JP7288112B1 - Manufacturing method of recycled plastic - Google Patents

Abstract

Kind Code: A1 An object of the present invention is to provide a recycled plastic with excellent moldability that can be efficiently and easily recycled as a material from a printed matter or a laminated laminate without performing a step of separating a base material and a printed layer. It is to provide a manufacturing method. A recycled plastic manufacturing method for obtaining a recycled plastic (B) from a printed matter or a laminated laminate (A) using an extrusion device equipped with a screw and a discharge part, comprising: ) contains a substrate layer and a printed layer, has a chlorine content of 0.4% by mass or less, and contains 80% by mass or more of a polyolefin resin, and the printed matter or laminated laminate ( A) is heated and melted and kneaded to obtain a resin composition (a), and the resin composition (a) is extruded from the discharge port of an extrusion device at a pressure of 18 MPa or less. How plastic is made. [Selection figure] None

Description

TECHNICAL FIELD The present invention relates to a method for producing a recycled plastic by material recycling a laminate containing a polyolefin resin.

In recent years, packages made of plastic films, plastic bottles, and other plastic products have been discarded or dumped into the ocean as garbage, causing environmental pollution problems. Plastic products are pulverized in seawater to become submicron-sized fragments (microplastics) and float in seawater. Microplastics are ingested by marine organisms such as fish and concentrated in their bodies. Therefore, there are concerns about the health effects of seabirds and humans that consume marine organisms as food.

Various plastic substrates such as polyester substrates, nylon substrates (NY), polypropylene substrates (PP), and polyethylene substrates (PE) are used as film substrates in multi-layered food packaging packages. . A multi-layered food packaging package, for example, is printed with printing ink on a first film substrate, and a second film substrate is attached onto the printed layer via an adhesive layer as necessary. After being combined, it is cut and heat-sealed to form the package. However, due to compatibility and other problems, it is difficult to recycle a multi-layered food packaging package containing a plurality of dissimilar materials.

Food packaging packages are usually discarded as garbage, but in some cases they are recycled. When recycling the package, first, impurities contained in the package are removed, pulverized, alkali treatment etc. are performed as necessary (Patent Document 1), and the washed material is melted as a raw material and made into pellets. The obtained pellets are then processed into new products. However, in the recycling method described above, most of the printed layer contained in the package remains without being removed, and the quality of the obtained pellets and the like is poor.

Recently, as in Patent Documents 2 and 3, a technique is disclosed in which a primer layer and a detachable printed layer are provided on a plastic substrate, and the printed pattern and laminated packaging material are separated and detached. However, increasing the number of processes increases the time it takes to complete processing and the amount of setup work that involves humans, which may lead to a decrease in production volume.

In other words, there is a need for a method of producing high-quality recycled plastics by simple separation, washing, and dehydration without the step of removing the printed layer.

Japanese Patent Application Laid-Open No. 2014-19003 Japanese Patent Application Laid-Open No. 2001-031899 JP 2020-196855 A

The problem to be solved by the present invention is that it is possible to efficiently and simply recycle the material from the printed material or the laminated laminate without performing the detachment process of the base material and the printed layer, and has excellent moldability. To provide a plastic manufacturing method.

As a result of extensive studies, the present inventors have found that the above problems can be solved by using the method for producing recycled plastic described below, and have completed the present invention.

That is, the present invention is a method for producing a recycled plastic, in which a recycled plastic (B) is obtained from a printed matter or a laminated laminate (A) using an extrusion device equipped with a screw and a discharge part,
The printed matter or laminated laminate (A) includes a substrate layer and a printed layer, has a chlorine content of 0.4% by mass or less in the total mass of the printed matter or laminated laminate (A), and contains a polyolefin resin. , containing 80% by mass or more of the total mass of the printed matter or laminate (A),
a step of heating, melting, and kneading the printed matter or laminated laminate (A) in the extruder to obtain a resin composition (a);
The present invention relates to a method for producing a recycled plastic, comprising a step of extruding the resin composition (a) from a discharge port of an extrusion device at a pressure of 18 MPa or less.

The present invention also provides a method for producing a recycled plastic, in which a recycled plastic (B) is obtained from a printed matter or a laminated laminate (A) using an extrusion device equipped with a screw and a discharge section,
The printed matter or laminated laminate (A) includes a substrate layer and a printed layer, has a chlorine content of 0.4% by mass or less in the total mass of the printed matter or laminated laminate (A), and contains a polyolefin resin. , containing 80% by mass or more of the total mass of the printed matter or laminate (A),
A step of heating and melting the printed material or laminated laminate (A) at 120 to 280° C. in the extruder and further kneading to obtain a resin composition (a);
The present invention relates to a method for producing a recycled plastic, including the step of extruding the resin composition (a) from a discharge port of an extrusion device.

The present invention also relates to the method for producing the recycled plastic, wherein the polyolefin resin contained in the printed matter or laminate (A) is a polyethylene resin and/or a polypropylene resin.

The present invention also relates to the method for producing recycled plastic according to any one of claims 1 to 3, wherein the printed matter or laminated laminate (A) further comprises a barrier layer.

In addition, according to the present invention, the printed matter or the barrier layer of the laminated laminate (A) is one or more selected from the group consisting of a vapor deposition layer containing a vapor deposition film, a barrier coat layer, and a barrier adhesive layer. 2. It relates to the method for producing the recycled plastic described in .

The present invention also relates to a method for producing the above recycled plastic, which further includes a water cooling step.

The present invention also relates to the method for producing the recycled plastic, wherein the melt mass flow rate of the printed matter or laminate (A) is 0.5 to 15 g/10 minutes.

The present invention also relates to the method for producing the above recycled plastic, wherein the printed matter or the printed layer of the laminated laminate (A) contains a pigment and a binder resin, and the chlorine content of the binder resin is 5% by mass or less.

The present invention also relates to the above-mentioned method for producing recycled plastic, wherein the screw rotation speed of the extruder is 50 to 1000 RPM.

The present invention also relates to the method for producing the recycled plastic, wherein the pigment content is 30% by mass or less in the total mass of the printed layer.

In addition, the present invention relates to the above recycled plastic, wherein the printed matter or laminated laminate (A) further includes an adhesive layer, and the adhesive layer is a reaction product of a reactive urethane adhesive containing polyisocyanate and polyol. It relates to a manufacturing method.

The present invention also relates to a method for manufacturing a molded product of recycled plastic manufactured by the method for manufacturing recycled plastic.

According to the present invention, there is provided a method for manufacturing a recycled plastic with excellent moldability, which enables efficient and simple material recycling from a printed matter or a laminated laminate without performing a detachment step between a base material and a printed layer. has been able to provide.

Embodiments of the present invention will be described in detail below, but the described embodiments or descriptions of requirements are examples of embodiments of the present invention, and the present invention is not limited to these contents as long as they do not exceed the gist of the present invention. .

In the present invention, the printed matter or laminated laminate (A) may be abbreviated simply as "printed matter or laminate (A)", but has the same meaning.

(Extruder equipped with a screw)
The extrusion device used in the present invention is equipped with a screw. The extrusion device is a device capable of melting and molding commonly used thermoplastic resins, and for example, a known extrusion device described in JP-A-2017-148997 can be used.
Specifically, a supply port for supplying a material, a melt-kneading unit for melting and kneading the material such as a thermoplastic resin supplied from the supply port, and the thermoplastic resin melted and kneaded in the melt-kneading unit. It has a discharge part for discharging.
The melt-kneading unit has a screw, and the material is melted and kneaded by rotation of the screw, shear heat generated from a heat source such as an electric heater, and the material itself. The melted material passes through the mesh of the ejection section and is ejected. Examples of the extrusion apparatus include twin-screw extruders, single-screw extruders, and rotor-type twin-screw kneaders.

(Method for producing recycled plastic (B))
The method for producing the recycled plastic (B) of the present invention preferably has, for example, the following embodiments.
In one embodiment, the printed matter or laminate (A) is preferably in a fragmented shape by cutting or crushing. A method such as crushing is used for fragmentation.
Moreover, the printed matter or laminate (A) is preferably washed, and in the present invention, preferably has a washing step. After that, the printed matter or laminate (A) is processed to obtain a recycled plastic (B). Processing includes heating and melting processes and extrusion processes, which are described in detail below.

(crushing)
Crushing is effective for fragmenting the shape of the printed matter or laminate (A). The crushing method 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 size of the piece of printed matter or laminate (A) is preferably 1 mm to 40 mm in side length, more preferably 8 mm to 20 mm.

(Washing)
The printed matter or laminate (A) or the fragmented printed matter or laminate (A) is preferably washed. The cleaning method may be batch type or continuous type, and may use water, detergent, neutralizer, or alkaline aqueous solution. Also, the washed printed matter or laminate (A) is preferably dehydrated and dried. A centrifugal dehydration method is suitable as a dehydration method, and a hot air drying method is suitable as a drying method.

