WO2020145404A1 - Papier d'impression, son application et procédé de fabrication de papier d'impression - Google Patents

Papier d'impression, son application et procédé de fabrication de papier d'impression Download PDF

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Publication number
WO2020145404A1
WO2020145404A1 PCT/JP2020/000751 JP2020000751W WO2020145404A1 WO 2020145404 A1 WO2020145404 A1 WO 2020145404A1 JP 2020000751 W JP2020000751 W JP 2020000751W WO 2020145404 A1 WO2020145404 A1 WO 2020145404A1
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Prior art keywords
resin
mass
resin coating
base material
layer
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PCT/JP2020/000751
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English (en)
Japanese (ja)
Inventor
祐太郎 菅俣
亮太 遠山
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株式会社ユポ・コーポレーション
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Priority to JP2020565235A priority Critical patent/JP7213894B2/ja
Publication of WO2020145404A1 publication Critical patent/WO2020145404A1/fr

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    • 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
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • 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
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/04—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps to be fastened or secured by the material of the label itself, e.g. by thermo-adhesion

Definitions

  • the present invention relates to a recording sheet, its use, and a manufacturing method of the recording sheet.
  • recording paper such as printing paper, poster paper, label paper, inkjet recording paper, thermal recording paper, thermal transfer receiving paper, pressure-sensitive transfer recording paper, electrophotographic recording paper, etc.
  • Recording sheets have been proposed.
  • a thermal transfer recording sheet having a resin coating formed by applying a coating liquid containing an olefin copolymer emulsion and drying the coating liquid for improving water resistance and stabilizing the coating film of a recording layer. has been proposed (for example, see Patent Document 1).
  • This recording paper is one in which the olefinic copolymer particles derived from the emulsion in the surface treatment layer are softened by heating and fused with the liquid toner, so that the adhesiveness with the liquid toner or the base material is improved. ..
  • an adhesive film in which an adhesive layer is provided on the back surface of a thermoplastic resin film, and an in-mold label have been proposed (see, for example, Patent Documents 3 and 4).
  • the in-mold label for example, a heat-sealing layer that is heat-sealed to a resin container is provided on the base material layer, and the heat-sealing layer is softened at the product temperature or mold temperature of the preform during biaxial stretch blow molding.
  • an in-mold label in which the label is precisely arranged by adhering it to the surface of a biaxially stretched blow-molded product to improve the adhesiveness with the molded product.
  • -In-mold labels are usually provided with a printing layer by printing letters, designs, etc. on the surface of the base material opposite to the heat-sealing layer.
  • the resin coating made of the emulsion-type thermoplastic resin composition described in Patent Document 1 or 2 has improved water resistance, there is room for improvement in the adhesion between the substrate surface and the resin coating. found.
  • the olefin polymer particles derived from the emulsion are fused to each other by heat and the surface shape of the resin coating is easily deformed, in addition to the anti-blocking property when recording paper is stored at high temperature, UV curing type and heat It was found that there is room for improvement in the gloss change of the printed surface before and after printing with a fixing type or before or after in-mold molding.
  • the present invention has high adhesiveness, especially high water-resistant adhesiveness, little ink transfer failure and decrease in ink adhesiveness of printed matter, and less blocking, little change in paper quality after printing and molding, recording paper, adhesive label,
  • An object is to provide a method for manufacturing an in-mold label and a recording sheet.
  • the present invention is as follows. (1) A recording sheet having a base material made of a thermoplastic resin film, and a resin coating provided on at least one surface of the base material, The value (O/C) of the composition ratio of the number of oxygen atoms (O) and the number of carbon atoms (C) on the surface of the substrate facing the resin coating is 0.01 or more and 0.5 or less,
  • the resin coating contains a resin which is a reaction product of a cationic water-soluble polymer and a silane coupling agent, The content of the silane coupling agent component with respect to 100 parts by mass of the cationic water-soluble polymer component in the resin coating is 15 to 60 parts by mass, In the resin coating, does not contain thermoplastic resin particles,
  • a recording paper, wherein the content of the inorganic filler with respect to 100 parts by mass of the cationic water-soluble polymer component in the resin film is 9 parts by mass or less.
  • the (meth)acrylic polymer or ethyleneimine polymer having the amino group or ammonium salt structure has a primary to tertiary amino group or a primary to tertiary ammonium salt structure.
  • silane coupling agent is an epoxy silane coupling agent.
  • a cationic water-soluble polymer and a silane cup for a laminated resin film having a base material made of a thermoplastic resin film and a surface layer made of a thermoplastic resin composition disposed on at least one surface of the base material.
  • the content of the inorganic filler is 9 parts by mass or less based on 100 parts by mass of the cationic water-soluble polymer, followed by drying.
  • a resin film is formed on the laminated resin film according to the above method.
  • the value (O/C) of the composition ratio of the number of oxygen atoms (O) and the number of carbon atoms (C) on both surfaces of the substrate is 0.01 or more and 0.5 or less
  • the resin coating contains a resin which is a reaction product of a cationic water-soluble polymer and a silane coupling agent,
  • the content of the silane coupling agent component with respect to 100 parts by mass of the cationic water-soluble polymer component in the resin coating is 15 to 60 parts by mass
  • In the resin coating does not contain thermoplastic resin particles
  • Content of the inorganic filler with respect to 100 mass parts of cationic water-soluble polymer components in the said resin film is 9 mass parts or less
  • the adhesive label characterized by the above-mentioned.
  • An in-mold label in which a heat seal layer is provided on one surface of a base material made of a thermoplastic resin film, With a resin coating provided on the surface of the substrate opposite to the heat seal layer, The value (O/C) of the composition ratio of the number of oxygen atoms (O) and the number of carbon atoms (C) on the surface of the substrate facing the resin coating is 0.01 or more and 0.5 or less,
  • the resin coating contains a cationic water-soluble polymer and a resin which is a reaction product of a silane coupling agent,
  • the content of the silane coupling agent component with respect to 100 parts by mass of the cationic water-soluble polymer component in the resin coating is 15 to 60 parts by mass,
  • In the resin coating does not contain thermoplastic resin particles
  • the in-mold label, wherein the content of the inorganic filler with respect to 100 parts by mass of the cationic water-soluble polymer component in the resin coating is 9 parts by mass or less.
  • the resin coating contains a cationic water-soluble polymer and a resin which is a reaction product of a silane coupling agent,
  • the content of the silane coupling agent component with respect to 100 parts by mass of the cationic water-soluble polymer component in the resin coating is 15 to 60 parts by mass,
  • In the resin coating does not contain thermoplastic resin particles,
  • the content of the inorganic filler with respect to 100 parts by mass of the cationic water-soluble polymer component in the resin film is 9 parts by mass or less, and the in-mold label according to (8) above.
  • a method for manufacturing an in-mold label and a recording sheet can be provided.
  • FIG. 3 is a cross-sectional view showing the structure of the recording sheet according to the embodiment of the present invention. It is sectional drawing which shows the structure of the recording paper of other one Embodiment of this invention. It is sectional drawing which shows the structure of the adhesive label of one Embodiment of this invention. It is sectional drawing which shows the structure of the adhesive label of other one Embodiment of this invention. It is sectional drawing which shows the structural example of the in-mold label of one Embodiment of this invention. It is sectional drawing which shows the other structural example of the in-mold label of one Embodiment of this invention.
  • 7 is a photograph of the surface of the resin coating on the recording paper of Comparative Example 3.
  • 3 is a photograph of the surface of the resin coating on the recording paper of Example 1.
  • 5 is a photograph of the surface of the base material used for the recording sheets of Comparative Example 3 and Example 1.
  • (meth)acrylic indicates both acrylic and methacrylic.
  • (co)polymer refers to both homopolymers and copolymers.
  • the numerical range represented by using “to” means a range including the numerical values described before and after “to” as the lower limit value and the upper limit value.
  • the recording paper of the present invention includes a base material and a resin coating provided on at least one surface of the base material.
  • FIG. 1 shows a configuration example of a recording sheet as an embodiment of the present invention.
  • the recording paper 10 includes a base material 1 and a resin coating 3 provided on one surface of the base material 1.
  • the base material and the resin coating provided on at least one surface of the base material are collectively referred to as a recording sheet.
  • a laminated body including the resin coating 3 and the base material 1 is referred to as a recording paper 10.
  • the surface-treated portion of the base material is shown as the surface-treated portion 2 in FIG. 1 as described later.
  • the substrate is made of a thermoplastic resin film, and the value (O/C) of the composition ratio of the number of oxygen atoms (O) and the number of carbon atoms (C) on the surface thereof is within a specific range.
  • ⁇ O/C value of substrate surface >> The value (O/C) of the composition ratio of the number of oxygen atoms (O) and the number of carbon atoms (C) of the surface of the base material on which the resin coating is provided, for example, the surface treatment portion 2 of the recording paper 10 shown in FIG. , 0.01 to 0.5.
  • the base material and the resin coating have high adhesiveness originally, the adhesion between the base material and the resin coating is further improved by providing the resin coating on the surface of the base material having a relatively high oxygen concentration.
  • the value of the composition ratio (O/C) can be controlled within the above range by subjecting the surface of the base material on which the resin coating is provided to surface treatment and activation.
  • Surface treatments that can be used include corona treatment, flame treatment, plasma treatment, glow discharge treatment, ozone treatment and the like, and these treatments can be combined.
  • corona treatment or plasma treatment is preferable, and among plasma treatment, low-temperature plasma treatment causes less damage to the base material, can suppress the generation of low molecular weight compounds, and can obtain good adhesion with the resin coating. , And more preferable.
  • the value of the composition ratio (O/C) is the relative sensitivity of each peak to the respective peak intensity areas of O1s and C1s obtained by XPS (X-ray electron photospectroscopy) measurement on the surface after the surface treatment. It is the abundance ratio (O/C) of the number of oxygen atoms (O) and the number of carbon atoms (C) obtained from the ratio of the multiplied values (for example, "Foundation and application of polymer surface (above)" by Yoshito Yoshito). , Kagaku Doujin, 1986, Chapter 4).
  • the thermoplastic resin used for the base material is polypropylene
  • the molecular formula of polypropylene is (C 3 H 6 ) n , and therefore oxygen atoms should not be present originally. It is considered that oxygen is added to increase the oxygen concentration.
  • the value (O/C) of the composition ratio is 0.01 or more, a sufficient number of functional groups for reaction with the resin film can be obtained and good adhesion can be ensured, and preferably 0.03 or more, It is more preferably 0.05 or more.
  • the equivalent value (O/C) is 0.5 or less, generation of low molecular weight compounds such as formic acid or acetic acid can be suppressed and good adhesion can be ensured, and preferably 0.4 or less, more preferably It is 0.25 or less.
  • the surface corresponding to the outermost layer of the base material is preferably surface-treated.
  • the treatment strength when performing plasma treatment or corona treatment is preferably 3,600 J/m 2 (60 W ⁇ min/m 2 ) or more from the viewpoint of obtaining a sufficient number of functional groups for reaction with the resin coating. It is more preferably at least 4,800 J/m 2 (80 W ⁇ min/m 2 ) and even more preferably at least 6,000 J/m 2 (100 W ⁇ min/m 2 ). Further, the above treatment strength is preferably 24,000 J/m 2 (400 W ⁇ min/m 2 ) or less, and more preferably 18,000 J/m 2 (from the viewpoint of suppressing lowering of the molecular weight of the thermoplastic resin. It is 300 W ⁇ min/m 2 ) or less, more preferably 12,000 J/m 2 (200 W ⁇ min/m 2 ) or less.
  • the base material is a thermoplastic resin film.
  • the thermoplastic resin film By using the thermoplastic resin film as the base material, it is possible to impart mechanical strength such as stiffness, water resistance, chemical resistance, and opacity, if necessary, to a recording paper or a printed matter using the recording paper.
  • thermoplastic resin used for the substrate is not particularly limited, and examples thereof include polyolefin resins such as polyethylene resin, polypropylene resin, polybutene, and 4-methyl-1-pentene (co)polymer; ethylene-vinyl acetate copolymer Polymer, ethylene-(meth)acrylic acid copolymer, metal salt of ethylene-(meth)acrylic acid copolymer (ionomer), ethylene-(meth)acrylic acid alkyl ester copolymer (where the carbon number of the alkyl group is 1
  • Functional group-containing olefin resins such as maleic acid-modified polyethylene and maleic acid-modified polypropylene; aromatic polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), aliphatic polyesters (polybutylene) Polyester resins such as succinate and polylactic acid; polyamide resins such as nylon-6, nylon-6,6, nylon-6,10, nylon
  • polyolefin-based resins or polyester-based resins are preferable because they have high water resistance and transparency and are easy to form a resin film described later.
  • polypropylene resin is more preferable among polyolefin resins, and polyethylene terephthalate is more preferable among polyester resins.
  • the effect of the present invention is remarkable when a polyolefin resin is used.
  • polypropylene resin examples include isotactic homopolypropylene obtained by homopolymerizing propylene, syndiotactic homopolypropylene, propylene as a main component, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl- Examples thereof include polypropylene-based copolymers having various stereoregularities obtained by copolymerizing ⁇ -olefins such as 1-pentene, 1-heptene and 1-octene.
  • the polypropylene-based copolymer may be a binary system or a ternary or higher ternary system, and may be a random copolymer or a block copolymer.
  • the substrate can include fillers to adjust the stiffness, whiteness and opacity of the substrate.
  • the filler include inorganic fillers and organic fillers, which may be used alone or in combination. When the base material containing the filler is stretched, a large number of fine pores having the core of the filler can be formed inside the base material, and whitening, opacity, and weight reduction can be achieved.
  • the inorganic filler examples include heavy calcium carbonate, light calcium carbonate, calcined clay, talc, diatomaceous earth, titanium oxide, zinc oxide, barium sulfate, silicon oxide, magnesium oxide, fatty acids, polymer surfactants and antistatic agents. Inorganic particles which have been surface-treated with the like. Of these, heavy calcium carbonate, light calcium carbonate, calcined clay or talc are preferable because they have good void formability and are inexpensive. From the viewpoint of improving whiteness and opacity, titanium oxide, zinc oxide or barium sulfate is preferable.
  • the organic filler is not particularly limited, but organic particles that are incompatible with the thermoplastic resin, have a melting point or a glass transition temperature higher than that of the thermoplastic resin, and are finely dispersed under the melt-kneading condition of the thermoplastic resin are preferable.
  • thermoplastic resin is a polyolefin resin
  • organic filler polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene, polyamide, polycarbonate, polyethylene sulfide, polyphenylene sulfide, polyimide, polyether ketone, polyether ether
  • organic particles such as a ketone, polymethylmethacrylate, poly-4-methyl-1-pentene, a homopolymer of a cyclic olefin, and a copolymer of a cyclic olefin and ethylene.
  • thermosetting resin such as a melamine resin
  • DSC differential scanning calorimetry
  • the inorganic filler and the organic filler one kind may be selected from the above and used alone, or two or more kinds may be used in combination. When two or more kinds are combined, a combination of an inorganic filler and an organic filler may be used.
