CN101935416A - Polyolefine resin sparkling sheet material - Google Patents

Polyolefine resin sparkling sheet material Download PDF

Info

Publication number
CN101935416A
CN101935416A CN201010214230XA CN201010214230A CN101935416A CN 101935416 A CN101935416 A CN 101935416A CN 201010214230X A CN201010214230X A CN 201010214230XA CN 201010214230 A CN201010214230 A CN 201010214230A CN 101935416 A CN101935416 A CN 101935416A
Authority
CN
China
Prior art keywords
resin
foam sheet
weight
sheet material
resin layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201010214230XA
Other languages
Chinese (zh)
Inventor
森田和彦
角田博俊
秋山照幸
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JSP Corp
Original Assignee
JSP Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JSP Corp filed Critical JSP Corp
Publication of CN101935416A publication Critical patent/CN101935416A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • 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
    • 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
    • C08J2205/00—Foams characterised by their properties
    • 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
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
    • 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
    • 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)

Abstract

The present invention relates to polyolefine resin sparkling sheet material.Though the invention provides thin thickness, amount is light, rigidity is strong and operability is excellent, can be suitable for the polyolefine resin sparkling sheet material of ground paper equivalent material such as the interval insulant of the lining paper of making precise electronic instruments such as glass substrate, container or assembling vessel starting material etc.Polyolefine resin sparkling sheet material of the present invention is that apparent density is that 60～350g/L, thickness are that 0.2～1.5mm, level ground amount are 50～200g/m 2Polyolefine resin sparkling sheet material, wherein, the bending elastic modulus that constitutes the substrate resin of this foam sheet is more than the 300MPa, the number of bubbles of the thickness direction of this foam sheet is 1～3 simultaneously.

