CN108699276A - Polyolefin foam sheet, its manufacturing method and adhesive tape - Google Patents

Polyolefin foam sheet, its manufacturing method and adhesive tape Download PDF

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Publication number
CN108699276A
CN108699276A CN201780014835.4A CN201780014835A CN108699276A CN 108699276 A CN108699276 A CN 108699276A CN 201780014835 A CN201780014835 A CN 201780014835A CN 108699276 A CN108699276 A CN 108699276A
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China
Prior art keywords
foam sheet
polyolefin foam
sheet
expandable composition
resin
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Inventor
永井健人
永井麻美
矢原和幸
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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Publication of CN108699276A publication Critical patent/CN108699276A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22After-treatment of expandable particles; Forming foamed products
    • C08J9/228Forming foamed products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/16Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • C09J7/26Porous or cellular plastics
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04Homopolymers or copolymers of ethene
    • C08J2323/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/066LDPE (radical process)
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00Polymer mixtures characterised by way of preparation
    • C08L2314/06Metallocene or single site catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)

Abstract

The polyolefin foam sheet of the present invention makes comprising vistanex and crosslinked expandable composition foaming has occurred and is formed, and average molecular weight is 15000~30000 between the crosslinking points in aforementioned expandable composition.Through the invention, even if the foam sheet with high flexibility, durability can be provided if in the case where sheet material to be thinned.

Description

Polyolefin foam sheet, its manufacturing method and adhesive tape
Technical field
The present invention relates to polyolefin foam sheet, its manufacturing method and adhesive tapes with polyolefin foam sheet.
Background technology
In the electronic equipments such as mobile phone, camera, game machine, electronic notebook, PC, use by foaming The sealing material or impact absorbing material and using foam sheet as adhesive tape of base material etc. that sheet material is formed.For example, for upper For the display device used in the electronic equipment stated, in general, with the knot for being provided with protection panels on the display panels such as LCD Structure uses to be bonded the protection panels with the frame part on the outside of display panel using foam sheet as the adhesive tape of base material.
In the past, as can be in the foam sheet that electronic equipment internal uses, it is known that make the hair for including thermal decomposable foaming agent Crosslinked polyolefin resin foam sheet is (for example, with reference to patent obtained from bubble property polyolefin-based resins sheet material foams and is crosslinked Document 1).
Existing technical literature
Patent document
Patent document 1:International Publication 2005/007731
Invention content
Problems to be solved by the invention
In addition, nowadays, the miniaturization of electronic equipment is in progress, on the other hand, the multifunction of various parts is also in progress, electricity The limitation in the space inside gas equipment becomes larger.For example, for the frame part on the outside of display panel, since electronics is set The enlargement of standby miniaturization and display device, causes space to become narrow gradually.Therefore, for foam sheet, not only for Thicker foam sheet requires high flexibility, durability, and in the case where being thinned, and also requires Gao Rou Soft, durability.
The present invention makes in view of the foregoing, even if project is to provide one kind as being thinned sheet material In the case of, it may have high flexibility, durability foam sheet.
Means for solving the problems
The present invention provides following [1]~[10].
[1]A kind of polyolefin foam sheet is to make comprising vistanex and crosslinked foaminess group has occurred Close object foaming and formed, between the crosslinking points in aforementioned expandable composition average molecular weight be 15000~30000.
[2]According to Shang Shu [1]The polyolefin foam sheet, wherein aforementioned polyolefins resin is polyvinyl resin.
[3]According to Shang Shu [2]The polyolefin foam sheet, wherein aforementioned polyolefins resin is with metallocene Close straight-chain low density polyethylene (LDPE) obtained by the polymerization catalyst polymerization of object.
[4]According to Shang Shu [1]~[3]Any one of described in polyolefin foam sheet, the degree of cross linking be 20~70 matter Measure %.
[5]According to Shang Shu [1]~[4]Any one of described in polyolefin foam sheet, impact resistance evaluation result exists In the range of 25~50cm, and 25% compressive strength is 10~2,000kPa.
[6]According to Shang Shu [1]~[5]Any one of described in polyolefin foam sheet, thickness be 0.02~0.8mm.
[7]According to Shang Shu [1]~[6]Any one of described in polyolefin foam sheet, expansion ratio be 1.2~ 8cm3/g。
[8]According to Shang Shu [1]~[7]Any one of described in polyolefin foam sheet, be make also include thermal decomposition The expandable composition of type foaming agent foams and is formed.
[9]Shang Shu [1]~[8]Any one of described in polyolefin foam sheet manufacturing method, wherein will include poly- It olefin resin and thermal decomposable foaming agent and crosslinked expandable composition has occurred is heated, and make aforementioned thermal decomposition Type foaming agent foam.
[10]A kind of adhesive tape has Shang Shu [1]~[8]Any one of described in polyolefin foam sheet and The adhesive phase being arranged in at least one side of aforementioned polyolefins system foam sheet.
The effect of invention
By means of the invention it is possible to provide even if in that case of being thinned sheet material, it may have high flexibility, durable The foam sheet of property.
Description of the drawings
Fig. 1 is the schematic diagram of impact resistance experimental rig.
Fig. 2 is the definition graph of interlaminar strength assay method.
Specific implementation mode
Hereinafter, explaining the present invention in detail using embodiment.
[Polyolefin Fa Paopiancai ]
Polyolefin foam sheet of the present invention is to make to include polyolefin tree (hereinafter, also referred to as " foam sheet ") It fat and has occurred the foaming of crosslinked expandable composition and is formed, the crosslinking in crosslinked expandable composition has occurred Average molecular weight is 15000~30000 between point.
