JP2003276322A - Recording body and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a recording body, which can quickly absorb ink, the ink having being absorbed in an ink receiving layer is hard to be removed even by applying water thereon, which has a high surface glossiness, which can be recorded with a color inkjet printer and which can realize so highly glossy, high quality and high grade recording as the silver salt photograph. <P>SOLUTION: In the recording body or an inkjet recording medium including a base material layer and the ink receiving layer provided on the base material layer, the water immersion density retention percentage of the ink receiving layer is set to be 30% or more and its surface gloss is set to be 55% or more. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material and a manufacturing method thereof, and more particularly to an inkjet recording material and a manufacturing method thereof.

[0002]

2. Description of the Related Art In recent years, with the spread of electronic still cameras or computers, hard copy technology for recording those images on a paper surface has been rapidly developed. The ultimate goal of these hard copies is silver salt photography, and in particular, how to bring color reproducibility, image density, gloss, weather resistance and the like closer to silver salt photography has become an issue for development. As a hard copy recording method, a variety of methods such as a sublimation type thermal transfer method, an ink jet method, an electrostatic transfer type method are known, in addition to a method of directly photographing a display on which an image is displayed by a silver halide photograph.

An ink jet printer is
It has become popular rapidly in recent years due to the ease of full colorization and low printing noise. The ink jet system ejects ink droplets from a nozzle toward a recording material at high speed, and contains a large amount of solvent in the ink. Therefore, the recording medium for inkjet is required to quickly absorb the ink and have excellent color forming property.

However, in the conventional ink jet recording medium, since the printed matter has poor water resistance, it is easy to remove the ink when water is applied after the ink is absorbed by the ink receiving layer, and the ink is quickly absorbed. Therefore, there is a problem that the continuous printing has show-through, and the surface gloss is inferior, so that it is not of high quality and high quality like a silver salt photograph.

[0005]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned problems, and its purpose is to provide excellent water resistance, high surface glossiness, recording by a color printer, and silver salt. The present invention provides a recording material having high glossiness like a photograph and capable of high-quality and high-quality recording, and a manufacturing method thereof.

[0006]

The present inventors have arrived at the present invention as a result of extensive studies to achieve the above object. That is, the present invention includes (1) a substrate layer and an ink receiving layer provided on the substrate layer, wherein the ink receiving layer has a water immersion concentration retention rate of 30% or more and a surface gloss of the ink receiving layer. To 55% or more. The preferred embodiment is as follows. (2) The recording material according to (1), which has an ink absorption time of 50 seconds or less at an ink amount of 0.1 to 1.0 μl / cm ² of the ink receiving layer. (3) The recording material according to (1), wherein the ink receiving layer contains an ink absorbing resin, a curing agent and a surfactant. (4) The recording material according to (3), wherein the ink receiving layer further contains a compound having a cationic group. (5) The ink absorbing resin is polyvinyl alcohol
Record body of (3). (6) The recording material according to (3), wherein the curing agent is a water-soluble melamine resin. (7) The recording material according to (3), wherein the content of the ink-absorbing resin is 10 to 99% by weight based on all components constituting the ink receiving layer. (8) The content of the curing agent is 0.
The recording material of (3), which is 1 to 20% by weight. (9) The recording material according to (3), in which the content of the surfactant is 0.5 to 20% by weight based on all components constituting the ink receiving layer. (10) The recording material according to (1), wherein the base material layer is a polyester film. Further, the present invention is to apply a composition containing an ink absorbing resin, a curing agent, a surfactant and a solvent onto a substrate layer, and this coating layer is not less than the boiling point of the solvent and has a boiling point of + 30 ° C.
The present invention relates to a method for producing a recording body, which includes heating to the following temperature and further heating at a temperature higher than the temperature to form an ink receiving layer. Preferably, a composition containing an ink-absorbing resin, a curing agent, a surfactant and water is applied onto the base material layer, and the applied layer is applied at 100 to 130 ° C.
Is a method for producing a recording material, in which the ink receiving layer is formed by heating to the temperature of 1 to 130 ° C. to 180 ° C.

The recording material of the present invention comprises a base material layer and an ink receiving layer provided on the base material. As the base material layer,
It is not particularly limited, but examples thereof include natural paper, synthetic paper, cloth, non-woven fabric, wood, metal, plastic film, glass, artificial leather, natural leather, and those obtained by laminating any two or more of these. The base material layer may be a single layer or a composite of two or more layers.

When the base material layer is a plastic film, the material is not particularly limited, and examples thereof include polyester resin, polyolefin resin, polyamide resin, polyacrylic resin, polyurethane resin,
Examples thereof include polyvinyl resins, polyether resins, polystyrene resins, and the like. Among them, particularly preferable are polyester resins described below.

Preferred polyester resins include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid or esters thereof and glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol and neopentyl glycol. It is a polyester produced by polycondensation. These polyesters include, in addition to a method of directly reacting an aromatic dicarboxylic acid and a glycol, a method of transesterifying an alkyl ester of an aromatic dicarboxylic acid and a glycol, followed by polycondensation, or a diglycol of an aromatic dicarboxylic acid. It can also be produced by a method such as polycondensing an ester.

