JP2000066333A - Supporting body for image material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellent resin coated paper type supporting body for an image material which uses paper as a base material capable of obtaining the quality excellent in a glossy feeling in the appearance of a print, adhesion, film adhesion, surface smoothness and image sharpness which are important characteristics as the supporting body for the image materials, moreover, much lower in oxygen permeability and further, without problems in the operation. SOLUTION: This supporting body for an image material uses paper mainly composed of natural-pulp as a base material and at least one surface of the base material is coated with a resin layer consisting of at least two layers. A white polyester resin layer is arranged on the side where an image forming layer is formed. The supporting body for the image material is laminated by the polyester resin layer substantially free from pores, arranged on the side of the base material and consisting of two layers and the base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a support for an image material, wherein at least one surface of a substrate is coated with at least two polyester resin layers, wherein the white polyester resin layer serves as an image forming layer. The present invention relates to a support for an image material, in which a base material and a polyester resin layer comprising at least two polyester resin layers disposed on a substrate side, the polyester resin layer being disposed on a side provided with substantially no voids, and a substrate are laminated.
More specifically, it is useful as a support for image materials such as a silver halide photographic material, an ink jet recording material, and a heat transfer type thermal transfer recording image receiving material, and has a high apparent gloss, adhesiveness, film forming property, surface smoothness. The present invention relates to a support for an image material, which is excellent in image quality and sharpness of an image, and has a much lower oxygen permeability.

[0002]

2. Description of the Related Art Usually, an image material is composed of a support for an image material and an image forming layer provided on the support. For example, a silver halide photographic material, an ink-jet recording material, a heat transfer type thermal transfer recording image-receiving material, a heat-sensitive recording material, and a light- and heat-sensitive recording material are respectively provided on a support for an image material, a silver halide photographic component layer, an ink image-receiving layer, An image forming layer such as a transfer type thermal transfer recording image receiving layer, a thermosensitive coloring layer, a photosensitive thermosensitive coloring layer, and the like, and an undercoat layer, a protective layer and the like are provided as required. In particular, the silver halide photographic constituent layer includes a silver halide photographic emulsion layer, a protective layer, an undercoat layer, an intermediate layer or an anti-color-mixing layer, an antihalation layer, or a filter layer, an ultraviolet absorbing layer, and a combination thereof. It is composed 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. Further, a multilayer silver halide color photographic material comprises an undercoat layer, a blue-sensitive silver halide photographic emulsion layer and an intermediate layer, a green-sensitive silver halide photographic emulsion layer and an ultraviolet absorbing layer, A silver halide photographic emulsion layer and a silver halide color photographic constituting layer such as a protective layer are provided in this order and are arranged in multiple layers.

Conventionally, a resin-coated paper-type support in which a base paper surface for a support for an image material is coated with a thermoplastic resin is well known. As a photographic material support for silver halide photographic material applications, for example, Japanese Patent Publication No. 55-12584 discloses a photographic material having a base paper coated with a film-forming resin, preferably a polyolefin resin. Techniques for supports are disclosed. U.S. Pat. No. 3,501,298 discloses a technique for a photographic material support in which both sides of a base paper are coated with a polyolefin resin. Further, since the rapid photographic development processing method of silver halide photographic materials was applied, supports for photographic materials in which both sides of a base paper were coated with a polyethylene resin have been mainly put to practical use for photographic printing paper. If necessary, the other side of the resin layer on which the image forming layer is provided usually contains a titanium dioxide pigment in order to impart sharpness.

Further, US Pat. No. 4,774,224 discloses that a resin coating has a surface roughness of 7.5 microinch-AA.
There has been proposed a thermal transfer recording image receiving element having, as a support, the following resin-coated paper, in particular, a polyethylene resin-coated paper in which the surface of a base paper is coated with a polyethylene resin. JP-A-63-307979 discloses a technique relating to an ink jet recording sheet having a resin-coated paper as a support.

At present, as a support for image materials represented by a support for photographic printing paper, resin-coated paper in which polyethylene resin is coated on both sides of a base paper is widely used. Polyethylene resins are used in large quantities for a long time because they are relatively inexpensive, have good extrusion coating properties, have good barrier properties to processing solutions for image materials, and have good adhesion to base paper and image forming layers. Have been.

However, the resin-coated paper coated with polyethylene resin suppresses the appearance of fine ripple-like surface irregularities (referred to as grainy) on the resin surface after melt extrusion coating due to its resin properties. Was extremely difficult. A support for an image material having such a surface quality, even when an image forming layer is provided thereon, cannot conceal the unevenness of the surface, has a poor glossiness in appearance, and has a low gloss of the finished product itself. Decrease value. This phenomenon is particularly remarkable when the image forming layer is a color image.

Further, the above resin-coated paper has a drawback that image discoloration after lapse of time tends to occur due to the relatively high oxygen permeability of polyethylene resin.

Recently, a technique has been disclosed in which a polyester resin is used instead of a polyethylene resin as a resin-coated paper used as a support for an image material.

For example, Japanese Patent Application Laid-Open No. Hei 5-13079 discloses a photographic printing paper support coated with a resin composition containing a polyester resin and a titanium dioxide pigment.

Japanese Patent Application Laid-Open Nos. Hei 7-20603 and Hei 7-20871 disclose a paper substrate mainly composed of natural pulp having a waterproof resin layer on one side and the other side of the paper substrate. In a photographic support having a film-forming resin layer on the side where the photographic constituent layer is provided, the film-forming resin layer is a polyester-based biodegradable resin layer, or a polyester-based biodegradable resin and a polyolefin resin. A photographic support having a resin layer containing an anchor coat layer or an adhesive layer between a paper substrate and a polyester biodegradable resin layer is disclosed.

Further, JP-A-7-120871 discloses an image in which one or both sides of a base paper are coated with an aliphatic polyester resin composition having a fixed blend ratio of an aliphatic polyester having a specific melt flow rate and titanium dioxide. A forming support is disclosed.

Further, Japanese Patent Application Laid-Open No. 10-10675 discloses that
A recording material in which a recording layer is provided on a support, wherein the support is a recording material having an oxygen permeability of a specific value or less, and a plastic film layer on which the recording layer is provided is formed of a polyester film or the like. A recording material is disclosed.

[0013] These disclosed techniques are intended to improve the smoothness and curlability of the surface of a photographic printing paper support, and to disclose that a polyolefin resin is difficult to biodegrade, such as a polyester biodegradable resin. By using a biodegradable image material support adapted to environmental issues, or, the adhesion between the base paper and the resin layer, fading, light resistance,
The purpose is to improve the long-term storability of an image.
However, the resin-coated paper-type image material support in which the surface on the side on which the image forming layer is provided of the substrate, particularly a substrate mainly composed of natural pulp, is coated with a resin layer still has some serious problems. The fact is that satisfactory results have not yet been obtained.

A problem in the case of a support for an image material, in particular, a photographic paper support, is a decrease in glossiness and sharpness caused by unevenness of the surface of a base material containing natural pulp as a main component, and support for a photographic paper. In order to improve coloring (edge stain) caused by infiltration of a developing solution or the like from a cut surface (edge) of a body, for example, Japanese Patent Application Laid-Open No. 63-200147 discloses a biaxial structure comprising a plurality of layers. A photographic reflection support in which titanium oxide is contained in the outermost layer of a stretched polyester film in an amount of 15% by weight or more is disclosed. According to the publication, the photographic reflection support is composed of only a resin layer composed of a plurality of biaxially stretched polyester films without using natural pulp. Although the stain has been improved, the natural pulp is not used, so it is too stiff and has the flexibility unique to paper (PAPER L).
IKE), and there are many practical problems such as disposal when not in use (it is not easily torn and discarded) and pollution at the time of disposal.

[0015] As a relatively recent technology, for example,
JP-A-8-160566 discloses that a film containing a large number of fine closed cells containing silica particles or titanium dioxide particles and a resin film containing scraps (recycled raw materials) of the film are coextruded and laminated. A microbubble-containing laminated polyester film for photographic paper is disclosed. According to the publication, a microbubble-containing laminated polyester film for photographic paper which is excellent in surface smoothness and whiteness and can be produced at low cost can be obtained. However, since the co-extruded laminated film according to the publication contains both bubbles,
Oxygen permeability is large, there is a problem in long-term image storability, and, similarly to the above, there are various drawbacks because it is constituted only by a resin layer.

As described above, when a polyester resin is applied to a support for an image material typified by a support for a photographic printing paper, the above-described problem arises when the polyester resin is constituted only by a polyester resin layer. There are various problems when applying a polyester resin to a base material mainly composed of natural pulp.

That is, when a polyester resin is applied to a resin-coated paper used as a support for an image material,
First of all, there is the problem of production technology. There are surging and neck-in as major problems when the polyester resin is applied on the surface of the base material by melt extrusion coating. Current,
Compared with polyethylene resins commonly used in melt extrusion coating, polyester resins are extremely easy to surging in terms of resin characteristics, and are also liable to cause neck-in, and thus have extremely poor extrusion stability. Even if an antioxidant is applied to improve this point, a sufficient effect cannot be obtained, and if used in a large amount, the adhesion to a substrate is significantly deteriorated. An aliphatic polyester resin having a long chain branch, which is said to be an improved type of a polyester resin having a large neck-in property, tends to have a relatively small neck-in but is insufficient.

Second, when a polyester resin is applied to a support for an image material, there is a problem of adhesion to a substrate. Polyester resins having poor surface activity tend to be inferior in adhesion to a substrate as compared with polyethylene resins.

In particular, as a major problem in quality of a support for an image material represented by a support for a photographic printing paper, there is a poor film-forming property. As mentioned above, a polyester resin having a poor surface activity has, for example, an adhesive property between a resin layer and a photographic emulsion layer, particularly an adhesive property when wet in a developing process (film-forming property).
The corona discharge treatment of the surface of the resin layer, which is widely used to improve the above, does not show the effect as well as the polyethylene resin. As a countermeasure, attempts have been made to provide various undercoat layers on the polyester resin layer on the side where the photographic emulsion layer is provided, but no satisfactory results have yet been obtained.

