JP2002046351A - Ink jet recording paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low cost ink jet recording paper, which has high lustrous properties and high durability and can quickly absorb an ink jet ink without developing bleeding. SOLUTION: In the ink jet recording paper equipped with an ink accepting layer on a porous resin film, the porous resin film consists of 30 to 90 wt.% of thermoplastic resin and 70 to 10 wt.% of inorganic and/or organic finely divided powder, which is surface-treated by a surface treating agent (A), made of a copolymer of a diallyl amine salt or an alkyl diallyl amine salt (a1) and non-ionic hydrophilic vinyl monomer (a2) and an anionic surface treating agent (B), and has a liquid absorbing volume measured by the 'Japan TAPPI No. 51-87' of 0.5 mL/m2 or more and the ink accepting layer includes 70 to 95 wt.% of an aluminum-based compound and the surface glossiness (measured according to JIS Z 8741 at 60 deg.) of 40% or more. Preferably, the alumina-based compound is an alumina and/or an alumina hydrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording sheet having high gloss, high durability and excellent ink jet suitability.

[0002]

2. Description of the Related Art Ink jet recording is a non-contact type recording method using an aqueous ink. In recent years, its high speed, low noise, ease of multicolor printing, great flexibility of recording patterns, development, It is characterized by the fact that fixing is not required, and is rapidly spreading in various applications, such as a hard copy device for color graphic information including kanji. Furthermore, in recent years, the speed of ink-jet printing has been increased and the definition has been advanced, and an image formed by an ink-jet method is not inferior to that of ordinary multi-color printing, for example, by offset printing. Because the inkjet printing method is cheaper than the plate making method, there has been a movement to apply the ink jet printing method not only to simple printing but also to the fields of multicolor printing and color photography. Also,
By changing dye inks having low water resistance to pigment inks having excellent water resistance and light resistance, there has been a movement to use ink jet printers for large posters and outdoor signboards.

[0003] With the development of such an ink jet printer device, at the same time, higher characteristics are required for a recording medium. For example, when considering the use of large posters and outdoor signboards, in addition to the water-based ink absorbency of the recording medium, water resistance in the sense that the printed portion does not disappear even in bad weather, and when the medium is pulled by wind etc. However, it is also required to have durability such as not to be broken. In addition, when a photograph output application such as outputting a photograph taken by a digital camera is taken into consideration, the recording medium is required to have high glossiness in addition to the water-based ink absorbency, from the viewpoint of the sense of quality of the printed matter.

[0004] As the ink jet paper for the above purpose,
Ink jet paper having a high gloss ink receiving layer on pulp paper, plastic film, or synthetic paper has been developed and is commercially available. However, in the case of paper using pulp paper as a support for the inkjet paper for the above purpose, the provision of a high-gloss ink-receiving layer allows the support to be easily broken, although the high-gloss and ink-absorbing properties are satisfied. There is a big problem in the durability of the. In addition, it has been proposed to use a plastic film or synthetic paper as a support having high durability. However, since the support has no water-based ink absorbency, it is necessary to provide a high coating amount ink receiving layer. There is a problem that the coating process has to be performed many times and the cost is high.

In order to solve the above problems, the present inventors have developed a surface treatment agent (A) comprising a copolymer of a thermoplastic resin, an amine salt selected from diallylamine salts and alkyldiallylamine salts, and a nonionic hydrophilic vinyl monomer. ) And an inorganic and / or organic fine powder treated with an anionic surface treatment agent (B).
o. 51-87 "is 0.
A porous resin film characterized by having a range of 5 ml / m ² or more has good water-based liquid absorption, and a porous resin film having a water contact angle of 110 ° or less on the surface has a low ink ejection amount. It has been found that even when the amount is large, the ink can be absorbed without density unevenness and is suitable as a recording medium such as an ink jet (Japanese Patent Application No. 11-351889).
issue). However, although the above porous resin film has high ink absorbency, in addition to ink bleeding easily,
Insufficient ink fixability results in low water resistance to dye inks and low surface gloss, which is unsatisfactory in terms of print appearance and improved in terms of ink bleeding, water resistance, and surface gloss Room is left.

[0006]

SUMMARY OF THE INVENTION The present invention provides a high gloss,
An object of the present invention is to provide an inexpensive inkjet recording paper that is highly durable and has excellent suitability for an inkjet printer.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies with the aim of solving the above-mentioned problems, and as a result, the porous resin film proposed by the present inventors (Japanese Patent Application No. Hei.
No. 351889) and an ink jet recording paper provided with an ink receiving layer containing a specific ratio of an aluminum compound, has high gloss and high durability, and absorbs ink jet ink quickly without causing bleeding. And completed the present invention. That is, the present invention provides an inkjet recording sheet having an ink receiving layer on a porous resin film, wherein the porous resin film is
A surface treatment agent (A) comprising a copolymer of 30 to 90% by weight of a thermoplastic resin, a diallylamine salt or an alkyldiallylamine salt (a1) and a nonionic hydrophilic vinyl monomer (a2), and an anionic surface treatment agent ( 70 to 10% by weight of inorganic and / or organic fine powder surface-treated by B)
"JAPAN TAPPI No. 51-8
The liquid absorption volume measured by 7 ”is 0.5 ml / m ²
And the ink receiving layer contains 70 to 95% of an aluminum compound, and has a surface glossiness (JIS-Z-
(8741: measured at 60 degrees) is 40% or more of the ink receiving layer.

When the aluminum compound is alumina and / or
Or an alumina hydrate having an average particle size of 350 n
m or less. Alumina is preferably δ-alumina, and alumina hydrate is preferably pseudoboehmite. Further, in the present invention,
A top coat layer is further provided on the ink receiving layer, and the surface glossiness (JIS-Z-8741: measured at 60 degrees) is 5
It is preferably 0% or more. Topcoat layer is 3
It is preferable to contain 70 to 95% by weight of an inorganic filler of 50 nm or less and 5 to 30% by weight of a binder resin. In addition, the porous resin film of the present invention can be used in “Japan
TAPPI No. 51-87 ", the liquid absorption volume is 5.0 ml / m ² or more, and the surface glossiness (JI
SZ-8741; measured at 60 degrees) is preferably 20% or more.

The porous resin film preferably has an average contact angle with water of 110 ° or less, has pores on its surface and inside, and preferably has a porosity of 10% or more. In addition, the porous resin film has 1 × 10 ⁶ pores / pore on the surface.
m ² or more, average diameter of pores on the surface is 0.01 to 50 μm
Is preferably within the range. In addition, it is preferable that at least a part of the surface and / or internal pores of the porous resin film has an inorganic and / or organic fine powder inside or around the pores.

[0010] The thermoplastic resin in the porous resin film is a polyolefin resin, and the average particle size of the inorganic and / or organic fine powder is preferably 0.01 to 20 µm, more preferably 2 to 10 µm. As a preferred embodiment of the compounding ratio of the constituent components, 30 to 90% by weight of a thermoplastic resin, 70 to 10% by weight of a surface-treated inorganic and / or organic fine powder, and 100 parts by weight of an inorganic and / or organic fine powder The amount of the surface treating agent (A) is 0.01 to 10 parts by weight, and the amount of the anionic surface treating agent (B) is 0.01 to 10 parts by weight.
It is in the range of parts by weight. In a more preferred embodiment, the porous resin film is stretched.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the ink jet recording paper of the present invention will be described in detail. <Porous resin film> Hereinafter, the porous resin film and the recording medium of the present invention will be described in detail.
The liquid absorption volume of the porous resin film of the present invention is 0.5 m
l / m ² or more, preferably 5.0 ml / m ^2, more preferably 5 to 100 ml / m ^2. If the liquid absorption volume is less than 0.5 ml / m ² , the absorption of the inkjet ink is insufficient. Further, in order to increase the absorption amount, it is necessary to consider the thickness of the porous film. Therefore, the upper limit is appropriately selected depending on the use.

The liquid absorption volume of the porous resin film of the present invention is “Japan TAPPI No. 51-87”.
(Paper and Pulp Technology Association, Paper and Pulp Test Method No. 51-8)
7, Bristow method)
In the present invention, the measured value of the absorption time within 2 seconds is defined as the liquid absorption volume. The measurement solvent is measured using a solvent obtained by adding a coloring dye with a mixed solvent of 70% by weight of water and 30% by weight of ethylene glycol as 100% by weight. As a coloring dye, malachite green or the like is used, and the amount is about 2 parts by weight, in addition to 100 parts by weight of the mixed solvent, provided that the surface tension of the solvent used for measurement does not significantly change. The type and amount of the coloring dye used are not particularly limited.

