WO2006035761A1 - 積層シート - Google Patents
積層シート Download PDFInfo
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- WO2006035761A1 WO2006035761A1 PCT/JP2005/017721 JP2005017721W WO2006035761A1 WO 2006035761 A1 WO2006035761 A1 WO 2006035761A1 JP 2005017721 W JP2005017721 W JP 2005017721W WO 2006035761 A1 WO2006035761 A1 WO 2006035761A1
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- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical group CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- JWHOQZUREKYPBY-UHFFFAOYSA-N rubonic acid Natural products CC1(C)CCC2(CCC3(C)C(=CCC4C5(C)CCC(=O)C(C)(C)C5CC(=O)C34C)C2C1)C(=O)O JWHOQZUREKYPBY-UHFFFAOYSA-N 0.000 description 1
- 229960004029 silicic acid Drugs 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229940083542 sodium Drugs 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- KYKFCSHPTAVNJD-UHFFFAOYSA-L sodium adipate Chemical compound [Na+].[Na+].[O-]C(=O)CCCCC([O-])=O KYKFCSHPTAVNJD-UHFFFAOYSA-L 0.000 description 1
- 239000001601 sodium adipate Substances 0.000 description 1
- 235000011049 sodium adipate Nutrition 0.000 description 1
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229960001790 sodium citrate Drugs 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 239000001540 sodium lactate Substances 0.000 description 1
- 235000011088 sodium lactate Nutrition 0.000 description 1
- 229940005581 sodium lactate Drugs 0.000 description 1
- PRWXGRGLHYDWPS-UHFFFAOYSA-L sodium malonate Chemical compound [Na+].[Na+].[O-]C(=O)CC([O-])=O PRWXGRGLHYDWPS-UHFFFAOYSA-L 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940001941 soy protein Drugs 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229920003066 styrene-(meth)acrylic acid ester copolymer Polymers 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 229920006352 transparent thermoplastic Polymers 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical group 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
-
- 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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/22—Polyalkenes, e.g. polystyrene
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/46—Non-macromolecular organic compounds
- D21H19/48—Diolefins, e.g. butadiene; Aromatic vinyl monomers, e.g. styrene; Polymerisable unsaturated acids or derivatives thereof, e.g. acrylic acid
-
- 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
- G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
-
- 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
- G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
- G03G7/002—Organic components thereof
- G03G7/0026—Organic components thereof being macromolecular
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/406—Bright, glossy, shiny surface
-
- 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
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
- B32B2323/046—LDPE, i.e. low density polyethylene
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/80—Paper comprising more than one coating
- D21H19/82—Paper comprising more than one coating superposed
- D21H19/824—Paper comprising more than one coating superposed two superposed coatings, both being non-pigmented
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/80—Paper comprising more than one coating
- D21H19/84—Paper comprising more than one coating on both sides of the substrate
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/46—Pouring or allowing the fluid to flow in a continuous stream on to the surface, the entire stream being carried away by the paper
- D21H23/48—Curtain coaters
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/08—Rearranging applied substances, e.g. metering, smoothing; Removing excess material
- D21H25/12—Rearranging applied substances, e.g. metering, smoothing; Removing excess material with an essentially cylindrical body, e.g. roll or rod
- D21H25/14—Rearranging applied substances, e.g. metering, smoothing; Removing excess material with an essentially cylindrical body, e.g. roll or rod the body being a casting drum, a heated roll or a calender
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24843—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] with heat sealable or heat releasable adhesive layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24934—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including paper layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31859—Next to an aldehyde or ketone condensation product
Definitions
- the present invention relates to a laminated sheet using paper as a base material and provided with a thermoplastic resin layer, particularly a recording sheet of the electrophotographic printing system.
- Patent Document 1 Japanese Patent No. 2763011 proposed by the present applicant is a laminate produced by laminating a thermoplastic resin on one side or both sides of a substrate by an extrusion lamination method, a coextrusion lamination method, etc. Paper is described, and by making the outermost layer a thermoplastic resin layer containing 20 to 80% by weight of inorganic filler, a technology for making printability with printing ink and writing with aqueous ink is disclosed ing.
- an electrophotographic recording sheet is prepared using a water-resistant processed paper or a polyolefin-based film as a substrate, and on this surface, to improve the transferability and adhesion of the toner, an image receiving layer composed of an inorganic pigment and binder is provided. It is known that it is (patent document 2: Unexamined-Japanese-Patent No. 2003-156866 gazette).
- Patent Document 3 Japanese Patent Application Laid-Open No. 6-324509) describes the improvement of the blocking resistance when stored before recording.
- Patent Document 4 Japanese Patent Application Laid-Open No. 09-255004 is a sheet in which one or more thermoplastic resins are laminated on both sides of a paper, and one outermost resin is against the other outermost resin. It is disclosed that a sheet having a water resistance and having a melting point of 20 ° C. or higher is used as a sheet for header labels.
- Patent Document 5 Japanese Patent Application Laid-Open No. 05-216322
- a color toner deposited on a transparent resin layer of a transfer body is heated by a belt-like transfer body moving under a member containing a heat source to
- the toner attached to the surface is secondarily subjected to heat and pressure treatment to fix the toner, which is melted in the oil layer, then cooled and fixed, and the transfer body is separated into a belt-like carrier to form a color image.
- Patent Document 6 Japanese Patent Application Laid-Open No.
- each thermoplastic resin is introduced in a molten state to a T-die using two or more extruders, and each T die is simultaneously extruded and laminated and bonded.
- Patent Document 7 Japanese 98 Z 03 730
- Patent Document 8 Japanese Patent Application Laid-Open No. 11-200284
- Patent Document 9 Japanese Patent Application Laid-open No. 11-350380
- Patent Document 10 Japanese Patent Application Laid-Open 2003-96694
- Patent Document 10 11 Japanese Patent Laid-Open No. 2003-96695
- the like disclose organic compounds having an action of inhibiting inter-fiber bonding of pulp.
- Patent document 12 Japanese Patent Application Laid-Open No. 2003-103714 relating to a water-resistant sheet proposed by the present applicant is provided with a toner fixing layer containing high molecular weight silicone having a number average molecular weight of 60 to 900,000. There is disclosed an invention which imparts a function capable of bleeding on the surface to impart abrasion resistance to the ink surface, and realizes a high quality printing surface.
- Patent Document 13 Japanese Patent Application Laid-Open No. 2002-9104 discloses a recording layer having a water resistant paper or a polyolefin film as a base layer, and a synthetic resin film force containing an inorganic fine powder on the surface of the base layer. An electrophotographic recording sheet is described.
- Patent Document 1 Patent No. 2763011
- Patent Document 2 Japanese Patent Application Laid-Open No. 2003-156866
- Patent Document 3 Japanese Patent Application Laid-Open No. 6-324509
- Patent Document 4 Japanese Patent Application Laid-Open No. 09-255004
- Patent Document 5 Japanese Patent Application Laid-Open No. 05-216322
- Patent Document 6 Japanese Patent Application Laid-Open No. 11-207882
- Patent Document 7 WO98Z03730
- Patent Document 8 Japanese Patent Application Laid-Open No. 11-200284
- Patent document 9 Unexamined-Japanese-Patent No. 11-350380
- Patent Document 10 Japanese Patent Application Laid-Open No. 2003-96694
- Patent Document 11 JP-A 2003-96695
- Patent document 12 Unexamined-Japanese-Patent No. 2003-103714
- Patent Document 13 Japanese Patent Application Laid-Open No. 2002-91049
- the recording sheet is passed through a heat roll at about 200 ° C. and thermally fused and fixed.
- the molten toner sinks into the gaps between the paper fibers to obtain good fixing properties.
- the toner fixing layer is inferior to the paper surface because the unevenness is small and the toner fixing property is poor. Therefore, the toner fixing layer is provided on the thermoplastic resin layer. Is effective.
- the thermoplastic resin layer is still disadvantageous with respect to toner fixing property, and it is difficult to form the toner fixing layer.
- the recording sheet such as a laser beam printer (LBP) will be discharged, and the next recording sheet will be discharged while the heat has not cooled down and the toner has not been fixed. It may be stacked on top of you.
- LBP laser beam printer
- the degree of adhesion on the back of the recording sheet increases, causing fusion. This is a phenomenon called toner blocking, and if it is attempted to cover the recording sheet one by one after printing, there is a problem that the toner peels off from the printing surface.
- the object of the present invention is to provide a laminated sheet suitable for an electrophotographic printing method, which is excellent in film forming property of toner fixing layer, good in toner fixing property and print quality, and in which toner blocking does not occur.
- a laminated sheet suitable for an electrophotographic printing method which is excellent in film forming property of toner fixing layer, good in toner fixing property and print quality, and in which toner blocking does not occur.
- An object of the present invention is to provide a laminated sheet having excellent sheet transportability, which has good releasability from a heat roll, in view of the above problems.
- the resin layer laminated on the surface may be fused to the heat rolls.
- the thermoplastic resin layer is two or more layers, if the adhesion between the resin layers is insufficient, peeling between the resin layers is likely to occur and paper entrainment is also likely to occur.
- the present invention improves the heat resistance and the adhesion inside the laminated sheet while using the laminated sheet in which the thermoplastic resin is laminated on the base material, and when recording by the electrophotographic printing method, between the heat rolls. It is an object of the present invention to provide a laminated sheet in which the surface resin does not fuse to the heat roll even when a paper jam occurs in the contact state.
- thermoplastic resin layer is softened as it passes between the heat rolls, and the surface texture of the heat roll is transferred to the softened resin. Gender may deteriorate and gloss and beauty may be lost.
- high-temperature heat rolls are the fixing device, and a mechanism to apply release oil to the heat rolls is adopted to prevent toner adhesion to these. There is.
- the release oil is transferred to the sheet surface through the heat roll, so the glossiness is greatly reduced after printing.
- a laminated sheet having a thermoplastic resin layer on the surface is coated with silicone on the heat roll in order to prevent the adhesion of the toner, particularly the melted toner, to the heat roll compared to ordinary paper.
- the transfer of this silicone to the paper surface has a problem that the writability after printing is inferior.
- writing after printing is improved, There is a drawback that toner is scattered and soiling is likely to occur).
- An object of the present invention is to obtain a laminated sheet provided with a toner fixing layer having a good film forming property.
- Another object of the present invention is to provide a laminate sheet having excellent toner fixability.
- Another object of the present invention is to provide a laminated sheet which exhibits good paper transportability at the time of printing by an electrophotographic apparatus.
- Another object of the present invention is to provide a laminated sheet which causes thermal roll fusion during printing by an electrophotographic printing apparatus.
- Another object of the present invention is to provide a laminated sheet having good adhesion between a resin layer or a resin layer and a substrate.
- Another object of the present invention is to provide a laminated sheet having improved writability after printing.
- the present application uses the following configuration as the main solution means of the invention.
- a laminated sheet comprising: A) and a hydrophilic polymer substance having a glass transition temperature of 50 ° C. or less.
- hydrophilic polymer substance (A) is a hydrophilic polymer substance having a glass transition temperature of 80 ° C. or more.
