WO2023249112A1 - 記録用紙 - Google Patents

記録用紙 Download PDF

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Publication number
WO2023249112A1
WO2023249112A1 PCT/JP2023/023357 JP2023023357W WO2023249112A1 WO 2023249112 A1 WO2023249112 A1 WO 2023249112A1 JP 2023023357 W JP2023023357 W JP 2023023357W WO 2023249112 A1 WO2023249112 A1 WO 2023249112A1
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WO
WIPO (PCT)
Prior art keywords
layer
print
recording paper
mass
receiving layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/023357
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English (en)
French (fr)
Japanese (ja)
Inventor
優佳 北村
祐太郎 菅俣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yupo Corp
Original Assignee
Yupo Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yupo Corp filed Critical Yupo Corp
Priority to JP2024529097A priority Critical patent/JP7791325B2/ja
Priority to US18/877,554 priority patent/US20250340049A1/en
Priority to EP23827294.2A priority patent/EP4545308A1/en
Priority to AU2023288301A priority patent/AU2023288301B2/en
Publication of WO2023249112A1 publication Critical patent/WO2023249112A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/04—4 layers
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/12—Coating on the layer surface on paper layer
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/026—Porous
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7166—Water-soluble, water-dispersible
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/75—Printability
    • 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
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/506—Intermediate layers
    • 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
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • 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
    • B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
    • 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
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B41M5/5281—Polyurethanes or polyureas

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 become mainstream.
  • inkjet printers that use solvent-based inks are also preferred due to their water resistance and good ink fixability.
  • Various studies have been made regarding printing by inkjet printers using solvent-based inks, for example, in Patent Documents 2 and 3.
  • Patent Document 2 discloses that on a support, at least one substance having an average particle diameter of 2 to 17 ⁇ m and selected from amorphous silica, alumina, alumina hydrate, aluminosilicate, and hydrotalcite group minerals is coated.
  • An inkjet recording medium comprising an ink-receiving layer containing a pigment and an adhesive, the adhesive containing a vinyl chloride-vinyl acetate copolymer is described. .
  • Patent Document 3 discloses that an oil-based ink-receptive gloss layer mainly composed of a vinyl chloride-acrylic copolymer having a glass transition temperature of 20 to 55° C. is formed on at least one surface of a support, and the oil-based ink-receptive gloss layer is formed on at least one surface of a support.
  • the 75 degree specular gloss of the layer surface specified in JIS P 8142:2005 "75 degree specular gloss test method" is 20 to 70%
  • the 75 degree specular gloss of the printed image forming area with oil-based ink is 20% to 70%.
  • a semi-gloss oil-based inkjet recording sheet is described which is characterized by having a specular gloss of 75 degrees or higher.
  • the surface of the print-receiving layer has a high liquid absorption rate, but if the liquid absorption rate is too fast, the ink color may fade or the surface of the print-receptive layer may It has also been found that granular patterns may occur due to bubbles ejected from the openings on the surface.
  • the ink receiving layer in Patent Document 2 is a coating layer containing a pigment, but although a certain level of ink drying performance can be obtained with the pigment coating as in Patent Document 2, water and dirt tend to adhere to it, and the strength of the receiving layer is reduced. may be relatively low. Moreover, print quality such as scratch resistance may be deteriorated thereby.
  • a receiving layer containing a vinyl chloride copolymer as in Patent Document 3 printing is done by corroding the vinyl chloride copolymer with the solvent absorbed from the ink and fixing the pigment, so there is no waviness caused by the solvent. , blocking may occur, and adverse effects on weather resistance may occur.
  • the present invention aims to provide recording paper that has excellent printing quality and drying properties, and is also excellent in weather resistance, so that it does not require water-resistant or anti-fouling treatment even when printed matter is exposed outdoors for a long period of time. purpose.
  • a recording paper having a coating layer, a print receiving layer and a liquid absorbing layer in this order,
  • the coat layer contains an aqueous binder as a resin component
  • Both the print receiving layer and the liquid absorbing layer are porous layers containing a thermoplastic resin
  • the liquid absorption rate on the surface of the print receiving layer side is 5 to 25 cc/m 2 ⁇ 0.5 s,
  • the liquid absorption amount is 10 cc/m 2 or more
  • a recording paper wherein the content of the inorganic filler in the coating layer is 9 parts by mass or less based on 100 parts by mass of the aqueous binder. 2.
  • the recording paper according to item 1 wherein the print receiving layer has a porosity of 30 to 50%, and the liquid absorbing layer has a porosity of 40 to 60%. 3. 3. The recording paper according to 1 or 2 above, wherein the print-receiving layer and the liquid-absorbing layer are both stretch layers containing 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 75% by mass. 5. 5. The recording paper according to any one of 1 to 4 above, which contains a hydrophobized surface-treated filler as a filler in the print-receiving layer. 6. 6.
  • 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)acrylate refers to both acrylate and methacrylate.
  • the recording paper according to the present embodiment is a recording paper having a coat layer, a print receiving layer, and a liquid absorbent layer in this order, wherein the coat layer contains an aqueous binder as a resin component, and the print receiving layer and the liquid absorbent layer include a water-based binder as a resin component.
  • Each layer is a porous layer containing a thermoplastic resin, and has a liquid absorption rate of 5 to 25 cc/m 2 ⁇ 0.5 s on the surface on the print receiving layer side, and a liquid absorption amount of 10 cc/m 2 or more. and the content of the inorganic filler in the coating layer is 9 parts by mass or less based on 100 parts by mass of the aqueous binder.
  • FIG. 1 is a cross-sectional view showing an example of recording paper according to this embodiment.
  • the recording paper 1 has a coating layer 13, a print receiving layer 12, and a liquid absorbing layer 11 in this order.
  • 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. Further, it is preferable that a back layer 9 is further provided on the surface opposite to the print-receiving layer 12 when viewed from the liquid-absorbing layer 11 .
  • FIG. 1 is a cross-sectional view showing an example of recording paper according to this embodiment.
  • the recording paper 1 has a coating layer 13, a print receiving layer 12, and a liquid absorbing layer 11 in this order.