In the present invention, when average molecular weight is less than 15000 or is more than 30000 between crosslinking points, impact resistance, interlaminar strength etc. Decline, durability becomes inadequate.In addition, desired range is not achieved in compressive strength, it is difficult to obtain having suitable soft The foam sheet of property.
In addition, from the viewpoint of keeping durability and flexibility excellent, between crosslinking points average molecular weight be preferably 20000~ 29000, more preferably 23000~29000.
(vistanex)
About the vistanex that can be used in foam sheet, polyvinyl resin, acrylic resin, ethylene-can be enumerated Vinyl acetate copolymer etc., in these, preferred polyvinyl resin.
As polyvinyl resin, can enumerate with Ziegler-Natta compound, metallocene compound, chromium oxide compounds etc. The polymerization catalyst of polyvinyl resin obtained from polymerization catalyst polymerization, preferable use metallocene compound polymerize and obtains The polyvinyl resin arrived.
In addition, as polyvinyl resin, preferred straight-chain low density polyethylene (LDPE).By using straight-chain low density polyethylene Alkene obtains high flexibility so as to the foam sheet that makes, and makes it possible the sheet of foam sheet.The straight-chain Low density polyethylene (LDPE) is more preferably the straight-chain low density polyethylene (LDPE) obtained using polymerization catalysts such as metallocene compounds.Separately Outside, straight-chain low density polyethylene (LDPE) more preferably by by ethylene (be 75 mass % or more for example, relative to whole amount of monomer, Preferably 90 mass % or more) with straight-chain low density polyethylene (LDPE) obtained by a small amount of alpha-olefin copolymer as needed.
As alpha-olefin, specifically, propylene, 1- butylene, 1- amylenes, 4-methyl-1-pentene, 1- hexenes, 1- can be enumerated Heptene and 1- octenes etc..Wherein, the preferred alpha-olefin of carbon atom number 4~10.
Polyvinyl resin, straight-chain low density polyethylene (LDPE) as escribed above density be preferably 0.870~0.910g/cm3, More preferably 0.875~0.907g/cm3, further preferably 0.880~0.905g/cm3.As polyvinyl resin, can also make With a variety of polyvinyl resins, in addition, can also add the polyvinyl resin other than above-mentioned density range.
In the present invention, by polyvinyl resin obtained by the polymerization catalyst of metallocene compound will be used to polymerize, especially Straight-chain low density polyethylene (LDPE) is crosslinked with the aftermentioned degree of cross linking, to which be easy will be on average molecular weight be adjusted between crosslinking points The range stated.
(metallocene compound)
As metallocene compound, can enumerate with the structure that transition metal is clamped with the unsaturated compound of pi-electron system The compounds such as bis- (cyclopentadienyl group) metal complexes.More specifically, it can enumerate in titanium, zirconium, nickel, palladium, hafnium and platinum etc. four On the transition metal of valence, 1 or 2 or more cyclopentadienyl rings or its analog are as chemical combination existing for ligand (ligand) Object.
For metallocene compound, the uniform properties of active site, each active site activity degree having the same.Due to making The high uniformity of molecular weight, molecular weight distribution, composition, the composition distribution of polymer synthesized with metallocene compound etc., therefore, In the case of comprising using the sheet material of the polymer of metallocene compound synthesis crosslinked, crosslinking equably carries out.By equably The sheet material being crosslinked equably foams, thus the size of bubble diameter is also easy to become uniform.In addition, due to can equably draw It stretches, therefore, the thickness of foam sheet can be made uniform.
As ligand, can enumerate such as cyclopentadienyl rings, indenyl rings.These ring type compounds can by alkyl, take For alkyl or hydrocarbon-substitution metalloid (metalloid) base substitution.As alkyl, can enumerate for example methyl, ethyl, various propyl, It is various butyl, various amyls, various hexyls, 2- ethylhexyls, various heptyl, various octyls, various nonyls, various decyls, each Kind cetyl, phenyl etc..It should be noted that so-called " various ", refer to including just, secondary, uncle, it is different including various isomeries Body.
In addition, it is possible to use oligomer is as ligand obtained from so that ring type compound is polymerize.
In addition, other than the unsaturated compound of pi-electron system, it is possible to use the anion ligand of the monovalencies such as chlorine, bromine or The anionic cheating ligand of divalent, hydrocarbon, alkoxide, aryl amide, fragrant and mellow salt (aryloxide), amide, aryl amide, phosphide, Diaryl-phosphide etc..
As the transition metal comprising tetravalence, the metallocene compound of ligand, such as three (diformazan of cyclopentadienyl group can be enumerated Base amino) titanium, methyl cyclopentadienyl three (dimethylamino) titanium, bis- (cyclopentadienyl group) titanium chloride, dimethyl silane Base tetramethyl-ring pentadienyl-tert-butylamino zirconium dichloride etc..
For metallocene compound, by being combined with specific co-catalyst (co-catalyst), in various alkene When the polymerization of hydrocarbon, the effect as catalyst is played.As specific co-catalyst, methylaluminoxane (MAO), boron system can be enumerated Compound etc..It should be noted that the use ratio of the co-catalyst for metallocene compound is preferably 10~100 Ten thousand moles times, more preferably 50~5,000 mole times.
About the vinyl-vinyl acetate copolymer used as vistanex, can enumerate for example containing 50 mass % The vinyl-vinyl acetate copolymer of the above ethylene.