- thermoplastic resin layer provided with one or more layers is characterized in that the thermoplastic resin layer located in the outermost layer is made of a thermoplastic resin having a melting point of 180 degrees or more. 5) The laminated sheet described in any of the above.
- thermoplastic resin having a melting point of 180 ° or more is polymethylpentene.
- thermoplastic resin layer provided with one or more layers is two or more layers, and the thermoplastic resin layer in contact with the substrate is a linear low density polyethylene in which a single site catalyst is synthesized.
- the cast coated paper is a cast coated paper finished by pressing and drying the cast coated layer with a heated mirror-finished surface while the cast coated layer provided on the base paper is in a wet state. And 50 parts by weight or more per 100 parts by weight of the inorganic pigment having a particle size distribution containing 65% or more by volume of particles having a cast coat layer strength in the range of 0.4 to 4.2 / zm, and The laminated sheet according to (12), which contains a plastic pigment.
- ISO (825-4) 75% glossiness is 80% or more, and image clarity by a measurement method according to JIS K-7105 is 50% or more.
- the toner fixing layer contains an inorganic filler, the smoothness of the surface of the laminated sheet is 200 seconds or more, and the surface resistivity is 5 ⁇ 10 8 to 1 ⁇ 10 11.
- the lamination sheet in any one of (1)-(15).
- the laminated sheet is a recording sheet for electrophotographic printing (1) to (17) The laminated sheet described in any one.
- a laminated sheet comprising paper as a base material and a thermoplastic resin layer formed on one side or both sides of the base material, wherein the thermoplastic resin layer on at least one side is a single sheet in contact with the base material.
- a resin for forming these layers is laminated on a substrate by a coextrusion method.
- the laminated sheet obtained by the present invention is excellent in the film forming property of the toner fixing layer. Further, the laminated sheet obtained by the present invention is excellent in toner fixability.
- the lamination sheet obtained by this invention is excellent in printing quality.
- the laminated sheet obtained by the present invention is excellent in toner blocking resistance. Further, the laminated sheet obtained by the present invention exhibits good sheet transportability at the time of printing by the electrophotographic printing apparatus.
- the laminated sheet obtained by the present invention does not cause thermal roll fusion during printing by an electrophotographic printing apparatus.
- the laminated sheet obtained by the present invention has good adhesion between the resin interlayer or the resin layer and the substrate.
- the laminated sheet obtained by the present invention has high gloss and excellent aesthetics, and the glossiness and the aesthetics are not impaired even after electrophotographic printing.
- the laminated sheet obtained by this invention is excellent in the water resistance of a cross section.
- the laminated sheet obtained by this invention is excellent in the writability after printing.
- the laminated sheet provided with the thermoplastic resin layer or the toner fixing layer obtained by the present invention is excellent in lightness.
- the laminated sheet obtained by the present invention is a laminated sheet having various surface properties, such as dross, semi-gloss, and mat. Further, the method for forming a plurality of laminated thermoplastic resin layers provided on a substrate provided by the present invention is excellent in forming thin resin layers and the like.
- the laminated sheet of the present invention is particularly resistant to combination by combining a hydrophilic high molecular weight substance having a high glass transition temperature (Tg) of 80 ° C. or higher and a hydrophilic high molecular weight substance having a low Tg of 50 ° C. or lower.
- Tg glass transition temperature
- the toner blocking property is improved.
- it is more effective to set the hydrophilic polymer substance having a high glass transition temperature (Tg) to 30% by weight or more as a binder component of the toner fixing layer.
- the hydrophilic polymer substance having a low Tg improves the film-forming property, so that both are satisfied by specifying the blending ratio.
- a high Tg hydrophilic polymer substance is present in a state of maintaining the particle shape without melting, in the low Tg hydrophilic polymer substance. Since the toner is fixed by the heat roll near 200 ° C. at the time of LBP printing etc., the high Tg hydrophilic polymer substance is also melted, and the adhesion between the toner fixing layer and the toner is extremely high. It is enhanced to obtain good toner fixing property. Since the high Tg hydrophilic polymer substance rapidly becomes glassy after toner fixing, it is considered that the toner fixing property is improved also by the anchor effect by the toner that has entered the interparticle space. Similarly, the presence of the high Tg hydrophilic polymer substance improves the peelability of the transport roll force of the high temperature part such as the fixing roll and the like also improves the transportability.
- a paper-based material is used as a base material, a thermoplastic resin layer is provided on the surface thereof to impart water resistance, and a toner fixing layer containing a hydrophilic polymer substance as a main component is further provided.
- a laminated sheet with improved printing performance.
- it is a laminated sheet suitable for printing and recording by an electrophotographic printing method such as a laser beam printer.
- the toner fixing layer is provided on the uppermost layer of the laminated sheet as a coating layer for performing recording by the electrophotographic printing method.
- the film forming property of the toner fixing layer is obtained by incorporating a hydrophilic thermoplastic emulsion in which the two types having different glass transition temperatures (Tg) are used in combination into the toner fixing layer as a binder. And the toner fixing property is improved and the toner blocking after printing is improved.
- the high Tg hydrophilic polymer substance alone has problems with the film forming property of the toner fixing layer and the toner fixing property.
- a low Tg hydrophilic polymer material melts and forms a film at a low temperature, and as soon as the hard toner fixing layer becomes soft and the adhesion with the toner becomes better, but a low Tg hydrophilic polymer material alone
- the toner fixing layer is sticky and adheres to another sheet. This causes blocking during white paper storage and causes toner blocking after printing.
- it has been found that these problems can be solved by using two types having different Tg in combination.
- thermoplastic resin layer is formed on a substrate such as paper, and a laminated sheet provided with a toner fixing layer containing two kinds of hydrophilic polymer substances having different Tg as a binder is provided. It is an offering.
- a toner fixing layer forming binder component comprising two or more hydrophilic polymer substances having different glass transition temperatures, wherein the hydrophilic polymer substance has a glass transition temperature of at least 50 ° C. or more.
- a polymer substance (A) and a hydrophilic polymer substance (B) having a glass transition temperature of 50 ° C. or less are contained.
- hydrophilic polymer substance (A) having a glass transition temperature of 50 ° C. or more a hydrophilic polymer substance having a glass transition temperature of 80 ° C. or more is particularly preferable.
- 50.degree. C. is a temperature at which the film-forming properties of the toner fixing layer can be favorably maintained, and 80.degree. C. is close to the sheet temperature at the time of discharge after printing. More preferably, (A) is 90 ° C. or more higher than the discharge temperature of the printing sheet, and (B) is 40 ° C. or lower lower than the film forming temperature.
- the hydrophilic polymer substance is preferably an emulsion having a hydrophilic functional group.
- hydrophilic means that the resin is dispersed or dissolved in water or a medium which also contains water and a small amount of organic solvent, and is stable. These resins are dispersed or dissolved in the form of particles in the coating solution, but when coated and dried, they form a film to form a toner adhesion layer.
- the drying step is usually carried out through a drier at 40 ° C. or higher. Since the film is formed by heating at a temperature above Tg, it is important that the binder contains a Tg component below this drying heating temperature.
- hydrophilic polymer substances examples include styrene, butadiene, various acrylic acids, and acrylonitrile. Homopolymers containing ethylene, propylene, vinyl acetate, butyl chloride and the like as monomer components
- Copolymers and Z or modified products thereof, and polyester resins, urethane resins, epoxy resins and the like may be used alone or in combination without mixing.
- These hydrophilic polymer substances are produced, for example, by a conventionally known polymerization method such as emulsion polymerization, soap-free emulsion polymerization and suspension polymerization, and desirably have a weight average molecular weight of 100,000 or more.
- acrylic polymers are also preferable for the toner fixability.
- acrylic polymers include polyacrylic acid esters, polymethacrylic acid esters, styrene / acrylic acid ester copolymers, and styrene / methacrylic acid ester copolymers.
- both of the hydrophilic polymer substances (A) and (B) are acrylic polymers.
- a core 'shell comprising a core part and a shell part by the hydrophilic polymer substances (A) and (B)
- one material can exert two performances, so the workability is good and it is preferably used.
- the acrylic polymer having a core-shell structure has a core portion having a glass transition temperature of 50 ° C. or higher and a shell portion having a glass transition temperature of 50 ° C. or lower, or One having a shell portion having a glass transition temperature and a core portion having a glass transition temperature of 50 ° C. or less, preferably a core portion having a glass transition temperature of 80 ° C. or more and a glass transition temperature of 50 ° C. or less Or a shell having a glass transition temperature of 80 ° C. or more and a core having a glass transition temperature of 50 ° C.
- the core comprising a hydrophilic polymer substance (A)
- the shell is a hydrophilic polymer substance (B)
- the film-forming property is good and a strong toner fixing layer is easily obtained, which is preferable.
- An acrylic polymer having such a core'shell structure is produced, for example, by the method described in JP-A-2001-323004.
- the shell portion is considered to be formed as a film covering the core portion and to be present like a protective colloid around the core portion which is not visible.
- the toner fixing layer various known methods can be employed. For example, an air knife coater, a blade coater, a mouth ⁇ ⁇ "Noreco 1 ⁇ " ta ' ⁇ "force. ⁇ ” Tea, No ⁇ "Ta ⁇ ⁇ ” Gravure co 1 ⁇ "Ta Coating on the surface of the thermoplastic thermoplastic resin layer provided on the substrate using a known coating method such as " ⁇ Tyco 1 to T ' 1 to T' 1 to C 1 to T '"
- the coating amount is not particularly limited, but may be 0.55 to 7.5 g Zm 2 (dry weight), preferably 1 to 5 g Zm 2 (dry weight). If but if less than 0.
- the toner fixing layer may lose surface force of the thermoplastic resin layer, and the toner fixing layer is preferably a water-based paint from the viewpoints of health of the workers and the load on the environment. With this In order to facilitate the formation of the toner fixing layer, it is desirable to subject the surface of the thermoplastic resin layer to corona treatment or the like.
- the toner fixing layer known hydrophilic polymer substances other than those described above may be used as a seeder as long as the effects of the present invention are not impaired.
- the paper transportability also contains no pigment, and U, which can be used to improve the roll adhesion during printing, such as silica.
- the glossiness is reduced.
- the pigment is used in about 5 parts by weight with respect to 100 parts by weight of the grinder.
- a lubricant for example, a crosslinking agent, an adhesion improver, an antifoamer, a coatability improver, a thickener, an antistatic agent, an ultraviolet light absorber, a dye and the like may be added.
- an antistatic agent when the recording sheet of the electrophotographic printing system is used, it is preferable to contain an antistatic agent.
- the fixing property of the toner is enhanced, and the high gloss is maintained even after the electrophotographic printing, and the releasability with the heat roll is excellent. It is possible to provide a laminated sheet with excellent properties.
- latent image toner is transferred to recording paper and fixed by heat fusion
- the surface of the toner fixing layer is damaged by the heat at that time, and the heat roll force is also transferred to the paper surface, and the release oil is transferred.
- the release oil is in the form of fine oil droplets on the surface of the sheet, which causes the glossiness of the sheet to be reduced.
- the toner fixing layer containing high molecular silicone on the surface of the sheet, the adhesion between the release oil and the surface of the sheet is improved, and the release oil spreads in the form of a thin film on the sheet surface. And decrease in gloss after printing.