(processing)
The fragmented or washed printed material or laminate (A) is heated, melted and kneaded in an extruder equipped with a screw to form a resin composition (a). When the resin composition (a) is cooled to 40° C. or lower, it becomes a recycled plastic (B).

Specifically, the steps of obtaining the recycled plastic (B) include a step of supplying the printed material or the laminate (A) from the supply port, and melting and kneading the printed material or the laminate (A) supplied from the supply port. A step of forming a resin composition (a), a step of discharging the resin composition (a) melt-kneaded in the melt-kneading unit, and cooling the resin composition (a) discharged from the discharge unit to produce a recycled plastic (B). The shape of the recycled plastic (B) is not particularly limited, and may be rod-like, particulate, cubic, rectangular parallelepiped, amorphous, and the like.

The printed material or laminate (A) is heated and melted at 120 to 280° C. and further kneaded to form the resin composition (a). Regarding the temperature range in this process, it is necessary to consider the glass transition temperature and melting temperature of the printed matter or laminate (A), the shape of the recycled plastic, and the pressure applied in the molding process. The melting temperature is preferably 160°C to 250°C, more preferably 170°C to 240°C, and even more preferably 180°C to 230°C. It is heated and melted in the temperature range and kneaded to form a uniform recycled plastic (B).
Further, the rotation speed of the screw during kneading is preferably 50 to 1000 RPM. Within the above range, it is possible to suppress the generation of insoluble matter and burning of the resin composition (a) and thus the recycled plastic (B). As a result, good moldability can be maintained.

In the step of obtaining the recycled plastic (B) by discharging the resin composition (a), the resin pressure at the tip discharge portion of the extrusion device is preferably 18 MPa or less, more preferably 15 MPa, and still more preferably 10 MPa. Due to the pressure, impurities are less likely to be contained, and recycled plastic (B) with stable purity can be obtained continuously.
It is preferred to use a screen mesh (metal mesh) at the discharge section of the extruder to remove foreign matter from the pellets being formed. The type of screen mesh (metal net) is not particularly limited, and examples thereof include woven fabrics such as plain weave, twill weave, plain dutch weave and twilled tatami, and punching metal types, with plain weave being preferred.
The size of the screen mesh is preferably 40 mesh or more, more preferably 80 mesh or more, still more preferably 120 mesh or more, in consideration of the pressure of the discharge part and clogging.

Examples of the method for cooling and shredding the discharged resin composition (a) to obtain the recycled plastic (B) include a hot cut method and a strand cut method, but are not particularly limited.

Cooling methods include, for example, air cooling, wind cooling, and water cooling. In the present invention, it is preferable to include a water cooling step. Cooling to 20°C to 80°C is preferable, and cooling to 30°C to 60°C is more preferable.

Moreover, after adding various additives and the like to the fragmented laminate (A), if necessary, the laminate may be processed by an extrusion device. Mixing of the cut or crushed material with optional ingredients can be performed using a Henschel mixer, a tumbler, a disper, or the like.

(Additives for recycled plastic (B), etc.)
The recycled plastic (B) of the present invention can further contain known additives and the like within a range that does not impair the effects of the present invention. Additives include, for example, at least one antioxidant selected from the group consisting of phenols and phosphorus; at least one selected from the group consisting of fatty acid amides, alkylene fatty acid amides, metal soaps, and esters; a hindered amine weather stabilizer; a wax having an acid value of 5 mgKOH/g or less; and at least one antistatic agent selected from the group consisting of fatty acid sulfonates and fatty acid esters.

(Printed matter or laminated laminate (A))
A printed matter or a laminated laminate (A) is used in the present invention. The printed matter or laminated laminate (A) includes a substrate layer and a printed layer.
Specific examples of the configuration include, but are not limited to, the following configurations. In the structural representations (1) to (20) below, "/" means the boundary of each layer. The adhesive layer is not limited to those composed of adhesives used in conventionally known methods such as dry lamination and non-sol lamination, but also includes polyolefin resins and other thermoplastic resins in extrusion lamination.
(1) Substrate/printing layer/adhesive layer/sealant (2) Substrate/printing layer/adhesive layer/intermediate substrate/adhesive layer/sealant (3) Substrate/printing layer/adhesive layer/first Intermediate substrate / adhesive layer / second intermediate substrate / adhesive layer / sealant (4) substrate / printed layer / thermoplastic resin layer (5) substrate / printed layer / (AC agent layer) / heat Plastic resin layer/sealant (6) Substrate/printing layer/(AC agent layer)/thermoplastic resin layer/intermediate substrate/(AC agent layer)/thermoplastic resin layer/sealant (7) Substrate/printing layer/ Adhesive layer/intermediate substrate/(AC agent layer)/thermoplastic resin layer/sealant (8) substrate/printing layer/(AC agent layer)/thermoplastic resin layer/intermediate substrate/adhesive layer/sealant ( 9) Printed layer/substrate (10) Printed layer/substrate/heat sealant layer (11) Printed layer/sealant (12) Printed layer/substrate/adhesive layer/sealant (13) Printed layer/substrate/ Adhesive layer/intermediate substrate/adhesive layer/sealant (14) printed layer/substrate/(AC agent layer)/thermoplastic resin layer/sealant

In the above configuration, the AC agent layer represents an anchor coat agent layer, and ( ) represents an arbitrary configuration. Moreover, each of the above structures preferably further includes a barrier layer, and the preferred form of the barrier layer is at least one selected from a vapor deposition layer, a barrier coat layer, and a barrier adhesive layer.

A preferred form including a barrier layer is shown below.
(15) Base material/deposited layer/printed layer/adhesive layer/sealant (16) Base material/printed layer/adhesive layer/deposited layer/intermediate base material/adhesive/sealant (17) Base material/printed layer/ Adhesive layer/evaporated layer/sealant (18) base material/barrier coat layer/printed layer/adhesive layer/sealant (19) base material/printed layer/barrier coat layer/adhesive layer/sealant (20) base material/ Print layer/barrier adhesive layer/sealant However, the form of the present invention is not limited to these.

The printed matter or laminate (A) contains 80% by mass or more of the polyolefin resin based on the total weight of the printed matter or laminate (A). The content is more preferably 85% or more, more preferably 90% by mass or more. By containing the polyolefin resin in the above range, the printed matter or laminate (A) is a molding material that has a simple separation process, high recyclability, good moldability, and can be used for various purposes. can be obtained. Preferably, the polyolefin is polypropylene and/or polyethylene. More preferably, the polypropylene is a copolymer with ethylene and/or butene.

(Aspect of printed matter or laminated laminate (A))
As for the embodiment of the printed matter or laminated laminate (A), when it has a base material and a sealant as a configuration, it is more preferable to have the following form.
(1) In this case, the base material and sealant both contain polypropylene, and the heat-melting temperature of the laminate (A) is preferably 150 to 250°C, more preferably 180 to 230°C, and still more preferably 190 to 220°C.
(2) In this case, the substrate contains polypropylene and the sealant contains polyethylene, the heat melting temperature of the laminate (A) is preferably 140 to 240°C, more preferably 170 to 220°C, and further preferably 180 to 210°C. .
(3) When both the base material and the sealant contain polyethylene, the heat melting temperature of the laminate (A) is preferably 130 to 230°C, more preferably 160 to 210°C, and still more preferably 170 to 200°C.

(evaporation layer)
When the printed matter or laminate laminate (A) has a vapor-deposited layer as a barrier layer, the vapor-deposited layer preferably contains a vapor-deposited film. It is preferable to use one or more selected from the group consisting of sealants having a film.
Since the printed matter or laminate (A) has a vapor deposition layer containing a vapor deposition film, the printed matter or laminate (A) has high gas barrier properties, specifically, oxygen barrier properties and water vapor barrier properties. In addition, the packaging container produced using the printed material or the laminate (A) can suppress the decrease in the mass of the contents filled therein.

Deposited films include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead It can be a deposited film of one or more inorganic substances or inorganic oxides such as (Pb), zirconium (Zr), yttrium (Y) and the like. The vapor deposition film can be composed of two or more layers, and may be composed of the same material or different materials.
Among the materials described above, from the viewpoint of adhesion and gas barrier properties, the deposited film is preferably made of aluminum, aluminum oxide (alumina), or silicon oxide (silica).

Also, the thickness of the deposited film is preferably 1 nm or more and 150 nm or less, more preferably 5 nm or more and 60 nm or less, and even more preferably 10 nm or more and 40 nm or less.
By setting the thickness of the deposited film to 1 nm or more, the oxygen barrier properties and water vapor barrier properties of the deposited layer can be further improved.
Further, by setting the thickness of the deposited film to 150 nm or less, the recycled plastic can be suitably used for manufacturing mono-material packaging containers, and cracks can be prevented from occurring in the deposited film.

