WO2022195843A1

WO2022195843A1 - Method for producing recycled resin composition

Info

Publication number: WO2022195843A1
Application number: PCT/JP2021/011343
Authority: WO
Inventors: 忠志立浪
Original assignee: 花王株式会社
Priority date: 2021-03-19
Filing date: 2021-03-19
Publication date: 2022-09-22
Also published as: JPWO2022195843A1

Abstract

A method for producing a recycled resin composition, the method comprising a step for melt-mixing a compound that is reactive with an amine, and a resin composition starting material that contains at least one material selected from the group consisting of resin composition starting materials for recycling, the resin composition starting materials containing a polyamide, and recycled resin composition starting materials containing a polyamide. With respect to this method for producing a recycled resin composition, the amine value of the recycled resin composition is 5 or less. A recycled resin composition according to the present invention is suitable for use in packaging materials, containers and the like.

Description

Method for producing recycled resin composition

The present invention relates to a recycled resin composition, a molded article of the recycled resin composition, a packaging material containing the molded article, a container containing the molded article, and a method for producing these.

Many packaging materials are made of thermoplastic composites and/or laminated materials and are formed, for example, into bottles, refillable pouches, and the like. These materials may be composed of completely different types of films, inorganics such as aluminum, inks, etc. for functional reasons. Therefore, when packaging materials and the like made of these materials are recovered and the resins are recycled, the materials contain unmelted materials such as ink and inorganic substances, and polymers incompatible with the main component polymer.

For example, in Patent Document 1, in order to obtain a recycled plastic material or the like having high physical properties, a plurality of types of polymers, at least one of which is used, are reacted with an oxazoline-based compatibilizer, an elastomer-based compatibilizer, and A sheet-like or film-like molded article composed of a plastic material containing at least one kind of compatibilizing agent selected from the group consisting of a sexual compatibilizing agent and a copolymer-based compatibilizing agent is disclosed.

Japanese Patent Application Laid-Open No. 2009-30062

The present invention relates to the following [1] to [6].
[1] Melting of a resin composition raw material containing one or more selected from the group consisting of a polyamide-containing resin composition raw material for regeneration and a polyamide-containing recycled resin composition raw material, and a compound that reacts with an amine. A method for producing a recycled resin composition comprising a kneading step, wherein the recycled resin composition has an amine value of 5 or less.
[2] A method for producing a molded body, comprising the step of molding the recycled resin composition obtained by the production method according to [1].
[3] Manufactured from a resin composition raw material containing one or more selected from the group consisting of a polyamide-containing resin composition raw material for regeneration and a polyamide-containing recycled resin composition raw material, containing a polyamide and an amine A recycled resin composition having a value of 5 or less.
[4] A film having a layer (A) made of the recycled resin composition according to [3].
[5] A packaging material comprising the film of [4].
[6] A container containing the film described in [4].

According to the present invention, a recycled resin composition having excellent seal strength between films when films are prepared, a method for producing the same, a molded article of the recycled resin composition and a method for producing the same, a packaging material containing the molded article, A container containing the molded article can be provided.

FIG. 3 shows a film of embodiment 3;

Detailed description of the invention

In the film using the recycled plastic material disclosed in Patent Document 1, the sealing strength between the films may be low, and further improvement is required.

The present invention provides a recycled resin composition that exhibits excellent sealing strength between films when films are prepared, a method for producing the same, a molded product of the recycled resin composition, a method for producing the same, a packaging material containing the molded product, and the molded product. Relating to a container containing a body.

As a result of extensive studies on the above problem, the present inventors newly discovered that when a film is prepared using a recycled resin composition containing polyamide as a raw material, the sealing strength between the films is significantly reduced. Furthermore, the inventors have newly found that a film having excellent seal strength can be prepared by using a recycled resin composition having an amine value of a specific value or less. Although this mechanism is not clear, it is presumed that the amount of amine transferred to the adhesive surface is suppressed.

[Method for producing recycled resin composition]
The method for producing a recycled resin composition of the present invention comprises a resin composition raw material containing at least one selected from the group consisting of a polyamide-containing resin composition raw material for recycling and a polyamide-containing recycled resin composition raw material. , a melt-kneading step with a compound that reacts with the amine. A resin composition raw material for recycling means a resin composition recovered from used products, factory waste materials, or the like as a raw material. Recycled resin composition raw materials are materials made from recycled resin compositions such as mechanically recycled resins and chemically recycled resins obtained by melt-kneading after being collected from used products and factory waste materials. means Also, the resin composition for regeneration (raw material) and the recycled resin composition (raw material) may be collectively referred to as "recycled resin (raw material)".