  • the average particle size of the inorganic filler and the organic filler is preferably large from the viewpoint of easy mixing with the thermoplastic resin. Further, the average particle size of the inorganic filler and the organic filler, when generating voids inside by stretching to improve opacity and printability, causes problems such as sheet breakage during stretching or strength reduction of the base material. From the viewpoint of making it difficult to make it difficult, it is preferably small. Specifically, the average particle size of the inorganic filler and the organic filler is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, and further preferably 0.5 ⁇ m or more. The average particle diameter is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, still more preferably 15 ⁇ m or less.
  • the average particle diameter of the inorganic filler and the organic filler is the average value when the cut surface of the base material is observed with an electron microscope and the maximum diameter of at least 10 particles is measured. It can be determined as the average dispersed particle diameter when dispersed.
  • the content of the filler in the base material is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more, from the viewpoint of imparting the opacity of the substrate. From the viewpoint of imparting rigidity to the base material and improving handleability of the recording paper, the content of the filler in the base material is preferably 45% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less. It is not more than mass %.
  • the base material may optionally contain known additives as necessary.
  • additives antioxidants, light stabilizers, ultraviolet absorbers, crystal nucleating agents, plasticizers, filler dispersants, slip agents such as fatty acid amides, anti-blocking agents, dyes, pigments, release agents, flame retardants.
  • Known auxiliary agents such as In particular, when durability is required, such as a poster paper which is used outdoors as a recording paper, it is preferable to contain an antioxidant or a light stabilizer.
  • antioxidants examples include sterically hindered phenolic antioxidants, phosphorus antioxidants, amine antioxidants and the like.
  • light stabilizer examples include a sterically hindered amine light stabilizer, a benzotriazole light stabilizer, and a benzophenone light stabilizer.
  • the content of the antioxidant and the light stabilizer is preferably within the range of 0.001 to 1% by mass based on the mass of the base material. Further, the content may be adjusted within a range that does not impair the adhesion with the substrate.
  • the transparency of the base material can be increased by containing a crystal nucleating agent.
  • the crystal nucleating agent include sorbitol-based nucleating agents, phosphoric acid ester metal salt-based nucleating agents, amide-based nucleating agents, aromatic metal salt nucleating agents, and talc.
  • the content of the crystal nucleating agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 1% by mass or less, with respect to the mass of the base material. , 0.5 mass% or less is more preferable, and 0.3 mass% or less is further preferable.
  • thermoplastic resin When a polyester resin is used as the thermoplastic resin, it can be plasticized by using a plasticizer.
  • the plasticizer include carboxylic acid esters such as phthalic acid ester and adipic acid ester; and triacetin.
  • the base material may have a single-layer structure or a multi-layer structure.
  • the base material may have a three-layer structure of a first surface layer/a core layer/a second surface layer, and the core layer may impart rigidity, opacity, lightness, etc. suitable for recording paper.
  • the types of components forming the first surface layer and the second surface layer, the ratios of the components, and the thicknesses may be the same or different.
  • a solid printing layer or a pigment-containing layer as a concealing layer inside the first surface layer or the second surface layer, printing on the other side does not show through when viewed from one side, and double-sided printing is possible.
  • the visibility at the time can also be improved, and a recording paper suitable for poster paper or the like can be obtained.
  • the base material 1 is composed of three layers of a first surface layer 12, a core layer 11, and a second surface layer 13.
  • the thickness of the base material is preferably 30 ⁇ m or more, and more preferably 50 ⁇ m or more, because it is easy to obtain a mechanical strength sufficient for use as a large poster paper to be displayed outdoors.
  • the thickness of the base material is preferably 500 ⁇ m or less, and more preferably 300 ⁇ m or less, because the weight of the recording paper is reduced and the handleability is easily improved.
  • the porosity representing the proportion of the pores in the base material is preferably 10% or more, and more preferably 12% or more from the viewpoint of obtaining opacity. It is preferably 15% or more, more preferably 20% or more. From the viewpoint of maintaining mechanical strength, the porosity is preferably 45% or less, more preferably 44% or less, further preferably 42% or less, and 40% or less. Is particularly preferable.
  • the method of measuring the porosity can be obtained from the area ratio of the pores in a certain area of the cross section of the base material observed with an electron microscope. Specifically, an arbitrary part of the base material is cut out, embedded in an epoxy resin and solidified, and then cut perpendicularly to the surface direction of the base material using a microtome, and the cut surface becomes an observation surface. Attach it to the observation sample stand as shown. Gold or gold-palladium is deposited on the observation surface, the holes are observed at an arbitrary magnification easy to observe with an electron microscope (for example, magnification of 500 to 3000 times), and the observed area is captured as image data. .. Image processing can be performed on the obtained image data by an image analysis device to obtain the area ratio (%) of the void portion to obtain the void ratio (%). In this case, the porosity can be obtained by averaging the measured values at arbitrary 10 or more observations.
  • thermoplastic resin film which is the base material can be usually obtained by mixing the above-mentioned thermoplastic resin with other components contained in the layer and then molding the mixture.
  • the molding method is not particularly limited, and various known molding methods can be used alone or in combination.
  • thermoplastic resin film for example, using a single-layer or multi-layer T die connected to a screw type extruder, cast molding for extruding the molten resin into a sheet by an I die, calendar molding, rolling molding, inflation molding, etc., It can be formed into a film.
  • a thermoplastic resin film may be formed by casting or calendering a mixture of a thermoplastic resin and an organic solvent or oil, and then removing the solvent or oil.
  • the base material may have a single-layer structure or a multi-layer structure.
  • the substrate has a multi-layered structure consisting of the first surface layer/core layer/second surface layer, these layers are molded individually and then the molded layers are laminated.
  • a base material having a multilayer structure may be obtained, or a base material having a multilayer structure may be obtained by collectively molding a plurality of layers.
  • thermoplastic resin film has a multi-layer structure
  • examples of the molding method when the thermoplastic resin film has a multi-layer structure include, for example, a feed block, a multi-layer die method using a multi-manifold, and an extrusion lamination method using a plurality of dice, and each method can be combined. ..
  • the thermoplastic resin film may be a non-stretched film or a stretched film.
  • the stretching method for example, a longitudinal stretching method using a peripheral speed difference of rolls, a lateral stretching method using a tenter oven, a sequential biaxial stretching method combining these, a rolling method, and a simultaneous two-direction method using a combination of a tenter oven and a pantograph.
  • Examples include an axial stretching method and a simultaneous biaxial stretching method using a combination of a tenter oven and a linear motor.
  • a simultaneous biaxial stretching (inflation molding) method in which a molten resin is extruded into a tubular shape by using a circular die connected to a screw type extruder and then air is blown into the extruded resin can be used.
  • thermoplastic resin film has a multi-layer structure
  • the layers may be individually stretched before being laminated, or may be collectively stretched after being laminated. Further, the stretched layers may be laminated and then stretched again.
  • the stretching temperature when performing the stretching is preferably in the range of the glass transition temperature of the thermoplastic resin or higher. Further, the stretching temperature in the case where the thermoplastic resin is a crystalline resin is within the range of not less than the glass transition point of the amorphous portion of the thermoplastic resin and not more than the melting point of the crystalline portion of the thermoplastic resin. Is preferable, and specifically, a temperature lower by 2 to 60° C. than the melting point of the thermoplastic resin is preferable.
  • the stretching speed of the thermoplastic resin film is not particularly limited, but it is preferably within the range of 20 to 350 m/min from the viewpoint of stable stretch molding. Further, the stretching ratio when stretching the thermoplastic resin film can also be appropriately determined in consideration of the characteristics of the thermoplastic resin used and the like. For example, when a thermoplastic resin film containing a propylene homopolymer or a copolymer thereof is stretched in one direction, the stretching ratio is usually about 1.2 times or more, preferably 2 times or more. It is usually 12 times or less, preferably 10 times or less. On the other hand, the stretching ratio in the case of biaxial stretching is an area stretching ratio of usually 1.5 times or more, preferably 10 times or more, while usually 60 times or less, preferably 50 times or less. is there.
  • the stretching ratio is usually 1.2 times or more, preferably 2 times or more, while it is usually 10 times or less. , Preferably 5 times or less.
  • the stretching ratio in the case of biaxial stretching is an area stretching ratio of usually 1.5 times or more, preferably 4 times or more, while it is usually 20 times or less, preferably 12 times or less.
  • the stretching ratio when stretching the substrate is within the above range, the desired porosity is obtained and the opacity is likely to be improved. Further, the thermoplastic resin film is less likely to be broken, and stable stretch molding tends to be performed.
  • the resin coating in the present invention contains a resin which is a reaction product of a cationic water-soluble polymer and a silane coupling agent, and optionally an inorganic filler, and does not contain thermoplastic resin particles.
  • the resin film in the present invention is usually a film on which characters, images and the like can be recorded by printing, writing instruments and the like.
  • the resin coating contains a cationic water-soluble polymer and a silane coupling agent on at least one surface of the base material and the surface having the above-mentioned composition ratio value (O/C value) within a specific range. Then, after coating with an aqueous solution containing an inorganic filler as necessary and containing no thermoplastic resin particles (hereinafter, sometimes referred to as a "coating solution for forming a resin film"), it is dried. Can be formed.
  • the reaction rate of the cationic water-soluble polymer and the silane coupling agent may not be 100%.
  • the resin coating may contain an unreacted cationic water-soluble polymer and a silane coupling agent in addition to the resin which is a reaction product (reaction product).
  • the coating liquid for forming a resin film can be obtained by mixing the cationic water-soluble polymer, the silane coupling agent and the aqueous solvent and then stirring the mixture.
  • the coating liquid for forming a resin film in the present invention may be obtained by mixing an aqueous solution of a cationic water-soluble polymer and an aqueous solution of a silane coupling agent.
  • the cationic water-soluble polymer (unreacted component), the silane coupling agent (unreacted component), and the reaction product of the cationic water-soluble polymer and the silane coupling agent in the resin coating are time-of-flight secondary ion mass spectrometry.
  • TOF-SIMS Time-of-Flight Secondary Ion Mass Spectrometry
  • the resin coating containing the resin which is the reaction product contains olefin-based copolymer particles derived from the emulsion as compared with the resin coating formed by applying the coating liquid containing the olefin-based copolymer emulsion.
  • olefin-based copolymer particles derived from the emulsion There is little unevenness on the surface. Therefore, a recording paper having high gloss and transparency and an excellent appearance can be obtained. Since the resin coating does not peel off easily, fuzzing is unlikely to occur.
  • this resin coating has sufficient adhesiveness with a homopolymer thermoplastic resin such as homopolypropylene, which generally has low adhesiveness with other resins, it is used for the object to which the resin coating is provided. The adhesiveness to the target can be enhanced regardless of the type of thermoplastic resin used.
  • the resin coating since the resin coating has high adhesion to the substrate, the resin coating can be directly provided on the substrate, but since the adhesion is further improved by the surface treatment, the surface treatment is performed on the recording paper of the present invention. It is provided on the base material surface.
  • the resin coating is suitable not only for ink used in general printing methods such as offset printing method and UV flexographic printing method using oil-based ink or UV ink, but also for UV inkjet printing method or dry electrophotographic printing method.
  • the liquid toner used in the wet electrophotographic printing method is used, sufficiently high adhesion, particularly water-resistant adhesion, can be obtained. Therefore, it is possible to provide a recording sheet having printability for various printing methods including the wet electrophotographic printing method.
  • the recording paper has high water resistance and can provide a printed matter in which ink or toner is less likely to fall off.
  • the cationic water-soluble polymer is contained as a resin which is a reaction product with the silane coupling agent.
  • the resin coating may contain unreacted cationic water-soluble polymer. Due to the polar group of the cationic water-soluble polymer, the resin coating is chemically bonded to the ink or toner (specifically, bonding by ionic bond) and dispersion bonding (specifically, bonding by Van der Waals force). It is estimated that the transferability and adhesion of the ink or toner to the resin coating are improved.
  • the water solubility of the cationic water-soluble polymer may be such that the aqueous medium containing the cationic water-soluble polymer is in a solution state when preparing the coating liquid for forming the resin film.
  • Examples of the cationic water-soluble polymer that can be used include (meth)acrylic polymers having an amino group or ammonium salt structure or ethyleneimine polymers, water-soluble polymers having a phosphonium salt structure, water-soluble polymers such as polyvinylpyrrolidone and polyvinyl alcohol. Examples thereof include vinyl polymers obtained by cationizing a polymer by modification, and one of these can be used alone or in combination of two or more. Of these, a (meth)acrylic polymer or an ethyleneimine polymer having an amino group or ammonium salt structure is preferable from the viewpoint of transferability and adhesion of the ink or toner to the resin film.
  • the (meth)acrylic polymer or ethyleneimine polymer having an amino group or ammonium salt structure is a primary to tertiary amino group or a primary to tertiary ammonium salt from the viewpoint of safety. It preferably has a structure, more preferably has a secondary to tertiary amino group or a secondary to tertiary ammonium salt structure, and has a tertiary amino group or a tertiary ammonium salt structure.
  • a primary to tertiary amino group or a secondary amino group or A primary to tertiary ammonium salt structure is preferred, a primary to secondary amino group or a primary to secondary ammonium salt structure is more preferred, and a primary amino group or primary The ammonium salt structure is more preferable.
  • the ethyleneimine-based polymer has a high affinity with inks or toners used in various printing methods, particularly with ultraviolet curable inks used in flexographic printing methods, and therefore the adhesion between the resin coating and the ink is high. Is improved, which is preferable.
  • ethyleneimine-based polymer examples include polyethyleneimine, poly(ethyleneimine-urea), ethyleneimine adduct of polyamine polyamide, alkyl modified products, cycloalkyl modified products, aryl modified products, allyl modified products, aralkyl modified products thereof, Examples thereof include benzyl modified products, cyclopentyl modified products, cycloaliphatic hydrocarbon modified products, glycidol modified products, and hydroxides thereof.
  • Examples of the modifier for obtaining the modified product include methyl chloride, methyl bromide, n-butyl chloride, lauryl chloride, stearyl iodide, oleyl chloride, cyclohexyl chloride, benzyl chloride, allyl chloride and cyclopentyl chloride.
  • the ethyleneimine-based polymer represented by the following general formula (I) is preferable from the viewpoint of transferability and adhesion of the ink or toner used for printing, especially the ultraviolet curable ink.
  • R 1 and R 2 are each independently a hydrogen atom; a linear or branched alkyl group having 1 to 12 carbon atoms; an alkyl group having an alicyclic structure having 6 to 12 carbon atoms. Alternatively, it represents an aryl group.
  • R 3 is a hydrogen atom; an alkyl group or an allyl group having a carbon number of 1 to 18 which may contain a hydroxy group; an alkyl group having an alicyclic structure having a carbon number of 6 to 12, which may contain a hydroxy group. Alternatively, it represents an aryl group.
  • m represents an integer of 2 to 6, and n represents an integer of 20 to 3000.
  • (meth)acryl-based polymer or ethyleneimine-based polymer having an amino group or ammonium salt structure commercially available products can also be used.
  • commercially available (meth)acrylic polymers having an amino group or ammonium salt structure include polyment (manufactured by Nippon Shokubai Co., Ltd.) and the like.
  • commercially available ethyleneimine-based polymers include Epomin (manufactured by Nippon Shokubai Co., Ltd.) and Polymin SK (manufactured by BASF).