In addition, as acrylic resin, such as polypropylene, propylene-α-alkene containing the 50 above propylene of mass % can be enumerated Hydrocarbon copolymer etc..1 kind to can be used alone in them, can also be used in combination of two or more.
As constitute propylene-alpha-olefin copolymers alpha-olefin, specifically, can enumerate ethylene, 1- butylene, 1- amylenes, 4-methyl-1-pentene, 1- hexenes, 1- heptene, 1- octenes etc., in these, the preferred alpha-olefin of carbon atom number 6~12.
About the vistanex for including in foam sheet, in the case of using above-mentioned straight-chain low density polyethylene (LDPE), Can be used alone above-mentioned straight-chain low density polyethylene (LDPE), can be also used in combination with other vistanexes, for example, can with it is above-mentioned Other vistanexes be used in combination.
In the case of containing other vistanexes, relative to straight-chain low density polyethylene (LDPE) and other vistanexes The ratio of other vistanexes for total amount is preferably 75 mass % hereinafter, more preferably 50 mass % are hereinafter, further Preferably 30 mass % or less.In addition, other vistanexes are preferably vinyl-vinyl acetate copolymer.
In addition, as the resin contained in expandable composition, vistanex is can be used alone, but also may include gathering Resin other than olefin resin, as long as not damaging the effect of the present invention.In foam sheet, vistanex is relative to resin The ratio of total amount is preferably 60 mass % or more, more preferably 70 mass % or more, further preferably 80 mass % or more.
As the resin other than vistanex, the ethylene, propylenes such as styrene series thermoplastic elastomer, EPDM system can be enumerated Thermoplastic elastomer (TPE) etc..
(degree of cross linking)
Foam sheet is that crosslinked sheet material has occurred, and the degree of cross linking is preferably 20~70 mass %.By making the degree of cross linking exist In such range, to be easy to get the foam sheet with average molecular weight between the crosslinking points in above-mentioned range.In addition, From the viewpoint, the degree of cross linking is more preferably 30~65 mass %, further preferably 35~60 mass %.
(expansion ratio)
The expansion ratio of foam sheet is preferably 1.2~8cm3/g.In the present invention, by making average mark between above-mentioned crosslinking points Son amount is in the range of above-mentioned regulation, so as in the expansion ratio of wide scope, be improved while ensuring flexibility resistance to The durabilities such as impact.
In addition, for foam sheet, by reducing expansion ratio in above-mentioned range, to make mechanical strength liter Height is easy to further increase durability, also, is easy to make the bubble miniaturization of foam sheet, is easy to reduce aftermentioned average air Bulb diameter.From the viewpoint, the expansion ratio of foam sheet is more preferably 1.3~3cm3/ g, further preferably 1.5 ~2.3cm3/g.It should be noted that in the present invention, the density of foam sheet is found out according to JIS K7222, by its conduct reciprocal Expansion ratio.
(independent air bubble rate)
The preferred bubble of foam sheet is independent air bubble.So-called bubble is independent air bubble, refers to:Relative to whole bubbles The ratio (being known as independent air bubble rate) of the independent air bubble of speech becomes 70% or more.Independent air bubble rate is preferably 80% or more, more excellent It is selected as 90% or more.
Independent air bubble rate can be found out according to ASTM D2856 (1998).In commercially available analyzer, it is automatic dry type can be enumerated Densitometer ア キ ュ ピ ッ Network 1330 etc..
More specifically, independent air bubble rate can be measured by following methods.The plane that the length of side is 5cm is cut out from foam sheet Square shape and have certain thickness test film.The thickness for measuring test film, calculates the apparent volume V of test film1, and And measure the weight W of test film1.Next, calculating the apparent volume V shared by bubble based on following formula2.It should be noted that constituting The density of the resin of test film is 1g/cm3
Apparent volume V shared by bubble2=V1-W1
Next, test film to be sunk to the depth of 23 DEG C of distilled water middle-range water surface 100mm, apply 15kPa to test film Pressure 3 minutes.It releases stress, then takes out test film from water in water, the moisture on the surface of test film will be attached to It removes, measures the weight W of test film2, continuous air bubbles rate F is calculated based on following formula1And independent air bubble rate F2
Continuous air bubbles rate F1(%)=100 × (W2-W1)/V2
Independent air bubble rate F2(%)=100-F1
(size of foam sheet)
The thickness of foam sheet is preferably 0.02~0.8mm.In the present invention, even if in such wider thickness range It is interior, within the limits prescribed by average molecular weight between making crosslinking points as described above, it also can not only ensure the soft of foam sheet It is soft, and improve the durabilities such as impact resistance.The thickness of foam sheet is preferably 0.08~0.50mm, further preferably 0.10~0.40mm.
Foam sheet is not particularly limited, and can be machined to thin-line-shaped foam sheet, for example, can make foam sheet Width uses for 10mm or less.In addition, for example can be 5mm hereinafter, can be 1mm or less in turn.If constriction foam sheet Width, then can suitably be used in the electronic equipment internal minimized.In addition, for the foam sheet of the present invention, Even if durability can be well maintained if constriction width.The lower limiting value of the width of foam sheet is not particularly limited, such as can be with It is 0.1mm or more, can also be 0.2mm or more.It should be noted that the flat shape of foam sheet is not particularly limited, it can Can be common quadrangle, circle etc. other than these shapes to be rectangular elongated shape, frame-shaped, L-shaped, U-shape etc. Other arbitrary shapes.
