WO2020116354A1 - 紙筒、及び紙筒用原紙 - Google Patents
紙筒、及び紙筒用原紙 Download PDFInfo
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- WO2020116354A1 WO2020116354A1 PCT/JP2019/046864 JP2019046864W WO2020116354A1 WO 2020116354 A1 WO2020116354 A1 WO 2020116354A1 JP 2019046864 W JP2019046864 W JP 2019046864W WO 2020116354 A1 WO2020116354 A1 WO 2020116354A1
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- Prior art keywords
- paper
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Links
- 238000013001 point bending Methods 0.000 claims abstract description 9
- 238000009841 combustion method Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000000123 paper Substances 0.000 description 180
- 239000000853 adhesive Substances 0.000 description 21
- 230000001070 adhesive effect Effects 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
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- 238000000034 method Methods 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
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- 229920003023 plastic Polymers 0.000 description 9
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
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- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 208000032484 Accidental exposure to product Diseases 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 241000270617 Cheloniidae Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
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- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 229920006319 cationized starch Polymers 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 238000010924 continuous production Methods 0.000 description 1
- 239000002761 deinking Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 238000010828 elution Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
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- 230000008020 evaporation Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
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- 229940014800 succinic anhydride Drugs 0.000 description 1
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
-
- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
- D21H27/40—Multi-ply at least one of the sheets being non-planar, e.g. crêped
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G21/00—Table-ware
- A47G21/18—Drinking straws or the like
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G21/00—Table-ware
- A47G21/18—Drinking straws or the like
- A47G21/186—Details of bendable straws
-
- 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
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- 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
- B32B29/00—Layered products comprising a layer of paper or cardboard
- B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B29/005—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to another layer of paper or cardboard layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing paper
-
- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
- D21H27/32—Multi-ply with materials applied between the sheets
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G2400/00—Details not otherwise provided for in A47G19/00-A47G23/16
- A47G2400/10—Articles made from a particular material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/04—4 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/05—5 or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/26—All layers being made of paper or paperboard
-
- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/72—Density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
-
- 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
- B32B2597/00—Tubular articles, e.g. hoses, pipes
Definitions
- the present invention relates to a paper cylinder having excellent rigidity and a paper cylinder base paper for manufacturing the paper cylinder.
- plastic Since plastic is inexpensive and easy to mold, it is widely used as a material for various products, and more than 300 million tons of plastic products are produced annually. Many plastic products are properly disposed of, but some of them are discharged to the environment as garbage due to poor management or illegal dumping, and eventually reach the sea. It is estimated that the amount of plastic waste that flows into the ocean is over 8 million tons per year, and most of these plastic wastes are non-biodegradable, so most of them are accumulated in the ocean.
- plastic straws consume 500 million in the United States and more than 1 billion in the world per day, but death cases due to accidental ingestion of seabirds and sea turtles have been reported, and environmental protection groups etc. , Have begun to call for not to use plastic straws.
- Patent Documents 1 and 2 propose paper straws.
- the straw made of paper is inferior in rigidity to the straw made of plastic and has a problem that it is easily bent.
- Patent Document 3 proposes tableware paper having improved water resistance and hot water resistance, and tableware such as a stirring stick and a spoon using the tableware paper.
- Patent Document 3 proposes a dish paper used as a stirring stick or a spoon.
- the dish paper of Patent Document 3 is required to have water resistance, heat resistance, and rigidity in order to be used as a stirring stick or a spoon, but the dish paper has too high rigidity and is difficult to be wound in a tubular shape. Is.
- the challenge is to provide a paper cylinder with excellent rigidity and a paper cylinder base paper for manufacturing this paper cylinder.
- Means for solving the problems of the present invention are as follows. Having 1.2 to 5 paper layers, The outermost layer, the innermost layer, or both of the paper layers have a density of 0.90 g/cm 3 or more, A paper cylinder having an elastic modulus of 2.0 GPa or more measured by a three-point bending test. 2. The ash content measured by the 525° C. combustion method described in JIS-P8251 is 1.5% by mass or less. The paper cylinder described in. 3. 1. The density of the outermost layer is 0.90 g/cm 3 or more. Or 2. The paper cylinder described in. 4. 1. The outer diameter is 3 mm or more and 20 mm or less. ⁇ 3. The paper cylinder according to any one of 1. 5.
