Molding material, molded body and manufacturing method thereof

Abstract

The present invention provides a molding material that has a high recyclability, can be colored to a desired color as needed, and can be used for a variety of applications, as well as a molded article that has a high recyclability and is molded from the material, and a method for producing the same. [Solution] The molding material of the present invention contains recycled polyolefin resin (Y) derived from flexible packaging having a polyolefin resin film (X) layer and a printed layer, and the recycled polyolefin resin (Y) has a total light transmittance of 30% or more in the form of a film with a thickness of 100 μm, and the content of recycled polyolefin resin (Y) is 50 mass% or more based on the total amount of the molding material.

Description

[Technical Field]

[0001] The present invention relates to a molding material, a molded article molded from the material, and a method for producing the same. [Background technology]

[0002] In recent years, plastic film packaging, plastic bottles, and other plastic products have been discarded and dumped into the ocean as litter, causing environmental pollution. Plastic products are broken down in seawater into submicron-sized fragments (microplastics), which float in the seawater. Microplastics are ingested by marine organisms such as fish and become concentrated in their bodies. Furthermore, there are concerns about the impact on the health of seabirds and humans, who consume marine organisms as food.

[0003] Plastic products include bottles and caps; single-layer film bags such as plastic shopping bags; and multi-layer food packaging made of plastic film. Generally, bottles, caps, and single-layer film bags are mono-material plastic products made primarily from one type of resin, making them relatively easy to recycle. In particular, collection systems have been established for polyester (PET) bottles and polystyrene (PS) food trays at government agencies and retailers such as supermarkets, enabling bottle-to-bottle and tray-to-tray recycling.

[0004] On the other hand, in the case of multi-layered food packaging, various plastic substrates are used as the film substrate, such as polyester substrate, nylon substrate (NY), polypropylene substrate (PP), and polyethylene substrate (PE). Multi-layered food packaging can be produced, for example, by printing a first film substrate with printing ink, laminating a second film substrate onto the printed layer, optionally via an adhesive layer, and then cutting and heat-sealing the resulting product. However, multi-layered food packaging containing multiple different materials that are incompatible with each other is difficult to recycle.

[0005] Attempts have been made to recycle polyolefin substrates by constructing packages using only polyolefin substrates such as polypropylene as the plastic substrate. However, even if a package containing a printed layer and, if necessary, an adhesive layer is recycled as is, only dark-colored plastic raw materials such as black or gray are obtained due to the presence of the printed layer and / or adhesive layer. Once colored, polyolefins such as PP are difficult to make colorless and transparent. It would be desirable to be able to material-recycle colorless and transparent polyolefins with no application restrictions.

[0006] Generally, recycled polyolefin resins containing printed and / or adhesive layers tend to have poor physical properties due to the resin components derived from the printed and / or adhesive layers. In such cases, virgin petroleum-derived resins must be mixed in. This makes it difficult to improve the recycling rate.

[0007] Regarding the removal of a printed layer from a laminate including a plastic substrate and a printed layer, Patent Document 1 discloses a technique in which an undercoat layer made of an acrylic resin or a styrene-maleic acid resin is provided on a plastic substrate, and a surface-printed printed layer disposed on this undercoat layer is removed using alkaline water. Patent Document 2 also discloses a technique in which an ink using a polyurethane resin or an acrylic resin having an acidic group as a binder resin is surface-printed, and the printed layer is removed using alkaline water. However, these patent documents only disclose a technique for removing the surface-printed ink from the outside of the package, and do not disclose a technique for removing the printed layer in the laminate and peeling the multiple film substrates from each other. Multi-layered food packaging that does not allow the multiple film substrates to be peeled from each other can only be recycled into either (1) plastic materials with poor mechanical properties or (2) dark-colored plastic materials, making high-quality material recycling difficult.

[0008] On the other hand, Patent Document 3 discloses a technique for removing a printed layer from a surface-printed or laminated laminate using a removal layer containing a polyurethane resin having a predetermined acid value. However, Patent Document 3 does not disclose any specific use of polyolefin resin recycled from laminated bodies as a molding material, and does not disclose any suitable embodiment of a molding material containing recycled polyolefin resin. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-131484 [Patent Document 2] Japanese Patent Application Publication No. 11-209677 [Patent Document 3] Japanese Patent Publication No. 2020-090627 Summary of the Invention [Problem to be solved by the invention]

[0010] An object of the present invention is to provide a molding material that has a high recyclability, can be colored to a desired color as needed, and can be used for a variety of applications, as well as a molded article that is molded from the material and has a high recyclability, and a method for producing the same. [Means for solving the problem]

[0011] The present inventors have conducted extensive research to solve the above problems and have completed the present invention. The present invention relates to a molding material containing recycled polyolefin resin (Y) derived from flexible packaging having a polyolefin resin film (X) layer and a printed layer, wherein the recycled polyolefin resin (Y) has a total light transmittance of 30% or more in the form of a 100 μm-thick film, and the content of recycled polyolefin resin (Y) is 50 mass% or more based on the total amount of the molding material.

[0012] The present invention relates to the molding material, wherein the recycled polyolefin resin (Y) has a melt mass-flow rate of 5 to 20 g / 10 min.

[0013] The present invention relates to the above molding material, wherein the polyolefin resin film (X) has a melt mass flow rate of 3 to 12 g / 10 min.

[0014] The present invention further relates to the molding material described above, which contains a masterbatch (Z).

[0015] The present invention further relates to the molding material, which contains at least one antioxidant selected from the group consisting of phenolic and phosphorus-based antioxidants.

[0016] The present invention further relates to the molding material, which contains at least one lubricant selected from the group consisting of fatty acid amide-based lubricants, metal soap-based lubricants, and fatty acid ester-based lubricants.

[0017] The present invention further relates to the molding material, which contains a hindered amine weathering stabilizer.

[0018] The present invention further relates to the molding material described above, which contains a wax having an acid value of 5 mgKOH / g or less.

[0019] The present invention further relates to the molding material, which contains at least one antistatic agent selected from the group consisting of anionic surfactants and nonionic surfactants.

[0020] The present invention relates to a molded article made from the above molding material.

[0021] The present invention provides A step 1 of treating cut or crushed pieces of a flexible packaging body having a polyolefin resin film (X) layer and a printed layer with an alkali to remove pieces of the polyolefin resin film (X) from the cut or crushed pieces; Step 2 of washing the polyolefin resin film (X) pieces with water; and step 3 of processing the pieces of polyolefin resin film (X) to obtain recycled polyolefin resin (Y).

[0022] The present invention further relates to a method for producing a molding material, which includes step 4 of mixing the recycled polyolefin resin (Y) obtained in step 3 with a masterbatch (Z). [Effects of the Invention]

[0023] The present invention can provide a molding material that has a high recyclability, can be colored to a desired color as needed, and can be used for a variety of applications, as well as a molded article that is molded from the material and has a high recyclability, and a method for producing the same. DETAILED DESCRIPTION OF THE INVENTION

[0024] <Molding material> The molding material of the present invention contains a recycled polyolefin resin (Y) obtained by recycling a flexible packaging body having a polyolefin resin film (X) layer and a printed layer, and is characterized in that the recycled polyolefin resin (Y) has a total light transmittance of 30% or more in the form of a film with a thickness of 100 μm, and the content of the recycled polyolefin resin (Y) is 50 mass% or more based on the total amount of the molding material.

