JPH0952435A - White film for ink jet recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a medium wherein ink is quickly absorbed, and even if water is dropped on an ink receptive layer after the ink receptive layer absorbed ink, the ink is difficult to be removed, recording can be carried out with a color ink jet printer, and recording of high glossiness, high quality, and high dignity such as a silver salt photograph can be carried out. SOLUTION: In an ink jet recording white film wherein an ink receptive layer containing ink absortive resin, a hardening agent, and a surface active agent is provided on a base material film, when printing is carried out with an ink jet printer, each drying time for cyan, magenta, yellow, and black ink is 50sec or shorter, a wetted density retention percentage is 30% or higher, a surface gloss of the ink receptive layer is 55% or over, and a light transmittance is 60% or less.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention relates to recording in a color ink jet printer, which absorbs ink quickly, and even if water is applied to the ink receiving layer after the ink is absorbed, the ink is difficult to remove and the surface glossiness is high. The present invention relates to a medium capable of producing a high-gloss high-gloss aesthetic appearance such as a silver salt photograph.

[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 halide photography. In particular, how to bring color reproducibility, image density, gloss, weather resistance, etc. close to silver halide photography has been a subject of development. As a hard copy recording method, various 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 silver halide photography.

An ink jet printer is
In recent years, it has been rapidly spreading due to its ease of full color printing and low printing noise. In the ink jet method, ink droplets are ejected from a nozzle toward a recording material at a high speed, and a large amount of solvent is contained in the ink. For this reason, a recording sheet for an ink jet printer is required to absorb ink quickly and have excellent color developing properties. These inkjet recordings are aimed at the characteristics of silver halide photography, but none of the prints of such a system have high quality, high quality, water resistance, and show-through in continuous printing.

[0004]

The present invention was devised in order to solve the above-mentioned drawbacks of the prior art. The purpose of the present invention is to quickly absorb ink and to absorb the ink in the ink receiving layer. It is an object of the present invention to provide a medium capable of recording with a color inkjet printer, capable of recording with a color ink jet printer, and having high gloss, high quality and high quality like silver halide photography, even if water is applied after that.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, have completed the present invention. That is, the present invention is an inkjet recording white film provided with an ink-absorbing resin, a curing agent, and a surfactant-containing ink receiving layer on a base film, cyan when printed by an inkjet printer, magenta, Each of the yellow and black inks has a drying time of 50 seconds or less, a water immersion density retention rate of 30% or more, a surface gloss of the ink receiving layer of 55% or more, and a light transmittance of 60% or less. It is a white film for inkjet recording.

The resin of the substrate film used in the present invention is not particularly limited, and examples thereof include polyolefin resin, polyamide resin, polyacrylic resin,
Polyurethane-based resins, polyvinyl-based resins, polyether-based resins, polystyrene-based resins and the like can be mentioned, and particularly preferred are polyester-based resins as described below. In the present invention, the preferred polyester resin is an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid or an ester thereof and a glycol such as ethylene glycol, diethylene glycol, 1,4-butanediol or neopentyl glycol. It is a polyester produced by condensation.
These polyesters can be prepared by directly reacting an aromatic dicarboxylic acid and a glycol, or by subjecting the alkyl ester of an aromatic dicarboxylic acid to a transesterification reaction with a glycol followed by polycondensation, or a diglycol ester of an aromatic dicarboxylic acid. Can be produced by a method such as polycondensation. Typical examples of such polyesters include polyethylene terephthalate, polyethylene butylene terephthalate or polyethylene-2,6.
-Naphthalate and the like. This polyester may be a homopolymer or a copolymer of the third component. In any case, in the present invention,
7 units of ethylene terephthalate units, butylene terephthalate units or ethylene-2,6-naphthalate units
A polyester having 0 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more is preferable.

In the present invention, it is preferable to use a substrate film containing a large number of fine cavities inside. Although the method is not particularly limited, it is particularly preferable that the polyester contains a large number of incompatible thermoplastic resins and / or particles therein, and is oriented uniaxially to form fine particles inside. This is a method of containing a large number of cavities.

