Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers

Definitions

• This disclosure relates to laminated bodies and molded bodies.
• Patent Document 1 discloses a thermoplastic resin composition in which a cellulose-based substance is blended with a styrene-based resin
• Patent Document 2 discloses a thermoplastic resin composition in which a cellulose ester and a thermoplastic elastomer are blended. Cellulose ester compositions are disclosed.
• a laminate including a reinforcing fiber layer containing cellulose nanofibers and a thermoplastic resin layer containing a rubber-reinforced styrene resin has dimensional stability and strength. We have found that the balance between heat resistance and heat resistance is excellent, and have completed the laminate according to one aspect of the present disclosure.
• the laminate according to one aspect of the present disclosure is composed of the following [1] to [5].
• [1] A laminate comprising a reinforcing fiber layer containing cellulose nanofibers and a thermoplastic resin layer containing a rubber-reinforced styrene resin.
• At least the thermoplastic resin layer is selected from the group consisting of acrylonitrile-styrene copolymer (AS), polycarbonate (PC), polybutylene terephthalate (PBT), polyamide (PA), and polylactic acid resin (PLA).
• AS acrylonitrile-styrene copolymer
• PC polycarbonate
• PBT polybutylene terephthalate
• PA polyamide
• PLA polylactic acid resin
• a laminate having an excellent balance of dimensional stability, strength and heat resistance it is possible to provide a laminate having an excellent balance of dimensional stability, strength and heat resistance. Further, by using the above-mentioned laminated body, a molded body having an excellent balance of dimensional stability, strength and heat resistance can be obtained.
• the reinforcing fiber layer in the laminate according to one aspect of the present disclosure contains cellulose nanofibers.
• the cellulose nanofiber is a fibrous cellulose having a fiber diameter of nano size, and means, for example, a fibrous cellulose having a diameter of 1 nm or more and 1000 nm or less.
• the average diameter and average length of cellulose nanofibers is preferably 800 nm or less, more preferably 500 nm or less.
• the average diameter of the cellulose nanofibers may be 300 nm or less, 200 nm or less, 100 nm or less, and may be 1 nm or more or 5 nm or more.
• the average diameter of the cellulose nanofibers may be 1-800 nm or 5-500 nm.
• the average length of the cellulose nanofibers is preferably 5000 nm or less, more preferably 1000 nm or less.
• the average length of the cellulose nanofibers may be 100 nm or more or 200 nm or more.
• the average length of the cellulose nanofibers may be 100-5000 nm or 200-1000 nm.
• the average diameter and length of the cellulose nanofibers can be determined by observing the cross section of the reinforcing fiber layer with a transmission electron microscope and measuring the diameter and length of 100 cellulose nanofibers in the cross section of the reinforcing fiber layer. It can be calculated from the average value.
• the method for producing cellulose nanofibers is not particularly limited, and may be oxidized and / or hydrophobized.
• the shape of the reinforcing fiber layer is not particularly limited, but it is preferably in the form of a sheet or a film from the viewpoint of excellent stackability with the thermoplastic resin layer. That is, the reinforcing fiber layer is preferably a sheet of cellulose nanofibers or a film of cellulose nanofibers.
• Examples of commercially available cellulose nanofiber sheets or films include the product name "Auro Veil (registered trademark)” manufactured by Oji Holdings Co., Ltd. and the product name "Nanoleaf (registered trademark)” series manufactured by Asahi Kasei Co., Ltd. , GS Alliance Co., Ltd., a biodegradable / cellulose nanofiber composite film, KRI Co., Ltd., a cellulose-induced flexible transparent film, and the like.
• the reinforcing fiber layer may consist of only cellulose nanofibers, and in addition to the cellulose nanofibers, one or two other fibers selected from the group consisting of carbon fibers, glass fibers, aromatic polyamide fibers and polyester fibers may be used. It may contain more than seeds.
• the reinforcing fiber layer may contain a resin component such as a thermoplastic resin.
• the content of the cellulose nanofibers in the reinforcing fiber layer is preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 30% by mass or more, based on the total amount of the reinforcing fiber layer. ..
• the content of the cellulose nanofibers in the reinforcing fiber layer may be 100% by mass or less, 80% by mass or less, or 50% by mass or less based on the total amount of the reinforcing fiber layer.
• Cellulose nanofibers may contain hydrophobized cellulose nanofibers.
• the reinforcing fiber layer may consist only of hydrophobized cellulose nanofibers.
