JPH11352636A - Base for image material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellent base for an image material of a resin coated paper type which is excellent in the glossy feel in the appearance of a print, adhesiveness, film deposition characteristic, oxygen permeability and center line average height which are important characteristics as the base for the image material and which is free from problem in operation. SOLUTION: This base for the image material is formed by using the paper consisting essentially of natural pulp as a main material and coating at least one surface of the base material with a resin layer. In such a case, the resin layer on the side to be provided with an image forming layer is a biaxially stretched polyester resin layer. After a sub-coating layer is imparted at the time of stretching to at least the image forming layer side surface of the biaxially stretched polyester resin layer, the side of the resin layer on the side opposite to the sub-coating layer and the base material are laminated, by which the base for the image material is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a support for an image material, wherein the resin layer on the side of the substrate on which the image forming layer is provided is covered with a biaxially stretched polyester resin layer, The present invention relates to a support for an image material in which a layer is provided with a subcoat layer at the time of stretching and then laminated with a substrate. 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 glossiness, excellent adhesiveness, and excellent film forming properties. The present invention also relates to a support for image materials having low oxygen permeability and excellent surface smoothness.

[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 constituting 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, a resin-coated paper-type image material support in which a surface of a substrate, particularly a substrate mainly composed of natural pulp, on which an image forming layer is provided, is coated with a resin layer, still has some serious problems. In fact, there are still many problems and satisfactory results have not yet been obtained.

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 typified 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.

[0018]

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 provides a support for image materials that has a high apparent glossiness, is excellent in adhesion and film-forming properties, has low oxygen permeability, and has excellent surface smoothness. It is something that is possible.

[0019]

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, in which at least one surface of the base material is a paper containing natural pulp as a main component and at least one surface of the base material is coated with a resin layer, and the resin on the side on which the image forming layer is provided. Layer is a biaxially stretched polyester resin layer, at least on the image forming layer side surface of the biaxially stretched polyester resin layer, after applying a subcoat layer during stretching,
An image material support, characterized in that the opposite side of the subcoat layer of the resin layer and the substrate are laminated.

2. In the above invention 1, the biaxially stretched polyester resin layer is any one of a naphthalenedicarboxylic acid polyester resin layer, a sulfonic acid-modified polyester resin layer and a biodegradable polyester resin layer.
A support for an image material, wherein the support is a seed.

3. The invention according to the invention 1 or 2, wherein the subcoat layer is provided between the longitudinal stretching and the transverse stretching.

4. In the above invention 1, 2 or 3, 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. A feature of the invention is a support for an image material.

5. In the above invention 4, the invention is directed to a support for an image material, wherein the subcoat layer contains the subcoat agent and colloidal silica.

6. Any one of the above inventions 1 to 5
In the invention, there is provided a support for an image material, wherein an undercoat layer containing gelatin as a main component is provided on the subcoat layer.

7. Any one of the above inventions 1 to 6
The invention provides a support for an image material, wherein the biaxially stretched polyester resin layer provided on the surface on which the image forming layer is provided is a white polyester resin layer.

8. In the above invention 7, the invention is directed to a support for image materials, 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, and is an invention of an image material support.

10. An invention according to the eighth aspect, wherein the organic particles in the white polyester resin layer are organic particles having no compatibility with the white polyester resin.

11. In any one of the above inventions 1 to 10, when laminating the biaxially stretched polyester resin layer and the base material, the biaxially stretched polyester resin layer and the base material are laminated via an adhesive layer. It is an invention of a support for an image material characterized by the following.

12. In the above invention 11, the invention is directed to a support for an image material, wherein a heating treatment is performed after laminating between a biaxially stretched polyester resin layer and a base material via an adhesive layer. It is.

13. In the above invention 12, the invention is directed to a support for an image material, wherein the heating treatment is performed at 35 ° C. to 100 ° C. for at least one hour.

14. In any one of the inventions described in the above inventions 1 to 13, the resin layer provided on the substrate on the side opposite to the side on which the image forming layer is provided may be a polyolefin resin layer. It is an invention.

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

16. In the above invention 15, the base material is:
The invention provides an image material support, wherein both ends thereof are heat-sealed.

17. In any one of the above inventions 1 to 16, JIS K-7 of the support for the image material may be used.
Oxygen permeability measured by method B of No. 126 is 40 cc / m
The invention is directed to a support for an image material, which is not more than ² / day.

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

19. The present invention relates to a method for producing a support for an image material, in which at least one surface of the base material is a paper containing natural pulp as a main component, and the image forming layer is provided with an image forming layer. The biaxially stretched polyester resin layer is a biaxially stretched polyester resin layer, and at least a surface of the biaxially stretched polyester resin layer on the image forming layer side is provided with a subcoat layer at the time of stretching. The invention provides a method for producing a support for an image material, comprising laminating a side and the substrate.

