CN111732785A - Packaging sheet - Google Patents

Packaging sheet Download PDF

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Publication number
CN111732785A
CN111732785A CN202010214010.0A CN202010214010A CN111732785A CN 111732785 A CN111732785 A CN 111732785A CN 202010214010 A CN202010214010 A CN 202010214010A CN 111732785 A CN111732785 A CN 111732785A
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China
Prior art keywords
polyolefin resin
sheet
mass
resin foam
antistatic agent
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CN202010214010.0A
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Chinese (zh)
Inventor
落合哲也
阿南伸一
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Sekisui Kasei Co Ltd
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Sekisui Plastics Co Ltd
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    • 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
    • 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
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0028—Use of organic additives containing nitrogen
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0047—Use of organic additives containing boron
    • 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
    • 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
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—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
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—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
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • 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
    • C08J2353/00—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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Buffer Packaging (AREA)

Abstract

The invention provides a packaging sheet which is less in migration of components to a packaged object and excellent in antistatic property. The means for solving the problems of the present invention is to provide a packaging sheet with a polyolefin resin foam sheet containing a donor/acceptor type antistatic agent.

Description

Packaging sheet
Technical Field
The present invention relates to a packaging sheet, and more particularly to a packaging sheet provided with a polyolefin resin foam sheet.
Background
Conventionally, expanded polyolefin resin sheets are widely used as packaging sheets and the like because they are softer and have superior cushioning properties as compared with expanded polystyrene resin sheets, expanded polyester resin sheets and the like.
As such a packaging sheet, a sheet of a foamed polyolefin resin sheet alone, a laminate sheet of a foamed polyolefin resin sheet and a surface decorative sheet laminated thereon, and the like are known.
As objects to be packaged by such packaging sheets, electric devices, electronic devices, and electric device members and electronic device members constituting the electric devices and the electronic devices are known.
The packaging sheet is used for protecting an object to be packaged from impact during storage and transportation, and is also used as a spacer paper or the like interposed between members such as a glass plate, a semiconductor plate, and a metal plate, which are substrates of a flat display panel, when the members are stored.
In order to avoid the generation of deposits on packaged objects due to static electricity, antistatic properties are sometimes required for such packaging sheets.
As a method for imparting antistatic properties to a polyolefin resin foam sheet, a method is known in which a polymeric antistatic agent called a high-molecular antistatic agent and a surfactant called a low-molecular antistatic agent are incorporated into a material for forming a polyolefin resin foam sheet.
Among them, surfactants are likely to adhere to the surface of an object to be protected because they exhibit antistatic properties by bleeding out to the sheet surface (see patent document 1 below).
On the other hand, the polymer type antistatic agent often contains metal ions, and the metal ions may migrate to the packaged object to cause adverse effects.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2010-42556
Disclosure of Invention
Problems to be solved by the invention
As described above, the packaging sheet is required to exhibit antistatic properties and to have less migration of components into the package, but such a need is not satisfied.
Accordingly, an object of the present invention is to provide a packaging sheet which is less likely to cause migration of components into a packaged article and has excellent antistatic properties.
Means for solving the problems
The present inventors have conducted detailed studies to solve the above problems, and as a result, have found that a polyolefin resin foam sheet containing a donor/acceptor type antistatic agent exhibits excellent antistatic properties and is less likely to cause migration and bleeding of metal ions, thereby completing the present invention.
That is, in order to solve the above-mentioned problems, the present invention provides a packaging sheet comprising a polyolefin resin foam sheet containing a donor/acceptor type antistatic agent, wherein the polyolefin resin foam sheet is exposed on at least one surface.
ADVANTAGEOUS EFFECTS OF INVENTION
In the polyolefin resin foam sheet containing a donor/acceptor type antistatic agent, since hole diffusion and electron diffusion are rapidly performed by coexistence of a donor such as a boron compound and an acceptor such as a nitrogen compound, excellent antistatic property can be exhibited without utilizing the action of metal ions such as sodium ions and lithium ions.
Further, the polyolefin resin foam sheet containing the donor/acceptor type antistatic agent can exhibit good antistatic properties even if it does not contain a compound that causes bleeding, such as a surfactant.
Therefore, a packaging sheet comprising such a polyolefin resin foam sheet so as to be exposed on at least one surface thereof can inhibit migration of components to a packaged article and exhibit excellent antistatic properties.
Drawings
Fig. 1 is a schematic view showing one use mode of a packaging sheet.
Fig. 2 is a schematic cross-sectional view of a packaging sheet according to an embodiment of the present invention.
Fig. 3 is a schematic view showing another embodiment of the packaging sheet.
Description of the reference numerals
1: polyolefin resin foam sheet
1 a: 1 st plane
1 b: the 2 nd surface
2: glass plate
10: laminated body
11. 12: coating film
100: packaging bag (WU JI KE LI)
100 a: dough sheet
100 b: dough reversing sheet
101: sealing part
102: opening part
X1: printed circuit board
Detailed Description
The packaging sheet of the present invention will be explained.