Specific examples of the above-mentioned polyester include polyethylene terephthalate, polybutylene terephthalate and polyethylene-2,6-naphthalate. The polyester may be a homopolymer, or may be a copolymer obtained by using two or more kinds of acid components and / or glycol components. In the present invention, a polyester in which ethylene terephthalate units, butylene terephthalate units or ethylene-2,6-naphthalate units account for 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more of the total polyester is preferred. .

If necessary, inorganic particles or organic particles may be added to the base film. As the particles that can be added, for example, silica, kaolinite, talc,
Examples thereof include calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, titanium oxide, crosslinked acrylic resin particles, and crosslinked polystyrene particles, but are not particularly limited. By containing such particles, the obtained recording material has good slidability, is easy to handle, and has good transportability in a printer. Further, instead of adding particles, an extremely thin layer may be provided on at least one surface of the film containing no particles in order to improve the handleability.

Since the above-mentioned base film is transparent, the recording material using such a base film is suitable for use in seeing through watermarks such as OHP and electric advertisement. When the recording material of the present invention is required to be opaque, it is preferable to use a substrate film having a large number of fine voids inside. The method is not particularly limited, but particularly preferable is the method described below, in which a large number of incompatible thermoplastic resins and / or particles are added to the polyester and the polyester is oriented at least uniaxially. This is a method of forming a large number of fine cavities inside. Such an opaque recording material does not show the back side and the printed material has a good appearance.

Thermoplastic resins incompatible with polyester are
It is not particularly limited as long as it is incompatible with polyester, and specific examples thereof include polystyrene resins, polyolefin resins, polyacrylic resins, polycarbonate resins, polysulfone resins, cellulose resins and polyamide resins. In particular, polystyrene resins or polyolefin resins such as polymethylpentene, polypropylene and cyclic olefins are preferably used.

The amount of the incompatible resin added to the polyester varies depending on the intended void amount, but is preferably 3 to 39% by weight, and particularly preferably 5 to 15% by weight in the base film. If it is less than 3% by weight, there is a limit to increase the amount of cavities formed, and it tends to be difficult to obtain the flexibility, lightness, or drawing property provided by the cavity formation. On the contrary, if it exceeds 39% by weight, the stretchability of the film tends to be impaired, and the heat resistance, strength and stiffness of the film tend to be impaired. The incompatible resins may be used alone or in combination of two or more. In addition, the particles used include the aforementioned inorganic and / or organic particles. The amount of such particles is preferably 0.1 to 2 in the substrate film for the same reason as the above incompatible resin.
0% by weight, more preferably 0.5 to 10% by weight,
The average particle size of the particles is preferably 0.1 to 10 μm.

The apparent specific gravity of such a base film is preferably 0.7 or more and less than 1.32, more preferably 1.0 or more and less than 1.25, and even more preferably 1.0.
The range is 5 or more and less than 1.25. Apparent specific gravity is 0.7
If it is less than the above range, the void content is too large, the strength of the film is remarkably impaired, and cracks or wrinkles are likely to occur on the surface of the film regardless of the balance between length and width, which is not preferable.
On the other hand, when the apparent specific gravity is 1.32 or more, the void content becomes too small, the cushioning property is poor, and the drawing property of the resulting recording material with a pencil is poor, which is not preferable.

The in-plane birefringence of such a film is preferably -0.02 to +0.04, more preferably 0 to +0.03. The in-plane birefringence is set to −0.
By setting it to be 02 or more, preferably 0 or more, a substrate film having substantially isotropic property can be obtained for the first time.
Here, the in-plane birefringence index being + (-) means that the history of longitudinal stretching remains larger (smaller) than the history of transverse stretching, and due to the so-called bowing phenomenon during transverse stretching. It may be accompanied by some distortion of the principal axis of the refractive index. And, the in-plane birefringence is −0.02 or more,
By setting it to preferably 0 or more, it is possible to prevent the film from tearing in the lateral direction. On the other hand, when the in-plane birefringence exceeds +0.04, on the contrary, the film is liable to be longitudinally torn, and when the film is slit, rupture occurs,
It is not preferable because the film is likely to be warped in the longitudinal direction when it is cut into sheets. The in-plane birefringence is -0.0.
If it is less than 2 or exceeds +0.04, it may cause wrinkles and curls of the obtained recording material in the printer, which is not preferable.

The method for producing such a base film is not particularly limited, but the most preferred production method is 3.0 or more in one or more stages in the longitudinal direction of the unstretched film.
This is a method in which after stretching at least twice, a relaxation treatment of 3% or more is carried out in the machine direction, and then transverse stretching / heat treatment is carried out at a draw ratio greater than the longitudinal stretching ratio after the relaxation treatment.

First, in the first longitudinal stretching step, stretching is performed between two or many rolls having different peripheral speeds. As a heating means at this time, a method using a heating roll or a non-contact heating method may be used, or they may be used in combination. However, in order to develop a large number of voids at the incompatible resin interface, the stretching temperature is set to the second-order transition temperature T of the polyester.
Stretching is carried out at a temperature of g + 10 ° C. to Tg + 50 ° C. or less and 3.0 times or more, preferably 3.2 to 5.0 times. If the draw ratio is less than 3.0, it is difficult to sufficiently develop fine cavities inside the substrate film and to make the apparent specific gravity less than 1.32. Further, if the longitudinal magnification exceeds 5.0 times, it becomes difficult to sufficiently perform the subsequent relaxation treatment,
It is substantially difficult to set the in-plane birefringence index of the base film to +0.04 or less, which is not preferable.