  • 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
  • FIG. 1 is a diagram illustrating a recording paper 1 including a coat layer 13, a print receiving layer 12, a liquid absorbing layer 11, a support layer 10, and a back layer 9.
  • the "print-receiving layer side surface" of the recording paper means the surface of the recording paper on the print-receiving layer side when viewed from the liquid-absorbing layer. In other words, this corresponds to the surface of the recording paper on the coat layer side.
  • the recording paper according to this embodiment has a liquid absorption speed of 5 to 25 cc/m 2 ⁇ 0.5 s on the surface on the print-receiving layer side.
  • the liquid absorption speed is 5 cc/m 2 ⁇ 0.5 s or more, preferably 7 cc/m 2 ⁇ 0.5 s or more, more preferably more than 10 cc/m 2 ⁇ 0.5 s, and 12 cc/m 2 ⁇ 0.5 s or more. is more preferable, and 13 cc/m 2 ⁇ 0.5 s or more is particularly preferable.
  • 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.
  • the liquid absorption speed is 25 cc/m 2 ⁇ 0.5 s or less, preferably 20 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 liquid absorption amount of the recording paper according to this embodiment is 10 cc/m 2 or more, preferably 13 cc/m 2 or more, more preferably 15 cc/m 2 or more, even more preferably 16 cc/m 2 or more, and 18 cc/m 2
  • the above is particularly 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 100 cc/m 2 or less, more preferably 90 cc/m 2 or less.
  • 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.
  • diethylene glycol ethyl methyl ether is used instead of water as the test solvent, and the contact time is 60 seconds.
  • the liquid absorption rate on the surface on the print receiving layer side is 5 to 25 cc/m 2 ⁇ 0.5 s, and the liquid absorption amount is 10 cc/m 2 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 present inventors have found that even if the liquid absorption capacity is relatively large, if the liquid absorption rate is relatively slow, sufficient drying performance may not be obtained.
  • the surface of the print-receiving layer has a high liquid absorption rate, but if the liquid absorption rate is too fast, the ink color may fade or the surface of the print-receptive layer may It has also been found that granular patterns may occur due to bubbles being ejected from the openings on the surface.
  • the recording paper has a print-receiving layer, a liquid-absorbing layer, and a predetermined coating layer, the liquid-absorbing speed of the surface of the recording paper on the print-receiving layer side is within a specific range, and the liquid-absorbing It has been discovered that when the amount is at least a specific value, a recording paper with good print quality, drying properties, and weather resistance can be obtained.
  • both the print-receiving layer and the liquid-absorbing layer are stretched layers containing filler.
  • 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. Moreover, the surface gloss is likely to be lost due to the pigment component.
  • the print-receiving layer is a layer made porous by stretching, it is easy to make it sufficiently porous with a smaller amount of filler than the above-mentioned coating layer, and it is easy to satisfy the desired liquid absorption rate and amount. .
  • the porous layer thus obtained is resistant to bending.
  • 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 coating layer contains an aqueous binder as a resin component.
  • aqueous binder as a resin component
  • printability such as adhesion with ink can be improved.
  • the antistatic agent described below is excluded from the aqueous binder.
  • the water-based binder include water-soluble resins and water-dispersible resins (aqueous resin emulsions).
  • the coating layer contains a water-dispersible resin, the liquid absorption rate can be adjusted to be higher than that of other water-based binders such as water-soluble resins.
  • the aqueous binder is preferably an ionic binder, more preferably a cationic binder, from the viewpoint of improving adhesion with the ink.
  • the cation equivalent is preferably 5 meq/g or less, more preferably 4 meq/g or less, and even more preferably 3 meq/g or less.
  • the coat layer can be formed by preparing a coating liquid for forming a coat layer containing an aqueous binder and applying the coating liquid to the surface of the laminated film.
  • the content of the resin component in the coating layer is preferably more than 80% by mass from the viewpoint of improving smoothness, more preferably 85% by mass or more, even more preferably 90% by mass or more, even if it is 100% by mass. good.
  • the content of the resin component in the coat layer refers to the solid content ratio of the total of these resin components in the coat layer, when the coat layer contains a resin component such as an antistatic agent in addition to the aqueous binder. say.
  • the coating layer may be made of only an aqueous binder, only an aqueous binder, an inorganic filler, and an auxiliary component described below, or a water-based binder and an auxiliary agent component to be described later. It may consist only of an auxiliary component.
  • the dry solid content (coating amount after drying) of the coating layer is preferably 0.05 g/m2 or more, more preferably 0.08 g/ m2 or more, and even more preferably 0.05 g/ m2 or more, from the viewpoint of improving adhesion with ink. .1 g/m2 or more .
  • the dry solid content (coating amount after drying) of the coating layer is preferably 10 g/ m2 or less, more preferably 5 g/m2 or less.
  • water-soluble resins include urethane resins, (meth)acrylic acid resins, and ethyleneimine polymers.
  • aqueous resin emulsion examples include urethane resin emulsion, (meth)acrylic acid resin, and olefin resin emulsion.
  • the (meth)acrylic acid resin more preferably has an amino group, a quaternary ammonium salt structure, or a phosphonium salt structure, and even more preferably an amino group or a quaternary ammonium salt structure.
  • the content (solid content) of the water-soluble resin in the coating layer is preferably 10% by mass or more, more preferably 20% by mass or more, from the viewpoint of improving adhesion with ink. , more preferably 25% by mass or more, particularly preferably 30% by mass or more. From the viewpoint of promoting ink penetration into the porous layer (print receiving layer and liquid absorbing layer) and obtaining drying properties and image clarity, the content (solid content) of the water-soluble resin in the coating layer is 100% by mass. The content may be 95% by mass or less, or 91% by mass or less.
  • ethyleneimine polymers include polyethyleneimine, poly(ethyleneimine-urea), ethyleneimine adducts of polyamine polyamides, modified products or hydroxides of these, and the like.
  • modified products include alkyl modified products, cycloalkyl modified products, aryl modified products, allyl modified products, aralkyl modified products, benzyl modified products, cyclopentyl modified products, cycloaliphatic hydrocarbon modified products, and glycidol.
