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WO2024043201A1 - Heat sealing paper - Google Patents

Heat sealing paper Download PDF

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Publication number
WO2024043201A1
WO2024043201A1 PCT/JP2023/029916 JP2023029916W WO2024043201A1 WO 2024043201 A1 WO2024043201 A1 WO 2024043201A1 JP 2023029916 W JP2023029916 W JP 2023029916W WO 2024043201 A1 WO2024043201 A1 WO 2024043201A1
Authority
WO
WIPO (PCT)
Prior art keywords
paper
weight
phbh
pva
heat
Prior art date
Application number
PCT/JP2023/029916
Other languages
French (fr)
Japanese (ja)
Inventor
望美 吉良
義雄 吉田
浩佑 角田
雅幸 藤田
五樹 日下部
康則 岡田
Original Assignee
日本製紙株式会社
株式会社カネカ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本製紙株式会社, 株式会社カネカ filed Critical 日本製紙株式会社
Publication of WO2024043201A1 publication Critical patent/WO2024043201A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00Layered products comprising a layer of paper or cardboard
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/14Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20Coatings 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
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/14Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/28Polyesters
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • the present invention relates to heat seal paper.
  • Coated paper which is paper coated with resin, can exhibit various functions depending on the resin coated.
  • the resin to be coated is derived from fossil resources or is non-biodegradable, the environmental impact reduction effect achieved by using paper will be diminished. Therefore, there is a need for coated paper in which a paper base material is coated with an aqueous dispersion of biodegradable plastic.
  • Aliphatic polyesters such as polylactic acid and polycaprolactone are known as biodegradable plastics.
  • aliphatic polyesters have a problem in that they take time to biodegrade at low temperatures and have a slow decomposition rate in natural environments such as the ocean.
  • poly(3-hydroxybutyrate) resin is a thermoplastic plastic produced by microorganisms that has excellent decomposition properties under aerobic and anaerobic conditions. It has the remarkable performance of Patent Document 1 describes a biodegradable product containing PHBH (poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)), which is a copolymer of 3-hydroxybutyrate and 3-hydroxyhexanoate.
  • Polyester aqueous dispersion has excellent film-forming properties, and when applied to paints, adhesives, fiber processing, sheet/film processing, paper processing, etc., it produces resin coatings that are flexible, stretchable, and resistant to bending. It is stated that it is given.
  • An object of the present invention is to provide a heat seal paper containing PHBH and having excellent coating layer strength.
  • Means for solving the problems of the present invention are as follows. 1. On at least one side of the paper base material, 7 parts by weight or more and 35 parts by weight of PVA (polyvinyl alcohol) per 100 parts by weight of PHBH (poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)). It has a heat-sealable coating layer containing the following: A heat seal paper characterized in that the degree of saponification of the PVA is 70 mol% or more and 95 mol% or less. 2. 1. The degree of polymerization of the PVA is 2000 or less. Heat seal paper as described in . 3. 1.
  • a coating amount (dry weight) of the heat-sealable coating layer is 1.0 g/m 2 or more and 50.0 g/m 2 or less per side. or 2.
  • the basis weight of the paper base material measured according to JIS P 8124 is 20 g/m 2 or more and 600 g/m 2 or less. ⁇ 3. Heat seal paper described in any of the above.
  • the heat-sealable paper of the present invention has excellent coating layer strength, and the paper base material and the heat-sealable coating layer are firmly bonded. Since the heat-sealable paper of the present invention can be biodegradable as a whole, even if it is released into the environment, it will be rapidly decomposed.
  • the heat-sealable paper of the present invention contains PVA (polyvinyl alcohol) per 100 parts by weight of PHBH (poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)) on at least one surface of the paper base material.
  • PVA polyvinyl alcohol
  • PHBH poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)
  • the saponification degree of the PVA is 70 mol% or more and 95 mol% or less.
  • the expression "A to B" (A and B are numerical values) means a numerical range including A and B, that is, "A to B".
  • the paper base material is a sheet mainly made of pulp (hereinafter also referred to as "base paper"), and is obtained by paper-making a paper stock that further contains fillers, various auxiliary agents, and the like.
  • Pulps include chemical pulps such as hardwood bleached kraft pulp (LBKP), softwood bleached kraft pulp (NBKP), hardwood unbleached kraft pulp (LUKP), softwood unbleached kraft pulp (NUKP), sulfite pulp, stone grind pulp, Mechanical pulp such as thermomechanical pulp, wood fibers such as deinked pulp and waste paper pulp, and non-wood fibers obtained from kenaf, bamboo, hemp, etc. can be used, and can be appropriately blended and used.
  • LLKP hardwood bleached kraft pulp
  • NKP softwood bleached kraft pulp
  • LKP hardwood unbleached kraft pulp
  • NUKP softwood unbleached kraft pulp
  • Mechanical pulp such as thermomechanical pulp, wood fibers such as deinked pulp and waste paper
  • the amount of chemical pulp such as LBKP and NBKP is 80% or more based on the total pulp, and it is particularly preferable that the amount of chemical pulp is 100%.
  • Fillers include 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.
  • Known fillers such as inorganic fillers such as calcium hydroxide, magnesium hydroxide, zinc hydroxide, barium sulfate, and calcium sulfate, and organic fillers such as urea-formalin resin, polystyrene resin, phenolic resin, and micro hollow particles are used. be able to. Note that the filler is not an essential material and may not be used.
  • auxiliary agents include rosin, alkyl ketene dimer (AKD), sizing agents such as alkenyl succinic anhydride (ASA), polyacrylamide polymers, polyvinyl alcohol polymers, cationized starches, various modified starches, urea, etc.
  • ASA alkenyl succinic anhydride
  • Formalin resin, dry paper strength enhancer such as melamine/formalin resin, wet paper strength enhancer, retention agent, freeness improver, coagulant, sulfuric acid, bulking agent, dye, optical brightener, pH adjuster Examples include antifoaming agents, ultraviolet inhibitors, antifading agents, pitch control agents, slime control agents, etc., and can be appropriately selected and used as required.
  • the surface of the paper base material may be treated with various chemicals.
  • the drug include oxidized starch, hydroxyethyl etherified starch, enzyme-modified starch, polyacrylamide, polyvinyl alcohol, surface sizing agents, water resistance agents, water retention agents, thickeners, lubricants, etc.
  • two or more types can be used in combination.
  • these various drugs and pigments may be used in combination.
  • Pigments include kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, and satin.
  • Inorganic pigments such as white and organic pigments such as solid type, hollow type, or core shell type can be used alone or in combination of two or more types.
  • the basis weight of the paper base material can be selected as appropriate depending on the desired quality and its use, but it is usually preferably 20 g/m 2 or more and 600 g/m 2 or less, and 25 g/m 2 or more and 600 g/m 2 or less. is more preferable.
  • the basis weight of the paper base material is preferably 30 g/m 2 or more and 150 g/m 2 or less.
  • the basis weight of the paper base material is preferably 20 g/m 2 or more and 100 g/m 2 or less, more preferably 35 g/m 2 or more and 80 g/m 2 or less.
  • the soft packaging material is a highly flexible packaging material that uses thin paper of about 20 g/m 2 to 100 g/m 2 among packaging materials.
  • the basis weight of the paper base material is preferably 150 g/m 2 or more and 300 g/m 2 or less.
  • the density of the paper base material can be appropriately selected depending on the desired various qualities, ease of handling, etc., but it is usually preferably 0.5 g/cm 3 or more and 1.0 g/cm 3 or less.
  • the manufacturing method (paper making) of the paper base material is not particularly limited, and may include a fourdrinier paper machine, cylinder paper machine, short wire paper machine, gap former type, hybrid former type (on-top former type), etc.
  • Known manufacturing (paper making) methods and paper machines can be selected, such as a twin wire paper machine.
  • the pH during papermaking may be any of the acidic region (acidic papermaking), pseudo-neutral region (pseudo-neutral papermaking), neutral region (neutral papermaking), and alkaline region (alkaline papermaking). Afterwards, an alkaline chemical may be applied to the surface of the paper layer.
  • the paper base material may have one layer or may be composed of two or more layers.
  • the surface treatment method is not particularly limited, and can be performed using a rod metal ring size press, a pound type size press, a gate roll coater, a spray coater, a blade coater, or a curtain coater.
  • a known coating device such as the like can be used.
  • the heat-sealing coating layer (hereinafter also referred to as heat-sealing layer) is a layer having heat-sealing properties formed by coating. Note that whether or not it is a coating layer can be determined by observing its cross section with an electron microscope or the like.
  • PHBH> PHBH is a copolymer of 3-hydroxybutyrate (hereinafter also referred to as 3HB) and 3-hydroxyhexanoate (hereinafter also referred to as 3HH), and is a biomolecule known to be produced by microorganisms. It is a degradable resin.
  • PHBH derived from microorganisms or petroleum resources may be used, but it is preferable to use one derived from microorganisms from the viewpoint of reducing environmental burden.
  • the microorganism that produces PHBH is not particularly limited as long as it is a microorganism that accumulates PHBH in its cells, but A. lipolytica, A. eutrophus, A.
  • Examples include bacteria of the genus Alcaligenes such as P. latus, Pseudomonas, Bacillus, Azotobacter, Nocardia, and Aeromonas.
  • strains such as Aeromonas caviae and Alcaligenes eutrophus AC32 (accession number FERM BP-6038, deposited August 7, 1997) into which genes for the PHA synthase group have been introduced are particularly preferred.
  • Patent Organism Depositary Center National Institute of Advanced Industrial Science and Technology, Address: Chuo 6, Higashi 1-1-1, Tsukuba, Ibaraki Prefecture, Japan) (J. Bacteriol., 179, pp. 4821-4830 (1997)), etc. is preferred.