As a method for forming a vapor deposition film, conventionally known methods can be employed, for example, physical vapor deposition methods (physical vapor deposition method, PVD method) such as vacuum deposition method, sputtering method, ion plating method, or plasma chemical vapor deposition. method, thermal chemical vapor deposition method, chemical vapor deposition method such as photochemical vapor deposition method (Chemical Vapor Deposition method, CVD method), and the like.

(Barrier coat layer)
When the printed matter or laminated laminate (A) has a barrier coat layer as a barrier layer, the barrier coat layer is formed from a barrier coat agent. The barrier coat layer is preferably adjacent to the substrate, intermediate substrate, sealant and/or print layer. Thereby, oxygen barrier properties and water vapor barrier properties can be improved.

Barrier coating agents include, for example, vinyl chloride-vinylidene chloride copolymer, vinyl acetate-vinylidene chloride copolymer, acrylic acid ester-vinylidene chloride copolymer, ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol, polyvinyl In addition to coating agents made of single resins, including gas barrier resins such as acrylonitrile, polyamide resins, polyester resins, polyurethane resins, and (meth)acrylic resins, coating agents made of the following inorganic layered compounds and resins are used. be able to.
The inorganic layered compound is, for example, clay minerals such as kaolinite group, smectite group and mica group, and is a crystalline inorganic compound having a layered structure. The kind, particle size, aspect ratio and the like of these inorganic layered compounds are appropriately selected and are not particularly limited. Among these, smectites such as montmorillonite, hectorite, and saponite are suitable, and easily incorporate the resin between the layers of the inorganic layered compound to form a composite. In particular, among this group, montmorillonite is the most excellent in stability in the molten state and coatability.

Moreover, the resin used for the barrier coating agent is not particularly limited as long as it is easily incorporated between the layers of the inorganic layered compound, but it is preferable to use a water-soluble polymer. Water-soluble polymers include polyvinyl alcohol (PVA), polyvinylpyrrolidone, starch, methylcellulose, carboxymethylcellulose, acrylic resins and sodium alginate. In particular, when polyvinyl alcohol (PVA) is used as the coating agent for the gas barrier laminate of the present invention, the gas barrier properties are most excellent.

Also, the barrier coat layer may have a composition further containing a hydrolysis/polycondensation product of a metal alkoxide. This metal alkoxide is a compound represented by the following general formula, M(OR)n, where M is a metal, R is an alkyl group, and n is the coordination number of an alkoxy group. Preferably, M is selected from the group consisting of Si, Ti, Ar and Zr, and R is selected from methyl and ethyl groups. In particular, when tetraethoxysilane [Si(OC ₂ H ₅ ) ₄ ], triisopropoxyaluminum [Al(O-2'-C ₃ H ₇ ) ₃ ], etc. are used, hydrolysis products of alkoxides are produced in aqueous systems. It is preferable because it exists relatively stably in a solvent.

Each of the components described above can be added to the coating agent alone or in combination, and within the range that does not impair the barrier properties of the coating agent, an isocyanate compound, a silane coupling agent, a dispersant, a stabilizer, or a viscosity adjuster. Known additives such as agents and coloring agents can be added.

The barrier coat layer can be formed by dissolving or dispersing the above materials in water or a suitable solvent, coating and drying. The barrier coat layer can also be formed by coating and drying a commercially available barrier coat agent.

Conventionally known methods such as dipping, roll coating, screen printing, and spraying, which are commonly used, are used as methods for applying the barrier coating agent.

The thickness of the barrier coat layer is preferably 0.01 μm or more and 10 μm or less, more preferably 0.1 μm or more and 5 μm or less, and even more preferably 0.3 μm or more and 3 μm or less.
By setting the thickness of the barrier coat layer to 0.01 μm or more, the oxygen barrier properties and water vapor barrier properties of the printed matter or laminate (A) can be improved. By setting the thickness of the barrier coat layer to 10 μm or less, the recycled plastic can be suitably used for manufacturing a monomaterial packaging container.

(Chlorine content)
A halogen element that may be contained in the printed material or the laminate (A) generates hydrogen chloride, which is a halogen gas or an acid gas, during pellet production, which may damage equipment or threaten human health. In addition, if air bubbles are generated during the production of pellets, when the produced pellets are used to produce a molded product, the surface tends to become uneven, and the surface condition of the molded product may deteriorate. Therefore, in the printed matter or laminate (A), the chlorine content is required to be 0.4% by mass or less in the total mass of the printed matter or laminate (A), and is 0.2% by mass or less. is preferred, and 0.1% by mass or less is more preferred.

(Method for measuring chlorine content in printed matter or laminate (A))
The chlorine content in the printed matter or laminate (A) can be measured using known methods such as ion chromatography (IC) and ICP mass spectrometer (ICP-MS). Specifically, it can be specified by a method similar to the chlorine content analysis method described later.

(Melt mass flow rate (MFR) of printed matter or laminate (A))
The melt mass flow rate (MFR) of the printed matter or laminate (A) in the present invention is carried out under the condition of crushing the side length to 5 mm to 10 mm and the sample having the highest content. The melt mass flow rate in the present invention is a value measured according to JISK7210. The MFR of the printed matter or laminate (A) is preferably 0.5 to 15 g/10 minutes, more preferably 3 to 12 g/10 minutes. In the case of the above range, the recycled plastic (B) is less likely to deteriorate during recycling, and the obtained molded article is more excellent.

(Base material)
The substrate in the printed matter or laminate (A) is preferably a plastic substrate mainly containing a polyolefin resin as a raw material. Film or sheet forms are preferred for use in packaging materials. Compared to ester base materials, base materials that mainly contain polyolefin resins have higher resistance to alkaline aqueous solutions and heat during the molding process, and are less likely to undergo thermal decomposition or hydrolysis, making it possible to maintain a high molecular weight. can.
Furthermore, from the viewpoint of ease of recovery after recycling, the polyolefin base material includes, for example, biaxially oriented polypropylene (OPP), non-oriented polypropylene (CPP), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) ), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), acid-modified polyethylene, acid-modified polypropylene, copolymerized polypropylene, and films obtained by laminating these. The thickness of the base material is not particularly limited, and is preferably 5 μm or more and 150 μm or less, more preferably 10 μm or more and 70 μm or less, in consideration of workability into a packaging container. Among them, films having heat-sealing properties are preferably used, such as CPP and heat-sealing OPP.

Moreover, it is also preferable that the base material is a barrier base material having a vapor deposition layer or a barrier coat layer as described above.

As the base material mainly containing polyolefin resin, olefin base materials may be simply laminated together, or a base material different from the olefin base material may be laminated via adhesion or the like. The "base material different from the olefin base material" includes films having different properties, regardless of the type. Moreover, in the case of a laminated base material, it may be in a form including an adhesive layer. The method for laminating plastics is not particularly limited, and conventionally known methods such as coextrusion, heat fusion, and pressure bonding via an adhesive layer can be used.

The base material includes (coated or kneaded) forms containing additives such as antistatic agents, antifogging agents, and UV inhibitors, and forms having an easily adhesive coating layer (for example, a layer containing polyvinyl alcohol and its derivatives), A form in which the surface of the substrate is subjected to corona treatment or low-temperature plasma treatment is preferable. The above additions and processing are also applied for the purpose of improving the wettability of printing inks and other coating agents, and for the purpose of imparting specific functionality to films, such as preventing fogging of packaging materials due to moisture. It is also suitably used to provide a packaging material with excellent visibility of contents.

(Print layer)
The printed matter or the printed layer in the laminated body (A) is used to impart decoration or aesthetics; arbitrary pictures, patterns, characters, symbols, etc. for the purpose of indicating contents, expiration dates, manufacturers or sellers, etc. can be a layer that displays The printed layer may be a solid printed layer without pictures, patterns, characters, symbols, and the like. The method of forming the printed layer is not particularly limited, and it can be formed using a known colorant (pigment and/or dye), but it is preferably formed using a printing ink containing a pigment and a binder resin. Moreover, the printed layer may have a single layer structure or a multilayer structure, and may be printed on the surface layer. The thickness of the printed layer is preferably 0.1-10 μm, more preferably 0.5-5 μm, particularly preferably 1-2.5 μm.