  • modified forms include modified forms.
  • the coating layer may further contain an ethyleneimine polymer. When the coating layer contains an ethyleneimine polymer, it has a strong affinity with various printing inks, especially ultraviolet curable inks, and therefore printability is easily improved.
  • the content of the ethyleneimine polymer in the coating layer is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more, from the viewpoint of improving adhesion with the ink.
  • the upper limit of the content is not particularly limited, but may be 100% by mass or less, 90% by mass or less, or 80% by mass or less.
  • the content (solid content) of the water-dispersible resin in the coating layer is preferably 20% by mass or more, more preferably 30% by mass or more, from the viewpoint of ink fixability. It is more preferably 40% by mass or more, even more preferably 60% by mass or more, particularly preferably 80% by mass or more.
  • the upper limit of the content may be 100% by mass.
  • the average particle diameter of the water-dispersible resin in the coating layer is preferably 5 ⁇ m or less from the viewpoint of promoting ink penetration into the porous layer (print receiving layer and liquid absorbing layer) and obtaining drying properties and image clarity. , more preferably 3 ⁇ m or less, still more preferably 1 ⁇ m or less, even more preferably 0.5 ⁇ m or less, particularly preferably 0.2 ⁇ m or less.
  • the minimum film forming temperature (MFT) of the water-dispersible resin is preferably 100°C or less.
  • MFT is preferably 80°C or lower, more preferably 40°C or lower, and even more preferably 10°C or lower.
  • the lower limit is not particularly specified, but is usually -20°C or higher.
  • the content of the inorganic filler in the coat layer is 9 parts by mass or less based on 100 parts by mass of the aqueous binder. That is, the coating layer does not contain an inorganic filler, or if it does, the content thereof is 9 parts by mass or less. If the content of the inorganic filler is 9 parts by mass or less per 100 parts by mass of the aqueous binder, it becomes difficult to fill the pores opened on the surface of the print-receiving layer, so the printing ink easily penetrates into the porous layer. It becomes easier to obtain drying properties and image clarity.
  • the content of the inorganic filler is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 0.1 parts by mass or less, and it is particularly preferred that no inorganic filler is contained. Further, from the same viewpoint, the content of the inorganic filler in the coating layer is preferably 9 parts by mass or less, more preferably 5 parts by mass or less, and 3 parts by mass or less based on 100 parts by mass of the resin component.
  • the content of the inorganic filler in the coating layer is 9 parts by mass or less, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 0.1 parts by mass based on 100 parts by mass of the aqueous binder. part or less, particularly preferably 0 part by mass (excluding).
  • the content of the inorganic filler in the coating layer is 0.1 parts by mass per 100 parts by mass of the aqueous binder. It is preferably at least 0.2 parts by mass, more preferably at least 0.3 parts by mass.
  • the inorganic filler that may be contained in the coating layer is not particularly limited, and may be the same as the inorganic particles described below as a filler that may be contained in the print-receiving layer or the like.
  • the coating layer may contain an antistatic agent from the viewpoint of preventing dust adhesion due to charging and transport failure during printing and improving handling properties as a recording paper.
  • an antistatic agent from the viewpoint of preventing dust adhesion due to charging and transport failure during printing and improving handling properties as a recording paper.
  • polymer-type antistatic agents are preferred from the viewpoint of reducing surface contamination due to bleed-out.
  • the polymer type antistatic agent is not particularly limited, and cationic, anionic, amphoteric, or nonionic antistatic agents can be used, and these can be used alone or in combination of two or more types. .
  • Examples of the cationic antistatic agent include antistatic agents having an ammonium salt structure, a phosphonium salt structure, and the like.
  • Examples of anionic antistatic agents include antistatic agents having the structure of alkali metal salts (lithium salts, sodium salts, potassium salts, etc.) of sulfonic acid, phosphoric acid, carboxylic acid, and the like.
  • the anionic antistatic agent may be an antistatic agent having an alkali metal salt structure such as acrylic acid, methacrylic acid, or (anhydrous) maleic acid in its molecular structure.
  • amphoteric antistatic agent is an antistatic agent containing the structures of both a cationic antistatic agent and an anionic antistatic agent in the same molecule.
  • amphoteric antistatic agents include betaine antistatic agents.
  • nonionic antistatic agents include ethylene oxide polymers having an alkylene oxide structure and polymers having an ethylene oxide polymerization component in the molecular chain.
  • Other antistatic agents include polymer type antistatic agents having boron in their molecular structure.
  • a cation type antistatic agent is preferable, a nitrogen-containing polymer type antistatic agent is more preferable, an antistatic agent having an ammonium salt structure is even more preferable, and a tertiary or quaternary ammonium salt is preferable.
  • Acrylic resins having a structure are particularly preferred, and acrylic resins having a quaternary ammonium salt structure are most preferred.
  • the content of the antistatic agent in the coating layer is preferably 0.01 part by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the aqueous binder. , more preferably 2 parts by mass or more.
  • the content of the antistatic agent in the coating layer is preferably 150 parts by mass or less, and preferably 140 parts by mass or less, based on 100 parts by mass of the aqueous binder. is more preferable, and even more preferably 130 parts by mass or less.
  • the coating layer can contain other auxiliary components such as a crosslinking agent, a crosslinking accelerator, a pH adjuster, and an antifoaming agent, if necessary.
  • auxiliary components such as a crosslinking agent, a crosslinking accelerator, a pH adjuster, and an antifoaming agent, if necessary.
  • the print-receiving layer is a porous layer containing thermoplastic resin.
  • the print-receiving layer is preferably a stretched layer containing filler as described above. That is, the print-receiving layer is preferably a stretched layer containing a thermoplastic resin and a 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 excellent 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 copolymers maleic acid-modified ethylene/vinyl acetate copolymers, ethylene/vinyl acetate copolymers, ethylene/acrylic acid copolymers, ethylene/acrylic acid alkyl ester copolymers, ethylene/alkyl methacrylates Ester copolymers, metal salts of ethylene/methacrylic acid copolymers (metals include zinc, aluminum, lithium, sodium, potassium, etc.), ethylene-cyclic olefin copolymers, (anhydrous) maleic acid-modified polyethylene, (anhydrous) maleic Examples include acid-modified polypropylene.
