WO2023190415A1 - Recording paper - Google Patents
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- WO2023190415A1 WO2023190415A1 PCT/JP2023/012346 JP2023012346W WO2023190415A1 WO 2023190415 A1 WO2023190415 A1 WO 2023190415A1 JP 2023012346 W JP2023012346 W JP 2023012346W WO 2023190415 A1 WO2023190415 A1 WO 2023190415A1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/32—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed at least two layers being foamed and next to each other
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
Definitions
- the present invention relates to recording paper.
- inkjet printers have become capable of producing images that are comparable to multicolor offset printing and color electrophotography.
- inkjet printers have become widely popular because they have lower running costs for color printing than electrophotographic printers.
- inkjet printers that use water-based inks, which are less likely to cause environmental and safety problems than oil-based inks, have recently become mainstream.
- Patent Document 1 proposes a porous resin film using calcium carbonate powder treated with a surface treatment agent having an HLB value of 5 to 100 and having a liquid absorption capacity of a specific value or more.
- the liquid absorption rate ink absorption rate
- the liquid absorption rate on the surface of the print receiving layer is high, but if the liquid absorption rate is too fast, the ink color may fade or the openings on the surface of the print receiving layer may occur. It has also been found that granular patterns may occur due to bubbles being sprayed from the surface.
- an object of the present invention is to provide a recording paper with excellent printing quality and drying properties.
- the present inventor has determined that by incorporating a filler that has undergone a specific surface treatment into the print-receiving layer of recording paper, the liquid absorption rate on the surface of the layer can be set within a specific range, and the amount of liquid absorbed can be controlled to a specific value.
- the present inventors have found that the above results can provide a recording paper with good printing quality and drying properties, and have completed the present invention.
- the print receiving layer contains a hydrophilic surface treated filler and a hydrophobic surface treated filler,
- the liquid absorption rate on the surface of the print receiving layer side is 3.5 to 10 cc/m 2 ⁇ 0.5 s, Recording paper with a liquid absorption amount of 10 cc/m 2 ⁇ 180 s or more.
- a recording paper that has excellent print quality and drying properties because the liquid absorption rate of the surface of the recording paper on the print-receiving layer side is within a specific range and the amount of liquid absorption is above a specific value. can.
- FIG. 1 is a sectional view showing an example of recording paper according to this embodiment.
- (meth)acrylic refers to both acrylic and methacrylic.
- (meth)acryloyl indicates both acryloyl and methacryloyl, and the description “(meth)acrylate” indicates both acrylate and methacrylate.
- the recording paper according to the present embodiment has a print-receptive layer and a liquid-absorbing layer, both of the liquid-absorbing layer and the print-receiving layer are porous layers containing a thermoplastic resin, and the print-receiving layer includes: Contains a hydrophilic surface-treated filler and a hydrophobic surface-treated filler, the liquid absorption rate on the surface of the print receiving layer side is 3.5 to 10 cc/m 2 ⁇ 0.5 s, and the liquid absorption amount is 10 cc/m 2 ⁇ It is 180 seconds or more.
- FIG. 1 is a cross-sectional view showing an example of recording paper according to this embodiment.
- a recording paper 1 has a print-receiving layer 12 and a liquid-absorbing layer 11.
- the liquid-absorbing layer 11 is preferably provided in contact with the print-receiving layer 12 .
- the recording paper according to this embodiment preferably includes a support layer 10 on the side opposite to the print-receiving layer 12 when viewed from the liquid-absorbing layer 11.
- FIG. 1 is a diagram illustrating a recording paper 1 having a structure in which a liquid absorbing layer 11 and a print receiving layer 12 are laminated in this order on a support layer 10.
- the recording paper according to this embodiment has a liquid absorption speed of 3.5 to 10 cc/m 2 ⁇ 0.5 s on the surface on the print receiving layer side.
- the liquid absorption speed is 3.5 cc/m 2 ⁇ 0.5 s or more, preferably 4 cc/m 2 ⁇ 0.5 s or more, and more preferably 5 cc/m 2 ⁇ 0.5 s or more.
- the liquid absorption speed is 10 cc/m 2 ⁇ 0.5 s or less, preferably 8.5 cc/m 2 ⁇ 0.5 s or less.
- the liquid absorption rate on the surface of the print receiving layer side is determined by Japan Tappi No. It is the amount of liquid transfer measured in accordance with the liquid absorption test method using the Bristow method described in 51:2000, and means the amount of absorption per unit area 500 milliseconds after dropping the measurement solution.
- the amount of liquid absorbed from the surface of the print-receiving layer of the recording paper according to this embodiment is 10 cc/m 2 ⁇ 180 s or more, preferably 20 cc/m 2 ⁇ 180 s or more, and more preferably 30 cc/m 2 ⁇ 180 s or more. preferable.
- the amount of liquid absorbed is equal to or greater than the above value, drying performance can be improved.
- the liquid absorption amount is preferably 50 cc/m 2 ⁇ 180 s or less, and more preferably 40 cc/m 2 ⁇ 180 s or less.
- the amount of liquid absorbed from the surface of the print receiving layer side may be 10 cc/m 2 ⁇ 180 s to 50 cc/m 2 ⁇ 180 s.
- the liquid absorption amount of the recording paper refers to the value measured for the amount of liquid absorbed from the surface of the print-receiving layer side, and is the Cobb water absorption value measured based on the provisions of JIS P8140:1998. However, instead of water, a 70% by mass ethanol aqueous solution is used as the test solvent, and the contact time is 180 seconds.
- the liquid absorption speed on the surface on the print receiving layer side is 3.5 to 10 cc/m 2 ⁇ 0.5 s, and the liquid absorption amount is 10 cc/m 2 ⁇ 180 s or more. . That is, in this embodiment, it is preferable that both the liquid absorption rate and the liquid absorption amount are within the above ranges. As mentioned above, the inventors have found that even if the liquid absorption capacity is relatively large, if the liquid absorption rate is relatively slow, sufficient drying properties may not be obtained.
- the liquid absorption rate on the surface of the print receiving layer is high, but if the liquid absorption rate is too fast, the ink color may fade or the openings on the surface of the print receiving layer may occur. It has also been found that granular patterns may occur due to bubbles being ejected from the surface.
- the liquid absorption rate of the surface of the print-receiving layer side of the recording paper is within a specific range, and the amount of liquid absorption is above a specific value, so that recording with good print quality and drying properties can be achieved. It was discovered that paper can be obtained.
- the print-receiving layer contains a hydrophilic surface-treated filler and a hydrophobic surface-treated filler.
- a hydrophilic surface-treated filler By containing both the hydrophilic surface-treated filler and the hydrophobic surface-treated filler, the liquid absorption rate can be easily adjusted to an appropriate range, ie, 3.5 to 10 cc/m 2 ⁇ 0.5 s.
- the surface strength on the print-receiving layer side surface is preferably 1.1 kg-cm or more, more preferably 1.2 kg-cm or more, and even more preferably 1.3 kg-cm or more.
- the upper limit of the surface strength is not particularly limited, but since increasing the surface strength of the layer tends to reduce the surface aperture ratio, from the viewpoint of improving drying properties, it is preferably 2.0 kg-cm or less, and 1.5 kg-cm or less. cm or less is more preferable.
- the surface strength on the print-receiving layer side surface may be from 1.1 kg-cm to 2.0 kg-cm.
- the surface strength on the print-receiving layer side surface can be measured using an internal bond tester.
- the liquid absorbent layer also contains a filler. More preferably, both the print-receiving layer and the liquid-absorbing layer are stretched layers containing filler. For example, by co-stretching the print-receiving layer and the liquid-absorbing layer and then co-stretching them, or by extruding and laminating the print-receiving layer on the liquid-absorbing layer and then co-stretching them, both the print-receptive layer and the liquid-absorbent layer can be made into stretched layers. This is preferable because the manufacturing process can be simplified and manufacturing costs can be suppressed.
- a coating layer containing a pigment and a binder is provided on the surface of a base material such as paper.
- a base material such as paper.
- calcium carbonate or kaolin is generally used as a pigment, but such coating layers contain a large amount of pigment and are therefore brittle and easily break when bent. Therefore, coated printing paper provided with such a coating layer tends to be difficult to use for layflat bookbinding.
- the print-receiving layer is a layer made porous by stretching a filler-containing resin composition, it is easy to make it sufficiently porous with a smaller amount of filler than in the above-mentioned coating layer, and the desired liquid absorption rate and absorption rate can be achieved.
- the porous layer thus obtained is resistant to bending.
- the print-receiving layer is a stretched layer containing a filler, and the surface strength on the print-receiving layer side is 1.1 kg-cm or more, there is a tendency for lay-flat bookbinding properties sufficient for practical use to be obtained. be.
- the print-receiving layer is formed by stretching, it is preferable to use the materials described below because the various physical properties described above can be easily achieved. Further, preferred embodiments of the liquid absorbing layer will also be described later.
- the print-receiving layer is a porous layer containing a thermoplastic resin, a hydrophilic surface-treated filler, and a hydrophobic surface-treated filler.
- the print-receiving layer is preferably a stretched layer as described above. That is, the print-receiving layer is preferably a stretched layer containing a thermoplastic resin, a hydrophilic surface-treated filler, and a hydrophobic surface-treated filler.
- coloring materials such as pigments and dyes remain on the surface layer of the print-receiving layer and develop color.
- the ink solvent passes through the print receiving layer and moves to the lower layer (liquid absorption layer).
- thermoplastic resin used in the print-receiving layer examples include olefin polymers, polyamides, polyesters, polycarbonates, polystyrenes, poly(meth)acrylates, polyvinyl chloride, and mixed resins thereof.
- olefin polymers are preferred from the viewpoint of water resistance and solvent resistance.
- propylene polymer As the olefin polymer, propylene polymer, ethylene polymer, etc. can be preferably used.
- propylene-based polymers include propylene homopolymers such as isotactic homopolypropylene and syndiotactic homopolypropylene, which are made by homopolymerizing propylene, and propylene-based polymers mainly composed of propylene such as ethylene, 1-butene, 1-hexene, and 1-heptene.
- propylene copolymers copolymerized with ⁇ -olefins such as , 1-octene, and 4-methyl-1-pentene.
- the propylene copolymer may be a binary system or a multi-component system having ternary or more components. Further, the propylene copolymer may be a random copolymer or a block copolymer.
- Ethylene-based polymers include, for example, high-density polyethylene, medium-density polyethylene, linear low-density polyethylene, ethylene as a main ingredient, and ⁇ -olefins such as propylene, butene, hexene, heptene, octene, and 4-methylpentene-1.
- Copolymerized copolymer maleic acid-modified ethylene/vinyl acetate copolymer, ethylene/vinyl acetate copolymer, ethylene/vinyl acetate copolymer, (meth)acrylic acid alkyl ester copolymer, ethylene/(meth)acrylic acid copolymer and its metal salt (metals include zinc, aluminum, lithium, sodium, potassium, etc.), ethylene-cyclic olefin copolymer, (anhydrous ) Maleic acid-modified polyethylene, (anhydrous) maleic acid-modified polypropylene, and the like.
- (maleic anhydride) refers to both maleic anhydride and maleic acid.
- propylene homopolymer ie, polypropylene, or high-density polyethylene is preferable from the viewpoint of improving moldability and suppressing cost.
- (anhydrous) maleic acid-modified polyethylene or (anhydrous) maleic acid-modified polypropylene is preferable.
- thermoplastic resins one kind can be used alone or two or more kinds can be used in combination.
- the print-receiving layer preferably contains a thermoplastic elastomer (hereinafter sometimes simply referred to as "elastomer”) from the viewpoint of increasing surface strength.
- the elastomer in the print-receiving layer is a thermoplastic elastomer such as polystyrene (TPS), olefin (TPO), polyvinyl chloride (TPVC), polyurethane (TPU), polyester (TPC), or polyamide (TPAE). It can be selected and used as appropriate.
- the elastomer is preferably one that has high compatibility with the resin that is the main component of the print-receiving layer, and is preferably an elastomer of the same type as the thermoplastic resin contained in the print-receiving layer.
- an olefin polymer as the thermoplastic resin
- the olefin elastomer has, for example, a polyolefin such as polypropylene or polyethylene as a hard segment and a rubber component such as ethylene propylene rubber (EPM, EPDM) as a soft segment.
- Olefin elastomers are broadly divided into three types: a blend type of polyolefin and a rubber component, a dynamic crosslinking type (TPV: sometimes referred to separately as Themoplastic Vulcanizates), and a polymerization type (R-TPO: Reactor-TPO).
- TPV dynamic crosslinking type
- R-TPO Reactor-TPO
- the toughness of the print-receiving layer containing a thermoplastic resin, preferably an olefin polymer, can be improved.
- the surface strength of the recording paper can be improved.
- the content of the elastomer is, for example, preferably 6 to 14% by mass, more preferably 8 to 12% by mass, based on the total amount of the thermoplastic resin and elastomer contained in the print-receiving layer.
- the amount of elastomer is at least the above lower limit, the modification effect tends to be sufficient.
- the amount of elastomer is below the above upper limit, it is possible to suppress the formation of pores, which may result in a decrease in dot gain, a decrease in the anchoring ability of the ink on the surface of the print receiving layer, or a decrease in the ink fixing ability. It is possible to suppress the decline, etc.
- Examples of the hydrophilic surface-treated filler and hydrophobic surface-treated filler used in the print-receiving layer include inorganic particles or organic particles subjected to the surface treatment described below. Inorganic particles and organic particles can be used alone or in combination. When a resin composition containing a filler and a thermoplastic resin is stretched, a large number of fine pores with particles as cores can be formed inside the stretched layer. Thereby, a porous layer can be obtained.
- the content of the filler in the print-receiving layer is preferably 45% by mass or more, more preferably 50% by mass or more, from the viewpoint of optimizing the pore-forming property.
- the filler content in the print-receiving layer is 45% by mass or more, it is possible to increase the porosity, help ink to penetrate into the liquid-absorbing layer, and increase the liquid-absorbing amount.
- the filler content in the print-receiving layer is preferably 65% by mass or less, from the viewpoint of suppressing the occurrence of surface defects and suppressing excessive porosity and liquid absorption rate, and 60% by mass or less. More preferred.
- the filler content in the print-receiving layer may be 45% to 65% by weight.
- the average particle diameter of the filler contained in the print-receiving layer is preferably 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more, from the viewpoint of obtaining suitable pore-forming properties. From the same viewpoint, the average particle diameter of the filler is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less.
- the average particle diameter of the filler is 0.1 ⁇ m or more, a sufficient number and size of pores are formed in the layer, so that the porous layer can be made porous to easily improve the permeability of the aqueous pigment ink. If the average particle diameter of the filler is 5 ⁇ m or less, the formation of coarse pores can be suppressed and the clarity of inkjet printed images can be easily improved.
- the filler contained in the print receiving layer may have an average particle diameter of 0.1 ⁇ m to 5 ⁇ m.
- the average particle diameter of the filler refers to the average primary particle diameter (D50). This is the volume-based median diameter measured by laser light diffraction/scattering method.
- inorganic particles include, but are not limited to, heavy calcium carbonate, light calcium carbonate, calcined clay, talc, titanium oxide, barium sulfate, alumina, silica, zinc oxide, zeolite, mica, glass fiber, hollow glass beads, and the like. Can be mentioned. Among them, heavy calcium carbonate, calcined clay, diatomaceous earth, etc. are cheap, and they are easy to form many pores by stretching the resin composition that forms the porous layer, and the porosity can be easily adjusted. ,preferable. In particular, heavy calcium carbonate or light calcium carbonate is preferable because its average particle size or particle size distribution can be easily adjusted to a range in which pore formation is easy. Among the above inorganic particles, one kind can be used alone or two or more kinds can be used in combination.
- Organic particles include, but are not particularly limited to, organic particles that are incompatible with the thermoplastic resin, have a melting point or glass transition temperature higher than that of the thermoplastic resin, and are finely dispersed under the melt-kneading conditions of the thermoplastic resin. preferable.
- thermoplastic resin contained in the print receiving layer polyethylene terephthalate, polybutylene terephthalate, polycarbonate, nylon-6, nylon-6,6, a cyclic olefin homopolymer, or a cyclic olefin
- a resin such as a copolymer of ethylene and a resin having a melting point of 120 to 300°C or a glass transition temperature of 120 to 280°C.
- ⁇ Hydrophilic surface treatment filler>> By including a hydrophilic surface-treated filler whose surface has been hydrophilized as a filler in the print-receiving layer, the affinity between the print-receptive layer and water-based ink is improved, and the liquid absorption rate on the surface of the print-receptor layer is increased. improves.
- the hydrophilic surface-treated filler can be obtained, for example, by applying a surface treatment agent to the filler surface by the method described below.
- the surface treatment agent examples include water-soluble cationic copolymers and water-soluble anionic surfactants.
- the water-soluble cationic copolymer includes a monomer (d1) selected from diallylamine salts, alkyldiallylamine salts, dialkyldiallylammonium salts, and tetraalkyl ammonium salts substituted with (meth)acryloyloxy groups, and a nonionic hydrophilic vinyl A copolymer with monomer (d2) is preferred.
- the amine salt in (d1) is preferably a compound in which the amino group is converted into a salt with hydrochloric acid, sulfuric acid, nitric acid, acetic acid, or the like.
- the anion that forms a salt with the ammonium structure is preferably selected from chloride ion, bromide ion, sulfate ion, nitrate ion, methylsulfate ion, ethylsulfate ion, and methanesulfonate ion.
- the alkyl group in (d1) is preferably an alkyl group having 1 to 4 carbon atoms.
- (d1) examples include diallylamine salt, methyldiallylamine salt, ethyldiallylamine salt; dimethyldiallylammonium, (meth)acryloyloxyethyltrimethylammonium, (meth)acryloyloxyethyldimethylethylammonium, and acryloyloxyethyldimethylammonium.
- Examples include quaternary ammonium salts obtained by alkylating N,N-dimethylaminoethyl (meth)acrylate with epoxy compounds such as epichlorohydrin, glycidol, and glycidyltrimethylammonium chloride. Particularly preferred among these are diallylamine salt, methyldiallylamine salt and dimethyldiallylammonium salt. These may be used alone or in combination.
- (d2) examples include acrylamide, methacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrodrine, 2-hydroxyethyl (meth)acrylate, 2-hydroxy (meth)acrylate, 3-hydroxy
- Examples include propyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and among these, acrylamide or methacrylamide is preferred. These may be used alone or in combination.
- the copolymerization ratio of (d1) and (d2) is arbitrary, but as a preferred range, (d1) is 10 to 99 mol%, more preferably 50 to 97 mol%, and even more preferably 65 to 95 mol%. , (d2) is 90 to 1 mol%, more preferably 50 to 3 mol%, even more preferably 35 to 5 mol%.
- the cationic copolymer can be produced, for example, by the method described in Japanese Patent Application Laid-Open No. 5-263010.
- water-soluble anionic surfactant examples include one or more sulfonates selected from the group consisting of sulfonates of alkylene oxide adducts of monohydric alcohols, alkyl sulfonates, and alkylbenzene sulfonates.
- sulfonates selected from the group consisting of sulfonates of alkylene oxide adducts of monohydric alcohols, alkyl sulfonates, and alkylbenzene sulfonates.
- cations that form salts with the sulfonic acid structure include sodium ions, potassium ions, lithium ions, and ammonium ions.
- alkyl sulfonates are preferred, and specifically, those having an alkyl group having 8 to 20 carbon atoms, such as octane sulfonate, dodecane sulfonate, tetradecane sulfonate, hexadecane sulfonate, and octadecane sulfonate. Particularly preferred. These may be used alone or in combination.
- the method for hydrophilizing the surface of the filler is not particularly limited, and can be carried out, for example, by introducing a surface treatment agent into a slurry containing inorganic particles or organic particles, followed by stirring and drying.
- a surface treatment agent preferably inorganic particles
- the mass ratio of calcium carbonate/aqueous medium is, for example, 70/30 to 30/70, preferably 60/40.
- an aqueous medium may be prepared by dissolving the cationic copolymer in an amount within the above range in advance, the aqueous medium may be mixed with calcium carbonate, and the mixture may be wet-pulverized by a conventional method.
- the print-receiving layer contains a hydrophilic surface treated filler as a filler
- a print-receiving layer in which the surface of the print-receiving layer absorbs liquid at a relatively high rate can be obtained.
- the liquid absorption rate is too high, there is a tendency for the ink to fade or to produce granular patterns due to bubbles ejected from the openings on the surface of the print-receiving layer.
- the openings refer to pores that are open by being formed on the surface of the print-receiving layer, which is a porous layer.
- by replacing a portion of the filler with a hydrophobized surface-treated filler it becomes easy to appropriately adjust the liquid absorption rate.
- the hydrophobized surface-treated filler contained in the print-receiving layer is preferably inorganic particles or organic particles whose surface has been hydrophobized with paraffin or a fatty acid having 12 to 22 carbon atoms or a salt thereof. More preferably, they are inorganic particles or organic particles whose surface has been subjected to hydrophobization treatment with a salt thereof.
- Examples of the fatty acid having 12 to 22 carbon atoms for hydrophobic surface treatment include lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, and eleostearin. Examples include acids.
- the surface treatment method is not particularly limited, and can be carried out, for example, by introducing an aqueous solution of a treatment agent into a slurry of inorganic particles or organic particles, as in the preparation of the hydrophilic surface-treated filler described above.
- surface-treated inorganic particles or organic particles that is, inorganic particles or organic particles having a surface-treated layer containing paraffin, a fatty acid having 12 to 22 carbon atoms, or a salt thereof on the surface.
- the ratio of the hydrophilic surface treated filler to the hydrophobic surface treated filler (hydrophilic surface treated filler/hydrophobic surface treated filler) in the print receiving layer is preferably from 95/5 to 55/45 in terms of mass ratio.
- the ratio is more preferably 85/15 to 65/35. It is preferable that the ratio of the hydrophilic surface-treated filler to the hydrophobic surface-treated filler is within this range because it makes it easier to adjust the liquid absorption rate to an appropriate range, ie, 3.5 to 10 cc/m 2 ⁇ 0.5 s.
- the total amount of the hydrophilic surface-treated filler and the hydrophobic surface-treated filler in the print-receiving layer is preferably 90% by mass or more, more preferably 95% by mass or more, based on the total amount of fillers contained in the print-receiving layer. Such total amount may be 100% by weight.
- the total amount of the hydrophilic surface-treated filler and the hydrophobic surface-treated filler is within the above range, it becomes easier to obtain a print-receiving layer whose liquid absorption rate is precisely controlled.
- an untreated filler that has not been subjected to surface treatment may be used in combination to the extent that the effects of the present invention are not impaired.
- the print-receiving layer can optionally contain known additives, if necessary.
- Additives include antioxidants, light stabilizers, ultraviolet absorbers, filler dispersants, crystal nucleating agents, anti-blocking agents, plasticizers, slip agents such as fatty acid amides, dyes, pigments, mold release agents, and flame retardants.
- Examples include known auxiliaries such as.
- the base layer preferably contains an antioxidant, a light stabilizer, and the like.
- the antioxidant include sterically hindered phenolic antioxidants, phosphorus antioxidants, amine antioxidants, and the like.
- the light stabilizer examples include sterically hindered amine light stabilizers, benzotriazole light stabilizers, benzophenone light stabilizers, and the like.
- the content of the antioxidant and light stabilizer is preferably 0.001 to 1% by mass based on the base layer.
- the print-receiving layer is porous, and its porosity is preferably 40 to 60%, more preferably 45 to 55%. It is preferable that the porosity is in this range because it becomes easier to achieve both liquid absorption rate and surface strength.
- the porosity is obtained as the area ratio of pores on the cross section, which is calculated by observing the cross section of the target layer using a scanning electron microscope, importing the observed image into an image analysis device, and performing image analysis on the observed area. be able to.
- the basis weight of the print-receiving layer is preferably 1 to 15 g/m 2 , more preferably 3 to 13 g/m 2 , even more preferably 4 to 10 g/m 2 . When the basis weight is within this range, it is preferable because it becomes easier to adjust the liquid absorption rate to a desired level.
- the thickness of the print-receiving layer depends on the porosity of the layer, but is preferably 1.0 to 18.0 ⁇ m, more preferably 4.0 to 16.0 ⁇ m, and even more preferably 5.0 to 12.0 ⁇ m. . It is preferable that the thickness is within this range because it becomes easier to adjust the liquid absorption rate to a desired level.