Hereinafter, embodiments of the present invention will be described by taking as an example a case where the packaging sheet is a single-layer sheet composed of only a foamed polyolefin resin sheet and both the front and back surfaces are composed of a foamed polyolefin resin sheet.
In addition, the following exemplifies a case where the polyolefin resin foamed sheet is an extruded foam.
More specifically, the embodiments of the present invention will be described below by way of example of the case where a packaging sheet including a polyolefin resin foamed sheet formed by extrusion foaming a polyolefin resin composition containing a polyolefin resin is used as a bag for an electronic component or a spacer for a glass plate.
Fig. 1 shows a state in which the packaging sheet of the present embodiment is used as a constituent material of a packaging bag 100 for housing a printed circuit board X1.
The packaging bag 100 of the present embodiment is composed of 2 packaging sheets, i.e., a front sheet 100a and a back sheet 100b, each having a rectangular shape and an area larger than that of the printed circuit board X1.
The packaging bag 100 of the present embodiment is obtained by 3-side sealing of a laminated product in which the front sheet 100a and the back sheet 100b are superposed so as to align their contours.
That is, the packaging bag 100 has a sealing portion 101 bonded to each other along 3 of the 4 edges of the front sheet 100a and the back sheet 100b, and an opening 102 for taking in and out the printed circuit board X1 is formed without being bonded along the remaining one edge.
In the packaging bag 100, the front sheet 100a and the back sheet 100b may be formed of the same sheet or different sheets.
The front sheet 100a and the back sheet 100b of the packaging bag 100 of the present embodiment are both composed of the same foamed polyolefin resin sheet 1.
Fig. 2 shows the cross-sectional shapes of the polyolefin resin foam sheets used as the front sheet 100a and the back sheet 100b in the present embodiment.
As shown in the drawing, the polyolefin resin foam sheet 1 of the present embodiment includes a 1 st surface 1a constituting the inner surface of the packaging bag 100 and contacting the printed circuit board X1, and a 2 nd surface 1b constituting the outer surface of the packaging bag 100.
The foamed polyolefin resin sheet 1 of the present embodiment is composed of a polyolefin resin composition containing a polyolefin resin as a base polymer and an antistatic agent.
Examples of the polyolefin-based resin contained in the polyolefin-based resin foam sheet 1 of the present embodiment include: polyethylene resins, polypropylene resins, ethylene-alpha olefin resins, and the like.
The polyolefin resin composition constituting the expanded polyolefin resin sheet does not need to contain 1 kind of polyolefin resin alone, and may contain 2 or more kinds.
The polyolefin resin contained in the polyolefin resin composition is preferably a polypropylene resin.
The polypropylene resin may be a homopolymer of propylene, i.e., a homopolypropylene (hPP), or a copolymer containing a small amount of ethylene, butene-1, or the like in addition to propylene.
The stereoregularity of the polypropylene resin is not particularly limited, and may be isotactic polypropylene (iPP), syndiotactic polypropylene (sPP), atactic polypropylene (aPP), or the like.
The copolymer may be random polypropylene (rPP) obtained by random copolymerization of propylene and ethylene.
The foregoing copolymer may also be the following block polypropylene (bPP): ethylene is introduced at the latter stage of the polymerization reaction of propylene, whereby the propylene-ethylene copolymer is dispersed in the matrix phase of homo-polypropylene so as to constitute a domain phase.
The block polypropylene may be an elastic material containing a propylene-ethylene copolymer in a content of 40% by mass or more, or may be a so-called olefinic thermoplastic elastomer (TPO) or the like.
The polypropylene resin may be a so-called high melt tension polypropylene (HMS-PP) or the like, which is capable of forming long chain branches by chemical crosslinking, electron beam crosslinking, or the like.
The polypropylene resin contained in the polyolefin resin foam sheet 1 is preferably block polypropylene (bPP) or high melt tension polypropylene (HMS-PP), and both are preferably used in combination.
The mass ratio (bPP/(bPP + HMS-PP)) of the block polypropylene (bPP) to the high melt tension polypropylene (HMS-PP) is preferably 20 mass% or more, more preferably 30 mass% or more, and particularly preferably 40 mass% or more.
The mass ratio (bPP/(bPP + HMS-PP)) is preferably 80 mass% or less, more preferably 70 mass% or less, and particularly preferably 60 mass% or less.
The high melt tension polypropylene preferably exhibits a melt tension of 3cN or more at 230 ℃.
The melt tension is preferably 4cN or more, and particularly preferably 5cN or more.
The melt tension is preferably 30cN or less, more preferably 28cN or less.
The melt tension can be determined, for example, by the following method.
(method of measuring melt tension)
The sample was used as it is when the measurement object was pellets, and when the measurement object was a sheet such as a polyolefin resin foamed sheet, a sample obtained by granulating the polyolefin resin foamed sheet with a granulator (for example, "HAND extruder model PM-1" manufactured by toyoyo seiki) under conditions of a cylinder temperature of 220 ℃ and a standby time of 2.5 minutes from filling of the sample to start of extrusion was used.
The melt tension was measured by using a double-hole capillary rheometer Rheologic5000T (Chiast, Italy).
