JP4406015B2 - Recorded matter, method for producing recorded matter, and method for improving image fastness - Google Patents

Description

  The present invention relates to a technique for improving the fastness of an image formed by an inkjet method or the like on an ink receiving layer having a porous structure.

  In order to obtain high-quality prints or images by ink jet recording, contrivances have been made mainly from the improvement of the ink composition and the improvement of the recording medium. The resulting image has no image blurring, excellent color reproducibility, etc., and the high quality image that has been formed is maintained for a long period of time, that is, deterioration due to sunlight, room light, etc., and further nitrogen oxidation in the air It is required to have resistance to deterioration caused by substances, sulfur oxides, hydrogen sulfide, chlorine, ozone, ammonia and other substances. In addition, it is required that the image has physical strength and that the image quality is not impaired by rubbing or the like due to exhibition, album storage, or the like.

  In addition, an ink jet recording method for recording images, characters, and the like by causing micro droplets of a recording liquid (recording liquid) such as ink to fly by various operating principles and adhere to a recording medium such as paper. Features such as high speed, low noise, easy multi-coloring, great flexibility in recording patterns, no need for development, and development to printers alone, copiers, word processors, facsimiles, plotters, etc. The development of the output unit in the information equipment is further performed and is rapidly spreading. Furthermore, in recent years, high-performance digital cameras, video cameras, scanners, and the like are being provided at low cost, and along with the widespread use of personal computers, there are printers that employ an inkjet recording method for outputting image information obtained therefrom. It has come to be used very suitably. In such a background, it has been required to easily output an image comparable to silver salt-based photography or plate-making multicolor printing by an ink jet recording method.

On the other hand, the storability of recorded images comparable to silver salt photographs has been demanded, and the ink composition and recording medium have been improved for the purpose of improving the storability of recorded images. ing. Specifically, as a method for improving the storage stability of an image, JP-B-6-30951 discloses a recording medium containing a special cationic compound, and JP-A-4-28232 discloses a light resistance improver. JP-A-4-34512 and JP-A-11-245504 disclose a recording medium containing a hindered amine compound as a light resistance improver. Japanese Patent Publication No. 8-13569 discloses the relationship between discoloration when a recorded image is stored indoors (mainly a phenomenon that black ink turns brown) and discoloration caused by ozone gas. It has been disclosed that silica-based pigments with reduced activity are effective against discoloration of images in the room.
Japanese Patent Publication No. 6-30951 Japanese Examined Patent Publication No. 4-28232 Japanese Patent Publication No. 4-34512 JP-A-11-245504 Japanese Patent Publication No. 8-13569

  However, for example, the fading phenomenon that occurs when a recorded image is displayed in a room is various, such as the entire image being reddish, greenish, or the non-printing portion being yellowed. . Further, the cause of the problem is not limited to light, but various factors such as various gases in the air and the influence of temperature and humidity can be considered. Therefore, there is a need for a method for solving the image fading phenomenon from comprehensive factors.

  Further, a recording medium capable of forming an image comparable to a silver salt photograph (hereinafter also referred to as a “photo recording element”) has a highly transparent material structure in order to achieve excellent dye colorability. In such a photographic recording element, if a large amount of additives such as the above-mentioned light fastness improver is contained in order to improve the storage stability of the image, the transparency of the recorded image is lowered and the image recording quality is lowered. There was a problem of inviting. Thus, in order to impart image fastness to a photo recording element, there is a problem to be further solved in terms of balance with recording characteristics.

  An object of the present invention is to provide a recorded matter having improved image fastness without deteriorating the image quality of an image obtained using an ink jet recording method or the like, and a method for producing the recorded matter. Further, the object of the present invention can be suitably used for a recorded matter formed by using a recording method in which ink is attached to a recording medium such as an ink jet recording method, and image quality such as image density, color tone, and resolution. It is an object of the present invention to provide a method capable of improving the fastness of a recorded image without lowering the image quality.

A recorded matter according to the present invention is a recorded matter comprising a porous structure ink-receiving layer, and the ink-receiving layer has a region in which an image is formed by a coloring material applied by an ink-jet method ,
The regions all or substantially all of the coloring material are distributed in the thickness direction of the ink-receiving layer does not dissolve the colorant, has a portion located in the non-volatile liquid,
The non-volatile liquid is a recorded matter comprising an ester of a saturated fatty acid and an alcohol represented by the following formula (4) or (5) .

The method for producing a recorded matter according to the present invention also includes a recorded matter comprising an ink receiving layer having a porous structure, and the ink receiving layer having an area in which an image is formed by a color material provided by an ink jet method . A manufacturing method of
(I) a step of applying an ink to the ink receiving layer by an ink jet method to obtain a region where an image is formed by a color material contained in the ink;
(Ii) in the ink-receiving layer, the process imparts a liquid containing non-volatile liquid which does not dissolve the colorant, and (iii) a region where the image has been formed, distributed in the thickness direction of the ink-receiving layer Forming a portion in which all or substantially all of the coloring material is in the non-volatile liquid,
The non-volatile liquid contains a saturated fatty acid and alcohol ester represented by the formula (4) or (5) described above .

The method for improving the image fastness of a recorded matter according to the present invention includes a region having an ink receiving layer having a porous structure, and the ink receiving layer is formed with a color material provided by an ink jet method. A method for improving image fastness of recorded matter comprising:
In a region where the image is formed, all or substantially all of the colorant distributed in the thickness direction of the ink-receiving layer does not dissolve the colorant, the portion that is in a non-volatile liquid Having a process of forming,
The non-volatile liquid contains an ester of a saturated fatty acid and an alcohol represented by the formula (4) or (5) described above, and is a method for improving image fastness.

  In the present invention, the image fastness-improving agent is an image fastness-improving agent for a recorded matter having a porous ink-receiving layer and the ink-receiving layer having a region where an image is formed of a color material. Thus, it mainly contains a non-volatile liquid having the above-described structure that does not dissolve the coloring material.

  The image fastness-improving kit for use in the present invention comprises a porous ink receiving layer, and the ink receiving layer has a region in which an image is formed of a color material. And a container containing the above-mentioned image fastness improving agent, and after supplying the liquid to the surface of the ink receiving layer, at least one of wiping and polishing is performed on the surface. And a member for the purpose.

  The dispenser used in the present invention includes the image fastness improving agent having the above-described configuration.

  The applicator for the image fastness improving agent used in the present invention comprises a storage portion for storing the image fastness improving agent having the above constitution and an application member for the image fastness improving agent, and the image in the storage portion is integrated. The fastness-improving agent is configured to be able to exude onto the surface of the application member.

  Furthermore, the image fastness-improving kit used in the present invention is characterized by comprising a recording medium having a porous ink-receiving layer and the image fastness-improving agent.

By adopting such a configuration, the robustness of a recorded matter having an image formed with aqueous ink or the like on a recording medium having an ink receiving layer such as coated paper, particularly against gases such as NO _x , SO _x and ozone. The fastness can be remarkably improved, and a further depth can be added to the color of the image itself. Japanese Patent Laid-Open No. 56-77154 describes filling the voids of an ink jet sheet having a porous structure with a non-volatile substance. However, there is no disclosure about the specific technique according to the present invention. Absent.

  According to the present invention, the robustness of an ink-jet recorded image is improved. In particular, even when the ink-jet recorded image is used for display in a normal indoor environment such as a home or office, it is possible to dramatically prevent the image from fading. . Further, according to the present invention, it is possible to improve the image fastness without deteriorating the recording quality of a recorded image having the same texture and image quality as a silver salt photograph.

  A detailed description will be given below with reference to a cross-sectional view of one example of a recorded matter according to the present invention. For example, as shown in FIG. 2B, the recorded matter according to the present invention includes a porous structure ink receiving layer (1003) containing fine particles (1005) on the surface of a support (1000), and the fine particles. A recording material having an area where an image is formed by the color material (1009) adsorbed on the surface of the ink, wherein at least a part of the area is distributed in the thickness direction of the ink receiving layer. All or substantially all is in the image fastness enhancer 1001 (hereinafter, enhancer). The recorded matter is improved in image fastness in an image area to which the improver is applied by making all of the color material distributed in the thickness direction of the ink receiving layer in the improver. Is achieved. Further, the ink receiving layer of the recorded matter according to the present invention is not particularly limited to those containing fine particles as long as it has a porous structure.