(pigment)
The printed matter or the printed layer in the laminate (A) is preferably formed using printing ink containing a pigment. Considering quality deterioration due to coloring of recycled plastic, the content of the colorant in the total mass of the printed layer is preferably 30% by mass or less, more preferably 25% by mass or less, and 23% by mass or less. It is even more preferable to have The coloring agent is preferably a pigment, and the pigment may be an organic pigment, an inorganic pigment, or an extender pigment. Examples of inorganic pigments include those containing titanium oxide, and extender pigments that include silica, Barium sulfate, kaolin, clay, calcium carbonate, magnesium carbonate and the like are preferred. Among organic pigments, it is preferable to use those composed of organic compounds and organometallic complexes. Colorants such as pigments may be used singly or in combination of two or more.

(organic pigment)
Examples of the above organic pigments include, but are not limited to, soluble azo, insoluble azo, azo, phthalocyanine, halogenated phthalocyanine, anthraquinone, anthrone, dianthraquinonyl, and anthrapyrimidine pigments. , perylene type, perinone type, quinacridone type, thioindigo type, dioxazine type, isoindolinone type, quinophthalone type, azomethineazo type, flavanthrone type, diketopyrrolopyrrole type, isoindoline type, indanthrone type, carbon black type, etc. pigments. Also, for example, Carmine 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange, Carmine FB, Chromophtal Yellow, Chromophtal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Magenta, Quinacridone Red, Indance Ron blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, daylight fluorescent pigments, and the like.

The hue of the organic pigment is preferably at least one selected from the group consisting of black pigments, indigo pigments, green pigments, red pigments, purple pigments, yellow pigments, orange pigments and brown pigments. Furthermore, at least one or two or more selected from the group consisting of black pigments, indigo pigments, red pigments, and yellow pigments are preferred. Specific examples of organic pigments include C.I. I. Indicate by number. Preferably C.I. I. Pigment Red 57:1, C.I. I. Pigment Red 48:1, C.I. I. Pigment Red 48:2, C.I. I. Pigment Red 48:3, C.I. I. Pigment Red 146, C.I. I. Pigment Red 242, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 14, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 13, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 139, C.I. I. Pigment Red 185, C.I. I. Pigment Red 122, C.I. I. Pigment Red 178, C.I. I. Pigment Red 149, C.I. I. Pigment Red 144, C.I. I. Pigment Red 166, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 37, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6, C.I. I. Pigment Green 7, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 64, C.I. I. Pigment Black 7.

Inorganic pigments include titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, aluminum particles, mica (mica), bronze powder, chromium vermillion, yellow lead, cadmium yellow, cadmium red, and ultramarine blue. , Prussian blue, red iron oxide, yellow iron oxide, iron black, titanium oxide, zinc oxide, etc. Aluminum is available in leafing type and non-leafing type, but non-leafing type is preferred.

(binder resin)
The binder resin refers to a binder resin in the printed matter or the printed layer of the laminate (A), and as described later, the chlorine content is preferably 5% by mass or less in the total binder resin.

Moreover, the binder resin is preferably a thermoplastic resin soluble in an organic solvent. As the binder resin, it is preferable to use a resin having a glass transition temperature of −60° C. or more and less than 40° C. and a resin having a glass transition temperature of 40° C. or more and 200° C. or less. More preferably, a resin having a glass transition temperature of -50°C to 0°C and a resin having a glass transition temperature of 50°C to 190°C are used together. In this specification, the glass transition temperature is a value measured by a differential scanning calorimeter (DSC).

Examples of binder resins include, but are not limited to, urethane resins, cellulose resins, polyamide resins, rosin resins, ethylene-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate copolymer resins, Vinyl acetate resin, acrylic resin, styrene resin, dammar resin, styrene-maleic acid copolymer resin, polyester resin, alkyd resin, terpene resin, phenol-modified terpene resin, ketone resin, cyclized rubber, butyral, polyacetal resin, petroleum resin, and modified resins thereof. These resins can be used alone or in combination of two or more. Among the above, it is preferable to contain one or more selected from the group consisting of resins other than vinyl chloride-vinyl acetate copolymer resins, and it is more preferable to contain urethane resins.

(urethane resin)
The method for producing the urethane resin is not particularly limited, and the urethane resin is appropriately produced by a known method. A urethane resin composed of a polyol and a polyisocyanate, a urethane resin obtained by reacting an isocyanate-terminated urethane prepolymer composed of a polyol and a polyisocyanate with a polyamine, and the like are preferable. Examples of the manufacturing method include the method described in JP-A-2013-256551.

(Chlorine content of binder resin)
The chlorine content is the chlorine atom content (% by mass) based on the mass of the binder resin. The binder resin in the present invention preferably has a chlorine content of 5% by mass or less, including a case of 0.
When the chlorine content is 5% by mass or less, the environmental safety is excellent, and free chlorine is less likely to occur. The chlorine content is more preferably 4% by mass or less, still more preferably 3% by mass or less, and particularly preferably 2% by mass or less.

The chlorine content can be measured using known methods such as ion chromatography (IC) and ICP mass spectrometer (ICP-MS). Examples of measuring instruments include LC-20ADsp manufactured by Shimadzu Corporation for IC and Agilent 7700x manufactured by Agilent Technologies for ICP-MS. Further, the chlorine content of the printed layer can be easily calculated from the chlorine content of each raw material constituting the printed layer by the following formula. The same applies to other layers.
Formula: chlorine content (%) in total solid mass of binder resin = mass of chlorine in total solid mass of binder resin/total solid mass of binder resin (%)
Formula: Chlorine content (%) in the total mass of solid content in the printing layer = mass of chlorine in the total mass of solid content in the printing layer / total mass of solid content in the printing layer (%)

In the present invention, the chlorine content is preferably measured according to JISK0127 (2013). In this measurement method, a sample pretreated by the combustion method is quantified by the ion chromatography method.

[Nitrification degree of binder resin]
The degree of nitrification is the degree of esterification of nitrate expressed in terms of nitrogen content (% by mass). For example, commercially available nitrocellulose is usually 10 to 12% by mass.
The binder resin in the printed matter or the printed layer of the laminate (A) preferably has a degree of nitrification of 1% by mass or less, including a case of 0. When the degree of nitrification is 1% by mass or less, NO _X gas generation can be suppressed, and a safer recycled plastic (B) can be provided.
The degree of nitrification of the binder resin is more preferably 0.6% by mass or less, still more preferably 0.4% by mass or less, and particularly preferably 0.2% by mass or less.
The degree of nitrification of the urethane resin is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and further preferably 0.1% by mass or less. Further, the degree of nitrification of the resin (P) described later is preferably 0.8% by mass or less, more preferably 0.6% by mass, and still more preferably 0.4% by mass.

[Resin (P)]
It is preferable that the binder resin in the printed matter or the printed layer of the laminate (A) further contains a urethane resin and a resin (P) other than the urethane resin.
The resin (P) is preferably a resin having a ring structure, and more preferably has at least one ring structure selected from the group consisting of an acetal ring structure, an aromatic ring structure, an alicyclic ring structure and a pyranose ring structure. resin having an acetal ring structure, and more preferably a resin having an acetal ring structure. These ring structures may have a double bond, or may have an alkyl group or other substituents. This is because of the compatibility with the recycled plastic (B).

The resin (P) preferably contains 40 to 95% by mass, more preferably 50 to 90% by mass, of structural units having a ring structure based on the mass of the resin (P).
When the resin (P) contains structural units having a ring structure within the above range, pigment dispersion in printing ink is promoted. In addition, the laminate (A) has excellent lamination strength, and deterioration over time can be suppressed. Furthermore, it becomes excellent in blocking resistance.
In the present specification, the mass of a monomer having a ring structure also includes groups substituted or adjacent to the ring structure, such as methyl groups and nitro groups. For example, when the resin (P) is a styrene-acrylic resin, the structural unit derived from α-methylstyrene is 50% by mass, and the structural unit derived from butyl methacrylate as an acrylic monomer is 50% by mass, the content of the ring structure is 50% by mass.

The content of structural units having a ring structure may be calculated by the following formula.
Formula: content of structural unit having a ring structure (% by mass)
= mass of monomer having ring structure x 100/total mass of all monomers constituting resin (P)

Examples of resins having a ring structure include polyvinyl acetal resins, cellulose ester resins, rosin resins, polystyrene resins, polyester resins having a ring structure, acrylic resins having a ring structure, and copolymer resins thereof, more preferably. contains at least one selected from the group consisting of polyvinyl acetal resins, cellulose ester resins, and rosin resins. More preferably, it contains a polyvinyl acetal resin.

(polyvinyl acetal resin)
Polyvinyl acetal resin is obtained by reacting polyvinyl alcohol with aldehyde such as butyraldehyde and/or formaldehyde to acetal cyclize, and preferably contains vinyl alcohol units, vinyl acetate units and acetal ring groups. The polyvinyl acetal resin preferably contains 60 to 90% by mass of acetal ring, 5 to 30% by mass of vinyl alcohol unit, and 0.5 to 10% by mass of vinyl acetate unit, more preferably a butyral ring as the acetal ring. It is a polyvinyl butyral resin with
The weight average molecular weight of the polyvinyl acetal resin is preferably 10,000 to 100,000, more preferably 10,000 to 80,000. The glass transition point of the polyvinyl acetal resin is preferably 50-80°C, more preferably 60-75°C.