Specifically, after a measuring sample resin was filled in a cylinder having a diameter of 15mm heated to a test temperature, and preheated for 5 minutes, the piston lowering speed (0.1546mm/s) was kept constant, the resin was extruded into a string form from a capillary tube die (diameter: 2.0mm, length: 20mm, inflow angle: flat) of the measuring apparatus, and the string form was passed through a tension detection pulley 27cm below the capillary tube die, and then wound up by a take-up roll at an initial speed of 8.7mm/s and an acceleration of 12mm/s2The winding speed was gradually increased, and the average of the maximum value and the minimum value immediately before the cutting of the rope was taken as the melt tension of the sample.
In the case where there are only 1 local maximum points in the tension map, the local maximum value is defined as the melt tension.
Examples of the polyolefin resin preferably contained in the polyolefin resin composition include low-density polyethylene resins other than the polypropylene resins described above.
Examples of the low-density polyethylene resin include: a linear low density polyethylene resin (LLDPE) polymerized by a medium-low pressure process, and a low density polyethylene resin (LDPE) having a long chain branch formed in the molecular structure by a high pressure process.
As the low density polyethylene resin (LDPE), it is preferable that the resin density is 910kg/m3Above 930kg/m3The following.
As the linear low density polyethylene resin (LLDPE), it is preferable that the resin density is 910kg/m3Above 925kg/m3The following.
The melt flow rate (hereinafter referred to as "MFR") of the low density polyethylene resin (LDPE) and the linear low density polyethylene resin (LLDPE) is preferably 1g/10min to 10g/10 min.
The melt flow rate is not particularly described in the present specification, and the MFR of a polymer antistatic agent to be described later is similarly defined as follows according to JIS K7210: 1999 "test method for melt Mass Flow Rate (MFR) and melt volume flow Rate (MVR) of Plastic-thermoplastic" the values determined by the method described under method B (wherein the test temperature is 190 ℃ C., and the load is 21.18N).
The donor/acceptor type antistatic agent contained in the polyolefin resin composition together with the polyolefin resin may be an antistatic agent composed of a combination of an organoboron compound and a basic nitrogen compound.
The donor/acceptor type antistatic agent is preferably excellent in compatibility with the polyolefin resin, and preferably has an alkyl chain having a certain length.
The donor/acceptor type antistatic agent is preferably a structure represented by the following general formula (1).
Figure BDA0002423779930000071
In the formula (1), "R" represents1"and" R2Each independently is R7CO-OCH2- "or" HOCH2- ", and at least one is" R7CO-OCH2- ". R in the above formula (1)3"and" R4Each independently is CH3-”、“C2H5-”、“HOCH2-”、“HOC2H4- "or" HOCH2CH(CH3) - ". R in the above formula (1)5is-C2H4- "or" -C3H6- ". R in the above formula (1)6"and" R7Each independently represents an alkyl group having 11 to 21 carbon atoms.
The donor/acceptor type antistatic agent may have a structure represented by the following general formula (2).
Figure BDA0002423779930000072
In the above formula (2), "R" represents1"and" R2Each independently is R7CO-OCH2- "or" HOCH2- ", and at least one is" R7CO-OCH2- ". R in the above formula (2)3"and" R4Each independently is CH3-”、“C2H5-”、“HOCH2-”、“HOC2H4- "or" HOCH2CH(CH3) - ". R in the above formula (2)5is-C2H4- "or" -C3H6- ". R in the above formula (2)6"and" R7Each independently represents an alkyl group having 11 to 21 carbon atoms.
In the above general formulae (1) and (2), the organoboron compound in the upper stage is partially a donor, and the basic nitrogen in the lower stage is an acceptor.
In the donor, "(-) -" indicates that the electron-withdrawing property of the boron atom is enhanced, and "(+)" indicates that the electron-donating property of the oxygen atom is enhanced.
In addition, "→" in the donor indicates a path through which electrons are attracted, and "- - -" indicates a state in which the interatomic bonding force is weak.
Further, "+" indicates that the covalent bond has a polarity.
Among the substances represented by the above general formulae (1) and (2), the donor/acceptor type antistatic agent in the present embodiment is preferably represented by the formula "C42H81O8Organoboron compounds represented by B' and compounds of the formula "C23H48ON2Combinations of basic nitrogen compounds, or of formula "C42H81O8Organoboron compounds represented by B' and compounds of the formula "C23H47O2N' represents a combination of basic nitrogen compounds.
The content of the donor/acceptor type antistatic agent in the polyolefin resin composition is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, and further preferably 0.3 part by mass or more, based on 100 parts by mass of the total amount of all polyolefin resins contained in the polyolefin resin composition.
The content of the donor/acceptor type antistatic agent in the polyolefin resin composition is preferably 3.0 parts by mass or less, more preferably 2.8 parts by mass or less, and still more preferably 2.6 parts by mass or less, based on 100 parts by mass of the total amount of all polyolefin resins contained in the polyolefin resin composition.
Since the foamed polyolefin resin sheet 1 of the present embodiment is produced by an extrusion foaming method, the polyolefin resin composition used in the extrusion foaming method may further contain components necessary for foaming in addition to the components described so far.
