WO2020235653A1 - セルロース樹脂組成物を収容するため容器及びこれとセルロース樹脂組成物とを有する包装体 - Google Patents
セルロース樹脂組成物を収容するため容器及びこれとセルロース樹脂組成物とを有する包装体 Download PDFInfo
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- WO2020235653A1 WO2020235653A1 PCT/JP2020/020184 JP2020020184W WO2020235653A1 WO 2020235653 A1 WO2020235653 A1 WO 2020235653A1 JP 2020020184 W JP2020020184 W JP 2020020184W WO 2020235653 A1 WO2020235653 A1 WO 2020235653A1
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- WIPO (PCT)
- Prior art keywords
- lignin
- container
- cellulose
- resin composition
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D5/00—Rigid or semi-rigid containers of polygonal cross-section, e.g. boxes, cartons or trays, formed by folding or erecting one or more blanks made of paper
- B65D5/42—Details of containers or of foldable or erectable container blanks
- B65D5/56—Linings or internal coatings, e.g. pre-formed trays provided with a blow- or thermoformed layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D31/00—Bags or like containers made of paper and having structural provision for thickness of contents
- B65D31/02—Bags or like containers made of paper and having structural provision for thickness of contents with laminated walls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D31/00—Bags or like containers made of paper and having structural provision for thickness of contents
- B65D31/04—Bags or like containers made of paper and having structural provision for thickness of contents with multiple walls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D5/00—Rigid or semi-rigid containers of polygonal cross-section, e.g. boxes, cartons or trays, formed by folding or erecting one or more blanks made of paper
- B65D5/42—Details of containers or of foldable or erectable container blanks
- B65D5/56—Linings or internal coatings, e.g. pre-formed trays provided with a blow- or thermoformed layer
- B65D5/60—Loose, or loosely attached, linings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
-
- 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
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
-
- 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
Definitions
- the present invention relates to a container for accommodating a cellulose resin composition, a package having the container and the cellulose resin composition, a method for suppressing discoloration of the cellulose resin composition during storage, and a resin containing the cellulose resin composition.
- the present invention relates to a method for producing a molded product.
- Patent Document 1 describes a paper packaging material for a product made of polyamide fiber or resin or a product thereof. The package described in Patent Document 1 can prevent yellowing of polyamide fibers or resins or products made of them to some extent.
- the present invention solves the above problems, a container capable of storing the cellulose resin composition without discoloration over time, a package having the container and the cellulose resin composition, and a cellulose resin composition using the container. It is an object of the present invention to provide a method for suppressing discoloration of a resin molded product and a method for producing a resin molded product including the use of the container.
- the present inventors have found that by containing the cellulose resin composition in a container having a specific structure, discoloration of the cellulose resin composition over time can be suppressed.
- the present invention has been completed. That is, the present invention includes the following aspects.
- a container for containing a cellulose resin composition containing a thermoplastic resin and cellulose contains a high lignin member having a lignin content of 10% by mass or more and a low lignin member having a lignin content of 1% by mass or less.
- the lignin content (Lc) of the cellulose is 20% by mass or less.
- the lignin content (Lo) of the high lignin member, the lignin content (Li) of the low lignin member, and the lignin content (Lc) of the cellulose are expressed by the following formulas: Lo> Lc ⁇ Li
- the low lignin member, JIS Z0208: 1976 is less than 50 g / m 2 ⁇ 24h water vapor transmission rate as measured by the method described in, container according to the above aspect 1 or 2.
- the container according to any one of the above aspects 1 to 3 having an outer body made of the high lignin member and an inner body made of the low lignin member.
- the outer body is a box body or a bag body.
- the container according to any one of the above aspects 1 to 4 wherein the inner body is a sheet body fixed or not fixed to the outer body.
- the container according to any one of the above aspects 1 to 5 wherein the high lignin member has a yellowness (YI) value of 20 or more.
- YI yellowness
- the container contains a high lignin member having a lignin content of 10% by mass or more and a low lignin member having a lignin content of 1% by mass or less.
- the lignin content (Lo) of the high lignin member, the lignin content (Li) of the low lignin member, and the lignin content (Lc) of the cellulose are expressed by the following formulas: Lo> Lc ⁇ Li
- the low lignin member, JIS Z0208: 1976 is less than 50g / m 2 ⁇ 24h water vapor transmission rate as measured by the method described in, packaging according to any of the above embodiments 9-11.
- the package according to any one of the above aspects 9 to 12 which has an outer body made of the high lignin member and an inner body made of the low lignin member.
- the outer body is a box body or a bag body.
- a method for suppressing discoloration of a cellulose resin composition containing a thermoplastic resin and cellulose during storage Including containing the cellulose resin composition in a container, The container contains a high lignin member having a lignin content of 10% by mass or more and a low lignin member having a lignin content of 1% by mass or less. A method in which the entire contact surface of the container with the cellulose resin composition is composed of the low lignin member.
- a method for producing a molded product containing a cellulose resin composition containing a thermoplastic resin and cellulose Including a step of preparing the cellulose resin composition contained in the container and a step of injection molding the cellulose resin composition contained in the container in a mold.
- the container contains a high lignin member having a lignin content of 10% by mass or more and a low lignin member having a lignin content of 1% by mass or less.
- the entire contact surface of the container with the cellulose resin composition is composed of the low lignin member.
- a method in which the YI value of the molded product is 50 or less.
- a container capable of storing the cellulose resin composition without discoloration over time, a package having the container and the cellulose resin composition, and the container are used to suppress discoloration of the cellulose resin composition.
- a method and a method for producing a resin molded product including the use of the container may be provided.
- One aspect of the present invention provides a container for containing a cellulose resin composition containing a thermoplastic resin and cellulose.
- the container comprises a high lignin member having a lignin content of 10% by mass or more and a low lignin member having a lignin content of 1% by mass or less.
- the entire inner surface (more specifically, 99 area% or more, particularly 100 area%), which is the contact surface of the container with the cellulose resin composition, is composed of a low lignin member.
- the "whole inner surface” does not exclude that a portion of the inner surface that is not composed of a low lignin member exists to the extent that the effect of the present invention is not impaired (for example, defects such as gouging and fraying). And it is not excluded that the low lignin member is not exposed on the inner surface due to seams or the like).
- the present inventor found that the resin composition containing cellulose causes remarkable discoloration during storage in the container as compared with the resin composition containing no cellulose, but the discoloration is remarkably suppressed by reducing the lignin content of the container. Found to be done. Although details are unknown, some chemical action between lignin and the resin composition due to the chemical structure of lignin (eg, phenolic hydroxyl group) (eg, the phenolic hydroxyl group in lignin contains nitrogen in the cellulose resin composition). It is considered that the coloring component (for example, production of nitrophenol) when reacting with the compound causes discoloration of the cellulose resin composition, and the reduction of the amount of lignin can suppress the action, and thus the discoloration is suppressed. .. Since discoloration due to lignin in a container is a peculiar phenomenon particularly noticeable in a cellulose resin composition, the container of the present disclosure is particularly suitable for a specific application of containing a cellulose resin composition. ..
- the high lignin member has a relatively high yellowness (YI) value.
- the YI value of the high lignin member may be 20 or more, 50 or more, or 70 or more in one embodiment, and may be 120 or less, 110 or less, or 100 or less in one embodiment.
- the yellowness (YI) value is a value measured in accordance with JIS K7373.
- the lignin content of the low lignin member is 1% by mass or less.
- the low lignin member examples include polymers of polyolefins (for example, polyethylene, polypropylene, etc.), metals such as aluminum, and the like.
- the low lignin member preferably contains a polyolefin and / or metal (particularly preferably aluminum), more preferably a polyolefin and / or metal (particularly preferably aluminum), in that the water absorption of the cellulose resin composition can be better suppressed. Consists of. Polyolefins are also advantageous in that they are low in cost.
- the low lignin member has a relatively low water vapor permeability.
- the low lignin member has a low lignin content and a low water vapor permeability, it is possible to suppress water absorption in addition to suppressing discoloration of the cellulose resin composition. Since water absorption causes deterioration due to hydrolysis of the components in the cellulose resin composition, it is preferable to suppress water absorption.
- Low lignin member, JIS Z0208 water vapor permeability as measured by the method described in 1976, in one aspect 50g / m 2 ⁇ 24h or less, or 20g / m 2 ⁇ 24h or less, or 10g / m 2 ⁇ 24h or less It may be.
- the water vapor permeability is preferably as low, in view of manufacturability of the container, for example, 1g / m 2 ⁇ 24h or more, or 5g / m 2 ⁇ 24h or more, or may be 10g / m 2 ⁇ 24h or more ..