- the elastic modulus measured by a 3-point bending test is 10.0 GPa or less.
- the paper cylinder according to any one of 1. It has a paper layer of 6.2 layers or more and 5 layers or less, The outermost layer, the innermost layer, or both of the paper layers have a density of 0.90 g/cm 3 or more.
- the paper cylinder of the present invention is mainly made of paper, and has a small load on the environment. Since the paper cylinder of the present invention has a high elastic modulus, it has excellent rigidity and is unlikely to bend during use. Therefore, the paper cylinder of the present invention can be suitably used for a beverage such as a straw or a muddler or a paper cylinder that comes into contact with the mouth (hereinafter, also referred to as a tableware paper cylinder).
- a paper cylinder having a paper layer with a high density as the outermost layer has a higher elastic modulus and excellent rigidity. Since water having a high density does not easily penetrate water, a paper cylinder having excellent water resistance can be obtained by using a high density paper as the outermost layer.
- this paper cylinder has a small sticking feeling to the lips and tongue when held, it can be used as a straw without feeling uncomfortable.
- a paper cylinder with a small amount of ash has a strong interfiber bond, in addition to being able to increase the elastic modulus, it is difficult for inorganic components to elute even when immersed in an acidic or alkaline liquid, and a tableware paper tube Suitable for
- the paper cylinder of the present invention has two or more and five or less paper layers, and the density of either or both of the outermost layer and the innermost layer of the paper layer is 0.90 g/cm 3 or more, and 3
- the elastic modulus measured by the point bending test is 2.0 GPa or more.
- the elastic modulus is a value indicating how hard the material is to deform, and the larger the elastic modulus, the less likely it is to deform.
- the elastic modulus is a value that depends on the material and not the cross-sectional shape. In this specification, the elastic modulus is calculated by the following formula (1).
- Elastic Modulus: E (L 3 /48I) ⁇ (P/y) Formula (1)
- L measurement span (distance between supporting points for 3-point bending)
- I moment of inertia of area
- P/y inclination of elastic deformation region of stress-strain curve
- the second moment of area (I) is a value depending on the cross-sectional shape, and is represented by the following formula (2) when the paper cylinder is a cylinder, for example.
- Second moment of area: I ( ⁇ /64) ⁇ (D 4 ⁇ d 4 ) Equation (2)
- D Outer diameter of cylinder (mandrel diameter + total thickness of paper for cylinders x 2)
- d Inner diameter of cylinder (diameter of mandrel)
- the stress (P) is expressed by the following equation (3).
- Stress: P M/Z Formula (3)
- the elastic modulus changes to the cross-sectional shape so that (D 4 ⁇ d 4 ) derived from the cross-sectional shape cancels each other out in the denominator and the numerator on the right side of the equation (1). It is a value that does not depend.
- High-density paper is excellent in strength because it is strongly crushed by a press, a calender or the like so that the fibers adhere to each other and have a strong interfiber bond. Further, high-density paper is less likely to be deformed than low-density paper, and therefore has a high elastic modulus.
- high-density and high-strength paper for the outermost layer, the innermost layer, or both of the paper cylinders, it is possible to manufacture a paper cylinder having a high elastic modulus.
- the density of either the outermost layer, the innermost layer, or both of the paper layers is preferably 0.92 g/cm 3 or more, and 0.95 g/cm 3 The above is more preferable.
- the density of the other layers of the paper layer is not particularly limited.
- the elastic modulus of the paper cylinder of the present invention measured by a three-point bending test (hereinafter, also simply referred to as “elastic modulus”) is 2.0 GPa or more, and it is hard to be deformed, and thus is difficult to bend.
- the elastic modulus of the paper cylinder is preferably 2.6 GPa or more, more preferably 2.8 GPa or more.