Description

Polyolefine resin sparkling sheet material
Technical field
The present invention relates to polyolefine resin sparkling sheet material, specifically, relate to can be suitable for the lining paper (Inter Paper that makes precise electronic instruments such as glass substrate), the polyolefine resin sparkling sheet material of interval insulant of container, ground paper equivalent material etc.
Background technology
In recent years, polyolefine resin sparkling sheet material is used as the lining paper that group is gone into the glass substrate of circuit.The employed foam sheet of this lining paper since when must volume can not increase operability also excellent, so required thickness is thin, light weight and resiliency excellence, the sag of chain during while cantilever (sheet is held Chi) is little, rigidity is strong.And, in recent years the polyethylene resin foaming sheet material that polyolefine resin sparkling sheet material and pottery in the past etc. use in the packing of article is usually compared, how much improve by the rigidity such as orientation of utilizing bubble, be used for the lining paper of glass substrate etc., but thin thickness and light be by force opposite characteristic with rigidity, be not the abundant strong polyolefine resin sparkling sheet material of rigidity that can satisfy their degree simultaneously.
Specifically, light and resiliency is excellent being 15～40 times polyethylene resin foaming sheet material as the expansion ratio of substrate resin as the known ldpe resin of cushioning material for packing, but there is the weak and shortcoming of operability difference of rigidity.In addition, though be that 5～15 times polyethylene resin foaming sheet material rigidity intensity is improved with ldpe resin as the expansion ratio of substrate resin, inflexible intensity is also insufficient sometimes according to purposes.In addition, expansion ratio is that 5～15 times the rigidity of expandable polypropylene resin sheet material is stronger than above-mentioned polyvinyl resin system foam sheet, but the problem that the big grade of the uneven thickness that has foam sheet integral body will solve, if as spacing sheet for glass substrate etc., then there are the excessive and shortcomings such as efficiency of loading reduction of loading height.In addition, expansion ratio be record in expandable polypropylene resin sheet material below 5 times or the patent documentation 1 the foam sheet with rigidity and resiliency (foam sheet that comprises the hybrid resin of ldpe resin and high-density polyethylene resin) though rigidity intensity be improved, from thin thickness, gently, rigidity was strong when resiliency was excellent angle consideration is also insufficient.
[patent documentation 1] TOHKEMY 2004-43813 communique
Summary of the invention
The objective of the invention is to, though thin thickness, light weight are provided, the operability excellence but rigidity is strong can be suitable for the polyolefine resin sparkling sheet material in the ground paper equivalent material such as the interval insulant of lining paper, container of the precise electronic instrument of making glass substrate etc. or assembling vessel material etc.
According to the present invention, provide polyolefine resin sparkling sheet material shown below.
[1] polyolefine resin sparkling sheet material, it is that apparent density is that 60～350g/L, thickness are that 0.2～1.5mm, level ground amount (level ground amount) are 50～200g/m 2Polyolefine resin sparkling sheet material, it is characterized in that the bending elastic modulus that constitutes the substrate resin of this foam sheet is 300MPa above the time, the number of bubbles of the thickness direction of this foam sheet is 1～3.
[2] polyolefine resin sparkling sheet material of above-mentioned 1 record is characterized in that, cooperates the polymer static inhibitor of 2～20 weight % in the substrate resin that constitutes above-mentioned foam sheet.
[3] polyolefine resin sparkling sheet material of above-mentioned 1 record is characterized in that, presses polyolefin resin layer on the upper strata of one side at least of above-mentioned foam sheet, cooperates the polymer static inhibitor of 5～55 weight % in the substrate resin that constitutes this resin layer.
[4] polyolefine resin sparkling sheet material of any record in above-mentioned 1～3, wherein, the substrate resin that constitutes above-mentioned foam sheet is that the fusion tension force under 190 ℃ is the acrylic resin of 15～400mN.
[5] polyolefine resin sparkling sheet material of any record in above-mentioned 1～3, wherein, the substrate resin that constitutes above-mentioned foam sheet is that the fusion tension force under 190 ℃ is that 15～400mN, density are the polyvinyl resin of 930～970g/L.
[6] polyolefine resin sparkling sheet material of any record in above-mentioned 1～3, wherein, the substrate resin that constitutes above-mentioned foam sheet be density to be following polyvinyl resin L 15～70 weight % of 930g/L surpass 930g/L and be the polyethylene resin composition of polyvinyl resin H 85～30 weight % below the 970g/L with density, polyvinyl resin L and polyvinyl resin H add up to 100 weight %.
Polyolefine resin sparkling sheet material of the present invention is the foam sheet that measure on specific apparent density, thickness and level ground, the bending elastic modulus height of substrate resin, the number of bubbles of the thickness direction of this foam sheet reduces simultaneously, and the thickness of walls increases, even light weight thus, rigidity are also strong, operability is excellent.In addition, the number of bubbles of the thickness direction by reducing foam sheet, during as packing packed articles such as assembling wrapping material, the visuality of packed article also improves.Therefore, for being suitable for lining paper, the interval insulant of container or the foam sheet of wrapping material of the precise electronic instrument of making glass substrate etc.
In polyolefine resin sparkling sheet material of the present invention, can make foam sheet or the resin layer that is laminated on the foam sheet contains static inhibitor, give anti-static function.This foam sheet is preferably used as lining paper, interval insulant, ground paper equivalent material of precise electronic instrument etc.
Description of drawings
[Fig. 1] Fig. 1 is the width cross section enlarged photograph of foam sheet of the present invention.
[Fig. 2] Fig. 2 is the width cross section enlarged photograph of foam sheet in the past.
[Fig. 3] Fig. 3 is the explanatory view of the sagging measuring method of cantilever.
Embodiment
Below polyolefine resin sparkling sheet material of the present invention is carried out specific description.
Polyolefine resin sparkling sheet material of the present invention (being designated hereinafter simply as foam sheet) though with polyolefin resin as substrate resin, and thin, light, have in the past foam sheet the rigidity that can not show.
The apparent density of foam sheet of the present invention is 60～350g/L, and thickness is 0.2～1.5mm, and the level ground amount is 50～200g/m 2
If this apparent density is low excessively, then might be able to not bring into play sufficient rigidity intensity.On the other hand, if this apparent density is too high, then might damage the desired resiliency of wrapping material of glass substrate etc.Consider that from this angle this apparent density is preferably 70～250g/L, 80～200g/L more preferably, more preferably 100～180g/L is preferably 120～170g/L especially.
In addition, if above-mentioned thickness is thin excessively, then insufficient to resiliency, the surface protection of precise electronic instrument, if the blocked up loading capacity of then damaging the precise electronic instrument.Consider that from this angle the thickness of this foam sheet is preferably 0.3～1.2mm, more preferably 0.4～1.1mm is preferably 0.6～1.0mm especially.
In addition, if above-mentioned level ground amount is too small, then rigidity intensity might can not be brought into play.On the other hand, if excessive, then might operability reduce and cause the cost rising.Consider that from this angle this level ground amount is preferably 60～190g/m 2, 65～180g/m more preferably 2, 70～170g/m more preferably 2
The substrate resin that constitutes foam sheet of the present invention is main component with the polyolefin resin.This polyolefin resin is the resin that contains 50 moles of above alkene compositions of %.As this polyolefin resin, can enumerate polyvinyl resin, acrylic resin etc.Polyolefin resin is low from surface hardness, flexibility is excellent, the preferred use considered in the excellent aspect of the surface protection of packaged body.And the main component of the substrate resin in this specification sheets refers to more than the 50 weight % that content is substrate resin, is preferably more than the 70 weight %, more preferably more than the 80 weight %.
As above-mentioned polyvinyl resin, for example can enumerate, the ethene composition is the above resins of 50 moles of %, specifically can enumerate straight chain shape new LDPE (film grade)s such as high density polyethylene(HDPE), new LDPE (film grade), ethene-1-Butylene copolymer, ethene-hexene-1 multipolymer, ethene-4-methylpentene-1 multipolymer, ethylene-octene-1 multipolymer, vinyl-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-propylene-1-Butylene copolymer, and their mixture more than 2 kinds etc.
In addition, as above-mentioned acrylic resin, can enumerate alfon or propylene and can with the multipolymer of the compositions such as other alkene of copolymerization of propylene.As can with other alkene of copolymerization of propylene, for example can enumerate, ethene, 1-butylene, iso-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 3, carbonatomss such as 4-dimethyl-1-butylene, 1-heptene, 3-methyl isophthalic acid-hexene are 4～10 alpha-olefin.In addition, above-mentioned multipolymer can be random copolymers or segmented copolymer etc., and then not only can also be terpolymer for copolymer.And, in the above-mentioned multipolymer can with other composition of copolymerization of propylene preferably with below the 25 weight %, especially preferably contain with the ratio below the 15 weight %.And, as this can copolymerization the lower value of content of other composition, consider the reason of selecting multipolymer etc., be about 0.3 weight %.In addition, these acrylic resins can mix 2 kinds with on use.
The bending elastic modulus that constitutes the substrate resin of foam sheet of the present invention is more than the 300MPa, is preferably more than the 400MPa, more preferably more than the 500MPa.If this bending elastic modulus is less than 300MPa, then flexural rigidity reduces, and the rigidity intensity of foam sheet is insufficient, and operability might reduce.On the other hand, its higher limit is preferably 2000MPa, more preferably 1800MPa, more preferably 1500MPa.If this bending elastic modulus is too high, then the resiliency of foam sheet might reduce.
Be noted that, the bending elastic modulus of substrate resin adopts following value: according to JISK7171 (1994), the test film of used thickness 2mm * width 25mm * length 40mm is that the radius R 1 of 30mm, pressure head is the value of measuring, calculating under the condition of 2mm/min for 2.0mm, trial speed for the radius R 2 of 5.0mm, brace table in span.And, as test film, use the following test film that obtains, foam sheet (is provided with under the situation of lamination foam sheet of resin layer, for removing the foam sheet of resin layer) use heating and pressurizing (adding Hot プ レ ス), cooling pressurization (cooling プ レ ス) to carry out the resin that deaeration forms non-foaming, with a plurality of coincidences of the resin of this non-foaming, use heating and pressurizing, cooling pressurization to obtain the non-foamed resin sheet of the thickness of above-mentioned test film, cut out above-mentioned test film size from this non-foamed resin sheet, obtain above-mentioned test film.
As the bending elastic modulus that constitutes foam sheet is substrate resin more than the 300MPa, considers the suitable property of foaming of substrate resin, preferably with the resin of following (i)～(iii) substrate resin as main component.
(i) the fusion tension force under 190 ℃ is the high fusion tension force acrylic resin (the following HMS-PP that also abbreviates as) of 15～400mN.
(ii) the fusion tension force under 190 ℃ is that 15～400mN, density are the high fusion tension force high-density polyethylene resin (the following HMS-HDPE that also abbreviates as) of 930～970g/L.
(iii) to be following polyvinyl resin (the following L-polyethylene that also abbreviates as) 15～70 weight % of 930g/L surpass 930g/L and be the polyethylene resin composition of high-density polyethylene resin (the following H-polyethylene that also abbreviates as) 30～85 weight % (wherein, the poly 100 weight % that add up to of L-polyethylene and H-) below the 970g/L with density density.
Object lesson as the HMS-PP of above-mentioned (i), can enumerate the branch index (branch divides か れ index) and the significant deformation that have less than 1 as Japanese kokai publication hei 7-53797 communique described (1) and solidify the polypropylene of elongation viscosity (び viscosity is stretched in askew body sclerosis), (2) (a) Z-average molecular weight (Mz) are 1.0 * 10 6More than or the ratio (Mz/Mw) of Z-average molecular weight (Mz) and weight-average molecular weight (Mw) be more than 3.0, (b) and equilibrium compliance J 0Be 12 * 10 -5Cm 2It is per second 5 * 10 that Sr/S is replied in the shearing strain above or unit stress of/dyne -5Cm 2The polypropylene that/dyne is above, (3) melting mixing under the temperature that acrylic resin fusion and radical polymerization initiator decompose such as the title complex by will containing free radical polymerization monomer such as vinylbenzene and radical polymerization initiator or additive etc., the acrylic resin of the modification that obtains, or (4) modified polypropylene resin that acrylic resin, isoprene monomer and radical polymerization initiator melting mixing are obtained.
As above-mentioned HMS-HDPE (ii), can enumerate: the ethene polymers that has vinyl by the end that vinyl polymerization is obtained, or by with ethene and carbonatoms be end that the olefin-copolymerization more than 3 obtains have vinyl, number-average molecular weight Mn is more than 2000, weight-average molecular weight is 2～5 with the ratio Mw/Mn of number-average molecular weight, in the presence of macromonomer, with ethene and arbitrarily carbonatoms be the ethylene copolymer that the olefinic polymerization more than 3 obtains.Wherein, macromonomer refers to the olefin polymer that end has vinyl, be preferably by the end that vinyl polymerization is obtained and have the ethene polymers of vinyl or by with ethene and carbonatoms being the ethylene copolymer that end that the olefin-copolymerization more than 3 obtains has vinyl, be long chain branch (that is usefulness, in the branch beyond the branch of the alkene 3 or more further preferably from arbitrarily used carbonatoms 13C-NMR measures the above branch of hexyl detect) have the straight chain shape ethene polymers or a straight chain shape ethylene copolymer of vinyl less than 0.01 end with respect to 1000 main chain mesomethylene carbon.
For specifying of HMS-HDPE, on the books in TOHKEMY 2006-96910 communique, TOHKEMY 2006-199872 communique.
The fusion tension force that is noted that HMS-PP, HMS-HDPE is crossed when hanging down, and the suitable property of foaming might be insufficient.Consider that from this angle this fusion tension force is more preferably more than the 17mN, more preferably more than the 20mN.
On the other hand, when this fusion tension force was too high, because the easy continuous air bubblesization of the foaming that causes because of the rising of die pressure when extrusion foaming, rigidity might reduce.Consider that from this angle this fusion tension force is preferably below the 400mN, more preferably below the 300mN.