  The reason why an improvement in color of a recorded matter (printed matter) and a remarkable improvement in gas resistance are achieved by the aqueous ink formed on a recording medium having an ink receiving layer according to the present invention are as follows. It is considered a thing.

  FIG. 1 schematically shows a cross-sectional structure of a so-called coated paper provided with a porous ink-receiving layer made of fine particles on a support made of paper or the like. In FIG. 1, reference numeral 1000 denotes a support, and 1003 denotes an ink receiving layer held on the support 1000. The ink receiving layer 1003 has a porous structure including fine particles 1005, and the fine particles are fixed by a binder 1007. Then, in the process in which the ink droplets applied to the coated paper soak into the ink receiving layer 1003, the color material 1009 contained in the ink is adsorbed on the surface of the fine particles 1005, and an image is formed.

As shown in FIG. 2A, the colorant distributed in the thickness direction of the ink receiving layer is simply supplied to the surface of the coated paper thus recorded as shown in FIG. Not all are necessarily in the improver. Therefore, when the rubbing treatment is performed after supplying the ink in order to make the coloring material in the deeper part of the ink receiving layer into the improving agent, the improving agent becomes a hole in the ink receiving layer 1003, here the fine particles 1005. The gap (gap) 1011 is filled. Since the improver is a non-aqueous substance, the aqueous medium of the aqueous ink trapped between the particles is successively replaced, and the periphery of the color material adsorbed on the surface of the fine particles is also covered. Finally, as shown in FIG. 2B, the gap 1011 is filled with the improving agent 1001, and all or substantially all of the color material distributed in the thickness direction of the ink receiving layer is improved. When it is inside, the colorant 1009 is disconnected from contact with gases such as SO _x and NO _x in the atmosphere or moisture containing them. As a result, it is considered that the deterioration of the color material in the ink receiving layer is suppressed and the fastness of the image is improved. Further, the effect of improving the color fastness, printing density, and glossiness obtained together with the effect of improving the fastness of the image according to the present invention is the effect of the substance forming the ink receiving layer and the pores (air), here fine particles. It is considered that the irregular reflection of light on the surface and inside of the ink receiving layer caused by the difference in refractive index between the gap and air (air) is suppressed by filling the gap with an improver.

  Japanese Laid-Open Patent Publication No. 9-48180 discloses that water resistance is improved by coating a water-based ink print with silicone oil or the like. However, the known document does not disclose any application of a protective agent to a printed matter formed using a recording medium having an ink receiving layer having a porous structure, and no effect is obtained. Not suggested. Further, according to the study by the present inventors, it was not possible to satisfactorily obtain the intended image fastness by simply covering the printed matter. This is considered to be because the holes not filled with the improver remain in the ink receiving layer, and the color material existing there deteriorates. This is because the surface of the recorded material is covered with the gas components and moisture remaining in the remaining holes, and the deterioration of the image gradually progresses from the holes due to the action of the gas and moisture that have lost the escape path. The effect of improving gas resistance according to the present invention can be explained by the phenomenon that the colorant in the ink receiving layer is covered with a fastness improver and is blocked from contact with air or moisture. It is thought that it is based on that. In other words, the present invention supplies sufficient improver to coat all or substantially all of the color material present in the thickness direction of the ink receiving layer, and sufficiently applies the improver to the ink by rubbing treatment or the like. It is gradually achieved through the work of filling the hole in the receiving layer, and only by spraying or applying to the surface of the recorded material, based on the idea of covering the surface of the ink receiving layer, It is difficult to reliably enjoy the effects such as the improvement of color and the improvement of gas resistance obtained by the present invention. In the present invention, more preferably, all or substantially all of the pores existing in the thickness direction of the ink receiving layer are filled with the improver so as not to leave air or moisture in the ink receiving layer. Yes, in this case, of course, all or substantially all of the colorant present in the thickness direction of the ink receiving layer is in the enhancer.

  The image fastness improver used in the present invention is applied to the ink receiving layer in a liquid state. Therefore, it can easily penetrate into the ink receiving layer and can be deformed according to the shape of the porous structure in the ink receiving layer, so that the effect of incorporating the coloring material into the improver can be fully exhibited. It is. In addition, the porous structure of the ink receiving layer, for example, the inner wall of the gap or the fine particles contained when the recording material causes an acceptable deformation by being held in the ink receiving layer as a liquid. The contact state of the improver with the outer wall is maintained well.

  On the other hand, when the improver is in the form of a solid state at a temperature of wax or the like, there is a problem that a pressure is required for the penetration into the ink receiving layer or a uniform penetration state is difficult to obtain. Furthermore, when it is applied in a state diluted with a volatile solvent and solidifies after application, or contains a component that solidifies after application in liquid form, it takes in moisture and bubbles during the solidification process. When the volume of the improver phase is reduced due to solidification, a void is generated between the improver phase and the porous structure, and the colorant has a protective function. May decrease. The image fastness improving agent used in the present invention is supplied in a liquid state and held in the ink receiving layer in a liquid state. Therefore, when such a solid or a solidified form after application is used. The inconvenience which arises can be avoided. Confirm that the ink receiving layer is held in a liquid state by confirming that there is no thermal behavior (endothermic or exothermic) at the time of dissolution by a method such as local thermal analysis of the ink receiving layer. It is possible.

  The rubbing treatment used in the present invention refers to at least one of wiping and polishing for positively filling the hole in the ink receiving layer with the fastness improving agent.

  In addition, the present inventors observed the cross-sectional structure of the printed matter with which the effect by this invention was fully acquired with SEM. The ink receiving layer of the printed matter used here is formed of fine particles. At this time, the improver was colored with a dye soluble in the improver so that the penetration tip of the improver could be recognized. As a result, the improver permeates through the entire thickness direction of the ink receiving layer, and the gap between the fine particles in the ink receiving layer is filled with the improving agent, and the colorant exists in the thickness direction of the ink receiving layer. It was confirmed that all of these were in the improver. From this, it will be understood that it is not a simple coating but the importance of positively filling the gap between the ink receiving layers with the improver.

Each component used in the present invention will be described below.
A: image fastness enhancing agent image fastness enhancing agent used in the present invention, in order to improve the robustness of the current mainstream is water-soluble image formed by an aqueous ink containing a dye of the ink jet printer Used . The image fastness improver used in the present invention is preferably a non-volatile substance that is in a liquid state at room temperature (15 to 30 ° C.) and normal pressure and does not dissolve the coloring material. If it is the range which achieves, the non-volatile substance which has the above-mentioned property is mainly included, and also another substance may be included. Specific examples of the substance preferably used as the image fastness improving agent used in the present invention include silicone oil, fatty acid ester, hindered amine, and the like . In the present invention, the above-described formula (4) or formula (5) is used. At least the fatty acid ester represented by is used. Furthermore, by using these improvers, the glossiness of the surface of the ink receiving layer can be obtained, and a recorded product that is more visually favorable can be obtained. The non-volatile substance is, for example, a substance having a weight change of 0.5% or less when 50 g of the substance is put in a 100 ml sample bottle having a diameter of 4.5 cm and stored at 100 ° C. for 300 hours in an open system. Even after the recorded matter produced by the production method according to the present invention using the non-volatile substance is left in a constant temperature bath at 80 ° C. for 5 hours, there is almost no change in image quality.

Aa: Silicone oil Examples of the silicone oil that can be used as an image fastness improver used in the present invention include straight silicone oil typified by dimethyl silicone oil and organic modification typified by alkyl group-modified silicone oil. Although silicone oil etc. are contained, the silicone oil as shown by following Structural formula (1) is especially preferable.