- the blending of the polymeric silicone can improve the releasability from the heat roll and also improve the paper transportability such as double feeding.
- polymeric silicones used in the present invention those having an average molecular weight of 60 to 100,000 are preferably polyalkylsiloxanes among them.
- the amount of addition is about 5% by weight or less in solid content ratio to the binder.
- a copying machine by an electrophotographic printing system or the like which employs a mechanism for applying a releasing oil to the heat roll to prevent toner adhesion to the fixing machine such as the heat roll. Even when printed with a laser printer, it produces a beautiful finish without losing its high gloss surface tone.
- Such a laminated sheet has a very high practical value which is suitable for various applications where high gloss and beauty are required other than posters.
- the high glossiness can be maintained by preventing the gloss reduction after printing.
- thermoplastic resin layers are formed on one side or both sides of the substrate. It is a thing.
- the thermoplastic resin layer can impart surface water resistance and gloss to the substrate, and can further ensure high temperature resistance and transportability by the electrophotographic printing apparatus.
- the thermoplastic resin layer is required to satisfy the adhesion to the toner fixing layer formed on the surface of the substrate.
- these thermoplastic resin layers should be thin layers that are often provided in two or more layers and should satisfy the forming method such as film forming property.
- thermoplastic resin that can be used in the present invention may be a resin that can be laminated, such as polypropylene, polyethylene, polyethylene, polyethylene terephthalate, polybutylene terephthalate, polymethylpentene, and the like.
- a single resin may be used in a single layer, or a plurality of resins may be used in multiple layers.
- the mechanism is to heat and fuse the toner to the paper to prevent the thermoplastic resin from being deformed. It is preferred to use thermoplastic resins having a high melting point. By providing the outermost layer made of such a resin, it is possible to prevent the fusion to the heat roll, and maintain high gloss and beautiful surface condition without deteriorating the surface property before and after recording.
- thermoplastic resin having a melting point of 180 ° C. or higher polymethylpentene resin, polyamide resin, polyester resin (eg, polyethylene terephthalate, polybutylene terephthalate, aliphatic polyester) and the like are preferable. Among them, polymethylpentene is preferred.
- Polymethylpentene is a crystalline olefin polymer mainly composed of 4-methylpentene-1, is a resin having a melting point of 220 to 240 ° C. and excellent in heat resistance.
- white inorganic pigments such as titanium oxide and calcium carbonate can also be blended for the purpose of imparting opacity, writability and the like.
- the blending amount of the inorganic pigment is preferably 25% by weight or less, preferably 15% by weight or less, based on the outermost layer to which it is blended. Increasing the blending amount may deteriorate the surface properties such as smoothness and gloss of the laminated sheet.
- the particle size of the inorganic pigment is preferably 0.1 to 20 m.
- thermoplastic resin and the base material that form the above-mentioned outermost layer! there are two or more thermoplastic resin layers. If the adhesion between the resin layers is poor when provided, it is also possible to apply or stack an adhesive layer on the substrate in advance, and with thermoplastic resin used for the outermost layer or other layers. It is also possible to co-extrude the adhesive resin. Adhesive resin is also a kind of thermoplastic resin, and acrylic resin, epoxy resin and the like are used.
- thermoplastic resin having a melting point of 180 ° C. or more when used as the outermost layer, the adhesion between the base material or the outermost layer and the thermoplastic resin layer laminated therebelow is enhanced immediately below that.
- the base material is a coated paper or another thermoplastic resin layer is present under the outermost layer, the adhesive resin sandwiched between the outermost layers is likely to peel off because the outermost layer tends to peel off. Select the one that has good adhesion to both the substrate and the thermoplastic resin layer located under the outermost layer.
- polymethylpentene resin originally has releasability, it is necessary to exhibit strong adhesion to such polymethylpentene resin.
- polymethylpentene resin has good adhesion to high-quality paper, it has poor adhesion to coated paper and other resin layers, so it is possible to interpose a layer made of such adhesive resin. preferable.
- Examples of the resin having adhesiveness include modified polyolefins, ionomers, and resin compositions and the like which are also capable of mixing them with a thermoplastic resin having a melting point of 180 ° C or more. Also, the same type or different types may be selected, and one or two or more layers may be stacked.
- a modified polyolefin a modified product obtained by graft-modifying a homopolymer or copolymer of an ⁇ -olephine having 2 to 20 carbon atoms with a polar group and a monomer having an ethylenic double bond can be used. However, it is not limited to these.
- maleic anhydride-modified polyethylene is preferably used because of its good adhesion to polymethylpentene resin.
- Examples of homopolymers and copolymers include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ultra low density linear polyethylene, polypropylene, ethylene 'pentene-1 Examples thereof include copolymers, ethylene • 4-methylpentene-1 copolymer, and ethylene-butene-1 copolymer.
- the melt flow rate of such a homopolymer or copolymer measured by ASTM-D-1238 is usually 0.1-30.
- the melting point is usually in the range of 50 to 170 ° C, often in the range of 80 to 150 ° C, and is usually in the range of 1 to 20 gZlO min. It is inside.
- the density measured by AS TM-D-1505 is usually 0.88 ⁇ 0.96g / cm 3, in the range of often 0.89 ⁇ 0.96g / cm 3.
- Examples of the monomer having a polar group and an ethylenic double bond which is used as a modifier for homopolymers or copolymers include (meth) acrylic acid, tetrahydrophthalic acid, maleic acid, itaconic acid, citraconic acid, Fumaric acid, crotonic acid, norbornene dicarboxylic acid, end-cis-bicyclo [2,2,1] hept-5-en-2,3-dicarboxylic acid (Nadic acid TM) and end-cis-bicyclo [ 2,2, 1] Carboxylic acids such as hept-5-ene -2-methyl-2,3-dicarboxylic acid (methyl nadic acid TM); maleic anhydride, itaconic anhydride, citraconic anhydride, fumaric anhydride Acid, crotonic acid, norbornene dicarboxylic acid anhydride, endo-cis-bicarboxylic acid [2,2,1] hept-5-en
- Ionomers are ion-containing polymers, especially metal ions or quaternary ammonium.
- the polymer is partially or completely neutralized by a small amount of (meth) acrylic acid, especially to ethylene polymer chains, and a portion of the (meth) acrylic acid can be converted to Na +, K +, Zn It is preferable to use one neutralized with ++, Mg ++ or the like. Among them, Zn is preferable because it has good gloss.
- Such ethylene ionomer resins are ethylene Z, ⁇ -unsaturated carboxylic acid copolymer (1), or ethylene Z, ⁇ -unsaturated carboxylic acid Z, ⁇ -unsaturated carboxylic acid ester copolymer ( A part of the carboxylic acid group of 5), usually 5 to 80%, is neutralized with metal ions.
- the ratio of E Ji Ren units usually about 75 to 99.5 mole 0/0, preferably be 88 to 98 mole 0/0
- the proportion of the ⁇ , ⁇ -unsaturated carboxylic acid units is usually about 0.5 to 15 mol%, preferably 1 to 6 mol%.
- the proportion of a, j8-unsaturated carboxylic acid ester units is usually from 0 to 10 mol%, preferably from 0 to 6 mol%. Furthermore, of the carboxylic acid groups in the copolymer of (I) or (II) above, the proportion of the carboxylic acid groups neutralized by metal ions (the degree of neutralization) is usually 5 to 80%, preferably 10 to 10%. It is 75%.
- thermoplastic resin having a melting point of 180 ° C. or more a thermoplastic resin having a melting point of 180 ° C. or more, or a thermoplastic resin having a melting point of 180 ° C. or more
- the ionomer and a thermoplastic resin having a melting point of 180 ° C. or more can be co-extruded, or extruded and used after mixing.
- SS-LLDPE linear low density polyethylene
- SS-LLDPE linear low density polyethylene
- transition metal atoms such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten are sandwiched between two cyclopentadiene rings.
- thermoplastic resin layer in addition to the above-mentioned thermoplastic resin layer, a thermoplastic resin layer may be appropriately provided.
- the thermoplastic resin forming such a layer is not particularly limited, and examples thereof include resins which can be laminated, such as polypropylene, polyethylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polymethylpentene and the like. Can do
- thermoplastic resin layer of the substrate is optional, and depending on the application, nothing may be provided, an adhesive may be applied, or a thermoplastic resin layer may be laminated.
- thermoplastic resin layers are present on both sides of the substrate, the types and stacking order of these thermoplastic resin layers are different even if they are identical on one side and the other side! /, Well.
- the laminated sheet passes between the heat roll and the roll while the recording surface side is in contact with the heat roll. Therefore,-The roll is also affected by the heat roll and is at the same temperature, so the outermost layer on the non-recording surface side is also made of a thermo-plastic resin with a melting point of 180 ° C or more. Fusion is more effectively prevented.
- thermoplastic resin layer on a substrate there are methods of bonding a film and a substrate by a wet lamination method, a dry lamination method, etc. other than the extrusion lamination method or coextrusion lamination method.
- a wet lamination method a dry lamination method, etc. other than the extrusion lamination method or coextrusion lamination method.
- the substrate is also covered by the film when the solvent is dried, so there is no escape place for the evaporated water. They are occluded, they expand and push up the film, and voids (non-adhered parts) called blisters are easily generated.
- the adhesion between the substrate and the film is sweetened.
- the water in the base material is evaporated and expanded by heating with a heat roll for fixing the toner, causing blisters or immediate processing becomes difficult. Therefore, when the laminated sheet of the present invention is used for printing or recording in the electrophotographic printing method, an extrusion lamination method or a coextrusion lamination method is preferable as a processing method.
- each thermoplastic resin is introduced in a molten state to a T-die using two or more extruders, and each T die is simultaneously extruded.
- a co-extrusion lamination method of laminating and bonding is suitable.
- the co-extrusion lamination method is to introduce each thermoplastic resin in a molten state to a T-die using two or more extruders, and simultaneously extrude from each T-die for laminating and bonding, for example, as disclosed in JP-A-11-207882.
- it is also known as a method for producing a multilayer film or the like.
- a co-push T-die for example, a single T-die, a co-push T-die can be mentioned.
- a force-co-push T-die can simultaneously extrude two or more kinds of resins, so that two or more layers can be formed on the substrate. It is preferable when laminating resin.
- co-pushing T-die in-die adhesion and out-of-die adhesion, among which co-pressing extra-die adhesion T-die is a point that two or more kinds of resins can be laminated simultaneously by changing temperature conditions. Is excellent.
- a cooling roll in contact with the molten resin is used as a cooling roll in contact with the molten resin for extrusion lamination or co-extrusion lamination.
- a high hardness roller as a roller, by pressing and pressing a resin and a base material or the like at a high linear pressure, the laminated resin surface can be made to have a high gloss.
- each layer and the whole of the thermoplastic resin layer is 10 to 80 m, preferably 15 to 40 per side. It is preferable to be in the range of / zm. If the total thickness of the resin layer is too thin, it will be difficult to laminate the layers by the extrusion lamination method or the coextrusion lamination method. In addition, if it is too thick, the manufacturing cost is high and the force is also likely to generate static electricity. Therefore, it is preferable to cope with the use of a conductive agent, etc., if necessary.