Examples of the component used for the foaming include a foaming agent and a bubble adjusting agent.
Examples of the blowing agent include hydrocarbons such as isobutane, n-butane, propane, pentane, hexane, cyclobutane, and cyclopentane, and inorganic gases such as carbon dioxide and nitrogen.
Among them, a mixed butane of isobutane and n-butane is preferable as the blowing agent.
If the mixed butane of isobutane/n-butane is used in this manner, rapid dissipation of the blowing agent in the extrusion process can be suppressed by isobutane.
On the other hand, n-butane, which has excellent compatibility with polyolefin resins, suppresses an increase in the open cell content, and therefore, a polyolefin resin foam sheet 1 having less shrinkage, a low open cell content, and excellent cushioning properties can be obtained.
The amount of the foaming agent used in the extrusion foaming is usually 5 parts by mass or more and 25 parts by mass or less based on 100 parts by mass of the polyolefin resin, although it depends on the desired degree of foaming.
In general, the reason why the ratio of the blowing agent to be added is in such a range is that there is a fear that: when the amount of the foaming agent is less than 5 parts by mass, sufficient foaming is difficult to obtain, and when the amount is more than 25 parts by mass, the cell film is broken, and a satisfactory polyolefin resin foamed sheet cannot be obtained.
Examples of the cell controlling agent for controlling the cells formed by the foaming agent include inorganic powders such as talc and silica. As the above-mentioned cell adjusting agent, a mixture of a polycarboxylic acid and sodium carbonate or sodium bicarbonate (sodium bicarbonate) used as a decomposition type foaming agent, azodicarboxylic acid amide, or the like can be used.
These may be used alone or in combination. The amount of the bubble control agent added is preferably 0.5 parts by mass or less per 100 parts by mass of the polyolefin resin.
The polyolefin resin foamed sheet 1 of the present embodiment may contain, in addition to the above components, additives such as a heat stabilizer, an ultraviolet absorber, an antioxidant, and a colorant as needed.
The ratio of components other than the polyolefin resin and the donor/acceptor type antistatic agent contained in the polyolefin resin foam sheet 1 is preferably 10% by mass or less, and more preferably 5% by mass or less.
That is, the total ratio of the polyolefin resin and the donor/acceptor type antistatic agent in the polyolefin resin composition constituting the polyolefin resin foam sheet 1 is preferably 90 mass% or more, and more preferably 95 mass% or more.
The density (apparent density) of the polyolefin resin foam sheet 1 composed of the polyolefin resin composition is not particularly limited as long as it can exhibit the cushioning property generally required, and is usually less than 150kg/m3Preferably 100kg/m3Hereinafter, it is particularly preferably 70kg/m3The following.
Such a density is preferably selected because excellent flexibility and cushioning properties can be reliably imparted to the expanded polyolefin resin sheet 1 by setting the density to an upper limit or lower, and because excellent strength can be exhibited by the expanded polyolefin resin sheet 1 by setting the density to a lower limit or higher.
From this point of view, the density of the polyolefin resin foam sheet 1 is preferably 10kg/m3Above, more preferably 15kg/m3The above.
The density of the polyolefin resin foam sheet 1 was measured according to JIS K7222: 1999 "measurement of foamed Plastic and rubber-apparent Density", the following method was used.
(Density measuring method)
From expanded sheets of polyolefin resinsTo make 100cm3The above samples were measured in accordance with JIS K7100: 1999, symbol 23/50, level 2 environment, the sample was conditioned for 16 hours, and then its size and mass were measured to calculate the apparent density by the following equation.
Apparent density (g/cm)3) Mass (g) of sample/volume (cm) of sample3)
For the measurement of the size of the sample, for example, model "DIGIMATIC" CD-15 manufactured by Mitutoyo Corporation can be used.
The thickness of the polyolefin resin foam sheet is preferably 0.1mm or more, more preferably 0.15mm or more, and still more preferably 0.3mm or more.
The thickness of the polyolefin resin foam sheet is preferably 6mm or less, more preferably 5mm or less, and still more preferably 4mm or less.
The thickness of the foamed polyolefin resin sheet 1 can be determined as an average value of the thicknesses measured at 10 or more measurement points selected at random, for example.
The weight per unit area of the polyolefin resin foam sheet is preferably 10g/m2Above, more preferably 15g/m2Above, it is more preferably 25g/m2The above.
The weight per unit area of the polyolefin resin foam sheet is preferably 600g/m2Hereinafter, it is more preferably 500g/m2Hereinafter, it is more preferably 400g/m2The following.
The weight per unit area of the polyolefin resin foamed sheet may be measured in accordance with JIS P8124: 2011 "paper and cardboard-basis weight measurement method".
Specifically, 10 pieces of 100cm can be cut2The mass and area of each of the above samples were measured and determined by the following equation.
Weight per unit area (g/m)2) 10000 (g) test piece mass/area (cm)2)
The amount of bleeding out of at least the 1 st surface 1a (surface in contact with the article to be packed) of the polyolefin resin foamed sheet is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and still more preferably 0.1% by mass or less.
