CN101844430B - Laminated polyethylene resin foaming sheet - Google Patents

Laminated polyethylene resin foaming sheet Download PDF

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Publication number
CN101844430B
CN101844430B CN201010149533.8A CN201010149533A CN101844430B CN 101844430 B CN101844430 B CN 101844430B CN 201010149533 A CN201010149533 A CN 201010149533A CN 101844430 B CN101844430 B CN 101844430B
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resin
foamed sheet
weight
sheet
lamination
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CN101844430A (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)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a laminated polyethylene resin foaming sheet, which could prevent foaming sheets from mutual attaching or attacking on packaged goods such as a glass substrate, has excellent packaged goods packing operation, avoids peeling static electricity and prevents dusts from attaching on packaged goods. The laminated polyethylene resin foaming sheet is laminated with a polyethylene resin layer including a polymeric antistatic agent on at least one surface and is a laminated sheet having a thickness of 0.2-2.0mm and an apparent density of 0.02-0.1g/cm3. The laminated polyethylene resin foaming sheet is characterized in that the laminated sheet at least meets optionally a requirement in specific conditions (i), (ii) and (iii).

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 using in slim TV, use the polyvinyl resin extrusion foaming sheet that is rich in flexibility and resiliency as its packaging material.For this glass substrate for display, require it to there is very high-caliber surface cleaning, therefore use the polyvinyl resin extrusion foaming sheet that contains Polymer Antistatic Agent as packaging material.This foamed sheet for example has the glass substrate lining paper of recording in patent documentation 1.
But, for the glass substrate recorded using patent documentation 1 with headed by lining paper, at present use as the padded coaming of precise electronic instrument, the foamed sheet of packaging material, in whole foamed sheet, all contain expensive Polymer Antistatic Agent.Carry out research to a certain degree can showing antistatic behaviour with a small amount of addition for this foamed sheet, but still leave, the shortcoming of high in cost of production has been carried out to room for improvement.
The inventor, in order to address this problem, has developed a kind of polyethylene resin foaming sheet, and the polyvinyl resin layer that it does not foam in the surface laminated of foamed sheet only adds Polymer Antistatic Agent in this resin bed.But, although this lamination foamed sheet can be brought into play good antistatic behaviour, have the poor problem of sliding.Specifically, in the time that this foamed sheet lamination is preserved, foamed sheet forms the state mutually adhering to and be difficult to peel off, or form and be easy to be attached on the packed articles such as glass substrate and the state that is difficult to peel off, in addition, in the time using this foamed sheet to cover the operation of packed article, because foamed sheet is difficult to slide, thereby on foamed sheet, produce pleat, the situation that has the workability of making to decline.And then, in the time that packed article is the article of the such taboo static of glass substrate, also have this foamed sheet being produced to the problem of peeling off static when glass substrate is peeled off.In addition, when this foamed sheet is used as to packaging material, although 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 between foamed sheet, mutually adhering to or being attached on the packed articles such as glass substrate, the bale packing workability excellence of packed article, and can prevent from peeling off static, and prevent that dust or dust are attached on 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 Polymer Antistatic Agent forms, thickness at least one side upper strata crimping 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 meet 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 foamed sheet is 6～100 μ m, and the average bubble number of thickness direction is below 2;
(ii) polyvinyl resin layer by the fusing point of 30～90 % by weight be greater than 115 ℃ and below 128 ℃ and density be 0.910～0.970g/cm 3the fusing point of polyvinyl resin (a), 0～60 % by weight be that 115 ℃ of following and density are 0.890～0.930g/cm 3polyvinyl resin (b) and the Polymer Antistatic Agent (c) (wherein, (a)+(b)+(c)=100 % by weight) of 10～50 % by weight form;
(iii) polyethylene resin foaming sheet is greater than 115 ℃ and be that 125 ℃ of following and density are 0.910～0.940g/cm by the fusing point of 10～50 % by weight 3the fusing point of polyvinyl resin (d), 50～90 % by weight be that 115 ℃ of following and density are 0.890～0.930g/cm 3polyvinyl resin (b) (wherein, (d)+(b)=100 % by weight) form.
[2] according to the laminated polyethylene resin foaming sheet described in above-mentioned 1, it is characterized in that, meet above-mentioned condition (i) simultaneously and be selected from above-mentioned condition (ii) and above-mentioned condition (iii) at least 1 condition.
[3] according to the laminated polyethylene resin foaming sheet described in above-mentioned 1 or 2, it is characterized in that, the applied voltage half-life after the washing of above-mentioned lamination foamed sheet is below 10 seconds.
Laminated polyethylene resin foaming sheet of the present invention is (following; also referred to as lamination foamed sheet or laminate) there is the surface protection of excellent packed article; simultaneously because polyvinyl resin layer contains Polymer Antistatic Agent; therefore there is the excellent characteristic that dust or dust adhere to that prevents, be preferably used as the packaging material of the precise electronic instruments such as glass substrate for display.
Further, although polyvinyl resin layer contains Polymer Antistatic Agent, but in polyethylene resin foaming sheet, do not need to contain in fact Polymer Antistatic Agent, therefore the content of the Polymer Antistatic Agent of lamination foamed sheet entirety is few, thereby can manufacture at an easy rate.
And, lamination foamed sheet of the present invention by meet in above-mentioned condition (i), (ii), (iii) at least any one, between lamination foamed sheet or lamination foamed sheet and packaged body be difficult to adhere to, excellent in sliding property, therefore be difficult to produce and peel off static, bale packing operating efficiency excellence.
In addition, lamination foamed sheet of the present invention is by meeting above-mentioned condition (i), and the sense of vision that can have packed article in the time of packing packed article concurrently improves effect.
Accompanying drawing explanation
Fig. 1 represents that an example, than the high high temperature side of main melting peak summit temperature and more than 110 ℃ regions, occurs the accompanying drawing of the DSC curve of protuberance (shoulder).
Fig. 2 represents that an example, than the high high temperature side of main melting peak summit temperature and more than 110 ℃ regions, occurs the accompanying drawing of the DSC curve of other melting peaks.
Fig. 3 (a) be the lamination foamed sheet of embodiment 1 gained at the sectional drawing of extruding direction (MD), Fig. 3 (b) is the sectional drawing of same layer foam sheet at width (TD).