- the thickness of the outermost layer is preferably 2 to 30 ⁇ m, and more preferably 10 to 20 / ⁇ . If the thickness of the outermost layer is too thin, in the case of the thermoplastic resin layer, the adhesion to the substrate will be insufficient, blistering will occur, and if it is two or more layers, the heat resistance will be insufficient, and the heat roll portion When a paper jam occurs, it is easy to generate trouble that fuses to the heat roll. On the other hand, if the thickness is about 30 m, the effect of the present invention can be sufficiently achieved.
- a layer made of a thermoplastic resin with a melting point of 180 ° C. or higher may be provided, but when in contact with the outermost layer, it is appropriate that the total thickness is within the above range. is there.
- the adhesive resin layer is provided below the outermost layer, it is preferably 2 to 20 / ⁇ , preferably 3 to 10 m.
- connects a base material is 10-70 micrometers, Preferably it is 10-25 micrometers.
- additives can be added to the outermost layer and other thermoplastic resin layers as long as the object of the present invention is not impaired, or coating agents can be applied.
- coating agents can be applied as these additives and coating agents.
- Commonly used additives and coating agents such as agents can be used.
- thermoplastic resin layers or substrates The following is a reference test for adhesion to thermoplastic resin layers or substrates.
- thermoplastic resin layer is in contact with the thermoplastic resin layer and the base material.
- the following evaluation was made on.
- the degree of fusion of the thermoplastic resin layer to the thermo roll is critical.
- Table 1 shows the layer configurations of each reference test example and each reference comparative example.
- Tables 2 and 3 show the evaluation results of each reference test example and each reference comparative example.
- a double-sided tape to the metal plate.
- a sample of 1.5 cm in width and 7 cm in length is cut, and the back surface (surface on which the thermoplastic resin is not laminated) of the sample base is attached to the double-sided tape attached to the metal plate.
- a transparent adhesive tape (trade name: Serotape (trade name)) made by Chiban is firmly adhered to the surface of the outermost layer of the thermoplastic resin, and this transparent adhesive tape is forcibly peeled off, according to the following criteria. It evaluated visually.
- thermoplastic resin A state in which the thermoplastic resin does not adhere to the adhesive surface of the tape and adhesion remains, and the thermoplastic resin layer adheres firmly and curls.
- thermoplastic resin layer adheres to the adhesive surface of the tape, and the thermoplastic resin layer remains on the base material. Delamination is observed, but there is high resistance at the time of peeling, so that there is no problem in practical use. The condition in which the oil layer is in close contact.
- thermoplastic resin adheres to the adhesive surface of the tape, the heat-composable resin remains on the substrate, delamination is observed, and there is some resistance during peeling, but the thermoplastic resin layer is sufficiently adhered. There is a problem in practical use.
- thermoplastic resin layers A state of easy peeling between the thermoplastic resin layers and insufficient adhesion.
- Cast Commercially available cast coated paper (CLC Cast, manufactured by Nippon Paper Industries Co., Ltd.) is used as the base material, and 100 parts by weight of polymethylpentene resin (melting point 234 ° C., trade name TPX DX 820, manufactured by Mitsui Engineering Co., Ltd.) is the outermost layer.
- polymethylpentene resin melting point 234 ° C., trade name TPX DX 820, manufactured by Mitsui Engineering Co., Ltd.
- Maleic anhydride-modified polyolefin resin (Mitsui Egaku Co., Ltd .; trade name Admer; SE800) 100 parts by weight as an adhesive resin of the layer immediately below the outer layer (hereinafter referred to as middle layer); 100 parts by weight of a linear low density polyethylene (trade name: KC650T, manufactured by Nippon Polytech, Co., Ltd.) synthesized with a site catalyst was coextrusion laminated at 320 ° C. in a three-layer, three-layer configuration. For the thickness of the laminated resin, the outermost layer Z intermediate layer Z base material side layer was 5 ⁇ 5 ⁇ 30; ⁇ ⁇ .
- Reference Test Example 5 Similar to Reference Test Example 1 except that 100 parts by weight of an ionomer resin (trade name HIMIRAN 1555 made by Mitsui DuPont Chemical Co., Ltd.) was used as the ethylene-methacrylic acid copolymer as the adhesive resin of the intermediate layer. I did it.
- an ionomer resin trade name HIMIRAN 1555 made by Mitsui DuPont Chemical Co., Ltd.
- thermoplastic resin o Performed in the same manner as in Reference Test Example 1 except that polyethylene terephthalate (manufactured by Mitsui DuPont Chemical Co., Ltd., trade name: PT7001, Melting point 254 ° C.) was used as the outermost layer thermoplastic resin o
- the same cast coated paper as in Reference Test Example 1 is used as a base, 100 parts by weight of a polymer polystyrene resin as a thermoplastic resin of the outermost layer, and a linear low density polyethylene 100 synthesized with a single site catalyst on the base surface.
- the parts by weight were coextrusion laminated at 320 ° C.
- the thickness of the laminated resin was 5Z30 / Zm for the outermost layer Z substrate side layer.
- the same cast coated paper as in Reference Test Example 1 was used as a base material, and 100 parts by weight of polypropylene resin (melting point: 158 ° C.) as the outermost layer thermoplastic resin was synthesized with a single site catalyst on the base material surface. 100 parts by weight of linear low density polyethylene were coextrusion laminated at 320 ° C. The thickness of the laminated resin was 20Z20 / Zm for the outermost layer Z substrate side layer.
- SS-LLDPE is an abbreviation of linear low density polyethylene synthesized with single site catalyst.
- Reference Comparative Example 1 in which the thermoplastic resin of the outermost layer was directly laminated on the substrate, the adhesion to the substrate was inferior.
- Reference Comparative Example 3 is excellent in adhesion to the base material without peeling between the thermoplastic resin layers, but the thermoplastic resin having a melting point of less than 180 ° C. is used as the outermost layer. Since it was used, it heat-sealed at the time of recording, and the entrainment to a heat roll occurred.
- thermoplastic resin have a thickness of 320 m at a temperature of 320 ° C, a laminate width of 500 mm, and a speed of 200 mZ.
- the appearance when extrusion lamination was carried out was visually evaluated according to the following criteria.
- Lamination width is difficult to process, but it is not a problem as a product.
- ⁇ A homogeneous molten resin film is formed, and a good resin layer can be obtained.
- the polypentene resin ( ⁇ ), which is superior only in its superiority, is preferred also in terms of processability such as processability and processability, and is preferably used.
- polybutylene terephthalate ( ⁇ ) and polyethylene terephthalate (PET) do not have ductility and are poor in fluidity, and therefore, when extruded on a substrate, the molten resin film meanders and is inferior in processing and formability.
- the substrate typically refers to a paper produced by intertwining vegetable fibers or vegetable fibers with other fibers and adhering them.
- High quality paper recycled paper, coated paper (coated paper), etc. It can be mentioned.
- type of pulp, etc. as a raw material for paper.
- wood fibers such as hardwood kraft pulp (LBKP), softwood kraft pulp (NBKP), thermomecocal pulp, ground pulp, and waste paper pulp (DIP), if necessary, cotton linters, kenaf, hemp, bamboo, etc.
- Non-wood fibers are available.
- filler to be compounded it is possible to use known fillers such as heavy calcium carbonate, light calcium carbonate, olivine, clay, talc, hydrated silica, white carbon, titanium oxide, synthetic resin filler and the like. It can.
- the amount of filler used is preferably 6% by weight or more per pulp weight.
- a sulfuric acid band, a sizing agent, a paper strength agent, a retention aid, a color pigment, a dye, an antifoaming agent, etc. may be contained.
- the method of paper making of paper is not particularly limited, and any of acid paper making, neutral paper making and alkaline paper making method using a long mesh machine including a top wire etc. and a round mesh machine etc. Of course, medium quality paper containing mechanical pulp can also be used. Furthermore, for the purpose of improving the surface strength and the size, a surface treatment agent containing a water-soluble polymer as a main component may be applied.
- a surface treatment agent containing a water-soluble polymer as a main component may be applied.
- water-soluble polymer those commonly used as surface treatment agents such as oxidized starch, hydroxyl etherified starch, enzyme-modified starch, polyacrylamide, polyvinyl alcohol and the like can be used alone or as a mixture thereof. .
- a paper strength agent for the purpose of water resistance and improvement of the surface strength and an external additive sizing agent for the purpose of imparting sizing can be added to the surface treatment agent.
- the surface treatment agent is applied by a coating machine such as a 2-roll size press coater, a gate roll coater, a blade metering size press coater, a rod metering size press coater, and a film transfer type roll coater such as shim sizer. be able to.
- the paper used in the present invention preferably further contains an organic compound having the function of inhibiting interfiber bonding of pulp.
- an organic compound hereinafter sometimes referred to as a bulking agent
- the fiber-to-fiber bonding of the pulp is inhibited, that is, the density is reduced (bulk). This increases the air gap and allows the same thickness but light weight.
- the heat heated by the heat roll is divided into the amount that the surface force is also dissipated at the time of discharge and the amount that is stored in the paper.
- the surface temperature of the paper after printing drops rapidly due to heat radiation, but when printing is performed in large quantities at high speed, the heat stored inside will transfer to the surface side, causing the surface temperature to rise again.
- the risk of toner blocking increases.
- the thermoplastic resin layer dissipates heat more slowly than paper, a lot of heat is accumulated inside the paper, and the risk of toner blocking is further increased.
- the heat storage performance is low due to the heat insulation performance and low density due to the large number of voids present, so the laminated sheet heated by the heat roll radiates the surface force and Due to the heat insulation and low heat storage capacity, the print sheet is deposited without heat storage inside. As a result, the occurrence of toner blocking is prevented.
- the central portion of the bulky paper is a heat insulating layer after deposition, heat conduction from the other side can be suppressed, and the influence of heat from the other side to the printing side can be suppressed. it can.
- the temperature rise can be suppressed even as a laminated sheet provided with a thermoplastic resin layer having poor heat dissipation, and as a result, the temperature rise of the paper can be suppressed. Toner blocking 'property is improved.
- An organic compound having the function of inhibiting interfiber bonding of pulp can be selected by the following test.
- This paper is also used as a base paper for cast coated paper, which is a type of base material described later.
- Experimental orientation paper machine using pulp slurry containing 0.3 part by weight of organic compound to be tested per 100 parts by weight of bone dry pulp and the norp composition of the paper of interest. Made at a rotational speed of 900 rpm, and pressed and dried according to the method of JIS P-8209. The drying conditions are treated with a blower dryer at 50 ° C. for 1 hour. After leaving this test paper in an environment of 23 ° C. and 50% relative humidity for 24 hours, the tensile strength is measured in accordance with JI SP-8113.
- the compound of decreasing tensile strength is an organic compound having the function of inhibiting the interfiber bonding of the present invention. If the reduction rate at this time is too small, the bulk increase effect is small, so it is necessary to add a large amount.
- the organic drug whose tensile strength decreases Any product can be used if its strength is reduced by 0.3%.
- a reduction rate of 5 to 30% is preferable, in particular 8 to 20%.