[0025] In the present invention, recycled polyolefin resin (Y) is used as a molding material. The recycled polyolefin resin (Y) has a sufficiently high total light transmittance and is preferably colorless, transparent, or pale in color. The recycled polyolefin resin is obtained by reducing or removing unnecessary components such as the printed layer from a flexible packaging material having a polyolefin resin film (X) layer and a printed layer, and processing the recovered polyolefin resin. In the present invention, recycled polyolefin resin (Y) from which unnecessary components such as printed layers have been removed is used, so that deterioration of the physical properties as a molding material, such as a decrease in melt flow rate (MFR), is suppressed, and a high-quality molding material can be obtained. The recycled polyolefin resin (Y) has a sufficiently high total light transmittance and is preferably colorless, transparent, or pale in color, and can be colored in any color, which is preferable. Furthermore, by containing the above-mentioned recycled polyolefin resin (Y) in a proportion of 50% by mass or more in the molding material, it is possible to obtain a molding material that has a high recycling utilization rate, good moldability, can be colored in any color as needed, and can be used for a variety of applications. The present invention will be described in detail below.

[0026] <Recycled polyolefin resin (Y)> The recycled polyolefin resin (Y) is obtained by recycling a flexible packaging body having a polyolefin resin film (X) layer and a printed layer, and is characterized by having a total light transmittance of 30% or more in the form of a film with a thickness of 100 μm. A total light transmittance of 30% or more is important from the viewpoint of increasing the recycle rate and enabling use in various applications. If the total light transmittance is less than 30%, the presence of impurities such as colorants derived from flexible packaging may make it difficult to increase the amount of recycled polyolefin resin (Y) blended into the molding material and thereby increase the recycle rate. Furthermore, if the total light transmittance is less than 30%, it becomes difficult to control the color of the molding material, and when the coloring masterbatch (Z) described below is blended, it is difficult to color the molding material to the desired color, which may limit the applications of the molding material. The total light transmittance of the recycled polyolefin resin (Y) in the form of a film having a thickness of 100 μm 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.

[0027] <Soft packaging> The flexible packaging material is not particularly limited as long as it has at least one polyolefin resin film (X) layer and a print layer, and examples thereof include flexible packaging materials used for foods, detergents, cosmetics, pharmaceuticals, and the like.

[0028] [Polyolefin resin film (X) layer] Examples of the polyolefin resin film (X) include sealant substrates such as polyethylene (PE), biaxially oriented polypropylene (OPP), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), acid-modified polyethylene, unoriented polypropylene (CPP), acid-modified polypropylene, and copolymer polypropylene. The thickness of the polyolefin resin film (X) layer is not particularly limited, but is preferably 5 to 200 μm, more preferably 10 to 150 μm.

[0029] The melt mass-flow rate (MFR) of the polyolefin resin film (X) is preferably 3 to 12 g / 10 min. A melt mass-flow rate of 3 g / 10 min or more is preferred because it provides excellent formability as a film used for flexible packaging. A melt mass-flow rate of 12 g / 10 min or less is preferred because the polyolefin resin film (X) is less likely to deteriorate during recycling, and the resulting molding material containing the recycled polyolefin resin (Y) has better formability. The melt mass-flow rate in this specification is a value measured in accordance with JIS K 7210.

[0030] The flexible packaging may have a substrate layer other than the polyolefin resin film (X) layer depending on the application or purpose of use. Examples of the substrate layer include plastic substrates other than polyolefin resins, gas barrier substrates, paper, and laminates thereof.

[0031] Examples of plastic substrates other than polyolefin resins include polyester resins, polyamide resins, polystyrene resins, vinyl chloride resins, vinyl acetate resins, ABS resins, acrylic resins, acetal resins, polycarbonate resins, and cellulose-based plastics.

[0032] Examples of gas barrier substrates include metal foils such as aluminum foil, plastic substrates having an inorganic vapor-deposited layer of aluminum, silica, alumina, etc., and plastic substrates having an organic layer of polyvinyl alcohol, etc. The thickness of the aluminum foil is preferably 3 to 50 μm from an economical standpoint. Aluminum and alumina are soluble in an alkaline aqueous solution and can be dissolved in the alkaline detachment step described below. Therefore, the polyolefin resin film (X) can be detached from a flexible packaging material containing a polyolefin resin film (X) layer and aluminum and / or alumina by alkaline treatment, and can be recycled.

[0033] The polyolefin resin film (X) layer and / or other substrate layers other than the (X) layer may contain additives such as antistatic agents and ultraviolet inhibitors, if necessary. The surface of the film or substrate may be subjected to a surface treatment such as corona treatment or low-temperature plasma treatment.

[0034] [Print layer] The printed layer can be a layer that displays any design, pattern, letter, symbol, etc. for the purpose of adding decoration or aesthetic appeal; indicating the contents, expiration date, manufacturer or seller, etc. The printed layer may also be a solid printed layer that does not have any design, pattern, letter, symbol, etc. The method for forming the printed layer is not particularly limited, and the printed layer can be formed using known pigments and / or dyes. The printed layer can preferably be formed using printing ink containing pigments and / or dyes. The printed layer can have a single layer structure or a multi-layer structure. The thickness of the printed layer is preferably 0.1 to 100 μm, more preferably 0.1 to 10 μm, and particularly preferably 1 to 5 μm.

[0035] [Adhesive layer] The flexible packaging may have an adhesive layer. The adhesive that forms the adhesive layer is generally a two-component urethane adhesive consisting of a polyol base and a polyisocyanate curing agent. In this case, the adhesive layer is a cured product of this urethane adhesive. The polyol base may be any compound having two or more hydroxyl groups and may be selected from known polyols, such as polyester polyols, polycarbonate polyols, polycaprolactone polyols, polyether polyols, polyolefin polyols, acrylic polyols, silicone polyols, castor oil-based polyols, and fluorine-based polyols. The polyol base may be an acid-modified product in which some of the hydroxyl groups in the polyol have been acid-modified, or a product in which urethane bonds have been introduced by reacting some of the hydroxyl groups in the polyol with diisocyanate. The polyisocyanate curing agent may be any compound having two or more isocyanate groups and may be selected from known polyisocyanates, such as aromatic polyisocyanates, araliphatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and modified products thereof. The polyol base agent may be used alone or in combination of two or more kinds. The same applies to the polyisocyanate curing agent.

[0036] (Removable adhesive layer) The adhesive layer may be a releasable adhesive layer to promote detachment of the adhesive layer in the recycling step described below. The releasable adhesive layer is preferably an adhesive layer made of an adhesive having an acid value of 5 to 40 mgKOH / g, and more preferably an adhesive layer made of an adhesive having an acid value of 5 to 40 mgKOH / g that contains a polyester polyol base and at least one polyisocyanate curing agent selected from the group consisting of aliphatic polyisocyanates and aralkyl polyisocyanates.