The amount of bleeding of the polyolefin resin foamed sheet can be determined as follows.
The sample was cut to a size of 100mm x 100mm and placed in a thicker sealed bag with attached clip chain of 120mm x 170 mm.
20ml of methanol was added to the sealed bag, the air was evacuated as much as possible and the zipper was closed, and the sealed bag was shaken by hand about 100 times.
After shaking, the zipper was opened, and the methanol in the sealed bag was taken out to a beaker and heated in a thermostat at 105 ℃ for 24 hours to evaporate the methanol to give a dry solid.
Thereafter, the beaker was placed in a desiccator, and cooled in the desiccator, and the mass of the evaporated and dried solid after returning to normal temperature was measured.
In principle, the measurement was performed 3 times using 3 samples cut out from different positions.
Then, the average value of the 3 measurements was defined as the amount of bleeding of the polyolefin resin foamed sheet.
The amount (total amount) of the alkali metal ions and alkaline earth metal ions in at least the 1 st surface 1a (surface in contact with the article to be packaged) of the foamed polyolefin resin sheet is preferably 2mg/m2The following.
The amount of the alkali metal ion and the alkaline earth metal ion in the 1 st surface 1a is more preferably 1mg/m2The concentration is more preferably 0.5mg/m or less2The following.
The amounts of the alkali metal ions and the alkaline earth metal ions in the polyolefin resin foam sheet can be determined by the following method.
The sample was cut to a size of 100mm x 100mm and placed in a thicker sealed bag with attached clip chain of 120mm x 170 mm.
20ml of ion exchange water was added to the sealed bag, air was removed as much as possible and the zipper was closed, and the sealed bag was held in a thermostatic bath at 60 ℃ and shaken by hand 10 times after 30 minutes.
After another 30 minutes, the sealed bag was similarly shaken by hand for 10 times, and then the sealed bag was opened to take out the ion-exchanged water. Then, the amounts of alkali metal ions and alkaline earth metal ions contained in the ion-exchanged water were measured using a multi-function ICP emission spectrometer (product name "ICPE-9000", manufactured by shimadzu corporation) under the following measurement conditions.
(measurement conditions)
Observation direction: axial direction
Exposure time: 30 seconds
High-frequency output: 1.20kW
Carrier flow rate: 0.7mL/min
Plasma flow rate: 10.0mL/min
Auxiliary flow rate: 0.6mL/min
The polyolefin resin foam sheet preferably has a surface resistivity of at least the 1 st surface 1a (surface in contact with a packaged article) which is a constant value even after wiping with ethanol.
Specifically, the surface resistivity of the polyolefin resin foam sheet measured at 20 ℃ and 60% RH is preferably 1 × 10 after wiping with ethanol8Omega or more, more preferably 1 × 109Omega or more, particularly preferably 1 × 1010Omega or more.
The surface resistivity is preferably 1 × 1012Omega or less, more preferably 1 × 1011Omega is less than or equal to.
The surface resistivity can be measured according to JIS K6911: 1995 "general test methods for thermosetting plastics" to determine the results.
The surface resistivity can be measured using a test apparatus (digital super high resistance/micro current meter, model "R3840" and RESISTIVITY CHAMBER, model "R12702A", available from edmunda, ltd.). The surface resistivity was calculated by pressing an electrode against a sample collected from a polyolefin resin foam sheet with a load of about 30N, charging the sample at 500V for 1 minute, and measuring the resistance value.
The sample had a width of 100mm, a length of 100mm and a thickness (the original thickness of the polyolefin resin foam sheet).
The measurement was carried out after adjusting the conditions at 20. + -. 2 ℃ and 65. + -. 5% RH for 24 hours or more, and the test conditions were 20. + -. 2 ℃ and 65. + -. 5% RH.
The number of samples (n number) was 5, and both front and back sides were measured in principle.
After the sample was adjusted, the surface was wiped with ethanol.
Wiping with ethanol was performed as follows.
The entire measurement surface of the 100mm square sample after the adjustment was wiped several times with a paper towel (for example, product name "Kim Wipes") to which a small amount of ethanol was applied.
For the surface resistivity, after the wiping, the wiping was performed after being kept for 1 hour under the test environment.
The surface resistivity of each sample was obtained by the following formula, and the measured values were calculated and averaged for all the samples, and the average value was defined as the surface resistivity of the polyolefin resin foamed sheet.
ρs＝(π(D+d)/(D-d))×Rs
ρ s: surface resistivity (M omega)
D: inner diameter (cm) of surface ring electrode
d: outer diameter (cm) of inner circle of surface electrode
Rs: surface resistance (M omega)
The polyolefin resin foam sheet 1 in the present embodiment may contain a small amount of a polymer type antistatic agent and a small amount of a surfactant within the range that exhibits the above surface properties.
Examples of the polymer type antistatic agent include: quaternary ammonium salts of polyethylene oxide, polypropylene oxide, polyethylene glycol, polyester amide, polyether ester amide, ethylene-methacrylic acid copolymer, polyethylene glycol methacrylate copolymer, etc., copolymers of an olefin block and a hydrophilic block as described in Japanese patent laid-open No. 2001-278985, etc.
