CN101844430A - Laminated polyethylene resin foaming sheet - Google Patents

Laminated polyethylene resin foaming sheet Download PDF

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Publication number
CN101844430A
CN101844430A CN201010149533A CN201010149533A CN101844430A CN 101844430 A CN101844430 A CN 101844430A CN 201010149533 A CN201010149533 A CN 201010149533A CN 201010149533 A CN201010149533 A CN 201010149533A CN 101844430 A CN101844430 A CN 101844430A
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foaming sheet
resin
weight
sheet
lamination
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Granted
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CN201010149533A
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CN101844430B (en
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森田和彦
后藤兼一
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JSP Corp
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JSP Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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

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  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

Problem of the present invention is to provide laminated polyethylene resin foaming sheet, adhering to mutually or adhering on packed articles such as glass substrate of its sheet that can prevent to foam, bale packing operation with excellent packed article, and can prevent to peel off static, and prevent that dust or dust from adhering on packed article.Laminated polyethylene resin foaming sheet of the present invention is that to close that the polyvinyl resin layer that contains the polymer electrolyte antistatic additive forms, thickness in the upper strata crimping of one side at least of polyethylene resin foaming sheet be that 0.2～2.0mm, apparent density are 0.02～0.1g/cm 3Laminate, it is characterized in that, this laminate satisfy specified conditions (i), (ii) and (iii) at least any one.

Description

Laminated polyethylene resin foaming sheet
Technical field
The present invention relates to laminated polyethylene resin foaming sheet.
Background technology
In recent years, for damage, the wound of the glass substrate for display that prevents from slim TV, to use, use to be rich in the polyvinyl resin extrusion foaming sheet of flexibility and resiliency as its packaging material.For this glass substrate for display, require it to have very high-caliber cleaning surfaces, therefore use and contain the polyvinyl resin extrusion foaming sheet of polymer electrolyte antistatic additive as packaging material.This foaming sheet for example has the glass substrate lining paper of record in the patent documentation 1.
But, for the glass substrate of patent documentation 1 record with headed by the lining paper, the padded coaming that uses at present, the foaming sheet of packaging material as the precise electronic instrument, in whole foaming sheet, all contain expensive polymer electrolyte antistatic additive.Carried out research to a certain degree showing antistatic behaviour by enough a spot of additions for this foaming sheet, the high shortcoming of cost has been carried out room for improvement but still leave.
The inventor has developed a kind of polyethylene resin foaming sheet in order to address this problem, and the polyvinyl resin layer that it does not foam in the surface laminated of foaming sheet only adds the polymer electrolyte antistatic additive in this resin bed.But,, the problem of the difference of sliding is arranged though this lamination foaming sheet can be brought into play good antistatic behaviour.Specifically, when the lamella that should foam is compressed into the row preservation, the foaming sheet forms the state that adheres to mutually and be difficult to peel off, perhaps form on the packed articles such as being easy to be attached to glass substrate and the state that is difficult to peel off, in addition, when carrying out covering the operation of packed article, because the foaming sheet is difficult to slide with this foaming sheet, thereby on the foaming sheet, produce pleat, the situation that makes operation decline is arranged.And then, when packed article is the article of the such taboo static of glass substrate, also have at the sheet that will foam when glass substrate is peeled off, to produce the problem of peeling off static.In addition, when the sheet that should foam is used as packaging material, though the resiliency excellence, existing problems aspect the sense of vision of packed article.
[background technology document]
[patent documentation]
Patent documentation 1 TOHKEMY 2005-194433
Summary of the invention
Problem of the present invention is, in view of above-mentioned existing problem, laminated polyethylene resin foaming sheet is provided, it can prevent to foam and adhere to mutually between the sheet or attached on the packed articles such as glass substrate, the bale packing operation excellence of packed article, and can prevent to peel off static, and prevent that dust or dust are attached on the packed article.
The invention provides laminated polyethylene resin foaming sheet shown below.
[1] laminated polyethylene resin foaming sheet, it is that to close that polyvinyl resin layer that (Plot Layer then) contain the polymer electrolyte antistatic additive forms, thickness in the upper strata crimping of one side at least of polyethylene resin foaming sheet be that 0.2～2.0mm, apparent density are 0.02～0.1g/cm 3Laminate, it is characterized in that, this laminate satisfy following condition (i), (ii) and (iii) at least any one,
(i) weight per unit area of polyvinyl resin layer (level ground amount) is 8g/m 2Below, the bubble thickness of foaming sheet is 6～100 μ m, and the average bubble number of thickness direction is below 2;
(ii) the polyvinyl resin layer by the fusing point of 30～90 weight % greater than 115 ℃ and below 128 ℃ and density be 0.910～0.970g/cm 3The fusing point of polyvinyl resin (a), 0～60 weight % be below 115 ℃ and density is 0.890～0.930g/cm 3Polyvinyl resin (b) and the polymer electrolyte antistatic additive (c) (wherein, (a)+(b)+(c)=100 weight %) of 10～50 weight % constitute;
(iii) polyethylene resin foaming sheet by the fusing point of 10～50 weight % greater than 115 ℃ and be below 125 ℃ and density is 0.910～0.940g/cm 3The fusing point of polyvinyl resin (d), 50～90 weight % be below 115 ℃ and density is 0.890～0.930g/cm 3Polyvinyl resin (b) (wherein, (d)+(b)=100 weight %) constitute.
[2] according to above-mentioned 1 described laminated polyethylene resin foaming sheet, it is characterized in that, satisfy above-mentioned condition (i) simultaneously and be selected from above-mentioned condition (ii) with at least 1 condition of above-mentioned condition in (iii).
According to above-mentioned 1 or 2 described laminated polyethylene resin foaming sheets, it is characterized in that [3] the applied voltage half-life after the washing of above-mentioned lamination foaming sheet is below 10 seconds.
Laminated polyethylene resin foaming sheet of the present invention (below; be also referred to as lamination foaming sheet or laminate) have a surface protection of excellent packed article; simultaneously because the polyvinyl resin layer contains the polymer electrolyte antistatic additive; therefore have the excellent characteristic that dust or dust adhere to that prevents, be preferably used as the packaging material of precise electronic instrument such as glass substrate for display.
Further, though the polyvinyl resin layer contains the polymer electrolyte antistatic additive, but in polyethylene resin foaming sheet, do not need in fact to contain the polymer electrolyte antistatic additive, so the content of the polymer electrolyte antistatic additive of lamination foaming sheet integral body is few, thereby can makes at an easy rate.
And, lamination of the present invention foaming sheet by satisfy above-mentioned condition (i), (ii), in (iii) at least any one, between the lamination foaming sheet or lamination foaming sheet and packaged body be difficult to adhere to excellent in sliding property, therefore be difficult to produce peel off static, bale packing operating efficiency excellence.
In addition, lamination foaming sheet of the present invention is by satisfying above-mentioned condition (i), and the sense of vision that can have packed article when the packing packed article concurrently improves effect.
Description of drawings
[Fig. 1] Fig. 1 represents that an example in high temperature side and the zone 110 ℃ or more higher than main melting peak summit temperature, the accompanying drawing of the DSC curve of protuberance (shoulder) occurs.