(cellulose ester resin)
Cellulose ester resins are preferably cellulose acetate alkynate resins such as cellulose acetate propionate and cellulose acetate butyrate.
The cellulose ester resin preferably has an alkyl group. The above alkyl group is preferably an alkyl group having 10 or less carbon atoms, and for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group and hexyl group are preferably used. The alkyl group may have a substituent.
The weight average molecular weight of the cellulose ester resin is preferably 5,000 to 200,000, more preferably 10,000 to 10,000, still more preferably 15,000 to 80,000. The glass transition point of the cellulose ester resin is preferably 120°C to 180°C, more preferably 130°C to 170°C.
By using a urethane resin and a cellulose ester resin together, printability, blocking resistance, etc. are improved.

(rosin resin)
A rosin resin is one having structural units derived from rosin acid (eg, abietic acid, neoabietic acid, parastric acid, pimaric acid, isopimaric acid, dehydroabietic acid) as a main component. Here, having a certain structural unit as a main component means that the structural unit is 50% by mass or more. The rosin acid or rosin resin may be hydrogenated.
The rosin resin is preferably at least one selected from the group consisting of rosin-modified phenol resins, rosin ester resins, rosin-modified maleic acid resins, and polymerized rosin resins.
The acid value of the rosin resin is preferably 350 mgKOH/g or less, more preferably 250 mgKOH/g or less, still more preferably 150 mgKOH/g or less.
As one embodiment, the acid value is preferably 100 mgKOH/g or less, more preferably 50 mgKOH/g or less.
The softening point of the rosin resin is preferably 60-180°C, more preferably 70-150°C. As used herein, the softening point is a value measured by the ring and ball method, and can be measured according to JISK2207.

(rosin ester)
The rosin resin is preferably a rosin ester, which is an ester condensation resin of a low-molecular-weight polyol having a molecular weight of 1,000 or less and rosin acid. The low-molecular-weight polyol preferably has 2 to 4 hydroxyl groups in one molecule (hereinafter sometimes abbreviated as 2- to 4-functional) and has a molecular weight of 50-500. Examples of such low-molecular-weight polyols include bifunctional low-molecular-weight polyols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,10-decanediol; Functional low-molecular-weight polyols; tetra-functional low-molecular-weight polyols such as erythritol and pentaerythritol; are preferably used. Among them, trifunctional and/or tetrafunctional low-molecular-weight polyols are preferred.
The weight average molecular weight of the rosin ester is preferably 500-2,000, more preferably 500-1,500.

(adhesive layer)
The printed matter or laminate (A) may further have an adhesive layer.
The adhesive layer is not particularly limited as long as each layer can be adhered, and olefin adhesive, acrylic adhesive, ethylene-vinyl acetate copolymer adhesive, reactive urethane adhesive (dry adhesive and (including non-sol type adhesives), imine anchor coating agents, other anchor coating agents, and thermoplastic resins used in extrusion lamination. The adhesive layer is preferably a reaction product of a reactive urethane adhesive composed of polyisocyanate and polyol.

The method for bonding (also referred to as lamination) each layer is not particularly limited, and conventionally known methods such as an extrusion lamination method, a dry lamination method, and a non-sol lamination method can be used.
As the reactive urethane adhesive for forming the adhesive layer, a two-component urethane adhesive composed of a polyol as a main agent and a polyisocyanate as a curing agent is preferred. In this case, the adhesive layer is the reactant of this urethane adhesive. The polyol may be any compound having two or more hydroxyl groups, and can be selected from known polyols. Examples of polyols include polyester polyols, polycarbonate polyols, polycaprolactone polyols, polyether polyols, polyolefin polyols, acrylic polyols, silicone polyols, castor oil-based polyols, and fluorine-based polyols. Among them, it is preferable to contain polyether polyol and/or polyester polyol. The polyol may be an acid-modified product in which some of the hydroxyl groups in the polyol have been acid-modified, or may be one in which some of the hydroxyl groups in the polyol are reacted with diisocyanate to introduce urethane bonds. The polyisocyanate may be any compound having two or more isocyanate groups, and can be selected from known polyisocyanates. Polyisocyanates include, for example, aromatic polyisocyanates, araliphatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and modified products thereof. Polyols may be used alone or in combination of two or more. The same applies to polyisocyanates.

(Barrier adhesive layer)
The printed matter or laminate (A) may have a barrier adhesive layer as a barrier layer. The barrier adhesive layer can be formed, for example, by applying and drying a commercially available barrier adhesive. Gas barrier adhesives such as TM-9310 (manufactured by Toyo Morton Co., Ltd.), Maxieve (manufactured by Mitsubishi Gas Co., Ltd.), and PASLIM (manufactured by DIC Corporation) are suitably used as barrier adhesives. The thickness of the adhesive layer is preferably 0.1-10 μm, more preferably 0.5-5 μm, and particularly preferably 1.0-2.5 μm.

(Intermediate base material layer)
The printed matter or laminate (A) may further have an intermediate substrate layer. A specific example of the intermediate base material layer is preferably a plastic base material containing mainly a polyolefin resin as a raw material, like the base material layer. For example, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), ethylene-vinyl acetate copolymer, propylene homopolymer, ethylene-propylene copolymer Examples thereof include polyolefin resins such as polymers, etc., and the preferred form is a gas barrier substrate having the vapor deposition layer and the barrier coat layer. Moreover, the composite base material by the co-extrusion manufacturing method may be used.

(sealant)
The print or laminate (A) may additionally have a sealant. The sealant has a surface on the inner layer side that comes into direct contact with the object to be packaged and plays a role of protecting the object to be packaged. It is preferable that the innermost layer of the sealant has a heat-sealing property in order to make the laminate bag-like. Materials constituting the sealant include, for example, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), ethylene-vinyl acetate copolymer, and propylene. Examples include polyolefin resins such as homopolymers and ethylene-propylene copolymers, and one or more of these resins can be used. The sealant may be composed of a single layer or multiple layers of two or more layers. It should be noted that the sealant is preferably a non-stretched film made of the resin described above in order to suppress shrinkage during heat sealing.

The thickness of the sealant is not particularly limited, and is appropriately set according to the use of the laminate and the type and properties of the object to be packaged, but it is usually preferably 10 to 200 μm. In the case of pouches (especially retort pouches), the thickness of the sealant is preferably 20-150 μm, more preferably 25-130 μm.

The sealant is preferably a sealant having a vapor deposition layer or a barrier coat layer as described above. Further, it may be a milky white base material kneaded with a pigment or the like, or a composite base material obtained by a co-extrusion method.

(Melt mass flow rate (MFR) of recycled plastic (B))
The melt mass flow rate (MFR) of the recycled plastic (B) is greatly affected by heat history such as molding temperature and cooling speed. Although it depends on the configuration of the flexible package, the recycling method, etc., it is preferably 0.5 to 20 g/10 minutes, more preferably 3 to 15 g/10 minutes. By having the melt mass flow rate within the above range, materials suitable for various molding can be provided.
In the present invention, it is also preferable to include a step of adjusting the melt mass flow rate (MFR) of the recycled plastic (B) by changing the heat history.

(Molding)
A molded article can be obtained by molding the recycled plastic (B) obtained by the present invention. The molding method is not particularly limited, and examples thereof include injection molding, extrusion molding, blow molding, and compression molding. Molded articles can be used in various applications such as home appliances, stationery, automobile parts, toys, sporting goods, medical supplies, and building/construction materials.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples. Parts and % in the present invention represent parts by mass and % by mass unless otherwise specified.

(hydroxyl value)
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group when 1 g of the sample is acetylated, and was measured by the method described in JIS K 0070.

(acid number)
The acid value is mg of potassium hydroxide required to neutralize free fatty acid, resin acid, etc. contained in 1 g of sample, and was measured by the method described in JIS K 0070.