- the liquid-absorbing layer is a layer that absorbs ink that has passed through the print-receiving layer, and is preferably provided in contact with the print-receiving layer.
- the liquid absorbing layer is a porous layer containing a thermoplastic resin, and preferably a layer containing a filler. More preferably, the liquid absorbing layer is a stretched layer containing filler. That is, the liquid absorbing layer is more preferably a stretched layer containing a thermoplastic resin and a filler.
- thermoplastic resin used in the liquid-absorbing layer examples include the same thermoplastic resins as those listed in the section of the print-receiving layer, and among them, the preferred ones are also the same as described above.
- the filler used in the liquid-absorbing layer the same fillers as those mentioned in the section of the print-receiving layer can be used.
- the filler used in the liquid-absorbing layer may or may not have been subjected to at least one of the above-mentioned hydrophilic surface treatment and hydrophobic surface treatment. From the viewpoint of obtaining a desired amount of liquid absorption, it is preferable that no surface treatment is performed.
- the filler content in the liquid absorption layer is preferably 45 to 65% by mass, more preferably 50 to 60% by mass.
- the filler content is at least the above lower limit, the amount of pores in the liquid absorbing layer is likely to be sufficient.
- the filler content is at most the above upper limit.
- the liquid-absorbing layer may contain other arbitrary components such as the various additives mentioned above.
- the thickness and porosity of the liquid absorbing layer may be adjusted so that the amount of liquid absorbed from the print receiving layer is 10 cc/ m2 or more, and a thin layer with high porosity may be provided, or a layer with high porosity may be formed thinly. It is also possible to provide a thick layer in which the resistance is not so high.
- the porosity is preferably 40% or more, more preferably 45% or more.
- the porosity is preferably 50% or less.
- the porosity of the liquid absorbing layer may be 40% to 50%.
- a support layer may be laminated on the opposite side of the liquid-absorbing layer from the print-receiving layer.
- the recording paper By configuring the recording paper to include such a support layer, it is possible to provide the recording paper with an appropriate thickness and stiffness suitable for printing. That is, by adjusting the thickness of the support layer, it is possible to adjust the thickness of the recording paper, give it a stiffness suitable for printing, and adjust its opacity and paper feeding/discharging properties. From the viewpoint of obtaining sufficient stiffness, the thickness of the support layer is preferably 15 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 30 ⁇ m or more.
- the thickness of the support layer is preferably 400 ⁇ m or less, more preferably 300 ⁇ m or less, and even more preferably 200 ⁇ m or less.
- the thickness of the support layer may be between 15 ⁇ m and 400 ⁇ m.
- the support layer may be a single layer or a laminate of two or more layers.
- the support layer is preferably a thermoplastic resin layer with excellent water resistance.
- the thermoplastic resin the same resins as those mentioned in the section of the print-receiving layer can be used.
- the support layer may contain a filler similarly to the print-receiving layer and the liquid-absorbing layer, and the support layer may be a porous layer. Further, the support layer may contain other arbitrary components such as the above-mentioned additives.
- the recording paper according to this embodiment may have layers other than those described above as long as the effects of the present invention are not impaired.
- the recording paper may have an adhesive layer between the liquid absorbent layer and the support layer, or may have an adhesive layer on the surface of the support layer opposite to the liquid absorbent layer side.
- any layer may be provided between the two layers as long as it does not impede ink permeation from the print-receiving layer to the liquid-absorbing layer.
- the method for manufacturing the recording paper of the present invention is not particularly limited, but examples include the following method.
- the laminated resin films constituting the print-receiving layer and the liquid-absorbing layer may be laminated.
- the print-receiving layer and the liquid-absorbing layer may be co-extruded using a multilayer die method using a feed block or multi-manifold, and then co-stretched to form a laminated resin film in which both layers are made porous.
- a laminated resin film in which both layers are made porous may be formed by extruding and laminating one layer onto the surface of the other layer using a plurality of dies, and stretching this.
- the support layer, liquid absorbent layer, and print receiving layer are all coextruded and then costretched, or after the support layer and liquid absorbent layer are coextruded, the print receiving layer is extrusion laminated on the surface of the liquid absorbent layer, and then the print receiving layer is coextruded and then costretched.
- the liquid-absorbing layer and the print-receiving layer are made porous and laminated with the support at the same time. It's okay. From the viewpoint of simple process and reduction of manufacturing cost, it is preferable to manufacture by coextrusion and/or costretching after extrusion lamination.
- a known method can be used as the stretching method.
- the recording paper according to this embodiment can be printed on the surface on the print-receiving layer side.
- the printing method performed on the print-receiving layer is not particularly limited, and in addition to various known plate printing methods such as gravure printing, offset printing, flexo printing, sticker printing, and screen printing, inkjet methods, electrophotographic methods, Alternatively, digital printing or fused thermal transfer printing using various printers such as liquid toner type printers can also be performed.
- inks are used depending on the printing method, such as ultraviolet curable ink, oil-based ink, oxidative polymerization-curable ink, fused heat transfer recording ink, water-based ink, powder toner, or liquid toner (electro ink). can do.
- the recording paper according to this embodiment is suitably used for inkjet printing, especially inkjet printing using water-based ink.
- the recording paper according to the present embodiment has excellent print quality and drying properties because the liquid absorption rate is within a specific range and the amount of liquid absorption is equal to or greater than a specific value.
- Table 1 shows the raw materials used in the Examples and Comparative Examples.
- MFR in the table means melt flow rate.
- D50 average particle diameter of surface-untreated calcium carbonate shown in Table 1 is the average primary particle diameter (D50), which is measured by the laser light diffraction/scattering method using Microtrack (manufactured by Nikkiso Co., Ltd.). This is the volume-based median diameter.
- Production of hydrophilic surface-treated calcium carbonate 40% by mass of heavy calcium carbonate (average particle size 8 ⁇ m, manufactured by Nippon Cement Co., Ltd., dry-pulverized product) and 60% by mass of water were sufficiently stirred and mixed to form a slurry, and the water-soluble cationic compound prepared in Production Example 1 was prepared. Add 0.06 parts by mass of the polymer per 100 parts by mass of heavy calcium carbonate, and wet-process using a table-type attritor-type media stirring mill (glass beads with a diameter of 1.5 mm, filling rate 170%, peripheral speed 10 m/sec). Shattered.
- a table-type attritor-type media stirring mill glass beads with a diameter of 1.5 mm, filling rate 170%, peripheral speed 10 m/sec.
- the average primary particle size of the obtained calcium carbonate was subjected to ultrasonic dispersion using an ultrasonic dispersion machine Model US-300T (manufactured by Nippon Seiki Co., Ltd.) for 60 seconds at 300 ⁇ A using ethanol as a solvent. When measured, it was 0.23 ⁇ m.
- Example 1 Manufacture of print-receiving layer resin composition
- 40 parts by mass of polypropylene product name: Novatec PP MA3Q, manufactured by Nippon Polypro Co., Ltd.
- 0.7 parts by mass of maleic anhydride-modified polypropylene product name: Modic P908, manufactured by Mitsubishi Chemical Corporation
- olefin elastomer product name: Tafmer PN20300
- Mitsui Chemicals 5.0 parts by mass, 13 parts by mass of hydrophobic surface-treated calcium carbonate obtained in Production Example 3, 37 parts by mass of hydrophilic surface-treated calcium carbonate obtained in Production Example 2, and surface 3.6 parts by mass of untreated calcium carbonate (trade name: Softon #1800, manufactured by Bihoku Funka Co., Ltd.) was blended and mixed with stirring using a mixer, followed by an extrusion process to obtain resin composition A.
- the resin composition C was melt-kneaded in an extruder set at 250°C, extruded into a sheet from a die, and cooled to 70°C in a cooling device to obtain a single-layer unstretched film. After this unstretched film was reheated to 145° C., it was stretched five times in the longitudinal direction using the difference in circumferential speed between the rolls to obtain a longitudinally uniaxially stretched film. Subsequently, the resin compositions A and B are supplied to an extruder, and each resin composition is extruded into a two-layer sheet, which is laminated so that the resin composition B is in contact with the uniaxially stretched film to form a three-layer structure. A laminate was obtained.
- the obtained laminate was reheated to 160° C. using an oven, and then stretched 9 times in the transverse direction using a tenter stretching machine. Then, it was heat-treated at 170° C. to produce a recording paper having a three-layer structure including one biaxially stretched layer and two uniaxially stretched layers.
- the basis weight of the obtained recording paper was 8 g/m 2 for the print receiving layer, 32 g/m 2 for the liquid absorbing layer, and 56 g/m 2 for the support layer.
- the liquid absorption rate, liquid absorption amount, and surface strength of the surface of the print-receiving layer were measured by the following methods. In addition, the following evaluations were performed. The results are shown in Table 2.
- Liquid absorption speed Liquid transfer amount (V) measured using a liquid dynamic absorption tester (Kumagai Riki Kogyo Co., Ltd.: Bristow tester KM500 model) according to the Bristow method (Japan Tappi No. 51:2000) was taken as the liquid absorption rate of the print receiving layer.
- a mixture of 30% by mass of distilled water and 70% by mass of ethanol and 2% by mass of stamp ink (red) manufactured by Shachihata Co., Ltd.
- the amount of absorption per unit area in seconds was determined.
- Adhesive tape (manufactured by Nichiban Co., Ltd., product name "Cello Tape (registered trademark)", product number: “CT-18") was pasted on the surface of the print-receiving layer to prevent air from entering, and JAPAN TAPPI No.
- the strength when peeling the adhesive tape was measured using an internal bond tester (manufactured by Kumagai Riki Kogyo Co., Ltd.) according to the method described in Section 18-2.
- the density of the solid image area was measured using a spectral color densitometer 530JP (manufactured by X-Rite). The evaluation criteria are as follows. A: The density of the solid image area exceeds 1.7. B: The density of the solid image area is more than 1.5 and less than 1.7. C: The density of the solid image area is more than 1.3 and less than 1.5. D: The density of the solid image area is more than 1.0 and less than 1.3.
- Ink fixability Ink fixability was evaluated using a dye fastness friction tester FR-20 (manufactured by Suga Test Instruments Co., Ltd.). The evaluation conditions were 100 Gakushin tests and a load of 400 g, and the images were visually observed after the test. The evaluation criteria are as follows. A: The image has not peeled off. B: Part of the image peeled off, and the density of the image area decreased. C: Part of the image was peeled off, and the surface of the support layer was visible. D: The image was completely peeled off and the surface of the support layer was visible.
- the printed recording paper was folded at 180 degrees with the solid image portion facing inside, rubbed with a finger 10 times, opened, and visually checked to see if the surface of the folded portion was damaged.
- the evaluation criteria are as follows. A: The entire surface of the folded portion is not broken. B: Part of the surface of the folded portion was broken, and the support layer was exposed. C: Half of the surface of the folded portion was broken, and the support layer was exposed. D: The entire surface of the folded portion was broken, and the support layer was exposed.
- Examples 2 to 11 Comparative Examples 1 to 3
- a recording paper was produced in the same manner as in Example 1, except that the raw materials for the print-receiving layer and the liquid-absorbing layer were changed as shown in Table 2. Further, in the same manner as in Example 1, the liquid absorption rate, liquid absorption amount, and surface strength were measured and various evaluations were performed. The results are shown in Table 2.
- the recording paper of the example was able to achieve both excellent printing quality and ink drying properties by having a liquid absorption rate within a specific range and a liquid absorption amount exceeding a specific value.
- Comparative Example 1 which had a low liquid absorption rate, had a large amount of blurring in the image, and conversely, Comparative Example 3, which had a very high liquid absorption rate, had roughness in the image, and sufficient image quality could not be obtained in either case.
- Comparative Example 2 which had a small amount of liquid absorption, the drying properties of printing were insufficient.
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Abstract
The present invention pertains to recording paper which has a printing-receptive layer and a liquid-absorbing layer, wherein: the liquid-absorbing layer and the printing-receptive layer are both porous layers which contain a thermoplastic resin; the printing-receptive layer contains a hydrophilized surface-treated filler and a hydrophobized surface-treated filler; the liquid absorption speed on the surface of the printing-receptive layer side is 3.5-10cc/m2·0.5s; and the liquid absorption amount is 10cc/m2·180s or more.
Description
本発明は、記録用紙に関する。
The present invention relates to recording paper.
インクジェット方式のプリンタは、近年、多色オフセット印刷やカラー電子写真方式と比較しても見劣りをしない画像を得られるようになってきている。加えて、インクジェット方式のプリンタは、カラー印字におけるランニングコストが電子写真方式のプリンタと比較して安いという特徴もあり、広く普及してきている。中でも、油性インクに比べて環境面や安全面に関する問題を生じにくい水性インクを利用したインクジェットプリンタは、最近の主流になっている。
In recent years, inkjet printers have become capable of producing images that are comparable to multicolor offset printing and color electrophotography. In addition, inkjet printers have become widely popular because they have lower running costs for color printing than electrophotographic printers. Among these, inkjet printers that use water-based inks, which are less likely to cause environmental and safety problems than oil-based inks, have recently become mainstream.
これに伴い、インクジェット記録用紙の使用用途はポスターや製図用途にも広がってきている。このため記録用紙や記録用インクについても、従来以上に印刷品質や耐擦過性等が求められるようになっている。
Along with this, the uses of inkjet recording paper are expanding to include posters and drawings. For this reason, recording paper and recording ink are required to have higher printing quality and scratch resistance than ever before.
また、商業印刷などの分野においては、可変情報をデジタル化して高速に印刷する、いわゆるオンデマンド印刷方式が導入されてきており、オンデマンド印刷方式を採用しているインクジェット印刷機も登場してきている。このようなオンデマンド印刷方式においては、情報を製版することなく紙などのメディアに直接印刷することが可能なために少部数の印刷にも適している。最近では、装置の高速化又は高精細化に著しい進歩が見られることによる用途の拡大に伴い、記録用紙に対しても乾燥性の向上が強く求められている。
例えば特許文献１には、ＨＬＢ値が５～１００の表面処理剤にて処理された炭酸カルシウム粉末を用い、液体吸収容積を特定値以上とした多孔性樹脂フィルムが提案されている。 Furthermore, in fields such as commercial printing, the so-called on-demand printing method, which digitizes variable information and prints at high speed, has been introduced, and inkjet printers that use the on-demand printing method have also appeared. . Such an on-demand printing method is suitable for printing a small number of copies because it is possible to directly print information on media such as paper without making a plate. Recently, there has been a strong demand for improved drying properties of recording paper as a result of remarkable progress in increasing the speed and definition of devices and expanding their uses.
For example,Patent Document 1 proposes a porous resin film using calcium carbonate powder treated with a surface treatment agent having an HLB value of 5 to 100 and having a liquid absorption capacity of a specific value or more.
例えば特許文献１には、ＨＬＢ値が５～１００の表面処理剤にて処理された炭酸カルシウム粉末を用い、液体吸収容積を特定値以上とした多孔性樹脂フィルムが提案されている。 Furthermore, in fields such as commercial printing, the so-called on-demand printing method, which digitizes variable information and prints at high speed, has been introduced, and inkjet printers that use the on-demand printing method have also appeared. . Such an on-demand printing method is suitable for printing a small number of copies because it is possible to directly print information on media such as paper without making a plate. Recently, there has been a strong demand for improved drying properties of recording paper as a result of remarkable progress in increasing the speed and definition of devices and expanding their uses.
For example,
しかし本発明者の検討によると、液体吸収容積が比較的大きくても、吸液速度（インク吸収速度）が比較的遅い場合は、十分な乾燥性が得られない場合があることが判明した。
加えて、印刷時のインク乾燥性を向上する観点からは、印刷受容層表面の吸液速度は高いほうが好ましいが、吸液速度が速すぎると、インクの色沈みや、印刷受容層表面の開口部からの泡噴きによる粒状模様が生じる場合があることも判明した。 However, according to studies conducted by the present inventors, it has been found that even if the liquid absorption capacity is relatively large, if the liquid absorption rate (ink absorption rate) is relatively slow, sufficient drying performance may not be obtained.
In addition, from the perspective of improving ink drying properties during printing, it is preferable that the liquid absorption rate on the surface of the print receiving layer is high, but if the liquid absorption rate is too fast, the ink color may fade or the openings on the surface of the print receiving layer may occur. It has also been found that granular patterns may occur due to bubbles being sprayed from the surface.
加えて、印刷時のインク乾燥性を向上する観点からは、印刷受容層表面の吸液速度は高いほうが好ましいが、吸液速度が速すぎると、インクの色沈みや、印刷受容層表面の開口部からの泡噴きによる粒状模様が生じる場合があることも判明した。 However, according to studies conducted by the present inventors, it has been found that even if the liquid absorption capacity is relatively large, if the liquid absorption rate (ink absorption rate) is relatively slow, sufficient drying performance may not be obtained.
In addition, from the perspective of improving ink drying properties during printing, it is preferable that the liquid absorption rate on the surface of the print receiving layer is high, but if the liquid absorption rate is too fast, the ink color may fade or the openings on the surface of the print receiving layer may occur. It has also been found that granular patterns may occur due to bubbles being sprayed from the surface.
そこで、本発明は、印刷品質及び乾燥性に優れる記録用紙を提供することを目的とする。
Therefore, an object of the present invention is to provide a recording paper with excellent printing quality and drying properties.
本発明者は鋭意検討の結果、記録用紙における印刷受容層に特定の表面処理を施したフィラーを含有させることにより、該層表面の吸液速度を特定の範囲とし、且つ吸液量を特定値以上とでき、これにより印刷品質及び乾燥性が良好な記録用紙が得られることを見出し、本発明を完成するに至った。
As a result of extensive studies, the present inventor has determined that by incorporating a filler that has undergone a specific surface treatment into the print-receiving layer of recording paper, the liquid absorption rate on the surface of the layer can be set within a specific range, and the amount of liquid absorbed can be controlled to a specific value. The present inventors have found that the above results can provide a recording paper with good printing quality and drying properties, and have completed the present invention.
すなわち、本発明は以下の１～６に関する。
１．印刷受容層および吸液層を有する記録用紙であって、
前記吸液層及び前記印刷受容層はいずれも熱可塑性樹脂を含有する多孔質層であり、
前記印刷受容層が、親水化表面処理フィラー及び疎水化表面処理フィラーを含有し、
前記印刷受容層側の表面における吸液速度が３．５～１０ｃｃ／ｍ２・０．５ｓであり、
吸液量が１０ｃｃ／ｍ２・１８０ｓ以上である、記録用紙。
２．前記印刷受容層側の表面における表面強度が１．１ｋｇ－ｃｍ以上である、前記１に記載の記録用紙。
３．前記吸液層がフィラーを含有する層である、前記１又は２に記載の記録用紙。
４．前記印刷受容層におけるフィラーの含有量が４５～６５質量％である、前記１～３のいずれか１に記載の記録用紙。
５．前記親水化表面処理フィラーと前記疎水化表面処理フィラーの比（親水化表面処理フィラー／疎水化表面処理フィラー）が、質量比で９５／５～５５／４５である、前記１～４のいずれか１に記載の記録用紙。
６．前記印刷受容層が、さらに熱可塑性エラストマーを含有する、前記１～５のいずれか１に記載の記録用紙。 That is, the present invention relates toitems 1 to 6 below.
1. A recording paper having a print-receiving layer and a liquid-absorbing layer,
Both the liquid absorbing layer and the print receiving layer are porous layers containing a thermoplastic resin,
The print receiving layer contains a hydrophilic surface treated filler and a hydrophobic surface treated filler,
The liquid absorption rate on the surface of the print receiving layer side is 3.5 to 10 cc/m 2 · 0.5 s,
Recording paper with a liquid absorption amount of 10 cc/m 2 ·180 s or more.
2. 1. The recording paper according toitem 1, wherein the surface strength on the print-receiving layer side is 1.1 kg-cm or more.
3. 3. The recording paper according to 1 or 2 above, wherein the liquid absorbing layer is a layer containing a filler.
4. 4. The recording paper according to any one of 1 to 3 above, wherein the print-receiving layer has a filler content of 45 to 65% by mass.
5. Any one of 1 to 4 above, wherein the ratio of the hydrophilic surface treated filler to the hydrophobic surface treated filler (hydrophilic surface treated filler/hydrophobic surface treated filler) is 95/5 to 55/45 in mass ratio. Recording paper described in 1.
6. 6. The recording paper according to any one of 1 to 5 above, wherein the print-receiving layer further contains a thermoplastic elastomer.
１．印刷受容層および吸液層を有する記録用紙であって、
前記吸液層及び前記印刷受容層はいずれも熱可塑性樹脂を含有する多孔質層であり、
前記印刷受容層が、親水化表面処理フィラー及び疎水化表面処理フィラーを含有し、
前記印刷受容層側の表面における吸液速度が３．５～１０ｃｃ／ｍ２・０．５ｓであり、
吸液量が１０ｃｃ／ｍ２・１８０ｓ以上である、記録用紙。
２．前記印刷受容層側の表面における表面強度が１．１ｋｇ－ｃｍ以上である、前記１に記載の記録用紙。
３．前記吸液層がフィラーを含有する層である、前記１又は２に記載の記録用紙。
４．前記印刷受容層におけるフィラーの含有量が４５～６５質量％である、前記１～３のいずれか１に記載の記録用紙。
５．前記親水化表面処理フィラーと前記疎水化表面処理フィラーの比（親水化表面処理フィラー／疎水化表面処理フィラー）が、質量比で９５／５～５５／４５である、前記１～４のいずれか１に記載の記録用紙。
６．前記印刷受容層が、さらに熱可塑性エラストマーを含有する、前記１～５のいずれか１に記載の記録用紙。 That is, the present invention relates to
1. A recording paper having a print-receiving layer and a liquid-absorbing layer,
Both the liquid absorbing layer and the print receiving layer are porous layers containing a thermoplastic resin,
The print receiving layer contains a hydrophilic surface treated filler and a hydrophobic surface treated filler,
The liquid absorption rate on the surface of the print receiving layer side is 3.5 to 10 cc/m 2 · 0.5 s,
Recording paper with a liquid absorption amount of 10 cc/m 2 ·180 s or more.
2. 1. The recording paper according to
3. 3. The recording paper according to 1 or 2 above, wherein the liquid absorbing layer is a layer containing a filler.
4. 4. The recording paper according to any one of 1 to 3 above, wherein the print-receiving layer has a filler content of 45 to 65% by mass.
5. Any one of 1 to 4 above, wherein the ratio of the hydrophilic surface treated filler to the hydrophobic surface treated filler (hydrophilic surface treated filler/hydrophobic surface treated filler) is 95/5 to 55/45 in mass ratio. Recording paper described in 1.
6. 6. The recording paper according to any one of 1 to 5 above, wherein the print-receiving layer further contains a thermoplastic elastomer.
本発明によれば、記録用紙における印刷受容層側の表面の吸液速度が特定の範囲にあり、且つ吸液量が特定値以上であることで、印刷品質及び乾燥性に優れる記録用紙を提供できる。
According to the present invention, there is provided a recording paper that has excellent print quality and drying properties because the liquid absorption rate of the surface of the recording paper on the print-receiving layer side is within a specific range and the amount of liquid absorption is above a specific value. can.
以下、本発明の実施形態に係る記録用紙について詳細に説明するが、本発明はこれらに限定されない。なお以下の説明において、「（メタ）アクリル」の記載は、アクリルとメタクリルの両方を示す。同様に「（メタ）アクリロイル」の記載はアクリロイルとメタクリロイルの両方を示し、「（メタ）アクリレート」の記載はアクリレートとメタクリレートの両方を示す。
Hereinafter, recording sheets according to embodiments of the present invention will be described in detail, but the present invention is not limited thereto. In the following description, the term "(meth)acrylic" refers to both acrylic and methacrylic. Similarly, the description "(meth)acryloyl" indicates both acryloyl and methacryloyl, and the description "(meth)acrylate" indicates both acrylate and methacrylate.
