WO2022004687A1 - Matériau de moulage, corps moulé et son procédé de production - Google Patents

Matériau de moulage, corps moulé et son procédé de production Download PDF

Info

Publication number
WO2022004687A1
WO2022004687A1 PCT/JP2021/024441 JP2021024441W WO2022004687A1 WO 2022004687 A1 WO2022004687 A1 WO 2022004687A1 JP 2021024441 W JP2021024441 W JP 2021024441W WO 2022004687 A1 WO2022004687 A1 WO 2022004687A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyolefin resin
molding material
layer
acid
material according
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.)
Ceased
Application number
PCT/JP2021/024441
Other languages
English (en)
Japanese (ja)
Inventor
佑樹 真嶋
誠 柳澤
渉 敷地
結科 早坂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Artience Co Ltd
Original Assignee
Toyo Ink SC Holdings Co Ltd
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 Toyo Ink SC Holdings Co Ltd filed Critical Toyo Ink SC Holdings Co Ltd
Priority to JP2021550248A priority Critical patent/JP7389127B2/ja
Publication of WO2022004687A1 publication Critical patent/WO2022004687A1/fr
Priority to JP2022025710A priority patent/JP7735895B2/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a molding material, a molded product molded from the material, and a method for manufacturing the same.
  • plastic products include bottles and caps; single-layer film bags such as plastic shopping bags; and multi-layered food packaging packages made of plastic films.
  • bottles, caps, and single-layer film bags are monomaterial plastic products mainly made from one type of resin and are relatively easy to recycle.
  • PET polyester
  • PS polystyrene
  • a multi-layered food packaging package various plastic base materials such as polyester base material, nylon base material (NY), polypropylene base material (PP), and polyethylene base material (PE) are used as the film base material. in use.
  • a first film base material is printed with printing ink, and a second film base material is placed on the print layer via an adhesive layer, if necessary. After bonding, it can be cut, heat-sealed, and manufactured.
  • the recycled polyolefin resin containing the print layer and / or the adhesive layer tends to deteriorate in physical properties due to the resin component derived from the print layer and / or the adhesive layer.
  • petroleum-derived virgin resin must be mixed and used. Therefore, it is difficult to improve the recycling rate.
  • Patent Document 1 provides an undercoat layer made of an acrylic resin or a styrene maleic acid-based resin on the plastic base material, and the undercoat layer is on the undercoat layer.
  • a technique for removing an arranged front print layer using alkaline water is disclosed.
  • Patent Document 2 discloses a technique of printing an ink using a polyurethane resin or an acrylic resin having an acidic group as a binder resin and removing the printing layer using alkaline water.
  • these patent documents do not disclose a technique for removing the printing layer in the laminated laminate and peeling off the plurality of film substrates with respect to the technique for removing the front printing ink on the outer side of the package.
  • a multi-layered food packaging package that cannot peel off multiple film substrates can only be recycled into either (1) plastic raw materials with low mechanical properties or (2) dark plastic raw materials, and is expensive. Difficult to recycle quality materials.
  • Patent Document 3 discloses a technique for desorbing a printed layer from a laminate having a front printing structure or a laminated structure by using a desorbing layer containing a polyurethane resin having a predetermined acid value.
  • Patent Document 3 does not disclose the specific use of the polyolefin resin recycled from the laminated body of the laminated structure as a molding material, and discloses a preferred embodiment of a molding material containing a recycled polyolefin resin. I haven't.
  • An object of the present invention is a molding material having a high recycling utilization rate, which can be colored into a desired color as needed and can be used for various purposes, and a molded article having a high recycling rate molded by the material and a molded body thereof.
  • the purpose is to provide a manufacturing method.
  • the present inventor has completed the present invention as a result of diligent studies to solve the above problems.
  • the present invention is a molding material containing a recycled polyolefin resin (Y) derived from a flexible package having a polyolefin resin film (X) layer and a printing layer, and the recycled polyolefin resin (Y) has a film form having a thickness of 100 ⁇ m.
  • the present invention relates to a molding material having a total light transmittance of 30% or more and a content of the recycled polyolefin resin (Y) of 50% by mass or more based on the total amount of the molding material.
  • the present invention relates to the above-mentioned molding material in which the melt mass flow rate of the regenerated polyolefin resin (Y) is 5 to 20 g / 10 minutes.
  • the present invention relates to the above-mentioned molding material in which the melt mass flow rate of the polyolefin resin film (X) is 3 to 12 g / 10 minutes.
  • the present invention further relates to the molding material, including a masterbatch (Z).
  • the present invention further relates to the above-mentioned molding material containing at least one antioxidant selected from the group consisting of phenol-based and phosphorus-based.
  • the present invention further relates to the molding material containing at least one lubricant selected from the group consisting of fatty acid amides, metal soaps, and fatty acid esters.
  • the present invention further relates to the above-mentioned molding material containing a hindered amine-based weathering stabilizer.
  • the present invention further relates to the above-mentioned molding material containing a wax having an acid value of 5 mgKOH / g or less.
  • the present invention further relates to the molding material, further comprising at least one antistatic agent selected from the group consisting of anionic surfactants and nonionic surfactants.
  • the present invention relates to a molded body made of the above-mentioned molding material.
  • the present invention Step 1 of alkaline-treating a cut or crushed material of a flexible package having a polyolefin resin film (X) layer and a printing layer to remove a piece of the polyolefin resin film (X) from the cut or crushed material. Step 2 of washing the polyolefin resin film (X) piece with water,
  • the present invention relates to the above-mentioned method for producing a molding material, which comprises sequentially including a step 3 of processing a piece of a polyolefin resin film (X) to obtain a recycled polyolefin resin (Y).
  • the present invention further relates to a method for producing a molding material, which comprises step 4 of mixing the regenerated polyolefin resin (Y) obtained in step 3 and the masterbatch (Z).
  • a molding material having a high recycling utilization rate which can be colored into a desired color as needed and can be used for various purposes, and a molded article having a high recycling rate molded from the material and a method for manufacturing the same. Can be provided.
  • the molding material of the present invention contains a recycled polyolefin resin (Y) obtained by recycling a flexible package having a polyolefin resin film (X) layer and a printing layer, and the recycled polyolefin resin (Y) has a thickness of 100 ⁇ m.
  • the total light transmittance in the film form is 30% or more, and the content of the recycled polyolefin resin (Y) is 50% by mass or more based on the total amount of the molding material.