(mechanical property)
25% compressive strength of foam sheet is preferably 10~2000kPa, more preferably 4000~2000kPa, further Preferably 800~1500kPa.By making 25% compressive strength for 2000kPa hereinafter, to make foam sheet that there is impact absorbing Property, leakproofness, can be used as snubber material and sealing material and suitably use.In addition, by improving compressive strength, it will It is easy that mechanical strength is made to become good.It should be noted that 25% compressive strength is carried out to foam sheet according to JISK6767 Obtained from measurement.
In addition, the impact resistance evaluation result of foam sheet is preferably in the range of 25~50cm.If impact resistance is evaluated As a result it is 25cm or more, even if then becoming abundant if the impact resistance of foam sheet in the case of constriction sheet width.This Outside, the interlaminar strength of foam sheet is preferably 4.3MPa or more, further preferably 4.8MPa or more.It should be noted that resistance to Impact is evaluated and the value of interlaminar strength is obtained from being measured according to the method for aftermentioned embodiment.
(mean air bubble diameter)
The bubble of foam sheet is that the mean air bubble diameter of MD and TD is respectively preferably 120 μm or less, more preferably 100 μm Below, be more preferably 80 μm or less, the mean air bubble diameter of ZD is 80 μm or less, is preferably 50m or less, is more preferably 40 μm so-called " microvesicle (microcell) " below.In the present invention, by reducing bubble diameter as described above, to make per unit The number of the walls of length becomes larger.Therefore, for foam sheet, for example, even if in the case of constriction width There are a large amount of walls in the narrow width for meeting, it will is easy to improve impact resistance etc..It should be noted that of the invention In, it is above-mentioned range by average molecular weight between making crosslinking points, and the degree of cross linking, expansion ratio is made to be above-mentioned preferred model It encloses, microvesicle is formed to be easy.
In addition, from the viewpoint of ease of manufacturing, the mean air bubble diameter of MD and TD are respectively preferably 10 μm or more, more Preferably 20 μm or more, further preferably 25 μm or more.In addition, the mean air bubble diameter of ZD is preferably 5 μm or more, more preferably For 10m or more, further preferably 15 μm or more.
It is further preferred, that the mean air bubble diameter of ZD the ratio between of the mean air bubble diameter of the MD of bubble relative to bubble (hereinafter also referred to as " MD/ZD ") is 1~8, also, the ratio between the mean air bubble diameter of the mean air bubble diameter of TD relative to ZD (with Under, also referred to as " TD/ZD ") it is 1~8.In turn, it is further preferred that it is 2~7 that MD/ZD, which is 2~7, TD/ZD,.
Mean air bubble diameter refers to the mean air bubble diameter obtained from following methods are measured.
Substance is as the foaming body sample of measurement obtained by foam sheet is cut into 50mm square by preparation.It is immersed in 1 minute in liquid nitrogen, then cut off in a thickness direction respectively along the directions MD, the directions TD and the directions ZD with razor.For the section, Shoot 200 times of enlarged photograph using digit microscope (Co., Ltd.'s キ ー エ Application ス systems " VHX-900 "), for the directions MD, The length of the difference in the directions TD and the directions ZD is whole bubbles present in the section of 2mm, measures bubble diameter, is repeated 5 operations.Moreover, using the average value of whole bubbles as the mean air bubble diameter in the directions MD, the directions TD and the directions ZD.
It should be noted that the directions MD refer to (longitudinal direction) Machine direction, it is and squeezes out the consistent sides such as direction To the directions TD refer to Transverse direction (transverse direction), are the directions orthogonal with the directions MD, in the foaming body of sheet It is the direction parallel with piece face in (foam sheet).In addition, the directions ZD are the thickness directions of foaming body, be with the directions MD and The vertical direction in the directions TD.
(thermal decomposable foaming agent)
The foam sheet of the present invention is preferably by making other than comprising above-mentioned resin, also to include thermal decomposable foaming agent Expandable composition foams and is formed.
As thermal decomposable foaming agent, organic foaming agent, inorganic foaming agent can be used.As organic system foaming agent, can lift Go out azo-compounds, the N such as azodicarbonamide, azoformic acid metal salt (Barium azodicarboxylate etc.), azobis isobutyronitrile, The nitroso compounds such as N '-dinitrosopentamethylene tetramines, hydrazo-dicarbonamide, 4,4 '-oxygroups bis- (benzene sulfonyl hydrazides), first Semicarbazide compounds such as the hydrazine derivates such as benzene sulfonyl hydrazide, toluene sulfonyl semicarbazide etc..
As inorganic system's foaming agent, sour ammonium, sodium carbonate, ammonium hydrogen carbonate, sodium bicarbonate, ammonium nilrite, hydroboration can be enumerated Sodium, one sodium of anhydrous citric acid etc..
In these, from the viewpoint and economy for obtaining fine bubble, from the viewpoint of secure context, preferred azo Close object, particularly preferred azodicarbonamide.These thermal decomposable foaming agents can be used alone, or combine two or more use.
It is excellent relative to 100 mass parts of resin for the use level of the thermal decomposable foaming agent in expandable composition It is selected as 1~10 mass parts, more preferably 1~7 mass parts, further preferably 1.5~3.5 mass parts.