20. In the above invention 19, the biaxially stretched polyester resin layer is any one selected from a naphthalenedicarboxylic acid polyester resin layer, a sulfonic acid-modified polyester resin layer, and a biodegradable polyester resin layer. The invention is directed to a method for producing a support for an image material.

21. The invention according to the invention 19 or 20, wherein the subcoat layer is provided between the stretching in the machine direction and the stretching in the cross paper direction.

22. In the above invention 19, 20, or 21, 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. Of a method for producing a support for an image material.

23. In the above invention 22, a method of producing a support for an image material, wherein the subcoat layer and the colloidal silica are contained in a subcoat layer.

24. The invention according to any one of the inventions 19 to 23, wherein a subbing layer containing gelatin as a main component is provided on the subcoat layer. .

25. The support for an image material according to any one of the inventions 19 to 24, wherein the biaxially stretched polyester resin layer provided on the surface on which the image forming layer is provided is a white polyester resin layer. It is an invention of a method for producing a body.

26. An invention of the above invention 25, 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. In any one of the inventions 19 to 28 described above, when laminating the biaxially stretched polyester resin layer and the base material, the lamination is performed between the biaxially stretched polyester resin layer and the base material via an adhesive layer. An invention of a method for producing a support for an image material, characterized in that:

30. In the above invention 29, an invention of a method of manufacturing a support for an image material, comprising laminating a biaxially stretched polyester resin layer and a base material via an adhesive layer, and then performing a heating treatment. It is.

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. The method according to any one of the inventions 19 to 31, 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. It is an invention of a method.

33. The invention according to any one of the inventions 19 to 32, wherein the base material is obtained by coating both surfaces 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. In any one of the inventions 19 to 34 described above, the JIS K-
The oxygen permeability measured by the B method of 7126 was 40 cc /
m ² / day or less, which is an invention of a method for producing a support for an image material, characterized by being not more than m ² / day.

36. 35. The method for producing a support for an image material according to any one of the inventions 19 to 35, wherein the average surface roughness (SRa) of the side on which the image forming layer is provided is 0.15 μm or less. Invention.

[0056]

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

In the present invention, the biaxially stretched polyester resin refers to not only a polyester resin obtained by biaxially stretching a thermoplastic resin consisting of polyester alone but also a range in which the resin properties of the main component polyester do not vary practically. Polyester resins which are biaxially stretched by adding other polymers, additives and the like are also included.

Examples of the biaxially stretched polyester resin used in the practice of the present invention include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid and ethylene glycol, 1,3-propanediol, 1,4 Polymers of condensates with glycols such as butanediol, for example polyethylene terephthalate,
Examples thereof include polyethylene 2,6-dinaphthalate, polypropylene terephthalate, polybutylene terephthalate, and the like, and copolymers of these materials that are biaxially stretched.

The biaxially stretched sulfonic acid-modified polyester resin used in the practice of the present invention is a biaxially oriented 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. It has been stretched. Specific examples of the aromatic dicarboxylic acid having a metal sulfonate include 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfoterephthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid, and the like. Compounds obtained by substituting sodium with another metal, for example, potassium, lithium, ammonium salts, phosphonium salts and the like can be mentioned. Further, an antistatic polyester film as disclosed in JP-A-4-24843 can also be used.

The biaxially stretched 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, melt flow rates, etc. (Hereinafter JIS
Test temperature 190 ° C, test load 2.
The melt flow rate measured under a condition of 16 kg may be abbreviated as MFR), a molecular weight and a molecular weight distribution can be used, and usually, the melting point is 85 to 130 ° C and the density is 1.0 g / cm ^3. As described above, the MFR is 0.1 to 50 g / 10 minutes,
Those having a number average molecular weight (Mn) of 30,000 to 60,000, a weight average molecular weight (Mw) of 140,000 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.

The above various polyester resins are:
What is necessary is just to perform a biaxial stretching process by a conventional method, and to make 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,
The film is stretched 2.5 to 4.0 times in the transverse direction at 80 ° C to 145 ° C, and heat-set at 180 ° C to 240 ° C as necessary.

It is preferable that the polyester resin before biaxial stretching contains various inorganic particles and / or organic particles. By doing so, at the time of biaxial stretching, voids are formed around the particles, and white opaque 2
An axially stretched polyester resin film is obtained.

Examples of the inorganic particles include titanium dioxide, barium sulfate, barium carbonate, calcium carbonate, lithopone, alumina white, zinc oxide, silica, antimony trioxide, and titanium phosphate. 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. Examples of titanium dioxide include those coated with an inorganic substance such as hydrated alumina treatment, hydrated silicon dioxide-based 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. It can be used as appropriate. 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. Further, known additives such as a fluorescent whitening agent and an antioxidant can be added to the resin constituting the biaxially stretched polyester resin film. 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, but is usually selected so as to be between 5% by weight and 40% by weight.

