³ . Further, as the high-density polyethylene resin, those having various production methods, density, melt flatness, molecular weight, and molecular weight distribution as described above can be used, and those having a density in the range of 0.95 to 0.97 g / cm ³ are preferable. Those having a density in the range of 0.960 to 0.97 g / cm ³ are more preferable. Further, from the viewpoint of improving the apparent glossiness, peeling unevenness and curl physical properties of the image material and its print, the content ratio of the high-density polyethylene resin is determined based on the total thermoplastic resin component in the upper layer (A). 15 --The amount is preferably not less than 20%, more preferably 20 to 75% by weight, and particularly preferably 25 to 65% by weight.

On the other hand, as the thermoplastic resin (b) used as an essential component in the lower layer (B), a resin having a melting point of 105 ° C. or lower and a melting point lower than that of the thermoplastic resin (a) is used. Although thermoplastic resin ^ ¹ various is available, from the viewpoint of the effect of improving the gloss of the image material and appearance of the print, is preferably the following 100 ° C its melting point, the following 95 ° C Is particularly preferred. Further, those having various densities, melt flow rates, molecular weights, and molecular weight distributions can be used alone or in combination. Polyethylene resin is preferably used as the thermoplastic resin β (b). Examples of such polyethylene resins include polyethylene resins produced using a metallocene polymerization catalyst, polyethylene resins produced using a metal catalyst other than a metallocene polymerization catalyst, and mixtures thereof. it can. Among them, a polyethylene resin produced by polymerization using a methacrylic acid polymerization catalyst is particularly preferred. In addition, ultra-low density polyethylene resin, low density polyethylene resin, linear low density polyethylene resin, copolymers of ethylene with olefins such as propylene and butylene, and carboxy-modified polyethylene resins, and the like. As long as the mixture is a mixture having a melting point of 105 ° C or lower and lower than that of the thermoplastic resin (a), those having various densities, melt velocities, molecular weights, and molecular weight distributions can be used.

As the thermoplastic resin (b), polyethylene resins produced by polymerization using a metallocene polymerization catalyst particularly preferably used in the practice of the present invention include JP-A-3-502710 and JP-A-60-35006. As disclosed in JP-T-63-501369, JP-A-3-234717, JP-A-3-234718, etc., it is preferable to use a zirconium-based or hafdium-based meta-opening. It is produced by polymerization using a catalyst with enhanced catalytic activity in combination with methylaluminoxane or the like as a polymerization catalyst. As the polyethylene resin produced by polymerization using these meta-opening polymerization catalysts, those having various densities, melt flow rates, molecular weights, and molecular weight distributions can be used, and usually, the density is 0.87 to 0.92 g / cm ³ , It is preferably in the range of 0.890 to 0.91 Og / cm ³ , particularly preferably in the range of 0.890 to 0.905 g / cm ³ , and the melt rate is 0.0. --

5 to 5 OO g / 10 min, preferably 0.08 to 30 O g / 10 min, particularly preferably 0.1 to 10 O g / 10 min, alone or as a mixture of two or more Can be used.

When the thermoplastic resin (a) and the thermoplastic resin (b) used in the practice of the present invention are used in combination with two or more polyethylene resins having different melting points or melt flow rates, the two resins used in combination are used. A compound resin composition prepared by previously melting and mixing at least one kind of polyethylene resin is preferable. For example, when a polyethylene resin having a melt flow rate of 5 to 4 Og / 10 minutes and a polyethylene resin having a melt flow rate of 0.2 to 4.5 g / 10 minutes are used in combination, It is preferably used as a compound tree composition prepared by melting and mixing in advance. The use of the compound resin prepared in this manner is preferable in terms of moldability and film uniformity, and in preventing non-uniform resin agglomeration called resin gel. Various methods can be used to prepare the compound resin composition. For example, using a kneading extruder, a heating roll kneader, a Banbury mixer, a pressurized die, etc., two or more types of polyethylene resins, and if necessary, other thermoplastic resins, antioxidants, release agents A method of adding various additives such as a molding agent, melting and mixing, and then pelletizing the mixture is advantageously used.

The upper layer (A) in the present invention indicates a surface layer in the multilayer resin sheet, and the lower layer (B) indicates one or more layers below the surface layer. In the present invention, from the viewpoint of the effects of the present invention, a multilayer resin sheet having a three-layer structure in which the upper layer (A) is the uppermost layer and the lower layer (B) is the intermediate layer and the lowermost layer, or the upper layer (A) A multilayer resin sheet having a two-layer structure composed of a lower layer (B) and a single layer is preferred, and a multilayer resin sheet having a two-layer structure is particularly preferred.

In the present invention, from the viewpoint of further improving the apparent glossiness and peeling unevenness of the image material and its print, the content ratio of the thermoplastic resin (a) used in the upper layer (A) is determined as follows. It is preferably at least 40% by weight, particularly preferably at least 50% by weight, based on the thermoplastic resin component.

When the upper layer (A) contains the thermoplastic resin (b), its content is preferably smaller than the content of the thermoplastic resin (b) in the lower layer (B).

Further, in the present invention, the glossiness and peeling appearance of the image material and its print are apparent. From the viewpoint of remarkably improving these properties, the content of the thermoplastic resin (b) used in the lower layer (B) is preferably at least 20% by weight based on the total thermoplastic resin component in the lower layer, More preferably, more preferably 40% by weight or more, even more preferably 50% by weight or more, still more preferably 60% by weight or more, and particularly preferably 70% by weight or more. Further, the lower layer (B) may optionally contain the thermoplastic resin (a) in an amount smaller than the content of the thermoplastic resin (a) in the upper layer (A).

In addition, in the upper layer (A) and the lower layer (B), other than thermoplastic resin (a) and thermoplastic resin (b) as long as the requirements of the present invention are satisfied without impairing the effects of the present invention. For example, a homopolymer such as polyethylene resin, polybutene, and polypentene; a copolymer of two or more monoolefins such as ethylene-butylene copolymer; and a polyester resin.

Further, in the present invention, from the viewpoint of improving the moldability of the resin composition for the lower layer containing the thermoplastic resin (b), and from the viewpoint of improving the desired properties of the support for the image material, It is preferable to include a polyethylene resin polymerized and produced by a high-pressure method. As the polyethylene resin, a polyethylene resin polymerized and produced by the high-pressure method as described above is useful, but a low-density polyethylene resin polymerized and produced by the high-pressure method is more preferable, and the density is 0.918 to 0.93 Og / cm ^3. Are more preferable, and those having a density in the range of 0.918 to 0.926 g / cm ³ are particularly preferable.

Melt flow as a total of resin components in the upper (A) and lower (B) resin layers containing the thermoplastic resin (a) and the thermoplastic resin (b), respectively, used in the practice of the present invention. Although the rate is not particularly limited, thermoplastic resin, which is a particularly preferred embodiment of the present invention, is preferred from the viewpoints of melt extrusion coating properties of the resin composition, moldability, and the effect of improving the apparent glossiness. When the resin is a polyethylene resin, the melt flow rate is preferably in the range of 2 to 15 g / 10 minutes, and more preferably in the range of 3 to 10 g / 10 minutes.

In the image material support 1 of the present invention, the surface of the base paper on which the image forming layer is provided is covered with at least two layers of a multilayer resin sheet comprising the upper layer (A) and the lower layer (B). Manufactured by pressure welding without heating. As for the pressure contact in the non-heated state, a calendar treatment using a calender using rolls of various materials is preferable, and a soft calendar treatment using a soft calender is more preferable.

In a preferred embodiment of the force-rendering treatment, particularly preferably the soft calendering treatment in the present invention, the treatment is carried out between two or more rolls including at least one metal roll.

As a particularly preferred embodiment of the soft calender treatment in the present invention, a soft calender treatment using a soft calender device in which one roll other than the metal opening is a rubber-coated roll is particularly preferable.

The hardness of the rubber-coated roll is preferably from 40 to 100 Shore hardness, and particularly preferably from 50 to 80 Shore hardness.

The press linear pressure during calendering, particularly preferably soft calendering, is preferably 7.5 to 55 kgf / cm, particularly preferably 15 to 45 kgf / cm.

The number of treatments may be one, but it can be carried out many times depending on the degree of effect. At this time, it is also a preferred embodiment of the present invention that the pressing in a non-heated state is performed in two or more lines.

In order to further remarkably improve the apparent glossiness of the image material and its print, the image material support 2 of the present invention has a surface on the side of the base paper on which the image forming layer is provided, and the upper layer (A) After being covered with at least two layers of the multilayer resin sheet comprising the lower layer (B), the multilayer resin sheet is pressed against the side of the multilayer resin sheet while maintaining heat.

As for the pressure welding while holding the heat, a heat calendering treatment using a heat calendering device using rolls of various materials is preferable, and a heat soft calendering treatment using a heat soft calendering device is particularly preferable.

In a preferred embodiment of the thermal power rendering, particularly preferably the thermal soft rendering, according to the invention, the surface temperature is between 40 ° C. and 150 ° C., preferably between 40 ° C. and 120 ° C. C, particularly preferably between two or more rolls including at least one metal roll at 50 ° C to 90 ° C.

The temperature at the time of performing the heat calendering treatment, particularly preferably the heat soft calendering treatment, -Normally, the surface temperature is 40 ° C to 150 ° C. Is determined in the context of

As a particularly preferred embodiment of the thermal soft calendering treatment in the present invention, a thermal soft calendering treatment using a thermal soft calendering device in which one roll other than the metal roll is a rubber-coated roll is particularly preferred.

'' The linear pressure of the press during the heat calendering treatment, particularly preferably the heat soft calendering treatment, is preferably 3 to 45 kgf / cm, more preferably 4 to 35 kgf / cm, and particularly preferably 5 to 5 kgf / cm. ~ 25 kgf / cm. In addition, it is also effective to perform processing in a so-called plain state, in which the processing is performed only by the weight of the press roll and the tension of the paper without applying a load as the press linear pressure.

The number of heat treatments may be one, but many times depending on the degree of effect. In this case, it is also a preferred embodiment of the present invention that the pressure welding while maintaining the heat is performed in two or more lines.

By performing such a heat calendering treatment, the apparent glossiness of the image material and the print thereof is remarkably improved, but the present invention can have still another feature.

That is, a lower layer containing a thermoplastic resin (b) having a melting point of 105 ° C. or less, preferably 100 ° C. or less, and particularly preferably 95 ° C. or less, on the side of the base paper on which the image forming layer is provided. The heat whose melting point is preferably higher than 105 ° C, more preferably 110 ° C or higher, still more preferably 115 ° C or higher, and particularly preferably 120 ° C or higher By providing an upper layer containing the plastic resin (a), an image material having a high apparent gloss and an image material support capable of providing a print thereof can be obtained even when a thermal calendar treatment is performed at a relatively low temperature. It is. In addition, since the heat calendering treatment can be performed at a relatively low temperature, a support for an image material can be obtained which does not cause blocking and therefore does not cause uneven peeling.

Further, in the present invention, calendar treatment in a non-heated state or at a relatively low temperature Since it is possible to perform heat-calendering in one place, it does not cause blocking. That is, stable production is possible.

Furthermore, the present invention has another very favorable advantage. In the present invention, the upper layer preferably contains a high-density polyethylene resin from the viewpoint of further improving the apparent glossiness and peeling unevenness of the image material and its print. In a general resin-coated paper-type image material support, the more the high-density polyethylene resin is included in the resin layer, the more the image material support, and further the image material and the print physical properties of the image material. There was a problem that the deterioration was remarkable. However, in the support for an image material in the present invention, the thermoplastic resin (b) in the lower layer has a low melting point and preferably a low density, usually a density of 0.87 to 0.92 g / cm ³ , Preferably, a polyethylene resin in the range of 0.890 to 0.910 g / cm ³ , particularly preferably 0.890 to 0.905 g / cm ³ is used. The present invention has the advantage of being able to provide a support for an image material having very good curl physical properties, and hence an image material having very good curl physical properties and a print thereof.

Next, the image material support 3 will be described.

The multilayer resin sheet in the support 3 can be divided into an upper layer, that is, a surface layer (C) and a lower layer, that is, one or more layers (D) below the surface layer.

In the upper layer (C), as the thermoplastic resin (c) used as an essential component, various thermoplastic resins may be used as long as the melting point is higher than the melting point of the thermoplastic resin (d) used as an essential component in the lower layer (D). A resin can be used, but a resin having a melting point of 115 ° C or more is preferable. Also, those having various densities, melt flow rates, molecular weights, and molecular weight distributions can be used alone or in combination.

As such a thermoplastic resin (c), a polyethylene resin is preferably used. This polyethylene resin is as described in the above-mentioned thermoplastic resin (a).

In the practice of the present invention, a polyester resin, a polycarbonate resin, or a mixture thereof can be used as the thermoplastic resin (c). This polyes -The telluric resin and the polycarbonate resin are as described in the thermoplastic resin (a) above.

The thermoplastic resin (c) used in the practice of the present invention has a melting point of 115 ° C. or more from the viewpoint of improving the apparent glossiness and peeling unevenness of the image material and its print. Preferably, it is more preferably at least 120 ° C, particularly preferably at least 125 ° C. That is, if the melting point of the thermoplastic resin (c) used in the practice of the present invention is too low, it is difficult to obtain a product having a high apparent glossiness aimed at by the present invention, and uneven peeling tends to occur. .

On the other hand, in the lower layer (D), as the thermoplastic resin (d) used as an essential component, various thermoplastic resins having a melting point lower than that of the thermoplastic resin (c) may be used. Although it can be used, it is preferable that the melting point is 5 ° C or more lower than the melting point of the thermoplastic resin (c), more preferably 10 ° C or more, from the viewpoint of improving the apparent glossiness. Those lower by 15 ° C or more are still more preferable, and those lower by 20 ° C or more are particularly preferable. Further, those having a melting point of 125 ° C or less are preferred, those having a melting point of 120 ° C or less are more preferred, and those having a melting point of 115 ° C or less are particularly preferred. Further, those having various densities, melt flow rates, molecular weights, and molecular weight distributions can be used alone or in combination.

As such a thermoplastic resin (d), a polyethylene resin is preferably used. Examples of such polyethylene resins include a polyethylene resin polymerized and produced by a high-pressure method, a polyethylene resin polymerized and produced using a methyl alcohol polymerization catalyst, and a polyethylene resin produced by polymerization using a metal catalyst other than a metallocene polymerization catalyst. Examples thereof include resins and mixtures thereof. Among them, a polyethylene-based resin polymerized and produced by a high-pressure method is preferable. In addition, ultra-low density polyethylene resin, low density polyethylene resin, medium density polyethylene resin, linear low density polyethylene resin, copolymers of ethylene with propylene, butylene, etc., or carboxy-modified polyethylene resin And mixtures thereof, and those having various melting points, melt flow rates, molecular weights, and molecular weight distributions can be used as long as the melting point is lower than the melting point of the thermoplastic resin (c).