Examples of the measuring device include a liquid absorption tester manufactured by Kumagai Riki Kogyo KK. Also,
Larger liquid absorption volume in shorter absorption time,
There is a tendency that the absorption speed of the ink for inkjet is increased. In the present invention, the liquid absorption volume within 40 ms is 0.8 ml / m ² or more, more preferably 1 to 500 ml.
/ M ² . Furthermore, the larger the liquid absorption rate measured in connection with the above-described measurement of the liquid absorption volume, the better the tendency to give better results to absorption and drying of the supercolored portion. The absorption rate between 20 milliseconds and 400 milliseconds is typically 0.02 ml / {m ² · (ms) ^1/2 }
The above range, more preferably 0.1 to 100 ml
/ {M ² · (ms) ^1/2 } or more.

The surface contact angle of the porous resin film of the present invention with water is 110 ° or less, preferably 0 to 100 °,
More preferably, it is in the range of 0 to 90 °. If the angle is more than 110 °, the ink-jet ink may not be sufficiently penetrated. Also, from the viewpoint of balancing the spread of the ink droplets for inkjet in the direction parallel to the film paper surface and the penetration in the thickness direction of the film,
The contact angle may have an appropriate range, and is appropriately selected according to the type of the ink. In addition, the water contact angle of the film surface in the present invention is measured using a commercially available contact angle meter, and one minute after dropping pure water onto the film surface, using the same contact angle meter. The measurement was performed 10 times for one sample.
The average value of the contact angles measured by replacing the film with an unmeasured film whose surface is not wet with pure water at each measurement is defined as the water contact angle. An example of a commercially available contact angle meter that can be used for the contact angle measurement of the present invention is Model CA-D manufactured by Kyowa Interface Chemical Co., Ltd.

Further, as the "difference between the maximum value and the minimum value" in the ten contact angle measurements is smaller, the absorption of the ink or the liquid using the aqueous medium tends to be more uniform,
It gives better print quality as a print medium, but as an example, the difference between the maximum value and the minimum value is within 40 °, preferably within 30 °, more preferably within 20 °. The porous resin film of the present invention has fine pores on the surface, and absorbs the aqueous ink or the aqueous liquid in contact with the surface by the pores. The number and shape of the pores on the surface of the porous film and the presence of at least a part of the inorganic and / or organic fine powder in the surface pores can be known by observation with an electron microscope.

Cut any part from the porous film sample
Sample and attach it to the observation sample table.
Evaporate palladium etc. and use an electron microscope, for example,
Using a scanning electron microscope S-2400 manufactured by Tachibana Seisakusho
Observe the surface pore shape at any magnification that is easy to observe.
The number of holes and know the size and shape of the holes
be able to. Per unit area of porous film surface
The number of holes is 1 × 10⁶Pieces / m^TwoAbove range, water
From the viewpoint of faster absorption of system liquid, preferred
Is 1 × 10⁷Pieces / m^TwoAbove, more preferably 1 × 10
⁸Pieces / m^TwoThat is all. Also, better surface strength
From the viewpoint of reducing the number of^FifteenPieces / m
^TwoBelow, more preferably 1 × 10¹²Pieces / m^TwoThe following range
It is.

The shape of the pores near the surface of the porous film is various, such as circular and elliptical. The maximum diameter (L) of each pore and the maximum diameter (M) in a direction perpendicular to the pore are shown. [(L + M) / 2] is defined as the average diameter of each pore. The measurement is repeated for at least 15 surface pores, and the average value is defined as the average diameter of the pores on the surface of the porous film of the present invention. The measurement is repeated for at least 20 surface vacancies, and the average value is defined as the average diameter. From the viewpoint of obtaining a better level of liquid absorbability, the average diameter is at least 0.01 μm, more preferably at least 0.1 μm, even more preferably at least 1 μm.
In order to improve the surface strength of the porous film, the average diameter is 50 μm or less, preferably 30 μm or less, more preferably 20 μm or less.

At least a part, preferably about 30% or more, of the pores on the surface or in the vicinity thereof has inorganic and / or organic fine particles inside or around the pores. The presence of powder is preferred, and the greater the number, the better the absorption capacity tends to be. The porous resin film of the present invention has a porous structure having fine pores therein, and has a porosity of 10% or more from the viewpoint of improving the absorption drying property of the aqueous ink. And preferably 20 to 75%, more preferably 30 to 65%.
% Range. When the porosity is 75% or less, the material strength of the film is at a good level.

It is preferable that at least some of the pores in the interior have inorganic and / or organic fine powder inside or around the pores. The absorption capacity tends to improve as the amount increases. The presence of pores inside and the presence of at least a part of the inorganic and / or organic fine powder in the internal pores can be confirmed by electron microscopic observation of a cross section. The porosity in the present specification indicates the porosity represented by the following formula or the area ratio (%) occupied by vacancies in a region obtained by observing a cross-sectional electron micrograph.

[0020]

(Equation 1)

Specifically, after a porous resin film is embedded in an epoxy resin and solidified, a cut surface parallel to, for example, the thickness direction of the film and perpendicular to the surface direction is formed using a microtome. After metallizing this cut surface, any magnification that is easy to observe with a scanning electron microscope,
For example, it can be observed at a magnification of 500 to 2000 times. As an example, the observed area is photographed, a hole is traced on a tracing film, and the filled figure is subjected to image processing with an image analyzer (Model: Luzex IID, manufactured by NIRECO Co., Ltd.). The porosity can also be determined by determining the area ratio. Further, in the case of a laminate having the porous resin film of the present invention on the surface, the thickness and basis weight (g / m ² ) of the laminate and the portion where the porous resin film layer of the present invention is removed therefrom Calculate the thickness and basis weight of the porous resin film layer, and calculate the density (ρ1)
, And the density (ρ0) of the non-porous portion is determined from the composition of the constituent components, and the density (ρ0) can be determined by the above equation.

Further, the shape and size of the internal pores may be adjusted to any magnification, for example, 50, which is easy to observe with a scanning electron microscope.
It can be observed at 0x or 2000x magnification. The dimensions of the internal holes are obtained by measuring the dimensions in the plane direction and the thickness direction of at least 10 internal holes and averaging the measured values. The average size in the plane direction of the pores of the porous film is 0.1 to 1000 μm, preferably 1 to 500 μm.
It is in the range of μm. From the viewpoint of improving the mechanical strength of the porous film to a better level, the maximum dimension of the pores in the surface direction of the film is preferably 1000 μm or less. From the viewpoint of obtaining a higher level of water-based liquid absorbability, the maximum dimension of the film in the surface direction is preferably 0.1 μm or more. The average size of the pores in the porous film in the thickness direction is usually 0.01 to 50 μm, preferably 0.1 to 10 μm. To improve the absorption of the aqueous liquid, it is better that the dimension in the thickness direction is large. However, from the viewpoint of obtaining an appropriate mechanical strength of the film, the upper limit can be selected according to the application.

<Composition and Production Method of Porous Resin Film> The porous resin film of the present invention comprises, as constituents, a combination of a thermoplastic resin and surface-treated inorganic and / or organic fine powder. As the thermoplastic resin used in the porous resin film of the present invention, high-density polyethylene, medium-density polyethylene, ethylene-based resin such as low-density polyethylene, or polyolefin-based resin such as propylene-based resin, polymethyl-1-pentene, Ethylene-cyclic olefin copolymer, nylon-6, nylon-6,6, nylon-6,10, nylon-6,1
2. Polyamide resin such as nylon-6, T, etc., thermoplastic polyester resin such as polyethylene terephthalate and its copolymer, polyethylene naphthalate, aliphatic polyester, polycarbonate, atactic polystyrene, syndiotactic polystyrene, polyphenylene sulfide, etc. Thermoplastic resin. These may be used in combination of two or more.

Among these, from the viewpoints of chemical resistance, low specific gravity, cost, etc., preferred are polyolefin-based resins such as ethylene-based resins and propylene-based resins.
More preferably, it is a propylene-based resin. Examples of the propylene-based resin include an isotactic polymer or a syndiotactic polymer obtained by homopolymerizing propylene. Also, ethylene, 1-butene,
Use of a copolymer containing α-olefin such as 1-hexene, 1-heptene, 4-methyl-1-pentene and propylene and propylene having various stereoregularities as a main component. Can also. The copolymer is 2
It may be a ternary system or a ternary or higher system, and may be a random copolymer or a block copolymer. The propylene-based resin is preferably used by blending a resin having a lower melting point than that of the propylene homopolymer in an amount of 2 to 25% by weight. Examples of such a resin having a low melting point include high-density or low-density polyethylene.