Next, 3% or more in the longitudinal direction, preferably 5%
% Relaxation treatment is applied. A more preferable relaxation rate varies depending on the longitudinal stretching ratio performed before the relaxation, but it is preferable to determine the longitudinal stretching ratio after relaxation to be 2.8 to 3.5 times. The in-plane birefringence is -0.02 to + only after the relaxation treatment of 3% or more is performed.
It is possible to industrially produce a base film having a thickness of 0.04. On the other hand, when the relaxation treatment of 3% or more is not performed, the transverse stretchability in the next step becomes remarkably poor and a film having an in-plane birefringence of -0.02 to +0.04 cannot be prepared. . Moreover, in the case of producing a film having an apparent specific gravity of 1.32 or more (a film having a small content of fine voids), it is possible to produce a film having isotropicity without performing the relaxation treatment. However, in this case, a base film having a preferable apparent specific gravity cannot be produced.

The preferred stretch ratio after longitudinal relaxation is 2.
8 to 3.5 times. If the longitudinal stretching ratio after relaxation is less than 2.8 times, the relaxation is not performed uniformly, resulting in a non-uniform base film, or the in-plane birefringence index after biaxial stretching is -0.0.
It may be less than 2, which is not preferable. On the other hand, if the longitudinal stretching ratio after relaxation exceeds 3.5, the stretchability during transverse stretching may be poor, or the in-plane birefringence after biaxial stretching may exceed +0.04. , Not preferable.

The relaxation treatment may be carried out by first cooling the film and then reheating it in an oven at 80 ° C. to 150 ° C., or immediately after longitudinal stretching without performing cooling. Method, or 60 ° C to 100
A method of performing relaxation treatment between driving rolls or free rolls heated to ℃. Alternatively, a method in which these are appropriately combined can be adopted. However, it is preferable to perform the relaxation treatment mainly by the method of performing the relaxation treatment without cooling immediately after the longitudinal stretching, and the uniform relaxation treatment can be efficiently performed.

Next, the longitudinally relaxed film is introduced into a tenter, and transversely stretched and heat-treated at a ratio equal to or higher than the longitudinal stretching ratio after the relaxation treatment. The preferred transverse stretching temperature is higher than the maximum temperature of the longitudinal stretching / relaxation treatment, and the melting point of the polyester is Tm-10.
It is below ℃. If the transverse stretching ratio is smaller than the longitudinal stretching ratio after the relaxation treatment, it is difficult to set the in-plane birefringence index to +0.04 or less. The upper limit of the transverse stretching ratio is not particularly limited, but the longitudinal stretching ratio after the relaxation treatment may be performed at a ratio of 1.0 times or less to secure the stretchability and to bring the in-plane birefringence to -0.02.
It is preferable to achieve the above.

The biaxially stretched film thus obtained is subjected to heat treatment, if necessary. The heat treatment is preferably carried out in a tenter, and the melting point of the polyester is Tm-50.
It is preferably carried out in the range of ° C to Tm. Further, re-transverse stretching and relaxation in the transverse direction may be carried out in parallel with the heat treatment.

The ink receiving layer is preferably a layer containing an ink absorbing resin, a curing agent and a surfactant. As the ink absorbing resin, any known resin having ink absorbing property can be used, and examples thereof include polyvinyl alcohol, acrylic resin, styrene-acrylic polymer, ethylene-vinyl acetate polymer, starch, polyvinyl butyral and gelatin. , Casein, ionomers (for example, ionomers such as polyester and polyolefin), gum arabic, carboxymethyl cellulose, polyvinylpyrrolidone, polyacrylamide, polyester resin, styrene-butadiene rubber, etc.
More than one species can be used if desired. Among them, polyvinyl alcohol is preferable, and one having a polymerization degree of 1400 to 2500 and a saponification degree of 85 to 90 is most preferable. The content of the ink-absorbent resin is based on the total components of the ink-receiving layer,
Preferably 10-99% by weight, more preferably 50-9
It is 9% by weight. If the content is less than 10% by weight, the ink absorption time may exceed 50 seconds at an ink amount of 0.1 to 1.0 μl / cm ^{2 in} the ink receiving layer, the ink may not be rapidly absorbed, and continuous printing may not be performed. It is not preferable because the show-through of the object may occur. On the other hand, the content is 99% by weight
If it exceeds 1, the content of the curing agent in the ink receiving layer may be low and the water retention concentration retention rate may be less than 30%, which is not preferable because the water resistance is insufficient.

The curing agent has a crosslinkable functional group such as melamine resin, epoxy resin, polyurethane resin, polyether resin, isocyanate compound, and maleic anhydride-isobutylene copolymer, and crosslinks the above-mentioned ink absorbing resin. Examples thereof include water-soluble melamine resins. By containing such a curing agent, the curing degree of the ink receiving layer is increased and the water resistance is improved. The content of the curing agent is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, based on the ink absorbing resin. When the content is less than 0.1% by weight, the ink-receiving layer may have a water immersion concentration retention rate of less than 30%.
The water resistance becomes insufficient, and it is not preferable to sprinkle water after the ink is absorbed by the ink receiving layer because the ink can be removed. On the other hand, when the content exceeds 20% by weight, the content of the ink absorbing resin in the ink receiving layer becomes low, and the content becomes 0.1 to 0.1%.
The ink absorption time at an ink amount of 1.0 μl / cm ² may exceed 50 seconds, which is not preferable because the ink absorption is insufficient. If necessary, a catalyst may be included to accelerate the reaction.