As the thermoplastic resin (d), a high-pressure method preferably used in the practice of the present invention is used. -Polyethylene resins produced by polymerization include various types of polyethylene resins having long-chain branching by a high-pressure production method using a photoclave type reactor, a tubular type reactor and the like. Polyethylene resins polymerized and produced by these high-pressure methods include low-density polyethylene resins, medium-density polyethylene resins, copolymers of ethylene with propylene, butylene, and other monoolefins, and carboxy-modified polyethylene resins. and the like and mixtures thereof, various density of a melt Furore over preparative molecular weight, can be used those having a molecular weight distribution, typically, density 0. 9 0~0. 9 5 g / cm 3 , preferably in the range Density ranges from 0.90 to 0.93 Og / 10 minutes, melt flow rate from 0.1 to 50 g / 10 minutes, preferably from 0.4 to 5 O g / 10 minutes can be used alone or in combination of two or more.

The thermoplastic resin (c) used in the practice of the present invention has a melting point of preferably at least 115 ° C, more preferably at least 120 ° C, from the viewpoint of improving the apparent glossiness and peeling unevenness. Particularly preferably, a polyethylene resin having a melting point lower than the melting point of the resin used as the main component, preferably a polyethylene resin having a melting point lower than 125 ° C. A resin composition mixed with a resin is advantageously used. As the resin composition, a compound resin composition prepared by melting and mixing in advance is preferable. The use of the compound resin prepared in this manner is preferable in terms of moldability and film uniformity and in preventing non-uniform resin agglomeration called resin gel. Various methods can be used to prepare the compound resin composition. For example, using a kneading extruder, a heated roll kneader, a Banbury mixer, a pressurized whisk, etc., two or more types of polyethylene-based resins, and if necessary, other thermoplastic resins and antioxidants A method of adding various additives such as a release agent and melting and mixing, and then pelletizing the mixture is advantageously used. In the practice of the present invention, it is preferable to use a mixture of thermoplastic resins having different physical properties in advance by melting and mixing them in advance. As described above, when a polyethylene-based resin with a high melting point is used as the main component and a polyethylene-based resin with a lower melting point is used in combination, especially when there is a large difference between the melt mouth opening rates of both, for example, as the main component The melt flow rate of the polyethylene resin used is 5 to 4 Og / 10 minutes, and the melt flow rate of the polyethylene resin used in combination is When the rate is 0.2 to 4.5 g / l0 min, it is particularly preferable to use a compound resin composition prepared by melting and mixing in advance.

In this support 3, the upper layer (C) contains more thermoplastic resin (c) than the lower layer (D), and the lower layer (D) contains more thermoplastic resin (d) than the upper layer (C). It is necessary to contain. The content of the thermoplastic resin (c) in the upper layer (C) and the content of the thermoplastic resin (d) in the lower layer (D) are different from the viewpoint of the apparent glossiness and the effect of improving the peeling unevenness. , 50% by weight or more, more preferably 60% by weight or more, particularly preferably 70% by weight or more.

Further, in the support 3, from the viewpoint of the effect of the present invention, a multilayer resin sheet having a three-layer structure in which the upper layer (C) is the uppermost layer and the lower layer (D) is the intermediate layer and the lowermost layer, or A multilayer resin sheet having a two-layer structure composed of an upper layer (C) and one lower layer (D) is preferred, and a multilayer resin sheet having a two-layer structure is particularly preferred.

In addition, in the upper layer (C) and the lower layer (D), other than thermoplastic resin (c) and thermoplastic resin (d) as long as the requirements of the present invention are satisfied without impairing the effects of the present invention. For example, a homopolymer such as polyethylene resin, polybutene, and polypentene; a copolymer of two or more of hyorefins such as an ethylene-butylene copolymer; and a polyester resin.

Melt opening as a total of resin components in the upper (C) and lower (D) resin layers containing the thermoplastic resin (c) and the thermoplastic resin (d) used in the practice of the present invention. The rate is not particularly limited, but it is a particularly preferred embodiment of the present invention in view of the melt extrusion coating property of the composition, the formability and the effect of improving the apparent glossiness. When the thermoplastic resin is a polyethylene resin, the melt mouth opening rate is preferably in the range of 2 to 15 g / 10 minutes, and more preferably in the range of 3 to 1 Og / 10 minutes.

In the image material support 3 of the present invention, the surface of the base paper on which the image forming layer is provided is covered with at least two layers of a multilayer resin sheet comprising the upper layer (C) and the lower layer (D). It is manufactured by being pressed against the multilayer resin sheet while holding heat. As for the pressure welding while holding the heat, it is preferable to use a heat calendering apparatus using rolls of various materials, and to use a heat calendering apparatus. --Thermal soft calendering is particularly preferred.

Preferred embodiments of the thermal power rendering treatment of the invention, particularly preferably the thermal soft calendering treatment, include a surface temperature of 50 ° C. to 150 ° C., preferably 55 ° C. to 100 ° C., Particularly preferably, the treatment is performed between two or more holes including at least one metal roll at 60 ° C to 90 ° C.

The temperature at the time of performing the heat calendering treatment, particularly preferably the thermal soft calendering treatment, is usually 50 ° C. to 150 ° C., but the thermoplastic resin (c ) And the melting point of the resin layer containing the thermoplastic resin (d).

As a particularly preferred embodiment of the heat soft calendering treatment of the present invention, a heat soft calendering treatment using a heat soft calendering device in which one roll other than the metal roll is a rubber-coated roll is particularly preferable.

The press linear pressure at the time of performing the heat calendering treatment, particularly preferably the heat soft calendering treatment, is preferably 3 to 45 kgf / cm, more preferably 4 to 35 kgf / cm, and particularly preferably 5 to 5 kgf / cm. ~ 25 kgf / cm. In addition, it is also effective to perform processing in a so-called plain state, in which the processing is performed only by the weight of the press roll and the tension of the paper without applying a load as the press linear pressure.

By performing the thermal calendering treatment in this manner, the apparent glossiness of the image material and its print is remarkably improved, but the present invention can have another feature.

That is, on the side of the base paper on which the image forming layer is provided, the upper layer (C) having a higher melting point of the thermoplastic resin (c) having a higher melting point than the thermoplastic resin (d) contained in the lower layer (D) than the lower layer (D) ), It is possible to obtain a support for an image material, which does not cause blocking and thus does not cause uneven peeling. --Even more remarkable is that despite the multi-layer resin sheet made of thermoplastic resin being subjected to thermal power rendering, it does not need to be reduced in speed to produce more than 20 Om / min and 250 m / min. As described above, high-speed and stable production is possible, especially at a production speed of 300 thighs / minute or more.

The back surface of the base paper of the image material support of the present invention (refers to image material supports 1, 2 and 3; the same applies hereinafter) is preferably coated with a resin having film forming ability. . Thermoplastic resins such as polyolefin resin, polycarbonate resin, polyester resin and polyamide resin are preferred as the resin having such film forming ability, and among them, polyolefin resin is more preferred in view of melt extrusion coating property, and polyethylene is more preferred. A system resin is particularly preferred. Further, it may be coated with an electron beam curing resin described in JP-B-60-17104.

The multilayer resin sheet on the front side of the image material support in the present invention may have a two-layer structure or a multilayer structure having more layers, but the two-layer structure efficiently achieves the object of the present invention. Especially preferred above. The support for an image material in the present invention is produced by a so-called melt extrusion coating method in which a resin composition that has been heated and melted is cast and coated on a running base paper. At that time, the so-called co-extrusion coating method in which two or more resin layers on the front side of the image material support are extrusion-coated at the same time may be used. A so-called sequential extrusion coating method in which the layers and then the resin layers are sequentially melt-extruded and coated at different stations, may be used. In the present invention, from the viewpoint of improving the apparent glossiness and peeling unevenness of the image material and its print, a support for the image material manufactured by using the sequential extrusion coating method is particularly preferable. Further, at the time of successive extrusion coating, at least the lowermost resin layer may or may not be subjected to activation treatment such as corona discharge treatment.

In the case of melt extrusion coating, the slit die is preferably a T-type die, an L-type die, or a flat die of a fish-til type die, and the slit opening diameter is desirably 0.1 to 2 thighs. The type of the multilayer co-extrusion die may be any of a feed block type, a multi-manifold type, a multi-slot type, and the like. The temperature of the molten film is 280 to 34 ° C. In this case, a temperature difference between the resin composition for the uppermost layer and the resin composition constituting the resin layer below the uppermost layer may be provided. For example, by lowering the temperature of the resin composition for the uppermost layer by 5 to 10 ° C lower than the temperature of the resin composition constituting the lower resin layer, the removability of the resin layer from the cooling port is reduced. Can be improved.

The coating thickness of the surface multilayer resin sheet of the image material support in the present invention is advantageously in the range of 8 to 1001111, preferably in the range of 12 to 60 / m, and is preferably in the range of 18 to The range of 4 is particularly preferred. Further, in the case of a multilayer structure in which a resin layer composed of a lower layer and an upper layer and a resin layer composed of at least an uppermost layer, which is a particularly preferred support for an image material in the present invention, is sequentially melt-extruded and coated, the lower layer The thickness of the resin layer is preferably 25% or more, more preferably 40%, of the thickness of the multilayer resin sheet from the viewpoint of improving the apparent glossiness and peeling unevenness of the image material and its print. The above thickness is more preferable, and the thickness of 50% or more is particularly preferable, but is not particularly limited. The back side of the base paper is preferably coated with a back resin layer mainly composed of a resin having film forming ability, but the resin is preferably a polyethylene-based resin, and the coating thickness of the front-side multilayer is It is preferable to set appropriately within a range that balances the resin sheet, and particularly the force balance. In general, a range of 8 to 100 zm is advantageous, but a range of 12 to 60 / m is preferable.

In practicing the present invention, it is preferable to perform an activation treatment such as a corona discharge treatment or a flame treatment on the base paper before coating the front and back resin compositions on the base paper. Further, as described in JP-B-61-42254, a resin layer may be coated on a running base paper after spraying an ozone-containing gas onto a molten resin composition in contact with the base paper. The front and back resin layers are preferably sequentially and preferably continuously extruded and coated on the base paper by a so-called tandem extrusion coating method, and if necessary, the back resin layer is coated. May be covered with a multilayer structure of two or more layers. The surface of the front multilayer resin sheet of the support for image materials can be processed into a glossy surface, a finely rough surface described in JP-B-62-19732, a matte surface or a silk surface, etc. Usually, it is preferable to add to the matte surface.

Various additives can be contained in the front multilayer resin sheet and the back resin layer of the image material support of the present invention, if necessary. Support whiteness and image sharpness --For the purpose of improving the degree, Japanese Patent Publication No. 60-3430, Japanese Patent Publication No. 63-11655, Japanese Patent Publication No. 1-38291, Japanese Patent Publication No. 1-38292, Japanese Patent Publication No. 1-105245, etc. It is preferable to include the titanium dioxide pigment described in (1). In addition to titanium dioxide, white pigments such as zinc oxide, talc, and calcium carbonate; release agents; fatty acid amides such as stearic acid amide and arachidic acid amide; and dispersants for pigments and stearin as a releasing agent. Fatty acid metal salts such as zinc oxide, calcium stearate, aluminum stearate, magnesium stearate, zinc palmitate, zinc myristate, calcium palmitate, and the like, hindered phenol, hindered amine, phosphorus described in JP-A-105245 And sulfur-based antioxidants, violet-based pigments and dyes such as Conoretable I, ultramarine, celianble, and phthalocyanine bull, and magenta pigments such as cobalt violet, fast violet, and manganese violet. Dye, described in JP-A-2-254440 Fluorescent whitening agent, various additives as appropriate in combination may be contained such as an ultraviolet absorber. These additives are preferably contained as a resin master batch or compound. In addition, from the viewpoint of improving the sharpness or whiteness of the print or the heat resistance, light resistance or release properties of the support for the image material, a white pigment such as titanium oxide, a fluorescent whitening agent, a coloring pigment or coloring. It is preferable to incorporate a dye or other additives such as an antioxidant, an ultraviolet absorber or a release agent in the uppermost layer at a higher concentration than in the resin layer below the uppermost layer. In particular, the content of the titanium dioxide pigment in the uppermost layer is preferably at least 7% by weight, more preferably at least 9% by weight, still more preferably at least 12% by weight, particularly preferably at least 15% by weight.

The base paper used in the practice of the present invention is preferably a natural pulp paper mainly composed of ordinary natural pulp. Further, a mixed paper made of natural pulp as a main component and synthetic pulp or synthetic fiber may be used. Examples of such natural pulp include those described in JP-A-58-37642, JP-A-60-67940, JP-A-60-69649, JP-A-61-35442 and the like. It is advantageous to use appropriately selected natural pulp. Natural pulp is treated with chlorine, hypochlorite, chlorine dioxide bleaching as usual bleaching treatment, alkali extraction or aluminum bleaching treatment and, if necessary, oxidative bleaching treatment with hydrogen peroxide, oxygen, etc., and combinations thereof. Wood pulp of treated softwood pulp, hardwood pulp, mixed softwood pulp is advantageously used, and kraft pulp, --Various types such as sulfite pulp and soda pulp can be used. Various additives can be contained in the stock slurry during preparation of the stock slurry, which is mainly composed of natural pulp used in the practice of the present invention. As the sizing agent, fatty acid metal salts are fatty acids, alkyl ketene dimer emulsions or epoxidized higher fatty acid amides, alkenyl or alkyl succinic anhydride anhydrous emulsions described in JP-B-62-7534, Rosin derivatives, etc. as dry paper strength enhancers, such as anionic, cationic or amphoteric polyacrylamide, polyvinyl alcohol, cationized starch, vegetable galactomannan, etc. As filler, clay, kaolin, calcium carbonate, titanium oxide, etc., as fixing agent, water-soluble aluminum salt such as aluminum chloride, bansulfate, etc., as pH regulator, caustic soda, sodium carbonate, sulfuric acid, etc. Others described in JP-A-63-204251, JP-A 1-266537, etc. Color pigments, coloring dyes, it is advantageous allowed to contain a combination of such appropriate fluorescent whitening agent.

Further, a composition comprising various water-soluble polymers or hydrophilic colloids or latexes, an antistatic agent, and additives is contained in or on the base paper mainly composed of natural pulp used in the practice of the present invention. It can be contained or applied by coating such as size press or tab size press or blade coating, air-knife coating. Examples of water-soluble polymers or hydrophilic colloids include starch-based polymers, polyvinyl alcohol-based polymers, gelatin-based polymers, polyacrylamide-based polymers, and cellulosic polymers described in JP-A 1-266537; Examples of latexes include petroleum resin emulsions and copolymers containing at least ethylene and acrylic acid (or methacrylic acid) described in JP-A-55-4027 and JP-A-1-80538. Emulsion or latex, styrene-butadiene, styrene-acrylic, vinyl acetate-acrylic, ethylene-vinyl acetate, butadiene-methyl methacrylate-based copolymer, and carboxy-modified copolymer emulsion or latex, etc. Sodium chloride, salt as antistatic agent Clay as a pigment, such as alkali metal salts such as potassium, alkaline earth metal salts such as calcium chloride and barium chloride, colloidal metal oxides such as colloidal silica, and organic antistatic agents such as polystyrene sulfonate , --Kaolin, calcium carbonate, talc, barium sulfate, titanium oxide, etc., pH regulators such as hydrochloric acid, phosphoric acid, citric acid, caustic soda, and other additives such as the coloring pigments, coloring dyes and fluorescent brighteners mentioned above It is advantageous to incorporate them in an appropriate combination.