  • the present invention is obtained by reducing or removing unnecessary components such as a printing layer from a flexible package having a polyolefin resin film (X) layer and a printing layer, and processing the recovered polyolefin resin to transmit all light.
  • a recycled polyolefin resin (Y) having a sufficiently high ratio and preferably colorless and transparent to light color is used as a molding material.
  • MFR melt flow rate
  • the regenerated polyolefin resin (Y) which has a sufficiently high total light transmittance and is preferably colorless and transparent to a light color, can be colored in any color and is preferable. Further, since the molding material contains the above-mentioned recycled polyolefin resin (Y) in a ratio of 50% by mass or more, the recycling utilization rate is high, the molding property is good, and any color is required. It is possible to obtain a molding material that can be colored and used for various purposes. Hereinafter, the present invention will be described in detail.
  • the recycled polyolefin resin (Y) is obtained by recycling a flexible package having a polyolefin resin film (X) layer and a printing layer, and has a total light transmittance of 30% or more in a film form having a thickness of 100 ⁇ m. It is a feature. It is important that the total light transmittance is 30% or more from the viewpoint of increasing the recycling utilization rate and making it usable for various purposes. When the total light transmittance is less than 30%, the amount of the recycled polyolefin resin (Y) blended in the molding material is increased due to the presence of impurities such as colorants derived from the flexible packaging, and the recycling utilization rate is increased. Can be difficult.
  • the total light transmittance of the regenerated polyolefin resin (Y) in the form of a film having a thickness of 100 ⁇ m is preferably 50% or more, more preferably 70% or more, and particularly preferably 75% or more.
  • the total light transmittance is a value measured in the thickness direction of the film in accordance with JIS K 7361.
  • the flexible packaging is not particularly limited as long as it has at least one polyolefin resin film (X) layer and a printing layer, and examples thereof include flexible packaging used for foods, detergents, cosmetics, pharmaceuticals, and the like.
  • Polyolefin resin film (X) layer examples of the polyolefin resin film (X) include polyethylene (PE), biaxially stretched polypropylene (OPP), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), and acid modification. Examples thereof include sealant substrates such as polyethylene, unstretched polypropylene (CPP), acid-modified polypropylene, and copolymerized polypropylene.
  • the thickness of the polyolefin resin film (X) layer is not particularly limited, and is preferably 5 to 200 ⁇ m, more preferably 10 to 150 ⁇ m.
  • the melt mass flow rate (MFR) of the polyolefin resin film (X) is preferably 3 to 12 g / 10 minutes. When the melt mass flow rate is 3 g / 10 minutes or more, it is preferable because the formability as a film used for a flexible package is excellent. When the melt mass flow rate is 12 g / 10 minutes or less, the polyolefin resin film (X) is less likely to deteriorate during recycling, and the moldability of the obtained molded material containing the regenerated polyolefin resin (Y) is more excellent, which is preferable.
  • the melt mass flow rate in the present specification is a value measured in accordance with JIS K7210.
  • the flexible packaging may have a base material layer other than the polyolefin resin film (X) layer, depending on the intended use or purpose of use.
  • the other base material layer include a plastic base material other than the polyolefin resin, a gas barrier base material, paper, and a laminate thereof.
  • plastic base material other than the polyolefin resin examples include polyester resin, polyamide resin, polystyrene resin, vinyl chloride resin, vinyl acetate resin, ABS resin, acrylic resin, acetal resin, polycarbonate resin, and fibrous plastic. ..
  • the gas barrier base material examples include metal foils such as aluminum foil; plastic base materials having an inorganic vapor deposition layer such as aluminum, silica, and alumina; and plastic base materials having an organic layer such as polyvinyl alcohol.
  • the thickness of the aluminum foil is preferably 3 to 50 ⁇ m from the economical point of view.
  • Aluminum and alumina have solubility in an aqueous alkaline solution and can be dissolved in the alkali desorption step described later. Therefore, the polyolefin resin film (X) can be removed from the flexible packaging containing the polyolefin resin film (X) layer and aluminum and / or alumina by alkaline treatment and recycled.
  • the base material layer other than the polyolefin resin film (X) layer and / or the (X) layer may contain additives such as an antistatic agent and an ultraviolet ray inhibitor, if necessary.
  • the surface of the film or the base material may be subjected to surface treatment such as corona treatment and low temperature plasma treatment.
  • the print layer may be a layer for displaying arbitrary patterns, patterns, characters, symbols, etc. for the purpose of imparting decoration or aesthetics; the contents, the expiration date, and the display of the manufacturer or the seller. can.
  • the print layer may be a solid print layer having no pattern, pattern, characters, symbols, or the like.
  • the method for forming the printed layer is not particularly limited, and the printed layer can be formed using a known pigment and / or dye.
  • the print layer can preferably be formed using a printing ink containing a pigment and / or a dye.
  • the print layer may have a single-layer structure or a multi-layer structure.
  • the thickness of the printed layer is preferably 0.1 to 100 ⁇ m, more preferably 0.1 to 10 ⁇ m, and particularly preferably 1 to 5 ⁇ m.
  • the flexible packaging may have an adhesive layer.
  • a two-component urethane adhesive composed of a polyol main agent and a polyisocyanate curing agent is generally used.
  • the adhesive layer is a cured product of this urethane adhesive.
  • the polyol main agent may be any compound having two or more hydroxyl groups, and can be selected from known polyols. Examples of the polyol include polyester polyol, polycarbonate polyol, polycaprolactone polyol, polyether polyol, polyolefin polyol, acrylic polyol, silicone polyol, castor oil-based polyol, and fluorine-based polyol.
  • the polyol main agent may be an acid-modified product in which a part of the hydroxyl group in the polyol is acid-modified, or a product in which a urethane bond is introduced by reacting a part of the hydroxyl group in the polyol with diisocyanate.
  • the polyisocyanate curing agent may be any compound having two or more isocyanate groups, and can be selected from known polyisocyanates. Examples of the polyisocyanate curing agent include aromatic polyisocyanates, aromatic aliphatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and modified products thereof.
  • the polyol main agent one type may be used alone, or two or more types may be used in combination. The same applies to the polyisocyanate curing agent.
  • the adhesive layer may be an adhesive layer having desorption property in order to promote desorption of the adhesive layer in the recycling step described later.
  • the adhesive layer having desorption property is preferably an adhesive layer composed of an adhesive having an acid value of 5 to 40 mgKOH / g, and more preferably a polyester polyol main agent, an aliphatic polyisocyanate, and an aromatic aliphatic.