Fig. 4 (a) is the sectional drawing of the MD of the lamination foamed sheet of embodiment 8 gained, and Fig. 4 (b) is the sectional drawing of the TD of same layer foam sheet.
Fig. 5 (a) is the sectional drawing of the MD of the lamination foamed sheet of comparative example 1 gained, and Fig. 5 (b) is the sectional drawing of the TD of same layer foam sheet.
Fig. 6 is the key diagram of one of manufacture method of presentation layer foam sheet example.
The specific embodiment
Below laminated polyethylene resin foaming sheet of the present invention is elaborated.
Lamination foamed sheet of the present invention is to close at least one side upper strata crimping of polyethylene resin foaming sheet (below also referred to as foamed sheet) laminate that the polyvinyl resin layer (below also referred to as resin bed) that contains Polymer Antistatic Agent forms.
Lamination foamed 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 using in slim TV, in addition, can also be suitable as the packaging material of the precise electronic instruments such as electronic product, precision instrument, channel base, silicon wafer.
Forming the foamed sheet of lamination foamed sheet of the present invention and resin bed that lamination is bonded on this foamed sheet is all the principal component using 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, more than in this description, the so-called principal component using polyvinyl resin as substrate resin refers to and contain 50 % by weight in substrate resin, preferably more than 70 % by weight, more preferably polyvinyl resin more than 80 % by weight.
Mixture of more than two kinds in vinyl copolymer and these polymer that polyvinyl resin in this description comprises the alpha-olefin that the Alathons 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 etc.
And the formation of the polyvinyl resin using in foamed sheet and resin bed must not be identical, as described below, in order to bring into play both features separately, can adopt different formations.
The fusing point of the polyvinyl resin in this description can be measured according to the method based on JIS K7121-1987.That is, carry out pre-treatment according to the condition of the status adjustment (2) of coupons in JIS K7121-1987 (wherein, cooling velocity is 10 ℃/min), heat up to obtain melting peak with the speed of 10 ℃/min.Using the temperature on the summit of gained melting peak as fusing point.When occurring when more than 2 melting peak, using the summit temperature of main melting peak (peak of area maximum) as fusing point.But, in the time existing in addition peak area to be more than 80% peak of peak area at maximum area peak, adopt the arithmetic mean of instantaneous value of summit temperature at the summit temperature at this peak and the peak of maximum area as fusing point.
In the substrate resin of formation foamed sheet of the present invention and resin bed, except principal component polyvinyl resin, not hindering in the scope of the object of the invention and effect, can also coordinate the elastomers such as the phenylethylene resin series such as propylene resin, polystyrene, ethylene propylene rubber such as vinyl-vinyl acetate copolymer, polypropylene, propylene-ethylene copolymers etc.And the content of above-mentioned resin is below 50 % by weight in substrate resin, be preferably below 30 % by weight, more preferably below 20 % by weight.
In addition, not hindering in the scope of the object of the invention and effect, in above-mentioned substrate resin, can contain the additives such as functional additive, inorganic filler such as such as bubble conditioning agent, nucleator, antioxidant, heat stabilizer, weather resisting agent, ultra-violet absorber, fire retardant, antiseptic, contraction preventing agent.
The resin bed that forms lamination foamed sheet of the present invention contains polyvinyl resin and Polymer Antistatic Agent 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, preferably 2000～100000, more preferably 5000～60000, particularly preferably 8000～40000.Therefore, this antistatic additive is the Polymer Antistatic Agent distinguishing with the antistatic additive take surfactant as principal component.
Above-mentioned number-average molecular weight is tried to achieve by high-temperature gel permeation chromatography method.For example, in the time that Polymer Antistatic Agent is the hydrophilic resin take polyether ester amides or polyethers as principal component, its number-average molecular weight is the following value of measuring,, make the sample solution concentration of 3mg/ml using o-dichlorohenzene as solvent, and using polystyrene as standard substance, be to measure under the condition of 135 ℃ at column temperature.The kind of above-mentioned solvent, column temperature can be according to the kinds of Polymer Antistatic Agent and appropriate change.
It is 10 that the Polymer Antistatic Agent using in the present invention can be enumerated specific volume resistance 5～10 11hydrophilic resin and the polyolefinic copolymer etc. of Ω cm.
This hydrophilic resin can use PTMEG, polyether diamine, with their polyethers such as modifier, there is the segment of PTMEG as the polyether ester amides of polyether segment forming component, there is the segment of PTMEG as the polyetheramides acid imide of polyether segment forming component, there is the segment of PTMEG as the polyether ester of polyether segment forming component, there is the segment of polyether diamine as the polyetheramides of polyether segment forming component, there is the hydrophilic resin that the segment of PTMEG or polyether diamine contains polyethers as the polyethers carbamate of polyether segment forming component (polyether urethane) etc., in molecule, there are 2～80 that separate with nonionic strand, the preferably cation property copolymer of 3～60 cationic groups, with dicarboxylic acids to there is sulfonyl and glycol or polyethers as must construction unit, and in molecule, there are 2～80, the preferably anionic property polymer of the sulfonyl of 3～60.
In addition, for make Polymer Antistatic Agent and polyvinyl resin compatibility improve, in giving excellent antistatic effect, the effect declining because adding the physical property that causes of antistatic additive can also be inhibited, preferably resin of the same race with polyvinyl resin or that compatibility is high is carried out to the resin that block copolymerization forms, the block copolymer that can to enumerate the number-average molecular weight (Mn) for example with following structure be 2000～60000, described structure is that polyolefinic block and specific volume resistance are 10 5～10 11the block of the above-mentioned hydrophilic resin of the Ω cm structure that alternately bonding forms repeatedly.Wherein, the above-mentioned compatibility excellence of polyethers and polyolefinic block copolymer, is therefore preferred.
Above-mentioned block copolymer has the block of polyolefinic block and hydrophilic resin by being selected from least a kind of key structure that alternately bonding forms repeatedly in ester bond, amido link, ehter bond, amino-formate bond, imide bond.