[0037] The polyester polyol base agent preferably includes polyester polyols obtained by reacting one or more carboxyl group components exemplified below with one or more hydroxyl group components exemplified below. Examples of the carboxy group component include dibasic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, and itaconic anhydride; dialkyl esters thereof; and combinations thereof. Examples of the hydroxyl group component include diols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, butylene glycol, neopentyl glycol, dineopentyl glycol, trimethylolpropane, glycerin, 1,6-hexanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, 1,9-nonanediol, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, polyether polyol, polycarbonate polyol, polyolefin polyol, acrylic polyol, and polyurethane polyol; and combinations thereof. As the polyester polyol base material, polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, and poly(β-methyl-γ-valerolactone) may be used.

[0038] The acid value of the polyester polyol base is preferably 8.0 mgKOH / g or more, more preferably 10.0 mgKOH / g or more, and is preferably 45.0 mgKOH / g or less, more preferably 40.0 mgKOH / g or less. When the adhesive contains a plurality of polyester polyol components, the acid value of the polyester polyol base can be determined from the acid value of each polyester polyol component and its mass ratio.

[0039] From the viewpoints of heat sterilization resistance and coatability, the number average molecular weight (Mn) of the polyester polyol base agent is preferably 3,000 to 20,000, more preferably 5,000 to 15,000, and particularly preferably 7,000 to 12,000. When the Mn of the polyester polyol base 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 release property are improved, which is preferable.

[0040] The polyester polyol base may contain multiple polyester polyol components to satisfy various physical properties required for packaging materials. The polyester polyol base may contain multiple polyester polyol components, including, for example, polyester polyols with Mn of 5,000 to 15,000. The polyester polyol base may contain a polyester polyol with Mn of less than 3,000 to improve adhesion to substrates. When a plurality of polyester polyol components are contained, the Mn of the polyester polyol base material can be determined from the Mn of each polyester polyol component and its mass ratio. In this specification, the number average molecular weight (Mn) and weight average molecular weight (Mw) are values ​​calculated using GPC (gel permeation chromatography) and converted into standard polystyrene.

[0041] The polyester polyol base agent may contain the following three types of polyols from the viewpoints of adhesive performance and alkali release properties. First polyol: polyester polyol having an acid value of 10 mg KOH / g or more; Second polyol: a polyester polyol having a number average molecular weight (Mn) of less than 3,000; Third polyol: 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.)

[0042] The first polyol component has the role of imparting releasability, the second polyol component improves substrate adhesion and contributes to improved coatability, and the third polyol component has the role of improving retort properties. The content of the first polyol component is preferably 50% by mass or more based on the total amount of the polyester polyol base material, from the viewpoint of exhibiting sufficient releasing properties. The first polyol component is preferably a polyester polyurethane polyol modified with an acid anhydride. The first polyol component preferably has an 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 mg KOH / g or less, more preferably 1 mg KOH / g or less. The third polyol component is preferably a polyester polyurethane polyol modified with an acid anhydride.The third polyol component preferably has an Mn of 5,000 to 10,000 and an acid value of 5 mgKOH / g or less.

[0043] The polyisocyanate curing agent is at least one selected from the group consisting of aliphatic polyisocyanates and araliphatic polyisocyanates.

[0044] The aliphatic polyisocyanate is not particularly limited, and known aliphatic diisocyanates, alicyclic diisocyanates, or derivatives thereof can be used. Examples of aliphatic diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methyl caproate. Examples of alicyclic diisocyanates include 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (hereinafter, isophorone diisocyanate), 4,4'-methylenebis(cyclohexyl isocyanate), methyl 2,4-cyclohexane diisocyanate, methyl 2,6-cyclohexane diisocyanate, 1,4-bis(isocyanatemethyl)cyclohexane, and 1,3-bis(isocyanatemethyl)cyclohexane. The aliphatic diisocyanate or 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.

[0045] The araliphatic polyisocyanate is not particularly limited, and known araliphatic diisocyanates or derivatives thereof can be used. Examples of the araliphatic diisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof; ω,ω'-diisocyanato-1,4-diethylbenzene; and 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene or a mixture thereof. The araliphatic 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.

[0046] [Soft packaging composition] The flexible packaging material only needs to have a polyolefin resin film (X) layer and a printed layer, and its configuration varies depending on the contents and application. The flexible packaging body may be configured as follows: Single layer film configurations such as print layer / HS-OPP, print layer / CPP, print layer / OPP / HS material, print layer / shrinkable PP, and OPP / print layer / HS material; Examples of multilayer film configurations include OPP / printing layer / adhesive layer / CPP, ONY / printing layer / adhesive layer / LLDPE, OPP / printing layer / adhesive layer / vapor-deposited CPP, PET / printing layer / adhesive layer / LLDPE, OPP / printing layer / adhesive layer / PET / adhesive layer / CPP, PET / printing layer / adhesive layer / AL / adhesive layer / ONY / adhesive layer / CPP, and PET / printing layer / adhesive layer / AL / adhesive layer / ONY / adhesive layer / LLDPE.

[0047] The abbreviations represent the following materials. HS: Heat seal, OPP: Biaxially oriented polypropylene, CPP: Non-oriented polypropylene, PP: Polypropylene, ONY: Biaxially oriented nylon film, LLDPE: Linear low density polyethylene, PET: polyethylene terephthalate, AL: Aluminum.

[0048] When the flexible packaging contains a plurality of layers of polyolefin resin film (X), the recycled polyolefin resin (Y) obtained by recycling is a mixture of these layers.

[0049] In order to promote alkaline detachment of the printed layer and detachment of the polyolefin resin film (X) in the recycling step described below, the detachment layer may be arranged in the flexible packaging so as to be in contact with the printed layer or the polyolefin resin film (X) layer. The release layer is a layer for releasing the printed layer or the polyolefin resin film (X) layer by alkali treatment. The release layer preferably contains a cured product of a primer composition containing a hydroxyl group-containing resin and a polyisocyanate. Such a release layer is preferred because it has excellent release properties and, by forming urethane crosslinks, suppresses penetration and bleeding of the printed layer formed on the release layer, thereby providing a printed layer with excellent image quality.

[0050] The hydroxyl group-containing resin is not particularly limited and can 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 preferred because of its good suitability for lamination.

[0051] The hydroxyl value of the hydroxyl-containing urethane resin is preferably 1 to 35 mgKOH / g, more preferably 10 to 30 mgKOH / g. A hydroxyl value of 1 mgKOH / g or more is preferred because it improves the releasability in a basic aqueous solution, while a hydroxyl value of 35 mgKOH / g or less is preferred because it improves the adhesion to substrates. 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. An acid value of 15 mgKOH / g or more is preferred because it improves releasability in a basic aqueous solution, and an acid value of 70 mgKOH / g is preferred because it improves substrate adhesion and retort resistance. Both the hydroxyl value and the acid value are values ​​measured in accordance with JIS K 0070.

[0052] 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 not more than 6. When the molecular weight distribution is not more than 6, the effects caused by excess high molecular weight components, unreacted components, side reaction components, and other low molecular weight components can be avoided, and the releasability, drying properties of the primer composition, and retort resistance are improved.

[0053] The smaller the molecular weight distribution, i.e., the sharper the molecular weight distribution, the more uniform the dissolution and peeling action by the alkaline aqueous solution occurs, improving the releasability, which is preferable. 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, and more preferably 1.2 or more.

[0054] The hydroxyl group-containing urethane resin may have an amine value. When the hydroxyl group-containing urethane resin has an amine value, the amine value is preferably 0.1 to 20 mgKOH / g, and more preferably 1 to 10 mgKOH / g.