Fusion tension force in this specification sheets is made made キ ヤ ピ ロ グ ラ Off 1D by the smart mechanism of Toyo Co., Ltd. and is measured.Specifically, use the barrel diameter to be 9.55mm, length is that barrel and the nozzle diameter of 350mm is 2.095mm, length is the nib of 8.000mm, the design temperature of barrel and nib is 190 ℃, the sample of necessary amount is joined in this barrel, place after 4 minutes, making velocity of piston is from nib molten resin to be extruded with band shape in 10mm/ minute, it is that the tension force of 45mm detects with on the belt pulley that this ribbon is hung over diameter, increase pulling speed (draw I and get り speed) with the constant speedup and make pulling speed in 4 minutes, draw ribbon with take off roll in 200m/ minute, the fusion tensile maximum value when obtaining ribbon and being about to rupture from increasing in 0m/ minute.Wherein, the sample of necessary amount is joined in this barrel, places after 4 minutes from the reason of nib with banded resin melt extrusion, the time that makes pulling speed reach 200m/ minute from 0m/ minute is that 4 minutes reason is, improves the circulation ratio of the value that obtains when suppressing the thermal degradation when of resin.For aforesaid operations, use different samples, carry out measuring for totally 10 times, remove three values successively, remove three values successively from the minimum value of above-mentioned maximum value from the maximum value of the above-mentioned maximum value that obtains for 10 times, the value that four the maximum value additions in remaining centre are on average obtained is as the fusion tension force (mN) among the present invention.
Wherein, carry out the fusion tensile by aforesaid method and measure, even pulling speed arrives when ribbon can not rupture yet in 200m/ minute, adopting and making pulling speed is that the value of the fusion tension force (mN) that obtains of 200m/ minute constant speed is as the maximum value in this mensuration.Specifically, similarly carry out with said determination, from nib molten resin is extruded with band shape, this ribbon is hung over tension force to be detected with on the belt pulley, rotation traction traction roller when increasing pulling speed and make pulling speed reach 200m/ minute from 0m/ minute in 4 minutes with the constant speedup waits for that speed of rotation arrives 200m/ minute.After speed of rotation reaches 200m/ minute, the typing of beginning fusion tensile data, after 30 seconds, the typing of end data.The fusion tensile mean value that will be obtained by the tension load curve that obtained between these 30 seconds is as fusion tension force.
And, certainly in said determination, when nib is extruded molten resin with band shape, do not make bubble enter into this ribbon as much as possible.In addition, in order to infer the fusion tension force of raw material from foam sheet, during by foam sheet formation determination sample, will with vacuum drying oven to foam sheet heat, deaeration and the foam sheet that obtains be as sample, this moment vacuum drying oven the deaeration condition for the above temperature of the fusing point of the polyolefin resin of the substrate resin that constitutes foam sheet and under reduced pressure.
In above-mentioned polyethylene resin composition (iii), if the poly content of above-mentioned H-is below the 85 weight %, then the continuous air bubbles rate of foam sheet can too not increase, and apparent density can be not too high.In addition, if the poly ratio of H-is more than the 30 weight %, sag of chain can be not excessive when then holding an end of foam sheet, and promptly so-called rigidity intensity can excessively not reduce.Consider from this angle, more preferably L-polyethylene 15～50 weight % and H-polyethylene 85～50 weight % are (wherein, the poly 100 weight % that add up to of L-polyethylene and H-) polyethylene resin composition, the polyethylene resin composition of L-polyethylene 30～50 weight % and H-polyethylene 70～50 weight % (wherein, the poly 100 weight % that add up to of L-polyethylene and H-) more preferably.
As above-mentioned L-polyethylene, can enumerate density is the following so-called new LDPE (film grade) of 930g/L, straight chain shape new LDPE (film grade), straight chain shape ultra-low density polyethylene etc.Wherein, be preferably the good new LDPE (film grade) of foaminess of the foam sheet that can obtain low bulk density.The lower limit of the poly density of L-is generally about 880g/L.
Further, the poly melt flow rate (MFR) of L-(MFR) is considered from the angle of the raising outward appearances such as surperficial no concave-convex of foam sheet, be preferably 0.3～20.0g/10 minute, more preferably 1.0～15.0g/10 minute, more preferably 2.0～10.0g/10 minute.In addition, to be 20mN～400mN preferred owing to can obtain the foam sheet of low bulk density easily for the fusion tension force under poly 190 ℃ of the L-.
As above-mentioned H-polyethylene, can enumerate density and surpass 930g/L and, specifically can enumerate high density polyethylene(HDPE) etc. for the following so-called straight chain shaped polyethylene of 970g/L.The poly density of this H-is considered from the inflexible angle of further raising foam sheet, is preferably more than the 940g/L, more preferably more than the 950g/L, more preferably more than the 955g/L.
In addition, the poly MFR of H-considers that from the angle of the raising outward appearances such as surperficial no concave-convex of foam sheet MFR was preferably more than 1.0g/10 minute, more preferably more than 2.0g/10 minute, more preferably more than 3.0g/10 minute.On the other hand, the higher limit of MFR never can reduce rigidity and the angle that improves the shock-resistance under the low temperature atmosphere gas is considered, is preferably 20.0g/10 minute, and more preferably 15.0g/10 minute, more preferably 10.0g/10 minute.
In addition, it is above and less than 60mN that the fusion tension force under poly 190 ℃ of this H-is generally 5mN, though therefore depend on expansion ratio, is difficult to keep separately bubble.The poly fusion tension force of H-is insufficient can be remedied by mixing the L-polyethylene.
In addition, the fusion tension force under 190 of above-mentioned polyethylene resin composition (iii) ℃ is preferably about 15～400mN.And the polyethylene resin composition that fusion tension force is about 15mN～400mN prepares by mixing L-polyethylene and H-polyethylene in the scope of above-mentioned weight ratio.This fusion tension force is crossed when hanging down, because foaminess reduces, might not can form the foam sheet of light weight, so this fusion tension force is more preferably more than the 17mN, more preferably more than the 20mN.On the other hand, when fusion tension force is too high since when extrusion foaming because the foaming that the rising of die pressure causes and easy continuous air bubblesization, rigidity, hot formability might reduce, so fusion tension force is more preferably below the 300mN.
In addition, the MFR of above-mentioned polyethylene resin composition (iii) preferably was about more than 0.3g/10 minute.And the polyethylene resin composition that MFR was about more than 0.3g/10 minute prepares by mixing L-polyethylene and H-polyethylene in the scope of above-mentioned weight ratio.By making the separated foam rate height of the foam sheet that this MFR obtains in above-mentioned scope, the flexural rigidity of foam sheet is excellent especially, and during with this foam sheet thermoforming, the elongation of foam sheet is good, and hot formability improves.Consider that from this angle this MFR was preferably more than 1.0g/10 minute, more preferably more than 2.0g/10 minute, more preferably more than 3.0g/10 minute.On the other hand, the higher limit of this MFR be 20.0g/10 minute preferred aspect the good foam sheet of the foam sheet that obtains low bulk density or hot formability.Consider that from this angle this MFR is more preferably below 15.0g/10 minute, more preferably below 10.0g/10 minute.
In this specification sheets, melt flow rate (MFR) (MFR), for polyvinyl resin, for based on JISK7210 (1976), under 190 ℃, the condition of load 21.18N, measure the value obtain, for acrylic resin, for based on JIS K7210 (1976), under 230 ℃, the condition of load 21.18N, measure the value that obtains.
And the relevant value of material resin that above-mentioned fusion tension force and MFR use for the preparation foam sheet time when being raw material with the hybrid resin, is difficult to try to achieve in advance correct the fusion tension force and the MFR of hybrid resin.Therefore, can try to achieve the general value of the fusion tension force and the MFR of hybrid resin, come the fusion tension force and the MFR of raw material hybrid resin are adjusted by carrying out the pre-mixing experiment.In addition, the foam sheet that obtains is carried out deaeration, measure fusion tension force and MFR, can infer the fusion tension force and the MFR of preferred hybrid resin thus with aforesaid method.
Constitute in the substrate resin of foam sheet,, can also contain elastomericss such as styrene resins such as polystyrene, styrol copolymer, ethylene propylene rubber, styrene-butadiene-styrene block copolymer etc. in the scope that does not hinder the object of the invention and effect.The content of this moment is preferably below the 40 weight %, more preferably below the 25 weight %, is preferably especially below the 10 weight %.
Foam sheet of the present invention can also contain various additives in above-mentioned substrate resin.As additive, for example can enumerate functional additives such as nucleator, antioxidant, thermo-stabilizer, static inhibitor, electroconductibility imparting agent, weather resisting agent, UV light absorber, fire retardant, inorganic additives etc.
The superior stiffness of foam sheet of the present invention, mainly the bending elastic modulus of the substrate resin by constituting foam sheet is that the number of bubbles of the thickness direction of foam sheet more than the 300MPa time is that the combination of formation such as 1～3 shows.That is, the number of bubbles of thickness direction be 1～3 foam sheet owing to take into account the apparent density of foam sheet, the thickness of bubble chamber film is thick.This bubble chamber film is made of the big resin of bending elastic modulus, during therefore crooked this foam sheet, must make bubble deformation with big power, and is therefore strong for the rigidity of bending.Consider that from this angle the number of bubbles of the thickness direction of foam sheet is preferably 1～2, more preferably 1～1.7, more preferably 1～1.5.
In the mensuration of the number of bubbles of this thickness direction, on the whole width of foam sheet, on width, determine to measure the position at interval with 10cm, try to achieve the number of bubbles (individual) of the thickness direction at this mensuration position, each is measured the arithmetical av of number of bubbles of thickness direction at position as the number of bubbles (individual) of the thickness direction among the present invention.And, the above-mentioned number of bubbles of respectively measuring the thickness direction at position for taking 100 times the foam sheet width cross-section photograph shown in Figure 1 of measuring the position, is drawn straight line on the foam sheet thickness direction on the photo that obtains, counting and the crossing whole number of bubbles of this straight line, the value of trying to achieve thus.And, in this cross section enlarged photograph, see that when accounting on the photo the visibly different fine bubble of most bubble, this fine bubble is disregarded in number of bubbles.
In addition, in foam sheet of the present invention, the mean air bubble diameter of thickness direction is 0.2～1.5mm, more preferably 0.3～1.2mm.Be preferably 0.3～0.9mm especially.In addition; consider from the surface protection equal angles of the mechanicalness rerum naturas such as stretching of foam sheet, outward appearance, surface smoothing, packed article; the mean air bubble diameter of extruding direction is preferably 0.2～1.7mm, 0.3～1.5mm more preferably, and the mean air bubble diameter of width is preferably 0.2～1.7mm, 0.3～1.5mm more preferably.
The value of the mean air bubble diameter of the thickness direction of above-mentioned foam sheet for trying to achieve by the mean thickness (mm) that removes foam sheet with the number of bubbles of above-mentioned thickness direction.
In addition, the width of above-mentioned foam sheet and the mean air bubble diameter of extruding direction are measured respectively based on the width cross section and with the orthogonal direction cross section of extruding of width foam sheet.Specifically, the length 3mm that marks on the enlarged photograph of the width cross section of foam sheet thickness two five equilibriums of foam sheet (considers the ratio of enlargement of enlarged photograph, 3mm multiply by the line segment of the length that ratio of enlargement obtains) medullary ray, try to achieve number of bubbles (n) with this line segment intersection.Based on the length 3mm of line segment and the number of bubbles of trying to achieve (n), try to achieve the mean value of the bubble diameter of width by the calculating formula of 3/ (n-1).Same operation is repeated in other width cross section at foam sheet, tries to achieve the mean value of the bubble diameter of the width at totally 5 positions, with their arithmetical av as the mean air bubble diameter of width of the present invention.In addition, except based on the extruding direction cross section enlarged photograph measures of foam sheet, the value of similarly trying to achieve with the measuring method of the mean air bubble diameter of width is as the mean air bubble diameter of extruding direction of the present invention.
In addition, the separated foam rate of foam sheet of the present invention is considered from the surface protection of the flexibility of foam sheet, packed article, suitable slipperiness equal angles, is preferably 25～85%, more preferably 35～80%.
Above-mentioned separated foam rate is according to the order C of ASTM-D2856-70, uses air comparison expression specific gravity hydrometer 930 types mensuration with the ベ of Toshiba Star Network マ Application Co., Ltd. (will be contained in the sample cup by the cutting sample that foam sheet is cut into 25mm * 25mm * 20mm and measure.And, foam sheet is thin excessively, in the time of can not cutting out the cutting sample of above-mentioned size, cut out the sample of multi-disc 25mm * 25mm * foam sheet thickness, by overlapping, the true volume Vx of foam sheet (cutting sample) the mensuration cutting sample of formation 25mm * 25mm * about 20mm) calculates separated foam rate S (%) by following formula (1).
S(％)＝(Vx-W/ρ)×100/(Va-W/ρ) (1)
Vx: the true volume (cm of the cutting sample of measuring by aforesaid method 3), be equivalent to constitute the volume of resin of cutting sample and the bubble cubic capacity sum of the part of the separated foam in the cutting sample.
Va: the volume (cm on the cutting sample that calculates by the outside dimension of measuring employed cutting sample (outer cun) apparent 3).
W: measure employed cutting sample gross weight (g).
ρ: the density (g/cm of the resin that the foam sheet deaeration is tried to achieve 3)
By add the polymer static inhibitor in foam sheet of the present invention, the surface resistivity that can make foam sheet is 1 * 10 7～1 * 10 14(Ω).
When this surface resistivity was excessive, it is insufficient that antistatic property becomes, and static charge is accumulated on the surface of foam sheet, easily adheres to dust.In order more to be difficult for adhering to dust, this surface resistivity is preferably 5 * 10 13Below the Ω, more preferably 1 * 10 13Below the Ω.On the other hand, no problem aspect antistatic property when surface resistivity is too small, but according to circumstances the desired antistatic property of wrapping material is strong excessively, and cost raises.
Surface resistivity in this specification sheets is measured according to JIS K6271 (2001) after the status adjustment of carrying out following test film.Promptly, will be as test film (the long 100mm * wide 100mm * thickness: determination object thing thickness) under the atmosphere gas of 20 ℃ of temperature, relative humidity 30%, placed 36 hours that cuts out from foam sheet or lamination foam sheet of determination object thing, after carrying out the status adjustment of test film thus, under the condition that applies voltage 500kV, begin to apply voltage according to JIS K6271 (2001), try to achieve through the surface resistivity after 1 minute.