[Fig. 2] Fig. 2 represents that an example in high temperature side and the zone 110 ℃ or more higher than main melting peak summit temperature, the accompanying drawing of the DSC curve of other melting peaks occurs.
[Fig. 3] Fig. 3 (a) is that the lamination of embodiment 1 gained foams sheet at the sectional drawing of extruding direction (MD), and Fig. 3 (b) is the sectional drawing of same lamination foaming sheet at width (TD).
[Fig. 4] Fig. 4 (a) is the sectional drawing of MD of the lamination foaming sheet of embodiment 8 gained, and Fig. 4 (b) is the sectional drawing of the TD of same lamination foaming sheet.
[Fig. 5] Fig. 5 (a) is the sectional drawing of MD of the lamination foaming sheet of comparative example 1 gained, and Fig. 5 (b) is the sectional drawing of the TD of same lamination foaming sheet.
[Fig. 6] is the key diagram of one of the manufacture method of presentation layer Hair Fixer bubble sheet example.
The specific embodiment
Below laminated polyethylene resin foaming sheet of the present invention is elaborated.
Lamination of the present invention foaming sheet is to close the laminate that the polyvinyl resin layer (the following resin bed that also abbreviates as) that contains the polymer electrolyte antistatic additive forms in the upper strata crimping of one side at least of polyethylene resin foaming sheet (the following foaming sheet that also abbreviates as).
Lamination foaming sheet of the present invention has excellent antistatic behaviour, sliding, fissility etc., therefore be suitable as the packaging material of the glass substrate for display that in slim TV, uses, in addition, can also be suitable as the packaging material of precise electronic instruments such as electronic product, precision instrument, channel base, silicon wafer.
Constituting the foaming sheet of lamination foaming sheet of the present invention and the resin bed that lamination is bonded on this foaming sheet all is with the principal component of polyvinyl resin as substrate resin.This polyvinyl resin is that case hardness is low, flexibility is excellent, is suitable for the thermoplastic resin of the surface protection of packaged body.And, in this specification so-called with polyvinyl resin as the principal component of substrate resin be meant in substrate resin, contain more than the 50 weight %, more than the preferred 70 weight %, the more preferably polyvinyl resin more than the 80 weight %.
Polyvinyl resin in this specification comprises vinyl copolymer that Alathon such as a chain low density polyethylene (LDPE), straight chain shape low density polyethylene (LDPE), straight chain shape ultra-low density polyethylene, straight chain shape high density polyethylene (HDPE), long-chain side chain high density polyethylene (HDPE) or ethene and carbon number are 3～10 alpha-olefin and the mixture more than 2 kinds in these polymer etc.
And the formation of the polyvinyl resin that uses in foaming sheet and resin bed must not be identical, as described below, in order to bring into play both characteristics separately, can adopt different formations.
The fusing point of the polyvinyl resin in this specification can be according to measuring based on the method for JIS K7121-1987.That is, carry out pre-treatment according to the condition (wherein, cooling velocity is 10 ℃/minute) of the status adjustment (2) of coupons among the JIS K7121-1987, heating up with 10 ℃/minute speed obtains melting peak.With the temperature on the summit of gained melting peak as fusing point.When 2 above melting peaks occurring, with the summit temperature of main melting peak (peak of area maximum) as fusing point.But when existing peak area to be the peak more than 80% of peak area at maximum area peak in addition, the arithmetic mean of instantaneous value of summit temperature at peak that adopts the summit temperature at this peak and maximum area is as fusing point.
In the substrate resin that constitutes foaming sheet of the present invention and resin bed, except the principal component polyvinyl resin, in the scope that does not hinder the object of the invention and effect, can also cooperate elastomers such as phenylethylene resin series such as propylene resins such as vinyl-vinyl acetate copolymer, polypropylene, propylene-ethylene copolymers, polystyrene, ethylene propylene rubber etc.And the content of above-mentioned resin is below the 50 weight % in substrate resin, is preferably below the 30 weight %, more preferably below the 20 weight %.
In addition, in the scope that does not hinder the object of the invention and effect, in above-mentioned substrate resin, can contain for example bubble conditioning agent, nucleator, antioxidant, heat stabilizer, weather resisting agent, ultra-violet absorber, fire retardant, antiseptic, contraction and prevent additives such as functional additive, inorganic filler such as agent.
The resin bed that constitutes lamination of the present invention foaming sheet contains polyvinyl resin and polymer electrolyte antistatic additive simultaneously, its antistatic property, prevents the excellent performance that antistatic additive shifts to packaged body.
The number-average molecular weight of this antistatic additive is more than 2000, and is preferred 2000～100000, more preferably 5000～60000, preferred especially 8000～40000.Therefore, this antistatic additive is and other polymer electrolyte antistatic additive of antistatic additive phase region that with the surfactant is principal component.
Above-mentioned number-average molecular weight uses the high-temperature gel permeation chromatography method to try to achieve.For example when the polymer electrolyte antistatic additive be when being the hydrophilic resin of principal component with polyether ester amides or polyethers, its number-average molecular weight is the value of following mensuration, promptly, make the sample solution concentration of 3mg/ml as solvent with o-dichlorohenzene, and with polystyrene as standard substance, be to measure under 135 ℃ the condition at column temperature.Above-mentioned solvent types, column temperature can be according to the kinds of polymer electrolyte antistatic additive and appropriate change.
It is 10 that the polymer electrolyte antistatic additive that uses among the present invention can be enumerated specific volume resistance 5～10 11The hydrophilic resin of Ω cm and polyolefinic copolymer etc.
This hydrophilic resin can use PTMEG; polyether diamine; with their polyethers such as modifier; segment with PTMEG forms the polyether ester amides of composition as polyether segment; segment with PTMEG forms the polyetheramides acid imide of composition as polyether segment; segment with PTMEG forms the polyether ester of composition as polyether segment; segment with polyether diamine forms the polyetheramides of composition as polyether segment; segment with PTMEG or polyether diamine forms the hydrophilic resin that the polyethers carbamate (polyether urethane) of composition etc. contains polyethers as polyether segment; in molecule, have 2～80 that separate with the nonionic strand; the cation property copolymer of preferred 3～60 cationic groups and with dicarboxylic acids with sulfonyl and glycol or polyethers as must construction unit; and have 2～80 in the molecule; the anionic property polymer of preferred 3～60 sulfonyl.
In addition, for the compatibility that makes polymer electrolyte antistatic additive and polyvinyl resin improve, when giving excellent antistatic effect, can also be inhibited because of adding the effect that rerum natura that antistatic additive causes descends, preferably resin of the same race with polyvinyl resin or that compatibility is high is carried out the resin that block copolymerization forms, can enumerate the number-average molecular weight (Mn) that for example has following structure and be 2000～60000 block copolymer, described structure is that polyolefinic block and specific volume resistance are 10 5～10 11The block of the above-mentioned hydrophilic resin of Ω cm replaces the structure that bonding forms repeatedly.Wherein, therefore the above-mentioned compatibility excellence of polyethers and polyolefinic block copolymer is preferred.