The thermoplastic resin incompatible with the polyester used in the present invention is not particularly limited as long as it is incompatible with the polyester. Specifically, polystyrene resin, polyolefin resin, polyacrylic resin, polycarbonate resin, polysulfone resin,
Cellulose resins, polyamide resins, etc. may be mentioned. In particular, polystyrene resins or polyolefin resins such as polymethylpentene, polypropylene and cyclic olefins are preferably used. The amount of the immiscible resin to be mixed with the polyester varies depending on the desired amount of cavities, but is preferably 3% by weight to 39% by weight, and particularly preferably 5% by weight to 15% by weight. If the content is less than 3% by weight, there is a limit in increasing the amount of cavities, and the desired flexibility, lightness, or drawing property cannot be obtained. On the other hand, if it exceeds 39% by weight, the stretchability of the film is significantly impaired, and the heat resistance, strength and stiffness of the film are impaired.
Further, two or more of these thermoplastic resins may be used in combination.

In addition, inorganic or organic particles may be added to the polyester film or the incompatible resin, if necessary, in order to contain fine voids in the base film or to improve the hiding property. You may add. Examples of particles that can be added include silica, kaolinite, talc, calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, titanium oxide, crosslinked acrylic particles, and crosslinked polystyrene particles, but are not particularly limited. Not something.

The base film of the present invention may be a single layer film or a composite film of two or more layers. The substrate film of the present invention has an apparent specific gravity of 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 1.05 or more and 1.
It is preferably in the range of less than 25. If the apparent specific gravity is less than 0.7, the void content is too large, the strength of the film is remarkably impaired, and wrinkles and wrinkles are easily generated on the film surface regardless of the vertical and horizontal balance. vice versa,
When the apparent specific gravity is 1.32 or more, the void content becomes too small, the cushioning property is lost, and the pencil drawability is lost.

The ink jet recording film of the present invention has a light transmittance of 60% or less, preferably 20% or less, more preferably 15% or less, still more preferably 10% or less. If the light transmittance exceeds 60%, the back side can be seen through, and the appearance of the printed matter becomes poor, which is not preferable.

The substrate film of the present invention preferably has an in-plane birefringence of -0.02 to +0.04, more preferably 0 to +0.03. In-plane birefringence is -0.02
By setting the above, preferably 0 or more,
A film having substantially isotropic property is obtained. here,
The in-plane birefringence of + (-) means that the history of longitudinal stretching remains larger (smaller) than the history of lateral stretching, and it may be a little caused by so-called bowing phenomenon during transverse stretching. The distortion of the principal axis of the refractive index may be accompanied. By setting the in-plane birefringence to -0.02 or more, preferably 0 or more, the film can be prevented from being torn in the lateral direction. On the other hand, the in-plane birefringence is +0.
On the other hand, when it exceeds 04, the film is liable to be vertically torn, and the film is liable to be broken at the time of slitting, or the film is liable to be cracked in the longitudinal direction at the time of cutting. The in-plane birefringence is less than -0.02 or +0.
If it is 04 or more, it may cause wrinkles and curls in the printer.

The method for producing the base film of the present invention is not particularly limited, but the most preferable production method is
The unstretched film is stretched 3.0 times or more in the longitudinal direction in one stage or multiple stages, then subjected to a relaxation treatment of 3% or more in the longitudinal direction, and then transversely stretched / heat-treated at a magnification of at least the longitudinal stretching ratio after the relaxation treatment. Is the way to do it.

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, a method using a non-contact heating method may be used, or both may be used. However, in order to develop a large number of cavities at the interface of the immiscible resin, the stretching temperature is set to the secondary transition temperature T of the polyester.
Stretching is performed at a temperature of g + 10 ° C. or higher and Tg + 50 ° C. or lower, and a stretching ratio of 3.0 times or more, preferably 3.2 to 5.0 times. When the stretching ratio is less than 3.0 times, it becomes difficult to sufficiently develop fine cavities inside the film and make the apparent specific gravity of the film less than 1.32. Further, if the longitudinal magnification exceeds 5.0 times, it becomes difficult to sufficiently perform the subsequent relaxation treatment, and it becomes substantially difficult to set the in-plane birefringence of the film to 0.04 or less.

Next, 3% or more in the longitudinal direction, preferably 5%
% Or more. The more preferable relaxation rate depends 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. Then, the in-plane birefringence is -0.02 to +0.
It is possible to industrially produce the film No. 04 in a stable manner. On the other hand, when the relaxation treatment of 3% or more is not performed, the lateral stretchability in the next step becomes extremely 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, the fine void-containing film having a preferable apparent specific gravity of the present invention cannot be produced.