[0055] The hydroxyl group-containing urethane resin is not particularly limited, and is preferably, for example, a resin obtained by reacting a polyol, a hydroxy acid, and a polyisocyanate. The use of a hydroxy acid can impart an acid value to the urethane resin, thereby improving the releasing property. More preferably, the resin is obtained by further reacting a polyamine with a resin obtained by reacting a polyol, a hydroxy acid, and a polyisocyanate.

[0056] The polyisocyanate constituting the release layer is not particularly limited and can be selected from known polyisocyanates, such as aliphatic polyisocyanates and araliphatic polyisocyanates.

[0057] As the aliphatic polyisocyanate, known ones can be used, and aliphatic diisocyanates, alicyclic diisocyanates, araliphatic diisocyanates, or derivatives thereof can be used. Aliphatic diisocyanates include aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanatomethyl caproate; 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), methyl 2,4- Examples of suitable diisocyanates include alicyclic diisocyanates such as cyclohexane diisocyanate, methyl 2,6-cyclohexane diisocyanate, 1,4-bis(isocyanatomethyl)cyclohexane, and 1,3-bis(isocyanatomethyl)cyclohexane; araliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω,ω'-diisocyanato-1,4-diethylbenzene, and 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene or a mixture thereof; and polyisocyanates such as allophanate, nurate, biuret, or adduct derivatives derived from these diisocyanates, or complexes thereof.

[0058] As the aromatic polyisocyanate, known ones can be used, and aromatic diisocyanates or derivatives thereof can also be used. Examples of aromatic diisocyanates include toluene diisocyanate, diphenylmethane diisocyanate, allophanate, nurate, biuret or adduct derivatives derived from these diisocyanates, or complexes thereof.

[0059] The polyisocyanate is preferably an adduct polyisocyanate (adduct form), biuret polyisocyanate (biuret form), or isocyanurate polyisocyanate (isocyanurate form) of tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), or hexamethylene diisocyanate (HDI), and more preferably a trimethylolpropane adduct form (HDI-TPM), biuret form, or isocyanurate form derived from hexamethylene diisocyanate.

[0060] [Alkaline treatment method] The method for recycling the recycled polyolefin resin (Y) from a flexible packaging having a polyolefin resin film (X) layer and a printed layer is not particularly limited, and examples thereof include a method of treating with an acid, a method of treating with an alkali, a method of irradiating with ultrasound, and a method of mechanically scraping off the printed layer. From the viewpoint of being able to remove the printed layer, adhesive layer, etc. from the flexible packaging and selectively recycle the polyolefin resin with high efficiency, alkali treatment is preferred as a recycling method.

[0061] The alkali treatment method can include a step of immersing a flexible packaging material having a polyolefin resin film (X) layer and a print layer in an alkaline aqueous solution. The alkaline aqueous solution penetrates into the flexible packaging from its edge, dissolving or swelling the printed layer, adhesive layer, release layer, aluminum layer, alumina layer, etc., and thereby removing the polyolefin resin film (X) layer. To efficiently remove the polyolefin resin film (X) layer, the flexible packaging is cut or crushed and then immersed in the alkaline aqueous solution. In this case, each layer, such as the printed layer, adhesive layer, release layer, aluminum layer, and alumina layer, is exposed on the cross section and comes into contact with the alkaline aqueous solution, which is preferable.

[0062] The alkaline compound used in the alkaline aqueous solution is not particularly limited, and examples thereof include sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH)), ammonia, barium hydroxide (Ba(OH)), and sodium carbonate (NaCO). More preferred 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 mass %, more preferably 1 to 5 mass %, based on the alkaline aqueous solution. Within this range, the alkaline aqueous solution can have sufficient alkalinity for desorption.

[0063] 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 packaging material 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 1,000 to 1,000,000 times the mass of the flexible packaging material. In order to improve the efficiency of removing the polyolefin resin film (X) layer, it is preferable to stir or circulate the alkaline aqueous solution during immersion. The rotation speed for stirring is preferably 80 to 250 rpm, more preferably 80 to 200 rpm.

[0064] The melt mass-flow rate (MFR) of the recycled polyolefin resin (Y) depends on the configuration of the flexible packaging and the recycling method, but is preferably 5 to 20 g / 10 min, more preferably 5 to 15 g / 10 min. By having a melt mass-flow rate within the above range, it is possible to provide a molding material suitable for various molding processes such as injection molding and extrusion molding.

[0065] <Method of manufacturing molding material> 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 order: When the molding material includes a masterbatch (Z), it further includes the following step 4. (Step 1) A step of treating cut or crushed pieces of a flexible packaging body having a polyolefin resin film (X) layer and a printed layer with an alkali to remove pieces of the polyolefin resin film (X) from the cut or crushed pieces; (Step 2) a step of washing the polyolefin resin film (X) piece with water; (Step 3) A step 3 of processing a piece of polyolefin resin film (X) to obtain recycled polyolefin resin (Y); (Step 4) A step of mixing the recycled polyolefin resin (Y) obtained in step 3 with the masterbatch (Z).

[0066] (Process 1) Step 1 is a step of immersing cut or crushed pieces of printed matter or laminated material, which is a flexible packaging material, in an alkaline aqueous solution to remove pieces of polyolefin resin film (X) from the cut or crushed pieces. The method for crushing the flexible packaging is not particularly limited, and examples thereof include methods using a jaw crusher, impact crusher, cutter mill, stamp mill, ring mill, roller mill, jet mill, or hammer mill. The conditions for immersing the cut or crushed material in the alkaline aqueous solution can be the same as those described above in the section [Alkali Treatment Method].

[0067] (Process 2) Step 2 is a step of washing with water the polyolefin resin film (X) pieces obtained in step 1 to remove the alkaline aqueous solution adhering to the polyolefin resin film (X) pieces. This step may further include a drying step, if necessary.

[0068] (Step 3) Step 3 is a step of processing the pieces of polyolefin resin film (X) obtained in step 2 to obtain recycled 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) pieces as needed before processing. Mixing of the polyolefin resin film (X) pieces with the optional components can be carried out using a Henschel mixer, a tumbler, a disper, or the like. The processing step involves melt-kneading the materials using a batch mixer such as a kneader, a roll mill, a super mixer, a Henschel mixer, a Schuggie mixer, a vertical granulator, a high-speed mixer, a Farmatrix, a ball mill, a steel mill, a sand mill, a vibration mill, an attritor, or a Banbury mixer; a twin-screw extruder, a single-screw extruder, or a rotor-type twin-screw kneader; and then processing the materials into a form suitable for use as a molding material using a pelletizer or the like. In step 3, it is preferable to use a twin-screw extruder for melt-kneading. Suitable forms of the molding material include pellets, powder, granules, beads, and the like.

[0069] <Masterbatch (Z)> The molding material of the present invention may further contain a masterbatch (Z). The masterbatch (Z) is not particularly limited as long as it is compatible with the recycled polyolefin resin (Y), and generally, a mixture of a thermoplastic resin such as a polyethylene resin or a polypropylene resin and a colorant can be used. The thermoplastic resin contained in the masterbatch (Z) may be used alone or in combination of two or more types.