Examples of the recycled resin raw material used in the melt-kneading process include various resin compositions containing polyamide, such as compositions containing resins such as polyolefin resins, polyester resins, and polyurethane resins. Among these, compositions containing polyolefin resins, polyester resins, etc. as main components are preferred from the viewpoint of promoting the recycling of resins that are widely used as packaging materials.

Examples of polyolefin resins include polyethylene (PE resin) and polypropylene (PP resin). Among these, it is preferable to contain polyethylene as a main component from the viewpoint of promoting regeneration of resins that are widely used as packaging materials. The content of the polyolefin resin in the recycled resin raw material (that is, the total amount of the resin composition raw material for recycling and the recycled resin composition raw material) is preferably 50% by mass or more, more preferably 75% by mass, from the viewpoint of adhesiveness. It is at least 85% by mass, more preferably at least 85% by mass, and preferably at most 99% by mass, more preferably at most 97% by mass, and even more preferably at most 95% by mass from the viewpoint of promoting regeneration. The content when two or more kinds of polyolefin resins are contained is the total amount of the polyolefin resins.

Examples of polyester resins include polyethylene terephthalate (PET resin), polytrimethylene terephthalate (PTT resin), polybutylene terephthalate (PBT resin), polyethylene naphthalate (PEN resin), polybutylene naphthalate (PBN resin), and the like. . Among these, it is preferable to contain polyethylene terephthalate (PET resin) or the like as a main component from the viewpoint of promoting recycling of resins that are widely used as packaging materials. The content of the polyester resin in the recycled resin raw material is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more from the viewpoint of promoting regeneration. , preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less. The content when two or more kinds of polyester resins are contained is the total amount of the polyester resins.

As the resin composition raw material in the melt-kneading step, a recycled resin raw material and a new resin raw material may be used in combination. More preferably, only the raw material is used. That is, the content of the recycled resin raw material in the resin composition raw material is preferably 50% by mass or more, more preferably 75% by mass or more, and still more preferably 90% by mass or more, from the viewpoint of promoting regeneration of the resin. Preferably it is 100% by mass. The content when two or more kinds of recycled resin raw materials are contained is the total amount of the recycled resin raw materials.

The content of the polyamide in the resin composition raw material in the melt-kneading step is preferably 0.01% by mass or more, more preferably 1% by mass or more, and still more preferably 3% by mass or more, from the viewpoint of promoting regeneration, and , from the viewpoint of adhesion, it is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

Compounds that react with amines include compounds with carbonyl groups and epoxy groups. Examples thereof include ethylene-glycidyl methacrylate (E-GMA), maleic anhydride-modified polyethylene (MAH-PE), ethylene-acrylic acid copolymer and the like.

The amount of the compound that reacts with amine in the melt-kneading step is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, from the viewpoint of reducing the amine value with respect to 100 parts by mass of the polyamide in the raw material of the resin composition. , more preferably 30 parts by mass or more, and from the viewpoint of moldability, it is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 70 parts by mass or less. When two or more kinds of compounds that react with amines are contained, the content is the total amount of the compounds that react with amines.

In the melt-kneading step, in addition to the above components, raw materials containing various additives as necessary are stirred with a Henschel mixer or the like, or mixed with a closed kneader, a single-screw or twin-screw extruder, an open-roll kneader, or the like. The kneading treatment can be performed using a known kneader. The melting temperature is preferably 120° C., more preferably 150° C. or higher, and even more preferably 180° C. or higher from the viewpoint of improving the rigidity, heat resistance, and appearance of the molded product. , preferably 280° C. or lower, more preferably 250° C. or lower.

In addition to the melt-kneading step, the production method of the present invention further includes steps such as a step of collecting used resin, a step of separating, a step of crushing/pulverizing, and a step of washing, if necessary. good too.