The block that above-mentioned block copolymer has polyolefinic block and hydrophilic resin replaces the structure that bonding forms repeatedly by at least a kind of key that is selected from ester bond, amido link, ehter bond, amino-formate bond, the imide bond.
In more detail, the preferred above-mentioned polymer electrolyte antistatic additive that uses can be set forth in the composition of putting down in writing in Japanese kokai publication hei 3-103466 communique, the TOHKEMY 2001-278985 communique among the present invention.The composition of Japanese kokai publication hei 3-103466 communique record be with (I) thermoplastic resin, (II) PEO or contain the block copolymer of the above poly-ethylene oxide block composition of 50 weight % and (III) and the slaine of the poly-ethylene oxide block composition solid solution in above-mentioned (II) be the composition of principal component.The composition of TOHKEMY 2001-278985 communique record is that number-average molecular weight (Mn) with following structure is 2000～60000 block copolymer, and described structure is that the block and the specific volume resistance of polyolefin (a) is 1 * 10 5～1 * 10 11The block of the hydrophilic resin of Ω cm (b) replaces the structure that bonding forms repeatedly.At least a kind of key that the block of above-mentioned (a) and block (b) have by being selected from ester bond, amido link, ehter bond, amino-formate bond, the imide bond replaces the structure that bonding forms repeatedly.The object lesson of this polymer electrolyte antistatic additive can be enumerated for example with Mitsui デ ユ Port Application Port リ ケ ミ カ Le Co., Ltd.'s system " SD100 ", Sanyo Chemical Industries, Ltd.'s system commercially available materials of trade name such as " ペ レ ス タ Star ト 300 ".
Above-mentioned polymer electrolyte antistatic additive can be distinguished use separately, also can multiplely be used in combination.
In addition, the fusing point of polymer electrolyte antistatic additive is preferably 70～270 ℃, and more preferably 80～230 ℃, preferred especially 80～200 ℃, this angle from the performance anti-static function considers it is preferred.
The fusing point of above-mentioned polymer electrolyte antistatic additive is a value same with the fusing point test method of above-mentioned polyvinyl resin, that measure based on JIS K7121-1987.
The content of the polymer electrolyte antistatic additive in the resin bed of the present invention is 10～50 weight % of whole resin bed preferably, more preferably 15～40 weight %, preferred especially 20～35 weight %.If this content is too few, then might be able to not bring into play as the desired antistatic property of the packaging material of precise electronic instrument.On the other hand, even this content is too many, though antistatic property without any problem, antistatic property culminates, and forms this aspect variation.
In foaming sheet of the present invention, must not add above-mentioned polymer electrolyte antistatic additive, but when causing added polymer electrolyte antistatic additive as the foaming sheet with raw material because of the recovery raw material that uses lamination foaming sheet, the sheet that foams has contained the polymer electrolyte antistatic additive.In this case, in order not hinder the foaminess of foaming sheet, the content of polymer electrolyte antistatic additive is ratio below 15 weight portions with respect to substrate resin 100 weight portions that constitute the foaming sheet preferably.Further, for the mechanical strength of sustaining layer Hair Fixer bubble sheet, this content is below 8 weight portions with respect to substrate resin 100 weight portions that constitute the foaming sheet preferably, more preferably below 5 weight portions.By in the foaming sheet, adding antistatic additive, can also expect the further raising of antistatic effect.
The thickness of lamination foaming sheet of the present invention is 0.2～2.0mm.If this thickness is too thin; then resiliency, the surface protection for packed articles such as precise electronic instruments becomes insufficient; if thickness is too thick; then when the packing of packed article or lamination foaming sheet when discarded, there is the cost of transportation of long-pending big problem of lamination foaming sheet or packing material uneconomical.Consider that from this angle the thickness of lamination foaming sheet is 0.3～1.5mm more preferably, preferred especially 0.4～1.3mm, most preferably 0.5～1.2mm.
The apparent density of lamination foaming sheet of the present invention is 0.02～0.1g/cm 3When this apparent density was too big, surface protection might reduce.On the other hand, when this apparent density too hour, mechanical strengths such as lamination foaming desired conformality that has of sheet or compressive strength are reduced, viscosity (コ シ) is weak, sagging (れ hangs down) of lamination foaming sheet becomes big.Consider that from aspects such as above-mentioned angles this apparent density is preferably 0.025～0.095g/cm 3, more preferably 0.03～0.09g/cm 3
Resin bed preferred unit area weight of the present invention is little, thin thickness.For example, if little, the thin thickness of this weight per unit area then in following formation (i), because thick the concavo-convex of foaming sheet surface of bubble also appears on the resin bed, has the effect that is difficult to be attached on the packaged body.
Consider that from above-mentioned angle this weight per unit area is preferably 8g/m 2Below, more preferably 1～6g/m 2, preferred especially 1.5～5g/m 2Make this weight per unit area can prevent that in above-mentioned scope the surface from too becoming sliding and too attenuation of resin bed that surpass essential level or have antistatic behaviour, this adheres to or is preferred from consideration aspect the stable antistatic behaviour at packed article from preventing lamination foaming sheet.And, as long as in the scope that realizes the object of the invention, effect, though resin bed a little some uneven thickness also have no relations.
The thickness of lamination foaming sheet integral body of the present invention is the arithmetic mean of instantaneous value of measuring the thickness (mm) of gained in the whole width range broad ways of lamination foaming sheet every 1cm.
Apparent density (the g/cm of lamination foaming sheet of the present invention 3) be to use the volume (cm of the weight (g) of the test film that cuts by lamination foaming sheet divided by this test film 3) numerical value of gained.
In addition, constitute the apparent density (g/cm of the foaming sheet of lamination foaming sheet 3) be the following value that obtains, promptly, deduct the weight (g) of the resin bed of following test film by the weight (g) of test film and try to achieve the foaming sheet weight of test film, deduct by the thickness of lamination foaming sheet following test film resin bed average thickness and try to achieve the foaming sheet thickness of test film, with the weight of this foaming sheet divided by the volume (cm that tries to achieve by the appearance and size of this foaming sheet 3) and obtain the value of apparent density.
In the present invention, the weight per unit area of above-mentioned resin bed can be tried to achieve by following method.
Utilize the suitably vertical cross section of the width of amplification layer Hair Fixer bubble sheet such as microscope, broad ways is equally spaced measured the thickness of 10 place's resin beds, with the arithmetic mean of instantaneous value of income value average thickness as resin bed, this average thickness be multiply by the density of the substrate resin that constitutes resin bed and carries out unit conversion, can be in the hope of the weight per unit area [g/m of resin bed 2].But this method is limited to the clear and definite situation in interface of resin bed and foaming sheet.
Density (the g/cm of the substrate resin of resin bed 3) the summation form of the value that can calculate multiply by the weight content ratio of each resin with each resin density that constitutes substrate resin tries to achieve.
And, when utilizing said method to be difficult to the analytical unit area weight, for the lamination foaming sheet of making by coextrusion, in the extrusion foaming condition, can be by discharge rate X[kg/ hour of resin bed], the width W [m] of gained lamination foaming sheet and lamination foamed length of a film L[m/ hour that the sheet time per unit extrudes], utilize following formula (1) to calculate the weight per unit area (g/m of resin bed 2).In addition, when on the two sides of foaming sheet when utilizing extruding layer platen press laminated resin layer, can try to achieve the weight per unit area of each resin bed according to the discharge rate of separately resin bed.