[0020]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned various problems, and an object of the present invention is to provide a support for an image material in which a polyester resin layer is laminated on a conventional substrate. Is a study from a completely different point of view, and has a high apparent glossiness, excellent adhesiveness, coating ability, surface smoothness, excellent image sharpness, and an oxygen material with much lower oxygen permeability. This is what we can offer.

[0021]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is,

1. The present invention provides a support for an image material, wherein a base material is a paper mainly composed of natural pulp, and at least one surface of the base material is coated with a resin layer composed of at least two layers. The layer is disposed on the side on which the image forming layer is provided, and the substrate is laminated with a polyester resin layer composed of at least two layers in which a substantially void-free polyester resin layer is disposed on the substrate side. Of a support for an image material.

2. In the above invention 1, at least 2
The invention provides a support for an image material, wherein a polyester resin layer comprising a layer is formed by co-extrusion.

3. In the above invention 1 or 2, the polyester resin layer composed of at least two layers has a thickness of 2
An image material support according to the invention, wherein the support is an axially stretched polyester resin layer, and a subcoat layer is provided at least on the surface on the image forming layer side at the time of stretching.

4. In the above invention 1, 2 or 3,
The invention provides a support for an image material, wherein the subcoat layer is provided between the stretching in the longitudinal direction and the stretching in the transverse direction.

[5] In any one of the above inventions 1 to 4, the substance constituting the subcoat layer is a subcoat agent containing at least one of a water-dispersible copolymer polyester, a vinylidene chloride copolymer latex, and a polyamine polyamide epichlorohydrin resin. An invention of a support for an image material, characterized in that:

6. In the above invention 5, the invention is directed to a support for image materials, wherein the subcoat layer contains the subcoat agent and colloidal silica.

7. The invention according to any one of the above inventions 1 to 6, wherein an undercoat layer containing gelatin as a main component is provided on the subcoat layer.

8. The invention according to any one of Inventions 1 to 7, wherein the white polyester resin layer contains at least one kind of inorganic particles or organic particles.

9. In the above invention 8, the inorganic material in the white polyester resin layer is a lightly alumina-surface-treated titanium dioxide pigment.

10. In the above invention 8, the organic material in the white polyester resin layer is an organic particle having no compatibility with the white polyester resin.

11. In any one of the above inventions 1 to 10, when laminating the polyester resin layer comprising at least two layers and the substrate, between the polyester resin layer and the substrate, it may be laminated via an adhesive layer. A feature of the invention is a support for an image material.

12. In the above invention 11, the support for an image material, characterized in that a heating treatment is performed after laminating the polyester resin layer comprising at least two layers and the base material with an adhesive layer interposed therebetween. It is an invention.

13. The invention according to the twelfth aspect, is an invention of an image material support, wherein the heating treatment is performed at 35 ° C. to 100 ° C. for at least one hour.

14. The invention according to any one of Inventions 1 to 13, wherein the resin layer provided on the substrate on the side opposite to the side on which the image forming layer is provided is a polyolefin resin layer. is there.

15. In the invention according to any one of the above inventions 1 to 14, the substrate is an invention for an image material support, wherein both sides of the paper are coated with a polyethylene resin.

16. In the above invention 15, the substrate is an invention for an image material support, wherein both ends of the substrate are heat-sealed.

17. In any one of the above inventions 1 to 16, JIS K-7126 of the support for the image material may be used.
35 cc / m ² / d
ay or less.

18. The invention according to any one of the above inventions 1 to 17, wherein the support for an image material has an average surface roughness (SRa) of 0.15 μm or less on the side on which the image forming layer is provided.

19. The present invention provides a support for an image material, wherein a base material is a paper mainly composed of natural pulp, and at least one surface of the base material is coated with a resin layer composed of at least two layers. The layer is disposed on the side on which the image forming layer is provided, and a polyester resin layer having substantially no voids is formed by laminating at least two polyester resin layers disposed on the substrate side and the substrate. This is an invention of a method for producing a support for an image material.

20. The invention of the above invention 19 is a method for producing a support for an image material, wherein at least two polyester resin layers are produced by coextrusion.

21. In the above invention 19 or 20, it is preferable that the polyester resin layer composed of at least two layers is a biaxially stretched polyester resin layer, and that a subcoat layer is provided at least on the surface on the image forming layer side at the time of stretching. It is an invention of a method for producing a support for an image material, which is characterized by the following.

22. The invention according to any one of the inventions 19, 20 and 21, wherein the subcoat layer is provided between the stretching in the longitudinal direction and the stretching in the transverse direction.

23. Any one of the above inventions 19 to 22
In the invention, a support for an image material, wherein the substance constituting the subcoat layer is a subcoating agent containing at least one of a water-dispersible copolymer polyester, a vinylidene chloride copolymer latex and a polyamine polyamide epichlorohydrin resin. Is an invention of a manufacturing method.

24. In the above invention 23, the invention is a method of manufacturing a support for an image material, wherein the subcoat layer contains the subcoat agent and colloidal silica.

25. Any one of the above inventions 19 to 24
In the invention, there is provided a method for producing a support for an image material, wherein an undercoat layer containing gelatin as a main component is provided on the subcoat layer.

26. Any one of the above inventions 19 to 25
In the invention, there is provided a method for producing a support for an image material, wherein the white polyester resin layer contains at least one kind of inorganic particles or organic particles.

27. In the above invention 26, the invention is a method for producing a support for an image material, wherein the inorganic particles in the white polyester resin layer are lightly alumina surface-treated titanium dioxide pigments.

28. In the above invention 26, the invention is a method for producing a support for an image material, wherein the organic particles in the white polyester resin layer are organic particles having no compatibility with the white polyester resin.

29. Any one of the above inventions 19 to 28
In the invention, the production of a support for an image material, characterized in that when laminating a polyester resin layer comprising at least two layers and a substrate, the polyester resin layer and the substrate are laminated via an adhesive layer. It is an invention of a method.

30. In the above invention 29, a method for producing a support for an image material, comprising laminating between a polyester resin layer composed of at least two layers and a substrate via an adhesive layer, and then performing a heating treatment. Invention.

31. In the above invention 30, the invention is a method of manufacturing a support for an image material, wherein the heating is performed at 35 ° C. to 100 ° C. for at least 1 hour or more.

32. Any one of the above inventions 19 to 31
In the invention, there is provided a method for producing a support for an image material, wherein the resin layer provided on the substrate on the side opposite to the side on which the image forming layer is provided is a polyolefin resin layer.

33. Any one of the above inventions 19 to 32
In the invention, there is provided an invention of a method for producing a support for an image material, characterized in that the base material is formed by coating both sides of a paper with a polyethylene resin.

34. In the above invention 33, a method of manufacturing a support for an image material, wherein both ends of the base material are heat-sealed.

35. Any one of the above inventions 19 to 34
In the invention, JIS K-712 of a support for an image material is used.
The oxygen permeability measured by the method B of No. 6 was 35 cc / m ² /
The present invention relates to a method for producing a support for an image material, wherein the support is not more than day.

36. Any one of the above inventions 19 to 35
In the invention, there is provided a method of manufacturing a support for an image material, characterized in that the center surface average roughness (SRa) on the side on which the image forming layer is provided is 0.15 μm or less.

[0058]

BEST MODE FOR CARRYING OUT THE INVENTION The support for an image material of the present invention will be described in detail below.

The polyester resin in the support for an image material coated with at least two resin layers according to the present invention means not only a thermoplastic resin consisting of polyester alone, but also the resin properties of the main component polyester. Polyester resins to which other polymers, additives and the like have been added are also included as long as they do not fluctuate.

The polyester resins used in the practice of the present invention include terephthalic acid, isophthalic acid, phthalic acid,
Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid and ethylene glycol, 1,3-propanediol, 1,4
And polymers of condensates with glycols such as -butanediol, such as polyethylene terephthalate, polyethylene 2,6-dinaphthalate, polypropylene terephthalate, polybutylene terephthalate, and copolymers thereof. In the present invention, polyester resins obtained by biaxially stretching these polyester resins are preferably used.

The sulfonic acid-modified polyester resin used in the practice of the present invention is preferably a polyester resin comprising an aromatic dicarboxylic acid having a metal sulfonate and / or a derivative thereof as a dicarboxylic acid copolymerization component of the polyester. Is a biaxially stretched polyester resin. Specific examples of the aromatic dicarboxylic acid having a metal sulfonate include 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid,
Examples thereof include 4-sodium sulfoterephthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid, and compounds obtained by substituting sodium with another metal such as potassium, lithium, ammonium salt, or phosphonium salt. Further, an antistatic polyester film as disclosed in JP-A-4-248843 can also be used.

The biodegradable polyester resin used in the practice of the present invention is not particularly limited as long as it is a biodegradable polyester resin, and various melting points, densities and melt flow rates (hereinafter, referred to as “melt flow rates”). JIS K72
Test temperature: 190 ° C, test load: 2.16 kg according to 10
The melt flow rate measured under the conditions
May be used, and those having a molecular weight and a molecular weight distribution can be used, but usually have a melting point of 85 to 130 ° C and a density of 1.
0 g / cm ³ or more, MFR 0.1 to 50 g / 10 min, number average molecular weight (Mn) 30,000 to 60,000, weight average molecular weight (Mw) 1
Those having 40,000 to 300,000 and Mn / Mw of 4.5 or more can be advantageously used alone or in combination. Specific examples of the polyester-based biodegradable resin include NUC-Null biodegradable resin series sold by Nippon Unicar Co., Ltd., and Pionore series of Showa Kogaku Co., Ltd.

In the practice of the present invention, the biaxially stretched polyester resin preferably used is obtained by subjecting the above various polyester resins to biaxial stretching treatment in a conventional manner.
What is necessary is just to make it a biaxially stretched polyester resin film. At this time, heat fixing is generally performed. Usually, various unstretched polyester resins are 2.5 to 4.0 times in the longitudinal direction at 70 ° C. to 120 ° C. and 2.times. In the horizontal direction at 80 ° C. to 145 ° C.
It is stretched 5 times to 4.0 times, and if necessary, 180 ° C to 240 ° C.
Heat setting is performed at ℃.

The white polyester resin layer on the side on which the image forming layer of the present invention is provided may be a polyester resin layer which has been whitened by any method. For the purpose of imparting sharpness, various inorganic particles are preferably contained. Further, various organic particles may be contained as needed.