The preferred stretching ratio after longitudinal relaxation is 2.
8 to 3.5. When the longitudinal stretching ratio after relaxation is less than 2.8, the relaxation may not be performed uniformly to form a non-uniform film, or the in-plane birefringence index after biaxial stretching may be −0.02 or less. It is not preferable because it may occur. 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, the relaxation treatment is carried out between the rolls without cooling. Method, or 60 ° C to 100
A method of performing relaxation treatment between the driving roll group or the free roll group heated to 0 ° C., a method of appropriately combining these, or the like can be adopted. However, a method in which the relaxation treatment is performed mainly by a method of performing the relaxation treatment without cooling immediately after the longitudinal stretching is preferable, and a uniform relaxation treatment can be efficiently performed.

Next, the film after the longitudinal relaxation treatment is introduced into a tenter, and transversely stretched and heat-treated at a draw ratio equal to or higher than the longitudinal stretching magnification 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 Tm-10 of polyester.
It is below ° C. 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 it is necessary to perform the stretching at a longitudinal stretching ratio of +1.0 or less after the relaxation treatment in order to secure the stretchability and to set the in-plane birefringence to -0.02 or more. Is preferred.

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, in parallel with the heat treatment, re-lateral stretching or relaxation in the transverse direction may be performed.

In the present invention, an ink jet recording medium can be obtained by providing an ink receiving layer on such a substrate film, but the ink receiving layer is not particularly limited and preferably ink absorbing layer. Contains a resin, a curing agent, and a surfactant. As the ink absorbing resin, known ones can be used, for example, polyvinyl alcohol, acrylic resin, styrene-acrylic polymer, ethylene-vinyl acetate polymer, starch, polyvinyl butyral, gelatin, casein, ionomer,
One or more kinds of resins such as gum arabic, carboxymethyl cellulose, polyvinylpyrrolidone, polyacrylamide, polyester resin, and styrene-butadiene rubber can be used if desired. Of these, polyvinyl alcohol is preferred.

The ink receiving layer contains a curing agent to increase the degree of curing of the receiving layer and improve the water resistance. Examples of such a curing agent include epoxy resin, polyurethane resin, and polyether resin, and although not particularly limited, water-soluble melamine resin is preferable. These curing agents are preferably added in an amount of 0.5 to 10% by weight based on the ink absorbing resin. In addition, silica, kaolinite, talc, calcium carbonate, zeolite, alumina,
Particles such as 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 the extent that surface gloss is not lowered. The ink receiving layer may be composed of one layer or may have a structure of two or more layers. The ink receiving layer can further improve ink absorbability by including a compound containing a cation group, for example, polyvinyl alcohol having a cation group or a dyeing agent having a cation group.

By adding a surfactant to the ink receiving layer, it is possible to make the surface of the ink receiving layer high in gloss while maintaining the ink absorbability and water resistance. In particular, in the case of adding a curing agent to the above-mentioned water-soluble melamine resin, it is difficult to achieve both ink absorbability and water resistance depending on the drying conditions during coating. That is, if the curing is sufficient, the ink absorbency becomes poor, and if the curing is stopped to such an extent that the ink is sufficiently absorbed, the water resistance becomes poor. Furthermore, when particles or the like are added to the receiving layer so as to improve the ink absorbing ability, the water resistance is improved, but the surface gloss is lowered,
Good-looking prints are impossible.

As the surfactant, any of cationic, anionic, nonionic and nonionic surfactants can be used, but silicon or fluorine surfactants are preferred. Silicon-based surfactants include 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 Examples include siloxane, fluorine-modified siloxane, alkyl group-modified siloxane, phenyl-modified siloxane, and alkylene oxide-modified siloxane. Examples of the fluorine-based surfactant include ethylene tetrafluoride, perfluoroalkyl ammonium salt, perfluoroalkyl sulfonamide, sodium perfluoroalkyl sulfonate, perfluoroalkyl potassium salt, perfluoroalkyl carboxylate, perfluoroalkyl sulfone Acid salt, perfluoroalkylethylene oxide adduct, perfluoroalkyltrimethylammonium salt, perfluoroalkylaminosulfonate, perfluoroalkylphosphate, perfluoroalkylalkyl compound, perfluoroalkylalkylbetaine, perfluoroalkylhalide, etc. Is mentioned. The amount of these surfactants added is 0.5 in the ink receiving layer after drying.
-20% by weight, preferably 1-10% by weight.
If it is less than 0.5% by weight or more than 20% by weight, ink absorbency and water resistance cannot be compatible with each other.