  • a method for obtaining PHBH from Aeromonas caviae which is a microorganism belonging to the genus Aeromonas, is disclosed in, for example, Japanese Patent Laid-Open No. 05-093049. Note that these microorganisms are used by culturing them under appropriate conditions to accumulate PHBH within their cells.
  • the carbon source and culture conditions used for culture can be obtained according to the methods described in JP-A-05-093049, JP-A-2001-340078, etc., but are not limited thereto.
  • the composition ratio of PHBH can be measured by NMR analysis of a powder obtained by centrifuging and drying an aqueous dispersion.
  • Microbially produced PHBH is a random copolymer.
  • there are methods such as selection of bacterial cells, selection of a carbon source as a raw material, blending with PHBH of a different molar ratio, and blending with a 3HB homopolymer.
  • the weight average molecular weight of PHBH is preferably 50,000 to 550,000, more preferably 100,000 to 500,000, and even more preferably 150,000 to 450,000.
  • the coating liquid containing PHBH has excellent coating properties.
  • the weight average molecular weight of PHBH was determined by gel permeation chromatography (GPC, Showa Denko Co., Ltd. "Shodex GPC-101", etc.) using a polystyrene gel column (Showa Denko Co., Ltd. "Shodex K-804" etc.). It can be determined as the molecular weight when converted to polystyrene using chloroform as the mobile phase. Note that, as the sample for measurement, a powder obtained by centrifuging an aqueous dispersion containing PHBH and then drying it is used.
  • PHBH is water dispersible.
  • the average particle size of PHBH in the coating liquid of the present invention is preferably 0.1 to 50 ⁇ m, more preferably 0.5 to 10 ⁇ m.
  • PHBH with an average particle size of less than 0.1 ⁇ m is difficult to achieve by microbial production, and even when obtained by chemical synthesis, an operation of micronization is required. If the average particle size exceeds 50 ⁇ m, uneven coating may occur on the surface when a coating solution containing PHBH is applied.
  • the average particle size of PHBH is determined by adjusting the aqueous suspension of PHBH to a predetermined concentration using a general-purpose particle size meter such as Microtrac particle size meter (Nikkiso Co., Ltd., FRA), and calculating the accumulated amount of 50% of all particles in a normal distribution.
  • a general-purpose particle size meter such as Microtrac particle size meter (Nikkiso Co., Ltd., FRA)
  • the particle size corresponding to In the present invention two or more PHBHs having different composition ratios, weight average molecular weights, etc. can be used as a mixture.
  • PVA used has a saponification degree of 70 mol% or more and 95 mol% or less. Although the mechanism is unknown, the heat seal paper of the present invention has excellent coating layer strength by using PVA with a degree of saponification within this range.
  • the degree of saponification of PVA is preferably 75 mol% or more, more preferably 78 mol% or more, even more preferably 85 mol% or more, and preferably 93 mol% or less, more preferably 90 mol% or less.
  • PVA is water soluble. Therefore, as the degree of polymerization increases, a coating solution containing PVA increases in viscosity, and handling and coating properties may decrease.
  • the degree of polymerization of PVA is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less.
  • two or more types of PVA having different saponification degrees, polymerization degrees, etc. can be used as a mixture.
  • the heat seal layer contains 7 parts by weight or more and 35 parts by weight or less of PVA based on 100 parts by weight of PHBH. By containing PHBH and PVA in this ratio, a heat seal layer with excellent coating layer strength can be obtained.
  • the heat seal layer preferably contains PVA in an amount of 10 parts by weight or more, and preferably 30 parts by weight or less, based on 100 parts by weight of PHBH.
  • the heat seal layer can contain other water-soluble resins and water-dispersible resins in addition to PHBH and PVA. Furthermore, the heat seal layer may contain a dispersant, a viscosity improver, a water retention agent, an antifoaming agent, a water resistance agent, a fluorescent dye, a colored dye, a colored pigment, a surfactant, a pH adjuster, a cationic resin, as necessary. , anionic resins, ultraviolet absorbers, metal salts, and other various auxiliary agents that are blended into coating liquids in the paper manufacturing field.
  • water-soluble or water-dispersible resins examples include fully saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, and olefin-modified polyvinyl alcohol.
  • Alcohol nitrile-modified polyvinyl alcohol, pyrrolidone-modified polyvinyl alcohol, silicone-modified polyvinyl alcohol, other modified polyvinyl alcohols, polyvinyl alcohols such as ethylene vinyl alcohol copolymers, starches such as oxidized starch, etherified starch, esterified starch, Cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, methylcellulose, ethylcellulose, carboxymethylcellulose, acetylcellulose, nanocellulose, partially saponified ethylene-vinyl acetate copolymer, styrene-butadiene copolymer latex, methyl methacrylate-butadiene copolymer.
  • the ratio of the total amount of PHBH and PVA to the total amount of water-soluble resin and water-dispersible resin is preferably 80% by weight or more, more preferably 90% by weight or more, and 95% by weight or more. More preferably, the content is 100% by weight, and most preferably 100% by weight.
  • the heat-sealing layer can exhibit properties derived from PHBH and PVA, and can be used, for example, as a water-resistant layer, an oil-resistant layer, etc.
  • the water-resistant layer is a layer with a water absorbency (Cobb value) of 20 g/m 2 measured at a contact time of 120 seconds in accordance with "Paper and Board - Water Absorption Test Method - Cobb Method" specified in JIS P 8140: 1998.
  • This water absorption is preferably 10 g/m 2 or less, more preferably 5 g/m 2 or less.
  • the oil-resistant layer is defined by J. TAPPI No.
  • the layer has a minimum kit number of 10 or more measured at any five points on the layer surface in accordance with "Paper and paperboard - Oil repellency test method - Kit method" specified in 41:2000.
  • the lowest value of this kit number is preferably 11 or more, and more preferably 12.
  • the heat seal paper of the present invention can be produced by applying a heat seal layer coating liquid to a paper base material and drying the coating liquid. Note that the heat seal layer can be provided on only one side or both sides of the paper base material.
  • the coating method for the heat-sealable coating layer is not particularly limited, and coating can be performed using a known coating device and coating system.
  • the coating device include a blade coater, a bar coater, an air knife coater, a curtain coater, a spray coater, a roll coater, a reverse roll coater, a size press coater, a gate roll coater, and the like.
  • the coating system include water-based coating using a solvent such as water, solvent-based coating using a solvent such as an organic solvent, and the like.
  • the heat-sealing paper of the present invention has the characteristics that PHBH is derived from biomass and is biodegradable, and PVA is biodegradable, and has a very small environmental load, so there is no environmental burden during the manufacturing process. It is preferable to use a water-based coating with a small amount.
  • the viscosity, solid content concentration, etc. of the coating liquid for the heat seal layer can be adjusted as appropriate depending on the coating device, coating system, etc. used.
  • a conventional method such as a steam heater, a gas heater, an infrared heater, an electric heater, a hot air heater, a microwave, a cylinder dryer, etc. can be used.
  • the drying temperature is not particularly limited, but in the case of water-based coating, it is preferably 105°C or higher and 160°C or lower. Since PHBH is dispersed in the aqueous coating liquid, PHBH is in the form of particles. As the drying temperature increases, particulate PHBH dissolves, promoting film formation and forming a uniform coating film, which tends to improve water resistance and oil resistance, but if film formation progresses too much, Heat sealability may be reduced. Therefore, the drying temperature is preferably 150°C or lower, more preferably 140°C or lower, and even more preferably 130°C or lower.
  • the coating amount (dry weight) of the heat seal layer is not particularly limited as long as its performance can be exhibited, but it is preferably 1.0 g/m 2 or more and 50.0 g/m 2 or less per side, for example. If the coating amount is less than 1.0 g/m 2 per side, sufficient heat sealing properties may not be exhibited. Furthermore, even if the coating amount exceeds 50.0 g/m 2 per side, hardly any further improvement in properties can be expected, leading to an increase in cost.
  • the coating amount (dry weight) of the heat seal layer is more preferably 3.0 g/m 2 or more per side, even more preferably 5.0 g/m 2 or more, even more preferably 7.0 g/m 2 or more, and , 40.0 g/m 2 or less is more preferable, 30.0 g/m 2 or less is even more preferable, and even more preferably 20.0 g/m 2 or less.
  • the coating amount (dry weight) of the heat seal layer is more preferably 18.0 g/m 2 or less, and even more preferably 15.0 g/m 2 or less. Preferably, 13.0 g/m 2 or less is even more preferable.
  • the heat seal layer may be one layer or two or more layers may be laminated. When there are two or more heat-sealing layers, it is preferable that the total coating amount of all the heat-sealing layers is within the above-mentioned range in terms of dry weight.
  • the heat seal paper of the present invention is easy to shape, maintain shape, and ensure sealing properties, it can be suitably used as paper bags, paper containers, paper boxes, paper cups, (soft) packaging materials, lid materials, etc. .
  • the heat-sealing paper of the present invention in which the heat-sealing layer is also a water-resistant layer, is suitable for wrapping paper, paper bags, paper containers, paper boxes, paper cups, (soft) packaging materials, paper plates, paper trays, posters used outdoors, etc. It can be used for.
  • the heat-sealing paper of the present invention in which the heat-sealing layer is also an oil-resistant layer, can be used as a (soft) packaging material for foods containing a lot of oil such as hamburgers, hot dogs, french fries, fried chicken, and potato chips, wrapping paper, and tempura. It can be suitably used as paper for frying, paper plates, paper trays, paper cups, etc.