  In the above formula (1), R1, R2, R3 and R4 are each independently selected from the group consisting of a phenyl group, a substituted or unsubstituted alkyl group, a functional substituent having UV absorption ability or antioxidant ability. . Examples of the alkyl group include linear or branched alkyl groups having 1 to 20 carbon atoms, and at least one hydrogen atom of the alkyl group is, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc. ) It may be substituted with a primary or secondary amino group or the like. As the functional substituent having UV absorbing ability or antioxidant ability, for example, the terminal of a linker selected from the following general formulas (17) to (19) is selected from the general formulas (20) to (22). The thing substituted by the substituent is mentioned.

  <Linker>

  R20 to R25 are each selected from the group consisting of a hydrogen atom, a C = 1-10 linear or branched alkyl group, a halogen atom, and an amino group, and the alkyl group is at least one alkyl group. The hydrogen atom may be substituted with, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a primary or secondary amino group, or the like. q is an integer of 1-20.

  <Substituent>

In the above formulae, Me represents a methyl group and t-C ₄ H ₉ represents a tert-butyl group.

  In addition, x and y in the general formula (1) are each independently 0 or a positive integer, and are appropriately selected so as to satisfy the preferable viscosity of the improver described later and the viscosity of the non-volatile liquid. Is preferred. However, x and y are not 0 at the same time. Among the silicone oils represented by the above formula (1), dimethyl silicone oil, a fluorine-modified silicone oil having a fluorinated alkyl group in the side chain, and an alkyl group in the side chain, particularly from the viewpoint of easy handling and an effect of improving image fastness. An alkyl-modified silicone oil having a primary amine in the side chain is preferred, and a fluorine-modified silicone oil represented by the following formula (2) or an alkyl-modified silicone represented by the following formula (23): Oil is most preferred.

  In the above formula (2), n is an integer of 50 to 600, and m and m ′ are each independently an integer of 1 to 20.

  In the above formula (23), R14 represents a substituted or unsubstituted alkyl group, and k and p each independently represent a positive integer. Examples of the alkyl group include a linear or branched alkyl group having 1 to 20 carbon atoms, and at least one hydrogen atom of the alkyl group is, for example, a halogen atom (fluorine atom, chlorine atom, bromine). Atoms, etc.) optionally substituted with primary or secondary amino groups, etc. It is preferable to select k and p as appropriate so as to satisfy the preferable viscosity of the improver and the viscosity of the nonvolatile liquid. k and p are not 0 at the same time.

  The reason why such a modified silicone oil is excellent in the effect of improving the fastness of the image is not clear, but according to the knowledge of the present inventors, the pores in the ink receiving layer are filled with such a modified silicone oil. Since the water repellency on the surface of the receiving layer is higher than that of ordinary silicone oil, it is possible to effectively prevent moisture from entering the receiving layer, and the colorant and water in the improver can be effectively suppressed. This may be because molecular contact can be further suppressed.

Ab: Silicone solubilizer The silicone oil that can be used in the image fastness improver used in the present invention is generally poor in solubility in various solvents, but is a branched monomer represented by the following structural formula (3). By using a silicone solubilizer containing an ester, it can be used without any problem. In other words, if other additives (hindered amine, UV absorber, antioxidant, etc.) are in powder form and are oil-soluble, adding this silicone solubilizer will make it a uniform liquid in silicone oil. Since it can be dissolved, the range of material selection of the image fastness improver used in the present invention can be expanded.

(In the above formula (3), R ₁₆ represents a branched alkyl group having 5 to 18 carbon atoms, and R ₁₇ represents a branched alkyl group having 3 to 18 carbon atoms).

Ac: Fatty acid ester Other materials that can be used as the fastness improver used in the present invention include fatty acid esters. Esters obtained from saturated fatty acids having 5 to 18 carbon atoms and alcohols having 2 to 30 carbon atoms are preferred. Among them, caprylic acid, capric acid, laurin are preferred from the viewpoints of ease of handling and the effect of improving image fastness. Acids, myristic acid, palmitic acid, stearic acid, isononanoic acid, isostearic acid or esters of saturated fatty acids such as 2-ethylhexanoic acid and bulky polyols typified by neopentyl polyol, or adipic acid More preferred are esters of valent saturated fatty acids and alcohols. One or a combination of two or more selected from these esters can be used. In particular, equation (4) shown above, (5) hindered esters and as shown in a preferred esters of trimethylol propanol having 8 and 10 saturated fatty acid carbon, the present invention Then, at least the hindered ester represented by the formula (4) or (5) shown above is contained. A more preferable embodiment is a case where the hindered ester represented by the formulas (4) and (5) shown above is included, and more preferably the hinder represented by the formula (4) and (5) shown above. In this case, the content of the hindered ester represented by the formula (4) is 50% or more with respect to the total mass of the improver.

The reason why the image fastness is improved by using the fatty acid ester is not clear, but by filling the hole in the ink receiving layer with an improver containing the fatty acid ester, the gas permeability of the ink receiving layer can be improved. It is considered that the fastness of the image is improved because the contact of the gas (air or the like) to the coloring material in the improver is suppressed. In particular, the use of the hindered ester, the effect is significant, also hindered esters than ordinary esters, high thermal stability, are needed use suitably for hydrolysis is also not likely.

Ad: Hindered amine compound As another material used as an image fastness improving agent, there is a hindered amine compound that also has an antioxidant and light stabilization effect. A hindered amine compound having one or more substituents represented by the following structural formula (6) is preferably used. Among them, a hindered amine compound that is an ester type of a tetracarboxylic acid represented by the following formula (7), A polyglycerin ester having a hindered amine moiety, a saturated fatty acid ester having a hindered amine moiety, and an organopolysiloxane having a hindered amine moiety are preferably used. In addition, when it has two or more substituents, even if several substituents are the same, two or more different substituents may be contained in several substituents.

  In said formula (6), R9 is H or an alkyl group, and a C1-C8 linear or branched thing is preferable. R10 to R13 are each independently H or a linear or branched alkyl group having 1 to 3 carbon atoms.

In the above formula (7), at least one of R _{5 to} R ₈ is a group represented by the above formula (6), and the other is a hydrogen atom or a monovalent organic residue. Examples of the monovalent organic residue include a linear or branched alkyl group having 1 to 20 carbon atoms and a substituent represented by the following formula (8). R _{5 to} R ₈ in the above formula (7) are the above formula (6) or a linear or branched alkyl group of C = 13, and each has at least one of each, Further, when R9 in the above formula (6) is a methyl group, the substance is a liquid, for supplying the image recording agent to the recording medium and for reliably filling the pores in the ink receiving layer. This is preferable in consideration of workability and efficiency.

  Moreover, what has two or more as said substituents (6) is used more preferably, and an exemplary compound is shown in following formula (8).

  Although the reason why the image fastness is improved by filling the gap between the ink receiving layers with the hindered amine is not clear, it is said that the hindered amine captures radicals generated by light or oxidative degradation, thereby preventing deterioration of the coloring material. In addition to the mechanism, unlike the case of the above-described silicone oil or the like, the bulk of the hindered amine surrounds the colorant molecules in the ink receiving layer, which makes the colorant less susceptible to chemical attack. Conceivable. In the field of ink-jet recording media, it is known to contain a hindered amine in the ink-receiving layer, but the hindered amine compound is contained in the recording medium after the image is formed, and the coloring material is dissolved. In addition, the non-volatile liquid is supplied, and all or substantially all of the color material existing in the thickness direction in the ink receiving layer is present in the liquid. There is also a significant difference compared to that when a hindered amine compound is added in the receiving layer. In the present invention, when a liquid containing a hindered amine compound together with silicone oil or fatty acid ester is used, the colorant of the chemical substance due to the blocking effect of the coloring material from air or moisture by the silicone oil or fatty acid ester and the bulkiness of the hindered amine compound. It is estimated that both of the effects of suppressing the attack of the material are synergistic.

  By the way, this hindered amine compound is more preferably used as long as it is liquid. However, even if it is in powder form, it can be used for inks and coloring materials in order to improve workability and / or fill gaps. Used by dissolving or diluting with an incompatible solvent. At this time, it is preferable to use the above-described silicone oil or saturated fatty acid ester as a solvent. A preferable addition amount of these hindered amine compounds is silicone oil or fatty acid ester: hindered amine compound = 100: 1 to 1: 100 by weight ratio, and 9: 1 to 5: 5 is more preferable.