In addition, expandable composition also contains bubble preferably other than containing above-mentioned resin and thermal decomposable foaming agent Core conditioning agent.As nuclei of bubbles conditioning agent, the zinc compounds such as zinc oxide, zinc stearate, citric acid, urea etc. can be enumerated and organised Object etc. is closed, in these, more preferable zinc oxide.It, will by also using nuclei of bubbles conditioning agent other than using above-mentioned foaming agent It can be easy to further decrease bubble diameter.It is excellent relative to 100 mass parts of resin for the use level of nuclei of bubbles conditioning agent It is selected as 0.4~8 mass parts, more preferably 0.5~5 mass parts, further preferably 0.8~2.5 mass parts.
For expandable composition, as needed, in addition to the foregoing, can also contain antioxidant, heat stabilizer, The additive that colorant, fire retardant, antistatic agent, packing material etc. usually use in foaming body.
[The Zhi Zaofangfa &#93 of foam sheet;
The manufacturing method of foam sheet is not particularly limited, such as can be by that will include that vistanex and heat decomposition type are sent out It infusion and crosslinked expandable composition has occurred is heated, manufactured to make thermal decomposable foaming agent foaming.More For body, which includes process below (1)~(4).
Process (1):It is mixed by vistanex and comprising the additive including thermal decomposable foaming agent, is molded into sheet Expandable composition (resin sheet) process
Process (2):To the expandable composition irradiation ionization property radioactive ray of sheet, and keep expandable composition crosslinked Process
Process (3):It is heated to crosslinked expandable composition has occurred, and thermal decomposable foaming agent is made to foam and shape At the process of micro air bubble
Process (4):After forming micro air bubble, the direction of the either or both in the directions MD or the directions TD carries out It stretches, micro air bubble is stretched, the process for obtaining foam sheet
The method of moulding resin sheet material is not particularly limited in process (1), for example, can moulding resin piece by the following method Material:Vistanex and additive are supplied into extruder, melting mixing is carried out, is squeezed out from extruder by expandable composition At sheet.
As in process (2) by the crosslinked method of expandable composition, using to resin sheet irradiating electron beam, alpha ray, The method of the ionization property radioactive ray such as β rays, gamma-rays.For the exposure of above-mentioned ionizing radiation, it is adjusted such that The degree of cross linking of obtained foam sheet become above-mentioned desired range, preferably 5~15Mrad, more preferably 6~ 13Mrad。
Heating temperature when being heated to expandable composition in process (3) and thermal decomposable foaming agent is made to foam is heat It is more than the blowing temperature of decomposition-type foaming agent, preferably 200~300 DEG C, more preferably 220~280 DEG C.
The stretching of foam sheet in process (4) can carry out after so that resin sheet foaming is obtained foam sheet, also may be used It is carried out while so that resin sheet is foamed.It should be noted that after so that resin sheet foaming is obtained foam sheet, to hair In the case that bubble sheet material is stretched, molten condition when foaming can be maintained, so in the case where not cooling down foam sheet Foam sheet is stretched afterwards, can also after foam sheet is cooled down, foam sheet is heated again and make its at After melting or soft state, foam sheet is stretched.
In process (4), the stretching ratio that a side or two sides in the directions MD of foam sheet and the directions TD stretch is preferred It is 1.1~5.0 times, more preferably 1.5~4.0 times.
If it is above-mentioned lower limiting value or more to make stretching ratio, the flexibility and tensile strength of foam sheet will be easy to become Well.On the other hand, if upper limit value hereinafter, can then prevent that foam sheet is broken in stretching or foamed gas is from foaming Foam sheet in overflow and expansion ratio made to be remarkably decreased, flexibility, the tensile strength of foam sheet become good, quality It is easy to become uniform.
In addition, when stretching, foam sheet is heated to such as 100~280 DEG C, preferably 150~260 DEG C.
Additionally, it is preferred that in the directions MD and the directions TD a side or after two sides stretch foam sheet, setting will The process of foam sheet rapid cooling.It can inhibit contraction, the expansion of the foam sheet after stretching as a result, it will be easy to make foaming The thickness of sheet material becomes uniform, also, will be easy to be adjusted to desired bubble diameter.The method for carrying out rapid cooling does not have The progress such as especially limitation, such as the available method for making foam sheet and circulation there is the metallic roll of cooling water to contact.
But this manufacturing method can also be used method other than the above and obtain foam sheet not by limitations described above. For example, irradiation ionization property radioactive ray can be replaced, using organic peroxide is coordinated in expandable composition in advance, to foaming Property the composition method etc. that is heated and organic peroxide is made to decompose be crosslinked.In addition, can be by process (4) i.e. foamed sheet The stretching of material is omitted.
The purposes of foam sheet is not particularly limited, such as is preferably used in electronic equipment internal.For the hair of the present invention For steeping sheet material, even if being thinned, it may have high-durability therefore especially, can be small in the space of configuration foam sheet It is suitably used inside various mancarried electronic aids.As mancarried electronic aid, can enumerate mobile phone, camera, game machine, Electronic notebook, PC etc..Foam sheet can be used in electronic equipment internal as impact absorbing material, sealing material. In addition, it can also be used to using foam sheet as the adhesive tape of base material.
Adhesive tape is, for example, the adhesive tape of the adhesive phase with foam sheet and at least one side for being set to foam sheet, It is preferred that being provided with the double-faced adhesive tape of adhesive phase on two sides.
The thickness for constituting the adhesive phase of adhesive tape is preferably 5~200 μm.The thickness of adhesive phase is more preferably 7~150 μm, further preferably 10~100 μm.When the range that the thickness of adhesive phase is 5~200 μm, it can be carried out using adhesive tape The thickness of fixed structure is thinning.
It as the adhesive used in adhesive phase, is not particularly limited, such as acrylic adhesive, amino can be used Formic acid esters system adhesive, elastomeric adhesive etc..
