JP4409306B2 - Support for imaging material and method for producing the same - Google Patents

Description

  In the present invention, a paper mainly composed of natural pulp is used as a substrate, and one paper substrate (hereinafter sometimes abbreviated as a base paper) is coated with a resin capable of forming a film, and an image on the opposite side is provided. The present invention relates to a support for image material whose base paper surface is coated with a polyolefin resin. More specifically, there is no cooling roll contamination, and the resinous smoke generated from the molten resin is reduced, resulting in the disadvantage of R sauce. Therefore, the present invention relates to a support for image material that can be eliminated, and hence a uniform image surface can be obtained and can be stably and rapidly produced, and a method for producing the same.

  2. Description of the Related Art Conventionally, a resin-coated paper image material support in which a base paper surface for the image material support is coated with a resin capable of forming a film is well known. For example, a technique for a support for image material in which both surfaces of a base paper are coated with a polyolefin-based resin is disclosed (for example, see Patent Document 1). In addition, since the rapid photographic development processing method for silver halide light-sensitive materials has been applied, photographic paper with both sides of the base paper coated with polyolefin resin has been mainly put into practical use. In order to impart sharpness, the resin layer on the forming side usually contains a titanium dioxide pigment.

  However, as a resin composition for coating the base paper surface on which the image constituent layer is provided (hereinafter, the base paper surface on which the image constituent layer is provided may be abbreviated as the front surface, and the opposite base paper surface may be abbreviated as the back surface). Even when the resin composition disclosed in 1) is used, it has been found that when producing a support for a resin-coated paper type image material using paper as a substrate, a serious problem occurs. Further, the support for resin-coated paper type image material still has a serious problem in quality.

  That is, first, a polyolefin resin-coated paper is formed by extruding a melted polyolefin resin composition from its slit die into a film on a base paper that normally travels, and casting and coating it. It is produced by a series of processes in which it is pressure-bonded between a roll and a cooling roll and peeled off from the roll after cooling. However, when a conventionally known polyolefin resin composition is used as the resin composition for covering the surface of the base paper, the main component is a polyolefin resin composition called a cooling roll stain or a modified product thereof on the cooling roll. There was a tendency for stains to occur. Production of polyolefin resin-coated paper is carried out by operating the melt extruder for at least 2-3 days from the start of operation, usually for one week, sometimes for one month, but if the continuous operation period is long The longer the length, the worse the cooling roll dirt, the more likely it was to accumulate.

  When a lot of cooling roll dirt begins to occur during the production of polyolefin resin-coated paper, the releasability of the polyolefin resin-coated paper from the cooling roll deteriorates, and the adhesiveness between the cooling roll and the resin layer increases, leading to the cooling roll side. Since the tendency of the resin layer to increase is increased, the adhesion between the base paper and the resin layer is unevenly weakened. As a resin-coated paper for this purpose, there is a problem that it is completely inappropriate and has no commercial value. Especially during high-speed production, accumulated cooling roll dirt is wound up while adhering to the resin layer, and after providing an image constituting layer, an inhomogeneous state appears on the image surface, for use as a support for image materials. However, this resin-coated paper sometimes causes a serious problem that a fatal quality failure occurs. For this reason, it is necessary to take sufficient measures to prevent the cooling roll from being soiled.

Secondly, a large amount of oily smoke that gives off an unpleasant odor is generated before the polyolefin resin composition is extruded from the slit die and solidified by a cooling roll. The oily smoke is a decomposition product of metal soap or resin, and when it adheres and accumulates on the smoke exhaust hood, it falls onto the cooling roll or the resin coating surface, and stains called R sauce occur. On the surface of the support for image material manufactured as it is, dirt adheres to the resin covering surface, and foreign matter appears on the surface of the support for image material. Moreover, although the apparatus technique which excludes oil smoke is disclosed (for example, refer patent document 2), if the amount of fumes derived from a resin composition is not reduced and the continuous operation time is long, the above-mentioned due to generation of R sagging It was not enough to solve the fundamental problem. Moreover, although the technique which uses a some metal soap for a polyethylene resin composition is described (for example, refer patent document 3), description about the effect of R sagging prevention by using a metal soap in combination is made. The problem of R sauce was not solved. For the reasons described above, there has been a problem that the image material support is inappropriate and the commercial value is lowered.
U.S. Pat. No. 3,501,298 JP-A-6-39902 JP 2002-148760 A

  Accordingly, an object of the present invention is to use a paper mainly composed of natural pulp as a substrate, one base paper surface of which is coated with a resin capable of forming a film, and the opposite base paper surface on which the image forming layer is provided is a polyolefin. In the support for an image material coated with a resin composition and a method for producing the same, there is no chill roll contamination, and the smoke generated from the molten resin is reduced, so that the drawbacks of R sagging are eliminated. An object of the present invention is to provide a support for an imaging material which can obtain a surface and can be stably produced at a high speed, and a method for producing the same.

As a result of intensive studies to solve the above problems, the present inventors have found the following present invention. That is, according to a first aspect of the present invention, there is provided a support for an image material in which a base paper surface on which an image constituting layer is provided is coated with a polyolefin resin layer, wherein the polyolefin resin layer is a single melting point in which two or more kinds of metal soaps are combined. A metal soap composite, a titanium dioxide pigment, and a resin composition mainly composed of a polyolefin resin formed by melt extrusion coating, the metal soap is composed of a saturated fatty acid having 14 or more carbon atoms, and the metal is lithium, It is an invention of a support for imaging material, comprising a combination of calcium or zinc .

  A second invention is a support for image material in which the heat loss at 350 ° C. of the metal soap composite in the first invention is 10% by mass or less.

3rd invention is invention of the support for image materials whose metal of one metal soap is zinc among the metal soap composites in 1st- 2nd invention.