  • Example 1 (Preparation of coating liquid for heat seal layer) A PHBH aqueous dispersion having a PHBH solid content concentration of 50% by weight was obtained by the method described in Patent Document 1. Next, this PHBH aqueous dispersion was hydrolyzed at 60° C. to adjust the molecular weight, thereby obtaining a PHBH aqueous dispersion having a weight average molecular weight of 230,000. Next, the PHBH aqueous dispersion and PVA (manufactured by Kuraray Co., Ltd.: 5-88, degree of saponification 88 mol%, degree of polymerization 500) were mixed so that the solid content weight ratio was 15 parts by weight of PVA to 100 parts by weight of PHBH. Then, water was further added and stirred to prepare a coating liquid for a coating layer having a solid content concentration of 38% by weight.
  • PVA manufactured by Kuraray Co., Ltd.: 5-88, degree of saponification 88 mol%, degree of polymer
  • Coating solution for the heat seal layer was coated on one side of the paper base material (unbleached kraft paper with a basis weight of 50 g/m 2 ) using a barblade method so that the dry weight coating amount was 10 g/m 2 per side.
  • the paper was processed and dried at 105°C to obtain heat seal paper.
  • Example 1 A heat seal paper was obtained in the same manner as in Example 1, except that PVA (manufactured by Kuraray Co., Ltd.: 5-98, degree of saponification 98 mol%, degree of polymerization 500) was used.
  • Example 2 Heat seal paper was obtained in the same manner as in Example 1, except that PVA (manufactured by Kuraray Co., Ltd.: 22-88, degree of saponification 88 mol%, degree of polymerization 1700) was used.
  • Heat seal paper was obtained in the same manner as in Example 1, except that PVA (manufactured by Kuraray Co., Ltd.: 28-98, degree of saponification 98 mol%, degree of polymerization 1700) was used.
  • PVA manufactured by Kuraray Co., Ltd.: 28-98, degree of saponification 98 mol%, degree of polymerization 1700
  • Heat seal paper was obtained in the same manner as in Example 1, except that 5 parts by weight of PVA (manufactured by Kuraray Co., Ltd.: 5-88, degree of saponification 88 mol%, degree of polymerization 500) was added to 100 parts by weight of PHBH. .
  • Heat seal paper was obtained in the same manner as in Example 1, except that 10 parts by weight of PVA (manufactured by Kuraray Co., Ltd.: 5-88, degree of saponification 88 mol%, degree of polymerization 500) was added to 100 parts by weight of PHBH. .
  • Example 4 Heat seal paper was obtained in the same manner as in Example 1, except that 20 parts by weight of PVA (manufactured by Kuraray Co., Ltd.: 5-88, degree of saponification 88 mol%, degree of polymerization 500) was added to 100 parts by weight of PHBH. .
  • Example 5 Heat seal paper was obtained in the same manner as in Example 1, except that 30 parts by weight of PVA (manufactured by Kuraray Co., Ltd.: 5-88, degree of saponification 88 mol%, degree of polymerization 500) was added to 100 parts by weight of PHBH. .
  • Heat seal paper was obtained in the same manner as in Example 1, except that 40 parts by weight of PVA (manufactured by Kuraray Co., Ltd.: 5-88, degree of saponification 88 mol%, degree of polymerization 500) was added to 100 parts by weight of PHBH. .
  • PVA manufactured by Kuraray Co., Ltd.: 5-98, degree of saponification 98 mol%, degree of polymerization 500
  • a heat seal paper was obtained in the same manner as in Example 5, except that PVA (manufactured by Kuraray Co., Ltd.: 5-98, degree of saponification 98 mol%, degree of polymerization 500) was used.
  • PVA manufactured by Kuraray Co., Ltd.: 5-98, degree of saponification 98 mol%, degree of polymerization 500

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The present invention addresses the problem of providing a heat sealing paper that contains PHBH and has superior coating layer strength. As a solution to the problem, provided is a heat sealing paper which has, on at least one surface of a paper base material, a heat-sealable coating layer containing 7-35 parts by weight of polyvinyl alcohol (PVA) with respect to 100 parts by weight of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), and in which the degree of saponification of the PVA is 70-95 mol%.

Description

ヒートシール紙heat seal paper
 本発明は、ヒートシール紙に関する。 The present invention relates to heat seal paper.
 近年、プラスチックごみによる環境破壊を防ぐための動きが高まっており、プラスチック製使い捨て製品を、環境への負荷の小さな材料で代替することが求められている。プラスチックの代替材料としては、生分解性プラスチック、木材、紙等が挙げられる。
 紙に樹脂を塗工した塗工紙は、塗工された樹脂に応じて様々な機能を発揮することができる。しかし、塗工される樹脂が、化石資源由来や非生分解性であると、紙を用いたことによる環境負荷低減効果を損ねてしまう。そのため、紙基材に、生分解性プラスチックの水性分散液を塗工した塗工紙が求められている。
In recent years, there has been a growing movement to prevent environmental destruction caused by plastic waste, and there is a need to replace disposable plastic products with materials that have a smaller impact on the environment. Examples of alternative materials to plastic include biodegradable plastic, wood, and paper.
Coated paper, which is paper coated with resin, can exhibit various functions depending on the resin coated. However, if the resin to be coated is derived from fossil resources or is non-biodegradable, the environmental impact reduction effect achieved by using paper will be diminished. Therefore, there is a need for coated paper in which a paper base material is coated with an aqueous dispersion of biodegradable plastic.
 生分解性プラスチックとして、ポリ乳酸やポリカプロラクトン等の脂肪族ポリエステルが知られている。しかし、脂肪族ポリエステルは、温度が低いと生分解に時間がかかり、海洋などの自然環境での分解速度が遅いという問題がある。
 一方、ポリ(3-ヒドロキシブチレート)系樹脂は、好気性、嫌気性下での分解性に優れた、微生物産生の熱可塑性プラスチックであり、海洋中などの水中でも微生物により短期間で分解されるという特筆すべき性能を有している。特許文献1には、3-ヒドロキシブチレートと3-ヒドロキシヘキサノエートとの共重合体であるPHBH(ポリ(3-ヒドロキシブチレート-co-3-ヒドロキシヘキサノエート))を含む生分解性ポリエステル水性分散液が、成膜性に優れ、かつ、塗料、接着剤、繊維加工、シート・フィルム加工、紙加工等に適用する際、柔軟で伸びがよく、折り曲げに対して強い樹脂塗膜を与えることが記載されている。
Aliphatic polyesters such as polylactic acid and polycaprolactone are known as biodegradable plastics. However, aliphatic polyesters have a problem in that they take time to biodegrade at low temperatures and have a slow decomposition rate in natural environments such as the ocean.
On the other hand, poly(3-hydroxybutyrate) resin is a thermoplastic plastic produced by microorganisms that has excellent decomposition properties under aerobic and anaerobic conditions. It has the remarkable performance of Patent Document 1 describes a biodegradable product containing PHBH (poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)), which is a copolymer of 3-hydroxybutyrate and 3-hydroxyhexanoate. Polyester aqueous dispersion has excellent film-forming properties, and when applied to paints, adhesives, fiber processing, sheet/film processing, paper processing, etc., it produces resin coatings that are flexible, stretchable, and resistant to bending. It is stated that it is given.
国際公開第2004/041936号International Publication No. 2004/041936
 本発明は、PHBHを含有し、塗工層強度に優れたヒートシール紙を提供することを目的とする。 An object of the present invention is to provide a heat seal paper containing PHBH and having excellent coating layer strength.
 本発明の課題を解決するための手段は、以下のとおりである。
1.紙基材の少なくとも一方の面上に、PHBH(ポリ(3-ヒドロキシブチレート-co-3-ヒドロキシヘキサノエート))100重量部に対し、PVA(ポリビニルアルコール)を7重量部以上35重量部以下含有するヒートシール性塗工層を有し、
 前記PVAのケン化度が、70モル%以上95モル%以下であることを特徴とするヒートシール紙。
2.前記PVAの重合度が、2000以下であることを特徴とする1.に記載のヒートシール紙。
3.前記ヒートシール性塗工層の塗工量(乾燥重量)が、片面あたり1.0g/m以上50.0g/m以下であることを特徴とする1.または2.に記載のヒートシール紙。
4.前記紙基材のJIS P 8124に準じて測定した坪量が、20g/m以上600g/m以下であることを特徴とする1.~3.のいずれかに記載のヒートシール紙。
Means for solving the problems of the present invention are as follows.
1. On at least one side of the paper base material, 7 parts by weight or more and 35 parts by weight of PVA (polyvinyl alcohol) per 100 parts by weight of PHBH (poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)). It has a heat-sealable coating layer containing the following:
A heat seal paper characterized in that the degree of saponification of the PVA is 70 mol% or more and 95 mol% or less.
2. 1. The degree of polymerization of the PVA is 2000 or less. Heat seal paper as described in .
3. 1. A coating amount (dry weight) of the heat-sealable coating layer is 1.0 g/m 2 or more and 50.0 g/m 2 or less per side. or 2. Heat seal paper as described in .
4. 1. The basis weight of the paper base material measured according to JIS P 8124 is 20 g/m 2 or more and 600 g/m 2 or less. ~3. Heat seal paper described in any of the above.
 本発明のヒートシール紙は、塗工層強度に優れ、紙基材とヒートシール性塗工層とが強固に結合している。本発明のヒートシール紙は、全体として生分解性とすることができるため、仮に環境中に流出しても、迅速に分解される。 The heat-sealable paper of the present invention has excellent coating layer strength, and the paper base material and the heat-sealable coating layer are firmly bonded. Since the heat-sealable paper of the present invention can be biodegradable as a whole, even if it is released into the environment, it will be rapidly decomposed.