The recycled resin composition obtained by the production method of the present invention contains polyamide. The amine value of the recycled resin composition obtained by the production method of the present invention is 5 or less, preferably 3 or less, more preferably 2 or less, and still more preferably 1 or less, from the viewpoint of seal strength. . As used herein, the amine value is measured according to the method described in Examples below.

[Recycled resin composition]
The recycled resin composition of the present invention is produced from a resin composition raw material containing at least one selected from the group consisting of a polyamide-containing resin composition raw material for recycling and a polyamide-containing recycled resin composition raw material, It contains polyamide and has an amine value of 5 or less. The type and amount of resin contained in the recycled resin composition of the present invention, the content of polyamide, the amine value, etc. are the same as those in the production method described above. The recycled resin composition of the present invention can be prepared by the production method of the present invention. However, as long as it is prepared using the resin composition raw material, it is prepared by other production methods. may be

When a film is prepared from the recycled resin composition of the present invention, it is excellent in sealing strength between the films, so that it can be suitably used by forming it into a film. In addition to films, the recycled resin composition of the present invention can also be used as various molded articles such as sheets, fibers, filaments, blow molded articles and injection molded articles. A laminate sheet forming method by co-extrusion processing or extrusion lamination processing using the recycled resin composition of the present invention is particularly effective, and the laminate sheet thus obtained can be suitably used.

The molded article can be prepared by a known molding process using the recycled resin composition of the present invention as a raw material. A preferred embodiment of the method for producing a molded article includes a production method comprising a step of molding the recycled resin composition obtained by the production method of the present invention.

A preferred embodiment of the molded article is a film having a layer (A) made of a resin composition containing the recycled resin composition of the present invention. The resin composition for layer (A) may be molded using only the recycled resin composition of the present invention as a raw material, or may optionally contain other resins, known additives, and the like. Moreover, in the embodiment of the film, in addition to the embodiment (embodiment 1) containing only the layer (A), layers may be arbitrarily laminated to form a multilayer structure.

For example, as another preferred aspect (aspect 2), 50 mass of ethylene-vinyl alcohol copolymer (hereinafter sometimes referred to as EVOH) having an elastic modulus of 2000 MPa or more, preferably 3000 MPa or more, more preferably 4000 MPa or more % or more of the resin composition and has a laminated structure of the layer (A) and the layer (B). The upper limit of the elastic modulus of the EVOH can be, for example, 10000 MPa or less. In this specification, the elastic modulus of EVOH is measured according to ISO527 and JISK7161.

EVOH can be obtained by a known method such as saponification of an ethylene-vinyl acetate copolymer. Commercially available EVOH having an elastic modulus of 2000 MPa or more include "EVAL F171B" (manufactured by Kuraray Co., Ltd.), " Soarnol D" (manufactured by Mitsubishi Chemical Corporation) or the like can be used.

The content of EVOH having an elastic modulus of 2000 MPa or more in the resin composition for the layer (B) is preferably 50% by mass or more, more preferably 55% by mass or more, and still more preferably 60% by mass, from the viewpoint of gas barrier properties. From the viewpoint of interlayer adhesion, the content is preferably 90% by mass or less, more preferably 80% by mass or less.

The resin composition for the layer (B) may optionally contain EVOH having an elastic modulus of 2000 MPa or more, a compound having a polar group and a polyolefin (excluding EVOH having an elastic modulus of 2000 MPa or more), and the like. .

Examples of polar groups in compounds having polar groups and polyolefins include organic isocyanate groups, (anhydrous) carboxylic acid groups, carboxylic acid halide groups, amino groups, hydroxy groups, epoxy groups, and ester groups. Examples of polyolefins include ethylene-based polymers [high-density polyethylene, medium-density polyethylene, low-density polyethylene, ethylene and one or more other vinyl compounds (eg, α-olefin, vinyl acetate, methacrylic acid, acrylic acid, etc.). copolymers, etc.], propylene-based polymers [polypropylene, copolymers of propylene and one or more other vinyl compounds, etc.], ethylene-propylene copolymers, polybutene, poly-4-methylpentene-1, etc. be done. Examples of compounds having a polar group and a polyolefin include maleic anhydride-modified polyethylene (MAH-PE), ethylene-glycidyl methacrylate copolymer, vinyl acetate, vinyl acetate-acrylic copolymer, and ethylene-vinyl acetate copolymer having an elastic modulus of less than 2000 MPa. Examples include saponified polymers.