4th invention is invention of the support for image materials in which lithium or calcium is contained in the metal of the other metal soap among the metal soap composites in 3rd invention.

5th invention is invention of the support for image materials in which the fatty acid group of the metal soap in 1st- 4th invention has a hydroxyl group.

A sixth invention is a method for producing a support for imaging material in which one base paper surface is coated with a resin capable of forming a film and the base paper surface on the side where the image constituting layer on the opposite side is provided is coated with a resin. metal soaps composites having a single melting point that combines metal soaps described above, by using a titanium pigment and a polyolefin resin dioxide, the resin composition a method for producing a melt-extrusion coating and image material support, the metal The soap is composed of a saturated fatty acid having 14 or more carbon atoms, and the metal is composed of a combination of lithium, calcium or zinc , and is extrusion coated at a resin temperature of 270 ° C. to 350 ° C. and 350 m / min or more. It is invention of the manufacturing method of the support body for image materials.

  In the present invention, a metal soap composite having a single melting point has a melting point derived from each composite metal soap alone in a spectrum obtained by differential scanning calorimetry (DSC) or differential calorimetry (DTA). In other words, only the eutectic point derived from the metal soap composite was observed. In this case, even if a shoulder is observed in the single peak of the eutectic point derived from the composite, it is within the present invention if the peak of the eutectic point forms a single peak.

  The melting point referred to in the present invention can be determined by performing DSC or DTA. The measurement conditions were 0.01 g of sample, nitrogen flow rate of 40 mL / min, heating rate of 10 ° C./min, heating from 30 ° C. to 300 ° C., and melting point from the spectrum obtained by measurement. Asked.

  The heating loss referred to in the present invention can be generally determined by performing thermogravimetric analysis (TGA). That is, the weight loss rate accompanying decomposition | disassembly can be calculated | required by heating the sample placed in nitrogen atmosphere at a fixed speed. As measurement conditions, the sample amount was 0.01 g, the air flow rate was 300 mL / min, the temperature increase rate was 10 ° C./min, and the sample was heated to 400 ° C. and held for 10 minutes. From the obtained graph, the heat loss at 350 ° C. was determined.

The present invention relates to a metal soap composite having a single melting point in which the polyolefin resin layer is a combination of two or more kinds of metal soaps, a titanium dioxide pigment, wherein the base paper surface on which the image forming layer is provided is coated with a polyolefin resin layer And a resin composition comprising a polyolefin resin as a main component by melt extrusion coating, wherein the metal soap is composed of a saturated fatty acid having 14 or more carbon atoms, and the metal is composed of a combination of lithium, calcium, or zinc. The cooling roll contamination is improved, the amount of oily smoke is reduced, the defects such as R sagging caused by falling on the cooling roll and the resin-coated surface are eliminated, and therefore a uniform image surface is obtained and stable. A support for image material that can be produced and a method for producing the same can be provided.

  As described above, the present invention provides a good support for an image material without the occurrence of cooling roll stains and R sagging. It became clear that the factor was decomposition of the metal soap contained in the polyolefin resin layer. That is, when a polyolefin resin containing a metal soap having low heat resistance is extruded from a slit die into a film state using a melt extruder, these substances are thermally decomposed because they are extruded at a high temperature. As a result, a sticky modified product is formed, and this sticky modified product is deposited on the cooling roll to generate chill roll contamination. On the other hand, the sticky denatured product is also contained in the oily smoke generated when it is extruded from the slit die in a molten state, and when it adheres to and accumulates on the smoke hood, it eventually falls and generates R sagging. It was confirmed that this phenomenon was remarkably promoted by the adhesive denatured product generated by thermal decomposition of metal soap used as a lubricant, rather than the low molecular weight composition contained in the polyolefin resin layer. We have surprisingly found that the use of a metal soap composite having a single melting point that is a combination of two or more types of metal soap improves the cooling roll dirt and R sagging, and is incorporated into the present invention. It came.

In the present invention, a metal soap composite having a single melting point obtained by combining two or more kinds of metal soaps, wherein the metal soaps are composed of saturated fatty acids having 14 or more carbon atoms, and the metals are composed of a combination of lithium, calcium or zinc And a polyolefin resin containing titanium dioxide.

  A metal soap composite having a single melting point forms an equimolar complex due to the difference in polarity, and has both internal and external slip properties. The single melting point is obtained by the eutectic phenomenon due to complex formation, can give a minimum melting point lower than the original metal soap, and even though the melting causes the melting point of the metal soap composite to decrease Less heat loss. If the heat loss of the metal soap composite is 10% by mass or less at 350 ° C., it is more preferable in the present invention because it has high heat resistance. When using metal soaps without compounding, it is natural to select metal soaps with a high melting point in order to prioritize the heat resistance of metal soaps. Since a highly complex can be obtained, a drop in melting point is not a problem. Moreover, when the melting point is lowered, good dispersibility can be obtained when the resin is kneaded. Therefore, the use of a metal soap composite having a single melting point is effective for improving the cooling roll contamination and R sagging. On the other hand, metal soap composites that do not have a single melting point include metal soaps that do not form a complex, and adhesive denatured products are generated due to thermal decomposition of the metal soap, which deteriorates cooling rolls and R sagging. . Therefore, in order to obtain a metal soap composite having a single melting point, it is preferable to composite an equimolar amount of metal soap.