 本発明のヒートシール紙は、紙基材の少なくとも一方の面上に、PHBH(ポリ(3-ヒドロキシブチレート-co-3-ヒドロキシヘキサノエート))100重量部に対し、PVA(ポリビニルアルコール)を7重量部以上35重量部以下含有するヒートシール性塗工層を有し、
 前記PVAのケン化度が、70モル%以上95モル%以下であることを特徴とする。
 なお、本明細書において「A~B」(A、Bは数値)との記載は、A、Bを含む数値範囲、すなわち「A以上B以下」を意味する。
The heat-sealable paper of the present invention contains PVA (polyvinyl alcohol) per 100 parts by weight of PHBH (poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)) on at least one surface of the paper base material. has a heat-sealable coating layer containing 7 parts by weight or more and 35 parts by weight or less,
The saponification degree of the PVA is 70 mol% or more and 95 mol% or less.
In this specification, the expression "A to B" (A and B are numerical values) means a numerical range including A and B, that is, "A to B".
(紙基材)
 紙基材は、主としてパルプからなるシート(以下、「基紙」ともいう。)であり、更に填料、各種助剤等を含む紙料を抄紙して得られる。
 パルプとしては、広葉樹漂白クラフトパルプ(LBKP)、針葉樹漂白クラフトパルプ(NBKP)、広葉樹未漂白クラフトパルプ(LUKP)、針葉樹未漂白クラフトパルプ(NUKP)、サルファイトパルプなどの化学パルプ、ストーングラインドパルプ、サーモメカニカルパルプなどの機械パルプ、脱墨パルプ、古紙パルプなどの木材繊維、ケナフ、竹、麻などから得られた非木材繊維などを用いることができ、適宜配合して用いることが可能である。これらの中でも、紙基材中への異物混入が発生し難いこと、古紙原料としてリサイクル使用する際に経時変色が発生し難いこと、高い白色度を有するため印刷時の面感が良好となり、特に包装材料として使用した場合の使用価値が高くなることなどの理由から、木材繊維の化学パルプ、機械パルプを用いることが好ましく、木材繊維の化学パルプを用いることがより好ましい。具体的には、全パルプに対するLBKP、NBKP等の化学パルプの配合量が80%以上であることが好ましく、化学パルプの配合量が100%であることが特に好ましい。
(Paper base material)
The paper base material is a sheet mainly made of pulp (hereinafter also referred to as "base paper"), and is obtained by paper-making a paper stock that further contains fillers, various auxiliary agents, and the like.
Pulps include chemical pulps such as hardwood bleached kraft pulp (LBKP), softwood bleached kraft pulp (NBKP), hardwood unbleached kraft pulp (LUKP), softwood unbleached kraft pulp (NUKP), sulfite pulp, stone grind pulp, Mechanical pulp such as thermomechanical pulp, wood fibers such as deinked pulp and waste paper pulp, and non-wood fibers obtained from kenaf, bamboo, hemp, etc. can be used, and can be appropriately blended and used. Among these, it is difficult for foreign matter to enter the paper base material, it is difficult to discolor over time when recycled as a waste paper raw material, and it has a high degree of whiteness, so it has a good surface feel when printing. For reasons such as increased utility value when used as a packaging material, it is preferable to use chemical pulp or mechanical pulp made of wood fibers, and it is more preferable to use chemical pulp made of wood fibers. Specifically, it is preferable that the amount of chemical pulp such as LBKP and NBKP is 80% or more based on the total pulp, and it is particularly preferable that the amount of chemical pulp is 100%.
 填料としては、タルク、カオリン、焼成カオリン、クレー、重質炭酸カルシウム、軽質炭酸カルシウム、ホワイトカーボン、ゼオライト、炭酸マグネシウム、炭酸バリウム、二酸化チタン、酸化亜鉛、酸化珪素、非晶質シリカ、水酸化アルミニウム、水酸化カルシウム、水酸化マグネシウム、水酸化亜鉛、硫酸バリウム、硫酸カルシウムなどの無機填料、尿素-ホルマリン樹脂、ポリスチレン樹脂、フェノール系樹脂、微小中空粒子等の有機填料等の公知の填料を使用することができる。なお、填料は、必須材料ではなく、使用しなくてもよい。 Fillers include 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. Known fillers such as inorganic fillers such as calcium hydroxide, magnesium hydroxide, zinc hydroxide, barium sulfate, and calcium sulfate, and organic fillers such as urea-formalin resin, polystyrene resin, phenolic resin, and micro hollow particles are used. be able to. Note that the filler is not an essential material and may not be used.
 各種助剤としては、ロジン、アルキルケテンダイマー(AKD)、アルケニルコハク酸無水物(ASA)などのサイズ剤、ポリアクリルアミド系高分子、ポリビニルアルコール系高分子、カチオン化澱粉、各種変性澱粉、尿素・ホルマリン樹脂、メラミン・ホルマリン樹脂などの乾燥紙力増強剤、湿潤紙力増強剤、歩留剤、濾水性向上剤、凝結剤、硫酸バンド、嵩高剤、染料、蛍光増白剤、pH調整剤、消泡剤、紫外線防止剤、退色防止剤、ピッチコントロール剤、スライムコントロール剤等が例示可能であり、必要に応じて適宜選択して使用可能である。 Various auxiliary agents include rosin, alkyl ketene dimer (AKD), sizing agents such as alkenyl succinic anhydride (ASA), polyacrylamide polymers, polyvinyl alcohol polymers, cationized starches, various modified starches, urea, etc. Formalin resin, dry paper strength enhancer such as melamine/formalin resin, wet paper strength enhancer, retention agent, freeness improver, coagulant, sulfuric acid, bulking agent, dye, optical brightener, pH adjuster, Examples include antifoaming agents, ultraviolet inhibitors, antifading agents, pitch control agents, slime control agents, etc., and can be appropriately selected and used as required.
 紙基材は、その表面が各種薬剤で処理されていてもよい。薬剤としては、酸化澱粉、ヒドロキシエチルエーテル化澱粉、酵素変性澱粉、ポリアクリルアミド、ポリビニルアルコール、表面サイズ剤、耐水化剤、保水剤、増粘剤、滑剤などを例示することができ、これらを単独あるいは2種類以上を混合して用いることができる。さらに、これらの各種薬剤と顔料を併用してもよい。顔料としてはカオリン、クレー、エンジニアードカオリン、デラミネーテッドクレー、重質炭酸カルシウム、軽質炭酸カルシウム、マイカ、タルク、二酸化チタン、硫酸バリウム、硫酸カルシウム、酸化亜鉛、珪酸、珪酸塩、コロイダルシリカ、サチンホワイトなどの無機顔料および密実型、中空型、またはコアーシェル型などの有機顔料などを単独または2種類以上混合して使用することができる。 The surface of the paper base material may be treated with various chemicals. Examples of the drug include oxidized starch, hydroxyethyl etherified starch, enzyme-modified starch, polyacrylamide, polyvinyl alcohol, surface sizing agents, water resistance agents, water retention agents, thickeners, lubricants, etc. Alternatively, two or more types can be used in combination. Furthermore, these various drugs and pigments may be used in combination. Pigments include kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, and satin. Inorganic pigments such as white and organic pigments such as solid type, hollow type, or core shell type can be used alone or in combination of two or more types.
 紙基材の坪量は、所望される各種品質やその用途等により適宜選択可能であるが、通常は20g/m以上600g/m以下が好ましく、25g/m以上600g/m以下がより好ましい。
 例えば、包装紙、紙袋、蓋材、敷き紙等の包装材、屋外で使用されるポスター等に使用する場合、紙基材の坪量は、30g/m以上150g/m以下が好ましい。軟包装材として使用する場合、紙基材の坪量は、20g/m以上100g/m以下が好ましく、35g/m以上80g/m以下がより好ましい。なお、軟包装材とは、包装材の中でも、特に20g/mから100g/m程度の薄手の紙を用いた、柔軟性に富んだ包装材である。また、紙コップ、紙容器、紙箱、紙皿、紙トレー等に使用する場合、紙基材の坪量は、150g/m以上300g/m以下が好ましい。
 また、紙基材の密度は、所望される各種品質や取り扱い性等により適宜選択可能であるが、通常は0.5g/cm以上1.0g/cm以下のものが好ましい。
The basis weight of the paper base material can be selected as appropriate depending on the desired quality and its use, but it is usually preferably 20 g/m 2 or more and 600 g/m 2 or less, and 25 g/m 2 or more and 600 g/m 2 or less. is more preferable.
For example, when used for packaging materials such as wrapping paper, paper bags, lids, and liners, posters used outdoors, etc., the basis weight of the paper base material is preferably 30 g/m 2 or more and 150 g/m 2 or less. When used as a soft packaging material, the basis weight of the paper base material is preferably 20 g/m 2 or more and 100 g/m 2 or less, more preferably 35 g/m 2 or more and 80 g/m 2 or less. Note that the soft packaging material is a highly flexible packaging material that uses thin paper of about 20 g/m 2 to 100 g/m 2 among packaging materials. Further, when used for paper cups, paper containers, paper boxes, paper plates, paper trays, etc., the basis weight of the paper base material is preferably 150 g/m 2 or more and 300 g/m 2 or less.
Further, the density of the paper base material can be appropriately selected depending on the desired various qualities, ease of handling, etc., but it is usually preferably 0.5 g/cm 3 or more and 1.0 g/cm 3 or less.