(amine value)
The amine value is the number of mg of potassium hydroxide equivalent to the equivalent of hydrochloric acid required to neutralize the amino groups contained in 1 g of the sample, and was measured according to JIS K 0070. That is, 0.5 to 2 g of the sample was accurately weighed (sample solid content: Sg). 50 mL of a mixed solution of methanol/methyl ethyl ketone=60/40 (mass ratio) was added to the accurately weighed sample to dissolve the sample. Bromophenol blue was added to the resulting solution as an indicator, and the resulting solution was titrated with a 0.2 mol/L ethanolic hydrochloric acid solution (potency: f). The point at which the color of the solution changed from green to yellow was defined as the end point, and the titration amount (AmL) at this time was used to determine the amine value by the following formula.
(Formula) Amine value = (A x f x 0.2 x 56.108) / S [mgKOH/g]

(Weight average molecular weight)
The weight-average molecular weight was obtained by measuring the molecular weight distribution using a gel permeation chromatography (GPC) device (HLC-8220 manufactured by Tosoh Corporation) and obtaining the converted molecular weight using polystyrene as a standard substance. Measurement conditions are shown below.
Column: The following columns were connected in series and used.
TSKgelSuperAW2500 manufactured by Tosoh Corporation
TSKgelSuperAW3000 manufactured by Tosoh Corporation
TSKgelSuperAW4000 manufactured by Tosoh Corporation
TSK gelguard column Super AWH manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Measurement conditions: Column temperature 40°C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL/min

(Glass transition point (Tg))
Glass transition points were determined by differential scanning calorimetry measurements (DSC). The measurement was performed using a DSC8231 manufactured by Rigaku Corporation under conditions of a measurement temperature range of -70 to 250°C and a heating rate of 10°C/min. The midpoint (inflection point) of the baseline shift based on the glass transition in the DSC curve was taken as the glass transition point.

(Chlorine content)
The chlorine content was measured according to JIS K0127 (2013). That is, a coating film was formed by applying ink or a binder resin on a transparent substrate so as to have a thickness of 2.0 μm. Dried at 80° C. and scraped off 0.5 g. The scraped coating film was subjected to pretreatment by a combustion method, and the chlorine content of the obtained sample was quantified by ion chromatography to determine the chlorine content.

(Measurement of melt mass flow rate (MFR))
MFR was measured by the method described in K 7210-1:2014. Laminate (A) was measured by crushing it into pieces with a side length of 5 mm to 10 mm. Measurement conditions such as temperature were the conditions for the sample with the highest content.

(Synthesis of urethane resin)
(Synthesis Example 1) Urethane resin PU1
100 parts of a polyester polyol having a number average molecular weight of 2,000 (hereinafter “MPD/SA”), which is a condensate of 3-methyl 1,5 pentanediol (MPD) and sebacic acid (SA), 1,4-butanediol ( 1 part of “1,4-BD” hereinafter), 28.5 parts of isophorone diisocyanate (hereinafter “IPDI”) and 32.1 parts of ethyl acetate are mixed and reacted at 90° C. for 5 hours under a nitrogen atmosphere to A urethane prepolymer of isocyanate was obtained.
Then, isophoronediamine (hereinafter "IPDA") 11.0 parts, N-(2-aminoethyl)ethanolamine (hereinafter "AEA") 1.0 parts, dibutylamine (hereinafter "DBA") 1.0 parts and mixed 298.1 parts of solvent 1 (ethyl acetate/isopropanol = 70/30 (mass ratio)) were stirred and mixed, and the obtained urethane prepolymer having terminal isocyanate was gradually added at 40°C.
A reaction was carried out at 80° C. for 1 hour to obtain a solution of urethane resin PU1 having a solid content of 30% by mass, an amine value of 6.5 mgKOH/g, a hydroxyl value of 3.8 mgKOH/g and a weight average molecular weight of 50,000. The chlorine content of the urethane resin PU1 is 0% by mass.

In the following ink preparation examples, the following were used.
PVB solution: Polyvinyl butyral resin having vinyl alcohol units, vinyl acetate units and vinyl butyral units and containing 73% by mass of butyral ring groups (glass transition point 70°C, weight average molecular weight 50,000, chlorine content 0% by mass) , nitrification degree 0 mass%) solid content 30% solution in ethyl acetate / isopropanol = 1/1 mixed solvent Vinyl chloride-vinyl acetate solution: vinyl chloride-vinyl acetate copolymer resin (manufactured by Nissin Chemical Co., Ltd. Solbin TA3, chlorine 30% solid content ethyl acetate solution with a content of 47.1% by mass and a degree of nitrification of 0% by mass

(Ink preparation)
[Gravure ink preparation example 1] Gravure ink X1
40 parts of urethane resin PU1 solution, 15 parts of polyvinyl butyral resin (PVB) solution, C.I. I. Pigment Blue 15:3 (manufactured by Toyocolor Co., Ltd., product name: LIONOL BLUE FG-7330, chlorine content 0% by mass, degree of nitrification 0% by mass) 5 parts, silica particles (hydrophilic silica, average particle size 3.0 μm, 0.8 parts of specific surface area of 300 m ² /g) and 36 parts of mixed solvent 2 (n-propyl acetate/isopropanol = 70/30 (mass ratio)) were mixed and dispersed in a bead mill for 20 minutes to obtain a pigment dispersion. . 0.8 parts of a chlorinated polypropylene solution, 3.5 parts of propylene glycol monomethyl ether (boiling point: 121.0° C.), and 1.5 parts of water were stirred and mixed with the resulting pigment dispersion to prepare an organic solvent-based gravure ink X1. got

[Gravure ink preparation example 2] Gravure ink X2
40 parts of urethane resin PU1 solution, 10 parts of polyvinyl butyral resin (PVB) solution, C.I. I. Pigment Blue 15:3 (manufactured by Toyocolor Co., Ltd., product name: LIONOL BLUE FG-7330, chlorine content 0% by mass, degree of nitrification 0% by mass) 10 parts, silica particles (hydrophilic silica, average particle diameter 3.0 μm, 0.8 parts of specific surface area of 300 m ² /g) and 36 parts of mixed solvent 2 (n-propyl acetate/isopropanol = 70/30 (mass ratio)) were mixed and dispersed in a bead mill for 20 minutes to obtain a pigment dispersion. . 0.8 parts of chlorinated polypropylene solution, 3.5 parts of propylene glycol monomethyl ether (boiling point: 121.0° C.), and 1.5 parts of water were stirred and mixed with the obtained pigment dispersion to obtain organic solvent-based gravure ink X2. got

[Gravure ink preparation example 3] Gravure ink X3
40 parts of urethane resin PU1 solution, 8 parts of polyvinyl butyral resin (PVB) solution, 2 parts of vinyl chloride-vinyl acetate solution (PVC) solution, C.I. I. Pigment Yellow 14 (chlorine content 10.8% by mass, degree of nitrification 0% by mass) 10 parts, silica particles (hydrophilic silica, average particle diameter 3.0 μm, specific surface area 300 m ² /g) 0.8 parts, mixed solvent 2 (n-propyl acetate/isopropanol=70/30 (mass ratio)) were mixed and dispersed for 20 minutes in a bead mill to obtain a pigment dispersion. 0.8 parts of a chlorinated polypropylene solution, 3.5 parts of propylene glycol monomethyl ether (boiling point: 121.0° C.), and 1.5 parts of water were stirred and mixed with the obtained pigment dispersion to obtain organic solvent-based gravure ink X3. got

[Gravure ink preparation example 4] Gravure ink Y1
35 parts of urethane resin PU1 solution, 20 parts of vinyl chloride-vinyl acetate solution (PVC) solution, C.I. I. Pigment Blue 15:3 (manufactured by Toyocolor, product name: LIONOL BLU
E FG-7330, chlorine content 0% by mass, degree of nitrification 0% by mass) 5 parts, silica particles (hydrophilic silica, average particle diameter 3.0 μm, specific surface area 300 m ² /g) 0.8 parts, mixed solvent 2 36 parts of (n-propyl acetate/isopropanol=70/30 (mass ratio)) were mixed and dispersed in a bead mill for 20 minutes to obtain a pigment dispersion. 0.8 parts of a chlorinated polypropylene solution, 3.5 parts of propylene glycol monomethyl ether (boiling point: 121.0° C.), and 1.5 parts of water were stirred and mixed with the resulting pigment dispersion to obtain an organic solvent-based gravure ink Y1. got

<Preparation of barrier coating agent>
8 parts of polyvinyl alcohol having a saponification degree of 98 mol% and a 4% aqueous solution viscosity of 30 mPa s, 2 parts of montmorillonite, and 90 parts of water are mixed and dissolved by heating and stirring at 90°C to obtain a gas barrier water-based resin composition. A barrier coating agent was obtained.

<Production of printed matter or laminate (A)>
(Production of laminate (A) 1) Laminate A1
Gravure ink X1 was diluted with a mixed solvent of ethyl acetate/isopropyl alcohol (mass ratio 70/30) to Zahn cup #3 (manufactured by Rigosha) for 15 seconds (25°C). After that, a corona-treated biaxially oriented polypropylene (OPP) film (thickness: 20 μm) was printed in this order using a gravure printing machine equipped with a gravure plate with a plate depth of 35 μm, dried at 50° C., and OPP/printed layer got Next, using a dry laminator, an adhesive ("TM-340V/CAT-29B" manufactured by Toyo-Morton Co., Ltd.) is applied onto the printed layer of this laminate, and after drying the solvent in an oven, Then, at a line speed of 40 m / min, a non-stretched polypropylene (CPP) film (thickness 30 μm) is laminated, kept at 40 ° C. for 1 day, and a laminate A1 having an OPP / printed layer / adhesive layer / CPP structure. Obtained. The coating amount after drying of the printed layer and the adhesive layer was 2.5 g/m ² . The MFR values are listed in Table 1.