[0070] The colorant is not particularly limited as long as it is one that is generally used in masterbatches, and examples thereof include inorganic pigments such as titanium oxide, chrome titanium iron, red iron oxide, ultramarine, and carbon black; and organic pigments such as azo pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments, and phthalocyanine pigments.

[0071] Examples of inorganic pigments include CI Pigment White 6, Pigment Brown 24, Pigment Red 101, Pigment Blue 29, and Pigment Black 7. Examples of azo pigments include CI Pigment Yellow 180, 181, Pigment Orange 64, and Pigment Red 144, 166, 214, and 221. Examples of quinacridone pigments include CI Pigment Violet 19 and Pigment Red 122. Examples of perylene pigments include CI Pigment Red 149 and 178. Examples of diketopyrrolopyrrole pigments include CI Pigment Red 254. Examples of phthalocyanine pigments include CI Pigment Blue 15:1 and 15:3, and Pigment Green 7 and 36. These colorants may be used alone or in combination of two or more.

[0072] <Optional ingredients> The molding material of the present invention may further contain optional components such as known additives, within the range that does not impair the effects of the present invention. The additive is preferably an additive that does not react with alkaline compounds or has very little reactivity with alkaline compounds. Examples of such additives include neutral or basic additives. In this case, the influence of alkaline compounds that may be contained in the recycled 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 flexible packaging. When the recycling process includes an alkali treatment, even if multiple water washing steps are performed after the alkali treatment, the resulting recycled polyolefin resin (Y) tends to contain trace amounts of alkaline compounds contained in the alkaline aqueous solution and exhibit alkaline properties. When an additive that does not react with alkali compounds or has very little reactivity with alkali compounds is used, it is possible to suppress the deterioration of low-molecular-weight components in the recycled polyolefin resin (Y) and the decrease in melt tension of the recycled polyolefin resin (Y) due to the thermal history of the recycling process such as the pelletizing process or the molding process. As a result, the molding material of the present invention can maintain good moldability, which is preferable.

[0073] Examples of additives that do not react with alkaline compounds or have very little reactivity with alkaline compounds include at least one antioxidant selected from the group consisting of phenolic and phosphorus-based antioxidants; fatty acid amide-based antioxidants, alkylene fatty acid amide-based antioxidants, metal soap-based antioxidants, and fatty acid at least one lubricant selected from the group consisting of ester-based lubricants; hindered amine-based weathering stabilizers; and waxes having an acid value of 5 mg KOH / g or less; Anionic surfactants and nonionic surfactants and at least one antistatic agent selected from the group consisting of: These additives do not react with alkaline compounds or have very little reactivity with alkaline compounds, so there is no risk of impairing the inherent properties of the material even when the molding material is placed under alkaline conditions.

[0074] Examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, 2,2'-methylene-bis-(4-methyl-6-t-butylphenol), 2,2'-methylene-bis-(4-ethyl-6-t-butylphenol), 4,4'-thiobis-(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis-(3-methyl-6-t-butylphenol), 3,9-bis[{1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methyl tetrakis-{methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate}methane, and bis{(3,3'-bis-4'-hydroxy-3'-t-butylphenyl)butyric acid}glycol ester.

[0075] Examples of phosphorus-based antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 4,4'-butylidene-bis-(3-methyl-6-t-butylphenyl-di-tridecyl) phosphite, cyclic neopentanetetraylbis(octadecyl phosphite), trisdiphenyl phosphite, diisodecylpentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenathren-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-methylenebis(4,6-t-butylphenyl)octylphosphite.

[0076] These antioxidants may be used alone or in combination of two or more. The amount of antioxidant added is preferably 0.01 to 1 mass %, more preferably 0.03 to 0.5 mass %, based on the mass of the molding material. An amount of 0.01 mass % or more is preferred in terms of antioxidant properties, and an amount of 1 mass % or less is preferred in terms of processability.

[0077] Examples of fatty acid amide lubricants include aliphatic monocarboxylic acid amides 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; N-substituted aliphatic monocarboxylic acid amides such as N-oleyl oleic acid amide, N-oleyl stearic acid amide, and N-stearyl oleic acid amide; aliphatic biscarboxylic acid amides such as methylene bisstearic acid amide and ethylene bisstearic acid amide; N,N'-ethylene-bis-oleylamide; N,N'-ethylene bisstearic acid amide; and N,N'-methylene bisstearic acid amide.

[0078] Examples of metal soap-based lubricants include metal salts of higher fatty acids such as calcium stearate, magnesium stearate, barium stearate, zinc stearate, aluminum stearate, lithium stearate, calcium laurate, magnesium laurate, barium laurate, zinc laurate, aluminum laurate, and lithium laurate.

[0079] Fatty acid ester lubricants are made by esterifying one or more fatty acids to an alcohol.

[0080] As the alcohol, a monohydric or polyhydric alcohol can be used. The monohydric alcohol is preferably a higher alcohol having 6 or more carbon atoms, more preferably a higher alcohol having 10 or more carbon atoms, such as mystyryl alcohol, stearyl alcohol, and oleyl alcohol. Examples of polyhydric alcohols include dihydric alcohols and trihydric or higher alcohols. Examples of dihydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, and 1,6-hexanediol. Examples of trihydric or higher alcohols include glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, mannitol, and sorbitol. Among these, glycerin, propylene glycol, pentaerythritol, and dipentaerythritol are preferred, and glycerin and dipentaerythritol are more preferred.

[0081] Examples of fatty acids include saturated fatty acids such as caproic acid, caprylic acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, behenic acid, lignocenic acid, cerotic acid, montanic acid, and melissic acid; unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid, linolenic acid, arachidonic acid, prasidic acid, erucic acid, and ricinoleic acid; hydroxy fatty acids such as 12-hydroxystearic acid; and aliphatic dicarboxylic acids such as adipic acid. Among 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.

[0082] These lubricants may be used alone or in combination of two or more. The amount of lubricant added is preferably 0.01 to 1 mass %, more preferably 0.03 to 0.5 mass %, based on the mass of the molding material. An amount of 0.01 mass % or more is preferred in terms of activity, and an amount of 1 mass % or less is preferred in terms of processability.

[0083] Examples of hindered amine weathering stabilizers include dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, 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-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate, bis(2,2,6,6-tetramethyl-4-piperidyl)separate, and bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-t-4-hydroxybenzyl)-2-n-butylmalonate.

[0084] Examples of waxes having an acid value of 5 mgKOH / g or less include natural waxes and synthetic waxes. Examples of natural waxes include vegetable waxes such as calidrilla wax, carnauba wax, rice wax, and Japan wax; animal waxes such as beeswax, lanolin, and spermaceti; mineral waxes such as montan wax, ozokerite, and ceresin; and petroleum waxes such as paraffin wax, microcrystalline wax, and petrolatum. Synthetic waxes include semi-synthetic waxes and fully synthetic waxes. Semi-synthetic waxes are natural waxes or natural wax-like materials that have been modified by chemical processes such as esterification, amidation, and neutralization with acidic waxes. Synthetic waxes include synthetic hydrocarbons such as polyethylene waxes, polypropylene waxes, and polystyrene waxes.

[0085] These waxes having an acid value of 5 mgKOH / g or less may be used alone or in combination of two or more kinds. The amount of wax having an acid value of 5 mgKOH / g or less added is preferably 0.5 to 50 mass %, more preferably 1 to 30 mass %, based on the mass of the molding material. An amount of 0.5 mass % or more is preferred in terms of fluidity adjustment, and an amount of 50 mass % or less is preferred in terms of processability.