  • An adhesive layer comprising at least one polyisocyanate curing agent selected from the group consisting of polyisocyanates and having an acid value of 5 to 40 mgKOH / g.
  • polyester polyol main agent examples include polyester polyols obtained by reacting one or more carboxy group components exemplified below with one or more hydroxyl group components exemplified below.
  • carboxy group component examples include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, phthalic acid anhydride, adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, and maleine anhydride.
  • Acids and dibasic acids such as itaconic acid anhydride; their dialkyl esters; their combinations;
  • the hydroxyl group include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, butylene glycol, neopentyl glycol, dineopentyl glycol, trimethylolpropane, glycerin, 1,6-hexanediol, 1, 4-Butandiol, 1,4-Cyclohexanedimethanol, 3-Methyl-1,5-Pentanediol, 3,3'-Dimethylolheptane, 1,9-Nonandiol, Polyoxyethylene Glycol, Polyoxypropylene Glycol, Examples thereof include diols such as polytetramethylene ether glycol, polyether polyol, polycarbonate polyol, polyolefin polyol, acrylic polyol, and polyurethane polyol; combinations thereof;
  • the acid value of the polyester polyol main agent is preferably 8.0 mgKOH / g or more, and more preferably 10.0 mgKOH / g or more.
  • the acid value of the polyester polyol main agent is preferably 45.0 mgKOH / g or less, and more preferably 40.0 mgKOH / g or less.
  • the acid value of the polyester polyol main agent can be obtained from the acid value of each polyester polyol component and its mass ratio.
  • the number average molecular weight (Mn) of the polyester polyol main agent is preferably 3,000 to 20,000, more preferably 5,000 to 15,000, and particularly preferably 5,000 to 15,000 from the viewpoint of heat sterilization resistance and coatability. It is 7,000 to 12,000.
  • Mn of the polyester polyol main agent is 3,000 or more, coatability and sufficient retort suitability can be exhibited, and when it is 20,000 or less, coatability and alkali desorption are improved. preferable.
  • the polyester polyol main agent may contain a plurality of polyester polyol components in order to satisfy various physical properties required for the packaging material.
  • the polyester polyol main agent can contain a plurality of polyester polyol components including, for example, Mn 5,000 to 15,000 polyester polyols.
  • the polyester polyol main agent may contain a polyester polyol having a Mn of less than 3,000 in order to improve the adhesion to the substrate.
  • the Mn of the polyester polyol main agent when a plurality of polyester polyol components are contained can be obtained from the Mn of each polyester polyol component and its mass ratio.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) in the present specification are values converted into standard polystyrene using GPC (gel permeation chromatography).
  • the polyester polyol main agent can contain the following three types of polyols from the viewpoint of adhesive performance and alkali desorption.
  • First polyol polyester polyol with an acid value of 10 mgKOH / g or more
  • Second polyol a polyester polyol having a number average molecular weight (Mn) of less than 3,000
  • Third polyol A polyester polyol having a number average molecular weight (Mn) of 5,000 or more. (However, the second polyol and the third polyol are different from the first polyol component.)
  • the first polyol component has a role of imparting desorption.
  • the second polyol component improves the adhesion to the base material and contributes to the improvement of coatability.
  • the third polyol component has a role of improving the retort property.
  • the content of the first polyol component is preferably 50% by mass or more with respect to the total amount of the polyester polyol main agent from the viewpoint of exhibiting sufficient desorption.
  • the first polyol component is preferably a polyester polyurethane polyol modified with acid anhydride.
  • the first polyol component preferably has Mn of 5,000 to 10,000 and an acid value of 15 to 40 mgKOH / g or less.
  • the second polyol component preferably has an acid value of 5 mgKOH / g or less, more preferably 1 mgKOH / g or less.
  • the third polyol component is preferably a polyester polyurethane polyol modified with acid anhydride.
  • the third polyol component preferably has Mn of 5,000 to 10,000 and an acid value of 5 mgKOH / g or less.
  • the polyisocyanate curing agent is at least one selected from the group consisting of aliphatic polyisocyanates and aromatic aliphatic polyisocyanates.
  • the aliphatic polyisocyanate is not particularly limited, and known aliphatic diisocyanates, alicyclic diisocyanates, or derivatives thereof can be used.
  • Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and 2, Included are 4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methyl caproate.
  • Examples of the alicyclic diisocyanate include 1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (hereinafter, isophorone diisocyanate), 4,4'-.
  • Examples thereof include methylenebis (cyclohexylisocyanate), methyl2,4-cyclohexanediisocyanate, methyl2,6-cyclohexanediisocyanate, 1,4-bis (isocyanatemethyl) cyclohexane, and 1,3-bis (isocyanatemethyl) cyclohexane.
  • the aliphatic diisocyanate or the alicyclic diisocyanate may be a polyisocyanate such as an allophanate type, a nurate type, a biuret type, or an adduct type derivative, or a complex thereof.
  • the aromatic aliphatic polyisocyanate is not particularly limited, and known aromatic aliphatic diisocyanates or derivatives thereof can be used.
  • Examples of the aromatic aliphatic diisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof; ⁇ , ⁇ '-diisocyanate-1,4-diethylbenzene; 1,3- or 1,4-bis (1,3- or 1,4-bis ().
  • the aromatic aliphatic diisocyanate may be a polyisocyanate such as an allophanate type, a nurate type, a biuret type, an adduct type derivative, or a complex thereof.
  • the flexible package may have a polyolefin resin film (X) layer and a printing layer, and the composition thereof varies depending on the contents and the application.
  • the structure of the flexible packaging is, for example, Single-layer film composition such as print layer / HS-OPP, print layer / CPP, print layer / OPP / HS material, print layer / shrink PP, and OPP / print layer / HS material; OPP / printed layer / adhesive layer / CPP, ONY / printed layer / adhesive layer / LLDPE, OPP / printed layer / adhesive layer / vapor deposition CPP, PET / printed layer / adhesive layer / LLDPE, OPP / printed layer / Adhesive layer / PET / Adhesive layer / CPP, PET / Print layer / Adhesive layer / AL / Adhesive layer / ONY / Adhesive layer / CPP, and PET / Print layer / Ad
  • HS Heat seal
  • OPP Biaxially stretched polypropylene
  • CPP unstretched polypropylene
  • PP Polypropylene
  • ONY Biaxially stretched nylon film
  • LLDPE Linear low density polyethylene
  • PET Polyethylene terephthalate
  • AL Aluminum.
  • the recycled polyolefin resin (Y) obtained by recycling is a mixture thereof.
  • the desorption layer is the printing layer or the polyolefin resin film (X) in order to promote the alkali desorption of the printing layer and the desorption of the polyolefin resin film (X) in the recycling step described later. It may be arranged so as to be in contact with the layer.
  • the desorption layer is a layer for desorbing the printing layer or the polyolefin resin film (X) layer by alkali treatment.
  • the desorbed layer preferably contains a cured product of a primer composition containing a hydroxyl group-containing resin and polyisocyanate. Such a desorbed layer is preferable because it is excellent in desorption property and can suppress the penetration and bleeding of the print layer formed on the desorbed layer by forming a urethane crosslink, and can provide a print layer having excellent image quality. ..