Examples of the inorganic particles include titanium dioxide, barium sulfate, barium carbonate, calcium carbonate, lithopone, alumina white, zinc oxide, silica, antimony trioxide, titanium phosphate and the like. These can be used alone or as a mixture. Among them, titanium dioxide and zinc oxide are preferable from the viewpoint of opacity, whiteness, dispersibility and stability, and titanium dioxide may be rutile type or anatase type, and they may be used alone or in combination. You may. Further, those manufactured by the sulfuric acid method or those manufactured by the chlorine method may be used. As titanium dioxide, those coated with an inorganic substance such as hydrated alumina treatment, hydrated silicon dioxide treatment or zinc oxide treatment, polyhydric alcohols such as trimethylolmethane, trimethylolethane, and trimethylolpropane, and methyltrimethoxy What has been surface-treated with a compound such as silane, a silane coupling agent such as N-β-aminoethyl-γ-aminopropyldimethoxysilane, a polysiloxane such as polydimethylsiloxane, ε-caprolactam, or a titanate coupling agent. Although it can be used as appropriate, trimethylolmethane, trimethylolethane, and trimethylolpropane are preferably used. In the present invention, (0.2 to 1.5 wt% surface-treated ones as Al ₂ O ₃ minutes for the titanium dioxide in hydrated aluminum) Mild alumina surface treated titanium dioxide pigment is particularly preferably used. These may be used in combination of two or more. The filling amount of the white pigment in the resin layer varies depending on the white pigment used and the thickness of the resin layer.
% To be between 40% by weight. Further, in the resin constituting the biaxially stretched polyester resin film preferably used in the practice of the present invention, known additives such as a coloring dye, a coloring pigment, an optical brightener, and an antioxidant may be added. It is possible.

The organic particles are polymers that are incompatible with the polyester resin and generate voids (void formation) around the particles during stretching. Such a polymer may be either thermoplastic or thermosetting. The void-forming polymer has an average particle size of 0.1 when dispersed in the polyester forming the polymer-containing layer.
It is preferably from 01 to 50 μm. As a method of adding and dispersing in the polyester, it may be added at the time of polymerization, or may be added after melt-kneading.

Specific examples of the organic particles used in the practice of the present invention include polyolefins such as polyethylene and polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, triacetyl cellulose, diacetyl cellulose, polycarbonate, and nylon resin. And polyphenylene sulfide.

A resin which has lost compatibility with the polyester resin by three-dimensionally cross-linking with a curing agent;
For example, styrene-divinylbenzene copolymer particles, polybutylene terephthalate to which a crosslinking agent is added, and the like can be used. In the present invention, polyamide and polymethylpentene are preferably used.

The organic particles used in the practice of the present invention are not limited to these specific examples. Any other polymer may be used as long as it is a polymer which can be added to a polyester resin and formed into white by forming voids by stretching. I can do it. Further, these may be used in combination of two or more kinds, or may be used in combination with the above various inorganic particles.

The polyester resin layer having substantially no voids disposed on the substrate side of the present invention is produced by using the above-mentioned various polyester resins. At this time, it may be used in a non-stretched state, but it is preferable to use a biaxially stretched polyester resin.

In the present invention, the substantially void-free polyester resin layer is a polyester resin layer having a porosity of less than 5%, preferably a polyester resin layer formed of a transparent film by various production methods. . Regarding the porosity, for example, the porosity when titanium dioxide is contained in the polyester resin layer, the porosity may be obtained by the method disclosed in JP-A-2-93842, other, various angles A predetermined number of cross sections may be created in the direction of and the porosity may be determined by microscopic measurement.

In the present invention, the reason why the polyester resin layer having substantially no voids is disposed on the substrate side is that, for the purpose of improving the long-term storability of the image and the sharpness of the image, the oxygen permeability of the support for the image material is improved. This is to make the degree sufficiently low. Therefore, a substantially void-free polyester resin layer is
Any material can be used as long as it has a function of suppressing the oxygen permeability sufficiently low. Therefore, in addition to the above-mentioned transparent film, in the range where the oxygen permeability is suppressed sufficiently low so as not to impair the long-term storage stability of the image, for example, various inorganic particles and organic particles for imparting opacity are used. You may make it contain in a polyester resin layer. Further, in the resin layer, a fluorescent whitening agent,
It is also possible to add known additives such as antioxidants.

In the present invention, various coloring pigments and / or coloring dyes are added to a white polyester resin layer and / or a substantially void-free polyester resin for the purpose of improving the visual whiteness of the support for image materials. It can be contained in at least two polyester resin layers. At this time, for example, by appropriately using various kinds of red mouth ultramarine and blue mouth ultramarine disclosed in JP-A-53-19021, it is possible to produce an image material support having a desired L value, a value, and b value. Can be.

By laminating at least two polyester resin layers consisting of a white polyester resin layer and a substantially void-free polyester resin layer on a substrate, the support for an image material of the present invention can be obtained. The above-mentioned at least two resin layers may be a non-stretched polyester resin layer, a longitudinally stretched polyester resin layer, or a horizontally stretched polyester resin layer. It is preferable to use a stretched polyester resin, and it is particularly preferable to use at least two polyester resin layers that are biaxially stretched after each of at least two resin layers are formed by coextrusion. To produce a film used as at least two polyester resin layers of the present invention,
For example, in the case of co-extrusion, a co-extrusion die, for example, a single manifold type or a multi-manifold type die may be used. Further, two or more extruders may be used to produce two or more polyester resin films. Furthermore, various extruders, kneading extruders and various dies as disclosed in, for example, JP-A-63-200147 can also be used. When three or more resin layers are used, the resin layer on the side where the image forming layer is provided is an essential component that is a white polyester resin layer,
There is no particular limitation except that it is essential that any one of the layers is a polyester resin layer having substantially no voids. Any resin can be used for a plurality of layers other than the essential two layers. And the order of lamination is not limited at all. This is not limited to the case of co-extrusion, but also applies to a case where a plurality of resin films are laminated and used. When laminating two or more resin layers other than co-extrusion, an existing adhesive may be used between the layers.

In the present invention, at least two polyester resin films, preferably a biaxially stretched polyester resin, used as the white polyester resin layer and the polyester resin layer having substantially no voids obtained as described above. The film may be bonded in advance with an existing adhesive, and then laminated on a substrate to form a support for an image material. The lamination method is not particularly limited, and may be appropriately selected from known lamination methods described in, for example, "Handbook of New Laminating Processes" edited by Processing Technology Research Group. For example, dry lamination, solvent-free dry lamination, thermal lamination, dry lamination using an electron beam or ultraviolet curable resin, or hot lamination can be employed.

The adhesive used at this time is not particularly limited, and an adhesive such as an existing urethane-based adhesive, emulsion-type adhesive, or oligomer-type adhesive can be used.

Dry lamination is carried out by applying an adhesive to a polyester resin film having at least two layers, preferably a biaxially stretched polyester resin film, used in the present invention, followed by drying. This is a method in which a stretched polyester resin film is heated and pressure-bonded. In this case, a solvent-type urethane resin, vinyl resin, acrylic resin, polyamide resin, epoxy resin, rubber resin, or the like is used as an adhesive. .1 to 1
5 g / m ^{2 are} used.

The solvent-free dry lamination is carried out on the polyester resin film of at least two layers used in the present invention, preferably a biaxially stretched polyester resin film, by using a one-component moisture-curable urethane-based adhesive or a two-component urethane-based adhesive. 0.1-1 reaction-curable adhesive such as
This is a method in which 0.0 g / m ^{2 is} applied, bonded to a substrate, and then aged to react and harden the adhesive to strengthen the adhesion between the polyester resin film and the substrate.

In the thermal lamination, a wax such as petroleum wax, synthetic wax and polybutene, a polybutene adhesive, and ethylene copolymer are added to the polyester resin film having at least two layers, preferably a biaxially stretched polyester resin film, used in the present invention. Polymer adhesives such as coalesced and polyolefin elastomers
This is a method of applying 1 to 15.0 g / m ² and bonding to a substrate. At this time, a tackifier resin may be used.

In applying these various lamination methods, in the present invention, the surface of the polyester resin film having at least two layers used in the present invention, preferably the surface on which the image forming layer of the biaxially stretched polyester resin film is formed, An adhesive layer is provided on the opposite side. Also, on the surface of the substrate opposite to the surface on which the image forming layer is formed,
When laminating a polyester resin film, preferably a biaxially stretched polyester resin film, an adhesive layer is provided on the surface to be bonded to the substrate. Of course, various surface treatments such as corona discharge treatment may be applied to the surface of the base material to be laminated.

In the practice of the present invention, after laminating the polyester resin layer composed of at least two layers used in the present invention, preferably a biaxially stretched polyester resin layer and a base material via an adhesive layer, It is preferable to perform a heating treatment. The temperature of the heating treatment is usually 35 ° C to 100 ° C.
For at least one hour.

In this way, a support for an image material obtained by laminating a base material and a polyester resin film having at least two layers, preferably a biaxially stretched polyester resin film, is obtained. A polyester resin film, or at least two polyester resin layers composed of a white polyester resin film and a substantially void-free polyester resin film, particularly preferably a white polyester resin film formed by coextrusion and a substantially void-free polyester In biaxial stretching of at least two polyester resin layers composed of a resin film, it is one of the most preferred embodiments to apply a subcoat to the white polyester resin surface on which the image forming layer is provided.

A conventional image material support in which a substrate and a polyester resin film are laminated and then a liquid containing a subcoat agent is applied to the image forming side is subjected to a subcoat application → drying ( Removal of water) → winding →
The product is made. At this time, the problem of the coating / drying process itself and the increase of the winding process increase the angle and the smooth polyester resin surface into a relatively large uneven surface (referred to as surface unevenness). However, even if an image forming layer is provided, a good image cannot be obtained, and only a support for an image material having an extremely inferior glossiness can be obtained. Also, after laminating the base material and the polyester resin film, after applying a sub-coat on the image forming side surface, even if the image forming layer is provided thereon, the film forming property is insufficient, so the image forming layer Has a large tendency to peel off.