In more detail, the above-mentioned Polymer Antistatic Agent preferably using in the present invention can be set forth in the composition of recording in Japanese kokai publication hei 3-103466 communique, TOHKEMY 2001-278985 communique.The composition that Japanese kokai publication hei 3-103466 communique is recorded is the composition take the slaine of (I) thermoplastic resin, (II) PEO or the block copolymer that contains poly-ethylene oxide block compositions more than 50 % by weight and the poly-ethylene oxide block composition solid solution (III) and in above-mentioned (II) as principal component.The composition that TOHKEMY 2001-278985 communique is recorded is the block copolymer that the number-average molecular weight (Mn) with following structure is 2000～60000, and described structure is that block and the specific volume resistance of polyolefin (a) is 1 × 10 5～1 × 10 11the block of the hydrophilic resin (b) of the Ω cm structure that alternately bonding forms repeatedly.The block of above-mentioned (a) and block (b) have by being selected from least a kind of key structure that alternately bonding forms repeatedly in ester bond, amido link, ehter bond, amino-formate bond, imide bond.The object lesson of this Polymer Antistatic Agent can be enumerated for example with commercially available materials of trade name such as Mitsui デ ユ Port Application Port リ ケ ミ カ Le Co., Ltd.'s system " SD100 ", Sanyo Chemical Industries, Ltd.'s systems " ペ レ ス タ Star ト 300 ".
Above-mentioned Polymer Antistatic Agent can be distinguished use separately, also can use by multiple combination.
In addition, the fusing point of Polymer Antistatic Agent is preferably 70～270 ℃, and more preferably 80～230 ℃, particularly preferably 80～200 ℃, this angle from performance anti-static function considers it is preferred.
The fusing point of above-mentioned Polymer Antistatic Agent is 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 Antistatic Agent in resin bed of the present invention is 10～50 % by weight of whole resin bed preferably, more preferably 15～40 % by weight, particularly preferably 20～35 % by weight.If this content is too few, likely can not bring into play the desired antistatic property of packaging material as precise electronic instrument.On the other hand, even if this content is too many, although antistatic property without any problem, antistatic property culminates, and forms this aspect variation.
In foamed sheet of the present invention, must not add above-mentioned Polymer Antistatic Agent, but when using the recovery raw material of lamination foamed sheet to cause having added Polymer Antistatic Agent with raw material as foamed sheet, foamed sheet contains Polymer Antistatic Agent.In this case, in order not hinder the foaminess of foamed sheet, the content of Polymer Antistatic Agent is preferably the ratio below 15 weight portions with respect to substrate resin 100 weight portions that form foamed sheet.Further, for the mechanical strength of sustaining layer foam sheet, this content is preferably below 8 weight portions with respect to substrate resin 100 weight portions that form foamed sheet, more preferably below 5 weight portions.By add antistatic additive in foamed sheet, can also expect the further raising of antistatic effect.
The thickness of lamination foamed sheet of the present invention is 0.2～2.0mm.If this thickness is too thin; become insufficient for resiliency, the surface protection of the packed articles such as precise electronic instrument; if thickness is too thick; in the time of the packing of packed article or when lamination foamed sheet is discarded, there is the cost of transportation of problem that lamination foamed sheet volume is large or packing material uneconomical.Consider more preferably 0.3～1.5mm of the thickness of lamination foamed sheet, particularly preferably 0.4～1.3mm, most preferably 0.5～1.2mm from this angle.
The apparent density of lamination foamed sheet of the present invention is 0.02～0.1g/cm 3.In the time that this apparent density is too large, surface protection likely reduces.On the other hand, when this apparent density too hour, likely make the desired mechanical strength such as conformality or compressive strength having of lamination foamed sheet reduce, viscosity (コ シ) is weak, sagging (れ hangs down) of lamination foamed sheet becomes large.From the viewpoint of above-mentioned angle etc., 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 this weight per unit area is little, thin thickness,, in following formation (i), due to concavo-convex also the appearing on resin bed on the thick foamed sheet surface of bubble, has and be difficult to be attached to the effect on packaged body.
Consider from above-mentioned angle, this weight per unit area is preferably 8g/m 2below, more preferably 1～6g/m 2, particularly preferably 1.5～5g/m 2.Make this weight per unit area in above-mentioned scope, can prevent that surface from too becoming sliding and exceed must level or have a too attenuation of resin bed of antistatic behaviour, this adheres to or is preferred from the viewpoint of stable antistatic behaviour at packed article from preventing layer foam sheet.And, as long as realizing in the scope of the object of the invention, effect, though resin bed a little some uneven thickness also have no relations.
The thickness of lamination foamed sheet entirety 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 foamed sheet every 1cm.
Apparent density (the g/cm of lamination foamed sheet of the present invention 3) be the weight (g) of using the test film being cut by the lamination foamed sheet volume (cm divided by this test film 3) numerical value of gained.
In addition, the apparent density (g/cm of the foamed sheet of constituting layer foam sheet 3) be the value obtaining as follows,, deduct the weight (g) of the resin bed of following test film and try to achieve the foamed sheet weight of test film by the weight (g) of test film, deducted by the thickness of lamination foamed sheet following test film resin bed average thickness and try to achieve the foamed sheet thickness of test film, by the weight of this foamed sheet divided by the volume (cm being tried to achieve by the appearance and size of this foamed 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 vertical cross section of the width of the suitable amplification layer foam sheets such as microscope, broad ways is equally spaced measured the thickness of 10 place's resin beds, average thickness using the arithmetic mean of instantaneous value of income value as resin bed, this average thickness is multiplied by the density of the substrate resin that forms 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 the method is limited to the clear and definite situation in interface of resin bed and foamed sheet.
Density (the g/cm of the substrate resin of resin bed 3) can be with forming that each resin density of substrate resin is multiplied by the weight content ratio of each resin and the summation form of the value that calculate is tried to achieve.
And, in the time utilizing said method to be difficult to analytical unit area weight, for the lamination foamed sheet of manufacturing by coextrusion, in extrusion foaming condition, can be by the discharge rate X[kg/ hour of resin bed], the width W [m] of gained lamination foamed sheet and the length of a film L[m/ hour that lamination foamed sheet time per unit is extruded], utilize following formula (1) to calculate the weight per unit area (g/m of resin bed 2).In addition, when utilize extruding layer platen press laminated resin layer on the two sides of foamed sheet, can try to achieve according to the discharge rate of resin bed separately the weight per unit area of each resin bed.