  • the hydroxyl group-containing resin is not particularly limited and may be selected from known resins, and one type may be used alone or two or more types may be used in combination.
  • Examples of the resin skeleton of the hydroxyl group-containing resin include acrylic resin, urethane resin, polyester resin, amino resin, phenol resin, epoxy resin, and cellulose. Urethane resin is preferable because it has good laminating suitability.
  • the hydroxyl value of the hydroxyl group-containing urethane resin is preferably 1 to 35 mgKOH / g, more preferably 10 to 30 mgKOH / g.
  • the acid value of the hydroxyl group-containing urethane resin is preferably 15 mgKOH / g or more, more preferably 15 to 70 mgKOH / g, and particularly preferably 20 to 50 mgKOH / g.
  • the acid value is 15 mgKOH / g or more, it is preferable because the desorption property by the basic aqueous solution is good, and when it is 70 mgKOH / g, the substrate adhesion and the retort resistance are good, so it is preferable.
  • Both the hydroxyl value and the acid value are values measured according to JIS K 0070.
  • the weight average molecular weight (Mw) of the hydroxyl group-containing urethane resin is preferably 10,000 to 100,000, more preferably 15,000 to 70,000, and particularly preferably 15,000 to 50,000. ..
  • the molecular weight distribution (Mw / Mn) of the hydroxyl group-containing urethane resin is preferably 6 or less. When the molecular weight distribution is 6 or less, the effects caused by excessive high molecular weight components, unreacted components, side reaction components, and other low molecular weight components can be avoided, and the desorption property and the drying property of the primer composition can be avoided. , And retort resistance becomes good.
  • the molecular weight distribution is more preferably 5 or less, and particularly preferably 4 or less.
  • the molecular weight distribution is preferably 1.5 or more, more preferably 1.2 or more.
  • the hydroxyl group-containing urethane resin may have an amine value.
  • the amine value is preferably 0.1 to 20 mgKOH / g, more preferably 1 to 10 mgKOH / g.
  • the hydroxyl group-containing urethane resin is not particularly limited, and for example, a resin obtained by reacting a polyol, a hydroxy acid, and a polyisocyanate is preferable.
  • a hydroxy acid an acid value can be imparted to the urethane resin, and the desorption property can be improved. More preferably, it is a resin obtained by reacting a resin obtained by reacting a polyol, a hydroxy acid, and a polyisocyanate with a polyamine.
  • the polyisocyanate constituting the desorbed layer is not particularly limited and can be selected from known polyisocyanates, and examples thereof include aliphatic polyisocyanates and aromatic aliphatic polyisocyanates.
  • aliphatic polyisocyanate known ones can be used, and an aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic aliphatic diisocyanate, or a derivative thereof can be used.
  • the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butyrene diisocyanate, 2,3-butylene diisocyanate, 1,3-butyrene diisocyanate, 2,4.
  • Alibo diisocyanates such as 4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methylcaproate; 1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate, 3-isocyanatomethyl- 3,5,5-trimethylcyclohexylisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), methyl2,4-cyclohexanediisocyanate, methyl2,6-cyclohexanediisocyanate, 1,4-bis (isocyanatemethyl) cyclohexane, and 1 , 3-Bis (isocyanate methyl) cyclohexane and other alicyclic diisocyanates; 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ⁇ , ⁇ '-diisocyanate-1,4-diethylbenzene
  • aromatic polyisocyanate known ones can be used, and aromatic diisocyanates or derivatives thereof can be used.
  • aromatic diisocyanate include toluene diisocyanate, diphenylmethane diisocyanate; allophanate-type, nurate-type, biuret-type, or adduct-type derivatives derived from these diisocyanates, or a complex thereof.
  • the polyisocyanate is preferably an adduct-type polyisocyanate (adduct-type), a biuret-type polyisocyanate (biuret-type), or an isocyanurate of tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), or hexamethylene diisocyanate (HDI).
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • It is a type polyisocyanate (isocyanurate form), more preferably a trimethylolpropane adduct form (HDI-TPM), a biuret form, or an isocyanurate form derived from hexamethylene diisocyanate.
  • Alkaline treatment method The method of recycling the recycled polyolefin resin (Y) from the flexible packaging having the polyolefin resin film (X) layer and the printing layer is not particularly limited, and for example, a method of treating with an acid, a method of treating with an alkali, or an ultrasonic wave. A method of irradiating the film and a method of mechanically scraping off the printed layer can be mentioned. Alkaline treatment is preferable as a recycling method from the viewpoint that the polyolefin resin can be selectively recycled with high efficiency by removing the printing layer, the adhesive layer and the like from the flexible packaging.
  • the alkaline treatment method can include a step of immersing a flexible package having a polyolefin resin film (X) layer and a printing layer in an alkaline aqueous solution.
  • the alkaline aqueous solution permeates the inside from the end of the flexible package, dissolves or swells the printing layer, the adhesive layer, the desorption layer, the aluminum layer, the alumina layer, etc., and desorbs the polyolefin resin film (X) layer. can do.
  • the flexible packaging is cut or crushed and then immersed in an alkaline aqueous solution. In this case, each layer such as a printing layer, an adhesive layer, a desorption layer, an aluminum layer, and an alumina layer is exposed on the cross section and comes into contact with an alkaline aqueous solution, which is preferable.
  • the alkaline compound used in the alkaline aqueous solution is not particularly limited, and is, for example, sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) 2 ), ammonia, barium hydroxide (Ba (OH)). 2 ) and sodium carbonate (Na 2 CO 3 ) are preferred. More preferably, it is at least one selected from the group consisting of sodium hydroxide and potassium hydroxide.
  • the content of the alkaline compound in the alkaline aqueous solution is preferably 0.5 to 15% by mass, more preferably 1 to 5% by mass, based on the alkaline aqueous solution. Within this range, the alkaline aqueous solution can have sufficient alkalinity for desorption.
  • the temperature of the alkaline aqueous solution is preferably 25 to 110 ° C, more preferably 30 to 90 ° C, and particularly preferably 30 to 80 ° C.
  • the immersion time of the flexible package in the alkaline aqueous solution is preferably 1 minute to 12 hours, and more preferably 1 minute to 6 hours.
  • the amount of the alkaline aqueous solution used is preferably 1 to 1 million times the mass of the flexible package.
  • the rotation speed of stirring is preferably 80 to 250 rpm, more preferably 80 to 200 rpm.
  • the melt mass flow rate (MFR) of the regenerated polyolefin resin (Y) is preferably 5 to 20 g / 10 minutes, more preferably 5 to 15 g / 10 minutes, although it depends on the composition of the flexible package and the recycling method.
  • MFR melt mass flow rate
  • the melt mass flow rate is within the above range, it is possible to provide a molding material suitable for various moldings such as injection molding and extrusion molding.