（記録用紙）
本実施形態に係る記録用紙は、印刷受容層および吸液層を有し、前記吸液層及び前記印刷受容層はいずれも熱可塑性樹脂を含有する多孔質層であり、前記印刷受容層が、親水化表面処理フィラー及び疎水化表面処理フィラーを含有し、前記印刷受容層側の表面における吸液速度が３．５～１０ｃｃ／ｍ２・０．５ｓであり、吸液量が１０ｃｃ／ｍ２・１８０ｓ以上である。 (Recording sheet)
The recording paper according to the present embodiment has a print-receptive layer and a liquid-absorbing layer, both of the liquid-absorbing layer and the print-receiving layer are porous layers containing a thermoplastic resin, and the print-receiving layer includes: Contains a hydrophilic surface-treated filler and a hydrophobic surface-treated filler, the liquid absorption rate on the surface of the print receiving layer side is 3.5 to 10 cc/m 2 · 0.5 s, and the liquid absorption amount is 10 cc/m 2・It is 180 seconds or more.
本実施形態に係る記録用紙は、印刷受容層および吸液層を有し、前記吸液層及び前記印刷受容層はいずれも熱可塑性樹脂を含有する多孔質層であり、前記印刷受容層が、親水化表面処理フィラー及び疎水化表面処理フィラーを含有し、前記印刷受容層側の表面における吸液速度が３．５～１０ｃｃ／ｍ２・０．５ｓであり、吸液量が１０ｃｃ／ｍ２・１８０ｓ以上である。 (Recording sheet)
The recording paper according to the present embodiment has a print-receptive layer and a liquid-absorbing layer, both of the liquid-absorbing layer and the print-receiving layer are porous layers containing a thermoplastic resin, and the print-receiving layer includes: Contains a hydrophilic surface-treated filler and a hydrophobic surface-treated filler, the liquid absorption rate on the surface of the print receiving layer side is 3.5 to 10 cc/m 2 · 0.5 s, and the liquid absorption amount is 10 cc/m 2・It is 180 seconds or more.
図１は、本実施形態に係る記録用紙の一例を示す断面図である。図１において、記録用紙１は、印刷受容層１２および吸液層１１を有する。吸液層１１は、好ましくは印刷受容層１２に接して設けられる。そして、後述するが、本実施形態に係る記録用紙は、吸液層１１からみて印刷受容層１２と反対側に支持体層１０を備えることが好ましい。換言すれば、図１は、支持体層１０上に吸液層１１及び印刷受容層１２がこの順で積層された構成の記録用紙１を例示する図である。
FIG. 1 is a cross-sectional view showing an example of recording paper according to this embodiment. In FIG. 1, a recording paper 1 has a print-receiving layer 12 and a liquid-absorbing layer 11. The liquid-absorbing layer 11 is preferably provided in contact with the print-receiving layer 12 . As will be described later, the recording paper according to this embodiment preferably includes a support layer 10 on the side opposite to the print-receiving layer 12 when viewed from the liquid-absorbing layer 11. In other words, FIG. 1 is a diagram illustrating a recording paper 1 having a structure in which a liquid absorbing layer 11 and a print receiving layer 12 are laminated in this order on a support layer 10.
本実施形態に係る記録用紙は、印刷受容層側の表面における吸液速度が３．５～１０ｃｃ／ｍ２・０．５ｓである。吸液速度は３．５ｃｃ／ｍ２・０．５ｓ以上であり、４ｃｃ／ｍ２・０．５ｓ以上が好ましく、５ｃｃ／ｍ２・０．５ｓ以上がより好ましい。吸液速度が上記値以上であることで、印刷時のインク乾燥性を向上でき、さらには、印刷の滲みを抑制できる。一方で、吸液速度は１０ｃｃ／ｍ２・０．５ｓ以下であり、８．５ｃｃ／ｍ２・０．５ｓ以下が好ましい。吸液速度が上記値以下であることで、インクの色沈みや、印刷受容層表面の開口部からの泡噴きによる粒状模様の発生を抑制でき、印刷品質を向上できる。
印刷受容層側の表面における吸液速度とは、Ｊａｐａｎ Ｔａｐｐｉ Ｎｏ．５１：２０００に記載のブリストー法による液体吸収性試験方法に準拠し測定される液体の転移量であり、測定溶液滴下後５００ミリ秒の単位面積当たりの吸収量を意味する。 The recording paper according to this embodiment has a liquid absorption speed of 3.5 to 10 cc/m 2 ·0.5 s on the surface on the print receiving layer side. The liquid absorption speed is 3.5 cc/m 2 ·0.5 s or more, preferably 4 cc/m 2 ·0.5 s or more, and more preferably 5 cc/m 2 ·0.5 s or more. When the liquid absorption rate is equal to or higher than the above value, ink drying properties during printing can be improved, and furthermore, bleeding in printing can be suppressed. On the other hand, the liquid absorption speed is 10 cc/m 2 ·0.5 s or less, preferably 8.5 cc/m 2 ·0.5 s or less. When the liquid absorption rate is equal to or lower than the above value, it is possible to suppress the color fading of the ink and the generation of granular patterns due to bubbles sprayed from the openings on the surface of the print-receiving layer, thereby improving the print quality.
The liquid absorption rate on the surface of the print receiving layer side is determined by Japan Tappi No. It is the amount of liquid transfer measured in accordance with the liquid absorption test method using the Bristow method described in 51:2000, and means the amount of absorption per unit area 500 milliseconds after dropping the measurement solution.
印刷受容層側の表面における吸液速度とは、Ｊａｐａｎ Ｔａｐｐｉ Ｎｏ．５１：２０００に記載のブリストー法による液体吸収性試験方法に準拠し測定される液体の転移量であり、測定溶液滴下後５００ミリ秒の単位面積当たりの吸収量を意味する。 The recording paper according to this embodiment has a liquid absorption speed of 3.5 to 10 cc/m 2 ·0.5 s on the surface on the print receiving layer side. The liquid absorption speed is 3.5 cc/m 2 ·0.5 s or more, preferably 4 cc/m 2 ·0.5 s or more, and more preferably 5 cc/m 2 ·0.5 s or more. When the liquid absorption rate is equal to or higher than the above value, ink drying properties during printing can be improved, and furthermore, bleeding in printing can be suppressed. On the other hand, the liquid absorption speed is 10 cc/m 2 ·0.5 s or less, preferably 8.5 cc/m 2 ·0.5 s or less. When the liquid absorption rate is equal to or lower than the above value, it is possible to suppress the color fading of the ink and the generation of granular patterns due to bubbles sprayed from the openings on the surface of the print-receiving layer, thereby improving the print quality.
The liquid absorption rate on the surface of the print receiving layer side is determined by Japan Tappi No. It is the amount of liquid transfer measured in accordance with the liquid absorption test method using the Bristow method described in 51:2000, and means the amount of absorption per unit area 500 milliseconds after dropping the measurement solution.
本実施形態に係る記録用紙の、印刷受容層側の表面からの吸液量は１０ｃｃ／ｍ２・１８０ｓ以上であり、２０ｃｃ／ｍ２・１８０ｓ以上が好ましく、３０ｃｃ／ｍ２・１８０ｓ以上がより好ましい。吸液量が上記値以上であることで、乾燥性を向上できる。一方で、生産性を向上する観点及びドライダウンを抑制する観点から、吸液量は５０ｃｃ／ｍ２・１８０ｓ以下が好ましく、４０ｃｃ／ｍ２・１８０ｓ以下がより好ましい。印刷受容層側の表面からの吸液量は１０ｃｃ／ｍ２・１８０ｓ～５０ｃｃ／ｍ２・１８０ｓであってもよい。
記録用紙の吸液量は、印刷受容層側の表面からの吸液量について測定される値をいい、ＪＩＳ Ｐ８１４０：１９９８の規定に基づき測定される、Ｃｏｂｂ吸水度の値である。但し、試験溶媒には水ではなく７０質量％エタノール水溶液を用い、接触時間は１８０秒とする。 The amount of liquid absorbed from the surface of the print-receiving layer of the recording paper according to this embodiment is 10 cc/m 2 ·180 s or more, preferably 20 cc/m 2 ·180 s or more, and more preferably 30 cc/m 2 ·180 s or more. preferable. When the amount of liquid absorbed is equal to or greater than the above value, drying performance can be improved. On the other hand, from the viewpoint of improving productivity and suppressing dry-down, the liquid absorption amount is preferably 50 cc/m 2 ·180 s or less, and more preferably 40 cc/m 2 ·180 s or less. The amount of liquid absorbed from the surface of the print receiving layer side may be 10 cc/m 2 ·180 s to 50 cc/m 2 ·180 s.
The liquid absorption amount of the recording paper refers to the value measured for the amount of liquid absorbed from the surface of the print-receiving layer side, and is the Cobb water absorption value measured based on the provisions of JIS P8140:1998. However, instead of water, a 70% by mass ethanol aqueous solution is used as the test solvent, and the contact time is 180 seconds.
記録用紙の吸液量は、印刷受容層側の表面からの吸液量について測定される値をいい、ＪＩＳ Ｐ８１４０：１９９８の規定に基づき測定される、Ｃｏｂｂ吸水度の値である。但し、試験溶媒には水ではなく７０質量％エタノール水溶液を用い、接触時間は１８０秒とする。 The amount of liquid absorbed from the surface of the print-receiving layer of the recording paper according to this embodiment is 10 cc/m 2 ·180 s or more, preferably 20 cc/m 2 ·180 s or more, and more preferably 30 cc/m 2 ·180 s or more. preferable. When the amount of liquid absorbed is equal to or greater than the above value, drying performance can be improved. On the other hand, from the viewpoint of improving productivity and suppressing dry-down, the liquid absorption amount is preferably 50 cc/m 2 ·180 s or less, and more preferably 40 cc/m 2 ·180 s or less. The amount of liquid absorbed from the surface of the print receiving layer side may be 10 cc/m 2 ·180 s to 50 cc/m 2 ·180 s.
The liquid absorption amount of the recording paper refers to the value measured for the amount of liquid absorbed from the surface of the print-receiving layer side, and is the Cobb water absorption value measured based on the provisions of JIS P8140:1998. However, instead of water, a 70% by mass ethanol aqueous solution is used as the test solvent, and the contact time is 180 seconds.
本実施形態に係る記録用紙において、印刷受容層側の表面における吸液速度が３．５～１０ｃｃ／ｍ２・０．５ｓであり、かつ、吸液量が１０ｃｃ／ｍ２・１８０ｓ以上である。すなわち本実施形態において、吸液速度と吸液量がともに上述の範囲にあるのが好ましい。上述の通り、本発明者は、液体吸収容積が比較的大きくても、吸液速度が比較的遅い場合は、十分な乾燥性が得られない場合があることを見出した。加えて、印刷時のインク乾燥性を向上する観点からは、印刷受容層表面の吸液速度は高いほうが好ましいが、吸液速度が速すぎると、インクの色沈みや、印刷受容層表面の開口部からの泡噴きによる粒状模様が生じる場合があることも見出された。これに対し、本発明は、記録用紙における印刷受容層側の表面の吸液速度が特定の範囲にあり、且つ吸液量が特定値以上であることにより、印刷品質及び乾燥性が良好な記録用紙が得られることを見出したものである。
印刷受容層は親水化表面処理フィラー及び疎水化表面処理フィラーを含有する。親水化表面処理フィラーと疎水化表面処理フィラーを共に含有することで、吸液速度を適切な範囲、すなわち３．５～１０ｃｃ／ｍ２・０．５ｓに調整しやすくなる。 In the recording paper according to this embodiment, the liquid absorption speed on the surface on the print receiving layer side is 3.5 to 10 cc/m 2 · 0.5 s, and the liquid absorption amount is 10 cc/m 2 · 180 s or more. . That is, in this embodiment, it is preferable that both the liquid absorption rate and the liquid absorption amount are within the above ranges. As mentioned above, the inventors have found that even if the liquid absorption capacity is relatively large, if the liquid absorption rate is relatively slow, sufficient drying properties may not be obtained. In addition, from the perspective of improving ink drying properties during printing, it is preferable that the liquid absorption rate on the surface of the print receiving layer is high, but if the liquid absorption rate is too fast, the ink color may fade or the openings on the surface of the print receiving layer may occur. It has also been found that granular patterns may occur due to bubbles being ejected from the surface. In contrast, in the present invention, the liquid absorption rate of the surface of the print-receiving layer side of the recording paper is within a specific range, and the amount of liquid absorption is above a specific value, so that recording with good print quality and drying properties can be achieved. It was discovered that paper can be obtained.
The print-receiving layer contains a hydrophilic surface-treated filler and a hydrophobic surface-treated filler. By containing both the hydrophilic surface-treated filler and the hydrophobic surface-treated filler, the liquid absorption rate can be easily adjusted to an appropriate range, ie, 3.5 to 10 cc/m 2 ·0.5 s.
印刷受容層は親水化表面処理フィラー及び疎水化表面処理フィラーを含有する。親水化表面処理フィラーと疎水化表面処理フィラーを共に含有することで、吸液速度を適切な範囲、すなわち３．５～１０ｃｃ／ｍ２・０．５ｓに調整しやすくなる。 In the recording paper according to this embodiment, the liquid absorption speed on the surface on the print receiving layer side is 3.5 to 10 cc/m 2 · 0.5 s, and the liquid absorption amount is 10 cc/m 2 · 180 s or more. . That is, in this embodiment, it is preferable that both the liquid absorption rate and the liquid absorption amount are within the above ranges. As mentioned above, the inventors have found that even if the liquid absorption capacity is relatively large, if the liquid absorption rate is relatively slow, sufficient drying properties may not be obtained. In addition, from the perspective of improving ink drying properties during printing, it is preferable that the liquid absorption rate on the surface of the print receiving layer is high, but if the liquid absorption rate is too fast, the ink color may fade or the openings on the surface of the print receiving layer may occur. It has also been found that granular patterns may occur due to bubbles being ejected from the surface. In contrast, in the present invention, the liquid absorption rate of the surface of the print-receiving layer side of the recording paper is within a specific range, and the amount of liquid absorption is above a specific value, so that recording with good print quality and drying properties can be achieved. It was discovered that paper can be obtained.
The print-receiving layer contains a hydrophilic surface-treated filler and a hydrophobic surface-treated filler. By containing both the hydrophilic surface-treated filler and the hydrophobic surface-treated filler, the liquid absorption rate can be easily adjusted to an appropriate range, ie, 3.5 to 10 cc/m 2 ·0.5 s.
印刷受容層側の表面における表面強度は１．１ｋｇ－ｃｍ以上が好ましく、１．２ｋｇ－ｃｍ以上がより好ましく、１．３ｋｇ－ｃｍ以上がさらに好ましい。表面強度が上記値以上であることにより、印刷の耐擦過性を向上できる。また、記録用紙のレイフラット製本適性を向上できる。表面強度の上限値は特に限定されないが、層の表面強度を高くすると表面開口率が低下する傾向にあるため、乾燥性を向上する観点から、２．０ｋｇ－ｃｍ以下が好ましく、１．５ｋｇ－ｃｍ以下がより好ましい。印刷受容層側の表面における表面強度は１．１ｋｇ－ｃｍ～２．０ｋｇ－ｃｍであってもよい。
印刷受容層側の表面における表面強度は、インターナルボンドテスターにより測定できる。 The surface strength on the print-receiving layer side surface is preferably 1.1 kg-cm or more, more preferably 1.2 kg-cm or more, and even more preferably 1.3 kg-cm or more. When the surface strength is at least the above value, the scratch resistance of printing can be improved. Furthermore, the suitability of the recording paper for lay flat binding can be improved. The upper limit of the surface strength is not particularly limited, but since increasing the surface strength of the layer tends to reduce the surface aperture ratio, from the viewpoint of improving drying properties, it is preferably 2.0 kg-cm or less, and 1.5 kg-cm or less. cm or less is more preferable. The surface strength on the print-receiving layer side surface may be from 1.1 kg-cm to 2.0 kg-cm.
The surface strength on the print-receiving layer side surface can be measured using an internal bond tester.
印刷受容層側の表面における表面強度は、インターナルボンドテスターにより測定できる。 The surface strength on the print-receiving layer side surface is preferably 1.1 kg-cm or more, more preferably 1.2 kg-cm or more, and even more preferably 1.3 kg-cm or more. When the surface strength is at least the above value, the scratch resistance of printing can be improved. Furthermore, the suitability of the recording paper for lay flat binding can be improved. The upper limit of the surface strength is not particularly limited, but since increasing the surface strength of the layer tends to reduce the surface aperture ratio, from the viewpoint of improving drying properties, it is preferably 2.0 kg-cm or less, and 1.5 kg-cm or less. cm or less is more preferable. The surface strength on the print-receiving layer side surface may be from 1.1 kg-cm to 2.0 kg-cm.
The surface strength on the print-receiving layer side surface can be measured using an internal bond tester.
さらに吸液層もフィラーを含有する層であることが好ましい。印刷受容層及び吸液層はいずれも、フィラーを含有する延伸層であるとより好ましい。例えば印刷受容層と吸液層を共押出後に共延伸する方法や、吸液層上に印刷受容層を押出ラミネートしたのち共延伸する方法によって、印刷受容層および吸液層をいずれも延伸層とすることで、製造プロセスをシンプルにでき、製造コストを抑制できるため好ましい。
Further, it is preferable that the liquid absorbent layer also contains a filler. More preferably, both the print-receiving layer and the liquid-absorbing layer are stretched layers containing filler. For example, by co-stretching the print-receiving layer and the liquid-absorbing layer and then co-stretching them, or by extruding and laminating the print-receiving layer on the liquid-absorbing layer and then co-stretching them, both the print-receptive layer and the liquid-absorbent layer can be made into stretched layers. This is preferable because the manufacturing process can be simplified and manufacturing costs can be suppressed.
また、一般の印刷用塗工紙の場合、紙などの基材表面に顔料とバインダーとを含有する塗工層が設けられる。そして、適切なインク受理性を付与するために、顔料として炭酸カルシウム又はカオリンなどを用いることが一般的であるが、このような塗工層は顔料を多量に含むため脆く、折り曲げると割れやすい。そのため、かかる塗工層を備える印刷用塗工紙はレイフラット製本に使用することが困難となりやすい。これに対し、印刷受容層がフィラー含有樹脂組成物の延伸によって多孔化された層である場合、前述の塗工層よりも少ないフィラー量で十分に多孔化させやすく、所望の吸液速度および吸液量を満たしやすい。そして、このように得られる多孔質層は曲げに強いものとなる。
特に、印刷受容層がフィラーを含有する延伸層であり、さらに、印刷受容層側の表面における表面強度が１．１ｋｇ－ｃｍ以上である場合、十分実用に足るレイフラット製本性を得られる傾向がある。印刷受容層が延伸により成形される場合、以下に述べる材料を使用することにより、前述の各種物性を達成しやすいため好ましい。また、吸液層の好ましい態様についても後述する。 Further, in the case of general coated paper for printing, a coating layer containing a pigment and a binder is provided on the surface of a base material such as paper. In order to impart appropriate ink receptivity, calcium carbonate or kaolin is generally used as a pigment, but such coating layers contain a large amount of pigment and are therefore brittle and easily break when bent. Therefore, coated printing paper provided with such a coating layer tends to be difficult to use for layflat bookbinding. On the other hand, when the print-receiving layer is a layer made porous by stretching a filler-containing resin composition, it is easy to make it sufficiently porous with a smaller amount of filler than in the above-mentioned coating layer, and the desired liquid absorption rate and absorption rate can be achieved. Easy to fill liquid volume. The porous layer thus obtained is resistant to bending.
In particular, when the print-receiving layer is a stretched layer containing a filler, and the surface strength on the print-receiving layer side is 1.1 kg-cm or more, there is a tendency for lay-flat bookbinding properties sufficient for practical use to be obtained. be. When the print-receiving layer is formed by stretching, it is preferable to use the materials described below because the various physical properties described above can be easily achieved. Further, preferred embodiments of the liquid absorbing layer will also be described later.
特に、印刷受容層がフィラーを含有する延伸層であり、さらに、印刷受容層側の表面における表面強度が１．１ｋｇ－ｃｍ以上である場合、十分実用に足るレイフラット製本性を得られる傾向がある。印刷受容層が延伸により成形される場合、以下に述べる材料を使用することにより、前述の各種物性を達成しやすいため好ましい。また、吸液層の好ましい態様についても後述する。 Further, in the case of general coated paper for printing, a coating layer containing a pigment and a binder is provided on the surface of a base material such as paper. In order to impart appropriate ink receptivity, calcium carbonate or kaolin is generally used as a pigment, but such coating layers contain a large amount of pigment and are therefore brittle and easily break when bent. Therefore, coated printing paper provided with such a coating layer tends to be difficult to use for layflat bookbinding. On the other hand, when the print-receiving layer is a layer made porous by stretching a filler-containing resin composition, it is easy to make it sufficiently porous with a smaller amount of filler than in the above-mentioned coating layer, and the desired liquid absorption rate and absorption rate can be achieved. Easy to fill liquid volume. The porous layer thus obtained is resistant to bending.
In particular, when the print-receiving layer is a stretched layer containing a filler, and the surface strength on the print-receiving layer side is 1.1 kg-cm or more, there is a tendency for lay-flat bookbinding properties sufficient for practical use to be obtained. be. When the print-receiving layer is formed by stretching, it is preferable to use the materials described below because the various physical properties described above can be easily achieved. Further, preferred embodiments of the liquid absorbing layer will also be described later.
（印刷受容層）
印刷受容層は、熱可塑性樹脂並びに親水化表面処理フィラー及び疎水化表面処理フィラーを含有する多孔質層である。印刷受容層は、上述の通り延伸層であることが好ましい。すなわち印刷受容層は、熱可塑性樹脂並びに親水化表面処理フィラー及び疎水化表面処理フィラーを含有する延伸層であることが好ましい。本実施形態に係る記録用紙の印刷受容層側の表面に印刷が施される場合、典型的には、顔料や染料といった色材は印刷受容層の表層に留まり発色することとなる。一方で、インク溶媒は印刷受容層を通過し、下層（吸液層）へ移動することとなる。 (Print receiving layer)
The print-receiving layer is a porous layer containing a thermoplastic resin, a hydrophilic surface-treated filler, and a hydrophobic surface-treated filler. The print-receiving layer is preferably a stretched layer as described above. That is, the print-receiving layer is preferably a stretched layer containing a thermoplastic resin, a hydrophilic surface-treated filler, and a hydrophobic surface-treated filler. When printing is performed on the print-receiving layer side surface of the recording paper according to this embodiment, typically, coloring materials such as pigments and dyes remain on the surface layer of the print-receiving layer and develop color. On the other hand, the ink solvent passes through the print receiving layer and moves to the lower layer (liquid absorption layer).
印刷受容層は、熱可塑性樹脂並びに親水化表面処理フィラー及び疎水化表面処理フィラーを含有する多孔質層である。印刷受容層は、上述の通り延伸層であることが好ましい。すなわち印刷受容層は、熱可塑性樹脂並びに親水化表面処理フィラー及び疎水化表面処理フィラーを含有する延伸層であることが好ましい。本実施形態に係る記録用紙の印刷受容層側の表面に印刷が施される場合、典型的には、顔料や染料といった色材は印刷受容層の表層に留まり発色することとなる。一方で、インク溶媒は印刷受容層を通過し、下層（吸液層）へ移動することとなる。 (Print receiving layer)
The print-receiving layer is a porous layer containing a thermoplastic resin, a hydrophilic surface-treated filler, and a hydrophobic surface-treated filler. The print-receiving layer is preferably a stretched layer as described above. That is, the print-receiving layer is preferably a stretched layer containing a thermoplastic resin, a hydrophilic surface-treated filler, and a hydrophobic surface-treated filler. When printing is performed on the print-receiving layer side surface of the recording paper according to this embodiment, typically, coloring materials such as pigments and dyes remain on the surface layer of the print-receiving layer and develop color. On the other hand, the ink solvent passes through the print receiving layer and moves to the lower layer (liquid absorption layer).
＜熱可塑性樹脂＞
印刷受容層に使用される熱可塑性樹脂としては、例えばオレフィン系重合体、ポリアミド、ポリエステル、ポリカーボネート、ポリスチレン、ポリ（メタ）アクリレート、ポリ塩化ビニル、及びこれらの混合樹脂等が挙げられる。なかでも、耐水性及び耐溶剤性の観点からは、オレフィン系重合体が好ましい。 <Thermoplastic resin>
Examples of the thermoplastic resin used in the print-receiving layer include olefin polymers, polyamides, polyesters, polycarbonates, polystyrenes, poly(meth)acrylates, polyvinyl chloride, and mixed resins thereof. Among these, olefin polymers are preferred from the viewpoint of water resistance and solvent resistance.