The surfactant is a cationic type, an anionic type,
Either nonionic or nonionic type may be used, but a silicon type or fluorine type surfactant is preferable. As the silicon-based surfactant, for example, dimethyl silicon, aminosilane, acrylsilane, vinylbenzylsilane, vinylbenzylaminosilane, glycidsilane, mercaptosilane, dimethylsilane, polydimethylsiloxane, polyalkoxysiloxane, hydrogen modified siloxane, vinyl modified siloxane, Hydroxy modified siloxane, amino modified siloxane, carboxyl modified siloxane, halogen modified siloxane, epoxy modified siloxane, methacryloxy modified siloxane, mercapto modified siloxane, fluorine modified siloxane, alkyl group modified siloxane, phenyl modified siloxane, alkylene oxide modified siloxane and the like. . Examples of the fluorine-based surfactant include tetrafluoroethylene, perfluoroalkyl ammonium salt, perfluoroalkyl sulfonic acid amide, sodium perfluoroalkyl sulfonate, perfluoroalkyl potassium salt, perfluoroalkyl carboxylic acid salt, perfluoroalkyl Sulfonate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl trimethyl ammonium salt,
Perfluoroalkylaminosulfonate, perfluoroalkyl phosphate ester, perfluoroalkylalkyl compound, perfluoroalkylalkylbetaine,
Examples include perfluoroalkyl halides. The content of these surfactants is preferably 0.5 to 20% by weight, and more preferably 1 to 10% by weight, based on all components constituting the ink receiving layer. 20% by weight
When it is more than 0.5% or less than 0.5% by weight, it is not preferable because it is difficult to achieve both ink absorbability and water resistance of the ink receiving layer.

By containing the above-mentioned amount of the surfactant, it is possible to obtain high surface gloss while maintaining the excellent ink absorbency and water resistance of the ink receiving layer.

The ink receiving layer preferably further contains a compound having a cation group, and more preferably contains polyvinyl alcohol having a cation group and a dyeing agent having a cation group. This makes it possible to further improve the ink absorbency. Further, instead of the above-mentioned compound having a cationic group, a cation-modified one of the above ink-absorbent resin may be used, and for example, polyvinyl alcohol having a cation group or the following compound is preferably used.

[0029]

[Chemical 1]

When used in combination with the above ink-absorbent resin, the content of such a compound is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight based on all the components constituting the ink receiving layer. % By weight.

In the ink receiving layer, if necessary, silica,
Kaolinite, talc, calcium carbonate, zeolite,
Particles such as alumina, barium sulfate, carbon black, zinc oxide, titanium oxide, organic white pigments, benzoguanamine particles, crosslinked polystyrene, crosslinked acrylic particles, and aluminum hydroxide may be added to an extent not impaired by surface gloss. The addition amount is appropriately selected depending on the case where the recording material of the invention is required to have transparency or opacity. The average particle size of the particles is preferably 0.1 μ
m or more, more preferably 0.3 μm or more. By adding such particles, the slipperiness of the recording material becomes good and the transportability in the printer becomes good. Also, the drawability with a pencil is improved.

The ink receiving layer may be composed of one layer or two or more layers.

The ink receiving layer is manufactured, for example, as follows. First, an ink receiving layer coating liquid containing an ink absorbing resin, a curing agent, a surfactant and a solvent is prepared. Here, examples of the solvent include water and polar solvents that are miscible with water, such as alcohol, glycol, and acetone. Next, this coating liquid is applied onto the base material layer. This coating method is not particularly limited, gravure coating method, kiss coating method, dip method, spray coating method, curtain coating method, air knife coating method, blade coating method,
A commonly used method such as a reverse roll coating method or a bar coating method can be applied. The coating amount at this time is preferably such that the ink-receiving layer has a thickness of 8 to 50 g / m ² after drying. When the coating amount is less than 8 g / m ² , the ink receiving layer is thin and cannot completely absorb the ink, which is not preferable. On the other hand, when the coating amount is less than 50 g / m ² , the ink is deeply absorbed and the printing density is lowered, which is not preferable.

Next, this coating layer is heated to dry and cure. In this heating step, if the curing is sufficiently performed, the ink absorbability of the ink receiving layer becomes poor, and conversely, if the curing is stopped to such an extent that the ink absorbability of the ink receiving layer is sufficient, the water resistance of the ink receiving layer becomes poor. become.
Therefore, it is necessary to adopt heating conditions that make the ink receiving layer compatible with the ink absorbency and water resistance.

In the present invention, the heating is preferably carried out in two steps at a temperature which gradually increases above the boiling point of the solvent. In the first stage, the solvent is mainly removed by heating at + 30 ° C. or lower, preferably based on the boiling point of the solvent, immediately after the start of drying.
The time at this time is preferably in the range of 1 to 10 minutes. Second
The step is preferably carried out at a temperature above that temperature to effect complete solvent removal and to heat cure the ink receptive layer to the desired extent while simultaneously migrating and localizing the surfactant to the surface. Further, the time at this time is preferably in the range of 0.5 to 10 minutes. Such a heating method is particularly effective in producing a recording body containing a water-soluble melamine resin as a curing agent. By adopting such a heating condition, it is possible to form an ink receiving layer having both excellent ink absorbency and water resistance and excellent surface gloss.