The support for an image material obtained in a preferred embodiment of the present invention comprises at least two layers of a white polyester resin layer and a substantially void-free polyester resin layer.
When the polyester resin layer of the layer is biaxially stretched, a sub-coating agent is applied to at least the surface on the image forming side (sub-coating may be applied to the opposite surface). Since the biaxial stretching is performed at a relatively high temperature and the sub-coating agent is applied at this time, only one step is required (on-line coating). The occurrence of surface irregularities can be suppressed extremely well without any problems associated with the above. After that, the heat fixing process performed as necessary may be performed for a very short time, and does not promote the occurrence of surface irregularities. What is worth mentioning is that
The support for an image material according to a preferred embodiment of the present invention to which the sub-coating agent is provided in this manner can provide a film with a remarkably excellent film-coating property that cannot be obtained by a conventional support for an image material. It is.

The application of the subcoating agent during the biaxial stretching may be performed at any stage of the longitudinal stretching, the transverse stretching, or the stretching in both directions. It is preferable to be performed in between. Performing at the time of stretching in both directions slightly improves the effect of improving film-forming properties,
It is not a good idea in terms of increase in the number of steps and cost of the subcoating agent. The amount of the applied sub-coating agent varies depending on the sub-coating agent to be used and cannot be unconditionally determined, but is usually 0.015 to 3.0 g / m ² (as the weight of the solid content after biaxial stretching).

The subcoating agent used in the practice of the present invention is not particularly limited, and may be a conventionally used subcoating agent, for example, mainly gelatin, which contains various additives. As an example, JP-A-8-2485
A subcoating agent containing a mixture of gelatin and a specific polymer, as disclosed in JP-A-69, can be mentioned.

In the practice of the present invention, a subcoating agent containing a water-dispersible copolymer polyester is used, and a subcoating agent containing colloidal silica as disclosed in, for example, JP-A-6-43617. Can be advantageously used.

Further, various latex copolymers, for example, those forming a hydrophobic subcoat layer containing vinylidene chloride, methyl acrylate and itaconic acid as disclosed in JP-A-9-101592 are also suitable. Used for Further, a subcoating agent containing a core-shell type vinylidene chloride copolymer-based latex as disclosed in, for example, JP-A-3-141346 is also preferably used. Further, a subcoating agent containing colloidal silica, an epoxy compound and a triazine-based compound in a vinylidene chloride copolymer latex as disclosed in, for example, JP-A-3-141347 is also preferably used. Further, for example, JP-A-6-230521 and JP-A-6-230521
Compounds based on polyamine polyamide epichlorohydrin resin, such as those disclosed in JP-A 301145, can also be used as a subcoating agent. Further, it can be used in combination with a subcoating agent containing the above-mentioned water-dispersible copolymer polyester as appropriate. Of course, when providing these various subcoat layers, various surface treatments such as corona discharge treatment may be performed in advance.

In the present invention, an undercoat layer mainly composed of, for example, gelatin and containing various additives is further provided on the sub-coat layer formed in the biaxial stretching treatment as described above. It may be provided. The applied amount of the applied undercoating varies depending on the undercoating used, and cannot be unconditionally determined, but is usually 0.015 to 1.5 g / m ² (as solid content weight). Of course, when providing these various undercoat layers, various surface treatments such as corona discharge treatment may be performed in advance.

When used as a support for an image material of the present invention, in particular, a photographic paper support, a resin layer having a film forming ability is provided on the substrate surface opposite to the side on which the image forming layer is provided. The resin layer having a film-forming ability may be any resin layer having a waterproof function, but is preferably a polyolefin resin layer.
Examples of the polyolefin resin used in the practice of the present invention include homopolymers such as polyethylene, polypropylene, polybutene and polypentene, copolymers composed of two or more α-olefins such as ethylene-butylene copolymer, and mixtures thereof. However, polyethylene-based resins are particularly preferred from the viewpoints of melt extrusion coating properties and adhesion to substrates. As the polyethylene resins, low-density polyethylene resin, medium-density polyethylene resin, high-density polyethylene resin, linear low-density polyethylene resin, ethylene and propylene, copolymers of α-olefins such as butylene, ethylene and ethyl Copolymers with alkyl acrylates such as acrylates, carboxy-modified polyethylene resins and the like, and mixtures thereof; various densities and melt flow rates (hereinafter referred to as JIS K6760).
The melt flow rate defined by is sometimes simply abbreviated as MI), molecular weight, and those having a molecular weight distribution can be used, but usually, the density is in the range of 0.90 to 0.97 g / cm ³ ,
MI is 0.2 to 50 g / 10 min, preferably MI is 0.4 to 4
Those having a range of 0 g / 10 minutes can be advantageously used alone or as a mixture.

The thus-obtained support for an image material of the present invention has a higher glossiness and apparent gloss than a support for a resin-coated image material produced by melt-extrusion coating of a general polyethylene resin. Surface smoothness and image sharpness are remarkably excellent,
In addition, despite being a resin-coated image material support made of a polyester resin, the film-forming property is extremely good, and of course, the adhesiveness between the substrate and the resin layer is also excellent. Further, generally, the support for an image material of the present invention comprises J
An image material support having an oxygen permeability measured by the method B of IS K-7126 of 35 cc / m ² / day or lower, which is much lower, excellent in fading and light fastness, and excellent in long-term preservation of images.

The support for an image material of the present invention as described above includes
Although useful as a support for image materials, in particular, a support for photographic printing paper, the support for image materials of the present invention produced according to the following embodiments has excellent quality in the above various properties. And particularly excellent in appearance. That is, an adhesive layer is provided on the opposite side of the white polyester resin film, on which both sides of the base material are coated with a polyethylene resin, and the image forming layer of the white polyester resin film to which the subcoat layer is provided at the time of stretching. After providing the adhesive layer on the polyethylene resin layer on the side where the image material support and the image forming layer are provided, the image forming of the polyester resin film provided with the sub-coat layer at the time of stretching is provided. An image material support laminated on the surface opposite to the side on which the layers are provided. At this time, in the above description, an adhesive layer may be provided on both surfaces of the polyethylene resin layer and the polyester resin layer to be bonded.

Further, in the above-mentioned base material, both ends thereof are heat-sealed, so that excellent quality can be obtained in the above-mentioned various characteristics, and especially, scattering of paper powder from the paper end (edge). Since there is no paper powder, it is useful as a support for an image material which avoids paper dust trouble.

In order to produce a substrate in which both sides of the paper are coated with a polyethylene resin, the polyethylene resin may be resin-coated on both sides of the paper by melt extrusion coating.
A film in which a polyethylene resin has been formed by various film forming methods in advance may be laminated by pasting it on paper or the like. The adhesive layer provided between the polyethylene resin layer and the polyester resin film layer on the side where the image forming layer is provided may be formed using the above-mentioned various adhesives, and the heat treatment may be similarly performed.

The support for various image materials according to the present invention includes:
Various properties, namely, apparent glossiness, surface smoothness,
Excellent image sharpness, very good film-forming properties,
Of course, the adhesiveness between the substrate and the polyester resin film layer is also excellent. Further, it is an excellent support for image materials having an even lower oxygen permeability, excellent fading and light fastness, and excellent long-term storage of images. The image material support of the present invention,
Exhibiting excellent effects in the above various properties is
An image material support comprising a base paper made of natural pulp as a base material and at least one surface of the base material covered with at least two resin layers, wherein a white polyester resin layer is used for image formation. This is based on the fact that a polyester resin layer having at least two layers disposed on the substrate side and a polyester resin layer having substantially no voids disposed on the side on which the layer is provided are laminated with the substrate. That is,
The image material support comprising a resin layer comprising only a white polyester resin layer containing inorganic particles and / or organic particles on a paper base mainly composed of natural pulp is used for the image material of the present invention. Oxygen permeability is higher than the support,
Although there is a tendency for the long-term storability of the image to be slightly inferior, the support for the image material of the present invention has a polyester having substantially no voids in the lower layer (resin layer on the substrate side) of the white polyester resin layer. By providing the resin layer, the oxygen permeability can be suppressed low. Further, the content of the inorganic particles and the organic particles as needed in the white polyester resin layer provided on the upper layer, the content of the inorganic particles and the organic particles as needed in the resin layer consisting of only the white polyester resin layer If the amount is slightly increased, the same sharpness of the image can be obtained and the operation can be performed with almost no adverse effect on the productivity. further,
In the white polyester resin layer in the image material support coated with at least two resin layers of the present invention,
It is also a great advantage of the present invention that the sharpness of the image is dramatically improved by increasing the content of the inorganic particles and, if necessary, the organic particles. Naturally, the image material support of the present invention is different from the image material support consisting only of a polyester resin film, in which a paper base mainly composed of natural pulp and a polyester resin are laminated. Therefore, the unique flexibility of paper (PAP
ERLIQUE) will not be lost.

As the base material used in the practice of the present invention, natural pulp paper containing ordinary natural pulp as a main component is useful.
Further, a mixed paper made of natural pulp as a main component and synthetic pulp and synthetic fiber may be used. Such natural pulp is described or exemplified 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 such appropriately selected natural pulp. Natural pulp was subjected to normal bleaching treatment of chlorine, hypochlorite, chlorine dioxide bleaching and alkali extraction or alkali treatment and, if necessary, oxidative bleaching treatment with hydrogen peroxide, oxygen, etc., and a combination treatment thereof Softwood pulp, hardwood pulp,
Wood pulp of softwood mixed hardwood pulp is advantageously used, and various pulp such as kraft pulp, sulfite pulp, and soda pulp can be used.

The base material mainly composed of natural pulp used in the practice of the present invention may contain various additives during preparation of the stock slurry. As sizing agents, fatty acid metal salts or fatty acids, alkyl ketene dimer emulsions described or exemplified in JP-B-62-7534 or epoxidized higher fatty acid amides, alkenyl or alkyl succinic anhydride emulsions, rosin derivatives, etc., dry paper As a force enhancer, anionic, cationic or amphoteric polyacrylamide, polyvinyl alcohol, cationized starch, vegetable galactomannan, etc., as a wet paper strength enhancer, polyamine polyamide epichlorohydrin resin, etc., as a filler, clay, kaolin, carbonate calcium,
Titanium oxide, etc .; water-soluble aluminum salts such as aluminum chloride and bansulfate as fixing agents; caustic soda, sodium carbonate, sulfuric acid, etc. as pH regulators;
It is advantageous to incorporate various known additives, such as the fluorescent brighteners described or exemplified in JP-A-204251 and JP-A-1-66537, as appropriate.