  The metal of the metal soap composite having a single melting point combining two or more kinds of metal soap used in the present invention is not particularly limited as long as the effect of the present invention is not impaired, and lithium, calcium, zinc, Magnesium, aluminum, or the like can be used. In particular, when two or more kinds of metal soaps in which the metal is lithium, calcium, or zinc is used in combination as a metal soap composite, generation of cooling roll stains and R sagging is greatly suppressed, which is more preferable. In general, the processing lubricity of a lubricant is divided into internal lubricity and external lubricity. Improves the fluidity of the resin and pigments and other additives to facilitate uniform mixing, prevents decomposition due to frictional heat generated locally between molecules, and facilitates extrusion from the melt extruder. The action is called internal lubricity. On the other hand, the adhesion of the resin to the processing machine at the processing temperature and the action of preventing the adhesion to the mold that occurs when the mold is molded and cooled are called external lubricity. The function of the metal soap has both internal and external lubrication functions. In particular, in the polyolefin resin, the metal soap whose metal is lithium or calcium has the function of internal lubrication, and the metal whose metal is zinc. Soap has a great effect as external lubricity. Therefore, a composite of a metal soap whose external slippery metal is zinc and a metal soap whose internal slippery metal is lithium or calcium has both external slippery and internal slippery functions. Is more preferable. In the metal soap used for the metal soap composite whose weight loss on heating at 350 ° C. is 10 mass% or less, when the metal soap whose metal is calcium is used, the blocking property is larger than the metal soap whose metal is lithium. The peelability between the cooling roll and the resin deteriorates. Therefore, the manufactured support for image material may not be able to obtain a uniform surface quality, which may be a problem. Therefore, the combination of lithium and zinc is most preferable as the metal used in the metal soap composite having a single melting point obtained by combining two or more kinds of metal soaps.

  Further, the fatty acid of the metal soap composite having a single melting point combining two or more kinds of metal soaps used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, and stearic acid, palmitic acid Acid, montanic acid, behenic acid and the like can be used, and any combination of fatty acids may be used. In particular, in order to provide heat resistance as a metal soap, it is preferable to use a fatty acid having 14 or more carbon atoms.

  In the present invention, the fatty acid of each metal soap used in the metal soap composite having a single melting point preferably has a purity of 80% or more. When a product with a purity of less than 80% is used, physical properties such as freezing point depression are caused by fatty acids with a small number of carbon atoms contained as impurities, and the effect of inhibiting the formation of a complex is caused. The effect of the composite may be reduced.

  In addition, as the fatty acid of the metal soap composite having a single melting point obtained by combining two or more kinds of metal soaps used in the present invention, a metal soap having a fatty acid group having a hydroxyl group can be used. For example, as the metal soap using 12-hydroxystearic acid, lithium 12-hydroxystearate, calcium 12-hydroxystearate, zinc 12-hydroxystearate and the like are preferably used.

  In the present invention, a method for preparing a metal soap composite having a single melting point is prepared by mixing a plurality of different metal soaps and melting them uniformly, or saponified when synthesizing a metal soap. A plurality of different metal salt aqueous solutions may be added to the fatty acid aqueous solution.

  In the present invention, the concentration of the metal soap contained in the polyolefin resin layer that covers the surface on the side on which the image constituent layer of the base paper of the image material support is provided is in the range of 0.02 to 2.0% by mass. Although useful, the range of 0.2-0.5 mass% is more preferable.

  In the present invention, the base paper surface on which the image forming layer is provided may be coated with a plurality of layers with a polyolefin resin. When considering cooling roll contamination, cooling roll contamination can be improved if at least the metal soap composite at the uppermost layer of the image forming layer has heat resistance among those coated with a plurality of layers. At that time, although it is more preferable that the remaining intermediate layer and the lowermost layer resin also contain a metal soap composite having high heat resistance, for example, even if the specified value is slightly deviated, image formation Does not affect the layer. Accordingly, it is advantageous in terms of quality or manufacture to use a polyolefin resin excellent in curling properties or a polyolefin resin excellent in cost as required.

As the polyolefin resin to be coated on the side on which the image constituent layer of the base paper for the image material support in the present invention is provided, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, or a mixture thereof Is preferred. Among them, various densities, melt flow rates (hereinafter simply abbreviated as MFR), molecular weight, and molecular weight distribution can be used. Usually, the density ranges from 0.90 to 0.97 g / cm ³ and MFR = 0. Those having a range of 1 to 50 g / 10 min, preferably MFR = 0.3 to 40 g / 10 min can be advantageously used alone or in combination. Further, when the resin has a multilayer structure, for example, the outermost resin is MFR = 5 to 20 g / 10 min, and the lower resin is, for example, MFR = 2 to 10 g / 10 min. Resins having other properties and configurations can also be used.

  In the present invention, the coating thickness of the total polyolefin resin that covers the surface on the side of the image material support on the base paper of the image material support in the present invention is useful in the range of 4 to 70 μm, but in the range of 6 to 45 μm. The range of 9 to 35 μm is preferable.

  In the present invention, the metal soap composite is incorporated into the polyolefin resin in the polyolefin resin layer as a method for incorporating the metal soap composite into the polyolefin resin layer covering the surface of the base paper for the image material support on which the image constituting layer is provided. A so-called compound containing only the composition ratio is prepared and used, or a metal soap composite is prepared in advance as a resin composition containing a certain concentration in a polyolefin resin, and the resin composition is diluted with a polyolefin resin for dilution. You may dilute and mix to a ratio and use.

  In the present invention, the polyolefin resin layer covering the surface of the base material for the image material support on the side where the image constituting layer is provided contains a titanium dioxide pigment. As a method for incorporating the titanium dioxide pigment into the polyolefin resin for coating the base paper, a so-called compound in which the titanium dioxide pigment is incorporated in the polyolefin resin in a desired composition ratio is used. A so-called master batch in which a titanium pigment is contained at a constant concentration in a polyolefin resin can be prepared and used after being diluted and mixed in a desired ratio with a polyolefin resin for dilution.