By providing an intermediate layer between the base material layer and the receiving layer, the adhesiveness between the base material layer and the receiving layer can be improved. The compound constituting the intermediate layer is preferably a polyester resin, but in addition to this, a polyurethane resin,
Compounds and the like disclosed as means for improving the adhesiveness of ordinary polyester films such as polyacrylic resin and polyester urethane resin are applicable. These resins can be used alone or as a mixture.

The polyester resin of the intermediate layer is a polyester resin composed of dibasic acid and glycol and soluble in water, emulsified or dispersed. For example, the dibasic acid is a dicarboxylic acid in which 50 to 0.5 mol% of all dicarboxylic acids have a sulfonic acid metal base, and is a polyester copolymer obtained by copolymerizing these two layers of the dicarboxylic acid component and the glycol component. Examples of the dicarboxylic acid having a metal sulfonate group include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,
Metal salts such as 7-dicarboxylic acid and 5- [4-sulfophenoxy] isophthalic acid are mentioned, and particularly preferred is 5-
Sodium sulfoisophthalic acid and sodium sulfoterephthalic acid. The dicarboxylic acid having a metal sulfonate group is 50 to 50% based on the total dicarboxylic acid component.
It is 0.5 mol%, preferably 20 to 1 mol%. Fifty
If it exceeds mol%, the water resistance of the copolymer is lowered even if the dispersibility in water is improved, which is not preferable. The dispersibility of the polyester copolymer in water varies depending on the copolymerization composition, the type and amount of the water-soluble organic compound, etc., but the amount of the dicarboxylic acid component having the metal sulfonate group does not impair the dispersibility in water, The smaller the better.

As the usual dicarboxylic acid having no metal sulfonate group, aromatic, aliphatic and alicyclic dicarboxylic acids are used. Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid,
2,6-naphthalenedicarboxylic acid and the like can be mentioned. These aromatic dicarboxylic acids preferably account for 40 mol% or more of the total dicarboxylic acid components. 40 mol%
If it is less than the above range, the mechanical strength and water resistance of the polyester copolymer are deteriorated, which is not preferable. Aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid,
1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like can be mentioned. Addition of these aliphatic or alicyclic dicarboxylic acid components may enhance the adhesiveness, but generally the mechanical strength and water resistance of the polyester copolymer will deteriorate.

The glycol component to be reacted with the above dicarboxylic acid mixture is an aliphatic glycol having 2 to 8 carbon atoms, an alicyclic glycol having 6 to 12 carbon atoms, and a mixture of both, such as ethylene glycol, 1, 2-propylene glycol, 1,3-propanediol, 1,4
-Butanediol, neopentyl glycol, 1,6-
Hexanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, p-xylene glycol and the like can be mentioned. Examples of the aliphatic diol having 4 or more carbon atoms include diethylene glycol and triethylene glycol, and examples of the polyether include polyethylene glycol, polypropylene glycol and polytetramethylene glycol.

The above polyethylene copolymer can be obtained by usual melt polycondensation. That is, a direct esterification method in which the above-mentioned dicarboxylic acid component and glycol component are directly reacted, water is distilled off to be esterified, and then polycondensation is carried out,
Alternatively, it can be obtained by a transesterification method in which a dimethyl ester of a dicarboxylic acid component is reacted with a glycol component, methyl alcohol is distilled off to conduct transesterification and then polycondensation. In addition, the polymer can be obtained by solution polycondensation or interfacial polycondensation. However, the present invention is not limited to any of the above methods. At the time of melt polycondensation, an antioxidant, a slip agent, inorganic fine particles and an antistatic agent can be added if necessary. The above-mentioned polyether such as polyethylene glycol can be added by melt blending during melt polycondensation or after polymerization.

As the polyurethane resin for the intermediate layer,
(1) a compound having two or more active hydrogen atoms in the molecule, (2) an organic polyisocyanate having two or more isocyanate groups in the molecule, or (3) at least two compounds in the molecule if necessary. Polyurethane having an isocyanate group at the terminal, which is obtained by reacting a chain extender having an active hydrogen atom, can be used.

The compounds generally known as the above-mentioned compound (1) are those having two or more hydroxyl groups, carboxyl groups, amino groups or mercapto groups at the terminal or in the molecule. Examples thereof include ether polyols, polyester polyols and polyether ester polyols. As the polyether polyol, for example, alkylene oxides such as ethylene oxide and propylene oxide,
Or compounds obtained by polymerizing styrene oxide, epichlorohydrin, etc., or random copolymerization thereof,
Examples thereof include compounds obtained by block copolymerization or addition polymerization of polyhydric alcohol. Polyester polyols and polyether ester polyols mainly include linear or branched compounds, such as polyvalent saturated and unsaturated carboxylic acid anhydrides such as succinic acid, adipic acid, phthalic acid and maleic anhydride. And polyhydric saturated and unsaturated alcohols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol and trimethylolpropane, relatively low molecular weight polyethylene glycol, polypropylene It can be produced by condensing a polyalkylene ether glycol such as glycol or a mixture of these alcohols. Further, polyester polyols include polyesters obtained from lactones and hydroxy acids, and polyether ester polyols include polyether esters obtained by adding ethylene oxide or propylene oxide to previously produced polyesters.