  • the weight average molecular weight of the (meth)acrylic polymer having an amino group or ammonium salt structure or the ethyleneimine polymer has a weight average molecular weight of 10,000 or more from the viewpoint of improving the adhesiveness with a substrate and the adhesiveness with ink or the like. It is preferable that it is 20,000 or more. On the other hand, the weight average molecular weight is preferably 1,000,000 or less, and more preferably 500,000 or less. In the present invention, the weight average molecular weight and the number average molecular weight of the resin can be obtained by converting the values measured by GPC (Gel Permeation Chromatography) method into polystyrene.
  • GPC Gel Permeation Chromatography
  • the resin for forming a resin film may contain a polymer other than the cationic water-soluble polymer, as long as the excellent effect of the resin film is not significantly impaired.
  • the silane coupling agent is contained as a resin which is a reaction product with the cationic water-soluble polymer.
  • the resin coating may contain an unreacted silane coupling agent.
  • the silane coupling agent contributes to the development of the function of enhancing the adhesiveness between the base material and the resin coating.
  • the silane coupling agent has a functional group having high reactivity with an organic material, and this functional group causes a cross-linking reaction between the thermoplastic resin of the base material and the cationic water-soluble polymer to form a bond with the base material. It is presumed that the adhesiveness is improved and the infiltration of water between the base material and the resin coating is prevented. Therefore, it is presumed that peeling of the resin film, and eventually peeling of the ink or toner from the printed matter is suppressed to enhance the scratch resistance.
  • the silane coupling agent causes a cross-linking reaction between the cationic water-soluble polymers to form a network structure, and this network structure enhances transferability and adhesion of the ink or toner. Furthermore, it is estimated that the silane coupling agent improves the water resistance by cross-linking reaction with the cationic water-soluble polymer and increasing the hydrophilic component (polar resin component) of the cationic water-soluble polymer to a higher molecular weight. To be done.
  • silane coupling agent a silane coupling agent having a group capable of reacting with a cationic water-soluble polymer, for example, various functional groups such as silanol groups can be used.
  • the group that reacts with the cationic water-soluble polymer means a group that reacts with the atom or atomic group of the cationic water-soluble polymer to form a bond.
  • the bond formed by the reaction may be any of covalent bond, ionic bond, hydrogen bond and the like, and is not particularly limited.
  • silane coupling agent having at least one functional group other than the silanol group can be used.
  • the silane coupling agent has a silanol group that undergoes a condensation reaction with the thermoplastic resin of the base material, while a functional group other than the silanol group is contained in the resin coating and has a structure of an amino group or an ammonium salt structure (meth)acrylic polymer. ) It is presumed that the acrylic acid residue or the amino group in the ethyleneimine-based polymer undergoes a condensation reaction to carry out a crosslinking reaction.
  • the silane coupling agent causes a silanol group to undergo a condensation reaction with a (meth)acrylic acid residue in a (meth)acrylic polymer having an amino group or an ammonium salt structure or an amino group in an ethyleneimine-based polymer, while a silanol group is present. It is presumed that the cross-linking reaction is carried out when functional groups other than those are bonded to the thermoplastic resin of the base material with high affinity.
  • the content of the alkoxysilyl group or the silanol group hydrolyzed by the alkoxysilane group in the silane coupling agent is 25% from the viewpoint of firmly adhering the base material and the resin coating and firmly adhering the resin coating and the ink or toner. It is preferably not less than 50%, more preferably not less than 50%, and more preferably not more than 75%.
  • the content of the reactive functional group other than the alkoxysilyl group or the silanol group hydrolyzed by the alkoxysilane group in the silane coupling agent is preferably 25% or more, while it is preferably 75% or less, and 50% or less. Is more preferable.
  • silane coupling agent examples include, for example, epoxy silane coupling agents, vinyl silane coupling agents, (meth)acrylic silane coupling agents, amino silane coupling agents, and ureido silane coupling agents. , Mercapto-based silane coupling agents, and isocyanate-based silane coupling agents.
  • epoxy-based silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and the like. Of these, 3-glycidoxypropyltrimethoxysilane is preferable from the viewpoint of adhesion with ink or toner.
  • vinyl-based silane coupling agents examples include vinyltrimethoxysilane and vinyltriethoxysilane.
  • Examples of the (meth)acrylic silane coupling agent include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, Examples thereof include 3-acryloxypropyltrimethoxysilane.
  • amino-based silane coupling agents examples include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane.
  • Silane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2 -Aminoethyl-3-aminopropyltrimethoxysilane and the like can be mentioned.
  • Examples of the ureido silane coupling agent include 3-ureidopropyltriethoxysilane and the like.
  • Examples of the mercapto-based silane coupling agent include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.
  • Examples of the isocyanate-based silane coupling agent include 3-isocyanatepropyltriethoxysilane.
  • silane coupling agents examples include KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1003, KBE-1003, KBM-502, manufactured by Shin-Etsu Chemical Co., Ltd.
  • KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBE-585, KBM- 802, KBM-803, KBE-9007 all are trade names
  • Z-6043, Z-6040, Z-6519, Z-6300, Z-6030, Z-6011, Z- made by Toray Dow Corning Co., Ltd. 6094, Z-6062 both are trade names or the like can be used.
  • epoxy-based silane coupling agents from the viewpoint of adhesion with ink or toner, epoxy-based silane coupling agents, amino-based silane coupling agents, mercapto-based silane coupling agents or isocyanate-based silane coupling agents are preferable, and epoxy-based silane coupling agents are preferred. Agents or amino-based silane coupling agents are more preferred, and epoxy-based silane coupling agents are even more preferred. From the viewpoint of ease of cross-linking reaction with the primary to tertiary amino groups of the cationic water-soluble polymer, epoxy-based silane coupling agents, ureido-based silane coupling agents or isocyanate-based silane coupling agents are preferred. Epoxy silane coupling agents are more preferable.
  • a vinyl silane coupling agent or a (meth)acrylic silane coupling agent is preferable.
  • metal oxide particles such as an inorganic filler are present on the surface of the base material
  • an amino-based silane coupling agent and a ureido-based silane coupling agent are used from the viewpoint of strongly bonding to the particles and enhancing the adhesion to the base material. It is preferable to use an agent or a mercapto-based silane coupling agent.
  • the silane coupling agent can control the hydrolysis rate depending on the type of the alkoxysilyl group, and this property is utilized to prevent deterioration of the coating liquid for resin film formation due to self-condensation of the silane coupling agent. It can be suppressed and stability over time can be increased. From the viewpoint of high solubility in water, easy preparation of a coating liquid for forming a resin film, and high stability over time, an epoxy silane coupling agent is preferable as the silane coupling agent, and among them, 3-glycidoxypropyltrimethoxysilane is preferred.
  • the alkoxysilane group in the molecule of the silane coupling agent has been changed to a silanol group by hydrolysis, and the silanol group on the thermoplastic resin film, which is the base material, is particularly surface treated.
  • the adhesiveness between the base material and the resin coating is improved by chemically bonding a functional group such as a hydroxy group or a carboxy group on the applied thermoplastic resin film with a hydrogen bond.
  • the silanol groups undergo a condensation reaction to improve the cohesive force of the resin coating itself and also improve the physical strength of the resin coating itself.
  • the unreacted silane coupling agent contained in the resin film forming coating liquid is not too much. If the amount of unreacted silane coupling agent is too large, the resin coating obtained may become hard, fail to follow the bending of the recording paper, and may be cracked or the ink or toner may peel off. In addition, it is preferable that the amount of unreacted cationic water-soluble polymer is small in that the resin film has excellent water resistance. From these viewpoints, the amount of the silane coupling agent in the resin coating forming coating liquid is 15 parts by mass or more, and preferably 17 parts by mass or more, based on 100 parts by mass of the cationic water-soluble polymer.
  • the cationic water-soluble polymer component (the total amount of the unreacted component and the reacted component in the resin coating).
  • the recording paper according to the present invention when used in a wet electrophotographic printing method using a liquid toner, the adhesion with the toner is sufficient, the water resistance is high, and the toner falls off. It can be a difficult printed matter.
  • the content of the inorganic filler in the resin coating forming coating liquid is 9 parts by mass or less based on 100 parts by mass of the cationic water-soluble polymer. That is, the content of the inorganic filler is 9 parts by mass or less.
  • the content of the inorganic filler is 9 parts by mass or less with respect to 100 parts by mass of the cationic water-soluble polymer, it is possible to effectively prevent white spots in the printed part due to the unevenness of the resin coating due to the inorganic filler, and to achieve a high ink transfer rate. Can be realized.
  • the content of the inorganic filler is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, further preferably less than 0.1 parts by mass, and particularly preferably no inorganic filler. That is, the content of the inorganic filler in the resin coating in the present invention is 9 parts by mass or less, preferably 5 parts by mass or less, and more preferably 3 parts by mass or less with respect to 100 parts by mass of the cationic water-soluble polymer component. %, more preferably less than 0.1 part by mass, and particularly preferably 0 part by mass (not included).
  • the content of the inorganic filler in the resin coating forming coating liquid is 100% by mass of the cationic water-soluble polymer.
  • the amount is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, and further preferably 0.3 part by mass or more. That is, the content of the inorganic filler in the resin coating in the present invention is preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more with respect to 100 parts by mass of the cationic water-soluble polymer component. , 0.3 parts by mass or more is more preferable.
  • the coating liquid for forming a resin film may contain other auxiliary components such as an antistatic agent, a cross-linking accelerator, an anti-blocking agent, a pH adjusting agent and a defoaming agent, if necessary. That is, the resin coating may contain other auxiliary components such as an antistatic agent, a cross-linking accelerator, an anti-blocking agent, a pH adjuster and an antifoaming agent, if necessary.
  • the resin film preferably contains an antistatic agent from the viewpoints of preventing dust adhesion due to electrification and conveyance failure during printing, and improving handleability as recording paper.
  • an antistatic agent polymer type antistatic agents are preferable from the viewpoint of reducing surface contamination due to bleed-out.
  • the polymer type antistatic agent is not particularly limited, and a cationic type, anionic type, amphoteric type or nonionic type antistatic agent can be used, and these can be used alone or in combination of two or more kinds. ..
  • Examples of cationic antistatic agents include antistatic agents having an ammonium salt structure, a phosphonium salt structure, and the like.
  • Examples of the anionic antistatic agent include antistatic agents having a structure of an alkali metal salt such as sulfonic acid, phosphoric acid and carboxylic acid (lithium salt, sodium salt, potassium salt, etc.).
  • the anion type antistatic agent may be an antistatic agent having a structure of an alkali metal salt such as acrylic acid, methacrylic acid or (anhydrous) maleic acid in the molecular structure.
  • amphoteric antistatic agent examples include an antistatic agent containing both a cationic antistatic agent and an anionic antistatic agent in the same molecule.
  • amphoteric antistatic agent examples include betaine antistatic agents.
  • nonionic antistatic agent examples include an ethylene oxide polymer having an alkylene oxide structure and a polymer having an ethylene oxide polymerization component in its molecular chain.
  • Other antistatic agents include polymeric antistatic agents having boron in the molecular structure.
  • a cationic type antistatic agent is preferable, a nitrogen-containing polymer type antistatic agent is more preferable, an antistatic agent having an ammonium salt structure is further preferable, and a tertiary or quaternary ammonium salt is preferable.
  • An acrylic resin having a structure is particularly preferable, and an acrylic resin having a quaternary ammonium salt structure is most preferable.
  • commercially available products such as Saftomer ST-1000, ST-1100, ST-3200 (trade name) manufactured by Mitsubishi Chemical Corporation can be used.
  • a compound that reacts with the silane coupling agent may be used, or a compound that does not react may be used.
  • a compound that does not react with the silane coupling agent is preferable from the viewpoint of easily exhibiting the antistatic performance.
  • the amount of the antistatic agent contained in the resin coating forming coating liquid is preferably 0.01 parts by mass or more, and more preferably 1 part by mass or more, relative to 100 parts by mass of the cationic water-soluble polymer. More preferably, it is more preferably 2 parts by mass or more.
  • the amount of the antistatic agent contained in the resin film-forming coating liquid is preferably 45 parts by mass or less, and 40 parts by mass with respect to 100 parts by mass of the cationic water-soluble polymer.
  • the content is more preferably not more than 35 parts by mass, still more preferably not more than 35 parts by mass.
  • Crosslinking accelerator examples include phosphoric acid, sulfuric acid, citric acid, succinic acid and the like.
  • the thickness of the resin coating is preferably 0.01 to 5 ⁇ m. From the viewpoint of stably forming a uniform resin coating, the thickness of the resin coating is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and further preferably 0.03 ⁇ m or more. preferable. Further, from the viewpoint of effectively suppressing bleed-out of additives and low-molecular compounds contained in the base material and having good ink transferability even after being stored in a high temperature and high humidity environment, the resin coating should be relatively thick. Is preferred. Specifically, it is preferably 0.1 ⁇ m or more, more preferably 0.25 ⁇ m or more, and further preferably 0.3 ⁇ m or more.
  • the thickness of the resin coating is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and more preferably 1.5 ⁇ m or less from the viewpoint of effectively preventing the adhesion of the resin coating to the substrate from being reduced due to cohesive failure. Is more preferable.
  • the resin coating is preferably relatively thin. Specifically, it is preferably 1.0 ⁇ m or less, more preferably 0.8 ⁇ m or less, still more preferably 0.5 ⁇ m or less.
  • thermoplastic resin particles are particles derived from an emulsion of a thermoplastic resin such as an olefin-based copolymer, which is dispersed in a dispersion medium in a coating liquid for forming a resin film.
  • a thermoplastic resin such as an olefin-based copolymer
  • the adhesion to the toner, especially the liquid electrophotographic printing liquid toner using the liquid toner is improved, and even when the thermoplastic resin used for the base material contains homopolypropylene, Also improves the adhesion.
  • the fact that the resin coating does not contain thermoplastic resin particles and the surface uniformity of the resin coating can be confirmed by observation with a scanning electron microscope or the like.
  • the olefin-based copolymer emulsion is an emulsion obtained by dispersing or emulsifying an olefin-based copolymer in the form of fine particles in an aqueous dispersion medium, as disclosed in WO 2014/092142.
  • a nonionic or cationic surfactant, a nonionic or cationic water-soluble polymer, or the like may be used as a dispersant.
  • Examples of the olefin-based copolymer to be dispersed or emulsified in the emulsion include an olefin-based copolymer containing a structural unit containing a carboxy group or a salt thereof as a copolymerization component.
  • a copolymer of an olefinic monomer and an unsaturated carboxylic acid or an anhydride thereof and a salt thereof can be exemplified.
  • ethylene-(meth)acrylic acid copolymers examples include ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylic acid ester copolymers, alkali (earth) metal salts of ethylene-(meth)acrylic acid copolymers, ethylene-( (Meth)acrylic acid ester-maleic anhydride copolymer, (meth)acrylic acid graft polyethylene, ethylene-vinyl acetate copolymer, maleic anhydride graft polyethylene, maleic anhydride graft ethylene-vinyl acetate copolymer, maleic anhydride Grafted (meth)acrylic acid ester-ethylene copolymer, maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-propylene copolymer, maleic anhydride grafted ethylene-propylene-butene copolymer, maleic anhydride grafted ethylene-butene Examples thereof include cop
  • the olefin-based copolymer particles in the emulsion are usually particles having a volume average particle size of about 0.2 to 3 ⁇ m.