Weight per unit area [g/m 21000X/]=[(L × W)] (1)
Lamination foamed sheet of the present invention, due to as mentioned above, resin bed contains Polymer Antistatic Agent, therefore excellent antistatic property.Specifically, the applied voltage half-life after washing was preferably below 10 seconds, more preferably below 7 seconds, further preferably below 5 seconds.If this applied voltage half-life is below 10 seconds, use by the padded coaming using lamination foamed sheet as precise electronic instruments such as glass substrate for display, packaging material, can prevent that dust from adhering on precise electronic instrument.In addition, though this lamination foamed sheet after washing, the applied voltage half-life also reduces hardly, can bring into play sufficient antistatic behaviour, it,, with current to bring into play the packaging material of antistatic behaviour by surfactant different, can bring into play antistatic behaviour steady in a long-term.And for the lower limit of this applied voltage half-life, little value is more preferred.The lower limit of this applied voltage half-life is probably 0.5 second.
The mensuration of applied voltage half-life in this description be lamination foamed sheet after washing be to measure sample, the value of measuring based on JIS L1094 (1988) A method.Specifically, the test film cutting from lamination foamed sheet (longitudinally 40mm × laterally 40mm × thickness: determination object thing thickness) is joined beaker with together with the water 300ml of 40 ℃, stir and wash for 10 minutes, then test film is taken out from warm water, 23 ℃ of temperature, relative humidity is to place 36 hours under 50% atmosphere, carry out thus the status adjustment of test film, then utilize JIS L1094 (1988) A method, be 1300rpm in turntable (turn table) rotary speed, applied voltage (+) is 10kV, under the additional condition of 30 seconds, try to achieve the applied voltage half-life.
Laminate of the present invention meet 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 foamed sheet is 6～100 μ m, and the average bubble number of thickness direction is below 2;
(ii) polyvinyl resin layer is greater than 115 ℃ and be that 128 ℃ of following and density are 0.910～0.970g/cm by the fusing point of 30～90 % by weight 3the fusing point of polyvinyl resin (a), 0～60 % by weight be that 115 ℃ of following and density are 0.890～0.930g/cm 3polyvinyl resin (b) and the Polymer Antistatic Agent (c) (wherein, (a)+(b)+(c)=100 % by weight) of 10～50 % by weight form;
(iii) polyethylene resin foaming sheet is greater than 115 ℃ and be that 125 ℃ of following and density are 0.910～0.940g/cm by the fusing point of 10～50 % by weight 3the fusing point of polyvinyl resin (d), 50～90 % by weight be that 115 ℃ of following and density are 0.890～0.930g/cm 3polyvinyl resin (b) (wherein, (d)+(b)=100 % by weight) form.
The lamination foamed sheet that meets above-mentioned (i) is the common few foamed sheet of number of bubbles thick, thickness direction of bubble chamber film Thickness Ratio, that is, be the foamed sheet being mainly made up of thick bubble.Meet should (i) foamed sheet on laminated thin and weight per unit area are 8g/m as described above 2in the lamination foamed sheet that following resin bed forms, the concavo-convex resin layer surface that appears at of thick bubble, the contact area of this lamination foamed sheet and packaged body is little, and also high for the rigidity of the compression of bubble etc.Therefore, although lamination foamed sheet of the present invention in surface laminated the resin bed that contains more Polymer Antistatic Agent, lamination foamed sheet self is difficult to be attached on packaged body.Consider from above-mentioned viewpoint, this bubble thickness is preferably 6～70 μ m, more preferably 7～50 μ m, and particularly preferably 10～35 μ m, this number of bubbles is preferably below 1.7, more preferably below 1.5.In addition, the bubble diameter that meets the lamination foamed sheet of above-mentioned (i) is compared greatly with existing foamed sheet, and the number of bubbles of thickness direction is also few, therefore light transmission is high, while use as packaging material, can improve sense of vision, be able to the degree of confirming that packed article is what.
In the present invention, (μ m) can utilize following formula to try to achieve to average bubble thickness th.
th(μm)＝(0.46/ρp)ρf·D
Wherein, mean air bubble diameter that D is foamed sheet (μ m), the density (g/cm of the substrate resin that ρ p is foamed sheet 3), the apparent density (g/cm that ρ f is foamed sheet 3).
And the mean air bubble diameter D of foamed sheet is based on ASTM D3576-77, the value calculating by following formula.
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 foamed sheet 3) can try to achieve as got off, that is, cut foamed sheet by lamination foamed sheet in the mode of not resinous layer, the foamed sheet cutting is utilized to hot-press arrangement de-soak and solidization (ソ リ Star De), measure the density of gained sample.In addition, can also be by each resin density (g/cm of the substrate resin of formation foamed sheet 3) the summation form of the value that calculates to be multiplied by the weight content ratio of each resin by the density of each resin that forms substrate resin tries to achieve.
In addition, the density p p (g/cm of the substrate resin of foamed sheet 3) can calculate according to density and the thickness of the resin bed of the thickness of the apparent density of lamination foamed sheet and foamed sheet, lamination foamed sheet.
In addition, the apparent density ρ f (g/cm of foamed sheet 3) can as following, try to achieve, , the weight per unit area that deducts resin bed by the weight per unit area of lamination foamed sheet calculates the weight per unit area of foamed sheet, then use the thickness of the foamed sheet that the thickness that deducts above-mentioned resin bed from the thickness of lamination foamed sheet obtains except the weight per unit area of foamed sheet, and carry out unit conversion and try to achieve, by using, by lamination foamed sheet, by hot-press arrangement de-soak, the density of the sample that solidification obtains is multiplied by the thickness of lamination foamed sheet and carries out unit conversion and try to achieve the weight per unit area of described lamination foamed sheet, the weight per unit area of described resin bed is by being multiplied by the thickness of resin bed and carrying out unit conversion and try to achieve by the density of resin bed.
This average bubble thickness can utilize the apparent density of foamed sheet and the mean air bubble diameter of foamed sheet to regulate.The change of the apparent density of foamed sheet can regulate by the addition of blowing agent.
On the other hand, die head internal pressure condition when the mean air bubble diameter of foamed sheet can be by the kind of blowing agent or bubble conditioning agent or addition, extrusion foaming etc. regulates.For example, when the kind of blowing agent and addition are a timing, the pressure can be by extrusion foaming time in die head and the addition of bubble conditioning agent regulate mean air bubble diameter.Specifically, under the kind of blowing agent and addition are certain condition, increase the pressure in die head and/or increase the amount of bubble conditioning agent, more can reduce the mean air bubble diameter of foamed sheet.