The type of the inorganic and / or organic fine powder used in the porous resin film of the present invention is not particularly limited, and specific examples thereof include the following.
As the inorganic fine powder, heavy calcium carbonate, light calcium carbonate, aggregated light calcium carbonate, silica having various pore volumes, zeolite, clay, talc, titanium oxide, barium sulfate, zinc oxide, magnesium oxide,
A composite inorganic fine powder having aluminum oxide or hydroxide around the core of a hydroxyl group-containing inorganic fine powder such as diatomaceous earth, silicon oxide, and silica can be exemplified. The organic fine powder is selected from those having a higher melting point or glass transition point than the thermoplastic resin used as the above-mentioned non-hydrophilic thermoplastic resin and being incompatible with each other for the purpose of forming pores. Specific examples include polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, polyethylene naphthalate, polystyrene, acrylic acid or methacrylic acid ester polymer or copolymer, melamine resin, polyethylene sulfite,
Examples include polyimide, polyethyl ether ketone, and polyphenylene sulfide. Above all,
When a polyolefin resin is used as the non-hydrophilic thermoplastic resin, a resin obtained from polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, polyethylene naphthalate, or polystyrene is preferable.

Among inorganic and / or organic fine powders,
From the viewpoint that the amount of heat generated during combustion is small, inorganic fine powder is more preferable. Of these, heavy calcium carbonate, clay, and diatomaceous earth are preferred because they are inexpensive and when formed by stretching, have good porosity. The average particle diameter of the inorganic and / or organic fine powder used in the present invention is preferably in the range of 0.01 to 20 μm, more preferably 2 to 10 μm. From the viewpoint of improving the absorbability of the aqueous solvent or the aqueous ink, the fine powder preferably has a large particle size, more preferably 0.01 μm or more. Also,
In the case where voids are generated inside by stretching to improve the absorbency, from the viewpoint that it is difficult to cause troubles such as sheet breakage and strength reduction of the surface layer during stretching, 20 μm
The following is preferred.

The particle diameter of the surface-treated inorganic and / or organic fine powder used in the present invention is, for example, a particle measuring device, for example, a laser diffraction particle measuring device “Microtrack” (manufactured by Nikkiso Co., Ltd. It can be measured by a particle size corresponding to 50% in cumulative (product name) (cumulative 50% particle size). The particle size of the fine powder dispersed in the non-hydrophilic resin or the hydrophilic resin by melt-kneading and dispersing is determined by measuring at least 20 of the particles by electron microscopic observation of the cross section of the porous film and calculating the particle size accumulation. , An average value.

As the inorganic and / or organic fine powder used in the present invention, those having various specific surface areas and oil absorptions can be used. The specific surface area is measured by a BET method, for example, 0.1 to 1000 m ² / g, more preferably 0.2 to 1000 m ² / g.
５００500 m ² / g. When an inorganic and / or organic fine powder having a large specific surface area is used, the absorption of an aqueous solvent or ink may be improved, and as an example, the oil absorption (JIS-K5101-1991 etc.) is 1 to 300 m.
1/100 g, preferably in the range of 10 to 200 ml / g.

As the fine powder used in the porous resin film of the present invention, one kind may be selected from the above and used alone, or two or more kinds may be used in combination. Is also good. When two or more kinds are used in combination, a combination of an organic fine powder and an inorganic fine powder may be used. The treating agent (A) of the present invention is a copolymer of a diallylamine salt or an alkyldiallylamine salt (a1) and a nonionic hydrophilic vinyl monomer (a2). Hereinafter, the “salt” in the treatment agent (A) means that the anion forming the salt is selected from chloride ion, bromide ion, sulfate ion, nitrate ion, methyl sulfate ion, ethyl sulfate ion, and methanesulfonic acid ion. Is shown.

Specific examples of (a1) include diallylamine salts, alkyldiallylamine salts having 1 to 4 carbon atoms and dialkyldiallylamine salts, ie, methyldiallylamine salts, ethyldiallylamine salts, dimethyldiallylamine salts, methacryloyloxyethyltrimethylammonium, The acryloyloxyethyltrimethylammonium, methacryloyloxyethyldimethylethylammonium, acryloyloxyethyldimethylethylammonium chloride, bromide, metsulfate, or ethosulfate, N, N-dimethylaminoethyl methacrylate or N, N-dimethylaminoethyl acrylate Epoxy compounds such as chlorohydrin, glycidol, glycidyltrimethylammonium chloride In such quaternary ammonium salts obtained by alkylation can be cited, among these, preferably diallylamine salts, methyldiallylamine salts and dimethyl diallyl amine salt.

Specific examples of (a2) include acrylamide, methacrylamide, N-vinylformamide, N-
Vinylacetamide, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate,
Examples thereof include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, and (meth) acrylic acid butyl ester, and among these, acrylamide and methacrylamide are preferable. The copolymerization ratio of (a1) and (a2) is optional, but a preferred range is (a)
1) is from 10 to 99 mol%, more preferably from 50 to 97 mol%, even more preferably from 65 to 95 mol%, and (a)
2) is 90 to 1 mol%, more preferably 50 to 3 mol%, and further preferably 35 to 3 mol%.

The treating agent (A) is prepared by heating the above monomer mixture in an aqueous medium using an initiator exemplified by ammonium persulfate, 2,2-azobis (2-amidinopropane) dihydrochloride or the like at 40 ° C. It can be obtained by reacting at 100 ° C., for example, 50 to 80 ° C. for 2 to 24 hours. The polymer can be produced by the methods disclosed in JP-A-5-263010, JP-A-7-300568, and the like, and can be used to achieve the object of the present invention. Of these, some of those disclosed in JP-A-57-48340 and JP-A-63-235377 can be used. Of these, diallylamine or diallyldimethylamine hydrochloride, sulfate and It is a copolymer of methacrylamide and acrylamide.

When the molecular weight of the polymer is represented by the intrinsic viscosity at 25 ° C. in a 1N aqueous solution of sodium chloride, it is usually 0.05%.
To 3, preferably 0.1 to 0.7, particularly preferably 0.1 to 0.7.
It is in the range of 1 to 0.45. In addition, the weight average molecular weight measured by gel permeation chromatography (GPC) is about 5,000 to 950,000, preferably 10,000 to 150,000, and more preferably 1,000.
It is in the range of 0-80000. The surface treatment agent within the above range has a large effect of improving the absorbability of the porous film of the present invention with an aqueous solvent or an aqueous ink.

The anionic surface treating agent (B) has an anionic functional group in the molecule, and specific examples thereof include the following, which are appropriately selected so as to obtain the effects of the present invention. . Hereinafter, the anionic surface treatment agent (B)
Abbreviated as "treatment agent (B)". The “salt” in the treating agent (B) refers to a lithium salt, a sodium salt, a potassium salt, a calcium salt, a magnesium salt, a primary to quaternary ammonium salt, and a primary to quaternary phosphonium salt. A lithium salt, a sodium salt, a potassium salt, a quaternary ammonium salt, and more preferably a sodium salt or a potassium salt. As a specific example of the treatment agent (B), (B
1) A sulfonate having a hydrocarbon group having 4 to 40 carbon atoms, (B2) a phosphate ester salt having a hydrocarbon group having 4 to 40 carbon atoms, a higher alcohol having 4 to 40 carbon atoms Salts of phosphoric acid mono- or diesters, salts of phosphate esters of ethylene oxide adducts of higher alcohols having 4 to 40 carbon atoms, (B3) alkyl betaines having a hydrocarbon group having 4 to 40 carbon atoms And alkylsulfobetaine.

(B1) As the sulfonic acid salt having a hydrocarbon group having 4 to 40 carbon atoms, a hydrocarbon having a linear, branched or cyclic structure having 4 to 40 carbon atoms, preferably 8 to 20 carbon atoms. A sulfonate having a group, a sulfoalkanecarboxylate, specifically having 4 to 40 carbon atoms,
Alkyl benzene sulfonic acid salt preferably in the range of 8-20, salt of naphthalene sulfonic acid, alkyl naphthalene sulfonic acid salt having a linear, branched or cyclic structure having 4-30, preferably 8-20 carbon atoms, carbon Number 1
Diphenyl ether or biphenyl sulfonate having an alkyl group having a linear or branched structure in a range of 30, preferably 8 to 20; a linear or branched or cyclic diphenyl ether or a biphenyl in a range of 8 to 20; Alkanesulfonic acid salt having a structure; having 1 to 30 carbon atoms, preferably 8 carbon atoms
Salts of alkyl sulfates in the range of from 20 to 20; salts of sulfoalkanecarboxylates; sulfonates of alkylene oxide adducts of alkyl alcohols having from 8 to 30 carbon atoms, preferably from 10 to 20 carbon atoms. .