Weight per unit area [g/m 2]=[1000X/ (L * W)] (1)
Lamination foaming sheet of the present invention, because as mentioned above, resin bed contains the polymer electrolyte antistatic additive, so excellent antistatic property.Specifically, the applied voltage half-life after the washing was preferably below 10 seconds, and is more preferably below 7 seconds, further preferred below 5 seconds.If this applied voltage half-life is below 10 seconds, then use as the padded coaming of precise electronic instruments such as glass substrate for display, packaging material by sheet that lamination is foamed, can prevent that dust from adhering on the precise electronic instrument.In addition, though this lamination foaming sheet after washing, the applied voltage half-life also reduces hardly, can bring into play sufficient antistatic behaviour, it can bring into play the antistatic behaviour of long-term stability with to bring into play the packaging material of antistatic behaviour by surfactant at present different.And for the lower limit of this applied voltage half-life, little value is preferred more.The lower limit of this applied voltage half-life probably is 0.5 second.
Applied voltage half life determination in this specification is to serve as to measure sample with the lamination foaming sheet after the washing, the value of measuring based on JIS L1094 (1988) A method.Specifically, will be from the lamination test film that the sheet cuts (vertical 40mm * thickness of 40mm * laterally: determination object thing thickness) join the beaker that foams with 40 ℃ water 300ml, stir and washed in 10 minutes, then test film is taken out from warm water, 23 ℃ of temperature, relative humidity is to place 36 hours under 50% the atmosphere, carry out the status adjustment of test film thus, utilizing JIS L1094 (1988) A method then, is 1300rpm in turntable (turn table) rotary speed, applied voltage (+) is 10kV, try to achieve the applied voltage half-life under 30 seconds the condition that adds.
Laminate of the present invention satisfy following condition (i), (ii) and (iii) at least any one.
(i) weight per unit area of polyvinyl resin layer is 8g/m 2Below, the bubble thickness of foaming sheet is 6～100 μ m, and the average bubble number of thickness direction is below 2;
(ii) the polyvinyl resin layer by the fusing point of 30～90 weight % greater than 115 ℃ and be below 128 ℃ and density is 0.910～0.970g/cm 3The fusing point of polyvinyl resin (a), 0～60 weight % be below 115 ℃ and density is 0.890～0.930g/cm 3Polyvinyl resin (b) and the polymer electrolyte antistatic additive (c) (wherein, (a)+(b)+(c)=100 weight %) of 10～50 weight % constitute;
(iii) polyethylene resin foaming sheet by the fusing point of 10～50 weight % greater than 115 ℃ and be below 125 ℃ and density is 0.910～0.940g/cm 3The fusing point of polyvinyl resin (d), 50～90 weight % be below 115 ℃ and density is 0.890～0.930g/cm 3Polyvinyl resin (b) (wherein, (d)+(b)=100 weight %) constitute.
The lamination foaming sheet that satisfies above-mentioned (i) is the foaming sheet that bubble chamber film thickness lacks than common number of bubbles thick, thickness direction, that is, be the foaming sheet that mainly is made of thick bubble.Laminated thin and weight per unit area are 8g/m as described above satisfying on should the foaming sheet of (i) 2In the lamination foaming sheet that following resin bed forms, the concavo-convex resin layer surface that appears at of thick bubble, the contact area of this lamination foaming sheet and packaged body is little, and also high for the rigidity of the compression of bubble etc.Therefore, although lamination of the present invention foaming sheet in surface laminated contain the resin bed of more polymer electrolyte antistatic additive, lamination foaming sheet self is difficult to be attached on the packaged body.Consider that from above-mentioned viewpoint this bubble thickness is preferably 6～70 μ m, more preferably 7～50 μ m, preferred especially 10～35 μ m, this number of bubbles is preferably below 1.7, more preferably below 1.5.In addition, satisfy the bubble diameter of the lamination foaming sheet of above-mentioned (i) and compare greatly with existing foaming sheet, the number of bubbles of thickness direction is also few, so light transmission height, when using, can improve sense of vision, be able to the degree of confirming that packed article is what as packaging material.
In the present invention, average bubble thickness th (μ m) can utilize following formula to try to achieve.
th(μm)＝(0.46/ρp)ρf·D
Wherein, D is the mean air bubble diameter (μ m) of foaming sheet, and ρ p is the density (g/cm of the substrate resin of foaming sheet 3), ρ f is the apparent density (g/cm of foaming sheet 3).
And the mean air bubble diameter D of foaming sheet is based on ASTM D3576-77, the value of calculating by following formula.
The arithmetic mean of instantaneous value (μ m)/0.616 of the average bubble chord length of D=3 direction (thickness direction, width and extrude direction)
In addition, the density p p (g/cm of the substrate resin of foaming sheet 3) can try to achieve as getting off, that is, cut the foaming sheet in the mode of not resinous layer by lamination foaming sheet, utilize hot-press arrangement to remove bubble and solidization (ソ リ Star Deization) the foaming sheet that cuts, measure the density of gained sample.In addition, can also each resin density (g/cm of the substrate resin of foaming sheet will be constituted 3) multiply by the weight content ratio of each resin and the summation form of the value calculated is tried to achieve with density with each resin that constitutes substrate resin.
In addition, the density p p (g/cm of the substrate resin of foaming sheet 3) can calculate according to the foam density and the thickness of resin bed of thickness, lamination foaming sheet of the apparent density of sheet and foaming sheet of lamination.
In addition, the apparent density ρ f (g/cm of foaming sheet 3) can as following, try to achieve, promptly, the weight per unit area that deducts resin bed by the weight per unit area of lamination foaming sheet is calculated the weight per unit area of foaming sheet, then use the thickness that from the thickness of lamination foaming sheet, deducts the resulting foaming sheet of thickness of above-mentioned resin bed to remove the weight per unit area of foaming sheet, and carry out unit conversion and try to achieve, the weight per unit area of described lamination foaming sheet foams with lamination that sheet is gone to steep by hot-press arrangement and the density of the sample that solidification obtains multiply by the thickness of lamination foaming sheet and carries out unit conversion and try to achieve by using, and the weight per unit area of described resin bed multiply by the thickness of resin bed by the density with resin bed and carries out unit conversion and try to achieve.
This average bubble thickness can utilize the apparent density of foaming sheet and the mean air bubble diameter of foaming sheet to regulate.The change of the apparent density of foaming sheet can be regulated by the addition of blowing agent.
On the other hand, the die head internal pressure condition when kind that the mean air bubble diameter of foaming sheet can be by blowing agent or bubble conditioning agent or addition, extrusion foaming etc. is regulated.For example, when the kind of blowing agent and addition are one regularly, the pressure in the time of can be by extrusion foaming in the die head and the addition of bubble conditioning agent are regulated mean air bubble diameter.Specifically, under the kind of blowing agent and addition are certain condition, increase the pressure in the die head and/or increase the amount of bubble conditioning agent, the mean air bubble diameter of the sheet that can reduce more to foam.