As the organic polyisocyanate of the above (2), isomers of toluylene diisocyanate, 4,
Aromatic diisocyanates such as 4'-diphenylmethane diisocyanate, aromatic aliphatic diisocyanates such as xylylene diisocyanate, aliphatic diisocyanates such as isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate, or a single compound or plural compounds thereof. Examples thereof include polyisocyanates pre-added with trimethylolpropane.

As the chain extender having at least two active hydrogen atoms in the above (3), ethylene glycol, diethylene glycol, 1,4-butanediol and 1,
Glycols such as 6-hexanediol, polyhydric alcohols such as glycerin, trimethylolpropane and pentaerythritol, diamines such as ethylenediamine, hexamethylenediamine and piperazine, amino alcohols such as monoethanolamine and diethanolamine, thiodiethylene glycol, etc. Examples thereof include thiodiglycols and water.

The polyacrylic resin for the intermediate layer is obtained by polymerizing acrylic acid or a derivative thereof and, if necessary, a monomer other than acrylic acid (derivative) having a vinyl group. As the monomer used, acrylic acid, methacrylic acid (hereinafter, acrylic acid and / or methacrylic acid are referred to as (meth) acrylic acid) (meth) acrylic acid lower alkyl ester (for example, methyl, ethyl, propyl,
Butyl, amyl, hexyl, heptyl, octyl, 2-
Ethylhexyl ester), methyl methacrylate,
It is prepared using hydroxymethyl acrylate, styrene, glycidyl methacrylate, methyl acrylate, ethyl acrylate and the like.

If necessary, particles having an average particle size of 0.1 μm or more, preferably particles having an average particle size of 0.3 μm or more may be blended in the intermediate layer. As the particles that can be added, silica, kaolinite, talc, calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, titanium oxide, organic white pigment (crosslinked acrylic particles,
Crosslinked styrene particles) are exemplified, but the present invention is not limited to these. If the average particle size of the particles is less than 0.1 μm, the drawability with a pencil is insufficient, which is not preferable.

As the method for providing the intermediate layer, there are commonly used methods such as a gravure coating method, a kiss coating method, a dipping method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method and a reverse roll coating method. Applicable. As the step of applying, any method such as a method of applying before stretching the film, a method of applying after longitudinal stretching, a method of applying to the film surface after the orientation treatment, and the like are possible.

In the present invention, a slipping layer may be provided on the surface of the base material layer opposite to the ink receiving layer. The technique of providing the above-mentioned intermediate layer can be directly applied to this easily slipping layer.
Further, this easy-slipping layer may contain an antistatic agent, a fluorescent whitening agent, an ultraviolet absorber, etc. inside. Those usually used are used. In this case, it is preferable that the centerline two-dimensional surface roughness of the easy-slip layer is larger than that of the ink receiving layer. Therefore, it is preferable to contain the particles as described above. When the roughness is small, the slip between the ink receiving layer and the easy-sliding layer is poor, and the transportability of the paper inside the printer is poor, which is not preferable.

The recording medium thus obtained quickly absorbs the ink and is difficult to remove even if water is applied to the ink-receiving layer after the ink has been absorbed, and the recording can be carried out by a color ink jet printer to obtain a silver salt photographic image. It is possible to record with high gloss, high quality and high quality.

The water retentivity of the ink receiving layer of the recording material of the present invention is 30% or more, preferably 40% or more, more preferably 50% or more. If the water immersion concentration retention rate is less than 30%, the water resistance of the ink receiving layer is poor, and the ink will flow out when the printed matter is splashed with water, or the ink receiving layer will peel off from the substrate, resulting in the original printed matter. Disappears. As a method of setting the water immersion concentration retention rate in the above range,
Although not particularly limited, as described above, a method of containing a specific amount of a curing agent in the ink receiving layer, a method of using specific heating conditions in the ink receiving layer forming step, and the like are suitably adopted. Here, the water retention rate means that after printing on the recording medium,
The printed surface was immersed in water, and the ink density before and after the immersion was calculated.

The surface gloss of the ink receiving layer of the recording material of the present invention is 55% or more, preferably 70% or more, more preferably 80% or more, still more preferably 90% or more. When the surface gloss is less than 55%, the printed matter does not have high gloss and high quality and high image quality similar to silver halide photographs. As a method of setting the surface gloss in the above range,
Although not particularly limited, as described above, a method of containing a specific amount of a surfactant in the ink receiving layer, a method of applying a specific heating condition in the ink receiving layer forming step, and the like are suitably adopted.

The ink absorbency of the ink receiving layer of the recording material of the present invention is determined by the drying time when printed on an ink jet printer, that is, 0.1 to 1.0 μm.
The ink absorption time for an ink amount of 1 / cm ² is preferably 50 seconds or less, more preferably 30 seconds or less, further preferably 15 seconds or less, and particularly preferably 5 seconds or less. If the ink absorption time exceeds 50 seconds, the ink absorption may be poor and the show-through may occur when printing a plurality of sheets. The method for setting the ink absorption time in the above range is not particularly limited, but as described above, a method of containing a specific amount of the ink absorbing resin in the ink receiving layer, a specific heating condition in the ink receiving layer forming step is adopted. The method and the like are preferably adopted.