  In the image fastness improving agent used in the present invention, one kind of the above-mentioned substances may be used as necessary, and two or more kinds may be mixed and used if they have affinity for each other. In this case, the attributes may be different like a mixture of silicone oil and saturated fatty acid ester.

  Furthermore, the image fastness improving agent used in the present invention may further contain, as an additive, a substance that can be dissolved or uniformly dispersed in the non-volatile liquid. As an additive, for example, an antioxidant, a light stabilizer, a radical quencher, an ultraviolet absorber, a thickener, a fragrance, a polishing agent, a bactericidal agent, a pesticide, a drug having a medicinal effect, etc. Is possible. Among them, antioxidants, hindered amines, hindered phenols, vitamins as radical stabilizers, stable radicals as radical quenchers, phenyl salicylate, hindered phenyl, benzotriazole, Benzophenone series is preferable, and agents having medicinal effects such as thickeners, fragrances, polishes, bactericides, and insecticides are appropriately added for further function addition. When an additive is included, the liquid as an active ingredient of the above-mentioned image fastness improving agent functions as a solvent or a dispersion medium for these additives. If the solubility of these compounds in the image fastness improver is insufficient, if they are volatile, or if dispersed in a large particle state, the image quality and effect will be reduced after coating. The most suitable is a silicone oil that is in the liquid state at normal temperature and normal pressure and the specific gravity is substantially equal to the fatty acid ester, or a substance that is completely soluble only in the above-mentioned active ingredient, As long as the effects of the present invention can be achieved, additives can be added without particular limitation. Preferred additives will be described below.

Ae: Ultraviolet Absorber Examples of the ultraviolet absorber added to the image fastness improving agent include those represented by the following structural formulas (9) to (16).

In the above formula, t-C ₄ H ₉ represents a tret-butyl group, and t-C ₈ H ₁₇ represents a tert-octyl group.

Af: Thickener As a thickener added to the image fastness improving agent used in the present invention, for example, a compound represented by the following structural formula (24) may be mentioned.

In the above formula, R26 represents a behenic acid residue (—CO— (CH ₂ ) ₂₀ —CH ₃ ) or a hydrogen atom.

  As an image fastness improving agent, supply to the ink receiving layer is difficult from the viewpoint of see-through when applied to a recording medium, filling in the gap in the ink receiving layer, and fixing to the gap. In the environment of the rubbing process, the dynamic viscosity of the improver when applied to the recording medium is preferably 50 cs to 600 cs. In particular, for example, when the improver is applied using an instrument as shown in FIGS. 4 and 5 described below, the dynamic viscosity is preferably 100 to 400 cs, more preferably 200 cs to 400 cscs. When the improver is applied by a machine as shown in FIG. 2, the dynamic viscosity is preferably 50 to 200 cs. Further, the dynamic viscosity of the improver after being applied to the recording medium is 150 to 300 cs in order to make it difficult to move in the hole and to improve the retention stability of the improver filling. Is preferred. The dynamic viscosity was measured according to JISK-2283.

  The surface tension of the image fastness improving agent used in the present invention is 20 to 30 mN / m considering the ease of filling the ink receiving layer and the difficulty of leaching to the surface of the ink receiving layer after filling. The degree is preferred. Further, from the viewpoint of being liquid at normal temperature and normal pressure, the boiling point and melting point are ranges in which the image fastness improver becomes liquid at normal temperature, and the refractive index (from the viewpoint of ensuring transparency in the recording medium ( 25 ° C.) is preferably 1.3 to 1.5, and the specific gravity is preferably in the range of 0.95 to 1.4 from the viewpoint of smooth penetration into the ink receiving layer of the recording medium and fixability.

  Further, as another effect of the liquid, it is possible to improve the glossiness of the surface of the ink receiving layer and to obtain a visually high-quality recorded matter.

B: Recording medium The recording medium that can be used in the present invention may be any recording medium that has a porous ink-receiving layer and performs recording by adhering ink. it can. However, in the present invention, since the recording medium is impregnated with an image fastness improving agent such as silicone oils and fatty acid esters, it is preferable that the recording medium is a medium that does not show through. The recording medium used in the present invention is particularly suitable when a recording medium in which the porous structure of the ink receiving layer is formed of fine particles and the coloring material is adsorbed to the fine particles uses the inkjet method. It is. Such an ink jet recording medium is preferably a so-called absorption type in which ink is absorbed by a gap formed in an ink receiving layer on a support. The absorption type ink receiving layer is mainly composed of fine particles, and has a porous structure containing a binder and other additives as required. Examples of fine particles include inorganic pigments such as silica, clay, talc, calcium carbonate, kaolin, alumina or alumina hydrate, diatomaceous earth, titanium oxide, hydrotalcite, zinc oxide, urea formalin resin, ethylene resin And organic pigments such as styrene resins, and one or more of these are used. Examples of suitable binders include water-soluble polymers and latex. For example, polyvinyl alcohol or a modified product thereof, starch or a modified product thereof, gelatin or a modified product thereof, gum arabic, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, SBR latex, NBR latex, methyl methacrylate-butadiene copolymer Polymer latex, functional group-modified polymer latex, vinyl copolymer latex such as ethylene vinyl acetate copolymer, polyvinyl pyrrolidone, maleic anhydride or its copolymer, acrylate copolymer, etc. Accordingly, two or more kinds can be used in combination. In addition, additives can also be used. For example, a dispersant, a thickener, a pH adjuster, a lubricant, a fluidity modifier, a surfactant, an antifoaming agent, a mold release agent, a fluorescence enhancer, if necessary. Whitening agents, ultraviolet absorbers, antioxidants and the like are used.

A recording medium particularly suitable in the present invention is preferably a recording medium having an ink receiving layer mainly composed of fine particles having an average particle diameter of 1 μm or less as the fine particles. Particularly preferable examples of the fine particles include silica or aluminum oxide fine particles. The reason why it is particularly effective in aluminum oxide fine particles and silica is considered as follows. That is, it was found that the color material adsorbed on the aluminum oxide fine particles and silica is susceptible to fading of the color material due to gases such as NO _x , SO _x , and ozone. This is because gas is present in the vicinity of and the colorant is likely to fade. A preferable silica fine particle is a silica fine particle typified by colloidal silica. Colloidal silica itself is also available from the market, and particularly preferable examples include those described in Japanese Patent Nos. 2803134 and 2881847. Preferable examples of the aluminum oxide fine particles include alumina hydrate fine particles. A suitable example of such an alumina pigment is an alumina hydrate represented by the following general formula (25).

Al ₂ O _3-n (OH) _2n · _m H ₂ O (25)
In said formula (25), n represents either the integer of 1, 2, or 3, m represents 0-10, Preferably the value of 0-5 is represented. However, m and n are not 0 at the same time. Since mH ₂ O often represents a detachable aqueous phase that does not participate in the formation of the mH ₂ O crystal lattice, m can take an integer or a non-integer value. Also, when this type of material is heated, m can reach a value of zero. Alumina hydrate is generally used for hydrolysis of aluminum alkoxide and sodium aluminate as described in U.S. Pat. No. 4,242,271 and U.S. Pat. No. 4,420,870. It is preferable to use a solution prepared by a known method such as a method of neutralizing by adding an aqueous solution of sodium sulfate, aluminum chloride or the like to an aqueous solution of sodium aluminate or the like described in US Pat.

Furthermore, the ink jet recording medium using these alumina hydrates has excellent affinity, absorbability and fixability with the image fastness improver used in the present invention, and realizes the above-mentioned photographic image quality. Therefore, the present invention is more suitable for applying the present invention because of its excellent glossiness, transparency, and fixability of coloring materials in recording liquids such as dyes. The mixing ratio between the fine particles of the ink jet recording medium used in the present invention and the binder is preferably in the range of 1: 1 to 100: 1. By setting the amount of the binder within the above range, it is possible to maintain a pore volume suitable for impregnation of the image fastness improving agent into the ink receiving layer. The preferable content of aluminum oxide fine particles or silica fine particles in the ink receiving layer is 50% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, and 99% by weight or less. Most preferred. The coating amount of the ink receiving layer, is preferably 10 g / m ² or more on a dry solid basis for the impregnation of image fastness enhancing agent good, 10 to 30 g / m ² is most preferred is there.

