CN111267437A - Polystyrene resin multilayer foamed sheet and separation paper using the same - Google Patents

Polystyrene resin multilayer foamed sheet and separation paper using the same Download PDF

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Publication number
CN111267437A
CN111267437A CN201911232354.8A CN201911232354A CN111267437A CN 111267437 A CN111267437 A CN 111267437A CN 201911232354 A CN201911232354 A CN 201911232354A CN 111267437 A CN111267437 A CN 111267437A
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China
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layer
resin
multilayer
sheet
foamed sheet
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CN201911232354.8A
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Chinese (zh)
Inventor
山形明生
岩崎聪
青木健
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JSP Corp
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JSP Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/22—All layers being foamed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0221—Vinyl resin
    • B32B2266/0228—Aromatic vinyl resin, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/025—Polyolefin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B32B2323/043—HDPE, i.e. high density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B32B2323/046—LDPE, i.e. low density polyethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/06—Pectin; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Buffer Packaging (AREA)

Abstract

The invention provides a foam sheet which is inhibited from adhering to a packaged object by a component derived from a polymer type antistatic agent, has excellent antistatic performance and high rigidity and has good use and handling properties, and a separation paper using the foam sheet. The multilayer foamed sheet of the present invention is a multilayer foamed sheet comprising a polystyrene resin foamed layer and a polyolefin resin layer laminated on at least one side of the foamed layer, wherein the resin layer comprises a surface layer on the outermost surface side of the sheet and an intermediate layer laminated and bonded to the surface layer, the surface layer comprises a polyolefin resin and does not substantially contain a polymer-type antistatic agent, the intermediate layer comprises a polyolefin resin and a polymer-type antistatic agent, the thickness of the surface layer is 2 to 20 [ mu ] m, and the surface resistivity of the multilayer foamed sheet on the side where the resin layers are laminated is less than 1.0X 1013Ω。

Description

Polystyrene resin multilayer foamed sheet and separation paper using the same
Technical Field
The present invention relates to a polystyrene resin multilayer foamed sheet and a separator paper using the multilayer foamed sheet.
Background
Polystyrene resin foam is excellent in lightweight properties, high in rigidity, and excellent in handling properties, and therefore is preferably used as a cushioning packaging material. In recent years, polystyrene resin foams have been required to have antistatic properties as required in some applications. For example, antistatic performance can be imparted by blending a polymer type antistatic agent (patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2017-71122.
Disclosure of Invention
Problems to be solved by the invention
On the other hand, the polystyrene resin foam described in patent document 1 has a possibility that a component derived from the polymer type antistatic agent adheres to the article to be packaged and contaminates the article to be packaged depending on the packaged state and the environment in which the article to be packaged is placed. In particular, when friction or the like occurs in a state where the cushioning packaging material is in contact with the object to be packaged, the amount of the component derived from the antistatic agent tends to increase, and the possibility of contaminating the object to be packaged becomes higher.
Therefore, polystyrene resin foams which have excellent rigidity and exhibit good antistatic properties and in which adhesion of components derived from a polymer type antistatic agent to an article to be packaged is suppressed have been desired.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a foam sheet which is excellent in antistatic property, high in rigidity, and excellent in handling property while suppressing adhesion of a component derived from a polymer type antistatic agent to an article to be packed, and a separator using the foam sheet.
Means for solving the problems
In order to solve the above problems, the present invention provides a multilayer foamed sheet comprising a polystyrene resin foamed layer and a polyolefin resin layer laminated on at least one side of the foamed layer,
the resin layer comprises a surface layer on the outermost surface side of the sheet and an intermediate layer laminated and bonded to the surface layer,
the surface layer contains a polyolefin resin and does not substantially contain a polymer type antistatic agent,
the intermediate layer contains a polyolefin resin and a polymer antistatic agent,
the thickness of the surface layer is 2 to 20 μm,
the surface resistivity of the resin layer laminated side of the multilayer foamed sheet is less than 1.0X 1013Ω。
The separation paper of the invention is composed of the multilayer foaming sheet.
Effects of the invention
The multilayer foamed sheet and the barrier paper using the same of the present invention are excellent in antistatic performance, high in rigidity and good in handling property, while suppressing adhesion of a component derived from a polymer type antistatic agent to an object to be packaged.
Drawings
Fig. 1 is a longitudinal sectional view schematically showing an example of a part of a multilayer foamed sheet of the present invention.
Description of the reference numerals
1 multilayer foamed sheet
2 polystyrene series resin foaming layer
3 polyolefin resin layer
3a surface layer
3b an intermediate layer.
Detailed Description
The present invention will be described in detail below.
The multilayer foamed sheet of the present invention has a polystyrene resin foamed layer and a polyolefin resin layer laminated on at least one side of the foamed layer.
Fig. 1 schematically shows an example of the present invention, and a multilayer foamed sheet 1 of the present invention has a polystyrene resin foamed layer 2 and a polyolefin resin layer 3 laminated on the foamed layer 2. The resin layer 3 includes a surface layer 3a and an intermediate layer 3b, the surface layer 3a being located on the outermost surface side of the sheet and containing substantially no antistatic agent, and the intermediate layer 3b being laminated and bonded to the surface layer 3a and containing a polymer type antistatic agent. While the multilayer foamed sheet 1 having the polystyrene resin foamed layer 2 and the polyolefin resin layer 3 laminated on both side surfaces of the foamed layer 1 as shown in fig. 1(a) is a preferable embodiment, the multilayer foamed sheet 1 may have the polystyrene resin foamed layer 2 and the polyolefin resin layer 3 laminated on one side surface of the foamed layer 1 as shown in fig. 1 (b).
The multilayer foamed sheet of the present invention has a polystyrene resin foamed layer to ensure rigidity and improve handling properties. That is, when the multilayer foamed sheet of the present invention is used as a paper spacer, the amount of sagging when held by hand is small (rigidity is high), and the workability when inserting a packaged object such as a glass plate between the packaged objects is good. Further, since the sagging of the portion protruding from the glass plate or the like after the insertion into the glass plate or the like is suppressed, the workability when removing the foamed sheet is also excellent.
The polystyrene resin foamed layer is composed of a polystyrene resin composition. The polystyrene resin composition is made of a polystyrene resin alone or as a main component, and the content of the polystyrene resin in the polystyrene resin composition is preferably 50 mass% or more, and more preferably 60 mass% or more.
The polystyrene resin is a polymer mainly composed of styrene, and not only a styrene homopolymer but also a copolymer of styrene and a vinyl monomer copolymerizable with styrene can be used. Specific examples thereof include polystyrene, high impact polystyrene, styrene-acrylonitrile copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-maleic anhydride copolymer, polystyrene-polyphenylene ether copolymer, and a mixture of polystyrene and polyphenylene ether. These polystyrene resins may be used in combination of two or more.