[0086] Examples of anionic surfactant-based antistatic agents include carboxylates such as alkali metal salts of higher fatty acids; sulfates such as higher alcohol sulfates and higher alkyl ether sulfates; sulfonates such as alkylbenzene sulfonates, alkyl sulfonates and paraffin sulfonates; and phosphates such as higher alcohol phosphates.

[0087] Examples of nonionic surfactants include 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; and polyhydric alcohol-type nonionic surfactants such as fatty acid esters of polyethylene oxide or glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbit or sorbitan, alkyl ethers of polyhydric alcohols, and fatty amides of alkanolamines.

[0088] These antistatic agents may be used alone or in combination of two or more. The antistatic agent is preferably at least one antistatic agent selected from the group consisting of fatty acid sulfonates and fatty acid esters. The amount of the antistatic agent added is preferably 0.05 to 1 mass %, more preferably 0.1 to 0.5 mass %, based on the mass of the molding material. An amount of 0.05 mass % or more is preferred in terms of antistatic properties, and an amount of 1 mass % or less is preferred in terms of transparency and low bleeding properties.

[0089] <Molded body> A molded article 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. The molding material of the present invention contains a recycled polyolefin resin (Y) that has a high recyclability, good moldability, and a sufficiently high total light transmittance, and is preferably colorless, transparent, or light in color, and therefore can provide molded articles colored to desired colors, from colorless, transparent, to light, or light to dark, regardless of the molding method. The molded articles of the present invention can be used for a variety of purposes, such as home appliances, stationery, automobile parts, toys, sporting goods, medical supplies, and building and construction materials. [Example]

[0090] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, the units "parts" and "%" used for the blend amounts and solid content concentrations in the examples represent "parts by mass" and "% by mass," respectively.

[0091] <Measurement of total light transmittance> The recycled polyolefin resin (Y) was melt-extruded at 200°C using a T-die film molding machine to produce a film with a thickness of 100 μm. The total light transmittance of the produced film was measured using Haze Guard Plus (Gardner) in accordance with JIS K 7361.

[0092] <Melt Mass Flow Rate (MFR) Measurement> The MFR was measured in accordance with JIS K-7210.

[0093] <Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn)> Mw, Mn and molecular weight distribution (Mw / Mn) were measured by GPC (gel permeation chromatography) and calculated as molecular weights converted using polystyrene as a standard substance. The measurement conditions are shown below. GPC equipment: Showa Denko Shodex GPC-104, Column: Two Showa Denko "Shodex LF-404" columns and one Showa Denko "Shodex LF-G" column connected in series. Detector: RI (differential refractometer), Measurement conditions: column temperature 40°C, Eluent: tetrahydrofuran, Flow rate: 0.3mL / min.

[0094] <Acid value (AV) measurement> Approximately 1 g of sample was precisely weighed into a stoppered Erlenmeyer flask and dissolved in 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2 / 1). Phenolphthalein test solution was added as an indicator and the mixture was allowed to stand for 30 seconds. The solution was then titrated with 0.1 N alcoholic potassium hydroxide solution until it turned a pale pink color. The acid value was calculated using the following formula: Acid value (mgKOH / g) = {(5.611 x a x F) / S} / (solid concentration of sample / 100) In the above formula, the abbreviations represent the following parameters. S: sample amount (g), a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml), F: Potency of 0.1N alcoholic potassium hydroxide solution.

[0095] <Hydroxyl value (OHV) measurement> Approximately 1 g of sample was precisely weighed into a stoppered Erlenmeyer flask and dissolved in 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2 / 1). Exactly 5 ml of an acetylating agent (25 g of acetic anhydride dissolved in pyridine to a volume of 100 ml) was then added and stirred for approximately 1 hour. Phenolphthalein test solution was added as an indicator and the mixture was stirred for 30 seconds. The solution was then titrated with 0.1 N alcoholic potassium hydroxide solution until it turned a pale pink color. The hydroxyl value was calculated using the following formula: Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (solid concentration of sample / 100) + D In the above formula, the abbreviations represent the following parameters. S: sample amount (g), a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml), b: Consumption of 0.1N alcoholic potassium hydroxide solution in the blank experiment (ml); F: Potency of 0.1N alcoholic potassium hydroxide solution; D: Acid value (mgKOH / g).

[0096] <Production of Primer Composition 1> In a reactor equipped with a reflux condenser, a dropping funnel, a gas inlet, a stirrer, and a thermometer, 198.0 parts of poly(propylene glycol) adipate diol with a number average molecular weight (Mn) of 2,000, 13.3 parts of 2,2-dimethylolbutanoic acid, 76.0 parts of isophorone diisocyanate, and 200 parts of methyl ethyl ketone were charged while introducing nitrogen gas. The mixture was reacted at 90 ° C for 5 hours to obtain a urethane prepolymer solution having terminal isocyanate groups. A mixture of 12.2 parts of 2-(2-aminoethylamino)ethanol, 0.4 parts of ethanolamine, and 350 parts of isopropyl alcohol was added dropwise to the resulting urethane prepolymer solution at room temperature over 60 minutes, and then reacted at 70 ° C for 3 hours. The solids concentration was then adjusted to 30% using 150 parts of methyl ethyl ketone to obtain a polyurethane resin solution. The resulting polyurethane resin had Mw=33,000, Mw / Mn=2.9, an acid value of 16.8 mgKOH / g, and a hydroxyl value of 23.2 mgKOH / g. 87 parts of the above polyurethane resin solution, 5 parts of ethyl acetate, 5 parts of isopropyl alcohol, and 3 parts of silica (hydrophilic silica particles with an average particle size of 3.8 μm, manufactured by Mizusawa Chemical Industries, Ltd., "P-73") were stirred and mixed using a disper to obtain primer composition 1.

[0097] <Production of Releasable Adhesive 2> A four-neck separable flask was charged with 82 parts of terephthalic acid, 682 parts of isophthalic acid, 236 parts of adipic acid, 236 parts of ethylene glycol, 525 parts of neopentyl glycol, and 405 parts of 1,6-hexanediol, and an esterification reaction was carried out at 220 to 260°C. After distilling off a predetermined amount of water, the pressure was gradually reduced to 1 mmHg or less, and a deglycolization reaction was carried out at 240 to 260°C for 5 hours. Then, 2 parts of isophorone diisocyanate was gradually added, and the reaction was carried out at 150°C for approximately 2 hours to obtain a polyesterurethane polyol. 2.83 parts of trimellitic anhydride were added to 100 parts of this polyesterurethane polyol, and the reaction was carried out at 180°C for approximately 2 hours. The mixture was then diluted with ethyl acetate to a solids concentration of 50%, yielding a partially acid-modified polyesterurethane polyol solution. The resulting partially acid-modified polyester urethane polyol had Mn=6,000 and an acid value of 16.5 mgKOH / g. 100 parts of the polyesterurethane polyol solution and 7.94 parts of an ethyl acetate solution of HDI biuret with a solids concentration of 95% were mixed, and then ethyl acetate was added to obtain a solution of adhesive 2 with releasability with a solids concentration of 30%.