  The recording medium used in the present invention preferably has a support for supporting the ink receiving layer described above, but the support is not particularly limited, and the ink receiving layer having the porous structure described above is formed. Any material can be used as long as it provides rigidity that can be transported by a transport mechanism such as an ink jet printer. As a more preferable recording medium, it is formed by applying paper with moderate sizing between the support and the ink receiving layer, or applying an inorganic pigment such as barium sulfate together with a binder on a fibrous base material. (For example, baryta paper) having a porous layer (for example, baryta layer) denser than the ink receiving layer. Such a recording medium is a more preferable embodiment of the present invention described above. “All or substantially all of the holes in which the image forming area exists in the thickness direction of the ink receiving layer are filled with the improver. It is more effective when it is used for a “recorded material having a portion that is covered”. In other words, the recorded matter in which all or substantially all of the holes existing in the thickness direction of the ink receiving layer are filled with the improver is left in a high temperature / high humidity environment for a long time. However, it is possible to extremely effectively suppress the occurrence of stickiness of the surface due to the exudation of the improver on the surface of the recorded material, and it is possible to obtain a recorded material that is extremely excellent in storability. The reason why the above-described effect can be obtained is not clear, but as described above, it is supplied to fill all or substantially all of the pores existing in the thickness direction of the ink receiving layer with the improver. Since the enhancer is dense and has low air permeability, for example, it is difficult to pass through the baryta layer, the pores are reliably filled with the enhancer, and the air present in the pores in the ink receiving layer is also ensured. As schematically shown in FIG. 3, the ink-receiving layer is transferred to or adsorbed to the dense porous layer (1301) in accordance with the filling process of the fastness-improving agent into the pores. It is thought that this is because it is possible to suppress or prevent air and moisture from remaining inside.

  This assumption is made when the image fastness improving method according to the present invention is applied to a recording medium in which an ink receiving layer is provided on a plastic sheet support having no air permeability or water absorption. Although the effect of the period can be obtained, it is supported by the experimental fact that when the recorded matter is stored under high temperature and high humidity conditions, the oozing of the fastness improver to the surface of the ink receiving layer is observed. It is what As a recording medium applicable to the present invention, the form having a porous layer on the surface layer is not limited to a porous ink receiving layer formed on a substrate, and anodized or the like can also be used.

C: Method for producing recorded matter and method for improving image fastness (1) As one embodiment of the method for producing recorded matter or the method for improving image fastness according to the present invention, as described above, an ink having a porous structure The above-mentioned fastness-improving agent is provided on the surface of the ink-receiving layer of a recording sheet which has a receiving layer and on which images such as letters and pictures are recorded by applying water-based ink or water-based ink droplets to the ink-receiving layer There is a method of supplying and then performing a rubbing process. Here, the improver may be supplied and applied only to at least a part of the image recording portion of the recording sheet, but it is most preferable to apply it to the entire surface of the recording sheet. This makes it possible to colorant in the ink receiving layer is more reliably prevented from being attacked by the gas, such as NO _X and SO _X and ozone.

  Further, as described above, in a more preferable aspect of the present invention, all or substantially all of the holes existing in the thickness direction of the ink receiving layer are filled with the improver. In this case, it is appropriate that the supply amount of the improver is an amount that takes into consideration the amount of time required for painting and the amount that the hole is completely filled and the amount absorbed by the coating member. Here, the amount that the hole portion is completely filled is considered from the degree of porosity (oil absorption amount, etc.) of the ink receiving layer in the case of an ink receiving layer made of fine particles. By supplying and applying such an amount of the improver, it is possible to almost certainly fill the pores of the ink receiving layer with the improver. Specifically, for example, when a silicone oil as shown in the above formula (1) is used as an improving agent, the fastness of an image formed on a recording medium having an oil absorption of 0.3 cc is improved. Can be provided with an improving agent of about 0.3 g and subjected to rubbing treatment to obtain a sufficient effect of improving fastness. This not only covers the surface portion of the ink receiving layer but also represents that the effect of the present invention is achieved by filling the pores of the ink receiving layer with the fastness improving agent. .

  The present invention can be achieved by having all or substantially all of the colorant present in the thickness direction of the ink receiving layer in the improver. There is no problem even if the amount of improver applied is less than the oil absorption.

  The following are examples of specific methods for achieving the present invention. As a specific method for achieving the present invention, for example, as shown in FIG. 5, a function 5001 (spray, pump, etc.) capable of supplying a certain amount of an improving agent to the surface of the ink receiving layer is provided. This can be realized by using an image fastness improving kit in which a container 5003 (dispenser or the like) containing the improving agent and a rubbing member are set.

  As other embodiments, as shown in FIGS. 4A and 4B, an image fastness improving agent storage unit 4001 containing a fastness improving agent, and an application member 4002 of the improving agent. And an improvement agent in the storage part may be used to perform the supply of the improvement agent and the rubbing process at the same time using an applicator configured such that the improvement agent in the storage part can be oozed out on the surface of the application member. In addition, when the improvement agent of the application member 4002 is decreasing, the structure may be such that the improvement agent soaks into the application member by applying pressure to the image fastness improving agent storage unit 4001. Reference numeral 4003 denotes a lid 4002. In order to obtain a recorded matter excellent in image fastness by the method according to the present invention, an image having high fastness can be easily obtained by using a set of the recording medium and the image recording property improver. .

  (2) As another embodiment of the method for producing a recorded matter or the method for improving image fastness according to the present invention, there can be mentioned a method for processing without manual intervention in the recording apparatus. FIG. 6 is a schematic cross-sectional view of an apparatus for obtaining a recorded matter having excellent image fastness, and performs recording of an image on a recording medium by an inkjet method and processing for imparting fastness to the formed image. Each means is provided. In FIG. 6, reference numeral 25 denotes a casing, and reference numeral 1 denotes a stacked unused recording medium, which is placed substantially horizontally on a supply tray (paper feeding cassette) 2. Reference numeral 3 denotes a suction cup, which is moved from the position a in the drawing to a position b in contact with the uppermost one of the unused recording sheets 1 by a suction cup moving mechanism (not shown), and sucks the uppermost sheet. Can be lifted. At this time, a suction mechanism (not shown) reduces the pressure inside the suction cup 3 while the suction cup 3 is in contact with the recording paper, and adsorbs the uppermost sheet of the recording paper 1 to remove the recording paper from the other. Separate the recording paper. In this state, the suction cup moving mechanism moves to the position c in the figure, and the leading edge of the separated recording sheet can be inserted between the conveying rollers 4 and 5. Thereafter, the suction operation by the suction mechanism is stopped, the suction force of the suction cup 3 is released, and the restraint of the recording paper by the suction cup 3 can be released.

  The transport rollers 4 and 5 are rotationally driven by a drive source such as a transport motor (not shown) via a clutch mechanism (not shown). Reference numerals 6 and 7 are guide plates which are arranged to face each other with a predetermined interval, and form a supply path for recording paper to be conveyed by the rotation of the conveying rollers 4 and 5. The cross-sectional shape of the supply path formed by the guide plates 6 and 7 is substantially semicircular, and extends from the vicinity of the conveying rollers 4 and 5 to the upper sub-scanning rollers 8 and 9. These sub-scanning rollers 8 and 9, together with a second sub-scanning roller pair 10 and 11 arranged in parallel in the left direction in the figure, sandwich the conveyed recording paper, and will be described later with a control unit (not shown). ) And so on. A guide plate 15 regulates the position of the recording paper between the sub-scanning rollers 8, 9, 10, and 11. A recording head (inkjet head) 12 has a plurality of ink ejection nozzles arranged in the conveyance direction of the recording paper 1. Note that the recording head 12 may include a plurality of inkjet heads that discharge inks of different colors. An ink tank 13 stores ink to be supplied to the recording head 12. The recording head 12 and the ink tank 13 are mounted on a carriage, and can be moved in a direction substantially orthogonal to the recording paper conveyance direction by a carriage guide disposed substantially parallel to the rotation axis of the sub-scanning rollers 8 to 11. Is held in.