- the upper limit of the elastic modulus is not particularly limited, but in the case of a paper cylinder manufactured only from the paper layer and the adhesive agent for adhering the same, the upper limit is about 4.5 GPa or less. In the case of a paper cylinder having a layer other than the paper layer (for example, a water resistant varnish or a water resistant layer made of a water resistant resin), it is preferably about 10.0 GPa or less.
- the density of the outermost layer is preferably 0.90 g/cm 3 or more in order to prevent the deformation (buckling) of the paper cylinder.
- the density of the outermost layer is 0.90 g/cm 3 or more, the water resistance will be improved, and the lips and tongue will be held when the paper tube is held. It can be suitably used as a straw because it has a reduced feeling of adsorption to.
- the ash content of the paper cylinder of the present invention measured by the 525° C. combustion method described in JIS-P8251 is preferably 1.5% by mass or less.
- a paper cylinder with a low ash content has a low content of filler in the paper layer and a large number of pulp bonds (interfiber bonds) that make up the paper layer, resulting in excellent paper layer strength and a high elastic modulus. can do.
- a paper cylinder having a small amount of ash content is suitable for a tableware paper cylinder because the inorganic component is little eluted even when immersed in an acidic or alkaline liquid.
- the ash content is more preferably 1.0% by mass or less, further preferably 0.8% by mass or less, and most preferably 0.5% by mass or less.
- the total thickness of the paper layers formed by laminating two or more and five or less sheets of paper is preferably 150 ⁇ m or more and 600 ⁇ m or less.
- the total thickness of the paper layers in the paper cylinder of the present invention is the total thickness of two or more and five or less papers and the adhesive agent for adhering these papers, and the paper cylinder is formed by spiral winding. If there is, it is the thickness measured while avoiding the step.
- the elastic modulus increases as the total thickness of the paper layer increases, but if the total thickness exceeds 600 ⁇ m, it may be difficult to wind the paper layer. On the other hand, when the total thickness of the paper layer is less than 150 ⁇ m, the elastic modulus of the present invention may not be satisfied.
- the lower limit of the total thickness of the paper layer is preferably 170 ⁇ m or more, more preferably 200 ⁇ m or more.
- the upper limit of the total thickness of the paper layer is preferably 550 ⁇ m or less, more preferably 500 ⁇ m or less, and further preferably 450 ⁇ m or less.
- the thickness of the paper constituting each of the paper layers may be the same or different.
- the step in the overlapping portion of the paper in the paper width direction becomes small, and a smoother paper cylinder can be formed. Therefore, the outermost paper has a thickness of 80 ⁇ m or less. Is preferred.
- the paper cylinder of the present invention has two to five paper layers.
- the paper layer is more preferably 3 layers or more and 5 layers or less.
- the paper layer is preferably 4 layers or 5 layers.
- the shape of the paper cylinder is not particularly limited, and may be a cylinder, a polygonal cylinder, or the like.
- the cylindrical paper cylinder is easy to manufacture.
- a polygonal paper cylinder has a single diagonal line in its cross-sectional shape as a reference, and by making the sum of the lengths of one side and the length of the other side equal, the diagonal line is the center line. It can be crushed into a flat plate and stored compactly.
- the thickness of the paper cylinder of the present invention is not particularly limited, and can be various thicknesses depending on its use.
- the paper tube of the present invention has excellent rigidity and is difficult to bend, it can be suitably used as a tableware paper tube.
- the paper cylinder of the present invention when used as a straw, it is preferably a cylinder having an outer diameter of 3 mm or more and 20 mm or less, more preferably 4 mm or more and 15 mm or less, and 6 mm or more and 10 mm or less. It is more preferable that there is.
- the method for producing the paper cylinder of the present invention is not particularly limited, and it can be produced by a known method such as spiral winding or flat winding, but spiral winding is preferable because continuous production is possible.
- the base paper for a paper cylinder for producing the paper cylinder of the present invention has two or more and five or less paper layers, and the density of either the outermost layer, the innermost layer, or both of the paper layers is 0. It is 90 g/cm 3 or more.