In the present invention, various coloring pigments and / or coloring dyes can be contained in the paper base for the purpose of improving the visual whiteness of the support for image materials.
At this time, for example, as disclosed in the full text of Japanese Utility Model Application Laid-Open No. 53-45028, a paper substrate for an image material support having desired L value, a value, and b value is manufactured. be able to.

Further, a composition comprising various water-soluble polymers or hydrophilic colloids or latexes, an antistatic agent, and additives is provided in or on a substrate mainly composed of natural pulp used in the practice of the present invention. The material can be contained or coated by a size press, a tab size press, a blade coating, an air knife coating or the like. As a water-soluble polymer or a hydrophilic colloid, starch-based polymers described or exemplified in JP-A-1-266537, polyvinyl alcohol-based polymers,
Gelatin-based polymer, polyacrylamide-based polymer,
Cellulose-based polymers, such as emulsions and latexes, as petroleum resin emulsions, at least a constituent element of ethylene and acrylic acid (or methacrylic acid) described or exemplified in JP-A-55-4027 and JP-A-1-80538. Emulsion or latex of a copolymer, styrene-butadiene, styrene-acrylic,
Vinyl acetate-acrylic, ethylene-vinyl acetate, butadiene-methyl methacrylate-based copolymers and emulsions or latexes of their carboxy-modified copolymers, as antistatic agents, sodium chloride, alkali metal salts such as potassium chloride, Alkaline earth metal salts such as calcium chloride and barium chloride; colloidal metal oxides such as colloidal silica; organic antistatic agents such as polystyrene sulfonate; pigments such as clay, kaolin, calcium carbonate, talc, barium sulfate It is advantageous to add a pH adjuster such as titanium oxide, titanium oxide, or the like, or an appropriate combination of additives such as a coloring pigment, a coloring dye, and a fluorescent whitening agent such as hydrochloric acid, phosphoric acid, citric acid, and caustic soda.

The thickness of the substrate used in the practice of the present invention is not particularly limited, but the basis weight is 30 to 250 g.
/ M ² are preferred.

The support for various image materials according to the present invention includes:
In addition to the various excellent characteristics described above, there is a feature that the surface has excellent surface smoothness. The center plane average roughness (SRa) measured using the following stylus type three-dimensional surface roughness meter is 0.15 μm or less, and has extremely good surface smoothness. In the support for image materials of the present invention, the center plane average roughness (SRa) is preferably 0.12 μm or less, particularly preferably 0.10 μm or less.

As the base material containing natural pulp as a main component used for obtaining the support for an image material of the present invention having excellent surface smoothness as described above, the apparent glossiness of the image material and its print is remarkable. From the viewpoint of improving the surface roughness, the center plane average roughness (SRa) in the papermaking direction at a cutoff value of 0.8 mm measured using a stylus type three-dimensional surface roughness meter on the front side of the substrate.
(Hereinafter, the term “center plane average roughness SRa in the papermaking direction at a cutoff value of 0.8 mm measured using a stylus type three-dimensional surface roughness meter on the front side of the base material” is simply referred to as “center plane average roughness”. SRa
It is preferably 1.5 μm or less, more preferably 1.4 μm or less, still more preferably 1.3 μm or less, and particularly preferably 1.2 μm or less.

The center plane average roughness (SRa) at a cut-off value of 0.8 mm measured using a stylus type three-dimensional surface roughness meter referred to in this specification is defined by the following equation (1). is there.

[0104]

(Equation 1)

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

More specifically, as a stylus type three-dimensional surface roughness meter and a three-dimensional roughness analysis device, SE-produced by Kosaka Laboratory Co., Ltd.
Using a 3AK type machine and a SPA-11 type machine, the cutoff value is 0.8 mm, Wx = 20 mm, Wy = 8 mm, and therefore Sa = 1.
It can be obtained under the condition of 60 mm2. In the data processing in the X-axis direction, sampling was performed at 500 points, and
The scanning in the axial direction is performed for 17 lines or more.

The paper used as the base material of the present invention preferably has a center plane average roughness (SRa) of 1.5 μm or less. Specifically, a preferred image material support can be obtained by using the following method, preferably by using a combination of two or more, more preferably three or more of the following methods.

(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. Further, the fiber length of the pulp measured on the pulp after beating before the paper chemical is added is preferably 0.42 mm.
~ 0.70mm, more preferably 0.45mm ~ 0.65mm,
It is even more preferable to use a beaten and prepared one that has been beaten to a range of 0.47 mm to 0.61 mm, particularly preferably 0.49 mm to 0.57 mm. If the fiber length of the pulp is too short, the internal bond strength of the paper is weakened, and the stiffness is lowered. On the other hand, if the fiber length of the pulp is too long, the center plane average roughness (SRa) of the paper tends to increase. . In addition, the fiber length of the pulp referred to in the present specification refers to the pulp after beating,
JAPAN TAPPI Paper Pulp Test Method No. 52-89
It means the value expressed by the length-weighted average fiber length (mm) measured in accordance with the "paper and pulp fiber length test method".

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

(3) Various water-soluble polymers, hydrophilic colloids or polymer latexes are contained or coated in or on paper. Specifically, various water-soluble polymers or hydrophilic colloids or polymer latexes in paper or on paper are subjected to size press or tab size press, blade coating, air knife coating or the like to obtain a solid coating amount of 1.0 g. / M ² or more, preferably 2.2 g / m ² or more.

(4) After the paper is made, at least two or more series of calendar treatments are performed on the paper using a machine calendar, a super calendar, a heat calendar, or the like. Specifically, for example, a paper is subjected to a machine calendar process and / or a thermal machine calendar process as a first series calendar process, and then further subjected to a machine calendar process as necessary as a second series calendar process thereafter. ,
It is preferable to carry out the thermal soft calendering treatment described or exemplified in JP-A-4-110939.

After performing an activation treatment such as a corona discharge treatment or a flame treatment on the back surface of the image material support in the present invention, various back layers can be coated for antistatic purposes and the like. . In the back layer,
JP, JP-B-57-9059, JP-B-57-53940, JP-B-58-56859, JP-A-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 or exemplified in JP-A-58-184144 can be incorporated in an appropriate combination.

The support for an image material in the present invention is coated with various photographic constituent layers, and is used for color photographic paper, black and white photographic paper, typesetting photographic paper, copy photographic paper, reversal photographic material, The silver salt diffusion transfer method can be used for various purposes such as negative and 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 component layer for a silver salt diffusion transfer method can be provided. As a binder for these photographic constituent layers, in addition to ordinary gelatin, hydrophilic high-molecular substances such as polyvinylpyrrolidone, polyvinyl alcohol and polysaccharide sulfate compounds can be used. Further, the above-mentioned photographic constituent layer can contain various additives. For example, as sensitizing dyes, cyanine dyes, merocyanine dyes, etc., as chemical sensitizers, water-soluble gold compounds, sulfur compounds, etc., as antifoggants or stabilizers, hydroxy-triazolopyrimidine compounds, mercapto-heterocyclic compounds, etc. , Hardening agents such as formalin, vinylsulfone compounds and aziridine compounds, coating aids such as alkylbenzenesulfonates and sulfosuccinate salts, etc., dialkylhydroquinone compounds etc. as antifouling agents, and other fluorescent brighteners, improving sharpness Dye, antistatic agent, pH adjuster,
A fogging agent and a water-soluble iridium compound, a water-soluble rhodium compound, and the like can be added in appropriate combination during the generation and dispersion of silver halide.

The photographic material according to the present invention is subjected to exposure, development, and stoppage according to the photographic material, as described in "Photosensitive Materials and Handling Methods" (Kyoritsu Shuppan, Goro Miyamoto, Photographic Technology Course 2). , Fixing, bleaching, and stabilization. Further, the multi-layer silver halide color photographic material may be treated with a developer containing a development accelerator such as benzyl alcohol, thallium salt, phenidone or the like, or may be treated with a developer substantially free of benzyl alcohol. it can.

The support for an image material in 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.

In the heat transfer type thermal transfer recording image receiving layer according to the present invention, a releasing agent, a pigment and the like may be added in addition to the synthetic resin. As the release agent, polyethylene wax,
Examples include solid waxes such as amide wax and Teflon powder, fluorine-based and phosphate-based surfactants, and silicone oils. Among these release agents, silicone oil is most preferred. As the silicone oil, an oily substance can be used, but a curable type is preferred. As setting type silicone oil, reaction setting type,
A photo-curing type, a catalyst-curing type and the like can be mentioned, and a reaction-curing 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 0.1 to 2 in the image receiving layer.
0 wt% is preferred. As the pigment, extenders such as silica, calcium carbonate, titanium oxide, and zinc oxide are preferable. The thickness of the image receiving layer is 0.5 to 20 μm.
Is preferably 2 to 10 μm.

The support for an image material in the present invention can be used as a support for various ink-jet recording materials by coating various ink image-receiving layers. Various binders can be contained in the ink image receiving layer for the purpose of improving the drying property of the ink and the sharpness of the image. Specific examples of such binders include lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, and gelatin derivatives such as various gelatins such as phthalic acid, maleic acid, and gelatin reacted with dibasic acid anhydrides such as fumaric acid. , Normal polyvinyl alcohols of various saponification degrees, carboxy-modified, cationic-modified and amphoteric polyvinyl alcohols and their derivatives, starches such as oxidized starch, cationized starch, etherified starch, and cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose , Polyvinylpyrrolidone, polyvinylpyridium halide, sodium polyacrylate, methacrylic acid copolymer salt, polyethylene glycol, polypropylene glycol, polyvinyl ether, alkyl vinyl ether, anhydrous male Phosphate copolymer, styrene
Maleic anhydride copolymers and salts thereof, synthetic polymers such as polyethyleneimine, conjugated diene copolymer latex such as styrene / butadiene copolymer, methyl methacrylate / butadiene copolymer, polyvinyl acetate, vinyl acetate / maleic Acid ester copolymer, vinyl acetate
Acrylate ester copolymer, vinyl acetate polymer latex such as ethylene / vinyl acetate copolymer, acrylate ester polymer, methacrylate ester polymer, ethylene / acrylate ester copolymer, styrene / acrylate ester copolymer Latex of acrylic polymer or copolymer such as polymer, latex of vinylidene chloride copolymer or functional group-modified polymer latex with functional group-containing monomer such as carboxyl group of these various polymers,
Aqueous adhesives such as thermosetting synthetic resins such as melamine resin and urea resin, and synthetic resin adhesives such as polymethyl methacrylate, polyurethane resin, unsaturated polyester resin, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral, and alkyd resin JP-B No. 3-24906, JP-A-3-281383, and alumina sol described or exemplified in Japanese Patent Application No. 4-240725, inorganic binders such as silica sol, and the like. It can be contained in combination.