Being determined as follows of the number of bubbles of above-mentioned thickness direction carried out: the whole width range broad ways at foamed sheet determines that at interval of 1cm a place locates, obtain the number of bubbles (individual) of the determined thickness locating (mm) and this thickness direction that locates, by the number of bubbles of the thickness direction that respectively locates (individual) divided by this thickness locating (mm), the number of bubbles (individual/mm) using the arithmetic mean of instantaneous value of the number of bubbles of the tried to achieve thickness direction that respectively locates as thickness direction of the present invention.And the above-mentioned number of bubbles that respectively locates thickness direction is that the thickness direction by locating is drawn straight line, and the number of the counting bubble crossing with this straight line value of trying to achieve.
Meet in the lamination foamed sheet of above-mentioned (ii), its resin bed is greater than 115 ℃ and be that 128 ℃ of following and density are 0.910～0.970g/cm by the fusing point of 30～90 % by weight 3polyvinyl resin (a), the density of 0～60 % by weight be 0.890～0.930g/cm 3and fusing point is that the Polymer Antistatic Agent (c) (wherein, (a)+(b)+(c)=100 % by weight) of 115 ℃ of following polyvinyl resins (b) and 10～50 % by weight forms.
The excellent rigidity of polyvinyl resin (a), thereby the resin bed that contains this polyvinyl resin (a) is rich in rigidity, heat resistance.Therefore, meet should (ii) lamination foamed sheet there is excellent antistatic behaviour, there is on the whole sufficient rigidity simultaneously, therefore wrap in the operation on packaged body, the operation of tearing becomes easy.In addition, the heat resistance that meets the lamination foamed sheet entirety of being somebody's turn to do (ii) also improves.
In addition, this lamination foamed sheet meets specific apparent density and thickness condition, therefore the resin of laminate entirety composition is, in whole polyvinyl resins, contains a small amount of polyvinyl resin (a) that the polyvinyl resin (a) because being included in resin bed causes.
Therefore, the lamination foamed sheet of above-mentioned for meeting (ii), on the DSC curve obtaining as described below, as shown in Figure 1 at the high high temperature side of the summit temperature than main melting peak and be more than 110 ℃ main melting peak regions, occurred the protuberance being caused by polyvinyl resin (a), described DSC curve is the curve by obtaining take laminate as sample, by carry out the heat stream differential scanning calorimetry of 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 this DSC curve being carried out to the existence that second-order differential confirms flex point with incidental software of DSC determinator etc.
And, in the time also containing polyvinyl resin (a) in the polyvinyl resin that is forming foamed sheet, also has following situation,, in above-mentioned DSC curve, to cover and hide than the protuberance of the high high temperature side of main melting peak summit temperature and the appearance of more than 110 ℃ regions, and occurring melting peak.
Above-mentioned polyvinyl resin (a) further preferably fusing point is greater than 115 ℃ and be that 125 ℃ of following and density are 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).
From have expectation rigidity angle consider, the content of polyvinyl resin (a) is preferably 40～90 % by weight, more preferably 45～85 % by weight.
In the time that the content of above-mentioned polyvinyl resin (b) is too much, the content of polyvinyl resin (a) tails off, therefore the rigidity deficiency of resin bed, by lamination foamed sheet wrap in the operation on packaged body, the workability of the operation of tearing can not improve as expected.Consider from above-mentioned angle, the content of polyvinyl resin (b) is preferably 0～45 % by weight, more preferably 0～30 % by weight.
Above-mentioned polyvinyl resin (b) can be enumerated so-called chain low density polyethylene (LDPE).
In the time that the content of above-mentioned Polymer Antistatic Agent (c) is very few, likely can not bring into play the desired antistatic property of packaging material as precise electronic instrument.On the other hand, even if this content is too much, although antistatic property aspect without any problem, antistatic property culminates, thus cost aspect variation.Consider from above-mentioned angle, the content of Polymer Antistatic Agent (c) is preferably 15～40 % by weight, more preferably 20～35 % by weight.
Meet in the lamination foamed sheet of above-mentioned (iii), its foamed sheet is greater than 115 ℃ and be that 125 ℃ of following and density are 0.910～0.940g/cm by the fusing point of 10～50 % by weight 3polyvinyl resin (d) and the density of 50～90 % by weight be 0.890～0.930g/cm 3and fusing point is that 115 ℃ of following polyvinyl resins (b) (wherein, (d)+(b)=100 % by weight) form.
Meet in the lamination foamed sheet of above-mentioned (iii), its foamed sheet contains fusing point and is greater than 115 ℃ and be that 125 ℃ of following and density are 0.910～0.940g/cm 3polyvinyl resin (d).Thereby because polyvinyl resin contained in foamed sheet (d) causes the polyvinyl resin (d) that contains more amount in the resin composition of whole lamination foamed sheet.
Polyvinyl resin (d) has excellent rigidity, and the foamed sheet that therefore contains polyvinyl resin (d) is rich in rigidity.Therefore, the lamination foamed sheet that meets above-mentioned (iii) has sufficient rigidity on the whole, wraps in the operation on packaged body, the operation of tearing becomes easily, can manufacture good foamed sheet.
Consider from above-mentioned viewpoint, the content of polyvinyl resin (d) is preferably 20～50 % by weight, more preferably 25～45 % by weight, and the content of polyvinyl resin (b) is preferably 50～80 % by weight, more preferably 55～75 % by weight.
Above-mentioned polyvinyl resin (d) can be enumerated so-called straight chain shape low density polyethylene (LDPE).
In the lamination foamed sheet that meets above-mentioned (iii), polyethylene resin foaming sheet contains fusing point and is greater than 115 ℃ and be that 125 ℃ of following and density are 0.910～0.940g/cm 3polyvinyl resin (d), therefore on the DSC curve obtaining as following, as shown in Figure 2 at the high high temperature side of the summit temperature than main melting peak and be more than 110 ℃ main melting peak regions, occurred other melting peaks that caused by polyvinyl resin (d), described DSC curve is the curve by obtaining take laminate as sample, by carry out the heat stream differential scanning calorimetry of 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 foamed sheet of the present invention preferably meets above-mentioned condition (i) and above-mentioned condition (ii) simultaneously, and this lamination foamed sheet is formed by the foamed sheet that is rich in the resin bed of rigidity and be mainly made up of thick bubble.Therefore, the contact area of this lamination foamed sheet and packaged body is little, is difficult to be attached on packaged body, has sufficient rigidity simultaneously, and the operation, the operation of tearing etc. that wrap on packaged body become easily, and excellent antistatic property.