- ⁇ Paper Paper consists of pulp and various auxiliaries.
- a paper material that is approved as a food additive or has been FDA-certified and is suitable for food safety is used.
- a paper material that is approved as a food additive or has been FDA-certified and is suitable for food safety is used.
- a food additive or has been FDA-certified and is suitable for food safety is used.
- pulp examples include chemical bleached kraft pulp (NBKP) of softwood, unbleached kraft pulp (NUKP), bleached kraft pulp of hardwood (LBKP), unbleached kraft pulp (LUKP), and chemical pulp of wood such as sulfite pulp (SP).
- NNKP chemical bleached kraft pulp
- NUKP unbleached kraft pulp
- LLKP bleached kraft pulp of hardwood
- LKP unbleached kraft pulp
- SP chemical pulp of wood such as sulfite pulp
- GP Ground pulp
- RGP refiner ground pulp
- SGP stone ground pulp
- CGP chemiground pulp
- SCP semi-chemical pulp
- TMP thermomechanical pulp
- CMP chemithermomechanical pulp
- Known pulp such as mechanical pulp of wood such as kenaf, non-wood pulp obtained from kenaf, bagasse, bamboo, hemp, straw etc., used paper as a raw material, and used paper pulp obtained by removing the ink contained in the used paper in the deinking process Can be appropriately mixed and used.
- the paper tube of the present invention is used as a tableware paper tube, it is preferable to use chemical pulp such as LBKP or NBKP in which foreign matter is hard to occur, and it is preferable that the amount of used paper pulp is small.
- the blending amount of the chemical pulp with respect to the total amount of pulp is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and 100% by mass. Is most preferred.
- filler talc, kaolin, calcined kaolin, clay, heavy calcium carbonate, light calcium carbonate, white carbon, zeolite, magnesium carbonate, barium carbonate, titanium dioxide, zinc oxide, silicon oxide, amorphous silica, aluminum hydroxide.
- fillers such as inorganic fillers such as calcium hydroxide, magnesium hydroxide, zinc hydroxide, zinc hydroxide, barium sulfate and calcium sulfate, organic fillers such as urea-formalin resin, polystyrene resin, phenol resin and fine hollow particles. You can The filler is not an essential material and may not be used.
- the ash content of the paper cylinder measured by the 525° C.
- combustion method described in JIS-P8251 is roughly classified into those derived from the filler and those derived from the inorganic content in the pulp. In order to reduce the ash content to 1.5% by mass or less, it is preferable to reduce the amount of the filler used, and it is more preferable not to use the filler.
- auxiliaries include sizing agents such as rosin, alkyl ketene dimer (AKD) and alkenyl succinic anhydride (ASA), polyacrylamide polymers, polyvinyl alcohol polymers, cationized starch, various modified starches, urea, Formalin resin, dry paper strength enhancer such as melamine/formalin resin, wet paper strength enhancer, retention agent, drainage improver, coagulant, sulfuric acid band, bulking agent, dye, optical brightener, pH adjuster, Examples of the antifoaming agent, ultraviolet ray preventing agent, anti-fading agent, pitch controlling agent, slime controlling agent, etc. can be selected and used as needed.
- sizing agents such as rosin, alkyl ketene dimer (AKD) and alkenyl succinic anhydride (ASA), polyacrylamide polymers, polyvinyl alcohol polymers, cationized starch, various modified starches, urea, Formalin resin, dry paper strength enhancer such as mel
- the paper preferably contains a wet strength agent.
- a wet strength agent polyamide polyamine epichlorohydrin resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, polyvinylamine resin, polyethyleneimine resin and the like can be used. Among them, polyamide polyamine epichlorohydrin resin is preferable.
- the wet strength agent is preferably added in an amount of 0.1% by mass or more and 1.5% by mass or less, and 0.5% by mass or more and 1.0% by mass or less, based on the total pulp in the manufacturing process. More preferably, it is added between.