- the container can, in one aspect, be substantially composed of a high lignin member and a low lignin member, and in one aspect can have a high lignin member, a low lignin member, and an additional member.
- the additional members include all members that are not included in any of the "high lignin members” and "low lignin members” of the present disclosure. Examples of the additional member include an adhesive and the like.
- the mass ratio of the high lignin member to the entire container may be, for example, 10% by mass or more, 30% by mass or more, or 50% by mass or more from the viewpoint of reducing the cost of the container by using the high lignin member, and the low lignin member. From the viewpoint of obtaining the advantage of using the above, for example, it may be 99.9% by mass or less, 99% by mass or less, or 90% by mass or less.
- the mass ratio of the low lignin member to the entire container may be, for example, 0.1% by mass or more, 1% by mass or more, or 10% by mass or more, and is high, from the viewpoint of obtaining the advantages of using the low lignin member. From the viewpoint of reducing the cost of the container by using the lignin member, it may be, for example, 90% by mass or less, 70% by mass or less, or 50% by mass or less.
- the mass ratio of the additional member to the entire container can be appropriately selected depending on the purpose of using the additional member, for example, 0.01% by mass to 90% by mass, or 0.1% by mass to 50% by mass, or It may be 1% by mass to 30% by mass.
- the container has an outer body made of a high lignin member and an inner body made of a low lignin member.
- at least the inner body may form most of the inner surface of the container (that is, the contact surface with the cellulose resin composition).
- the outer body constitutes the outer surface of the container, but a member that is not a high lignin member (for example, a coating layer) is arranged on the surface of the outer body, so that the high lignin member is formed on the outer surface of the container. Can also be unexposed.
- another member may be arranged between the outer body and the inner body.
- each of the outer body and the inner body can be a laminated body having a plurality of layers, in which case another member may be arranged between the layers.
- the combination of the outer body and the inner body a combination in which the outer body is a box body or a bag body and the inner body is a sheet body fixed or not fixed to the outer body can be exemplified.
- the container in which the inner body is not fixed to the outer body include a container in which the outer body is a box body or a bag body and the inner body is a box body or a bag body arranged inside the outer body.
- An example of such a container is a box or bag whose outer body is made of a paper material (preferably a paper material obtained from unbleached pulp and / or used paper), and whose inner body is a bag containing polyolefin. It is a container that is.
- At least a part of the inner body and at least a part of the outer body in the above-mentioned container in which the inner body is not fixed to the outer body are fixed with an adhesive or the like.
- Examples thereof include a container in which the outer body is a bag and the inner body is a coating or a laminate laminated directly on the inner surface of the bag or via an adhesive or the like.
- the thickness of the outer body is 0.01 mm or more, 0.1 mm or more, or from the viewpoint of obtaining good mechanical strength for accommodating the cellulose resin composition and from the viewpoint of satisfactorily suppressing water absorption of the cellulose resin composition. It may be 1 mm or more, and may be 20 mm or less, 10 mm or less, or 5 mm or less from the viewpoint of handleability and cost.
- the shape and dimensions of the container are not limited and can be appropriately selected according to the purpose.
- the box body can have various deformed shapes in addition to a rectangular parallelepiped and a cube.
- the box body may have a deformed shape according to the shape of the molded product.
- the bag body can have various deformed shapes in addition to rectangles and squares (as well as shapes with gussets attached thereto).
- the dimensions of the box can be a maximum length of 50 mm to 2000 mm x a maximum width of 50 mm to 2000 mm x a maximum height of 50 mm to 2000 mm.
- the dimensions of the bag body can be a maximum length of 50 mm to 2000 mm x a maximum width of 50 mm to 2000 mm x a maximum gusset of 50 mm to 2000 mm.
- One aspect of the present invention provides a package having a container and a cellulose resin composition containing a thermoplastic resin and cellulose contained in the container.
- the container included in the package of the present disclosure may be the container of the present disclosure described above. Therefore, the container includes a high lignin member having a lignin content of 10% by mass or more and a low lignin member having a lignin content of 1% by mass or less.
- the preferred embodiment of the container contained in the package may be the same as illustrated in the “Container” section of the present disclosure.
- thermoplastic resin a polyamide resin, a polyester resin, a polyacetal resin, a polycarbonate resin, a polyacrylic resin, and a polyphenylene ether resin (modified polyphenylene modified by blending or graft-polymerizing polyphenylene ether with another resin).
- ether (Including ether), polyarylate resin, polysulfone resin, polyphenylene sulfide resin, polyether sulfone resin, polyketone resin, polyphenylene ether ketone resin, polyimide resin, polyamideimide resin, polyetherimide resin, Examples thereof include polyurethane-based resins, polyolefin-based resins (for example, ⁇ -olefin (co) polymers), and various ionomers.
- thermoplastic resin examples include high-density polyethylene, low-density polyethylene (for example, linear low-density polyethylene), polypropylene, polymethylpentene, cyclic olefin resin, poly1-butene, poly1-pentene, polymethylpentene.
- Ethylene / ⁇ -olefin copolymer Ethylene / ⁇ -olefin copolymer, ethylene / butene copolymer, EPR (ethylene-propylene copolymer), modified ethylene / butene copolymer, EEA (ethylene-ethylacrylate copolymer), modified EEA, modified EPR, modified EPDM (ethylene-propylene-diene ternary copolymer), ionomer, ⁇ -olefin copolymer, modified IR (isoprene rubber), modified SEBS (styrene-ethylene-butylene-styrene copolymer), halogenated Isobutylene-paramethylstyrene copolymer, ethylene-acrylic acid modified product, ethylene-vinyl acetate copolymer and its acid modified product, (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxy
- Butadiene rubber various styrene-butadiene copolymer rubber, isoprene rubber, butyl rubber, bromide of copolymer of isobutylene and p-methylstyrene, butyl halide rubber, acrylonitrilobutadiene rubber, chloroprene rubber, ethylene-propylene copolymer rubber , Ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide Acrylonitrile-based copolymers mainly composed of acrylics such as rubber, silicone rubber, fluororubber, urethane rubber, polyvinyl chloride, polystyrene, polyacrylic
- thermoplastic resin modified with at least one compound selected from unsaturated carboxylic acids, acid anhydrides thereof or derivatives thereof can also be used.
- polyolefin resins polyamide resins, polyester resins, polyacetal resins, polyacrylic resins, polyphenylene ether resins, and polyphenylene sulfide resins
- a polyamide resin tends to be easily discolored by a phenolic hydroxyl group and absorb moisture.
- the container according to one aspect of the present invention is particularly advantageous for accommodating a cellulosic resin composition containing such a polyamide resin.
- the polyolefin-based resin is a polymer obtained by polymerizing a monomer unit containing olefins (for example, ⁇ -olefins).
- olefins for example, ⁇ -olefins
- Specific examples of the polyolefin-based resin are not particularly limited, but are exemplified by low-density polyethylene (for example, linear low-density polyethylene), high-density polyethylene, ultra-low-density polyethylene, ultra-high-density polyethylene, and the like.
- Polypropylene-based (co) copolymers such as coalescence, polypropylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, etc., ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene Examples thereof include a copolymer of ⁇ -olefin represented by a glycidyl methacrylate copolymer and the like and another monomer unit.
- polypropylene is mentioned as the most preferable polyolefin resin.
- polypropylene having a melt mass flow rate (MFR) of 3 g / 10 minutes or more and 60 g / 10 minutes or less measured at 230 ° C. and a load of 21.2 N in accordance with ISO1133 is preferable.
- MFR melt mass flow rate
- the lower limit of MFR is more preferably 5 g / 10 minutes, even more preferably 6 g / 10 minutes, and most preferably 8 g / 10 minutes.
- the upper limit is more preferably 25 g / 10 minutes, even more preferably 20 g / 10 minutes, and most preferably 18 g / 10 minutes. It is desirable that the MFR does not exceed the above upper limit value from the viewpoint of improving the toughness of the composition, and it is desirable not to exceed the above lower limit value from the viewpoint of the fluidity of the composition.
- an acid-modified polyolefin resin can also be preferably used in order to enhance the affinity with cellulose.
- the polyamide-based resin preferable as the thermoplastic resin is not particularly limited, but is obtained by a polycondensation reaction of lactams, polyamide 6, polyamide 11, polyamide 12, etc .; 1,6-hexanediamine, 2-methyl-1,5. -Pentanediamine, 1,7-heptanediamine, 2-methyl-1-6-hexanediamine, 1,8-octanediamine, 2-methyl-1,7-heptanediamine, 1,9-nonanediamine, 2-methyl- Diamines such as 1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamide, m-xylylene diamine, butane diic acid, pentanic acid, hexane diic acid , Heptane diic acid, octane diacid, nonane diic acid, decane diic acid, benzene-1,2-dicarboxylic acid, benzene-1,3
- polyamide-based resins aliphatic polyamides such as polyamide 6, polyamide 11, polyamide 12, polyamide 6, 6, polyamide 6, 10, polyamide 6, 11, polyamide 6, 12 and polyamide 6, C, polyamide 2 M5, C
- the alicyclic polyamide such as is more preferable.