- the organic compound having the action of inhibiting the interfiber bonding of the pulp of the present invention (hereinafter abbreviated as "bonding inhibitor”) is a compound having a hydrophobic group and a hydrophilic group, and has a tensile strength in the above test. It has a hypotensive effect.
- a low density binder (or bulking agent) for paper making and bulking up of paper is suitable as a binding inhibitor of the present invention, for example, W098 / 03730, JP-A No. 11-
- the compounds disclosed in JP-A-2002284, JP-A-11-350380, JP-A-2003-96694, JP-A-2003-96695 and the like can be mentioned.
- ethylene and Z or propylene oxide adducts of higher alcohols ethylene and Z or propylene oxide adducts of higher alcohols, polyhydric alcohol type nonionic surfactants, ethylene oxide adducts of higher fatty acids
- Esterified compound of polyhydric alcohol and fatty acid, ethylene oxide adduct of ester compound of polyhydric alcohol and fatty acid, or fatty acid polyamidoamine, fatty acid diamidoamine, fatty acid monoamide, or polyalkylene polyamine 'fatty acid' epichlorohydrin Condensates and the like can be used, and these can be used alone or in combination of two or more.
- Preferred are ester compounds of a polyhydric alcohol and a fatty acid, fatty acid diamidoamines, fatty acid monoamides, polyalkylene polyamines' fatty acids and epichlorohydrin condensates.
- the fiber-to-fiber bonding inhibitor of pulp is contained in an amount of 0.1 to 1: L parts by weight per 100 parts by weight of pulp. It is preferable to contain 0 parts by weight.
- a stock was prepared by adding and mixing 0.3 parts of a slurry shown in Table 5 with 30 parts of NBKP and 1 part of a refiner ground pulp (RGP) 70 as a 1% slurry.
- Bear this stock Paper was produced at a rotational speed of 900 rpm using an experimental orientation paper machine manufactured by Tani Chemical Co., Ltd., and pressed and dried according to the method of JIS P-8209. The drying conditions were treated with a blower dryer at 50 ° C. for 1 hour to obtain a test paper for testing.
- the test paper was left at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours, and then the tensile strength was measured according to JIS P-8113. The results are shown in Table 1.
- the tensile strength reduction rate was determined relative to the tensile strength when no binding inhibitor was added.
- the highly smooth substrate is one having a surface roughness Rz of 5.0 m or less on one side or both sides, more preferably 1. O / z m or less, still more preferably 0.6. m or less.
- high quality paper, coated paper and the like can be used, but it is preferable to use coated paper, particularly cast coated paper, in order to give a silver-plated photographic impression. Since paper, which is a base material of the laminated sheet, is composed of vegetable fibers and the like intricately intertwined, there are innumerable minute unevenness on the surface.
- the molten resin extruded as a thin film on the substrate surface follows the irregularities on the surface. Will be stacked. Such irregularities are brought into contact with the molten resin when the substrate and the molten resin are pressed and pressed, and as a cooling roll which presses the same, a mirror finish having a highly smooth peripheral surface is used.
- the force to be corrected to a certain extent for the convex portion remains a concave that can not be corrected even by this, and this becomes a minute depression on the surface of the laminated sheet, causing deterioration of the beauty.
- the present invention it was found that by using a substrate having a surface roughness Rz of 5. O / zm or less, high gloss and good aesthetics can be obtained. A laminated sheet with 50% or more is obtained.
- the image clarity indicates the appearance of an object reflected on the surface, and is an indicator that the higher the value, the more clearly the object is reflected like a mirror. Therefore, the fact that this value is high means that the beauty is good.
- image clarity ISK-7105].
- the outline of the measurement method is to measure the degree of sharpness (in the case of the present invention, reflection) of the image transmitted or reflected by the test piece, and the light is irradiated through a moving engineering comb and calculated.
- indexes for measuring the smoothness of paper include Oken's smoothness, Beck's smoothness, etc. These measurement methods measure how many seconds the air is blown on the surface and it passes by. There is a small difference between the paper in which the convex portion is corrected but the concave portion remains and the paper in which the concave portion as well as the convex portion is corrected.
- the surface roughness selected in the present invention is a measurement method in which the surface is traced with a stylus. I will not miss it.
- the surface roughness referred to in the present invention is a ten-point average roughness (Rz) measured according to JIS B-0601, and the outline of the measurement method is a plane perpendicular to the average surface of the surface to be measured.
- Rz ten-point average roughness
- the contour (cross section curve) that appears at the cut force Forces the third of the highest straight lines of the straight line parallel to the average line of the portion extracted by the reference length Select the one that passes through the second valley bottom, measure the distance between these two straight lines in the direction of the longitudinal magnification of the cross-sectional curve, and express that value in micrometers. It is
- the method for obtaining the base material of the present invention by improving the surface roughness of paper is not particularly limited, and for example, there is a method of squashing a convex portion of the paper surface by a calender, or a method of providing a coat layer on the surface such as coated paper.
- a method of squashing a convex portion of the paper surface by a calender or a method of providing a coat layer on the surface such as coated paper.
- the rigidity of the laminated sheet on which the thermoplastic resin is laminated by the extrusion lamination method or the co-extrusion lamination method depends on the rigidity of the base material.
- the method of providing the coat layer on the surface is a method of filling the concave portion of the paper to make it flat, and therefore, it is more suitable to be used as the base material of the laminated sheet of the present invention.
- Coated paper is generally a base paper provided with a coating layer mainly containing a binder and an organic or inorganic pigment, and is widely used as printing paper or recording paper according to various methods. Methods for producing coated paper are also known, and commonly used materials and equipment are used as appropriate.
- the binder include polyvinyl alcohol, styrene polymer, styrene-butadiene copolymer, styrene-acrylic copolymer, ethylene-acetate-coal copolymer and derivatives thereof.
- the pigment include kaolin, calcined clay, calcium carbonate, talc, silica, alumina and the like.
- a coat layer is provided by coating on the surface of the base paper using a mouth 1 to noreco 1 to a force 1 to force 1 to 10 1 to a gravureer, a die coater or the like.
- cast coated paper is a paper obtained by pressing a coated layer in a wet state against a heated mirror metal drum and drying it to obtain a smooth surface, and is a substrate capable of improving surface smoothness.
- Cast coated paper can be produced by the following method.
- the paper coated with the coating liquid does not pass through the drying equipment, and the coated side is pressed against the cast drum.
- the water in the coating liquid evaporates from the back of the paper.
- cast dora The surface is a mirror drum force, and the surface (coated surface) on the side pressed against the cast drum has high gloss.
- the coating solution on the coated surface is gelled with a coagulating solution and then pressed against a cast drum, and then solidified once dried, and then pressed onto a cast drum.
- the cast coated paper obtained by any manufacturing method can be used as the substrate of the present invention.
- a coating composition for a coating layer comprising a specific pigment and an adhesive as main components, and a mirror surface heated to a wet coating layer is used. It has been found that the cast coating paper produced by the rewet method, pressed against the finished surface and dried and finished, is further excellent in the glossiness and the aesthetics, and the water resistance of the cross section is improved.
- this aspect will be described in detail.
- the cast coat layer is formed by preparing a coating composition containing a pigment, a binder, and various other additives as required, and coating the same on a base paper.
- the pigment contained in the cast coat layer of the present invention is in the range of 0.4 to 4. 50 parts by weight or more, preferably 60 parts by weight or more, more preferably 70 parts by weight or more of kaolin having a particle size distribution containing 65% or more of particles on a volume basis per 100 parts by weight of the inorganic pigment.
- the particle size distribution is determined by measuring the volume particle size distribution of particles using a laser diffraction Z scattering type particle size distribution measuring device (manufactured by Malvern Co., Ltd., device name: Mastersizer One S). The percentage of particles falling within the ⁇ m range is calculated.
- the content preferably containing a plastic pigment is preferably 5 to 50 parts by weight, more preferably 10 to 45 parts by weight, still more preferably 20 parts by weight with respect to 100 parts by weight of the inorganic filler. It is to contain 45 parts by weight.
- the plastic pigment used in the present invention may be used singly or in combination of two or more, as required, in a solid, hollow or plastic Z-cored plastic pigment.
- the blending amount of the solid type plastic pigment is preferably 10 to 50 parts by weight, and more preferably 20 to 45 parts by weight with respect to 100 parts by weight of the inorganic pigment. Further, the blending amount of the hollow type plastic pigment is preferably 5 to 25 parts by weight, and more preferably 10 to 23 parts by weight with respect to 100 parts by weight of the inorganic pigment.
- the constituent polymer component of the plastic pigment preferably, monomers such as styrene and Z or methyl methacrylate, etc. are used as a main component, and other monomers copolymerizable therewith are used as needed.
- copolymerizable monomers examples include ⁇ -methylstyrene, olefin-based aromatic monomers such as chlorostyrene and dimethylstyrene, methyl (meth) acrylate, hydroxyethyl (meth) acrylate and (meth) acrylic acid.
- Monoolefin monomers such as butyl, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate and (meth) acrylate-tolyl, and monomers such as butyl acetate.
- alefin-based unsaturated monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, monomers of hydroxylic acid, hydroxylyl, hydroxyl acrylate methacrylate, etc.
- Olefin-based unsaturated hydroxy monomers such as hydroxy propyl acrylate, and olephine-based unsaturated amide monomers such as acrylamide, methacrylamide, ⁇ ⁇ -methylol acrylamide, ⁇ -methoxymethyl acrylamide, ⁇ -methoxymethyl methacrylamide and the like
- amide monomers such as acrylamide, methacrylamide, ⁇ ⁇ -methylol acrylamide, ⁇ -methoxymethyl acrylamide, ⁇ -methoxymethyl methacrylamide and the like.
- dimer vinyl monomers and the like such as divinylbenzene and the like.
- these monomers are illustrative and other copolymerizable monomers may be used. Nomers can be used.
- the plastic objects used in the present invention have an average particle diameter of 0.1 to 1.
- kaolin other than the above clay, delaminated clay, ground calcium carbonate, light calcium carbonate, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide other than the above, which is conventionally used for coated paper.
- Inorganic pigments such as caiic acid, caiic acid salt, colloidal silica, and satin white can be used by selecting one or more kinds as needed.
- kaolin having a particle size distribution containing 65% or more of particles in the range of 0.4 to 4.2 m on a volume basis is more preferably 50 parts by weight or more per 100 parts by weight of the inorganic pigment.
- the white paper glossiness and the printing glossiness are improved, and the appearance of the cast surface is excellent.
- the adhesive (binder) used in the cast coat layer is not particularly limited, and conventionally used for coated paper, and is conventionally used as styrene 'butadiene type, styrene' acrylic type, ethylene. , Various copolymers such as butadiene 'methyl methacrylate and butyl acetate', and synthetic adhesives such as polyvinyl alcohol, maleic anhydride copolymer, acrylic acid / methyl methacrylate copolymer, etc. Casein, soy protein
- Synthetic protein proteins Synthetic protein proteins, oxidized starches, positive starches, etherified starches such as urea phosphate esterified starches, hydroxyl etherified starches, starches such as dextrin;
- etherified starches such as urea phosphate esterified starches, hydroxyl etherified starches, starches such as dextrin;
- cellulose derivatives such as cenolerose or hydroxymethinoresenoreulose are appropriately selected and used. These adhesives are used in an amount of about 5 to 50 parts by weight, preferably about 5 to 30 parts by weight, per 100 parts by weight of the inorganic pigment.