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 whose compatibility with a polyester resin has been eliminated by three-dimensionally crosslinking 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, and any other polymer may be used as long as it is a polymer that 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.

In the present invention, the various biaxially stretched polyester resin films obtained as described above may be 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.

In the dry lamination, an adhesive is applied to the biaxially stretched polyester resin film provided with the subcoat layer of the present invention, dried, and then the substrate and the biaxially stretched polyester resin film are heated at about 100 ° C. In this case, a solvent type urethane-based resin, a vinyl-based resin, an acrylic-based resin, a polyamide-based resin, an epoxy-based resin, a rubber-based resin, or the like is used as the adhesive.
１５15 g / m ^{2 are} used.

The solvent-free dry lamination is a reaction-curing adhesive such as a one-component moisture-curable urethane adhesive or a two-component urethane adhesive to the biaxially stretched polyester resin film provided with the subcoat layer of the present invention. 0.1 to 1
This is a method of applying 0.0 g / m ² and bonding to a base material, and then allowing the adhesive to react and harden by allowing time to elapse, thereby firmly bonding the biaxially stretched polyester resin film and the base material.

In the thermal lamination, a wax such as petroleum wax, synthetic wax and polybutene and a polymer such as polybutene adhesive, ethylene copolymer and polyolefin elastomer are added to the biaxially stretched polyester resin film provided with the subcoat layer of the present invention. This is a method in which an adhesive of the type 0.1 to 15.0 g / m ^{2 is} applied and bonded to a substrate. At this time, a tackifier resin may be used. In applying these various lamination methods,
In the present invention, an adhesive layer is provided on the surface of the biaxially stretched polyester resin layer opposite to the surface on which the image forming layer is formed. When a biaxially stretched polyester resin film is laminated on the surface of the substrate opposite to the surface on which the image forming layer is formed, 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, it is preferable to heat the laminate after laminating it between the biaxially stretched polyester resin layer and the substrate via an adhesive layer. The temperature of the heating treatment is usually from 35 ° C. to 100 ° C. for at least one hour.

In this manner, a support for an image material obtained by laminating a base material and a biaxially stretched polyester resin film is obtained. In the practice of the present invention, a subcoat applied during the biaxial stretching process can be applied. , Is one of the most important matters.

A conventional image material support in which a substrate and a polyester resin film are laminated and a liquid containing a sub-coating agent is applied to the image forming side is subjected to a sub-coating and 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 of the present invention is provided with a sub-coating agent applied to at least the image-forming side when the polyester resin is biaxially stretched (sub-coating may be applied to the opposite side). It is. Biaxial stretching is performed at a relatively high temperature, and at this time, a sub-coating agent is applied.
Since the process is completed (on-line coating), the occurrence of surface irregularities can be suppressed extremely well without the above-described problems of the application / drying process itself and the problems associated with the increase in the number of winding processes. 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 particularly noteworthy is that the image material support of the present invention to which the subcoating agent has been applied in this way is
What is required is to obtain a film having a remarkably excellent film-forming property, which cannot be obtained with a conventional support for image materials.

The application of the subcoating agent in 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 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. Also, 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 containing, for example, gelatin as a main component 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 an apparent glossiness and a higher glossiness than a support for a resin-coated image material produced by melt-extrusion coating of an ordinary polyethylene resin. The surface smoothness is remarkably excellent, and in spite of 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 base material and the resin layer is also excellent. It is a thing. Further, generally, the support for an image material of the present invention is JIS K-71.
Oxygen permeability measured by Method B of No. 26 is 40 cc / m ^2.
/ Day, and is excellent in fading property and light fastness, and is an excellent support for image materials having long-term image preservability.

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, the substrate is coated with a polyethylene resin on both surfaces thereof, and is adhered to the surface of the biaxially stretched polyester resin film to which the sub-coat layer is applied at the time of stretching, on the side opposite to the side on which the image forming layer is provided. After providing the adhesive layer, after providing the adhesive layer on the polyethylene resin layer on the side where the image material support or the image forming layer provided with the base material laminated with the image material,
This is a support for an image material, which is laminated on a surface of the biaxially stretched polyester resin film to which a subcoat layer is provided at the time of stretching, on the side opposite to the side on which the image forming layer is provided. In this case, in the above description, an adhesive layer may be provided on both surfaces of the polyethylene resin layer and the biaxially stretched polyester resin layer to be bonded.

Further, the above-mentioned base material having both ends heat-sealed provides excellent quality in the above-mentioned various properties, and particularly, the paper powder from the paper end (kobako). Since there is no scattering, it is useful as a support for image materials that repels paper dust troubles.