- the amount of the wet strength agent can be quantified by elemental analysis such as Kjeldahl method and energy dispersive X-ray analysis.
- the amount of the wet strength agent contained in the paper layer refers to a conversion value when all nitrogen elements determined by the Kjeldahl method are derived from the polyamide polyamine epichlorohydrin resin.
- the paper preferably contains the wet paper strength enhancer in an amount of 0.05% by mass or more and 0.70% by mass or less based on the total amount of pulp.
- any known adhesive can be used without particular limitation.
- a highly safe water-soluble adhesive or water-dispersible adhesive is used. It is preferable to use an adhesive.
- the water-dispersible adhesive is more preferable because the time from the application of the adhesive to the evaporation of water to develop the adhesive strength can be shortened by increasing the solid content concentration.
- water-soluble adhesive examples include polyvinyl alcohol-based, polyethylene oxide-based, polyacrylamide-based, starch-based, gelatin, casein, ether-based cellulose, phenol resin-based, water glass, and other water-soluble adhesives.
- water-dispersible adhesive examples include acrylic, vinyl acetate-based, ethylene-vinyl acetate copolymer-based, styrene-butadiene copolymer-based, urethane-based, ⁇ -olefin-based water-dispersible adhesives.
- polyvinyl alcohol type and phenol resin type are used as the water-soluble adhesive
- acrylic type and styrene-butadiene copolymer type are used as the water-dispersible adhesive. Is preferred.
- the paper manufacturing (papermaking) method and the type of the paper machine are not particularly limited, and the Fourdrinier paper machine, the twin wire paper machine, the cylinder paper machine, the gap former, the hybrid former (on-top former), etc.
- the publicly known manufacturing (papermaking) method and paper machine can be selected.
- the pH during papermaking may be any of acidic region (acidic papermaking), pseudo-neutral region (pseudo-neutral papermaking), neutral region (neutral papermaking), and alkaline region (alkaline papermaking). After that, an alkaline chemical may be applied to the surface of the paper layer.
- the method of adhering the paper to form the paper layer is not particularly limited, and paper making, a method of adhering the dried paper after cutting it to a predetermined width, a method of adhering the paper made paper in a wet state, and cutting after drying, etc. Can be mentioned.
- Table 1 shows the density and paper thickness of the paper used.
- the used paper does not contain any filler.
- Example 1 A water-dispersible adhesive (acrylic) was coated on a mandrel having a diameter of 6 mm from the innermost layer side so that the stacking order was A/B/C so that the solid content of each layer was 20 g/m 2. Then, the paper layer was spirally wound and adhered to obtain a cylindrical paper tube made of a paper tube base paper having a total thickness of 318 ⁇ m.
- Example 2 In the same manner as in Example 1 except that the stacking order was A/B/B/A from the innermost layer side, a paper tube made of a paper tube base paper having a total thickness of 360 ⁇ m was obtained.
- Example 3 A paper tube made of a paper tube base paper having a total thickness of 381 ⁇ m was obtained in the same manner as in Example 1 except that the stacking order was A/C/C/A from the innermost layer side.
- Example 4" A paper tube made of a paper tube base paper having a total thickness of 310 ⁇ m was obtained in the same manner as in Example 1 except that the stacking order was B/B/A from the innermost layer side.
- Comparative Example 1 A paper tube made of a paper tube base paper having a total thickness of 399 ⁇ m was obtained in the same manner as in Example 1 except that the stacking order was B/B/B from the innermost layer side.
- Comparative example 2 A paper tube made of a paper tube base paper having a total thickness of 430 ⁇ m was obtained in the same manner as in Example 1 except that the order of stacking was C/C/C from the innermost layer side.
- a test sample is placed on a support point at a distance of 70 mm, and an indenter with a radius of 3.18 mm located above the test sample is placed at a position equidistant from the two support points (a distance from the support point is 35 mm) at a speed of 10 mm. Lower at a speed of / minute.