(Production of laminate (A) 2) Laminate A2
A laminate A2 having an OPP/printing layer/adhesive layer/CPP structure was obtained in the same manner as in the production process of the laminate A1, except that the gravure ink X1 was changed to the gravure ink X2. The coating amount after drying of the printed layer and the adhesive layer was 2.5 g/m ² .

(Production of laminate (A) 3) Laminate A3
A laminate A3 having an OPP/printing layer/adhesive layer/VMCPP structure was obtained in the same manner as in the manufacturing process of the laminate A1, except that the sealant was changed to an aluminized unstretched polypropylene (VMCPP) film (thickness: 30 μm). . The coating amount after drying of the printed layer and the adhesive layer was 2.5 g/m ² .

(Production of laminate (A) 4) Laminate A4
A laminate A4 having a configuration of AOPP/printing layer/adhesive layer/CPP was obtained in the same manner as in the manufacturing process of the laminate A1, except that the base material was changed to a polyvinyl alcohol-coated OPP (AOPP) film (thickness: 20 μm). . The coating amount after drying of the printed layer and the adhesive layer was 2.5 g/m ² .

(Production of laminate (A) 5) Laminate A5
An OPP/printed layer was obtained in the same procedure as the printing process in the manufacturing process of the laminate A1. Next, using a non-sol laminating machine, an adhesive (“EA-N373 A/B” manufactured by Toyo-Morton Co., Ltd.) is applied on the printed layer of this laminate, and the line speed is set to 40 m / min. Then, a non-stretched polypropylene (CPP) film (thickness: 30 μm) was laminated and kept at 40° C. for 1 day to obtain a laminate A5 having an OPP/printing layer/adhesive layer/CPP structure. The coating amount of the printed layer after drying was 2.5 g/m ² , and the coating amount of the adhesive layer was 2.0 g/m ² .

(Production of laminate (A) 6) Laminate A6
An OPP/printed layer was obtained in the same procedure as the printing process in the manufacturing process of the laminate A1. Next, using an extrusion laminator, a polyethyleneimine anchor coating agent (EL-420 manufactured by Toyo-Morton Co., Ltd.) is diluted with a solvent consisting of methanol:water=70:30 (mass ratio) on the printed layer of this laminate. A solution of 1% solid content (weight ratio, methanol / water = 70/30) was applied, and after drying the solvent in an oven, a polypropylene resin (Novatec FL02A, Japan Polypropylene Co., Ltd.) melted at 330 ° C. was applied to the coated surface. (thickness 15 μm), and at the same time, a non-stretched polypropylene (CPP) film (thickness 30 μm) is laminated to create an OPP/printing layer/AC agent/PP resin layer/CPP structure. A laminate A6 was obtained. The coating amount of the printed layer after drying was 2.5 g/m ² .

(Production of laminate (A) 7 and 8) Laminate A7 and 8
Laminate A1 except that the substrate was changed to a high-density polyethylene film (HDPE) film (thickness 20 μm) and the sealant was changed to a linear low-density polyethylene (LLDPE) film (thickness 40 μm / laminate A7, 150 μm / laminate A8). Laminates A7 and A8 each having a HDPE/printing layer/adhesive layer/LLDPE structure were obtained in the same manner as in the manufacturing process. The coating amount after drying of the printed layer and the adhesive layer was 2.5 g/m ² .

(Production of laminate (A) 9) Laminate A9
Except for changing the base material to a high-density polyethylene film (HDPE) film (thickness 20 μm), the molten resin to a low-density polyethylene (Novatec LC600, manufactured by Japan Polychem), and the sealant to a linear low-density polyethylene (LLDPE) film (thickness 40 μm). obtained a laminate A9 having a structure of HDPE/printing layer/AC agent/PE layer/LLDPE in the same manner as the laminate A6. The coating weight of each printed layer after drying was 2.5 g/m ² .

(Production of laminate (A) 10, 11) Laminates A10, A11
OPP/printing layer/adhesive layer in the same manner as in the manufacturing process of laminate A1, except that the sealant was changed to a linear low-density polyethylene (LLDPE) film (thickness 40 μm/laminate A10, thickness 25 μm/laminate A11). /LLDPE laminates A10 and A11 were obtained. The coating amount after drying of the printed layer and the adhesive layer was 2.5 g/m ² .

(Production of laminate (A) 12) Laminate A12
OPP/printing was performed in the same manner as in the manufacturing process of laminate A6, except that the molten resin was changed to low-density polyethylene (Novatec LC600, manufactured by Nippon Polychem Co., Ltd.) and the sealant was changed to linear low-density polyethylene (LLDPE) film (thickness 40 μm). A laminate A12 having a structure of layer/AC agent/PE resin layer/LLDPE was obtained. The coating amount after drying of the printed layer and the adhesive layer was 2.5 g/m ² .

(Production of laminate (A) 13) Laminate A13
An OPP/printed layer was obtained in the same procedure as the printing process in the manufacturing process of the laminate A1. Next, using a dry laminator, the OPP surface of this laminate is coated with an adhesive ("TM-340V/CAT-29B" manufactured by Toyo-Morton Co., Ltd.), and after drying the solvent in an oven, , At a line speed of 40 m / min, a non-stretched polypropylene (CPP) film (thickness: 30 μm) was laminated and kept at 40 ° C. for 1 day to obtain a laminate A13 having a print layer / OPP / adhesive layer / CPP structure. rice field. The coating amount after drying of the printed layer and the adhesive layer was 2.5 g/m ² .

(Production of laminate (A) 14) Laminate A14
A laminate A14 having an OPP/printing layer/adhesive layer/CPP structure was obtained in the same manner as in the production process of the laminate A1, except that the gravure ink X1 was changed to the gravure ink X3. The coating amount after drying of the printed layer and the adhesive layer was 2.5 g/m ² .

(Production of laminate (A) 15) Laminate A15
OPP / printed layer / adhesive layer / heat seal OPP configuration in the same manner as the manufacturing process of laminate A1, except that the sealant was changed to a single-sided heat-sealable biaxially oriented polypropylene (heat seal OPP) film (thickness 30 μm) A laminate A15 was obtained. The coating amount after drying of the printed layer and the adhesive layer was 2.5 g/m ² .

(Production of laminate (A) 16) Laminate A16
Laminate A16 with LLDPE/printing layer/adhesive layer/LLDPE structure was produced in the same manner as in the manufacturing process of laminate A1, except that the substrate and sealant were changed to linear low-density polyethylene (LLDPE) film (thickness: 40 μm). Obtained. The coating amount after drying of the printed layer and the adhesive layer was 2.5 g/m ² .

(Production of laminate (A) 17) Laminate A17
A medium-density polyethylene (MDPE) was formed into a single-layer extrusion film by an inflation method, and then stretched 5 times in the longitudinal direction (MD direction) by a stretching device to prepare a base material (thickness: 20 μm).

An ethylene-vinyl alcohol copolymer, maleic anhydride-modified polyethylene, and linear density polyethylene were co-extruded into a film by a T-die method to obtain a sealant (thickness: 50 μm). In the obtained sealant, the thickness of the layer composed of the ethylene-vinyl alcohol copolymer was 2 μm, the thickness of the layer composed of the maleic anhydride-modified polyethylene was 3 μm, and the thickness of the layer composed of the linear low-density polyethylene was 3 μm. was 45 μm.
An aluminum deposition film having a thickness of 30 nm was formed on the surface of the ethylene-vinyl alcohol copolymer of the sealant by PVD.

A laminate A17 having a structure of MDPE/printed layer/adhesive layer/coextruded multilayer film was obtained in the same manner as in the production process of the laminate A1, except that the base material and sealant were changed as described above. The coating amount of the printed layer and the adhesive layer after drying was 2.5 g/m ² .

(Production of laminate (A) 18) Laminate A18
A medium-density polyethylene (MDPE) was formed into a single-layer extrusion film by an inflation method, and then stretched 5 times in the longitudinal direction (MD direction) by a stretching device to prepare a base material (thickness: 20 μm).
An ethylene-vinyl alcohol copolymer, maleic anhydride-modified polyethylene, and a medium-density polyethylene resin were co-extruded into a film by an inflation molding method, and then stretched 5 times in the longitudinal direction (MD direction) using a stretching device. In the obtained intermediate base material, the thickness of the layer composed of the ethylene-vinyl alcohol copolymer was 2 μm, the thickness of the maleic anhydride-modified polyethylene layer was 3 μm, and the thickness of the layer composed of the medium-density polyethylene resin was 20 μm. there were.