The thickness of the base paper used in the practice of the present invention is not particularly limited, but preferably has a basis weight of 30 to 25 Og / m ² .

The base paper mainly composed of natural pulp used in the practice of the present invention includes a three-dimensional stylus on the front side of the base paper from the viewpoint of remarkably improving the apparent glossiness of the image material and its print. Cut-off value measured using a surface roughness tester Center plane average roughness in the papermaking direction at 0.8 thigh SRa (hereinafter, cut-off value measured using a stylus type 3D surface roughness tester on the front side of the base paper) The center plane average roughness SRa in the papermaking direction at 0.8 thighs may be simply abbreviated as the center plane average roughness SRa), preferably 1.5 m or less, more preferably 1.4 111 or less. , 1.3 // m or less is more preferable, and 1.2 / m or less is particularly preferable.

The cut-off value measured using a stylus type three-dimensional surface roughness meter referred to in this specification is 0.8. The center plane average roughness S Ra at a thigh is defined by the following equation 1.

₁ Wx Wy

SRa = —

Sa f o f If (x, y) I dx, dy (expression

o

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

Specifically, as a stylus-type 3D surface roughness meter and 3D roughness analyzer, SE-3AK and SPA-11 machines manufactured by Kosaka Laboratories Co., Ltd. were used, and the cut-off value was 0.8 thigh. , Wx = 20 Yuzuru, Wy = 8顧, thus be determined under the condition of S a = 160 thigh ² coming out. Note that 500 data points are sampled in the X-axis direction, and 17 lines or more are scanned in the Y-axis direction.

The base paper having a center plane average roughness SR a of 1.5 μm or less is specifically, preferably using the following method, preferably combining two or more of the following methods, and more preferably combining three or more of the following methods. It is clear from the study of the present inventors that it can be obtained by using --

(1) As the natural pulp to be used, hardwood bleached kraft pulp or a combination of hardwood bleached kraft pulp and hardwood bleached sulphite pulp is preferable. Also, the fiber length of the pulp, measured on the pulp after beating before adding the paper chemicals, is preferably 0.42 to 0.70, more preferably 0.45 to 0.65, more preferably 0.47 to 0.61 thigh, particularly preferably 0.49mn! Use beaten and prepared so that it is within the range of 0.57mm. If the fiber length of the pulp is too short, the internal bond strength of the base paper becomes weak, and the stiffness decreases.On the other hand, if the fiber length of the pulp is too long, the center surface average roughness SR a tends to increase. is there. The fiber length of pulp referred to in this specification is the length of pulp after beating measured in accordance with JAPAN TA PP I Paper Pulp Test Method No. 52-89 “Paper and Pulp Fiber Length Test Method”. This is expressed as the weighted average fiber length (thigh).

(2) Use a tension press during the drying of the wet paper. Specifically, for example, a multi-stage tension press as described in JP-A-3-29955 is performed on the wet paper.

(3) Incorporate or coat various water-soluble polymers, hydrophilic colloids or polymer latex in or on the base paper. Specifically, various water-soluble polymers or hydrophilic colloids or polymer latexes are coated on the base paper or on the base paper by size press or tab size press, blade coating, jaw knife coating, etc. It is preferable that the solid content is 1.0 Og / m ² or more, preferably 2.2 g / m ² or more, or the solid coating amount is applied.

(4) After the base paper is formed, at least two series of calendar treatments are performed on the base paper using a machine calendar, a super calendar, a heat calendar, etc. Specifically, for example, the base paper is subjected to machine calendar processing and / or thermal machine power rendering processing as the first series of calendar processing, and then to the machine calendar as needed as the second series and subsequent power rendering processing. After performing the treatment, it is preferable to carry out a thermal soft calendar treatment described in JP-A-4-110939.

The surface of the surface multilayer resin sheet of the image material support of the present invention is subjected to an activation treatment such as a corona discharge treatment or a flame treatment, and thereafter, is disclosed in Japanese Patent Publication No. 61-84643 and Japanese Patent Application Laid-Open No. 1-92740. , JP-A 1-102551, JP-A 1-166035 JP undercoat layer as described in --Can be painted. Further, on the surface of the backing resin layer of the image material support in the present invention, after performing an activation treatment such as a corona discharge treatment or a flame treatment, various back coat layers are applied for antistatic treatment or the like. be able to. The back coat layer includes JP-B-52-18020, JP-B-57-9059, JP-B-57-53940, JP-B-58-56859, and JP-B-59-214849, An inorganic antistatic agent, an organic antistatic agent, a hydrophilic binder, a latex, a curing agent, a pigment, a surfactant, and the like described in Japanese Patent Application Publication No. 58-184144 can be included in an appropriate combination.

The support for image materials of the present invention is coated with various photographic constituent layers, and is used for color photographic printing paper, black and white photographic printing paper, typesetting printing paper, copy printing paper, reversing photographic material, silver salt diffusion. It can be used for various purposes such as transfer method negative, positive, and printing materials. For example, a silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide emulsion layer can be provided. The silver halide photographic emulsion layer may contain a color coupler to provide a multilayer silver halide color photographic constituting layer. Further, a photographic constituent layer for silver salt diffusion transfer method can be provided. As binders for these photographic constituent layers, besides ordinary gelatin, hydrophilic high-molecular substances such as polyvinylpyrrolidone, polyvinyl alcohol and ester sulfate compounds of polysaccharides can be used. Further, various additives can be contained in the above-mentioned photographic constituent layer. For example, sensitizing dyes such as cyanine dyes and merocyanine dyes; chemical sensitizers such as water-soluble gold compounds and thio compounds; and anti-capri or stabilizers such as hydroxy-triazolopyrimidine compounds and mercapto- Heterocyclic compounds, hardening agents such as formalin, vinylsulfone compounds, and aziridine compounds; coating aids such as alkylbenzene sulfonic acid salts and sulfosuccinic acid ester salts; and anti-staining agents such as alkylhydridoquinone compounds. In addition, a fluorescent whitening agent, a sharpness improving dye, an antistatic agent, a pH regulator, a fogging agent, and the formation of silver halide. be able to.

The photographic material according to the present invention may be used in accordance with the photographic material, such as exposure, development, stop, fixation, as described in "Photosensitive Materials and Handling Methods" (Kyoritsu Shuppan, Goro Miyamoto, Photographic Technology Course 2). Processing such as bleaching and stabilization can be performed. Also, multi-layer halogenation Silver color photographic materials can be processed with a developer containing a development accelerator such as benzyl alcohol, thallium salt, phenidone, or with a developer containing substantially no benzyl alcohol. .

The support for an image material of the present invention can be used as a support for various heat transfer type thermal transfer recording image receiving materials by coating various heat transfer type thermal transfer recording image receiving layers. Synthetic resins used for the heat transfer type thermal transfer recording image receiving layer include polyester resin, polyacrylate resin, polycarbonate resin, polyvinyl acetate resin, polyvinyl butyral resin, styrene acrylate resin, and vinyl toluene acrylate. Resin having ester bond such as late 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, and other polycaprolactam Resins, styrene resins, polyvinyl chloride resins, vinyl chloride-vinyl acetate copolymer resins, polyacrylonitrile resins, and the like. In addition to these resins, mixtures or copolymers thereof can also be used.

In the heat transfer type thermal transfer recording image-receiving layer according to the present invention, a release agent, a pigment, and the like may be added in addition to the synthetic resin. Examples of the release agent include solid waxes such as polyethylene wax, polyamide, and Teflon powder, fluorine-based and phosphate-based surfactants, and silicone oils. Among these release agents, silicone rolls are most preferred. As the silicone oil, an oily substance can be used, but a curable type is preferred. Examples of the curable silicone oil include a reaction-curable type, a photo-curable type, and a catalyst-curable type, and a reaction-hardened type silicone oil is particularly preferable. Examples of the reaction-curable silicone oil include an amino-modified silicone oil and an epoxy-modified silicone oil. The amount of the reactive silicone oil added is preferably 0.1 to 2 wt% in the image receiving layer. As the pigment, extenders 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 zm, more preferably 2 to 10 zm. The support for an image material of the present invention can be used as a support for various ink jet recording materials by coating various ink image receiving layers. These ink image receiving layers contain various binders for the purpose of improving the drying property of the ink and the sharpness of the image. --You can have it. Specific examples of such binders include lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, and gelatin derivatives, such as gelatin reacted with dibasic acid anhydrides such as phthalic acid, maleic acid, and fumaric acid. Various gelatins, ordinary polyvinyl alcohols of various saponification degrees, carboxy-modified, cation-modified and amphoteric polyvinyl alcohols and their derivatives, starches such as oxidized starch, cationized starch, etherified starch, carboxymethylcellulose, Cellulose derivatives such as hydroxyethyl cellulose, polyvinylpyrrolidone, polyvinylpyridyl halide, sodium polyacrylate, methacrylic acid copolymer salt, polyethylene glycol, polypropylene glycol, polyvinyl ether, alkyl vinyl ether Ter 'maleic anhydride copolymer, styrene' maleic anhydride copolymers and their salts, synthetic polymers such as polyethyleneimine, styrene 'butylene copolymer, methyl methacrylate' butadiene copolymer, etc. Gen-based copolymer latex, polyvinyl acetate, vinyl acetate-maleic acid ester copolymer, vinyl acetate-acrylic acid ester copolymer, ethylene-vinyl acetate polymer latex such as vinyl acetate copolymer, acrylic acid ester Acrylic polymers or copolymers such as polymers, methacrylic acid ester polymers, ethylene / acrylic acid ester copolymers, styrene / acrylic acid ester copolymers, latexes of vinylidene chloride copolymers, etc. Alternatively, it is possible to use a functional group-containing monomer such as a carboxyl group of these various polymers. Group-modified polymer latex, melamine resin, urea resin and other thermosetting synthetic resin-based aqueous adhesives and polymethyl methyl acrylate, polyurethane resin, unsaturated polyester resin, vinyl chloride 'vinyl acetate copolymer, polyvinyl butyral An inorganic binder such as an alumina sol or silica sol described in Japanese Patent Publication No. 3-24906, Japanese Patent Application Laid-Open No. 3-281383, Japanese Patent Application No. 4-240725, etc. These can be used alone or in combination.

The ink receiving layer of the ink jet recording material according to the present invention may contain various additives in addition to the binder. Examples of the surfactant include anionic surfactants such as a long-chain alkylbenzene sulfonate, a long-chain, preferably branched alkylsulfosuccinate, and a long-chain, preferably a branched alkyl group. ― ― Nonionic surfactants such as polyalkylene oxide ethers of phenols contained therein and polyalkylene oxide ethers of long-chain alkyl alcohols, etc., JP-B-47-9303, US Pat. No. 3,589,906 As a fluorinated surfactant, silane coupling agents such as a-aminopropyltriethoxysilane, N-? (Aminoethyl) -a-aminopropyl pyrtrimethoxysilane, and as polymer hardeners A hardening agent such as an active halogen compound, a vinyl sulfone compound, an aziridine compound, an epoxy compound, an acryloyl compound, an isocyanate compound; and as a preservative, a p-hydroxybenzoic acid ester compound described in JP-A-1-02551. Benzoisothiazolone compounds, isothiazolone compounds, etc., JP-A-63-204251, Ultraviolet rays such as coloring pigments, coloring dyes, fluorescent whitening agents, etc. described in JP-A 1-266537, etc., and sodium hydroxide such as sodium hydroxymethanesulfonate and sodium p-toluenesulfinate as yellowing inhibitors. As an absorbent, as a benzotriazole compound having a hydroxydi-alkylphenyl group at the 2-position, as an antioxidant, as a polyhindered phenol compound described in JP-A-1-105245, as a pencil brushing agent Organic or inorganic fine particles having a particle size of 0.2 to 5 μm, such as starch granules, barium sulfate, and silicon dioxide; organopolysiloxane compounds described in JP-B-4-1337, etc .; Various additives such as octyl alcohol and silicon-based antifoaming agents such as caustic soda, sodium carbonate, sulfuric acid, hydrochloric acid, phosphoric acid, and citric acid can be appropriately combined and contained. That. Hereinafter, the present invention will be described in detail with reference to examples, but the contents of the present invention are not limited to the examples.

Manufacture of paper base>

Fiber length of pulp after beating a mixed pulp consisting of 85% by weight of hardwood bleached kraft pulp and 15% by weight of hardwood bleached sulphite pulp (JAPANTAPPI Paper Pulp Test Method No. 5 2 -89 After the beating so that the length-weighted average fiber length measured in accordance with the “Method” is 0.60, the beating is performed. 3 parts by weight of cationized starch, 0.2 part by weight of anionized polyacrylamide, 0.4 part by weight of alkyl ketene dimer emulsion (as ketene dimer per minute) per 100 parts by weight of lup -丄-Polyamide epichlorohydrin resin 0.4 parts by weight and appropriate amounts of a fluorescent brightener, a blue dye and a red dye were added to prepare a stock slurry. Thereafter, the stock slurry is placed on a fourdrinier paper machine running at 200 m / min to form a paper web while giving an appropriate evening pressure, and the wet part is subjected to a linear pressure in the range of 15 to 10 Okgf / cm. After performing a three-stage wet press in which the pressure has been adjusted, processing with a smoothing roll is performed, and in a subsequent drying part, a two-stage tension press in which the linear pressure is adjusted in the range of 30 to 7 Okgf / cm is performed. It was dried. Thereafter, middle carboxy-modified polyvinyl alcohol 4 parts by weight of the dry, 0.05 part by weight of brightener fluorescent, 0.002 parts by weight blue dye, sodium chloride 4 parts by weight and the size press solution 25 g / m ² size press comprising water 92 parts by weight The base paper is finally dried so that the moisture content of the base paper becomes 8% by weight in terms of absolute dry moisture, machine-processed with a linear pressure of 7 Okgf / cm, and the center of the basis weight 1 Ί Og / m ² A base paper for an image material support having an average surface roughness SRa of 1.30 m was produced.

Formation of backside resin layer>

Next, after the base paper surface (reverse surface) opposite to the side on which the image forming layer is coated is subjected to corona discharge treatment, a low-density polyethylene resin [density 0.924 g / cm ³ , The melt flow rate of polyethylene resin is abbreviated as MFR) = lg 0 minutes] A compound consisting of 30 parts by weight and 70 parts by weight of high-density polyethylene resin (density 0.967 g / cm ³ , MFR = 15 g / 10 minutes) The resin composition was melt-extruded and coated at a resin temperature of 320 ° C and a resin thickness of 25 µm at a running speed of the base paper of 200 m / min. At this time, as the cooling roll, a roll having a surface roughness such that the center surface average roughness SRa of the back layer surface after applying the following back layer was 1.15 μm was used. The cooling rolls used were roughened by the liquid honing method and operated at a cooling water temperature of 12 ° C. Subsequently, the surface multilayer resin sheet was coated as described below to produce a support for an image material.