When the recording material of the present invention is used in applications requiring transparency such as OHP, the light transmittance thereof is preferably 60% or more, more preferably 80% or more. When the light transmittance is less than 60%, it is difficult to see through a printed matter, which is not suitable for OHP and the like. Examples of the method of adjusting the light transmittance within the above range include a method of reducing the amount of particles added for handling the base film. When the recording material of the present invention is required to be opaque, the light transmittance thereof is preferably not more than 60%, more preferably 20% or less, further preferably 15% or less. 60% light transmittance
In the above case, the back side can be seen through, and the appearance of the printed matter is poor, which is not preferable. As a method of setting the light transmittance in the above range, as described above, there is a method of forming the base material layer into a film containing fine voids, and the amount of the incompatible resin or particles to be added is appropriately selected. However, the specific stretching and relaxation conditions in the manufacturing process are adopted.

[0054]

EXAMPLES Next, the present invention will be explained with reference to examples and comparative examples, but the present invention is not limited to these.
First, the measurement / evaluation methods used in the present invention are shown below.

1) Ink absorption time Ink jet printer (Seiko Epson M
(J-700V2C), a line having a width of 3 mm and a length of 15 cm is printed on the recording medium in cyan and black. After the printing was completed, the line was rubbed with a finger, and the time when the line did not rub was obtained. At this time, the ink amount is about 0.4.
μl / cm ² .

2) The same printing as the show-through 1) is printed on the recording medium with cyan, magenta, yellow and black (B) inks, and after the printing is completed, a paper (PPC paper TYPE6 manufactured by Ricoh Co., Ltd.) is printed.
000) was placed on the top, and when the ink was not printed on the paper, it was marked with ◯, and when it was printed with x.

3) A printer having a water immersion density retention rate of 1) printed cyan (C), magenta (M), yellow (Y), and black (B) inks on a recording medium in a size of 5 × 5 cm ² , and printed the surface 3 Soak in running water for 1 minute. The reflection density was measured with a Macbeth densitometer (TR-927) for the density of each color before and after the immersion in the running water, and the water immersion density retention rate = (density after water immersion / density before water immersion) × 100
Calculated as (%).

4) Surface gloss Using Nippon Denshoku Industries Co., Ltd. VGS-1001DP,
The reflectance of the recording material at incident light and reflected light of 60 degrees was determined.

5) Light transmittance According to JIS-K6714, Poic integrating sphere type H.264. T.
The light transmittance of the recording material was measured using an R meter (manufactured by Nippon Seimitsu Optical Co., Ltd.). The smaller this value is, the higher the hiding property is.

6) Apparent specific gravity The base material film is accurately cut into a square of 5.00 cm × 5.00 cm, its thickness is measured at 50 points, the average thickness is t (μm), and its weight is 0.1 mg unit. Was measured up to w (g) and calculated by the following formula. Apparent specific gravity (−) = w × 10000 / (5 × 5 × t)

7) Surface coverage of fluorine atoms by ESCA MgCA was used as a light source by ESCA (850) manufactured by Shimadzu Corporation.
Output 9kV × 30mA using Kα ray (1254eV)
Then, the area of the peaks derived from fluorine, carbon, oxygen, nitrogen, and hydrogen of the ink receiving layer was obtained, and the area was multiplied by the coefficient depending on the detection sensitivity of each element, and converted into the number of atoms to obtain the ratio. This shows the degree of localization of the fluorine compound used as the surfactant on the surface of the ink receiving layer.

Example 1 Polyvinyl alcohol (cationic, CM-manufactured by Kuraray Co., Ltd.) was used for all components constituting the ink receiving layer coating liquid.
318) 9.2% by weight, water-soluble melamine resin (Sumimall manufactured by Sumitomo Chemical Co., Ltd.) 0.6% by weight, surfactant (perfluoro compound, Sumitomo 3M Florad F)
C-430) 0.2 wt% and water 90 wt% were mixed to prepare an ink receiving layer coating liquid. On the other hand, the base film (Crisper G2312 125 manufactured by Toyobo Co., Ltd.)
Polyester resin (Vylon MD-16 manufactured by Toyobo Co., Ltd.) is applied to the high gloss surface of 0.2 g / m ^{2 in} advance.
Coated to form an intermediate layer. The above-mentioned coating liquid for ink receiving layer was applied onto the intermediate layer of the base film so that the coating amount after drying was 18 g / m ^2, and the coating was carried out at 120 ° C. for 1 minute.
A recording material was obtained by drying at 50 ° C. for 3 minutes. With respect to this medium, the ink absorption time of the ink receiving layer, show-through, water immersion concentration retention and surface gloss were evaluated. The results are shown in Table 1.

Comparative Example 1 A recording material was obtained by the same method as in Example 1 except that the drying was carried out at 120 ° C. for 4 minutes only.

Example 2 In Example 1, 9.0% by weight of polyvinyl alcohol (GH-20 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), water-soluble melamine resin (based on all components constituting the ink receiving layer coating liquid) Sumitomo Chemical Co., Ltd. Sumimal) 0.7% by weight, cationic compound (dimethyldiallylammonium chloride, Nippon Kayaku Co., Ltd. Kayafix UR)
0.1% by weight, 0.2% by weight of a surfactant (perfluoroalkylethylene oxide adduct, Megafac F-142D manufactured by Dainippon Ink and Chemicals, Inc.) and water 89
A recording material was obtained by the same method as in Example 1 except that the coating liquid for the ink-receiving layer was mixed in an amount of wt%.