- sodium chloride, sodium chloride, zinc chloride, magnesium chloride, sodium sulfate, potassium sulfate, ammonium sulfate in addition to the above-mentioned pigment and adhesive Sodium, zinc sulfate, magnesium sulfate, ammonium nitrate, sodium monophosphate, sodium phosphate, calcium phosphate, sodium polyphosphate, sodium hexametaphosphate, sodium formate Thorium, ammonium formate, sodium acetate, potassium acetate, sodium monochlorate, sodium malonate, sodium tartrate, potassium tartrate, sodium citrate, potassium citrate, potassium lactate, sodium lactate, sodium darconate, sodium adipate, Various additives such as ammonium salt metal salts of inorganic acids and organic acids such as sodium dioctyl sulfocolate, metal salts of organic acids, methylamine, diethanolamine, diethylenediamine, diisopropylamine and the like can be used as appropriate
- auxiliary agent conventional additives such as dispersant, thickener, water retention agent, defoamer, coloring agent, mold release agent, flow modifier, water resistance agent, preservative, printability improver, etc.
- auxiliary agents to be blended into the coating composition for coated paper are suitably used.
- a coating liquid containing a pigment and an adhesive used for general coated paper is used as the above-mentioned coating machine It is also possible to use a paper previously coated using a paper, or a paper coated with a blade coater, a wheel coater, an air knife coater or the like after applying and drying the surface treatment agent. In this case, it is desirable that the coating amount be about 5 to 30 g Zm 2 in dry weight per one side. Furthermore, if necessary, this precoated base paper can be subjected to smoothing treatment such as super calendering and soft calendering in advance.
- the basis weight is preferably force that can be used about two 30 ⁇ 200gZm is 50 ⁇ 180GZm 2.
- a 2-roll size press coater As a method for applying the cast coating composition to the base paper, a 2-roll size press coater, a gate roll coater, a blade metering size press coater, an open metering press size, a shim sizer
- film transfer type nozzles such as JF sizer, flat-blade Z-blade coaters, jet fountain Z-blade coaters, short dwell time applicator-type coaters, etc.
- the coating can be carried out by using a known coater such as a rod metal ring coater, an air knife coater, a curtain coater or a die coater, and the coating amount is preferably 5 to 30 gZm 2 per one side of the base paper. 10 to 20 g z m (?
- Direct method to mirror finish in wet condition after coating, solidify wet coated layer The mirror surface finish solidification method, the wet coat layer is once dried, and the rewet liquid is used to re-wet the coat layer with the rewet liquid to make the mirror surface finish.
- the above-mentioned heating cylinder, hot air drier, gas heater drier, electric heater drier, infrared heater drier or the like of various types such as an infrared heater drier may be used alone or in combination.
- the degree of drying of the coated paper varies depending on the type of base paper, the type of coating composition, etc., but generally it is in the range of about 1 to 10% as the paper moisture, and drying in the range of about 2 to 7% is desirable.
- the dried coated layer may be mirror-finished by the rewetting method as it is, but the dried coated paper may be smoothed to improve the paper gloss, the smoothness and the printing glossiness.
- a method of surface treatment such as surface treatment that is preferred, super calenders using a cotton roll as an elastic roll, soft calenders using a synthetic resin roll as an elastic roll, known surface treatments such as brushing etc.
- An apparatus can be used. In particular, by setting the glossiness of coated paper to 70% (75 °) or more before mirror surface finishing, the quality such as white paper glossiness and print glossiness is improved.
- Mirror finish is achieved by pressing wet coated paper against the surface of a heated mirror roll with a press roll and drying, and a cast drum etc. can be used as the mirror roll.
- a heated mirror roll with a press roll and drying, and a cast drum etc.
- the surface temperature of the heated mirror roll is 80 to 200 ° C.
- the pressing pressure at the pressure contact is approximately 30 to 250 kg Z cm. it can.
- the re-wetting liquid is not particularly limited, and for example, 0.1 to 3 weight of a release agent such as polyethylene emulsion, fatty acid stone, calcium stearate, microcrystalline wax, surfactant, and funnel oil.
- a conventional re-wetting solution such as an aqueous solution or emulsion containing about 1% is used.
- alkali, phosphates such as sodium hexametaphosphate, urea, organic acids and the like may be used in combination to promote the plastic deformation of the dry coating layer.
- the cast coated paper used in the present invention is more effective when the white paper glossiness (20 °) is 30% or more or the image property is 70% or more.
- the reason why the gloss and the beauty are excellent is not clear! / ⁇ is estimated as follows.
- the filling factor of the pigment particles in the coat layer is lowered to improve the coatability, and the pressure contact with the mirror surface is achieved.
- the adhesion is enhanced, and the toner fixing layer surface formed on the surface of the laminated sheet of the present invention can easily copy a mirror-finished surface.
- plastic pigments are softened by the heat of the mirror-finished surface, and the adhesion with the mirror-finished surface is further enhanced to make it easy to copy the mirror surface.
- the glossiness of the coated paper is improved, and the glossiness of the thermoplastic resin after lamination is considered to be also high.
- the glossiness can be further improved by smoothing the coated layer before rewet with the rewetting liquid using a calender or the like.
- the invention relating to the cast coat layer formed by the above rewet method was filed as International Application No. PCTTZJP2004Z15275.
- the influence on the cross-section water resistance is very low compared to the inorganic pigments which are generally used, since the water absorbency of the plastic pigment contained in the cast coat layer is It is believed that the coating layer acts to prevent water absorption and improve cross-section water resistance.
- the degree of inundation from the laminated sheet end was evaluated by the following method. For the sample cut into 4 cm square, after dipping for 10 minutes in 50 ° C warm water colored in blue, repeat the process of drying for 10 minutes with an air blower set at 60 ° C. for 5 times, from the end The inundation distance was measured.
- kaolin as pigment 70 parts of kaolin as pigment, 30 parts of light calcium carbonate, 5 parts of styrene butadiene latex as binder, 5 parts of casein, 2 parts of calcium stearate as mold release agent were added to prepare a coating solution having a solid content of 43%.
- a high-quality paper with a basis weight of 139 gm 2 was used as the coated base paper.
- polymethylpentene (melting point 234 ° C., MFR 200 g ZlO min, density 0.84 g Zcm, trade name TPX DX 820 manufactured by Mitsui Chemicals, Inc.) on the cast coated side of the above cast coated paper as a substrate Extrusion is carried out so that the resin layer thickness becomes 20 m at an extrusion temperature of 300 ° C, and immediately, these molten resin and cast coated paper are mirror-polished with a cooling roll and a 95 ° hardness roll. Use a pressure of 15 kgf and a linear pressure of 15 kgf.
- the molten resin and the cast coated paper were pressure-bonded at a linear pressure of 15 kgf Zcm using a mat-finished cooling roll and a 95 degree hardness roll to obtain a base laminate sheet.
- a cationic core-shell acrylic ⁇ (concentration 34.5 wt 0/0, the core portion Tg: 50 ° C, shell Tg: 40 ° C, the core portion Z shell 50Z50) to 100 parts by weight, the charge
- a coating liquid having a solid content concentration of 10% by weight was prepared.
- the coating solution was coated on both sides of the base laminate sheet using a gravure coating machine so as to have a dry solid content of lgZm 2 and dried to provide a toner fixing layer to obtain a laminate sheet.
- 0.1 part of sodium polyacrylate as a dispersant was mixed with 100 parts of kaolin as a pigment and dispersed to prepare a clay slurry having a concentration of 70%.
- This clay slurry 50 parts, heavy calcium carbonate slurry 50 parts, styrene-butadiene copolymer latex 12 parts, starch 4 parts, and fluorescent dye are added, and water is further added to make the coating liquid 2 with a solid content concentration of 64%. Obtained.
- the coated base paper used was a high-quality paper with a basis weight of 123 g / m 2 and containing 7 parts of light calcium carbonate as a filler, 100 parts of a pulp for making paper and 100% of a clay pulp.
- the above base paper was coated on both sides with a blade coater so that the coating amount per side is 8 g Zm 2 at a coating speed of 500 mZ, and after drying, coating liquid 2 per side Double-side coating was performed with a blade coater so that the coating amount was 9 gZm 2 and dried. After drying, surface treatment with a super calender was performed to obtain coated paper.
- Surface roughness R 0.6 ⁇ m
- a laminated sheet was obtained in the same manner as Reference Example 21 except that the above-mentioned coated paper was used as a substrate.
- a wood free paper having a basis weight of 157 g / m 2 and a size degree of 40 seconds was obtained, containing 100 parts of chemical pulp as papermaking nops, 6 parts of light calcium carbonate as filler and 0.4 parts of sizing agents as internal chemicals. Size: Measured according to IS P 8122.
- a laminated sheet was obtained in the same manner as in Reference Test Example 21 except that the above-mentioned high-quality paper was calendered (temperature 60 ° C., 120 kg Z cm 2 , 8-p) to obtain a base material.
- Kaolin from Brazil as a pigment (trade name: Kapim DGZ manufactured by Rio Force Pim Co., Ltd., volume distribution particle size 0.4 to 4.2 ⁇ ⁇ ⁇ : 71.7%) 100 parts, solid plastic pigment (trade name: V- 1004Z Nippon Zeon, average particle size: 0.32 / ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ , glass transition temperature: 85 ° C) 30 parts of a pigment made by adding 0 1 part of sodium polyacrylate as a dispersing agent % Pigment slurry was prepared. To 100 parts of this pigment slurry, 14 parts of a styrene-butadiene copolymer latex and 4 parts of starch were added, and water was further added to obtain a coating liquid having a solid content concentration of 60%.
- the coated base paper used was a high-quality paper with a basis weight of 116 g / m 2 , containing 7 parts of light calcium carbonate as a filler, and 100 parts of pulp for papermaking and 100 ⁇ m pulp.
- a laminated sheet was obtained in the same manner as in Reference Test Example 21 except that the above-described cast-coated paper was used as a substrate.
- a laminated sheet was obtained in the same manner as in Reference Test Example 21 except that the wood free paper obtained in Reference Test Example 23 was used as a substrate without being subjected to calendering.
- Comparative Comparative Example 21 Although high gloss, the image clarity is low and the beauty is inferior. Regarding the image clarity, each reference test example is significantly improved compared to Reference Comparative Example 21. Ru. In particular, it is recognized that the difference in the surface roughness (Rz) contributes to the improvement of the image clarity by comparison between Reference Test Example 23 and Reference Comparative Example 21. By comparing the reference test example 23 with other reference test examples, it is recognized that the image clarity is improved as the surface roughness (Rz) is further reduced.
- Reference Test Example 25 uses a low density base paper using a binding inhibitor and is more transparent than Reference Test Example 24 using wood free paper
- Reference test Example 24 is the same as Reference Example 22 in that high-quality paper is used as the base paper, but the configuration of the coat layer is different, and the coat layer using a combination of kaolin and plastic pigment with narrow particle size distribution improves the cross-section water resistance. It can be judged that it contributes to By using a strong sizing agent, the water resistance of wood free paper can be improved as a result of Reference Test Example 23.