The evaluations of the image material supports obtained in Examples and Comparative Examples were performed according to the following methods.

(1) Degree of uneven peeling

The surface state of the mirror surface on the front side of the image material support obtained in each of the Examples and Comparative Examples was oblique. --

Observation was made with light, and the degree of occurrence of peeling unevenness was visually judged by a monitor of 10 persons, and a 10-grade evaluation was performed. The evaluation criteria (larger grade value means less occurrence of peeling unevenness, smaller grade value means more occurrence of peeling unevenness) are as follows.

Grade 10 to 9: Extremely good, with very little or no uneven peeling.

Grade 8-7: Good with little uneven peeling.

Grade 6 to 5: Some uneven peeling, but practical.

Grade 4-1: Peeling unevenness often occurs, causing practical problems.

(2) Photographic print glossiness

A blue emulsion layer containing a yellow color coupler, an intermediate layer containing a color-mixing inhibitor, a green emulsion layer containing a magente evening color coupler, and an ultraviolet ray are arranged adjacently on the undercoat layer of the image material support. An ultraviolet absorbing layer containing an absorber, a red-sensitive emulsion layer containing a cyan coloring coupler, and a protective layer were applied by an E-bar for multilayer coating to prepare a blank printing paper having a total amount of gelatin of 7 g / m ² . 0 colors sensitive emulsion layer in the silver nitrate. 6 g / m comprises the corresponding silver chlorobromide to ^2, further the formation of the silver halide, other gelatin required dispersion and film formation, an appropriate amount of Capri inhibitor, increasing Contains dyes, coating aids, hardeners, thickeners, and appropriate amounts of filter dyes. Next, store the prepared color photographic paper at 35 ° C and normal humidity for 5 days, bake the group photo, develop, bleach and fix it, develop it stably, and then dry it to make a photo print. Done. In addition, separate samples were prepared for white solid (unexposed) and black solid (black). In addition, a series of processes of exposure, development, and drying were performed by an automatic printer and an automatic developing machine. The color development was performed in the order of color development (45 seconds), bleaching and fixing (45 seconds), stable (1 minute 30 seconds), and> drying.

For the obtained group photo, white solid and black solid photographic prints, the visual glossiness of the photographic prints was visually judged comprehensively by the monitor of 10 people, and the grade of the 10th grade was evaluated. went. The evaluation criteria (the higher the grade value, the higher the apparent glossiness, and the lower the grade value, the lower the apparent glossiness) are as follows.

Grade 10-9: Very or very high glossiness in appearance. --Grade 8 to 6: High gloss appearance.

Grade 5-4: The glossiness is slightly low, but practical.

Grade 3 to 1: Low apparent glossiness, causing practical problems.

(3) Curl properties

In the same manner as in (2) above, a photo print (collection photo) measuring 8.2 cm x 11.7 cm was created. The curl condition of this photo print at 20 ° C and 40% RH was checked by 10 people. Judgment was made by visual evaluation using a monitor (1), and a 10-grade evaluation was performed. The evaluation criteria for the curl properties (the higher the grade value, the better the curl properties, and the lower the grade value, the worse the curl properties) are as follows.

Grade 10 to 9: Slightly negative curl (curl toward the back layer side) to flat, extremely excellent curl physical properties.

Grade 8-7: Slightly positive curl (curl toward image forming layer side), but good curl physical properties.

Grade 6 to 5: Positive curl, but no practical problem.

Grade 4-1: Positive curl is large, which is a practical problem.

Comparative Examples 1-3

After subjecting the surface of the base paper to corona discharge treatment, the surface was subjected to a high-pressure low-density polyethylene resin obtained using a autoclave reactor [density 0.920 g / cm \ MFR = 4.5 g / 10 min, melting point 109 ° C, or less, low density abbreviated as polyethylene resin (LDPE-1)] 47.1% by weight, anatase surface-treated with (a 1 ₂ 0 ₃ minutes to 0.50 wt% with respect to pair two Sani匕titanium) hydrated aluminum oxide Type titanium dioxide pigment 50% by weight and ultramarine

(Daiichi Kasei Kogyo Co., Ltd., # 2000) 0.4% by weight, 2.5% by weight of zinc stearate and tetrakis [methylene-13 (3,5-di-tert-butyl-14-hydroxyphenyl) propionate] methane 150% 1 ppm of titanium dioxide pigment mass consisting of ppm (hereinafter abbreviated as MB-1 batch) A resin composition consisting of 25 parts by weight and 75 parts by weight of low-density polyethylene resin (LDPE-1) Using a melt extruder at 315 ° C and a thickness of 30 zm at a running speed of the base paper of 200 m / min, the coating was melt-extruded at a linear pressure of 4 Okgf / cm between the mirror cooling roll and the press roll. --The melt extrusion coating of the polyethylene resin on the front and back sides was performed by the so-called tandem method in which the melt extrusion coating was performed sequentially. At that time, the surface of the resin layer containing the titanium dioxide pigment of the resin-coated paper was processed to a glossy surface. Furthermore, do not apply the calendar treatment between the processing of the front and back resin layers before winding, or the on-machine soft calendar treatment under the conditions of the press linear pressure and the number of series shown in Table 2. (Applying only pressure welding without applying heat) or apply on-machine thermal soft calendering at the conditions of press temperature, press linear pressure, and number of series shown in Table 2, and the back of resin-coated paper in the zone following bow I After the corona discharge treatment on the resin layer surface, the following coating solution for the back layer was applied on-machine. As the dry weight content, colloids like silica force: styrene latex = 1: consists of one, the latex back layer coating solution, including more polystyrene sodium sulfonate 0, 02 lg / m ² of other suitable amount of coating aid The coating amount was 0.2 lg / m ² in terms of minute (calculated on solid weight).

In addition, after the back layer is applied and before the resin-coated paper is wound up, the front resin surface is subjected to corona discharge treatment, and lime-treated gelatin 1.2 g, low molecular weight gelatin (Nitta Gelatin Co., Ltd. — 3226) 0.3 g, 1.5 g of Shiridani vinylidene-based latex, 0.3 g of a 10% by weight methanol solution of butyl para-benzoate, and 5% by weight of methanol of sulfosuccinic acid-2-ethylhexyl ester salt mixed with water The undercoating solution containing 0.45 g of the solution and adjusted to 100 g with water was uniformly applied on-machine so as to have a gelatin coating amount of 0.06 g / m ² to obtain a support for image materials.

Comparative Examples 4 to 6

Polyethylene resin produced by polymerization using a metallocene polymerization catalyst in place of the resin composition used in Comparative Example 2 [(ML4): density 0.898 _g / cm ³ , melting point 93] C] 75 parts by weight of a compound resin composition composed of 52.1 parts by weight and 22.9 parts by weight of a low-density polyethylene resin (LDPE-1), and a resin composition composed of 25 parts by weight of a mass batch (MB-1) Same as Comparative Example 2 except that it was used and soft calendering under the processing conditions shown in Table 2 (treatment only for pressure welding without applying heat), heat soft calendering, or no calendering Thus, a support for an image material was obtained.

Comparative Examples 7 to 10 --After corona discharge treatment of the surface of the base paper, the same resin composition for the surface resin layer and the resin composition for the upper layer as in Comparative Example 2 with a thickness of 15 m was used as the resin composition for the lower layer on the surface. The same resin composition for the surface resin layer as in Comparative Example 2 having a thickness of 15 / m was prepared by using a two-layer co-extruder at a resin temperature of 315 ° C and a traveling speed of the base paper of 20 Om / min. The two layers were simultaneously extruded at a linear pressure of 4 Okgf / cm between the cooling roll on the mirror surface and the press roll to coat the surface layer, and the soft calender treatment under the processing conditions shown in Table 2 A support for an image material was obtained in the same manner as in Comparative Example 2 except that pressure treatment was not applied, or thermal soft calendering was performed or force rendering was not performed.

Comparative Example 11: L 4

Instead of the resin composition for the lower layer and the upper layer used in Comparative Example 8, as the resin composition for the lower layer, the same resin composition for the surface resin layer as in Comparative Example 5 having a thickness of 15 // m, the upper layer The same resin composition for the surface resin layer as in Comparative Example 5 having a thickness of 15 m was used as the resin composition for the soft coating, and a soft calendering treatment under the processing conditions shown in Table 2 (when heat was applied). A support for an image material was obtained in the same manner as in Comparative Example 8 except that a treatment using only a soft pressing method was performed, or a thermal soft calendar treatment was performed, or no calendar treatment was performed. Comparative Example 15

Instead of the resin composition for the lower layer used in Comparative Example 7, a polyethylene-based resin produced by polymerization using a methyl acetate catalyst [(ML4): Density 0.898 g / cm ³ , Melting point 93 ° C] 52.1 weight Comparative Example, except that a compound resin composition consisting of 22.9 parts by weight of a low-density polyethylene resin (LDPE-1) and 25 parts by weight of a mass-batch (MB-1) was used and that no force-rendering treatment was applied. In the same manner as in 7, an image material support was obtained.

Examples 1 to 6

Instead of the resin composition for the lower layer used in Comparative Example 8, a polyethylene-based resin [(ML1) to (ML5)] 5 2.1 wt. And a low-density polyethylene resin (LDPE-1) (22 parts and 9 parts by weight). Press linear pressure and series number A support for an image material was obtained in the same manner as in Comparative Example 8, except that the soft calendering treatment (treatment of only pressure welding without applying heat) was performed in the above-mentioned cases.

The polyethylene resin (ML 1) for Example 1 has a density of 0.908 g / cm ³ and a melting point of 103 ° C. Polyethylene resin (ML 2) for Example 2 Density 0.904 g / cm ³ , melting point 98 ° C.

Polyethylene resin (ML3) for Example 3: density 0.900 g / cm ³ , melting point 95. C.

Polyethylene resin (ML 4) for Examples 4 and 5: density 0.898 g / cm ³ , melting point 93 ° C _C Polyethylene resin (ML 5) for Example 6: density 0.895 g / cm ³ , melting point 90 ° C.

Examples 7 to 12

Instead of the resin composition for the lower layer used in Comparative Example 9, polyethylene resins [(ML1) to (ML5)] 5 2.1 parts by weight which were produced by polymerization using the following five types of MEC polymerization catalysts A resin composition consisting of 75 parts by weight of a compound resin composition consisting of 22.9 parts by weight of a low-density polyethylene resin (LDPE-1) and 25 parts by weight of a mass batch (MB-1) and a press described in Table 2 A support for an image material was obtained in the same manner as in Comparative Example 9, except that a thermal soft calendar treatment under the conditions of temperature, press linear pressure and the number of series was performed.

Polyethylene resin (ML 1) for Example 7: density 0.908 g / cm ³ , melting point 103 ° (. Polyethylene resin (ML 2) for Example 8: density 0.904 g / cm \ melting point 98 ° C.

Polyethylene resin (ML 3) for Example 9: density 0.900 g / cm ³ , melting point 95 ° C.

Polyethylene resin (1 ^ 1 ^ 4) for Examples 10 and 11: density 0.898 § / {} 111 ³ , melting point 93 ° C.

Polyethylene resin (1 ^ 5) for Example 12: density 0.8958 / (; 111 ³ , melting point 90 ° C. Front side of the support for image material obtained in Comparative Examples 1 to 15 and Examples 1 to 12 above The melting point and content ratio of the thermoplastic resin in the resin layer in the single-layer or two-layer resin sheet of Table 1 are shown in Table 1. The content of thermoplastic resin in Table 1 (Note 1) The content ratio of each thermoplastic resin with respect to the total thermoplastic resin component is shown by weight% (wt%).

Table 2 shows the evaluation results of the appearance of glossiness and the occurrence of peeling unevenness of the photographic print of the support for image materials. - - table 1

¾ W ί ί¾.¾

Giving giving giving

Example Example Example 1 Melting point of thermoplastic resin in resin layer of front resin sheet (° c)

789111 and content ratio (Note 1)

Example Comparative example 1 109 (100wt¾)

Comparative Example 21

Comparative Example 3 9 Same U Same Same

^ Upper upper

Comparative Example 4 93 (60.Owt%) and 109 (40.Owt%)

Comparative Example 5 Same as above

Comparative Example 6 Same as above Example Lower layer Upper layer Comparative example 7

Comparative Example 8

Comparative Example 9 1 1 1 o o

Comparative Example 10 o

Same same same same same same same same same same same

^ Upper upper upper ^ Upper upper upper upper ^ Upper upper upper upper

Comparative Example 1 1 93 (60.0wt%) and 109 (40.0wt) 93 (60.0wt%) and 109 (40.0wt%) Comparative Example 1 2 Same as above \ /-Comparative Example 1 3 Same as above

Comparative example 1 4 Same as above Comparative example 1 5 93 (60.0 wt%) and 109 (40.0 wt%) 109 (100 wt%) Example 1 103 (60.0 wt%) and 109 (40.0 wt%)

Example 2 98 (60.0wt%) and 109 (40.0wt%)

Example 3 95 (60.0wt) and 109 (40.0wt%)

Example 4 93 (60.0wt%) and 109 (40.0wt%)

Example 5 93 (60.0wt%) and 109 (40.0wt%)

Example 6 90 (60.0wt%) and 109 (40.0wt%)

103 (60.0wt%) and 109 (40.0wt%)

98 (60.0wt) and 109 (40.0wt%)

95 (60.0wt) and 109 (40.0wt%)

93 (60.0wt%) and 109 (40.0wt%)

93 (60.0wt%) and 109 (40.0wt)

90 (60.0wt5 and 109 (40.0wt%) -Table 2 Example Layer composition (heat) soft, calendar--Processing conditions

ii 3 ¾ Θ ¾ Θ ¾ ¾ ¾ ⁰ less less rf extraction ii teaching iS J 7L i vtQi

(° C) (kgf / cm) Tot Toshi 1 1 0 Tot i $ Example 2 FF contact only 3 0 1 zp ^ 10,000 | 1 o 0 Tot i¾ = Example ¾ 5 5 1 o 2 Extraction || Comparative example 4 Single layer 2 3 3 1 1 Example 5 PF contact j only 3 o 1 2 ζzΓίm U 0 9 ά Toto Example 6 ~ me 5 5 1 0 2 gang 1 | 1 1 Comparative example 7 2 layers-None 2 5 Comparative example 8 2 layers Pressure welding only 3 0 1 series 2 5 Comparative example 9 2 layers 5 5 1 0 1 series 2 5 Comparative example 1 0 2 layers 5 5 1 0 2 series 2 4

Q

'J M / tv> 1 9

Utto if example 1? FF culture only 3 o 1 2z | m U 0

Example 1 3 ^ 5 5 1 o 1 system || 9

■ fU ii example 1 4 * ΐ 55 1 o 2 system | —system 1 'J | 1 Comparative example 1 5 2 layers None

1 2 5 Keio Example 1 2nd layer FF contact only 3 0 1 system ζΓ train ^, J 4

JUi example l J 2 Same as above 3 o 1 system Γ system ii 4 a Room example 3 M Same as above 3 o 1 system ζΓ system (JI Ri Kei example 4 2 m Same as above 3 0 1 series J 6

Example 5 2 layers Same as above 3 0 2 line 7 6 Example 6 2 layers Same as above 3 0 1 line 7 6 Example Ί 2 layers 5 5 1 0 1 line 5 5 Example 8 2 layers 5 5 1 0 1 line 5 6 Example 9 2 layers 5 5 1 0 1 line 6 6 Example 1 0 2 layers 5 5 1 0 1 line 7 6 Example 1 1 2 layers 5 5 1 0 2 lines 8 6 Example 1 2 2 layers 5 5 1 0 1 series 8 6 From the results in Table 2, it can be seen that the upper side of the base paper containing natural pulp as a main component contains more thermoplastic resin (a) than the lower layer (B), and the lower layer (B) contains thermoplastic resin (b). A thermoplastic resin (a) having a melting point higher than 100 ° C, and a thermoplastic resin (b) It has a melting point of 105 ° C. or lower and is lower than the melting point of the thermoplastic resin (a), and after the coating of the two-layer resin sheet, the support for the image material is heated, particularly by applying heat to the two-layer resin sheet side. The support for an image material of the present invention (Examples 1 to 12) pressed in a non-heated or heat-retained state provides a photographic print with a high apparent gloss and no uneven peeling. It can be seen that this is an excellent support for image materials. In addition, in view of the effect of improving the apparent glossiness of the photographic print, the image material support (Examples? To 12) pressed (heat soft calendering) while maintaining heat is more excellent. It is clear that there is.