• the content of the hydrophobicized cellulose nanofibers in the reinforcing fiber layer is preferably 1% by mass or more, more preferably 10% by mass or more, and more preferably 30% by mass or more, based on the total amount of the reinforcing fiber layer. Is even more preferable.
• the content of the hydrophobicized cellulose nanofibers in the reinforcing fiber layer may be 100% by mass or less, 70% by mass or less, or 50% by mass or less based on the total amount of the reinforcing fiber layer. By adjusting to the above range, the adhesiveness with the thermoplastic resin layer tends to be excellent.
• the thickness of the reinforcing fiber layer is not particularly limited, but the thickness of the reinforcing fiber layer is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more.
• the thickness of the reinforcing fiber layer may be 100 ⁇ m or less.
• the method for producing the reinforcing fiber layer is not particularly limited, and for example, it can be produced by the following method.
• a method for producing an aqueous dispersion or a solution dispersion containing cellulose nanofibers by directly adhering them onto a thermoplastic resin layer by one method selected from spraying, coating, and impregnating (B) A method for producing an aqueous dispersion or a solution dispersion containing cellulose nanofibers by making a nonwoven fabric by a papermaking method, an electrospinning method, or the like.
• C A method for producing cellulose nanofibers by a molding method such as ordinary sheet molding, inflation molding, blow molding or the like after melt-kneading a plasticizer or lubricant as a binder component and a thermoplastic resin.
• the thermoplastic resin layer in the laminate according to one aspect of the present disclosure contains a rubber-reinforced styrene resin.
• the rubber-reinforced styrene-based resin is one in which a rubbery polymer is dispersed in the styrene-based resin.
• the rubbery polymer include conjugated diene rubbers such as polybutadiene rubber, styrene-butadiene rubber (SBR), and acrylonitrile-butadiene rubber (NBR); ethylene-propylene rubber, ethylene-propylene-non-conjugated diene (ethylidene norbornene, dicyclo).
• Ethylene-propylene rubber such as rubber; acrylic rubber such as polybutylacrylate rubber; silicone rubber and the like can be mentioned.
• the rubbery polymer may be used alone or in combination of two or more.
• ABS acrylonitrile-conjugated diene rubber-styrene copolymer
• AES acrylonitrile-ethylene-propylene rubber-styrene copolymer
• ABS acrylonitrile-, which is obtained by graft-polymerizing a styrene resin to a rubbery polymer.
• ASA acrylic rubber-styrene copolymer
• ABS acrylonitrile-conjugated diene rubber-styrene copolymer
• the thermoplastic resin layer may further contain a resin other than the rubber-reinforced styrene resin.
• Resins other than the rubber-reinforced styrene resin include polystyrene (PS), acrylonitrile-styrene copolymer (AS), polycarbonate (PC), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), and polybutylene terephthalate. (PBT), polymethylmethacrylate (PMMA), polyamide (PA), thermoplastic polyurethane resin (TPU), polylactic acid resin (PLA), polyether sulfone (PES), polyphenylene sulfide (PPS) and the like.
• the thermoplastic resin layer is preferably at least selected from the group consisting of acrylonitrile-styrene copolymer (AS), polycarbonate (PC), polybutylene terephthalate (PBT), polyamide (PA), and polylactic acid resin (PLA). Including one more.
• the molecular weight and molecular weight distribution of the tetrahydrofuran-soluble portion of the thermoplastic resin constituting the thermoplastic resin layer are not particularly limited, but from the viewpoint of the strength and formability of the molded product using the laminated body, the polystyrene-equivalent number average molecular weight is 20000. It is preferably in the range of -80,000.
• the glass transition temperature of the thermoplastic resin is not particularly limited, but it is preferably 120 ° C. or lower, more preferably 100 ° C. or lower, from the viewpoint of moldability of the molded product using the laminated body.
• the glass transition temperature of the thermoplastic resin can be measured using a differential scanning calorimeter (DSC), and when it has two or more glass transition temperatures, the glass transition temperature in the present invention is the lowest glass transition temperature. Means.
• the thermoplastic resin layer may contain various additives in addition to the above-mentioned thermoplastic resin.
• the additive include a light stabilizer, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, a flame retardant aid, a pigment, a dye and the like.
• the thermoplastic resin layer may contain fibers such as carbon fiber, glass fiber, aromatic polyamide fiber, and polyester fiber.
• the thickness of the thermoplastic resin layer is not particularly limited, but the thickness of the thermoplastic resin layer is preferably 500 ⁇ m or more, more preferably 1000 ⁇ m or more.