- 2. Record a graph (stress-strain curve) showing the relationship between the amount of indentation of the indenter and the stress, and confirm the slope of the elastic deformation region (the region where the relationship between the stress and strain is a straight line).
- the elastic modulus is calculated according to the above equation (1). Since the paper cylinder manufactured in this example is a cylinder, the above equation (2) is used as the second moment of area.
- the outermost layer, the innermost layer, or both of the paper layers of the present invention having a density of 0.90 g/cm 3 or more has a high elastic modulus of 2.0 GPa or more and is excellent in rigidity. ..
- the elastic modulus was less than 2.0 GPa and the rigidity was poor.
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Abstract
Description
プラスチック製品の多くは、適切に処分されているが、その一部は、管理不十分や不法投棄により、環境中にごみとして流出してしまい、最終的に海に到達する。海洋中に流出するプラスチックごみの量は、年間800万トン以上にのぼると推測され、これらのプラスチックごみの多くは非生分解性であるため、そのほとんどが海洋中に蓄積される。
例えば、特許文献1、2には、紙製のストローが提案されている。ただし、紙製のストローは、プラスチック製ストローと比較すると剛性に劣り、折れ曲がりやすいという問題がある。また、特許文献3には、耐水性及び耐熱水性を向上させた食器用紙、及びこの食器用紙を用いた撹拌用スティックやスプーン等の食器が提案されている。
特許文献3には、撹拌スティックやスプーンとして利用する食器用紙が提案されている。特許文献3の食器用紙は、撹拌スティックやスプーンとして利用するために、耐水性、耐熱性、剛度が要求されているが、この食器用紙は剛性が強すぎて、筒状に巻き回すことが困難である。
1.2層以上5層以下の紙層を有し、
前記紙層の最外層、最内層のいずれか、または両方の密度が、0.90g/cm3以上であり、
3点曲げ試験により測定した弾性率が、2.0GPa以上であることを特徴とする紙筒。
2.JIS―P8251に記載の525℃燃焼法で測定した灰分が、1.5質量%以下であることを特徴とする1.に記載の紙筒。
3.前記最外層の密度が、0.90g/cm3以上であることを特徴とする1.または2.に記載の紙筒。
4.外径が3mm以上20mm以下であることを特徴とする1.~3.のいずれかに記載の紙筒。
5.3点曲げ試験により測定した弾性率が、10.0GPa以下であることを特徴とする1.~4.のいずれかに記載の紙筒。
6.2層以上5層以下の紙層を有し、
前記紙層の最外層、最内層のいずれか、または両方の密度が、0.90g/cm3以上であることを特徴とする紙筒用原紙。
最外層に密度が高い紙層を有する紙筒は、より高弾性率で剛性に優れている。密度の高い紙は、水が浸透しにくいため、最外層を高密度の紙とすることにより、耐水性に優れた紙筒を得ることができる。さらに、この紙筒は、咥えた際に唇や舌への吸着感が小さいため、違和感を感じることなくストローとして使用することができる。
また、灰分量の少ない紙筒は、強固な繊維間結合を有するため、弾性率を高くすることができることに加え、酸性、アルカリ性の液体に浸けても、無機成分が溶出しにくく、食器用紙筒に好適である。
本発明の紙筒は、2層以上5層以下の紙層を有し、この紙層の最外層、最内層のいずれか、または両方の密度が、0.90g/cm3以上であり、3点曲げ試験により測定した弾性率が、2.0GPa以上であることを特徴とする。