  • (maleic anhydride) refers to both maleic anhydride and maleic acid.
  • propylene homopolymer that is, polypropylene, or high-density polyethylene is preferable from the viewpoint of improving moldability, suppressing cost, and suppressing deflection due to solvent ink.
  • (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.
  • Fillers include inorganic particles and organic particles. 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 filler content in the print-receiving layer is preferably 45% by mass or more, and 50% by mass or more, from the viewpoint of reducing the amount of resin used and reducing the environmental load, and from the viewpoint of making the pore forming property suitable. It is more preferable that On the other hand, the filler content in the print-receiving layer is preferably 75% by mass or less, more preferably 65% by mass or less, from the viewpoint of suppressing the occurrence of surface defects.
  • 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 is 75% by mass or less, it is possible to prevent the porosity and liquid absorption rate from becoming excessive.
  • the average particle diameter of the filler contained in the print-receiving layer is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, from the viewpoint of obtaining suitable pore-forming properties and controlling the liquid absorption rate. Further, from the same viewpoint, the average particle diameter of the filler is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and even more preferably 0.9 ⁇ m or less. When the average particle diameter of the filler is 0.1 ⁇ m or more, the porous layer is made porous and the permeability of the ink is easily increased.
  • 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.
  • the print-receiving layer preferably contains a hydrophobized surface-treated filler as a filler, and may contain only a hydrophobized surface-treated filler as a filler.
  • the hydrophobized surface-treated filler is preferably an inorganic particle or an organic particle 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 surface-treated inorganic particles or organic particles.
  • 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 or organic particles.
  • 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.
  • an untreated filler without surface treatment or a hydrophilic surface-treated filler with hydrophilic surface treatment may be used in combination, as long as the effects of the present invention are not impaired.
  • the content of the hydrophobized surface treated filler in the filler contained in the print receiving layer is preferably 50% by mass or more, more preferably 60% by mass or more, and preferably 70% by mass or more. The content is more preferably 80% by mass or more, even more preferably 90% by mass or more. All of the fillers contained in the print-receiving layer may be hydrophobized surface-treated fillers.
  • 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.
  • known auxiliary agents include.
  • 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 32% or more, more preferably 34% or more, and even more preferably 35% or more. Further, the porosity of the print-receiving layer is preferably 50% or less, more preferably 45% or less. 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 g/m 2 or more, more preferably 1.5 g/m 2 or more, and even more preferably 2 g/m 2 or more.
  • the basis weight of the print-receiving layer is preferably 15 g/m 2 or less, more preferably 12 g/m 2 or less, even more preferably 10 g/m 2 or less. 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 average pore diameter of the print-receiving layer is preferably 0.5 ⁇ m or more, more preferably 0.7 ⁇ m or more, and even more preferably 0.8 ⁇ m or more from the viewpoint of suppressing the liquid absorption rate from becoming too low.
  • the average pore diameter of the print-receiving layer is preferably 20 ⁇ m or less, more preferably 14 ⁇ m or less, and even more preferably 7 ⁇ m or less, from the viewpoint of suppressing a decrease in sharpness due to sinking of ink pigments.
  • the average pore diameter of the print-receiving layer is determined by the same image analysis as when determining the porosity.
  • 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 is preferably a stretched layer containing a filler. That is, the liquid absorbing layer is 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.
  • the filler used in the liquid-absorbing layer is preferably not surface-treated from the viewpoint of obtaining a desired liquid-absorbing amount.
  • the filler content in the liquid absorption layer is preferably 45 to 70% by mass, more preferably 50 to 65% 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. From the viewpoint of increasing the continuity and ensuring the capacity for liquid absorption, the porosity of the liquid absorption layer is preferably 40% or more, more preferably 45% or more. On the other hand, from the viewpoint of increasing productivity, the porosity is preferably 60% or less.
  • the basis weight of the liquid absorbing layer is preferably 5 g/m 2 or more, more preferably 10 g/m 2 or more, even more preferably 15 g/m 2 or more, and even more preferably 19 g/m 2 or more. Even more preferably, it is 21 g/m 2 or more. Further, the basis weight of the liquid absorbing layer is preferably 50 g/m 2 or less, more preferably 40 g/m 2 or less, and even more preferably 37.5 g/m 2 or less. It is preferable for the basis weight to be within this range because it makes it easier to adjust the amount of liquid absorbed to the desired level.
  • 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 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 back layer is preferably provided on the surface of the support layer opposite to the print-receiving layer.
  • the back layer mainly has the function of promoting evaporation of the solvent after printing from the receiving layer and suppressing the waviness of the paper surface caused by the solvent when the recording sheets are stacked and stored.
  • the same material as the print-receiving layer can be used for the back layer.
  • the filler content in the back layer if an inorganic filler and an organic filler are used together, the total amount
  • the total amount must be 5 to 60% by mass from the viewpoint of appropriate surface roughness and static friction coefficient. is preferable, and 10 to 50% by mass is more preferable.
  • the thickness of the back layer can be appropriately determined depending on the thickness of the support layer described above.
  • the thickness of the back layer is preferably 1 to 50 ⁇ m, more preferably 1 to 20 ⁇ m, and even more preferably 2 to 10 ⁇ m, from the viewpoint of developing appropriate surface roughness.
  • the porosity of the back layer is preferably 5 to 60%, more preferably 5 to 50%, and even more preferably 10 to 40%.
  • the presence of pores tends to make it possible to control the surface roughness of the back layer within a predetermined range.
  • a coating layer can also be further provided on the surface of the back layer.
  • the coating layer can contain an anchoring agent, a polymeric antistatic agent, and the like.
  • an anchor agent when an inkjet printing layer is provided on the coating layer, the adhesion between the coating layer and the inkjet printing layer tends to be improved.
  • an antistatic agent there is a tendency that the antistatic performance of the back layer side can be improved.