印刷受容層に使用される熱可塑性樹脂としては、例えばオレフィン系重合体、ポリアミド、ポリエステル、ポリカーボネート、ポリスチレン、ポリ（メタ）アクリレート、ポリ塩化ビニル、及びこれらの混合樹脂等が挙げられる。なかでも、耐水性及び耐溶剤性の観点からは、オレフィン系重合体が好ましい。 <Thermoplastic resin>
Examples of the thermoplastic resin used in the print-receiving layer include olefin polymers, polyamides, polyesters, polycarbonates, polystyrenes, poly(meth)acrylates, polyvinyl chloride, and mixed resins thereof. Among these, olefin polymers are preferred from the viewpoint of water resistance and solvent resistance.
オレフィン系重合体としては、プロピレン系重合体、エチレン系重合体等を好ましく使用できる。
プロピレン系重合体としては、例えばプロピレンを単独重合させたアイソタクティックホモポリプロピレン、シンジオタクティックホモポリプロピレン等のプロピレン単独重合体、プロピレンを主体とし、エチレン、１－ブテン、１－ヘキセン、１－ヘプテン、１－オクテン、４－メチル－１－ペンテン等のα－オレフィン等を共重合させたプロピレン共重合体等が挙げられる。プロピレン共重合体は、２元系でもよいし、３元系以上の多元系でもよい。また、プロピレン共重合体は、ランダム共重合体でもブロック共重合体でもよい。 As the olefin polymer, propylene polymer, ethylene polymer, etc. can be preferably used.
Examples of propylene-based polymers include propylene homopolymers such as isotactic homopolypropylene and syndiotactic homopolypropylene, which are made by homopolymerizing propylene, and propylene-based polymers mainly composed of propylene such as ethylene, 1-butene, 1-hexene, and 1-heptene. Examples include propylene copolymers copolymerized with α-olefins such as , 1-octene, and 4-methyl-1-pentene. The propylene copolymer may be a binary system or a multi-component system having ternary or more components. Further, the propylene copolymer may be a random copolymer or a block copolymer.
プロピレン系重合体としては、例えばプロピレンを単独重合させたアイソタクティックホモポリプロピレン、シンジオタクティックホモポリプロピレン等のプロピレン単独重合体、プロピレンを主体とし、エチレン、１－ブテン、１－ヘキセン、１－ヘプテン、１－オクテン、４－メチル－１－ペンテン等のα－オレフィン等を共重合させたプロピレン共重合体等が挙げられる。プロピレン共重合体は、２元系でもよいし、３元系以上の多元系でもよい。また、プロピレン共重合体は、ランダム共重合体でもブロック共重合体でもよい。 As the olefin polymer, propylene polymer, ethylene polymer, etc. can be preferably used.
Examples of propylene-based polymers include propylene homopolymers such as isotactic homopolypropylene and syndiotactic homopolypropylene, which are made by homopolymerizing propylene, and propylene-based polymers mainly composed of propylene such as ethylene, 1-butene, 1-hexene, and 1-heptene. Examples include propylene copolymers copolymerized with α-olefins such as , 1-octene, and 4-methyl-1-pentene. The propylene copolymer may be a binary system or a multi-component system having ternary or more components. Further, the propylene copolymer may be a random copolymer or a block copolymer.
エチレン系重合体としては、例えば高密度ポリエチレン、中密度ポリエチレン、直鎖線状低密度ポリエチレン、エチレンを主体とし、プロピレン、ブテン、ヘキセン、ヘプテン、オクテン、４－メチルペンテン－１等のα－オレフィンを共重合させた共重合体、マレイン酸変性エチレン・酢酸ビニル共重合体、エチレン・酢酸ビニル共重合体、エチレン・
（メタ）アクリル酸アルキルエステル共重合体、エチレン・（メタ）アクリル酸共重合体及びその金属塩（金属は亜鉛、アルミニウム、リチウム、ナトリウム、カリウム等）、エチレン－環状オレフィン共重合体、（無水）マレイン酸変性ポリエチレン、（無水）マレイン酸変性ポリプロピレン等が挙げられる。ここで「（無水）マレイン酸」の記載は、無水マレイン酸とマレイン酸の両方を示す。 Ethylene-based polymers include, for example, high-density polyethylene, medium-density polyethylene, linear low-density polyethylene, ethylene as a main ingredient, and α-olefins such as propylene, butene, hexene, heptene, octene, and 4-methylpentene-1. Copolymerized copolymer, maleic acid-modified ethylene/vinyl acetate copolymer, ethylene/vinyl acetate copolymer, ethylene/vinyl acetate copolymer,
(meth)acrylic acid alkyl ester copolymer, ethylene/(meth)acrylic acid copolymer and its metal salt (metals include zinc, aluminum, lithium, sodium, potassium, etc.), ethylene-cyclic olefin copolymer, (anhydrous ) Maleic acid-modified polyethylene, (anhydrous) maleic acid-modified polypropylene, and the like. Here, the description of "(maleic anhydride)" refers to both maleic anhydride and maleic acid.
（メタ）アクリル酸アルキルエステル共重合体、エチレン・（メタ）アクリル酸共重合体及びその金属塩（金属は亜鉛、アルミニウム、リチウム、ナトリウム、カリウム等）、エチレン－環状オレフィン共重合体、（無水）マレイン酸変性ポリエチレン、（無水）マレイン酸変性ポリプロピレン等が挙げられる。ここで「（無水）マレイン酸」の記載は、無水マレイン酸とマレイン酸の両方を示す。 Ethylene-based polymers include, for example, high-density polyethylene, medium-density polyethylene, linear low-density polyethylene, ethylene as a main ingredient, and α-olefins such as propylene, butene, hexene, heptene, octene, and 4-methylpentene-1. Copolymerized copolymer, maleic acid-modified ethylene/vinyl acetate copolymer, ethylene/vinyl acetate copolymer, ethylene/vinyl acetate copolymer,
(meth)acrylic acid alkyl ester copolymer, ethylene/(meth)acrylic acid copolymer and its metal salt (metals include zinc, aluminum, lithium, sodium, potassium, etc.), ethylene-cyclic olefin copolymer, (anhydrous ) Maleic acid-modified polyethylene, (anhydrous) maleic acid-modified polypropylene, and the like. Here, the description of "(maleic anhydride)" refers to both maleic anhydride and maleic acid.
上記オレフィン系重合体のなかでも、成形性を向上する観点及びコストを抑制する観点からは、プロピレン単独重合体すなわちポリプロピレン、又は高密度ポリエチレンが好ましい。また空孔形成性およびフィラー結着性を好適なものとする観点からは、（無水）マレイン酸変性ポリエチレンまたは（無水）マレイン酸変性ポリプロピレンが好ましい。
上記熱可塑性樹脂のうち、１種を単独で又は２種以上を組み合わせて使用することができる。 Among the above-mentioned olefin polymers, propylene homopolymer, ie, polypropylene, or high-density polyethylene is preferable from the viewpoint of improving moldability and suppressing cost. In addition, from the viewpoint of optimizing pore-forming properties and filler binding properties, (anhydrous) maleic acid-modified polyethylene or (anhydrous) maleic acid-modified polypropylene is preferable.
Among the above thermoplastic resins, one kind can be used alone or two or more kinds can be used in combination.
上記熱可塑性樹脂のうち、１種を単独で又は２種以上を組み合わせて使用することができる。 Among the above-mentioned olefin polymers, propylene homopolymer, ie, polypropylene, or high-density polyethylene is preferable from the viewpoint of improving moldability and suppressing cost. In addition, from the viewpoint of optimizing pore-forming properties and filler binding properties, (anhydrous) maleic acid-modified polyethylene or (anhydrous) maleic acid-modified polypropylene is preferable.
Among the above thermoplastic resins, one kind can be used alone or two or more kinds can be used in combination.
＜熱可塑性エラストマー＞
印刷受容層は、表面強度を高める観点から、熱可塑性エラストマー（以下、単に「エラストマー」という場合がある。）を含有することが好ましい。
印刷受容層におけるエラストマーは、ポリスチレン系（ＴＰＳ）、オレフィン系（ＴＰＯ）、ポリ塩化ビニル系（ＴＰＶＣ）、ポリウレタン系（ＴＰＵ）、ポリエステル系（ＴＰＣ）、またはポリアミド系（ＴＰＡＥ）などの熱可塑性エラストマーから適宜選択して使用することができる。エラストマーとしては、印刷受容層の主成分となる樹脂との相溶性が高いものが好ましく、印刷受容層に含まれる熱可塑性樹脂と同系のエラストマーが好ましい。例えば熱可塑性樹脂としてオレフィン系重合体を使用する場合には、オレフィン系エラストマーを使用することが好ましい。
オレフィン系エラストマーは、例えば、ポリプロピレンやポリエチレン等のポリオレフィンをハードセグメントとし、エチレン・プロピレンゴム（ＥＰＭ、ＥＰＤＭ）などのゴム成分をソフトセグメントとして有するものである。オレフィン系エラストマーは、ポリオレフィンとゴム成分のブレンドタイプ、それらの動的架橋タイプ（ＴＰＶ：Ｔｈｅｍｏｐｌａｓｔｉｃ Ｖｕｌｃａｎｉｚａｔｅｓとして区別して呼ぶこともある）、及び重合タイプ（Ｒ－ＴＰＯ：Ｒｅａｃｔｏｒ－ＴＰＯ）の３タイプに大別できる。本実施形態において使用されるエラストマーとしては、これらのいずれであってもよい。 <Thermoplastic elastomer>
The print-receiving layer preferably contains a thermoplastic elastomer (hereinafter sometimes simply referred to as "elastomer") from the viewpoint of increasing surface strength.
The elastomer in the print-receiving layer is a thermoplastic elastomer such as polystyrene (TPS), olefin (TPO), polyvinyl chloride (TPVC), polyurethane (TPU), polyester (TPC), or polyamide (TPAE). It can be selected and used as appropriate. The elastomer is preferably one that has high compatibility with the resin that is the main component of the print-receiving layer, and is preferably an elastomer of the same type as the thermoplastic resin contained in the print-receiving layer. For example, when using an olefin polymer as the thermoplastic resin, it is preferable to use an olefin elastomer.
The olefin elastomer has, for example, a polyolefin such as polypropylene or polyethylene as a hard segment and a rubber component such as ethylene propylene rubber (EPM, EPDM) as a soft segment. Olefin elastomers are broadly divided into three types: a blend type of polyolefin and a rubber component, a dynamic crosslinking type (TPV: sometimes referred to separately as Themoplastic Vulcanizates), and a polymerization type (R-TPO: Reactor-TPO). We can separate. The elastomer used in this embodiment may be any of these.
印刷受容層は、表面強度を高める観点から、熱可塑性エラストマー（以下、単に「エラストマー」という場合がある。）を含有することが好ましい。
印刷受容層におけるエラストマーは、ポリスチレン系（ＴＰＳ）、オレフィン系（ＴＰＯ）、ポリ塩化ビニル系（ＴＰＶＣ）、ポリウレタン系（ＴＰＵ）、ポリエステル系（ＴＰＣ）、またはポリアミド系（ＴＰＡＥ）などの熱可塑性エラストマーから適宜選択して使用することができる。エラストマーとしては、印刷受容層の主成分となる樹脂との相溶性が高いものが好ましく、印刷受容層に含まれる熱可塑性樹脂と同系のエラストマーが好ましい。例えば熱可塑性樹脂としてオレフィン系重合体を使用する場合には、オレフィン系エラストマーを使用することが好ましい。
オレフィン系エラストマーは、例えば、ポリプロピレンやポリエチレン等のポリオレフィンをハードセグメントとし、エチレン・プロピレンゴム（ＥＰＭ、ＥＰＤＭ）などのゴム成分をソフトセグメントとして有するものである。オレフィン系エラストマーは、ポリオレフィンとゴム成分のブレンドタイプ、それらの動的架橋タイプ（ＴＰＶ：Ｔｈｅｍｏｐｌａｓｔｉｃ Ｖｕｌｃａｎｉｚａｔｅｓとして区別して呼ぶこともある）、及び重合タイプ（Ｒ－ＴＰＯ：Ｒｅａｃｔｏｒ－ＴＰＯ）の３タイプに大別できる。本実施形態において使用されるエラストマーとしては、これらのいずれであってもよい。 <Thermoplastic elastomer>
The print-receiving layer preferably contains a thermoplastic elastomer (hereinafter sometimes simply referred to as "elastomer") from the viewpoint of increasing surface strength.
The elastomer in the print-receiving layer is a thermoplastic elastomer such as polystyrene (TPS), olefin (TPO), polyvinyl chloride (TPVC), polyurethane (TPU), polyester (TPC), or polyamide (TPAE). It can be selected and used as appropriate. The elastomer is preferably one that has high compatibility with the resin that is the main component of the print-receiving layer, and is preferably an elastomer of the same type as the thermoplastic resin contained in the print-receiving layer. For example, when using an olefin polymer as the thermoplastic resin, it is preferable to use an olefin elastomer.
The olefin elastomer has, for example, a polyolefin such as polypropylene or polyethylene as a hard segment and a rubber component such as ethylene propylene rubber (EPM, EPDM) as a soft segment. Olefin elastomers are broadly divided into three types: a blend type of polyolefin and a rubber component, a dynamic crosslinking type (TPV: sometimes referred to separately as Themoplastic Vulcanizates), and a polymerization type (R-TPO: Reactor-TPO). We can separate. The elastomer used in this embodiment may be any of these.
印刷受容層がエラストマーを含むことにより、熱可塑性樹脂、好ましくはオレフィン系重合体を含む印刷受容層の靭性を向上できる。これにより、記録用紙の表面強度を向上できる。
By containing the elastomer in the print-receiving layer, the toughness of the print-receiving layer containing a thermoplastic resin, preferably an olefin polymer, can be improved. Thereby, the surface strength of the recording paper can be improved.
エラストマーの含有量は、印刷受容層に含まれる上記熱可塑性樹脂とエラストマーとの合計量に対して、例えば６～１４質量％が好ましく、より好ましくは８～１２質量％である。エラストマー量が上記下限値以上であることで、改質効果が十分なものとなりやすい。また、エラストマー量が上記上限値以下であることで、空孔が形成され難くなるのを抑制でき、これにより、ドットゲインの低下、印刷受容層表面のインクの投錨性の低下又はインク定着性の低下等を抑制できる。
The content of the elastomer is, for example, preferably 6 to 14% by mass, more preferably 8 to 12% by mass, based on the total amount of the thermoplastic resin and elastomer contained in the print-receiving layer. When the amount of elastomer is at least the above lower limit, the modification effect tends to be sufficient. In addition, when the amount of elastomer is below the above upper limit, it is possible to suppress the formation of pores, which may result in a decrease in dot gain, a decrease in the anchoring ability of the ink on the surface of the print receiving layer, or a decrease in the ink fixing ability. It is possible to suppress the decline, etc.
＜フィラー＞
印刷受容層に使用される親水化表面処理フィラー及び疎水化表面処理フィラーとしては、無機粒子または有機粒子に後述する表面処理を施したものが挙げられる。
無機粒子及び有機粒子は、それぞれ単独で又は組み合わせて使用することができる。フィラー及び熱可塑性樹脂を含む樹脂組成物を延伸した場合、粒子を核とした微細な空孔を延伸層内部に多数形成することができる。これにより、多孔質層を得ることができる。 <Filler>
Examples of the hydrophilic surface-treated filler and hydrophobic surface-treated filler used in the print-receiving layer include inorganic particles or organic particles subjected to the surface treatment described below.
Inorganic particles and organic particles can be used alone or in combination. When a resin composition containing a filler and a thermoplastic resin is stretched, a large number of fine pores with particles as cores can be formed inside the stretched layer. Thereby, a porous layer can be obtained.
印刷受容層に使用される親水化表面処理フィラー及び疎水化表面処理フィラーとしては、無機粒子または有機粒子に後述する表面処理を施したものが挙げられる。
無機粒子及び有機粒子は、それぞれ単独で又は組み合わせて使用することができる。フィラー及び熱可塑性樹脂を含む樹脂組成物を延伸した場合、粒子を核とした微細な空孔を延伸層内部に多数形成することができる。これにより、多孔質層を得ることができる。 <Filler>
Examples of the hydrophilic surface-treated filler and hydrophobic surface-treated filler used in the print-receiving layer include inorganic particles or organic particles subjected to the surface treatment described below.
Inorganic particles and organic particles can be used alone or in combination. When a resin composition containing a filler and a thermoplastic resin is stretched, a large number of fine pores with particles as cores can be formed inside the stretched layer. Thereby, a porous layer can be obtained.
印刷受容層におけるフィラーの含有量は、空孔形成性を好適なものとする観点から、４５質量％以上であることが好ましく、５０質量％以上であることがより好ましい。印刷受容層におけるフィラーの含有量が４５質量％以上であることにより、空孔率を高めてインクの吸液層への浸透を助け、吸液量を高めることができる。一方で、印刷受容層におけるフィラーの含有量は、表面欠陥の発生を抑制し、空孔率及び吸液速度が過大となることを抑制する観点から６５質量％以下が好ましく、６０質量％以下がより好ましい。印刷受容層におけるフィラーの含有量は、４５質量％～６５質量％であってもよい。
The content of the filler in the print-receiving layer is preferably 45% by mass or more, more preferably 50% by mass or more, from the viewpoint of optimizing the pore-forming property. When the filler content in the print-receiving layer is 45% by mass or more, it is possible to increase the porosity, help ink to penetrate into the liquid-absorbing layer, and increase the liquid-absorbing amount. On the other hand, the filler content in the print-receiving layer is preferably 65% by mass or less, from the viewpoint of suppressing the occurrence of surface defects and suppressing excessive porosity and liquid absorption rate, and 60% by mass or less. More preferred. The filler content in the print-receiving layer may be 45% to 65% by weight.
印刷受容層に含有されるフィラーの平均粒子径は、好適な空孔形成性を得る観点から、０．１μｍ以上が好ましく、０．３μｍ以上がより好ましい。また同様の観点から、フィラーの平均粒子径は５μｍ以下が好ましく、３μｍ以下がより好ましい。フィラーの平均粒子径が０．１μｍ以上であれば層中に十分な数および大きさの細孔が形成されるため、多孔質層を多孔として水性顔料インクの浸透性を高めやすい。フィラーの平均粒子径が５μｍ以下であれば粗大な空孔の形成を抑えてインクジェット印刷画像の鮮明性を高めやすい。印刷受容層に含有されるフィラーの平均粒子径は、０．１μｍ～５μｍであってもよい。ここで、フィラーの平均粒子径とは、平均一次粒径（Ｄ５０）のことをいう。これは、レーザー光回折・散乱法によって測定される体積基準のメジアン径である。
The average particle diameter of the filler contained in the print-receiving layer is preferably 0.1 μm or more, more preferably 0.3 μm or more, from the viewpoint of obtaining suitable pore-forming properties. From the same viewpoint, the average particle diameter of the filler is preferably 5 μm or less, more preferably 3 μm or less. When the average particle diameter of the filler is 0.1 μm or more, a sufficient number and size of pores are formed in the layer, so that the porous layer can be made porous to easily improve the permeability of the aqueous pigment ink. If the average particle diameter of the filler is 5 μm or less, the formation of coarse pores can be suppressed and the clarity of inkjet printed images can be easily improved. The filler contained in the print receiving layer may have an average particle diameter of 0.1 μm to 5 μm. Here, the average particle diameter of the filler refers to the average primary particle diameter (D50). This is the volume-based median diameter measured by laser light diffraction/scattering method.
＜＜無機粒子＞＞
無機粒子としては、特に限定されないが、例えば重質炭酸カルシウム、軽質炭酸カルシウム、焼成クレイ、タルク、酸化チタン、硫酸バリウム、アルミナ、シリカ、酸化亜鉛、ゼオライト、マイカ、ガラスファイバー、中空ガラスビーズ等が挙げられる。なかでも、重質炭酸カルシウム、焼成クレイ、珪藻土等は、安価で、多孔質層を形成する樹脂組成物の延伸によって多くの空孔を形成しやすく、空孔率の調整が容易であることから、好ましい。特に、重質炭酸カルシウム又は軽質炭酸カルシウムは、その平均粒子径又は粒度分布を空孔形成しやすい範囲に調整しやすいことから、好ましい。上記無機粒子のうち、１種を単独で又は２種以上を組み合わせて使用することができる。 <<Inorganic particles>>
Examples of inorganic particles include, but are not limited to, heavy calcium carbonate, light calcium carbonate, calcined clay, talc, titanium oxide, barium sulfate, alumina, silica, zinc oxide, zeolite, mica, glass fiber, hollow glass beads, and the like. Can be mentioned. Among them, heavy calcium carbonate, calcined clay, diatomaceous earth, etc. are cheap, and they are easy to form many pores by stretching the resin composition that forms the porous layer, and the porosity can be easily adjusted. ,preferable. In particular, heavy calcium carbonate or light calcium carbonate is preferable because its average particle size or particle size distribution can be easily adjusted to a range in which pore formation is easy. Among the above inorganic particles, one kind can be used alone or two or more kinds can be used in combination.
無機粒子としては、特に限定されないが、例えば重質炭酸カルシウム、軽質炭酸カルシウム、焼成クレイ、タルク、酸化チタン、硫酸バリウム、アルミナ、シリカ、酸化亜鉛、ゼオライト、マイカ、ガラスファイバー、中空ガラスビーズ等が挙げられる。なかでも、重質炭酸カルシウム、焼成クレイ、珪藻土等は、安価で、多孔質層を形成する樹脂組成物の延伸によって多くの空孔を形成しやすく、空孔率の調整が容易であることから、好ましい。特に、重質炭酸カルシウム又は軽質炭酸カルシウムは、その平均粒子径又は粒度分布を空孔形成しやすい範囲に調整しやすいことから、好ましい。上記無機粒子のうち、１種を単独で又は２種以上を組み合わせて使用することができる。 <<Inorganic particles>>
Examples of inorganic particles include, but are not limited to, heavy calcium carbonate, light calcium carbonate, calcined clay, talc, titanium oxide, barium sulfate, alumina, silica, zinc oxide, zeolite, mica, glass fiber, hollow glass beads, and the like. Can be mentioned. Among them, heavy calcium carbonate, calcined clay, diatomaceous earth, etc. are cheap, and they are easy to form many pores by stretching the resin composition that forms the porous layer, and the porosity can be easily adjusted. ,preferable. In particular, heavy calcium carbonate or light calcium carbonate is preferable because its average particle size or particle size distribution can be easily adjusted to a range in which pore formation is easy. Among the above inorganic particles, one kind can be used alone or two or more kinds can be used in combination.
＜＜有機粒子＞＞
有機粒子としては、特に限定されないが、前記熱可塑性樹脂とは非相溶であり、融点又はガラス転移温度が熱可塑性樹脂よりも高く、熱可塑性樹脂の溶融混練条件下で微分散する有機粒子が好ましい。例えば、印刷受容層に含まれる熱可塑性樹脂としてオレフィン系樹脂を使用する場合には、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリカーボネート、ナイロン－６、ナイロン－６，６、環状オレフィンの単独重合体や環状オレフィンとエチレンとの共重合体等であり、融点が１２０～３００℃、ないしはガラス転移温度が１２０～２８０℃である樹脂から選択して使用することが好ましい。 <<Organic particles>>
Examples of organic particles include, but are not particularly limited to, organic particles that are incompatible with the thermoplastic resin, have a melting point or glass transition temperature higher than that of the thermoplastic resin, and are finely dispersed under the melt-kneading conditions of the thermoplastic resin. preferable. For example, when using an olefin resin as the thermoplastic resin contained in the print receiving layer, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, nylon-6, nylon-6,6, a cyclic olefin homopolymer, or a cyclic olefin It is preferable to select and use a resin such as a copolymer of ethylene and a resin having a melting point of 120 to 300°C or a glass transition temperature of 120 to 280°C.