- the concentration of terminal carboxyl groups in the polyamide resin is not particularly limited, but the lower limit is preferably 20 ⁇ mol / g, more preferably 30 ⁇ mol / g.
- the upper limit of the terminal carboxyl group concentration is preferably 150 ⁇ mol / g, more preferably 100 ⁇ mol / g, and further preferably 80 ⁇ mol / g.
- the ratio of carboxyl terminal groups to total terminal groups is preferably 0.30 to 0.95.
- the lower limit of the carboxyl end group ratio is more preferably 0.35, even more preferably 0.40, and most preferably 0.45.
- the upper limit of the carboxyl end group ratio is more preferably 0.90, even more preferably 0.85, and most preferably 0.80.
- the carboxyl terminal group ratio is preferably 0.30 or more from the viewpoint of dispersibility of cellulose in the resin composition, and is preferably 0.95 or less from the viewpoint of the color tone of the obtained resin composition.
- a known method can be used as a method for adjusting the terminal group concentration of the polyamide resin.
- Examples thereof include a method of adding a terminal modifier that reacts with an terminal group to the polymerization solution.
- aliphatic monocarboxylic acids aliphatic monocarboxylic acids
- alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid
- aromatic products such as benzoic acid, toluic acid, ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid, etc.
- Carboxylic acids and a plurality of mixtures arbitrarily selected from these.
- acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, etc. in terms of reactivity, stability of the sealing end, price, etc.
- One or more terminal modifiers selected from the group consisting of benzoic acid and benzoic acid are preferable, and acetic acid is most preferable.
- Aliphatic compounds such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine are examples of the terminal modifier that reacts with the terminal carboxyl group.
- one or more terminals selected from the group consisting of butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine and aniline from the viewpoints of reactivity, boiling point, stability of sealing terminal, price and the like. Regulators are preferred.
- the concentrations of these amino-terminal groups and carboxyl-terminal groups are preferably obtained by 1 H-NMR from the integrated value of the characteristic signal corresponding to each terminal group in terms of accuracy and simplicity.
- a method for determining the concentration of those terminal groups specifically, the method described in JP-A-7-228775 is recommended. When this method is used, heavy trifluoroacetic acid is useful as a measurement solvent.
- the number of integrations of 1 1 H-NMR requires at least 300 scans even when measured with an instrument having sufficient resolution.
- the concentration of the terminal group can also be measured by a measurement method by titration as described in JP-A-2003-055549. However, in order to reduce the influence of mixed additives, lubricants, etc. as much as possible, 1 H-NMR quantification is more preferable.
- the polyester-based resin preferable as the thermoplastic resin is not particularly limited, but is not particularly limited, but is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene succinate (PBS), polybutylene succinate adipate ( Selected from PBSA), polybutylene terephthalate (PBAT), polyallylate (PAR), polyhydroxyalkanoic acid (PHA) (polyester resin composed of 3-hydroxyalkanoic acid), polylactic acid (PLA), polycarbonate (PC), etc.
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PEN polyethylene naphthalate
- PBS polybutylene succinate
- PBS polybutylene succinate adipate
- PAR polyallylate
- PHA polyhydroxyalkanoic acid
- PDA polylactic acid
- PC polycarbonate
- more preferable polyester-based resins include PET, PBS,
- thermoplastic resins include homopolyacetal made from formaldehyde and copolyacetal containing trioxane as a main monomer and, for example, 1,3-dioxolane as a comonomer component, and both can be used.
- copolyacetal can be preferably used.
- the type of cellulose can be selected according to the desired properties of the cellulose resin composition, and for example, cellulose fiber can be preferably used.
- the lignin content of cellulose is, in one embodiment, 20% by mass or less. The lower the lignin content, the more preferable, and 0% by mass (that is, no lignin is contained) is most preferable. For example, by using a lignin-free raw material such as cotton linter, the lignin content can be set to 0% by mass. In the cellulose resin composition in which the lignin content of cellulose is 20% by mass or less, the discoloration prevention effect by using the container of the present disclosure is particularly remarkable.
- the lignin content (Lc) of cellulose is 20% by mass or less, the lignin content (Lo) of a high lignin member, the lignin content (Li) of a low lignin member, and the lignin content of cellulose (Li).
- Lc) is the following formula: Lo> Lc ⁇ Li Satisfy the relationship.
- the cellulose is cellulose nanofibers (that is, cellulose fibers having an average fiber diameter of 1000 nm or less).
- cellulose nanofibers are not particularly limited, but for example, cellulose nanofibers made from cellulose pulp or one or more modified products of these celluloses can be used. Among these, one or more modified cellulose products can be preferably used from the viewpoint of stability, performance and the like.
- the average fiber diameter of the cellulose nanofibers is 1000 nm or less, preferably 500 nm or less, and more preferably 200 nm or less, from the viewpoint of obtaining good mechanical strength (particularly tensile elastic modulus) of the resin molded product.
- the average fiber diameter is preferably small, but from the viewpoint of ease of processing, it can be preferably 10 nm or more, more preferably 20 nm or more, and further preferably 30 nm or more.
- the average fiber diameter is a value obtained as a spherical equivalent diameter (volume average particle diameter) of particles when the integrated volume becomes 50% by a laser diffraction / scattering method particle size counter.
- centrifuge for example, manufactured by Kubota Shoji Co., Ltd., trade name “6800 type centrifuge”, rotor type RA-400 type
- processing conditions centrifugal force 39200 m 2 / s 10
- the supernatant is centrifuged for 45 minutes, and the supernatant is centrifuged at 116000 m 2 / s for 45 minutes, and the supernatant after centrifugation is collected.
- a laser diffraction / scattering method particle size distribution counter for example, manufactured by Horiba Seisakusho Co., Ltd., trade name "LA-910” or trade name "LA-950", ultrasonic treatment 1 minute, refractive index 1.
- the integrated 50% particle diameter in the volume frequency particle size distribution obtained in 20 (that is, the spherical equivalent diameter of the particles when the integrated volume becomes 50% with respect to the total volume of the particles) is defined as the volume average particle diameter. ..
- the L / D ratio of cellulose nanofibers is 20 or more.
- the lower limit of L / D of the cellulose nanofibers is preferably 30, more preferably 40, more preferably 50, and even more preferably 100.
- the upper limit is not particularly limited, but is preferably 10,000 or less from the viewpoint of handleability. In order to exhibit the good mechanical properties of the resin composition of the present disclosure with a small amount of cellulose nanofibers, it is desirable that the L / D ratio of the cellulose nanofibers is within the above range.
- the length (L), diameter (D) and L / D ratio of the cellulose nanofibers are such that the aqueous dispersion of the cellulose nanofibers is a high-shear homogenizer (for example, manufactured by Nippon Seiki Co., Ltd., trade name "Excel".
- a high-shear homogenizer for example, manufactured by Nippon Seiki Co., Ltd., trade name "Excel”.
- ED-7 an autohomogenizer ED-7 "
- SEM high-resolution scanning microscope
- AFM atomic force microscope
- the length (L) and diameter (D) of 100 randomly selected cellulose nanofibers in the observation field adjusted so that at least 100 cellulose nanofibers are observed. Is measured and the ratio (L / D) is calculated.
- the length and diameter of the cellulose nanofibers disclosed in the present disclosure are the number average values of the above 100 celluloses.
- Cellulose nanofibers are crushed by a pulverization method using a high-pressure homogenizer, microfluidizer, ball mill, disc mill, etc. after treating pulp or the like with hot water or the like at 100 ° C. or higher to hydrolyze and weaken the hemicellulose portion. It may be delicate cellulose.
- the cellulose nanofibers may be modified products (ie, modified cellulose nanofibers).
- modified cellulose nanofibers are those in which cellulose is modified by one or more modifiers selected from esterifying agents, silylating agents, isocyanate compounds, halogenating alkylating agents, alkylene oxides and / or glycidyl compounds. Can be mentioned.
- the cellulose resin composition may optionally contain additional components in addition to the thermoplastic resin and cellulose.
- additional component include surface treatment agents, antioxidants, inorganic fillers, lubricating oils and the like. Each of these components may be used alone or in combination of two or more. Further, these components may be commercially available reagents or products.