In the film of aspect 2, the laminated structure of the layer (A) and the layer (B) may be directly laminated without containing an interlayer adhesive between the layer (A) and the layer (B), or It may be laminated via an agent (adhesive resin layer).

Examples of interlayer adhesives include compounds having a polar group and polyolefin (excluding EVOH with an elastic modulus of 2000 MPa or more), compounds having urethane bonds, and the like, and one or more of them can be used. Details of the compound having a polar group and polyolefin are the same as described above.

Examples of compounds having urethane bonds include polyurethane compounds obtained from polyol compounds (polyester polyol, polyester polyurethane polyol, polyether polyurethane polyol, etc.) and isocyanate compounds (tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, etc.). compound and the like.

In the embodiment containing an interlayer adhesive between the layer (A) and the layer (B), the content of the interlayer adhesive is preferably 5 mass from the viewpoint of interlayer adhesion with respect to 100 parts by mass of the resin constituting the film. parts or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and from the viewpoint of cost, preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less. is. Here, the "resin constituting the film" refers to two layers of resin laminated via an interlayer adhesive. For example, the content of the interlayer adhesive in a film laminated as layer (A1)/interlayer adhesive/layer (B)/layer (A2) is the total amount of resin of layer (A1) and layer (B) 100 parts by mass.

Another preferred embodiment (embodiment 3) is a film 1 having a structure in which layer (A) 2, layer (B) 3, and layer (A) 4 are laminated in this order (Fig. 1). In this embodiment, the resin compositions of layer (A) 2 and layer (A) 4 may be the same or different. In addition, the presence or absence and amount of the interlayer adhesive between the layers may be the same or different.

The thickness of the film is preferably 0.01 mm or more, more preferably 0.02 mm or more, and still more preferably 0.03 mm or more from the viewpoint of workability, and is preferably 0.03 mm or more from the viewpoint of reducing environmental load. 0.7 mm or less, more preferably 0.2 mm or less, still more preferably 0.15 mm or less, still more preferably 0.1 mm or less, and even more preferably 0.08 mm or less.

The film of each of the above aspects has excellent sealing strength, so it can be suitably used for packaging materials, containers, and the like. In particular, since the films of

aspects

2 and 3 are also excellent in gas barrier properties, examples include a container that constitutes an air circuit of an AFB (Air in Film Bottle) that uses air pressure and a pouch that has an air circuit for holding. be done.

The film of each aspect described above can be produced by a known method such as an extrusion molding method or an inflation molding method using the resin compositions of the layers (A) and (B).

Regarding the above-described embodiments, the present invention further discloses the following method for producing a recycled resin composition.

<1>
A melt-kneading step of a resin composition raw material containing one or more selected from the group consisting of a polyamide-containing resin composition raw material for regeneration and a polyamide-containing recycled resin composition raw material, and a compound that reacts with an amine. , wherein the recycled resin composition has an amine value of 5 or less.