For the surface resistivity that makes foam sheet is 1 * 10 7～1 * 10 14Ω, preferably the ratio with 2～20 weight % cooperates the polymer static inhibitor in foam sheet.If this use level is very few, then required antistatic property might can not be brought into play.On the other hand, even this use level is too much, aspect antistatic property,, still in the scope that can not hinder foaming, use without any problem.Consider that from this angle the use level of the static inhibitor in the foam sheet is preferably 3～15 weight %, more preferably 4～12 weight %.
The number-average molecular weight of polymer static inhibitor is more than 2000, is preferably 2000～100000, more preferably 5000～60000, be preferably 8000～40000 especially.Therefore, this static inhibitor is the static inhibitor with other polymer of surfactant type static inhibitor phase region.And the upper limit of the number-average molecular weight of this polymer static inhibitor is about 1000000.Number-average molecular weight by making the polymer static inhibitor is in above-mentioned scope, prevents that static inhibitor from shifting and pollute the packed article surface to packed article.
And above-mentioned number-average molecular weight uses high-temperature gel permeation chromatography to try to achieve.For example, at the polymer static inhibitor when being the hydrophilic resin of main component with polyether ester amides or polyethers, for orthodichlorobenzene as solvent, making sample concentration is 3mg/ml, as primary standard, column temperature is to measure the value that obtains under 135 ℃ the condition with polystyrene.And above-mentioned solvent types, column temperature are according to the kind appropriate change of polymer static inhibitor.
As the polymer static inhibitor that uses among the present invention, can enumerate volume specific resistance is 10 5～10 11The hydrophilic resin of Ω cm and polyolefinic multipolymer.
As this hydrophilic resin; can use polyether glycol; polyether diamine and their polyethers such as modifier; segment with polyether glycol forms the polyether ester amides of composition as polyether segment; segment with polyether glycol forms the polyetheramides imide of composition as polyether segment; segment with polyether glycol forms the polyether ester of composition as polyether segment; segment with polyether diamine forms the polyetheramides of composition as polyether segment; segment with polyether glycol or polyether diamine forms the hydrophilic resin that the poly(ether-urethene) of composition etc. contains polyethers as polyether segment; have 2～80 that separate with the nonionic molecular chain at intramolecularly; the cation property copolymer of preferred 3～60 cationic groups, and with dicarboxylic acid with alkylsulfonyl and glycol or polyethers as must structural unit and intramolecularly have 2～80; the anionic property polymkeric substance of preferred 3～60 alkylsulfonyls.
In addition, as the polymer static inhibitor, in order to be improved with the consistency of polyolefin resin, to give excellent antistatic effect, suppress simultaneously because of adding the effect that rerum natura that static inhibitor causes reduces, be preferably and make the static inhibitor that obtains with the high resin block copolymerization of kind or consistency with polyolefin resin, for example can enumerate, having polyolefinic block and volume specific resistance is 10 5～10 11It is 2000～60000 segmented copolymer that the block of the above-mentioned hydrophilic resin of Ω cm repeats the number-average molecular weight (Mn) of the structure of bonding alternately.Wherein, polyethers and polyolefinic segmented copolymer are preferred because above-mentioned consistency is also excellent.
And at least a kind of key that the block of said polyolefins and the block of hydrophilic resin have by being selected from ester bond, amido linkage, ehter bond, ammonia ester bond, the imide bond repeats the alternately structure of bonding.
In addition, as the polyolefinic block of the above-mentioned multipolymer that is preferably used as the polymer static inhibitor, be preferably at two ends of polymkeric substance the polyolefine that has the polyolefine of carboxyl, has carbonyl at an end of polymkeric substance.
More particularly, as above-mentioned polymer static inhibitor, can enumerate the composition of putting down in writing in Japanese kokai publication hei 3-103466 communique, the TOHKEMY 2001-278985 communique.The composition of Japanese kokai publication hei 3-103466 communique record with following (I)～(III) as main component: (I) thermoplastic resin, (II) polyethylene oxide or contain the segmented copolymer of the above poly-ethylene oxide block composition of 50 weight %, and (III) and the metal-salt of the poly-ethylene oxide block composition solid solution in above-mentioned (II).The composition of TOHKEMY 2001-278985 communique record is for block and the volume specific resistance with polyolefine (a) is 1 * 10 5～1 * 10 11It is 2000～60000 segmented copolymer that the block of the hydrophilic resin of Ω cm (b) repeats the number-average molecular weight (Mn) of the structure of bonding alternately.The block of above-mentioned (a) repeats to replace the structure that bonding forms with at least a kind of key that block (b) has by being selected from ester bond, amido linkage, ehter bond, ammonia ester bond, the imide bond.This polymer static inhibitor, for example commercially available with Mitsui デ ユ Port Application Port リ ケ ミ カ Le Co., Ltd.'s system " SD100 ", Sanyo Chemical Industries, Ltd.'s system trade(brand)names such as " ペ レ ス タ Star ト 300 ".
In the foam sheet of the present invention, can press polyolefin resin layer (below be also referred to as resin layer) on the upper strata of one side at least of above-mentioned foam sheet.By the laminating resin layer, the physical strength of foam sheet improves, and then if add above-mentioned polymer static inhibitor in resin layer, then compares with the situation of adding in foam sheet, even be more a spot of addition, also can make surface resistivity is 1 * 10 7～1 * 10 14(Ω).At this moment, even mismatch static inhibitor in the foam sheet, also obtain having the lamination foam sheet of excellent antistatic property.
But, when resin layer adds the polymer static inhibitor, different with the situation of in foam sheet, adding, the formation of the conductive network structure of the polymer static inhibitor that the stretching in the time of can not expecting by extrusion foaming realizes is strengthened, and therefore preferably contains the polymer static inhibitor of 10～50 weight %.If this addition is very few, then required antistatic property might can not be brought into play.On the other hand, even this addition is too much, though aspect antistatic property without any problem, because antistatic property reaches capacity the sexual valence ratio.Consider that from this angle static inhibitor is to the addition of resin layer more preferably 10～40 weight %, more preferably 15～35 weight %.
Constitute above-mentioned resin layer polyolefin resin, be engaged in wherein other resin or above-mentioned identical with for foam sheet such as additive, wherein, foam sheet there is no need identical with the structure of resin layer, as long as both can lamination, just can in said polyolefins resin category, adopt different structures.
The level ground amount of this resin layer for one side, is preferably 0.5g/m 2More than, 0.7g/m more preferably 2More than, 1g/m more preferably 2More than.If the level ground of this resin layer amount is about 0.5g/m 2More than, then can productivity form resin layer well.The upper limit to the level ground amount does not limit, but considers that from the angle of resiliency, light weight its upper limit is preferably 100g/m 2Below, 60g/m more preferably 2, 50g/m more preferably 2Below.When particularly resin layer forms by coextrusion, owing to can make the thin thickness of resin layer, so the level ground of resin layer amount is preferably 0.5～10g/m 2, 0.7～5g/m more preferably 2, 1～3g/m more preferably 2
In addition, the preferred homogeneous of the thickness of resin layer, but if in the scope of reaching purpose of the present invention, effect, even then exist uneven thickness a little also can.The level ground amount of the resin layer among the present invention can be tried to achieve by the following method.
In the method for this level ground flow measurement, the vertical cross-section of lamination foam sheet is suitably amplified with microscope etc., thickness for resin layer, on width, equally spaced measure 10 points, with the arithmetical av of the value that obtains mean thickness as resin layer, this mean thickness multiply by the density of the substrate resin that constitutes resin layer, carries out the level ground amount (g/m that unit conversion is tried to achieve resin layer 2).This method is limited to the clear and definite situation in interface of resin layer and foaming layer.
In the level ground flow measurement when interface of resin layer and foaming layer is indeterminate, make under the situation of lamination foam sheet by coextrusion or extruding layer compacting, when making the lamination foam sheet, can be by discharge-amount X[kg/ hour of the resin layer in the extrusion foaming condition], the length L [m/ hour] of the lamination foam sheet made of the width W [m] of the lamination foam sheet that obtains and unit time, try to achieve the level ground of resin layer with following formula (2) and measure [g/m 2].And, on the two sides of foam sheet, during the laminating resin layer, try to achieve the level ground amount of each resin layer by the discharge-amount of each resin layer.
Level ground amount [g/m 2]=[1000X/ (L * W)] (2)
And when by heat lamination film lamination being provided with resin layer, for the level ground amount of resin layer, the level ground of known film amount is equivalent to the level ground amount of resin layer before lamination.
Then, the manufacture method to polyolefine resin sparkling sheet material of the present invention describes.
Foam sheet of the present invention can be made by extrusion foaming.
For example, with polyolefin resin, additives such as polymer static inhibitor of Tian Jiaing and bubble conditioning agent supply in the forcing machine as required, heating and melting carries out mixing, be pressed into pneumatogen then, further carry out mixing formation foam sheet formation resin melt, in forcing machine, this resin melt is adjusted to the temperature that can foam, be expressed in the atmosphere by annular die, make this resin melt foaming form the tubular foam, the inner face of this tubular layer Hair Fixer foam is drawn simultaneously and cuts along cylindric refrigerating unit refrigerative, can obtain foam sheet thus.And the device of above-mentioned annular die, forcing machine, cylindric refrigerating unit, incision tubular foam etc. can use the well known device that all the time uses in the extrusion foaming field.
And, can also use a flat mouthful die head to substitute annular die and carry out extrusion foaming.
As above-mentioned pneumatogen, for example can enumerate aliphatic hydrocarbons such as propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, normal hexane, isohexane, alicyclic hydrocarbon such as pentamethylene, hexanaphthene, hydrochloric ether such as methyl chloride, monochloroethane, 1,1,1,2-Tetrafluoroethane, 1, organic class pneumatogens such as hydrofluoric ether such as 1-C2H4F2 C2H4F2, mineral-type pneumatogens such as oxygen, nitrogen, carbonic acid gas, air, water, can also and with decomposition-type foaming agents such as azodicarboamides.Above-mentioned pneumatogen can mix 2 kinds with on use.Wherein, particularly, be preferably organic class pneumatogen, wherein be preferably with normal butane, Trimethylmethane or their mixture whipping agent as main component from considering with the consistency of polyolefin resin, the angle of foaminess.
As main additive, add the bubble conditioning agent usually.As the bubble conditioning agent, can use in the bubble conditioning agent of bubble conditioning agent, mineral-type of organic class any one.As mineral-type bubble conditioning agent, can enumerate borate metal salts such as zinc borate, magnesium borate, borax, sodium-chlor, aluminium hydroxide, talcum, zeolite, silicon-dioxide, lime carbonate, sodium bicarbonate etc.In addition,, can enumerate 2,2-methylene-bis (4, the 6-tert-butyl-phenyl) sodium phosphate, Sodium Benzoate, calcium benzoate, aluminum benzoate, sodium stearate etc. as organic class bubble conditioning agent.In addition, combination such as an alkali metal salt of citric acid and sodium bicarbonate, citric acid and sodium bicarbonate etc. also can be used as the bubble conditioning agent.These bubble conditioning agents can mix 2 kinds with on use.
The addition of pneumatogen is regulated according to kind, the purpose apparent density of whipping agent.In addition, the addition of bubble conditioning agent is regulated according to the purpose bubble diameter.For example, for the butane mixture that uses Trimethylmethane 30 weight % and normal butane 70 weight % as whipping agent, obtain the foam sheet of above-mentioned density range, the addition of butane mixture is with respect to polyolefin resin 100 weight parts, is 0.3～7 weight part, is preferably 0.5～5 weight part, 1～4 weight part more preferably.In addition, the addition of bubble conditioning agent is with respect to polyolefin resin 100 weight parts, is 0.01～5 weight part, is preferably 0.03～3 weight part.
Above-mentioned foam sheet forms with in the resin melt, as mentioned above in the scope that does not hinder purpose of the present invention and effect, can add other resin such as styrene resin, elastomerics, or additive such as thermo-stabilizer.
Be controlled at 1～3 method as number of bubbles with the thickness direction of foam sheet, can enumerate the addition of regulating the bubble conditioning agent at least, the die lip that has parallel land (parallel ラ Application De) in the setting of annular die front end, when forming with the expansion (swell) of the thickness direction of resin melt, extrudes the inhibition foam sheet, bring out some shear heat evolution at parallel land when preventing the generation of ripple thus, realize the combination between the bubble, thus the method for the abscess number of control thickness direction.
When being laminated to resin layer on the foam sheet, can be by on the surface of the foam sheet of making in advance, utilizing heat lamination with the method for film lamination or utilize extruding layer to compress into the laminated method of row and make.In addition, can also make the lamination foam sheet by the coextrusion foaming.In these methods, make the lamination foam sheet because the lamination foam that the bonding force between resin layer and the foam sheet is strong when can obtain making the thin thickness of resin layer and preferred by the coextrusion foaming.
Make by the coextrusion foaming in the method for lamination foam sheet, have use coextrusion with flat mouthful of die head coextrusion be foamed into sheet carry out laminated method and use coextrusion with annular die with tubular layer Hair Fixer foam coextrusion foaming, cut the tubular foam sheet then and form the method etc. that the platy layer Hair Fixer steeps sheet material.Wherein, use coextrusion with the method for annular die owing to can suppress to be called as the generation of the wavy pattern of ripple, can easily make width is the above wide lamination foam of 1000mm, think preferable methods.
When using above-mentioned annular die to carry out coextrusion, use to connect foam sheet in coextrusion on mould and form the device that forms with forcing machine with forcing machine and resin layer formation.
At first, as mentioned above, form with base feed in the forcing machine, form foam sheet formation resin melt to foam sheet.Simultaneously, form the polymer static inhibitor of supplying with polyolefin resin and adding as required with in the forcing machine to resin layer, carry out heating and melting mixing after, add volatile plasticizer as required and carry out melting mixing, form resin layer formation resin melt.
And in the coextrusion method, if can in annular die foam sheet formation be formed with resin melt lamination interflow with resin melt and resin layer, the above-mentioned melts lamination that then also can will extrude outside the outlet of die head collaborates.And above-mentioned coextrusion can be used the well known device that all the time uses with annular die is first-class in the extrusion foaming field.