- the strength of the results of Reference Test 25 and 26 show that the low density base paper using a binding inhibitor and the low density base paper. It has been shown that the combination of a coating layer containing kaolin having a narrow particle size distribution and a plastic pigment provides an equivalent cross-section water resistance.
- the laminated sheet of the present invention is obtained by forming a transparent thermoplastic resin layer on a substrate, and has glossiness.
- a laminated sheet having higher gloss and excellent aesthetics can be obtained.
- high gloss means that the 75 degree gloss according to ISO 8254-1 is 80% or more, more preferably 90% or more, and is hereinafter referred to as Darros tone.
- the glossiness is about 45%, and those having such glossiness are referred to as semi-gloss.
- the laminated sheet of the present invention for recording by the electrophotographic printing method
- a thermoplastic resin having a melting point of 180 ° C. or more is used as the outermost layer of the thermoplastic resin layer
- a heat roll is used.
- the laminated sheet having a glossy area can maintain the gloss even after recording by the electrophotographic printing method.
- the base material itself such as cast coated paper is itself It is important that the adhesion between the laminated thermoplastic resin layers or between the thermoplastic resin layer and the substrate is good and the inside of the laminated sheet is flat and smooth, as well as the smoothness and the glossiness of the sheet. Conceivable. Therefore, a thermoplastic resin having a melting point of 180 ° C. or more is selected as the thermoplastic resin used for the outermost layer, and a specific adhesive resin is used as an intermediate layer to contact the outermost layer and the substrate in contact therewith. Alternatively, the adhesion with other thermoplastic resins is improved, and a smooth and flat laminated sheet can be obtained.
- thermoplastic resin having a melting point of 180 ° C. or higher
- modified polyolefin resin is used as an adhesive resin
- heat is applied because the adhesive resin is cross-linked with a polyfunctional group or metal.
- the bond strength is likely to change due to heat treatment, and rapid heating during lamination is considered to strengthen the adhesion.
- SS-LLDPE or the like having good adhesion in contact with the substrate, mutual adhesion between the substrate and the thermoplastic resin layer thereon can be further improved.
- SS-LLDPE is a soft resin that can easily soften at a temperature that can be heated during electrophotographic printing, it maintains high viscosity even if softened, and maintains a viscosity during lamination. It is thought that it contributes to the improvement of glossiness by pushing out the air taken in at the interface to prevent the occurrence of craters.
- latent image toner is transferred to a toner fixing layer and fixed by heat fusion.
- a laminated sheet obtained by laminating a thermoplastic resin on the surface is inferior in writability when compared to ordinary paper etc.
- silicone is used in the hot hole.
- the transfer of this silicone to the paper surface tends to reduce the writability after printing.
- Patent Document 13 Japanese Patent Application Laid-Open No. 2002-91049
- fogging a state in which toner scatters on the white paper and causes soiling
- the toner fixing layer is blended with an inorganic filler having a small particle size, and the toner fixing layer has a surface smoothness of 200 seconds or more and a surface resistivity of 5 ⁇ 10 8 to 1 ⁇ 10 11.
- the sheet although the glossiness is not high, a laminate sheet is provided which has good toner fixability, suppression of fogging phenomenon, and good writability with pencils and ball pens before and after recording by electrophotographic printing method. is there.
- Such a toner fixing layer containing an inorganic pigment so as to emphasize writability and the like is hereinafter referred to as a matte tone.
- the inorganic filler to be blended in the toner fixing layer those having an average particle diameter of 2.5 m or less can be suitably used. Thereby, the toner fixability and the writing property of the laminated sheet can be improved, and a laminated sheet suitable for various uses outdoors can be provided. More preferably, it is 2. 0 to 0. l / z m. If it is too large, it will cause fogging, and if it is too small, it will cause deterioration of writing performance.
- the average particle size is a value measured by Coulter counter.
- Types of inorganic fillers include, but are not limited to, clay, silica, calcium carbonate, talc and the like.
- the blending ratio of the inorganic filler to the binder in the toner fixing layer is preferably 8: 2 to 2: 8 in view of the writing property. If the compounding ratio of the binder is less than 8: 2, and the compounding ratio of the less effective binder is more than 2: 8, most of the inorganic filler will be buried in the binder and will not fulfill its function, so after printing Writeability is inferior.
- the toner fixing layer is not limited to the matte tone including the inorganic pigment, and the surface is smooth even if it has the above-mentioned dross tone or semi-gloss tone having glossiness.
- the degree of smoothness is preferably 200 seconds or more, preferably 1000 seconds or more, according to the Ohken-type smoothness measurement method.
- the Oken type smoothness is measured in accordance with JAPAN TAPPI Paper and Pulp Test No. 5-2.
- the outline of the measurement method is as follows.
- Toner fogging is apt to occur as the surface is extremely rough. This is considered to be because the convex portions present on the sheet surface are strongly pressed to the toner transfer drum and the toner transfer belt from the concave portions, and the toner is easily attached selectively.
- an inorganic filler or the like is added to the toner fixing layer, and these protrusions appear on the surface, and as the protrusions become larger, the unevenness becomes larger and fogging tends to occur. Therefore, it is desirable to use inorganic pigments having a small particle size.
- the toner fixing layer is not limited to the matte tone including the inorganic pigment, and the above-mentioned dross tone having glossiness. Even if semi-glossy, it is desirable that the surface electrical resistivity is 5. OX 10 8 to 5 OX 10 11 . Preferably, 1. 0 x 10 9 1. 1. OX 10 1 G is good. As the surface's electrical resistivity is higher, the power to attract the toner to the paper becomes larger as the electricity escapes, and it is thought that the toner scatters and causes fog.
- the surface resistivity is too small, electricity may be released and even the toner to be transferred to the image part may not be transferred immediately, resulting in a transfer failure.
- a known antistatic agent to the thermoplastic resin layer or toner fixing layer, or to apply an antistatic agent to the surface of the thermoplastic resin layer or toner fixing layer.
- Antistatic agent type and amount added The amount is suitably adjusted so as to obtain a desired surface electrical resistance which is not particularly limited.
- a coating method of the antistatic agent any of known coating methods can be adopted.
- Measurement was carried out using Mitsubishi Chemical's HIREST-UP MCP-HT450 in accordance with Mitsubishi Chemical Method (MCC-A) under conditions of an applied voltage of 500 V and a measurement time of 60 seconds under an environment of 23 ° C. and 50% RH. .
- A3 size sample is printed using Fuji Xerox Co., Ltd. color laser beam printer docuprint C3530, and the printed matter is written using a pencil (HB) and a ballpoint pen under constant load and constant speed conditions, visually It was evaluated and indicated by the following criteria.
- a visual evaluation was conducted as to the presence or absence of fogging when 10 A3 size samples were printed using Fuji Xerox Co., Ltd. color laser beam printer docuprint C3530.
- Melt polymethylpentene (melting point: 234 ° C, product name TPX DX820, manufactured by Mitsui Engineering Co., Ltd.) was used on both sides of a high-quality paper with a basis weight of 157 g / m 2 , using a T-die.
- the extrusion lamination is carried out so that the oil layer thickness becomes 20 m, and these molten resin and fine paper are immediately pressed using a cooling roll and a 95 degree hardness roll with a linear pressure of 15 kgf Z cm Then, a base material laminated sheet was obtained.
- the toner fixing layer does not contain 80 parts by weight of clay having a particle size of 1 ⁇ m or less, 20 parts by weight of silica having an average particle size of 1.6 ⁇ m, and a coating liquid having a solid content concentration of 7.5% by weight.
- a toner fixing layer was formed in the same manner as in Reference Test Example 31 except that adjustments were made.
- a toner fixing layer was formed as a toner fixing layer in the same manner as in Reference Test Example 31 except that the antistatic agent was not contained.
- Reference Comparative Example 32 does not contain an inorganic pigment in the toner fixing layer, which results in poor writing after printing, and fogging occurs, and Reference Comparative Example 33 does not contain an antistatic agent, and therefore, the surface is surfaced. An electrical resistivity of 1.0 x 10 15 or more is observed, and a large occurrence of fogging is observed.
- Table 8 shows the results of the following evaluation of the obtained laminated sheet V.
- a white cotton cloth was applied to the toner fixing layer with a fastness tester (manufactured by Suga Test Instruments Co., Ltd.), and the appearance after sliding 100 reciprocations with a load of 250 g Zcm 2 was visually observed and evaluated according to the following criteria.
- the number of paper jams or the number of feed misses was measured when 1000 sheets of A4 size were printed using a color laser beam printer Speedo N5300 manufactured by Casio Computer Co., Ltd., and the results were shown according to the following criteria.
- a double-sided tape to the metal plate.
- a sample of 1.5 cm in width and 7 cm in length is cut, and the back surface (surface on which the thermoplastic resin is not laminated) of the sample base is attached to the double-sided tape attached to the metal plate.
- a transparent adhesive tape (trade name: Serotape (trade name)) made by Chiban is firmly adhered to the surface of the outermost layer of the thermoplastic resin, and this transparent adhesive tape is forcibly peeled off, according to the following criteria. It evaluated visually.
- thermoplastic resin A state in which the thermoplastic resin does not adhere to the adhesive surface of the tape and adhesion remains, and the thermoplastic resin layer adheres firmly and curls.
- thermoplastic resin layer adheres to the adhesive surface of the tape, and the thermoplastic resin layer remains on the base material. Delamination is observed, but there is high resistance at the time of peeling, so that there is no problem in practical use. The condition in which the oil layer is in close contact.
- thermoplastic resin layer does not adhere sufficiently but there is a practical problem, although there is some resistance during peeling.
- thermoplastic resin layers A state of easy peeling between the thermoplastic resin layers and insufficient adhesion.
- the degree of inundation from the laminated sheet end was evaluated by the following method. For the sample cut into 4 cm square, after dipping for 10 minutes in 50 ° C warm water colored in blue, repeat the process of drying for 10 minutes with an air blower set at 60 ° C. for 5 times, from the end The inundation distance was measured.
- A3 size sample is printed using Fuji Xerox Co., Ltd. color laser beam printer docuprint C3530, and the printed matter is written using a pencil (HB) and a ballpoint pen under constant load and constant speed conditions, visually It was evaluated and indicated by the following criteria.
- the Oken type smoothness was measured.
- Measurement was carried out using Mitsubishi Chemical's HIREST-UP MCP-HT450 in accordance with Mitsubishi Chemical Method (MCC-A) under conditions of an applied voltage of 500 V and a measurement time of 60 seconds under an environment of 23 ° C. and 50% RH. .
- thermoplastic resin layer 100 parts by weight of polymethylpentene (melting point: 234 ° C., trade name “TPX DX820” manufactured by Mitsui Chemicals, Inc.) on both sides of a high-quality paper (weighing weight: 157 g, Zm 2 ) as a base material using a T-die
- the extrusion lamination is carried out so that the resin layer thickness becomes 20 / z m at a temperature of 300 ° C., and these molten resin and fine paper are immediately used with a cooling roll and a 95 degree hardness roll.