  • the anchoring agent include polyimine polymers and ethyleneimine adducts of polyamine polyamides.
  • examples of the polymer type antistatic agent include those having an ammonium salt structure or a phosphonium salt structure.
  • the antistatic agent is preferably 0 to 200 parts by mass, more preferably 0 to 200 parts by mass, based on 100 parts by mass of the anchoring agent in terms of solid content ratio.
  • the amount is 20 to 150 parts by weight, more preferably 30 to 100 parts by weight.
  • the recording paper is also suitable for use in bulletin boards such as posters, and in the case of use in bulletin boards, it is preferable that it has a certain degree of rigidity from the viewpoint of ease of handling during pasting.
  • the bending resistance of the recording paper is preferably 0.3 mN or more, more preferably 0.4 mN or more, and even more preferably 0.5 mN or more.
  • the bending resistance of the recording paper is preferably 10 mN or less, more preferably 5 mN or less, and even more preferably 3 mN or less. If the bending resistance of the recording paper is within the above range, the recording paper itself will have stiffness and will be easy to handle.
  • the bending resistance in this embodiment is based on the bending repulsion A method (Gurley method) according to JIS L1096:2010. Note that a specific method for measuring the bending resistance of recording paper using the Gurley method will be explained in Examples to be described later.
  • the glossiness of the surface of the recording paper on the print-receiving layer side is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more. If the glossiness of the surface of the print-receiving layer side is equal to or higher than the above lower limit, it can be said that a sufficiently high glossiness has been obtained, at least compared to recording paper using a pigment coating, etc., and the image is clear and the appearance is good. It tends to get better.
  • the glossiness in this embodiment is based on the glossiness according to JIS P 8142:1993. Note that a specific method for measuring the glossiness of the surface of the recording paper on the print-receiving layer side will be explained in Examples described later.
  • the surface strength of the print-receiving layer side is preferably 0.7 kgf/cm or more, more preferably 0.9 kgf/cm or more, and even more preferably 1.0 kgf/cm or more.
  • the surface strength of the receptor layer may be 2.0 kgf/cm or less, 1.5 kgf/cm or less, or 1.2 kgf/cm or less. If the surface strength of the print-receiving layer side is within the above range, the surface of the print-receiving layer side will be less likely to be scraped by sand etc. when the recording paper is posted outdoors, and the weather resistance will be high, so the printed image will not be visible. They tend to be able to be maintained for long periods of time. Note that a specific method for measuring the surface strength on the print-receiving layer side will be explained in Examples described later.
  • the smoothness of the surface of the print-receiving layer side is preferably 1000 seconds or more, more preferably 1300 seconds or more, and even more preferably 1800 seconds or more, from the viewpoint of clear images and good appearance. preferable.
  • the surface smoothness of the print-receiving layer side is preferably 10,000 seconds or less, more preferably 9,000 seconds or less, and even more preferably 8,000 seconds or less. preferable. Note that a specific method for measuring the smoothness of the surface of the print-receiving layer side will be explained in Examples described later.
  • the method for manufacturing the recording paper of the present invention is not particularly limited, but examples include the following method.
  • the recording paper includes a print-receiving layer, a liquid-absorbing layer, a support layer, and a back layer
  • the laminated resin that constitutes the print-receiving layer and the liquid-absorbing layer is The film may be laminated on one side of the support layer and the back layer on the other side.
  • the print-receiving layer and the liquid-absorbing layer are coextruded onto one side of the support layer using a multilayer die method using a feed block and multi-manifold, and the back layer is extruded onto the other side, followed by co-stretching.
  • a laminated resin film in which these layers are made porous may be formed, or by extruding and laminating one layer on the surface of the other layer using multiple dies, and then stretching this.
  • a laminated resin film in which both layers are made porous may be formed.
  • the support layer, liquid absorbent layer, print receiving layer, and back layer may all be coextruded and then co-stretched, or the support layer, liquid absorbent layer, and back layer may be coextruded and then the print receiving layer is formed on the surface of the liquid absorbent layer.
  • extrusion lamination is performed to form a printing receiving layer on the surface of the liquid absorption layer and a back layer on the surface of the support layer, and then co-stretching, or alternatively, the liquid absorption layer is formed on one side of the support layer.
  • the print-receiving layer is co-stretched after extrusion lamination of the back layer on the other side of the support layer, thereby making the liquid-absorbing layer and the print-receiving layer porous and laminating them with the support in parallel.
  • a known method can be used as the stretching method.
  • Film stretching methods include, for example, a longitudinal stretching method using a difference in the peripheral speed of a group of rolls, a lateral stretching method using a tenter oven, a sequential biaxial stretching method that combines these methods, a rolling method, and a combination of a tenter oven and a pantograph.
  • Examples include a simultaneous biaxial stretching method, a simultaneous biaxial stretching method using a combination of a tenter oven and a linear motor, and the like.
  • a simultaneous biaxial stretching (inflation molding) method in which a molten resin is extruded into a tube shape using a circular die connected to a screw extruder and air is blown into the tube can also be used.
  • each layer may be stretched individually before being laminated, or may be stretched all together after being laminated. Alternatively, the stretched layers may be stretched again after being laminated.
  • the stretching temperature is preferably in a range equal to or higher than the glass transition temperature of the thermoplastic resin.
  • the stretching temperature must be within a range that is above the glass transition point of the amorphous portion of the thermoplastic resin and below the melting point of the crystalline portion of the thermoplastic resin.
  • the temperature is preferably 2 to 60°C lower than the melting point of the thermoplastic resin.
  • the stretching ratio is usually 1.2 times or more, preferably 2 times or more, but usually 10 times or less, preferably 5 times or less.
  • the area stretching ratio is usually 1.5 times or more, preferably 4 times or more, but usually 20 times or less, preferably 12 times or less. If the stretching ratio is within the above range, there is a tendency for stable stretch forming. Also, when using a resin composition containing a thermoplastic resin and a filler, as long as the stretching ratio is within the above range, the desired porosity can be obtained, the opacity can be easily improved, and the film is less likely to break.
  • a coat layer can be formed by applying the above-mentioned coating liquid for forming a coat layer to the stretched laminated resin film and drying it.