- the surface treatment agent include a compound having a hydrophilic segment and a hydrophobic segment in the molecule, and more specifically, a compound giving a hydrophilic segment (for example, polyethylene glycol) and a hydrophobic segment.
- a copolymer for example, a block copolymer of propylene oxide and ethylene oxide, tetrahydrofuran obtained by using one or more of each of the given compounds (for example, polypropylene glycol, poly (tetramethylene ether) glycol (PTMEG), polybutadiene diol, etc.) Block copolymer of ethylene oxide) and the like.
- the preferable content of the surface treatment agent in the cellulose resin composition is preferably 0.1% by mass or more, 0.2% by mass or more, or 0.2% by mass or more from the viewpoint of enhancing the dispersibility of cellulose in the cellulose resin composition. From the viewpoint of suppressing plasticization of the cellulose resin composition and maintaining good strength, it is preferably 50% by mass or less, 30% by mass or more, or 20% by mass or more, or 18 It is 1% by mass or more, 15% by mass or more, 10% by mass or more, or 5% by mass or more.
- the preferable amount of the surface treatment agent with respect to 100 parts by mass of cellulose is preferably 0.1 part by mass or more, 0.5 parts by mass or more, or 1 part by mass from the viewpoint of enhancing the dispersibility of cellulose in the cellulose resin composition.
- the content is preferably 100 parts by mass or less, 99 parts by mass or less, 90 parts by mass or less, or 80 parts by mass or less. Or 70 parts by mass or less, 50 parts by mass or less, or 40 parts by mass or less.
- a hindered phenol-based antioxidant a sulfur-based antioxidant, and a phosphorus-based antioxidant are preferable from the viewpoint of the effect of preventing deterioration due to heat, and a phosphorus-based antioxidant and a hindered phenol-based oxidation are preferable.
- Inhibitors are more preferred, and phosphorus-based antioxidants and / or hindered phenol-based antioxidants in combination with hindered amine-based light stabilizers (HALS) are even more preferred.
- HALS hindered amine-based light stabilizers
- the preferable amount of the antioxidant is 0.01% by mass or more, 0.02% by mass or more, or 0.03% by mass or more, or 0.05% by mass or more based on the whole cellulose resin composition. Yes, preferably 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, or 1% by mass or less.
- the inorganic filler examples include fibrous particles, plate-like particles, and inorganic pigments.
- the fibrous particles and the plate-like particles may have an average aspect ratio of 5 or more.
- the amount of the inorganic filler in the cellulose resin composition is preferably 0.002 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin from the viewpoint of improving the handleability when molding the cellulose resin composition into a resin molded product. It is 50 parts by mass.
- lubricating oils examples include natural oils (engine oils, cylinder oils, etc.), synthetic hydrocarbons (paraffin oils, naphthenic oils, aroma oils, etc.), silicone oils, and the like.
- the molecular weight of the lubricating oil may be, for example, 100 or more, 400 or more, or 500 or more, and may be, for example, 5 million or less, 2 million or less, or 1 million or less.
- the melting point of the lubricating oil may be, for example, -50 ° C or higher, -30 ° C or higher, or -20 ° C or higher, and may be, for example, 50 ° C or lower, 30 ° C or lower, or 20 ° C or lower.
- the melting point is 2.5 ° C. lower than the pour point of the lubricating oil, and the pour point can be measured in accordance with JIS K2269.
- the total amount of the additional components in the cellulose resin composition may be, for example, 0% by mass or more, 1% by mass or more, or 10% by mass or more, and for example, 70% by mass or less, or 50% by mass or less, or 30. It may be mass% or less.
- the cellulose resin composition comprises 30% by mass to 99% by mass of the thermoplastic resin, 1% by mass to 60% by mass of cellulose, and 0% by mass to 69% by mass of additional components.
- the cellulose resin composition comprises 50% to 97% by mass of thermoplastic resin, 3% to 20% by mass of cellulose, and 0% to 47% by mass of additional components, or the thermoplastic resin 65. It contains from mass% to 95% by mass, 5% to 15% by mass of cellulose, and 0% to 20% by mass of additional components.
- the shape of the cellulose resin composition is not particularly limited, and may be, for example, a processing material (pellets, powder, etc.) or a molded product. Molded products include a wide range of products such as electronic device parts, vehicle parts, building materials, and daily necessities.
- the amount of the cellulose resin composition contained in the container can be 0.01 kg or more, 1 kg or more, or 20 kg or more in one embodiment, and 550 kg or less, 100 kg or less, or 30 kg in one embodiment. It can be:
- the water absorption rate of the cellulose resin composition measured by the method (Karl Fischer method) described in JIS K0113: 2005 shall be 1000 mass ppm or less, 900 mass ppm or less, or 800 mass ppm or less in one embodiment. Can be done.
- using a container having a combination of a high lignin member and a low lignin member gives an advantage of reducing the water absorption rate of the cellulose resin composition.
- the water absorption rate of the cellulose resin composition is preferably low from the viewpoint of maintaining good quality of the cellulose resin composition, but from the viewpoint of ease of manufacturing the package, in one embodiment, it is 10 mass ppm or more or 100 mass by mass. It may be ppm or more, or 500 mass pmm or more.
- the yellowness of the cellulose resin composition before the high temperature and high humidity treatment When the package is treated at a temperature of 60 ° C., a relative humidity of 75%, an atmosphere, and a normal pressure for 720 hours (that is, 30 days) at a high temperature and a high humidity, the yellowness of the cellulose resin composition before the high temperature and high humidity treatment.
- the difference between the (YI) value and the yellowness (YI) value after the high temperature and high humidity treatment (hereinafter, also referred to as YI difference) can be 25 or less, 20 or less, or 16 or less.
- the smaller the YI difference the better the discoloration of the cellulose resin composition is suppressed.
- the YI difference is preferably low from the viewpoint of maintaining good quality of the cellulose resin composition, but is 1 or more, 10 or more, or 20 or more in one embodiment from the viewpoint of ease of manufacturing the package. You may.
- One aspect of the present invention is a method for producing a molded product containing a cellulose resin composition containing a thermoplastic resin and cellulose, a step of preparing a cellulose resin composition contained in a container, and cellulose contained in the container.
- a method including a step of injection molding a resin composition in a mold may be the container of the present disclosure described above. Therefore, the container includes a high lignin member having a lignin content of 10% by mass or more and a low lignin member having a lignin content of 1% by mass or less.
- a preferred embodiment of the container used in the method may be the same as illustrated in the ⁇ Container >> section of the present disclosure.
- the YI value of the molded product obtained by the above method for producing a molded product can be 50 or less, 40 or less, or 30 or less, or 25 or less.
- the YI value of the molded product is preferably small from the viewpoint of achieving good quality of the molded product, but from the viewpoint of ease of manufacturing the molded product, in one embodiment, it is 1 or more, 5 or more, or 10 or more. It may be.
- ⁇ Average fiber diameter and average L / D of cellulose> make cellulose into a pure water suspension at a concentration of 1% by mass, and use a high-shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name "Excel Auto Homogenizer ED-7", treatment conditions: rotation speed 15,000 rpm x 5 minutes).
- the dispersed aqueous dispersion was diluted with pure water to 0.1 to 0.5% by mass, cast on mica, and air-dried, which was measured with an atomic force microscope (AFM).
- AFM atomic force microscope
- the measurement was performed by adjusting the magnification so that at least 100 cellulose fibers were observed, and the major axis (L), minor axis (D) and the ratio (L / D) of 100 randomly selected cellulose fibers were selected. ) was calculated, and the added average of 100 celluloses was calculated.
- YI ⁇ Yellowness
- the YI value of the cellulose resin composition or the comparative resin composition in the package was measured, and the difference between the YI value at the initial stage and after curing was defined as ⁇ YI.
- the cellulose resin composition obtained in Examples and Comparative Examples or the package of the comparative resin composition was cured under high temperature and high humidity conditions of 60 ° C. and 75% relative humidity for 720 hours and then opened to obtain pellets. It was.
- the cylinder temperature of the injection molding machine with a maximum mold clamping pressure of 4000 tons was set to 250 ° C. for the polyamide resin composition and 200 ° C. for the polypropylene resin, and after purging 10 times using the pellets, Molding was performed, and the odor was evaluated in the following three stages.
- (cellulose) Cellulose 1 was prepared by the following procedure. The filter paper is cut and heated in hot water at 120 ° C. or higher for 3 hours using an autoclave, and the purified pulp obtained by removing the hemicellulose portion is squeezed and has a solid content of 1.5 mass in pure water. After being highly shortened and fibrillated by beating treatment so as to be%, defibrated cellulose was obtained by defibrating with a high-pressure homogenizer (operation pressure: treated 10 times at 85 MPa) at the same concentration.