In the coextrusion method, preferably in forming with resin melt, resin layer adds volatile plasticizer.As volatile plasticizer, use to have when reducing resin layer and form function with the melt viscosity of resin melt after resin layer forms, volatilize and can not be present in volatile plasticizer the resin layer from this resin layer.In forming with resin melt, add volatile plasticizer to resin layer, during with the coextrusion of lamination foam, the extrusion temperature that resin layer is formed with resin melt forms with the extrusion temperature of resin with resin melt near foam sheet, can significantly improve the fusion elongation of the resin layer of molten state simultaneously.If so, then be difficult for destroying the bubble structure of foam sheet because of the heat of resin layer in when foaming, and then the elongation of the elongation of this resin layer when following the foaming of foam sheet, prevent that therefore the be full of cracks that causes because of the elongation of resin layer is insufficient from producing.
As volatile plasticizer, preferred use that to be selected from carbonatoms be that 2～7 aliphatic hydrocarbon or alicyclic hydrocarbon, carbonatoms are that 1～4 fatty alcohol or carbonatoms are the volatile plasticizer more than a kind or 2 kinds in 2～8 the fatty ether.Make when with lubricator waiting low material of volatility as softening agent, lubricant etc. remain in the resin layer, might pollute the surface of packaged body.Therewith relatively, volatile plasticizer is difficult for remaining in the resin layer that obtains the aspect from resin plasticized, the volatile plasticizer itself that makes resin layer effectively and considers preferred.
As above-mentioned carbonatoms is 2～7 aliphatic hydrocarbon or alicyclic hydrocarbon, for example can enumerate ethane, propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, neopentane, pentamethylene, normal hexane, isohexane, hexanaphthene, normal heptane etc.
As above-mentioned carbonatoms is 1～4 fatty alcohol, for example can enumerate methyl alcohol, ethanol, propyl alcohol, butanols, Virahol, isopropylcarbinol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol etc.
It as above-mentioned carbonatoms 2～8 fatty ether, for example can enumerate dimethyl ether, Anaesthetie Ether, propyl ether, isopropyl ether, methyl ethyl ether, methyl-propyl ether, methyl isopropyl ether, methyl butyl ether, methyl-isobutyl ether, methyl amylether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl-butyl ether, ethyl isobutyl ether, ethyl pentyl group ether, ethyl isoamyl ether, vinyl ether, allyl ethers, methylvinylether, methallyl ether, ethyl vinyl ether, ethyl allyl ether etc.
The boiling point of volatile plasticizer is preferably below 120 ℃, more preferably below 80 ℃ from easily considering from resin layer evaporable angle.If the boiling point of volatile plasticizer is in this scope, then after coextrusion, if place the lamination foam sheet that obtains, then by the heat after the firm coextrusion, and then by after at room temperature gas permeation, volatile plasticizer is waved naturally from resin layer and is loose and be removed naturally.The lower value of this boiling point is about-50 ℃.
The addition of volatile plasticizer is preferably 0.5 weight part～7 weight parts with respect to mixing resin 100 weight parts of polyolefin resin and the polymer static inhibitor that adds as required etc.If the addition of volatile plasticizer is more than about 0.5 weight part, then because the heat release that shearing caused (temperature decreasing effect) can fully suppress because of the polyolefin resin that constitutes resin layer etc. mixing the time, the rising that the foam sheet that becomes lamination and have the foam sheet of resin layer forms with the resin temperature of resin melt is inhibited.Therefore, when foam sheet formation is foamed with resin melt, prevent problems such as the broken bubble of bubble.Further, volatile plasticizer also has raising and follow the stretchiness (stretchiness improve effect) of resin layer formation with resin melt when foam sheet formation is foamed with resin melt, forms the effect of thin resin layer equably.Consider that from this angle the addition of volatile plasticizer is preferably more than 0.7 weight part, more preferably more than 1 weight part.
On the other hand, if the addition of volatile plasticizer is about below 7 weight parts, the rerum natura that then can not cause resin layer itself reduces, volatile plasticizer is impregnated into resin layer and forms with in the resin melt and by fully mixing, therefore volatile plasticizer can not spray from die lip, form concavo-convex being fully suppressed in resin layer perforate or surface, thereby form the lamination foam sheet of surface smoothing excellence.Consider that from this angle the addition of volatile plasticizer is preferably below 4 weight parts, more preferably below 3 weight parts, more preferably below 2.5 weight parts.Addition by making volatile plasticizer is in above-mentioned scope, and the resin layer in the time of can guaranteeing coextrusion forms and improves effect with the temperature decreasing effect and the stretchiness of resin melt.
In addition, resin layer forms with in the resin melt, can also add various additives in the scope of not damaging the object of the invention in the polyolefin resin that forms this melts.As various additives, for example can enumerate antioxidant, thermo-stabilizer, weather resisting agent, UV light absorber, fire retardant, weighting agent, antiseptic-germicide etc.The addition of this moment is preferably below 10 weight parts with respect to these resin 100 weight parts, more preferably below 5 weight parts, is preferably especially below 3 weight parts.Lower limit is about 0.01 weight part.But, when using foam sheet of the present invention as lining paper of glass substrate etc. etc., if contain low-molecular-weight organic matter matter such as anti-caking agent (Block ロ Star キ Application グ prevents drug) or surfactant type static inhibitor in the foam sheet, then on this low-molecular-weight organic matter matter surface attached to packed article, become the reason that packed article pollutes, therefore preferably reduce the addition of this material or do not add this material.
When making the lamination foam by coextrusion, as mentioned above, use foam sheet to form and form foam sheet formation resin melt with forcing machine, use resin layer to form and form resin layer formation resin melt with forcing machine, in foam sheet forms with forcing machine, foam sheet formation is adjusted to the temperature that can foam with resin melt, in resin layer forms with forcing machine, resin layer formation is adjusted to resin melt can the temperature of coextrusion after, foam sheet formation is imported in the coextrusion annular die with resin melt with resin melt and resin layer formation, make both lamination interflow, and then be coextruded in the atmosphere, foam sheet is formed to foam with resin melt, be formed on the tubular layer Hair Fixer foam that the foam sheet upper strata is pressed with resin layer, the inner face of this tubular layer Hair Fixer foam is accessed simultaneously and cuts along cylindric refrigerating unit refrigerative, can obtain the lamination foam sheet thus.
[embodiment]
Then, enumerate specific embodiment and comparative example the present invention is carried out more specific description.
Form with the polyolefin resin shown in the polyolefin resin use table 1 with polyolefin resin, resin layer as foam sheet formation.
Figure BSA00000171396600191
As the bubble conditioning agent, use the bubble conditioning agent masterbatch that cooperates the talcum (Ishihara Sangyo Kaisha, Ltd.'s system trade(brand)name " Ha イ Off イ ラ one #12 ") of 20 weight % to form with respect to ldpe resin 80 weight %.
As the polymer static inhibitor, use Sanyo Chemical Industries, Ltd.'s system with " ペ レ ス タ Star ト 300 " (fusing point 136 ℃, number-average molecular weight 14000, the density 990g/L) of polyethers-polypropylene block copolymer as main component.
As pneumatogen, use the mixed butanes that constitutes by normal butane 70 weight % and Trimethylmethane 30 weight %.
Embodiment 1,2, comparative example 1
As polyolefine resin sparkling sheet material formation extrusion device, use by screw diameter to first forcing machine of 90mm and screw diameter to the series connection forcing machine that second forcing machine of 120mm constitutes, use outlet that the device of die lip diameter as the annular die of 175mm is installed at second forcing machine.And, in embodiment 1,2, use at resin extruded leading section and have the annular die of length as the parallel land portion (part that the resin stream is identical at interval) of 2mm, in comparative example 1, the annular die in the past of using the resin stream do not have this parallel land portion, resin extruded leading section to narrow down gradually at interval.
With the whole drug マ ス タ one バ Star チ of the bubble conditioning agent masterbatch (Genki Pao Tone of the polyolefin resin of kind shown in the table 2, amount and the amount of Table 2) supply to the raw material input port of first forcing machine of series connection forcing machine, add hot milling, form and be adjusted to about 200 ℃ molten resin mixture.Then, in this molten resin mixture, be pressed into the pneumatogen of the amount of Table 2, then import in second forcing machine in the downstream side that is connected above-mentioned first forcing machine, temperature regulation is to the extrusion resin temperature shown in the table 2, form foam sheet formation resin melt, with the discharge-amount shown in the table 2 its foaming is extruded and made to this foam sheet formation with resin melt, form the tubular foam.For the tubular foam of extruding, be to cut in cylindric refrigerating unit (axle) traction time of 350mm along the refrigerative diameter, obtain foam sheet.By correcting in the process furnace, obtaining width is that 1000mm, length are the lithographic plate shape sample of 2000mm with the sheet material that obtains.At this moment, will in process furnace, keep the both ends of sheet material to cut about 50mm, form end article.
Figure BSA00000171396600211
Embodiment 3～7, comparative example 2～6
As polyolefine resin sparkling sheet material formation extrusion device, use the series connection forcing machine that constitutes as second forcing machine of 120mm as first forcing machine of 90mm and screw diameter by screw diameter, forcing machine is used in formation as polyolefin resin layer, uses three forcing machine of screw diameter as 50mm, L/D=50.Further, coextrusion exports with each of annular die and second forcing machine and the 3rd forcing machine and is connected, can be in annular die each molten resin of lamination.
The bubble conditioning agent masterbatch of the polyolefin resin of kind shown in the table 2, amount and the amount of Table 2 is supplied to the raw material input port of first forcing machine of series connection forcing machine, add hot milling, form and be adjusted to about 200 ℃ molten resin mixture.Then, in this molten resin mixture, be pressed into the pneumatogen of the amount of Table 2, then supply company is connected in second forcing machine in downstream side of above-mentioned first forcing machine, temperature regulation is to the extrusion resin temperature shown in the table 2, form foam sheet formation resin melt, with the discharge-amount shown in the table 2 this foam sheet is formed with resin melt and import to coextrusion with in the annular die.
Simultaneously, the polymer static inhibitor of kind shown in the polyolefin resin of kind shown in the table 2, amount and the table 2, amount is supplied in the 3rd forcing machine, add hot milling, and then carry out mixing, be adjusted to the extrusion resin temperature shown in the table 2, form resin layer formation resin melt, with the discharge-amount shown in the table 2 this resin layer is formed with resin melt and import to coextrusion with in the annular die.And, in embodiment 3～7, use at resin extruded leading section and have the coextrusion annular die of length as the parallel land portion (part that the resin stream is identical at interval) of 2mm, in comparative example 2～6, the coextrusion annular die in the past of using the resin stream do not have this parallel land portion, resin extruded leading section to narrow down gradually at interval.
Form the outside and the la m pressing stream resin layer formation resin melt of using resin melt with mobile foam sheet in the annular die in coextrusion, to atmosphere, extrude the lamination melts from die head, form the tubular layer Hair Fixer foam of the three-decker that constitutes by resin layer/foam/resin layer.Is to cut in cylindric refrigerating unit (axle) traction time of 350mm for the tubular layer Hair Fixer foam of extruding along the refrigerative diameter, obtains the lamination foam sheet.After the sheet material that obtains added hot straightening similarly to Example 1, the formation width was that 1000mm, length are the lithographic plate shape sample of 2000mm.
Each rerum natura of the lamination foam sheet that obtains in embodiment, the comparative example is as shown in table 3.
Figure BSA00000171396600231
Measuring method that the cantilever of table 3 is sagging and metewand
＜measuring method 〉
As the longitudinal direction test sample, make the sheet material that obtains to extrude direction consistent with the length direction of test film, foam sheet that obtains from embodiment, comparative example or lamination foam sheet cut out the test film of 5 wide 25mm * long 150mm.Similarly, make the width of the sheet material that obtains and the length direction of test film as one man cut out 5 test films.
As shown in Figure 3, the test film that cuts out under the state of the outstanding about 100mm of substrate (earthen platform), is stated from the substrate, the mounting weight is fixed thereon.
The front end of determination test sheet and the distance of substrate.(when not sagging, measured value is 100mm, and the low more expression of measured value is sagging big more)
With the determination data arithmetical mean, as sag of chain.
Metewand
At first measure sag of chain by aforesaid method.Then, and then owing to consider the thickness factor, the method conversion sag of chain by following uses this result to estimate.
(1) measured value is under the situation of 100mm when not sagging fully (), directly adopts data, as the conversion sag of chain.
(2) measured value is under the following situation of 99mm, removes measured value with thickness, should be worth as the conversion sag of chain.(wherein, when the conversion sag of chain surpassed 100mm, the conversion sag of chain was 100mm.)
With following metewand the conversion sag of chain that obtains by aforesaid method is estimated.
◎ conversion sag of chain 95～100mm
More than the zero conversion sag of chain 86mm and less than 95mm
* conversion sag of chain is less than 86mm
The heavy ね of the plyability (Plot body of table 3) measuring method and judgement criteria
Evaluation method
To foam sheet or the lamination foam sheet that obtains in embodiment and the comparative example, fixed from the end to the end portion thickness with 10mm spacing used thickness instrumentation, confirm that the maximum of measured value and minimum difference are in the 0.2mm.Then, be basic point with 25%, 50%, 75% position from the sheet material end to total width, cut out the test film (the foam sheet width amounts to 100mm) of 10 wide 10mm * long 25mm successively.The foam sheet that obtains in this example since for 1000mm wide, with from the end to 250mm, the position of 500mm, 750mm is basic point, amounts to the test film that 100mm cuts out 10 wide 10mm * long 25mm successively continuously at the width of foam sheet.By this operation, with from the end to 250mm, 500mm, 750mm everybody be changed to basic point, respectively cut out the sample of 10 (amounting to 30).Then, repeat 10 times identical operations, cut out and amount to 300 samples.Make the position that cuts out of width coincide and make the sample that cuts out form each 10 eclipsed bundle (bundle), with 10 eclipsed Shu Zuowei working samples of 30.Then, each overlapping height of 30 working sample is measured.The overlapping height arithmetical mean that obtains is obtained mean value.Then, try to achieve the standard deviation of the overlapping height of 30 working samples by calculating.According to following benchmark the standard deviation value that obtains is estimated.
Metewand
◎: below 0.15
Zero: above 0.15 and less than 0.2
△: more than 0.2 and less than 0.25
*: more than 025