 紙基材の製造(抄紙)方法は特に限定されるものではなく、長網抄紙機、円網抄紙機、短網抄紙機、ギャップフォーマー型、ハイブリッドフォーマー型(オントップフォーマー型)等のツインワイヤー抄紙機等、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工してもよい。また、紙基材は1層であってもよく、2層以上の多層で構成されていてもよい。
 また、紙基材の表面を薬剤で処理する場合、表面処理の方法は特に限定されるものでなく、ロッドメタリングサイズプレス、ポンド式サイズプレス、ゲートロールコーター、スプレーコーター、ブレードコーター、カーテンコーターなど公知の塗工装置を用いることができる。
The manufacturing method (paper making) of the paper base material is not particularly limited, and may include a fourdrinier paper machine, cylinder paper machine, short wire paper machine, gap former type, hybrid former type (on-top former type), etc. Known manufacturing (paper making) methods and paper machines can be selected, such as a twin wire paper machine. In addition, the pH during papermaking may be any of the acidic region (acidic papermaking), pseudo-neutral region (pseudo-neutral papermaking), neutral region (neutral papermaking), and alkaline region (alkaline papermaking). Afterwards, an alkaline chemical may be applied to the surface of the paper layer. Further, the paper base material may have one layer or may be composed of two or more layers.
In addition, when treating the surface of the paper base material with a chemical, the surface treatment method is not particularly limited, and can be performed using a rod metal ring size press, a pound type size press, a gate roll coater, a spray coater, a blade coater, or a curtain coater. A known coating device such as the like can be used.
(ヒートシール性塗工層)
 ヒートシール性塗工層(以下、ヒートシール層ともいう)は、塗工により形成されたヒートシール性を有する層である。なお、塗工層であるか否かは、その断面を電子顕微鏡等で観察することにより判定することができる。
<PHBH>
 PHBHは、3-ヒドロキシブチレート(以下、3HBともいう。)と3-ヒドロキシヘキサノエート(以下、3HHともいう。)との共重合体であり、微生物が産生することが知られている生分解性樹脂である。本発明において、PHBHは、微生物由来のものを用いてもよく、石油資源由来のものを用いてもよいが、微生物由来のものを用いることが環境負荷低減の点から好ましい。
(Heat-sealable coating layer)
The heat-sealing coating layer (hereinafter also referred to as heat-sealing layer) is a layer having heat-sealing properties formed by coating. Note that whether or not it is a coating layer can be determined by observing its cross section with an electron microscope or the like.
<PHBH>
PHBH is a copolymer of 3-hydroxybutyrate (hereinafter also referred to as 3HB) and 3-hydroxyhexanoate (hereinafter also referred to as 3HH), and is a biomolecule known to be produced by microorganisms. It is a degradable resin. In the present invention, PHBH derived from microorganisms or petroleum resources may be used, but it is preferable to use one derived from microorganisms from the viewpoint of reducing environmental burden.
 PHBHを産生する微生物としては、細胞内にPHBHを蓄積する微生物であれば特に限定されないが、A.lipolytica、A.eutrophus、A.latusなどのアルカリゲネス属(Alcaligenes)、シュウドモナス属(Pseudomonas)、バチルス属(Bacillus)、アゾトバクター属(Azotobacter)、ノカルディア属(Nocardia)、アエロモナス属(Aeromonas)などの菌が挙げられる。なかでも、PHBHの生産性の点で、特にアエロモナス・キャビエなどの菌株、さらにはPHA合成酵素群の遺伝子を導入したアルカリゲネス・ユウトロファス AC32(受託番号FERM BP-6038、寄託日平成9年8月7日、独立行政法人産業技術総合研究所 特許生物寄託センター、あて名;日本国茨城県つくば市東1丁目1番地1 中央第6))(J.Bacteriol.,179,4821-4830頁(1997))などが好ましい。また、アエロモナス属の微生物であるアエロモナス・キャビエ(Aeromonas.caviae)からPHBHを得る方法は、たとえば、特開平05-093049号公報に開示されている。なお、これらの微生物は、適切な条件下で培養して、菌体内にPHBHを蓄積させて用いられる。
 培養に用いる炭素源、培養条件は、特開平05-093049号公報、特開2001-340078号公報等に記載の方法に従い得ることができるが、これらには限定されない。
The microorganism that produces PHBH is not particularly limited as long as it is a microorganism that accumulates PHBH in its cells, but A. lipolytica, A. eutrophus, A. Examples include bacteria of the genus Alcaligenes such as P. latus, Pseudomonas, Bacillus, Azotobacter, Nocardia, and Aeromonas. Among them, in terms of PHBH productivity, strains such as Aeromonas caviae and Alcaligenes eutrophus AC32 (accession number FERM BP-6038, deposited August 7, 1997) into which genes for the PHA synthase group have been introduced are particularly preferred. Patent Organism Depositary Center, National Institute of Advanced Industrial Science and Technology, Address: Chuo 6, Higashi 1-1-1, Tsukuba, Ibaraki Prefecture, Japan) (J. Bacteriol., 179, pp. 4821-4830 (1997)), etc. is preferred. Furthermore, a method for obtaining PHBH from Aeromonas caviae, which is a microorganism belonging to the genus Aeromonas, is disclosed in, for example, Japanese Patent Laid-Open No. 05-093049. Note that these microorganisms are used by culturing them under appropriate conditions to accumulate PHBH within their cells.
The carbon source and culture conditions used for culture can be obtained according to the methods described in JP-A-05-093049, JP-A-2001-340078, etc., but are not limited thereto.
 PHBHの組成比(モル%)は、3HB:3HH=97:3~75:25が好ましく、95:5~85:15がより好ましい。3HHの組成が3モル%未満ではPHBHの特性が3HBホモポリマーの特性に近くなり柔軟性が失われるとともに成膜加工温度が高くなりすぎて好ましくない傾向がある。3HHの組成が25モル%を超えると結晶化速度が遅くなりすぎ成膜加工に適さず、また、結晶化度が下がることで、樹脂が柔軟になり曲げ弾性率が低下する傾向がある。PHBHの組成比は、水性分散液を遠心分離したのち、乾燥させて得られたパウダーをNMR分析により測定することができる。
 微生物産生PHBHはランダム共重合体である。共重合体のモル比を調整するために、菌体の選択、原料となる炭素源の選択、異なるモル比のPHBHとのブレンド、3HBホモポリマーとのブレンドなどの方法がある。
The composition ratio (mol%) of PHBH is preferably 3HB:3HH=97:3 to 75:25, more preferably 95:5 to 85:15. When the composition of 3HH is less than 3 mol%, the properties of PHBH become close to those of 3HB homopolymer, resulting in a loss of flexibility and an undesirable tendency for the film-forming temperature to become too high. When the composition of 3HH exceeds 25 mol %, the crystallization rate becomes too slow, making it unsuitable for film forming processing, and the crystallinity decreases, which tends to make the resin soft and reduce its flexural modulus. The composition ratio of PHBH can be measured by NMR analysis of a powder obtained by centrifuging and drying an aqueous dispersion.
Microbially produced PHBH is a random copolymer. In order to adjust the molar ratio of the copolymer, there are methods such as selection of bacterial cells, selection of a carbon source as a raw material, blending with PHBH of a different molar ratio, and blending with a 3HB homopolymer.
 本発明の一実施形態において、PHBHの重量平均分子量は、5万~55万が好ましく、10万~50万がより好ましく、15万~45万がさらに好ましい。PHBHの重量平均分子量が上記範囲内であることにより、PHBHを含む塗工液の塗工性に優れている。なお、PHBHの重量平均分子量は、ゲル浸透クロマトグラフィー(GPC、昭和電工社製「Shodex GPC-101」等)によって、カラムにポリスチレンゲル(昭和電工社製「Shodex K-804」等)を用い、クロロホルムを移動相とし、ポリスチレン換算した場合の分子量として求めることができる。なお、測定用試料としては、PHBHを含む水性分散液を遠心分離した後、乾燥させて得られたパウダーを用いる。 In one embodiment of the present invention, the weight average molecular weight of PHBH is preferably 50,000 to 550,000, more preferably 100,000 to 500,000, and even more preferably 150,000 to 450,000. When the weight average molecular weight of PHBH is within the above range, the coating liquid containing PHBH has excellent coating properties. The weight average molecular weight of PHBH was determined by gel permeation chromatography (GPC, Showa Denko Co., Ltd. "Shodex GPC-101", etc.) using a polystyrene gel column (Showa Denko Co., Ltd. "Shodex K-804" etc.). It can be determined as the molecular weight when converted to polystyrene using chloroform as the mobile phase. Note that, as the sample for measurement, a powder obtained by centrifuging an aqueous dispersion containing PHBH and then drying it is used.
 PHBHは水分散性である。本発明の塗工液中のPHBHの平均粒径は、0.1~50μmであることが好ましく、0.5~10μmであることがより好ましい。平均粒径が0.1μm未満のPHBHは微生物産生では達成困難であり、また、化学合成法で得る場合にも、微粒子化するという操作が必要となる。平均粒径が50μmを超えるとPHBHを含有する塗工液を塗布した場合に表面に塗布むらが起こる場合がある。なお、PHBHの平均粒径は、マイクロトラック粒度計(日機装製、FRA)など汎用の粒度計を用い、PHBHの水懸濁液を所定濃度に調整し、正規分布の全粒子の50%蓄積量に対応する粒径をいう。
 本発明において、PHBHとして、組成比、重量平均分子量等が異なる2種以上を混合して用いることができる。
PHBH is water dispersible. The average particle size of PHBH in the coating liquid of the present invention is preferably 0.1 to 50 μm, more preferably 0.5 to 10 μm. PHBH with an average particle size of less than 0.1 μm is difficult to achieve by microbial production, and even when obtained by chemical synthesis, an operation of micronization is required. If the average particle size exceeds 50 μm, uneven coating may occur on the surface when a coating solution containing PHBH is applied. The average particle size of PHBH is determined by adjusting the aqueous suspension of PHBH to a predetermined concentration using a general-purpose particle size meter such as Microtrac particle size meter (Nikkiso Co., Ltd., FRA), and calculating the accumulated amount of 50% of all particles in a normal distribution. The particle size corresponding to
In the present invention, two or more PHBHs having different composition ratios, weight average molecular weights, etc. can be used as a mixture.