In order to produce a substrate in which both sides of the paper are coated with a polyethylene resin, the polyethylene resin may be coated on both sides with a resin 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 on the side on which the image forming layer is provided and the biaxially stretched polyester resin film layer may be formed using the above-mentioned various adhesives, and if the heat treatment is also performed in the same manner. Good.

The support for various image materials according to the present invention includes:
Various properties, that is, the apparent glossiness and surface smoothness are much more excellent, the film forming property is extremely good, and, of course, the adhesiveness between the substrate and the biaxially stretched polyester resin film layer is also excellent. . In addition, oxygen permeability is low, fading,
It is an excellent support for image materials having excellent light fastness and excellent long-term image preservability.

As the substrate used in the practice of the present invention, natural pulp paper mainly composed of ordinary natural pulp 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 can 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 color pigments, coloring dyes, fluorescent brighteners and the like described or exemplified in JP-A-204251, JP-A-1-66537 and the like in an appropriate combination.

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-based, butadiene-methyl methacrylate-based copolymers and emulsions or latexes of carboxy-modified copolymers thereof, 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 incorporate pH adjusters such as titanium oxide and titanium oxide, hydrochloric acid, phosphoric acid, citric acid, caustic soda, and other additives such as the above-mentioned coloring pigments, coloring dyes, and fluorescent brightening agents as appropriate.

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 with the following stylus type three-dimensional surface roughness meter is 0.18 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 0.18 μm or less, more preferably 0.15 μm or less, still more preferably 0.12 μm or less, and 0.10 μm or less. The following are particularly preferred.

As the base material mainly composed of natural pulp used for obtaining the support for an image material of the present invention having excellent surface smoothness, 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.

[0096]

(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 the area of the sample surface area.

More specifically, as a stylus type three-dimensional surface roughness meter and a three-dimensional roughness analyzer, 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) The natural pulp to be used is preferably a hardwood bleached kraft pulp or a combination of a hardwood bleached kraft pulp and a hardwood bleached sulphite pulp. 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
As described above, it is preferable to contain or coat at least 2.2 g / m ² or more.

(4) After the paper is made, at least two or more series of calendering processes are performed on the paper using a machine calender, a super calender, a heat calender, 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.

On the back surface of the image material support of the present invention, after performing an activation treatment such as a corona discharge treatment or a flame treatment, it is possible to coat various back coat layers for the purpose of preventing static charge and the like. it can. The back coat layer includes JP-B-52-18020, JP-B-57-9059, and JP-B-57-53.
No. 940, Japanese Patent Publication No. 58-56859, Japanese Patent Application No. 59-214849
JP, JP-A-58-184144 and the like or inorganic antistatic agents described or exemplified, an organic antistatic agent, a hydrophilic binder, a latex, a curing agent, a pigment, a surfactant and the like may be appropriately combined and contained. it can.

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, reverse 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 at the time of generation and dispersion of silver halide may be incorporated in an appropriate combination.

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 processed with a developer containing a development accelerator such as benzyl alcohol, thallium salt, phenidone, or 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, amide wax, solid waxes such as Teflon powder,
Fluorine-based, phosphate-based surfactants, silicone oils, and the like. Among these release agents, silicone oil is most preferred. As the above silicone oil,
An oily substance can be used, but a curable type is preferred. Examples of the curable silicone oil include a reaction curable type, a photocurable type, and a catalyst curable type, and a reaction curable type silicone oil is particularly preferable. Examples of the reaction-curable silicone oil include an amino-modified silicone oil and an epoxy-modified silicone oil. The amount of the reactive silicone oil added is preferably 0.1 to 20% by weight in the image receiving layer. As the pigment, silica, calcium carbonate,
Extenders such as titanium oxide and zinc oxide are preferred. Also,
The thickness of the image receiving layer is preferably 0.5 to 20 μm,
-10 μm is more preferred.

The support for an image material in the present invention can be used as a support for various ink jet recording materials provided with 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, the sharpness of the image, and the like. Specific examples of the binder 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 an anhydride of dibasic acid such as fumaric acid. , Ordinary polyvinyl alcohol of various saponification degrees,
Carboxy-modified, cationic-modified and amphoteric polyvinyl alcohol and their derivatives, starches such as oxidized starch, cationized starch, etherified starch, cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose, polyvinylpyrrolidone, polyvinylpyridium halide, polyacryl Synthetic polymers such as acid soda, acrylic acid methacrylic acid copolymer salt, polyethylene glycol, polypropylene glycol, polyvinyl ether, alkyl vinyl ether / maleic anhydride copolymer, styrene / maleic anhydride copolymer and salts thereof, and polyethyleneimine Conjugated diene copolymer latex such as styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, polyvinyl acetate, vinyl acetate
Maleic acid ester copolymer, vinyl acetate / acrylic acid ester copolymer, vinyl acetate polymer latex such as ethylene / vinyl acetate copolymer, acrylic acid ester polymer, methacrylic acid ester polymer, ethylene / acrylic acid ester Acrylic polymer or copolymer latex such as copolymer, styrene / acrylate copolymer, vinylidene chloride copolymer latex, etc., or functional group-containing monomer such as carboxyl group of these various polymers Functional group-modified polymer latex, melamine resin, aqueous adhesive such as thermosetting synthetic resin such as urea resin and polymethyl methacrylate, polyurethane resin, unsaturated polyester resin, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral, Synthetic resin-based adhesive such as alkyd resin, Japanese Patent Publication 3-24906 No., JP-A-3-281383,
Inorganic binders such as alumina sol and silica sol described in or exemplified in Japanese Patent Application No. 4-407725 can be used, and these can be used alone or in combination.