In addition, lamination foamed sheet of the present invention preferably meets above-mentioned condition (i) and above-mentioned condition (iii) simultaneously.And, meet at the same time in the lamination foamed sheet of above-mentioned condition (i) and above-mentioned condition (iii), also further comprise the lamination foamed sheet that simultaneously meets above-mentioned condition (i), above-mentioned condition (ii) and above-mentioned condition (iii).The lamination foamed sheet that simultaneously meets above-mentioned condition (i) and above-mentioned condition (iii) has the resin bed of excellent antistatic property and is rich in rigidity and the formation of the foamed sheet that bubble is thick.Therefore, the contact area of this lamination foamed sheet and packaged body is little, is difficult to be attached on packaged body, has sufficient rigidity simultaneously, and the operation, the operation of tearing etc. that wrap on packaged body become easily, and excellent antistatic property.
And the resin bed being arranged on the foamed sheet of satisfy condition (iii) preferably meets above-mentioned condition (i).
Then, the manufacture method of laminated polyethylene resin foaming sheet of the present invention is described.
As the manufacture method of lamination foamed sheet of the present invention, preferably adopt the coextrusion foaming that the molten resin of the molten resin of formation resin bed and formation foamed sheet is flowed and carried out extrusion foaming in the pressing of die head internal layer.This coextrusion foaming method can make the thickness attenuation of resin bed, can obtain the high lamination foamed sheet of bonding force between resin bed and foamed sheet simultaneously, is therefore preferred.But, in the present invention, also can apply by extrusion foaming and manufacture foamed sheet, utilize extruding layer to be pressed in the current known method such as laminated resin layer on foamed sheet.
Manufacturing by coextrusion foaming in the method for lamination foamed sheet of sheet, there is the method that uses coextrusion flat die to foam with sheet coextrusion and make platy layer foam sheet, foam with tubular coextrusion by coextrusion annular die and the method etc. that obtains the lamination foaming body of tubular, then cut this tubular foaming body and form the lamination foamed sheet of sheet.Wherein, using coextrusion can easily manufacture width by the method for annular die is wide lamination foamed sheet more than 1000mm, is therefore preferred method.
Below the situation that uses above-mentioned annular die to carry out coextrusion is elaborated.
First, as shown in Figure 6, the polyvinyl resin that comprises polyvinyl resin (a) or polyvinyl resin (b) etc. and Polymer Antistatic Agent (C) are supplied to resin bed formation with in extruder 11, carry out heating and melting and mixing after, add as required volatile plasticizer (E1) melting mixing, make polyvinyl resin layer and form with resin melt (F1).The additives (G) such as the bubble conditioning agent of the polyvinyl resin that comprises polyvinyl resin (b) or straight chain shaped polyethylene resin (d) etc. and interpolation are as required supplied to foamed sheet forms with in extruder 12 simultaneously, heating and melting and mixing after, 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 coextrusion method, can in annular die, resin bed be formed with resin melt (F1) and foamed sheet and form and use resin melt (F2) lamination, also the above-mentioned fused mass of extruding can be carried out to lamination in the outside of die head exit.
As the volatile plasticizer (E1) of interpolation in resin melt (F1) is used in above-mentioned resin bed formation, use function, the while that the melt viscosity with resin melt of making (F1) reduces after formation polyvinyl resin layer (J), volatilized by this polyvinyl resin layer and be not present in the plasticizer in resin bed.By add volatile plasticizer (E1) in resin melt, can be in the time that lamination foamed sheet be carried out to coextrusion, make resin bed form the extrusion temperature of using resin melt (F2) with the extrusion temperature of resin melt (F1) close to foamed sheet formation, can significantly improve the melting percentage elongation of the resin bed (J) of soft state simultaneously.Like this, when the bubble of foamed sheet (I) is difficult to because of foaming, the heat of resin bed is destroyed, and elongation when foamed sheet (I) foaming is followed in the elongation of this resin bed (J), therefore can prevent that the be full of cracks being caused by the elongation deficiency of resin bed (J) from occurring.
Volatile plasticizer (E1) preferably uses and is selected from carbon number is in 3～7 aliphatic hydrocarbon or ester ring type hydrocarbon, the carbon number aliphatic alcohol that is 1～4 or the carbon number fatty ether that is 2～8 a kind or two or more.In the time using the so low material of volatility of so-called lubricant (sliding drug) to replace volatile plasticizer (E1), this lubricant remains in resin bed (J), has the surperficial situation of polluting packaged body.With respect to this, volatile plasticizer (E1) from can make efficiently the resin plasticized of resin bed (J), 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 such as 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, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl-butyl ether, ethyl isobutyl ether, ethyl pentyl group ether, ethyl isoamyl ether, vinyl ethers, allyl ether, methyl vinyl ether, methallyl ether, ethyl vinyl ether, ethyl allyl ether.
Consider from the aspect that is easy to volatilization from resin bed (J), the 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, as long as gained lamination foamed sheet (H) is placed after coextrusion, utilize heat after just coextrusion or and then at room temperature see through afterwards gas, volatile plasticizer (E1) can be waved loose removing naturally from the resin bed of lamination foamed sheet (J).The lower limit of the boiling point of this volatile plasticizer (E1) is probably-50 ℃.
The addition of volatile plasticizer (E1) is preferably 5 weight portion～50 weight portions with respect to substrate resin 100 weight portions of mixing thing that are mainly polyvinyl resin and Polymer Antistatic Agent (C).If the addition of volatile plasticizer (E1) is more than 5 weight portions, the heating that the shearing of the polyvinyl resin etc. that can suppress to form resin bed (J) when mixing causes, foamed sheet that therefore can inhibition layer pressurizing resin layer (J) forms the rising (temperature decreasing effect) with the resin temperature of resin melt (F2).Therefore, forming by resin melt and carry out coextrusion when foaming with resin bed, can prevent that foamed sheet from forming while foaming by resin melt (F2) drawbacks such as bubble breaks.Foamed sheet forms to be extruded and forms foamed sheet (I) by resin melt (F2) under normal pressure from die head.