<PVA>
 PVAは、ケン化度70モル%以上95モル%以下のものを用いる。メカニズムは不明であるが、本発明のヒートシール紙は、ケン化度がこの範囲内のPVAを用いることにより、塗工層強度に優れている。PVAのケン化度は、75モル%以上が好ましく、78モル%以上がより好ましく、85モル%以上がさらに好ましく、また、93モル%以下が好ましく、90モル%以下がより好ましい。
 PVAは水溶性である。そのため、重合度が高くなるにつれてPVAを含む塗工液は増粘し、取り扱い性、塗工性が低下する場合がある。PVAの重合度は、2000以下であることが好ましく、1500以下であることがより好ましく、1000以下であることがさらに好ましい。
 本発明において、PVAとして、ケン化度、重合度等が異なる2種以上を混合して用いることができる。
<PVA>
PVA used has a saponification degree of 70 mol% or more and 95 mol% or less. Although the mechanism is unknown, the heat seal paper of the present invention has excellent coating layer strength by using PVA with a degree of saponification within this range. The degree of saponification of PVA is preferably 75 mol% or more, more preferably 78 mol% or more, even more preferably 85 mol% or more, and preferably 93 mol% or less, more preferably 90 mol% or less.
PVA is water soluble. Therefore, as the degree of polymerization increases, a coating solution containing PVA increases in viscosity, and handling and coating properties may decrease. The degree of polymerization of PVA is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less.
In the present invention, two or more types of PVA having different saponification degrees, polymerization degrees, etc. can be used as a mixture.
 ヒートシール層は、PHBH100重量部に対し、PVAを7重量部以上35重量部以下含有する。PHBHとPVAとをこの割合で含むことにより、塗工層強度に優れたヒートシール層を得ることができる。ヒートシール層は、PHBH100重量部に対し、PVAを10重量部以上含むことが好ましく、また、30重量部以下含むことが好ましい。 The heat seal layer contains 7 parts by weight or more and 35 parts by weight or less of PVA based on 100 parts by weight of PHBH. By containing PHBH and PVA in this ratio, a heat seal layer with excellent coating layer strength can be obtained. The heat seal layer preferably contains PVA in an amount of 10 parts by weight or more, and preferably 30 parts by weight or less, based on 100 parts by weight of PHBH.
 ヒートシール層は、PHBHとPVA以外に、他の水溶性樹脂、水分散性樹脂を含むことができる。さらに、ヒートシール層は、必要に応じて、分散剤、粘性改良剤、保水剤、消泡剤、耐水化剤、蛍光染料、着色染料、着色顔料、界面活性剤、pH調整剤、カチオン性樹脂、アニオン性樹脂、紫外線吸収剤、金属塩など、製紙分野において塗工液に配合される各種助剤を含むことができる。 The heat seal layer can contain other water-soluble resins and water-dispersible resins in addition to PHBH and PVA. Furthermore, the heat seal layer may contain a dispersant, a viscosity improver, a water retention agent, an antifoaming agent, a water resistance agent, a fluorescent dye, a colored dye, a colored pigment, a surfactant, a pH adjuster, a cationic resin, as necessary. , anionic resins, ultraviolet absorbers, metal salts, and other various auxiliary agents that are blended into coating liquids in the paper manufacturing field.
 他の水溶性または水分散性樹脂としては、例えば、完全ケン化ポリビニルアルコール、アセトアセチル化ポリビニルアルコール、カルボキシ変性ポリビニルアルコール、アマイド変性ポリビニルアルコール、スルホン酸変性ポリビニルアルコール、ブチラール変性ポリビニルアルコール、オレフィン変性ポリビニルアルコール、ニトリル変性ポリビニルアルコール、ピロリドン変性ポリビニルアルコール、シリコーン変性ポリビニルアルコール、その他の変性ポリビニルアルコール、エチレンビニルアルコール共重合体などのポリビニルアルコール類、酸化澱粉、エーテル化澱粉、エステル化澱粉などの澱粉類、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、メチルセルロース、エチルセルロース、カルボキシメチルセルロース、アセチルセルロース、ナノセルロースなどのセルロース誘導体、部分ケン化エチレン-酢酸ビニル共重合体、スチレン-ブタジエン共重合体ラテックス、メチルメタクリレート-ブタジエン共重合体の共役ジエン系重合体ラテックス、アクリル系重合体ラテックス、スチレン-無水マレイン酸共重合体ラテックス、ポリ塩化ビニルラテックス、ポリ酢酸ビニルラテックス等が挙げられる。
 本発明において、水溶性樹脂と水分散性樹脂の総量に対するPHBHとPVAの合計量の割合は、80重量%以上であることが好ましく、90重量%以上であることがより好ましく、95重量%以上であることがさらに好ましく、100重量%であることが最も好ましい。
Examples of other water-soluble or water-dispersible resins include fully saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, and olefin-modified polyvinyl alcohol. Alcohol, nitrile-modified polyvinyl alcohol, pyrrolidone-modified polyvinyl alcohol, silicone-modified polyvinyl alcohol, other modified polyvinyl alcohols, polyvinyl alcohols such as ethylene vinyl alcohol copolymers, starches such as oxidized starch, etherified starch, esterified starch, Cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, methylcellulose, ethylcellulose, carboxymethylcellulose, acetylcellulose, nanocellulose, partially saponified ethylene-vinyl acetate copolymer, styrene-butadiene copolymer latex, methyl methacrylate-butadiene copolymer. Examples include conjugated diene polymer latex, acrylic polymer latex, styrene-maleic anhydride copolymer latex, polyvinyl chloride latex, and polyvinyl acetate latex.
In the present invention, the ratio of the total amount of PHBH and PVA to the total amount of water-soluble resin and water-dispersible resin is preferably 80% by weight or more, more preferably 90% by weight or more, and 95% by weight or more. More preferably, the content is 100% by weight, and most preferably 100% by weight.
 ヒートシール層は、ヒートシール性以外にも、PHBHとPVAに由来する性能を発揮することができ、例えば、耐水層、耐油層等として用いることができる。
 耐水層とは、JIS P 8140:1998に規定される「紙及び板-吸水度試験方法-コッブ法」に準拠して、接触時間120秒で測定した吸水度(コッブ値)が20g/m以下の層である。この吸水度は、10g/m以下であることが好ましく、5g/m以下であることがより好ましい。
 耐油層とは、J.TAPPI No.41:2000に規定される「紙及び板紙-はつ油度試験方法-キット法」に準拠して、層表面の任意の5点で測定したキットナンバーの最低値が10以上の層である。このキットナンバーの最低値は、11以上であることが好ましく、12であることがより好ましい。
In addition to heat-sealability, the heat-sealing layer can exhibit properties derived from PHBH and PVA, and can be used, for example, as a water-resistant layer, an oil-resistant layer, etc.
The water-resistant layer is a layer with a water absorbency (Cobb value) of 20 g/m 2 measured at a contact time of 120 seconds in accordance with "Paper and Board - Water Absorption Test Method - Cobb Method" specified in JIS P 8140: 1998. The following layers are included. This water absorption is preferably 10 g/m 2 or less, more preferably 5 g/m 2 or less.
The oil-resistant layer is defined by J. TAPPI No. The layer has a minimum kit number of 10 or more measured at any five points on the layer surface in accordance with "Paper and paperboard - Oil repellency test method - Kit method" specified in 41:2000. The lowest value of this kit number is preferably 11 or more, and more preferably 12.
<ヒートシール紙の製造方法>
 本発明のヒートシール紙は、紙基材に、ヒートシール層用塗工液を、塗工、乾燥することにより、製造することができる。なお、ヒートシール層は、紙基材の片面のみ、または両面に設けることができる。
<Method for manufacturing heat seal paper>
The heat seal paper of the present invention can be produced by applying a heat seal layer coating liquid to a paper base material and drying the coating liquid. Note that the heat seal layer can be provided on only one side or both sides of the paper base material.
 ヒートシール性塗工層の塗工方法は特に限定されるものではなく、公知の塗工装置および塗工系で塗工することができる。例えば、塗工装置としてはブレードコーター、バーコーター、エアナイフコーター、カーテンコーター、スプレーコーター、ロールコーター、リバースロールコーター、サイズプレスコーター、ゲートロールコーター等が挙げられる。また、塗工系としては、水等の溶媒を使用した水系塗工、有機溶剤等の溶媒を使用した溶剤系塗工などが挙げられる。本発明のヒートシール紙は、PHBHがバイオマス由来かつ生分解性であり、PVAが生分解性であるという特性を有し、環境への負荷が非常に小さいため、製造工程においても環境への負荷が小さい水系塗工であることが好ましい。
 ヒートシール層用塗工液の粘度、固形分濃度等は、用いる塗工装置、塗工系等に応じて、適宜調整することができる。
The coating method for the heat-sealable coating layer is not particularly limited, and coating can be performed using a known coating device and coating system. For example, examples of the coating device include a blade coater, a bar coater, an air knife coater, a curtain coater, a spray coater, a roll coater, a reverse roll coater, a size press coater, a gate roll coater, and the like. Further, examples of the coating system include water-based coating using a solvent such as water, solvent-based coating using a solvent such as an organic solvent, and the like. The heat-sealing paper of the present invention has the characteristics that PHBH is derived from biomass and is biodegradable, and PVA is biodegradable, and has a very small environmental load, so there is no environmental burden during the manufacturing process. It is preferable to use a water-based coating with a small amount.