The mensuration of the number of bubbles of above-mentioned thickness direction is following carries out: the every interval 1cm of whole width range broad ways at the foaming sheet determines that a place locates, obtain the number of bubbles (individual) of the determined thickness that locates (mm) and this thickness direction that locates, with the number of bubbles (individual) of the thickness direction that respectively locates divided by this thickness that locates (mm), with the arithmetic mean of instantaneous value of the number of bubbles of the thickness direction that respectively locates of being tried to achieve as the number of bubbles of thickness direction of the present invention (individual/mm).And the above-mentioned number of bubbles that respectively locates thickness direction is by drawing straight line at the thickness direction that locates, and the number of the crossing bubble of counting and this straight line value of trying to achieve.
Satisfy in the above-mentioned lamination foaming sheet (ii), its resin bed by the fusing point of 30～90 weight % greater than 115 ℃ and be below 128 ℃ and density is 0.910～0.970g/cm 3Polyvinyl resin (a), the density of 0～60 weight % be 0.890～0.930g/cm 3And fusing point is that the polymer electrolyte antistatic additive (c) (wherein, (a)+(b)+(c)=100 weight %) of polyvinyl resin (b) below 115 ℃ and 10～50 weight % constitutes.
The excellent rigidity of polyvinyl resin (a), thereby the resin bed that contains this polyvinyl resin (a) is rich in rigidity, hear resistance.Therefore, satisfy this lamination foaming sheet (ii) and have excellent antistatic behaviour, have sufficient rigidity simultaneously on the whole, therefore wrap in the operation on the packaged body, the operation of tearing becomes easy.In addition, the hear resistance that satisfies this lamination foaming sheet integral body (ii) also improves.
In addition, this lamination foaming sheet satisfies specific apparent density and thickness condition, so the resin of laminate integral body composition is in whole polyvinyl resins, to contain a small amount of polyvinyl resin (a) that causes because of the polyvinyl resin (a) that is included in the resin bed.
Therefore, for satisfying above-mentioned lamination foaming sheet (ii), on the DSC curve that obtains as described below, as shown in Figure 1 than the high high temperature side of the summit temperature of main melting peak and be main melting peak zone more than 110 ℃, the protuberance that caused by polyvinyl resin (a) occurred, described DSC curve is the curve by being sample with the laminate, obtaining by the heat stream differential scanning calorimetry of carrying out the melting heat after certain heat treatment based on JIS K7122-1987.And the existence of the protuberance on Fig. 1 can be judged by with incidental software of DSC determinator etc. this DSC curve being carried out the existence that second-order differential confirms flex point.
And, when also containing polyvinyl resin (a) in the polyvinyl resin that is constituting the foaming sheet, also have following situation, promptly, in above-mentioned DSC curve, will cover at the protuberance that occurs than the high high temperature side of main melting peak summit temperature and the zone more than 110 ℃ and hide, and melting peak occur.
The further preferred fusing point of above-mentioned polyvinyl resin (a) is greater than 115 ℃ and be below 125 ℃ and density is 0.910～0.940g/cm 3Polyvinyl resin.
Above-mentioned polyvinyl resin (a) can be enumerated so-called straight chain shape low density polyethylene (LDPE), high density polyethylene (HDPE).
Consider that from the angle of rigidity the content of polyvinyl resin (a) is preferably 40～90 weight %, more preferably 45～85 weight % with expectation.
When the content of above-mentioned polyvinyl resin (b) was too much, the content of polyvinyl resin (a) tailed off, so the rigidity deficiency of resin bed, with lamination foam sheet wrap in the operation on the packaged body, the operation of tearing operation can not as the expectation improve.Consider that from above-mentioned angle the content of polyvinyl resin (b) is preferably 0～45 weight %, more preferably 0～30 weight %.
Above-mentioned polyvinyl resin (b) can be enumerated so-called chain low density polyethylene (LDPE).
When the content of above-mentioned polymer electrolyte antistatic additive (c) is very few, might be able to not bring into play as the desired antistatic property of the packaging material of precise electronic instrument.On the other hand, even this content is too much, though the antistatic property aspect without any problem, antistatic property culminates, thus cost aspect variation.Consider that from above-mentioned angle the content of polymer electrolyte antistatic additive (c) is preferably 15～40 weight %, more preferably 20～35 weight %.
Satisfy in the above-mentioned lamination foaming sheet (iii), its foaming sheet by the fusing point of 10～50 weight % greater than 115 ℃ and be below 125 ℃ and density is 0.910～0.940g/cm 3Polyvinyl resin (d) and the density of 50～90 weight % be 0.890～0.930g/cm 3And fusing point is that the polyvinyl resin (b) (wherein, (d)+(b)=100 weight %) below 115 ℃ constitutes.
Satisfy in the above-mentioned lamination foaming sheet (iii), its foaming sheet contains fusing point greater than 115 ℃ and be below 125 ℃ and density is 0.910～0.940g/cm 3Polyvinyl resin (d).Thereby the polyvinyl resin (d) that causes in the resin of whole lamination foaming sheet is formed, containing more amount owing to contained polyvinyl resin (d) in the foaming sheet.
Polyvinyl resin (d) has superior stiffness, and the foaming sheet that therefore contains polyvinyl resin (d) is rich in rigidity.Therefore, satisfy above-mentioned lamination foaming sheet (iii) and have sufficient rigidity on the whole, wrap in the operation on the packaged body, the operation of tearing becomes easily, can make good foaming sheet.
Consider that from above-mentioned viewpoint the content of polyvinyl resin (d) is preferably 20～50 weight %, more preferably 25～45 weight %, the content of polyvinyl resin (b) is preferably 50～80 weight %, more preferably 55～75 weight %.
Above-mentioned polyvinyl resin (d) can be enumerated so-called straight chain shape low density polyethylene (LDPE).
In satisfying above-mentioned lamination foaming sheet (iii), polyethylene resin foaming sheet contains fusing point greater than 115 ℃ and be below 125 ℃ and density is 0.910～0.940g/cm 3Polyvinyl resin (d), therefore on the DSC curve that as following, obtains, as shown in Figure 2 than the high high temperature side of the summit temperature of main melting peak and be main melting peak zone more than 110 ℃, other melting peaks of being caused by polyvinyl resin (d) occurred, described DSC curve is the curve by being sample with the laminate, obtaining by the heat stream differential scanning calorimetry of carrying out the melting heat after certain heat treatment based on JIS K7122-1987.And the existence at second peak on Fig. 2 can be confirmed by estimating this DSC curve.
Lamination of the present invention foaming sheet preferably satisfies above-mentioned condition (i) and above-mentioned condition (ii) simultaneously, and this lamination foaming sheet is formed by resin bed that is rich in rigidity and the main foaming sheet that is made of thick bubble.Therefore, the contact area of this lamination foaming sheet and packaged body is little, is difficult to be attached on the packaged body, has sufficient rigidity simultaneously, and wrap in the operation on the packaged body, the operation of tearing etc. and become easily, and excellent antistatic property.