  Reference numeral 16 denotes an unused second recording paper stored in a stacked manner in the upper recording paper storage unit. Reference numeral 17 denotes a pressure plate on which the stacked recording paper 16 is placed and appropriately pressed in the direction of the separation roller 18. Reference numerals 19 and 20 denote guide plates, which form a second supply path for guiding the leading edge of one recording sheet taken out by the separation roller 18 to the sub-scanning rollers 8 and 9.

  21, 22, 23, and 24 are means for detecting the presence and the quality of each recording paper 1 and 16 disclosed in, for example, JP-A-1-264879. 21 and 23 are light sources for irradiating the surfaces of the recording papers 1 and 16 with light of a predetermined wavelength, and 22 and 24 are photodetectors for receiving the light reflected from the surface of the recording papers. is there.

  Such detection of the quality of the recording paper by reflected light is caused by the fact that the roughness of the surface differs depending on the type of recording paper, and the degree of light diffusion varies accordingly. . For example, when the surface of plain paper is viewed microscopically, the fibers are intertwined and the diffusion of the surface is large, so the outputs of the detectors 22 and 24 are small. On the other hand, in the case of a sheet having a smooth surface and a low degree of light diffusion, the outputs of the detectors 22 and 24 become large. Whether the recording paper corresponding to the first separation mechanism using the suction cup 3 or the second separation mechanism using the separation roller 18 is loaded in the corresponding cassette by using such light detection means. It is possible to determine whether or not a recording sheet suitable for recording is loaded.

  Reference numerals 26 and 27 denote guide plates that form a conveyance path for guiding the recording paper discharged along with the rotation of the sub-scanning rollers 10 and 11 after the recording by the recording head 12 is completed. A planar heater (not shown) is attached to the guide plate, and heats the recording paper in the conveyance path formed by the guide plates 26 and 27 to accelerate the drying of the ink ejected on the recording paper. .

  An image fastness improving agent is supplied to the recording surface of the recorded matter thus obtained, and an area filled with the image fastness improving agent is formed in the ink receiving layer of the recorded matter.

  The liquid 52 is an image fastness improving agent according to the present invention, and is supplied to the container 51 from a tank (not shown) by a supply device (not shown), and the liquid level in the container 51 is always within a predetermined range. Is automatically supplied and controlled. 53 is a roller for applying a fastness improver, and its surface 53 a has a sponge-like structure into which the fastness improver 52 can permeate, and a part thereof is in contact with the fastness improver 52 in the container 51. Thus, when the liquid application roller 53 is rotated by driving a drive source (not shown), the fastness improving agent 52 can be uniformly infiltrated into the surface portion 53a. Reference numeral 54 denotes a conveyance roller for nipping and conveying the recording medium in cooperation with the application roller 53. The transport roller 54 is separated from the application roller 53 when the recording medium is not sandwiched so that the fastness improving agent 52 does not adhere to the surface, and only when the recording medium is interposed. It is desirable to sandwich the recording medium in contact with the application roller 53 and the conveyance roller 54. A drying heater 55 is used to dry the recording paper coated with the fastness improving agent 52.

  With the above configuration, after the recording by the recording head 12 is completed, before the trailing edge of the recording sheet is separated from the second sub-scanning roller pair 10, 11, the leading edge of the recording medium is the conveying roller 54 and the coating roller 53. To reach the position. The recording medium is sandwiched between the conveying roller 54 and the application roller 53, and the fastness improving agent 52 is uniformly supplied to one surface of the recording medium as the rollers 53 and 54 rotate. Further, it is rubbed to fill the gaps of the ink receiving layer. The recording paper filled with the liquid is further rubbed as necessary, and is then discharged out of the apparatus through the discharge outlet 34 by the rotation of the discharge roller 33. In FIG. 6, the image recording apparatus in which the ink jet recording and the filling of the image fastness improving agent are processed in the same apparatus has been described. However, the present invention is not limited to this, and the image recording unit and the fastness improvement are described. An image recording apparatus having a configuration in which the liquid filling part is separated, and further, an image fastness improving liquid coating apparatus in which the fastness improving liquid filling part is independent of the image forming part may be provided.

  In addition, the inventors of the present invention are recording materials (also referred to as printed materials) that are produced using a recording medium provided with an ink-receiving layer having a porous structure of fine particles and that sufficiently achieve the effects of the present invention. The cross-sectional structure of the ink receiving layer was observed with an electron microscope. As a result, the printed matter before applying the fastness improving agent is shown in FIG. 7, whereas the printed matter after applying the fastness improving agent used in the present invention is as shown in FIG. In FIG. 7, black portions are alumina fine particles or aggregates thereof, and white portions are gaps. In FIG. 8, 801 is considered to be an aggregate of alumina fine particles. Many aggregates are elongated in the thickness direction of the ink receiving layer, that is, oriented in a shape longer in the thickness direction than the width in the direction perpendicular to the thickness direction, and extend in the thickness direction between the aggregates There is a region filled with an improving agent mainly composed of. That is, the region filled with the improver is also roughly oriented in the thickness direction of the receiving layer along the orientation of the aggregate. Here, in the recorded matter shown in FIG. 8, specifically, a fastness improver mainly containing a saturated fatty acid ester is applied to an ink receiving layer having a porous structure containing alumina fine particles based on the porosity of the receiving layer. A sufficient amount for filling the gap in the receiving layer was applied and then wiped off.

  The reason why the cross-sectional structure of the ink receiving layer is changed in this way by adding the fastness-improving agent is not clear, but the present inventors thought that the reason is as follows.

  The recorded matter according to the present invention is made by penetrating the fastness improving agent imparted on the ink receiving layer in the thickness direction of the ink receiving layer. The fatty acid ester in the improving agent constitutes the ink receiving layer. Since it has an affinity for the alumina fine particles, it is considered that the alumina fine particles also move in the thickness direction of the receiving layer in a form that is pulled by the improver when the improver penetrates. In addition, since no change in the image is recognized after filling with the improver, this movement is considered to be at a very micro level.

  Furthermore, as a result of positively supplying the improver to the ink receiving layer by wiping or polishing, the improver penetrates deep into the ink receiving layer, and the alumina fine particles move in the deep part of the receiving layer. It seems that the shape of the gap in the layer also changes gradually. That is, it is considered that the gap that existed almost uniformly in the receiving layer changes to a gap extending in the thickness direction from the surface in the process of forming a flow path for the penetration of the improver. Then, it is considered that this gap finally becomes the improver-filled region and the structure as shown in FIG. 8 is formed.

In addition, the inventors have adsorbed the coloring material relatively to the alumina fine particles existing in the vicinity of the surface of the ink receiving layer before the improvement agent is applied (FIG. 10). It has been confirmed that the layer ( 101 ) on which the color material near the surface of the layer has adsorbed has disappeared, and it is considered that the movement of the color material to the inside of the receiving layer is caused by the above phenomenon. Here, 103 is a portion inside the ink receiving layer to which no color material is adsorbed, and 109 , which is a combination of 101 and 103 , is an ink receiving layer. 105 is a porous layer, and 107 is a support. The reason why the fastness is improved is that the colorant moves into the receiving layer as it is filled with the improver, and further, the colorant is filled with the improver so that it is in contact with air or gas. It is considered that the suppression of the above can be performed at a higher level, and the excellent effect of improving fastness, which is the effect of the present invention, is achieved. In general, when the color material penetrates into the ink receiving layer, the deep color material does not contribute to the color development of the image, so the print density of the recorded matter is lowered. However, in the present invention, the improvement is shown in FIG. The filling area of the agent is formed in the thickness direction of the receiving layer, and since the difference in refractive index between the improver and the alumina fine particles is small, the color material present in the ink receiving layer also contributes to the color development of the image. It is considered that the printing density is improved with the improvement of the fastness.