  • the volume average particle diameter means a volume average particle diameter measured by using a laser diffraction particle size distribution measuring device (manufactured by Shimadzu Corporation: SALD-2200).
  • thermoplastic resin particles other than the olefin-based copolymer particles for example, acrylic-based copolymer particles and urethane-based copolymer particles
  • the recording paper of the present invention has a resin coating on the surface of a substrate that has been surface-treated (that is, the value of the composition ratio (O/C) of the surface is within a specific range).
  • the resin coating may be formed not only on the surface but also on both surfaces of the base material.
  • both surfaces of the base material may be subjected to the above surface treatment, and a resin coating film may be formed on each surface.
  • the recording paper of the present invention may have an underlayer having an indentation elastic modulus of 50 to 1200 MPa between the base material and the resin coating.
  • the value (O/C) of the composition ratio of the number of oxygen atoms (O) and the number of carbon atoms (C) on the surface of the underlayer (that is, the surface facing the resin coating) is 0.01 to 0.5. It is more preferable to set it within the range.
  • the indentation elastic modulus of the underlayer is measured from the surface side of the underlayer by a nanoindentation test.
  • the stress generated at the interface between the resin coating and the substrate surface is dispersed (relaxed), and strong adhesion is provided between the substrate and resin coating. it can.
  • the water resistance is improved, and the peeling of the printing layer is greatly reduced even in an environment wet with water or in a high humidity environment, so that the durability of the recording paper is improved.
  • Such recording paper is particularly useful as an in-mold label for liquid containers such as beverages.
  • the indentation elastic modulus of the underlayer is preferably 70 MPa or more, more preferably 100 MPa or more, from the viewpoint of reducing blocking due to an increase in the adhesive force of the underlayer during the manufacturing process, and the adhesiveness to the ink or toner in the printing layer is From the viewpoint of suppressing the decrease, 1000 MPa or less is preferable, and 900 MPa or less is more preferable.
  • the indentation elastic modulus of the underlayer can be adjusted within the above range by controlling the type, content, thickness, viscoelasticity, additives, etc. of the thermoplastic resin used.
  • the indentation elastic modulus can be adjusted to be low by using a tackifier, various additives such as wax described below, and an olefin resin having a low surface free energy. Further, the indentation elastic modulus can be adjusted to be high by increasing the thickness.
  • thermoplastic resin that can be used for the underlayer is not limited as long as the effects of the present invention are not impaired, and the same thermoplastic resin as the base material can be used.
  • thermoplastic resins listed as the material for the base material a polyolefin resin or a functional group-containing olefin resin is preferable, and a polyolefin resin is more preferable, from the viewpoint of excellent film processability.
  • polyolefin resins polyethylene resins and polypropylene resins are preferable from the viewpoints of chemical resistance, processability and low cost.
  • the undercoat layer may contain additives such as tackifiers, waxes, lubricants, etc., if necessary, within a range that does not impair the object of the present invention.
  • the underlayer preferably contains a tackifier.
  • tackifiers that can be used in the underlayer include petroleum resins such as aliphatic copolymers, aromatic copolymers, aliphatic-aromatic copolymers and alicyclic copolymers, and terpene-based resins. Examples thereof include resins, terpene-phenolic resins, rosin-based resins, alkylphenol-based resins, xylene-based resins, and hydrogenated products thereof.
  • the content of the tackifier in the underlayer is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, while 10.0% by mass or less is preferable and 8% by mass or less is more preferable.
  • the thickness of the underlayer is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, from the viewpoint of enhancing the adhesion between the base material and the resin coating. Further, the thickness of the recording paper is preferably 500 ⁇ m or less from the viewpoints of reducing the weight of the recording paper itself and facilitating the handling. Therefore, in order to adjust the range, the thickness of the underlayer is preferably 100 ⁇ m or less, and 50 ⁇ m or less. The following is more preferable, and 30 ⁇ m or less is further preferable.
  • the resin film in the recording paper of the present invention is a recordable film.
  • Examples of the recording method include recording with printing and writing instruments.
  • the recording paper of the present invention can be printed by various methods including offset printing, letterpress printing, gravure printing, flexographic printing, and screen printing, and has excellent ink adhesion of the obtained printed matter, and water resistance. Because of its excellent weather resistance and durability, it is suitable as a paper for posters used indoors and outdoors, stickers used indoors and outdoors, labels for frozen food containers, industrial product nameers (labels with usage instructions, precautions), etc. Used for.
  • the recording paper of the present invention is particularly excellent in toner adhesion of a printed matter obtained by a wet electrophotographic printing method using a liquid toner, and is suitable for use in small lot printing and variable information printing. .. Further, the recording paper of the present invention is excellent not only in the printed matter but also in the laminated printed matter, and therefore, it is suitably used as a paper for menus, photo books, posters, stickers and the like used indoors and outdoors.
  • a printing layer such as ink is formed on the surface of the resin coating of the recording paper.
  • the printing layer 5 is formed on the surface of the resin coating 3 of the recording paper.
  • a protective layer may be further provided on the printed layer.
  • the protective layer is located on the outermost surface on the resin coating 3 side on which the printed layer is provided.
  • the recording sheet of the present invention may have the structure illustrated in FIG. 1 as described above.
  • the resin film 3 is not only a good print receiving layer, but also has excellent adhesion to the substrate.
  • the surface of the base material 1 between the resin coating 3 and the resin coating 3 is surface-treated, and the value (O) of the composition ratio of the number of oxygen atoms (O) and the number of carbon atoms (C) on the surface-treated surface (O It is presumed that the adhesion between the base material 1 and the resin coating 3 is further improved by the surface treatment so that /C) has a specific value.
  • the recording paper of the present invention has high adhesiveness, particularly high water-resistant adhesiveness, less ink transfer failure and lower ink adhesiveness of printed matter, and less change in paper quality after blocking and printing, as shown in Examples described later. Estimated to be recording paper.
  • the adhesive label of the present invention includes a base material, a resin coating on both surfaces of the base material, and an adhesive layer.
  • FIG. 3 shows a configuration example of an adhesive label as an embodiment of the present invention.
  • the adhesive label 40 includes a base material 1 and a resin coating film 31 and a resin coating film 32 disposed on both surfaces of the base material 1. Further, the adhesive label 40 includes an adhesive layer 4 arranged on the surface opposite to the base material 1 with respect to the resin coating film 32 arranged on one surface of the base material 1.
  • FIG. 4 a schematic diagram showing the structure of the pressure-sensitive adhesive label when the substrate has a multi-layer structure of a three-layer structure is shown in FIG. 4, the same components as those in FIG. 3 are designated by the same reference numerals.
  • the base material 1 is composed of three layers of a first surface layer 12, a core layer 11, and a second surface layer 13.
  • the base material and the resin coatings provided on both surfaces of the base material are collectively referred to as recording paper.
  • the laminated body including the resin coating 31, the base material 1 and the resin coating 32 is also referred to as a recording sheet 10.
  • the adhesive label 40 is a stack of the recording paper 10 and the adhesive layer 4.
  • the surface-treated portion of the base material is shown as the surface-treated portion 21 or the surface-treated portion 22 in FIGS. 3 and 4.
  • the base material is a thermoplastic resin film.
  • the thermoplastic resin, the filler, and the other components contained in the thermoplastic resin film include the same as those described in the section of (Recording paper), and preferable materials and preferable contents are also the same. ..
  • the porosity of the base material, the O/C value of the base material surface, and the manufacturing method are as described in the section of (Recording paper), and the preferred embodiments are also the same.
  • the layer structure and thickness of the base material are also as described in the section of (Recording paper), and the preferred embodiments are also the same.
  • the thickness of the substrate is preferably 30 ⁇ m or more, and more preferably 50 ⁇ m or more, because it is easy to obtain a mechanical strength sufficient for use as an adhesive label.
  • the thickness of the substrate is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, from the viewpoint of reducing the weight of the label itself and improving the handleability.
  • the resin coatings provided on both sides of the base material contain a resin which is a reaction product of a cationic water-soluble polymer and a silane coupling agent, and do not contain thermoplastic resin particles.
  • a resin film can be formed by using an aqueous solution containing a cationic water-soluble polymer and a silane coupling agent and containing no thermoplastic resin particles. Specifically, it can be formed by the same method as the method of manufacturing the resin coating described in the section (Recording paper).
  • the types of components constituting the resin coating on both surfaces of the substrate and the proportions of the components may be the same or different.
  • the cationic water-soluble polymer, silane coupling agent, inorganic filler, and other components are all the same as those described in the section of (Recording paper).
  • the thickness of the resin coating is also as described in the section of (Recording paper), and the preferred embodiment is also the same.
  • the resin film is a film on which characters, images and the like can be recorded by printing, writing instruments and the like, and is also a layer having good adhesiveness to an adhesive layer described later.
  • the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer include rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives and the like.
  • the rubber-based pressure-sensitive adhesive include polyisobutylene rubber, butyl rubber, and a mixture thereof, or a tackifier such as abietic acid rosin ester, a terpene/phenol copolymer, or a terpene/indene copolymer in these rubber-based pressure-sensitive adhesives.
  • Compounded substances and the like can be mentioned.
  • the acrylic adhesive for example, 2-ethylhexyl acrylate/n-butyl acrylate copolymer, 2-ethylhexyl acrylate/ethyl acrylate/methyl methacrylate copolymer having a glass transition point of ⁇ 20° C. or lower
  • the silicone-based pressure-sensitive adhesive include an addition-curable pressure-sensitive adhesive that uses a platinum compound or the like as a catalyst, a peroxide-curable pressure-sensitive adhesive that is cured with benzoyl peroxide, and the like.
  • the form of the pressure-sensitive adhesive include various forms such as a solution type, an emulsion type and a hot melt type.
  • the adhesive layer may be formed by directly applying an adhesive on the surface of the recording sheet, or after forming an adhesive layer by applying an adhesive on the surface of a release sheet to be described later, the adhesive layer of the recording sheet is formed. It may be applied to the surface.
  • the adhesive coating device include a bar coater, a blade coater, a comma coater, a die coater, an air knife coater, a gravure coater, a lip coater, a reverse coater, a roll coater, and a spray coater.
  • An adhesive layer is formed by smoothing a coating film of an adhesive or the like applied by these coating devices, if necessary, and performing a drying step.
  • the coating amount of the pressure-sensitive adhesive is not particularly limited, but the solid content after drying is preferably 3 g/m 2 or more, more preferably 10 g/m 2 or more, and 60 g/m 2 or less. It is preferably 40 g/m 2 or less, and more preferably 40 g/m 2 or less. If necessary, the adhesive layer may be provided with a release sheet on the surface opposite to the surface on which the adhesive layer contacts the recording paper.
  • the release sheet is provided on the surface of the pressure-sensitive adhesive layer that does not come into contact with the recording paper, if necessary, for the purpose of protecting the pressure-sensitive adhesive layer surface.
  • the release sheet high-quality paper or kraft paper as it is, high-quality paper or kraft paper calendered, resin coated, film laminated, or glassine paper, coated paper, plastic film, etc. treated with silicone Etc. can be used. Among these, it is preferable to use the silicone-treated surface of the adhesive layer, which has good peelability from the adhesive layer.
  • the resin film is a recordable film.
  • Examples of the recording method include recording with printing and writing instruments.
  • the pressure-sensitive adhesive label of the present invention can be used as a recording sheet that can be attached to other articles by having the pressure-sensitive adhesive layer via the resin coating.
  • the printing method is the same as that described in the section of (Recording paper).
  • a protective layer may be provided to protect the printed layer (printed surface), and the material of the protective layer is the same as described above.
  • the adhesive label of the present invention can have the structure illustrated in FIG. 3, as described above.
  • the resin film 31 is not only a good print receiving layer, but also has excellent adhesion to the substrate. Further, the surface of the base material 1 between the resin coating film 31 and the resin coating 31 is surface-treated, and the value (O) of the composition ratio of the number of oxygen atoms (O) and the number of carbon atoms (C) on the surface-treated surface (O It is presumed that the adhesion between the base material 1 and the resin coating 31 is further improved by the surface treatment such that /C) has a specific value.
  • the adhesive label of the present invention has high adhesiveness, particularly high water-resistant adhesiveness, little ink transfer failure and decrease in ink adhesiveness of printed matter, and causes adhesive residue. Moreover, it is presumed that the adhesive label will have little change in paper quality after blocking and printing.
  • the in-mold label of the present invention has a base material made of a thermoplastic resin film, a heat seal layer provided on one surface of the base material, and a resin coating film provided on the other surface of the base material. ..
  • the resin coating is provided on the surface of the base material opposite to the heat-sealing layer, and the composition ratio (O/C) of the number of oxygen atoms (O) and the number of carbon atoms (C) is within a specific range. Does not contain thermoplastic resin particles.
  • the in-mold label of the present invention may further have a printed layer formed on the resin film by printing.
  • Adhesion to ink or toner, especially water-resistant adhesion, is enhanced by the resin coating. Further, since the resin coating has high adhesiveness to any kind of thermoplastic resin, the resin coating alone can enhance the adhesiveness to the base material, but the number of oxygen atoms (O When the value (O/C) of the composition ratio of () and the number of carbon atoms (C) is in a specific range, the adhesion between the base material and the resin coating is further enhanced. As a result, the water resistance of the entire in-mold label is improved, and excellent printability and in-mold molding suitability are obtained.
  • the resin coating in the present invention does not contain thermoplastic resin particles, there is little blocking due to heat fusion of the thermoplastic resin particles and change in gloss of the resin coating surface.
  • the in-mold label of the present invention is further heat-treated from the viewpoint of improving the adhesion between the PET resin container and the heat seal layer. It is preferable to have a resin coating on the surface of the seal layer opposite to the base material. From the viewpoint of enhancing the adhesion between the heat seal layer and the resin coating, the value (O/C) of the composition ratio of the number of oxygen atoms (O) and the number of carbon atoms (C) on the surface of the heat seal layer on which the resin coating is provided is It is preferably 0.01 to 0.5.
  • the PET resin has a lower melt viscosity than polyethylene resin or the like, and a stretch blow method is used in which the PET resin is heated to near the softening point instead of the melting point during molding.
  • a low-melting resin is used for the heat-sealing layer so that it can be sufficiently heat-sealed even under such a low-temperature molding condition.
  • the resin coating has high adhesiveness with the low-melting resin, and as described later, a polar group is used. Since it contains a cationic water-soluble polymer having, the adhesiveness with the PET resin is also high. That is, the resin coating further enhances the adhesion between the heat seal layer and the PET resin container, and improves the water resistance.
  • the in-mold label is less likely to be peeled off when wet with water, and is particularly useful for a liquid container such as a beverage.
  • the two resin coatings in this case may be the same or different in the type and proportion of the components constituting each resin coating as long as the effect of the present invention can be obtained.
  • FIG. 5 shows a configuration example of the in-mold label 50a as one embodiment of the present invention.
  • the in-mold label 50 a has the base material 1, the heat seal layer 6, and the resin coating 31.
  • the heat seal layer 6 is provided on one surface of the base material 1.