有機粒子としては、特に限定されないが、前記熱可塑性樹脂とは非相溶であり、融点又はガラス転移温度が熱可塑性樹脂よりも高く、熱可塑性樹脂の溶融混練条件下で微分散する有機粒子が好ましい。例えば、印刷受容層に含まれる熱可塑性樹脂としてオレフィン系樹脂を使用する場合には、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリカーボネート、ナイロン－６、ナイロン－６，６、環状オレフィンの単独重合体や環状オレフィンとエチレンとの共重合体等であり、融点が１２０～３００℃、ないしはガラス転移温度が１２０～２８０℃である樹脂から選択して使用することが好ましい。 <<Organic particles>>
Examples of organic particles include, but are not particularly limited to, organic particles that are incompatible with the thermoplastic resin, have a melting point or glass transition temperature higher than that of the thermoplastic resin, and are finely dispersed under the melt-kneading conditions of the thermoplastic resin. preferable. For example, when using an olefin resin as the thermoplastic resin contained in the print receiving layer, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, nylon-6, nylon-6,6, a cyclic olefin homopolymer, or a cyclic olefin It is preferable to select and use a resin such as a copolymer of ethylene and a resin having a melting point of 120 to 300°C or a glass transition temperature of 120 to 280°C.
＜＜親水化表面処理フィラー＞＞
印刷受容層に含まれるフィラーとして、表面が親水化処理された親水化表面処理フィラーを含有することにより、印刷受容層と水性インクとの親和性が良好となり、印刷受容層表面の吸液速度が向上する。親水化表面処理フィラーは、例えば後述する方法にてフィラー表面に表面処理剤を付与することにより得られる。 <<Hydrophilic surface treatment filler>>
By including a hydrophilic surface-treated filler whose surface has been hydrophilized as a filler in the print-receiving layer, the affinity between the print-receptive layer and water-based ink is improved, and the liquid absorption rate on the surface of the print-receptor layer is increased. improves. The hydrophilic surface-treated filler can be obtained, for example, by applying a surface treatment agent to the filler surface by the method described below.
印刷受容層に含まれるフィラーとして、表面が親水化処理された親水化表面処理フィラーを含有することにより、印刷受容層と水性インクとの親和性が良好となり、印刷受容層表面の吸液速度が向上する。親水化表面処理フィラーは、例えば後述する方法にてフィラー表面に表面処理剤を付与することにより得られる。 <<Hydrophilic surface treatment filler>>
By including a hydrophilic surface-treated filler whose surface has been hydrophilized as a filler in the print-receiving layer, the affinity between the print-receptive layer and water-based ink is improved, and the liquid absorption rate on the surface of the print-receptor layer is increased. improves. The hydrophilic surface-treated filler can be obtained, for example, by applying a surface treatment agent to the filler surface by the method described below.
表面処理剤としては、水溶性カチオン性共重合体及び水溶性アニオン系界面活性剤が挙げられる。
水溶性カチオン性共重合体としては、ジアリルアミン塩、アルキルジアリルアミン塩、ジアルキルジアリルアンモニウム塩及び（メタ）アクリロイルオキシ基で置換されたテトラアルキルアンモニウム塩より選ばれるモノマー（ｄ１）と、非イオン親水性ビニルモノマー（ｄ２）との共重合体が好ましい。（ｄ１）におけるアミン塩は塩酸、硫酸、硝酸、酢酸等によりアミノ基部分が塩になっている化合物が好ましい。アンモニウム構造と塩を形成する陰イオンは、塩化物イオン、臭化物イオン、硫酸イオン、硝酸イオン、メチル硫酸イオン、エチル硫酸イオン、メタンスルホン酸イオンより選ばれるものであることが好ましい。また（ｄ１）におけるアルキル基は炭素数１～４のアルキル基であることが好ましい。 Examples of the surface treatment agent include water-soluble cationic copolymers and water-soluble anionic surfactants.
The water-soluble cationic copolymer includes a monomer (d1) selected from diallylamine salts, alkyldiallylamine salts, dialkyldiallylammonium salts, and tetraalkyl ammonium salts substituted with (meth)acryloyloxy groups, and a nonionic hydrophilic vinyl A copolymer with monomer (d2) is preferred. The amine salt in (d1) is preferably a compound in which the amino group is converted into a salt with hydrochloric acid, sulfuric acid, nitric acid, acetic acid, or the like. The anion that forms a salt with the ammonium structure is preferably selected from chloride ion, bromide ion, sulfate ion, nitrate ion, methylsulfate ion, ethylsulfate ion, and methanesulfonate ion. Further, the alkyl group in (d1) is preferably an alkyl group having 1 to 4 carbon atoms.
水溶性カチオン性共重合体としては、ジアリルアミン塩、アルキルジアリルアミン塩、ジアルキルジアリルアンモニウム塩及び（メタ）アクリロイルオキシ基で置換されたテトラアルキルアンモニウム塩より選ばれるモノマー（ｄ１）と、非イオン親水性ビニルモノマー（ｄ２）との共重合体が好ましい。（ｄ１）におけるアミン塩は塩酸、硫酸、硝酸、酢酸等によりアミノ基部分が塩になっている化合物が好ましい。アンモニウム構造と塩を形成する陰イオンは、塩化物イオン、臭化物イオン、硫酸イオン、硝酸イオン、メチル硫酸イオン、エチル硫酸イオン、メタンスルホン酸イオンより選ばれるものであることが好ましい。また（ｄ１）におけるアルキル基は炭素数１～４のアルキル基であることが好ましい。 Examples of the surface treatment agent include water-soluble cationic copolymers and water-soluble anionic surfactants.
The water-soluble cationic copolymer includes a monomer (d1) selected from diallylamine salts, alkyldiallylamine salts, dialkyldiallylammonium salts, and tetraalkyl ammonium salts substituted with (meth)acryloyloxy groups, and a nonionic hydrophilic vinyl A copolymer with monomer (d2) is preferred. The amine salt in (d1) is preferably a compound in which the amino group is converted into a salt with hydrochloric acid, sulfuric acid, nitric acid, acetic acid, or the like. The anion that forms a salt with the ammonium structure is preferably selected from chloride ion, bromide ion, sulfate ion, nitrate ion, methylsulfate ion, ethylsulfate ion, and methanesulfonate ion. Further, the alkyl group in (d1) is preferably an alkyl group having 1 to 4 carbon atoms.
（ｄ１）として具体的には、ジアリルアミン塩、メチルジアリルアミン塩、エチルジアリルアミン塩；ジメチルジアリルアンモニウム、（メタ）アクリロイルオキシエチルトリメチルアンモニウム、（メタ）アクリロイルオキシエチルジメチルエチルアンモニウム、及びアクリロイルオキシエチルジメチルアンモニウムなどの塩；Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレートをエピクロロヒドリン、グリシドール、グリシシジルトリメチルアンモニウムクロライドなどのエポキシ化合物でアルキル化して得られる４級アンモニウム塩などが挙げられる。これらの中で特に好ましいものは、ジアリルアミン塩、メチルジアリルアミン塩およびジメチルジアリルアンモニウム塩である。これらは単独で使用してもよいし、複数種併用してもよい。
Specific examples of (d1) include diallylamine salt, methyldiallylamine salt, ethyldiallylamine salt; dimethyldiallylammonium, (meth)acryloyloxyethyltrimethylammonium, (meth)acryloyloxyethyldimethylethylammonium, and acryloyloxyethyldimethylammonium. Examples include quaternary ammonium salts obtained by alkylating N,N-dimethylaminoethyl (meth)acrylate with epoxy compounds such as epichlorohydrin, glycidol, and glycidyltrimethylammonium chloride. Particularly preferred among these are diallylamine salt, methyldiallylamine salt and dimethyldiallylammonium salt. These may be used alone or in combination.
（ｄ２）の具体例としては、アクリルアミド、メタクリルアミド、Ｎ－ビニルホルムアミド、Ｎ－ビニルアセトアミド、Ｎ－ビニルピロドリン、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシ（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、（メタ）アクリル酸メチルエステル、（メタ）アクリル酸エチルエステル、（メタ）アクリル酸ブチルエステルなどが挙げられ、これらの中でも好ましくはアクリルアミドまたはメタクリルアミドである。これらは単独で使用しても、複数種併用してもよい。
Specific examples of (d2) include acrylamide, methacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrodrine, 2-hydroxyethyl (meth)acrylate, 2-hydroxy (meth)acrylate, 3-hydroxy Examples include propyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and among these, acrylamide or methacrylamide is preferred. These may be used alone or in combination.
（ｄ１）と（ｄ２）の共重合比は任意であるが、好ましい範囲として、（ｄ１）は１０～９９モル％、より好ましくは５０～９７モル％、さらに好ましくは６５～９５モル％であり、（ｄ２）は９０～１モル％、より好ましくは５０～３モル％、さらに好ましくは３５～５モル％である。なおカチオン性共重合体は、例えば日本国特開平５－２６３０１０号公報に記載された方法により製造することができる。
The copolymerization ratio of (d1) and (d2) is arbitrary, but as a preferred range, (d1) is 10 to 99 mol%, more preferably 50 to 97 mol%, and even more preferably 65 to 95 mol%. , (d2) is 90 to 1 mol%, more preferably 50 to 3 mol%, even more preferably 35 to 5 mol%. The cationic copolymer can be produced, for example, by the method described in Japanese Patent Application Laid-Open No. 5-263010.
水溶性アニオン系界面活性剤としては、一価アルコールのアルキレンオキサイド付加物のスルホン酸塩、アルキルスルホン酸塩及びアルキルベンゼンスルホン酸塩からなる群より選ばれる１種以上のスルホン酸塩などが挙げられる。スルホン酸構造と塩を形成する陽イオンとしては、ナトリウムイオン、カリウムイオン、リチウムイオン及びアンモニウムイオンなどが挙げられる。
これらの中でもアルキルスルホン酸塩が好ましく、具体的にはオクタンスルホン酸塩、ドデカンスルホン酸塩、テトラデカンスルホン酸塩、ヘキサデカンスルホン酸塩、オクタデカンスルホン酸塩などの炭素数８～２０のアルキル基を有するものが特に好ましい。これらは単独で使用しても、複数種併用してもよい。 Examples of the water-soluble anionic surfactant include one or more sulfonates selected from the group consisting of sulfonates of alkylene oxide adducts of monohydric alcohols, alkyl sulfonates, and alkylbenzene sulfonates. Examples of cations that form salts with the sulfonic acid structure include sodium ions, potassium ions, lithium ions, and ammonium ions.
Among these, alkyl sulfonates are preferred, and specifically, those having an alkyl group having 8 to 20 carbon atoms, such as octane sulfonate, dodecane sulfonate, tetradecane sulfonate, hexadecane sulfonate, and octadecane sulfonate. Particularly preferred. These may be used alone or in combination.
これらの中でもアルキルスルホン酸塩が好ましく、具体的にはオクタンスルホン酸塩、ドデカンスルホン酸塩、テトラデカンスルホン酸塩、ヘキサデカンスルホン酸塩、オクタデカンスルホン酸塩などの炭素数８～２０のアルキル基を有するものが特に好ましい。これらは単独で使用しても、複数種併用してもよい。 Examples of the water-soluble anionic surfactant include one or more sulfonates selected from the group consisting of sulfonates of alkylene oxide adducts of monohydric alcohols, alkyl sulfonates, and alkylbenzene sulfonates. Examples of cations that form salts with the sulfonic acid structure include sodium ions, potassium ions, lithium ions, and ammonium ions.
Among these, alkyl sulfonates are preferred, and specifically, those having an alkyl group having 8 to 20 carbon atoms, such as octane sulfonate, dodecane sulfonate, tetradecane sulfonate, hexadecane sulfonate, and octadecane sulfonate. Particularly preferred. These may be used alone or in combination.
フィラーの表面を親水化処理する方法は特に限定されず、例えば無機粒子又は有機粒子を含むスラリーに、表面処理剤を導入し、攪拌・乾燥することにより行うことができる。フィラーとして、湿式粉砕により製造される炭酸カルシウム（無機粒子）を使用する場合には、炭酸カルシウム／水性媒体（好ましくは水）の質量比が例えば７０／３０～３０／７０、好ましくは６０／４０～４０／６０の範囲となるように炭酸カルシウムに水性媒体を加え、ここにカチオン性共重合体を、固形分として炭酸カルシウム１００質量部当たり０．０５～２質量部、好ましくは０．１～１質量部添加し、常法により湿式粉砕すればよい。さらに、上記範囲の量となるカチオン性共重合体を予め溶解してなる水性媒体を準備し、該水性媒体を炭酸カルシウムと混合し、常法により湿式粉砕してもよい。
The method for hydrophilizing the surface of the filler is not particularly limited, and can be carried out, for example, by introducing a surface treatment agent into a slurry containing inorganic particles or organic particles, followed by stirring and drying. When using calcium carbonate (inorganic particles) produced by wet grinding as a filler, the mass ratio of calcium carbonate/aqueous medium (preferably water) is, for example, 70/30 to 30/70, preferably 60/40. Add an aqueous medium to calcium carbonate so that the ratio is in the range of ~40/60, and add the cationic copolymer thereto as a solid content of 0.05 to 2 parts by mass, preferably 0.1 to 2 parts by mass, per 100 parts by mass of calcium carbonate. What is necessary is just to add 1 part by mass and wet-pulverize it by a conventional method. Furthermore, an aqueous medium may be prepared by dissolving the cationic copolymer in an amount within the above range in advance, the aqueous medium may be mixed with calcium carbonate, and the mixture may be wet-pulverized by a conventional method.
印刷受容層がフィラーとして、親水化表面処理フィラーを含むことにより、印刷受容層表面の吸液速度が比較的速い印刷受容層が得られる。一方で、上述の通り、吸液速度は速すぎると、インクの色沈みや、印刷受容層表面の開口部からの泡噴きによる粒状模様などが生じる傾向がある。なお開口部とは、多孔質層である印刷受容層の表面に形成されることで開口している空孔部のことである。これに対し、フィラーの一部を疎水化表面処理フィラーに置き換えることにより、吸液速度を適切に調整することが容易になる。
When the print-receiving layer contains a hydrophilic surface treated filler as a filler, a print-receiving layer in which the surface of the print-receiving layer absorbs liquid at a relatively high rate can be obtained. On the other hand, as described above, if the liquid absorption rate is too high, there is a tendency for the ink to fade or to produce granular patterns due to bubbles ejected from the openings on the surface of the print-receiving layer. Note that the openings refer to pores that are open by being formed on the surface of the print-receiving layer, which is a porous layer. On the other hand, by replacing a portion of the filler with a hydrophobized surface-treated filler, it becomes easy to appropriately adjust the liquid absorption rate.
＜＜疎水化表面処理フィラー＞＞
印刷受容層に含まれる疎水化表面処理フィラーは、パラフィン又は炭素数１２～２２の脂肪酸若しくはその塩により疎水化表面処理された無機粒子又は有機粒子であることが好ましく、炭素数１２～２２の脂肪酸又はその塩により疎水化表面処理された無機粒子又は有機粒子であることがより好ましい。 <<Hydrophobized surface treatment filler>>
The hydrophobized surface-treated filler contained in the print-receiving layer is preferably inorganic particles or organic particles whose surface has been hydrophobized with paraffin or a fatty acid having 12 to 22 carbon atoms or a salt thereof. More preferably, they are inorganic particles or organic particles whose surface has been subjected to hydrophobization treatment with a salt thereof.
印刷受容層に含まれる疎水化表面処理フィラーは、パラフィン又は炭素数１２～２２の脂肪酸若しくはその塩により疎水化表面処理された無機粒子又は有機粒子であることが好ましく、炭素数１２～２２の脂肪酸又はその塩により疎水化表面処理された無機粒子又は有機粒子であることがより好ましい。 <<Hydrophobized surface treatment filler>>
The hydrophobized surface-treated filler contained in the print-receiving layer is preferably inorganic particles or organic particles whose surface has been hydrophobized with paraffin or a fatty acid having 12 to 22 carbon atoms or a salt thereof. More preferably, they are inorganic particles or organic particles whose surface has been subjected to hydrophobization treatment with a salt thereof.
疎水化表面処理するための上記炭素数１２～２２の脂肪酸としては、例えばラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、アラキジン酸、ベヘン酸、オレイン酸、リノール酸、リノレン酸、及びエレオステアリン酸等が例示できる。
表面処理の方法は特に限定されず、前述の親水化表面処理フィラーの調製と同様、例えば無機粒子又は有機粒子のスラリーに、処理剤の水溶液を導入することにより、行うことができる。これにより、表面処理された無機粒子又は有機粒子、すなわちパラフィン又は炭素数１２～２２の脂肪酸若しくはその塩を含有する表面処理層を表面に有する無機粒子又は有機粒子を得ることができる。 Examples of the fatty acid having 12 to 22 carbon atoms for hydrophobic surface treatment include lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, and eleostearin. Examples include acids.
The surface treatment method is not particularly limited, and can be carried out, for example, by introducing an aqueous solution of a treatment agent into a slurry of inorganic particles or organic particles, as in the preparation of the hydrophilic surface-treated filler described above. Thereby, it is possible to obtain surface-treated inorganic particles or organic particles, that is, inorganic particles or organic particles having a surface-treated layer containing paraffin, a fatty acid having 12 to 22 carbon atoms, or a salt thereof on the surface.
表面処理の方法は特に限定されず、前述の親水化表面処理フィラーの調製と同様、例えば無機粒子又は有機粒子のスラリーに、処理剤の水溶液を導入することにより、行うことができる。これにより、表面処理された無機粒子又は有機粒子、すなわちパラフィン又は炭素数１２～２２の脂肪酸若しくはその塩を含有する表面処理層を表面に有する無機粒子又は有機粒子を得ることができる。 Examples of the fatty acid having 12 to 22 carbon atoms for hydrophobic surface treatment include lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, and eleostearin. Examples include acids.
The surface treatment method is not particularly limited, and can be carried out, for example, by introducing an aqueous solution of a treatment agent into a slurry of inorganic particles or organic particles, as in the preparation of the hydrophilic surface-treated filler described above. Thereby, it is possible to obtain surface-treated inorganic particles or organic particles, that is, inorganic particles or organic particles having a surface-treated layer containing paraffin, a fatty acid having 12 to 22 carbon atoms, or a salt thereof on the surface.
印刷受容層における親水化表面処理フィラーと疎水化表面処理フィラーの比（親水化表面処理フィラー／疎水化表面処理フィラー）は、質量比で９５／５～５５／４５であることが好ましい。かかる比は、８５／１５～６５／３５がより好ましい。親水化表面処理フィラーと疎水化表面処理フィラーの比がこの範囲にあることで、吸液速度を適切な範囲、すなわち３．５～１０ｃｃ／ｍ２・０．５ｓに調整しやすくなるため好ましい。
The ratio of the hydrophilic surface treated filler to the hydrophobic surface treated filler (hydrophilic surface treated filler/hydrophobic surface treated filler) in the print receiving layer is preferably from 95/5 to 55/45 in terms of mass ratio. The ratio is more preferably 85/15 to 65/35. It is preferable that the ratio of the hydrophilic surface-treated filler to the hydrophobic surface-treated filler is within this range because it makes it easier to adjust the liquid absorption rate to an appropriate range, ie, 3.5 to 10 cc/m 2 ·0.5 s.
印刷受容層における親水化表面処理フィラーと疎水化表面処理フィラーの合計量は、印刷受容層に含まれるフィラーの合計量に対し、９０質量％以上が好ましく、９５質量％以上がより好ましい。かかる合計量は、１００質量％であってもよい。親水化表面処理フィラーと疎水化表面処理フィラーの合計量が上記範囲にあることで、吸液速度が精密に調整された印刷受容層を得やすくなる。
なお、印刷受容層に含まれるフィラーとして、本発明の効果を損なわない範囲で、表面処理を施していない無処理フィラーを併用してもよい。 The total amount of the hydrophilic surface-treated filler and the hydrophobic surface-treated filler in the print-receiving layer is preferably 90% by mass or more, more preferably 95% by mass or more, based on the total amount of fillers contained in the print-receiving layer. Such total amount may be 100% by weight. When the total amount of the hydrophilic surface-treated filler and the hydrophobic surface-treated filler is within the above range, it becomes easier to obtain a print-receiving layer whose liquid absorption rate is precisely controlled.
Note that as the filler contained in the print-receiving layer, an untreated filler that has not been subjected to surface treatment may be used in combination to the extent that the effects of the present invention are not impaired.
なお、印刷受容層に含まれるフィラーとして、本発明の効果を損なわない範囲で、表面処理を施していない無処理フィラーを併用してもよい。 The total amount of the hydrophilic surface-treated filler and the hydrophobic surface-treated filler in the print-receiving layer is preferably 90% by mass or more, more preferably 95% by mass or more, based on the total amount of fillers contained in the print-receiving layer. Such total amount may be 100% by weight. When the total amount of the hydrophilic surface-treated filler and the hydrophobic surface-treated filler is within the above range, it becomes easier to obtain a print-receiving layer whose liquid absorption rate is precisely controlled.
Note that as the filler contained in the print-receiving layer, an untreated filler that has not been subjected to surface treatment may be used in combination to the extent that the effects of the present invention are not impaired.
＜その他の成分＞
印刷受容層は、必要に応じて公知の添加剤を任意に含むことができる。添加剤としては、酸化防止剤、光安定剤、紫外線吸収剤、フィラーの分散剤、結晶核剤、アンチブロッキング剤、可塑剤、脂肪酸アミド等のスリップ剤、染料、顔料、離型剤、難燃剤等の公知の助剤が挙げられる。
屋外での耐久性を高める観点からは、基材層は、酸化防止剤、光安定剤等を含むことが好ましい。
酸化防止剤としては、立体障害フェノール系酸化防止剤、リン系酸化防止剤、アミン系酸化防止剤等が挙げられる。
光安定剤としては、立体障害アミン系光安定剤、ベンゾトリアゾール系光安定剤、ベンゾフェノン系光安定剤等が挙げられる。
酸化防止剤及び光安定剤の含有量は、基材層に対して、０．００１～１質量％であることが好ましい。 <Other ingredients>
The print-receiving layer can optionally contain known additives, if necessary. Additives include antioxidants, light stabilizers, ultraviolet absorbers, filler dispersants, crystal nucleating agents, anti-blocking agents, plasticizers, slip agents such as fatty acid amides, dyes, pigments, mold release agents, and flame retardants. Examples include known auxiliaries such as.
From the viewpoint of increasing durability outdoors, the base layer preferably contains an antioxidant, a light stabilizer, and the like.
Examples of the antioxidant include sterically hindered phenolic antioxidants, phosphorus antioxidants, amine antioxidants, and the like.
Examples of the light stabilizer include sterically hindered amine light stabilizers, benzotriazole light stabilizers, benzophenone light stabilizers, and the like.
The content of the antioxidant and light stabilizer is preferably 0.001 to 1% by mass based on the base layer.
印刷受容層は、必要に応じて公知の添加剤を任意に含むことができる。添加剤としては、酸化防止剤、光安定剤、紫外線吸収剤、フィラーの分散剤、結晶核剤、アンチブロッキング剤、可塑剤、脂肪酸アミド等のスリップ剤、染料、顔料、離型剤、難燃剤等の公知の助剤が挙げられる。
屋外での耐久性を高める観点からは、基材層は、酸化防止剤、光安定剤等を含むことが好ましい。
酸化防止剤としては、立体障害フェノール系酸化防止剤、リン系酸化防止剤、アミン系酸化防止剤等が挙げられる。
光安定剤としては、立体障害アミン系光安定剤、ベンゾトリアゾール系光安定剤、ベンゾフェノン系光安定剤等が挙げられる。
酸化防止剤及び光安定剤の含有量は、基材層に対して、０．００１～１質量％であることが好ましい。 <Other ingredients>
The print-receiving layer can optionally contain known additives, if necessary. Additives include antioxidants, light stabilizers, ultraviolet absorbers, filler dispersants, crystal nucleating agents, anti-blocking agents, plasticizers, slip agents such as fatty acid amides, dyes, pigments, mold release agents, and flame retardants. Examples include known auxiliaries such as.
From the viewpoint of increasing durability outdoors, the base layer preferably contains an antioxidant, a light stabilizer, and the like.
Examples of the antioxidant include sterically hindered phenolic antioxidants, phosphorus antioxidants, amine antioxidants, and the like.
Examples of the light stabilizer include sterically hindered amine light stabilizers, benzotriazole light stabilizers, benzophenone light stabilizers, and the like.