The ink image-receiving layer of the ink-jet recording material according to the present invention may contain various additives in addition to the binder. For example, as a surfactant, an anionic surfactant such as a long-chain alkyl benzene sulfonate, a long-chain, preferably a branched alkyl sulfosuccinate, a polyalkylene oxide of a long-chain, preferably a branched alkyl group-containing phenol. Nonionic surfactants such as ethers and polyalkylene oxide ethers of long-chain alkyl alcohols, JP-B-47-930
Silane coupling agents such as γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, such as fluorinated surfactants described in JP-A-3,589,906 and the like. ,
As a hardener for the polymer, a hardener such as an active halogen compound, a vinyl sulfone compound, an aziridine compound, an epoxy compound, an acryloyl compound, or an isocyanate compound, and as a preservative, P-mentioned or described in JP-A-1-102551. Hydroxybenzoic acid ester compound,
Benzisothiazolone compounds, isothiazolone compounds, etc., JP-A-63-204251, coloring pigments described or exemplified in JP-A 1-266537, etc., coloring dyes, fluorescent whitening agents, etc., hydroxymethane sulfone as a yellowing inhibitor Acid sorbents, sodium P-toluenesulfinate, ultraviolet absorbers such as benzotriazole compounds having a hydroxy-di-alkylphenyl group at the 2-position, antioxidants described in JP-A-1-105245 or examples thereof. Organic or inorganic fine particles having a particle size of 0.2 to 5 μm, such as starch granules, barium sulfate, and silicon dioxide, and organoorganic compounds described or exemplified in Japanese Patent Publication No. 4-1337, etc. Polysiloxane compound, as a pH regulator, caustic soda, sodium carbonate,
Various additives such as octyl alcohol and silicon-based antifoaming agents such as sulfuric acid, hydrochloric acid, phosphoric acid, and citric acid can be appropriately combined and contained.

[0119]

EXAMPLES The present invention will be described below in detail with reference to examples, but the contents of the present invention are not limited to the examples.

<Manufacture of paper> Hardwood bleached kraft pulp 8
Fiber length of pulp after beaten mixed pulp consisting of 5% by weight and 15% by weight of hardwood bleached sulfite pulp (JAPA
N TAPPI Paper Pulp Test Method No. After beating so that the length-weighted average fiber length measured in accordance with 52-89 "Paper and Pulp Fiber Length Test Method" is 0.60 mm, 100 parts by weight of pulp is cationized. Starch 3 parts by weight, anionized polyacrylamide 0.2 parts by weight, alkyl ketene dimer emulsion (as ketene dimer) 0.4 parts by weight, polyamide epichlorohydrin resin 0.4 parts by weight and an appropriate amount of fluorescent whitening agent, blue Dye and red dye were added to prepare a stock slurry. Thereafter, the stock slurry was placed on a fourdrinier paper machine running at 200 m / min to form a web while giving appropriate turbulence, and the linear pressure was adjusted in the wet part in the range of 15 to 100 kgf / cm. After performing a three-stage wet press, processing with a smoothing roll, and performing a two-stage tension press in which a linear pressure is adjusted in a range of 30 to 70 kgf / cm in a subsequent drying part,
Dried. Thereafter, during the drying, 2 parts by weight of the carboxy-modified polyvinyl alcohol, 0.05 parts by weight of the optical brightener,
25 g / m ^{2 of a} size press solution consisting of 0.002 parts by weight of blue dye, 4 parts by weight of sodium chloride and 94 parts by weight of water
The paper is subjected to size press, dried so that the finally obtained paper has a moisture content of 8% by weight in terms of absolute dry moisture, machine calendered at a linear pressure of 70 kgf / cm, and a center plane average weight of 170 g / m ^2. An image material support paper having a roughness (SRa) of 1.30 μm was produced.

<Formation of Back Resin Layer> Next, the paper surface (back surface) opposite to the side on which the image forming layer is coated is subjected to corona discharge treatment, and then a low-density polyethylene resin (density = 0.
30 parts by weight of 924 g / cm ³ , MI = 1 g / 10 min. And high-density polyethylene resin (density = 0.967 g / cm ³ , MI = 15 g /
10 minutes) A 70% by weight compound resin composition was applied at a resin temperature of 320 ° C. to a resin thickness of 25 μm and a paper running speed of 2 μm.
Melt extrusion coating was performed at 00 m / min. At this time, the cooling roll was roughened by a liquid honing method, and the center surface average roughness (S
Ra) having a roughness of 1.15 μm was used.

For the back layer, the following back layer coating solution was applied by on-machine coating after the back surface resin layer was subjected to corona discharge treatment. As a dry weight, a back layer coating liquid containing colloidal silica: styrene-based latex = 1: 1, and further containing 0.021 g / m ² of sodium polystyrene sulfonate and an appropriate amount of a coating aid was added to the latex (solid). It was applied at a coating amount of 0.21 g / m ² as calculated by weight.

<Production of Surface Two-Layer Polyester Resin Film> 100 parts by weight of a polyethylene terephthalate resin having an intrinsic viscosity of 0.65 and hydrous aluminum hydroxide (0.75% by weight as Al ₂ O _{3 based} on titanium dioxide). The raw material to which 20 parts by weight of the surface-treated anatase type titanium dioxide pigment was added was kneaded in a Banbury mixer to obtain a polyethylene terephthalate resin composition containing the titanium dioxide pigment. Separately, 100 parts by weight of a polyethylene terephthalate resin having an intrinsic viscosity of 0.65 and two extruders equipped with two hoppers and two screws,
Using a single-manifold type die, co-extrude into the layer configuration shown in Table 1, solidify and adhere to a cooling rotating roll, and form two layers of a white polyester resin containing a titanium dioxide pigment and a polyester resin having substantially no voids. Unstretched films used for the supports for image materials of Examples 1 to 5 were obtained. Subsequently, the unstretched film was longitudinally stretched 3.5 times at 110 ° C. by a roll stretching machine, and then transversely stretched 3.7 times at 120 ° C. with a tenter, and heat-fixed at 210 ° C. A biaxially stretched polyester resin film consisting of two layers having a thickness was obtained. In this case, after longitudinal stretching and before transverse stretching, a subcoating agent composition comprising 20 parts by weight of vinylidene chloride latex, 5 parts by weight of N-methylpyrrolidone, and 1.5 parts by weight of colloidal silica (Snowtex ZL: manufactured by Nissan Chemical Industries, Ltd.) Was added to water to give a total amount of 100 parts by weight.
m (solid content). In addition, the following core-shell type latex was used as vinylidene chloride latex.

Core-shell type latex (core part 9
0% by weight, shell part 10% by weight) Core part Vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: acrylic acid (93: 3:
3: 0.9: 0.1) Shell part Vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: acrylic acid (88: 3:
3: 3: 3) (Average molecular weight 38000)

Examples 1 to 5 A urethane-based compound was mainly applied to a substantially void-free polyester resin surface of a biaxially stretched polyester resin film having two layers having five types of layers obtained as described above. An adhesive as a component is applied at 4 g / m ² (solid content), and a paper surface on the opposite side on which the backside resin layer obtained as described above is formed (hereinafter referred to as a paper surface). Sometimes)
Were superimposed, and then bonded by pressing with a press roll. Thereafter, the resultant was subjected to a heating treatment at 50 ° C. for 2 days in a heating chamber to produce the image material supports of Examples 1 to 5.

Example 6 The same procedure as in Example 3 was carried out except that in the above <Preparation of paper>, a paper size-pressed with a size press solution containing three times the amount of carboxy-modified polyvinyl alcohol was used.
A support for an image material of Example 6 was produced.

Example 7 A resin having a thickness of 15 μm was formed on the surface of the paper provided with the backside resin layer obtained in the above <Formation of Backside Resin Layer> as follows.
m of polyethylene resin layer, and both ends are 2 m each.
A support for an image material of Example 7 was produced in the same manner as in Example 3 except for using a substrate coated with resin on both sides after heat sealing with an m width. After corona discharge treatment of the paper surface, a low density polyethylene resin (density = 0.9)
47.5 parts by weight of 20 g / cm ³ , MI = 8.5 g / 10 minutes, anatase type titanium dioxide pigment surface-treated with hydrous aluminum hydroxide (0.75% by weight as Al ₂ O ₃ parts based on titanium dioxide) 20 parts by weight of a titanium dioxide pigment master batch consisting of 50 parts by weight and 2.5 parts by weight of zinc stearate and a low-density polyethylene resin (density = 0.920 g / cm ³ ,
(MI = 4.5 g / 10 min) A resin composition consisting of 80 parts by weight was charged into a twin screw extruder and melt-extruded to a resin thickness of 15 μm at a paper traveling speed of 200 m / min. The surface of the polyethylene resin layer containing was processed into a glossy surface. At that time, a chromium-plated fine rough surface was used as the cooling roll.

Example 8 A support for an image material of Example 8 was produced in the same manner as in Example 3 except that the layer constitution shown in Table 1 was used.

Example 9 <Production of surface two-layer polyester resin film>
, 1.5 g of lime-treated gelatin, 0.3 g of a 10% by weight methanol solution of butyl parahydroxybenzoate, 5 g of methanol of sulfosuccinic acid-2-ethylhexyl ester salt and 5 ml of water on the sub-coated layer.
Example 3 except that the undercoat liquid containing 0.45 g of a weight% mixed solution and the total amount was adjusted to 100 g with water was uniformly applied on-machine so that the gelatin coating amount was 0.12 g / m ^2. In the same manner as in the above, an image material support of Example 9 was produced.