[0098] <Production of flexible packaging having a polyolefin resin film (X) layer> (Manufacturing of soft packaging body 1) Primer composition 1 was diluted with an ethyl acetate / isopropyl alcohol mixed solvent (70 / 30 by mass) to a Zahn cup #3 (manufactured by Rigo Co., Ltd.) for 15 seconds (25°C). Primer composition 1 and ink 1 (organic solvent-based gravure ink "PANNECO AM 92 Black" manufactured by Toyo Ink Co., Ltd.) were then printed in that order onto a corona-treated oriented polypropylene (OPP) film (thickness 20 μm, MFR 6 g / 10 min) using a gravure printing machine equipped with a gravure plate with a plate depth of 35 μm, and dried at 50°C to obtain flexible packaging 1 having a configuration of OPP substrate / release layer 1 / printed layer 1.

[0099] (Manufacture of soft packaging body 2) Using the same manufacturing process as for flexible packaging 1, release layer 1 and printed layer 1 were sequentially formed on the OPP substrate, yielding a laminate having a configuration of OPP substrate / release layer 1 / printed layer 1. Using a dry laminating machine, adhesive 1 ("TM-340V / CAT-29B" manufactured by Toyo-Morton) was applied to the OPP substrate of this laminate, and an aluminum-deposited non-oriented polypropylene (VMCPP) film (thickness 25 μm, MFR 4 g / 10 min) was laminated thereon at a line speed of 40 m / min, yielding flexible packaging 2 having a configuration of VMCPP substrate / adhesive layer 1 / OPP substrate / release layer 1 / printed layer 1. The amount of adhesive 1 applied after drying was 10 g / m 2 It was decided.

[0100] (Manufacturing of soft packaging body 3) Flexible packaging 3 was obtained using the same manufacturing process as flexible packaging 2, except that ink 1 was changed to ink 2 (organic solvent-based gravure ink "Lio Alpha S R92 Ink" manufactured by Toyo Ink Co., Ltd.), and had a configuration of VMCPP substrate / adhesive layer 1 / OPP substrate / release layer 1 / printing layer 2.

[0101] (Production of soft packaging body 4) Flexible packaging body 4 was obtained using the same manufacturing process as flexible packaging body 2, except that adhesive 1 was changed to adhesive 2, and had a configuration of VMCPP substrate / adhesive layer 2 / OPP substrate / release layer 1 / printed layer 1.

[0102] (Manufacturing of soft packaging body 5) Using the same manufacturing process as for flexible packaging 1, release layer 1 and printed layer 1 were formed in sequence on the OPP substrate, yielding a laminate having a configuration of OPP substrate / release layer 1 / printed layer 1. Using a dry laminating machine, adhesive 1 was applied to printed layer 1 of this laminate, and a VMCPP film was then laminated onto this at a line speed of 40 m / min, yielding flexible packaging 5 having a configuration of OPP substrate / release layer 1 / printed layer 1 / adhesive layer 1 / VMCPP substrate. The amount of adhesive 1 applied after drying was 10 g / m 2 It was decided.

[0103] (Manufacture of soft packaging body 6) Flexible packaging body 6, which has a structure of OPP substrate / release layer 1 / printed layer 1 / adhesive layer 2 / VMCPP substrate, was manufactured using the same manufacturing process as flexible packaging body 5, except that adhesive 1 was changed to adhesive 2.

[0104] <Production of recycled polyolefin resin (Y)> (Production of recycled polyolefin resin (Y1)) Flexible packaging 1 was cut into pieces measuring 4 cm x 4 cm, immersed in a 2% aqueous sodium hydroxide solution, and stirred at 40°C for 30 minutes to remove the OPP substrate pieces, which were then washed with water and dried. The OPP substrate pieces were placed in a single-screw extruder, melt-extruded at 200°C, and cut using a pelletizer. In this way, pellets of recycled polyolefin resin (Y1) recycled from flexible packaging were obtained.

[0105] (Production of Recycled Polyolefin Resins (Y2) to (Y6)) In the same manner as for the recycled polyolefin resin (Y1), OPP or CPP substrate pieces were removed from flexible packaging materials 2 to 6, washed with water, and dried. The obtained OPP or CPP substrate pieces were placed in 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 flexible packaging materials were obtained.

[0106] (Production of recycled polyolefin resin (Y7)) The flexible packaging 1 was cut into pieces measuring 4 cm x 4 cm. The pieces of the flexible packaging were fed 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 colored recycled polyolefin resin (Y7) were obtained.

[0107] (Production of recycled polyolefin resin (Y8)) The flexible packaging 5 was cut into pieces measuring 4 cm x 4 cm. The pieces of the flexible packaging were fed 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 colored recycled polyolefin resin (Y8) were obtained.

[0108] The total light transmittance and MFR of the resulting recycled polyolefin resin (Y) were measured. The main production conditions and evaluation results of recycled polyolefin resin (Y) are shown in Table 1.

[0109] [Table 1]

[0110] <Manufacturing of Masterbatch (Z1)> 70 parts of polypropylene resin 1 (Prime Polypro J105P manufactured by Prime Polymer Co., Ltd.) and 30 parts of carbon black (Mitsubishi Carbon #30 manufactured by Mitsubishi Chemical Corporation) were placed in a Super Mixer (manufactured by Kawata Co., Ltd.) and stirred at 25°C for 3 minutes to obtain a mixture. This mixture was then placed in a twin-screw extruder (manufactured by Nippon Placon Co., Ltd.), melt-extruded at 200°C, and cut with a pelletizer to obtain masterbatch (Z1). The blending composition is shown in Table 2.

[0111] (Manufacturing of Masterbatches (Z2) to (Z22)) Masterbatches (Z2) to (Z22) were obtained in the same manner as for masterbatch (Z1), except that the blending compositions were changed as shown in Table 2.

[0112] [Table 2]

[0113] The abbreviations in Table 2 are as follows: 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 (Asahi Kasei Corporation "Suntech M2270") Mitsubishi Carbon #30: Carbon black (manufactured by Mitsubishi Chemical Corporation), Irganox 1010: phenolic antioxidant (manufactured by BASF), Irganox 1076: phenolic antioxidant (manufactured by BASF), Irganox 245: phenolic antioxidant (manufactured by BASF), Irgafos168: Phosphorus-based antioxidant (manufactured by BASF), ADK STAB PEP-36: Phosphorus-based antioxidant (ADEKA Corporation's "ADK STAB PEP-36") IrganoxPS 802 FL: sulfur-based antioxidant (manufactured by BASF), Nocrac CD: Amine antioxidant (Ouchi Shinko Chemical Industry Co., Ltd.'s "Nocrac CD") Erucic acid amide: fatty acid amide lubricant (Lion Specialty Chemicals' "Armoslip E Powder") Oleic acid amide: fatty acid amide lubricant (Lion Specialty Chemicals' "Armoslip CP Powder") Ethylene bisstearic acid amide: fatty acid amide lubricant (NOF Corp. "Alflo H-50L") Calcium stearate: metal soap lubricant (manufactured by Taihei Chemical Industry Co., Ltd.), Magnesium stearate: metal soap lubricant (manufactured by Taihei Chemical Industry Co., Ltd.), Stearic acid triglyceride: aliphatic ester lubricant (manufactured by Tokyo Chemical Industry Co., Ltd.), CHIMASORB 770DF: Hindered amine weathering stabilizer (manufactured by BASF), CHIMASORB 2020FDL: Hindered amine weathering stabilizer (manufactured by BASF), Hiwax NL500: Polyethylene wax, acid value 1 mg KOH / g or less (Mitsui Chemicals, Inc.) Viscol 550-p: Polypropylene wax, acid value 1 mg KOH / g or less (Sanyo Chemical Industries, Ltd.) LICOWAX E: Polypropylene wax, acid value 15 mg KOH / g (Clariant), TS-2: Stearyldiethanolamine (Kao Corporation "Electrostripper TS-2") TS-5: Glycerin monostearate (Kao Corporation's "Electrostripper TS-5") Catiogen: stearic acid dimethylaminopropylamide (Dai-ichi Kogyo Seiyaku Co., Ltd.).