Thereafter, a 30 nm-thick aluminum oxide deposited film was formed on the surface of the ethylene-vinyl alcohol copolymer layer by PVD to obtain an intermediate base material including a deposited layer.

In the same procedure as the printing process in the manufacturing process of the laminate A1, printing was performed on the MDPE base material produced above to obtain an MDPE/printed layer. Next, using a dry laminator, an adhesive (“TM-340V/CAT-29B” manufactured by Toyo Morton Co., Ltd.) is applied to the printed surface of this laminate, and after drying the solvent in an oven, , at a line speed of 40 m/min. After that, the non-vapor-deposited surface of the intermediate substrate of this laminate was similarly coated with an adhesive, and a linear low-density polyethylene (LLDPE) film (40 μm thick) was laminated. After keeping the temperature at 40° C. for 1 day, a laminate A18 consisting of MDPE/printing layer/adhesive layer/coextruded multilayer film/adhesive layer/LLDPE was obtained. The coating amount after drying of the printed layer and the adhesive layer was 2.5 g/m ² .

(Production of laminate (A) 19) Laminate A19
A barrier coating agent is applied to a corona-treated biaxially oriented polypropylene (OPP) film (thickness 20 μm) using a gravure printing machine equipped with a gravure plate, and the solvent is dried in an oven to obtain an OPP/barrier coating layer. rice field.
After that, a laminate A19 having a configuration of OPP/barrier coat layer/printing layer/adhesive layer/CPP was obtained in the same manner as in the manufacturing process of the laminate A1. The coating amount of the printed layer and the adhesive layer after drying was 2.5 g/m ² , and the coating amount of the barrier coat layer after drying was 2.0 g/m ² .

(Production of laminate (A) 20) Laminate A20
An OPP/printing layer/barrier adhesive layer/CPP structure was formed in the same manner as in the manufacturing process of laminate A1, except that the adhesive was changed to a barrier adhesive (“TM-9310/CAT-1980” manufactured by Toyo-Morton Co., Ltd.). A laminate A20 was obtained. The coating amount after drying of the printed layer and the adhesive layer was 2.5 g/m 2 .

(Production of Laminate (A) 21) Laminate A21
The substrate is made of single-sided heat-sealable biaxially oriented polypropylene (heat seal OPP)
A printed layer/heat-sealed OPP laminate A21 was obtained in the same manner as in the printing process for the laminate A1, except that the film (thickness: 50 μm) was used. The coating amount of the printed layer after drying was 2.5 g/m ² .

(Production of laminate (A) 22) Laminate S1
A laminate S1 having an OPP/printing layer/adhesive layer/CPP structure was obtained in the same manner as in the production process of the laminate A1, except that the gravure ink X1 was changed to the gravure ink Y1. The coating amount after drying of the printed layer and the adhesive layer was 2.5 g/m ² .

(Production of laminate (A) 23) Laminate S2
A laminate S2 having a structure of NY/printing layer/adhesive layer/CPP was obtained in the same manner as in the manufacturing process of the laminate A1, except that the base material was changed to a nylon (NY) film (thickness: 15 μm). The coating amount after drying of the printed layer and the adhesive layer was 2.5 g/m ² .

<Production of recycled plastic (B)>
(Example 1) Recycled plastic B1
The laminate A1 was cut into a size of 4 cm×4 cm, washed with water and dried. The OPP base material pieces were put into a single-screw extruder, melted and kneaded at a screw speed of 250 rpm and 220° C., and extruded at a pressure of 4 MPa from the discharge port of the extruder using a 150-mesh filter. After that, it was immediately cut with a pelletizer and cooled by immersing it in cold water. Thus, a pellet B1, which is a recycled plastic (B) recycled from the laminate A1, was obtained.

(Examples 2 to 25) Recycled plastics B2 to B25
According to the conditions shown in Table 1, pellets B2 to B25, which are recycled plastics recycled from the laminate, were obtained in the manufacturing process of recycled plastic B1.

(Comparative Examples 1-4) Recycled plastics B26-B29
According to the conditions shown in Table 1, pellets B26 to B29, which are recycled plastics recycled from the laminate, were obtained in the manufacturing process of recycled plastic B1.

<Evaluation of film molding>
Pellets of recycled plastics B1 to B29 were each extruded at 220° C. using a T-die extruder to produce a film-like molded body with a thickness of 50 μm. The number of visually identifiable foreign matter per 0.5 m ² of the obtained film was counted and evaluated according to the following criteria. Table 1 shows the evaluation results.
A (good): the number of foreign substances is less than 50,
B (acceptable): the number of foreign objects is 50 or more and less than 100,
C (acceptable): the number of foreign substances is 100 or more and less than 200,
D (defective): The number of foreign matter is 200 or more.

<Evaluation of bottle-shaped compact>
Pellets of recycled plastics B1 to B29 were each blow-molded at 220° C. using a blow-molding machine to produce bottle-shaped moldings each having a thickness of 1 mm. Regarding the bottles obtained in each example, the number of bottles per 50 bottles in which visually discernable foaming was observed was counted.
Table 1 shows the evaluation results.
A (Good): 1 or less out of 50 bottles in which foaming was observed,
B (acceptable): 2 to 3 out of 50 bottles in which foaming was observed,
C (acceptable): 4 to 5 out of 50 bottles in which foaming was observed,
D (defective): 6 or more out of 50 bottles showed foaming.

From the above results, it was found that the molded article using the recycled plastic obtained by the production method of the present invention can provide a high-quality recycled product with little or no foreign matter and foam. It is presumed that the content of chlorine in the laminate of 0.4% by mass or less suppressed the amount of air bubbles in the pellets of the recycled plastic and lowered the water content after cooling the pellets. It is believed that this improved the surface properties during the production of the molded article. In addition, the generation of foreign substances such as insolubles, burns, and carbides is suppressed by selecting the type of base material for the printed matter or laminate (A), controlling the heating and melting temperature, and controlling the resin pressure at the tip discharge part of the extrusion device. presumed to have been

Claims (12)

Using an extruder equipped with a screw and a discharge part, printed matter that has not undergone a step of separating the substrate and the printed layer, or a laminate (A) that has not undergone a step of separating the substrate and the printed layer A method for producing recycled plastic to obtain recycled plastic (B),
The printed matter or the laminated laminate (A) includes a substrate layer and a printed layer, and the chlorine content is 0.4% by mass or less in the total mass of the printed matter or the laminated laminate (A), and , a polyolefin resin containing 80% by mass or more of the total mass of the printed matter or the laminate (A),
a step of heating, melting, and kneading the printed material or the laminate (A) in the extruder to obtain a resin composition (a);
A method for producing a recycled plastic, comprising the step of extruding the resin composition (a) from a discharge port of an extrusion device at a pressure of 18 MPa or less. The method for producing a recycled plastic according to claim 1, wherein the melting temperature is 120 to 280°C. 3. The method for producing a recycled plastic according to claim 1, wherein the polyolefin resin contained in the printed matter or laminate (A) is a polyethylene resin and/or a polypropylene resin. The method for producing a recycled plastic according to any one of claims 1 to 3, wherein the printed matter or laminated laminate (A) further comprises a barrier layer. 5. The recycled plastic according to claim 4, wherein the barrier layer of the printed matter or laminated laminate (A) is one or more selected from the group consisting of a vapor deposition layer containing a vapor deposition film, a barrier coat layer, and a barrier adhesive layer. Production method. The recycled plastic production method according to any one of claims 1 to 5, further comprising a water cooling step. The method for producing a recycled plastic according to any one of claims 1 to 6, wherein the melt mass flow rate of the printed matter or laminate (A) is 0.5 to 15 g/10 minutes. The recycled plastic according to any one of claims 1 to 7, wherein the printed matter or the printed layer of the laminated laminate (A) contains a pigment and a binder resin, and the chlorine content of the binder resin is 5% by mass or less. manufacturing method. The method for producing a recycled plastic according to any one of claims 1 to 8, wherein the extruder has a screw with a rotation speed of 50 to 1000 RPM. 9. The method for producing a recycled plastic according to claim 8, wherein the pigment content is 30% by mass or less in the total mass of the printed layer. According to any one of claims 1 to 10, wherein the printed matter or laminated laminate (A) further comprises an adhesive layer, said adhesive layer being a reaction product of a reactive urethane adhesive containing polyisocyanate and polyol. A method for producing the described recycled plastic. A method for producing a molded product of recycled plastic, which is produced by the method for producing recycled plastic according to any one of claims 1 to 11.