In addition, lamination of the present invention foaming sheet preferably satisfies above-mentioned condition (i) and above-mentioned condition (iii) simultaneously.And, satisfy at the same time in above-mentioned condition (i) and the above-mentioned condition lamination foaming sheet (iii), also further comprise satisfy simultaneously above-mentioned condition (i), above-mentioned condition (ii) with above-mentioned condition lamination foaming sheet (iii).Satisfying above-mentioned condition (i) and above-mentioned condition lamination foaming sheet (iii) simultaneously has the resin bed of excellent antistatic property and is rich in rigidity and the formation of the foaming sheet that bubble is thick.Therefore, the contact area of this lamination foaming sheet and packaged body is little, is difficult to be attached on the packaged body, has sufficient rigidity simultaneously, and wrap in the operation on the packaged body, the operation of tearing etc. and become easily, and excellent antistatic property.
And the resin bed that is arranged on the foaming sheet that satisfies condition (iii) preferably satisfies above-mentioned condition (i).
Then, the manufacture method to laminated polyethylene resin foaming sheet of the present invention describes.
As the manufacture method of lamination of the present invention foaming sheet, the molten resin that preferred employing will form the molten resin of resin bed and form the foaming sheet flows and carries out the coextrusion foaming of extrusion foaming in the pressing of die head internal layer.This coextrusion foaming method can make the thickness attenuation of resin bed, can access the high lamination foaming sheet of bonding force between resin bed and the foaming sheet simultaneously, is preferred therefore.But, in the present invention, also can use by extrusion foaming manufacturing foaming sheet, utilize extruding layer to be pressed on the foaming sheet known method at present such as laminated resin layer.
In the method for the lamination foaming sheet of making sheet by the coextrusion foaming, have use coextrusion with flat die with sheet coextrusion foaming and make the method for platy layer Hair Fixer bubble sheet, use coextrusion to foam with the tubular coextrusion and obtain the lamination foaming body of tubular, then cut the foam method etc. of sheet of lamination that this tubular foaming body forms sheet with annular die.Wherein, using coextrusion can easily make width as the above wide lamination foaming sheet of 1000mm with the method for annular die, is preferable methods therefore.
Below the situation of using above-mentioned annular die to carry out coextrusion is elaborated.
At first, as shown in Figure 6, the polyvinyl resin and the polymer electrolyte antistatic additive (C) that will comprise polyvinyl resin (a) or polyvinyl resin (b) etc. supply to resin bed formation with in the extruder 11, carry out heating and melting and mixing after, add volatile plasticizer (E1) and melting mixing as required, make the polyvinyl resin layer and form with resin melt (F1).The additives (G) such as bubble conditioning agent that will comprise the polyvinyl resin of polyvinyl resin (b) or straight chain shaped polyethylene resin (d) etc. simultaneously and add as required supply to the foaming sheet and form with in the extruder 12, after heating and melting is also mixing, be pressed into physical blowing agent (E2), further carry out the mixing polyethylene resin foaming sheet of making and form with resin melt (F2).
And, in the coextrusion method, can in annular die, resin bed be formed with resin melt (F1) and foaming sheet formation resin melt (F2) lamination, also the above-mentioned fused mass of extruding can be carried out lamination in the outside of die head exit.
As the volatile plasticizer (E1) that adds in forming with resin melt (F1) at above-mentioned resin bed, use function that melt viscosity with resin melt of making (F1) reduces, volatilize by this polyvinyl resin layer and be not present in plasticizer in the resin bed forming polyvinyl resin layer (J) back simultaneously.By in resin melt, adding volatile plasticizer (E1), can be when sheet that lamination is foamed carries out coextrusion, make resin bed form extrusion temperature with resin melt (F1) sheet that approaches to foam and form extrusion temperature with resin melt (F2), the while can significantly improve the fusion percentage elongation of the resin bed (J) of soft state.Like this, the bubble of foaming sheet (I) be difficult to because of when foaming resin bed heat destroy, therefore the and elongation of the elongation of this resin bed (J) when following foaming sheet (I) foaming can prevent that the be full of cracks that the elongation deficiency by resin bed (J) causes from taking place.
Volatile plasticizer (E1) is preferred use be selected from carbon number be 3～7 aliphatic hydrocarbon or ester ring type hydrocarbon, carbon number be 1～4 aliphatic alcohol or carbon number be in 2～8 the fatty ether more than a kind or 2 kinds.When so low material of volatility replaced volatile plasticizer (E1), this lubricant remained in the resin bed (J) when using so-called lubricant (sliding drug), and the situation on the surface of polluting packaged body is arranged.With respect to this, volatile plasticizer (E1) from the resin plasticized that can make resin bed (J) efficiently, gained resin bed (J), be difficult to residual volatile plasticizer self this respect and consider it is preferred.
Above-mentioned carbon number is that 3～7 aliphatic hydrocarbon or ester ring type hydrocarbon can be enumerated for example propane, normal butane, iso-butane, pentane, isopentane, neopentane, pentamethylene, n-hexane, isohexane, cyclohexane, normal heptane etc.
Above-mentioned carbon number is that 1～4 aliphatic alcohol can be enumerated for example methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol, isobutanol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol.
Above-mentioned carbon number is that 2～8 fatty ether can be enumerated for example dimethyl ether, diethyl ether, propyl ether, isopropyl ether, methyl ethyl ether, methyl-propyl ether, methyl isopropyl ether, methyl butyl ether, methyl-isobutyl ether, methyl amylether, the methyl isoamyl ether, ethyl propyl ether, the ethyl isopropyl ether, ethyl-butyl ether, the ethyl isobutyl ether, ethyl pentyl group ether, the ethyl isoamyl ether, vinyl ethers, allyl ether, methyl vinyl ether, methallyl ether, ethyl vinyl ether, ethyl allyl ether.
Consider that from the aspect that is easy to volatilization from resin bed (J) boiling point of volatile plasticizer (E1) is preferably below 120 ℃, more preferably below 80 ℃.If the boiling point of volatile plasticizer (E1) is in above-mentioned scope, then as long as after coextrusion, gained lamination foaming sheet (H) is placed, utilize after the coextrusion just heat or and then at room temperature see through gas afterwards, volatile plasticizer (E1) can be waved naturally to loose and removes from the foam resin bed (J) of sheet of lamination.The lower limit of the boiling point of this volatile plasticizer (E1) probably is-50 ℃.
The addition of volatile plasticizer (E1) is preferably 5 weight portions～50 weight portions with respect to substrate resin 100 weight portions that mainly are the mixing thing of polyvinyl resin and polymer electrolyte antistatic additive (C).If the addition of volatile plasticizer (E1) is more than 5 weight portions, the heating that shearing caused of the polyvinyl resin etc. that then can suppress to constitute resin bed (J) when mixing, the foaming sheet that therefore can suppress laminated resin layer (J) forms the rising (temperature decreasing effect) with the resin temperature of resin melt (F2).Therefore, forming when carrying out the coextrusion foaming bubble drawback such as the break when sheet that can prevent to foam forms and foams with resin melt (F2) with resin melt with resin bed.The foaming sheet forms with resin melt (F2) and extrudes from die head under normal pressure and form the sheet (I) that foams.