[0114] <Preparation of molding material and production of film-shaped molded body> [Examples 1 to 6] The pellets of the recycled polyolefin resins (Y1) to (Y6) were used as molding materials 1 to 6. The obtained molding materials were extruded at 200°C using a T-die extruder to produce film-like molded products 1 to 6 with a thickness of 50 μm. All molding materials were moldable, and colorless and transparent films were obtained. The blending compositions are shown in Table 3.

[0115] [Example 7] 65 parts of recycled polyolefin resin (Y1) and 35 parts of masterbatch (Z1) were tumbled to prepare molding material 7. Except for using the obtained molding material, a film-shaped molded product 7 was produced in the same manner as in Examples 1 to 6. The moldable product was able to obtain a film colored in the desired color. The blending composition is shown in Table 3.

[0116] [Examples 8 to 33] Molding materials 8 to 14 and 19 to 39 were obtained in the same manner as molding material 7, except that the types and compounding ratios of the recycled polyolefin resin (Y) and masterbatch (Z1) were changed as shown in Table 3. Film-like molded products 8 to 14 and 19 to 39 were produced in the same manner as in Example 7, except that the obtained molding materials were used. All molding materials could be molded, and films colored in the desired colors were obtained.

[0117] [Comparative Examples 1 to 4] Molding materials 15 to 18 were obtained in the same manner as molding material 7, except that the types and compounding ratios of recycled polyolefin resin (Y) and masterbatch (Z1) were changed as shown in Table 3. Film-like molded bodies 15 to 18 were produced in the same manner as in Example 7, except that the obtained molding materials were used. None of the molding materials could be molded. Furthermore, recycled polyolefin resins (Y7) and (Y8) were deeply colored due to printed layers derived from flexible packaging, and films colored in the desired colors could not be obtained.

[0118] <Evaluation of film-shaped molded product> The obtained film was 0.5 m 2 The number of foreign matters per bottle that could be visually identified was counted and evaluated according to the following criteria. Note that Comparative Examples 1 to 4 were not evaluated because bottles could not be molded. The evaluation results are shown in Table 3. 〇 (Good): The number of foreign objects is less than 50, △ (Acceptable): The number of foreign objects is 50 or more but less than 200. × (defective): The number of foreign objects is 200 or more.

[0119] [Table 3]

[0120] <Production of Bottle-Shaped Molded Article> [Examples 51 to 56] Molding materials 1 to 6 were each blow molded at 200°C using a blow molding machine to produce bottle-shaped molded bodies 51 to 56 with a thickness of 1 mm. All were moldable, and colorless, transparent bottles were obtained. 50 bottles were produced for each example. The blending compositions are shown in Table 4.

[0121] [Examples 57 to 85] Molding materials 19 to 39 were blow molded in the same manner as in Examples 51 to 56 to produce bottle-shaped molded products 57 to 85. All of them were moldable, and bottles colored to the desired colors were obtained. 50 bottles were produced for each Example. The blending compositions are shown in Table 4.

[0122] [Comparative Examples 5 to 8] Molding materials 15 to 18 were blow molded in the same manner as in Examples 51 to 56 to produce bottle-shaped molded bodies 86 to 89. None of them could be molded. Furthermore, recycled polyolefin resins (Y7) and (Y8) were deeply colored due to printed layers derived from flexible packaging, and bottles colored to the desired color could not be obtained. The blending compositions are shown in Table 4.

[0123] <Evaluation of bottle-shaped molded product> For the bottles obtained in each example, the number of bottles in which visually noticeable bubbles were observed per 50 bottles was counted. Note that Comparative Examples 5 to 8 were not evaluated because bottles could not be molded. The evaluation results are shown in Table 4. Good: Effervescence was observed in 1 or less bottles out of 50. △ (Acceptable): 2 to 5 bottles out of 50 showed bubbles. × (bad): Foaming was observed in 6 or more bottles out of 50.

[0124] [Table 4]

[0125] From the above results, it was found that the molding material of the present invention has a high recyclability and good moldability, and can provide molded articles such as films and bottles that are colorless, transparent, or of a desired color. It was also found that the molding material of the present invention can be used to provide high-quality molded articles that are free of or have little foreign matter and foaming. It is presumed that the use of neutral or basic additives that do not react with alkaline compounds or have low reactivity with alkaline compounds suppresses the generation of foreign matter and foam-causing components such as moisture that are caused by alkaline compounds remaining in the recycled polyolefin resin (Y).

[0126] This application claims priority based on Japanese Patent Application No. 2020-111681, filed on June 29, 2020, the disclosure of which is incorporated herein in its entirety.

Claims

1. A molding material comprising a recycled polyolefin resin (Y) derived from a flexible packaging material having a polyolefin resin film (X) layer and a printed layer, The recycled polyolefin resin (Y) is a recycled resin obtained by recycling the flexible packaging body, including alkali treatment, and contains residual alkaline compounds; the molding material contains at least one additive selected from the group consisting of a phenol-based antioxidant, a phosphorus-based antioxidant, a fatty acid amide-based lubricant, a metal soap-based lubricant, a fatty acid ester-based lubricant, a hindered amine-based weather stabilizer, a wax having an acid value of 5 mgKOH / g or less, and an antistatic agent composed of a nonionic surfactant; The recycled polyolefin resin (Y) has a total light transmittance of 70% or more in the form of a film having a thickness of 100 μm, A molding material, wherein the content of recycled polyolefin resin (Y) is 95 mass% or more based on the total amount of the molding material.

2. The molding material according to claim 1, wherein the recycled polyolefin resin (Y) has a melt mass flow rate of 5 to 20 g / 10 min.

3. The molding material according to claim 1 or 2, wherein the polyolefin resin film (X) has a melt mass flow rate of 3 to 12 g / 10 min.

4. The molding material according to any one of claims 1 to 3, further comprising a colorant.

5. A molded body made from the molding material described in any one of claims 1 to 4.

6. A step 1 of treating cut or crushed pieces of a flexible packaging body having a polyolefin resin film (X) layer and a printed layer with an alkali to remove pieces of the polyolefin resin film (X) from the cut or crushed pieces; Step 2 of washing the polyolefin resin film (X) piece with water; Step 3 of processing the polyolefin resin film (X) pieces to obtain recycled polyolefin resin (Y); The method for producing the molding material according to any one of claims 1 to 4, further comprising the step of mixing the recycled polyolefin resin (Y) obtained in step 3 with at least one of the additives.

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