The method for providing the ink receiving layer is not particularly limited, but it is usually used such as gravure coating method, kiss coating method, dip method, spray coating method, curtain coating method, air knife coating method, blade coating method, reverse roll coating method. The method can be applied. Contains a silicon-based or fluorine-based surfactant,
In addition, it is possible to achieve both ink dryability and water resistance by drying and heat curing according to the method described below. The coating amount at this time is 8 g / m ² or more after drying, 5
It is preferably 0 g / m ² or less. The drying condition of the coat layer is preferably set to the boiling point of the solvent of the coating liquid + 30 ° C. or less immediately after the start of drying, and thereafter higher than that temperature to obtain an ink receiving layer having both ink drying property and water resistance. be able to. Although no detailed study has been made on this phenomenon, it is expected that there is some relationship between the presence state of the surfactant in the ink receiving layer and the drying conditions.

The ink absorbency of the recording medium thus obtained is 50% or less, preferably 30 seconds or less when the cyan, magenta, yellow and black inks are dried on the recording medium by an ink jet printer. It is more preferably 15 seconds or less, still more preferably 5 seconds or less. When the number of prints exceeds 50 seconds, the lower printed ink appears on the upper substrate when printing a plurality of sheets. It is necessary that the retention rate of the water immersion concentration of the inkjet recording film is 30% or more, preferably 40% or more. If it is less than 30%, the water resistance is insufficient, and when the printed matter is splashed with water, the ink flows out or the ink receiving layer peels off from the substrate, and the original printed matter cannot be seen. The surface gloss of the ink receiving layer is 55% or more, preferably 70% or more, more preferably 80% or more, and further preferably 90%.
% Is preferable. If it is less than 55%, the glossiness is similar to that of a silver halide photograph, and a printed matter of high quality and high image quality cannot be obtained.

By providing an intermediate layer between the base film and the receiving layer, the adhesiveness between the base and the receiving layer can be improved. The compound constituting the intermediate layer is preferably a polyester resin, but in addition to this, a compound disclosed as a means for improving the adhesiveness of a normal polyester film such as a polyurethane resin, a polyacrylic resin or a polyester urethane resin. Etc. 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, which is soluble, emulsifiable or dispersible in water. For example, a dibasic acid is a polyester copolymer in which 50 to 0.5 mol% of all dicarboxylic acids are metal sulfonate-containing dicarboxylic acids, and these two dicarboxylic acid components and glycol components are copolymerized. Examples of the dicarboxylic acid containing a metal sulfonate group include sulfoterephthalic acid, 5-sulfoisophthalic acid, and 4
-Metal salts of sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5 [4-sulfophenoxy] isophthalic acid and the like are mentioned, and particularly preferred are metals of 5-sodium sulfoisophthalic acid and sodium sulfoterephthalic acid. It is salt. These metal sulfonate-containing dicarboxylic acids contain 50 to 0.5 of all dicarboxylic acid components.
It is mol%, preferably 20 to 1 mol%. 50 mol%
If it exceeds, the water resistance of the copolymer decreases even if the dispersibility in water is improved. 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 sulfonic acid metal group-containing dicarboxylic acid component is small unless the dispersibility in water is impaired. Better.

As the usual dicarboxylic acid containing 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. The content of these aromatic dicarboxylic acids is preferably at least 40 mol% 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. As the aliphatic and alicyclic dicarboxylic acids, succinic acid, adipic acid, sebacic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclodicarboxylic acid, 1,4- Examples include cyclohexanedicarboxylic acid. The addition of these aromatic dicarboxylic acid components may improve the adhesiveness in some cases, but in general, the mechanical strength and water resistance of the polyester copolymer 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, neobenzyl 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 polyester 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 active hydrogen atoms in the molecule. A compound having an isocyanate group at the terminal, which is obtained by reacting the chain extender with the compound, can be used.