- operation pressure treated 10 times at 85 MPa
- Cellulose 2 is a mixture of cellulose 1 described above and cellulose 4 described later in a ratio of cellulose 1: cellulose 4 (mass ratio) 65:35.
- Cellulose 3 is a mixture of cellulose 1 described above and cellulose 4 described later in a ratio of cellulose 1: cellulose 4 (mass ratio) 32:68.
- Acetylated cellulose was prepared by the following procedure. 1 part by mass of cotton linter pulp was stirred at 500 rpm for 1 hour at room temperature in 30 parts by mass of dimethyl sulfoxide (DMSO) using a uniaxial stirrer (DKV-1 ⁇ 125 mm dissolver manufactured by IMEX). Subsequently, it was fed to a bead mill (NVM-1.5 manufactured by Imex) with a hose pump and circulated for 180 minutes using only DMSO to prepare a fine cellulose fiber slurry having a solid content of 3.2% by mass of slurry S1 (DMSO solvent). ) was obtained.
- DMSO dimethyl sulfoxide
- the rotation speed of the bead mill was 2500 rpm and the peripheral speed was 12 m / s, and the beads used were made of zirconia, ⁇ 2.0 mm, and the filling rate was 70% (the slit gap of the bead mill was 0.6 mm).
- the slurry temperature was controlled to 40 ° C. by a chiller in order to absorb the heat generated by friction.
- Outer body (as a high lignin member)
- Outer body 1 A bag body made of used newspaper (vertical length 850 mm ⁇ horizontal length 500 mm ⁇ gusset 150 mm, a flat bag with a sealed lower part and an open upper part) was used.
- Outer body 2 A kraft paper bag (vertical length 850 mm ⁇ horizontal length 500 mm ⁇ gusset 150 mm, a flat bag having a sealed lower part and an open upper part) made of unbleached kraft paper was used.
- Outer body 3 A commercially available cardboard box (length 600 mm ⁇ width 400 mm ⁇ height 350 mm) was used.
- Inner body 1 Polypropylene bag (thickness 25 ⁇ m) "F109V" manufactured by Prime Polymer Co., Ltd. was used. It was melt-kneaded with an extruder to pelletize it. Subsequently, it was melt-extruded from an extruder equipped with a T-die and rapidly cooled with a cooling roll at 20 ° C. to obtain a sheet having a thickness of 1500 ⁇ m. Subsequently, this sheet was stretched at a temperature of 130 ° C. using the difference in peripheral speeds of the rolls to obtain a biaxially stretched polypropylene film having a thickness of 25 ⁇ m.
- Inner body 2 Polypropylene bag (thickness 2.5 ⁇ m) An inner body 2 was obtained in the same manner as the inner body 1 except that stretching was performed until the thickness became 2.5 ⁇ m.
- Inner body 3 Polypropylene bag (thickness 75 ⁇ m) An inner body 3 was obtained in the same manner as the inner body 1 except that stretching was performed until the thickness became 75 ⁇ m.
- Inner body 4 Polypropylene bag (thickness 1000 ⁇ m) An inner body 4 was obtained in the same manner as the inner body 1 except that stretching was performed until the thickness became 1000 ⁇ m.
- Inner body 5 High-density polyethylene (HDPE) bag (thickness 25 ⁇ m) An inner body 5 was obtained in the same manner as the inner body 1 except that "HY420" manufactured by Mitsubishi Chemical Corporation was used.
- Inner body 6 Low density polyethylene (LDPE) bag (thickness 25 ⁇ m) An inner body 6 was obtained in the same manner as the inner body 1 except that "LF128” manufactured by Mitsubishi Chemical Corporation was used.
- Inner body 7 Low density polyethylene (LDPE) bag (thickness 2.5 ⁇ m) An inner body 7 was obtained in the same manner as the inner body 6 except that stretching was performed until the thickness became 2.5 ⁇ m.
- Inner body 8 An aluminum bag (thickness 200 ⁇ m) (“Aluminum Lamizip” manufactured by AS ONE) was used.
- Inner body 9 Polypropylene bag (thickness 100 ⁇ m) An inner body 9 was obtained in the same manner as the inner body 1 except that stretching was performed until the thickness became 100 ⁇ m.
- Cellulose Resin Composition 1 The aqueous dispersion of cellulose 1 (3% by mass) was concentrated using a centrifuge until the cellulose ratio reached 20% by mass. After the concentrated dispersion was dried, it was pulverized to obtain powdered cellulose.
- the above polyamide 6 (100 parts by mass) and the above cellulose 1 (11 parts by mass) are mixed, melt-kneaded with a TEM48SS extruder manufactured by Toshiba Machine Co., Ltd. at a screw rotation speed of 350 rpm and a discharge rate of 140 kg / hr, and vacuumed.
- Cellulose Resin Composition 2 The cellulose resin composition 2 was obtained in the same procedure as in the production of the cellulose resin composition 1 except that the cellulose 2 was used instead of the cellulose 1.
- Cellulose Resin Composition 3 The cellulose resin composition 3 was obtained in the same procedure as in the production of the cellulose resin composition 1 except that the cellulose 3 was used instead of the cellulose 1.
- Cellulose Resin Composition 4 The cellulose resin composition 4 was obtained in the same procedure as in the production of the cellulose resin composition 1 except that the polypropylene was used instead of the polyamide 6.
- Container 1 The inner body 1 was inserted into the outer body 1 to obtain a container 1 in which the outer body was used paper and the inner body was polypropylene (thickness 25 ⁇ m).
- Container 2 The inner body 1 was inserted into the outer body 2 to obtain a container 2 in which the outer body was unbleached kraft paper and the inner body was polypropylene (thickness 25 ⁇ m).
- Container 3 A container 3 was obtained in the same procedure as the container 2 except that the inner body was changed to the inner body 2 (polypropylene (thickness 2.5 ⁇ m)).
- a container 4 was obtained in the same procedure as the container 2 except that the inner body was changed to the inner body 3 (polypropylene (thickness 75 ⁇ m)).
- a container 5 was obtained in the same procedure as the container 2 except that the inner body was changed to the inner body 4 (polypropylene (thickness 1000 ⁇ m)).
- a container 6 was obtained in the same procedure as the container 2 except that the inner body was changed to the inner body 5 (HDPE (thickness 25 ⁇ m)).
- a container 7 was obtained in the same procedure as the container 2 except that the inner body was changed to the inner body 6 (LDPE (thickness 25 ⁇ m)).
- a container 8 was obtained in the same procedure as in Example 2 except that the inner body was changed to the inner body 7 (LDPE (thickness 2.5 ⁇ m)).
- a container 9 was obtained in the same procedure as in Example 2 except that the inner body was changed to the inner body 8 (aluminum bag (thickness 200 ⁇ m)).
- the inner body 1 was inserted into the outer body 3 to obtain a container 10 in which the outer body was corrugated cardboard and the inner body was polypropylene (thickness 25 ⁇ m).
- a container 11 was obtained in the same procedure as the container 10 except that the inner body was changed to the inner body 9 (polypropylene (thickness 100 ⁇ m)).
- a container 12 was obtained in the same manner as the container 2 except that the inner body was not provided.
- Examples 1 to 18, Comparative Examples 1 to 4, Reference Examples 1 to 2 The combinations of the cellulose resin composition or the comparative resin composition and the container are as shown in Tables 1 to 3, and 25 kg of each cellulose resin composition or the comparative resin composition is contained in each container, and the opening of the inner body is taped. It was sealed to obtain a package according to Examples and Comparative Examples.
- Examples 8 and 9 are examples in which the same container and cellulose resin composition are used, in Example 8, the "initial" is set to room temperature (23 ° C.) and after standing in the air for 2 hours. This is different from Example 9.
- Tables 1 to 3 show the configurations and evaluation results of the container, the cellulose resin composition and the package.
- the container according to the present invention can suppress discoloration of the cellulose resin composition, it can be particularly preferably used in the application of accommodating the cellulose resin composition.