  • the method for producing the molding material of the present invention is not particularly limited, and preferably includes the following steps 1 to 3 in sequence.
  • the molding material contains a masterbatch (Z)
  • the following step 4 is further included.
  • Step 1) A step of alkali-treating a cut or crushed material of a flexible package having a polyolefin resin film (X) layer and a printing layer to remove a piece of the polyolefin resin film (X) from the cut or crushed material.
  • Step 2 A step of washing a piece of the polyolefin resin film (X) with water, (Step 3) Step 3 of processing a piece of the polyolefin resin film (X) to obtain a recycled polyolefin resin (Y). (Step 4) A step of mixing the regenerated polyolefin resin (Y) obtained in step 3 and the masterbatch (Z).
  • Step 1 is a step of immersing the cut or crushed material of the printed matter or the laminated laminated body which is a flexible package in an alkaline aqueous solution to remove the polyolefin resin film (X) piece from the cut or crushed material.
  • the method for crushing the flexible package is not particularly limited, and examples thereof include a method using a jaw crusher, an impact crusher, a cutter mill, a stamp mill, a ring mill, a roller mill, a jet mill, or a hammer mill.
  • the conditions for immersing the cut or crushed material in an alkaline aqueous solution the description in the above-mentioned [Alkaline treatment method] can be incorporated.
  • Step 2 is a step of washing the polyolefin resin film (X) piece obtained in step 1 with water to remove the alkaline aqueous solution adhering to the polyolefin resin film (X) piece. This step may further include a drying step, if necessary.
  • Step 3 is a step of processing the piece of the polyolefin resin film (X) obtained in step 2 to obtain a regenerated polyolefin resin (Y) derived from the polyolefin resin film (X).
  • optional components such as various additives may be added to the polyolefin resin film (X) piece before processing.
  • the polyolefin resin film (X) piece and the optional component can be mixed using a Henschel mixer, a tumbler, a disper, or the like.
  • the processing process is a batch kneader such as a kneader, a roll mill, a super mixer, a henschel mixer, a sugar mixer, a vertical granulator, a high speed mixer, a fur matrix, a ball mill, a steel mill, a sand mill, a vibration mill, an attritor, and a Banbury mixer.
  • This is a step of melt-kneading a material using a twin-screw extruder, a single-screw extruder, a rotor-type twin-screw kneader, or the like, and then processing the material into a form suitable as a molding material using a pelletizer or the like.
  • a twin-screw extruder for melt kneading.
  • Suitable forms as a molding material include pellets, powders, granules, beads and the like.
  • the molding material of the present invention can further contain a masterbatch (Z).
  • the masterbatch (Z) is not particularly limited as long as it is compatible with the regenerated polyolefin resin (Y), and generally, a thermoplastic resin such as a polyethylene resin or a polypropylene resin is kneaded with a colorant. Can be used.
  • a thermoplastic resin such as a polyethylene resin or a polypropylene resin is kneaded with a colorant.
  • the thermoplastic resin contained in the masterbatch (Z) one type may be used alone, or two or more types may be used in combination.
  • the colorant is not particularly limited as long as it is generally used for a master batch, and is, for example, an inorganic pigment such as titanium oxide, chromium titanium ero, valve handle, ultramarine blue, and carbon black; azo pigment, quinacridone.
  • inorganic pigment such as titanium oxide, chromium titanium ero, valve handle, ultramarine blue, and carbon black
  • azo pigment quinacridone
  • organic pigments such as system pigments, perylene system pigments, diketopyrrolopyrrole system pigments, and phthalocyanine system pigments.
  • Examples of the inorganic pigment include C.I. I. Pigment White 6, Pigment Brown 24, Pigment Red 101, Pigment Blue 29, and Pigment Black 7.
  • Examples of the azo pigment include C.I. I. Pigment Yellow 180, 181 and Pigment Orange 64, and Pigment Red 144, 166, 214, 221.
  • Examples of the quinacridone pigment include C.I. I. Pigment Violet 19 and Pigment Red 122.
  • Examples of the perylene-based pigment include C.I. I. Pigment Red 149, 178.
  • Examples of the diketopyrrolopyrrole pigment include C.I. I. Pigment Red 254 may be mentioned.
  • Examples of the phthalocyanine pigment include C.I. I. Pigment Blue 15: 1, 15: 3, and Pigment Green 7, 36. These colorants may be used alone or in combination of two or more.
  • the molding material of the present invention can further contain arbitrary components such as known additives as long as the effects of the present invention are not impaired.
  • an additive that does not react with the alkaline compound or has a very low reactivity with the alkaline compound is preferable.
  • examples of such additives include neutral or basic additives. In this case, the influence of the alkaline compound that may be contained in the regenerated polyolefin resin (Y) can be reduced, which is preferable.
  • the molding material of the present invention contains a recycled polyolefin resin (Y) obtained by recycling a flexible package.
  • the obtained recycled polyolefin resin (Y) contains a small amount of the alkaline compound contained in the alkaline aqueous solution even if the washing step is carried out a plurality of times after the alkaline treatment, and tends to show alkalinity. It is in.
  • an additive that does not react with the alkaline compound or has a very low reactivity with the alkaline compound is used, deterioration of the low molecular weight component in the regenerated polyolefin resin (Y) and deterioration due to the thermal history of the regeneration step such as the pelletizing step or the molding step and It is possible to suppress a decrease in the melt tension of the regenerated polyolefin resin (Y).
  • the molding material of the present invention can maintain good moldability and is preferable.
  • Examples of the additive that does not react with the alkaline compound or has a very low reactivity with the alkaline compound include at least one antioxidant selected from the group consisting of phenol-based and phosphorus-based; fatty acid amide-based and alkylene fatty acid amide-based. , Metal soap, and at least one lubricant selected from the group consisting of ester type; hindered amine type weather resistant stabilizer; wax having an acid value of 5 mgKOH / g or less; selected from the group consisting of fatty acid sulfonate and fatty acid ester type. At least one antistatic agent; Since these additives do not react with the alkaline compound or have very low reactivity with the alkaline compound, there is no risk of impairing the original properties of the molding material even under alkaline conditions.
  • phenolic antioxidant examples include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisol, 2,6-di-t-butyl-4-ethylphenol, and 2,2'.
  • Examples of the phosphorus-based antioxidant include triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, and 4,4'-butylidene-bis- (3-methyl-6-t-butylphenyl-di-).
  • Tridecyl) Phosphite Cyclic Neopentanetetraylbis (Octadecylphosphite), Trisdiphenylphosphite, Diisodecinorepentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenaslen- 10-Oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9 , 10-dihydro-9-oxa-10-phosphaphenanthrene, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6) -Di-t-methylphenyl) phosphite and 2,2-
  • antioxidants may be used alone or in combination of two or more.
  • the amount of the antioxidant added is preferably 0.01 to 1% by mass, more preferably 0.03 to 0.5% by mass, based on the mass of the molding material.