  • 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.
  • ink For printing, various types of ink, such as ultraviolet curable ink, oil-based ink, oxidative polymerization-curable ink, fused thermal transfer recording ink, water-based ink, solvent ink, powder toner, or liquid toner (electro ink), are used depending on the printing method. Ink can be used.
  • the recording paper according to this embodiment is suitably used for inkjet printing, especially inkjet printing using water-based ink or solvent ink, and especially inkjet printing using solvent ink.
  • the recording paper according to this embodiment has a print-receiving layer, a liquid-absorbing layer, and a predetermined coating layer, and has a liquid-absorbing speed within a specific range and a liquid-absorbing amount of a specific value or more, which improves print quality. , excellent drying and weather resistance.
  • Solvent-based inks generally contain a solvent and a colorant specific to solvent-based inks.
  • the solvent used in the solvent-based ink include glycol ether-based solvents such as polyoxyethylene glycol dialkyl ether, polyoxyethylene glycol monoalkyl ether, and polypropylene glycol monoalkyl ether.
  • coloring materials used in solvent-based inks include oil-soluble dyes such as naphthol dyes, azo dyes, metal complex dyes, anthraquinone dyes, quinoimine dyes, indigo dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, and benzoquinone dyes.
  • pigments carbonium dyes, naphthoquinone dyes, naphthalimide dyes, phthalocyanine dyes, perinine dyes, and the like.
  • organic pigments include insoluble azo pigments, condensed azo pigments, chelate azo pigments, perinone pigments, nitro pigments, nitroso pigments, perylene pigments, and aniline black.
  • 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.).
  • 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 ⁇ m.
  • 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.
  • Coating compositions Coating liquids (coating liquids) a to d were obtained by mixing the respective materials so as to have the formulations (solid content ratio, parts by mass) shown in Table 2.
  • a blank column in Table 2 means that the solid content ratio is 0 parts by mass.
  • Example 1 After melt-kneading the resin composition a listed in Table 1 in an extruder set at 230°C, it was fed to an extrusion die set at 250°C and extruded into a sheet, which was then cooled to 60°C with a cooling device. A non-stretched sheet was obtained. This unstretched sheet was heated to 140° C. and stretched 5 times in the longitudinal direction using the difference in circumferential speed between the roll groups. Next, resin compositions c and e are melt-kneaded in an extruder set at 230°C, and then extruded into a sheet so that resin composition c is in contact with the stretched sheet and laminated on the first side of the stretched sheet.
  • resin composition a was melt-kneaded in one extruder set at 230°C, extruded into a sheet, and laminated on the second side of the stretched sheet to obtain a four-layer laminated sheet.
  • a laminated resin film having a thickness (2 ⁇ m/42 ⁇ m/46 ⁇ m/30 ⁇ m) and the number of stretching axes for each layer (1 axis/1 axis/2 axis/1 axis) was obtained.
  • the coating composition was applied to the surface of the laminated resin film so that the coating amount after drying was 0.15 g/m 2 .
  • the coating film was dried in an oven at 60° C. to form a coat layer, and the recording paper of Example 1 was obtained.
  • Examples 2-11 and 13-14 Recording sheets of Examples 2 to 11 and 13 to 14 were obtained in the same manner as in Example 1, except that the types of resin compositions and coating compositions used, and stretching conditions were changed as shown in Table 3. The thicknesses of the support layer and back layer in Examples 2 to 11 and 13 to 14 are the same as in Example 1.
  • Example 12 After melt-kneading the resin composition a listed in Table 1 in an extruder set at 230°C, it was fed to an extrusion die set at 250°C and extruded into a sheet, which was then cooled to 60°C with a cooling device. A non-stretched sheet was obtained. Next, resin compositions c and e are melt-kneaded in an extruder set at 230°C, and then extruded into a sheet so that resin composition c is in contact with the non-stretched sheet, and is applied to the first surface of the non-stretched sheet.
  • resin composition a was melt-kneaded in one extruder set at 230°C, extruded into a sheet, and laminated on the second side of the stretched sheet to obtain a 4-layer laminated sheet.
  • a laminated resin film having a thickness (2 ⁇ m/42 ⁇ m/46 ⁇ m/30 ⁇ m) and the number of stretching axes for each layer (1 axis/1 axis/1 axis/1 axis) was obtained.
  • the coating composition was applied to the surface of the laminated resin film so that the coating amount after drying was 0.15 g/m 2 .
  • the coating film was dried in an oven at 60° C. to form a coat layer, and a recording paper of Example 12 was obtained.
  • Coat layer composition c was prepared by mixing and dispersing 25 parts by mass of "Acronal YJ-2870D” manufactured by ), solid content concentration 50% by mass.
  • a coating layer composition was applied to one side of the laminated resin film obtained above and dried to form a coating layer with a thickness of 20 ⁇ m. After drying in an oven at 70° C. for 60 seconds, a coating layer with a thickness of 120 ⁇ m was obtained. Comparative Example 1 Record sheets were obtained.
  • Comparative example 2 The resin composition h listed in Table 1 was kneaded and rolled for 5 minutes using two 9-inch test rolls (steam heating type manufactured by Nishimura Koki Co., Ltd.) set at 160°C to obtain a vinyl chloride-based resin composition with a thickness of 140 ⁇ m. A resin sheet was produced (calendering). The obtained vinyl chloride resin sheet was pressed using a 37t hydraulic molding machine (manufactured by Oji Kikai Co., Ltd.) at a temperature of 170°C, applying a maximum pressure of 70 kg/cm 2 to give a mirror-like surface finish and a thickness of 140 ⁇ m. A recording paper of Comparative Example 2 was obtained.
  • a laminated resin film having a thickness (1 ⁇ m/20 ⁇ m/25 ⁇ m/25 ⁇ m) and the number of stretching axes for each layer was obtained.
  • the coating composition was applied to the surface of the laminated resin film so that the coating amount after drying was 0.15 g/m 2 .
  • the coating film was dried in an oven at 60° C. to form a coat layer, and a recording paper of Comparative Example 3 was obtained.