• the thickness of the thermoplastic resin layer may be 10,000 ⁇ m or less, or 5000 ⁇ m or less.
• thermoplastic resin layer is not particularly limited, and a method for manufacturing by injection molding, sheet extrusion molding, inflation molding, blow molding, sheet molding, calendar molding, etc. can be appropriately used.
• the structure of the laminate according to one aspect of the present disclosure is not particularly limited as long as it has a reinforcing fiber layer and a thermoplastic resin layer, and the reinforcing fiber layer is laminated on one side or both sides of the thermoplastic resin layer.
• the structure may be such that a thermoplastic resin layer is laminated on one side or both sides of the reinforcing fiber layer.
• the number of reinforcing fiber layers and thermoplastic resin layers to be laminated and the combination method are not particularly limited, and can be adopted according to the purpose. Further, another film such as a hot-melt adhesive film for enhancing the adhesiveness may be used between the layers according to the purpose as long as the object of the present disclosure is not impaired.
• the laminating method for obtaining the laminated body according to one aspect of the present disclosure is not particularly limited, and for example, a thermal laminating method, a thermal pressing method, a sheet molding method, a method using an adhesive, or the like may be adopted depending on the purpose. Is possible.
• the laminate according to one aspect of the present disclosure preferably has a tensile elastic modulus of 10 GPa or more, and more preferably 15 GPa or more. By adjusting to this range, the strength of the final product tends to be excellent.
• the laminate according to one aspect of the present disclosure can be obtained by processing by a processing method according to the purpose such as injection molding, multi-layer extrusion molding, film molding, sheet molding, inflation molding, press molding and the like. Is possible. In order to obtain a molded product, it is possible to add a step of performing preliminary shaping as needed.
• the processing temperature of the molded product is not particularly limited, but the processing temperature of the molded product is preferably 250 ° C. or lower due to the characteristics of the cellulose nanofibers.
• the molded body according to one aspect of the present disclosure has an excellent balance of dimensional stability, strength and heat resistance, it can be suitably applied to automobile products, particularly parts such as door garnish and licensed garnish.
• ABS resin (manufactured by Nippon A & L Inc., trade name GA-501)
• PC / ABS resin manufactured by Nippon A & L Inc., trade name PAX-1439
• PA / ABS resin manufactured by Nippon A & L Inc., trade name TA-1500
• PBT / ABS resin manufactured by Nippon A & L Inc., trade name TB-1701
• PLA / ABS resin thermoplastic resin composition obtained by melt-kneading PLA and ABS
• Example 1 to 5 A dumbbell test piece was prepared according to the ISO test method 294 using the resin for forming the thermoplastic resin layer shown in Table 1. Next, a sheet of cellulose nanofibers (reinforced fiber layer) was attached to both sides of the prepared dumbbell test piece using a two-component mixed type epoxy adhesive, and left at room temperature for 24 hours under a load of 5 kg to reinforce the fiber. A laminated body in which a layer, a thermoplastic resin layer, and a reinforcing fiber layer were laminated in this order was obtained. The thickness of the thermoplastic resin layer of the obtained laminate was 4 mm, the thickness of the reinforcing fiber layer was 0.05 mm, and the thickness of the entire laminate was 4.1 mm. Then, various physical properties were measured using the laminated body. For Comparative Examples 1 to 5, various physical properties were measured using a dumbbell test piece of a thermoplastic resin not provided with a reinforcing fiber layer. The results are shown in Table 1.
• ABS ABS resin PC / ABS: PC / ABS resin
• PA / ABS PA / ABS resin
• PBT / ABS PBT / ABS resin
• PLA / ABS PLA / ABS resin
• CNF cellulose nanofiber
• the laminates of Examples 1 to 5 are excellent in dimensional stability, strength and heat resistance in a well-balanced manner.
• the laminates of Comparative Examples 1 to 5 were inferior in at least one of dimensional stability, strength and heat resistance.
• the laminate of the present disclosure has a property of having an excellent balance of dimensional stability, strength and heat resistance. Further, since the laminated body of the present disclosure is lightweight, it is suitable as a molded body, for example, for automobile parts and electric appliances.

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Citations (6)

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• 2021
  • 2021-12-17 JP JP2022570084A patent/JP7407311B2/ja active Active
  • 2021-12-17 WO PCT/JP2021/046820 patent/WO2022131375A1/ja not_active Ceased

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