The styrene component of the polystyrene resin in the present invention is 50 mol% or more, preferably 60 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more.
In the multilayer foamed sheet of the present invention, the resin composition in the foamed layer is preferably a polystyrene resin composition (a) containing a polystyrene resin, a polyolefin resin, and a styrene elastomer. In this case, the material is excellent in the balance between the physical properties of rigidity and impact resistance, is excellent in the resistance to bending breakage, and can be produced at low cost.
In the polystyrene resin composition (a), examples of the polyolefin resin include a polyethylene resin and a polypropylene resin.
Examples of the polyethylene resin include low-density polyethylene, ultra-low-density polyethylene, linear low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, and ethylene-ethyl acrylate. Here, the ethylene component of the polyethylene resin is 50 mol% or more, preferably 60 mol% or more, more preferably 80 mol% or more, and further preferably 90 mol% or more.
Examples of the polypropylene resin include polypropylene, propylene-ethylene random copolymer, and block polypropylene.
Among these, the polyolefin resin is preferably a polyethylene resin. Among them, Low Density Polyethylene (LDPE) is preferable from the viewpoints of extrusion foamability in producing the foam, balance between impact resistance and rigidity of the foam, and cost property.
In the case of using low-density polyethylene as the polyethylene resin constituting the foamed layer, the balance between the extrusion foamability and the physical properties of the foam is determined in accordance with JIS K7210-1: 2014 (test temperature: 190 ℃, load 2.16kg), the MFR of the low density polyethylene resin is preferably 0.05 to 5g/10min, more preferably 0.1 to 3g/10 min.
In the polystyrene resin composition (a), a known general styrene elastomer can be used as the styrene elastomer. Examples thereof include a styrene-ethylene-butylene-styrene block copolymer (hereinafter abbreviated as SEBS), a styrene-butadiene-butylene-styrene block copolymer (hereinafter abbreviated as SBBS), a styrene-butadiene-styrene block copolymer (SBS), and a styrene-isoprene-styrene block copolymer (SIS). Among them, SEBS and SBBS can be suitably used from the viewpoint of adhesion to a resin layer and convenience in use as a recycled material.
The styrene component ratio of the styrene-based elastomer is not particularly limited as long as the object and effect of the present invention are achieved, but is preferably approximately 20 to 50% by mass, more preferably 25 to 45% by mass.
In the polystyrene resin composition (a), the content of the polystyrene resin is preferably 60 to 94% by mass (however, the total of the polystyrene resin, the polyolefin resin, and the styrene elastomer is 100% by mass). When the content of the polystyrene-based resin is within the above range, the foamed sheet is more excellent in rigidity and further excellent in handling property when used as a separator. From the above viewpoint, the content of the polystyrene resin is more preferably 65 to 90% by mass, and still more preferably 70 to 85% by mass.
In the polystyrene resin composition (a), the content of the polyolefin resin is preferably 5 to 30 mass% (however, the total of the polystyrene resin, the polyolefin resin, and the styrene elastomer is 100 mass%). When the content of the polyolefin-based resin is within the above range, the adhesiveness between the foamed layer and the resin layer is more excellent, and the balance between the impact resistance and the rigidity of the foamed sheet is also more excellent. Further, the foam sheet maintains a closed cell ratio and has an excellent appearance.
From the above viewpoint, the content of the polyolefin resin is more preferably 10 to 25% by mass, and still more preferably 15 to 23% by mass.
In the polystyrene resin composition (a), the content of the styrene elastomer is preferably 1 to 10 mass% (however, the total of the polystyrene resin, the polyolefin resin, and the styrene elastomer is 100 mass%). When the content of the styrene-based elastomer is within the above range, the rigidity of the foamed sheet can be maintained and the impact resistance and the bending breakage resistance are also excellent. The dispersion state of the polyolefin resin in the polystyrene resin composition (a) is good, and the surface state of the foamed sheet is excellent.
From the above viewpoint, the content of the styrene-based elastomer is more preferably 1.5 to 9% by mass, and still more preferably 2 to 8% by mass.
In the polystyrene resin composition (a), the mass ratio of the polyolefin resin to the styrene elastomer is preferably 100: 15-100: 80. when the mass ratio is within the above range, a foamed sheet having good adhesion between the foamed layer and the resin layer and having an excellent balance among rigidity, impact resistance and cost can be obtained.
From the above viewpoint, the mass ratio of the polyolefin resin to the styrene-based elastomer is more preferably 100: 15-100: 70, more preferably 100: 15-100: 60.
in the polystyrene resin composition (a), when the content of the polystyrene resin is 60 to 94% by mass, the content of the polyolefin resin is 5 to 30% by mass, and the content of the styrene elastomer is 1 to 10% by mass (however, the total amount of the polystyrene resin, the polyolefin resin, and the styrene elastomer is 100% by mass), the composition has sufficient rigidity and is also good in balance with physical properties of impact resistance, and the like, and is more preferable in this point.
The polystyrene resin composition (a) may contain other resins and elastomers than the above-mentioned polyolefin resin and styrene elastomer, within a range not to impair the object of the present invention. In this case, the amount of the other resin or elastomer to be blended is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably not blended, based on 100% by mass of the polystyrene resin composition (a) including these components.
The multilayer foamed sheet of the present invention may contain other components such as a cell regulator, a heat stabilizer, an ultraviolet screening agent, an antioxidant, and a colorant in the polystyrene resin composition constituting the polystyrene resin foamed layer, within a range not to impair the object of the present invention.
Conventionally, when a mixed resin composition containing a polystyrene resin and a polyolefin resin is used as a resin constituting a foamed layer to produce a foamed sheet having a small thickness, pinholes tend to be generated in the surface of the foamed sheet during drawing, and the foamed sheet tends to have a poor appearance due to uneven stretching of the resin, as compared with the case of using a single resin. The foamed sheet of the present invention is a multilayer foamed sheet having a foamed layer made of a resin composition containing a polystyrene resin and a polyolefin resin, but has no such problem and an excellent appearance.
In the multilayer foamed sheet of the present invention, the polyolefin resin layer includes a plurality of layers composed of a polyolefin resin composition (B) containing a polyolefin resin. The plurality of layers include a surface layer and an intermediate layer.
The polyolefin resin composition (B) constituting the resin layer is made of only a polyolefin resin or is made of a polyolefin resin as a main component, and the content of the polyolefin resin in the polyolefin resin composition is preferably 50 mass% or more, and more preferably 60 mass% or more.
Examples of the polyolefin resin include polyethylene resins and polypropylene resins.
Examples of the polyethylene resin include low-density polyethylene, ultra-low-density polyethylene, linear low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, and ethylene-ethyl acrylate.
Examples of the polypropylene resin include polypropylene resins such as polypropylene, propylene-ethylene random copolymer, and block polypropylene.