The viscosity, solid content concentration, etc. of the coating liquid for the heat seal layer can be adjusted as appropriate depending on the coating device, coating system, etc. used.
 ヒートシール性塗工層を乾燥させる手法としては、例えば、蒸気加熱ヒーター、ガスヒーター、赤外線ヒーター、電気ヒーター、熱風加熱ヒーター、マイクロウェーブ、シリンダードライヤー等の通常の方法が用いられる。
 乾燥温度は、特に制限されないが、水系塗工の場合、105℃以上160℃以下が好ましい。水系塗工液中ではPHBHは分散しているため、PHBHは粒子状である。乾燥温度が高くなるにつれて、粒子状のPHBHが溶解して成膜が促進されて均一な塗工膜となるため、耐水性、耐油性が向上する傾向が見られるが、成膜が進みすぎるとヒートシール性が低下する場合がある。そのため、乾燥温度は、150℃以下が好ましく、140℃以下がより好ましく、130℃以下がさらに好ましい。
As a method for drying the heat-sealable coating layer, a conventional method such as a steam heater, a gas heater, an infrared heater, an electric heater, a hot air heater, a microwave, a cylinder dryer, etc. can be used.
The drying temperature is not particularly limited, but in the case of water-based coating, it is preferably 105°C or higher and 160°C or lower. Since PHBH is dispersed in the aqueous coating liquid, PHBH is in the form of particles. As the drying temperature increases, particulate PHBH dissolves, promoting film formation and forming a uniform coating film, which tends to improve water resistance and oil resistance, but if film formation progresses too much, Heat sealability may be reduced. Therefore, the drying temperature is preferably 150°C or lower, more preferably 140°C or lower, and even more preferably 130°C or lower.
 ヒートシール層の塗工量(乾燥重量)は、その性能を発揮できるのであれば特に制限されないが、例えば、片面あたり1.0g/m以上50.0g/m以下であることが好ましい。塗工量が片面あたり1.0g/m未満では、ヒートシール性が十分に発揮できない場合がある。また、塗工量が片面あたり50.0g/mを超えても、それ以上の特性向上はほとんど望めず、コストが増加する。ヒートシール層の塗工量(乾燥重量)は、片面あたり3.0g/m以上がより好ましく、5.0g/m以上がさらに好ましく、7.0g/m以上がよりさらに好ましく、また、40.0g/m以下がより好ましく、30.0g/m以下がさらに好ましく、20.0g/m以下がよりさらに好ましい。さらに、本発明のヒートシール紙を軟包装材に用いる場合は、ヒートシール層の塗工量(乾燥重量)は、18.0g/m以下がより好ましく、15.0g/m以下がさらに好ましく、13.0g/m以下がよりさらに好ましい。
 ヒートシール層は、1層であっても2層以上を積層してもよい。ヒートシール層が2層以上である場合は、全てのヒートシール層の塗工量を合計した塗工量が、乾燥重量で上記した範囲であることが好ましい。
The coating amount (dry weight) of the heat seal layer is not particularly limited as long as its performance can be exhibited, but it is preferably 1.0 g/m 2 or more and 50.0 g/m 2 or less per side, for example. If the coating amount is less than 1.0 g/m 2 per side, sufficient heat sealing properties may not be exhibited. Furthermore, even if the coating amount exceeds 50.0 g/m 2 per side, hardly any further improvement in properties can be expected, leading to an increase in cost. The coating amount (dry weight) of the heat seal layer is more preferably 3.0 g/m 2 or more per side, even more preferably 5.0 g/m 2 or more, even more preferably 7.0 g/m 2 or more, and , 40.0 g/m 2 or less is more preferable, 30.0 g/m 2 or less is even more preferable, and even more preferably 20.0 g/m 2 or less. Furthermore, when the heat seal paper of the present invention is used for flexible packaging materials, the coating amount (dry weight) of the heat seal layer is more preferably 18.0 g/m 2 or less, and even more preferably 15.0 g/m 2 or less. Preferably, 13.0 g/m 2 or less is even more preferable.
The heat seal layer may be one layer or two or more layers may be laminated. When there are two or more heat-sealing layers, it is preferable that the total coating amount of all the heat-sealing layers is within the above-mentioned range in terms of dry weight.
 本発明のヒートシール紙は、成形、形状の維持、密封性の確保が容易であるため、紙袋、紙容器、紙箱、紙コップ、(軟)包装材、蓋材等として好適に用いることができる。
 ヒートシール層が耐水層でもある本発明のヒートシール紙は、包装紙、紙袋、紙容器、紙箱、紙コップ、(軟)包装材、紙皿、紙トレー、屋外で使用されるポスター等として好適に用いることができる。
 ヒートシール層が耐油層でもある本発明のヒートシール紙は、ハンバーガー、ホットドッグ、フライドポテト、唐揚げ、ポテトチップス等の油分を多く含む食品用の(軟)包装材や包装紙、天ぷら等の揚げ物用の敷き紙、紙皿、紙トレー、紙コップ等として好適に用いることができる。
Since the heat seal paper of the present invention is easy to shape, maintain shape, and ensure sealing properties, it can be suitably used as paper bags, paper containers, paper boxes, paper cups, (soft) packaging materials, lid materials, etc. .
The heat-sealing paper of the present invention, in which the heat-sealing layer is also a water-resistant layer, is suitable for wrapping paper, paper bags, paper containers, paper boxes, paper cups, (soft) packaging materials, paper plates, paper trays, posters used outdoors, etc. It can be used for.
The heat-sealing paper of the present invention, in which the heat-sealing layer is also an oil-resistant layer, can be used as a (soft) packaging material for foods containing a lot of oil such as hamburgers, hot dogs, french fries, fried chicken, and potato chips, wrapping paper, and tempura. It can be suitably used as paper for frying, paper plates, paper trays, paper cups, etc.
 以下に実施例を挙げて、本発明を具体的に説明するが、本発明は、もちろんこれらの例に限定されるものではない。なお、特に断らない限り、例中の部および%は、それぞれ重量部、重量%を示す。なお、得られた塗工紙について以下に示す様な評価法に基づいて試験を行った。 The present invention will be specifically explained below with reference to Examples, but the present invention is of course not limited to these Examples. In addition, unless otherwise specified, parts and % in the examples indicate parts by weight and % by weight, respectively. The obtained coated paper was tested based on the evaluation method shown below.
[実施例1]
(ヒートシール層用塗工液の調製)
 特許文献1に記載の方法で、PHBHの固形分濃度が50重量%のPHBH水性分散液を得た。次いで、このPHBH水性分散液を60℃で加水分解して分子量を調整することにより、PHBHの重量平均分子量が23万のPHBH水性分散液を得た。
 次いで、前記PHBH水性分散液及びPVA(クラレ社製:5-88、ケン化度88モル%、重合度500)を、固形分重量比でPHBH100重量部に対してPVA15重量部となるように混合し、さらに水を加えて撹拌し、固形分濃度が38重量%の塗工層用塗工液を調製した。
[Example 1]
(Preparation of coating liquid for heat seal layer)
A PHBH aqueous dispersion having a PHBH solid content concentration of 50% by weight was obtained by the method described in Patent Document 1. Next, this PHBH aqueous dispersion was hydrolyzed at 60° C. to adjust the molecular weight, thereby obtaining a PHBH aqueous dispersion having a weight average molecular weight of 230,000.
Next, the PHBH aqueous dispersion and PVA (manufactured by Kuraray Co., Ltd.: 5-88, degree of saponification 88 mol%, degree of polymerization 500) were mixed so that the solid content weight ratio was 15 parts by weight of PVA to 100 parts by weight of PHBH. Then, water was further added and stirred to prepare a coating liquid for a coating layer having a solid content concentration of 38% by weight.
(ヒートシール紙の作製)
 紙基材(坪量50g/mの未晒クラフト原紙)の片面に、ヒートシール層用塗工液を乾燥重量で塗工量が片面あたり10g/mとなるようにバーブレード法で塗工し、105℃で乾燥して、ヒートシール紙を得た。
(Preparation of heat seal paper)
Coating solution for the heat seal layer was coated on one side of the paper base material (unbleached kraft paper with a basis weight of 50 g/m 2 ) using a barblade method so that the dry weight coating amount was 10 g/m 2 per side. The paper was processed and dried at 105°C to obtain heat seal paper.
[比較例1]
 PVA(クラレ社製:5-98、ケン化度98モル%、重合度500)を用いた以外は、実施例1と同様にして、ヒートシール紙を得た。
[実施例2]
 PVA(クラレ社製:22-88、ケン化度88モル%、重合度1700)を用いた以外は、実施例1と同様にして、ヒートシール紙を得た。
[比較例2]
 PVA(クラレ社製:28-98、ケン化度98モル%、重合度1700)を用いた以外は、実施例1と同様にして、ヒートシール紙を得た。
[Comparative example 1]
A heat seal paper was obtained in the same manner as in Example 1, except that PVA (manufactured by Kuraray Co., Ltd.: 5-98, degree of saponification 98 mol%, degree of polymerization 500) was used.
[Example 2]
Heat seal paper was obtained in the same manner as in Example 1, except that PVA (manufactured by Kuraray Co., Ltd.: 22-88, degree of saponification 88 mol%, degree of polymerization 1700) was used.
[Comparative example 2]
Heat seal paper was obtained in the same manner as in Example 1, except that PVA (manufactured by Kuraray Co., Ltd.: 28-98, degree of saponification 98 mol%, degree of polymerization 1700) was used.