The compounds generally known as the above-mentioned compound (1) are those containing two or more hydroxyl groups, carboxyl groups, amino groups or mercapto groups at the end or in the molecule, and particularly preferred are polyethers. Examples thereof include polyols, polyester polyols and polyether ester polyols. As the polyether polyol, for example, a compound obtained by polymerizing alkylene oxides such as ethylene oxide and propylene oxide, or styrene oxide and epichlorohydrin, or random copolymerization thereof, block copolymerization or addition polymerization to a polyhydric alcohol is obtained. There are compounds. 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 single 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 of the intermediate layer is obtained by polymerizing acrylic acid or its derivative and, if necessary, a monomer other than acrylic acid (derivative) having a vinyl group. Examples of the monomer used include acrylic acid, methacrylic acid (hereinafter, acrylic acid and / or methacrylic acid are (meth) acrylic acid) (meth) acrylic acid lower alkyl ester (for example, methyl, ethyl, propyl,
Butyl, amyl, hexyl, hebutyl, 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 contained in the intermediate layer and / or the ink receiving layer. As particles that can be added, silica, kaolinite, talc, calcium carbonate, zeolite, alumina, barium sulfate,
Examples thereof include carbon black, zinc oxide, titanium oxide, and organic white pigments (crosslinked acrylic particles, crosslinked styrene particles), but are not limited thereto. When the average particle size of the particles is less than 0.1 μm, the drawability with a pencil is insufficient.

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, and a method of applying to the surface of the film after the orientation treatment is possible.

In the present invention, a slipping layer may be provided on the surface of the base film 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, slippage between the ink receiving layer and the easy-sliding layer is poor, and the paper transportability inside the printer is poor.

The recording medium thus obtained absorbs the ink promptly 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.

[0040]

Next, examples of the present invention and comparative examples will be described. First, the measurement / evaluation methods used in the present invention are shown below. (1) Apparent specific gravity The film is accurately cut into a square of 5.00 cm × 5.00 cm, the thickness is measured at 50 points, and the average thickness is tμ.
m, and the weight was measured up to a unit of 0.1 mg to be wg, which was calculated by the following formula. Apparent specific gravity (−) = [w / (5 × 5 × t)] × 1000
0 (2) Surface roughness According to JIS-B0601-1982, Surfcom 30
Using a 0A type surface roughness meter (manufactured by Tokyo Seimitsu), stylus diameter 2 μm,
Stylus pressure 30mg, measurement pressure 30mg, cutoff 0.8m
The center line average thickness was measured in g. (3) Heat shrinkage The film has a width of 10 mm and a length of 250 mm and is 200 m
Mark at m intervals, fix under a constant tension of 5 g, and measure the mark spacing A. Then, 150 minutes without tension for 30 minutes
The distance B between the marks after being placed in an oven in an atmosphere of ° C was measured, and the heat shrinkage rate was calculated by the following formula. Heat shrinkage rate (%) = (A−B) / A × 100 (%)

(4) Light transmittance According to JIS-K6714, the Poick integrating sphere type H. T.
The light transmittance of the film was measured using an R meter (manufactured by Nippon Seimitsu Optical Co., Ltd.). The smaller this value, the higher the concealing property. (5) Presence or absence of wrinkles on the printer A4 size printing was performed with an inkjet printer (MJ-700V2C manufactured by Seiko Epson). At this time, it was evaluated as ○ when wrinkles did not occur, and as × when wrinkles occurred. (6) Ink drying time Inkjet printer (Made by Seiko Epson M
J-700V2C) 3mm wide, 15cm long line made by Epson, genuine Mach jet color ink MJIC
2C (cyan (C), magenta (M), yellow (Y)), and MJIC2 (black (B)) are used for printing. After the printing was completed, the line was rubbed with a finger, and the time when the line did not rub was obtained. The amount of ink at this time was about 0.4 μl / cm ² .

(7) Show-through Using the same printer as in (6) and printing with cyan, magenta, yellow and black inks, paper (PPC paper TYPE6 from Ricoh Co., Ltd.) is printed after printing.
000) was placed on top, and when the ink was not printed on the paper, it was marked with ◯, and when it was printed with x. (8) Retention rate of water immersion concentration Using the same printer as in (6), cyan (C), magenta (M), yellow (Y), and black (B) inks were printed at 5 × 5 cm ² , and the printed surface was printed. Soak in running water for 3 minutes. The reflection density was measured with a Macbeth densitometer (TR-927) for the density of each color before and after applying it to the running water,
The water immersion concentration retention rate was measured by the following formula. Inundation concentration retention rate = Concentration after inundation / Concentration before inundation x 100
(%) (9) Gloss Using Nippon Denshoku Industries Co., Ltd. VGS-1001DP,
The reflectance at incident light and reflected light of 60 degrees was obtained. (10) Conveyability Using the printer of (6), if the conveyance of the film is constant and the prints do not overlap in rows or fall out, ○, and if not
And