Further, volatile plasticizer (E1) also has following effect, that is, the draftability that can make resin bed formation follow the foaming sheet with resin melt (F1) when forming the resin bed of lamination foaming sheet improves (draftability is improved effect), makes the thickness of resin bed (J) even and thin.Consider that from above-mentioned angle the addition of volatile plasticizer (E1) is preferably more than 7 weight portions, more preferably more than 10 weight portions.
On the other hand, when the addition of volatile plasticizer (E1) is too much, following possibility is arranged, promptly, the rerum natura that causes resin bed (J) self reduces, or volatile plasticizer (E1) can not fully be dissolved in resin bed and form with in the resin melt (F1) volatile plasticizer being sprayed from die lip, or the thickness thickness of perforate or resin bed too becomes big on resin bed (J).Consider that from above-mentioned angle the addition of volatile plasticizer (E1) is preferably below 40 weight portions, more preferably below 30 weight portions, further below preferred 25 weight portions.Addition by making volatile plasticizer (E1) is in above-mentioned scope, and resin bed forms and improves effect with the sufficient temperature decreasing effect and the draftability of resin melt in the time of can guaranteeing coextrusion.
In addition, form with in the resin melt (F1), in the scope of not damaging the object of the invention, also can in the resin that forms this fused mass (F1), add various additives for resin bed.Various additives can be enumerated for example antioxidant, heat stabilizer, weather resisting agent, ultra-violet absorber, fire retardant, filler, antiseptic etc.The addition of this moment can suitably determine according to purpose, the effect of additive, but it is preferably below 10 weight portions separately with respect to substrate resin 100 weight portions, more preferably below 5 weight portions, below preferred especially 3 weight portions.
As the physical blowing agent (E2) that adds in forming with resin melt (F2) at above-mentioned foaming sheet, can enumerate for example chlorinated hydrocabons, 1 such as clicyclic hydrocarbons such as aliphatic hydrocarbons such as propane, normal butane, iso-butane, pentane, isopentane, n-hexane, isohexane, pentamethylene, cyclohexane, chloromethanes, chloroethanes, 1,2,2-HFC-134a, 1, organic physical blowing agents such as fluorinated hydrocarbons such as 1-Difluoroethane, inorganic physical blowing agents such as nitrogen, carbon dioxide, air, water.According to circumstances, also can use decomposition-type foaming agents such as Celogen Az.Above-mentioned physical blowing agent can mix 2 kinds with on share.Wherein, from considering that with the compatibility of polyvinyl resin, the angle of foaminess preferred especially organic physical blowing agent is the blowing agent of principal component with normal butane, iso-butane or their mixture especially preferably wherein.
The addition of physical blowing agent (E2) can be regulated according to kind, the purpose apparent density of blowing agent.The addition of bubble conditioning agent is regulated according to the purpose bubble diameter in addition.For example, obtain the lamination foaming sheet of above-mentioned density range as blowing agent for the butane mixture that uses iso-butane 30 weight % and normal butane 70 weight %, the addition of butane mixture is 3～30 weight portions with respect to per 100 weight portion substrate resins, be preferably 4～20 weight portions, more preferably 6～18 weight portions.
As the main type of the additive (G) that adds in forming with resin melt (F2) at above-mentioned foaming sheet, can add the bubble conditioning agent usually.The bubble conditioning agent can use any one in organic bubble conditioning agent, the inorganic bubble conditioning agent.Inorganic bubble conditioning agent can be enumerated borate metal salts such as Firebrake ZB, antifungin, borax, sodium chloride, aluminium hydroxide, talcum, zeolite, silica, calcium carbonate, sodium acid carbonate etc.Organic in addition bubble conditioning agent can be enumerated phosphoric acid-2,2-di-2-ethylhexylphosphine oxide (4, the 6-tert-butyl-phenyl) sodium, Sodium Benzoate, calcium benzoate, aluminum benzoate, odium stearate etc.In addition, also can use citric acid and sodium acid carbonate, the alkali salt of citric acid and the material that sodium acid carbonate is formed by combining etc. as the bubble conditioning agent.These bubble conditioning agents also can use mixing more than 2 kinds.
The addition of bubble conditioning agent is 0.01～3 weight portion, is preferably 0.03～1 weight portion with respect to per 100 weight portion substrate resins.The lamination foaming sheet of above-mentioned in order to be met (i), for example in the thickness of the adjustment of considering the resin bed weight per unit area and foaming sheet, apparent density etc., make the average bubble number of mean air bubble diameter, thickness direction satisfy the addition that above-mentioned (i) regulate the bubble conditioning agent and get final product.
As mentioned above, in the scope of not damaging the object of the invention and effect, can be in polyethylene resin foaming sheet forms with resin melt (F2) styrene be other resin or additive such as heat stabilizer such as resin or elastomer.
As described above, when coming out to make lamination foaming sheet by co-extrusion, using extruder 11 to form resin bed forms with resin melt (F1), using extruder 12 to form the foaming sheet forms with resin melt (F2), in extruder 12, resin melt (F2) is adjusted to foamable temperature, in extruder 11 with resin melt (F1) but be adjusted to the temperature of coextrusion, then resin bed is formed with resin melt (F1) and the formation of foaming sheet and import coextrusion with in the annular die 13 with resin melt (F2), with both laminations, further be coextruded in the atmosphere, the foaming sheet is formed with resin melt (F2) foaming, be formed on the tubular layer Hair Fixer foam that the laminated resin layer forms on the foaming body, the inner surface of this tubular layer Hair Fixer foam is cooled off along cylindric cooling device, cut while pulling simultaneously, can obtain lamination foaming sheet thus.Wherein, resin bed forms that form with resin melt (F1) and foaming sheet can be as described above at the inside of annular die lamination with the lamination of resin melt (F2), also can be near outlet or the outlet of die head outside lamination.In addition, the device of above-mentioned annular die, extruder, cylindric cooling device, incision tubular layer Hair Fixer foam etc. can use the well known device that uses in the extrusion foaming field at present.
In addition, for the value that makes the average bubble number of thickness direction in the above-mentioned condition of the present invention (i) diminishes, can regulate by as described below, promptly, transfer the addition of bubble conditioning agent few, the protuberance (リ Star プ) that has parallel back-up ring (ラ Application De) in the setting of annular die front end, pinning the foaming sheet on one side forms with the expansion (swell) of resin melt to thickness direction, extrude on one side, can prevent the generation of abscess striped (コ Le ゲ one ト) thus, the sheet that will foam in parallel back-up ring simultaneously forms with resin melt and shears and make its heating a little, realizes the combination between the bubble.
Embodiment
Below, based on embodiment the present invention is described in further detail.But, the invention is not restricted to embodiment.
The bubble conditioning agent uses the bubble conditioning agent masterbatch that cooperates talcum (Ishihara Sangyo Kaisha, Ltd. produces, and commodity are called (Ha イ Off イ ラ one #12)) 20 weight % to form with respect to ldpe resin 80 weight %.
The kind of the polyvinyl resin that uses when forming resin bed and forming the foaming sheet, manufacturer, density, fusing point, MFI (190 ℃, load 21.18N) are shown in table 1.