In addition to the surface layer and the intermediate layer, a resin layer substantially containing no antistatic agent may be provided on the polyolefin resin layer within a range that can achieve the intended purpose of the present invention. For example, an adhesive layer for bonding the surface layer and the intermediate layer may be provided between the surface layer and the intermediate layer, or an adhesive layer for bonding the intermediate layer and the foamed layer may be provided between the intermediate layer and the foamed layer.
The surface layer of the polyolefin resin layer is located on the outermost surface side of the sheet and contains substantially no antistatic agent.
The surface layer does not substantially contain an antistatic agent, so that the surface of the foam sheet does not contain a polymer type antistatic agent, thereby preventing the components derived from the antistatic agent from adhering to the article to be packaged and contaminating the article to be packaged. In particular, even when friction or the like occurs in a state where the foam sheet is in contact with the object to be packed, the adhesion of components derived from the antistatic agent to the object to be packed is suppressed, and the contamination of the object to be packed is reduced.
In the present invention, the phrase "the surface layer is located on the outermost surface side of the sheet" means that the surface layer is a layer having a surface exposed to the outside.
The phrase "substantially not containing an antistatic agent" in the present invention means that the antistatic agent is substantially 3 mass% or less (inclusive of 0), more preferably 1 mass% or less (inclusive of 0), and still more preferably not contained (0 mass%) with respect to 100 mass% of the entire surface layer.
The resin layer which is provided in the polyolefin resin layer other than the surface layer and the intermediate layer and which does not substantially contain an antistatic agent is preferably not more than about 3 mass% (inclusive of 0), more preferably not more than 1 mass% (inclusive of 0), and still more preferably not more than 0 mass%, relative to 100 mass% of the entire resin layer.
From the viewpoint of maintaining the foamability of the foamed layer, the foamed layer is also preferably substantially free of an antistatic agent, and more specifically, preferably substantially 3 mass% or less (inclusive of 0), more preferably 1 mass% or less (inclusive of 0), and even more preferably free of (i.e., 0 mass%) relative to 100 mass% of the entire foamed layer.
The polyolefin resin in the polyolefin resin composition (B) of the surface layer is preferably a polyethylene resin (hereinafter, referred to as a polyethylene resin composition). In this case, a foam sheet having more excellent cushioning properties can be obtained. Here, the ethylene component of the polyethylene resin is 50 mol% or more, preferably 60 mol% or more, more preferably 80 mol% or more, and further preferably 90 mol% or more.
The polyethylene resin composition constituting the surface layer may contain other resins, elastomers, and the like in addition to the polyethylene resin, but is preferably composed of only the polyethylene resin.
Among them, the polyolefin resin of the surface layer is a polyethylene resin, and the polyethylene resin is more preferably a polyethylene resin containing Low Density Polyethylene (LDPE) and High Density Polyethylene (HDPE). In this case, the slidability can be ensured, and the handleability is further improved. In particular, when the foam sheet is used as a paper spacer, the slidability between the object to be packaged such as a glass plate and the foam sheet is good, and the workability of the foam sheet during insertion and removal is further excellent. Further, the foam sheet has more excellent cushioning properties and flexibility on the surface, and also has more excellent bending breakage resistance. Further, even when friction or the like occurs in a state where the foam sheet is in contact with the object to be packed, the amount of the component derived from the antistatic agent adhering to the foam sheet can be further reduced. From the above viewpoint, the mass ratio of the low density polyethylene to the high density polyethylene constituting the surface layer is preferably 10: 90-80: 20, more preferably 20: 80-70: 30, more preferably 25: 75-60: 40.
as for the low-density polyethylene contained in the surface layer, the polyethylene composition is based on JIS K7210-1: 2014 (test temperature: 190 ℃ C., load 2.16kg) is preferably 0.2 to 10g/10 min. When the MFR of the low-density polyethylene contained in the surface layer is within the above range, the occurrence of pinholes on the surface of the foamed sheet is reduced, and the adhesion of the component derived from the antistatic agent to the article to be packed is suppressed. Further, even when the surface layer is thin, the surface layer having a uniform thickness is easily formed, and the entire foam sheet can exhibit good antistatic performance at every position. From the above-mentioned viewpoint, the MFR of the low-density polyethylene contained in the surface layer is more preferably 1g/10min or more, and still more preferably 2g/10min or more. Further, the MFR is more preferably 8g/min or less, and still more preferably 7g/10min or less.
As for the high-density polyethylene contained in the surface layer, the polyethylene composition is based on JIS K7210-1: 2014 (test temperature: 190 ℃, load 2.16kg) is preferably 4 to 20g/10 min. When the MFR of the high-density polyethylene contained in the surface layer is within the above range, the resin ductility at the time of film formation of the surface layer is good, and therefore, even when the thickness of the surface layer is thin, the surface layer having a uniform thickness is easily formed, and good antistatic performance can be exhibited at every position of the entire foam sheet. From the above-mentioned viewpoint, the MFR of the high-density polyethylene contained in the surface layer is more preferably 5g/10min or more, and still more preferably 6g/10min or more. Further, the MFR is more preferably 15g/10min or less, and still more preferably 12g/10min or less.
The melting point of the low-density polyethylene contained in the surface layer is preferably 80 to 130 ℃. When the melting point of the low-density polyethylene contained in the surface layer is within the above range, the foam sheets and the object to be packed can be prevented from sticking to each other even when used or stored in a high-temperature environment. From the above viewpoint, the melting point of the low density polyethylene contained in the surface layer is more preferably 90 ℃ or higher. The melting point is more preferably 120 ℃ or lower.
The high-density polyethylene contained in the surface layer has a melting point of preferably 110 ℃ or higher, more preferably 120 ℃ or higher, from the same viewpoint as the melting point of the low-density polyethylene. The melting point is preferably 150 ℃ or lower, more preferably 140 ℃ or lower.
In the present invention, the melting point of the resin is the peak temperature of the melting peak determined in accordance with JIS K7121-2012. When two or more peaks appear in the DSC curve, the melting point is the peak temperature of the peak with the largest peak area. The measurement sample used was a raw material used for producing each layer.
The surface layer of the multilayer foamed sheet of the present invention has a thickness of 2 to 20 μm. By making the surface layer within the above range, the multilayer foam sheet of the present invention can exhibit sufficient antistatic performance even in the case where the surface layer substantially not containing an antistatic agent is provided. In addition, even when friction or the like occurs in a state where the foam sheet is in contact with the object to be packaged, adhesion of components derived from the polymer type antistatic agent can be suppressed.
When the thickness of the surface layer is excessively thick, there is a possibility that antistatic performance is insufficient. On the other hand, when the thickness of the surface layer is too thin, it is difficult to form the surface layer satisfactorily, and there is a possibility that pinholes, cracks, and the like are generated on the surface of the foamed sheet. As a result, the polymer type antistatic agent is exposed on the surface of the foamed sheet, and there is a possibility that the amount of the component derived from the polymer type antistatic agent attached to the article to be packaged increases. From the above viewpoint, the thickness is preferably 2.5 μm or more, more preferably 3.0 μm or more, and further preferably 3.5 μm or more. The thickness is preferably 15 μm or less, more preferably 12 μm or less, and still more preferably 10 μm or less. In the present specification, when an adhesive layer or the like is provided between the surface layer and the intermediate layer, the thickness of the surface layer is the total thickness of the surface layer and the adhesive layer.