The content of the antioxidant and light stabilizer is preferably 0.001 to 1% by mass based on the base layer.
印刷受容層は多孔質であり、その空孔率は４０～６０％が好ましく、４５～５５％がより好ましい。空孔率がこの範囲であることにより、吸液速度と表面強度を両立しやすくなるため好ましい。なお空孔率は、対象となる層の断面を走査型電子顕微鏡により観察し、画像解析装置に観察画像を取り込み、同観察領域を画像解析することによって算出した、断面上の空孔の面積率として得ることができる。
The print-receiving layer is porous, and its porosity is preferably 40 to 60%, more preferably 45 to 55%. It is preferable that the porosity is in this range because it becomes easier to achieve both liquid absorption rate and surface strength. The porosity is obtained as the area ratio of pores on the cross section, which is calculated by observing the cross section of the target layer using a scanning electron microscope, importing the observed image into an image analysis device, and performing image analysis on the observed area. be able to.
印刷受容層の坪量は、１～１５ｇ／ｍ２であることが好ましく、３～１３ｇ／ｍ２であることがより好ましく、４～１０ｇ／ｍ２であることがさらに好ましい。坪量がこの範囲であることにより、目的の吸液速度に調整しやすくなるため好ましい。印刷受容層の厚みは、層の空孔率にもよるが、好ましくは１．０～１８．０μｍ、より好ましくは４．０～１６．０μｍ、さらに好ましくは５．０～１２．０μｍである。厚みがこの範囲であることにより、目的の吸液速度に調整しやすくなるため好ましい。
The basis weight of the print-receiving layer is preferably 1 to 15 g/m 2 , more preferably 3 to 13 g/m 2 , even more preferably 4 to 10 g/m 2 . When the basis weight is within this range, it is preferable because it becomes easier to adjust the liquid absorption rate to a desired level. The thickness of the print-receiving layer depends on the porosity of the layer, but is preferably 1.0 to 18.0 μm, more preferably 4.0 to 16.0 μm, and even more preferably 5.0 to 12.0 μm. . It is preferable that the thickness is within this range because it becomes easier to adjust the liquid absorption rate to a desired level.
（吸液層）
吸液層は、印刷受容層を通過したインクを吸収する層であり、印刷受容層に接して設けられることが好ましい。吸液層は熱可塑性樹脂を含有する多孔質層であり、フィラーを含有する層であることが好ましい。吸液層はフィラーを含有する延伸層であることがより好ましい。すなわち吸液層は、熱可塑性樹脂とフィラーを含有する延伸層であることがより好ましい。 (Liquid absorption layer)
The liquid-absorbing layer is a layer that absorbs ink that has passed through the print-receiving layer, and is preferably provided in contact with the print-receiving layer. The liquid absorbing layer is a porous layer containing a thermoplastic resin, and preferably a layer containing a filler. More preferably, the liquid absorbing layer is a stretched layer containing filler. That is, the liquid absorbing layer is more preferably a stretched layer containing a thermoplastic resin and a filler.
吸液層は、印刷受容層を通過したインクを吸収する層であり、印刷受容層に接して設けられることが好ましい。吸液層は熱可塑性樹脂を含有する多孔質層であり、フィラーを含有する層であることが好ましい。吸液層はフィラーを含有する延伸層であることがより好ましい。すなわち吸液層は、熱可塑性樹脂とフィラーを含有する延伸層であることがより好ましい。 (Liquid absorption layer)
The liquid-absorbing layer is a layer that absorbs ink that has passed through the print-receiving layer, and is preferably provided in contact with the print-receiving layer. The liquid absorbing layer is a porous layer containing a thermoplastic resin, and preferably a layer containing a filler. More preferably, the liquid absorbing layer is a stretched layer containing filler. That is, the liquid absorbing layer is more preferably a stretched layer containing a thermoplastic resin and a filler.
＜熱可塑性樹脂＞
吸液層に用いられる熱可塑性樹脂としては、印刷受容層の項で挙げたものと同様の熱可塑性樹脂が挙げられ、その中で好ましいものも上述と同様である。 <Thermoplastic resin>
Examples of the thermoplastic resin used in the liquid-absorbing layer include the same thermoplastic resins as those listed in the section of the print-receiving layer, and among them, the preferred ones are also the same as described above.
吸液層に用いられる熱可塑性樹脂としては、印刷受容層の項で挙げたものと同様の熱可塑性樹脂が挙げられ、その中で好ましいものも上述と同様である。 <Thermoplastic resin>
Examples of the thermoplastic resin used in the liquid-absorbing layer include the same thermoplastic resins as those listed in the section of the print-receiving layer, and among them, the preferred ones are also the same as described above.
＜フィラー＞
吸液層に用いられるフィラーとしては、印刷受容層の項で挙げたものと同様のフィラーが使用できる。但し、吸液層に用いられるフィラーは、上述の親水化表面処理及び疎水化表面処理の少なくとも一方が行われたものであってもよく、行われていないものであってもよい。所望の吸液量を得る観点からは、表面処理が行われていないものであることが好ましい。 <Filler>
As the filler used in the liquid-absorbing layer, the same fillers as those mentioned in the section of the print-receiving layer can be used. However, the filler used in the liquid-absorbing layer may or may not have been subjected to at least one of the above-mentioned hydrophilic surface treatment and hydrophobic surface treatment. From the viewpoint of obtaining a desired amount of liquid absorption, it is preferable that no surface treatment is performed.
吸液層に用いられるフィラーとしては、印刷受容層の項で挙げたものと同様のフィラーが使用できる。但し、吸液層に用いられるフィラーは、上述の親水化表面処理及び疎水化表面処理の少なくとも一方が行われたものであってもよく、行われていないものであってもよい。所望の吸液量を得る観点からは、表面処理が行われていないものであることが好ましい。 <Filler>
As the filler used in the liquid-absorbing layer, the same fillers as those mentioned in the section of the print-receiving layer can be used. However, the filler used in the liquid-absorbing layer may or may not have been subjected to at least one of the above-mentioned hydrophilic surface treatment and hydrophobic surface treatment. From the viewpoint of obtaining a desired amount of liquid absorption, it is preferable that no surface treatment is performed.
吸液層におけるフィラー含有量は、好ましくは４５～６５質量％であり、より好ましくは５０～６０質量％である。フィラー含有量が上記下限値以上であることで、吸液層の空孔量が十分なものとなりやすい。一方で、層の延伸性を好適なものとする観点、表面欠陥の抑制効果を得る観点から、フィラー含有量が上記上限値以下であることが好ましい。
The filler content in the liquid absorption layer is preferably 45 to 65% by mass, more preferably 50 to 60% by mass. When the filler content is at least the above lower limit, the amount of pores in the liquid absorbing layer is likely to be sufficient. On the other hand, from the viewpoint of optimizing the stretchability of the layer and obtaining the effect of suppressing surface defects, it is preferable that the filler content is at most the above upper limit.
＜その他の成分＞
吸液層は、印刷受容層と同様に、上述した各種の添加剤など、その他任意の成分を含有していてもよい。 <Other ingredients>
The liquid-absorbing layer, like the print-receiving layer, may contain other arbitrary components such as the various additives mentioned above.
吸液層は、印刷受容層と同様に、上述した各種の添加剤など、その他任意の成分を含有していてもよい。 <Other ingredients>
The liquid-absorbing layer, like the print-receiving layer, may contain other arbitrary components such as the various additives mentioned above.
吸液層の厚みと空孔率は、印刷受容層からの吸液量が１０ｃｃ／ｍ２以上となるよう調整すればよく、空孔率の高い層を薄く設けてもよいし、空孔率がそれほど高くない層を厚く設けてもよい。例えば、吸液層の厚みを４０～５０μｍ程度とした場合、空孔率は好ましくは４０％以上、より好ましくは４５％以上である。一方で、生産性を高める観点から、空孔率は５０％以下が好ましい。吸液層の空孔率は４０％～５０％であってもよい。
The thickness and porosity of the liquid absorbing layer may be adjusted so that the amount of liquid absorbed from the print receiving layer is 10 cc/ m2 or more, and a thin layer with high porosity may be provided, or a layer with high porosity may be formed thinly. It is also possible to provide a thick layer in which the resistance is not so high. For example, when the thickness of the liquid absorbing layer is about 40 to 50 μm, the porosity is preferably 40% or more, more preferably 45% or more. On the other hand, from the viewpoint of increasing productivity, the porosity is preferably 50% or less. The porosity of the liquid absorbing layer may be 40% to 50%.
（支持体層）
本実施形態に係る記録用紙において、吸液層の、印刷受容層とは反対側に、支持体層が積層されてもよい。記録用紙がかかる支持体層を備える構成であることで、記録用紙に適切な厚みを付与したり、印刷に適したコシを付与したりできる。すなわち、支持体層の厚みを調整することにより、記録用紙の厚みを調節し、印刷に適したコシを与えたり、不透明度や給排紙性を調整することができる。支持体層の厚さは、十分なコシを得る観点から、１５μｍ以上であることが好ましく、２０μｍ以上がより好ましく、３０μｍ以上がさらに好ましい。また、印刷時の取り扱い性を向上する観点から支持体層の厚さは４００μｍ以下であることが好ましく、３００μｍ以下がより好ましく、２００μｍ以下がさらに好ましい。支持体層の厚さは１５μｍ～４００μｍであってもよい。
支持体層は単層でもよいし、２層以上の積層体でもよい。 (Support layer)
In the recording paper according to this embodiment, a support layer may be laminated on the opposite side of the liquid-absorbing layer from the print-receiving layer. By configuring the recording paper to include such a support layer, it is possible to provide the recording paper with an appropriate thickness and stiffness suitable for printing. That is, by adjusting the thickness of the support layer, it is possible to adjust the thickness of the recording paper, give it a stiffness suitable for printing, and adjust its opacity and paper feeding/discharging properties. From the viewpoint of obtaining sufficient stiffness, the thickness of the support layer is preferably 15 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more. Further, from the viewpoint of improving handling properties during printing, the thickness of the support layer is preferably 400 μm or less, more preferably 300 μm or less, and even more preferably 200 μm or less. The thickness of the support layer may be between 15 μm and 400 μm.
The support layer may be a single layer or a laminate of two or more layers.
本実施形態に係る記録用紙において、吸液層の、印刷受容層とは反対側に、支持体層が積層されてもよい。記録用紙がかかる支持体層を備える構成であることで、記録用紙に適切な厚みを付与したり、印刷に適したコシを付与したりできる。すなわち、支持体層の厚みを調整することにより、記録用紙の厚みを調節し、印刷に適したコシを与えたり、不透明度や給排紙性を調整することができる。支持体層の厚さは、十分なコシを得る観点から、１５μｍ以上であることが好ましく、２０μｍ以上がより好ましく、３０μｍ以上がさらに好ましい。また、印刷時の取り扱い性を向上する観点から支持体層の厚さは４００μｍ以下であることが好ましく、３００μｍ以下がより好ましく、２００μｍ以下がさらに好ましい。支持体層の厚さは１５μｍ～４００μｍであってもよい。
支持体層は単層でもよいし、２層以上の積層体でもよい。 (Support layer)
In the recording paper according to this embodiment, a support layer may be laminated on the opposite side of the liquid-absorbing layer from the print-receiving layer. By configuring the recording paper to include such a support layer, it is possible to provide the recording paper with an appropriate thickness and stiffness suitable for printing. That is, by adjusting the thickness of the support layer, it is possible to adjust the thickness of the recording paper, give it a stiffness suitable for printing, and adjust its opacity and paper feeding/discharging properties. From the viewpoint of obtaining sufficient stiffness, the thickness of the support layer is preferably 15 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more. Further, from the viewpoint of improving handling properties during printing, the thickness of the support layer is preferably 400 μm or less, more preferably 300 μm or less, and even more preferably 200 μm or less. The thickness of the support layer may be between 15 μm and 400 μm.
The support layer may be a single layer or a laminate of two or more layers.
支持体層を構成する材料に特に制限は無いが、例えば、支持体層は耐水性に優れる熱可塑性樹脂層であることが好ましい。熱可塑性樹脂としては、印刷受容層の項で挙げたものと同様の樹脂が使用できる。なお支持体層は、印刷受容層および吸液層と同様に、フィラーを含有してもよく、支持体層は多孔質層であってもよい。また支持体層は、上述した添加剤など、その他任意の成分を含有していてもよい。
Although there is no particular restriction on the material constituting the support layer, for example, the support layer is preferably a thermoplastic resin layer with excellent water resistance. As the thermoplastic resin, the same resins as those mentioned in the section of the print-receiving layer can be used. Note that the support layer may contain a filler similarly to the print-receiving layer and the liquid-absorbing layer, and the support layer may be a porous layer. Further, the support layer may contain other arbitrary components such as the above-mentioned additives.
（その他の層）
本実施形態に係る記録用紙は、本発明の効果を損なわない範囲で、上述以外の層を有していてもよい。例えば記録用紙は吸液層と支持体層の間に接着層を有したり、支持体層の吸液層側とは反対側の表面に粘着層を有したりしてもよい。また印刷受容層から吸液層へのインク透過を妨げない限り、両層の間に任意の層を有していてもよい。 (Other layers)
The recording paper according to this embodiment may have layers other than those described above as long as the effects of the present invention are not impaired. For example, the recording paper may have an adhesive layer between the liquid absorbent layer and the support layer, or may have an adhesive layer on the surface of the support layer opposite to the liquid absorbent layer side. Further, any layer may be provided between the two layers as long as it does not impede ink permeation from the print-receiving layer to the liquid-absorbing layer.
本実施形態に係る記録用紙は、本発明の効果を損なわない範囲で、上述以外の層を有していてもよい。例えば記録用紙は吸液層と支持体層の間に接着層を有したり、支持体層の吸液層側とは反対側の表面に粘着層を有したりしてもよい。また印刷受容層から吸液層へのインク透過を妨げない限り、両層の間に任意の層を有していてもよい。 (Other layers)
The recording paper according to this embodiment may have layers other than those described above as long as the effects of the present invention are not impaired. For example, the recording paper may have an adhesive layer between the liquid absorbent layer and the support layer, or may have an adhesive layer on the surface of the support layer opposite to the liquid absorbent layer side. Further, any layer may be provided between the two layers as long as it does not impede ink permeation from the print-receiving layer to the liquid-absorbing layer.
（製造方法）
本発明の記録用紙の製造方法は特に限定されないが、例えば次のような方法が挙げられる。例えば、支持体層を構成する熱可塑性樹脂フィルムを形成した後、印刷受容層及び吸液層を構成する積層樹脂フィルムを積層してもよい。その場合、印刷受容層と吸液層はフィードブロック、マルチマニホールドを使用した多層ダイス方式にて共押出した後、共延伸することにより両層が多孔化された積層樹脂フィルムを形成してもよく、また複数のダイスを使用して、一方の層表面に他方の層を押出しラミネーションし、これを延伸することにより両層が多孔化された積層樹脂フィルムを形成してもよい。 (Production method)
The method for manufacturing the recording paper of the present invention is not particularly limited, but examples include the following method. For example, after forming the thermoplastic resin film constituting the support layer, the laminated resin films constituting the print-receiving layer and the liquid-absorbing layer may be laminated. In that case, the print-receiving layer and the liquid-absorbing layer may be co-extruded using a multilayer die method using a feed block or multi-manifold, and then co-stretched to form a laminated resin film in which both layers are made porous. Alternatively, a laminated resin film in which both layers are made porous may be formed by extruding and laminating one layer onto the surface of the other layer using a plurality of dies, and stretching this.
本発明の記録用紙の製造方法は特に限定されないが、例えば次のような方法が挙げられる。例えば、支持体層を構成する熱可塑性樹脂フィルムを形成した後、印刷受容層及び吸液層を構成する積層樹脂フィルムを積層してもよい。その場合、印刷受容層と吸液層はフィードブロック、マルチマニホールドを使用した多層ダイス方式にて共押出した後、共延伸することにより両層が多孔化された積層樹脂フィルムを形成してもよく、また複数のダイスを使用して、一方の層表面に他方の層を押出しラミネーションし、これを延伸することにより両層が多孔化された積層樹脂フィルムを形成してもよい。 (Production method)
The method for manufacturing the recording paper of the present invention is not particularly limited, but examples include the following method. For example, after forming the thermoplastic resin film constituting the support layer, the laminated resin films constituting the print-receiving layer and the liquid-absorbing layer may be laminated. In that case, the print-receiving layer and the liquid-absorbing layer may be co-extruded using a multilayer die method using a feed block or multi-manifold, and then co-stretched to form a laminated resin film in which both layers are made porous. Alternatively, a laminated resin film in which both layers are made porous may be formed by extruding and laminating one layer onto the surface of the other layer using a plurality of dies, and stretching this.
また支持体層、吸液層および印刷受容層を全て共押出後に共延伸するか、支持体層と吸液層を共押出した後、吸液層表面に印刷受容層を押出ラミネーションし、次いで共延伸するか、或いは支持体層上に、吸液層および印刷受容層を押出ラミネーションした後共延伸することにより、吸液層および印刷受容層の多孔化と支持体との積層を並行して行ってもよい。プロセスがシンプルであること、また製造コスト抑制の点から、共押出及び／又は押出ラミネーション後に共延伸する方法で製造することが好ましい。延伸方法は、公知の方法が採用できる。
Alternatively, the support layer, liquid absorbent layer, and print receiving layer are all coextruded and then costretched, or after the support layer and liquid absorbent layer are coextruded, the print receiving layer is extrusion laminated on the surface of the liquid absorbent layer, and then the print receiving layer is coextruded and then costretched. By stretching or co-stretching after extrusion lamination of the liquid-absorbing layer and the print-receiving layer on the support layer, the liquid-absorbing layer and the print-receiving layer are made porous and laminated with the support at the same time. It's okay. From the viewpoint of simple process and reduction of manufacturing cost, it is preferable to manufacture by coextrusion and/or costretching after extrusion lamination. A known method can be used as the stretching method.
（印刷）
本実施形態に係る記録用紙は、印刷受容層側の表面に対し印刷が施され得るものである。印刷受容層に対して行われる印刷方法としては特に限定されず、グラビア印刷、オフセット印刷、フレキソ印刷、シール印刷、スクリーン印刷等の公知の各種有版印刷のほかに、インクジェット方式、電子写真方式、又は液体トナー方式等の各種プリンタによるデジタル印刷や溶融熱転写印刷も行うことができる。 (printing)
The recording paper according to this embodiment can be printed on the surface on the print-receiving layer side. The printing method performed on the print-receiving layer is not particularly limited, and in addition to various known plate printing methods such as gravure printing, offset printing, flexo printing, sticker printing, and screen printing, inkjet methods, electrophotographic methods, Alternatively, digital printing or fused thermal transfer printing using various printers such as liquid toner type printers can also be performed.
本実施形態に係る記録用紙は、印刷受容層側の表面に対し印刷が施され得るものである。印刷受容層に対して行われる印刷方法としては特に限定されず、グラビア印刷、オフセット印刷、フレキソ印刷、シール印刷、スクリーン印刷等の公知の各種有版印刷のほかに、インクジェット方式、電子写真方式、又は液体トナー方式等の各種プリンタによるデジタル印刷や溶融熱転写印刷も行うことができる。 (printing)
The recording paper according to this embodiment can be printed on the surface on the print-receiving layer side. The printing method performed on the print-receiving layer is not particularly limited, and in addition to various known plate printing methods such as gravure printing, offset printing, flexo printing, sticker printing, and screen printing, inkjet methods, electrophotographic methods, Alternatively, digital printing or fused thermal transfer printing using various printers such as liquid toner type printers can also be performed.
印刷には、印刷方法に合わせて、紫外線硬化型インク、油性インク、酸化重合硬化型インク、溶融熱転写記録用インク、水性インク、粉体トナー、又は液体トナー（エレクトロインキ）等の各種インクを使用することができる。
For printing, various inks are used depending on the printing method, such as ultraviolet curable ink, oil-based ink, oxidative polymerization-curable ink, fused heat transfer recording ink, water-based ink, powder toner, or liquid toner (electro ink). can do.
なかでも、本実施形態に係る記録用紙は、インクジェット印刷、なかでも水性インクを用いたインクジェット印刷に好適に用いられる。本実施形態に係る記録用紙は、吸液速度が特定の範囲にあり、かつ吸液量が特定値以上であることで、印刷品質及び乾燥性に優れる。
Among these, the recording paper according to this embodiment is suitably used for inkjet printing, especially inkjet printing using water-based ink. The recording paper according to the present embodiment has excellent print quality and drying properties because the liquid absorption rate is within a specific range and the amount of liquid absorption is equal to or greater than a specific value.
以下、実施例をあげて本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。
Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples.
［原料］
実施例及び比較例にて使用した原料は表１のとおりである。なお、表中のＭＦＲはメルトフローレートを意味する。また、表１に示す表面無処理炭酸カルシウムの平均粒子径（Ｄ５０）は、平均一次粒径（Ｄ５０）であり、マイクロトラック（日機装株式会社製）を用いてレーザー光回折・散乱法によって測定された体積基準のメジアン径である。 [material]
Table 1 shows the raw materials used in the Examples and Comparative Examples. In addition, MFR in the table means melt flow rate. In addition, the average particle diameter (D50) of surface-untreated calcium carbonate shown in Table 1 is the average primary particle diameter (D50), which is measured by the laser light diffraction/scattering method using Microtrack (manufactured by Nikkiso Co., Ltd.). This is the volume-based median diameter.
実施例及び比較例にて使用した原料は表１のとおりである。なお、表中のＭＦＲはメルトフローレートを意味する。また、表１に示す表面無処理炭酸カルシウムの平均粒子径（Ｄ５０）は、平均一次粒径（Ｄ５０）であり、マイクロトラック（日機装株式会社製）を用いてレーザー光回折・散乱法によって測定された体積基準のメジアン径である。 [material]
Table 1 shows the raw materials used in the Examples and Comparative Examples. In addition, MFR in the table means melt flow rate. In addition, the average particle diameter (D50) of surface-untreated calcium carbonate shown in Table 1 is the average primary particle diameter (D50), which is measured by the laser light diffraction/scattering method using Microtrack (manufactured by Nikkiso Co., Ltd.). This is the volume-based median diameter.
［製造例１：水溶性カチオン性共重合体の製造］
環流冷却器、温度計、滴下ロート、撹拌装置およびガス導入管を備えた反応器に、ジアリルアミン塩酸塩（６０％濃度の水溶液）５００質量部、アクリルアミド（４０％濃度の水溶液）１３質量部および水４０質量部を入れ、窒素ガスを流入させながら系内温度を８０℃に昇温した。攪拌下で、重合開始剤として過硫酸アンモニウム（２５％濃度の水溶液）３０質量部を滴下ロートを用いて４時間に渡り滴下した。滴下終了後１時間反応を続け、粘稠な淡黄色液状物を得た。これを５０質量部取り、５００質量部のアセトン中に注ぐと白色の沈殿を生じた。沈殿を濾別しさらに２回１００質量部のアセトンでよく洗浄した後、真空乾燥して白色固体状の重合体（水溶性カチオン性共重合体）を得た。得られた重合体の重量平均分子量をＧＰＣより求めたところ５５，０００であった。 [Production Example 1: Production of water-soluble cationic copolymer]
In a reactor equipped with a reflux condenser, a thermometer, a dropping funnel, a stirring device and a gas inlet tube, 500 parts by mass of diallylamine hydrochloride (60% aqueous solution), 13 parts by mass of acrylamide (40% aqueous solution) and water were added. 40 parts by mass was added, and the temperature inside the system was raised to 80°C while nitrogen gas was introduced. While stirring, 30 parts by mass of ammonium persulfate (25% aqueous solution) as a polymerization initiator was added dropwise over 4 hours using a dropping funnel. After the dropwise addition was completed, the reaction was continued for 1 hour to obtain a viscous pale yellow liquid. When 50 parts by mass of this was taken and poured into 500 parts by mass of acetone, a white precipitate was produced. The precipitate was filtered, thoroughly washed twice with 100 parts by mass of acetone, and then vacuum dried to obtain a white solid polymer (water-soluble cationic copolymer). The weight average molecular weight of the obtained polymer was determined by GPC and was 55,000.