  • the surface 21 of the base material 1 on the side opposite to the heat seal layer 6 is a surface where the value (O/C) of the composition ratio of the number of oxygen atoms (O) and the number of carbon atoms (C) is within the above specific range. ..
  • the resin coating 31 is provided on the surface 21.
  • the in-mold label 50a may have the printed layer 5 on the resin coating 31 by printing.
  • FIG. 6 shows a configuration example of an in-mold label 50b suitable for a PET resin container. 6, the same components as those of the in-mold label 50a of FIG. 5 are designated by the same reference numerals.
  • the in-mold label 50b has the heat-sealing layer 6 on one surface of the base material 1 similarly to the in-mold label 50a.
  • the surface 21 of the base material 1 on the opposite side of the heat seal layer 6 and the surface 22 of the heat seal layer 6 on the opposite side of the base material 1 are values of the composition ratio of the number of oxygen atoms (O) and the number of carbon atoms (C) ( O/C) is within the above specified range.
  • the in-mold label 50 b has the resin coating 31 on the surface 21 of the base material 1 and also has the resin coating 32 on the surface 22 of the heat seal layer 6.
  • the printed layer 5 is provided on the resin film 31.
  • the base material and the resin coating on the base material may be collectively referred to as recording paper.
  • the laminated body of the base material 1 and the resin coating 3 is the recording paper 10.
  • the laminated body of the base material 1 and the resin coating film 31 is the recording paper 10.
  • the base material is a thermoplastic resin film.
  • the base material can impart mechanical strength such as stiffness, water resistance, chemical resistance, and opacity to the in-mold label, if necessary.
  • the thermoplastic resin, the filler, and the other components contained in the thermoplastic resin film include the same as those described in the section of (Recording paper), and preferable materials and preferable contents are also the same. ..
  • the porosity of the base material and the O/C value of the surface of the base material are as described in the section of (Recording paper), and the preferred embodiments are also the same.
  • the base material may have a single-layer structure, but preferably has a multi-layer structure, and more preferably has a multi-layer structure in which each layer has a unique property.
  • the base material may have a three-layer structure of a first surface layer/a core layer/a second surface layer, and the core layer may impart rigidity, opacity, and lightness suitable for an in-mold label.
  • the first surface layer and the second surface layer may be the same or different in the types of components constituting the two layers and the ratio of the components.
  • the first surface layer is a layer having a high affinity for the base layer
  • the second surface layer is a layer having a high affinity for the heat seal layer.
  • the base material may be a non-stretched film or a stretched film.
  • the substrate has a multilayer structure, it is possible to combine the layers of the unstretched film and the layer of the stretched film, or it is possible to combine the stretched films having the same or different stretching axis numbers in each layer, but at least one of them Is preferably stretched.
  • the thickness of the base material is preferably 20 ⁇ m or more, and more preferably 40 ⁇ m or more, from the viewpoint of suppressing the generation of wrinkles during printing and facilitating the fixing to a regular position when inserting the mold.
  • the thickness of the base material is preferably 200 ⁇ m or less, and more preferably 150 ⁇ m or less from the viewpoint of suppressing the decrease in strength due to the thinning of the container at the label boundary when the in-mold label is provided on the container. Therefore, the thickness of the substrate is preferably 20 to 200 ⁇ m, more preferably 40 to 150 ⁇ m.
  • the resin coating provided on one surface of the base material is formed using an aqueous solution containing a cationic water-soluble polymer and a silane coupling agent, and containing no thermoplastic resin particles.
  • the cationic water-soluble polymer, silane coupling agent, inorganic filler, and other components are all the same as those described in the section of (Recording paper). The same applies to preferable materials and preferable contents.
  • the thickness of the resin coating is also as described in the section of (Recording paper), and the preferred embodiment is also the same.
  • the resin coating film of the present invention has high adhesion to the base material, the resin coating film can be provided on the base material as it is, but since the adhesion is further enhanced by the surface treatment, the surface-treated base material surface It is provided in. As a result, it is possible to provide an in-mold label excellent in moldability, in which ink or toner does not drop off even after in-mold molding.
  • the resin film has high adhesion to the heat seal layer described later and also high adhesion to the PET resin. Therefore, particularly when the in-mold label of the present invention is applied to a PET resin container, it is preferable to form a resin film also on the surface of the heat seal layer.
  • the resin coating provided on the base material and the resin coating provided on the heat-sealing layer may be the same or different in the type and content of each constituent, as long as the effects of the present invention can be obtained. Good.
  • the in-mold label may also have an underlayer between the resin coating and the substrate.
  • the physical properties, composition, thickness, etc. of the underlayer are as described above.
  • the heat seal layer imparts excellent adhesiveness to the resin container to the in-mold label.
  • an in-mold label is provided inside the mold so that the container and the heat seal layer face each other.
  • the heat seal layer is melted by the heat at the time of in-mold molding and heat-sealed to the surface of the container.
  • In-mold molding methods include a direct blow method using a raw resin parison and a stretch blow method using a raw resin preform.
  • the direct blow method is a method in which a raw material resin is heated to a temperature equal to or higher than a melting point to be melted to form a parison, and air is applied to the parison in a mold to expand the parison to form a container.
  • the stretch blow method is a method of forming a container by heating a preform formed in advance from a raw material resin to near the softening point of the raw material resin, stretching the preform with a rod in a mold, and expanding by applying air pressure. Is.
  • PET resin container Since a polyethylene terephthalate (PET) resin container has a low melt viscosity of PET and it is difficult to maintain the shape of the parison in a molten state, it is usually formed by a stretch blow method of heating not to the melting point but to the vicinity of the softening point. Therefore, thermal fusion of the in-mold label to the PET resin container is also performed in the heating temperature range near the softening point, not the melting point of the PET resin.
  • the in-mold label for a PET resin container molded in this way has a heat treatment from the viewpoint of sufficiently melting and improving the adhesiveness to the container even under a low-temperature molding condition as compared with the direct blow method of heating to a melting point or higher.
  • the sealing layer is preferably a thermoplastic resin film having a low melting point of 60 to 130°C. Since the lower the melting point, the more sufficient adhesiveness can be obtained with a smaller amount of heat, the melting point of the thermoplastic resin used for the heat-sealing layer is more preferably 110° C. or lower, and further preferably 100° C. or lower. Further, since the higher the melting point is, the easier the film is formed and the sticking to the roll during the film production is easily reduced, the melting point of the thermoplastic resin is more preferably 70° C. or higher, and further preferably 75° C. or higher. Therefore, the melting point of the thermoplastic resin is more preferably 70 to 110°C, further preferably 75 to 100°C. The melting point can be measured by a differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • Polyethylene ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid alkyl ester copolymer, ethylene-methacrylic acid alkyl ester copolymer having an alkyl group having 1 to 8 carbon atoms, ethylene- A polyethylene resin having a melting point of 60 to 130° C., such as a metal salt of methacrylic acid copolymer such as Zn, Al, Li, K and Na, is preferable.
  • low density or medium density polyethylene having a crystallinity of 10 to 60% and a number average molecular weight of 10,000 to 40,000 measured by X-ray method, or linear polyethylene is preferable.
  • thermoplastic resin of the heat seal layer use a copolymer containing a polar structural unit and a nonpolar structural unit. Is preferred. Examples of such a copolymer include those described in International Publication No. 2018/062214.
  • thermoplastic resin In the heat seal layer, one kind of thermoplastic resin may be used alone, or two or more kinds of thermoplastic resin may be mixed and used. In the latter case, from the viewpoint of suppressing peeling, It is preferable that the two or more resins to be mixed have high compatibility.
  • the heat-sealing layer is, if necessary, a tackifier, a plasticizer, an antifogging agent, a lubricant, an antiblocking agent, an antistatic agent, an antioxidant, a heat stabilizer, a light stabilizer, a weather resistance stabilizer, an ultraviolet absorber.
  • Additives generally used in the field of polymers such as
  • the heat seal layer may have a single-layer structure or a multi-layer structure.
  • the thickness of the heat-sealing layer is preferably 0.5 ⁇ m or more, more preferably 0.7 ⁇ m or more, still more preferably 1 ⁇ m or more, from the viewpoint of enhancing the adhesiveness.
  • the thickness is preferably 10 ⁇ m or less, more preferably 3 ⁇ m or less, and further preferably 2 ⁇ m or less. Therefore, the thickness of the heat-sealing layer having a single layer structure is preferably 0.5 to 10 ⁇ m, more preferably 0.7 to 3 ⁇ m, and further preferably 1 to 2 ⁇ m.
  • the composition of the number of oxygen atoms (O) and the number of carbon atoms (C) on the surface of the heat-sealing layer on which the resin coating is provided is improved from the viewpoint of enhancing the adhesion to the resin coating.
  • the ratio value (O/C) is preferably 0.01 to 0.5.
  • the value (O/C) of the composition ratio is more preferably 0.03 or more, further preferably 0.05 or more, more preferably 0.4 or less, and further preferably 0.25 or less.
  • the value (O/C) of the composition ratio in the heat seal layer can be controlled within the above range by the same surface treatment as that for the substrate.
  • the resin film in the present invention is a recordable layer.
  • the recording method include recording with printing and writing instruments.
  • the in-mold label of the present invention can be used as a recording sheet that can be attached to other articles by having a heat seal layer on the surface opposite to the resin coating.
  • the printing method is the same as that described in the section of (Recording paper).
  • a protective layer may be provided to protect the printed layer (printed surface), and the material of the protective layer is the same as described above.
  • the thickness of the in-mold label is preferably 25 ⁇ m or more, more preferably 45 ⁇ m or more, from the viewpoint of suppressing wrinkles and the like of the label. Further, from the viewpoint of suppressing the strength reduction due to the thinning of the container at the label boundary portion when the in-mold label is provided on the container, the same thickness is preferably 200 ⁇ m or less, and more preferably 150 ⁇ m or less. Therefore, the thickness of the in-mold label is preferably 25 to 200 ⁇ m, more preferably 45 to 150 ⁇ m.
  • the gloss of the resin coating surface of the in-mold label of the present invention is preferably capable of maintaining the gloss of the substrate surface.
  • the glossiness it is possible to use a 75-degree specularity measured according to JIS P 8142:1993.
  • the resin coating in the present invention is also preferable in that the change in glossiness before and after in-mold molding is small.
  • the haze of the in-mold label before the printing layer is provided is preferably low in that the transparency of the label is easily improved. In addition, it is preferable that the haze is high in terms of ease of production.
  • the lower limit of the haze of the in-mold label of the present invention is preferably 1%, more preferably 2%.
  • the upper limit of haze is preferably 10%, more preferably 5%.
  • the haze refers to a value measured using a haze meter (cloudiness meter) according to JIS K7136:2000. The haze can be adjusted by the type of the base material, the thickness of the base material, the shape of the base material surface, the type of material used for the resin coating, the thickness of the resin coating, and the like.
  • the in-mold label of the present invention is particularly excellent in adhesion to liquid toner used in a wet electrophotographic printing method, and is suitable for applications such as small lot printing and variable information printing.
  • the method for producing a recording paper of the present invention comprises a thermoplastic resin film so that the value (O/C) of the composition ratio of the number of oxygen atoms (O) and the number of carbon atoms (C) on the surface becomes a specific value.
  • the surface-treated base material contains a cationic water-soluble polymer and a silane coupling agent, and optionally contains an inorganic filler in an amount of 9 parts by mass or less based on 100 parts by mass of the cationic water-soluble polymer component, Further, the method is characterized by including a step of forming a resin film on the base material by applying an aqueous solution containing no thermoplastic resin particles and then drying. In this way, it is possible to manufacture a recording paper in which the resin coating is formed on at least one surface of the base material.
  • the recording paper of the present invention comprises a coating liquid for forming a resin film, which comprises a thermoplastic resin film, and has a composition ratio value (O/C) of the number of oxygen atoms (O) and the number of carbon atoms (C) on the surface.
  • a coating liquid for forming a resin film which comprises a thermoplastic resin film, and has a composition ratio value (O/C) of the number of oxygen atoms (O) and the number of carbon atoms (C) on the surface.
  • the recording paper according to the present invention can be manufactured roll-to-roll to improve productivity. Since the thickness of the resin coating can be adjusted by the coating amount of the coating liquid for forming the resin coating, maintain the printability and reduce the thickness of the resin coating to produce the target recording paper. You can
  • the coating liquid for forming a resin film can be prepared by dissolving each component such as a cationic water-soluble polymer and a silane coupling agent in an aqueous solvent.
  • the aqueous solvent may be water, or may contain water as a main component and a water-soluble organic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, ethyl acetate, toluene and xylene.
  • Having water as a main component means that 50% by mass or more of the whole is water.
  • the use of an aqueous solvent facilitates process control and is preferable from the viewpoint of safety.
  • the total amount of the cationic water-soluble polymer and the silane coupling agent contained in the resin coating forming coating liquid is preferably 0.5% by mass or more based on the total amount of the resin coating forming coating liquid, It is more preferably 10% by mass or more. Further, the total amount of the cationic water-soluble polymer and the silane coupling agent contained in the coating liquid for forming a resin film is preferably 40% by mass or less, and more preferably 25% by mass or less.
  • the coating of the coating liquid for forming a resin film and the drying of the coating film according to the present invention may be performed in-line or offline according to the molding of the substrate.
  • the coating of the coating liquid for forming a resin film can be performed using a coating device such as a die coater, a bar coater, a roll coater, a lip coater, a gravure coater, a spray coater, a blade coater, a reverse coater, and an air knife coater. ..
  • the coating amount of the coating liquid for forming a resin film can be appropriately adjusted in consideration of the thickness of the resin film after drying, the concentration of contained components, and the like.
  • a drying device such as a hot air blower or an infrared dryer can be used. It is presumed that by drying the coating film, the dehydration condensation reaction by the silane coupling agent in the coating film proceeds, and a resin that is a reaction product of the silane coupling agent and the cationic water-soluble polymer is produced.
  • the adhesive label of the present invention can be produced by providing an adhesive layer on the surface of the recording paper obtained by the method described in the section (Method for producing recording paper). More specifically, both surfaces of the base material are surface-treated so that the value (O/C) of the composition ratio of the number of oxygen atoms (O) and the number of carbon atoms (C) on each surface becomes a specific value. To do. Next, a resin coating forming coating solution is applied to both surfaces of the base material and dried to form a resin coating film on both surfaces of the base material, thereby producing a recording paper.
  • the composition, coating method, drying method and the like of the resin film forming coating solution are the same as those described in the section of (Recording paper manufacturing method). It may be formed by directly applying an adhesive on the surface of the obtained recording paper, or by applying an adhesive on the surface of the release sheet described above to form an adhesive layer, and then applying this to the surface of the recording paper. May be applied to.
  • the method for producing an in-mold label of the present invention includes the step of performing a surface treatment on the other surface of the substrate having the heat-sealing layer provided on one surface, and the above-described step on the surface-treated surface of the substrate.
  • a step of forming the resin film by applying a resin film-forming coating liquid and then drying.
  • the in-mold label of the present invention can be manufactured roll-to-roll to improve productivity. Since the thickness of the resin coating can be adjusted by the coating amount of the coating liquid for forming the resin coating, it is possible to manufacture the intended in-mold label by maintaining the printability and reducing the thickness of the resin coating. it can.