本明細書において、弾性率は、下記式(1)で算出される。
弾性率:E=(L3/48I)×(P/y) 式(1)
L :測定スパン(3点曲げの支持点間の距離)
I :断面2次モーメント
P/y:応力-ひずみ曲線の弾性変形領域の傾き
断面二次モーメント:I=(π/64)×(D4-d4) 式(2)
D:円筒の外径(マンドレルの直径+紙筒用原紙の総厚
さ×2)
d:円筒の内径(マンドレルの直径)
また、応力-ひずみ曲線の弾性変形領域(P/y)において、応力(P)は、下記式(3)で表される。
応力:P=M/Z 式(3)
M:曲げモーメント
Z:断面係数、円筒の場合、Z=(π/32)×(D4-
d4)
本発明の紙筒の製造方法は特に制限されず、スパイラル巻き、平巻き等の公知の方法で製造することができるが、連続生産が可能なためスパイラル巻きが好ましい。
本発明の紙筒を製造するための紙筒用原紙は、2層以上5層以下の紙層を有し、この紙層の最外層、最内層のいずれか、または両方の密度が、0.90g/cm3以上である。この紙筒用原紙を用いることにより、剛性に優れた紙筒を製造することができる。
紙は、パルプ、各種助剤等からなる。
本発明の紙筒用原紙を、食器用紙筒の原紙として使用する場合、紙の材料として、食品添加物として認可を受けている、またはFDA認証取得済み等、食品安全性に適合したものを使用することが好ましい。
ただし、本発明の紙筒を、食器用紙筒として使用する場合、異物混入が発生し難いLBKP、NBKP等の化学パルプが好ましく、また、古紙パルプの配合量が少ないことが好ましい。具体的には、パルプ全量に対する化学パルプの配合量が、80質量%以上であることが好ましく、90質量%以上であることがより好ましく、95質量%以上であることがさらに好ましく、100質量%であることが最も好ましい。
湿潤紙力増強剤の量は、ケルダール法、エネルギー分散型X線分析等による元素分析により定量することが可能である。本発明において、紙層に含まれる湿潤紙力増強剤の量は、ケルダール法を用いて定量した窒素元素が全てポリアミドポリアミンエピクロルヒドリン樹脂由来とした場合の換算値をいう。紙は、パルプ全量に対して、湿潤紙力増強剤を、0.05質量%以上0.70質量%以下含有することが好ましい。
接着剤としては、公知のものを特に制限することなく使用することができるが、紙筒を食器用紙筒として使用する場合は、安全性の高い水溶性接着剤、または、水分散性接着剤を使用することが好ましい。さらに、固形分濃度を高くすることで接着剤を塗工してから水が揮発して接着強度が発現するまでの時間を短くすることができるため、水分散性接着剤がより好ましい。接着強度が発現するまでの時間が短い水分散性接着剤を使用することにより、製造直後の紙層間の剥がれを効果的に防止することができる。また、紙を貼り合わせた後の養生処理を短く、さらには不要とすることができる。
紙の製造(抄紙)方法、抄紙機の型式は特に限定されるものではなく、長網抄紙機、ツインワイヤー抄紙機、円網抄紙機、ギャップフォーマー、ハイブリッドフォーマー(オントップフォーマー)等の公知の製造(抄紙)方法、抄紙機が選択可能である。
また、抄紙時のpHは酸性領域(酸性抄紙)、疑似中性領域(疑似中性抄紙)、中性領域(中性抄紙)、アルカリ性領域(アルカリ性抄紙)のいずれでもよく、酸性領域で抄紙した後、紙層の表面にアルカリ性薬剤を塗布してもよい。
直径6mmのマンドレルに最内層側からA/B/Cの積層順となるように、水分散性接着剤(アクリル系)を各層間あたり固形分で20g/m2となるように塗工して、紙層をスパイラル巻きして接着し、総厚さが318μmである紙筒用原紙からなる円筒状の紙筒を得た。
最内層側からA/B/B/Aの積層順となるようにした以外は実施例1と同様にして、総厚さが360μmである紙筒用原紙からなる紙筒を得た。
「実施例3」
最内層側からA/C/C/Aの積層順となるようにした以外は実施例1と同様にして、総厚さが381μmである紙筒用原紙からなる紙筒を得た。
「実施例4」
最内層側からB/B/Aの積層順となるようにした以外は実施例1と同様にして、総厚さが310μmである紙筒用原紙からなる紙筒を得た。
最内層側からB/B/Bの積層順となるようにした以外は実施例1と同様にして、総厚さが399μmである紙筒用原紙からなる紙筒を得た。
「比較例2」
最内層側からC/C/Cの積層順となるようにした以外は実施例1と同様にして、総厚さが430μmである紙筒用原紙からなる紙筒を得た。
<弾性率>