In addition, from the results of Examples 1 to 6 and Examples 7 to 12, the thermoplastic resin used for the lower layer (B) was improved from the viewpoint of improving the apparent glossiness and peeling unevenness of the photographic print.

As (b), those having a melting point of 100 ° C. or less are preferable, and those having a melting point of 95 ° C. or less are particularly preferable. In addition, from the results of Examples 4 to 5 and Examples 10 to 11, from the viewpoint of the effect of improving the apparent glossiness, the pressure welding was performed particularly without applying heat.

(Soft calender treatment) or pressure welding while maintaining heat (thermal soft calender-treatment) is clearly understood to be preferably performed in two or more series.

On the other hand, when the resin layer of the front resin sheet does not satisfy the requirements of the present invention, that is, when the melting point of the thermoplastic resin (a) contained in the upper layer is 100 ° C or lower (Comparative Examples 11 to 14), When the melting point of the thermoplastic resin (b) contained in is higher than 105 ° C (Comparative Example?

10) The image material outside the present invention when the front resin sheet is a single layer (Comparative Examples 1 to 6) and when the front resin sheet has the requirements of the present invention but is not pressed (Comparative Example 15) It can be clearly seen that the support for use has a problem in that the apparent glossiness of the photographic print tends to be low and the occurrence of uneven peeling tends to increase.

Example 13

Example 4 was the same as Example 4 except that the soft calendering process (the process of pressing only without applying heat) was performed under the conditions of the press linear pressure and the number of series shown in Table 3. In the same manner, a support for an image material was manufactured.

Table 3 shows the evaluation results of the apparent glossiness and the occurrence of uneven peeling of the photographic print of the obtained support for image materials.

Example 14

In Example 10, the same procedure as in Example 10 was carried out except that the thermal soft calendering treatment was performed under the conditions of the press temperature, the press linear pressure, and the number of series described in Table 3, and the support for the image material was performed. Body manufactured.

-Table 3

From the results in Table 3, it can be seen that the upper side of the base paper containing natural pulp as the main component contains more thermoplastic resin (a) than the lower layer (B), and the lower layer (B) contains thermoplastic resin (b). A thermoplastic resin (a) having a melting point higher than 100 ° C, and a thermoplastic resin (b) The melting point is 105 ° C or lower and lower than the melting point of the thermoplastic resin (a); Further, after the two-layer resin sheet is covered, the image material support is pressed against the two-layer resin sheet in a state where heat is not particularly applied or heat is held, and The support (Examples 13 to 14) can be clearly seen to be an excellent support for an image material, in which a photographic print having a high apparent gloss can be obtained, and peeling unevenness does not occur.

Further, when examined in relation to the press linear pressure based on the results of Examples 13 and 14, the press linear pressure in the pressure welding without applying heat (soft calendering) is 7.5 to 55. It is well understood that the treatment is preferably performed at kgf / cm, and particularly preferably performed at 15 to 45 kgf / cm. The press linear pressure in the pressure welding (heat soft calendering) while holding heat is preferably performed at 3 to 45 kgf / cm, more preferably at 4 to 35 kgf / cm. It is clear that the reaction is more preferably performed at 5 to 25 kgf / cm.

Comparative Example 16: L 7

In Comparative Example 9, a support for an image material was obtained in the same manner as in Comparative Example 9, except that the thermal soft calender treatment was performed under the conditions of the pressing temperature, the pressing linear pressure, and the number of series shown in Table 5.

Comparative Example 18-20

After the surface of the base paper is subjected to corona discharge treatment, the same resin composition for the surface resin layer as in Comparative Example 1 having a thickness of 15 μm as the lowermost resin layer, The same resin composition for the surface resin layer as in Comparative Example 1 having a thickness of 10 m, and the same resin composition for the surface resin layer as in Comparative Example 1 having a thickness of 5 / in was used as the uppermost resin layer. Using a three-layer co-extruder at a temperature of 315 ° C and a running speed of the base paper of 20 Om / min, a three-layer co-extrusion coating at a linear pressure of the mirrored cooling roll and press roll of 4 O kgf / cm Comparative example, except that the resin sheet was coated with a three-layer resin sheet as shown in Table 3 and subjected to thermal soft calendering or no calendering under the conditions of press temperature, linear pressure and number of series shown in Table 5. In the same manner as in 1, a support for an image material was obtained.

Example 15

In place of the resin composition for the upper layer used in Comparative Example 16, 25 parts by weight of the following master batch (MB-2) and a polycarbonate resin (PC-1, Mitsubishi Chemical Corporation) --Made by company, low viscosity type, softening point 190 ° C) Use a compound resin composition consisting of 75 parts by weight and heat soft under the conditions of breath temperature, press linear pressure and number of series shown in Table 5. A support for an image material was obtained in the same manner as in Comparative Example 16 except for performing a calendar treatment. The masterbatch (MB-2) uses the same parts by weight of the polycarbonate resin (PC-1) instead of the low-density polyethylene resin (LDPE-1) used to prepare the master batch (MB-1). Except for the above, it was prepared in the same manner as for the master batch (MB-1).

Example 16

It was used in Comparative Example 18, in place of the resin composition for the top layer of the intermediate layer and the thickness of the thick 10〃M 5〃 _m, flop-less according to and Table 5 using it it the followings A support for an image material was obtained in the same manner as in Comparative Example 18 except that a thermal soft calendar treatment was performed under the conditions of temperature, linear pressure of press, and number of series. As a resin composition for an intermediate layer having a thickness of 1 O zm, 25 parts by weight of a master batch (MB-1), 30 parts by weight of a low-density polyethylene resin (LDPE-1) and the following polyester resin (PET R-1, (Melting point: 224 ° C.) 45 parts by weight. Polyester resin (PETR-1) is copolymerized polyethylene terephthalate (all dicarboxylic acid components are composed of terephthalic acid, diol component is 88 mol% of ethylene glycol, 10 mol of 1,4-cyclohexanedimethanol %, Ethylene glycol 2 mol%, metal atom content 0.005% by weight, intrinsic viscosity [77] 0.7 ldl / g) 80 parts by weight and graft-modified with maleic anhydride 0.4% by weight 20 parts by weight of polymerized polyethylene resin (density 0.88 g / cm ³ , MFR = 2 g / 10 min, melting point 74 ° C), after sufficient drying, pellet blending and melt kneading with a twin screw extruder Then, it was cooled, pelletized and manufactured. The thickness 5 resin composition for the top layer of zm, master one batch of the following (MB-3) 25 parts by weight of polyester resin (PETR- 2, density of 1.33 g / cm ^3, an intrinsic viscosity [77] 0.7 dl / g, melting point: 224 ° C.) 75 parts by weight. Mass batch 1 (MB-3) uses the same parts by weight of polyester resin (PETR-2) instead of low density polyethylene resin (LDPE-1) used to prepare master batch 1 (MB-1). Other than that, one master batch (MB-1) -Prepared in the same manner as-.

Table 4 shows the melting point and content ratio of the thermoplastic resin in the resin layer in the front-side multilayer resin sheet of the support for image materials obtained in Comparative Examples 16 to 20 and Examples 15 and 16. . The content of thermoplastic resin (Note 1) in Table 4 indicates the content of each thermoplastic resin with respect to the total thermoplastic resin component in each resin layer in terms of% by weight (wt%). Table 5 shows the evaluation results of the appearance of the glossiness and the degree of occurrence of uneven peeling of the photographic print of the support for image materials.

Table 4 Example Table Melting point and content of thermoplastic resin in resin layer of multilayer resin sheet (Note 1) Lower layer Middle layer Upper layer Comparative example 16 112 (100 wt%) 112 (100 wt%) Comparative example 17 Same as above Same as above Comparative example 18 112 (100wt%) 112 (100wt%) 112 (100t%) Comparative Example 19 Same as above Same as above Comparative Example 20 Same as above Same as above Same as above Examples 15-1 93 (60.Owt¾) and 190 (100wt%)

112 (40.0 wt%) Example 15-2 Same as above Same as Example 16 1 I 93 (60.0 wt%), 112 (48.lwt%) and 224 (41.224 (100 wt%)

112 (40.0wt%) 5wt%) and 74 (10.4wt%) Example 16-2 Same as above Same as above

Table 5 Example Layer configuration Thermal soft calendering conditions Photographs. The degree off ^0-less temperature off ° less linear pressure sequence number luster appearance generation of lint peeling unevenness

(° C) (kgf / cm) Comparative example 16 80 10 1 line 2 3 Comparative example 1 80 10 2 line 2 2 Comparative example 18 None 2 5 Comparative example 19 90 10 1 line 1 2 Comparative example 20 90 10 2 line 1 1 Example 15- 1 90 10 1 line 8 8 Example 15-2 90 10 2 lines 10 8 Example 16- 1 1 10 10 1 line 8 8 Example 16-2 1 10 10 2 lines 10 8 (1) From the results in Table 5, it can be seen that the upper layer (A) containing more thermoplastic resin (a) than the lower layer (B) and the lower layer (B) containing thermoplastic resin (b) on the front side of the base paper mainly composed of natural pulp. ), Wherein the thermoplastic resin (a) has a melting point higher than 100 ° C, and the thermoplastic resin (b) It has a melting point of 105 ° C. or less and is lower than the melting point of the thermoplastic resin (a), and after coating the multilayer resin sheet, the image material support is heated to the multilayer resin sheet side. The support for an image material of the present invention (Examples 15 to 16) pressed in a holding state can provide a photographic print having a high glossiness in appearance, and is an excellent support for an image material without occurrence of peeling unevenness. You can see that it is a body. Further, from the viewpoint of the effect of improving the apparent glossiness, it can be clearly understood that it is preferable to perform the pressure welding (thermal soft calendering) while maintaining the heat in two or more series.

On the other hand, the support for image materials (Comparative Examples 16 to 20) outside the present invention in which the melting point of the thermoplastic resin (b) is higher than 105 ° C. has a low apparent glossiness of the photographic print, and uneven peeling. It is well understood that the occurrence of the problem is large and there is a problem.

Examples 17 to 22 and Comparative Example 21

In Example 11, the same resin composition as that for the upper layer of Example 11 was used as the resin composition for the upper layer, and the compounding amount (in parts by weight) shown in Table 6 was used as the resin composition for the lower layer. Polyethylene resin (ML4) polymerized and produced using a meta-opening polymerization catalyst of (a) (abbreviated as thermoplastic resin (b) in Table 6) and [75 parts by weight—polyethylene resin (ML4) Amount of resin (parts by weight)] A resin consisting of 75 parts by weight of a compound resin composition composed of a low-density polyethylene resin (LDPE-1) and 25 parts by weight of a masterbatch (MB-1) Example 11 was carried out in the same manner as in Example 11, except that the composition was used. The processing conditions for the thermal soft calendar treatment were the same as in Example 11, with a press temperature of 55 ° C, a linear pressure of 1 Okgf / cm, and two series. The content ratio of polyethylene resin (ML4) in Table 6 (Note 2) indicates the content ratio of the resin with respect to all the thermoplastic resin components in the lower layer by weight% (wt%).

Table 6 shows the evaluation results of the apparent glossiness and the degree of occurrence of uneven peeling of the photographic print of the obtained support for image materials. -Table 6

From the results in Table 6, it can be seen that the imaging material support of the present invention containing a thermoplastic resin (b) having a melting point of 105 ° C. or less in combination with a polyethylene resin polymerized and produced by a high pressure method (Examples 17 to 17) 22) clearly shows that the photographic print has a high apparent glossiness and is an excellent support for an image material with little occurrence of peeling unevenness. The content of the thermoplastic resin (b) having a melting point of 105 ° C. or less in the lower resin layer is selected from the viewpoints of improving the glossiness and peeling unevenness in appearance. --20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, still more preferably 60% by weight or more, based on the total thermoplastic resin component therein. It is well understood that the weight is more preferably 70 weight% or more.

Examples 23 to 30

In Example 11, the same resin composition as that for the lower layer of Example 11 was used as the resin composition for the lower layer, and 25% by weight of the master batch (MB-1) was used as the resin composition for the upper layer. Ziegler method high-density polyethylene resin with a blending amount (expressed as% by weight or wt%) described in Table 7 [density 0.967 g / cm ³ , MFR = 7.0 g / l 0 min, melting point 130 ° C, Hereinafter, abbreviated as high-density polyethylene resin (HDPE-1)] and the remaining weight% of low-density polyethylene resin (LDPE-1). The upper layer has a thickness of 12 zm and the lower layer has a thickness of 12 zm. Example 11 except that the thickness of the coating was 18 m, and that the thermal soft calendar treatment was performed under the conditions of a press temperature of 70 ° C, a press linear pressure of 1 Okgf / cm, and a number of series of 2. The same was done. The content ratio of high-density polyethylene resin in Table 7 (Note 3) indicates the content ratio of high-density polyethylene resin to all thermoplastic resin components in the upper layer in terms of% by weight (wt%).

Comparative Examples 22 to 29

Examples 23 to 30 were carried out in the same manner as in Examples 23 to 30, except that the resin composition of Comparative Example 10 was used as the resin composition for the lower layer.

Table 7 shows the evaluation results of the apparent glossiness, the degree of occurrence of uneven peeling, and the curl properties of the photographic prints of the supports for image materials obtained in Examples 23 to 30 and Comparative Examples 22 to 29.