  The form of the filling region of the fastness improving agent is considered to vary depending on the strength of the affinity between the fine particles and the improving agent, the physical properties (such as viscosity) of the improving agent, and the filling method. As another recorded matter according to the present invention, a fastness improver mainly containing silicone oil is applied to an ink receiving layer having a porous structure containing silica fine particles based on the porosity of the receiving layer. After providing a sufficient amount to fill the gap, a recorded product was produced by wiping, and as a result of observation similar to the above, a cross-sectional structure similar to the cross-sectional structure shown in FIG. 8 (FIG. 9) It was confirmed to have

Hereinafter, the present invention will be further described with reference to Examples , Reference Examples and Comparative Examples.

Reference Examples 1-9, Examples 1-2, Comparative Examples 1-4
(Preparation of image fastness improver)
The image fastness improver was prepared by mixing at least one of a silicone oil and a saturated fatty acid ester with a hindered amine compound in a liquid state at room temperature at a ratio shown in Table 2-1, Reference Examples 1 to 9 and Example 1. ˜2 image fastness improvers and comparative compounds 2-4 were prepared.
Group A. Silicone oil, saturated fatty acid ester A-1. Dimethyl silicone oil SH200 (Toray Dow Corning Silicone)

  A-2. Fluorine-modified silicone oil FS1265 (Toray Dow Corning Silicone)

  A-3. Alkyl-modified silicone oil SF8416 (Toray Dow Corning Silicone)

A-4. Saturated fatty acid ester of neopentyl polyol Product name: Unistar H-334R (manufactured by NOF Corporation)
A-5. Saturated fatty acid ester of neopentyl polyol Product name: Unistar C-3371A (manufactured by NOF Corporation)

Group B. Hindered amine compound that is liquid at room temperature B-1. Product name: TINUVIN 123 (Ciba Geigy)

  B-2. Product Name: TINUVIN 292 (Ciba Geigy)

B-3. Product Name: ADK STAB LA-62 (Asahi Denka Co., Ltd.)
This compound has a structure represented by the formula (7), wherein at least one of R _{5 to} R ₈ is a group having the following structure, and the other is C ₁₃ H ₂₇ —:

  B-4. Product name: ADK STAB LA-67 (Asahi Denka Kogyo Co., Ltd.).

This compound has the structure of the formula (7), and any one of R _{5 to} R ₈ is a group having the following structure, and the other is C ₁₃ H ₂₇ —:

  Group C: Additive

Comparative Examples 1-4
Comparative Example 1 is a case where no image fastness improving agent is used, and the materials used in Comparative Examples 2 to 4 are as follows.
Comparative Example 2: Cationic Resin Solution Dicyandiamide / Polyethyleneamine Product Name: Neofix Nikka Chemical Co., Ltd. Comparative Example 3: Acrylic Resin Solution Acrylic Resin Emulsion Product Name: Boncoat 4001 Dainippon Ink Chemical Co., Ltd. Comparative Example 4: Styrene Resin Solution Styrene-acrylic resin emulsion Product name: SAE-1014 Nippon Zeon Co., Ltd. <Examples of recording media>
Sodium aluminate was added to a 4 wt% solution of aluminum chloride to adjust the pH to 4. Then, it heated up to 90 degreeC, stirring, and stirred for a while. Thereafter, sodium aluminate was added again to adjust the pH to 10, and the aging reaction was carried out for 40 hours while maintaining the temperature. Then, it returned to room temperature and adjusted pH to 7-8. The dispersion was subjected to a desalting treatment, followed by a peptization treatment with acetic acid to obtain a colloidal sol. The colloidal sol of alumina hydrate was concentrated to obtain a 17% by weight solution. Polyvinyl alcohol PVA117 (trade name: manufactured by Kuraray Co., Ltd.) was dissolved in pure water to obtain a 9% by weight solution. The colloidal sol of alumina hydrate and the polyvinyl alcohol solution were mixed and stirred so that the alumina hydrate solid content and the polyvinyl alcohol solid content were 10: 1 by weight to obtain a dispersion.

This dispersion was applied to a base material (Beck smoothness 420 seconds, whiteness 89%) having a baryta layer by die coating at a dry weight of 30 g / m ² . The base material at this time is a dry weight of 30 g / m ² on a fibrous substrate having a basis weight of 150 g / m ² and a steecht size degree of 200 seconds, consisting of 10 parts by weight of gelatin with 100 parts by weight of barium sulfate. In this way, coating is performed and calendar processing is performed. In this way, a recording medium having an ink receiving layer on a substrate having a baryta layer was prepared. Using a rewetting cast coater on the surface of the ink receiving layer of this recording medium, a rewetting treatment using hot water was performed to obtain a recording medium. The oil absorption of the recording medium was about 21 cc / m ² .

<Creation of recorded material and solidification processing>
On the recording medium prepared above, a recorded matter in which an image is recorded by the following method is prepared. For the recorded matter, the image fastness improving agent of Comparative Examples 1 to 9 and Examples 1 and 2 and comparison Using the compounds of Examples 2 to 4, various image fastness tests were performed according to the following methods (1) to (5). Moreover, the recorded material which did not process anything was similarly evaluated as Comparative Example 1.

Inkjet printer (trade name: BJ-F870 made by Canon) and genuine ink tank (trade name: BCI-6BK, BCI-6Y, M, C, BCI-6PM, BCI-6PC) On the recording surface of the recording medium obtained above, 100%, 80% for each color of black, cyan, magenta and yellow as composite colors, composite black, leaf green, skin color and sky blue as composite colors 60%, 40%, 20%, and 10% solid patches of each density were printed to produce recorded matter. Note that the ink used for printing is a genuine product of the printer, and is a water-based ink that contains a water-soluble dye. Next, the above-mentioned various image fastness improvers and the compounds of Comparative Examples 2 to 4 were applied to the surface of the ink receiving layer of the recorded matter at a ratio of about 0.3 g per 126 mm × 89 mm area, and natural cotton was added. A rubbing process was performed on the entire surface of the image with a raw material rubbing member to obtain recorded materials of Reference Examples 1 to 9, Examples 1 to 2 and Comparative Examples 1 to 4. For each recorded matter, each color O.D. A patch having a D of about 1.0 was selected and used for the following image fastness tests.

Evaluation method of light resistance and gas resistance: The image density before the test and the image density after the test of the above recorded matter were measured using a spectrophotometer / spectrino (manufactured by Gretag Macbeth Co.). The light resistance and gas resistance evaluation were determined based on the criteria described below, and the results are shown in Table 1.
Test method (1) Light resistance test 1
According to the following test conditions, a light resistance exposure test was performed using a xenon fade meter. This test is an image fastness test that takes into account the effect of sunlight through windows.
Test conditions:
Irradiation amount: 70 klux
Test time: 100 hours Temperature and humidity conditions in the test chamber: 24 ° C, 60% RH
Filter: (Outer) Soda Lime, (Inner) Borosilicate Light Resistance Evaluation:
Evaluation was made based on the reflection density residual rate (ΔE) data after the light resistance exposure test with reference to the standard of ISO10977 (1993). Specifically, with respect to the recording portion using the single color ink, the reflection density remaining rate indicated by the recording portion after the test was measured and evaluated according to the criteria shown in Table 1 below. On the other hand, regarding the composite color recording part formed by overlapping a plurality of colors of ink, in addition to the reflection density remaining rate of each recording part after the test, each of a plurality of constituent colors constituting each composite color recording part The reflection density residual rate after the light resistance exposure test was measured, and the difference in the obtained reflection density residual rate was calculated and evaluated according to the criteria shown in Table 1. The reason for adding the difference in the reflection density residual ratio of the constituent colors constituting the composite color recording part to the evaluation of the composite color recording part is that the image fastness of the composite color recording part is only the reflection density residual ratio of the recording part itself. In other words, the degree of fading of each of the plurality of constituent colors constituting the composite color recording unit has a great influence on the visual image quality. That is, even when the reflection density residual ratio of the composite color recording portion itself is large, the reflection density has greatly changed before and after the test for any one of the constituent colors constituting the composite color. This is because the visual color balance may be lost and the color fading may be felt visually.