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Abstract
Description
すなわち、本発明は以下の態様を包含する。
前記容器が、リグニン含有率10質量%以上の高リグニン部材と、リグニン含有率1質量%以下の低リグニン部材とを含み、
前記容器の前記セルロース樹脂組成物との接触面の全部が前記低リグニン部材で構成されている、容器。
[2] 前記セルロースのリグニン含有率(Lc)が20質量%以下であり、
前記高リグニン部材のリグニン含有率(Lo)、前記低リグニン部材のリグニン含有率(Li)、及び前記セルロースのリグニン含有率(Lc)が、下記式:
Lo>Lc≧Li
の関係を満たす、上記態様1に記載の容器。
[3] 前記低リグニン部材の、JIS Z0208:1976に記載の方法で測定される水蒸気透過度が50g/m2・24h以下である、上記態様1又は2に記載の容器。
[4] 前記高リグニン部材で構成された外体と、前記低リグニン部材で構成された内体とを有する、上記態様1~3のいずれかに記載の容器。
[5] 前記外体が、箱体又は袋体であり、
前記内体が、前記外体に固定されており又は固定されていないシート体である、上記態様1~4のいずれかに記載の容器。
[6] 前記高リグニン部材の黄色度(YI)値が20以上である、上記態様1~5のいずれかに記載の容器。
[7] 前記高リグニン部材が、未晒パルプ及び/又は古紙から得られた紙材である、上記態様1~6のいずれかに記載の容器。
[8] 前記低リグニン部材がポリオレフィンを含む、上記態様1~7のいずれかに記載の容器。
[9] 容器と、前記容器内に収容された、熱可塑性樹脂及びセルロースを含むセルロース樹脂組成物とを有する、包装体であって、
前記容器が、リグニン含有率10質量%以上の高リグニン部材と、リグニン含有率1質量%以下の低リグニン部材とを含み、
前記容器の前記セルロース樹脂組成物との接触面の全部が前記低リグニン部材で構成されている、包装体。
[10] 前記セルロースのリグニン含有率が20質量%以下である、上記態様9に記載の包装体。
[11] 前記高リグニン部材のリグニン含有率(Lo)、前記低リグニン部材のリグニン含有率(Li)、及び前記セルロースのリグニン含有率(Lc)が、下記式:
Lo>Lc≧Li
の関係を満たす、上記態様10に記載の包装体。
[12] 前記低リグニン部材の、JIS Z0208:1976に記載の方法で測定される水蒸気透過度が50g/m2・24h以下である、上記態様9~11のいずれかに記載の包装体。
[13] 前記高リグニン部材で構成された外体と、前記低リグニン部材で構成された内体とを有する、上記態様9~12のいずれかに記載の包装体。
[14] 前記外体が、箱体又は袋体であり、
前記内体が、前記外体に固定されており又は固定されていないシート体である、上記態様9~13のいずれかに記載の包装体。
[15] 前記高リグニン部材の黄色度(YI)値が20以上である、上記態様9~14のいずれかに記載の包装体。
[16] 前記高リグニン部材が、未晒パルプ及び/又は古紙から得られた紙材である、上記態様9~15のいずれかに記載の包装体。
[17] 前記セルロースがセルロースナノファイバーである、上記態様9~16のいずれかに記載の包装体。
[18] 前記セルロース樹脂組成物がペレット形状である、上記態様9~17のいずれかに記載の包装体。
[19] 前記容器内に、0.01kg~550kgの前記セルロース樹脂組成物が収容されている、上記態様9~18のいずれかに記載の包装体。
[20] 前記セルロース樹脂組成物の、JIS K0113:2005に記載の方法で測定される吸水率が1000質量ppm以下である、上記態様9~19のいずれかに記載の包装体。
[21] 前記包装体を、温度60℃、相対湿度75%、大気下、常圧にて、720時間、高温高湿処理したときに、前記セルロース樹脂組成物の高温高湿処理前の黄色度(YI)値と高温高湿処理後の黄色度(YI)値との差が20以下である、上記態様9~20のいずれかに記載の包装体。
[22] 熱可塑性樹脂及びセルロースを含むセルロース樹脂組成物の保管時の変色を抑制する方法であって、
容器に前記セルロース樹脂組成物を収容することを含み、
前記容器が、リグニン含有率10質量%以上の高リグニン部材と、リグニン含有率1質量%以下の低リグニン部材とを含み、
前記容器の前記セルロース樹脂組成物との接触面の全部が前記低リグニン部材で構成されている、方法。
[23] 熱可塑性樹脂及びセルロースを含むセルロース樹脂組成物を含む成形体の製造方法であって、
容器に収容された前記セルロース樹脂組成物を用意する工程、及び
前記容器に収容された前記セルロース樹脂組成物を金型内で射出成形する工程
を含み、
前記容器が、リグニン含有率10質量%以上の高リグニン部材と、リグニン含有率1質量%以下の低リグニン部材とを含み、
前記容器の前記セルロース樹脂組成物との接触面の全部が前記低リグニン部材で構成されており、
前記成形体のYI値が、50以下である、方法。
本発明の一態様は、熱可塑性樹脂及びセルロースを含むセルロース樹脂組成物を収容するための容器を提供する。一態様において、容器は、リグニン含有率10質量%以上の高リグニン部材と、リグニン含有率1質量%以下の低リグニン部材とを含む。一態様においては、容器のセルロース樹脂組成物との接触面である内表面の全部(より具体的には99面積%以上、特に100面積%)が低リグニン部材で構成されている。上記「内表面の全部」とは、上記内表面のうち低リグニン部材で構成されていない部位が本発明の効果を損なわない程度で存在することを排除しない(例えば、えぐれ、ほつれ等の欠陥、及び縫い目等によって、低リグニン部材が内表面上に露出していない部位が存在することを排除しない)ことを意図する。
本発明の一態様は、容器と、該容器内に収容された、熱可塑性樹脂及びセルロースを含むセルロース樹脂組成物とを有する、包装体を提供する。
熱可塑性樹脂としては、種々の樹脂を使用できる。一態様において、熱可塑性樹脂は数平均分子量5000以上を有する。なお本開示の数平均分子量は、GPC(ゲルパーミエーションクロマトグラフィ)を用い、標準ポリメタクリル酸メチル換算で測定される値である。熱可塑性樹脂としては、100℃~350℃の範囲内に融点を有する結晶性樹脂、又は、100~250℃の範囲内にガラス転移温度を有する非晶性樹脂が挙げられる。熱可塑性樹脂は、ホモポリマーでもコポリマーでもよい1種又は2種以上のポリマーで構成されてよい。
セルロースの種類はセルロース樹脂組成物の所望の特性に応じて選択でき、例えばセルロースファイバーを好適に使用できる。セルロースのリグニン含有率は、一態様において、20質量%以下である。リグニン含有率は低いほど好ましく、0質量%(すなわちリグニンが含有されないこと)が最も好ましい。例えば、コットンリンター等のリグニン不含有の原料を用いることで、リグニン含有率を0質量%とすることができる。セルロースのリグニン含有率が20質量%以下であるようなセルロース樹脂組成物においては、本開示の容器を用いることによる変色防止効果が特に顕著である。
Lo>Lc≧Li
の関係を満たす。高リグニン部材、低リグニン部材及びセルロースのリグニン含有率が上記関係を満たす場合、本開示の容器を用いることによる変色防止効果が特に顕著である。
セルロース樹脂組成物は、熱可塑性樹脂及びセルロースに加えて、追加成分を任意に含んでよい。追加成分としては、表面処理剤、酸化防止剤、無機充填剤、潤滑油等が挙げられる。これらの成分は、各々、1種又は2種以上の組み合わせで使用してよい。またこれらの成分は市販の試薬又は製品であってもよい。
本発明の一態様は、熱可塑性樹脂及びセルロースを含むセルロース樹脂組成物の保管時の変色を抑制する方法であって、容器にセルロース樹脂組成物を収容することを含む方法を提供する。該方法において用いる容器は前述した本開示の容器であってよい。したがって、当該容器は、リグニン含有率10質量%以上の高リグニン部材と、リグニン含有率1質量%以下の低リグニン部材とを含む。該方法で用いる容器の好ましい態様は、本開示の≪容器≫の項で例示したのと同様であってよい。
本発明の一態様は、熱可塑性樹脂及びセルロースを含むセルロース樹脂組成物を含む成形体の製造方法であって、容器に収容されたセルロース樹脂組成物を用意する工程、及び容器に収容されたセルロース樹脂組成物を金型内で射出成形する工程を含む方法を提供する。該方法において用いる容器は前述した本開示の容器であってよい。したがって、当該容器は、リグニン含有率10質量%以上の高リグニン部材と、リグニン含有率1質量%以下の低リグニン部材とを含む。該方法で用いる容器の好ましい態様は、本開示の≪容器≫の項で例示したのと同様であってよい。
特性評価は以下の方法で行った。
秤量した試料を、90質量%フェノール水溶液に溶解し、25℃にて1/50N塩酸で電位滴定して算出した。