  • Examples of the method for laminating the heat seal layer on the substrate include a coextrusion method, an extrusion laminating method, a film laminating method, and a coating method.
  • the coextrusion method supplies the thermoplastic composition for the base material to the multilayer die, and the thermoplastic composition for the heat seal layer (there may be a plurality of each), in order to laminate and extrude in the multilayer die, Lamination is performed simultaneously with molding.
  • the extrusion laminating method the base material is first molded, the molten thermoplastic composition for the heat seal layer is laminated on the base material, and the nipping is performed with a roll while cooling.
  • the base material for example, the base material of the recording paper described above
  • the heat-sealing layer are formed into films, respectively, and the two are bonded together via a pressure-sensitive adhesive.
  • a polar resin layer is provided by a coating method on a base material having a non-polar resin layer laminated on one surface of the base material by the above method.
  • the coating method include a solvent coating method and a water-based coating method. Among these methods, the coextrusion method is preferable from the viewpoint of firmly adhering each layer.
  • extrusion molding (cast molding) with a T die, inflation molding with an O die, calender molding with a rolling roll, etc. can be mentioned.
  • a film forming method for a base material having a multilayer structure the above-mentioned coextrusion method, extrusion laminating method and the like can be used.
  • the base material and the heat seal layer may be a non-stretched film or a stretched film.
  • the stretching method for example, a longitudinal stretching method using a peripheral speed difference of rolls, a lateral stretching method using a tenter oven, a sequential biaxial stretching method combining these, a rolling method, and a simultaneous two-direction method using a combination of a tenter oven and a pantograph.
  • Examples include an axial stretching method and a simultaneous biaxial stretching method using a combination of a tenter oven and a linear motor.
  • a simultaneous biaxial stretching (inflation molding) method in which a molten resin is extruded into a tubular shape by using a circular die connected to a screw type extruder and then air is blown into the extruded resin can be used.
  • the base material and heat seal layer may be stretched individually before laminating each layer, or may be stretched collectively after laminating. Further, the stretched layers may be laminated and then stretched again.
  • the stretching temperature when performing the stretching is preferably in the range of the glass transition temperature of the thermoplastic resin or higher. Further, the stretching temperature in the case where the thermoplastic resin is a crystalline resin is within the range of not less than the glass transition point of the amorphous portion of the thermoplastic resin and not more than the melting point of the crystalline portion of the thermoplastic resin. Is preferable, and specifically, a temperature lower by 2 to 60° C. than the melting point of the thermoplastic resin is preferable.
  • the stretching speed is not particularly limited, but it is preferably within the range of 20 to 350 m/min from the viewpoint of stable stretch molding.
  • the stretching ratio when stretching the thermoplastic resin film can also be appropriately determined in consideration of the characteristics of the thermoplastic resin used and the like. For example, when a thermoplastic resin film containing a propylene homopolymer or a copolymer thereof is stretched in one direction, the stretching ratio is usually about 1.2 times or more, preferably 2 times or more. It is usually 12 times or less, preferably 10 times or less.
  • the stretching ratio in the case of biaxial stretching is an area stretching ratio and is usually 1.5 times or more, preferably 10 times or more, while it is usually 60 times or less, preferably 50 times or less. is there. When the stretching ratio is within the above range, the desired porosity can be obtained and the opacity can be easily improved. Further, the thermoplastic resin film is less likely to be broken, and stable stretch molding tends to be performed.
  • ⁇ Surface treatment> The above-mentioned surface treatment is applied to the surface of the base material opposite to the heat seal layer, and the value (O/C) of the composition ratio of the number of oxygen atoms and the number of carbon atoms is adjusted to the range of 0.01 to 0.5.
  • Examples of the surface treatment method include the method described in the section ⁇ O/C value of substrate surface>.
  • the surface treatment may be performed before providing the heat-sealing layer on the surface of the base material or after providing the heat-sealing layer.
  • the surface treatment may be performed after providing the heat seal layer.
  • Examples of the method for forming the resin film on the surface of the substrate which has been subjected to the surface treatment include the same as those described in the section (Method for producing recording paper), including the composition of the coating liquid for forming the resin film.
  • the surface treatment of the heat seal layer and the formation of the resin coating may be performed in the same manner as when the resin coating is provided on the surface of the base material.
  • a printing layer can be provided by printing on the resin film provided on the base material side.
  • a protective layer is provided on the outermost surface of the substrate opposite to the heat-sealing layer by applying a coating solution for the protective layer.
  • the in-mold label of the present invention is processed into a required shape and size by cutting or punching.
  • the cutting or punching can be performed before printing, but is preferably performed after printing for ease of work.
  • ⁇ Container with label> By in-molding the resin container with the in-mold label of the present invention, a labeled container having the in-mold label attached to the surface of the resin container can be obtained.
  • By adjusting the O/C value on the surface of the base material and the resin film provided thereon it is possible to provide a labeled container with less peeling of the ink or toner after printing or molding.
  • Further, by providing the resin coating on the heat-sealing layer it is possible to provide a labeled container that has high adhesiveness to a PET resin which is different from the base material and has less peeling.
  • the material of the resin container in which the in-mold label of the present invention can be used is not particularly limited, and for example, it can be used in a resin container of polyethylene resin, polypropylene resin, PET resin or the like.
  • the color of the container may be transparent or may be a natural color that does not include a coloring material such as a pigment or a dye, or may be an opaque color due to the coloring material or coloring.
  • the cross-sectional shape of the body of the container may be a perfect circle, an ellipse, or a rectangle. When the body has a rectangular cross-sectional shape, it is preferable that the corners have curvature. From the viewpoint of strength, the cross section of the body is preferably a perfect circle or an elliptical shape close to a perfect circle, and more preferably a perfect circle.
  • thermoplastic resin film was measured by XPS (X-ray electron spectroscopy) under the following devices and measurement conditions, and the ratio of the values obtained by multiplying the peak sensitivity areas of O1s and C1s by the relative sensitivities of the respective peaks to oxygen and carbon.
  • the abundance ratio (O/C) was determined (see, for example, Yoshito Yoshito, “Fundamentals and Applications of Polymer Surfaces (I)", Kagaku Dojin, 1986, Chapter 4).
  • thermoplastic resin film of the base material conforms to JIS B0601:2003, and is a three-dimensional roughness measuring device (manufactured by Kosaka Laboratory Ltd., trade name: SE). -3AK) and an analyzer (manufactured by Kosaka Laboratory Ltd., trade name: SPA-11).
  • the thickness ( ⁇ m) of each thermoplastic resin film when the substrate has a multi-layer structure is the same as that of the sample placed on a glass plate after cooling the sample to be measured to a temperature of ⁇ 60° C. or lower with liquid nitrogen.
  • a razor blade (made by Chic Japan Co., Ltd., trade name: Proline Blade) is applied at a right angle to cut a sample for cross-section observation, and the obtained sample is a scanning electron microscope (made by JEOL Ltd.). , Trade name: JSM-6490) is used to observe the cross section, the boundary line of each thermoplastic resin composition is discriminated from the composition appearance, and the thickness ratio of each layer to the total thickness of the thermoplastic resin film is observed. Calculated by multiplying.
  • the glossiness (°) of the resin coating surface of the recording paper of the present invention is preferably capable of maintaining the glossiness of the substrate surface.
  • As the glossiness a 75-degree specular glossiness measured according to JIS P 8142:1993 was used.
  • Preparation of resin composition ⁇ Preparation of resin composition (a)> Propylene homopolymer (manufactured by Nippon Polypro Co., Ltd., trade name: Novatec PP FY-4, MFR (230° C., 2.16 kg load): 5 g/10 min, melting point: 165° C.) 80 parts by mass, heavy calcium carbonate ( A resin composition (a) consisting of 20 parts by mass of Bihoku Powder Co., Ltd., trade name: Softon 1800, average particle size 1.2 ⁇ m (measurement method: air permeation method) was prepared.
  • Resin composition consisting of 100 parts by mass of propylene homopolymer (manufactured by Nippon Polypro Corporation, trade name: Novatec PP FY-4, MFR (230° C., 2.16 kg load): 5 g/10 minutes, melting point: 165° C.) c) was prepared.
  • composition (d) Resin consisting of 100 parts by mass of propylene-ethylene random copolymer (manufactured by Nippon Polypro Co., Ltd., trade name: Novatec PP FW4B, MFR (230° C., 2.16 kg load): 6.5 g/10 minutes, melting point: 140° C.) Composition (d) was prepared.
  • ⁇ Cationic water-soluble polymer (A2) aqueous solution A commercially available polyethyleneimine aqueous solution (BASF Japan, trade name: Polymine SK), which is a secondary amino group-containing polymer, was used as an aqueous solution of the cationic water-soluble polymer (A2).
  • ⁇ Silane coupling agent (B)> A commercially available silane coupling agent, 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-403) was used as the silane coupling agent (B).
  • ⁇ Antistatic agent (C)> In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas introduction tube, 35 parts by mass of dimethylaminoethyl methacrylate, 20 parts by mass of ethyl methacrylate, 20 parts by mass of cyclohexyl methacrylate and 25 parts of stearyl methacrylate 25 were used. Parts by mass, 150 parts by mass of ethyl alcohol, and 1 part by mass of 2,2'-azobisisobutyronitrile were added. After substituting the system with nitrogen, a polymerization reaction was carried out at a temperature of 80° C. for 6 hours under a nitrogen stream.
  • ⁇ Olefin-based copolymer emulsion> Using a twin-screw extruder (manufactured by Japan Steel Works Co., Ltd., device name: TEX30HSS), melt kneading and emulsification of the raw material resin were carried out by the following procedure to prepare an olefin-based copolymer emulsion. Specifically, pelletized ethylene-methacrylic acid-acrylic acid ester copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., trade name: Nucrel N035C) as an olefin-based copolymer was supplied to the extruder from the hopper. ..
  • the mixture was melted and kneaded under the conditions of a screw rotation speed of 230 rpm and a cylinder temperature of 160 to 250°C.
  • the above cationic water-soluble polymer (A1) was introduced from the injection port in the middle portion of the cylinder of the extruder so that the amount of the cationic water-soluble polymer (A1) was 5 parts by mass relative to 100 parts by mass of the olefin copolymer. It was continuously supplied to emulsify and disperse the olefin-based copolymer. Then, it was extruded from the extruder outlet to obtain a milky white aqueous dispersion.
  • Ion-exchanged water was added to this aqueous dispersion to adjust the total concentration of the cationic water-soluble polymer (A1) and the olefin-based copolymer to 45% by mass to obtain an olefin-based copolymer emulsion.
  • the volume average particle diameter of the olefinic copolymer particles in the emulsion was measured by a laser diffraction type particle size distribution analyzer (manufactured by Shimadzu Corporation, instrument name: SALD-2000), and it was 1.0 ⁇ m.
  • ⁇ Crosslinking agent> An epichlorohydrin adduct of polyamine polyamide (manufactured by Japan PMC, trade name: WS-4082) was used as a cross-linking agent other than the silane coupling agent.
  • Preparation of coating liquid for resin film formation ⁇ Preparation Example 1 of coating liquid (a) for forming resin film> 20 parts by mass of the cationic water-soluble polymer (A2) (converted to the solid content), 20 parts by mass of the silane coupling agent (B), and antistatic to 100 parts by mass of the cationic water-soluble polymer (A1) (converted to the solid content).
  • An aqueous solution containing 20 parts by mass of the agent (C) and 2 parts by mass of the inorganic filler was prepared as a coating liquid (a) for forming a resin film.
  • the content of the silane coupling agent (B) with respect to the cationic water-soluble polymer A (including A1 and A2) was 17% by mass.
  • ⁇ Preparation example 2 of coating liquid (b) for forming resin film > 25 parts by mass of the cationic water-soluble polymer (A2) (as solid content), 30 parts by mass of the silane coupling agent (B), and antistatic for 100 parts by mass of the cationic water-soluble polymer (A1) (as solid content).
  • An aqueous solution containing 20 parts by mass of the agent (C) was prepared as a coating liquid (b) for forming a resin film.
  • the content of the silane coupling agent (B) with respect to the cationic water-soluble polymer A (including A1 and A2) was 24% by mass.
  • An aqueous solution containing 20 parts by mass of the inhibitor (C) and 5 parts by mass of the inorganic filler was prepared as a coating liquid (c) for forming a resin film.
  • the content of the silane coupling agent (B) with respect to the cationic water-soluble polymer A (including A1 and A2) was 32% by mass.
  • ⁇ Preparation Example 4 of coating liquid (d) for forming resin film> As shown in Table 2, 5 parts by mass of the cationic water-soluble polymer (A2), 5 parts by mass of the silane coupling agent (B), and an antistatic agent with respect to 100 parts by mass of the olefin-based copolymer emulsion (solid content conversion). An aqueous solution containing 5 parts by mass of (C) and 2 parts by mass of an inorganic filler was prepared as a coating liquid (d) for forming a resin film. In the coating liquid (d) for forming a resin film, the content of the silane coupling agent (B) with respect to the cationic water-soluble polymer A (including A1 and A2) was 100% by mass.
  • Preparation example 5 of coating liquid (e) for forming resin film> Resin coating except that in the coating liquid (d) for forming resin coating, 5 parts by mass of a cross-linking agent was used instead of 5 parts by mass of the silane coupling agent (B) in the olefin copolymer emulsion.
  • a resin film-forming coating liquid (e) was prepared in the same manner as the forming coating liquid (d).
  • the content of the silane coupling agent (B) with respect to the cationic water-soluble polymer A (including A1 and A2) was 0% by mass.
  • the coating liquid for forming a resin film (b) is the same as the coating liquid for forming a resin film (b) except that the coating liquid for forming a resin film (b) contains 12 parts by mass of an inorganic filler.
  • the content of the silane coupling agent (B) with respect to the cationic water-soluble polymer A (including A1 and A2) was 24% by mass.
  • An aqueous solution containing 20 parts by mass of the agent (C) and 0.1 part by mass of an inorganic filler was prepared as a coating liquid (g) for forming a resin film.
  • the content of the silane coupling agent (B) with respect to the cationic water-soluble polymer A (including A1 and A2) was 45% by mass.
  • the content of the silane coupling agent (B) is 60 parts by mass
  • the content of the antistatic agent (C) is 15 parts by mass
  • the content of the inorganic filler is 1.
  • a coating solution (i) for forming a resin film was prepared in the same manner as the coating solution (h) for forming a resin film, except that the amount was 0 part by mass.
  • the content of the silane coupling agent (B) with respect to the cationic water-soluble polymer A (including A1 and A2) was 60% by mass.
  • the content of the silane coupling agent (B) is 65 parts by mass
  • the content of the antistatic agent (C) is 15 parts by mass
  • the content of the inorganic filler is 1.
  • a coating liquid (j) for forming a resin film was prepared in the same manner as the coating liquid (h) for forming a resin film, except that the amount was 0 part by mass.
  • the content of the silane coupling agent (B) with respect to the cationic water-soluble polymer A (including A1 and A2) was 65% by mass.
  • Tables 2 below show Preparation Examples 1 to 10 of the coating liquids (a) to (j) for forming a resin film.