Further, volatile plasticizer (E1) also has following effect, draftability raising (draftability is improved effect), the even thickness that makes resin bed (J) and thin that, can make resin bed form in the time forming the resin bed of lamination foamed sheet, to follow foamed sheet by resin melt (F1).Consider from above-mentioned angle, more than the addition of volatile plasticizer (E1) is preferably 7 weight portions, more preferably more than 10 weight portions.
On the other hand, in the time that the addition of volatile plasticizer (E1) is too much, there is following possibility,, the physical property that causes resin bed (J) self reduces, or volatile plasticizer (E1) can not fully be dissolved in resin bed and form with in resin melt (F1), volatile plasticizer being sprayed from die lip, or too become large in the thickness thickness of the upper perforate of resin bed (J) or resin bed.Consider from above-mentioned angle, the addition of volatile plasticizer (E1) is preferably below 40 weight portions, more preferably below 30 weight portions, further preferably below 25 weight portions.By making the addition of volatile plasticizer (E1) in above-mentioned scope, can guarantee coextrusion time, resin bed formation improves effect by sufficient temperature decreasing effect and the draftability of resin melt.
In addition, form with in resin melt (F1) for resin bed, not damaging in the scope of the object of the invention, also can in the resin that forms this fused mass (F1), add various additives.Various additives can be enumerated such as antioxidant, heat stabilizer, weather resisting agent, ultra-violet absorber, fire retardant, filler, antiseptic etc.Addition now can suitably determine according to the object of additive, effect, but it is preferably below 10 weight portions separately with respect to substrate resin 100 weight portions, more preferably below 5 weight portions, particularly preferably below 3 weight portions.
As forming at above-mentioned foamed sheet the physical blowing agent (E2) adding with in resin melt (F2), can enumerate the chlorinated hydrocabons, 1 such as the clicyclic hydrocarbons such as aliphatic hydrocarbon, pentamethylene, cyclohexane, chloromethanes, chloroethanes such as such as propane, normal butane, iso-butane, pentane, isopentane, n-hexane, isohexane, 1,2,2-HFC-134a, 1, organic physical blowing agents such as fluorinated hydrocarbons such as 1-Difluoroethane, the inorganic physical blowing agents such as nitrogen, carbon dioxide, air, water.According to circumstances, also can use the decomposition-type foaming agents such as Celogen Az.Above-mentioned physical blowing agent can mix two or more and share.Wherein, from considering with the compatibility of polyvinyl resin, the angle of foaminess, particularly preferably organic physical blowing agent, the wherein especially preferred blowing agent take normal butane, iso-butane or their mixture as principal component.
The addition of physical blowing agent (E2) can regulate according to the kind of blowing agent, object apparent density.The addition of bubble conditioning agent regulates according to object bubble diameter in addition.For example, for the butane mixture by iso-butane 30 % by weight and normal butane 70 % by weight obtains the lamination foamed sheet of above-mentioned density range as blowing agent, the addition of butane mixture is 3～30 weight portions with respect to every 100 weight portion substrate resins, be preferably 4～20 weight portions, more preferably 6～18 weight portions.
As forming the main Types with the additive (G) adding in resin melt (F2) at above-mentioned foamed sheet, conventionally can add bubble conditioning agent.Bubble conditioning agent can use any one in organic bubble conditioning agent, inorganic bubble conditioning agent.Inorganic bubble conditioning agent can be enumerated the borate metal salts such as Firebrake ZB, antifungin, borax, sodium chloride, aluminium hydroxide, talcum, zeolite, silica, calcium carbonate, sodium acid carbonate etc.Organic bubble conditioning agent can be enumerated phosphoric acid-2 in addition, 2-di-2-ethylhexylphosphine oxide (4,6-tert-butyl-phenyl) sodium, Sodium Benzoate, calcium benzoate, aluminum benzoate, odium stearate etc.In addition, also can use using alkali salt and the material that sodium acid carbonate is formed by combining etc. of citric acid and sodium acid carbonate, citric acid as bubble conditioning agent.These bubble conditioning agents also can mix two or more to use.
The addition of bubble conditioning agent is 0.01～3 weight portion, is preferably 0.03～1 weight portion with respect to every 100 weight portion substrate resins.The lamination foamed sheet of above-mentioned in order to be met (i), for example, in considering the adjustment of resin bed weight per unit area and thickness, the apparent density etc. of foamed sheet, make the average bubble number of mean air bubble diameter, thickness direction meet above-mentioned (i) to regulate the addition of bubble conditioning agent.
As mentioned above, not damaging in the scope of the object of the invention and effect, can polyethylene resin foaming sheet form with styrene in resin melt (F2) be other the additive such as resin or heat stabilizer such as resin or elastomer.
As described above, in the time out manufacturing lamination foamed sheet by co-extrusion, forming resin bed with extruder 11 forms with resin melt (F1), forming foamed sheet with extruder 12 forms with resin melt (F2), resin melt (F2) is adjusted to foamable temperature extruder 12 is interior, extruder 11 interior by resin melt (F1) be adjusted to can coextrusion temperature, then resin bed is formed with resin melt (F1) and foamed sheet and form and use resin melt (F2) to import coextrusion with in annular die 13, by both laminations, further be coextruded in atmosphere, foamed sheet is formed with resin melt (F2) foaming, be formed on the tubular layer Hair Fixer foam that on foaming body, laminated resin layer forms, the inner surface of this tubular layer Hair Fixer foam is carried out cooling along cylindric cooling device, while pulls while cuts, can obtain thus lamination foamed sheet.Wherein, resin bed form with resin melt (F1) and foamed sheet form with the lamination of resin melt (F2) can be as described above at the inside of annular die lamination, 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 using in extrusion foaming field at present.
In addition, for the value that makes the average bubble number of thickness direction in above-mentioned condition of the present invention (i) diminishes, can regulate by as described below, , the addition of bubble conditioning agent is adjusted few, there is the protuberance (リ Star プ) of parallel back-up ring (ラ Application De) in the setting of annular die front end, pin foamed sheet on one side and form the expansion (swelling) to thickness direction by resin melt, extrude on one side, can prevent thus the generation of abscess striped (コ Le ゲ mono-ト), in parallel back-up ring, its heating is sheared and made to foamed sheet formation a little by resin melt simultaneously, realize the combination between bubble.
Embodiment
Below, based on embodiment, the present invention is described in further detail.But, the invention is not restricted to embodiment.