環流冷却器、温度計、滴下ロート、撹拌装置およびガス導入管を備えた反応器に、ジアリルアミン塩酸塩（６０％濃度の水溶液）５００質量部、アクリルアミド（４０％濃度の水溶液）１３質量部および水４０質量部を入れ、窒素ガスを流入させながら系内温度を８０℃に昇温した。攪拌下で、重合開始剤として過硫酸アンモニウム（２５％濃度の水溶液）３０質量部を滴下ロートを用いて４時間に渡り滴下した。滴下終了後１時間反応を続け、粘稠な淡黄色液状物を得た。これを５０質量部取り、５００質量部のアセトン中に注ぐと白色の沈殿を生じた。沈殿を濾別しさらに２回１００質量部のアセトンでよく洗浄した後、真空乾燥して白色固体状の重合体（水溶性カチオン性共重合体）を得た。得られた重合体の重量平均分子量をＧＰＣより求めたところ５５，０００であった。 [Production Example 1: Production of water-soluble cationic copolymer]
In a reactor equipped with a reflux condenser, a thermometer, a dropping funnel, a stirring device and a gas inlet tube, 500 parts by mass of diallylamine hydrochloride (60% aqueous solution), 13 parts by mass of acrylamide (40% aqueous solution) and water were added. 40 parts by mass was added, and the temperature inside the system was raised to 80°C while nitrogen gas was introduced. While stirring, 30 parts by mass of ammonium persulfate (25% aqueous solution) as a polymerization initiator was added dropwise over 4 hours using a dropping funnel. After the dropwise addition was completed, the reaction was continued for 1 hour to obtain a viscous pale yellow liquid. When 50 parts by mass of this was taken and poured into 500 parts by mass of acetone, a white precipitate was produced. The precipitate was filtered, thoroughly washed twice with 100 parts by mass of acetone, and then vacuum dried to obtain a white solid polymer (water-soluble cationic copolymer). The weight average molecular weight of the obtained polymer was determined by GPC and was 55,000.
［製造例２：親水化表面処理炭酸カルシウムの製造］
重質炭酸カルシウム（平均粒子径８μｍ、日本セメント社製、乾式粉砕品）４０質量％と水６０質量％を充分に攪拌混合してスラリー状とし、製造例１にて製造した水溶性カチオン性共重合体を重質炭酸カルシウム１００質量部当たり０．０６質量部加え、テーブル式アトライター型媒体攪拌ミル（直径１．５ｍｍのガラスビーズ、充填率１７０％、周速１０ｍ／ｓｅｃ）を用いて湿式粉砕した。
次いで、主成分が炭素数１４のアルキルスルホン酸ナトリウムと炭素数１６のアルキルスルホン酸ナトリウムの混合物（２質量％濃度の水溶液）５０質量部を加えて攪拌した。その後、３５０メッシュのスクリーンを通して分級し、３５０メッシュを通過したスラリーを媒体流動乾燥機（株式会社奈良機械製作所製、ＭＳＤ－２００）で乾燥した。得られた炭酸カルシウムの平均一次粒径をマイクロトラック（日機装株式会社製）で測定したところ１．５μｍであった。 [Production Example 2: Production of hydrophilic surface-treated calcium carbonate]
40% by mass of heavy calcium carbonate (average particle size 8 μm, manufactured by Nippon Cement Co., Ltd., dry-pulverized product) and 60% by mass of water were sufficiently stirred and mixed to form a slurry, and the water-soluble cationic compound prepared in Production Example 1 was prepared. Add 0.06 parts by mass of the polymer per 100 parts by mass of heavy calcium carbonate, and wet-process using a table-type attritor-type media stirring mill (glass beads with a diameter of 1.5 mm, filling rate 170%, peripheral speed 10 m/sec). Shattered.
Next, 50 parts by mass of a mixture (2 mass % aqueous solution) of sodium alkyl sulfonate having 14 carbon atoms and sodium alkyl sulfonate having 16 carbon atoms as main components was added and stirred. Thereafter, the slurry was classified through a 350-mesh screen, and the slurry that passed through the 350-mesh screen was dried in a fluidized medium dryer (MSD-200, manufactured by Nara Kikai Seisakusho Co., Ltd.). The average primary particle size of the obtained calcium carbonate was measured with Microtrack (manufactured by Nikkiso Co., Ltd.) and was found to be 1.5 μm.
重質炭酸カルシウム（平均粒子径８μｍ、日本セメント社製、乾式粉砕品）４０質量％と水６０質量％を充分に攪拌混合してスラリー状とし、製造例１にて製造した水溶性カチオン性共重合体を重質炭酸カルシウム１００質量部当たり０．０６質量部加え、テーブル式アトライター型媒体攪拌ミル（直径１．５ｍｍのガラスビーズ、充填率１７０％、周速１０ｍ／ｓｅｃ）を用いて湿式粉砕した。
次いで、主成分が炭素数１４のアルキルスルホン酸ナトリウムと炭素数１６のアルキルスルホン酸ナトリウムの混合物（２質量％濃度の水溶液）５０質量部を加えて攪拌した。その後、３５０メッシュのスクリーンを通して分級し、３５０メッシュを通過したスラリーを媒体流動乾燥機（株式会社奈良機械製作所製、ＭＳＤ－２００）で乾燥した。得られた炭酸カルシウムの平均一次粒径をマイクロトラック（日機装株式会社製）で測定したところ１．５μｍであった。 [Production Example 2: Production of hydrophilic surface-treated calcium carbonate]
40% by mass of heavy calcium carbonate (average particle size 8 μm, manufactured by Nippon Cement Co., Ltd., dry-pulverized product) and 60% by mass of water were sufficiently stirred and mixed to form a slurry, and the water-soluble cationic compound prepared in Production Example 1 was prepared. Add 0.06 parts by mass of the polymer per 100 parts by mass of heavy calcium carbonate, and wet-process using a table-type attritor-type media stirring mill (glass beads with a diameter of 1.5 mm, filling rate 170%, peripheral speed 10 m/sec). Shattered.
Next, 50 parts by mass of a mixture (2 mass % aqueous solution) of sodium alkyl sulfonate having 14 carbon atoms and sodium alkyl sulfonate having 16 carbon atoms as main components was added and stirred. Thereafter, the slurry was classified through a 350-mesh screen, and the slurry that passed through the 350-mesh screen was dried in a fluidized medium dryer (MSD-200, manufactured by Nara Kikai Seisakusho Co., Ltd.). The average primary particle size of the obtained calcium carbonate was measured with Microtrack (manufactured by Nikkiso Co., Ltd.) and was found to be 1.5 μm.
［製造例３：疎水化表面処理炭酸カルシウムの製造］
ＢＥＴ比表面積が１６ｍ２／ｇの合成炭酸カルシウム（軽質炭酸カルシウム）５００質量部に水を加え、これを４０℃で撹拌して、固形分１０質量％の炭酸カルシウムスラリーを作製した。次に、９０℃のラウリン酸ナトリウムの１０質量％水溶液を調製し、当該調製液と炭酸カルシウムスラリーとを混合し撹拌することで、炭酸カルシウムを疎水化表面処理した。この疎水化表面処理した炭酸カルシウムスラリーを固形分が６０％になるまで乾燥させた。その後、乾燥機を用いて脱水し、疎水化表面処理を施した炭酸カルシウムを得た。得られた炭酸カルシウムの平均一次粒径を、超音波分散機Ｍｏｄｅｌ ＵＳ－３００Ｔ（日本精機株式会社製）を使用し、溶媒としてエタノールを使用し、３００μＡの条件下で６０秒間、超音波分散を行い測定したところ０．２３μｍであった。 [Production Example 3: Production of hydrophobized surface-treated calcium carbonate]
Water was added to 500 parts by mass of synthetic calcium carbonate (light calcium carbonate) having a BET specific surface area of 16 m 2 /g, and the mixture was stirred at 40° C. to prepare a calcium carbonate slurry with a solid content of 10% by mass. Next, a 10% by mass aqueous solution of sodium laurate at 90° C. was prepared, and the prepared solution and calcium carbonate slurry were mixed and stirred to perform a hydrophobizing surface treatment on calcium carbonate. This hydrophobized surface-treated calcium carbonate slurry was dried until the solid content became 60%. Thereafter, it was dehydrated using a dryer to obtain calcium carbonate that had been subjected to a hydrophobizing surface treatment. The average primary particle size of the obtained calcium carbonate was subjected to ultrasonic dispersion using an ultrasonic dispersion machine Model US-300T (manufactured by Nippon Seiki Co., Ltd.) for 60 seconds at 300 μA using ethanol as a solvent. When measured, it was 0.23 μm.
ＢＥＴ比表面積が１６ｍ２／ｇの合成炭酸カルシウム（軽質炭酸カルシウム）５００質量部に水を加え、これを４０℃で撹拌して、固形分１０質量％の炭酸カルシウムスラリーを作製した。次に、９０℃のラウリン酸ナトリウムの１０質量％水溶液を調製し、当該調製液と炭酸カルシウムスラリーとを混合し撹拌することで、炭酸カルシウムを疎水化表面処理した。この疎水化表面処理した炭酸カルシウムスラリーを固形分が６０％になるまで乾燥させた。その後、乾燥機を用いて脱水し、疎水化表面処理を施した炭酸カルシウムを得た。得られた炭酸カルシウムの平均一次粒径を、超音波分散機Ｍｏｄｅｌ ＵＳ－３００Ｔ（日本精機株式会社製）を使用し、溶媒としてエタノールを使用し、３００μＡの条件下で６０秒間、超音波分散を行い測定したところ０．２３μｍであった。 [Production Example 3: Production of hydrophobized surface-treated calcium carbonate]
Water was added to 500 parts by mass of synthetic calcium carbonate (light calcium carbonate) having a BET specific surface area of 16 m 2 /g, and the mixture was stirred at 40° C. to prepare a calcium carbonate slurry with a solid content of 10% by mass. Next, a 10% by mass aqueous solution of sodium laurate at 90° C. was prepared, and the prepared solution and calcium carbonate slurry were mixed and stirred to perform a hydrophobizing surface treatment on calcium carbonate. This hydrophobized surface-treated calcium carbonate slurry was dried until the solid content became 60%. Thereafter, it was dehydrated using a dryer to obtain calcium carbonate that had been subjected to a hydrophobizing surface treatment. The average primary particle size of the obtained calcium carbonate was subjected to ultrasonic dispersion using an ultrasonic dispersion machine Model US-300T (manufactured by Nippon Seiki Co., Ltd.) for 60 seconds at 300 μA using ethanol as a solvent. When measured, it was 0.23 μm.
［実施例１］
（印刷受容層樹脂組成物の製造）
ポリプロピレン（商品名：ノバテック ＰＰ ＭＡ３Ｑ、日本ポリプロ社製）４０質量部、無水マレイン酸変性ポリプロピレン（商品名：モディック Ｐ９０８、三菱ケミカル社製）０．７質量部、オレフィン系エラストマー（商品名：タフマーＰＮ２０３００、三井化学社製）５．０質量部、製造例３にて得られた疎水化表面処理炭酸カルシウム１３質量部、製造例２にて得られた親水化表面処理炭酸カルシウム３７質量部、及び表面無処理炭酸カルシウム（商品名：ソフトン＃１８００、備北粉化社製）３．６質量部を配合し、ミキサーで撹拌混合した後、押出工程を得て、樹脂組成物Ａを得た。 [Example 1]
(Manufacture of print-receiving layer resin composition)
40 parts by mass of polypropylene (product name: Novatec PP MA3Q, manufactured by Nippon Polypro Co., Ltd.), 0.7 parts by mass of maleic anhydride-modified polypropylene (product name: Modic P908, manufactured by Mitsubishi Chemical Corporation), olefin elastomer (product name: Tafmer PN20300) , manufactured by Mitsui Chemicals) 5.0 parts by mass, 13 parts by mass of hydrophobic surface-treated calcium carbonate obtained in Production Example 3, 37 parts by mass of hydrophilic surface-treated calcium carbonate obtained in Production Example 2, and surface 3.6 parts by mass of untreated calcium carbonate (trade name: Softon #1800, manufactured by Bihoku Funka Co., Ltd.) was blended and mixed with stirring using a mixer, followed by an extrusion process to obtain resin composition A.
（印刷受容層樹脂組成物の製造）
ポリプロピレン（商品名：ノバテック ＰＰ ＭＡ３Ｑ、日本ポリプロ社製）４０質量部、無水マレイン酸変性ポリプロピレン（商品名：モディック Ｐ９０８、三菱ケミカル社製）０．７質量部、オレフィン系エラストマー（商品名：タフマーＰＮ２０３００、三井化学社製）５．０質量部、製造例３にて得られた疎水化表面処理炭酸カルシウム１３質量部、製造例２にて得られた親水化表面処理炭酸カルシウム３７質量部、及び表面無処理炭酸カルシウム（商品名：ソフトン＃１８００、備北粉化社製）３．６質量部を配合し、ミキサーで撹拌混合した後、押出工程を得て、樹脂組成物Ａを得た。 [Example 1]
(Manufacture of print-receiving layer resin composition)
40 parts by mass of polypropylene (product name: Novatec PP MA3Q, manufactured by Nippon Polypro Co., Ltd.), 0.7 parts by mass of maleic anhydride-modified polypropylene (product name: Modic P908, manufactured by Mitsubishi Chemical Corporation), olefin elastomer (product name: Tafmer PN20300) , manufactured by Mitsui Chemicals) 5.0 parts by mass, 13 parts by mass of hydrophobic surface-treated calcium carbonate obtained in Production Example 3, 37 parts by mass of hydrophilic surface-treated calcium carbonate obtained in Production Example 2, and surface 3.6 parts by mass of untreated calcium carbonate (trade name: Softon #1800, manufactured by Bihoku Funka Co., Ltd.) was blended and mixed with stirring using a mixer, followed by an extrusion process to obtain resin composition A.
（吸液層樹脂組成物の製造）
ポリプロピレン（商品名：ノバテック ＰＰ ＭＡ３Ｑ、日本ポリプロ社製）３８質量部、高密度ポリエチレン（商品名：ノバテック ＬＬ ＵＳ０７０Ｇ、日本ポリエチレン社製）３．５質量部、及び表面無処理炭酸カルシウム（商品名：ソフトン＃１８００、備北粉化社製）５８質量部を配合し、ミキサーで撹拌混合した後、押出工程を得て、樹脂組成物Ｂを得た。 (Manufacture of liquid-absorbing layer resin composition)
38 parts by mass of polypropylene (product name: Novatec PP MA3Q, manufactured by Nippon Polypropylene Co., Ltd.), 3.5 parts by mass of high-density polyethylene (product name: Novatec LL US070G, manufactured by Nippon Polyethylene Co., Ltd.), and surface-untreated calcium carbonate (product name: 58 parts by mass of Softon #1800 (manufactured by Bihoku Funka Co., Ltd.) were blended and stirred and mixed using a mixer, followed by an extrusion process to obtain resin composition B.
ポリプロピレン（商品名：ノバテック ＰＰ ＭＡ３Ｑ、日本ポリプロ社製）３８質量部、高密度ポリエチレン（商品名：ノバテック ＬＬ ＵＳ０７０Ｇ、日本ポリエチレン社製）３．５質量部、及び表面無処理炭酸カルシウム（商品名：ソフトン＃１８００、備北粉化社製）５８質量部を配合し、ミキサーで撹拌混合した後、押出工程を得て、樹脂組成物Ｂを得た。 (Manufacture of liquid-absorbing layer resin composition)
38 parts by mass of polypropylene (product name: Novatec PP MA3Q, manufactured by Nippon Polypropylene Co., Ltd.), 3.5 parts by mass of high-density polyethylene (product name: Novatec LL US070G, manufactured by Nippon Polyethylene Co., Ltd.), and surface-untreated calcium carbonate (product name: 58 parts by mass of Softon #1800 (manufactured by Bihoku Funka Co., Ltd.) were blended and stirred and mixed using a mixer, followed by an extrusion process to obtain resin composition B.
（支持体層樹脂組成物の製造）
ポリプロピレン（商品名：ノバテック ＰＰ ＭＡ３Ｑ、日本ポリプロ社製）６０質量部、高密度ポリエチレン（商品名：ノバテック ＬＬ ＵＳ０７０Ｇ、日本ポリエチレン社製）１０質量部、及び表面無処理炭酸カルシウム（商品名：ソフトン＃１８００、備北粉化社製）３０質量部を配合し、ミキサーで撹拌混合した後、押出工程を得て、成形支持層を形成するための樹脂組成物Ｃを得た。 (Manufacture of support layer resin composition)
60 parts by mass of polypropylene (product name: Novatec PP MA3Q, manufactured by Nippon Polypropylene Co., Ltd.), 10 parts by mass of high-density polyethylene (product name: Novatec LL US070G, manufactured by Nippon Polyethylene Co., Ltd.), and surface-untreated calcium carbonate (product name: Softon #) 1800 (manufactured by Bihoku Funka Co., Ltd.), 30 parts by mass were blended and stirred and mixed using a mixer, followed by an extrusion process to obtain a resin composition C for forming a molded support layer.
ポリプロピレン（商品名：ノバテック ＰＰ ＭＡ３Ｑ、日本ポリプロ社製）６０質量部、高密度ポリエチレン（商品名：ノバテック ＬＬ ＵＳ０７０Ｇ、日本ポリエチレン社製）１０質量部、及び表面無処理炭酸カルシウム（商品名：ソフトン＃１８００、備北粉化社製）３０質量部を配合し、ミキサーで撹拌混合した後、押出工程を得て、成形支持層を形成するための樹脂組成物Ｃを得た。 (Manufacture of support layer resin composition)
60 parts by mass of polypropylene (product name: Novatec PP MA3Q, manufactured by Nippon Polypropylene Co., Ltd.), 10 parts by mass of high-density polyethylene (product name: Novatec LL US070G, manufactured by Nippon Polyethylene Co., Ltd.), and surface-untreated calcium carbonate (product name: Softon #) 1800 (manufactured by Bihoku Funka Co., Ltd.), 30 parts by mass were blended and stirred and mixed using a mixer, followed by an extrusion process to obtain a resin composition C for forming a molded support layer.
（フィルム成形）
上記樹脂組成物Ｃを２５０℃に設定した押出機で溶融混練した後、ダイスからシート状に押出し、冷却装置にて７０℃まで冷却して単層無延伸フィルムを得た。この無延伸フィルムを１４５℃に再加熱した後、ロール間の周速差を利用して縦方向に５倍に延伸し、縦一軸延伸フィルムを得た。
続いて上記樹脂組成物Ａ、Ｂを押出機に供給し、各樹脂組成物を２層シート状に押出し、これを樹脂組成物Ｂが上記一軸延伸フィルムに接するように積層し、３層構造の積層体を得た。
得られた積層体を、オーブンを用いて１６０℃に再加熱した後、テンター延伸機を用いて横方向に９倍延伸した。次いで１７０℃で熱処理し、二軸延伸層が１層、一軸延伸層が２層の３層構造を有する記録用紙を作製した。
得られた記録用紙の坪量は、印刷受容層が８ｇ／ｍ２、吸液層が３２ｇ／ｍ２、支持体層が５６ｇ／ｍ２であった。
得られた記録用紙につき、以下の方法にて印刷受容層表面の吸液速度、吸液量、及び表面強度を測定した。また、以下の評価を行った。結果を表２に記す。 (Film molding)
The resin composition C was melt-kneaded in an extruder set at 250°C, extruded into a sheet from a die, and cooled to 70°C in a cooling device to obtain a single-layer unstretched film. After this unstretched film was reheated to 145° C., it was stretched five times in the longitudinal direction using the difference in circumferential speed between the rolls to obtain a longitudinally uniaxially stretched film.
Subsequently, the resin compositions A and B are supplied to an extruder, and each resin composition is extruded into a two-layer sheet, which is laminated so that the resin composition B is in contact with the uniaxially stretched film to form a three-layer structure. A laminate was obtained.
The obtained laminate was reheated to 160° C. using an oven, and then stretched 9 times in the transverse direction using a tenter stretching machine. Then, it was heat-treated at 170° C. to produce a recording paper having a three-layer structure including one biaxially stretched layer and two uniaxially stretched layers.
The basis weight of the obtained recording paper was 8 g/m 2 for the print receiving layer, 32 g/m 2 for the liquid absorbing layer, and 56 g/m 2 for the support layer.
Regarding the obtained recording paper, the liquid absorption rate, liquid absorption amount, and surface strength of the surface of the print-receiving layer were measured by the following methods. In addition, the following evaluations were performed. The results are shown in Table 2.
上記樹脂組成物Ｃを２５０℃に設定した押出機で溶融混練した後、ダイスからシート状に押出し、冷却装置にて７０℃まで冷却して単層無延伸フィルムを得た。この無延伸フィルムを１４５℃に再加熱した後、ロール間の周速差を利用して縦方向に５倍に延伸し、縦一軸延伸フィルムを得た。
続いて上記樹脂組成物Ａ、Ｂを押出機に供給し、各樹脂組成物を２層シート状に押出し、これを樹脂組成物Ｂが上記一軸延伸フィルムに接するように積層し、３層構造の積層体を得た。
得られた積層体を、オーブンを用いて１６０℃に再加熱した後、テンター延伸機を用いて横方向に９倍延伸した。次いで１７０℃で熱処理し、二軸延伸層が１層、一軸延伸層が２層の３層構造を有する記録用紙を作製した。
得られた記録用紙の坪量は、印刷受容層が８ｇ／ｍ２、吸液層が３２ｇ／ｍ２、支持体層が５６ｇ／ｍ２であった。
得られた記録用紙につき、以下の方法にて印刷受容層表面の吸液速度、吸液量、及び表面強度を測定した。また、以下の評価を行った。結果を表２に記す。 (Film molding)
The resin composition C was melt-kneaded in an extruder set at 250°C, extruded into a sheet from a die, and cooled to 70°C in a cooling device to obtain a single-layer unstretched film. After this unstretched film was reheated to 145° C., it was stretched five times in the longitudinal direction using the difference in circumferential speed between the rolls to obtain a longitudinally uniaxially stretched film.
Subsequently, the resin compositions A and B are supplied to an extruder, and each resin composition is extruded into a two-layer sheet, which is laminated so that the resin composition B is in contact with the uniaxially stretched film to form a three-layer structure. A laminate was obtained.
The obtained laminate was reheated to 160° C. using an oven, and then stretched 9 times in the transverse direction using a tenter stretching machine. Then, it was heat-treated at 170° C. to produce a recording paper having a three-layer structure including one biaxially stretched layer and two uniaxially stretched layers.
The basis weight of the obtained recording paper was 8 g/m 2 for the print receiving layer, 32 g/m 2 for the liquid absorbing layer, and 56 g/m 2 for the support layer.
Regarding the obtained recording paper, the liquid absorption rate, liquid absorption amount, and surface strength of the surface of the print-receiving layer were measured by the following methods. In addition, the following evaluations were performed. The results are shown in Table 2.
（吸液速度）
ブリストー法（Ｊａｐａｎ Ｔａｐｐｉ Ｎｏ．５１：２０００）に準拠し、液体動的吸収性試験機（熊谷理機工業株式会社製：ブリストー試験機ＫＭ５００型）を使用して測定した液体の転移量（Ｖ）を印刷受容層の吸液速度とした。測定溶液として、蒸留水３０質量％エタノール７０質量％の混合溶媒に、着色用染料としてスタンプインキ（赤）（シヤチハタ株式会社製）を２質量％混合したものを用いて、測定溶液滴下後５００ミリ秒の単位面積当たりの吸収量を求めた。 (Liquid absorption speed)
Liquid transfer amount (V) measured using a liquid dynamic absorption tester (Kumagai Riki Kogyo Co., Ltd.: Bristow tester KM500 model) according to the Bristow method (Japan Tappi No. 51:2000) was taken as the liquid absorption rate of the print receiving layer. As the measurement solution, a mixture of 30% by mass of distilled water and 70% by mass of ethanol and 2% by mass of stamp ink (red) (manufactured by Shachihata Co., Ltd.) as a coloring dye was used. The amount of absorption per unit area in seconds was determined.