  In Table 1, for example, the density residual ratio of 90% or more means that the lowest residual density among the reflection density residual ratios of black, cyan, magenta, yellow, composite black, leaf green, flesh color, and sky blue recording portions. It indicates 90% or more. In addition, for example, the difference in density residual ratio is less than 5% because, in the above-described four-color composite color recording section, the reflection density residual ratio before each test of the constituent colors constituting each composite color recording section. This is the case where the maximum value difference is less than 5%. The difference in density residual ratio is 5% or more and less than 10% because the maximum value of the difference in reflection density residual ratio of each component color constituting each of the four-color composite color recording portions is 5% or more and 10%. It is a case of less than%.

The evaluation results are shown in Table 2-1 and Table 2-2.
(2) Light resistance test 2
According to the following test conditions, a light exposure test was conducted using a fluorescent light resistance tester. This test is an image fastness test considering the influence of fluorescent light in the room.
Test conditions;
Irradiation amount: 70 klux
Test time: 520 hours Temperature and humidity conditions in the test layer: 24 ° C / 60% RH
Filter: Soda lime light resistance evaluation;
The light resistance was evaluated using the same evaluation criteria as in (1) above from the concentration residual rate data after the light resistance exposure test with reference to the standard of ISO10977 (1993). The results are shown in Table 2-1 and Table 2-2.
(3) Gas resistance test (3) -1.
According to the following test conditions (ANSI / ISA-S71.04-1985), a gas exposure test was performed using a gas corrosion tester. This test is an image fastness test considering the influence of various gases in the room.
Test conditions:
Exposure gas composition: H ₂ S ₁₀ ppb; SO ₂ 100 ppb; NO ₂ 125 ppb; Cl _{2 2} ppb; O ₃ 25 ppb.
Test time: 168 hours Temperature and humidity conditions in the test layer: 30 ° C / 80% RH
Gas resistance evaluation;
Concentration residual rate data after the gas resistance test was evaluated using the same evaluation criteria as in the above (1). The results are shown in Table 2-1 and Table 2-2.
(3) -2.
A gas exposure test was performed using a gas corrosion tester according to the test conditions below (ANSI / ISA-S71.04-1985). This test consists of (3) -1. This is an image fastness test performed under more severe conditions, and the evaluation was performed in the same manner as (3) -1. The results are shown in Table 2-1 and Table 2-2.
Test conditions;
Exposure gas composition: H ₂ S50 ppb; SO ₂ 300 ppb; NO ₂ 1250 ppb; Cl ₂ 10 ppb; O ₃ 100 ppb.
Test time: 240 hours Temperature and humidity conditions in the test layer: 24 ° C / 60% RH
(4) Yellowing test / test method and evaluation method For the unprinted recording medium, each of the improvers of Reference Examples 1 to 9, Examples 1 and 2, and the compounds of Comparative Examples 2 to 4 is the same as described above. The samples of Reference Examples 1-9, Examples 1-2 , and Comparative Examples 2-4 are prepared by rubbing, and an untreated sample as Comparative Example 1 is added to the sample in the following environment. Each sample was allowed to stand, and the color of the recording surface before and after the test was compared. The results are shown in Table 2-1 and Table 2-2.
Test conditions;
Test layer temperature and humidity conditions: 50 ° C, 80% RH
Test time: 240 hours

(5) Glossiness test A new sample was prepared by applying each of Reference Example 2 and Example 1 to the unprinted recording medium in the same manner as described above, followed by rubbing, and Comparative Example 1 An untreated sample was prepared. The glossiness of each of these three samples after storage at room temperature for 24 hours was measured by the method specified in JIS-Z-8741. The results are shown in Table 3.

After newly preparing the recorded material of Reference Example 2 and Example 1 (100% solid patch) and the recorded material of Comparative Example 1 (100% solid patch) in the same manner as the sample used in (1) and storing it at room temperature for 24 hours The density of each image was measured with Gretag Spectuloino (manufactured by Gretag Macbeth). The results are shown in Table 4.

It is a schematic sectional drawing which shows typically the cross-sectional structure of the recording medium used for this invention. It is a schematic explanatory drawing of the improvement method of the image fastness used for this invention, (a) is a schematic sectional drawing which shows the state which provided the fastness improving agent on the ink receiving layer, (b) is in an ink receiving layer. It is a schematic sectional drawing which shows the state with which the improvement agent was filled into the gap | interval. FIG. 4 is an explanatory diagram of the behavior of water molecules in the ink receiving layer when a recording medium support having a dense porous layer on the surface of the ink receiving layer is used. It is one embodiment of the applicator used for this invention. (A) is a schematic perspective view which shows the form at the time of use, (b) is a schematic perspective view which shows the form where the application part was protected with the lid | cover suitable for accommodation or carrying. It is a schematic sectional drawing of the atomizer used for this invention. It is a schematic sectional drawing of the inkjet recording device used for this invention. FIG. 3 is a cross-sectional view of an ink receiving layer of a recording medium that can be used in the present invention. It is an example of sectional drawing of the ink receiving layer of the recorded matter concerning this invention. It is another example of sectional drawing of the ink receiving layer of the recorded matter concerning this invention. FIG. 3 is a cross-sectional view of a recorded material before recording on a recording medium that can be used in the present invention and before applying a fastness improver .

801 Alumina particle aggregate 1000 Support 1001 Image fastness improver 1003 Ink receiving layer 1005 Fine particle 1007 Binder 1009 Colorant 1011 Gaps 1301 in ink receiving layer Dense porous layer 4001 Image fastness improver storage unit 4002 Image Fastness improver application part 4003 Lid 5001 Dispensing means (spray part)
5003 Image fastness improving agent storage

Claims (8)

A recorded matter comprising a porous structure ink-receiving layer, and the ink-receiving layer has an area where an image is formed by a color material applied by an ink-jet method ,
The region has a portion in which all or substantially all of the color material distributed in the thickness direction of the ink receiving layer is in a non-volatile liquid that does not dissolve the color material,
The recorded matter, wherein the non-volatile liquid contains an ester of a saturated fatty acid and an alcohol represented by the following formula (4) or (5) .
A method for producing a recorded matter comprising an ink receiving layer having a porous structure, and the ink receiving layer having a region where an image is formed by a color material applied by an ink jet method ,
(I) a step of applying an ink to the ink receiving layer by an ink jet method to obtain a region where an image is formed by a color material contained in the ink;
(Ii) in the ink-receiving layer, the process imparts a liquid containing non-volatile liquid which does not dissolve the colorant, and (iii) a region where the image has been formed, distributed in the thickness direction of the ink-receiving layer Forming a portion in which all or substantially all of the coloring material is in the non-volatile liquid,
The method for producing a recorded matter, wherein the nonvolatile liquid contains an ester of a saturated fatty acid and an alcohol represented by the following formula (4) or (5) .
  3. The method for producing a recorded matter according to claim 2, wherein the porous structure of the ink receiving layer is formed by fine particles, and the colorant is adsorbed on the surface of the fine particles.   In the step (iii), all or substantially all of the holes existing in the thickness direction of the ink receiving layer in at least a part of the region where the image is formed are filled with the non-volatile liquid. The method for producing a recorded matter according to claim 2, further comprising a step of: Recording according to any one of claims 2-4 which comprises a porous layer between the support for supporting the ink-receiving layer and the ink receiving layer, and further the ink receiving layer and the support Manufacturing method. The method for producing a recorded matter according to claim 5 , wherein the porous layer contains barium sulfate. The method for producing a recorded matter according to any one of claims 3 to 6 , wherein the fine particles are made of alumina. A method for improving the image fastness of a recorded matter comprising a porous structure ink-receiving layer, and the ink-receiving layer having a region where an image is formed by a color material applied by an ink-jet method ,
In a region where the image is formed, all or substantially all of the colorant distributed in the thickness direction of the ink-receiving layer does not dissolve the colorant, the portion that is in a non-volatile liquid Having a process of forming,
The method for improving image fastness, wherein the non-volatile liquid contains an ester of a saturated fatty acid and an alcohol represented by the following formula (4) or (5) .