The polymer electrolyte antistatic additive use Sanyo Chemical Industries, Ltd.'s system with " ペ レ ス タ Star ト 300 " (fusing point be 136 ℃, number-average molecular weight be 14000, density be 990g/L) of polyethers polypropylene block copolymer as principal component.
Physical blowing agent uses the mixed butanes that is made of normal butane 70 weight % and iso-butane 30 weight %.
Figure GSA00000068897500191
Embodiment 1～11, comparative example 1～3
As the extruder that is used to form polyethylene resin foaming sheet (12), use the series connection extruder that is made of as second extruder of 120mm as first extruder of 90mm and diameter diameter, the extruder (11) that is used to form the polyvinyl resin layer uses three extruder of diameter as 50mm, L/D=50.Further, connect second extruder and the outlet separately of the 3rd extruder on annular die, each molten resin can be carried out lamination in annular die in coextrusion.
To supply in the 3rd extruder by the polyvinyl resin and the polymer electrolyte antistatic additive that cooperate shown in the table 2, and heat mixing, the above-mentioned mixed butanes that is pressed into the amount of Table 2 is as volatile plasticizer, further mixing, be adjusted to the extrusion resin temperature shown in the table 2 and make resin bed formation resin melt, this resin bed is formed the discharge rate that constitutes with the weight per unit area that can form " resin bed/foaming sheet/resin bed " shown in the table 2 with resin melt import to coextrusion with in the annular die.
Simultaneously, add polyvinyl resin and the bubble conditioning agent masterbatch that cooperates shown in mouthful supply schedule 2, add hot milling, form and be adjusted to about 200 ℃ molten resin mixture to the raw material of first extruder of series connection extruder.Then, be pressed into the physical blowing agent of the amount of Table 2 in this molten resin mixture, then supply in second extruder in the downstream that is connected above-mentioned first extruder, transfer to the extrusion resin temperature shown in the table 2 and make foaming sheet formation resin melt, this foaming sheet is formed the discharge rate that constitutes with the weight per unit area that can form " resin bed/foaming sheet/resin bed " shown in the table 2 with resin melt import to above-mentioned coextrusion with in the annular die.
The foaming sheet of the resin flow path in importing to coextrusion usefulness annular die and in die head forms the outside and the inboard with resin melt, form with resin melt lamination interflow with the resin bed in the annular die importing to coextrusion, and the layered product of fused mass is expressed into the atmosphere from die head, form the tubular layer Hair Fixer foam of the 3-tier architecture of forming by resin bed/foaming body/resin bed.The cylindric cooling device (reel (mandrel)) that cools off along the tubular layer Hair Fixer foam that will extrude cuts while pulling, and obtains lamination foaming sheet.
Figure GSA00000068897500211
Each rerum natura of resulting lamination foaming sheet is shown in table 3 in embodiment and the comparative example.
Figure GSA00000068897500231
The mensuration of the average bubble number of the mean air bubble diameter in the table 3, thickness direction, bubble thickness, applied voltage is to utilize said method that each lamination foaming sheet is measured 5 places respectively, with the arithmetic mean of instantaneous value of measured value as separately measurement result.
The mensuration of the peel strength in the table 3 is as described below carries out.
The sheet that will foam is cut into the size of horizontal 40mm * vertical 76mm.Then, with the foaming sheet that cut and glass sheet under the atmosphere of 60 ℃ of temperature, humidity 50%RH with 130g/cm 2Load pressing 18 hours.Mensuration will be pressed together on foaming sheet on the glass sheet load when peeling off by 90 ° of disbonded tests with the speed of 100mm/min under these conditions.Each lamination foaming sheet is measured 6 places respectively, with the arithmetic mean of instantaneous value of measured value as peel strength (gf/40mm).
The measurement result of peel strength is estimated by standard shown below.
◎: less than 0.7gf/40mm
Zero: more than the 0.7gf/40mm and less than 1.3gf/40mm
More than △: the 1.3gf/40mm and less than 1.9gf/40mm
*: more than the 1.9gf/40mm
Confficient of static friction in the table 3 is the value of measuring according to JIS K7125-1999.At first, cut the slide plate that is of a size of horizontal 100mm * vertical 100mm from lamination foaming sheet.In addition, cut the test film that is of a size of horizontal 130mm * vertical 200mm from the foaming sheet identical with slide plate.Friction is 100cm by making contact area 2The square slide plate of (length of side on 1 limit is 100mm) moves horizontally on test film and produces.The heavy burden of slide plate is adjusted to 125g ± 1.2g, and making the translational speed of the test film that causes friction is 500mm/min, measures thus.The direction that makes test film, slide plate, slip all with consistent test of length (indulging) direction of sheet material.Carry out Determination of Friction Coefficient according to the said determination order, with the peak load of beginning during fricting movement divided by the value of the load gained of slide plate value as confficient of static friction.And said determination is between the surface of lamination foaming sheet and carry out at 5 places respectively between the back side, with the mean value of 10 place's confficients of static friction of trying to achieve as measured value.
The measurement result of confficient of static friction is estimated by standard shown below.
◎: less than 0.7
More than zero: 0.7 and less than 1.2
*: more than 12

Claims (3)

1. laminated polyethylene resin foaming sheet, it is that to close that the polyvinyl resin layer that contains the polymer electrolyte antistatic additive forms, thickness in the upper strata crimping of one side at least of polyethylene resin foaming sheet be that 0.2～2.0mm, apparent density are 0.02～0.1g/cm 3Laminate, it is characterized in that, this laminate satisfy following condition (i), (ii) and (iii) at least any one,
(i) weight per unit area of polyvinyl resin layer is 8g/m 2Below, the bubble thickness of foaming sheet is 6～100 μ m, and the average bubble number of thickness direction is below 2;
(ii) the polyvinyl resin layer by the fusing point of 30～90 weight % greater than 115 ℃ and be below 128 ℃ and density is 0.910～0.970g/cm 3The fusing point of polyvinyl resin (a), 0～60 weight % be below 115 ℃ and density is 0.890～0.930g/cm 3Polyvinyl resin (b) and the polymer electrolyte antistatic additive (c) (wherein, (a)+(b)+(c)=100 weight %) of 10～50 weight % constitute;
(iii) polyethylene resin foaming sheet by the fusing point of 10～50 weight % greater than 115 ℃ and be below 125 ℃ and density is 0.910～0.940g/cm 3The fusing point of polyvinyl resin (d), 50～90 weight % be below 115 ℃ and density is 0.890～0.930g/cm 3Polyvinyl resin (b) (wherein, (d)+(b)=100 weight %) constitute.
2. laminated polyethylene resin foaming sheet according to claim 1 is characterized in that, satisfy above-mentioned condition (i) simultaneously and be selected from above-mentioned condition (ii) with above-mentioned condition at least a kind of condition (iii).
3. laminated polyethylene resin foaming sheet according to claim 1 and 2 is characterized in that, the applied voltage half-life after the washing of above-mentioned lamination foaming sheet is below 10 seconds.
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CN108713037A (en) * 2016-09-30 2018-10-26 积水化学工业株式会社 Independent air bubble foamed resin and its manufacturing method
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CN103395265A (en) 2013-11-20

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