The ink-receiving layer of the ink-jet recording material according to the present invention may contain various additives in addition to the binder. For example, as a surfactant, a long-chain alkylbenzene sulfonate, a long-chain, preferably an anionic surfactant such as a branched alkyl sulfosuccinate ester salt, a long-chain, preferably a polyalkylene oxide of a phenol containing a branched alkyl group. Nonionic surfactants such as ethers and polyalkylene oxide ethers of long-chain alkyl alcohols, JP-B-47-9303
Silane coupling agents such as γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, such as fluorinated surfactants described in US Pat. No. 3,589,906 and the like; As a polymer hardener, an active halogen compound, a vinyl sulfone compound, an aziridine compound, an epoxy compound,
Acryloyl compounds, hardening agents such as isocyanate compounds, as preservatives, P-hydroxybenzoic acid ester compounds described or exemplified in JP-A-1-102551, benzisothiazolone compounds, isothiazolone compounds, and the like, JP-A-63-204251 Publication, JP-A 1-266537 JP or illustrated or exemplified color pigments, coloring dyes, fluorescent whitening agents,
Sodium hydroxymethanesulfonate and sodium P-toluenesulfinate as yellowing inhibitors; benzotriazole compounds having a hydroxy-dialkylphenyl group at the 2-position as ultraviolet absorbers; JP-A No. 105337/1992 discloses fine or organic particles such as starch granules, barium sulfate and silicon dioxide having a particle size of 0.2 to 5 μm, such as polyhindered phenol compounds described or exemplified in JP-B-105245. Organopolysiloxane compounds described or exemplified in gazettes and the like, p
As the H regulator, various additives such as octyl alcohol, silicon-based antifoaming agent such as caustic soda, sodium carbonate, sulfuric acid, hydrochloric acid, phosphoric acid, and citric acid can be appropriately combined and contained.

[0111]

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, after the corona discharge treatment is applied to the paper surface (back surface) opposite to the side on which the image forming layer is coated, 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 the liquid honing method,
The surface roughness of the back layer surface after application of the following back layer was such that the center surface average roughness (SRa) was 1.15 μm.
In addition, the back layer applied the following back layer coating liquid on-machine after corona discharge treatment to the back surface resin layer. As dry weight, colloidal silica: styrene latex =
The coating liquid for the back layer containing 0.21 g / m ² of sodium polystyrene sulfonate and an appropriate amount of a coating aid in addition to 1.01 g / m ² in terms of latex (calculated on solid weight). Coating was performed with the coating amount.

<Production of Biaxially Stretched Polyester Resin Film for Surface> 100 parts by weight of a polyethylene terephthalate resin having an intrinsic viscosity of 0.65 and hydrous aluminum hydroxide (0.75% by weight in terms of Al ₂ O _{3 with} respect to titanium dioxide) The raw material to which 20 parts by weight of the anatase type titanium dioxide pigment surface-treated was added was kneaded in a Banbury mixer to obtain a polyethylene terephthalate resin composition containing the titanium dioxide pigment. This was put into a twin screw extruder, melted and extruded with a slit die, and solidified and adhered to a cooling rotary roll to obtain an unstretched sheet containing a titanium dioxide pigment.
Subsequently, the unstretched sheet was longitudinally stretched 3.5 times at 110 ° C. with a roll stretching machine, and then stretched to 120 ° C. with a tenter.
And then heat-set at 210 ° C to a thickness of 3
A 6 μm biaxially stretched polyester resin film was obtained. At this time, after the longitudinal stretching and before the transverse stretching, 20 parts by weight of vinylidene chloride latex, 5 parts by weight of N-methylpyrrolidone, colloidal silica (Snowtex ZL: manufactured by Nissan Chemical Industries, Ltd.)
Water was added to 5 parts by weight of the subcoating agent composition, and the total amount of the subcoating solution was adjusted to 100 parts by weight. The thickness of one side of the biaxially stretched polyester resin film was 0.74 μm (solid content).
It applied so that it might become. In addition, the following core-shell type latex was used as vinylidene chloride latex. Core-shell type latex (core 90% by weight, shell 10% by weight) Core 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)

Example 1 On the side of the biaxially stretched polyester resin film obtained as described above on which the subcoat layer was not provided, an adhesive containing a urethane compound as a main component was added at 4 g / m ² (solid Min.), And a paper surface on the opposite side on which the back surface resin layer obtained as described above is formed (hereinafter, may be referred to as a paper surface) is overlaid thereon. They were bonded together by pressure bonding with a roll. Thereafter, the support was heated at 50 ° C. for 2 days in a heating chamber to produce the image material support of Example 1.