  • Comparative example 4 A recording paper of Comparative Example 4 was obtained in the same manner as in Example 1 except that the coating layer was not applied.
  • Comparative Examples 5 to 7 Recording sheets of Comparative Examples 5 to 7 were obtained in the same manner as in Example 1, except that the types of the resin composition and coating composition used and the stretching conditions were changed as shown in Table 3. Note that the thicknesses of the support layer and back layer in Comparative Examples 5 to 7 are the same as in Example 1.
  • Liquid absorption amount The amount of liquid absorbed by the recording paper was measured using a water absorption tester specified in JIS P 8140. First, a solvent (diethylene glycol ethyl methyl ether manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was brought into contact with the surface of the test piece on the print-receiving layer side for 60 seconds, and after removing excess solvent, the mass of the test piece was measured. Next, the measured mass of the test piece was subtracted from the mass of the original test piece, and the mass of the solvent absorbed per 1 m 2 was determined as the solvent absorption amount (cc/m 2 ).
  • a solvent diethylene glycol ethyl methyl ether manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
  • the liquid absorption rate on the print-receiving layer side surface of the recording paper was measured using a water absorption tester specified in JIS P 8140.
  • a solvent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., diethylene glycol ethyl methyl ether
  • the amount of solvent absorbed was calculated, and the value divided by the solvent contact time was determined as the liquid absorption rate. (cc/ m2 ⁇ 0.5s).
  • the surface strength of the print receiving layer side of the recording paper was measured as follows.
  • Cellophane tape manufactured by Nichiban Co., Ltd., trade name: CT-18
  • JAPAN TAPPI No. 18-2 internal bond strength test method
  • an internal bond tester trade name, manufactured by Kumagai Riki Kogyo Co., Ltd.
  • the thickness (total thickness) of the recording paper was measured in accordance with JIS K7130:1999 using a constant pressure thickness measuring device (manufactured by Techlock Co., Ltd., trade name: PG-01J).
  • the thickness of each layer on the recording paper can be determined by cooling the sample to be measured with liquid nitrogen to a temperature below -60°C, placing it on a glass plate, and using a razor blade (manufactured by Schick Japan Co., Ltd., commercially available).
  • a sample for cross-sectional observation was prepared by cutting the sample at right angles with a Proline Blade.
  • Table 3 shows the thicknesses of the print-receiving layer and the liquid-absorbing layer determined by this method. Note that since the recording papers of Comparative Examples 1 and 2 do not have a print-receiving layer and a liquid-absorbing layer, the thickness of the coating layer for Comparative Example 1 and the thickness of the support layer for Comparative Example 2 are shown in Table 3. Indicated.
  • the Gurley bending resistance of the recording paper is determined in accordance with JIS L1096:2010 using a Gurley bending resistance tester (Daiei Kagaku Seiki Seisakusho) in the MD direction of the recording paper in an environment of 23°C and 50% RH. Measurement was performed using GAS-100 (manufactured by Co., Ltd., trade name: GAS-100).
  • the Oken-type smoothness of the surface of the print-receiving layer side of the recording paper was measured using a digital Oken-type air permeability and smoothness tester (Asahi Seiko Co., Ltd.) according to JIS P 8155:2010 "Paper and paperboard - Smoothness test method - Oken method”. It was measured with "EYO-55-1M” manufactured by Co., Ltd.).
  • the average pore diameter of the print-receiving layer was determined by the following method. The surface of the target layer was observed using a scanning electron microscope, the observed image was imported into an image analysis device, and the observed area was image analyzed to determine the average pore diameter of the pores on the surface.
  • solvent inkjet printing A sample image was printed on the print-receiving layer side surface of the recording paper using a solvent inkjet printer "SureColor SC-S80650" (manufactured by Seiko Epson Corporation).
  • gauze impregnated with 20 ⁇ L of pure water at room temperature was attached to a weight with a weight of 215 g, and the surface of the printed image area was rubbed with this weight 100 times, and the degree of ink removal was visually observed. Observed. Abrasion was evaluated based on the following criteria. 5 (Good): 95% or more of the rubbed image portion remained. 4 (Good): 90% or more of the rubbed image portion remained. 3 (fair, practical lower limit): 80% or more of the rubbed image portion remained. 2 (unacceptable, not suitable for practical use): 70% or more of the rubbed image portion remained.
  • the residual rate of the rubbed image portion was less than 70%.
  • the adhesive side of cellophane tape manufactured by Nichiban Co., Ltd., trade name: Cellotape (registered trademark) CT-18
  • the residual rate of ink on the recording paper was measured using a small general-purpose image analysis device (manufactured by Nireco, model name: LUZEX-AP). was calculated.
  • the image obtained by photographing the printed surface was subjected to binarization processing, and the percentage of the area occupied by the ink was calculated as the residual rate.
  • Ink adhesion was evaluated based on the calculated residual rate of ink using the following criteria. 5 (Good): The residual rate of ink was 80% or more. 3 (fair, practical lower limit): The residual rate of ink was 50% or more and less than 80%. 1 (unacceptable, not suitable for practical use): The residual rate of ink was less than 50%.
  • Blocking A solid black color is printed on the print-receiving layer side surface of the recording paper using a solvent inkjet printer "SureColor SC-S80650" (manufactured by Seiko Epson Corporation). After being stored for one day in an atmosphere of 40° C. and 50% relative humidity, it was observed whether it was possible to pull out smoothly from the roll without causing blocking. Blocking was evaluated based on the following criteria. 5 (Good): The sample could be pulled out smoothly without any peeling sound. 3 (fair, practical lower limit): There was a peeling sound, but the appearance of the base material layer after taking it off was not impaired. 1 (unsuitable, not suitable for practical use): There was a loud peeling sound, and the appearance of the base material layer after being removed was impaired.
  • Super accelerated weathering tester manufactured by Daipra Wintes Co., Ltd., product name "Metal Weather KU-R5N-A", metal halide lamp type) and a glass filter "KF-2 filter” that transmits ultraviolet light of 295 to 450 nm ( (product name) was used.