  • the addition amount is preferably 0.01% by mass or more in terms of antioxidant properties, and preferably 1% by mass or less in terms of processability.
  • fatty acid amide-based lubricant examples include aliphatic monocarboxylic acids such as lauric acid amide, palmitic acid amide, oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, ricinoleic acid amide, and hydroxystearic acid amide.
  • Amides; N-substituted aliphatic monocarboxylic acid amides such as N-oleyloleic acid amides, N-oleylstearic acid amides, and N-stearyloleic acid amides
  • fats such as methylenebisstearic acid amides and ethylenebisstearic acid amides.
  • metal soap-based lubricants include calcium stearate, magnesium stearate, barium stearate, zinc stearate, aluminum stearate, lithium stearate, calcium laurate, magnesium laurate, barium laurate, zinc laurate, and lauryl.
  • metal salts of higher fatty acids such as aluminum acid and lithium laurate.
  • a fatty acid ester-based lubricant is an alcohol in which one or more fatty acids are ester-bonded.
  • the alcohol monohydric or polyhydric alcohol can be used.
  • the monohydric alcohol is preferably a higher alcohol having 6 or more carbon atoms, and more preferably a higher alcohol having 10 or more carbon atoms.
  • the polyhydric alcohol include bihydric alcohols and trihydric or higher alcohols.
  • the dihydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, and 1,6-hexanediol.
  • trihydric or higher alcohols examples include glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, mannitol, and sorbitol.
  • glycerin, propylene glycol, pentaerythritol, and dipentaerythritol are preferable, and glycerin and dipentaerythritol are more preferable.
  • fatty acid examples include saturated fatty acids such as caproic acid, capric acid, undesic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, behenic acid, lignosenoic acid, cellotic acid, montanic acid, and melicic acid; Unsaturated fatty acids such as oleic acid, ellagic acid, linoleic acid, linolenic acid, arachidonic acid, placidic acid, erucic acid, and ricinolic acid; hydroxy fatty acids such as 12-hydroxystearic acid; aliphatic dicarboxylic acids such as adipic acid; Can be mentioned. Of these, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, and oleic acid are preferred. Particularly preferred are triglycerides of stearic acid or 12-hydroxystearic acid.
  • the amount of the lubricant added is preferably 0.01 to 1% by mass, more preferably 0.03 to 0.5% by mass, based on the mass of the molding material.
  • the addition amount is preferably 0.01% by mass or more in terms of activity, and preferably 1% by mass or less in terms of processability.
  • hindered amine-based weather-resistant stabilizer examples include dimethyl-1- (2-hydroxyethyl) succinate-2,2,6,6-tetramethylpiperidine polycondensate and poly [ ⁇ 6- (1). , 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ 2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ ], N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2, 2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) separate, and 2 -(3,5-di-t-4-hydroxybenzyl)
  • Examples of the wax having an acid value of 5 mgKOH / g or less include natural wax and synthetic wax.
  • Natural waxes include, for example, vegetable waxes such as calidelilla wax, carnauba wax, rice wax, and wood wax; animal waxes such as beeswax, lanolin, and whale wax; minerals such as montan wax, ozokelite, and celesin.
  • Examples of waxes are paraffin waxes, microcrystallin waxes, and petroleum waxes such as petrolatum.
  • Synthetic waxes include semi-synthetic waxes and total synthetic waxes.
  • the semi-synthetic wax is a natural wax or a natural wax-like material modified by chemical treatment such as esterification, amidation, and neutralization with an acidic wax.
  • Examples of the synthetic wax include synthetic hydrocarbons such as polyethylene wax, polypropylene wax, and polystyrene wax.
  • waxes having an acid value of 5 mgKOH / g or less may be used alone or in combination of two or more.
  • the amount of the wax having an acid value of 5 mgKOH / g or less is preferably 0.5 to 50% by mass, more preferably 1 to 30% by mass, based on the mass of the molding material.
  • the addition amount is preferably 0.5% by mass or more in terms of fluidity adjustment, and is preferably 50% by mass or less in terms of processability.
  • anionic surfactant-based antistatic agent examples include carboxylates such as alkali metal salts of higher fatty acids; sulfate esters such as higher alcohol sulfate esters and higher alkyl ether sulfate esters; alkylbenzene sulfonates. , Alkyl sulfonates, and sulfonates such as paraffin sulfonates; phosphate ester salts such as higher alcohol phosphates;
  • Nonionic surfactants include, for example, polyethylene glycol-type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; polyethylene oxide or glycerin.
  • polyethylene glycol-type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts
  • polyethylene oxide or glycerin examples thereof include polyhydric alcohol-type nonionic surfactants such as fatty acid esters, pentaerythlit fatty acid esters, sorbit or sorbitan fatty acid esters, polyhydric alcohol alkyl ethers, and alkanolamine aliphatic amides.
  • the amount of the antistatic agent added is preferably 0.05 to 1% by mass, more preferably 0.1 to 0.5% by mass, based on the mass of the molding material.
  • the addition amount is preferably 0.05% by mass or more from the viewpoint of antistatic property, and preferably 1% by mass or less from the viewpoint of transparency and low bleeding property.
  • a molded product can be obtained by molding the molding material of the present invention.
  • the molding method is not particularly limited, and examples thereof include injection molding, extrusion molding, blow molding, and compression molding. Since the molding material of the present invention contains a recycled polyolefin resin (Y) having a high recycling utilization rate, good moldability, a sufficiently high total light transmittance, and preferably a colorless transparent to a light color, it is molded. Regardless of the method, it is possible to provide a molded product colored in a desired color of colorless transparent to light color or light color to dark color.
  • the molded body of the present invention can be used for various purposes such as home appliances, stationery, automobile parts, toys, sporting goods, medical supplies, and construction / construction materials.
  • the recycled polyolefin resin (Y) was melt-extruded at 200 ° C. with a T-die film molding machine to prepare a film having a thickness of 100 ⁇ m.
  • the total light transmittance of the produced film was measured using Haze Guard Plus (manufactured by Gardner) in accordance with JIS K 7361.
  • melt mass flow rate (MFR)> MFR was measured according to JIS K-7210.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Mw / Mn molecular weight distribution
  • GPC device Showa Denko's Shodex GPC-104, Column: Two Showa Denko “Shodex LF-404" and one Showa Denko "Shodex LF-G” connected in series, Detector: RI (Differential Refractometer), Measurement conditions: Column temperature 40 ° C, Eluent: Tetrahydrofuran, Flow rate: 0.3 mL / min.
  • S Sample collection amount (g)
  • a Consumption (ml) of 0.1N alcoholic potassium hydroxide solution
  • F Titer of 0.1N alcoholic potassium hydroxide solution.
  • ⁇ Measurement of hydroxyl value (OHV)> Approximately 1 g of the sample was precisely weighed in a stoppered Erlenmeyer flask, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol 2/1) mixed solution was added and dissolved. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added, and the mixture was stirred for about 1 hour. Phenolphthalein test solution was added to this as an indicator and lasted for 30 seconds.