Example 2 In the above <Manufacture of paper>, a paper having an average roughness (SRa) of 1.70 μm was used by appropriately adjusting the length-weighted average fiber length and beating. Is
In the same manner as in Example 1, the image material support of Example 2 was produced.

Example 3 The same procedure as in Example 1 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 3 was produced.

Example 4 A resin having a resin 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.
The image material support of Example 4 was produced in the same manner as in Example 1 except that the base material coated with the resin on both sides after the m-width heat sealing was used. 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 put into a twin screw extruder, and melt-extruded and coated to a resin thickness of 15 μm at a paper traveling speed of 200 m / min. The surface of the containing polyethylene resin layer was processed into a glossy surface. At that time, a chromium-plated fine rough surface was used as the cooling roll.

Example 5 In the above <Manufacture of paper>, the paper having a center plane average roughness (SRa) of 1.80 μm was used by appropriately adjusting the length-weighted average fiber length and beating. Except that it was heated at 50 ° C for 55 minutes in the heating room,
In the same manner as in Example 1, the image material support of Example 5 was produced.

Example 6 In the above <Production of Biaxially Stretched Polyester Resin Film for Surface>, on the sub-coated layer, 1.5 g of lime-treated gelatin and 10% by weight methanol solution of butyl parahydroxybenzoate were added. 0.35 g, 0.45 g of a 5% by weight mixture of methanol and water of sulfosuccinic acid-2-ethylhexyl ester salt.
0.1 g of gelatin coating amount
A support for an image material of Example 6 was produced in the same manner as in Example 1 except that on-machine coating was performed so as to be / m ² .

Comparative Example 1 In the above <Production of Biaxially Stretched Polyester Resin Film for Surface>, except that no subcoat was applied, the biaxially oriented film was produced in the same manner as in Example 1 except that the image forming layer was provided. A sub-coat liquid containing the same sub-coat agent composition as in Example 1 was applied to the polyester resin layer at a thickness of 0.2 μm.
(Comparative Example 1) An image material support of Comparative Example 1 was produced in the same manner as in Example 1, except that the composition was applied so as to have a solid content and dried at 180 ° C. for 3 minutes.

Comparative Example 2 100 parts by weight of a polyester resin for extrusion coating (Kodapet G: manufactured by Eastman Chemical Co., Ltd.) on the surface of the paper provided with the backside resin layer obtained in the above <Formation of Backside Resin Layer>. And hydrous aluminum hydroxide (A for titanium dioxide)
A raw material to which 20 parts by weight of an anatase type titanium dioxide pigment surface-treated with 0.75% by weight (as L ₂ O ₃ ) was added and kneaded in a Banbury mixer to obtain a polyethylene terephthalate resin composition containing the titanium dioxide pigment. A support for an image material produced in the same manner as in Example 1 except that this resin composition was charged into a twin-screw extruder and subjected to melt extrusion coating to a resin thickness of 36 μm was used as Comparative Example 2. At that time, a chromium-plated fine rough surface was used as the cooling roll.

Comparative Example 3 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 1 was melt-extruded and coated to a resin thickness of 36 μm using a twin-screw extruder in the same manner as in Example 4.
A sub-coat liquid containing the same sub-coat agent composition as in Example 1 was applied on the polyethylene resin layer to a thickness of 0.2 μm.
A support for an image material manufactured by coating so as to have (solid content) was Comparative Example 3.

The supports for image materials obtained in the respective Examples and Comparative Examples were 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-blinding inhibitor, and a magenta color coupler are 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 so that 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,
Contains 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 developed stably. After drying, a photographic print was prepared. Alternatively, burned samples of white solid (unexposed) and black solid (black color) were separately 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 processing 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 visual glossiness of the photographic prints was visually judged comprehensively by 10 monitors, and 1
Grade evaluation was performed on a scale of 0. 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> As an evaluation method of the adhesion between the paper of the image material support and the polyester resin layer, the paper layer of the sample and the polyester resin layer on the surface were evaluated. 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. Evaluation criteria are as follows: Δ: 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 4 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 the 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 is determined according to JIS K 712 for each support.
The oxygen permeability (cc / m ² / da) of the image material support was determined by measuring under the following measurement conditions in accordance with Method B (isobaric method) of No. 6.
y). 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.