Furthermore it is possible to further be bonded the peeling sheets such as processing release paper over the binder layer.
The method that adhesive phase is formed in at least one side of foam sheet is not particularly limited.For example, can enumerate:It uses The coating machines such as spreader, the method for coating adhesive in at least one side of foam sheet;Using sprayer to foam sheet At least one side sprays adhesive and the method that is coated;Use the side of bristle coating adhesive in at least one side of foam sheet Method;The method that the adhesive phase formed on peeling sheet is transferred to at least one side of foam sheet;Etc..
Embodiment
Illustrate the present invention in further detail by embodiment, but the present invention is not by any restrictions of these examples.
[Ce Dingfangfa ]
The assay method of each physical property and evaluation method is as follows described.
Average molecular weight > between < crosslinking points
For average molecular weight between crosslinking points, for crosslinked expandable composition has occurred, shearing elasticity is measured Modulus G ' finds out average molecular weight between crosslinking points according to the following formula based on classical rubber elasticity theory.
Mc=2 × (1+ μ) × ρ × RT/E '
(wherein, Mc:Average molecular weight (g/mol), μ between crosslinking points:Poisson's ratio (is set as 0.5), ρ:Expandable composition Density (g/m3), R:Gas constant 8.314J/Kmol, T:Measure the temperature (K) when storage modulus, E ':Storage modulus (Pa).Separately Outside, E '=3G ' is substituted into).
(coefficient of rigidity G ')
For coefficient of rigidity G ', filled using ア ィ テ ィ ー Meter Measuring Machine device Co. Ltd. system Measurement of Dynamic Viscoelasticity DVA-200 is set, is heated up within the temperature range of 40~150 DEG C with 5 DEG C/min of speed on one side, is in angular frequency on one side 1Hz, dependent variable are measured under conditions of being 1%.
In addition, using エ system ア Application ド ケ ー Co. Ltd. systems high precision mode (model) densimeter SD-200L, to survey Determine the density (g/m of expandable composition3)。
< mean air bubble diameters >
It is measured according to above-mentioned method.
< apparent densities and expansion ratio >
For foam sheet, apparent density is measured according to JIS K7222, regard its inverse as expansion ratio.
< degrees of cross linking >
The test film of about 100mg, the weight A (mg) of precision weighing test film are taken from foam sheet.Next, by the experiment Piece is impregnated in 120 DEG C of dimethylbenzene 30cm3In, it places 24 hours, then, is filtered with the woven wire of 200 mesh, acquisition gold Belong to the insoluble component on silk screen, is dried in vacuo, the weight B (mg) of precision weighing insoluble component.By obtained value, under utilization Formula calculates the degree of cross linking (quality %).
The degree of cross linking (quality %)=100 × (B/A)
< independent air bubble rates >
It is measured according to above-mentioned method.
< impact resistances >
(impact resistance evaluates the preparation of sample)
On the two sides of the foam sheet obtained in embodiment, comparative example, the adhesive obtained using following methods is laminated Layer is made using following methods using foam sheet as the double-faced adhesive tape of base material.
(production method of double-faced adhesive tape)
To with thermometer, blender, condenser pipe reactor in, addition butyl acrylate 75 mass parts, acrylic acid 2- 22 mass parts of ethylhexyl, 3 mass parts of acrylic acid, 0.2 mass parts of acrylic acid 2- hydroxy methacrylates and 80 mass parts of ethyl acetate, Nitrogen displacement is carried out, then reactor is heated, starts to flow back.Next, into above-mentioned reactor, addition is as polymerization 0.1 mass parts of azobis isobutyronitrile of initiator.Reflux 5 hours, obtains the solution of acrylic acid series copolymer (z).For obtaining Acrylic acid series copolymer (z) measured using GPC method using Water societies system " 2690Separations Model " as column Weight average molecular weight, result are 600,000.
The solid-state for the acrylic acid series copolymer (z) for including in solution relative to obtained acrylic acid series copolymer (z) at Divide 100 mass parts, adds 15 mass parts of newtrex ester, ethyl acetate (only chemicals strain formula meeting that softening point is 135 DEG C Society's system) 125 mass parts, isocyanates system crosslinking agent (East ソ ー Co. Ltd. systems, U ロ ネ ー ト L45) 2 mass parts, stirred It mixes, thus obtains adhesive (Z).It should be noted that the degree of cross linking of acrylic adhesive is 33 mass %.
Prepare the processing release paper that thickness is 150 μm, the coating adhesive (Z) in the demoulding process face of the processing release paper, in 100 DEG C Drying in 5 minutes is carried out, forms the acrylic adhesive layer that thickness is 50 μm as a result,.By the acrylic adhesive layer with by The surface fitting for the base material that foam sheet is formed.Next, using same procedure, on the opposite surface of base material also fitting with Above-mentioned identical acrylic adhesive layer.It is obtained as a result, with thickness being the coating double-faced adhesive tape of 150 μm of processing release paper.
(making of impact resistance experimental rig)
The schematic diagram of impact resistance experimental rig is shown in Fig. 1.
Impact resistance experimental rig is made using following step.
First, becoming width 15.0mm, length 15.0mm, internal diameter with outer diameter becomes width 13.6mm, length 13.6mm Mode is punched the double-faced adhesive tape above obtained, the test film 1 for the quadrangle frame-shaped that the width for making each frame side is 0.7mm.