Example 3 The same method as in Example 2 except that the surfactant of the ink receiving layer was a silicone type (Painted PT-32 manufactured by Dow Corning Asia Co., Ltd.). To obtain a recording body.

The recording materials obtained in Examples 1 to 3 and Comparative Example 1 and the special glossy film (Comparative Example 2) manufactured by Seiko Epson Corporation were evaluated. The results are shown in Table 1.

[0067]

[Table 1]

The recording materials of Examples 1 to 3 have a short ink absorption time, no show-through, a high water immersion density retention rate and a high surface gloss, and are suitable for ink jet printers (MJ-700V2C manufactured by Seiko Epson Corporation). The printed matter had a high gloss similar to a silver halide photograph, high quality, high quality, and good aesthetics. However, the recording body of Comparative Example 1 had a low water immersion concentration retention rate, and the recording body of Comparative Example 2 had low surface gloss and lacked quality.

[0069]

As is apparent from the above description, according to the present invention, the ink is quickly absorbed, and even if water is applied to the ink receiving layer after the ink is absorbed, it is difficult to remove the ink and the glossiness of the surface is increased. It is possible to provide a recording material suitable for ink jet recording, which can be recorded by a color printer, and can record with high gloss, high quality and high quality like a silver halide photograph.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 30, 2003 (2003.5.3)
0)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

Wherein the ink receiving layer, the ink-jet recording material according to claim 1, characterized by containing a compound further having a cationic group.

Wherein the ink absorptive resin is Inkuji according to claim 1, wherein the polyvinyl alcohol
Recorder for wet .

4. The inkjet recording material according to claim 1, wherein the curing agent is a water-soluble melamine resin.

Content of 5. The ink absorptive resin is, the inkjet apparatus according to claim 1, characterized in that 10 to 99% by weight relative to the total components constituting the ink-receiving layer <br/> Recording body.

6. The inkjet recording material according to claim 1 , wherein the content of the curing agent is 0.1 to 20% by weight with respect to the ink absorbing resin.

7. A composition containing an ink-absorbing resin, a curing agent, a surfactant and a solvent is applied onto a base material layer, and the applied layer is at least the boiling point of the solvent and + 30 ° C.
Heating to a temperature below further comprising forming an ink-receiving layer heated in the temperature higher than the temperature Lee
Manufacturing method of recording body for ink jet .

8. A composition containing an ink-absorbing resin, a curing agent, a surfactant and water is applied onto a substrate layer,
Heating this coating layer to a temperature of 100 to 130 ° C.,
The method for producing an inkjet recording material according to claim 7 , further comprising heating at 130 to 180 ° C to form an ink receiving layer.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

The ink-receiving layer is composed of a single layer.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

In the present invention, the heating is preferably carried out in two steps at a temperature which gradually increases above the boiling point of the solvent. In the first stage, immediately after the start of drying, heating is preferably performed at + 30 ° C. or lower based on the boiling point of the solvent . Also, the time at this time is 1
A range of 10 minutes is preferred. The second step is preferably carried out at a temperature above that temperature and to the desired extent the ink receiving layer.
The heat curing. Time when this is in the range of 0.5 to 10 minutes is preferable. Such a heating method is particularly effective in producing a recording body containing a water-soluble melamine resin as a curing agent. By adopting such a heating condition, it is possible to form an ink receiving layer having both excellent ink absorbency and water resistance and excellent surface gloss.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshitake Suzuki             2-1 1-1 Katata, Otsu City, Shiga Prefecture Toyobo             Koki Co., Ltd. F-term (reference) 2C056 EA13 FC06                 2H086 BA15 BA19 BA31 BA35 BA37                       BA41

Claims (10)

[Claims] 1. A substrate layer comprising a plastic film, and an ink receiving layer provided on the substrate layer,
The water retentivity of the ink receiving layer is 30% or more, the surface gloss of the ink receiving layer is 55% or more, and the ink absorption time is 50 seconds or less when the ink amount of the ink receiving layer is 0.1 to 1.0 μl / cm ^2. A recording medium characterized by being. 2. The recording material according to claim 1, wherein the ink receiving layer contains an ink absorbing resin, a curing agent and a surfactant. 3. The recording material according to claim 2, wherein the ink receiving layer further contains a compound having a cationic group. 4. The recording material according to claim 2, wherein the ink absorbing resin is polyvinyl alcohol. 5. The recording material according to claim 2, wherein the curing agent is a water-soluble melamine resin. 6. The recording material according to claim 2, wherein the content of the ink absorbing resin is 10 to 99% by weight with respect to all components constituting the ink receiving layer. 7. The recording material according to claim 2, wherein the content of the curing agent is 0.1 to 20% by weight based on the ink absorbing resin. 8. The recording material according to claim 2, wherein the content of the surfactant is 0.5 to 20% by weight based on all components constituting the ink receiving layer. 9. A composition containing an ink-absorbing resin, a curing agent, a surfactant and a solvent is applied onto a substrate layer, and the applied layer is at least the boiling point of the solvent and + 30 ° C.
A method for producing a recording body, which comprises heating to the following temperature and further heating at a temperature higher than the temperature to form an ink receiving layer. 10. A composition containing an ink absorbing resin, a curing agent, a surfactant and water is applied onto a base material layer, the applied layer is heated to a temperature of 100 to 130 ° C., and further 130. The method for producing a recording medium according to claim 9, which comprises heating at -180 ° C to form an ink receiving layer.