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

[0133]

[Table 1] Note 1) * The adhesiveness of Example 5 tended to peel off at the adhesive layer. Note 2) ** The average roughness of the center plane of Comparative Example 1 had many surface irregularities, and was itself meaningless to measure.

<Evaluation> An image material support in which a paper containing natural pulp as a main component is used as a base material and at least one surface of the base material is coated with a resin layer, and a side on which an image forming layer is provided. Is a biaxially stretched polyester resin layer,
At least a surface of the biaxially stretched polyester resin layer on the image forming layer side is provided with a subcoat layer at the time of stretching, and then the opposite side of the resin layer from the subcoat layer and the substrate are laminated. It has been found that the support for image materials of the present invention can be obtained with excellent quality. Example 1, which is one embodiment of the present invention, shows the important quality characteristics as a support for an image material, such as the apparent glossiness, adhesiveness, film-forming property, oxygen permeability and center plane average roughness of a photographic print. Excellent results were obtained for all five items.

Further, the center plane average roughness (SRa) is 1.7
The image material support of Example 2 obtained in the same manner as in Example 1 except that the paper having a thickness of 0 μm was used was different from that of Example 1 in the apparent glossiness and the average center plane of the photographic print. Although the surface tended to be slightly inferior in terms of roughness, a support for an image material was obtained which still had a high apparent glossiness and a quality in which the center-surface average roughness was practically no problem at all.

The image material support of Example 3 obtained in the same manner as in Example 1 except that the paper was produced by size-pressing with a size press solution containing three times the amount of carboxy-modified polyvinyl alcohol when producing the paper. As in Example 1, an excellent quality image material support was obtained as in Example 1, but the apparent glossiness of the photographic print was more excellent. Above all, significantly better results were obtained in oxygen permeability.

<Formation of Back Resin Layer> A paper obtained by heat-sealing both ends of a paper coated with a double-sided resin having a 15 μm-thick polyethylene resin layer formed on the surface of the paper provided with the back resin layer obtained in the above step. The support for an image material of Example 4 obtained in the same manner as in Example 1 was used in all of the five items which are important quality characteristics as a support for an image material.
In addition to excellent results, no paper dust was generated,
It could be advantageously used as a support for an image material which avoids paper dust trouble.

The procedure of Example 1 was repeated, except that paper having a center plane average roughness (SRa) of 1.80 μm was used, and that heating was performed at 50 ° C. for 55 minutes in a heating chamber. In the support for image materials of Example 5, the apparent glossiness, oxygen permeability and center-plane average roughness of the photographic print tended to be slightly inferior, but were within the practical range. In addition, although the adhesiveness tended to peel off at the adhesive layer, the film-forming property was good.

The image material support of Example 6, in which an undercoat layer was further provided on the image material support of Example 1, exhibited excellent properties as in Example 1. In particular, excellent results were obtained with respect to film-forming properties.

<Production of Biaxially Stretched Polyester Resin Film for Surface> In the same manner as in Example 1 except that the subcoat was not applied, the biaxially stretched polyester resin layer on the side on which the image forming layer is provided, A subcoating solution containing the same subcoating agent composition as in Example 1 was applied to a thickness of 0.
The image material support of Comparative Example 1 obtained in the same manner as in Example 1 except that it was coated at 2 μm (solid content) and then dried at 180 ° C. for 3 minutes has an adhesive property and an oxygen permeability. Was good, but the film sticking property was only about the lower limit of practical use. In particular, the photographic print has a low apparent glossiness and is problematic in practical use. In particular, the surface roughness is remarkable, and the measurement of the center plane average roughness can only provide a support for an image material of a meaningless quality. I couldn't.

<Formation of Backside Resin Layer> The procedure of Example 1 was repeated except that the surface of the paper provided with the backside resin layer obtained in Step 1 was melt-extruded and coated to a polyester resin thickness of 36 μm for extrusion coating. The image material support of Comparative Example 2 obtained in the same manner gave good results with respect to the apparent glossiness, oxygen permeability and center plane average roughness of the photographic print, but the adhesiveness and film-forming properties were good. For, only remarkably inferior results were obtained. In addition, during operation, there is a very serious problem in terms of workability, such as a large neck-in and occurrence of surging.

<Formation of Back Resin Layer> The surface of the paper provided with the back resin layer obtained in the above was subjected to corona discharge treatment, and then a titanium dioxide pigment-containing polyethylene resin composition was melt-extruded to a resin thickness of 36 μm. The support for an image material of Comparative Example 3 obtained by coating the surface of paper with a titanium dioxide pigment-containing polyethylene resin composition having good adhesion and film-forming properties,
Although the apparent glossiness of the photographic print was in a practically usable range, only a support for an image material having a high oxygen permeability was obtained.