  • the irradiance on the surface of the test piece was 90 W/m 2 and the black panel temperature was 63°C.
  • the acceleration treatment was carried out in two cycles, with one cycle consisting of 5 hours of exposure at a temperature of 63°C and a relative humidity of 50% and 3 hours of exposure at a temperature of 30°C and a relative humidity of 98%. Therefore, the radiation exposure to the printed surface was 5.18 ⁇ 10 6 J/m 2 .
  • the test piece subjected to the weather resistance promotion treatment was subjected to a friction test and evaluation in the same manner as in the case of abrasion resistance. 5 (Good): 95% or more of the rubbed image portion remained. 3 (fair, practical lower limit): 80% or more of the rubbed image portion remained. 1 (unacceptable, not suitable for practical use): The residual rate of the rubbed image portion was less than 80%.
  • the recording papers of Examples 1 to 14 were equipped with a print-receiving layer, a liquid-absorbing layer, and a predetermined coating layer, had a liquid-absorbing speed within a specific range, and had a liquid-absorbing amount of at least a specific value. As a result, we were able to achieve both excellent print quality, drying properties, and weather resistance. On the other hand, the recording papers of Comparative Examples 1 to 7 had results that were not suitable for practical use in any one or more evaluation items, and were unable to achieve both print quality, drying performance, and weather resistance.
  • Comparing Examples 1 to 3 there was a tendency for the liquid absorption rate to increase as the basis weight of the print-receiving layer decreased. Additionally, in conjunction with this, in the recording papers of Examples 1 to 3, there was a tendency for the evaluation of bleeding to be better as the liquid absorption rate increased. Comparing Examples 3 and 4, in Example 3, the basis weight of the liquid-absorbing layer was larger and the amount of liquid absorbed was larger. The recording paper of Example 3 had a better evaluation of drying properties than the recording paper of Example 4. Comparing Examples 1, 5, and 6, it is found that the type (average particle size and surface treatment) and composition of the filler used in the print-receiving layer are different, which causes the average pore size of the print-receptor layer to differ and the liquid absorption rate to change.
  • Example 10 has a larger coating amount of the coat layer after drying and a lower liquid absorption rate.
  • the recording paper of Example 1 had a better evaluation of bleeding than the recording paper of Example 10. Comparing Examples 1 and 11, the coating compositions used for the coating layers are different. The recording paper of Example 11 had a better scratch evaluation than the recording paper of Example 1 by using a water-dispersible resin in the coating composition. Comparing Examples 1 and 12, although the number of stretching axes of the support layer was different, the evaluation results for the recording sheets of Examples 1 and 12 were the same. Comparing Examples 11 and 13, the recording paper of Example 13 had a better evaluation of bleeding because the coating composition was composed only of an aqueous binder.
  • the recording paper of Comparative Example 1 has a coating layer containing a pigment, but the coating layer contains a large amount of inorganic filler.
  • the recording paper of Comparative Example 1 had an evaluation result that was not suitable for practical use in terms of abrasion resistance compared to the recording paper of Example 1 in which the coating layer did not contain an inorganic filler.
  • the recording paper of Comparative Example 2 includes a layer containing a vinyl chloride copolymer, and does not include a porous layer such as a coating layer, a print-receiving layer, or a liquid-absorbing layer.
  • the recording paper of Comparative Example 2 had evaluation results that were not suitable for practical use in terms of waviness, blocking, and weather resistance.
  • the recording paper of Comparative Example 3 does not have a porous layer, both the amount of liquid absorbed and the rate of liquid absorption are too small.
  • the recording paper of Comparative Example 2 had evaluation results that were unsuitable for practical use in terms of bleeding and drying.
  • the recording paper of Comparative Example 4 does not have a coat layer.
  • the recording paper of Comparative Example 4 had evaluation results that were not suitable for practical use in terms of density, scratching, and ink fixation.
  • the recording paper of Comparative Example 5 has too little liquid absorption.
  • the recording paper of Comparative Example 5 had an evaluation result that was not suitable for practical use regarding drying.
  • the recording paper of Comparative Example 6 has too little liquid absorption.
  • the recording paper of Comparative Example 6 had evaluation results that were unsuitable for practical use in terms of bleeding and drying.
  • the recording paper of Comparative Example 7 has a liquid absorption rate that is too high.
  • the recording paper of Comparative Example 7 had evaluation results that were not suitable for practical use in terms of density and scratches.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ink Jet (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
PCT/JP2023/023357 2022-06-24 2023-06-23 記録用紙 Ceased WO2023249112A1 (ja)

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JP2001270238A (ja) 2000-01-17 2001-10-02 Oji Paper Co Ltd インクジェット記録媒体
JP2010234677A (ja) 2009-03-31 2010-10-21 Hokuetsu Kishu Paper Co Ltd セミグロス油性インクジェット記録シート
WO2021241489A1 (ja) * 2020-05-25 2021-12-02 株式会社ユポ・コーポレーション 多孔質層を有する積層体、及びインクジェット用紙
WO2022113846A1 (ja) * 2020-11-25 2022-06-02 株式会社ユポ・コーポレーション 積層体、インクジェット用紙及び粘着ラベル
JP2022102227A (ja) 2020-12-25 2022-07-07 エルジー エナジー ソリューション リミテッド 非水系電解液の酸又は水分低減剤、それを含む非水系電解液、及び非水電解液を含むリチウム二次電池、並びに非水系電解液の酸又は水分を低減する方法

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JP2001164017A (ja) 1999-12-07 2001-06-19 Yupo Corp 多孔性樹脂フィルム
JP2001270238A (ja) 2000-01-17 2001-10-02 Oji Paper Co Ltd インクジェット記録媒体
JP2010234677A (ja) 2009-03-31 2010-10-21 Hokuetsu Kishu Paper Co Ltd セミグロス油性インクジェット記録シート
WO2021241489A1 (ja) * 2020-05-25 2021-12-02 株式会社ユポ・コーポレーション 多孔質層を有する積層体、及びインクジェット用紙
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AU2023288301B2 (en) 2026-03-12
AU2023288301A1 (en) 2025-01-02

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