Bubble conditioning agent uses the bubble conditioning agent masterbatch that coordinates talcum (Ishihara Sangyo Kaisha, Ltd. produces, and commodity are called (Ha イ Off イ ラ mono-#12)) 20 % by weight to form with respect to ldpe resin 80 % by weight.
The kind of the polyvinyl resin using when forming resin bed and forming foamed sheet, manufacturer, density, fusing point, MFI (190 ℃, load 21.18N) are shown in table 1.
Polymer Antistatic Agent uses " ペ レ ス タ Star ト 300 " (fusing point is 136 ℃, and number-average molecular weight is 14000, and density is 990g/L) take polyethers polypropylene block copolymer as principal component of Sanyo Chemical Industries, Ltd.'s system.
Physical blowing agent uses the mixed butanes being made up of normal butane 70 % by weight and iso-butane 30 % by weight.
Embodiment 1～11, comparative example 1～3
As the extruder (12) that is used to form polyethylene resin foaming sheet, the series connection extruder that the second extruder that the first extruder that use is 90mm by diameter and diameter are 120mm forms, the extruder (11) that is used to form polyvinyl resin layer uses the 3rd extruder that diameter is 50mm, L/D=50.Further, with connecting the second extruder and the 3rd extruder outlet separately in annular die, each molten resin can be carried out in annular die to lamination in coextrusion.
To be supplied in the 3rd extruder by the polyvinyl resin and the Polymer Antistatic Agent that coordinate shown in table 2, and heat mixing, be pressed into the above-mentioned mixed butanes of the amount of Table 2 as volatile plasticizer, further mixing, be adjusted to the extrusion resin temperature shown in table 2 and make resin bed formation resin melt, this resin bed is formed and imported in coextrusion use annular die with the discharge rate that can form the weight per unit area of " resin bed/foamed sheet/resin bed " shown in table 2 and form by resin melt.
Meanwhile, add to the raw material of the first extruder of series connection extruder the polyvinyl resin and the bubble conditioning agent masterbatch that shown in mouthful supply schedule 2, coordinate, add hot milling, form the molten resin mixture that is adjusted to approximately 200 ℃.Then, toward the physical blowing agent that is pressed into the amount of Table 2 in this molten resin mixture, then be supplied in second extruder in the downstream that is connected to above-mentioned the first extruder, be adjusted to the extrusion resin temperature producing foamed sheet formation resin melt shown in table 2, this foamed sheet is formed and imported in above-mentioned coextrusion use annular die with the discharge rate that can form the weight per unit area of " resin bed/foamed sheet/resin bed " shown in table 2 and form by resin melt.
Form outside and the inner side by resin melt at the foamed sheet that imports to the resin flow path of coextrusion in annular die and in die head, form with resin melt lamination interflow importing to the resin bed of coextrusion in annular die, and the layered product of fused mass is expressed into atmosphere from die head, form the tubular layer Hair Fixer foam of the 3-tier architecture being formed by resin bed/foaming body/resin bed.Pull while cut along the tubular layer Hair Fixer foam of extruding being carried out to cooling cylindric cooling device (reel (mandrel)), obtain lamination foamed sheet.
Each physical property of the lamination foamed sheet obtaining in embodiment and comparative example is shown in table 3.
The mensuration of the mean air bubble diameter in table 3, the average bubble number of thickness direction, bubble thickness, applied voltage is to utilize said method to measure respectively 5 places to each lamination foamed sheet, using the arithmetic mean of instantaneous value of measured value as measurement result separately.
Peel strength in table 3 be determined as follows described carrying out.
Foamed sheet is cut into horizontal 40mm × longitudinally size of 76mm.Then, by cut foamed sheet and glass sheet under the atmosphere of temperature 60 C, humidity 50%RH with 130g/cm 2load pressing 18 hours.Measure the load when being pressed together under these conditions foamed sheet on glass sheet and peeling off by 90 ° of disbonded tests with the speed of 100mm/min.Each lamination foamed sheet is measured respectively 6 places, using the arithmetic mean of instantaneous value of measured value as peel strength (gf/40mm).
The measurement result of peel strength is evaluated by standard shown below.
◎: be less than 0.7gf/40mm
Zero: 0.7gf/40mm is above and be less than 1.3gf/40mm
△: 1.3gf/40mm is above and be less than 1.9gf/40mm
×: more than 1.9gf/40mm
Confficient of static friction in table 3 is the value of measuring according to JIS K7125-1999.First, cut and be of a size of horizontal 100mm × longitudinally slide plate of 100mm from lamination foamed sheet.In addition, cut and be of a size of horizontal 130mm × longitudinally test film of 200mm from the foamed 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 to produce on test film.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 the mensuration of coefficient of friction according to said determination order, using start peak load when fricting movement divided by the value of the load gained of slide plate the value as confficient of static friction.And said determination is carrying out at 5 places respectively between the surface of lamination foamed sheet and between the back side, using 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 evaluated by standard shown below.
◎: be less than 0.7
Zero: 0.7 above and be 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 Polymer Antistatic Agent forms, thickness at least one side upper strata crimping 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 meet 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 foamed sheet is 6～100 μ m, and the average bubble number of thickness direction is below 2;
(ii) polyvinyl resin layer is greater than 115 ℃ and be that 128 ℃ of following and density are 0.910～0.970g/cm by the fusing point of 30～90 % by weight 3the fusing point of polyvinyl resin (a), 0～60 % by weight be that 115 ℃ of following and density are 0.890～0.930g/cm 3polyvinyl resin (b) and the Polymer Antistatic Agent (c) of 10～50 % by weight form, wherein, (a)+(b)+(c)=100 % by weight;
(iii) polyethylene resin foaming sheet is greater than 115 ℃ and be that 125 ℃ of following and density are 0.910～0.940g/cm by the fusing point of 10～50 % by weight 3the fusing point of polyvinyl resin (d), 50～90 % by weight be that 115 ℃ of following and density are 0.890～0.930g/cm 3polyvinyl resin (b) form, wherein, (d)+(b)=100 % by weight.
2. laminated polyethylene resin foaming sheet according to claim 1, is characterized in that, meets above-mentioned condition (i) simultaneously and is selected from above-mentioned condition (ii) and at least a kind of condition of above-mentioned 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 foamed sheet is below 10 seconds.
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KR20100107410A (en) 2010-10-05
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JP2010247529A (en) 2010-11-04
TW201105504A (en) 2011-02-16

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