  • the resin composition (a) is melted and kneaded by an extruder set at 250° C., and then extruded into a sheet to obtain the first surface of the resin layer formed of the resin composition (a) previously formed. Laminated on the opposite second side.
  • a laminated sheet was obtained in which three layers of the resin layer composed of the resin composition (c), the resin layer composed of the resin composition (a), and the resin layer composed of the resin composition (a) were laminated. ..
  • the three-layer laminated sheet is cooled to 60° C., the laminated sheet is heated to about 150° C. by using a tenter oven and stretched 8.5 times in the transverse direction, and then further heated to 160° C. to be heat treated. went.
  • This substrate has a three-layer structure, and the resin layer made of the uniaxially stretched resin composition (c) corresponds to the first surface layer, and the layer made of the biaxially stretched resin composition (a) is The core layer and the layer composed of the uniaxially stretched resin composition (a) correspond to the second surface layer.
  • the above resin composition (c) is melt-kneaded by two extruders set at 250° C., then extruded into a sheet shape, and laminated on the first surface of the resin layer comprising the above resin composition (b). At the same time, it was laminated on the second surface to obtain a laminated sheet in which three layers were laminated.
  • the mixture is cooled to 60° C., the ears are slit, and the thickness is 100 ⁇ m, the resin composition of each layer (c/b/c), the thickness of each layer (20 ⁇ m/60 ⁇ m/20 ⁇ m), the number of axes of stretching of each layer (unstretched/2
  • a base material (axial/non-stretched) was obtained.
  • This base material has a three-layer structure, and the resin layer made of the biaxially stretched resin composition (b) corresponds to the core layer and is made of the resin composition (c) laminated on the first surface of the core layer.
  • the resin layer corresponds to the first surface layer, and the layer made of the resin composition (c) laminated on the second surface of the core layer corresponds to the second surface layer.
  • ⁇ Anti-blocking property 1> The recording paper obtained in each of the examples and comparative examples was wound in a roll shape and stored for 1 day in an atmosphere of a temperature of 40° C. and a relative humidity of 50%, without blocking when pulled out from the roll. Whether the smooth withdrawal was possible or not, the winding blocking was evaluated by the following method. ⁇ : There is no peeling noise and it can be pulled out smoothly. ⁇ : There is peeling noise, but the appearance of the substrate after picking is not impaired (lower limit of practical use). ⁇ : There is a large peeling noise and the appearance of the substrate after being taken off is impaired (not suitable for practical use)
  • the recording paper obtained in each of the examples and comparative examples was conditioned for 3 hours in an environment of a temperature of 23° C. and a relative humidity of 50%. Then, using a wet electrophotographic printer (manufactured by Japan HP, device name: Indigo7800) in the same environment as during humidity control, a solid image with a density of 100% and a black ink with a density of 30% are printed on one side of the recording paper. A halftone dot pattern was printed.
  • the printer has multiple color liquid toners (manufactured by Japan Hewlett-Packard Company, product name: HPElectroInkLightCyanQ4045A, HPElectroInkLightMagentaQ4046A, HPElectroInk, DigitalMatt4.0,3CartridgesQ4037A, HPElectroInkDigitalMatt4.0,9. It is equipped with Cartridges Q4038A).
  • ⁇ Toner transferability> The state of the image on the recording paper after the printing was magnified with a magnifying glass and visually observed, and the toner transfer property was evaluated as follows. ⁇ : The image is clear and the toner transferability is good. ⁇ : The ink bleeding is indistinct by visual observation, but the dot area is widened by observation with a magnifying glass (the lower limit of practical use). X: The image is blurred and the toner transferability is low (not suitable for practical use)
  • the adhered cellophane tape was peeled off by hand at a speed of 300 m/min in the direction of 180 degrees, and then the residual rate of ink on the recording paper was measured using a small general-purpose image analyzer (manufactured by Nireco, model name: LUZEX-AP).
  • a small general-purpose image analyzer manufactured by Nireco, model name: LUZEX-AP.
  • the image obtained by photographing the printed surface was binarized, and the ratio of the area occupied by the toner was calculated as the residual rate.
  • the ink adhesion was ranked according to the following criteria.
  • ⁇ Toner residual rate is 80% or more
  • ⁇ Toner residual rate is 50% or more and less than 80% (lower limit of practical use)
  • X The residual rate of the toner is less than 50% (not suitable for practical use)
  • ⁇ Gloss change during printing> Hold one sheet of recording paper in a thermal tilt tester (TYPE HG-100, manufactured by Toyo Seiki Seisakusho, Ltd.) so that the printing surface is pressed, and set the temperature at 90°C to 170°C in 20°C steps for 5 seconds. Pressurized. The 75-degree specular glossiness of the pressed portion was measured in accordance with JIS P 8142:1993, and the gloss change during printing was evaluated according to the following evaluation criteria from the difference from the glossiness of unpressurized recording paper. It was judged. ⁇ : 130° C. or higher but lower than 170° C., gloss difference less than 5% ⁇ : 100° C. or higher and lower than 130° C., gloss difference less than 10% (lower limit of practical use) X: less than 100°C, gloss difference of 10% or more (not suitable for practical use)
  • Super accelerated weather resistance tester manufactured by Daipla Wintes Co., Ltd., trade 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 ( Trade name) was used.
  • a test piece obtained by cutting the recording paper printed according to the above procedure into a size of 90 mm ⁇ 150 mm is provided with aluminum foil tape “AL-T” on four sides (Takeuchi Industry Co., Ltd.) so that the printed surface is the exposed surface. It was attached to a stainless plate (100 mm ⁇ 200 mm) with a product (trade name) and fixed, and this was installed in the tester.
  • the irradiance of the surface of the test piece was 90 W/m 2 , and the black panel temperature was 63°C.
  • Two cycles of acceleration treatment were carried out, with one cycle consisting of 5 hours of exposure at a temperature of 63° C. and 50% relative humidity and 3 hours of exposure at a temperature of 30° C. and 98% relative humidity. Therefore, the radiation exposure amount on the printed surface was 5.18 ⁇ 10 6 J/m 2 .
  • the test piece that had been subjected to the weather resistance acceleration treatment was subjected to a friction test and evaluation in the same manner as in the case of wet A having abrasion resistance.
  • Example 9 Print evaluation of water-based inkjet printing method
  • the recording papers obtained in Example 9 and Comparative Example 5 were evaluated for printing by an aqueous inkjet printing method.
  • a blank recording paper is used, and for other than that, an aqueous pigment inkjet printer (model name: TM-C3500, manufactured by Seiko Epson Corp.) and standard cyan, magenta, yellow and black aqueous pigments for the printer are used.
  • An ink (model number: SJIC22) was used to evaluate the printability of the water-based inkjet printing method.
  • the water absorption of the resin coating was measured for the recording papers obtained in Example 9 and Comparative Example 5.
  • the amount of water absorption was determined by measuring the amount of water absorption after contacting for 120 seconds using a Cobb size measuring device (made by Kumagai Riki Kogyo Co., Ltd.) in accordance with the Cobb method (JIS P8140: 1998), and measuring 3 points. The average value of the data was used as the measured value.
  • Example 9 and Comparative Example 5 The recording paper obtained in Example 9 and Comparative Example 5 was printed with a N5 pattern of JIS X9201:2001 (high-definition color digital standard image (CMYK/SCID)) on one side of the recording paper using the above printing machine. It was printed by the inkjet method. The image printed by the water-based pigment inkjet printer was visually observed immediately after printing, and the dots of the image were observed with a microscope, and bleeding was determined as follows. ⁇ : No bleeding is seen at all ⁇ : Line outline becomes thick or unclear, and bleeding is seen in places (lower limit of practical use) ⁇ : Bleeding is seen in the entire image (not suitable for practical use)
  • ⁇ Drying property> Immediately after printing, the paper was pressed onto the image printed by the above procedure, and the drying property of the ink was determined as follows. ⁇ : Ink cannot be visually recognized as a liquid on the surface, and no ink is transferred to the paper even if the paper is lightly pressed. ⁇ : Ink cannot be visually recognized as a liquid on the surface, but when the paper is pressed, the ink of the entire image is transferred to the paper. Transfer (lower limit of practical use) ⁇ : The ink can be visually recognized as a liquid on the surface (not suitable for practical use)
  • ⁇ Scratch resistance> The image portion printed by the above procedure was cut into a size of 30 mm ⁇ 120 mm one day after printing, and set in a Gakshin tester (manufactured by Suga Test Instruments Co., Ltd.). As an evaluation under dry conditions, gauze dried at room temperature was attached to a weight with a load of 215 g, the surface of the image portion printed with this weight was rubbed 100 times, and the degree of ink peeling was evaluated by visual observation.
  • Example 9 The evaluation results of Example 9 and Comparative Example 5 are shown in Table 5 below.
  • the recording papers of Examples have printability in all of toner transferability, toner adhesion and abrasion resistance even when printing is performed by a wet electrophotographic printing method using liquid toner. Was confirmed to be good. Since the result is good even under the wet condition, it can be seen that the water resistance is particularly excellent. Further, it was confirmed that the recording papers of the examples are excellent in anti-blocking property and weather resistance, and thus blocking or change in paper quality is unlikely to occur when the printed matter is stored at high temperature. Furthermore, it was confirmed that the gloss change before and after printing was small. In addition, as shown in Table 5, the recording papers of Examples have good printability in terms of bleeding, dryness, and scratch resistance even when printed by an aqueous inkjet printing method, and cause blocking.
  • the recording papers of Examples are recording papers having high adhesiveness, particularly high water-resistant adhesiveness, causing no ink transfer failure and deterioration of ink adhesiveness of printed matter, and having no blocking and no change in paper quality after printing. I understand.
  • the recording paper of the comparative example contains the olefinic copolymer particles, the toner transferability and the adhesiveness are obtained, but the adhesiveness is deteriorated under wet conditions, and the water resistance and the weather resistance are deteriorated. It was confirmed.
  • the resin coating containing neither the silane coupling agent nor the cationic water-soluble polymer does not have sufficient printability in any printing method. Further, the resin coating film containing too much silane coupling agent component was too hard, and stress was concentrated on the interface between the resin coating film and the toner, so that sufficient toner adhesion could not be obtained.
  • FIGS. 7 to 9 show photographs taken by a scanning electron microscope after gold was vapor-deposited on the surfaces of the recording paper of Comparative Example 3, the recording paper of Example 1 and the substrate before the resin coating was formed. ..
  • the photographs in FIGS. 7 and 9 are taken with a scanning electron microscope (model number: SM-200) manufactured by Topcon, and the photographs in FIG. 8 are taken with a scanning electron microscope (model number: JCM-6000) manufactured by JEOL Ltd. did.
  • the magnification at the time of shooting is 3000 times in all cases.
  • Comparative Example 3 has many fine irregularities on the surface and is easily fluffed. It is considered that the irregularities originate from the olefin-based copolymer particles.
  • Example 1 has a surface structure with few irregularities on the surface and is uniform, and has a fluff-free surface structure.
  • FIG. 8 is compared with FIG. 9 which is a photograph of the base material, large particles can be confirmed in all cases, and thus the particles are considered to be the filler in the base material shown in FIG. 9.
  • the resin composition (c) is melt-kneaded by two extruders set at 250° C., then extruded in a sheet shape, and laminated on the first surface of the resin layer formed of the resin composition (a). At the same time, it was laminated on the second surface to obtain a three-layer laminated sheet.
  • the three-layer laminated sheet is cooled to 60° C.
  • the three-layer laminated sheet is heated to about 150° C. by using a tenter oven and stretched 8.5 times in the transverse direction, and then further heated to 160° C. to be heat treated. I went.
  • it is cooled to 60° C., the ears are slit, and the thickness is 80 ⁇ m
  • the resin composition of each layer (c/a/c), the thickness of each layer (10 ⁇ m/60 ⁇ m/10 ⁇ m), the number of axes of stretching of each layer (uniaxial/2 Axis/1 axis)] was obtained.
  • An adhesive layer was placed on the base material as described below. In the substrate, the resin layer made of the resin composition (c) not on the adhesive layer side corresponds to the first surface layer, and the resin layer made of the resin composition (c) on the adhesive layer side corresponds to the second surface layer. ..
  • the resin composition (c) is melted and kneaded by two extruders set at 250° C., and then extruded into a sheet shape to form a single-layer biaxially stretched sheet of a resin layer composed of the resin composition (c).
  • a resin layer composed of the resin composition (c). was laminated on the first surface and simultaneously on the second surface to obtain a laminated sheet in which three layers were laminated.
  • the mixture is cooled to 60° C., the ears are slit, and the thickness is 80 ⁇ m, the resin composition of each layer (c/c/c), the thickness of each layer (20 ⁇ m/60 ⁇ m/20 ⁇ m), the number of axes of stretching of each layer (unstretched/2 An axial/unstretched laminate was obtained as a substrate.
  • Production Example 21 of recording paper the same as Production Example 1 of recording paper except that the base material and the resin coating were changed as shown in Table 7 below and the strength of the corona discharge treatment was changed as shown in Table 7. Then, recording sheets of Production Examples 22 to 38 were obtained.
  • Table 7 below shows Examples 21 to 38 of recording paper.
  • Example 21 Using a silicone-treated glassine paper (G7B, manufactured by Oji Tack Co., Ltd.) as a release sheet layer, a solvent-based acrylic pressure-sensitive adhesive (Olivine BPS1109, manufactured by Toyochem Co., Ltd.) and an isocyanate group were used on the silicone-treated surface of the glassine paper.
  • a cross-linking agent (Olivine BHS8515, manufactured by Toyochem Co., Ltd.) and toluene were mixed at a ratio of 100:3:45, and the mixture was coated with a comma coater so that the basis weight after drying was 25 g/m 2. Then, it was dried to form an adhesive layer. Then, this adhesive layer was laminated so that the second surface layer side of the substrate was in contact, and the recording paper obtained in Production Example 21 and glassine paper were pressure-bonded with a pressure roll to form an adhesive layer on the recording paper. did.
  • Examples 22 to 32 and Comparative Examples 21 to 26 were carried out in the same manner as Example 1 except that the recording paper 21 obtained in Production Example 1 was changed to the recording papers obtained in Production Examples 22 to 38. ⁇ 26 adhesive labels were obtained.
  • Tables 8 below show Examples 21 to 32 and Comparative Examples 21 to 26.
  • the PET film was laminated on the printing surface of the adhesive label printed by the above procedure using a cold lamination technique.
  • the PET film used here had an adhesive formed on one side (trade name: PRO SHIELD Cold UV-HG50, manufactured by Jetgraph Co., Ltd.), and the lamination process adhered the adhesive side of the PET film at 23°C. It was carried out by superposing on the printing surface of the label and press-bonding. Then, these were immersed in water at 23° C. for 24 hours. The surface water taken out from the water was wiped gently with a waste cloth, and after 5 minutes, the PET film was slowly peeled off by hand. By visually observing the state of the printed surface after peeling the PET film, the laminating property was evaluated according to the following criteria.
  • the release sheet of the pressure-sensitive adhesive label was peeled off, the pressure-sensitive adhesive layer surface was attached to a transparent and highly smooth glass plate, and the glass sheet was rubbed three times with a finger for sufficient adhesion.