The content of the polymer type antistatic agent in the polyolefin resin foam sheet is preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less.
The polyolefin resin foam sheet of the present embodiment preferably does not contain a polymer type antistatic agent.
Examples of the surfactant include: nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and the like.
The content of the surfactant in the polyolefin resin foam sheet is preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less.
The polyolefin resin foam sheet of the present embodiment particularly preferably does not contain a surfactant.
In the polyolefin resin foam sheet 1 of the present embodiment, it is preferable that not only the 1 st surface 1a but also the 2 nd surface 1b have the surface properties as described above, in terms of the possibility of being used without distinction between the front and back surfaces.
However, since the 2 nd surface 1b does not contact the printed circuit board X1 as the object to be packaged, the packaging sheet (front surface sheet 100a, back surface sheet 100b) of the present embodiment may have a multilayer structure in which any of a fiber sheet (paper, cloth, and the like), a film (resin film, metal film, composite film, and the like), a resin foam sheet containing no donor/acceptor type antistatic agent, and the like are laminated on one surface of the polyolefin resin foam sheet 1.
That is, the packaging sheet in the present embodiment may be provided so that the polyolefin resin foam sheet kneaded with the donor/acceptor type antistatic agent is exposed on at least one surface.
In the above description, the use of the packaging bag 100 as a packaging sheet has been exemplified, but the packaging sheet in the present embodiment can be used for other applications.
Another embodiment of the packaging sheet according to the present embodiment will be described with reference to fig. 3 as an example.
The packaging sheet shown in fig. 3 is a single-layer sheet composed only of the polyolefin resin foam sheet 1, and is used as a spacer paper to be interposed between adjacent glass plates 2 when the glass plates 2 are stacked in the vertical direction to form a laminate 10.
The glass plate 2 in the present embodiment is a glass plate for a flat display panel such as a plasma display panel or a liquid crystal display panel.
The packaging sheet constituting the packaging bag 100 is used such that only one side (the 1 st surface 1a) of both surfaces is in contact with the printed circuit board X1 as the object to be packaged, but in the packaging sheet shown in fig. 3, both the 1 st surface 1a and the 2 nd surface 1b of the polyolefin resin foam sheet 1 are in contact with the contact surface of the glass plate 2 as the object to be packaged.
Therefore, the packaging sheet used in this embodiment is preferably provided so that the polyolefin resin foam sheet mixed with the donor/acceptor type antistatic agent is exposed on both surfaces.
When the polyolefin resin foam sheet is required to be exposed on both surfaces, the packaging sheet does not need to be composed of a single polyolefin resin foam sheet 1, and may be a laminate sheet in which 2 polyolefin resin foam sheets 1 are laminated directly or with another sheet interposed therebetween.
That is, the packaging sheet may have a 2-layer structure in which the 1 st surface layer provided on one surface side and the 2 nd surface layer provided on the other surface side are each composed of a polyolefin resin foam sheet containing a donor/acceptor type antistatic agent, or may have a laminated structure of 3 or more layers including 1 or 2 or more intermediate layers between the 1 st surface layer and the 2 nd surface layer, and the 1 st surface layer and the 2 nd surface layer are each composed of a polyolefin resin foam sheet containing a donor/acceptor type antistatic agent.
When the packaging sheet includes a plurality of foamed polyolefin resin sheets as described above, the thickness of one foamed polyolefin resin sheet and the other foamed polyolefin resin sheets, the content of the donor/acceptor type antistatic agent, and the like may be the same or different.
The expanded polyolefin resin sheet 1 as described above is produced by the extrusion foaming method in the present embodiment, as described above.
Specifically, the polyolefin resin foamed sheet 1 can be produced by performing the following extrusion steps: the polyolefin resin composition is continuously extruded and foamed into a sheet form through a Circular die (Circular die) or the like attached to the tip of an extruder to produce an extruded and foamed sheet.
In the extrusion step, the donor-and-receiver type antistatic agent exhibits affinity for the polyolefin resin, and therefore, the donor-and-receiver type antistatic agent is contained in the polyolefin resin foam sheet in a well-dispersed state.
Known examples of antistatic agents include coating type agents used by coating the surface of a resin product or the like, and kneading type agents used by kneading the resin product.
As described above, in the present embodiment, the donor/acceptor type antistatic agent is used as the kneading type antistatic agent.
The polyolefin resin foam sheet 1 into which the donor/acceptor type antistatic agent is kneaded not only exhibits excellent antistatic properties but also has less migration of its components to a material to be contacted.
In the extrusion step, the bleeding of the donor/acceptor type antistatic agent to the surface of the polyolefin resin foam sheet 1 can be suppressed.
In the extrusion step in the present embodiment, the tubular foam continuously extruded from the circular die is subjected to 1 cooling in which cooling air is blown from the inside and outside to perform air cooling immediately after the extrusion, and 2 cooling in which the air-cooled foam is further cooled by the cooling plug.
In the extrusion step, the tubular foam is taken out while being cut in the extrusion direction by a cutter provided on the downstream side of the cooling plug.