Specific examples thereof include alkanesulfonic acid and aromatic sulfonic acid, that is, octanesulfonic acid salt, dodecanesulfonic acid salt, hexadecanesulfonic acid salt, octadecanesulfonic acid salt, 1- or 2-dodecylbenzenesulfonic acid. Acid salt, 1- or 2-hexadecylbenzenesulfonate, 1- or 2-octadecylbenzenesulfonate, various isomers of dodecylnaphthalenesulfonate, salts of β-naphthalenesulfonic acid formalin condensate, octylbiphenyl Various isomers of the sulfonate, dodecyl biphenyl sulfonate, various isomers of dodecyl phenoxybenzene sulfonate, dodecyl diphenyl ether disulfonate, dodecyl lignin sulfonate; alkyl sulfates, i.e., dodecyl sulfate; F A salt of sulfoalkanecarboxylic acid, that is, a dialkyl ester of sulfosuccinic acid, wherein the alkyl group has a linear or branched or cyclic structure having 1 to 30 carbon atoms, preferably 4 to 20 carbon atoms; Specifically, a salt of di (2-ethylhexyl) sulfosuccinate, N-methyl-N- (2-sulfoethyl)
Alkyl amide salts (the alkyl group has 1 to 30, preferably 12 to 18), for example, an amide compound derived from N-methyltaurine and oleic acid,
0, preferably 10-18 salt of 2-sulfoethyl ester of carboxylic acid; triethanolamine lauryl sulfate, ammonium lauryl sulfate; polyoxyethylene lauryl sulfate, polyoxyethylene cetyl sulfate; 8-30 carbon atoms, preferably Examples of the sulfonates of alkylene oxide adducts of alkyl alcohols having 10 to 20 carbon atoms include sulfates of lauryl alcohol ethylene oxide adducts, sulfates of cetyl alcohol ethylene oxide adducts, and stearyl alcohol ethylene oxides. And sulfuric ester salts of adducts.

(B2) a mono- or di-phosphate salt or a triester phosphate having a hydrocarbon group having a linear, branched or cyclic structure having 4 to 40 carbon atoms;
Preferably, specific examples of mono- or di-ester salts or triesters of phosphate having a hydrocarbon group having a linear, branched or cyclic structure having 8 to 20 carbon atoms include dodecyl phosphate. Disodium or dipotassium salt, disodium or dipotassium hexadecyl phosphate, disodium or potassium salt of didodecyl phosphate, sodium or potassium salt of dihexadecyl phosphate, triphosphate of ethylene oxide adduct of dodecyl alcohol Esters and the like.

(B3) 4 to 30 carbon atoms, preferably 10 carbon atoms
Specific examples of alkyl betaines and alkyl sulfo betaines having a hydrocarbon group in the range of -20 to 20 include lauryl dimethyl betaine, stearyl dimethyl betaine, dodecyl dimethyl (3-sulfopropyl) ammonium inner salt, and cetyl dimethyl (3-sulfopropyl) ammonium Inner salt, stearyl dimethyl (3-sulfopropyl) ammonium inner salt, 2-octyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, 2-lauryl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine And the like. Of these, preferably,
(B1), more preferably a salt of an alkanesulfonic acid having 10 to 20 carbon atoms, a salt of an aromatic sulfonic acid having an alkyl group having 10 to 20 carbon atoms, and a range of 10 to 20 carbon atoms. And a sulfuric acid ester salt of an alkylene oxide adduct of an alkyl alcohol.

(Surface Treatment Method for Inorganic and / or Organic Fine Powder) In the present invention, after the treating agent (A) is adhered to the surface of the inorganic and / or organic fine powder in the first step and subjected to surface treatment, Next, as a second step, the surface treatment is performed by adhering the treating agent (B) to the surface. As the surface treatment method, various known methods can be applied, and there is no particular limitation. The mixing device and the mixing temperature and time are also appropriately selected according to the properties and physical properties of the components used. L / D (shaft length / shaft diameter) of various mixers used, shape of stirring blade, shear rate, specific energy, residence time, treatment time, treatment temperature, etc. are selected according to the properties of the components used. It is possible.

As the treatment method of the first stage, (I) the treatment agent (A) is dissolved or dispersed in a powder, a liquid, a paste, a solvent such as water or an organic solvent, or When a solvent is used in the production of (A), the solvent is not removed or a part thereof is removed, and a fine powder is obtained in the form of a solution or dispersion of the treating agent (A) having an appropriate concentration. (II) Add the treating agent (A) to the fine powder suspended in a solvent such as water or an organic solvent. Or, conversely, dissolving the treating agent (A) in a solvent, adding the fine powder, mixing the two, removing the solvent, drying and adhering to the periphery of the fine powder, (III) dry or wet method In the case of fine powder produced by the pulverization method of A method in which the treating agent (A) is added and adhered to the periphery of the fine powder during the pulverization process. (IV) A required amount of the treating agent (A) is higher than the required concentration for a part of the fine powder to be used. A master batch consisting of the fine powder and the treating agent (A) is prepared by adding the above, mixed with the remaining fine powder, adhered to the periphery of the fine powder and mixed with the thermoplastic resin, (V) synthesized by polymerization In the case of the organic fine powder to be treated, before, during, or after the polymerization, the treating agent (A) is added to the fine powder in the form of powder, liquid, paste, or dissolved or dispersed in a solvent. (VI) In the case of an organic fine powder to be dispersed in a thermoplastic resin continuous phase by melt-kneading, a thermoplastic resin or an undispersed organic fine powder or Thermoplastic resin and undispersed fine powder The method of depositing a surface treatment agent on the periphery of the organic fine powder in the course of and melt kneaded by adding a surface treatment agent to disperse the organic fine powder finely in the mixture, and the like.

Among these, in the case of inorganic fine powder produced by wet grinding, for example, calcium carbonate particles, a necessary amount of treatment is applied to 100 parts by weight of heavy calcium carbonate particles having a relatively large particle size of 10 to 50 μm. In the presence of the agent (A), the mixture is wet-pulverized in an aqueous medium to a desired particle size, and then dried. The obtained product is further treated with an treating agent (B) in an aqueous medium. It can be obtained by drying. As the raw material calcium carbonate, heavy calcium carbonate particles obtained by dry grinding, classified and sieved calcium carbonate particles, and the like are used. The calcium carbonate particles are dispersed in an aqueous medium.

Heavy calcium carbonate is wet-pulverized in the presence of the treating agent (A). Specifically, calcium carbonate /
The weight ratio with the aqueous medium (preferably water) is 70 / 30-3.
0/70, preferably 60/40 to 40/60, an aqueous medium is added to the calcium carbonate, and the cationic copolymer dispersant is used as a solid component in the amount of 0.01 to 100 parts by weight of calcium carbonate. 10 to 10 parts by weight, preferably 0.1 to 5 parts by weight, is wet-pulverized by a conventional method.
Further, an aqueous medium prepared by previously dissolving the treating agent (A) in the above range may be prepared, and the aqueous medium may be mixed with calcium carbonate and wet-pulverized by a conventional method. The wet pulverization may be a batch type or a continuous type, and it is preferable to use a mill using a pulverizing device such as a sand mill, an attritor, and a ball mill. By performing the wet pulverization in this manner, the average particle size is 2 to 20 μm, preferably 2.2 to 5 μm.
μm calcium carbonate particles are obtained.

Next, the wet pulverized product is dried. Before the drying, a classification step is provided to remove coarse powder such as 350 mesh on. Drying can be performed by a known method such as hot-air drying or powder-jet drying, but is preferably performed by medium fluidized drying. Fluid drying of a medium means that a slurry-like substance is supplied into a group of fluidized particles (fluidized bed) in a fluidized state by hot air (80 to 150 ° C.) in a drying tower, and the supplied slurry-like substance is actively fluidized. This is a method in which various substances are dried by being dispersed in a fluidized bed while adhering to the surface of the medium particles in a film form and receiving a drying action by hot air. Such media fluidized drying, for example,
It can be easily performed using a media fluidizing dryer “Media Slurry Dryer” manufactured by Nara Machinery Co., Ltd. It is preferable to use the medium fluidized drying because drying and pulverization of the aggregated particles (removal of primary particles) are performed simultaneously.

When the wet pulverized slurry obtained by this method is fluidized and dried in a medium, calcium carbonate having an extremely small amount of coarse powder can be obtained. However, it is also effective to pulverize and classify the particles by a desired method after the fluidized-drying of the medium. On the other hand, when the wet pulverized product is dried by ordinary hot air drying instead of the fluidized flow drying of the medium, the obtained cake is preferably subjected to further pulverization and classification of the particles by a desired method. The dry cake of a wet-ground product obtained by this method is easily crushed, and calcium carbonate fine particles can be easily obtained.
Therefore, it is not necessary to provide a step of pulverizing the dried cake. The calcium carbonate fine particles thus obtained are further treated with a treating agent (B) in an aqueous medium.

When the treating agent (A) is dissolved or dispersed in a solvent or mixed with an inorganic and / or organic fine powder in the form of a paste, the mixing temperature depends on the properties of the fine powder and the surface treating agent. As an example, the temperature is in the range of room temperature to 120 ° C., and the temperature when drying is required is in the range of 40 to 120 ° C., preferably 80 to 120 ° C. Further, if necessary, drying under reduced pressure, use of a dry gas or hot air can also be performed. The treatment with the treatment agent (B)
A method performed after the above-mentioned wet pulverization, a method in which the fine powder is dispersed in an aqueous solvent (preferably water), and then a treatment with the treatment agent (A) and then with the treatment agent (B). And mixing and melting and kneading the fine powder surface-treated with a thermoplastic resin at the same time. Among these, preferably, a method of adding (A) in a wet pulverizing step of fine particles and then treating with a treating agent (B), and treating the treating agent (A) with the fine particles dispersed in water. And then treating with a treating agent (B), and simultaneously adding or melting the fine powder surface-treated with the treating agent (A) with a thermoplastic resin. is there.