The polyolefin resin layer has an intermediate layer laminated and bonded to a surface layer, and contains a polymer type antistatic agent.
The polyolefin resin in the polyolefin resin composition (B) of the intermediate layer is preferably a polyethylene resin (hereinafter, referred to as a polyethylene resin composition). By using a polyethylene resin as the polyolefin resin, the flexibility of the foamed sheet can be improved, and even when the foamed layer is made of a polystyrene resin composition, the foamed sheet can have excellent bending breakage resistance. From the above viewpoint, the polyolefin resin in the polyolefin resin composition (B) of the intermediate layer is more preferably low-density polyethylene.
For the low density polyethylene contained in the intermediate layer, the polyethylene composition is based on JIS K7210-1: 2014 (test temperature: 190 ℃ C., load 2.16kg) is preferably 0.2 to 10g/10 min. When the MFR of the low density polyethylene contained in the intermediate layer is within the above range, the polymeric antistatic agent is easily dispersed in the intermediate layer, and the antistatic agent property becomes better. Further, since the ductility of the resin is good when the intermediate layer is formed, the thickness of the intermediate layer is easily made more uniform, and the antistatic performance can be more stably exhibited. From the above-mentioned viewpoint, the MFR of the low-density polyethylene contained in the intermediate layer is more preferably 1g/10min or more, and still more preferably 2g/10min or more. Further, the MFR is more preferably 8g/10min or less, and still more preferably 7g/10min or less.
The low-density polyethylene contained in the intermediate layer preferably has a melting point of 80 to 130 ℃, more preferably 90 to 120 ℃ from the viewpoint of heat resistance and the like. The melting point can be determined by the same method as the melting point of the polyethylene resin contained in the surface layer.
The polyethylene resin composition constituting the intermediate layer may be composed of only a polyethylene resin, or a polyethylene resin composition may be blended with a resin other than the polyethylene resin, an elastomer, or the like.
Examples of the resin and elastomer include a polystyrene resin, a polypropylene resin such as a propylene homopolymer and an ethylene-propylene copolymer, a styrene elastomer, and a hydrogenated product thereof. When a polystyrene resin is blended as the resin composition constituting the intermediate layer, the adhesiveness to the foamed layer can be further improved and the rigidity of the foamed sheet can be further improved. Polypropylene resins (m-PP) polymerized using a metallocene polymerization catalyst are preferably used as the polypropylene resin, and in this case, the bending resistance (ヒンジ -property, repeated bendability) can be improved.
In addition, as the styrene-based elastomer, styrene-ethylene-butylene-styrene block copolymer (SEBS) or the like can be suitably used, and in this case, the adhesiveness between the intermediate layer and the foamed layer can be improved.
Among them, it is preferable to blend a styrene-based elastomer such as a styrene-ethylene-butylene-styrene block copolymer (SEBS) as the resin composition constituting the intermediate layer.
When other resin, elastomer, or the like is blended, the blending amount thereof is within a range that allows adhesion between the foamed layer and the intermediate layer and achieves the intended object of the present invention, and is preferably approximately 50% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass or less, particularly preferably 30% by mass or less, and most preferably 25% by mass or less with respect to 100% by mass of the polyethylene resin composition of the intermediate layer.
Specific examples of the polymer type antistatic agent include those having a volume resistivity of 1 × 105～1×1011And omega-cm hydrophilic polymers (hereinafter, simply referred to as hydrophilic polymers), block polymers of hydrophilic polymer blocks and hydrophobic polymer blocks, ionomers, and the like. Examples of the hydrophilic polymer include a polyether, a cationic polymer, and an anionic polymer. On the other hand, examples of the hydrophobic polymer block include polyolefin, polyamide and the like. Examples of the bonding between the hydrophilic polymer block and the hydrophobic polymer block include ester bonding, amide bonding, and ether bonding. Among them, in order to impart an excellent antistatic effect and obtain an effect of suppressing a decrease in physical properties by adding an antistatic agent, a block copolymer having a polyether block as a hydrophilic polymer and a polyolefin block as a hydrophobic polymer block is preferable. Further, the surface resistivity is preferably 1 × 10 in order to obtain a desired antistatic effect with a small amount of addition and to suppress the amount of migration of organic substances to a small extent7Omega is less than or equal to.
The melting point of the polymer antistatic agent used in the present invention is preferably 150 ℃ or lower, more preferably 135 ℃ or lower, further preferably 125 ℃ or lower, and particularly preferably 120 ℃ or lower. When the melting point of the polymeric antistatic agent is within the above range, since the dispersion thereof in the polyolefin-based resin is more excellent, the dispersion state of the polymeric antistatic agent in the intermediate layer is optimized, and uniform antistatic properties are exhibited throughout the entire multilayer foamed sheet.
Further, the absolute value of the difference between the melting point of the polymer type antistatic agent and the melting point of the polyolefin-based resin constituting the intermediate layer is preferably less than 40 ℃. When the absolute value of the difference between the melting point of the polymeric antistatic agent and the melting point of the polyolefin-based resin constituting the intermediate layer is within the above range, the polymeric antistatic agent in the intermediate layer is more dispersed, and uniform antistatic properties are exhibited throughout the entire multilayer foamed sheet. From the above viewpoint, the absolute value of the difference is more preferably less than 30 ℃ and still more preferably less than 20 ℃.
In the present invention, the melting point of the polymer type antistatic agent is the peak temperature of the melting peak determined in accordance with JIS K7121-2012. When two or more peaks appear in the DSC curve, the melting point is the peak temperature of the peak with the largest peak area. The measurement sample used was a raw material used for producing each layer.
In addition, the melt flow rate of the polymer type antistatic agent is preferably 1-50 g/10min or more. When the melt flow rate is within the above range, the dispersion state of the polymer type antistatic agent in the polyolefin-based resin is optimized, and the antistatic property of the multilayer foamed sheet is further improved. From the above-mentioned viewpoint, the melt flow rate of the polymer type antistatic agent is more preferably 5g/10min or more, and still more preferably 10g/10min or more. Further, the MFR is more preferably 45g/10min or less, and still more preferably 40g/10min or less.
The melt flow rate of the polymeric antistatic agent in the present invention is in accordance with JIS K7210-1: 2014 measured at 190 deg.C under 2.16kg load.