[0143]

According to the present invention, excellent quality can be achieved in terms of print glossiness, adhesion, film adhesion, oxygen permeability and center plane average roughness, which are important properties as a support for image materials. The present invention can provide an excellent resin-coated paper-type image material-based support made of paper and having no problem in operation.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI B41M 5/40 G03C 1/91 5/38 B29C 55/12 G03C 1/91 B41M 5/26 B // B29C 55/12 101A B29K 67:00

Claims (36)

[Claims] 1. An image material support comprising a paper mainly composed of natural pulp as a base material and at least one surface of the base material covered with a resin layer, on the side on which the image forming layer is provided. The resin layer is a biaxially stretched polyester resin layer, and at least a surface of the biaxially stretched polyester resin layer on the image forming layer side is provided with a subcoat layer at the time of stretching. A support for an image material, wherein the support is laminated with the substrate. 2. The biaxially stretched polyester resin layer is one of a naphthalenedicarboxylic acid polyester resin layer, a sulfonic acid-modified polyester resin layer and a biodegradable polyester resin layer. The support for an image material according to claim 1. 3. The support for an image material according to claim 1, wherein the subcoat layer is provided between the longitudinal stretching and the transverse stretching. 4. A subcoating agent comprising at least one of a water-dispersible copolymer polyester, a vinylidene chloride copolymer latex and a polyamine polyamide epichlorohydrin resin. 4. The support for an image material according to 2, 3 or 4. 5. The sub-coat layer contains the sub-coat agent and colloidal silica.
The support for an image material as described above. 6. An undercoat layer comprising gelatin as a main component is provided on the sub-coat layer.
The support for image materials according to 2, 3, 4 or 5. 7. The method according to claim 1, wherein the biaxially stretched polyester resin layer provided on the surface on which the image forming layer is provided is a white polyester resin layer. Support for image materials. 8. The support for an image material according to claim 7, 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 biaxially stretched polyester resin layer and the base material, the biaxially stretched polyester resin layer and the base material are laminated via an adhesive layer. The support for image materials according to 2, 3, 4, 5, 6, 7, 8, 9 or 10. 12. The image material support according to claim 11, wherein a heating treatment is performed after laminating between the biaxially stretched polyester resin layer and the base material via an adhesive layer. body. 13. The heat treatment at 35 ° C. to 100 ° C. for at least one hour.
2. The support for an image material 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
Oxygen permeability measured by Method B of No. 26 is 40 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 method for producing a support for an image material, wherein a paper mainly composed of natural pulp is used as a base material, and at least one surface of the base material is coated with a resin layer. The resin layer on the side to be provided is a biaxially stretched polyester resin layer, and at least a surface of the biaxially stretched polyester resin layer on the image forming layer side is provided with a subcoat layer at the time of stretching.
A method for producing a support for an image material, comprising laminating the opposite side of the subcoat layer of the resin layer and the substrate. 20. The biaxially stretched polyester resin layer is one selected from the group consisting of a naphthalenedicarboxylic acid polyester resin layer, a sulfonic acid-modified polyester resin layer, and a biodegradable polyester resin layer. A method for producing a support for an image material according to claim 19. 21. The method for producing a support for an image material according to claim 19, wherein the subcoat layer is provided between the stretching in the machine direction and the stretching in the transverse direction. 22. A 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. 22. The method for producing a support for an image material according to claim 20, 20 or 21. 23. The method for producing a support for an image material according to claim 22, wherein the subcoat layer contains the subcoat agent and colloidal silica. 24. An undercoat layer comprising gelatin as a main component is provided on the subcoat layer.
24. The method for producing a support for an image material according to 9, 20, 21, 22 or 23. 25. The method according to claim 19, wherein the biaxially stretched polyester resin layer provided on the surface on which the image forming layer is provided is a white polyester resin layer.
25. The method for producing a support for an image material according to 22, 22, 23 or 24. 26. The method according to claim 25, wherein at least one of inorganic particles and organic particles is contained in the white polyester resin layer. 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 biaxially stretched polyester resin layer and the base material, the biaxially stretched polyester resin layer and the base material are laminated via an adhesive layer. 20, 21, 22, 23, 24, 25, 2,
29. The method for producing a support for an image material according to 6, 27 or 28. 30. The support for an image material according to claim 29, wherein the laminate is interposed between the biaxially stretched polyester resin layer and the base material via an adhesive layer, and then subjected to a heating treatment. Production method. 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 base material opposite to the side on which the image forming layer is provided is a polyolefin resin layer.
The method for producing a support for image materials according to 4, 25, 26, 27, 28, 29, 30 or 31. 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 40 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.