In the extrusion step in the present embodiment, cooling is performed 2 times using a cooling plug having an outer diameter larger than the diameter of the circular die.
Therefore, the 2-time cooling is performed by bringing the outer peripheral surface of the cooling plug into sliding contact with the inner peripheral surface of the cylindrical foam subjected to the 1-time cooling.
In the 2-time cooling, the tubular foam after 1-time cooling was cooled and the diameter thereof was expanded by the cooling plug.
The foam cut by the cutter in the extrusion direction as described above is unwound into a tape and then wound to form the reel.
In the present embodiment, in order to allow the polyolefin resin foam sheet 1 to exhibit excellent cushioning properties, at least one of the high melt tension polypropylene (HMS-PP) and the block polypropylene (bPP), preferably both of them, are preferably used as the polyolefin resin contained in the polyolefin resin composition, and the polyolefin resin composition is preferably made to have a lower crystallinity than that of the homopolypropylene (hPP) or the like.
The heat of fusion of the crystals of the desired crystals of polypropylene is 209J/g, and the crystallinity of homopolypropylene (hPP) is usually 50% to 70%.
From the above viewpoint, the crystallinity of the polyolefin resin composition is preferably 40% or less, and more preferably 30% or less.
That is, the heat of crystallization of the polyolefin resin composition is preferably 83J/g or less, and more preferably 62J/g or less.
The heat of crystallization of the polyolefin resin composition can be controlled by JIS K7122: 2012 "method for measuring conversion heat of plastics".
Specifically, it can be obtained by the following method.
(method of determining crystallization Heat quantity)
About 6mg of a sample was charged into the bottom of an aluminum measurement container without a gap by using a differential scanning calorimeter (for example, model "DSC 6220" manufactured by SII nanotechnology), and the temperature was decreased from 30 ℃ to-40 ℃ under a nitrogen flow rate of 20mL/min, then kept for 10 minutes, increased from-40 ℃ to 220 ℃ (first heating), decreased from 220 ℃ to-40 ℃ (cooling) after keeping for 10 minutes, and increased from-40 ℃ to 220 ℃ (second heating) after keeping for 10 minutes, to obtain a DSC curve.
All temperature increases and decreases were performed at a rate of 10 ℃/min, and alumina was used as a reference material.
The heat of crystallization is determined from the area of the crystallization peak observed during cooling.
The heat of crystallization can be calculated from the area of the portion enclosed by the DSC curve and a straight line connecting a point at which the DSC curve deviates from the baseline on the high temperature side and a point at which the DSC curve returns to the baseline on the low temperature side again, using analysis software attached to the apparatus.
In the present embodiment, in order to impart excellent cushioning properties to the expanded polyolefin resin sheet 1, the expanded polyolefin resin sheet may be rapidly cooled to a temperature not higher than the crystallization temperature by the cooling air or the cooling plug, thereby suppressing the formation of polypropylene crystals inside.
The inhibition of crystallization of the polyolefin resin foam sheet 1 can be confirmed by the fact that the heat of fusion in the "first heating" in the operation of determining the heat of crystallization is lower than the heat of fusion determined in the "second heating".
The ratio (Qm1/Qm2) of the heat of fusion (Qm1) in the "first heating" to the heat of fusion (Qm2) in the "second heating" of the polyolefin resin foam sheet 1 is preferably 0.9 or less.
The ratio (Qm1/Qm2) is more preferably 0.8 or less.
The heat of fusion of the polyolefin resin foam sheet can be determined using analysis software attached to the apparatus, similarly to the heat of crystallization, and can be calculated from the area of the portion enclosed by the DSC curve and the line connecting the point at which the DSC curve deviates from the baseline on the low temperature side and the point at which the DSC curve returns to the baseline on the high temperature side again.
In the present embodiment, as described above, the case of producing the foamed polyolefin resin sheet by extrusion foaming is exemplified in terms of easily adjusting the foamed polyolefin resin sheet to an appropriate state and using it as a packaging sheet, but the foamed polyolefin resin sheet provided in the packaging sheet of the present invention may be produced by another production method.
In the present embodiment, a printed circuit board and a glass plate are exemplified as the object to be packaged in a packaging sheet, but the object to be packaged is preferably a member for an electric device or a member for an electronic device, such as a silicon wafer, a hard disk, a microprocessor, a light emitting diode, a sapphire wafer, a disk substrate, an IC chip, a magneto-optical disk (MO), a DVD, a BD, various memories, a liquid crystal filter, a magneto-resistive head for a hard disk, a CCD, or a Reticle (Reticle).
The packaged object may be so-called electric or electronic equipment such as a computer, a monitor, a video recorder, a smart phone, or a tablet computer, in which these components are incorporated.
That is, the use of the packaging sheet of the present invention is not particularly limited.
The packaging sheet of the present invention is not limited to the above examples, as far as the use is concerned.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
(example 1)
As the extruder, a tandem extruder comprising a single-screw extruder having a diameter of 90mm in the first stage (upstream side) and a single-screw extruder having a diameter of 115mm in the second stage (downstream side) was used to produce a polypropylene resin foamed sheet.