(11) In-plane birefringence index The test film is cut into a size of 10 cm × 10 cm, and its weight W (g) is weighed. Then, using the specific gravity ρ (g / cc) when there are no voids inside the film, the actual thickness T (cm) of the film, which is irrelevant to the void content, is calculated by the following formula. T = W / (ρ × 100) Next, a molecular orientation meter “MOA-200” manufactured by Kanzaki Paper Co., Ltd.
1A ”was used and the thickness T obtained above was substituted to obtain the refractive index in the microwave region along the longitudinal principal axis and the transverse principal axis, and the in-plane birefringence was determined by the following formula. In-plane birefringence = longitudinal principal axis refractive index-horizontal principal axis refractive index

Example 1 As raw materials, 83% by weight of polyethylene terephthalate resin having an intrinsic viscosity of 0.62, 13% by weight of general-purpose polystyrene (T575-57U manufactured by Mitsui Toatsu Chemicals, Inc.) and anatase type titanium dioxide (Fuji titanium ( Co., Ltd. TA-3
00) 4% by weight of the mixture was fed to the extruder,
It was melt extruded at 0 ° C. and cast on a cooling drum at 30 ° C. using an electrostatic contact method to prepare an unstretched film having a thickness of 950 μm. Then this film is 7
It was preheated with a roll heated to 0 ° C., further heated with an infrared heater, and stretched 3.7 times in the machine direction between rolls having different peripheral speeds. At this time, the temperature of the high-speed roll (drawing roll) was 70 ° C. Immediately after the stretching, 14% relaxation treatment was performed between the rolls without cooling. Therefore, the longitudinal stretching ratio after relaxation was 3.2. Then guide the film after longitudinal relaxation to a tenter,
3. Preheat at 140 ° C for 8 seconds and then at the same temperature in the transverse direction 3.
The film was stretched 6 times. Then, after heat-treating at 220 ° C. for 5 seconds, it was further re-stretched in the transverse direction by 8% at the same temperature, and further heat-treated at the same temperature for 5 seconds. In this way, a polyester film containing fine voids having a thickness of 100 microns was obtained.

On one side of this film, a polyvinyl alcohol resin (GH-2 manufactured by Nippon Synthetic Chemical Industry) was used as an intermediate layer.
0) and an isocyanate-containing polyurethane resin (Elastron H-3 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) each in an amount of about 2% by weight in a 7/3 (weight ratio) mixed solution of water and isopropyl alcohol. ) Was applied. Then, it was dried at 80 ° C. for 2 minutes and 170 ° C. for 30 seconds. On the other side, a copolymerized polyester resin (Vylon MD-16 manufactured by Toyobo Co., Ltd.) was used as an easy-slip layer.
And isocyanate-containing polyurethane resin (Elastron H-3 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) at 2% by weight, and 1% by weight of a cationic acrylic resin (ADEKA CATIOACE PD-50, manufactured by Asahi Denka Kogyo Co., Ltd.) as an antistatic agent. 1% by weight of organic particles having a particle size of 1.5 μm (Eposter MS manufactured by Nippon Shokubai Co., Ltd.) was mixed with a 7/3 (weight ratio) mixed solution of water and isopropyl alcohol.
It was applied with a wire bar (# 5). Then, at 80 ° C, 2
It was dried for 30 minutes at 170 ° C. for 30 minutes.

Further, 9.2% by weight of polyvinyl alcohol (CM-318 manufactured by Kuraray Co., Ltd.) and melamine resin (Sumitex M- manufactured by Sumitomo Chemical Co., Ltd.) were formed on the intermediate layer.
3) 0.6% by weight, 0.2% by weight of a surfactant (Sumitomo 3M Fluorad FC-430), and 90% by weight of water.
Was mixed and coated, and dried at 120 ° C. for 1 minute and 150 ° C. for 3 minutes to obtain an inkjet recording film. The coating amount was 18 g / m ² after drying. The coated film printed with an inkjet printer (MJ-700V2C manufactured by Seiko Epson Corp.) had a good appearance similar to a silver salt photograph.