<2>
The production method according to <1>, wherein the recycled resin composition has an amine value of preferably 3 or less, more preferably 2 or less, and still more preferably 1 or less.
<3>
<1> or <2>, wherein the polyamide content in the resin composition raw material is preferably 0.01% by mass or more, more preferably 1% by mass or more, and still more preferably 3% by mass or more. Production method.
<4>
<1> to <3>, wherein the polyamide content in the resin composition raw material is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less. Production method.
<5>
The production method according to any one of <1> to <4>, wherein the compound that reacts with an amine includes a compound having one or more groups selected from the group consisting of a carbonyl group and an epoxy group.
<6>
The production method according to any one of <1> to <5>, wherein the compound that reacts with amine includes any one of ethylene-glycidyl methacrylate, maleic anhydride-modified polyethylene, and ethylene-acrylic acid copolymer.
<7>
The amount of the compound that reacts with the amine in the melt-kneading step is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 30 parts by mass with respect to 100 parts by mass of the polyamide in the raw material of the resin composition. The production method according to any one of <1> to <6>, which is at least parts by mass.
<8>
The amount of the compound that reacts with the amine in the melt-kneading step is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and still more preferably 70 parts by mass with respect to 100 parts by mass of the polyamide in the raw material of the resin composition. The production method according to any one of <1> to <7>, which is not more than parts by mass.
<9>
The production method according to any one of <1> to <8>, wherein in the melt-kneading step, the melt temperature is preferably 120°C, more preferably 150°C or higher, and still more preferably 180°C or higher.
<10>
The production method according to any one of <1> to <9>, wherein in the melt-kneading step, the kneading is performed at a melting temperature of preferably 280°C or lower, more preferably 250°C.
<11>
The resin composition raw material for recycling or the recycled resin composition raw material contains, as a main component, one or more selected from the group consisting of polyethylene (PE resin) and polypropylene (PP resin) <1> to <10> The production method according to any one of the above.
<12>
The content of the polyolefin resin in the total amount of the resin composition raw material for regeneration and the recycled resin composition raw material is preferably 50% by mass or more, more preferably 75% by mass or more, and still more preferably 85% by mass or more. The manufacturing method according to any one of <1> to <11>.
<13>
The content of the polyolefin resin in the total amount of the resin composition raw material for regeneration and the recycled resin composition raw material is preferably 99% by mass or less, more preferably 97% by mass or less, and still more preferably 95% by mass or less. The manufacturing method according to any one of <1> to <12>.
<14>
The resin composition raw material for recycling or the recycled resin composition raw material includes polyethylene terephthalate (PET resin), polytrimethylene terephthalate (PTT resin), polybutylene terephthalate (PBT resin), polyethylene naphthalate (PEN resin), and The production method according to any one of <1> to <13>, containing as a main component one or more selected from the group consisting of polybutylene naphthalate (PBN resin).
<15>
The content of the polyester resin in the total amount of the resin composition raw material for regeneration and the recycled resin composition raw material is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more. The manufacturing method according to any one of <1> to <14>.
<16>
The content of the polyester resin in the total amount of the resin composition raw material for regeneration and the recycled resin composition raw material is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less. The manufacturing method according to any one of <1> to <15>.
<17>
The content of the resin composition raw material for regeneration and the recycled resin composition raw material in the resin composition raw material is preferably 50% by mass or more, more preferably 75% by mass or more, and still more preferably 90% by mass or more. The production method according to any one of <1> to <16>, wherein the content is preferably 100% by mass.
<18>
Any one of <1> to <17>, further comprising one or more steps selected from the group consisting of a step of collecting used resin, a step of separating, a step of crushing/pulverizing, and a step of washing. manufacturing method.
<19>
A method for producing a molded body, comprising a step of molding the recycled resin composition obtained by the production method according to any one of <1> to <18>.
<20>
The manufacturing method according to <19>, wherein the molded article is a film, sheet, fiber, filament, blow-molded article, or injection-molded article.
<21>
Manufactured from a resin composition raw material containing one or more selected from the group consisting of a polyamide-containing resin composition raw material for regeneration and a polyamide-containing recycled resin composition raw material, contains a polyamide, and has an amine value of 5. The recycled resin composition is as follows.
<22>
The recycled resin composition according to <21>, wherein the amine value is preferably 3 or less, more preferably 2 or less, and still more preferably 1 or less.
<23>
<21> or <22>, wherein the polyamide content in the resin composition raw material is preferably 0.01% by mass or more, more preferably 1% by mass or more, and still more preferably 3% by mass or more. Recycled resin composition.
<24>
<21> to <23>, wherein the polyamide content in the resin composition raw material is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less. Recycled resin composition.
<25>
A film having a layer (A) made of a resin composition containing the recycled resin composition according to any one of <21> to <24>.
<26>
It further contains a layer (B) made of a resin composition containing 50% by mass or more of an ethylene-vinyl alcohol copolymer having an elastic modulus of 2000 MPa or more, and has a laminated structure of the layer (A) and the layer (B). , the film according to <25>.
<27>
The content of the ethylene-vinyl alcohol copolymer having an elastic modulus of 2000 MPa or more in the resin composition for the layer (B) is preferably 50% by mass or more, more preferably 55% by mass or more, and still more preferably 60% by mass. The film according to <25> or <26> above.
<28>
The content of the ethylene-vinyl alcohol copolymer having an elastic modulus of 2000 MPa or more in the resin composition for the layer (B) is preferably 90% by mass or less, more preferably 80% by mass or less. <27> The film according to any one of them.
<29>
Any of <25> to <28>, wherein the resin composition for the layer (B) further contains a compound having a polar group and a polyolefin (excluding an ethylene-vinyl alcohol copolymer having an elastic modulus of 2000 MPa or more) The film described in Crab.
<30>
The film according to any one of <25> to <29>, having a structure in which the layer (A), the layer (B), and the layer (A) are laminated in this order.
<31>
The film according to any one of <25> to <30>, further comprising an interlayer adhesive between the layer (A) and the layer (B).
<32>
The interlayer adhesive contains one or more selected from the group consisting of a compound having a polar group and a polyolefin (excluding an ethylene-vinyl alcohol copolymer having a modulus of elasticity of 2000 MPa or more) and a compound having a urethane bond. , the film according to any one of <25> to <31>.
<33>
The compound having a polar group and a polyolefin is maleic anhydride-modified polyethylene (MAH-PE), ethylene-glycidyl methacrylate copolymer, vinyl acetate, vinyl acetate-acrylic copolymer, and ethylene vinyl acetate having an elastic modulus of less than 2000 MPa. The film according to any one of <25> to <32>, which is at least one selected from the group consisting of saponified copolymers.
<34>
The compound having a urethane bond is a polyurethane compound obtained from a polyol compound (polyester polyol, polyester polyurethane polyol, polyether polyurethane polyol, etc.) and an isocyanate compound (tolylene diisocyanate, 4-4'diphenylmethane diisocyanate, hexamethylene diisocyanate, etc.). The film according to any one of <25> to <33>.
<35>
The content of the interlayer adhesive is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more with respect to 100 parts by mass of the resin constituting the film. <34> The film according to any one of them.
<36>
The content of the interlayer adhesive is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 30 parts by mass or less with respect to 100 parts by mass of the resin constituting the film. <35> The film according to any one of them.
<37>
The film according to any one of <25> to <36>, having a thickness of preferably 0.01 mm or more, more preferably 0.02 mm or more, and even more preferably 0.03 mm or more.
<38>
<25>-<37> The film according to any one of the above.
<39>
The film according to any one of <25> to <38>, which is used for packaging materials or containers.
<40>
<25> to <39>, wherein the packaging material or the container is a container that forms an air circuit of an AFB (Air in Film Bottle) that uses air pressure or a pouch that has an air circuit for gripping. the film.
<41>
A packaging material comprising the film according to any one of <25> to <40>.
<42>
A container comprising the film according to any one of <25> to <40>.
<43>
<25> to <40> A pouch having an air circuit for gripping or a container constituting an air circuit of an AFB (Air in Film Bottle) using air pressure, comprising the film according to any one of <25> to <40>.