  In the present invention, in order to improve the dispersibility of the titanium dioxide pigment when the titanium dioxide pigment is included in the polyolefin resin layer covering the surface of the base material for the image material on which the image constituting layer is provided, It is more preferable to include a composite. In addition, as a method of including the metal soap composite and the titanium dioxide pigment in the polyolefin resin for covering the base paper, the metal soap composite and the titanium dioxide pigment are contained in the polyolefin resin in a desired composition ratio. A so-called masterbatch in which a so-called compound is prepared and used, or a metal soap composite and a titanium dioxide pigment are previously contained in a polyolefin resin at a constant concentration, is prepared with a polyolefin resin for dilution. Can be used by diluting and mixing at a ratio of

  In order to produce these master batches or compounds, a Banbury mixer, a kneader, an extruder for kneading, a roll kneader or the like can be usually used, and two or more of these various kneaders may be used in combination. .

As the polyolefin resin used for preparation of a masterbatch or compound polyolefin resin composition comprising these titanium dioxide pigment and polyolefin resin, those having suitable physical properties relating to kneading properties of the titanium dioxide pigment and polyolefin resin are preferable. Specifically, a low-viscosity polyolefin resin or a medium-viscosity polyolefin resin having a density in the range of 0.917 to 0.925 g / cm ³ and an MFR of ³ to 12 g / 10 minutes is preferable.

  When preparing a polyolefin resin composition comprising a titanium dioxide pigment and a polyolefin resin, it is preferable to adjust the polyolefin resin composition in the presence of an appropriate amount of an antioxidant. Specifically, hindered phenol-based antioxidants described or exemplified in JP-A-1-105245, hindered amines, sulfur other than phosphorus-based antioxidants described or exemplified in JP-A-55-142335. An appropriate amount of various antioxidants such as a system is preferably present, but it is particularly preferable that an appropriate amount of a hindered phenol-based antioxidant is present. As the abundance of the antioxidant during the preparation of these polyolefin resin compositions, the smaller the amount, the better. However, the range of 50 to 3000 ppm is preferable, and the range of 50 to 1000 ppm is more preferable.

  In the present invention, the polyolefin resin that covers the surface of the image material support on which the image constituting layer is provided may contain various additives in addition to the titanium dioxide pigment, the metal soap, and the antioxidant. White pigments such as zinc oxide, talc and calcium carbonate, fatty acid amides such as stearic acid amide and arachidic acid amide, blue pigments and dyes such as cobalt blue, ultramarine blue, ceria blue and phthalocyanine blue, cobalt violet, fast violet, manganese Various additives such as magenta pigments and dyes such as violet, fluorescent whitening agents and ultraviolet absorbers described or exemplified in JP-A-2-254440 can be appropriately combined and contained.

  The base paper surface opposite to the side on which the image constituting layer of the support for image material in the present invention is provided is coated with a resin capable of forming a film. The resin capable of forming a film is preferably a thermoplastic resin such as a polyolefin resin, a polycarbonate resin, a polyester resin, or a polyamide resin. Among them, the above-described polyolefin resin is more preferable from the viewpoint of melt extrusion coating property, and a polyethylene resin is particularly preferable. Further, it may be coated with an electron beam curable resin described in JP-B-60-17104 or exemplified.

  In the resin coating layer having a film forming ability on the base paper surface opposite to the side on which the image constituting layer of the support for image material of the present invention is provided, in the same manner as the polyolefin resin layer on the side on which the image constituting layer is provided, a white pigment, fatty acid amide , Fatty acid metal salts, various antioxidants, blue pigments and dyes, magenta pigments and dyes, fluorescent whitening agents, ultraviolet absorbers, and other various additives may be included in appropriate combinations.

  Further, the surface of the image material support opposite to the side on which the image forming layer of the base paper is provided is coated with a film-forming resin, and the resin is preferably the same resin as the front-side resin, and the coating thickness It is preferable to set it appropriately within the range of taking the curl balance with the resin on the front side. Generally, the range of 4 to 70 μm is useful, but the range of 6 to 45 μm is preferable, and the range of 9 to 35 μm is preferable. Is particularly preferred.

  The processing speed for coating with the resin of the present invention is characterized in that processing at a higher speed is possible. In order to provide a fixed amount of the coating resin layer on the base paper surface as the traveling speed during processing increases, the number of extrusions of the molten resin must be increased by increasing the number of rotations of the extrusion screw. Therefore, as the running speed is increased, the shear stress of the molten resin increases, and as a result, the frequency of occurrence of R sagging associated with the increase in smoke generation due to cooling roll contamination accompanying the promotion of resin degradation increases. At a traveling speed in a relatively low speed region of 150 m / min or less, even if the frequency of occurrence of cooling roll dirt and R sagging is low, if the running speed becomes higher, the frequency of occurrence of cooling roll dirt and R sagging increases. is there. In the present invention, processing at a higher speed is possible. Specifically, the effect appears at 200 m / min or more. From the viewpoint of using the effect of the present invention, the effect is used at 270 m / min or more. It can be used more effectively in the high-speed machining area of 350 m / min, preferably 400 m / min or more, and high-speed machining can be realized.

  As a method of coating the resin on the base paper surface of the image material support in the present invention, the resin composition is cast on the traveling base paper using a melt extruder, and is coated in a film form from the slit die. It is preferable to coat by the so-called melt extrusion coating method. In that case, it is preferable that resin temperature is 270 degreeC-350 degreeC. When the resin temperature is less than 270 ° C., the adhesion between the base paper and the resin is lowered, and a uniform surface quality cannot be obtained, so that it is unsuitable as a support for image materials. When the resin temperature exceeds 350 ° C., the deterioration of the resin is promoted, so that the cooling roll dirt and the R sagging are deteriorated and it becomes difficult to obtain a uniform surface quality.