In the multilayer foamed sheet of the present invention, the content of the polymeric antistatic agent in the intermediate layer is preferably 8 to 60% by mass, based on 100% by mass of the total of the polyolefin resin composition and the polymeric antistatic agent constituting the intermediate layer. In the middle layerWhen the content of the antistatic agent (2) is within the above range, the antistatic performance of the multilayer foam sheet is more excellent. In particular, within the ranges of the thickness of the surface layer, the sum of the thicknesses of the surface layer and the intermediate layer, and the ratio of the thicknesses, exemplified in the present specification, the surface resistivity of the multilayer foamed sheet on the surface layer side can be more easily made to be less than 1.0 × 1013Omega. From the above viewpoint, the content is more preferably 10% by mass or more, further preferably 15% by mass or more, and particularly preferably 20% by mass or more. The content is more preferably 55% by mass or less, still more preferably 40% by mass or less, and particularly preferably 30% by mass or less.
The multilayer foamed sheet of the present invention may contain other components such as inorganic fillers, heat stabilizers, ultraviolet absorbers, antioxidants, colorants, and antibacterial agents in the resin composition constituting the surface layer, the intermediate layer, and the like, which are the layers of the resin layer, within a range not to impair the object of the present invention.
The surface resistivity of the multilayer foamed sheet of the present invention on the side of the resin layer lamination surface is less than 1.0X 1013Omega. That is, the intermediate layer of the multi-layer foamed sheet of the present invention contains a polymer type antistatic agent (polymer type antistatic agent) for which the surface resistivity of the multi-layer foamed sheet is less than 1 × 1013(omega), preferably 1X 1012(omega) or less, more preferably 1X 1011(Ω) or less, a polymer-type antistatic agent is blended in the resin composition constituting the intermediate layer. The lower limit of the surface resistivity is not particularly limited, but is approximately 1 × 108(Ω)。
By setting the surface resistivity within the above range, a multilayer foamed sheet having excellent antistatic properties can be obtained.
The surface resistivity in the present invention was measured in accordance with JIS K6271 (2001). Specifically, 3 or more predetermined test pieces (for example, 100mm in length × 100mm in width × thickness: test piece thickness) were cut out from the obtained multilayer foamed sheet, and after the test pieces were left to stand at 23 ℃ for 24 hours under a humidity of 50%, the surface resistivity was measured, and the average of the obtained measurement values was taken as the surface resistivity.
In the present invention, the thickness of the resin layer is typically the total thickness of the surface layer and the intermediate layer, and is preferably 5 to 50 μm. When the thickness is within the above range, the foam sheet is excellent in cushioning properties and lightweight properties, and also excellent in surface smoothness. In addition, since the occurrence of pinholes on the surface of the foam sheet can be suppressed, the possibility of contaminating the packaged article becomes smaller. Further, even when the intermediate layer and the surface layer are laminated on the foamed layer by coextrusion described later, the foamed sheet has good extrusion foamability and excellent appearance with suppressed waviness at the time of production. From the above viewpoint, the thickness is more preferably 6 μm or more, and still more preferably 7 μm or more. The thickness is more preferably 40 μm or less, and still more preferably 30 μm or less.
For the multi-layer foamed sheet of the present invention, the ratio of the surface layer thickness to the intermediate layer thickness is preferably 1: 0.3-1: 10. when the ratio of the thicknesses of the surface layer and the intermediate layer is within the above range, the antistatic property is more excellent, and the thicknesses of the surface layer and the intermediate layer are more uniform, so that the variation of the antistatic property due to the difference of the portions can be suppressed. Further, since the thickness of the surface layer with respect to the intermediate layer can be appropriately secured, the possibility that the polymer type antistatic agent is exposed on the surface is reduced, and the contamination of the packaged article is also reduced. Further, even when a multilayer foamed sheet is produced by coextrusion described later, pinholes and the like do not occur in the surface layer, and contamination of the packaged article is further reduced. From these viewpoints, the ratio of the surface layer thickness to the intermediate layer thickness is preferably 1: 0.4-1: 5, more preferably 1: 0.5-1: 4, more preferably 1: 0.6-1: 3.
in the multilayer foamed sheet of the present invention, the thickness of the intermediate layer and the surface layer is measured by the following method.
First, the multilayer foamed sheet is cut in a direction orthogonal to the extrusion direction to cut a vertical section. Next, in the vertical cross section of each surface of the multilayer foamed sheet, 10 or more magnified photographs were taken at equal intervals in the sheet width direction for a total of 20 or more points. The thicknesses of the intermediate layer and the surface layer at the respective points of the shot were measured, and the arithmetic mean values of the obtained values were taken as the thicknesses of the intermediate layer and the surface layer.
Note that the thickness of the intermediate layer [ μm ]]The amount of discharge X [ kg/hr ] of the intermediate layer per one side in the production of the multilayer foamed sheet was known]The width W [ m ] of the obtained multilayer foamed sheet]The length per unit time L [ m/hr ] of the obtained multilayer foamed sheet]In the case of (2), the density ρ 1[ g/cm ] of the base resin constituting the intermediate layer may be used3]The amount of discharge Y [ kg/hr ] from the surface layer per one side was determined from the following equation (1)]In the case of (2), the density ρ 2[ g/cm ] of the base resin constituting the surface layer may be used3]The expression (2) below was used.
Thickness of intermediate layer [ μm ] - [ X/(1000 × L × W × ρ 1) ] … (1)
Thickness [ μm ] - [ Y/(1000 × L × W × ρ 2) ] … (2) of the surface layer
The apparent density of the multilayer foam sheet of the present invention is preferably 20 to 350kg/m3. When the apparent density of the multilayer foamed sheet is within the above range, the balance between mechanical properties such as strength and rigidity and lightweight properties and cushioning properties is excellent. From this viewpoint, the apparent density is more preferably 35 to 260kg/m3More preferably 50 to 210kg/m3。
The multilayer foamed sheet of the present invention preferably has a gram weight of 30 to 1000g/m2More preferably more than 30g/m2And 220g/m2The following. When the grammage of the multilayer foamed sheet is within the above range, the balance between the light weight and the mechanical properties is good, the rigidity is further excellent, and the sheet is a light-weight sheet and is excellent in handling properties as a separator. From the above viewpoint, the grammage of the multilayer foamed sheet is more preferably more than 40g/m2And 200g/m2Hereinafter, it is more preferably more than 50 and 180g/m2The following.
In the present invention, the method of measuring the apparent density of the multilayer foamed sheet is as follows. First, the thickness of the multilayer foamed sheet was measured by the above-described method, and then the grammage was measured. The method comprises cutting a predetermined test piece from a multi-layer foam sheet, measuring the mass of the test piece, and dividing the mass by the area of the test pieceAnd then the basis weight of the foamed sheet is converted to obtain the grammage [ g/m ]2]. Further, the determined grammage [ g/m ] can be used2]Divided by the thickness of the multilayer foamed sheet [ mm ]]And then the unit conversion is performed to obtain the apparent density [ kg/m ]3]。
The grammage of the intermediate layer and the surface layer is determined by multiplying the thickness of each layer by the density of the base resin constituting each layer and performing unit conversion. When the surface layer contains a filler (inorganic filler), the grammage (g/m) of the surface layer is determined by multiplying the density of the filler-containing surface layer by the density of the base resin of the surface layer, and calculating the unit conversion2). In addition, similarly to the method of determining the thickness from the discharge amount as described above, the discharge amount X [ kg/hr ] of the intermediate layer can be used]And the discharge amount of the surface layer is Y [ kg/hr ]]The width W [ m ] of the obtained multilayer foamed sheet]The length per unit time L [ m/hr ] of the obtained multilayer foamed sheet]The expression is obtained from the following expressions (3) and (4).