Next, as shown in Fig. 1 (a), prepare that center is provided with the glued plate 3 of magnesium system in rectangular hole 2, in magnesium The upper surface for making glued plate 3 one week is bonded the test film 1 for having removed processing release paper throughout the peripheral side in the hole 2.
Next, the glued overlapping of plate 4 of the glass system of the size in coating hole 2 above-mentioned is fitted on test film 1, it is coating Hole 2 above-mentioned, assembles impact resistance experimental rig.
Then, impact resistance experimental rig is spun upside down, in the case where making the glued plate 3 of magnesium system become states above, from Glued 3 side of plate of magnesium system applies the pressure 5 seconds of 5kgf, will be crimped with test film positioned at the glued plate of upper and lower magnesium system 3, in room temperature It is lower to place 36 hours.
(judgement of impact resistance)
As shown in Fig. 1 (b), the impact resistance experimental rig of making is fixed on supporting table 5, with the side of through hole 2 Formula makes the iron ball 6 of the 50g weights of the size by the hole 2 formed on the glued plate of magnesium system 3 fall.Slowly increase and falls iron ball Height, fall iron ball when measuring the impact that applies by based on falling for iron ball and test film being made to be removed with glued plate Height, impact resistance is evaluated.The case where height is more than 50cm is evaluated as " S ", is 25cm or more 50cm by height Following situation is evaluated as " A ", and height is evaluated as " B " less than the case where 25cm.
< interlaminar strengths >
(making of interlaminar strength test sample)
As shown in Figure 2, primer coating (セ メ ダ イ Application Co., Ltd. within the scope of the 25mm square of foam sheet 7 Make " PPX priming paint "), then, (the セ メ ダ イ Application strain formula meetings of bonding agent 8 of a diameter of 5mm or so are dripped in the center of coated portion Society's system " PPX ").The fixture 9 for placing the aluminum of 25mm square in the part of drippage bonding agent immediately after, will using bonding agent 8 Foam sheet 7 is crimped with fixture 9.Then, according to the size of fixture 9, foam sheet is cut.In the foam sheet 7 being cut into Primer coating on the face of non-bonding jig 9 drips the bonding agent 10 of a diameter of 5mm or so in the center of coated portion.Then it stands The fixture 11 that the aluminum of 10mm square is placed in the part of drippage bonding agent, using bonding agent 10 by foam sheet 7 and fixture 11 crimping.The bonding agent wiped away in the exposing of the periphery of fixture 11 is formed on foam sheet and is cut then according to the size of fixture 11 Trace 12.By placing it at room temperature 30 minutes, to conserve bonding agent, interlaminar strength test sample is made.
(judgement of interlaminar strength)
Next, in such a way that the piece face of foam sheet 7 is vertical with dip direction, interlaminar strength test sample is pacified (" テ Application シ ロ Application is omnipotent for Co., Ltd.'s エ ー ア Application De デ イ systems for testing machine loaded on the load cell provided with 1kN Material Testing Machine ").Fixture 9 is lifted vertically upward with 100mm/ minutes speed, only by the range of the 1cm square of foam sheet Splitting.Peak load at this time is measured, as the 1st measurement result.3 same operations are repeated, are put down Mean value is as interlaminar strength.It is excellent that the situation that interlaminar strength is 4.8MPa or more is evaluated as interlaminar strength, is denoted as " A ".In addition, It is good that interlaminar strength is that 4.3MPa less than the case where 4.8MPa is evaluated as interlaminar strength, is denoted as " B ".In addition, by layer Between to be evaluated as interlaminar strength insufficient intensity the case where being less than 4.3MPa, be denoted as " C ".
25% compressive strength > of <
For foam sheet, 25% compressive strength is measured according to JIS K6767.
&#91;Embodiment 1&#93;
By 100 mass parts of straight-chain low density polyethylene (LDPE) obtained using the polymerization catalyst of metallocene compound, as 2.1 mass parts of azodicarbonamide of thermal decomposable foaming agent, as 1.0 mass parts of zinc oxide of nuclei of bubbles conditioning agent and anti- 0.5 mass parts of oxidant are supplied to extruder, are carried out melting mixing in 130 DEG C, are extruded into the tree for the strip that thickness is 290 μm Fat sheet material.
It should be noted that as above-mentioned straight-chain low density polyethylene (LDPE), the trade name of ダ ウ ケ ミ カ Le society has been used " ア Off ィ ニ テ ィ ー PL1850 " (density:0.902g/cm3).In addition, as above-mentioned zinc oxide, Sakai chemical industry strain has been used The trade name " OW-212F " of formula commercial firm.
Next, the electron beam for being 500kV to the two sides irradiation accelerating potential of the resin sheet of above-mentioned strip Resin sheet is crosslinked by 7.4Mrad, then, crosslinked resin sheet is continually fed into and utilizes hot wind and infrared heating Device is remained in 250 DEG C of foaming furnace and is heated, and makes its foaming, obtains the foam sheet that thickness is 300 μm.
Next, obtained foam sheet is continuously sent out from foaming furnace, then, by the two sides of the foam sheet Temperature is maintained in the state of 200~250 DEG C and is stretched as described below to the foam sheet.Along the side TD of foam sheet To being stretched to foam sheet with 2.0 times of stretching ratio, also, the speed to be sent into foaming furnace than resin sheet (feed speed) winding speed winds foam sheet faster, is stretched as a result, to foam sheet along the directions MD, makes itself and stream It is connected with the circumferential surface contact of the metallic roll of cooling water.In the manner described above, along the directions TD and the directions MD to the bubble of foam sheet into Row stretches and makes its deformation, obtains foam sheet.It should be noted that considering the edge caused by the foaming of resin sheet itself The swell increment in the directions MD, and the winding speed of above-mentioned foam sheet is adjusted.According to above-mentioned evaluation method to obtaining Foam sheet is evaluated, and table 1 is the results are shown in.