Comparative Example 1 An ink jet recording film was obtained in the same manner as in Example 1 except that the surfactant was not added.

Comparative Examples 2 and 3 In Example 1, the drying temperature was 120 ° C. for 4 minutes only (Comparative Example 2) or 150 ° C. for 4 minutes only (Comparative Example 3).
An ink jet recording film was obtained in exactly the same manner except that the above was carried out.

Example 2 9.1% by weight of polyvinyl alcohol (GH-20 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), melamine resin (Sumitex M-3 manufactured by Sumitomo Chemical Co., Ltd.) on the intermediate layer.
6% by weight, cationic compound (Kayafix UR manufactured by Nippon Kayaku Co., Ltd.) 0.1% by weight, surfactant (Megafac F-142D manufactured by Dainippon Ink and Chemicals, Inc.)
An inkjet recording film was obtained in the same manner as in Example 1 except that 2% by weight and 90% by weight of water were mixed and coated.

Example 3 A fine void-containing polyester film of Comparative Example 3 was obtained in the same manner as in Example 1 except that the longitudinal stretching ratio was 3.2 and the longitudinal relaxation treatment was not performed.

Example 4 An ink jet recording film was obtained in the same manner as in Example 1 except that the slipping layer was not provided.

Comparative Example 4 The same printing was performed using a special glossy film manufactured by Seiko Epson Corporation. Due to the low surface gloss,
There was a lack of quality.

Example 5 An ink jet recording film was prepared in the same manner as in Example 2 except that the surfactant of the ink receiving layer was changed to silicone (Painted PT-32 manufactured by Dow Corning Asia Co., Ltd.). Obtained.

The film properties of Examples 1-5 and Comparative Examples 1-4 are shown in Table 1.

[Table 1]

[0055]

EFFECTS OF THE INVENTION By adopting the above-mentioned constitution, the film of the present invention absorbs ink quickly, and the ink is hard to be removed even if water is applied to the ink-receiving layer after the ink is absorbed, and the film is suitable for a color inkjet printer. Can be recorded, and high-quality and high-quality recording with high gloss like silver halide photographs is possible.

Claims (13)

[Claims] 1. An ink-absorbent resin on a base film,
In a white film for inkjet recording, which is provided with an ink receiving layer containing a curing agent and a surfactant, each of the cyan, magenta, yellow and black inks has a drying time of 50 seconds or less when printed by an inkjet printer, and a water immersion concentration is maintained. A white film for inkjet recording, wherein the rate is 30% or more, the surface gloss of the ink receiving layer is 55% or more, and the light transmittance is 60% or less. 2. The white film for inkjet recording according to claim 1, wherein the ink receiving layer contains a compound having a cationic group. 3. The white film for inkjet recording according to claim 1, wherein the ink receiving layer contains a fluorine compound and / or a silicon compound. 4. The white film for inkjet recording according to claim 1, wherein the ink absorbing resin is polyvinyl alcohol. 5. The white film for inkjet recording according to claim 1, wherein the curing agent is a water-soluble melamine resin. 6. The surfactant according to claim 1, which is a fluorine compound and / or a silicon compound.
The white film for inkjet recording according to any one of 1. 7. The in-plane birefringence index of the base film is -0.0.
It is 2 or more and +0.04 or less, The claim 1 characterized by the above-mentioned.
The white film for inkjet recording according to any one of 1 to 6. 8. The white film for inkjet recording according to claim 1, wherein the base film is polyester. 9. The base film contains a large number of fine voids, and the base film has an apparent specific gravity of 0.70 or more and 1.32.
The white film for inkjet recording according to any one of claims 1 to 8, wherein the white film is less than 10. 10. The white film for inkjet recording according to claim 1, wherein an intermediate layer is provided between the base film and the ink receiving layer. 11. The white film for inkjet recording according to claim 10, wherein the intermediate layer contains one or more kinds of polyester resin, polyurethane resin, or polyacrylic resin. 12. An easy sliding layer is provided on the surface of the base film opposite to the ink receiving layer.
1. The white film for inkjet recording according to any one of 1. 13. The slippery layer is one or more of polyester resin, polyurethane resin or polyacrylic resin,
The white film for inkjet recording according to claim 12, which contains particles and an antistatic agent.