(評価方法)
 得られたヒートシール紙について、以下に示す評価を行った。結果を表1に示す。
(1)塗工層強度(セロピック)
 ヒートシール層表面にセロハンテープ(幅18mm、長さ15cm)を貼合し、セロハンテープの上で幅130mm、重量1.8kgのゴムローラーを自重で10往復させて、セロハンテープをヒートシール層表面に密着させた。直後にデジタルフォースゲージ(SHIMPO社)を用いてセロハンテープを一定速度で剥がし、その時の引張強さを測定し、平均値を求めた。
 この試験により、ヒートシール層は紙に付着したままのものと、セロハンテープに付着したものとに分かれるため、引張強さは塗工層の強度を表している。
(Evaluation method)
The obtained heat seal paper was evaluated as shown below. The results are shown in Table 1.
(1) Coating layer strength (seropic)
Laminate cellophane tape (width 18 mm, length 15 cm) on the surface of the heat seal layer, and move a rubber roller with a width of 130 mm and a weight of 1.8 kg over the cellophane tape 10 times using its own weight to attach the cellophane tape to the heat seal layer surface. It was placed in close contact with the Immediately thereafter, the cellophane tape was peeled off at a constant speed using a digital force gauge (SHIMPO), the tensile strength at that time was measured, and the average value was determined.
As a result of this test, the heat-sealing layer is divided into those that are still attached to the paper and those that are attached to the cellophane tape, so the tensile strength represents the strength of the coating layer.
(2)ヒートシール適性
 得られたヒートシール紙から1辺100mmの正方形の試験片を2枚切り出し、塗工層同士を接触させて、加圧温度130℃、加圧圧力2kgf/cm、加圧時間0.5秒でヒートシールした。
 ヒートシールした試験片をテンシロン引張試験機で剥離させた際の引張強さを測定し、最大値を求めた。また、剥離部分を目視で観察し、以下の基準でヒートシール適性を評価した。
 [評価基準]
  〇:紙基材内で剥離する(紙基材が破壊される)。
  △:大部分が紙基材内で剥離する(紙基材が破壊される)。
  ×:塗工層間で剥離する。
(2) Heat-sealing suitability Two square test pieces of 100 mm on a side were cut out from the obtained heat-sealing paper, and the coating layers were brought into contact with each other at a pressure of 130°C and a pressure of 2 kgf/cm 2 . Heat sealing was performed with a pressure time of 0.5 seconds.
The tensile strength was measured when the heat-sealed test piece was peeled off using a Tensilon tensile tester, and the maximum value was determined. In addition, the peeled portion was visually observed, and the suitability for heat sealing was evaluated based on the following criteria.
[Evaluation criteria]
○: Peeling within the paper base material (paper base material is destroyed).
Δ: Most of the sample peels off within the paper base material (the paper base material is destroyed).
×: Peeling occurs between coating layers.
[比較例3]
 PHBH100重量部に対し、PVA(クラレ社製:5-88、ケン化度88モル%、重合度500)を5重量部とした以外は、実施例1と同様にして、ヒートシール紙を得た。
[実施例3]
 PHBH100重量部に対し、PVA(クラレ社製:5-88、ケン化度88モル%、重合度500)を10重量部とした以外は、実施例1と同様にして、ヒートシール紙を得た。
[実施例4]
 PHBH100重量部に対し、PVA(クラレ社製:5-88、ケン化度88モル%、重合度500)を20重量部とした以外は、実施例1と同様にして、ヒートシール紙を得た。
[実施例5]
 PHBH100重量部に対し、PVA(クラレ社製:5-88、ケン化度88モル%、重合度500)を30重量部とした以外は、実施例1と同様にして、ヒートシール紙を得た。
[Comparative example 3]
Heat seal paper was obtained in the same manner as in Example 1, except that 5 parts by weight of PVA (manufactured by Kuraray Co., Ltd.: 5-88, degree of saponification 88 mol%, degree of polymerization 500) was added to 100 parts by weight of PHBH. .
[Example 3]
Heat seal paper was obtained in the same manner as in Example 1, except that 10 parts by weight of PVA (manufactured by Kuraray Co., Ltd.: 5-88, degree of saponification 88 mol%, degree of polymerization 500) was added to 100 parts by weight of PHBH. .
[Example 4]
Heat seal paper was obtained in the same manner as in Example 1, except that 20 parts by weight of PVA (manufactured by Kuraray Co., Ltd.: 5-88, degree of saponification 88 mol%, degree of polymerization 500) was added to 100 parts by weight of PHBH. .
[Example 5]
Heat seal paper was obtained in the same manner as in Example 1, except that 30 parts by weight of PVA (manufactured by Kuraray Co., Ltd.: 5-88, degree of saponification 88 mol%, degree of polymerization 500) was added to 100 parts by weight of PHBH. .
[比較例4]
 PHBH100重量部に対し、PVA(クラレ社製:5-88、ケン化度88モル%、重合度500)を40重量部とした以外は、実施例1と同様にして、ヒートシール紙を得た。
[比較例5]
 PVA(クラレ社製:5-98、ケン化度98モル%、重合度500)を用いた以外は、実施例4と同様にして、ヒートシール紙を得た。
[比較例6]
 PVA(クラレ社製:5-98、ケン化度98モル%、重合度500)を用いた以外は、実施例5と同様にして、ヒートシール紙を得た。
[Comparative example 4]
Heat seal paper was obtained in the same manner as in Example 1, except that 40 parts by weight of PVA (manufactured by Kuraray Co., Ltd.: 5-88, degree of saponification 88 mol%, degree of polymerization 500) was added to 100 parts by weight of PHBH. .
[Comparative example 5]
A heat seal paper was obtained in the same manner as in Example 4, except that PVA (manufactured by Kuraray Co., Ltd.: 5-98, degree of saponification 98 mol%, degree of polymerization 500) was used.
[Comparative example 6]
A heat seal paper was obtained in the same manner as in Example 5, except that PVA (manufactured by Kuraray Co., Ltd.: 5-98, degree of saponification 98 mol%, degree of polymerization 500) was used.

Claims (4)

  1.  紙基材の少なくとも一方の面上に、PHBH(ポリ(3-ヒドロキシブチレート-co-3-ヒドロキシヘキサノエート))100重量部に対し、PVA(ポリビニルアルコール)を7重量部以上35重量部以下含有するヒートシール性塗工層を有し、
     前記PVAのケン化度が、70モル%以上95モル%以下であることを特徴とするヒートシール紙。
    On at least one side of the paper base material, 7 parts by weight or more and 35 parts by weight of PVA (polyvinyl alcohol) per 100 parts by weight of PHBH (poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)). It has a heat-sealable coating layer containing the following:
    A heat seal paper characterized in that the degree of saponification of the PVA is 70 mol% or more and 95 mol% or less.
  2.  前記PVAの重合度が、2000以下であることを特徴とする請求項1に記載のヒートシール紙。 The heat seal paper according to claim 1, wherein the PVA has a polymerization degree of 2000 or less.
  3.  前記ヒートシール性塗工層の塗工量(乾燥重量)が、片面あたり1.0g/m以上50.0g/m以下であることを特徴とする請求項1または2に記載のヒートシール紙。 The heat seal according to claim 1 or 2, wherein the coating amount (dry weight) of the heat sealable coating layer is 1.0 g/m 2 or more and 50.0 g/m 2 or less per side. paper.
  4.  前記紙基材のJIS P 8124に準じて測定した坪量が、20g/m以上600g/m以下であることを特徴とする請求項1または2に記載のヒートシール紙。  The heat seal paper according to claim 1 or 2, wherein the paper base material has a basis weight of 20 g/m 2 or more and 600 g/m 2 or less, as measured according to JIS P 8124.
PCT/JP2023/029916 2022-08-22 2023-08-21 Heat sealing paper WO2024043201A1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0657691A (en) * 1992-07-31 1994-03-01 Unitika Chem Kk Coating agent for paper
JP2001011294A (en) * 1999-07-02 2001-01-16 Miyoshi Oil & Fat Co Ltd Aqueous dispersion of biodegradable resin and biodegradable composite material
JP2003128888A (en) * 2001-10-24 2003-05-08 Mitsui Chemicals Inc Laminate
JP2019210593A (en) * 2019-09-05 2019-12-12 王子ホールディングス株式会社 Paper substrate for barrier paper container, sheet for barrier paper container, and foam thermal insulation paper container
WO2021256381A1 (en) * 2020-06-16 2021-12-23 日本製紙株式会社 Coated paper
WO2022003195A1 (en) * 2020-07-02 2022-01-06 Aquaspersions Limited Aqueous biopolymer dispersions
WO2022097708A1 (en) * 2020-11-06 2022-05-12 中京油脂株式会社 Aqueous dispersion, coating liquid containing this aqueous dispersion, method for producing polylactic acid film using this coating liquid, and sheet material

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0657691A (en) * 1992-07-31 1994-03-01 Unitika Chem Kk Coating agent for paper
JP2001011294A (en) * 1999-07-02 2001-01-16 Miyoshi Oil & Fat Co Ltd Aqueous dispersion of biodegradable resin and biodegradable composite material
JP2003128888A (en) * 2001-10-24 2003-05-08 Mitsui Chemicals Inc Laminate
JP2019210593A (en) * 2019-09-05 2019-12-12 王子ホールディングス株式会社 Paper substrate for barrier paper container, sheet for barrier paper container, and foam thermal insulation paper container
WO2021256381A1 (en) * 2020-06-16 2021-12-23 日本製紙株式会社 Coated paper
WO2022003195A1 (en) * 2020-07-02 2022-01-06 Aquaspersions Limited Aqueous biopolymer dispersions
WO2022097708A1 (en) * 2020-11-06 2022-05-12 中京油脂株式会社 Aqueous dispersion, coating liquid containing this aqueous dispersion, method for producing polylactic acid film using this coating liquid, and sheet material

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