  • acetylating agent a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml
  • Printing was performed in this order on a gravure printing machine equipped with a gravure plate having a plate depth of 35 ⁇ m, and the film was dried at 50 ° C. to obtain a flexible package 1 having an OPP base material / desorption layer 1 / printing layer 1. ..
  • VMCPP aluminum-deposited unstretched polypropylene
  • VMCPP base material / adhesive layer in the same manner as in the manufacturing process of the flexible packaging 2 except that the ink 1 was changed to the ink 2 (organic solvent-based gravure ink "Rio Alpha S R92 ink” manufactured by Toyo Ink Co., Ltd.).
  • the configuration is the VMCPP base material / adhesive layer 2 / OPP base material / desorption layer 1 / printing layer 1 in the same manner as in the manufacturing process of the flexible packaging 2 except that the adhesive 1 is changed to the adhesive 2.
  • a flexible package 4 was obtained.
  • the structure is the same as in the manufacturing process of the flexible packaging 5, except that the adhesive 1 is changed to the adhesive 2, and the composition is OPP base material / desorption layer 1 / printing layer 1 / adhesive layer 2 / VMCPP base material.
  • the flexible package 6 was manufactured.
  • the OPP base material piece or the CPP base material piece was removed from the flexible packaging bodies 2 to 6 in the same manner as in the regenerated polyolefin resin (Y1), washed with water and dried.
  • the obtained OPP base material piece or CPP base material piece was put into a single-screw extruder, melt-extruded at 200 ° C., and cut with a pelletizer. In this way, pellets of recycled polyolefin resins (Y2) to (Y6) recycled from the flexible packaging were obtained.
  • the flexible package 1 was cut into a size of 4 cm ⁇ 4 cm.
  • the flexible package piece was put into a single-screw extruder without undergoing an alkali treatment step, melt-extruded at 200 ° C., and cut with a pelletizer. In this way, pellets of the colored recycled polyolefin resin (Y7) were obtained.
  • the flexible package 5 was cut into a size of 4 cm ⁇ 4 cm.
  • the flexible package piece was put into a single-screw extruder without undergoing an alkali treatment step, melt-extruded at 200 ° C., and cut with a pelletizer. In this way, pellets of the colored recycled polyolefin resin (Y8) were obtained.
  • Table 1 shows the main production conditions and evaluation results of the regenerated polyolefin resin (Y).
  • the compounding composition is shown in Table 2.
  • Master batches (Z2) to (Z22) were obtained in the same manner as in the master batch (Z1) except that the compounding composition was changed as shown in Table 2.
  • J105P Polypropylene resin ("Prime Polypro J105P” manufactured by Prime Polymer Co., Ltd.), R730: Polypropylene resin ("Prime Polypro R730” manufactured by Prime Polymer Co., Ltd.), F2270P: Polyethylene resin ("Suntech M2270” manufactured by Asahi Kasei Corporation), Mitsubishi Carbon # 30: Carbon Black (manufactured by Mitsubishi Chemical Corporation), Irganox 1010: Phenolic Antioxidant (manufactured by BASF), Irganox 1076: Phenolic Antioxidant (manufactured by BASF), Irganox245: Phenolic Antioxidant (manufactured by BASF), Irgafos 168: Phosphorus-based antioxidant (manufactured by BASF), ADK STAB PEP-36: Phosphorus-based antioxidant ("ADEKA STAB PEP-36” manufactured by ADEKA), IrganoxPS
  • Example 7 65 parts of the recycled polyolefin resin (Y1) and 35 parts of the masterbatch (Z1) were tumbled to obtain the molding material 7.
  • a film-shaped molded body 7 was produced in the same manner as in Examples 1 to 6 except that the obtained molding material was used. A formable and colored film of the desired color was obtained.
  • the compounding composition is shown in Table 3.
  • Molding materials 8 to 14, 19 to 39 were used in the same manner as the molding material 7, except that the types and compounding ratios of the recycled polyolefin resin (Y) and the masterbatch (Z1) were changed as shown in Table 3. Obtained. Film-shaped molded bodies 8 to 14 and 19 to 39 were produced in the same manner as in Example 7 except that the obtained molding material was used. Any molding material can be molded, and a film colored in a desired color was obtained.
  • Molding materials 15 to 18 were obtained in the same manner as the molding material 7 except that the types and compounding ratios of the regenerated polyolefin resin (Y) and the masterbatch (Z1) were changed as shown in Table 3. Film-shaped molded bodies 15 to 18 were produced in the same manner as in Example 7 except that the obtained molding material was used. None of the molding materials could be molded. Further, the recycled polyolefin resins (Y7) and (Y8) were deeply colored by the printing layer derived from the flexible packaging, and a film colored in a desired color could not be obtained.
  • Example 51 to 56 The molding materials 1 to 6 were blow molded at 200 ° C. using a blow molding machine, respectively, to prepare bottle-shaped molded bodies 51 to 56 having a thickness of 1 mm. Both were moldable, and a colorless and transparent bottle was obtained. For each example, 50 bottles were produced.
  • the compounding composition is shown in Table 4.
  • Example 57 to 85 The molding materials 19 to 39 were blow molded in the same manner as in Examples 51 to 56 to prepare bottle-shaped molded bodies 57 to 85. Both were moldable, and bottles colored in the desired color were obtained. For each example, 50 bottles were produced.
  • the compounding composition is shown in Table 4.
  • the molding material of the present invention has a high recycling utilization rate, has good moldability, and can provide a molded product such as a film and a bottle, which is colorless and transparent or has a desired color. It has been found that the molding material of the present invention can be used to provide a high-quality molded product free of foreign matter and foaming. Foreign matter generated by the alkaline compound remaining in the regenerated polyolefin resin (Y) by using a neutral or basic additive that does not react with the alkaline compound or has low reactivity with the alkaline compound as the additive. It is presumed that the generation of foaming components such as water and moisture was suppressed.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne : un matériau de moulage qui présente un taux d'utilisation élevé de matériaux recyclés et qui est capable d'être utilisé dans diverses applications, tout en étant capable d'être coloré en une couleur souhaitée, si nécessaire ; un corps moulé qui est formé de ce matériau de moulage et présente un taux de recyclage élevé ; et un procédé de production dudit corps moulé. Un matériau de moulage selon la présente invention contient une résine de polyoléfine recyclée (Y) dérivée d'emballages souples comprenat un film de résine de polyoléfine (X) et une couche d'impression ; la résine de polyoléfine recyclée (Y) ayant une transmittance totale de la lumière de 30 % ou plus sous la forme d'un film ayant une épaisseur de 100 µm ; et la teneur de la résine de polyoléfine recyclée (Y) étant de 50 % en masse ou plus sur la base de la quantité totale du matériau de moulage.
PCT/JP2021/024441 2020-06-29 2021-06-29 Matériau de moulage, corps moulé et son procédé de production Ceased WO2022004687A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2021550248A JP7389127B2 (ja) 2020-06-29 2021-06-29 成形用材料、並びに、成形体とその製造方法
JP2022025710A JP7735895B2 (ja) 2020-06-29 2022-02-22 成形用材料、並びに、成形体とその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-111681 2020-06-29
JP2020111681 2020-06-29