Comparative Example 1 The above <Production of surface two-layer polyester resin film>
In (1), a polyester resin layer having substantially no voids should not be provided (a layer structure composed of only a white polyester resin layer), that is, a polyethylene terephthalate resin composition containing a titanium dioxide pigment should be put into two hoppers for production. A support for an image material of Comparative Example 1 was produced in the same manner as in Example 3 except for the above.

Comparative Example 2 The above <Production of surface two-layer polyester resin film>
In (2), a white polyester resin layer is not provided (layer structure composed of only a polyester resin layer having substantially no voids).
Example 3 except that the product was put into the hoppers and manufactured.
In the same manner as in the above, an image material support of Comparative Example 2 was produced. However, in this case, the subcoat liquid was applied to the resin surface on the side where the image forming layer of the polyester resin layer having substantially no voids was provided.

Comparative Example 3 A support for an image material of Comparative Example 3 was produced in the same manner as in Comparative Example 1 except that the layer constitution shown in Table 1 was used.

Comparative Example 4 A support for an image material of Comparative Example 4 was produced in the same manner as in Example 3 except that the layer constitution shown in Table 1 was used. However, in this case, the polyester resin layer having substantially no voids is disposed on the side on which the image forming layer is provided, and the white polyester resin layer is disposed on the base material side. The subcoat liquid was applied to the resin surface on the side where the image forming layer was provided.

Comparative Example 5 The surface of the paper provided with the backside resin layer obtained in the above <Formation of Backside Resin Layer> was subjected to corona discharge treatment.
The same titanium dioxide pigment-containing polyethylene resin composition as in Example 3 was extruded to a resin thickness of 36 μm using an extruder in the same manner as in Example 7, and then the polyethylene resin layer was subjected to on-machine sub-coating as in Example 3 A support for image materials produced by applying a subcoat liquid containing the agent composition to a thickness of 0.2 μm (solid content) was used as Comparative Example 5.

Comparative Example 6 The above <Production of surface two-layer polyester resin film>
, A white polyester resin and a polyester resin having substantially no voids were separately extruded using an extruder to obtain these two types of unstretched polyester resin films. White polyester resin film is 10
0 μm, and the polyester resin film having substantially no voids is stretched to 131 μm after biaxial stretching, respectively.
On the side of the white polyester resin film where the image forming layer is not provided, an adhesive containing a urethane compound as a main component is applied at 2 g / m ^2.
(Solid content) A support for an image material produced by coating and bonding was used as Comparative Example 6.

The support for image material obtained in each of the examples and comparative examples was evaluated by the following test methods.

<Preparation of color photographic paper> A blue-sensitive emulsion layer containing a yellow color coupler, an intermediate layer containing a color-mixing inhibitor, and a magenta color coupler were sequentially arranged adjacent to the image forming layer side of the image material support. Containing green emulsion layer, first containing ultraviolet absorber
An ultraviolet absorbing layer, a red-sensitive emulsion layer containing a cyan coloring coupler,
A second UV-absorbing layer containing a UV-absorbing agent and a protective layer were applied by an E-bar for multilayer coating and the total amount of gelatin was 7 g / m ^2.
Color photographic paper. Each color-sensitive emulsion layer contains silver chloride-rich silver halide equivalent to 0.45 g / m ² in terms of silver nitrate. In addition to gelatin necessary for silver halide generation, dispersion and film formation, an appropriate amount of antifoggant Sensitizing dyes, coating aids, hardeners, thickeners and appropriate amounts of filter dyes.

<Evaluation Method for Visual Glossiness of Photographic Print> The prepared color photographic paper was stored at 35 ° C. and normal humidity for 5 days, and then the group photo was baked, developed, bleached / fixed, and stably developed. Thereafter, it was dried to produce a photographic print.
Separately, burned samples of solid white (unexposed) and solid black (colored black) were also prepared. 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 / fixing (45 seconds) → stable (1 minute 30 seconds) → drying.

With respect to the obtained group photograph, white solid and black solid photographic prints, the glossiness of the photographic prints was visually judged comprehensively by 10 monitors,
A 10-grade evaluation was performed. 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.

Grades 10 to 9: Very or very high apparent glossiness. Grade 8 to 6: High glossiness in appearance. Grade 5-4: The glossiness is slightly low in appearance, but practical. Grade 3-1: The appearance has a low glossiness, and there is a problem in practical use.

<Evaluation Method of Adhesion between Paper and Polyester Resin Layer> The evaluation method of the adhesion between the paper of the image material support and the polyester resin layer is determined by using the paper layer of the sample and the polyester resin layer on the surface. The adhesiveness between the paper and the polyester resin layer was evaluated by measuring the area ratio of the paper layer adhered to the peeled polyester resin layer. The evaluation criteria were as follows: ：: 100% area ratio is good, Δ: 1 area ratio
Less than 00% is 80% or more, and the adhesiveness is slightly poor but there is no practical problem. X: The area ratio is less than 80%,
Poor adhesion, indicating some practical problems. In addition, about Example 7 and Comparative Example 3, the adhesiveness of the paper layer and the polyethylene resin layer was evaluated.

<Evaluation Method with Emulsion Film> The evaluation method of the image forming layer with an emulsion film is such that the produced color printing paper is kept at 40 ° C. and normal humidity for 5 days to have a gray density of 1.5 or more. And after color development, evaluation of the presence of an emulsion film was performed.
With the emulsion film, after the color development, scratch the emulsion surface with a nail at 1 cm intervals vertically and horizontally, make a grid-like scratch, and then rub the surface with your fingertip in running water, and the emulsion layer for the area rubbed with your fingertip The area (%) of the area that was not peeled was evaluated (the larger the value, the stronger the emulsion film attached, and the smaller the value, the weaker the emulsion film attached). The evaluation criteria are as follows. 100% to 97%: No or little peeling of the emulsion layer, good adhesion with emulsion film. Less than 97% to 80%: slight peeling of the emulsion layer, but no practical problem. Less than 80% to 60%: peeling of the emulsion layer is slightly large, but practically the lower limit. Less than 60%: peeling of the emulsion layer is large, and there is a practical problem with an emulsion film.

<Method of Measuring Oxygen Permeability> The oxygen permeability of a support for an image material was determined according to JIS K71 for each support.
The oxygen permeability (cc / m ² / d) of the image material support was determined by measuring under the following measurement conditions according to Method B (isobaric method) of No. 26.
ay). Measurement environment: 23 ° C, 65% relative humidity. Gas flow rate: oxygen; 20 ml / min, carrier gas (nitrogen /
Hydrogen gas); 10 ml / min. Test cell area: 5cm ² (using aluminum foil mask). Diffusion direction: On the back resin layer side from the image forming resin layer side.

<Sharpness of Image> The sharpness of the image of the image material support is the same as in the above <Preparation of color photographic paper> and <Evaluation method of apparent glossiness of photographic print> for each support. 1 for the sharpness of the group photo obtained
It was visually evaluated by 0 monitors.

The evaluation criteria for the sharpness of the printed image are as follows. ：: Sharpness is high. □: Sharpness is slightly high. Δ: Sharpness is slightly low, but practical. X: Sharpness is low and there is a problem in practical use.

Table 1 shows the results obtained by the above test method.
Shown in

[0147]

[Table 1] Note 1) The upper layer and the lower layer of the layer constitution indicate the resin thickness ratio of the white polyester resin layer: the polyester resin layer having substantially no voids (unit: μm). Note 2) * The upper layer versus the lower layer in Comparative Example 4 indicates the resin thickness ratio of the polyester resin layer: white polyester resin layer having substantially no voids. Note 3) ** Comparative Example 5 shows polyethylene resin. Note 4) The sheet of Comparative Example 6 shows a support for an image material comprising only a white polyester resin layer and a polyester resin layer having substantially no voids.

<Evaluation> A paper composed mainly of natural pulp was used as a base material, and at least one surface of the base material was at least 2
An image material support coated with a resin layer consisting of a layer, wherein a white polyester resin layer is disposed on the side where the image forming layer is provided, and a substantially void-free polyester resin layer is disposed on the substrate side. It has been found that the image material support of the present invention, in which at least two polyester resin layers and a substrate are laminated, has excellent quality. Examples 1 to 5, which are embodiments in which the layer configuration of the present invention is changed,
Excellent in all six items, which are important quality characteristics as a support for image materials, such as apparent glossiness of photo prints, adhesiveness, film forming property, oxygen permeability, center plane average roughness and image sharpness. Results were obtained.

In the comprehensive evaluation of six items, which are important quality characteristics described above, Examples 1 to 4 were excellent, and Examples 2 and 3 were particularly excellent. In Example 5, although the sharpness of the image tended to be slightly inferior to Examples 1 to 4, it was still in a practical range, and particularly excellent results were obtained with oxygen permeability. .

The image material support of Example 6 obtained in the same manner as in Example 3 except that the paper was subjected to size press with a size press solution containing 3 times the amount of carboxy-modified polyvinyl alcohol during the production of the paper. As in Example 3, an excellent quality image material support was obtained as in Example 3, but the apparent glossiness of the photographic print was further improved.
Even better results were obtained in oxygen permeability.

<Formation of Backside Resin Layer> Both ends of a double-sided resin-coated base material having a 15 μm-thick polyethylene resin layer formed on the surface of the paper provided with the backside resin layer obtained in the step were heat-sealed. The image material support of Example 7 obtained in the same manner as in Example 3 obtained excellent results in all six items, which are important quality characteristics as the image material support. In addition, since there is no generation of paper dust, as a support for image materials to avoid paper dust trouble,
It could be used particularly advantageously.

White polyester resin layer: Example 8 obtained in the same manner as in Example 3 except that the resin thickness ratio of the polyester resin layer having substantially no voids was 15:16 (resin thickness: 31 μm). The support for the image material tended to be slightly inferior to Example 3 in terms of the apparent glossiness and the average roughness of the center plane of the photographic print, but the support for the image material was excellent in other items. The body is obtained.

The image material support of Example 9 in which an undercoat layer was further provided on the image material support of Example 3 exhibited excellent properties as in Example 3. In particular, excellent results were obtained in terms of film-forming properties.