Claims (6)

1. polyolefine resin sparkling sheet material, it is that apparent density is that 60～350g/L, thickness are that 0.2～1.5mm, level ground amount are 50～200g/m 2Polyolefine resin sparkling sheet material, it is characterized in that the bending elastic modulus that constitutes the substrate resin of this foam sheet is more than the 300MPa, the number of bubbles of the thickness direction of this foam sheet is 1～3 simultaneously.
2. polyolefine resin sparkling sheet material as claimed in claim 1 is characterized in that, in the substrate resin that constitutes described foam sheet, cooperates the polymer static inhibitor of 2～20 weight %.
3. polyolefine resin sparkling sheet material as claimed in claim 1 is characterized in that, presses polyolefin resin layer on the upper strata of one side at least of described foam sheet, cooperates the polymer static inhibitor of 5～55 weight % in the substrate resin that constitutes this resin layer.
4. as any described polyolefine resin sparkling sheet material in the claim 1～3, wherein, the substrate resin that constitutes described foam sheet is that the fusion tension force under 190 ℃ is the acrylic resin of 15～400mN.
5. as any described polyolefine resin sparkling sheet material in the claim 1～3, wherein, the substrate resin that constitutes described foam sheet is that the fusion tension force under 190 ℃ is that 15～400mN, density are the polyvinyl resin of 930～970g/L.
6. as any described polyolefine resin sparkling sheet material in the claim 1～3, wherein, the substrate resin that constitutes described foam sheet be density to be following polyvinyl resin L 15～70 weight % of 930g/L surpass 930g/L and be the polyethylene resin composition of the polyvinyl resin H85～30 weight % below the 970g/L with density, polyvinyl resin L and polyvinyl resin H add up to 100 weight %.
CN201010214230XA 2009-06-25 2010-06-25 Polyolefine resin sparkling sheet material Pending CN101935416A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009150766A JP5557309B2 (en) 2009-06-25 2009-06-25 Polyolefin resin foam sheet
JP2009-150766 2009-06-25