The present invention will be specifically described below with reference to examples. It should be noted that this example is merely an illustration of the present invention and does not imply any limitation. Parts in the examples are parts by weight unless otherwise specified, and % is % by weight. In addition, "ordinary pressure" indicates 101.3 kPa, and "ordinary temperature" indicates 25°C.

Multilayer film preparation Examples 1-3, Comparative Examples 1-3
With the composition described in Table 1, the resin composition raw material is kneaded using a twin-screw extruder (TEX-28V screw diameter 28 mm, L / D = 42, manufactured by Japan Steel Works) Pellets for layer (A) got Using a multilayer film molding machine (manufactured by Soken), a layer (A) made of a recycled resin composition, a layer (C) made of an adhesive resin (MAH-PE: Admer NF528, manufactured by Mitsui Chemicals, Inc.), EVOH (EVAL F171B, A multilayer film (Layer A/Layer C/Layer B/Layer C/Layer A) consisting of a layer (B) made of Kuraray Co., Ltd., with an elastic modulus of 4500 MPa was obtained. The thickness of each layer was 40 μm for layer (A), 5 μm for layer (C), and 6 μm for layer (B).

Details of the raw materials used in Table 1 are shown below.
Recycled resin: Recycled polyethylene resin (manufactured by Iwai Kasei Co., Ltd., composition: 80% polyethylene, 10% polyamide, 10% polyester)
MAH-PE: Admer HE810 (manufactured by Mitsui Chemicals)
E-GMA: Bond Fast BF-E (manufactured by Sumitomo Chemical Co., Ltd.)

<Measurement of amine value>
A bromcresol green indicator solution was added to a predetermined amount of the regenerated resin composition, titration was performed with a 0.2 mol/L alcoholic hydrochloric acid standard solution, and calculation was performed using equations (1) and (2). Table 1 shows.