ブリストー法（Ｊａｐａｎ Ｔａｐｐｉ Ｎｏ．５１：２０００）に準拠し、液体動的吸収性試験機（熊谷理機工業株式会社製：ブリストー試験機ＫＭ５００型）を使用して測定した液体の転移量（Ｖ）を印刷受容層の吸液速度とした。測定溶液として、蒸留水３０質量％エタノール７０質量％の混合溶媒に、着色用染料としてスタンプインキ（赤）（シヤチハタ株式会社製）を２質量％混合したものを用いて、測定溶液滴下後５００ミリ秒の単位面積当たりの吸収量を求めた。 (Liquid absorption speed)
Liquid transfer amount (V) measured using a liquid dynamic absorption tester (Kumagai Riki Kogyo Co., Ltd.: Bristow tester KM500 model) according to the Bristow method (Japan Tappi No. 51:2000) was taken as the liquid absorption rate of the print receiving layer. As the measurement solution, a mixture of 30% by mass of distilled water and 70% by mass of ethanol and 2% by mass of stamp ink (red) (manufactured by Shachihata Co., Ltd.) as a coloring dye was used. The amount of absorption per unit area in seconds was determined.
（吸液量）
ＪＩＳ Ｐ８１４０：１９９８の規定に基づいてＣｏｂｂ吸水度を測定し、吸液量の値とした。但し、試験溶媒には水ではなく７０質量％エタノール水溶液を用い、接触時間は１８０秒とした。 (Liquid absorption amount)
The Cobb water absorption was measured based on the regulations of JIS P8140:1998, and was taken as the value of the amount of liquid absorbed. However, instead of water, a 70% by mass ethanol aqueous solution was used as the test solvent, and the contact time was 180 seconds.
ＪＩＳ Ｐ８１４０：１９９８の規定に基づいてＣｏｂｂ吸水度を測定し、吸液量の値とした。但し、試験溶媒には水ではなく７０質量％エタノール水溶液を用い、接触時間は１８０秒とした。 (Liquid absorption amount)
The Cobb water absorption was measured based on the regulations of JIS P8140:1998, and was taken as the value of the amount of liquid absorbed. However, instead of water, a 70% by mass ethanol aqueous solution was used as the test solvent, and the contact time was 180 seconds.
（表面強度）
印刷受容層の表面に粘着テープ（ニチバン株式会社製、商品名「セロテープ（登録商標）」、品番：「ＣＴ－１８」）を空気が入らないように貼着し、ＪＡＰＡＮ ＴＡＰＰＩ Ｎｏ．１８－２に記載の方法に準拠し、インターナルボンドテスター（熊谷理機工業株式会社製）にて粘着テープを剥離する際の強度を測定した。 (Surface strength)
Adhesive tape (manufactured by Nichiban Co., Ltd., product name "Cello Tape (registered trademark)", product number: "CT-18") was pasted on the surface of the print-receiving layer to prevent air from entering, and JAPAN TAPPI No. The strength when peeling the adhesive tape was measured using an internal bond tester (manufactured by Kumagai Riki Kogyo Co., Ltd.) according to the method described in Section 18-2.
印刷受容層の表面に粘着テープ（ニチバン株式会社製、商品名「セロテープ（登録商標）」、品番：「ＣＴ－１８」）を空気が入らないように貼着し、ＪＡＰＡＮ ＴＡＰＰＩ Ｎｏ．１８－２に記載の方法に準拠し、インターナルボンドテスター（熊谷理機工業株式会社製）にて粘着テープを剥離する際の強度を測定した。 (Surface strength)
Adhesive tape (manufactured by Nichiban Co., Ltd., product name "Cello Tape (registered trademark)", product number: "CT-18") was pasted on the surface of the print-receiving layer to prevent air from entering, and JAPAN TAPPI No. The strength when peeling the adhesive tape was measured using an internal bond tester (manufactured by Kumagai Riki Kogyo Co., Ltd.) according to the method described in Section 18-2.
＜評価＞
印刷品質評価のため、記録用紙の印刷受容層側表面に以下の方法にて印刷を行った。
各実施例及び比較例にて得られた記録用紙の印刷受容層表面に、ＪＩＳ Ｘ９２０１：２００１（高精細カラーディジタル標準画像（ＣＭＹＫ／ＳＣＩＤ））のＮ５の絵柄をインクジェット方式で印刷した。印刷には、水性顔料インクジェットプリンタ（形式名：ＴＭ－Ｃ３５００、セイコーエプソン社製）と、当該プリンタ標準のシアン、マゼンタ、イエロー及び黒の水性顔料インク（型番：ＳＪＩＣ２２）を用いた。得られた印刷済み記録用紙を用い、以下の各種評価を行った。結果を表２に示す。 <Evaluation>
To evaluate printing quality, printing was performed on the surface of the recording paper on the print-receiving layer side using the following method.
An N5 pattern of JIS X9201:2001 (high-definition color digital standard image (CMYK/SCID)) was printed by an inkjet method on the surface of the print-receiving layer of the recording paper obtained in each Example and Comparative Example. For printing, an aqueous pigment inkjet printer (model name: TM-C3500, manufactured by Seiko Epson Corporation) and cyan, magenta, yellow, and black aqueous pigment inks (model number: SJIC22) standard for the printer were used. The following various evaluations were performed using the obtained printed recording paper. The results are shown in Table 2.
印刷品質評価のため、記録用紙の印刷受容層側表面に以下の方法にて印刷を行った。
各実施例及び比較例にて得られた記録用紙の印刷受容層表面に、ＪＩＳ Ｘ９２０１：２００１（高精細カラーディジタル標準画像（ＣＭＹＫ／ＳＣＩＤ））のＮ５の絵柄をインクジェット方式で印刷した。印刷には、水性顔料インクジェットプリンタ（形式名：ＴＭ－Ｃ３５００、セイコーエプソン社製）と、当該プリンタ標準のシアン、マゼンタ、イエロー及び黒の水性顔料インク（型番：ＳＪＩＣ２２）を用いた。得られた印刷済み記録用紙を用い、以下の各種評価を行った。結果を表２に示す。 <Evaluation>
To evaluate printing quality, printing was performed on the surface of the recording paper on the print-receiving layer side using the following method.
An N5 pattern of JIS X9201:2001 (high-definition color digital standard image (CMYK/SCID)) was printed by an inkjet method on the surface of the print-receiving layer of the recording paper obtained in each Example and Comparative Example. For printing, an aqueous pigment inkjet printer (model name: TM-C3500, manufactured by Seiko Epson Corporation) and cyan, magenta, yellow, and black aqueous pigment inks (model number: SJIC22) standard for the printer were used. The following various evaluations were performed using the obtained printed recording paper. The results are shown in Table 2.
（乾燥性）
印刷直後の印刷画像上のインクの状態を目視で観察し、かつ印刷画像上に指を押し当てて、次の通りインク乾燥性を判定した。評価基準は以下の通りである。
Ａ（優）：擦れがなく、指にインクが付かず、表面が完全に乾燥している。
Ｂ（良）：擦れがなく、指にインクが付かない。
Ｃ（可、実用下限）：擦れがあり、指にインクが付く、若しくは表面が湿っている。
Ｄ（不可、実用に適さない）：擦れがあり、指にインクが付き、表面が濡れている。 (drying)
Immediately after printing, the state of the ink on the printed image was visually observed, and the printed image was pressed with a finger to determine ink drying properties as follows. The evaluation criteria are as follows.
A (Excellent): There is no rubbing, no ink sticks to fingers, and the surface is completely dry.
B (Good): No rubbing and no ink on fingers.
C (fair, practical lower limit): There is some rubbing, ink sticks to the fingers, or the surface is wet.
D (unacceptable, not suitable for practical use): There is rubbing, ink is on the fingers, and the surface is wet.
印刷直後の印刷画像上のインクの状態を目視で観察し、かつ印刷画像上に指を押し当てて、次の通りインク乾燥性を判定した。評価基準は以下の通りである。
Ａ（優）：擦れがなく、指にインクが付かず、表面が完全に乾燥している。
Ｂ（良）：擦れがなく、指にインクが付かない。
Ｃ（可、実用下限）：擦れがあり、指にインクが付く、若しくは表面が湿っている。
Ｄ（不可、実用に適さない）：擦れがあり、指にインクが付き、表面が濡れている。 (drying)
Immediately after printing, the state of the ink on the printed image was visually observed, and the printed image was pressed with a finger to determine ink drying properties as follows. The evaluation criteria are as follows.
A (Excellent): There is no rubbing, no ink sticks to fingers, and the surface is completely dry.
B (Good): No rubbing and no ink on fingers.
C (fair, practical lower limit): There is some rubbing, ink sticks to the fingers, or the surface is wet.
D (unacceptable, not suitable for practical use): There is rubbing, ink is on the fingers, and the surface is wet.
（画質）
印刷画像を目視観察し、滲み、及びザラツキ（粒状模様、泡吹き）の２項目について以下の基準で評価した。
（滲み）
画像の輪郭の鮮明性を判定した。
Ａ（優）：画像の輪郭が鮮明である。
Ｂ（良）：画像の輪郭が若干滲んでいる。
Ｃ（可、実用下限）：画像の輪郭が滲んでいる。
Ｄ（不可、実用に適さない）：画像の輪郭が不鮮明である。 (image quality)
The printed image was visually observed and evaluated in terms of two items: bleeding and roughness (granular pattern, bubbling) using the following criteria.
(bleed)
The sharpness of the image outline was determined.
A (excellent): The outline of the image is clear.
B (Good): The outline of the image is slightly blurred.
C (fair, practical lower limit): The outline of the image is blurred.
D (unacceptable, not suitable for practical use): The outline of the image is unclear.
印刷画像を目視観察し、滲み、及びザラツキ（粒状模様、泡吹き）の２項目について以下の基準で評価した。
（滲み）
画像の輪郭の鮮明性を判定した。
Ａ（優）：画像の輪郭が鮮明である。
Ｂ（良）：画像の輪郭が若干滲んでいる。
Ｃ（可、実用下限）：画像の輪郭が滲んでいる。
Ｄ（不可、実用に適さない）：画像の輪郭が不鮮明である。 (image quality)
The printed image was visually observed and evaluated in terms of two items: bleeding and roughness (granular pattern, bubbling) using the following criteria.
(bleed)
The sharpness of the image outline was determined.
A (excellent): The outline of the image is clear.
B (Good): The outline of the image is slightly blurred.
C (fair, practical lower limit): The outline of the image is blurred.
D (unacceptable, not suitable for practical use): The outline of the image is unclear.
（ザラツキ）
ベタ画像部の濃度均一性および表面欠陥の有無を判定した。評価基準は以下の通りである。
Ａ（良）：画像のベタ画像部の濃度が一定である。
Ｂ（可、実用下限）：画像のベタ画像部の、一部の濃度が低下するが、実用上許容されるレベルにある。
Ｃ（不可、実用に適さない）：画像のベタ画像部の一部の濃度が低下し、実用上許容されるレベルではない。
Ｄ（不可、実用に適さない）：画像のベタ画像部に粒状の模様（泡噴き）が生じ、実用上許容されるレベルではない。 (Rough)
The density uniformity of the solid image area and the presence or absence of surface defects were determined. The evaluation criteria are as follows.
A (Good): The density of the solid image portion of the image is constant.
B (fair, practical lower limit): The density of some solid image areas of the image decreases, but is at a practically acceptable level.
C (unacceptable, not suitable for practical use): The density of a part of the solid image area of the image is reduced and is not at a practically acceptable level.
D (unacceptable, not suitable for practical use): A granular pattern (bubbling) occurs in the solid image area of the image, which is not at a practically acceptable level.
ベタ画像部の濃度均一性および表面欠陥の有無を判定した。評価基準は以下の通りである。
Ａ（良）：画像のベタ画像部の濃度が一定である。
Ｂ（可、実用下限）：画像のベタ画像部の、一部の濃度が低下するが、実用上許容されるレベルにある。
Ｃ（不可、実用に適さない）：画像のベタ画像部の一部の濃度が低下し、実用上許容されるレベルではない。
Ｄ（不可、実用に適さない）：画像のベタ画像部に粒状の模様（泡噴き）が生じ、実用上許容されるレベルではない。 (Rough)
The density uniformity of the solid image area and the presence or absence of surface defects were determined. The evaluation criteria are as follows.
A (Good): The density of the solid image portion of the image is constant.
B (fair, practical lower limit): The density of some solid image areas of the image decreases, but is at a practically acceptable level.
C (unacceptable, not suitable for practical use): The density of a part of the solid image area of the image is reduced and is not at a practically acceptable level.
D (unacceptable, not suitable for practical use): A granular pattern (bubbling) occurs in the solid image area of the image, which is not at a practically acceptable level.
（インク濃度）
分光色彩濃度計５３０ＪＰ（エックスライト社製）を用いて、ベタ画像部の濃度測定を行った。評価基準は以下の通りである。
Ａ：ベタ画像部の濃度が１．７を超える。
Ｂ：ベタ画像部の濃度が１．５を超えて、１．７以下である。
Ｃ：ベタ画像部の濃度が１．３を超えて、１．５以下である。
Ｄ：ベタ画像部の濃度が１．０を超えて、１．３以下である。 (ink density)
The density of the solid image area was measured using a spectral color densitometer 530JP (manufactured by X-Rite). The evaluation criteria are as follows.
A: The density of the solid image area exceeds 1.7.
B: The density of the solid image area is more than 1.5 and less than 1.7.
C: The density of the solid image area is more than 1.3 and less than 1.5.
D: The density of the solid image area is more than 1.0 and less than 1.3.
分光色彩濃度計５３０ＪＰ（エックスライト社製）を用いて、ベタ画像部の濃度測定を行った。評価基準は以下の通りである。
Ａ：ベタ画像部の濃度が１．７を超える。
Ｂ：ベタ画像部の濃度が１．５を超えて、１．７以下である。
Ｃ：ベタ画像部の濃度が１．３を超えて、１．５以下である。
Ｄ：ベタ画像部の濃度が１．０を超えて、１．３以下である。 (ink density)
The density of the solid image area was measured using a spectral color densitometer 530JP (manufactured by X-Rite). The evaluation criteria are as follows.
A: The density of the solid image area exceeds 1.7.
B: The density of the solid image area is more than 1.5 and less than 1.7.
C: The density of the solid image area is more than 1.3 and less than 1.5.
D: The density of the solid image area is more than 1.0 and less than 1.3.
（インク定着性）
インク定着性は染色堅ろう度摩擦試験機ＦＲ－２０（スガ試験機社製）を用いて評価した。評価条件は学振回数１００回、荷重４００ｇとし、試験後に画像を目視で観察した。
評価基準は以下の通りである。
Ａ：画像が剥がれていない。
Ｂ：画像が一部剥がれ、画像部の濃度が低下した。
Ｃ：画像が一部剥がれ、支持体層表面が見えている。
Ｄ：画像が全面剥がれ、支持体層表面が見えている。 (Ink fixability)
Ink fixability was evaluated using a dye fastness friction tester FR-20 (manufactured by Suga Test Instruments Co., Ltd.). The evaluation conditions were 100 Gakushin tests and a load of 400 g, and the images were visually observed after the test.
The evaluation criteria are as follows.
A: The image has not peeled off.
B: Part of the image peeled off, and the density of the image area decreased.
C: Part of the image was peeled off, and the surface of the support layer was visible.
D: The image was completely peeled off and the surface of the support layer was visible.
インク定着性は染色堅ろう度摩擦試験機ＦＲ－２０（スガ試験機社製）を用いて評価した。評価条件は学振回数１００回、荷重４００ｇとし、試験後に画像を目視で観察した。
評価基準は以下の通りである。
Ａ：画像が剥がれていない。
Ｂ：画像が一部剥がれ、画像部の濃度が低下した。
Ｃ：画像が一部剥がれ、支持体層表面が見えている。
Ｄ：画像が全面剥がれ、支持体層表面が見えている。 (Ink fixability)
Ink fixability was evaluated using a dye fastness friction tester FR-20 (manufactured by Suga Test Instruments Co., Ltd.). The evaluation conditions were 100 Gakushin tests and a load of 400 g, and the images were visually observed after the test.
The evaluation criteria are as follows.
A: The image has not peeled off.
B: Part of the image peeled off, and the density of the image area decreased.
C: Part of the image was peeled off, and the surface of the support layer was visible.
D: The image was completely peeled off and the surface of the support layer was visible.
（製本適性）
印刷後の記録用紙を、ベタ画像部を内側にして１８０度に折り曲げ、１０回指で擦り、開いた後、折り部表面が材破していないか目視で確認した。評価基準は以下の通りである。
Ａ：折り部表面が全面材破していない。
Ｂ：折り部表面の一部が材破し、支持体層が露出している。
Ｃ：折り部表面の半分が材破し、支持体層が露出している。
Ｄ：折り部表面の全面が材破し、支持体層が露出している。 (Bookbinding suitability)
The printed recording paper was folded at 180 degrees with the solid image portion facing inside, rubbed with afinger 10 times, opened, and visually checked to see if the surface of the folded portion was damaged. The evaluation criteria are as follows.
A: The entire surface of the folded portion is not broken.
B: Part of the surface of the folded portion was broken, and the support layer was exposed.
C: Half of the surface of the folded portion was broken, and the support layer was exposed.
D: The entire surface of the folded portion was broken, and the support layer was exposed.
印刷後の記録用紙を、ベタ画像部を内側にして１８０度に折り曲げ、１０回指で擦り、開いた後、折り部表面が材破していないか目視で確認した。評価基準は以下の通りである。
Ａ：折り部表面が全面材破していない。
Ｂ：折り部表面の一部が材破し、支持体層が露出している。
Ｃ：折り部表面の半分が材破し、支持体層が露出している。
Ｄ：折り部表面の全面が材破し、支持体層が露出している。 (Bookbinding suitability)
The printed recording paper was folded at 180 degrees with the solid image portion facing inside, rubbed with a
A: The entire surface of the folded portion is not broken.
B: Part of the surface of the folded portion was broken, and the support layer was exposed.
C: Half of the surface of the folded portion was broken, and the support layer was exposed.
D: The entire surface of the folded portion was broken, and the support layer was exposed.
［実施例２～１１、比較例１～３］
印刷受容層および吸液層の原料を表２に記載のように変更した以外は、実施例１と同様に記録用紙を作製した。また実施例１と同様に、吸液速度、吸液量、及び表面強度の測定並びに各種評価を行った。結果を表２に示す。 [Examples 2 to 11, Comparative Examples 1 to 3]
A recording paper was produced in the same manner as in Example 1, except that the raw materials for the print-receiving layer and the liquid-absorbing layer were changed as shown in Table 2. Further, in the same manner as in Example 1, the liquid absorption rate, liquid absorption amount, and surface strength were measured and various evaluations were performed. The results are shown in Table 2.
印刷受容層および吸液層の原料を表２に記載のように変更した以外は、実施例１と同様に記録用紙を作製した。また実施例１と同様に、吸液速度、吸液量、及び表面強度の測定並びに各種評価を行った。結果を表２に示す。 [Examples 2 to 11, Comparative Examples 1 to 3]
A recording paper was produced in the same manner as in Example 1, except that the raw materials for the print-receiving layer and the liquid-absorbing layer were changed as shown in Table 2. Further, in the same manner as in Example 1, the liquid absorption rate, liquid absorption amount, and surface strength were measured and various evaluations were performed. The results are shown in Table 2.
表２に示す通り、実施例の記録用紙は、吸液速度が特定の範囲にあり、かつ吸液量が特定値以上であることで、優れた印刷品質とインクの乾燥性とを両立できた。一方、吸液速度が低い比較例１は画像の滲みが大きく、逆に吸液速度が高すぎる比較例３は画像にザラツキが生じ、いずれも十分な画質を得ることができなかった。また吸液量が少ない比較例２は印刷の乾燥性が不十分であった。
As shown in Table 2, the recording paper of the example was able to achieve both excellent printing quality and ink drying properties by having a liquid absorption rate within a specific range and a liquid absorption amount exceeding a specific value. . On the other hand, Comparative Example 1, which had a low liquid absorption rate, had a large amount of blurring in the image, and conversely, Comparative Example 3, which had a very high liquid absorption rate, had roughness in the image, and sufficient image quality could not be obtained in either case. Furthermore, in Comparative Example 2, which had a small amount of liquid absorption, the drying properties of printing were insufficient.
本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は、２０２２年３月２９日出願の日本特許出願（特願２０２２－０５４４６９）及び２０２２年８月２６日出願の日本特許出願（特願２０２２－１３５３８８）に基づくものであり、その内容はここに参照として取り込まれる。
Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on the Japanese patent application filed on March 29, 2022 (Japanese patent application No. 2022-054469) and the Japanese patent application filed on August 26, 2022 (Japanese patent application No. 2022-135388). Incorporated here as a reference.
１ 記録用紙
１０ 支持体層
１１ 吸液層
１２ 印刷受容層 1 Recordingpaper 10 Support layer 11 Liquid absorbing layer 12 Print receiving layer
１０ 支持体層
１１ 吸液層
１２ 印刷受容層 1 Recording
Claims (6)
- 印刷受容層および吸液層を有する記録用紙であって、
前記吸液層及び前記印刷受容層はいずれも熱可塑性樹脂を含有する多孔質層であり、
前記印刷受容層が、親水化表面処理フィラー及び疎水化表面処理フィラーを含有し、
前記印刷受容層側の表面における吸液速度が３．５～１０ｃｃ／ｍ２・０．５ｓであり、
吸液量が１０ｃｃ／ｍ２・１８０ｓ以上である、記録用紙。 A recording paper having a print-receiving layer and a liquid-absorbing layer,
Both the liquid absorbing layer and the print receiving layer are porous layers containing a thermoplastic resin,
The print receiving layer contains a hydrophilic surface treated filler and a hydrophobic surface treated filler,
The liquid absorption rate on the surface of the print receiving layer side is 3.5 to 10 cc/m 2 · 0.5 s,
Recording paper with a liquid absorption amount of 10 cc/m 2 ·180 s or more. - 前記印刷受容層側の表面における表面強度が１．１ｋｇ－ｃｍ以上である、請求項１に記載の記録用紙。 The recording paper according to claim 1, wherein the surface strength on the print-receiving layer side is 1.1 kg-cm or more.
- 前記吸液層がフィラーを含有する層である、請求項１に記載の記録用紙。 The recording paper according to claim 1, wherein the liquid absorbent layer is a layer containing filler.
- 前記印刷受容層におけるフィラーの含有量が４５～６５質量％である、請求項１に記載の記録用紙。 The recording paper according to claim 1, wherein the content of filler in the print receiving layer is 45 to 65% by mass.
- 前記親水化表面処理フィラーと前記疎水化表面処理フィラーの比（親水化表面処理フィラー／疎水化表面処理フィラー）が、質量比で９５／５～５５／４５である、請求項１に記載の記録用紙。 The record according to claim 1, wherein the ratio of the hydrophilic surface treated filler to the hydrophobic surface treated filler (hydrophilic surface treated filler/hydrophobic surface treated filler) is 95/5 to 55/45 in mass ratio. Paper.
- 前記印刷受容層が、さらに熱可塑性エラストマーを含有する、請求項１に記載の記録用紙。 The recording paper according to claim 1, wherein the print-receiving layer further contains a thermoplastic elastomer.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022054469 | 2022-03-29 | ||
| JP2022-054469 | 2022-03-29 | ||
| JP2022-135388 | 2022-08-26 | ||
| JP2022135388 | 2022-08-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023190415A1 true WO2023190415A1 (en) | 2023-10-05 |
Family
ID=88202392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2023/012346 WO2023190415A1 (en) | 2022-03-29 | 2023-03-27 | Recording paper |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2023190415A1 (en) |
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| JP2008213488A (en) * | 2008-04-28 | 2008-09-18 | Jgc Catalysts & Chemicals Ltd | Recording sheet with glossy film |
| JP2011005821A (en) * | 2009-06-29 | 2011-01-13 | Jgc Catalysts & Chemicals Ltd | Recording sheet with ink receiving layer and coating liquid for forming ink receiving layer |
| WO2017099179A1 (en) * | 2015-12-11 | 2017-06-15 | 株式会社ユポ・コーポレーション | Polyolefin stretched porous film |
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| JPH11348192A (en) * | 1998-06-04 | 1999-12-21 | Oji Yuka Synthetic Paper Co Ltd | Multilayer resin stretched film |
| JP2002059639A (en) * | 2000-08-21 | 2002-02-26 | Catalysts & Chem Ind Co Ltd | Recording sheet with glossy film |
| JP2002200707A (en) * | 2000-10-31 | 2002-07-16 | Yupo Corp | Easily peelable multi-layer resin drawn film |
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