  The slit die is preferably a flat die such as a T-type die, an L-type die, or a fishtail die, and the slit opening diameter is preferably 0.1 to 2 mm. Moreover, it is preferable to subject the base paper to activation treatment such as corona discharge treatment and flame treatment before coating the resin composition on the base paper. Also, the resin layer can be coated on the base paper that travels after the ozone-containing gas is sprayed on the molten resin composition in contact with the base paper described or exemplified in Japanese Patent Publication No. 61-42254. Moreover, it is preferable to coat the base paper by a so-called tandem extrusion coating method in which the front and back resin layers are extrusion-coated sequentially or continuously.

  Further, the surface resin layer side of the image material support on which the image constituting layer is to be coated is processed into a glossy surface, fine rough surface, matte surface or silky surface as described in JP-B-62-19732. In general, it is preferable to process the back resin layer on the opposite side to a matte surface.

  The titanium dioxide pigment used in the present invention is preferably a surface treated with an organic substance. Examples of organic substances used for the surface treatment include onoganopolysiloxane compounds such as dimethylpolysiloxane, dimethylphenylpolysiloxane, and methylhydrogenpolysiloxane described or exemplified in Japanese Patent Publication No. 61-26652, and Japanese Patent Publication No. 60-3430. A silane coupling agent such as alkyltrimethoxysilane or γ-aminopropyltriethoxysilane described in or exemplified above, a polyhydric alcohol compound such as trimethylolethane or trimethylolpropane described or exemplified in JP-B-3-35652, Examples include alkanolamine compounds of alkanolamines such as triethanolamine and triisopropanolamine, or inorganic salts thereof, but it is more preferable to use a titanium dioxide pigment treated with a silane coupling agent. Masui.

  The treatment amount of these organic surface treatment agents is preferably as small as possible for the reasons described above, but is preferably in the range of 0.05 to 2.5% by mass with respect to the titanium dioxide pigment, 0.05 to The range of 1.5% by mass is more preferable.

  The titanium dioxide pigment used in the practice of the present invention may be surface treated with an inorganic substance such as hydrous aluminum oxide or hydrous silicon oxide before being surface treated with an organic substance. In that case, appropriate processing as described or exemplified in Japanese Patent Publication No. 63-11655, Japanese Patent Publication No. 1-38291, Japanese Patent Publication No. 1-38292, Japanese Patent Publication No. 1-105245 is performed. It is preferable.

  The base paper mainly composed of natural pulp used in the present invention includes normal bleaching treatment such as chlorine, hypochlorite, chlorine dioxide bleaching, and alkali extraction or alkali treatment, and hydrogen peroxide as necessary. , Wood pulp of softwood pulp, hardwood pulp, mixed softwood hardwood pulp that has been subjected to oxidative bleaching treatment with oxygen, etc., and combinations thereof, and various types such as kraft pulp, sulfite pulp, soda pulp, etc. Can be used.

  The base paper used in the present invention can contain various additives at the time of preparing the paper slurry. Fatty acid metal salt or fatty acid as sizing agent, alkyl ketene dimer emulsion described or exemplified in JP-B-62-2534, epoxidized higher fatty acid amide, alkenyl or alkyl succinic anhydride emulsion, rosin derivative, etc., dry paper Anionic, cationic or amphoteric polyacrylamide, polyvinyl alcohol, cationized starch, vegetable galactomannan, etc. as a power enhancer, polyamine polyamide epichlorohydrin resin, etc. as a wet paper strength enhancer, clay, kaolin, carbonic acid as filler Calcium, titanium dioxide, etc., fixing agents such as water-soluble aluminum salts such as aluminum chloride and sulfuric acid bands, etc., pH regulators such as caustic soda, sodium carbonate, sulfuric acid, etc., other JP-A-63-204251, JP-A-1 -266537 Colored pigment according or exemplified in Japanese, colored dye, that allowed to contain appropriately combining a fluorescent whitening agent is advantageous.

  In addition, a composition comprising various water-soluble polymers or hydrophilic colloids or latexes, antistatic agents, and additives is applied to the base paper used in the practice of the present invention by size press or tab size press or blade coating. It can be contained or applied by coating such as coating or air knife coating. As a water-soluble polymer or hydrophilic colloid, starch-based polymer, polyvinyl alcohol-based polymer, gelatin-based polymer, polyacrylamide-based polymer, cellulose-based polymer, etc. described or exemplified in JP-A-1-266537 can be used as emulsions and latexes. Petroleum resin emulsion, emulsion or latex of copolymer comprising at least ethylene and acrylic acid (or methacrylic acid) as described or exemplified in JP-A-55-4027 and JP-A-1-180538, styrene -Emulsions or latexes of butadiene, styrene-acrylic, vinyl acetate-acrylic, ethylene-vinyl acetate, butadiene-methyl methacrylate copolymers and their carboxy-modified copolymers, etc. Examples of the inhibitor include alkali metal salts such as sodium chloride and potassium chloride, alkaline earth metal salts such as calcium chloride and barium chloride, colloidal metal oxides such as colloidal silica, and organic antistatic agents such as polystyrene sulfonate. As pigments, clay, kaolin, calcium carbonate, talc, barium sulfate, titanium dioxide, etc. As pH adjusters, hydrochloric acid, phosphoric acid, citric acid, caustic soda, etc. It is advantageous to contain these additives in appropriate combinations.

The thickness of the base paper used in the present invention is not particularly limited, but the basis weight is preferably 50 to 250 g / m ² .

  In the present invention, the surface of the polyolefin resin layer on the side where the image constituting layer of the support for image material is provided can be subjected to activation treatment such as corona discharge treatment or flame treatment. Further, after the activation treatment, the undercoat layer treatment described or exemplified in JP-A-1-102551 and JP-A-1-166035 can be performed.

  On the back resin layer surface of the support for image material in the present invention, various back coat layers can be applied for antistatic purposes after performing activation treatment such as corona discharge treatment and flame treatment. . In addition, the back coat layer includes JP-B-52-18020, JP-B-57-9059, JP-B-57-53940, JP-B-58-56859, JP-A-59-214849, JP-A-58-184144. An inorganic antistatic agent, an organic antistatic agent, a hydrophilic binder, latex, a curing agent, a pigment, a surfactant, and the like described or exemplified in each publication such as No. 1 can be contained in appropriate combinations.