The image material of Comparative Example 1 obtained in the same manner as in Example 3 except that the polyester resin layer having substantially no voids was not provided in the above <Production of surface two-layer polyester resin film>. For the support, relatively good results were obtained for the five items except for the oxygen permeability.
Oxygen permeability was poor.

In the above <Production of surface two-layer polyester resin film>, except that the white polyester resin layer was not provided, the support for image material of Comparative Example 2 obtained in the same manner as in Example 3 was used. Excellent results were obtained in five items except for the sharpness of the image, but the sharpness of the image was extremely poor and not practical.

In the above <Production of Two-Layer Polyester Resin Film for Surface>, except that the polyester resin layer having substantially no void was not provided, and the thickness of the white polyester resin layer was set to 31 μm. The support for image material of Comparative Example 3 obtained in the same manner as in Example 3 provided relatively good results for the five items except for the oxygen permeability, but had a problem in that the oxygen permeability was large. .

In the above <Production of Surface Two-Layer Polyester Resin Film>, the upper layer and the lower layer of the layer structure are a polyester resin layer having substantially no voids: a white polyester resin layer, and the resin thickness ratio is 12:24. Except that, the image material support of Comparative Example 4 obtained in the same manner as in Example 3 obtained good results in five items except for the sharpness of the image. It was extremely bad and not practical.

The surface of the paper provided with the backside resin layer obtained in the above <Formation of Backside Resin Layer> is subjected to corona discharge treatment, and then the titanium dioxide pigment-containing polyethylene resin composition is treated with:
The support for an image material of Comparative Example 5 obtained by extrusion coating and coating the surface of paper with a polyethylene resin composition containing a titanium dioxide pigment having a resin thickness of 36 μm has an adhesive property, a film forming property, and a sharp image. The degree of gloss was good, and the apparent glossiness of the photographic print was in a practically usable range, but the center plane average roughness was slightly inferior, and in particular, only a support for image materials having extremely high oxygen permeability was obtained.

In the above <Production of Two-Layer Polyester Resin Film for Surface>, a white polyester resin and a polyester resin having substantially no voids are used. Polyester resin film is 131 μm after biaxial stretching
The image material support of Comparative Example 6 was prepared by applying an adhesive containing a urethane compound as a main component on the side of the white polyester resin film on which the image forming layer was not provided, and then laminating. Has good film-coating properties, oxygen permeability and center plane average roughness, and the apparent glossiness and sharpness of images of photographic prints were within a practical range, but the flexibility characteristic of paper (PAPERLIKE) ) And only those of practically problematic quality were obtained.

[0160]

According to the present invention, it is possible to obtain a print having excellent qualities such as glossiness, adhesion, film-coating property, surface smoothness and image sharpness which are important properties as a support for an image material. An excellent paper-based resin-coated paper-type image material support that is obtained, has much lower oxygen permeability, and has no operational problems can be provided.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) D21H 19/28 G03C 1/91 G03C 1/91 1/95 1/95 B41M 5/26 101H F-term (Reference) 2H023 FA04 FA06 FA12 FA13 FB01 2H086 BA19 2H111 BB04 CA23 4F100 AA00C AA00H AA20D AA20H AA21D AA21H AJ04A AJ09E AK03E AK04E AK16D AK16J AK41B AK41C AK41D AK41J AK80D AL01D AP00A BA03 BA04 BA05 BA06 BA07 BA10A BA10C BA10D BA10E BA13 CB00 CC00D CC00E DB01 DB013 DE01C DE01H DG10A EC033 EC181 EH20B EH20C EH461 EH462 EJ371 EJ372 EJ38B EJ38C EJ42 EJ423 GB90 HB00C JD03 JK06 JK15 JL10C JM01D JN21 YY00 4L055 AG16 AG18 AG19 AG53 AG56 AG59 AG67 AG82 AG84 AG87 AG89 AG97 AG98 AH01 AH02 AH12 AH13 A14 GA32

Claims (36)

[Claims] 1. A support for an image material, wherein a base material is a paper mainly composed of natural pulp, and at least one surface of the base material is coated with at least two resin layers,
A white polyester resin layer is disposed on the side on which the image forming layer is provided, and the substrate is laminated with at least two polyester resin layers each having a substantially void-free polyester resin layer disposed on the substrate side. A support for an image material, comprising: 2. The image material support according to claim 1, wherein the polyester resin layer comprising at least two layers is formed by co-extrusion. 3. A polyester resin layer comprising at least two layers, each of which is a biaxially stretched polyester resin layer, and a subcoat layer is provided on at least a surface on the image forming layer side at the time of stretching. Claim 1
Or the support for image materials according to 2. 4. The support for an image material according to claim 1, wherein said subcoat layer is provided between a longitudinal stretching and a transverse stretching. 5. A subcoating agent comprising at least one of a water-dispersible copolymer polyester, a vinylidene chloride copolymer latex and a polyamine polyamide epichlorohydrin resin. 5. The support for an image material according to 2, 3, or 4. 6. The sub-coat layer contains the sub-coat agent and colloidal silica.
The support for an image material as described above. 7. An undercoat layer comprising gelatin as a main component is provided on said sub-coat layer.
7. The support for an image material according to 2, 3, 4, 5 or 6. 8. The support for an image material according to claim 1, wherein the white polyester resin layer contains at least one kind of inorganic particles or organic particles. . 9. The support for an image material according to claim 8, wherein the inorganic particles in the white polyester resin layer are lightly alumina surface-treated titanium dioxide pigments. 10. The support for an image material according to claim 8, wherein the organic particles in the white polyester resin layer are organic particles having no compatibility with the white polyester resin. 11. The method according to claim 1, wherein when laminating the polyester resin layer comprising at least two layers and the substrate, the polyester resin layer and the substrate are laminated via an adhesive layer. 11. The support for an image material according to 3, 4, 5, 6, 7, 8, 9 or 10. 12. After laminating via an adhesive layer between a polyester resin layer comprising at least two layers and a substrate,
The support for an image material according to claim 11, wherein the support has been subjected to a heating treatment. 13. The heat treatment at 35 ° C. to 100 ° C. for at least one hour.
2. The support for image materials according to item 2. 14. The method according to claim 1, wherein the resin layer provided on the substrate on the side opposite to the side on which the image forming layer is provided is a polyolefin resin layer.
The support for an image material according to 8, 9, 10, 11, 12, or 13. 15. The substrate according to claim 1, wherein both sides of the paper are resin-coated with a polyethylene resin. 11, 1
15. The support for an image material according to 2, 13, or 14. 16. The support for an image material according to claim 15, wherein both ends of the base material are heat-sealed. 17. JIS K-71 of a support for an image material
The oxygen permeability measured by the method B of No. 26 is 35 cc / m ^2.
/ Day or less,
3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 1
17. The support for an image material according to 3, 14, 15 or 16. 18. The method according to claim 1, wherein the average surface roughness (SRa) on the side on which the image forming layer is provided is 0.15 μm or less. 9, 10,
The support for an image material according to 11, 12, 13, 14, 15, 16 or 17. 19. A support for image material, comprising a base paper made of natural pulp as a main component and at least one surface of the base coated with a resin layer comprising at least two layers, wherein a white polyester is used. The resin layer is disposed on the side on which the image forming layer is provided, and a polyester resin layer having substantially no voids is formed by laminating a polyester resin layer composed of at least two layers disposed on the substrate side and the substrate. Of producing a support for an image material. 20. The method according to claim 19, wherein at least two polyester resin layers are produced by coextrusion. 21. A polyester resin layer comprising at least two layers, each of which is a biaxially stretched polyester resin layer, and a subcoat layer is provided at least on the surface on the image forming layer side during stretching. Claim 19
21. The method for producing a support for an image material according to item 20. 22. The method according to claim 19, wherein the sub-coat layer is provided between the longitudinal stretching and the transverse stretching.
22. The method for producing a support for an image material according to 0 or 21. 23. A subcoating agent comprising at least one of a water-dispersible copolymer polyester, a vinylidene chloride copolymer latex, and a polyamine polyamide epichlorohydrin resin. , 20, 21 or 22. 24. The method according to claim 23, wherein the subcoat layer contains the subcoat agent and colloidal silica. 25. An undercoat layer comprising gelatin as a main component is provided on the sub-coat layer.
9. The method for producing a support for an image material according to 9, 20, 21, 22, 23 or 24. 26. The support according to claim 19, wherein the white polyester resin layer contains at least one of inorganic particles and organic particles. How to make the body. 27. The method for producing a support for an image material according to claim 26, wherein the inorganic particles in the white polyester resin layer are lightly alumina-treated titanium dioxide pigments. 28. The method according to claim 26, wherein the organic particles in the white polyester resin layer are organic particles having no compatibility with the white polyester resin. 29. The method according to claim 19, wherein when laminating the polyester resin layer comprising at least two layers and the base material, the polyester resin layer and the base material are laminated via an adhesive layer. , 21,22,23,24,2
29. The method for producing a support for an image material according to 5, 26, 27 or 28. 30. After laminating an adhesive layer between a polyester resin layer comprising at least two layers and a substrate,
The method for producing a support for an image material according to claim 29, wherein a heating treatment is performed. 31. The heating treatment is performed at 35 ° C. to 100 ° C. for at least one hour.
The method for producing a support for an image material as described above. 32. The resin layer provided on the substrate on the side opposite to the side on which the image forming layer is provided is a polyolefin resin layer.
24, 25, 26, 27, 28, 29, 30 or 31
The method for producing a support for an image material as described above. 33. The substrate according to claim 1, wherein both sides of the paper are resin-coated with polyethylene resin.
9, 20, 21, 22, 23, 24, 25, 26, 2,
The method for producing a support for an image material according to 7, 28, 29, 30, 31, or 32. 34. The method according to claim 33, wherein both ends of the base material are heat-sealed. 35. JIS K-71 of a support for an image material
The oxygen permeability measured by the method B of No. 26 was 35 cc / m ^2.
/ Day or less.
0, 21, 22, 23, 24, 25, 26, 27, 2
The method for producing a support for an image material according to 8, 29, 30, 31, 32, 33 or 34. 36. The method according to claim 19, wherein the average surface roughness (SRa) on the side on which the image forming layer is provided is 0.15 μm or less.
26, 27, 28, 29, 30, 31, 32, 33, 3
36. The method for producing a support for an image material according to 4 or 35.