The following compounds were prepared: for a scan at 50: a mixed polypropylene resin containing high melt tension polypropylene (HMS-PP) and block polypropylene (bPP) at a mass ratio of 50 (100 parts by mass), a donor/acceptor type antistatic agent (a mixture of an organoboron compound and a basic nitrogen compound) was added at a ratio of 0.5 parts by mass, and a bubble adjusting agent (a talc type bubble adjusting agent) was added at a ratio of 0.2 parts by mass.
This mixture was fed to a hopper of an extruder having a diameter of 90mm in the first stage, heated and melted at 200 ℃, and butane (isobutane/n-butane: 35/65) as a blowing agent was pushed in from the middle of the extruder in the first stage so that the ratio to 100 parts by mass of the molten resin became 4 parts by mass, and melt-kneaded by the extruder.
The kneaded product obtained by melt kneading was supplied to an extruder in the second stage through a connecting pipe, and the temperature of the kneaded product was reduced to 170 ℃ while continuing the kneading of the kneaded product in the extruder.
Thus, the kneaded product having been cooled was extruded in a cylindrical shape into the atmosphere through an annular slit of a circular die having a bore diameter of 140mm and a slit gap of 0.95mm connected to the tip of the extruder so that the extrusion output became 98.5 kg/hr, and the kneaded product was foamed to form a cylindrical foam.
Using a cooled mandrel (mandrel diameter:
Figure BDA0002423779930000191
length: 500mm) and the foam was expanded in diameter and extracted, air was blown to the outer surface of the foam using an air cooling ring to cool the foam, and the cooled foam was cut with a cutter to produce a polyolefin resin foamed sheet.
(example 2)
A polyolefin resin foamed sheet was produced in the same manner as in example 1, except that low-density polyethylene (LDPE) was used instead of the mixed polypropylene resin, the amount of the donor/acceptor type antistatic agent was changed from 0.5 part by mass to 0.3 part by mass, and the extrusion conditions were changed.
(example 3)
A polyolefin resin foamed sheet was produced in the same manner as in example 2, except that the amount of the donor/acceptor type antistatic agent was changed from 0.3 part by mass to 2.0 parts by mass.
Comparative example 1
A polyolefin resin foamed sheet was produced in the same manner as in example 1, except that a polymer type antistatic agent was used instead of the donor/acceptor type antistatic agent, and the amount of the polymer type antistatic agent added was 8 parts by mass with respect to 100 parts by mass of the mixed polypropylene resin.
Comparative example 2
A polyolefin resin foam sheet was produced in the same manner as in example 2, except that a surfactant (glycerol monostearate) was used in place of the donor/acceptor type antistatic agent, and the amount of the surfactant was 1.5 parts by mass per 100 parts by mass of the Low Density Polyethylene (LDPE).
Comparative example 3
A polyolefin resin foamed sheet was produced in the same manner as in comparative example 2, except that the surfactant was changed from stearic acid monoglyceride to alkyl diethanolamide, and the amount of the surfactant was changed from 1.5 parts by mass to 3.4 parts by mass with respect to 100 parts by mass of low-density polyethylene (LDPE).
The physical properties of the obtained expanded polyolefin resin sheet are shown in the table.
(evaluation items of physical Properties)
Thickness: thickness of polyolefin resin foam sheet
Weight per unit area: weight per unit area of polyolefin resin foam sheet
Surface resistivity: surface resistivity measured at 20 ℃ and 60% RH after the surface of the polyolefin resin foam sheet was wiped with ethanol
The amount of exudation: bleeding amount from the surface of a polyolefin resin foam sheet
Amount of metal ions: the total amount of alkali metal ions and alkaline earth metal ions on the surface of the expanded polyolefin resin sheet
TABLE 1
Figure BDA0002423779930000201
From the above results, it is found that the migration of components into the article to be packaged can be effectively reduced by providing the packaging sheet with the polyolefin resin foam sheet containing the donor/acceptor type antistatic agent.
That is, as described above, the packaging sheet of the present invention is less likely to cause migration of components into the article to be packaged and is excellent in antistatic properties.

Claims (3)

1. A packaging sheet comprising a polyolefin resin foam sheet containing a donor/acceptor type antistatic agent, wherein the polyolefin resin foam sheet is exposed on at least one surface.
2. The packaging sheet according to claim 1, wherein the content of the antistatic agent contained in the polyolefin resin foamed sheet is 0.1 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the polyolefin resin contained in the polyolefin resin foamed sheet.
3. The packaging sheet according to claim 1 or 2, wherein the polyolefin resin foam sheetHas a thickness of 0.15mm to 5mm and a weight per unit area of 15g/m2Above and 500g/m2In the following, the following description is given,
in the surface of the polyolefin resin foam sheet,
the amount of bleeding is 0.2 mass% or less,
the amount of alkali metal ion and alkaline earth metal ion is 1mg/m2Are as follows, and
the surface resistivity after wiping with ethanol was 1 × 10 as measured at 20 ℃ and 60% RH9Omega is 1 × 1012Omega is less than or equal to.
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