A: Amount (mL) of 0.2 mol/L alcoholic hydrochloric acid standard solution required for sample titration
f: Factor of 0.2 mol/L alcoholic hydrochloric acid standard solution

<Seal strength, interlayer adhesion>
The seal strength (layer A/layer A) and interlayer adhesive strength (layer B/layer C) of the multilayer film of each example and comparative example were measured according to JISK6854-3. In the seal strength test, two multilayer films were sealed with an impulse sealer at 170° C. for 2 seconds and measured using a sample. A seal strength of 15 N/15 mm or more and an interlayer adhesion strength of 5 N/15 mm or more can be judged to be excellent. Table 1 shows the results.

As shown in Table 1, the layer (A) made of the recycled resin composition having an amine value of 5 or less was excellent in seal strength. Moreover, unexpectedly, the interlayer adhesion strength between the layers (B) and (C) was also excellent.

The recycled resin composition of the present invention can be suitably used for packaging materials, containers, and the like.

1 film 2 layer (A)
3 layer (B)
4 layer (A)

Claims

A melt-kneading step of a resin composition raw material containing one or more selected from the group consisting of a polyamide-containing resin composition raw material for regeneration and a polyamide-containing recycled resin composition raw material, and a compound that reacts with an amine. , wherein the recycled resin composition has an amine value of 5 or less.
The production method according to claim 1, wherein the recycled resin composition has an amine value of 3 or less.
The production method according to claim 1 or 2, wherein the polyamide content in the resin composition raw material is 0.01% by mass or more and 30% by mass or less.
The production method according to any one of claims 1 to 3, wherein the compound that reacts with amines includes a compound having one or more groups selected from the group consisting of carbonyl groups and epoxy groups.
The production method according to any one of claims 1 to 4, wherein the compound that reacts with amines includes any one of ethylene-glycidyl methacrylate, maleic anhydride-modified polyethylene, and ethylene-acrylic acid copolymer.
Any one of claims 1 to 5, wherein the amount of the compound that reacts with the amine in the melt-kneading step is 5 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the polyamide in the raw material of the resin composition. Method of manufacture as described.
The production method according to any one of claims 1 to 6, wherein in the melt-kneading step, the kneading treatment is performed at a melting temperature of 120°C or higher.
The production method according to any one of claims 1 to 7, wherein the resin composition raw material for recycling or the recycled resin composition raw material contains polyethylene as a main component.
The production method according to any one of claims 1 to 8, wherein the content of the resin composition raw material for regeneration and the recycled resin composition raw material in the resin composition raw material is 50% by mass or more.
A method for producing a molded body, comprising the step of molding the recycled resin composition obtained by the production method according to any one of claims 1 to 9.
The manufacturing method according to claim 10, wherein the molded body is a film.
Manufactured from a resin composition raw material containing one or more selected from the group consisting of a polyamide-containing resin composition raw material for regeneration and a polyamide-containing recycled resin composition raw material, contains a polyamide, and has an amine value of 5. The recycled resin composition is as follows.
The recycled resin composition according to claim 12, which has an amine value of 3 or less.
The recycled resin composition according to claim 12 or 13, wherein the polyamide content in the resin composition raw material is 0.01% by mass or more and 30% by mass or less.
A film having a layer (A) made of a resin composition containing the recycled resin composition according to any one of claims 12 to 14.
It further contains a layer (B) made of a resin composition containing 50% by mass or more of an ethylene-vinyl alcohol copolymer having an elastic modulus of 2000 MPa or more, and has a laminated structure of the layer (A) and the layer (B). 16. The film of claim 15.
The film according to claim 15 or 16, having a structure in which the layer (A), the layer (B), and the layer (A) are laminated in this order.
The film according to any one of claims 15 to 17, further comprising an interlayer adhesive between said layer (A) and said layer (B).
The interlayer adhesive contains one or more selected from the group consisting of a compound having a polar group and a polyolefin (excluding an ethylene-vinyl alcohol copolymer having a modulus of elasticity of 2000 MPa or more) and a compound having a urethane bond. 19. The film of claim 18.
A packaging material comprising the film according to any one of claims 15-19.
A container containing the film according to any one of claims 15-19.