-Table Ύ

From the results in Table 7, the support for the image material of the present invention (Examples 23 to 30) was It can be clearly seen that this is an excellent support for an image material that can provide a photographic print having a high glossiness, has little occurrence of peeling unevenness, and can provide an image material having good curl physical properties. In addition, high-density polyethylene resin with a melting point of 130 ° C or more used in combination with low-density polyethylene resin in the upper layer contains 15% by weight or more of the total thermoplastic resin component in the upper layer. The body (Examples 24 to 30) gives a photographic print with an extremely high apparent glossiness, has less occurrence of peeling unevenness, and is clearly a better support for image materials. Further, in the support for image materials of the present invention in which the upper layer contains a high-density polyethylene resin, the content ratio of the high-density polyethylene resin in the upper layer is reduced from the viewpoint of overall performance including curl physical properties. Those with 20 to 75% by weight (Examples 25 to 30) with respect to the total heatable resin component are more excellent, and those with 25 to 65% by weight (Examples 26 to 29) It is clear that it is particularly excellent.

On the other hand, non-inventive imaging material supports (Comparative Examples 22 to 29) which do not contain a thermoplastic resin (b) having a melting point of 105 ° C or lower in the lower layer have low apparent glossiness of photographic prints. It is clear that even if high-density polyethylene resin is contained in the upper layer, the problem is that the physical properties of the steel deteriorate.

Examples 31 to 37 and Comparative Example 30

Example 29 was carried out in the same manner as in Example 29 except that the following resin compositions (R1) to (R8) were used instead of the resin composition for the upper layer used in Example 29. The processing conditions for the thermal soft calender treatment were the same as in Example 29: the press temperature was 70 ° C, the press linear pressure was 1 Okgf / cm, and the number of series was two. The content of the thermoplastic resin (a) contained in the upper layer was 60.0% by weight with respect to all the thermoplastic resin components in the upper layer, except for Example 32. Since polyethylene resin is used, the content is 100% by weight based on the total thermoplastic resin component in the upper layer.)

Comparative Example 30 Upper Layer Resin Composition (R1): Polyethylene Resin Polymerized and Produced Using Meta-Centacene Polymerization Catalyst (ML 2: Density 0.904 g / cm ³ , Melting Point 98 ° C) 52.1 parts by weight A resin composition comprising 75 parts by weight of a compound resin composition comprising 22.9 parts by weight of a low-density polyethylene resin (LDPE-1) and 25 parts by weight of a mass batch (MB-1). 1-Resin composition for upper layer for Example 31 (R2): polyethylene resin produced by polymerization using a meta-opening polymerization catalyst (ML 1: density 0.908 g / cm ³ , melting point 103 ° C) 5 2.1 parts by weight A resin composition comprising 75 parts by weight of a compound resin composition comprising 22.9 parts by weight of a low-density polyethylene resin (LDPE-1) and 25 parts by weight of a masterbatch (MB-1).

Resin composition for upper layer (R 3) for Example 32: low-density polyethylene resin (LDP E-1: density 0.92 Og / cm ³ , melting point 109 ° C, MF R = 4.5 g / 10 min) 75 parts by weight And a master batch (MB-1) and a resin composition comprising 25 parts by weight (the same resin composition for the upper layer as used in Example 23).

Resin composition for upper layer for Example 33 (R4): Low-density polyethylene resin produced by polymerization using an autoclave-type reactor by a high-pressure method (density 0.926 _g / cm ³ , melting point 111 ° C, MFR = 3.5 g / 10 A resin composition consisting of 52.1 parts by weight, 22.9 parts by weight of a low-density polyethylene resin (LDPE-1) and 25 parts by weight of a batch (MB-1).

Resin composition for upper layer for Example 34 (R5): polyethylene resin produced by polymerization using a meta-opening polymerization catalyst (density 0.92 lg / cm ³ , melting point 115 ° C) 52.1 parts by weight of low-density polyethylene resin ( LDPE-1) A resin composition comprising 75 parts by weight of a compound resin composition comprising 22.9 parts by weight and 25 parts by weight of a batch (MB-1).

Resin composition for upper layer for Example 35 (R 6): Linear low-density polyethylene resin polymerized and produced by Philips method (density 0.904 g / cm ³ ₅ melting point 120 ° C) 52.1 weight parts and low-density polyethylene A resin composition comprising 75 parts by weight of a compound resin composition comprising 22.9 parts by weight of a resin (LDPE-1) and 25 parts by weight of a batch (MB-1).

Resin composition for upper layer for Example 36 (R7): Linear low-density polyethylene resin polymerized and produced by the Philips method (density 0.927 g / cm ³ , melting point 125 ° C) 52.1 parts by weight and low-density polyethylene A resin composition comprising 75 parts by weight of a compound resin composition comprising 22.9 parts by weight of a resin (LDPE-1) and 25 parts by weight of a masterbatch (MB-1). -Resin composition for upper layer for Example 37 (R 8): high-density polyethylene resin (HDPE = 1: density 0.967 g / cm ³ , melting point 130 ° C, MFR = 7. Og / 10 min) 52.1 weight Resin composition consisting of 22.9 parts by weight of a low density polyethylene resin and 25 parts by weight of a master batch (MB-1) (the same resin composition for the upper layer as used in Example 29) Table 8 shows the evaluation results of the appearance of photographic print gloss and the occurrence of uneven peeling. Table 8

From the results in Table 8, it can be seen that the imaging material support of the present invention (Examples 31 to 37) containing the thermoplastic resin (a) having a melting point higher than 100 ° C. in the upper layer more than in the lower layer has an apparent luster. Excellent photographic prints with excellent image quality and less peeling unevenness --It is clear that it is a support for. Further, as the thermoplastic resin (a), those having a melting point higher than 105 ° C are preferable, and those having a melting point of 110 ° C or higher are more preferable, from the viewpoints of improvement in appearance glossiness and uneven peeling. , 1 1 5. It is clear that those having a temperature of C or higher are more preferable, and those having a temperature of 120 ° C. or higher are particularly preferable.

On the other hand, the support for an image material (Comparative Example 30) outside the present invention, in which the melting point of the thermoplastic resin (a) is 100 ° C. or less, has a low apparent glossiness of a photographic print, and has an uneven peeling. It is well understood that the occurrence is large and there is a problem.

Example 3 8 to 4 2

In the above <Manufacture of base paper>, except that pulp beaten to the fiber length shown in Table 9 was used and that the linear pressure of the machine calendar was appropriately adjusted, the same as described in Table 9 was used. A base paper having a center plane average roughness SR a was manufactured. These base papers were used in place of the base paper used in Example 27, and a thermal soft calendar was used under the conditions of a press temperature of 70 ° C, a press linear pressure of 1 O kgf / cm, and the number of series shown in Table 9. The same procedure as in Example 27 was performed, except that one treatment was performed.

Table 9 shows the evaluation results of the apparent glossiness and the degree of occurrence of uneven peeling of the photographic print of the obtained support for image materials.

-Table 9

From the results in Table 9, it can be seen that the image material support of the present invention (Example 3842) is an excellent image material support capable of obtaining a photographic print having a high gloss appearance and having no occurrence of peeling unevenness. You can see that. The base paper used in the practice of the present invention preferably has a center plane average roughness SRa of 1.5 以下 m or less, more preferably 1.4〃m or less, and more preferably 1.3 / m or less. It is further understood that those having an even more preferable size and those having a size of 1.2 m or less are particularly preferable. In addition, it can be seen that the number of series in one heat calender process is much better in two series than in one series. Example 43-51

Instead of the resin coating of the surface multilayer resin sheet performed in Example 27, the surface of the base paper was subjected to a corona discharge treatment, and then the surface multilayer resin sheet was formed. m, the following resin compositions (R9) to (R11), and as the resin composition for the upper layer, the following resin compositions (R12) to (R13) having a coating thickness of 15 μm. At the temperature of the resin composition shown in Table 10, and at a running speed of the base paper of 30 Om / min, using a melt extruder with separate stations in the order of lower layer and then upper layer. Each of the mirror surface rolls and the press rolls was sequentially melt-extruded at a linear pressure of 4 Okgf / cm to cover the multi-layer resin sheet. Okgf / cm, same as Example 27 except that the number of series was 2 It was carried out as follows.

Lower layer resin composition (R9): The same lower layer resin composition as used in Example 27 [ie, the content of polyethylene resin (ML4) was 60.0% with respect to the total thermoplastic resin component in the lower layer. % By weight].

Lower layer resin composition (R10): A compound resin composition consisting of 60 parts by weight of a polyethylene resin (ML4) and 40 parts by weight of a low-density polyethylene resin (LDPE-1).

Lower layer resin composition (R11): Polyethylene resin (ML4) 60 parts by weight and high-pressure low-density polyethylene resin using a tube type reactor (density 0.924 g / cm ³ , melting point 110 ° C, 1 \? 1 = 4.05 80 minutes) A compound resin composition consisting of 40 parts by weight.

Resin composition for upper layer (R12): Same resin composition for upper layer as used in Example 27 [that is, the content ratio of titanium dioxide pigment (as a ratio to the weight of the upper layer) was 12.5%, Upper layer resin composition in which the content of polyethylene resin (HDPE-1) is 40.1% by weight based on the total thermoplastic resin component in the upper layer].

Resin composition for upper layer (R13): Resin consisting of 30 parts by weight of masterbatch (MB-1), 36.3 parts by weight of low-density polyethylene resin (LDPE-1) and 33.7 parts by weight of high-density polyethylene resin (HDPE-1) The composition [ie the content of titanium dioxide pigment (as a percentage of the weight of the upper layer) is 15% by weight, Resin composition in which the content ratio of 1-lene resin (HDPE-1) is 40.1% by weight based on the total thermoplastic resin component in the upper layer].

Table 10 shows the evaluation results of the appearance of glossiness and the occurrence of uneven peeling of the photographic print of the obtained support for image materials. o

From the results in Table 10, it can be seen that the support for image materials of the present invention (Examples 43 to 51) is an excellent support for image materials that can provide a photographic print with high apparent gloss and that does not cause uneven peeling. You can see that it is a body. Further, in the present invention, a photographic print In view of the effect of improving the apparent glossiness and peeling unevenness, when the resin composition for the surface multilayer resin sheet having a multilayer structure is melt-extruded and coated, the temperature of the upper layer resin composition is adjusted to the lower layer. It is well understood that it is preferable to lower the temperature of the resin composition. Further, even if the content of additives such as titanium dioxide pigment, coloring pigment, release agent and antioxidant in the lower layer is lower than the content of additives in the upper layer, there is no problem in the effect of the present invention. It is clear that it is economically advantageous.

Examples 52 to 54

In Example 11, the running speed of the base paper was set to the running speed shown in Table 11, and the resin composition for the lower layer was the same as that used in Example 47 having a coating thickness of 15 μm. The same resin composition for the lower layer (R 10), and the same resin composition for the upper layer (R 13) as the resin composition for the upper layer, which is the same as that used in Example 47 with a coating thickness of 1, The procedure was performed in the same manner as in Example 11 except that the thermal soft calender treatment conditions were a press temperature of 70 ° C., a press linear pressure of 2 O kgf / cm, and the number of series was two. The melt extrusion coating of the two-layer resin composition for the surface resin layer was performed by a co-extrusion method in the same manner as in Example 11.

Example 5 5-6 2

In Example 47, the running speed of the base paper was set to the running speed shown in Table 11, and the coating thickness of the upper and lower layers of the multilayer resin sheet in the table was changed to the coating thickness shown in Table 11. Except for, the procedure was the same as in Example 47. The processing conditions of the thermal soft calender treatment were the same as in Example 47, with a breath temperature of 70 ° C, a press linear pressure of 2 Okgf / cm, and two series. Further, the melt extrusion coating of the two resin compositions for the surface resin layer was performed by a sequential melt extrusion coating method (abbreviated as a sequential method in Table 11) as in Example 47.

Table 11 shows the evaluation results of the apparent glossiness and the degree of occurrence of uneven peeling of the photographic prints of the support for image materials obtained in Examples 55 to 62 described above. --

From the results shown in Table 11, among the image material supports of the present invention, the thickness of the lower layer is 25% of the thickness of the multilayer resin sheet from the viewpoint of the effect of improving the apparent glossiness and peeling unevenness of the photographic print. It is clear that the above is preferable, 40% or more is more preferable, and 50% or more is particularly preferable. Examples 52 and 55 (each with a base paper traveling speed of 200 m / min), Examples 53 and 56 (each with a base paper traveling speed of 250 m / min), and From the comparison of the results of Example 54 and Example 60 (each of the running speed of the base paper of 30 Om / min), the running speed of the base paper (that is, the manufacturing speed of the support for the image material) must be higher. In other words, when the traveling speed of the base paper is 200 m / min or more, further 250 m / min or more, particularly 300 m / min or more --In some cases, from the viewpoint of improving the apparent glossiness and peeling unevenness of the photographic print, the surface multilayer resin sheet was formed by the sequential melt extrusion coating method among the image material supports of the present invention. It can be clearly seen that the support for the image material is particularly preferred. Further, the image material support is often a particularly excellent image material support capable of obtaining an image material having a high apparent gloss and a print thereof, having no occurrence of peeling unevenness, and capable of high-speed and stable production. Understand.

Example 63 and Comparative Example 31

An ink jet recording material was prepared by coating the following ink image receiving layer on the support for the image material used in Example 47 and Comparative Example 7 instead of the layer constituting the image of the silver halide silver halide toner image. . As a result, the ink jet recording material (Example 63 corresponding to the support) having the image material support of the present invention (Example 47) had a high apparent glossiness and was excellent. On the other hand, the ink jet recording material (Comparative Example 31 corresponding to the support) having the image material support (comparative example 7) outside the present invention has a poor glossiness in appearance. There was a problem.

The ink receiving layer is composed of 30 g of a 10% by weight aqueous solution of gelatin treated with an alkali-treated gelatin having a molecular weight of 70,000, sodium carboxymethyl cellulose (a degree of etherification of 0.7 to 0.8, and a B-type viscometer. 37.5 g of an 8% by weight aqueous solution of a 2% by weight aqueous solution having a viscosity of 5 cp or less, 37.5 g of an epoxy compound (NER—010, manufactured by Nagase & Co., Ltd.) 0.3 g of a methanol solution, 0.3 g of sulfosuccinic acid 1 2 — A coating solution consisting of 0.5 g of a mixture of 5% by weight of ethyl hexyl ester salt and water and 31.7 g of pure water is formed by applying a solid content of 7 g / m for ² minutes. Was done.

Example 6 4 and Comparative Example 3 2

The following heat transfer type thermal transfer recording image receiving layer was coated on the support for the image material used in Example 47 and Comparative Example 7 instead of the silver halide color image forming layer, and the heat transfer type heat transfer was performed. A recording image receiving material was prepared. As a result, the heat transfer type thermal transfer recording image-receiving material (Example 64 corresponding to the support) having the image material support (Example 47) of the present invention has a high apparent glossiness. On the other hand, the heat transfer type thermal transfer recording image-receiving material (Comparative Example 32 corresponding to the support) having the image material support (comparative example 7) outside the present invention has an apparent glossiness. Was inferior and problematic. (1) The thermal transfer recording image receiving layer is composed of 10 parts by weight of a saturated polyester resin (TP-220: manufactured by Nippon Kasei Co., Ltd.), 0.5 parts by weight of an amino-modified silicone (KF-393: manufactured by Shin-Etsu Chemical Co., Ltd.) and a solvent ( Xylene / methyl ethyl ketone = 1/1) A coating composition consisting of 30 parts by weight was formed by applying a solid content of 5 g / m ² using a wire bar.