&#91;Embodiment 2&#93;
Instead of the resin of embodiment 1, the group of resin is made to become straight-chain low density polyethylene (LDPE) (ダ ウ ケ ミ カ Le society system, quotient The name of an article " ア Off ィ ニ テ ィ ー PL1850 ", density:0.902g/cm3) 30 mass parts and vinyl-vinyl acetate copolymer (East ソ ー Co. Ltd. systems, trade name " ウ Le ト ラ セ Application 636 ") 70 mass parts.In addition, making the azo two in expandable composition The use level of formamide is 1.9 mass parts.In addition to the foregoing, implement similarly to Example 1.By obtained foam sheet Evaluation result is shown in table 1.
&#91;Embodiment 3&#93;
It is 2.5 mass parts to make the use level of the azodicarbonamide in expandable composition, also, makes electron beam irradiation amount For 9.0Mrad, it is that 57.0 mass % are implemented similarly to Example 1 other than above-mentioned aspect to make the degree of cross linking.By what is obtained Foam sheet evaluation result is shown in table 1.
&#91;Comparative example 1&#93;
It is 1.6 mass parts to make the use level of the azodicarbonamide in expandable composition, also, makes electron beam irradiation amount For 4.7Mrad, it is that 16.2 mass % are implemented similarly to Example 1 other than above-mentioned aspect to make the degree of cross linking.By what is obtained Foam sheet evaluation result is shown in table 1.
&#91;Comparative example 2&#93;
Instead of the resin of embodiment 1, the group of resin is made to become straight-chain low density polyethylene (LDPE) (ダ ウ ケ ミ カ Le society system, quotient The name of an article " ア Off ィ ニ テ ィ ー PL1850 ", density:0.902g/cm3) 30 mass parts and vinyl-vinyl acetate copolymer (East ソ ー Co. Ltd. systems, trade name " ウ Le ト ラ セ Application 636 ") 70 mass parts.In addition, making the azo two in expandable composition The use level of formamide is 1.5 mass parts, also, the exposure of electron beam is made to be 4.7Mrad, and it is 19.2 matter to make the degree of cross linking Measure %.In addition to the foregoing, implement similarly to Example 1.By obtained foam sheet evaluation result is shown in table 1.
&#91;Comparative example 3&#93;
The electron beam 7.4Mrad that the two sides irradiation accelerating potential of the foam sheet obtained into comparative example 1 is 500kV, will Foam sheet is crosslinked, and it is 71.0 mass % to make the degree of cross linking.By obtained foam sheet evaluation result is shown in table 1.
&#91;Table 1&#93;
Table 1
As it appears from the above, for embodiment 1 and 3,25% compressive strength, interlaminar strength and impact resistance are good, can Be understood by make crosslinking points between average molecular weight be defined range, so as to while being well maintained flexibility, make Durability is good.In addition, for embodiment 2, compared with embodiment 1 and 3, poor impact resistance, but interlaminar strength is good, and it is soft Soft and durability is good.In contrast, for comparative example 1 and 2, average molecular weight is big between crosslinking points, accordingly, it is difficult to fill Ground is divided to improve durability.For comparative example 3, average molecular weight is small between crosslinking points, it is difficult to fully improve durability.
Reference sign
1 test film
2 holes
The glued plate of 3 magnesium systems
The glued plate of 4 glass systems
5 supporting tables
6 iron balls
7 foam sheets
8 bonding agents
9 fixtures
10 bonding agents
11 fixtures
12 cut marks.

Claims (10)

1. a kind of polyolefin foam sheet is to make comprising vistanex and crosslinked expandable composition has occurred Foaming and formed, between the crosslinking points in the expandable composition average molecular weight be 15000~30000.
2. polyolefin foam sheet as described in claim 1, the vistanex is polyvinyl resin.
3. polyolefin foam sheet as claimed in claim 2, the vistanex is the polymerization with metallocene compound Straight-chain low density polyethylene (LDPE) obtained by polymerization catalyst.
4. polyolefin foam sheet according to any one of claims 1 to 3, the degree of cross linking is 20~70 mass %.
5. polyolefin foam sheet as described in any one of claims 1 to 4, impact resistance evaluation result is in 25~50cm In the range of, and 25% compressive strength is 10~2,000kPa.
6. such as polyolefin foam sheet according to any one of claims 1 to 5, thickness is 0.02~0.8mm.
7. such as polyolefin foam sheet according to any one of claims 1 to 6, expansion ratio is 1.2~8cm3/g。
8. it is to make also to include thermal decomposable foaming agent such as polyolefin foam sheet according to any one of claims 1 to 7 Expandable composition foaming and formed.
9. the manufacturing method of polyolefin foam sheet according to any one of claims 1 to 8, wherein will include polyolefin Resin and thermal decomposable foaming agent and the heating of crosslinked expandable composition has occurred, and makes the thermal decomposable foaming agent Foaming.
10. a kind of adhesive tape has polyolefin foam sheet according to any one of claims 1 to 8 and described poly- The adhesive phase being arranged in at least one side of olefin-based foam sheet.
CN201780014835.4A 2016-09-30 2017-09-29 Polyolefin foam sheet, its manufacturing method and adhesive tape Pending CN108699276A (en)

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