(Amount Ratio of Constituent Components) The preferred range of the amount ratio of the components constituting the porous resin film of the present invention is 30 to 90% by weight of the thermoplastic resin, 70 to 90% of the surface-treated inorganic and / or organic fine powder. 10% by weight. A more preferable range of the thermoplastic resin is 30 to 60% by weight, and further preferably 35 to 55% by weight. From the viewpoint of increasing the strength of the film, the content is 30% by weight or more. In order to further increase the absorbability of an aqueous solvent or ink, 90% by weight is required.
It is as follows. The amount of the surface-treated organic and / or inorganic fine powder is, for example, 70 to 10% by weight. In the case of the inorganic fine powder, the amount is preferably 70 to 40% by weight, more preferably 65 to 45% by weight. Range. It is better to increase the amount of the fine powder in order to increase the number of pores, but for the purpose of setting the strength of the surface of the porous resin film to a good level, the amount is 70% by weight or less. In the case of organic fine powder, the specific gravity is often low, preferably in the range of 10 to 50% by weight, more preferably 15 to 40% by weight.

The amount of the treating agent (A) varies depending on the use of the porous resin film of the present invention, but is usually 0.01 to 10 parts by weight, preferably 100 parts by weight, based on 100 parts by weight of inorganic and / or organic fine powder. It is in the range of 0.04 to 5 parts by weight, more preferably 0.07 to 2 parts by weight. 0.01 parts by weight or more is preferable from the viewpoint of increasing the absorbability of the aqueous solvent or the aqueous ink. If it exceeds 10 parts by weight, the effect of the surface treatment agent reaches a plateau. The amount of the treatment agent (B) varies depending on the use of the porous resin film of the present invention, but is usually 0.01 to 10 parts by weight per 100 parts by weight of the inorganic or organic fine powder,
Preferably 0.05 to 5 parts by weight, more preferably 0.5 to 5 parts by weight
The range is 4 parts by weight. 0.01 parts by weight or more is preferable from the viewpoint of increasing the absorbability of the aqueous solvent or the aqueous ink.
If it exceeds 10 parts by weight, the effect of the surface treatment agent reaches a plateau.

(Optional components) When these fine powders are mixed and kneaded in a thermoplastic resin, a dispersing agent, an antioxidant, a compatibilizer, a flame retardant, an ultraviolet stabilizer, a coloring pigment and the like are added as necessary. can do. When the porous resin film of the present invention is used as a durable material, it is preferable to add an antioxidant, an ultraviolet stabilizer and the like. As a method of mixing the components of the porous resin film of the present invention,
Various known methods can be applied, and there is no particular limitation, and the temperature and time of mixing are appropriately selected according to the properties of the components used. Mixing in a state of being dissolved or dispersed in a solvent, roll kneading, and melt kneading are listed, and the melt kneading is preferable because of its high production efficiency. After mixing an inorganic and / or organic fine powder surface-treated with a thermoplastic resin or a treating agent (A) in a powder or pellet state and a treating agent (B) with a Henschel mixer, a ribbon blender, a super mixer, or the like. Melting and kneading with a uniaxial or biaxial kneader, extruding into a strand and cutting and pelletizing, or extruding into water from a strand die and cutting with a rotary blade attached to the tip of the die Can be Various L / D (shaft length / shaft diameter), sending speed, specific energy, residence time, temperature, etc. can be selected as the single-shaft or twin-shaft kneader to be used according to the properties of the components used. It is.

The porous resin film and the recording medium of the present invention can be produced by combining various methods known to those skilled in the art. A porous resin film or a recording medium produced by any method is included in the scope of the present invention as long as a porous resin film satisfying the conditions of the present invention is used. As a method for producing the porous resin film of the present invention having a liquid absorption volume of 0.5 ml / m ² or more, various known film production techniques and combinations thereof are possible. For example, a stretched film method utilizing void generation by stretching, a rolling method or a calendering method for generating voids during rolling, a foaming method using a blowing agent, a method using void-containing particles, a solvent extraction method, A method of dissolving and extracting a mixed component is exemplified. Of these, the stretched film method is preferred.

When stretching, it is not always necessary to stretch only the porous resin film of the present invention. For example,
When finally manufacturing a recording medium in which the porous resin film of the present invention is formed on a base material layer, the unstretched porous resin film and the base material layer are laminated and then stretched together. It does not matter. If they are laminated and stretched in advance, they are simpler and less expensive than the case where they are separately stretched and laminated. Further, the control of the pores formed in the porous resin film of the present invention and the substrate layer becomes easier. In particular, when used as a recording medium, the porous resin film of the present invention is controlled so that more pores are formed than the substrate layer, and the porous resin film is a layer that can improve ink absorbency. It is preferable to make it function effectively.

Various known methods can be used for stretching. The stretching temperature is higher than the glass transition temperature of the thermoplastic resin to be used in the case of non-crystalline resin, and is higher than the glass transition temperature of the non-crystal part in the case of crystalline resin, but is lower than the melting point of the crystalline part. It can be performed within a suitable temperature range. Specifically, longitudinal stretching using the peripheral speed difference of the roll group, transverse stretching using a tenter oven, rolling, inflation stretching using a mandrel on a tubular film, simultaneous biaxial stretching using a combination of a tenter oven and a linear motor Stretching can be performed by such methods.

The stretching ratio is not particularly limited, and is appropriately determined in consideration of the purpose of use of the porous resin film of the present invention and the characteristics of the thermoplastic resin used. For example, when using a propylene homopolymer or a copolymer thereof as the thermoplastic resin, when stretching in one direction, about 1.2 to 12 times,
It is preferably 2 to 10 times, and in the case of biaxial stretching, the area ratio is 1.5 to 60 times, preferably 10 to 50 times.
When using other thermoplastic resins, when stretched in one direction is 1.2 to 10 times, preferably 2 to 7 times, and in the case of biaxial stretching, 1.5 to 20 times in area magnification, Preferably it is 4 to 12 times.

Further, a heat treatment at a high temperature can be performed if necessary. The stretching temperature is a temperature 2 to 60 ° C. lower than the melting point of the thermoplastic resin to be used, and the stretching speed is 10 to 3
Preferably it is 50 m / min. The thickness of the porous resin film of the present invention is not particularly limited, but from the viewpoint of further increasing the absorption of the aqueous solvent or the aqueous ink, for example, 5μ
m or more, preferably 25 μm or more, more preferably 30 μm or more.
μm or more. The upper limit is appropriately selected according to the required absorption amount of the aqueous liquid, but is, for example, 1000 μm or less, preferably 500 μm, more preferably 300 μm.
It is as follows.

The porous resin film of the present invention may be used as it is, or may be further used as another thermoplastic film.
It may be used by laminating it on laminated paper, pulp paper, nonwoven fabric, cloth and the like. Further, as another thermoplastic film to be laminated, for example, a transparent or opaque film such as a polyester film, a polyamide film, and a polyolefin film can be laminated. Thus, the recording medium formed by laminating the porous resin film of the present invention and another film has, for example, an overall thickness of 5 μm.
It can be about 0 μm to 1 mm.

The surface of the porous resin film or the laminate using the same can be subjected to a surface oxidation treatment, if necessary. In some cases, the surface oxidation treatment improves the hydrophilicity and absorptivity of the surface, or improves the coating properties of the ink fixing agent or the ink receiving layer and the adhesion to the substrate. Specific examples of the surface oxidation treatment include corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, and a treatment method selected from ozone treatment, preferably corona treatment and flame treatment, and more preferably corona treatment. .

The processing amount is 600 to 1 in the case of corona treatment.
2,000 J / m^Two(10-200W · min / m^Two), Good
Preferably 1200 to 9,000 J / m^Two(20-180
W · min / m^Two). Enough effect of corona discharge treatment
600 J / m to get^Two(10W / min / m^Two)Above
Yes, 12,000 J / m^Two(200W / min / m^Two)Super
In 12,000 J / m, because the effect of processing reaches a plateau
^Two(200W / min / m^TwoThe following is sufficient. flame
For processing, 8,000-200,000 J / m ^Two, Good
Preferably 20,000-100,000 J / m^TwoUsed by
Can be In order to clearly obtain the effect of frame processing, it is necessary to use 8,0
00J / m^Two200,000 J / m^TwoIn super
Is 200,000 J / m because the effect of the treatment reaches a plateau
^TwoThe following is sufficient.