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN201310481871.5A Division CN103642107A (en) 2009-06-25 2010-06-25 Foamed polyolefin resin sheet

Publications (1)

Publication Number Publication Date
CN101935416A true CN101935416A (en) 2011-01-05

Family

ID=43389002

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201310481871.5A Pending CN103642107A (en) 2009-06-25 2010-06-25 Foamed polyolefin resin sheet
CN201010214230XA Pending CN101935416A (en) 2009-06-25 2010-06-25 Polyolefine resin sparkling sheet material

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201310481871.5A Pending CN103642107A (en) 2009-06-25 2010-06-25 Foamed polyolefin resin sheet

Country Status (3)

Country Link
JP (1) JP5557309B2 (en)
KR (1) KR101564116B1 (en)
CN (2) CN103642107A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103338912A (en) * 2011-02-03 2013-10-02 株式会社Jsp Polyolefin resin laminated foam sheet
CN103570966A (en) * 2012-08-03 2014-02-12 株式会社Jsp Process for producing polyethylene resin foam sheet
CN104520366A (en) * 2012-08-23 2015-04-15 株式会社Jsp Polyethylene resin extrusion-foamed sheet, and interleaving paper for glass plates
CN105492515A (en) * 2013-08-26 2016-04-13 日东电工株式会社 Foam sheet
CN105492559A (en) * 2014-03-28 2016-04-13 积水化学工业株式会社 Adhesive tape and method for producing adhesive tape
CN109016758A (en) * 2014-03-05 2018-12-18 株式会社Jsp Multi-layer foam sheet and interlayer liner for glass plate
CN109044845A (en) * 2018-09-29 2018-12-21 河北盛世天昕电子科技有限公司 One kind is made up a prescription surplus alarm method and device
CN112074403A (en) * 2018-03-29 2020-12-11 积水化学工业株式会社 Foamed composite sheet, adhesive tape, cushioning material for electronic component, and adhesive tape for electronic component