Grammage of the intermediate layer [ g/m ]2]＝〔X/(1000×L×W)〕…(3)
Grammage of surface layer [ g/m ]2]＝〔Y/(1000×L×W)〕…(4)
The grammage of the intermediate layer and the grammage of the surface layer are the grammages of only one side of the layers laminated on both sides of the foamed layer.
The total thickness of the multilayer foamed sheet of the present invention is preferably 0.1 to 10mm, more preferably 0.2 to 5mm, and still more preferably 0.3 to 3 mm. The multilayer foam sheet of the present invention has no pinholes or the like even in the form of a sheet, and is a foam sheet having a beautiful surface.
In the present invention, the thickness of the multilayer foamed sheet was measured as follows.
First, the multilayer foamed sheet is cut in a direction orthogonal to the extrusion direction, and a vertical cross section in the width direction is cut. In the vertical section, the thickness of the multilayer foamed sheet was measured at 10 points at equal intervals in the width direction of the multilayer foamed sheet, and the arithmetic average of the obtained values was taken as the thickness of the multilayer foamed sheet.
In the multilayer foamed sheet of the present invention, the ratio of the thickness of the resin layer to the total thickness is preferably 0.001 to 0.1, and more preferably 0.005 to 0.05. When the ratio is within the above range, the foam sheet is more excellent in surface smoothness, cushioning properties, and the like.
The closed-cell ratio of the multilayer foam sheet of the present invention is preferably 50% or more, and more preferably 55% or more, from the viewpoint of obtaining a multilayer foam sheet having good rigidity and compressive strength.
In the present invention, the closed cell ratio of the multilayer foamed sheet: s (%) is the true volume of the multilayer foamed sheet measured according to procedure C of ASTM D2856-70 using an air comparison type densitometer model 930 manufactured by toshiba beckmann corporation (imperial china sesame ベックマン corporation): vx is calculated from the following expression (5).
S(％)＝(Vx-W/ρ)×100/(Va-W/ρ)…(5)
Wherein, in the above formula (5), Vx is a true volume (cm) measured by using the above method3) This corresponds to the sum of the volume of the resin constituting the multilayer foamed sheet used for measurement and the total cell volume of the closed cell portion in the multilayer foamed sheet used for measurement. Further, Va, W, ρ in the above formula (5) are as follows.
Va: apparent volume (cm) of the multilayer foamed sheet calculated from the outer dimensions of the multilayer foamed sheet used in the measurement3)
W: total mass (g) of the multilayer foamed sheet used in the measurement
ρ: density (g/cm) of resin constituting multilayer foamed sheet3)
The density ρ of the resin constituting the multilayer foamed sheet can be determined from the obtained sample by removing bubbles from the multilayer foamed sheet by a hot press.
The cell ratio of closed cells was measured using a volume of 2.5cm in the vertical and horizontal directions and an apparent volume of 25cm3The test piece of (1). However, when the apparent volume of the multilayer foamed sheet is less than 25cm3In the case of (2), at a distance of closest to 25cm3A plurality of test pieces for measurement cut out from the multilayer foamed sheet were used in combination as a test piece.
The multilayer foamed sheet of the present invention can be produced by a known method. As a representative method thereof, for example, a method of producing a multilayer foamed sheet by laminating an intermediate layer and a surface layer in this order on both sides of a foamed layer by a multilayer coextrusion method and performing extrusion foaming is preferable. However, the production of the multilayer foamed sheet is not limited to the multilayer coextrusion method. Examples thereof include: one method is a method of producing a foamed layer (foamed sheet), introducing a laminated film of an intermediate layer and a surface layer from a production line or another line, laminating the surface layer on one surface of the foamed layer via a heat roll with the intermediate layer interposed therebetween, and laminating the intermediate layer and the surface layer on the other surface of the foamed layer in the same manner; another method is a method of producing a foamed layer, supplying a resin melt to form an intermediate layer from a production process line or another line, simultaneously supplying a polyolefin resin film to form a surface layer, and laminating the intermediate layer and the surface layer on one surface of the foamed layer and similarly laminating the intermediate layer and the surface layer on the other surface of the foamed layer. In this case, in order to laminate and bond the foamed layer and the intermediate layer, an adhesive layer may be provided by lamination or the like to laminate and bond the two layers, and the same applies to a case where the intermediate layer and the surface layer are laminated and bonded.
Among these methods, the multilayer coextrusion method is a preferred method in terms of cost because it is simpler in process than the other methods. Further, by using the multilayer coextrusion method, a multilayer foamed sheet having good adhesive strength between the foamed layer and the resin layer can be stably obtained.
Further, as a method for obtaining a multilayer foamed sheet by multilayer coextrusion, there are (1) a method of coextruding a sheet and laminating the same by using a flat die and (2) a method of producing a cylindrical multilayer foam by coextrusion using a ring die and then cutting the cylindrical multilayer foam as a multilayer foamed sheet. Among the above, from the viewpoint of easily obtaining a multilayer foamed sheet having a width of 1000mm or more and a length, a multilayer coextrusion method using an annular die can be suitably used.
The foamed layer constituting the multilayer foamed sheet of the present invention can be produced by a conventionally known method. In this case, as the foaming agent, an inorganic physical foaming agent, an organic physical foaming agent, a decomposition type foaming agent, or the like can be used. As the inorganic physical foaming agent, carbon dioxide, air, nitrogen, or the like can be used. As the organic physical foaming agent, an aliphatic hydrocarbon such as propane, n-butane, isobutane, n-pentane or isopentane, an alicyclic hydrocarbon such as cyclopentane, a halogenated hydrocarbon such as methyl chloride, ethyl chloride or 1, 3, 3, 3-tetrafluoropropene, and the like can be used. Further, as the decomposition type foaming agent, azodicarbonamide, azobisisobutyronitrile, sodium hydrogen carbonate, or the like can be used. These blowing agents can be suitably used in combination.
The foaming agent is generally adjusted to a range of approximately 1 to 30 parts by mass per 100 parts by mass of the resin constituting the foamed layer, although the foaming agent varies depending on the type of the foaming agent, the desired expansion ratio, and the like.