Ink receiving layer In the present invention, in order to obtain high glossiness in addition to ink absorbency, the surface gloss (JIS-Z-8741: measured at 60 degrees) containing 70 to 95% by weight of an aluminum compound is 40.
% Or more of the ink receiving layer. Alumina compounds are
The surface of the particles has a positive charge and is excellent in fixability of a negatively charged inkjet ink. The alumina-based compound is preferably alumina and / or alumina hydrate from the viewpoint of safety and availability, and has an average particle size of 350 nm or less from the viewpoint of easily developing gloss. preferable.

Specific examples of alumina include α-alumina, β-alumina, γ-alumina, δ-alumina, and η-alumina.
Alumina, θ-alumina and the like can be mentioned, and δ-alumina is preferable from the viewpoint of ink absorption. Specific examples of the alumina hydrate include alumina hydrate having a pseudo-boehmite structure (pseudo-boehmite) and alumina hydrate having an amorphous structure (amorphous alumina hydrate). Pseudo-boehmite is preferred from the viewpoint of ink absorption. In the present invention, a binder resin is used as an adhesive in addition to the inorganic filler in the ink receiving layer. 5-30 binder resin
% By weight.

Specific examples of the binder resin include polyvinyl alcohol and its derivatives, water-soluble resins such as polyvinylpyrrolidone, polyacrylamide, hydroxyethylcellulose, casein, and starch; urethane resins, ester resins, epoxy resins, and ethylene resins. Resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer resin, acrylic resin , Methacrylic acid-based resin, polybutyral-based resin, silicone resin, nitrocellulose resin, styrene-acrylic copolymer resin,
A water-insoluble resin resin such as a styrene-butadiene-based copolymer resin or an acrylonitrile-butadiene-based copolymer resin can be used. The water-soluble resin is used as an aqueous solution, and the water-insoluble resin is used as a solution, emulsion, or latex.

Among the above binder resins, polyvinyl alcohol is preferred from the viewpoint of miscibility with inorganic fillers and ink absorption. In particular, polyvinyl alcohol having a degree of polymerization of 2,000 or more and a degree of saponification of 80 to 100% is preferable from the viewpoint of coating film strength. Further, in the present invention, in order to improve the water resistance of the binder resin, a crosslinking agent may be used in the range of 1 to 20% by weight of the ink receiving layer. Specific examples of the crosslinking agent include urea-formaldehyde resin,
Examples include melamine-formaldehyde resin, polyamide polyurea-formaldehyde resin, glyoxal, epoxy-based cross-linking agent, polyisocyanate resin, boric acid, borax, and various borates.

In the ink receiving layer of the present invention, a dispersant, a thickener, a defoamer, a preservative, an ultraviolet absorber, an antioxidant, an interface Various assistants called activators can also be included. The coating amount of the ink receiving layer of the present invention is appropriately selected according to the liquid absorption capacity of the porous resin film used as the support. ~ 30
g / m ² . When the coating amount is less than 5 g / m ² , the gloss, bleeding property and water resistance are insufficient, and when it exceeds 30 g / m ² , the ink absorption amount can be satisfied, but the surface strength of the ink receiving layer is low. descend.

In the present invention, the surface glossiness (JIS-JIS) is further provided on the ink receiving layer for the purpose of improving glossiness and surface abrasion.
Z-8741 (measured at 60 degrees) is preferably provided with a top coat layer of 50% or more. The top coat layer of the present invention comprises an inorganic filler having an average particle size of 350 nm or less,
It is preferable to contain 5% by weight and 5 to 30% of a binder resin. Specific examples of the inorganic filler include spherical colloidal silica, spherical colloidal calcium carbonate, amorphous silica, pearl necklace-shaped colloidal silica, and an aluminum compound used in the ink receiving layer.

As the binder resin, the same type of binder as used in the ink receiving layer can be used.
The coating amount of the top coat layer of the present invention is appropriately selected depending on the porous resin film and the ink receiving layer.
5.0 g / m ^2, it is preferable preferably from 0.5 to 3.0 g / m ^2. When the coating amount is less than 0.1 g / m ² , the effect of the top coat layer is not sufficiently exhibited, and
If it exceeds 0 g / m ² , the effect is saturated. In the top coat layer of the present invention, a dispersant, a thickener, an antifoaming agent, a preservative, an ultraviolet absorber, which is generally used in coated paper as necessary,
Various auxiliaries such as an antioxidant and a surfactant can be contained.

Coating Method The method for applying the ink receiving layer and the top coat layer to the porous resin film can be appropriately selected from known methods. Examples of the coating method include a blade coating method, a rod bar coating method, a roll coating method, an air knife coating method, a spray coating method, a gravure coating method, a curtain coating method, a die coating method, and a comma coating method. Other recording methods In addition to being usable as recording paper for an ink jet printer, the ink jet recording paper of the present invention can be used as a recording paper for a fusing thermal transfer printer or a sublimation thermal transfer printer using an ink ribbon, or even a page printer. is there.

[0065]

EXAMPLES The present invention will be described more specifically with reference to Preparation Examples, Experimental Examples, Production Examples, Examples and Comparative Examples of Surface Treatment Agent A. The materials, usage amounts, ratios, operations, and the like shown below can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. The percentages described below are based on weight unless otherwise specified. The materials used are summarized in Table 1. A recording medium using the porous resin film of the present invention and a comparative resin film was manufactured according to the following procedure.

[Preparation Example 1 of Surface Treatment Agent A] A reflux condenser,
500 parts by weight of diallylamine hydrochloride (60% by weight), 21 parts by weight of acrylamide (40% by weight) and 90 parts by weight of water were charged into a reactor equipped with a thermometer, a dropping funnel, a stirrer, and a gas inlet tube. The temperature in the system was raised to 80 ° C. while flowing. Under stirring, 30 parts of ammonium persulfate (25% by weight) as a polymerization initiator was added dropwise over 4 hours. The reaction was carried out at the same temperature for 1 hour to obtain a viscous pale yellow liquid. When 50 g of this was taken and poured into 500 ml of acetone, a white precipitate was formed. The precipitate was separated by filtration, washed twice more with 100 ml of acetone, and dried in vacuo to obtain a surface treatment agent (abbreviation: A1) of a cationic polymer as a white solid (95% yield). ). The intrinsic viscosity of the obtained polymer in a 1N aqueous sodium chloride solution at 25 ° C. was 0.33 dl / g, and the weight average molecular weight determined by GPC was 55,000.

[Preparation Example 2 of Surface Treatment Agent A] A reflux condenser,
500 parts by weight of diallylamine hydrochloride (60% by weight), 45 parts by weight of acrylamide (40% by weight) and 190 parts by weight of water were charged into a reactor equipped with a thermometer, a dropping funnel, a stirrer, and a gas inlet tube. The temperature in the system was raised to 80 ° C. while flowing. Under stirring, 30 parts of ammonium persulfate (25% by weight) as a polymerization initiator was added dropwise over 4 hours. The reaction was carried out at the same temperature for 1 hour to obtain a viscous pale yellow liquid. When 50 g of this was taken and poured into 500 ml of acetone, a white precipitate was formed. The precipitate was separated by filtration, washed well twice with 100 ml of acetone, and then dried under vacuum to obtain a white solid cationic polymer surface treating agent (abbreviation: A2) (96% yield). . The intrinsic viscosity of the obtained polymer in a 1N aqueous sodium chloride solution at 25 ° C. was 0.38 dl / g, and the weight average molecular weight determined by GPC was 64000.

[Production of surface-treated heavy calcium carbonate] <Experimental example 1> Heavy calcium carbonate (average particle diameter 3 μm) was used as fine powder.
m, specific surface area 1.8m ^Two/ G, JIS-K5101-1
Oil absorption measured by 991 is approximately 31ml / 100g
No .: Charcoal 1) 40% by weight of water and 60% by weight of water were sufficiently stirred and mixed.
Into a slurry, and furthermore, the surface treatment agent (A1)
0.1 parts by weight per 100 parts by weight of calcium carbonate
Mixing and stirring, and then Anstex SAS (main component is
Sodium alkane sulfonate having 14 carbon atoms and 1 carbon atom
6 mixture of sodium alkane sulfonate, Toho Chemical
2% by weight aqueous solution of trade name, abbreviation: B1) manufactured by Kogyo Co., Ltd.
50 parts by weight (per 100 parts by weight of heavy calcium carbonate)
(2.5 parts by weight of solid content) and stirred.
Rally the medium flow of Nara Machinery Works, Ltd. MSD-200
Heavy calcium carbonate dried and surface-treated with a dryer
Obtained. The abbreviation of this is SF1. In addition, of this specification
The particle size of the calcium carbonate powder used in the examples
The diffraction type particle measurement device "Microtrack" (Stock Association)
Cumulative 50% particle size as measured by Nikkiso Co., Ltd., trade name)
is there.

<Experimental Example 2> In place of Anstex SAS, a 5% by weight aqueous solution of dodecylbenzenesulfonic acid (abbreviation: B2), 20 parts by weight (solid content of 2.5 parts by weight based on 100 parts by weight of heavy calcium carbonate) Part) was used, and a surface-treated calcium carbonate was obtained by the same operation as in Experimental Example 1 (abbreviation: SF2).