Publications (1)

Publication Number Publication Date
WO2022004687A1 true WO2022004687A1 (fr) 2022-01-06

Family

ID=79316231

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/024441 Ceased WO2022004687A1 (fr) 2020-06-29 2021-06-29 Matériau de moulage, corps moulé et son procédé de production

Country Status (2)

Country Link
JP (2) JP7389127B2 (fr)
WO (1) WO2022004687A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7215625B1 (ja) 2022-05-24 2023-01-31 東洋インキＳｃホールディングス株式会社 再生プラスチック製造方法および当該製造方法で製造されてなる再生プラスチック
JP2023176821A (ja) * 2022-06-01 2023-12-13 東洋インキＳｃホールディングス株式会社 再生ポリエチレンの製造方法

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7834565B2 (ja) * 2022-05-02 2026-03-24 株式会社三共 遊技機
JP7834568B2 (ja) * 2022-05-02 2026-03-24 株式会社三共 遊技機
JP7834569B2 (ja) * 2022-05-02 2026-03-24 株式会社三共 遊技機
JP7834567B2 (ja) * 2022-05-02 2026-03-24 株式会社三共 遊技機
JP2023170419A (ja) * 2022-05-19 2023-12-01 Dic株式会社 成形用又は成型用材料及びその製造方法
JP2024051211A (ja) * 2022-09-30 2024-04-11 大王製紙株式会社 衛生用品包装体の製造方法、及び衛生用品包装体
JP7832518B2 (ja) * 2024-01-05 2026-03-18 ダイキン工業株式会社 加工助剤、マスターバッチ、熱可塑性樹脂組成物及び成形体、並びに、これらの製造方法
WO2025146806A1 (fr) * 2024-01-05 2025-07-10 ダイキン工業株式会社 Adjuvant d'usinage, mélange-maître, composition de résine thermoplastique ainsi que corps moulé, et procédé de fabrication de ceux-ci
WO2025253765A1 (fr) * 2024-06-06 2025-12-11 株式会社フジシール Procédé de production de matériau recyclé

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008088326A (ja) * 2006-10-03 2008-04-17 Sekisui Chem Co Ltd 押出成形体及びその製造方法
JP2009102633A (ja) * 2007-10-03 2009-05-14 Tokyo Printing Ink Mfg Co Ltd マスターバッチ
JP2010180318A (ja) * 2009-02-05 2010-08-19 Polyplastics Co ペレット混合物、成形体、及び成形体の製造方法
JP2013136792A (ja) * 2013-04-09 2013-07-11 Polyplastics Co 成形体の製造方法及び成形体
JP2019518805A (ja) * 2017-03-30 2019-07-04 エルエス ケーブル アンド システム リミテッド． 非ハロゲン系難燃性ポリオレフィン絶縁組成物，及び該絶縁組成物から成る絶縁層を含む電線
JP2019189861A (ja) * 2018-04-20 2019-10-31 株式会社日本触媒 ビニル重合体微粒子並びにそれを用いたマスターバッチ及び樹脂フィルム
JP6638802B1 (ja) * 2018-12-06 2020-01-29 東洋インキＳｃホールディングス株式会社 有機溶剤系印刷インキ、印刷物および積層体
JP2020084049A (ja) * 2018-11-27 2020-06-04 東洋インキＳｃホールディングス株式会社 樹脂組成物、マスターバッチ、および成形体

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210187790A1 (en) 2018-09-19 2021-06-24 Dic Corporation Method for separating and recovering layered film
JP6631964B1 (ja) * 2019-05-29 2020-01-15 東洋インキＳｃホールディングス株式会社 脱離能を有する有機溶剤系印刷インキ、印刷物および積層体

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008088326A (ja) * 2006-10-03 2008-04-17 Sekisui Chem Co Ltd 押出成形体及びその製造方法
JP2009102633A (ja) * 2007-10-03 2009-05-14 Tokyo Printing Ink Mfg Co Ltd マスターバッチ
JP2010180318A (ja) * 2009-02-05 2010-08-19 Polyplastics Co ペレット混合物、成形体、及び成形体の製造方法
JP2013136792A (ja) * 2013-04-09 2013-07-11 Polyplastics Co 成形体の製造方法及び成形体
JP2019518805A (ja) * 2017-03-30 2019-07-04 エルエス ケーブル アンド システム リミテッド． 非ハロゲン系難燃性ポリオレフィン絶縁組成物，及び該絶縁組成物から成る絶縁層を含む電線
JP2019189861A (ja) * 2018-04-20 2019-10-31 株式会社日本触媒 ビニル重合体微粒子並びにそれを用いたマスターバッチ及び樹脂フィルム
JP2020084049A (ja) * 2018-11-27 2020-06-04 東洋インキＳｃホールディングス株式会社 樹脂組成物、マスターバッチ、および成形体
JP6638802B1 (ja) * 2018-12-06 2020-01-29 東洋インキＳｃホールディングス株式会社 有機溶剤系印刷インキ、印刷物および積層体

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7215625B1 (ja) 2022-05-24 2023-01-31 東洋インキＳｃホールディングス株式会社 再生プラスチック製造方法および当該製造方法で製造されてなる再生プラスチック
WO2023228476A1 (fr) * 2022-05-24 2023-11-30 東洋インキＳｃホールディングス株式会社 Méthode de production de plastique recyclé
JP2023172449A (ja) * 2022-05-24 2023-12-06 東洋インキＳｃホールディングス株式会社 再生プラスチック製造方法および当該製造方法で製造されてなる再生プラスチック
JP2023176821A (ja) * 2022-06-01 2023-12-13 東洋インキＳｃホールディングス株式会社 再生ポリエチレンの製造方法
JP7448756B2 (ja) 2022-06-01 2024-03-13 ａｒｔｉｅｎｃｅ株式会社 再生ポリエチレンの製造方法

Also Published As

Publication number Publication date
JP7389127B2 (ja) 2023-11-29
JP2022075685A (ja) 2022-05-18
JPWO2022004687A1 (fr) 2022-01-06
JP7735895B2 (ja) 2025-09-09

Similar Documents

Publication Publication Date Title
JP7389127B2 (ja) 成形用材料、並びに、成形体とその製造方法
JP7100750B1 (ja) 包装材、リサイクル成形用材料及びその製造方法
JP7088360B2 (ja) 包装材、及びリサイクル基材製造方法
JP7215625B1 (ja) 再生プラスチック製造方法および当該製造方法で製造されてなる再生プラスチック
JP2023075977A (ja) 積層体の分離回収方法
WO2020111226A1 (fr) Adhésif, matériau d'emballage, et procédé de fabrication de réceptacle d'emballage et de substrat recyclé
JP7263661B1 (ja) 積層体の分離回収方法
JP7318775B1 (ja) 再生プラスチック製造方法
JP7425948B1 (ja) 再生プラスチックの製造方法
JP7416320B1 (ja) 積層体の製造方法
JP7401015B1 (ja) プラスチック基材の分離回収方法
US20250367859A1 (en) Method for separating and recovering laminate
JP2025033323A (ja) 積層体の分離回収方法
JP7679343B2 (ja) プラスチック基材の分離回収方法
JP7401019B1 (ja) 積層体の分離回収方法
JP7291881B1 (ja) 積層体、包装体、積層体の分離回収方法
JP7193025B1 (ja) 積層体、包装体、積層体の分離回収方法
JP2025166328A (ja) 処理液、分離回収方法、成形用材料の製造方法、及び成形体の製造方法
JP2024089196A (ja) フラフ、及び、樹脂基材の分離回収方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2021550248

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21834384

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21834384

Country of ref document: EP

Kind code of ref document: A1