When the foamed layer is obtained, a bubble controlling agent may be added to the melt-kneaded product of the resin and the foaming agent as needed. Examples of the bubble controlling agent include inorganic powders such as talc and silica, acid salts of polycarboxylic acids, and reaction mixtures of polycarboxylic acids with sodium carbonate or sodium hydrogencarbonate. Preferably, the bubble control agent is added in an amount of about 0.01 to 10 parts by mass per 100 parts by mass of the resin constituting the foamed layer. Further, additives such as a heat stabilizer, an ultraviolet screening agent, an antioxidant, and a colorant may be added as necessary.
The separator of the present invention is composed of the above-described multi-layer foamed sheet of the present invention.
The separator of the present invention is excellent in cushioning properties, rigidity and antistatic properties, and is suitable for use as a separator for a plate-like object in which migration of low molecular weight components to a packed article is suppressed.
In particular, as shown in fig. 1(a), when the multilayer foamed sheet has a polystyrene resin foamed layer and polyolefin resin layers laminated on both sides of the foamed layer, antistatic performance can be exhibited on both sides, and therefore, the multilayer foamed sheet is more suitable for use in paper barriers and the like.
[ examples ] A method for producing a compound
The present invention will be described in further detail below with reference to examples, but the present invention is not limited to these examples.
The raw materials used in the examples and comparative examples are as follows.
Foaming layer
(polystyrene series resin PS1)
Polystyrene resin, "G9305" manufactured by PS Japan (PS ジャパン Co.), "MFR1.4g/10 min (230 ℃ C., load 2.16kg)
(polyethylene resin PE1)
Low-density polyethylene ("NS-1" manufactured by NIKA (R.) K.K.; manufactured by NIPPON ユニカー K.K.), MFR0.41g/10 min (190 ℃ C., load 2.16kg), melting point 108.5 deg.C
(styrene elastomer TPS1)
SEBS, "H1041" manufactured by Asahi Kasei corporation, MFR3.0g/10 min (190 ℃, load 2.16kg)
(foaming agent)
Mixed butane of isobutane 30 wt% and n-butane 70 wt%
Intermediate layer
(polyethylene resin PE2)
Low-density polyethylene, "NUC 8008" manufactured by Nippon UNIKA (R.P.) (JP ユニカー B.), MFR4.7g/10 min (190 ℃ C., 2.16kg load), mp 108 ℃ C
(styrene elastomer TPS2)
SEBS, "H1052" manufactured by Asahi Kasei corporation, MFR3.0g/10 min (190 ℃, load 2.16kg)
(Polymer type antistatic agent)
"PELECTRON LMP (ペレクトロン LMP)" manufactured by Sanyo chemical industry Co., Ltd, melting point 114 ℃ and MFR30 g/10min (190 ℃ C., load 2.16kg)
Surface layer
(Low-density polyethylene resin PE2)
Low-density polyethylene, "NUC 8008" manufactured by Nippon UNIKA (R.P.) (JP ユニカー B.), MFR4.7g/10 min (190 ℃ C., 2.16kg load), mp 108 ℃ C
(high-density polyethylene resin PE3)
High density polyethylene, "NH 2500" manufactured by Tosoh corporation, MFR8.0g/10 min (190 ℃, 2.16kg load), melting point 131.3 DEG C
(styrene elastomer TPS2)
SEBS, "H1052" manufactured by Asahi Kasei corporation, MFR3.0g/10 min (190 ℃, load 2.16kg)
(Polymer type antistatic agent)
"PELECTRON LMP (ペレクトロン LMP)" manufactured by Sanyo chemical industry Co., Ltd, melting point 114 ℃ and MFR30 g/10min (190 ℃ C., load 2.16kg)
(Talc MB)
Talc masterbatch, "PMA 140" (containing talc 40 mass%, particle diameter 10 μm) manufactured by Sonmura industries, Ltd
In the apparatus used, two extruders, a first extruder having an inner diameter of 90mm and a second extruder having an inner diameter of 120mm, were connected in series to form a foamed layer, a third extruder having a diameter of 65mm was used as an extruder for forming the intermediate layer, a fourth extruder having an inner diameter of 50mm was used as an extruder for forming the surface layer, and the outlet of the second extruder, the outlet of the third extruder, and the outlet of the fourth extruder were connected to a ring-shaped die for coextrusion. The annular die for coextrusion has a structure such that: the melts for forming the intermediate layer were merged and laminated on both surfaces of the melt for forming the foamed layer, and the melts for forming the surface layer were merged and laminated on both surfaces, and the lip diameter of the die outlet was 136 mm. In example 3, a fourth extruder having a diameter of 65mm was used as the extruder for forming the surface layer, and in example 6, a third extruder having a diameter of 50mm was used as the extruder for forming the intermediate layer.
A raw material in which 1 part by mass of a bubble control agent master batch as a bubble control agent was mixed with 100 parts by mass of the raw materials of the types and amounts shown in table 1A was supplied to a raw material inlet of a first extruder and heated and kneaded to form a molten resin mixture. To this molten resin mixture, mixed butane (n-butane/isobutane: 70% by mass/30% by mass) in an amount shown in table 1A was pressed as a physical blowing agent, and then supplied to a second extruder connected on the downstream side of the first extruder, and the temperature of the extruded resin was adjusted to the temperature shown in table 2, to obtain a resin melt for forming a foamed layer.
At the same time, the raw materials of the types and amounts shown in table 1A were supplied to the raw material inlet of the third extruder, and the extrusion resin temperature was adjusted to the one shown in table 2, thereby obtaining a resin melt for forming the intermediate layer.
At the same time, the raw materials of the types and amounts shown in table 1B were supplied to the raw material inlet of the fourth extruder, and the extrusion resin temperature was adjusted to the one shown in table 2, thereby obtaining a resin melt for forming the surface layer.
The resin melt for forming the foamed layer, the resin melt for forming the intermediate layer, and the resin melt for forming the surface layer were introduced into a ring-shaped die for coextrusion at discharge amounts shown in table 2, respectively, and the resin melt for forming the intermediate layer was converged and laminated on both the inner and outer surfaces of the resin melt for forming the foamed layer, and further the resin melt for forming the surface layer and the resin melts for forming the respective intermediate layers were converged and laminated, and then, the foam was coextruded from the ring-shaped die, to form a cylindrical multilayer foam in which the intermediate layers were laminated and bonded to both the inner and outer surfaces of the foamed layer, and the surface layers were further laminated and bonded to the respective intermediate layers. The extruded tubular laminated foam was stretched while passing through a tubular stretching device having a diameter of 368mm, and the stretching speed was adjusted so that the overall grammage shown in table 3 was attained, and the tubular laminated foam was cut to obtain a polystyrene resin multilayer foamed sheet having a five-layer structure including a foamed layer and resin layers laminated and bonded to both surfaces of the foamed layer. The surface of the multilayer foamed sheet stretched while being in contact with the cylindrical widening device is referred to as an M-surface, and the surface of the multilayer foamed sheet on the other side is referred to as an S-surface.