<Experimental Example 3> Coarse-grained heavy calcium carbonate having an average particle size of 30 μm (a dry-pulverized product manufactured by Nippon Cement Co., Ltd.) and water were blended in a weight ratio of 40/60, and a surface treating agent was added thereto. (A1) was added in an amount of 0.08 part by weight per 100 parts by weight of heavy calcium carbonate, and glass beads having a diameter of 1.5 mm were used at a filling rate of 170% at a peripheral speed of 10 m / sec using a table-type attritor-type medium stirring mill. Wet pulverized. Next, 20 parts by weight of a 5% by weight aqueous solution of dodecylbenzenesulfonic acid (abbreviation: B2) (2 parts by weight of solids added to 100 parts by weight of heavy calcium carbonate) was added and stirred. Then, it was classified through a 350 mesh screen,
The slurry that passed through the 50 mesh was dried using a Nara Machinery Co., Ltd. MSD-200 media fluidized dryer. The obtained calcium carbonate was used for micro-tracking [manufactured by Nikkiso Co., Ltd.]
Was 2.2 μm (abbreviation: SF)
3).

<Experimental Example 4> Heavy carbon dioxide was used as the fine powder.
Lucium (average particle diameter 3 μm, specific surface area 1.8 m ^Two/
g, absorption measured according to JIS-K5101-1991.
Oil amount 31 ml / 100 g Abbreviation: Charcoal 1) 40% by weight
And 60% by weight of water are sufficiently stirred and mixed to form a slurry.
And 100 weights of heavy calcium carbonate
Add 0.1 parts by weight per part and mix and stir.
5% by weight aqueous solution of silbenzenesulfonic acid (abbreviation: B2)
20 parts by weight of liquid (100 parts by weight of heavy calcium carbonate
2 parts by weight of the solid content), and the mixture is stirred.
Manufactured by Nara Machinery Co., Ltd .;
Drying with a dryer to obtain surface-treated heavy calcium carbonate
Was. The symbol of this is SF4.

<Experimental Example 5> Coarse-grained heavy calcium carbonate having an average particle diameter of 30 μm (dry-pulverized product manufactured by Nippon Cement Co., Ltd.) and water were blended in a weight ratio of 40/60, and a surface treating agent was added thereto. (A1) was added to 0.08 parts by weight per 100 parts by weight of heavy calcium carbonate, and glass beads having a diameter of 1.5 mm were used at a filling rate of 120% and a peripheral speed of 5 m / sec using a table-type attritor-type medium stirring mill. Wet pulverized. Then
5% by weight of dodecylbenzenesulfonic acid (abbreviation: B2)
20 parts by weight of an aqueous solution (2 parts by weight of solid content added to 100 parts by weight of heavy calcium carbonate) was added and stirred. Then, it was classified through a 350 mesh screen,
The slurry having passed through the 0 mesh was dried with a fluid drying dryer for MSD-200 medium manufactured by Nara Machinery Co., Ltd. The average particle size of the obtained calcium carbonate measured by Microtrac (manufactured by Nikkiso Co., Ltd.) was 9.5 μm (abbreviation: SF)
5).

(Production Example 1) <Preparation of base layer and longitudinal stretching> Melt flow rate (MF
R: 230 ° C., 2.16 kg load) 75% by weight of polypropylene at 1 g / 10 min and melt flow rate (MF
R: 190 ° C., 2.16 kg load) in a mixture with 5% by weight of high-density polyethylene of 8 g / 10 min.
A composition [A] containing 20% by weight of calcium carbonate of 20 μm was kneaded with an extruder set at a temperature of 250 ° C., extruded into strands, and cut into pellets. This composition [a] was extruded into a sheet from a T-die connected to an extruder set at 250 ° C., and was cooled by a cooling device to obtain a non-stretched sheet. Next, after heating this unstretched sheet to 145 ° C., it was stretched 4.5 times in the machine direction to obtain a stretched sheet. In the melt kneading of the resin component or the mixture of the resin component and the fine powder in each Example, the total weight of the resin component and the fine powder was set to 100 parts by weight, and in addition, BHT as an antioxidant was added.
(4-methyl-2,6-di-t-butylphenol)
0.2 parts by weight and 0.1 parts by weight of Irganox 1010 (phenolic antioxidant, trade name, manufactured by Ciba Geigy) were added.

<Formation of Surface Porous Resin Film> Separately, polypropylene 4 having an MFR of 20 g / 10 min.
0% by weight (abbreviation: PP1) and 60% by weight of the surface-treated calcium carbonate (abbreviation: SF1) described in Experimental Example 1 are sufficiently mixed in a powder state and melt-kneaded by a twin-screw kneader set at 240 ° C. The mixture was extruded and cut into strands to obtain pellets (composition [b]). This composition was added to 230
The sheet was extruded from a T-die connected to an extruder set at a temperature of ° C (temperature a). The obtained sheet was laminated on both sides of the 4.5-fold stretched sheet prepared by the above-described operation, and 50
After cooling to 154 ° C. (temperature b), the film was heated to 154 ° C. (temperature c) and stretched 8.5 times in the transverse direction with a tenter. Thereafter, annealing treatment is performed at 155 ° C. (temperature d),
(Temperature e), the ear part is slit, and three layers (absorption layer [b] on the front side / base layer [a] / absorption layer on the back side [b]: wall thickness 55 μm / 40 μm / 35 μm) structure Of a porous resin film having a total thickness of 130 μm. This porous resin film is used as a support a. Table 1 also shows the composition and production conditions, as well as the results of performance evaluation as a support. The performance evaluation of the porous resin film was performed by the following method. Table 1 shows the performance evaluation results.

<Performance Evaluation> (1) Liquid Absorption Volume The liquid absorption volume is "Japan TAPPI No. 5
1-87 "(Paper and Pulp Technology Association, Paper and Pulp Test Method N)
o. 51-87, Bristow method), and the liquid absorption volume was measured using a liquid absorption tester manufactured by Kumagai Riki Kogyo Co., Ltd. The measurement solvent is a mixture of 70% by weight of water and 30% by weight of ethylene glycol, and 2 parts by weight of malachite green as a coloring dye is dissolved in 100 parts by weight of the mixed solvent. (2) Average contact angle of porous resin film with water, difference between the maximum value and minimum value The contact angle of the surface of the porous film was measured by contact angle meter (Kyowa) one minute after dropping pure water on the film surface. Surface Chemistry Co., Ltd.
(Model CA-D). This measurement is
(The film was replaced with an unmeasured film whose surface was not wetted with pure water for each measurement), and the average value of the contact angles measured 10 times and the difference between the maximum value and the minimum value were determined.

(3) Confirmation of Existence of Surface Vacancies and Measurement of Surface Vacancy Number and Surface Vacancy A part of the porous film was cut out, and it was confirmed that pores existed on the surface and in the cross section. Cut any part from the porous film sample, paste it on the observation sample table,
Gold or gold-palladium was vapor-deposited on the observation surface, and a scanning electron microscope S-2400 manufactured by Hitachi, Ltd. was used.
Confirm the presence of vacancies on the surface by magnifying 00 times, and the presence of inorganic fine powder in the majority of vacancies of at least about 50% or more of the total vacancies or at the ends of the vacancies. did. An electron microscope image was output on a thermal paper or photographed, and the number of pores on the surface was measured. As a result, about 3.5 × 10 ⁹ / m ²
Met. Next, as a result of averaging the measured values of the 89 holes, the major axis was 14.5 μm, the minor axis was 3.4 μm, and the average diameter was 9 μm. In addition, when each two holes were connected to the left and right or up and down of the fine powder, the two holes were measured as one connected hole assuming that the holes were formed around the fine powder.

(4) Confirmation of existence of internal pores and measurement of internal porosity After embedding the above-mentioned porous resin film in epoxy resin and solidifying it, using a microtome, in the thickness direction of the film, After making a cut surface parallel and perpendicular to the surface direction, and metallizing this cut surface with gold-palladium,
Using a scanning electron microscope S-2400 manufactured by Hitachi, Ltd., observed at a magnification of 1000 times, the presence of internal voids and the presence of fine powder in at least a part of the internal voids It was confirmed. Overall thickness and basis weight (g / m ² )
Is measured, and then the surface absorbing layer is peeled off a certain area,
The basis weight and thickness of the remaining film were measured, and the thickness and basis weight (g / m ² ) of the porous resin film layer were determined from the difference between the ^two, and the basis weight was divided by the thickness to be absorbed. Layer density (ρ1
) Was calculated. Next, the composition [b] was formed into a pressed sheet having a thickness of 1 mm at 230 ° C., the density (ρ0) was measured, and the porosity was calculated by the following equation.