  • the glass plate to which the adhesive label was adhered was heat-treated for 24 hours in an environment of a temperature of 40° C., and then immersed in water of 23° C. for 24 hours. Then, after 5 minutes after taking out from water and lightly wiping off moisture with a waste cloth, the adhered adhesive label was peeled by hand at a speed of 300 m/min in the direction of 180 degrees.
  • the haze at the location where the adhesive label of the glass plate was peeled off was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model name: NDH2000) according to JIS K7136:2000. From the difference between the measured haze and the haze of a solid glass plate, the adhesive residue of the pressure-sensitive adhesive was judged according to the following criteria. ⁇ : Haze difference is less than 5% ⁇ : Haze difference is 5% or more and less than 10% (practical lower limit) X: Haze difference of 10% or more (not suitable for practical use)
  • Table 8 below shows the evaluation results of the adhesive labels produced in Examples 21 to 32 and Comparative Examples 21 to 26.
  • the pressure-sensitive adhesive labels of Examples 21 to 32 have any of toner transferability, toner adhesion, and scratch resistance even when printed by a wet electrophotographic printing method using a liquid toner. Also, good printability was confirmed. Regarding the toner adhesion, good results are obtained even under wet conditions, and particularly the water resistance adhesion is high. It was also confirmed that the adhesive labels of Examples 21 to 32 did not cause adhesive residue and did not cause blocking and change in paper quality after printing.
  • composition ratio (O/C) of the number of oxygen atoms (O) and the number of carbon atoms (C)> The composition ratio (O/C) of the number of oxygen atoms (O) and the number of carbon atoms (C) on the surface of the base material and the heat seal layer is the same as the above-mentioned ⁇ number of oxygen atoms (O) and number of carbon atoms (C). Composition ratio (O/C)> was obtained.
  • ⁇ Layer thickness ( ⁇ m)> The total thickness of the in-mold label was determined in the same manner as the above ⁇ layer thickness ( ⁇ m)>.
  • resin composition consisting of 100 parts by mass of long-chain low-density polyethylene (manufactured by Nippon Polyethylene Corporation, trade name: Novatec LL UF240, MFR (190°C, 2.16 kg load): 2.1 g/10 minutes, melting point: 123°C)
  • the product (e) was prepared.
  • Table 9 below shows the components of the resin compositions (a), (c), (d) and (e) used in the following Examples and Comparative Examples.
  • the resin composition (c) is melt-kneaded by an extruder set at 250° C., then extruded into a sheet and laminated on one surface of the uniaxially stretched sheet, and at the same time, the resin composition (e) is obtained. After melt-kneading with an extruder set at 250° C., it is extruded into a sheet and laminated on the other surface of the above uniaxially stretched sheet, and a metal cooling roll and a matte rubber roll with #150 wire gravure embossing are formed. And led.
  • the obtained three-layer laminated sheet is cooled to 60° C., the three-layer laminated sheet is heated to about 150° C. using a tenter oven, and stretched 8.5 times in the transverse direction, and then further heated to 160° C. for heat treatment. I went. Then, it is cooled to 60° C., the ears are slit, the resin composition of each layer is (c/a/e), the thickness of all layers is 80 ⁇ m, the thickness of each layer is (15 ⁇ m/60 ⁇ m/5 ⁇ m), and each layer is stretched.
  • a base material with an HS layer having the number of axes (1 axis/2 axes/1 axis) was obtained.
  • the layer formed by using the resin composition (e) corresponds to the heat seal layer.
  • the layer formed using the resin composition (a) corresponds to the core layer of the base material, and the layer formed using the resin composition (c) corresponds to the surface layer of the base material.
  • the resin composition (c) was melt-kneaded by an extruder set at 250° C., then extruded in a sheet shape and laminated on one surface of the biaxially stretched sheet.
  • the resin composition (e) was melt-kneaded by an extruder set at 250° C., then extruded in a sheet shape and laminated on the other surface of the biaxially stretched sheet, and a #150 wire gravure emboss was applied. Guided between a shaped metal cooling roll and a matte rubber roll. While sandwiching between the metal cooling roll and the matte rubber roll by pressing them together, the embossed pattern is transferred to the thermoplastic resin side, cooled to room temperature with the cooling roll, and the resin composition (c) is used.
  • a three-layer laminated sheet was obtained in which the formed layer, the layer formed using the resin composition (c), and the layer formed using the resin composition (e) were laminated in this order. Then, the mixture is cooled to 60° C., the ears are slit, the resin composition of each layer is (c/c/e), the thickness of all layers is 100 ⁇ m, the thickness of each layer is (20 ⁇ m/60 ⁇ m/20 ⁇ m), and each layer is stretched.
  • a substrate with an HS layer having the number of axes (unstretched/biaxial/unstretched) was obtained. The layer formed using the resin composition (e) corresponds to the HS layer.
  • the layer formed using the resin composition (c) located on the HS layer side corresponds to the core layer of the base material, and the resin composition (c) located on the opposite side with the HS layer and the base material sandwiched therebetween.
  • the layer formed by using corresponds to the surface layer of the substrate.
  • Example 41 Corona discharge treatment was applied to the surface of the base material obtained in Production Example 41 of the above-mentioned HS layer, which was opposite to the surface on which the heat-sealing layer was provided, under the condition of 60 W ⁇ min/m 2 .
  • the coating liquid (a) for forming a resin film prepared in Preparation Example 1 was applied on the surface of the base material subjected to corona discharge treatment by a roll coater so that the thickness after drying was 0.03 ⁇ m.
  • the coating film was dried in an oven at 60° C. to form a resin film, and the in-mold label of Example 41 was obtained.
  • Examples 42 to 48, 50 to 53 and Comparative Examples 41 to 46 In-mold labels of Examples 42 to 48, 50 to 53 and Comparative Examples 41 to 46 were obtained in the same manner as in Example 41 except that each layer was changed as shown in Table 10 below. ..
  • Example 49 Table 10 was prepared on both surfaces of the base material obtained in Production Example 49 of base material with HS layer, that is, on the surface of the base material opposite to the surface on which the heat seal layer was provided, and on the surface of the heat seal layer. Corona discharge treatment was performed under the conditions described in.
  • the coating liquid (b) for resin film formation prepared in Preparation Example 2 was applied by a roll coater so that the thickness of each surface subjected to corona discharge treatment after drying was 0.03 ⁇ m.
  • the coating film was dried in an oven at 60° C. to form a resin film on both surfaces of the HS layer-containing substrate, and the in-mold label of Example 49 was obtained.
  • Table 10 below shows the configuration of the in-mold label of each Example and Comparative Example.
  • the number of stretching axes and the thickness in Table 10 are described in the order of the surface layer of the base material (layer located on the side opposite to the heat seal layer)/core layer of the base material/heat seal layer.
  • ⁇ Toner adhesion 2> The print surface of the in-mold label printed in the same manner as in the evaluation of ⁇ Toner Adhesion> was scratched with a cutter in a grid pattern (width 10 mm, length 10 mm) at 1 mm intervals, and after immersion in water at 23° C. for 24 hours. , I took it out of the water and wiped off the water lightly with a waste cloth. Five minutes after the wiping, an adhesive surface of cellophane tape (product name: Cellotape (registered trademark) CT-18, manufactured by Nichiban Co., Ltd.) was attached to the printing surface of the recording paper, and rubbed with a finger three times for sufficient adhesion. ..
  • cellophane tape product name: Cellotape (registered trademark) CT-18, manufactured by Nichiban Co., Ltd.
  • the ink remained on the recording paper using a small general-purpose image analyzer (manufactured by Nireco, model name: LUZEX-AP). The rate was calculated. Specifically, the image obtained by photographing the printed surface was binarized, and the ratio of the area occupied by the toner was calculated as the residual rate. From the calculated ink residual rate, the ink adhesion was ranked according to the following criteria. ⁇ : Toner residual rate is 80% or more ⁇ : Toner residual rate is 50% or more and less than 80% (lower limit of practical use) X: The residual rate of the toner is less than 50% (not suitable for practical use)
  • ⁇ Scratch resistance Wet C>
  • the printed in-mold label was immersed in ethanol at 23° C. for 24 hours, then taken out from ethanol and lightly wiped with a waste cloth. After 5 minutes from wiping, it is attached to a Gakushin-type dyeing friction fastness tester (manufactured by Suga Test Instruments Co., Ltd., device name: Friction Tester II type) and rubbed 100 times with a white cotton cloth moistened with water under a load of 500 g. A friction test was conducted. The abrasion resistance was evaluated from the residual rate of the toner on the recording paper after the friction test, based on the same criteria as the evaluation of toner adhesion 2.
  • the printed in-mold label obtained in Example 49 was punched into a rectangle having a width of 60 mm and a length of 80 mm.
  • the processed in-mold label was placed inside the molding die of a stretch blow molding machine (manufactured by Nissei ASB Co., device name: ASB-70DPH) so that the heat seal layer faced the cavity side and clamped. ..
  • the mold was controlled so that the surface temperature on the cavity side was within the range of 20 to 45°C.
  • a polyethylene terephthalate resin preform preheated to 100° C. was introduced between the molds and stretch blow molded for 1 second under a blow pressure of 5 to 40 kg/cm 2 .
  • ⁇ Toner adhesion 3> The surface of the in-mold label of the labeled container obtained by the above method was scratched with a cutter, immersed in water at 23° C. for 24 hours, and then taken out from the water. After gently wiping off the water with a waste cloth, attach the adhesive surface of cellophane tape (Nichiban Co., Ltd., trade name: Cellotape (registered trademark) CT-18) to the scratched area with a cutter in a direction perpendicular to the scratched area. And rubbed 3 times to get a sufficient contact.
  • cellophane tape Niban Co., Ltd., trade name: Cellotape (registered trademark) CT-18
  • the adhered cellophane tape was peeled off by hand at a speed of 300 m/min in the 180° direction, and then the toner remained on the in-mold label using a small general-purpose image analyzer (manufactured by Nireco, model name: LUZEX-AP) The rate was calculated. From the calculated residual rate of the toner, the adhesion of the toner was ranked according to the following criteria. ⁇ : Toner residual rate is 80% or more ⁇ : Toner residual rate is 50% or more and less than 80% (lower limit of practical use) X: The residual rate of the toner is less than 50% (not suitable for practical use)
  • the in-mold labels of the examples have any of toner transferability, toner adhesion, and scratch resistance even when printing is performed by a wet electrophotographic method using a liquid toner. It was confirmed that the printability was good and the blocking was small. Since the result is good even under the wet condition, it can be seen that the water resistance is particularly excellent. Further, excellent in-mold molding suitability is obtained, in which it adheres sufficiently to the container even during in-mold molding, and there is almost no peeling of the print after the in-mold molding and there is no change in gloss. According to Example 49 in which the resin film is provided also on the heat seal layer side, it can be seen that the PET resin container also has high suitability for in-mold molding.
  • the recording paper of the present invention has excellent appearance, and not only the adhesiveness between the support and the resin coating, but also the adhesiveness with inks or toners of various printing methods, in particular, the water-resistant adhesiveness is high. It can be widely used as label paper, ink jet recording paper, thermal recording paper, thermal transfer receiving paper, pressure-sensitive transfer recording paper, electrophotographic recording paper and the like.
  • the pressure-sensitive adhesive label of the present invention is excellent in appearance and not only the adhesiveness between the base material and the resin coating, but also the high adhesiveness with the ink or toner of various printing methods, especially the high water-resistant adhesiveness, and therefore, the adhesive label for packaging. Alternatively, it can be widely used as a display label, a tag, etc. for clothing.
  • the in-mold label of the present invention has excellent appearance, excellent adhesion not only to the adhesion between the substrate and the resin coating but also to the ink or toner of various printing methods, and high water-resistant adhesion.
  • the molded article can be widely used as a label provided on the surface of a resin container such as a PET resin container or a polyethylene resin container. In particular, it is useful for liquid containers such as beverages, cosmetics and pharmaceuticals.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

La présente invention concerne un papier d'impression qui présente une adhérence élevée, en particulier une adhérence résistante à l'eau, le papier d'impression étant conçu de telle sorte que des défauts dans le transfert d'encre sur la matière imprimée et des réductions de la force adhésive de l'encre ne se produisent pas, et de telle sorte que la qualité du papier ne change pas après le blocage et/ou l'impression.　Le papier d'impression selon l'invention a un matériau de base comprenant un film de résine thermoplastique et un revêtement de résine disposé sur au moins une surface du matériau de base. Selon l'invention : dans la surface du matériau de base qui fait face au revêtement de résine, la valeur (O/C) du rapport de composition du nombre d'atomes d'oxygène (O) et du nombre d'atomes de carbone (C) est de 0,01 à 0,5 (inclus) ; le revêtement de résine contient une résine qui est un produit de réaction d'un polymère cationique soluble dans l'eau et d'un agent de couplage au silane ; la teneur en agent de couplage au silane du revêtement de résine est de 15 à 60 parties en masse par rapport à 100 parties en masse du composant polymère cationique soluble dans l'eau ; le revêtement de résine ne contient pas de particules de résine thermoplastique ; et la teneur en charge inorganique du revêtement de résine est de 9 parties en masse ou moins par rapport à 100 parties en masse du composant polymère cationique soluble dans l'eau.
PCT/JP2020/000751 2019-01-11 2020-01-10 Papier d'impression, son application et procédé de fabrication de papier d'impression WO2020145404A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022180998A1 (fr) * 2021-02-25 2022-09-01 Ａｇｃ株式会社 Film, son procédé de fabrication et procédé de fabrication d'un boîtier de semi-conducteur
WO2022208966A1 (fr) * 2021-03-31 2022-10-06 株式会社ユポ・コーポレーション Papier d'impression

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005125515A (ja) * 2003-10-21 2005-05-19 Dainippon Ink & Chem Inc インクジェット受理層用組成物、及びそれを用いた被記録材
WO2014092142A1 (fr) * 2012-12-14 2014-06-19 株式会社ユポ・コーポレーション Papier d'impression
WO2018182026A1 (fr) * 2017-03-31 2018-10-04 株式会社ユポ・コーポレーション Étiquette destinée au moulage dans le moule et article moulé en résine étiqueté
WO2019013005A1 (fr) * 2017-07-12 2019-01-17 株式会社ユポ・コーポレーション Papier d'impression et son procédé de fabrication

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005125515A (ja) * 2003-10-21 2005-05-19 Dainippon Ink & Chem Inc インクジェット受理層用組成物、及びそれを用いた被記録材
WO2014092142A1 (fr) * 2012-12-14 2014-06-19 株式会社ユポ・コーポレーション Papier d'impression
WO2018182026A1 (fr) * 2017-03-31 2018-10-04 株式会社ユポ・コーポレーション Étiquette destinée au moulage dans le moule et article moulé en résine étiqueté
WO2019013005A1 (fr) * 2017-07-12 2019-01-17 株式会社ユポ・コーポレーション Papier d'impression et son procédé de fabrication

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022180998A1 (fr) * 2021-02-25 2022-09-01 Ａｇｃ株式会社 Film, son procédé de fabrication et procédé de fabrication d'un boîtier de semi-conducteur
WO2022208966A1 (fr) * 2021-03-31 2022-10-06 株式会社ユポ・コーポレーション Papier d'impression

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