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011000399A1 (en) * 2011-01-28 2012-08-02 Benecke-Kaliko Ag Process for producing a multilayer plastic film
JP5694832B2 (en) * 2011-04-07 2015-04-01 株式会社ジェイエスピー Foam sheet for packaging
JP6266901B2 (en) * 2013-06-07 2018-01-24 株式会社ジェイエスピー Polyethylene resin multilayer foam sheet
JP6429322B2 (en) * 2014-03-05 2018-11-28 株式会社ジェイエスピー Glass board slip
JP6302731B2 (en) * 2014-03-31 2018-03-28 株式会社ジェイエスピー Polyethylene resin foam sheet
CN105328958B (en) * 2014-08-15 2017-12-12 湖北航天化学技术研究所 Diaphragm High-transparent polyethylene film
JP6901894B2 (en) * 2017-03-31 2021-07-14 日本発條株式会社 Urethane synthetic leather, urethane synthetic leather manufacturing method, cosmetic puffs, and members with synthetic leather

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001219457A (en) * 2000-02-09 2001-08-14 Jsp Corp Polypropylene resin foamed sheet
JP2001226509A (en) * 2000-02-17 2001-08-21 Jsp Corp Polypropylene resin foamed sheet for thermoforming and laminated polypropylene resin foamed sheet for thermoforming
JP2001287262A (en) * 2000-04-07 2001-10-16 Jsp Corp Non-crosslinked polypropylene resin foamed sheet for molding and non-crosslinked polypropylene resin multilayered foamed sheet for molding
JP2001310429A (en) * 2000-04-26 2001-11-06 Jsp Corp Polypropylene resin foamed sheet laminate
JP2004043813A (en) * 2002-07-09 2004-02-12 Jsp Corp Polyethylene-based resin extruded and foamed sheet, shaped product of the foamed sheet, assembled box, lining sheet for concrete formwork, and manufacturing method of the formed sheet
CN1670069A (en) * 2004-01-08 2005-09-21 株式会社Jsp Polyolefin resin foam and manufacturing method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2898460B2 (en) * 1992-02-24 1999-06-02 株式会社ジェイエスピー Propylene resin foam sheet for molding
JP4157310B2 (en) * 2002-03-04 2008-10-01 電気化学工業株式会社 Antistatic polypropylene-based resin laminated foam sheet and molded article for packaging
JP5075046B2 (en) * 2002-10-08 2012-11-14 株式会社ジェイエスピー Foam sheet
JP2008056863A (en) * 2006-09-01 2008-03-13 Kaneka Corp Polypropylene-based resin foamed sheet and molded article obtained by thermally molding the foamed sheet
JP4195719B2 (en) * 2007-04-02 2008-12-10 株式会社ジェイエスピー Interleaving paper for glass substrate
JP4901589B2 (en) * 2007-06-07 2012-03-21 株式会社ジェイエスピー POLYOLEFIN RESIN EXTRUSION FOAM SHEET, GLASS SUBSTRATE COMPOSITION COMPRISING THE FOAM SHEET AND PACKAGING MATERIAL

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001219457A (en) * 2000-02-09 2001-08-14 Jsp Corp Polypropylene resin foamed sheet
JP2001226509A (en) * 2000-02-17 2001-08-21 Jsp Corp Polypropylene resin foamed sheet for thermoforming and laminated polypropylene resin foamed sheet for thermoforming
JP2001287262A (en) * 2000-04-07 2001-10-16 Jsp Corp Non-crosslinked polypropylene resin foamed sheet for molding and non-crosslinked polypropylene resin multilayered foamed sheet for molding
JP2001310429A (en) * 2000-04-26 2001-11-06 Jsp Corp Polypropylene resin foamed sheet laminate
JP2004043813A (en) * 2002-07-09 2004-02-12 Jsp Corp Polyethylene-based resin extruded and foamed sheet, shaped product of the foamed sheet, assembled box, lining sheet for concrete formwork, and manufacturing method of the formed sheet
CN1670069A (en) * 2004-01-08 2005-09-21 株式会社Jsp Polyolefin resin foam and manufacturing method thereof

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103338912B (en) * 2011-02-03 2015-03-25 株式会社Jsp Polyolefin resin laminated foam sheet
CN103338912A (en) * 2011-02-03 2013-10-02 株式会社Jsp Polyolefin resin laminated foam sheet
CN103570966A (en) * 2012-08-03 2014-02-12 株式会社Jsp Process for producing polyethylene resin foam sheet
CN103570966B (en) * 2012-08-03 2018-09-18 株式会社Jsp The manufacturing method of polyethylene-based resin foamed sheet material
US9631060B2 (en) 2012-08-23 2017-04-25 Jsp Corporation Extruded polyethylene-based resin foam sheet and interleaf sheet for glass plates
CN104520366A (en) * 2012-08-23 2015-04-15 株式会社Jsp Polyethylene resin extrusion-foamed sheet, and interleaving paper for glass plates
CN104520366B (en) * 2012-08-23 2016-04-20 株式会社Jsp The polyvinyl resin foam sheet extruded and the interlayer liner for sheet glass
CN105492515A (en) * 2013-08-26 2016-04-13 日东电工株式会社 Foam sheet
US10105929B2 (en) 2013-08-26 2018-10-23 Nitto Denko Corporation Foamed sheet
CN105492515B (en) * 2013-08-26 2018-12-25 日东电工株式会社 Foamed sheet
CN109016758A (en) * 2014-03-05 2018-12-18 株式会社Jsp Multi-layer foam sheet and interlayer liner for glass plate
CN109016758B (en) * 2014-03-05 2020-11-20 株式会社Jsp Multilayer foam sheet and interlayer gasket for glass panels
CN105492559A (en) * 2014-03-28 2016-04-13 积水化学工业株式会社 Adhesive tape and method for producing adhesive tape
CN105492559B (en) * 2014-03-28 2019-11-22 积水化学工业株式会社 The manufacturing method of splicing tape and splicing tape
CN112074403A (en) * 2018-03-29 2020-12-11 积水化学工业株式会社 Foamed composite sheet, adhesive tape, cushioning material for electronic component, and adhesive tape for electronic component
CN112074403B (en) * 2018-03-29 2022-11-04 积水化学工业株式会社 Foamed composite sheet, adhesive tape, cushioning material for electronic component, and adhesive tape for electronic component
CN109044845A (en) * 2018-09-29 2018-12-21 河北盛世天昕电子科技有限公司 One kind is made up a prescription surplus alarm method and device

Also Published As

Publication number Publication date
CN103642107A (en) 2014-03-19
KR101564116B1 (en) 2015-10-28
KR20100138814A (en) 2010-12-31
JP2011006567A (en) 2011-01-13
JP5557309B2 (en) 2014-07-23

Similar Documents

Publication Publication Date Title
CN101935416A (en) Polyolefine resin sparkling sheet material
CN101280067B (en) Spacing sheet for glass substrate
CN100513468C (en) Polyolefin resin foam and manufacturing method thereof
EP0520028B1 (en) Polypropylene foam sheets
JP5425318B2 (en) Polyolefin resin laminated foam sheet
CN101844430B (en) Laminated polyethylene resin foaming sheet
CN1986618B (en) Polystyrene resin laminated foam
US20100112335A1 (en) Laminated film or sheet having a foamed resin layer and process for producing the same
JP5877633B2 (en) Glass board slip
JP2014055248A (en) Method of manufacturing polyethylene-based resin foamed sheet
CN101909887A (en) Surface protection film
CN102470652B (en) Surface protection film
JP5075046B2 (en) Foam sheet
CA2585376A1 (en) Elastomeric compositions with improved resistance to necking for high speed sheet extrusion applications
JP4493000B2 (en) Polyolefin resin foam sheet
CN101384628A (en) Ethylene polymer and products of molding thereof
JP3351967B2 (en) Non-crosslinked polypropylene resin foam sheet for thermoforming
EP3075779A1 (en) Polyethylene-based resin foam sheet
JP2016068963A (en) Tabular partition member
US6548628B2 (en) Process for producing a film or layer
US20200269542A1 (en) Laminated foam sheet
JP5567852B2 (en) Interleaving paper for glass substrate
JPH115860A (en) Non-crosslinked polypropylene resin foam sheet
JP6430701B2 (en) Paper
JP2004291626A (en) Propylene-based resin made multi-layered foamed sheet and returnable box

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20110105