秤量した試料を、160℃のベンジルアルコールに溶解し、指示薬に25℃にて1/50N塩酸で電位滴定して算出した。
「第14改正日本薬局方」(廣川書店発行)の結晶セルロース確認試験(3)に規定される銅エチレンジアミン溶液による還元比粘度法により測定した。
<セルロースの結晶形、結晶化度>
X線回折装置(株式会社リガク製、多目的X線回折装置)を用いて粉末法にて回折像を測定(常温)し、Segal法で結晶化度を算出した。また、得られたX線回折像から結晶形についても測定した。
セルロースを、1質量%濃度で純水懸濁液とし、高剪断ホモジナイザー(日本精機(株)製、商品名「エクセルオートホモジナイザーED-7」、処理条件:回転数15,000rpm×5分間)で分散させた水分散体を、0.1~0.5質量%まで純水で希釈し、マイカ上にキャストし、風乾したものを、原子間力顕微鏡(AFM)で測定した。測定は、少なくとも100本のセルロース繊維が観測されるように倍率を調整して行い、無作為に選んだ100本のセルロースの長径(L)、短径(D)及びこれらの比(L/D)を求め、100本のセルロースの加算平均を算出した。
クラーソン法に従い、下記手順で測定した。
セルロースの分散液、又はセルロース樹脂組成物から樹脂を溶解除去して得たセルロースの再分散液から分散媒を除去し、セルロース残渣を回収して、105℃で乾燥した乾燥試料の質量を測定した。乾燥したセルロース残渣を粉砕して、粉砕試料をソックスレー抽出器でアルコール(エタノール)/ベンゼン混合溶媒で6時間抽出した後、アルコールでさらに4時間抽出を行って脱脂試料を得た。
脱脂試料300mgに、72質量%硫酸3mLを加え、30℃で1時間静置した後、蒸留水84mLで耐圧びん(125mL容量)に流し入れた。120℃で1時間のオートクレーブ処理を行い、冷める前にガラスフィルターでろ過して酸不溶性リグニンをろ別し、ろ液も回収した。酸不溶性リグニンは蒸留水で洗浄して105℃で乾燥後、酸不溶性リグニン画分の質量を測定し、ろ液は紫外可視分光光度計で吸光度を測定した。
酸不溶性リグニン(%) = 酸不溶性リグニン画分(g)/試料量(無水ベース)(g)×100
酸可溶性リグニン(%)=((d × v ×(As-Ab))/(a × w))×100
リグニン(%)=酸不溶性リグニン(%)+酸可溶性リグニン(%)
d : 希釈倍率
v : ろ液定容量(L)
As: 試料溶液の吸光度
Ab: ブランク溶液の吸光度
a : リグニンの吸光係数(110 L/g・cm)
w : 試料量(無水ベース)(g)
JIS Z0208:1976に準拠して測定した。
JIS K0113:2005に準拠して測定した。包装体の作製直後(初期)、及び温度23℃、相対湿度50%の条件下での24時間保管後の各々について、包装体中のセルロース樹脂組成物又は比較の樹脂組成物の吸水率を測定した。
JIS K7373に準拠して測定した。なおセルロース樹脂組成物又は比較の樹脂組成物のYIについては、包装体の作製直後(初期)、及び温度60℃、相対湿度75%の高温高湿条件下での720時間養生後の各々について、包装体中のセルロース樹脂組成物又は比較の樹脂組成物のYI値を測定し、また初期と養生後とでのYI値の差をΔYIとした。
実施例及び比較例で得られたセルロース樹脂組成物又は比較の樹脂組成物の包装体を、温度60℃、相対湿度75%の高温高湿条件下で720時間養生した後開封し、ペレットを得た。最大型締圧力4000トンの射出成形機のシリンダー温度をポリアミド樹脂組成物の場合は250℃に、ポリプロピレン樹脂の場合は200℃に設定し、該ペレットを用いて10回パージ作業を行った後、成形を行い、以下の3段階で臭気を評価した。
良 成型機周辺で感知できる程度の甘い臭気
可 成型機周辺で感知できる程度の焦げた臭気
不良 室内全域で感知できるほどの焦げた臭気
また、上記と同様の成形実験を行い、以下の3段階で成形性を評価した。
良 成形における特筆するべき問題無し
可 シルバー、ボイドなどの不良が発生
不良 計量不良により、成形ができない
[セルロース樹脂組成物]
(熱可塑性樹脂)
ポリアミド6:宇部興産(株)製「1013B」(カルボキシル末端基比率 [COOH]/[全末端基]=0.65)
ポリプロピレン:プライムポリマー(株)製「J704LB」
セルロース1は、下記手順で調製した。
ろ紙を裁断し、オートクレーブを用いて、120℃以上の熱水中で3時間加熱し、ヘミセルロース部分を除去して得た精製パルプを、圧搾し、純水中に固形分率が1.5質量%になるように叩解処理により高度に短繊維化及びフィブリル化させた後、そのままの濃度で高圧ホモジナイザー(操作圧:85MPaにて10回処理)により解繊することにより解繊セルロースを得た。ここで、叩解処理においては、ディスクリファイナーを用い、カット機能の高い叩解刃(以下カット刃と称す)で4時間処理した後に解繊機能の高い叩解刃(以下解繊刃と称す)を用いてさらに1.5時間叩解を実施し、セルロース1を得た。得られたセルロース1の特性を前述の方法で評価した。結果を下記に示す。
平均L/D=300
平均繊維径=90nm
結晶化度=80%
重合度=600
平均L/D=300
平均繊維径=85nm
結晶化度=80%
重合度=550
コットンリンターパルプを1質量部、一軸撹拌機(アイメックス社製 DKV-1 φ125mmディゾルバー)を用いジメチルスルホキサイド(DMSO)30質量部中で500rpmにて1時間、常温で攪拌した。続いて、ホースポンプでビーズミル(アイメックス社製 NVM-1.5)にフィードし、DMSOのみで180分間循環運転させ、微細セルロース繊維スラリーとして、固形分率3.2質量%のスラリーS1(DMSO溶媒)を得た。
(外体)(高リグニン部材として)
外体1:古紙である新聞紙で形成された袋体(縦長850mm×横長500mm×マチ150mmで、下部がシールされているとともに上部が開口している平袋)を用いた。
外体2:未晒クラフト紙で形成されたクラフト紙袋(縦長850mm×横長500mm×マチ150mmで、下部がシールされているとともに上部が開口している平袋)を用いた。
外体3:市販の段ボール箱(長さ600mm×幅400mm×高さ350mm)を用いた。
(内体)(低リグニン部材として)
内体1:ポリプロピレン袋(厚み25μm)
プライムポリマー社製の「F109V」を用いた。押出機にて溶融混練してペレット化した。続いてTダイを備えた押出機より溶融押出し、20℃の冷却ロールで急冷することにより厚さ1500μmのシートを得た。続いてこのシートを、ロールの周速差を利用して130℃の温度で延伸し、厚さ25μmの二軸延伸ポリプロピレンフィルムを得た。これを袋状に接着し、内体1を得た。
内体2:ポリプロピレン袋(厚み2.5μm)
厚さ2.5μmとなるまで延伸を行う以外は内体1と同様にして、内体2を得た。
内体3:ポリプロピレン袋(厚み75μm)
厚さ75μmとなるまで延伸を行う以外は内体1と同様にして、内体3を得た。
内体4:ポリプロピレン袋(厚み1000μm)
厚さ1000μmとなるまで延伸を行う以外は内体1と同様にして、内体4を得た。
内体5:高密度ポリエチレン(HDPE)袋(厚み25μm)
三菱ケミカル社製の「HY420」を用いた以外は内体1と同様にして、内体5を得た。
内体6:低密度ポリエチレン(LDPE)袋(厚み25μm)
三菱ケミカル社製の「LF128」を用いた以外は内体1と同様にして、内体6を得た。
内体7:低密度ポリエチレン(LDPE)袋(厚み2.5μm)
厚さ2.5μmとなるまで延伸を行う以外は内体6と同様にして、内体7を得た。
内体8:アルミ袋(厚み200μm)(アズワン製の「アルミラミジップ」)を用いた。
内体9:ポリプロピレン袋(厚み100μm)
厚さ100μmとなるまで延伸を行う以外は内体1と同様にして、内体9を得た。
(セルロース樹脂組成物1)
セルロース1の水分散液(3質量%)を、遠心分離機を用いて、セルロース比率が20質量%になるまで濃縮した。濃縮した分散液を乾燥処理した後、粉砕処理を実施して、粉末状セルロースを得た。上記ポリアミド6(100質量部)と上記セルロース1(11質量部)とを混合し、東芝機械(株)製のTEM48SS押出機で、スクリュー回転数350rpm、吐出量140kg/hrで溶融混練し、真空脱揮した後、ダイからストランド状に押出し、水浴で冷却し、ペレタイズした。
(セルロース樹脂組成物2)
上記セルロース1に代えて上記セルロース2を用いた他はセルロース樹脂組成物1の製造と同様の手順で、セルロース樹脂組成物2を得た。
(セルロース樹脂組成物3)
上記セルロース1に代えて上記セルロース3を用いた他はセルロース樹脂組成物1の製造と同様の手順で、セルロース樹脂組成物3を得た。
(セルロース樹脂組成物4)
上記ポリアミド6に代えて上記ポリプロピレンを用いた他はセルロース樹脂組成物1の製造と同様の手順で、セルロース樹脂組成物4を得た。