The measurement and evaluation of various physical properties in table 3 were carried out as follows.
[1] The apparent density, grammage, and overall thickness of the multilayer foamed sheet were measured as follows.
First, the multilayer foamed sheet was cut into a length of 100mm in the extrusion direction (MD) across the width direction, and further cut into a width direction (TD) orthogonal to the extrusion direction) The test piece was defined as a portion of 1000mm in the center in the width direction at each end of (1). The test piece was further divided into 10 equal parts in the width direction, and the thickness of the test piece in the vicinity of the center thereof was measured by a micrometer. The thickness of the multilayer foam sheet was determined by arithmetically averaging the thicknesses of the respective measurement points. The mass of the test piece was measured, and the mass was divided by the area (specifically, 1000 mm. times.100 mm) of the test piece, and the unit was converted to g/m2As the grammage of the multilayer foamed sheet. The apparent density of the multilayer foamed sheet was determined by dividing the grammage by the thickness and performing unit conversion.
Further, the thicknesses of the surface layer and the intermediate layer were calculated from the conditions in the production of the multilayer foamed sheet using the above formulas (1) and (2).
[2] Surface resistivity
Three foamed sheets were cut out in the width direction perpendicular to the extrusion direction of the multilayer foamed sheet, in the vicinity of the central portion and both end portions of the multilayer foamed sheet, in a length of 100mm in the longitudinal direction by 100mm in the transverse direction by a thickness of: test piece thickness. A voltage of 500V was applied to the test piece in accordance with JIS K6271(2001), and the surface resistivity of the test piece after 1 minute of application was used. The surface resistivity was determined by measuring both surfaces of the test piece (6 times in total) and calculating the average value of the obtained measurement values. The measurement apparatus used was a device in which "SM-8220" and "M-8310" were connected to each other by a Japanese Dynasty (Ltd.).
[3] Abrasion adhesion test
Three foamed sheets were cut out in the width direction perpendicular to the extrusion direction of the multilayer foamed sheet, in the vicinity of the center and both ends of the multilayer foamed sheet, 40mm in length × 40mm in width: test piece thickness. Thereafter, 7.42g/cm was applied from above the test piece using an abrasion tester (Nihon Rigaku Kogyo Co., manufactured by LTD.)2The test piece was subjected to abrasion of the S-face and glass at a speed of 1200mm/min 500 times under load. The glass after the test was observed under magnification of 4000 times using VHX-6000 (manufactured by KEYENCE (キーエンス) and the surface of the glass to which the foreign matter had adhered was photographed. The photographed picture is processed to calculate the area of the position where the foreign matter is attached. According to the obtained area of the foreign matter attachment positionAnd the area of the whole shot picture, and the area per 1mm was obtained by using the following formula (6)2The attachment area of (a).
Wear attachment area [ mu m2/mm2]Area of foreign matter adhering position [ μm2]Area of photograph entirety [ mm ÷ photograph2](6)
Thereafter, the wear adhesion area was measured for the M-plane in the same manner, and the wear adhesion area of the S-plane and the M-plane [ μ M ]2/mm2]The average value of (A) is defined as the wear adhesion area of the multilayer foamed sheet.
[4] Closed cell content
The closed cell ratio S (%) of the multilayer foam sheet was calculated from the above formula (5) based on the true volume of the multilayer foam sheet measured using an air comparison type densitometer model 930 manufactured by toshiba beckmann corporation (imperial manufactured by imperial sesame ベックマン ltd) according to the procedure C described in ASTM D2856-70. The density of the resin constituting the multilayer foamed sheet was determined from a sample obtained by removing bubbles from the multilayer foamed sheet by a hot press.
In the measurement of the closed cell ratio, 2.5cm × 2.5cm × thickness was cut from the multilayer foam sheet: test piece thickness of test piece, to the nearest 25cm3A plurality of the test pieces were combined, and the combined pieces were measured as test pieces.
The compounding ratios of the raw materials of the foamed layer, the intermediate layer and the surface layer in examples and comparative examples are shown in table 1A, B, and the production conditions are shown in table 2. The physical properties of the multilayer foamed sheets obtained in examples and comparative examples are shown in table 3.
Figure BDA0002303901630000211
Figure BDA0002303901630000221
TABLE 2
Figure BDA0002303901630000231
Figure BDA0002303901630000241
The multilayer foamed sheet of the examples had a polystyrene resin foamed layer, and therefore had high rigidity and good handleability. In addition, the area of attachment of foreign matter in the abrasion attachment test is small, and the attachment of a component derived from the polymer type antistatic agent to the object to be packed is suppressed. In addition, the surface resistivity value is small, and the antistatic property is excellent.

Claims (10)

1. A multilayer foamed sheet comprising a polystyrene resin foamed layer and a polyolefin resin layer laminated on at least one side of the foamed layer, characterized in that,
the resin layer comprises a surface layer on the outermost surface side of the sheet and an intermediate layer laminated and bonded to the surface layer,
the surface layer contains a polyolefin resin and does not substantially contain a polymer type antistatic agent,
the intermediate layer contains a polyolefin resin and a polymer antistatic agent,
the thickness of the surface layer is 2 to 20 μm,
the surface resistivity of the multilayer foamed sheet on the side of the resin layer lamination surface is less than 1.0X 1013Ω。
2. The multilayer foam sheet of claim 1,
the thickness of the resin layer is 5-50 μm.
3. The multilayer foamed sheet according to claim 1 or 2,
the ratio of the thickness of the surface layer to the thickness of the intermediate layer is 1: 0.3-1: 10.
4. the multilayer foam sheet of claim 1,
the content of the polymeric antistatic agent in the intermediate layer is 8-60 mass% relative to 100 mass% of the intermediate layer.
5. The multilayer foam sheet of claim 1,
the resin composition constituting the foamed layer is a polystyrene resin composition containing a polystyrene resin, a polyolefin resin and a styrene elastomer,
the polystyrene resin composition contains 60 to 94 mass% of polystyrene resin, 5 to 30 mass% of polyolefin resin and 1 to 10 mass% of styrene elastomer, when the total amount of the polystyrene resin, the polyolefin resin and the styrene elastomer is 100 mass%.
6. The multilayer foam sheet of claim 1,
the multilayer foamed sheet has the polystyrene resin foamed layer and the polyolefin resin layer laminated on both sides of the foamed layer.
7. The multilayer foam sheet of claim 1,
the polyolefin resin constituting the surface layer is a polyethylene resin.
8. The multilayer foam sheet of claim 7,
the polyethylene resin is a polyethylene resin containing low density polyethylene and high density polyethylene.
9. The multilayer foam sheet of claim 1,
the multilayer foamed sheet has a gram weight of more than 30g/m2And 220g/m2The following.
10. A kind of paper separator, in which,
a multilayer foamed sheet according to any one of claims 1 to 9.
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