- the substrate sheet was obtained by pressure-pressing with a linear pressure of 15 kgf Zcm.
- corona discharge treatment was applied to the surface of the thermoplastic resin layer.
- a binder for a toner fixing layer cationic core 'shell type acrylic ⁇ (concentration 34.5 wt 0/0, the core portion Tg: 50.C, shell Tg: 40.C, the core unit Z shell
- a coating liquid having a solid content concentration of 30% by weight was prepared. The coating solution was coated on both sides of the above base sheet at 7 g / m 2 using a gravure coating machine to provide a toner fixing layer, to obtain a laminated sheet.
- An aqueous component of a styrene acrylic ester copolymer as a binder for a toner fixing layer 20 parts by weight of powder (concentration 37% by weight, Tg: 102 ° C.) and 80 parts by weight of aqueous dispersion of styrene acrylic copolymer (concentration 43% by weight, Tg: 10 ° C.)
- a laminated sheet was obtained in the same manner as Example 1.
- Tg: 10 ° C., and 50 parts by weight were used.
- the core 'shell acrylic ⁇ (concentration 33.5 wt 0/0, the core portion Tg: 130.C, shell Tg: 30.C, the core unit Z shell 40Z60
- a laminated sheet was obtained in the same manner as in Example 1 except that 100 parts by weight was used.
- styrene methacrylic acid ester copolymer resin concentration 30% by weight, Tg: 106 ° C.
- styrene acrylic copolymer resin resin concentration 25% by weight, Tg: 45 C
- a coating solution having a solid content of 43% 70 parts of kaolin as pigment, 30 parts of light calcium carbonate, 5 parts of styrene butadiene latex as binder, 5 parts of casein, 2 parts of calcium stearate as mold release agent were added to prepare a coating solution having a solid content of 43%.
- a high-quality paper with a basis weight of 139 gm 2 was used as the coated base paper.
- the resulting coating solution is applied to a coated base paper by a roll coater so that the dry solid content becomes 18 g Zm 2
- the solution is applied to a coating drum and then solidified with a 10% aqueous solution of zinc formate as a coagulant, and pressed and dried on a cast drum having a mirror surface heated to 100 ° C. while the coating is in a wet state. to obtain a cast coated paper of Zm 2.
- thermoplastic resin layer was subjected to corona discharge treatment.
- the surface resistivity of the antistatic agent is 1.0 ⁇ 10 1 G using 95 parts by weight
- a coating liquid having a solid content concentration of 6% by weight was prepared. The coating solution was coated on both sides of the above base sheet at 7 g / m 2 using a gravure coating machine to form a toner fixing layer, to obtain a laminated sheet.
- Kaolin from Brazil as a pigment (trade name: Kapim DGZ manufactured by Rio Force Pim Co., Ltd., volume distribution particle size 0.4 to 4.2 ⁇ m: 71.7%) 100 parts, solid plastic pigment (trade name: V- 1004Z Nippon Zeon, average particle diameter 0.32 ⁇ m, glass transition temperature 85 ° C) 30 parts of pigment, 0.1 parts of sodium polyacrylate as a dispersant is mixed and dispersed, 70% pigment A slurry was prepared. To 100 parts of this pigment slurry, 14 parts of a styrene-butadiene copolymer latex and 4 parts of starch were added, and water was further added to obtain a coating liquid having a solid content concentration of 60%.
- the coated base paper contains 0.4 parts of a binding inhibitor between pulp fibers (Kao Co., Ltd. KB-115), 7 parts of light calcium carbonate as a filler, 100 parts of pulp for making paper pulp and so on.
- a high-quality paper with a basis weight of 116 g Zm 2 was used.
- the above base paper, as the coated amount per one surface a coating liquid mentioned above is 12GZm 2, row duplex coating using a blade coater at a coating speed of 50 OMZ min, and dried. After drying, the surface was treated with a super calender.
- maleic anhydride modified polyolefin Resin (Product name Admar manufactured by Mitsui Chemicals, Inc .; SE 800) 100 parts by weight, linear low density synthesized with single site catalyst as a substrate side layer 100 parts by weight of polyethylene (trade name: NH725N, manufactured by Nippon Polytech Co., Ltd.) is coextruded and laminated at 320 ° C.
- the substrate sheet was press-bonded at a linear pressure of 15 kgfZcm using a roll and a 95 degree hardness roll.
- the thickness of the laminated resin was 15 ⁇ 5 ⁇ / ⁇ as the outermost layer Z intermediate layer Z base material side layer.
- the other side of the cast coated paper was laminated in the same manner as the cast coated side except that a matte finish cooling roll was used.
- the surface of the thermoplastic resin layer was subjected to corona discharge treatment.
- styrene acrylic acid ester copolymer Concentration 37% by weight, Tg: 102 ° C.
- cationic core-shell type acrylic resin (concentration 34.5)
- 0.7% by weight of the coating solution is added, and an antistatic agent is mixed so that the surface electrical resistivity becomes 1.
- the coating solution with a solid content concentration of 6% by weight is mixed. I prepared it.
- the coating solution using a gravure coater so that the coated amount of 8GZm 2, by coating the thermoplastic ⁇ layer surface of the substrate sheet to obtain a laminated sheet.
- toner fixing layer cationic core 'shell type acrylic resin as a binder in an aqueous solution in which 80 parts by weight of clay having a particle size of 1 ⁇ m or less and 20 parts by weight of silica having an average particle size of 1.6 ⁇ m are dispersed.
- a laminated sheet was prepared in the same manner as in Example 1 except that an aqueous dispersion of styrene acrylic acid ester copolymer (concentration 37% by weight, Tg: 102 ° C.) was used as a binder for the toner fixing layer. Obtained.
- a laminated sheet was obtained in the same manner as in Example 3 except that an aqueous dispersion of styrene acrylic copolymer (concentration 43% by weight, Tg: 10 ° C.) was used as a binder for the toner fixing layer, except that 100 parts by weight was used. .
- a binder for toner fixing layer 30 parts by weight of a non-ionic acrylic acid ester copolymer resin (concentration 40% by weight, Tg: 49 ° C.), an aqueous dispersion of styrene acrylic copolymer (concentration 43% by weight, Tg) 10 ° C.)
- Tg 49 ° C.
- Tg styrene acrylic copolymer
- a laminated sheet was obtained in the same manner as in Example 1 except that the toner fixing layer was not provided.
- test data of these Examples and Comparative Examples suggest various things. Described below The thing to do is the main thing, and it is not limited to this.
- the present embodiment has good toner fixability.
- it is good in Examples 1, 5, 7, 8 and 9 in which high temperature Tg and low temperature Tg binders of a core'shell type are combined as a binder used for the toner fixing layer.
- Comparative Example 5 in which printing was performed directly on the thermoplastic resin layer without providing the toner fixing layer, a defect was recognized.
- the toner toner blocking property is good. This is presumed to be attributable to the use of the high-temperature Tg hydrophilic polymer substance (A), when examined in combination with other examples and comparative examples 2 to 4.
- the toner blocking resistance of Examples 7 to 9 is ⁇ only by adding 5% by weight of the one used in Example 1 at Tgl 02 ° C. to the binder used in the toner fixing layer, and the degree Shows that there is not much improvement. It is apparent from the comparison between Example 2 and Example 3 that the high temperature Tg hydrophilic polymer substance (A) is preferably contained in an amount of 30% by weight or more.
- Example 1 suppresses the occurrence of blank paper blocking due to the inorganic filler addition by adopting a core-shell type binder.
- Examples 7 to 9 have a surface finish of high gloss and dross like, and in the case of force and dross like, the coefficient of friction generally tends to be high. Although it is well known that heavy transport is likely to occur, the addition of silicone to the toner fixing layer reduces the coefficient of friction and improves the transportability, as in Examples 7 and 8. By contrast with 9 It is clear. In Examples 1 to 6 and Comparative Examples 2 to 4, the surface glossiness is 45% and the surface glossiness is semi-glossy with 45%, and since the surface is rough with minute unevenness, there is no addition of silicone. However, the paper transportability is good. Furthermore, in Examples 10 and 11, although the inorganic filler is added to reduce the glossiness to make the surface tone matte, the friction coefficient tends to be high also in such a case, and silicone is used. It is effective to add it.
- the surface glossiness is 85% or more daross tone, about 40 to 60% semi-gloss tone, less than matt tone, and surface property rich in notion in glossiness before printing. It is possible to provide a laminated sheet of tone. In particular, in Examples 7 to 9 in which cast coated paper is used as the substrate, 85% of high gloss can be secured even after printing. It also exhibits excellent image clarity.
- Example 9 using a cast-coated paper in which a coat layer containing a pigment is provided by a cast coating method is used as a substrate.
- Example 9 using high quality paper as a base material is good, it is presumed that a large amount of internal sizing agent is added to make the size strong.
- the present invention can provide a laminated sheet rich in variety of mat tightness up to Daro's as a recording sheet for electrophotographic printing.
- it is excellent in surface water resistance and cross section water resistance, and can be used outdoors or in places where water is strong. And it can cope with the case where writing is necessary even after printing.
- the weight can be reduced by using a substrate with a small 1S specific gravity, which can improve the handleability.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Laminated Bodies (AREA)
- Paper (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/576,242 US7749591B2 (en) | 2004-09-30 | 2005-09-27 | Laminated sheet |
CN2005800332701A CN101040223B (zh) | 2004-09-30 | 2005-09-27 | 层压片材 |
DE112005003537T DE112005003537T5 (de) | 2004-09-30 | 2005-09-27 | Laminierter Bogen |
JP2006537749A JP4571147B2 (ja) | 2004-09-30 | 2005-09-27 | 積層シート |
GB0718579A GB2439293B (en) | 2004-09-30 | 2007-09-24 | Laminated sheet |
Applications Claiming Priority (2)
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JP2004-285677 | 2004-09-30 | ||
JP2004285677 | 2004-09-30 |
Publications (1)
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WO2006035761A1 true WO2006035761A1 (ja) | 2006-04-06 |
Family
ID=36118907
Family Applications (1)
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PCT/JP2005/017721 WO2006035761A1 (ja) | 2004-09-30 | 2005-09-27 | 積層シート |
Country Status (7)
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US (1) | US7749591B2 (ja) |
JP (1) | JP4571147B2 (ja) |
KR (1) | KR20070072865A (ja) |
CN (1) | CN101040223B (ja) |
DE (1) | DE112005003537T5 (ja) |
GB (1) | GB2439293B (ja) |
WO (1) | WO2006035761A1 (ja) |
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CN101040223B (zh) | 2010-12-08 |
GB2439293B (en) | 2010-05-26 |
JP4571147B2 (ja) | 2010-10-27 |
JPWO2006035761A1 (ja) | 2008-07-31 |
US7749591B2 (en) | 2010-07-06 |
DE112005003537T5 (de) | 2009-06-18 |
KR20070072865A (ko) | 2007-07-06 |
US20070292665A1 (en) | 2007-12-20 |
CN101040223A (zh) | 2007-09-19 |
GB0718579D0 (en) | 2007-10-31 |
GB2439293A (en) | 2007-12-27 |
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