(比較の樹脂組成物5)
上記ポリアミド6を比較の樹脂組成物5とした。
(比較の樹脂組成物6)
上記のポリプロピレンを比較の樹脂組成物6とした。
(セルロース樹脂組成物7)
上記セルロース1に代えて上記アセチル化セルロースを用いた他はセルロース樹脂組成物1の製造と同様の手順で、セルロース樹脂組成物7を得た。
(セルロース樹脂組成物8)
上記セルロース1に代えて上記アセチル化セルロースを用いた他はセルロース樹脂組成物4の製造と同様の手順で、セルロース樹脂組成物8を得た。
(容器1)
外体1に内体1を挿入して、外体が古紙、内体がポリプロピレン(厚み25μm)である容器1を得た。
(容器2)
外体2に内体1を挿入して、外体が未晒クラフト紙、内体がポリプロピレン(厚み25μm)である容器2を得た。
(容器3)
内体を内体2(ポリプロピレン(厚み2.5μm))に変更した他は容器2と同様の手順で容器3を得た。
(容器4)
内体を内体3(ポリプロピレン(厚み75μm))に変更した他は容器2と同様の手順で容器4を得た。
(容器5)
内体を内体4(ポリプロピレン(厚み1000μm))に変更した他は容器2と同様の手順で容器5を得た。
(容器6)
内体を内体5(HDPE(厚み25μm))に変更した他は容器2と同様の手順で容器6を得た。
(容器7)
内体を内体6(LDPE(厚み25μm))に変更した他は容器2と同様の手順で容器7を得た。
(容器8)
内体を内体7(LDPE(厚み2.5μm))に変更した他は実施例2と同様の手順で容器8を得た。
(容器9)
内体を内体8(アルミ袋(厚み200μm))に変更した他は実施例2と同様の手順で容器9を得た。
(容器10)
外体3に内体1を挿入して、外体が段ボール、内体がポリプロピレン(厚み25μm)である容器10を得た。
(容器11)
内体を内体9(ポリプロピレン(厚み100μm))に変更した他は容器10と同様の手順で容器11を得た。
(容器12)
内体を設けない他は容器2と同様にして、容器12を得た。
セルロース樹脂組成物又は比較の樹脂組成物と容器との組合せを表1~3のとおりとし、各容器に各セルロース樹脂組成物又は比較の樹脂組成物を25kg収容して内体の開口をテープで封止し、実施例及び比較例に係る包装体を得た。なお実施例8と実施例9とは同じ容器及びセルロース樹脂組成物を用いた例であるが、実施例8は「初期」を室温(23℃)、大気中で2時間の静置後、とした点で実施例9と異なる。容器、セルロース樹脂組成物及び包装体の構成及び評価結果を表1~3に示す。
Claims (23)
- 熱可塑性樹脂及びセルロースを含むセルロース樹脂組成物を収容するための容器であって、
前記容器が、リグニン含有率10質量%以上の高リグニン部材と、リグニン含有率1質量%以下の低リグニン部材とを含み、
前記容器の前記セルロース樹脂組成物との接触面の全部が前記低リグニン部材で構成されている、容器。 - 前記セルロースのリグニン含有率(Lc)が20質量%以下であり、
前記高リグニン部材のリグニン含有率(Lo)、前記低リグニン部材のリグニン含有率(Li)、及び前記セルロースのリグニン含有率(Lc)が、下記式:
Lo>Lc≧Li
の関係を満たす、請求項1に記載の容器。 - 前記低リグニン部材の、JIS Z0208:1976に記載の方法で測定される水蒸気透過度が50g/m2・24h以下である、請求項1又は2に記載の容器。
- 前記高リグニン部材で構成された外体と、前記低リグニン部材で構成された内体とを有する、請求項1~3のいずれか一項に記載の容器。
- 前記外体が、箱体又は袋体であり、
前記内体が、前記外体に固定されており又は固定されていないシート体である、請求項1~4のいずれか一項に記載の容器。 - 前記高リグニン部材の黄色度(YI)値が20以上である、請求項1~5のいずれか一項に記載の容器。
- 前記高リグニン部材が、未晒パルプ及び/又は古紙から得られた紙材である、請求項1~6のいずれか一項に記載の容器。
- 前記低リグニン部材がポリオレフィンを含む、請求項1~7のいずれか一項に記載の容器。
- 容器と、前記容器内に収容された、熱可塑性樹脂及びセルロースを含むセルロース樹脂組成物とを有する、包装体であって、
前記容器が、リグニン含有率10質量%以上の高リグニン部材と、リグニン含有率1質量%以下の低リグニン部材とを含み、
前記容器の前記セルロース樹脂組成物との接触面の全部が前記低リグニン部材で構成されている、包装体。 - 前記セルロースのリグニン含有率が20質量%以下である、請求項9に記載の包装体。
- 前記高リグニン部材のリグニン含有率(Lo)、前記低リグニン部材のリグニン含有率(Li)、及び前記セルロースのリグニン含有率(Lc)が、下記式:
Lo>Lc≧Li
の関係を満たす、請求項10に記載の包装体。 - 前記低リグニン部材の、JIS Z0208:1976に記載の方法で測定される水蒸気透過度が50g/m2・24h以下である、請求項9~11のいずれか一項に記載の包装体。
- 前記高リグニン部材で構成された外体と、前記低リグニン部材で構成された内体とを有する、請求項9~12のいずれか一項に記載の包装体。
- 前記外体が、箱体又は袋体であり、
前記内体が、前記外体に固定されており又は固定されていないシート体である、請求項9~13のいずれか一項に記載の包装体。 - 前記高リグニン部材の黄色度(YI)値が20以上である、請求項9~14のいずれか一項に記載の包装体。
- 前記高リグニン部材が、未晒パルプ及び/又は古紙から得られた紙材である、請求項9~15のいずれか一項に記載の包装体。
- 前記セルロースがセルロースナノファイバーである、請求項9~16のいずれか一項に記載の包装体。
- 前記セルロース樹脂組成物がペレット形状である、請求項9~17のいずれか一項に記載の包装体。
- 前記容器内に、0.01kg~550kgの前記セルロース樹脂組成物が収容されている、請求項9~18のいずれか一項に記載の包装体。
- 前記セルロース樹脂組成物の、JIS K0113:2005に記載の方法で測定される吸水率が1000質量ppm以下である、請求項9~19のいずれか一項に記載の包装体。
- 前記包装体を、温度60℃、相対湿度75%、大気下、常圧にて、720時間、高温高湿処理したときに、前記セルロース樹脂組成物の高温高湿処理前の黄色度(YI)値と高温高湿処理後の黄色度(YI)値との差が20以下である、請求項9~20のいずれか一項に記載の包装体。
- 熱可塑性樹脂及びセルロースを含むセルロース樹脂組成物の保管時の変色を抑制する方法であって、
容器に前記セルロース樹脂組成物を収容することを含み、
前記容器が、リグニン含有率10質量%以上の高リグニン部材と、リグニン含有率1質量%以下の低リグニン部材とを含み、
前記容器の前記セルロース樹脂組成物との接触面の全部が前記低リグニン部材で構成されている、方法。 - 熱可塑性樹脂及びセルロースを含むセルロース樹脂組成物を含む成形体の製造方法であって、
容器に収容された前記セルロース樹脂組成物を用意する工程、及び
前記容器に収容された前記セルロース樹脂組成物を金型内で射出成形する工程
を含み、
前記容器が、リグニン含有率10質量%以上の高リグニン部材と、リグニン含有率1質量%以下の低リグニン部材とを含み、
前記容器の前記セルロース樹脂組成物との接触面の全部が前記低リグニン部材で構成されており、
前記成形体のYI値が、50以下である、方法。
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| JP7481416B2 (ja) | 2019-05-21 | 2024-05-10 | 旭化成株式会社 | セルロース樹脂組成物を収容するため容器及びこれとセルロース樹脂組成物とを有する包装体 |
| US12330848B2 (en) | 2019-05-21 | 2025-06-17 | Asahi Kasei Kabushiki Kaisha | Container for containing cellulose resin composition and package comprising same and cellulose resin composition |
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| EP3974342B1 (en) | 2023-09-13 |
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| EP3974342C0 (en) | 2023-09-13 |
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| JPWO2020235653A1 (ja) | 2021-06-10 |
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