紙筒を作成後、1週間常温で乾燥・シーズニング(養生処理)を実施し、その後JIS―P8111:1998に規定される方法で調湿した。調湿後、紙筒を長さ100mmに断裁して試験用サンプルを作成し、下記方法により3点曲げ法により曲げ試験を実施し、弾性率を算出した。
2.圧子の押込み量と応力の関係を示したグラフ(応力-ひずみ曲線)を記録し、弾性変形領域(応力とひずみの関係が直線となる領域)の傾きを確認する。
3.上記式(1)に従い、弾性率を算出する。なお、本実施例で製造した紙筒は円筒であるため、断面二次モーメントとして上記式(2)を使用する。
JIS―P8251:2003に規定される灰分試験方法(525℃燃焼法)に準拠し、測定した。
それに対し、紙層の最外層、最内層の両方の密度が、0.90g/cm3未満である比較例は、弾性率が2.0GPa未満であり、剛性に劣っていた。
Claims (6)
- 2層以上5層以下の紙層を有し、
前記紙層の最外層、最内層のいずれか、または両方の密度が、0.90g/cm3以上であり、
3点曲げ試験により測定した弾性率が、2.0GPa以上であることを特徴とする紙筒。 - JIS―P8251に記載の525℃燃焼法で測定した灰分が、1.5質量%以下であることを特徴とする請求項1に記載の紙筒。
- 前記最外層の密度が、0.90g/cm3以上であることを特徴とする請求項1または2に記載の紙筒。
- 外径が3mm以上20mm以下であることを特徴とする請求項1~3のいずれかに記載の紙筒。
- 3点曲げ試験により測定した弾性率が、10.0GPa以下であることを特徴とする請求項1~4のいずれかに記載の紙筒。
- 2層以上5層以下の紙層を有し、
前記紙層の最外層、最内層のいずれか、または両方の密度が、0.90g/cm3以上であることを特徴とする紙筒用原紙。
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JP2001063720A (ja) * | 1999-08-30 | 2001-03-13 | Toppan Printing Co Ltd | 紙製円筒状容器 |
JP2006168283A (ja) | 2004-12-17 | 2006-06-29 | Daio Paper Corp | 食器用紙及びそれを用いた食器 |
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JP3714124B2 (ja) * | 1999-06-24 | 2005-11-09 | 王子製紙株式会社 | 嵩高板紙 |
AU2001252594A1 (en) * | 2000-04-26 | 2001-11-07 | Kao Corporation | Insulating container |
JP4039006B2 (ja) * | 2000-05-31 | 2008-01-30 | 王子製紙株式会社 | 絞り成形加工用原紙及びそれを用いた紙製成形容器 |
CN100338309C (zh) * | 2000-10-03 | 2007-09-19 | 王子制纸株式会社 | 模塑原纸和由其生产的模塑纸容器 |
JP2002266294A (ja) * | 2001-03-01 | 2002-09-18 | Oji Paper Co Ltd | 成形容器用原紙及びそれを用いた成形容器 |
JP2007146326A (ja) * | 2005-11-29 | 2007-06-14 | Fujifilm Holdings Corp | 包装材料用原紙及び包装材料並びに包装体 |
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JPH06133840A (ja) | 1992-10-26 | 1994-05-17 | Shigeru Nakagawa | 紙 管 |
JP2001063720A (ja) * | 1999-08-30 | 2001-03-13 | Toppan Printing Co Ltd | 紙製円筒状容器 |
JP2006168283A (ja) | 2004-12-17 | 2006-06-29 | Daio Paper Corp | 食器用紙及びそれを用いた食器 |
JP2009233348A (ja) | 2009-07-10 | 2009-10-15 | Michitaka Kaida | 紙製ストロー |
JP3218847U (ja) * | 2018-08-31 | 2018-11-08 | 株式会社 サンテック | 紙製ストロー |
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