Comparative Examples 33 and 34

After the surface of the base paper is subjected to edge discharge treatment, a high-pressure method low-density polyethylene resin [density 0.920 g / cm ³ , MFR = 4.5 g ^ 0 min, melting point 109 ° C, below, low-density polyethylene resin (LDPE-1) and the abbreviated] 47.1 wt ¾, hydrated aluminum oxide (vs. a 1 relative Nisani匕titanium ₂ 0 ₃ minutes as the surface-treated Ana evening one peptidase type titanium dioxide pigment 50 wt 0.50 wt 5 And Gunsei (Daiichi Kasei Kogyo Co., Ltd., # 2000) 0.4% by weight, zinc stearate 2.5% by weight, and tetrakis [methylene-13 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane 150 A masterbatch of titanium dioxide pigment consisting of 25 ppm by weight [hereinafter abbreviated as masterbatch (MB-1)] A resin composition consisting of 25 parts by weight and 75 parts by weight of a low-density polyethylene resin (LDPE-1) was prepared at a resin temperature of 315 ° C. At a running speed of 200 m / min. Using an extruder, the melt-extrusion coating was performed at a linear pressure of 40 kgf / cm between the cooling roll and press roll on the mirror surface. At that time, the surface of the resin layer containing the titanium dioxide pigment of the resin-coated paper was processed to a glossy surface.

Furthermore, do not apply a calendering process between the processing of the front and back resin layers before winding, or use the on-machine under the conditions of the press temperature, press linear pressure, and number of rows shown in Table 13. A soft-rendering treatment was applied. In the subsequent zone, the backing resin layer surface of the resin-coated paper was subjected to corona discharge treatment, and the following back layer coating liquid was applied on-machine. As the dry weight content, colloids like silica: styrene latex = 1: consists of one further latex content of the back layer coating solution, including other suitable amount of coating aid of polystyrene sodium sulfonate 0.021 g / m ² (solid It was applied at a coating amount of 0.2 lg / m ² as calculated by weight. --In addition, after applying the back layer and before winding the resin-coated paper, the front resin surface is subjected to corona discharge treatment, lime-treated gelatin 1.2 g, low molecular weight gelatin (manufactured by Nitta Gelatin Co., Ltd.) , P-3226) 0.3 g, vinylidene chloride-based latex 1.5 g, butyl paraoxybenzoate 10 wt. Methanol solution 0.3 g, and 5 wt.% Sulfosuccinate-2-ethylhexyl ester salt methanol and water mixture 0.45 g. A subbing coating solution containing 100 g of water was prepared and uniformly coated on-machine so as to have a coating amount of gelatin of 0.06 g / m ² to obtain a support for an image material.

Comparative Examples 35 and 36

Instead of the resin composition used in Comparative Example 34, 25 parts by weight of a master batch (MB-1) and 22 parts by weight of a low density polyethylene resin (LDPE-1) and a high density polyethylene resin [density 0.967 g / cm ³ MFR = 7.0 g / l 0 min, melting point 130. C, hereafter abbreviated as high-density polyethylene resin (HDPE-1)] Use a resin composition consisting of 53 parts by weight, do not perform calendar treatment, or use the breath temperature and press linear pressure shown in Table 13. A support for an image material was obtained in the same manner as in Comparative Example 34 except that a thermal soft calendar treatment was performed under the conditions of the number of series.

Comparative Examples 37-39

After the surface of the base paper was subjected to corona discharge treatment, the surface was treated as a resin composition for the lower layer with the same resin composition for the front resin sheet and the resin composition for the upper layer as in Comparative Example 34 having a thickness of 15 m. Then, the same resin composition for the front resin sheet as in Comparative Example 34 having a thickness of 15 was mirror-polished using a two-layer co-extruder at a resin temperature of 315 ° C. and a running speed of the base paper of 200 m / min. Coating the surface resin sheet by simultaneous extrusion coating with a linear pressure of 4 Okgf / cm between the cooling roll and the press roll on the surface to cover the surface resin sheet, and do not apply the calendering process, or press temperature shown in Table 13. A support for an image material was obtained in the same manner as in Comparative Example 34, except that a thermal soft calender treatment was performed under the conditions of the press linear pressure and the number of series. Comparative Examples 40 to 42

Instead of the resin composition for the upper layer used in Comparative Example 39, 25 parts by weight of master batch (MB-1), 22 parts by weight of low density polyethylene resin (LDPE-1) and 22 parts by weight of high density polyethylene resin (HDPE-1) Use a resin composition consisting of 53 parts by weight and do not perform calendering, or use a press wire shown in Table 13. -An image material support was obtained in the same manner as in Comparative Example 39, except that a soft calender treatment (processing of only pressure welding without applying heat) was performed under the conditions of one pressure and the number of series.

Comparative Example 4 3 to 4 5

Comparative Example 4 In place of the resin composition for the lower layer used in 2, 25 parts by weight of master batch (MB-1), 22 parts by weight of low density polyethylene resin (LDPE-1) and 22 parts by weight of high density polyethylene resin (HDPE- 1) Do not use a resin composition consisting of 53 parts by weight and do not carry out calendering, or carry out a thermal soft calendering treatment under the conditions of press temperature, press linear pressure and number of series shown in Table 13. A support for an image material was obtained in the same manner as in Comparative Example 42 except that coating was performed.

Comparative Example 4 6 to 4 8

After the surface of the base paper is subjected to corona discharge treatment, the same resin composition for the front resin sheet as in Comparative Example 33 having a thickness of 15 m was formed on the surface as the lowermost resin layer. Sa

The same resin composition for the front resin sheet as 10 m in Comparative Example 33, the same resin composition for the front resin sheet as in Comparative Example 33 with a thickness of 5 / m as the uppermost resin layer The it's resin temperature

3 Three-layer coextrusion coating with a base roll running speed of 20 Om / min at 15 ° C and a linear pressure of 4 O kgf / cm for the mirror roll and press roll using a three-layer co-extrusion machine Do not cover the surface resin sheet and do not apply force render treatment.

A support for an image material was obtained in the same manner as in Comparative Example 33 except that a thermal softening treatment was performed under the conditions of the press temperature, the press linear pressure, and the number of series described in 3.

Example 6 5, 6 6

Comparative Example 41 In the same manner as in Comparative Example 41, except that the calendering treatment was performed under the conditions of the press temperature, the linear pressure of the press, and the number of series shown in Table 13 instead of the calendering treatment used in Comparative Example 41, This was performed to obtain a support for an image material.

Example 6 7

In place of the resin composition for the intermediate layer having a thickness of 10 / m and for the uppermost layer having a thickness of 5 m used in Comparative Example 47, the following was used as it is and described in Table 13. A support for an image material was obtained in the same manner as in Comparative Example 47, except that a thermal soft calender treatment was performed under the conditions of the press temperature, the linear pressure of the press, and the number of series. As a resin composition for the middle layer with a thickness of 10 m, 25 parts by weight of master batch (MB-1), --A compound resin composition comprising 30 parts by weight of a lithylene resin (LDPE-1) and 45 parts by weight of the following polyester resin (PETR-1, melting point: 224 ° C) was used.

Polyester resin (PETR-1) is a copolymerized polyethylene terephthalate (the dihydrouronic acid component is entirely composed of terephthalic acid, the diol component is 88 mol% of ethylene glycol, and 1,4-cyclohexanedimethanol is 10 mol. %, 2 mol% of dimethyl glycol, content of metal atom 0.005% by weight, intrinsic viscosity [7?] 0.7 ldl / g) 80% by weight and 0.4% by weight of maleic anhydride 20 parts by weight of a copolymerized polyethylene resin (density 0.88 g / cm ³ , MFR = 2 g / 10 min, melting point 74 ° C), and after thoroughly drying it, pellet blending is performed using a twin-screw extruder. It was produced by melt-kneading, cooling, and pelletizing. As a resin composition for the top layer with a thickness of 5 m, 25 parts by weight of the following master batch (MB-3) and polyester resin (PETR-2, density 1.33 g / cm ³ , intrinsic viscosity [r?] 0.7dl / g, melting point: 224 ° C) of 75 parts by weight. The masterbatch (MB-3) is a polyester resin instead of the low-density polyethylene resin (LDPE-1) used to prepare the mass batch (MB-1).

It was prepared in the same manner as the master batch (MB-1) except that the same parts by weight of (PETR-2) were used.

Example 68

In place of the resin composition for the upper layer used in Comparative Example 39, 25 parts by weight of the following master batch (MB-2) and a polycarbonate resin (PC-1, manufactured by Mitsubishi Chemical Corporation, low-viscosity rubber, softening point 190 Comparative Example 39 except that a compound resin composition consisting of 75 parts by weight and a hot zoft calender treatment under the conditions of press temperature, press linear pressure and series number shown in Table 13 were used. In the same manner, a support for an image material was obtained. The mass batch 1 (MB-2) replaces the low-density polyethylene resin (LDPE-1) used in the preparation of the master batch (MB-1) with the same parts by weight of the polycarbonate resin (PC-1). Except to use, mass batch 1 batch

It was prepared in the same manner as (MB-1).

Of the image material supports obtained in Comparative Examples 33 to 48 and Examples 65 to 68. Table 12 shows the melting point and the content of the thermoplastic resin in the resin layer in the single-layer or multilayer resin sheet on the front side. In Table 12, the content ratio of the thermoplastic resin (Note 1) indicates the content ratio of each thermoplastic resin with respect to the total thermoplastic resin component in each resin layer by weight% (wt%).

Table 13 shows the evaluation results of the appearance of glossiness and the occurrence of uneven peeling of the photographic print of the support for image materials.

-

Two

Table 1 3 Example Layer composition Thermal lift currentr "-Processing conditions Photo: ° Lint

00 appearance Degree of occurrence Free temperature Less linear pressure Number of lines Glossiness

(V) (kgf / cm)

Comparative example 3 3 Single layer ί «2 5 Comparative example 3 4 Single layer 8 0 1 0 2 system ι'J | 2 2 Comparative example 3 5 Single layer None 0 7 Comparative example 3 6 Single layer« n 1 n ώ Po JQ a

D

Comparative Example 3 7 1r

0 Comparative Example 3 8— 1 ο 0 3 1 Thread Row 9 4 Comparative Example 2

3 8—2 ο ϋ 5 Same as above 0 * A- ± Comparative example 3 8-3 2 严 1 o Ι 1Η J-port 9 OQ Comparative example 3 8-4 2 layer 8 0 2 0 Same as above 2 3 Comparative example 3 8 -5 2 layers 8 0 3 0 Same as above 1 2

6 2 layer 8 0 4 0 Same as above 1 2 Comparative example 3 8— 7 2 layer 8 0 5 0 Same as above 1 1 Comparative example 3 9 2 layer 8 0 1 0 2 series 2 2 Comparative example 4 0 fiS 17 Comparative example 4 1 2 layers Pressure welding only 2 0 1 line 3 7 Comparative example 4 2 2 layers Pressure welding only 2 0 2 line 3 7 Comparative example 4 3 2 layer _ None 3 7 Comparative example 4 4 2 layer 8 0 1 0 1 line J 3 7 Comparison Example 4 5 2 layers 8 0 1 0 2 system, row J 3 6 Comparative example 4 6 3 2 c; Comparative example 4 7 3 9 ϋ 10 1 Thread system 'J 1 9 Comparative example 4 8 9 ο 1 o ττ ^ ^ Il 1

₂ =

Example 6 5 1

On OU 1 (J ί system IJ Q 0 7 Example 6 6-18 0 3 1 series 5 7 Example 6 6-2 o U bl.) GO 7 Example 6 6-3 2 jg 8 0 1 0 Same as above 6 7 Example 6 6-4 2 layer 8 0 2 0 Same as above 6 7 Example 6 6-5 8 0 3 0 Same as above 5 7 Example 6 6-6 2 layer 8 0 4 0 Same as above 5 6 Example 6 6 — 7 8 0 5 0 Same as above 4 5 Example 6 7-1 1 2 0 1 0 1 series 7 8 Example 6 7-2 1 2 0 1 0 2 series 9 8 Example 6 8-1 1 0 0 1 0 1 line 7 8 Example 6 8-2 1 0 0 1 0 2 line 9 8 1-From the results shown in Table 13, the top side of the base paper mainly composed of natural pulp contains the upper layer (C) containing more thermoplastic resin (c) than the lower layer (D) and the upper layer containing thermoplastic resin (d). A thermoplastic resin (c) having a melting point of the thermoplastic resin (d), which is a support for an image material covered with a multilayer resin sheet comprising a lower layer (D) containing more than (C). The image material support according to the present invention, which is higher, and after being coated with the multilayer resin sheet, the image material support is pressed against the multilayer resin sheet side while holding heat (Example 6) 5 to 68) clearly show that the photographic print has a high glossiness and that it is an excellent support for an image material without occurrence of peeling unevenness.

In addition, from the viewpoint of the effect of improving the apparent glossiness of the photographic print, it can be clearly understood that the pressure welding (thermal soft calendering) while maintaining the heat is preferably performed in two or more series. Further, considering the relationship with the press linear pressure, the press linear pressure is preferably performed at 3 to 45 kgf / cm, more preferably at 4 to 35 kgf / cm, and more preferably 5 to 2 kgf / cm. It can be clearly seen that it is particularly preferred to carry out at 5 kgf / cm.

On the other hand, when pressure welding is not performed while maintaining heat (Comparative Examples 33, 35, 37, 40 to 43 and 46), or when the upper and lower layers are made of a thermoplastic resin with a relatively high melting point And the melting point of the main component resin in the upper and lower layers does not satisfy the requirements of the present invention (Comparative Examples 44 and 45), and when the surface resin layer is made of a thermoplastic resin having a relatively high melting point, It can be clearly seen that the support for an image material other than the present invention containing the largest amount and having a single layer (Comparative Example 36) has a problem in that the photographic print has a low apparent glossiness. In addition, when both the upper layer and the lower layer contain the most thermoplastic resin having a relatively low melting point, and the melting points of the main component resins in the upper layer and the lower layer do not satisfy the requirements of the present invention (Comparative Examples 38, 39) , 47 and 48) and the surface resin layer containing the largest amount of the thermoplastic resin having a relatively low melting point and having a single layer (Comparative Example 34), the image material support other than the present invention is, for example, Even if the conditions such as the press temperature, press linear pressure, and the number of series are changed, the apparent glossiness of the photographic prints is low, and there is a tendency to block on rolls by thermal soft calendering. The occurrence is poor, and it is obvious that there is a problem.

Examples 6 9 to 71 and Comparative Examples 49 to 50

In Example 65, the resin composition for the lower layer was the same as that for the lower layer in Example 65. 1-Using a resin composition, as a resin composition for the upper layer, 25 wt% of master batch (MB-1) and a high-density polyethylene resin having a blending amount (wt%, indicated as wi ^) shown in Table 14 Example 65 was carried out in the same manner as in Example 65, except that a resin composition comprising (HDPE-1) and a low-density polyethylene resin (LDPE-1) with the remaining weight% was used. The processing conditions for the heat soft calendering were the same as in Example 65, with a press temperature of 80 ° C, a press linear pressure of 1 Okgf / cm, and two series. The content ratio of high-density polyethylene resin (Note 2) in Table 14 indicates the content ratio of high-density polyethylene resin to the total thermoplastic resin component in the upper layer in weight% (wt%).