[0078]

(Equation 2)

(5) Suitability for Inkjet Printer Printer printing was performed under the following conditions, and various suitability for dye ink and pigment ink were evaluated. 6 Printer: EPSON PM-770C (dye ink) Printer: GRAPHTEC JP-2115 (pigment ink) Print sample: Japan Standards Association SCID color chart sample "S7" A4 (6.6 x 14.3 cm) Print settings: Recommended settings clean No color correction by driver, Operating environment: Windows (registered trademark) 95 Pent
ium II 300MHz, RAM128MB Parallel I / F Software: Adobe Photoshop 4.0
J

(Ink Absorption) After the printing was completed, the time when the ink completely disappeared from the printed portion was visually determined to be the drying time. The drying time was evaluated in the following four grades. ：: Drying time 0 minutes (the ink is completely absorbed at the end of printing) ：: Drying time 0 to 1 minute △: Drying time 1 to 3 minutes ×: Drying time 3 minutes or more (ink bleeding property) In the print samples used in the test, the presence or absence of ink bleeding was visually determined according to the following criteria. ：: No bleeding observed Δ: Bleeding observed only in heavy color portion ×: Bleeding observed in heavy color portion and single color portion (Waterfastness) Sufficient amount of print sample printed under the same conditions as in the above ink absorption test Was immersed in tap water (water temperature of 25 ° C.) for 4 hours, and then the paper surface was air-dried, and the degree of ink remaining was visually determined.

(Production Example 2) The same operation as in Example 1 was carried out except that heavy calcium carbonate SF2 was used in place of the surface-treated heavy calcium carbonate SF1 and the molding temperature was changed to the value shown in Table 1. By operation, a porous resin film was produced. Table 1 shows the evaluation results. The porous resin film was used as a support b. (Production Example 3) Surface-treated heavy calcium carbonate SF1
Instead of using heavy calcium carbonate SF3 and changing the molding temperature to the values shown in Table 1, a porous resin film was produced in the same manner as in Example 1. Table 1 shows the evaluation results. The porous resin film was used as a support c.

(Production Example 4) The same operation as in Example 1 was carried out except that heavy calcium carbonate SF4 was used instead of surface-treated heavy calcium carbonate SF1 and the molding temperature was changed to the value shown in Table 1. By operation, a porous resin film was produced. Table 1 shows the evaluation results. The porous resin film was used as a support d. (Production Example 5) Instead of the surface-treated calcium carbonate SF1, heavy calcium carbonate (average particle diameter: 3 μm, specific surface area by BET method: 1.8 m ² /
g, a calcium resin having an oil absorption of 31 ml / 100 g as measured according to JIS-K5101-1991) was used without any surface treatment, to produce a porous resin film in the same manner as in Example 1. . Table 1 shows the evaluation results. The porous resin film was used as a support e.

(Production Example 6) Instead of the surface-treated calcium carbonate SF1, the heavy calcium carbonate used in Experimental Example 1 (average particle diameter: 3 μm, specific surface area by BET method: 1.8 m ² / g, JIS- Same as Production Example 1 except that oil absorption measured by K5101-1991 was 31 ml / 100 g of calcium carbonate) and stearic acid was added as a surface treatment agent in an amount of 4 parts by weight based on 100 parts by weight of calcium carbonate. By the above operation, a porous resin film was produced. Table 1 shows the evaluation results. The porous resin film was used as a support f. (Production Example 7) Surface-treated heavy calcium carbonate SF1
Instead of using heavy calcium carbonate SF5, a porous resin film was prepared and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. The porous resin film was used as a support g.

(Examples 1 to 7, Comparative Examples 1 to 6) Ink-jet recording sheets were produced according to the following procedure using the materials shown in Table 2 in predetermined amounts. Alumina, a binder resin, a crosslinking agent, an ink fixing agent, and water were mixed to prepare a coating liquid for forming an ink receiving layer. This coating liquid was applied to the front side of the porous resin film with a Mayer bar so that the coating amount after drying became 20 g / m ^2, and dried and solidified in an oven at 110 ° C. for 5 minutes to form a receptor layer. Thus, an ink jet recording paper was obtained. The suitability of the ink jet recording paper for ink jet printer was evaluated in the same manner as for the porous resin film. Table 3 shows the formulation, surface glossiness, and ink jet suitability evaluation results.

(Examples 8 and 9) Ink-jet recording sheets were produced according to the following procedures using a predetermined amount of the materials shown in Table 2. Colloidal silica, a binder resin, an ink fixing agent, and water were mixed to prepare a coating liquid for a top coat layer. In the same manner as in Example 5, an ink receiving layer was formed on a porous resin film, and a top coat layer was coated with a Mayer bar so that the coating amount after drying was 1.0 g / m ^2. Apply the solution and heat in a 110 ° C oven.
After drying and solidifying for minutes, a top coat layer was formed to obtain an ink jet recording paper. Table 3 shows the formulation, surface glossiness, and the results of evaluating the suitability for inkjet printers.

[0086]

[Table 1]

[0087]

[Table 2]

[0088]

[Table 3]

As is apparent from Tables 1 to 3, the ink jet recording paper provided with the ink receiving layer containing the inorganic filler and the binder of the present invention (Examples 1 to 7)
In addition to high gloss, it shows high ink absorption without bleeding. By providing a top coat layer on the ink receiving layer (Examples 8 and 9), the surface glossiness is further improved. On the other hand, in the case of an ink jet recording paper using a porous film out of the specified range of the present invention (Comparative Examples 1 to 3) or an ink jet recording paper using an ink receiving layer out of the specified range of the present invention (Comparative Examples 4 to 6) )
Cannot satisfy the above characteristics and are inferior in performance.

[0090]

The ink-jet recording paper of the present invention is a high-performance ink-jet recording paper having high gloss and high durability and capable of rapidly absorbing ink-jet ink.

Claims (15)

[Claims] 1. In an ink jet recording paper comprising an ink receiving layer on a porous resin film, the porous resin film is composed of 30 to 90% by weight of a thermoplastic resin, a diallylamine salt or an alkyldiallylamine salt (a1) and a nonionic hydrophilic material. A surface treating agent (A) composed of a copolymer with a conductive vinyl monomer (a2), and an inorganic and / or organic fine powder 70-70 surface-treated with an anionic surface treating agent (B);
"Japan TAPPI N containing 10% by weight
o. 51-87 "is 0.
The ink receiving layer is 5 ml / m ² or more, and the ink receiving layer contains 70 to 95% by weight of an aluminum compound and has a surface glossiness (JIS-Z-8741: measured at 60 °) of 40% or more. An ink jet recording sheet characterized by the above-mentioned. 2. The method according to claim 1, wherein the aluminum compound is alumina and / or
Or an alumina hydrate and an average particle size of 350 nm
2. The ink jet recording paper according to claim 1, wherein: 3. An ink jet recording sheet according to claim 1, wherein the alumina is δ-alumina. 4. The ink jet recording paper according to claim 1, wherein the alumina hydrate is pseudo-boehmite. 5. A top coat layer is further provided on the ink receiving layer, and a surface gloss (JIS-Z-8741: 6) is provided.
The inkjet recording paper according to any one of claims 1 to 4, wherein 0% measurement is 50% or more. 6. An average particle diameter of 350 nm in the top coat layer.
6. The ink jet recording paper according to claim 5, comprising 70 to 95% by weight of the following inorganic filler and 5 to 30% by weight of a binder resin. 7. The method according to claim 7, wherein the porous resin film is “Japan
TAPPI No. Ink-jet recording sheet according to claim 1, the liquid absorbent capacity to be measured, characterized in that at 5.0 ml / m ² or more by 51-87 ". 8. The porous resin film having a surface glossiness (J
(IS-Z-8741; measured at 60 degrees) is 20% or more. 9. The porous resin film according to claim 1, wherein the average contact angle with water is 110 ° or less.
An ink jet recording sheet according to any one of claims 1 to 8. 10. The ink jet recording paper according to claim 1, wherein the porous resin film has pores on the surface and inside. 11. The ink jet recording paper according to claim 10, wherein the porous resin film has a porosity of 10% or more. 12. The method according to claim 1, wherein at least a part of the surface and / or the internal pores are formed by the presence of inorganic and / or organic fine powder inside the pores or around the pores. 11. The ink jet recording paper according to 10. 13. The ink jet recording paper according to claim 1, wherein the thermoplastic resin is a polyolefin resin. 14. A surface treating agent containing 30 to 90% by weight of a thermoplastic resin, 70 to 10% by weight of a surface-treated inorganic and / or organic fine powder, and 100 parts by weight of an inorganic and / or organic fine powder. The amount of (A) is 0.01 to 10 parts by weight, and the amount of the anionic surface treatment agent (B) is 0.01 to 10 parts.
The inkjet recording paper according to any one of claims 1 to 13, wherein the amount is in the range of parts by weight. 15. The ink jet recording paper according to claim 1, wherein the porous resin film is stretched.