  The image material support in the present invention is coated with various image forming layers, for color photographic printing paper, for black and white photographic printing paper, for phototypesetting printing paper, for electronic phototypesetting printing paper, for laser light sensitive printing paper, It can be used for various applications such as for copy photographic paper, reversal photographic material, silver salt diffusion transfer method negative, positive, and printing material.

  For example, a silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide photosensitive emulsion layer can be provided. A multilayer silver halide color image constituting layer can be provided by incorporating a color coupler into the silver halide light-sensitive emulsion layer. Further, an image constituting layer for silver salt diffusion transfer method can be provided. As binders for these image-constituting layers, hydrophilic polymer substances such as polyvinyl pyrrolidone, polyvinyl alcohol, and polysaccharide sulfate compounds can be used in addition to ordinary gelatin.

  Moreover, various additives can be contained in the above-mentioned image forming layer. For example, as sensitizing dyes, cyanine dyes, merocyanine dyes, chemical sensitizers, water-soluble gold compounds, sulfur compounds, antifoggants or stabilizers, hydroxy-triazolopyrimidine compounds, mercapto-heterocyclic compounds, etc. Formalin, vinyl sulphone compounds, aziridine compounds, etc. as hardening agents, alkylbenzene sulphonate, sulfosuccinate, etc. as coating aids, fluorescent whitening agents, sharpness improving dyes, antistatic agents, pH adjusters, and more A water-soluble iridium, a water-soluble rhodium compound and the like can be appropriately combined and contained during the production and dispersion of silver halide.

  The support for image material in the present invention can be used as a support for various ink jet recording materials by applying various ink image receiving layers. Various types of binders can be contained in these ink receiving images for the purpose of improving the drying property of the ink and the sharpness of the image. Specific examples of such binders include various types of gelatin such as lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives such as gelatin reacted with dibasic acid anhydrides such as phthalic acid, maleic acid, and fumaric acid. Ordinary polyvinyl alcohols of various saponification degrees, carboxy-modified, cation-modified and amphoteric polyvinyl alcohols and derivatives thereof, starches such as oxidized starch, cationized starch and etherified starch, cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose , Polyvinylpyrrolidone, polyvinylpyridium halide, polyacrylic acid soda, acrylic acid / methacrylic acid copolymer salt, polyethylene glycol, polypropylene glycol, polyvinyl ether, alkyl vinyl ether / maleic anhydride Polymers, styrene / maleic anhydride copolymers and their salts, synthetic polymers such as polyethyleneimine, conjugated diene copolymer latexes such as styrene / butadiene copolymers and methyl methacrylate / butadiene copolymers, 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 polymer such as acrylic ester copolymer, latex of styrene / acrylic acid ester copolymer or latex of copolymer, vinylidene chloride copolymer latex, etc. or functionalities such as carboxyl groups of these various polymers Functional group-modified polymer latex and group Water-based adhesives such as thermosetting synthetic resins such as vinyl resins and urea resins, and synthetic resin adhesives such as polymethyl methacrylate, polyurethane resins, unsaturated polyester resins, vinyl chloride / vinyl acetate copolymers, polyvinyl butyral, alkyd resins, etc. Agents, inorganic binders such as alumina sol and silica sol described or exemplified in Japanese Patent Publication No. 3-24906, JP-A-3-281383, Japanese Patent Application No. 4-240725, etc. may be mentioned alone or in combination. And can be contained.

  The ink image-receiving layer of the ink jet recording material according to the present invention can contain various additives in addition to the binder. For example, as a surfactant, an anionic surfactant such as a long chain alkylbenzene sulfonate, a long chain, preferably a branched alkylsulfosuccinate, a polyalkylene oxide of a long chain, preferably a branched alkyl group-containing phenol Nonionic surfactants such as ethers and polyalkylene oxide ethers of long-chain alkyl alcohols, fluorinated surfactants described in JP-B-47-9303, US Pat. No. 3,589,906, etc. Silane coupling agents such as aminopropyltriethoxysilane and N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and polymer hardeners such as active halogen compounds, vinyl sulfone compounds, aziridine compounds, epoxy compounds, acryloyl Compound, isocyanate As hardeners and preservatives such as compounds, P-hydroxybenzoate compounds, benzisothiazolone compounds, isothiazolone compounds and the like described or exemplified in JP-A-1-102551, JP-A-63-204251, As a UV absorber such as hydroxymethane sulfonic acid soda, P-toluene sulfinate sodium, etc. as a yellowing inhibitor, such as coloring pigments, coloring dyes, fluorescent brighteners, etc. described or exemplified in each publication such as 1-266537, As a antioxidant, such as a benzotriazole compound having a hydroxy-di-alkylphenyl group at the 2-position, as a pencil hinder such as a polyhindered phenol compound described or exemplified in JP-A-1-105245, starch granules, sulfuric acid Organic or inorganic particle diameter of barium, silicon dioxide, etc. 0.2 μm to 5 μm Fine particles, organopolysiloxane compounds described or exemplified in JP-B-4-1337, etc., pH regulators such as caustic soda, sodium carbonate, sulfuric acid, hydrochloric acid, phosphoric acid, citric acid, octyl alcohol, silicon-based antifoaming agents, etc. These various additives can be contained in appropriate combinations.

  The image material support in the present invention can be used as various electrophotographic recording material supports coated with various toner image-receiving layers. These toner images can contain various binders, antistatic agents, pigments and the like for the purpose of improving the image density, toner fixability, transportability and the like. Specific examples of binders include polyester resins, polyacrylate resins, polycarbonate resins, polyvinyl acetate resins, polyvinyl butyral resins, styrene acrylate resins, vinyl toluene acrylate resins and other ester bond resins, polyurethane resins and other urethane bonds. Resin having amide bond such as polyamide resin, resin having urea bond such as urea resin, other polycaprolactam resin, styrene resin, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, polyacrylonitrile Examples thereof include resins. In addition to these resins, mixtures or copolymers thereof can also be used. Specific examples of the antistatic agent are not particularly limited, and various antistatic agents can be used. For example, fatty acid salts, sulfate ester salts, sulfates of aliphatic amines and aliphatic amides, phosphate ester salts, sulfonate salts, aliphatic amine salts, quaternary ammonium salts, and betaine amphoteric salts, imidazoline amphoteric salts Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, aluminum oxide, magnesium oxide, and barium oxide. Specific examples of the pigment include, but are not limited to, various inorganic and organic pigments such as clay, talc, kaolin, aluminum hydroxide, potassium carbonate, titanium dioxide, barium sulfate, zinc oxide, satin white, and plastic pigment. Coating pigments can be used. Moreover, a mold release agent, a plasticizer, surfactant, dye, etc. can be suitably combined and contained as needed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not restricted to an Example.

(Example 1 and Comparative Examples 1-6)
After beating mixed pulp consisting of hardwood bleached kraft pulp, hardwood bleached sulfite pulp and softwood bleached sulfite pulp so that freeness (CSF) becomes 350 ml, cationized starch, anionized polyacrylamide, alkyl ketene dimer emulsion, polyamide A stock slurry was prepared by adding epichlorohydrin resin, fluorescent brightener, blue dye and red dye.

  After that, a paper web is formed while applying appropriate turbulence on a long paper machine running the paper stock slurry at 200 m / min, and the linear pressure is adjusted in the range of 15 kg / cm to 100 kg / cm at the wet part. After the three-stage wet press is performed, it is treated with a smoothing roll, followed by a two-stage machine calendar process in which the linear pressure is adjusted in the range of 30 kg / cm to 70 kg / cm in the subsequent drying part, followed by drying. did.

After that, a size press liquid consisting of carboxy-modified polyvinyl alcohol, fluorescent whitening agent, blue dye, sodium chloride and water was pressed in the middle of drying at 25 g / m ² size, and the finally obtained base paper moisture was absolutely dry moisture. It was dried to 8 mass%, and machine calendering was performed under the condition of a linear pressure of 50 kg / cm to produce a base paper for a support for image material having a basis weight of 170 g / m ² .

Next, after the corona discharge treatment was performed on the base paper surface (back surface) opposite to the side on which the image forming layer is provided, 35 parts by mass of low density polyethylene resin (density 0.92 g / cm ³ , MFR = 2 g / 10 min) A compound resin composition comprising 65 parts by mass of a high density polyethylene resin (density 0.96 g / cm ³ , MFR = 20 g / 10 min) was melted at a resin temperature of 320 ° C. to a thickness of 28 μm at a running speed of the base paper of 250 m / min. Extrusion coated.

Subsequently, after the corona discharge treatment was performed on the surface of the base paper, the low-density polyethylene resin (density 0.92 g / cm ³ ; MFR = 8.5 / 10 minutes) 50% by mass, hydrous aluminum oxide (Al to titanium dioxide) 0.75% by mass) surface-treated with anatase titanium dioxide content of 47.5% by weight ₂ O ₃ minutes, and antioxidants 1000 ppm, Table 1 metal soap or a metal with different molar ratios complexed A resin composition comprising 20 parts by mass of a titanium dioxide pigment masterbatch comprising 1.5% by mass of a soap composite and 80 parts by mass of a low density polyethylene resin (density 0.92 g / cm ³ ; MFR = 4.5 / 10 min). Were extruded and coated at a resin temperature of 315 ° C. to a thickness of 30 μm at a base paper running speed of 250 m / min. The surface of the resin layer of the resin-coated paper was processed into a mirror surface, and the surface quality of the back resin layer was processed into a matte surface such as paper.

Furthermore, after the corona discharge treatment on the back resin surface of the resin-coated paper, the following back coat coating solution was applied on-machine. As a dry weight, a back coat coating solution composed of colloidal silica: styrene-based latex = 1: 1 and further containing an appropriate amount of a coating aid such as polystyrene sulfonate sodium 0.021 g / m ² is a latex component (solid mass). As a result of calculation, it was coated at a coating amount of 0.21 g / m ² to obtain a support for image material.

  In the production of the image material support obtained as described above, the degree of occurrence of cooling roll contamination of the polyethylene resin composition, the amount of smoke generated during melt extrusion, R sagging, and image clarity as the image material support The evaluation method was evaluated by the method described below.

[Cooling roll dirt]
As a method for evaluating the cooling roll stain at the time of melt extrusion of the composition of the polyolefin resin for the surface resin layer, at the time of producing the support for image material under the above production conditions, on the cooling roll after 8 hours from the start of production. The occurrence of dirt was visually judged and evaluated. The evaluation criteria are as follows.
A: Very good with no chill roll contamination.
○: Good with little generation of dirt on the cooling roll.
Δ: Slightly more dirty cooling roll, but the effect is recognized.
X: There are many occurrences of cooling roll contamination, and there are practical problems.

[Fume generation]
Smoke generation is measured using a particle counter KC-01D manufactured by RION (optical system is a light scattering angle 70 ° side scatter method; light source is a laser diode), and the particle size is 2 to 5 μm. Based on the number, evaluation was made according to the following criteria.
A: The number of particles is less than 1000 and the amount of smoke generated is very small.
○: The number of particles is 1000 to 1500, and the amount of smoke generation is small.
(Triangle | delta): Although the number of particle | grains is 1500-2000 and smoke generation amount is a little large, an effect is recognized.
X: The number of particles is 2000 or more and the amount of smoke is large.

[R sauce]
The amount of smoke generated due to the R sauce 1 hour after the start of melt extrusion and the contamination of the smoke hood were visually determined and evaluated. The evaluation criteria are as follows.
(Double-circle): There is no generation | occurrence | production of the stain | pollution | contamination resulting from R sauce, and it is very favorable.
A: Good with little occurrence of dirt due to R sagging.
Δ: Slightly large amount of dirt caused by R sagging, but practically no problem.
X: There are many stains caused by R sagging, and there is a problem in practical use.

[Image clarity]
The image quality measuring device ICM-2DP type manufactured by Suga Test Instruments Co., Ltd. was used, and the support for image material coated with a resin using an optical comb width of 2 mm was evaluated. The evaluation criteria are as follows.
A: Image clarity is very good.
○: Good image clarity.
Δ: The image clarity is slightly inferior, but the effect is recognized.
X: The image clarity is poor and there is a problem in practical use.

  The obtained results are shown in Table 2.

<Result evaluation>
As is apparent from Table 2, the support for image material coated with the polyethylene resin using the metal soap composite having a single melting point according to claim 1 is coated with an extrusion material and has a good cooling roll stain and a small amount of smoke generation. It can be seen that the R sagging is good and the image clarity is also good. Moreover, in Comparative Examples 1 and 6, since it is not a metal soap composite according to claim 1, and in Comparative Examples 2 to 5, since it is not a metal soap composite having a single melting point according to claim 1, Since the cooling roll contamination, smoke generation amount, and R sagging deteriorated and a uniform surface quality cannot be obtained, the image clarity is also unsuitable as a support for image materials.

(Examples 2 to 8)
The same procedure as in Example 1 was performed except that 8 to 14 in which different types of metal soaps listed in Table 3 were combined with the metal soap composites were used.

  Table 4 shows the obtained results.

<Result evaluation>
As is apparent from Table 4, a support for an imaging material coated with a polyethylene resin composition using a metal soap composite having a single melting point, which is a combination of two or more metal soaps according to claim 1, is cooled. It can be seen that the roll stain is good, the amount of smoke generation is small, the R sagging is good, and the image clarity is good. Moreover, in Example 2, since the heat loss at 350 degreeC of Claim 2 is not 10 mass% or less, it is inferior also to Examples 3-8 also about cooling-roll dirt | pollution | contamination, smoke generation amount, R sauce, and image clarity. Met. In Examples 3 and 7, since the metal of one metal soap of the metal soap composite according to claims 4 and 5 is not zinc and the metal of the other metal soap is not lithium or calcium, external slipping or internal One of the sliding properties was poor, the cooling roll soil was deteriorated, and the image quality support was also inferior to Examples 4 to 6 and 8 in terms of image clarity.

(Examples 9 to 16 and Comparative Examples 7 to 10)
The same procedure as in Example 1 was performed except that metal soap 1 or metal soap composites 4 and 9 were used and the running speed of the base paper shown in Table 5 was used.

  The results obtained are shown in Table 6.

<Result evaluation>
As is apparent from Table 6, in Examples 13 to 16 using the metal soap composite having a single melting point in which two or more kinds of metal soaps according to claim 1 are combined, the running speed of the base paper is increased. Also, it is found that the cooling roll stain is good, the amount of smoke generation is small, the R sagging is good, and the image clarity is good. Moreover, in Comparative Examples 7-10, it is not the metal soap composite which has a single melting | fusing point which combined the 2 or more types of metal soap of Claim 1, and the heat loss at 350 degreeC of Claim 2 is 10 mass. %, The cooling roll contamination, smoke generation amount, and R sagging deteriorated, and the image clarity was unsuitable as a support for image materials. Moreover, in Examples 9-12, although the amount of smoke generation and R sauce tend to deteriorate as the traveling speed of the base paper increases, a single melting point combining two or more kinds of metal soaps according to claim 1. As a result of using a metal soap composite having, the cooling roll soiling is good, the amount of smoke generation is small, the R sagging is good, and the image clarity is good even when the running speed of the base paper is 350 m / min. It was.

  The support for image material of the present invention can be used for photographic paper, glossy ink jet recording paper, electrophotographic paper, and the like, and can be used for the production method of these support for image material.

Claims (6)

In a support for an image material in which the base paper surface on the side where the image constituting layer is provided is coated with a polyolefin resin layer, the polyolefin resin layer is a metal soap composite having a single melting point combining two or more kinds of metal soap, It is formed by melt extrusion coating of a resin composition mainly composed of a titanium pigment and a polyolefin resin , the metal soap is composed of a saturated fatty acid having 14 or more carbon atoms, and the metal is composed of a combination of lithium, calcium or zinc. A support for imaging material characterized by the above.   2. The support for an image material according to claim 1, which is a metal soap composite having a loss on heating at 350 ° C. of 10% by mass or less. The support for an image material according to claim 1 or 2 , wherein the metal of one of the metal soap composites is zinc. The support for an image material according to claim 3 , wherein the metal of the other metal soap in the metal soap composite contains lithium or calcium. The support for an image material according to claim 1, 2, 3 or 4 , wherein the fatty acid group of the metal soap has a hydroxyl group. One surface of the base paper is coated with a film-forming resin, and the other side of the base paper surface on which the image forming layer is provided is a metal soap composite having a single melting point combining two or more types of metal soap, titanium dioxide A method for producing a support for an image material by melt extrusion coating a resin composition using a pigment and a polyolefin resin , wherein the metal soap comprises a saturated fatty acid having 14 or more carbon atoms, and the metal is lithium, calcium Alternatively, a method for producing a support for imaging material , comprising a combination of zinc and extrusion coating at a resin temperature of 270 ° C. to 350 ° C. and 350 m / min or more.