Table 14 shows the evaluation results of the apparent glossiness and the degree of occurrence of peeling unevenness of the photographic print of the obtained support for image materials. Table 4 Example High density polyethylene photo in upper layer. Lint Appearance of blending amount and content of resin for uneven peeling Degree of occurrence

Glossiness

Compounding amount Content ratio

(wt%) (w) (Note 2) Comparative example 49 0 0 2 2 Comparative example 50 26 30. 0 4 4 Example 69 44 50. 7 6 5 Example 70 53 61. 1 8 7 Example 71 61 70 . 3 9 8 1-From the results in Table 14, it can be seen that the image material support of the present invention (Examples 69 to 71) is excellent in that a photographic print having a high apparent gloss can be obtained and peeling unevenness is less generated. It can be clearly seen that this was an image material support. Further, the content ratio of the thermoplastic resin (c), which has a higher melting point than the thermoplastic resin (d) contained in the lower resin layer more than the upper layer and which is contained more than the lower layer in the upper resin layer, depends on the apparent gloss. From the viewpoint of the effect of improving the feel and unevenness in peeling, the content is preferably 50% by weight or more, more preferably 60% by weight or more, and particularly preferably 70% by weight or more, based on all the thermoplastic resin components in the upper resin layer. Can be clearly understood.

On the other hand, the image material support (Comparative Examples 49 and 50) outside the present invention in which the thermoplastic resin (c) in the upper layer does not satisfy the requirements of the present invention has a low apparent glossiness of the photographic print, The occurrence of uneven peeling is poor, and it is clear that there is a problem.

Example 7 2 to 7 6

In the above <Manufacture of base paper>, except that pulp beaten to the fiber length shown in Table 15 was used and that the linear pressure of the machine calender was appropriately adjusted, A base paper having the described center plane average roughness SRa was produced. These base papers should be used in place of the base paper used in Example 65 and subjected to thermal soft calendering under the conditions of a press temperature of 80 ° C, a press linear pressure and the number of series shown in Table 15. Except for this, the procedure was the same as in Example 65.

Table 15 shows the evaluation results of the apparent glossiness and the degree of occurrence of peeling unevenness of the photographic print of the obtained support for image materials.

--Table 5

From the results in Table 15, it can be seen that the image material support of the present invention (Examples 72 to 76) is an excellent image material support which can provide a photographic print having a high glossiness and has no peeling unevenness. It is clearly understood that. The base paper used in the practice of the present invention preferably has a center plane average roughness SRa of 1.5 m or less, more preferably 1.4 zm or less, still more preferably 1.3 m or less. It is well understood that those having a thickness of 1.2 zm or less are particularly preferable. In addition, it can be seen that the number of series in one process of thermal soft calendar is much better than that of one series. --Examples 77 to 85

Instead of the surface multilayer resin sheet coating performed in Example 65, the surface of the base paper was subjected to a corona discharge treatment, and then a surface multilayer resin sheet was formed on the surface as a resin composition for a lower layer. The following resin compositions (R14) to (R16) for the upper layer, and the resin compositions (R17) to (R18) for the coating thickness 15 described below for the upper layer, At a temperature of the resin composition shown in Table 16 and a running speed of the base paper of 30 Om / min in the combination described in Table 16, the lower layer and then the upper layer were separated using a melt extruder in separate stages. The surface resin layer is coated by successively melt-extruding and coating at a linear pressure of 40 kgf / cm between the mirror surface roll and the press mouth, and the heat soft calendar is processed at a press temperature of 80 ° C and a press linear pressure of Performed in the same manner as in Example 65, except that the number of lines was 20 kgf / cm and the number of lines was 2.

Lower layer resin composition (R14): Same lower layer resin composition as used in Example 65.

Lower layer resin composition (R15): a resin composition that is a low-density polyethylene resin (LDPE-1).

Lower layer resin composition (R16): a resin composition that is a low-density polyethylene resin with a tuber method having a density of 0.924 g / cm ³ , MFR4.Og / 10 minutes, and a melting point of 110 ° C.

Upper layer resin composition (R17): Same upper layer resin composition as used in Example 65.

Resin composition for upper layer (R18): Resin consisting of 30 parts by weight of master batch (MB-1), 18.6 parts by weight of low density polyethylene resin (LDPE-1) and 51.4 parts by weight of high density polyethylene resin (HDPE-1) Composition.

Table 16 shows the evaluation results of the apparent glossiness and the occurrence of uneven peeling of the photographic print of the obtained support for image materials. 6

From the results in Table 16, it can be seen that the image material support of the present invention (Examples 77 to 85) can provide a photographic print having a high glossiness, and is an excellent image free from uneven peeling. It can be clearly seen that the support is a material support. In the present invention, the temperature of the resin composition for the upper layer is adjusted when the resin composition for the two-layer resin sheet is melt-extruded and coated from the viewpoint of improving the apparent glossiness and peeling unevenness of the photographic print. It is well understood that it is preferable that the temperature be lower than the temperature of the resin composition constituting the lower layer.In addition, the content ratio of additives such as titanium dioxide pigment, coloring pigment, release agent, antioxidant in the lower layer, It can be clearly seen that even if the content ratio of the additive is lower than that, there is no problem in the effect of the present invention, and it is economically advantageous. --Example 8 6 to 8 8

In Example 65, the traveling speed of the base paper was set to the traveling speed shown in Table 17, and the resin composition for the lower layer was the same as that used in Example 81 having a coating thickness of 15 μm. The same lower layer resin composition (R 15) and the same upper layer resin composition (R 18) as used in Example 81 with a coating thickness of 15 μm were used as the upper layer resin composition. The procedure was performed in the same manner as in Example 65 except that the thermal soft calendar was used at a pressing temperature of 80 ° C., a linear pressure of the press of 2 O kgf / cm, and the number of series was two. The melt extrusion coating of the resin composition for a two-layer resin sheet was performed by a co-extrusion method as in Example 65.

Example 8 9 to 9 6

In Example 81, the running speed of the base paper was set to the running speed shown in Table 17 and the coating thickness of the upper and lower layers of the two-layer resin sheet was set to the coating thickness shown in Table 17 Except for the above, the same procedure was performed as in Example 81. The processing conditions for the thermal softener treatment were the same as in Example 81: a press temperature of 80 ° C, a press linear pressure of 2 Okgf / cm, and a number of series of 2. Further, the melt extrusion coating of the resin composition for the two-layer resin sheet was performed by a sequential melt extrusion coating method (abbreviated as a sequential method in Table 17) in the same manner as in Example 81.

Table 17 shows the evaluation results of the apparent glossiness and the degree of occurrence of uneven peeling of the photographic prints of the supports for image materials obtained in Examples 86 to 96 described above.

-

Ύ

From the results in Table 17, among the image material supports of the present invention, the thickness of the lower layer is more than 25 times the thickness of the two-layer resin sheet in terms of the effect of improving the glossiness and peeling unevenness of the photographic print. It can be clearly seen that the thickness is preferably 40% or more, more preferably 50% or more. Examples 86 and 89 (each with a base paper traveling speed of 200 m / min), Examples 87 and 90 (each with a base paper traveling speed of 250 m / min), and From the comparison of the results of Example 88 and Example 94 (each of the running speed of the base paper: 300 m / min), if the running speed of the base paper (that is, the manufacturing speed of the support for the image material) increases, In other words, when the running speed of the base paper is 200 m / min or more, further 250 m / min or more, especially 300 m / min or more, the apparent gloss of the photographic print is From the viewpoint of the effect of improving the feel and peeling unevenness, it can be clearly understood that among the supports for the image material of the present invention, the support for the image material in which the surface two-layer resin sheet is formed by the sequential melt extrusion coating method is particularly preferable. Further, the image material support has an image having a high glossiness in appearance. --It is clear that the material and its print are obtained, there is no peeling unevenness, and high speed and stable production is possible.

Example 97 and Comparative Example 51

An ink jet recording material was prepared by coating the following ink image receiving layer on the image material support used in Example 81 and Comparative Example 33 instead of the silver halide color photographic component layer. As a result, the ink jet recording material (Example 97 corresponding to the support) having the image material support (Example 81) of the present invention had a high apparent glossiness and was excellent. On the other hand, the ink jet recording material (Comparative Example 51 corresponding to the support) having the image material support (Comparative Example 33) outside the present invention has a problem in that the apparent glossiness is inferior. Met.

The ink receiving layer is composed of 10 weights of alkali-treated gelatin having a molecular weight of 70,000. 30 g aqueous gelatin solution, sodium carboxymethyl cellulose (degree of etherification 0.7 to 0.8, viscosity of 2 wt% aqueous solution measured with a B-type viscometer is 5 cp. 37 · 5 g of an 8 wt% aqueous solution of the following), 0.3 g of a 5 wt% methanol solution of an epoxy compound (NER-010, manufactured by Nagase & Co., Ltd.), 5 wt% methanol of a sulfosuccinic acid-2-ethylhexyl ester salt A coating solution consisting of 0.5 g of a mixed solution of water and water and 31.7 g of pure water was applied by coating at a solid content of 7 g / m ² .

Example 98 and Comparative Example 52

The following heat transfer type thermal transfer recording image receiving layer was coated on the image material support used in Example 81 and Comparative Example 33 in place of the silver halide color photographic component layer, and It was created. As a result, the heat transfer type thermal transfer recording image-receiving material (Example 98 corresponding to the support) having the image material support (Example 81) of the present invention has a high apparent glossiness. On the other hand, the heat transfer type thermal transfer recording image-receiving material (Comparative Example 52 corresponding to the support) having the image material support (Comparative Example 33) out of the present invention has an apparent glossiness. Inferior and problematic.

The thermal transfer recording image receiving layer is composed of 10 parts by weight of a saturated polyester resin (TP-220: manufactured by Nippon Kasei Co., Ltd.), 0.5 parts by weight of an amino-modified silicone (KF-393: manufactured by Shin-Etsu Chemical Co., Ltd.) and a solvent (xylene) / Methylethyl ketone = 1/1) A coating composition consisting of 30 parts by weight was applied using a diabar with a solid content of 5 g / m2 for ² minutes. --

Was made. Industrial applicability

The support for an image material of the present invention can provide an image material and a print having a high apparent glossiness and no uneven gloss, and has an improved peeling property from a cooling roll at the time of manufacturing the support to improve unevenness of the peel. It is excellent in productivity and economy because it has no curl, has good curl properties, and is capable of high-speed and stable production.

Claims

Scope of word blue

1. An image material support comprising a paper mainly composed of natural pulp as a substrate, and a surface of the paper substrate on which an image forming layer is provided, covered with a multilayer resin sheet, wherein an upper layer of the multilayer resin sheet is provided. [Surface layer] (A) is a thermoplastic resin having a melting point higher than 100 ° C (a) contains at least 40% by weight and has a lower layer [one or more layers below the surface layer] (B) Contains a thermoplastic resin (b) that has a lower melting point than the above thermoplastic resin (a) at 105 ° C or lower, and may further include a thermoplastic resin (a) in the upper layer (A). A support for an image material, characterized in that it is contained in an amount smaller than the content of (a), and that the multilayer resin sheet is coated on a paper substrate and then pressed in a non-heated state.

2. The support for an image material according to claim 1, wherein the pressing is a soft calender treatment.

3. The thermoplastic resin (a) is at least one selected from the group consisting of a low-density polyethylene resin, a medium-density polyethylene resin, a high-density polyethylene resin, a polycarbonate resin, and a polyester resin. The support for the imaging material described in the above.

4. The support for imaging materials according to claim 1, wherein the thermoplastic resin (a) has a melting point of 110 ° C or more.

5. The support for an image material according to claim 1, wherein the thermoplastic resin (b) is a low-density polyethylene resin produced by using a meta-opening polymerization catalyst.

6. The imaging material support according to claim 1, wherein when the upper layer (A) contains the thermoplastic resin (b), the content thereof is smaller than the content of the thermoplastic resin (b) in the lower layer (B). body.

7. The imaging material support according to claim 1, wherein the thermoplastic resin (b) has a melting point of 95 ° C or lower.

8. The support for an image material according to claim 1, wherein the content of the thermoplastic resin (b) in the lower layer (B) is 20% by weight or more with respect to all the thermoplastic resin components in the lower layer (B). body.

9. A support for an image material, comprising a paper mainly composed of natural pulp as a substrate, and a surface of the paper substrate on which an image forming layer is provided, covered with a multilayer resin sheet. The upper layer [surface layer] (A) in the multilayer resin sheet contains at least 40% by weight of a thermoplastic resin (a) having a melting point higher than 100 ° C, and the lower layer [one or more layers below the surface layer] (B) contains a thermoplastic resin (b) having a melting point lower than that of the above-mentioned thermoplastic resin (a) at 105 ° C or lower, and may further contain the thermoplastic resin (a) in some cases. An image material comprising the plastic resin (a) in an amount smaller than the content thereof, and the multi-layer resin sheet is coated on a paper substrate and then pressed against the multi-layer resin sheet while holding heat. Support.

10. The support for an image material according to claim 9, wherein the pressing is a soft calender treatment.

11. The image material according to claim 9, wherein the pressure welding while maintaining the heat is a pressure welding between two or more rolls including at least one metal opening having a surface temperature of 40 to 150 ° C. Support.

12. The thermoplastic resin (a) is at least one selected from the group consisting of a low-density polyethylene resin, a medium-density polyethylene resin, a high-density polyethylene resin, a polycarbonate resin, and a polyester resin. The support for an image material described in 1. above.

13. The support for imaging materials according to claim 9, wherein the thermoplastic resin (a) has a melting point of 110 ° C. or higher.

14. The support for an image material according to claim 9, wherein the thermoplastic resin (b) is a low-density polyethylene resin produced using a meta-opening polymerization catalyst.

15. The support according to claim 9, wherein when the upper layer (A) contains the thermoplastic resin (b), the content thereof is smaller than the content of the thermoplastic resin (b) in the lower layer (B). body.

16. The support for imaging materials according to claim 9, wherein the thermoplastic resin (b) has a melting point of 95 ° C or lower.

17. The support according to claim 9, wherein the content of the thermoplastic resin (b) in the lower layer (B) is at least 20% by weight based on the total thermoplastic resin component in the lower layer (B). body.

18. An image material support comprising a paper mainly composed of natural pulp as a substrate, and a surface of the paper substrate on which an image forming layer is provided, covered with a multilayer resin sheet. [Surface layer] (C) is a lower layer of thermoplastic resin (c) [One or more layers below the surface layer] In addition to containing more than (D), the lower layer (D) contains more thermoplastic resin (d) than the upper layer (C). The melting point of the thermoplastic resin (c) is higher than the melting point of the thermoplastic resin (d), and after the multilayer resin sheet is coated on a paper substrate, pressure welding is performed while holding heat on the side of the multilayer resin sheet. A support for an image material, comprising: