CN105121529A - Resin foam composite - Google Patents

Resin foam composite Download PDF

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Publication number
CN105121529A
CN105121529A CN201480020767.9A CN201480020767A CN105121529A CN 105121529 A CN105121529 A CN 105121529A CN 201480020767 A CN201480020767 A CN 201480020767A CN 105121529 A CN105121529 A CN 105121529A
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China
Prior art keywords
resin
mentioned
layer
thickness
complex body
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CN201480020767.9A
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CN105121529B (en
Inventor
畑中逸大
斋藤诚
加藤和通
山成悠介
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Nitto Denko Corp
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Nitto Denko Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • 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
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/26—Porous or cellular plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3442—Mixing, kneading or conveying the foamable material
    • B29C44/3446—Feeding the blowing agent
    • B29C44/3453—Feeding the blowing agent to solid plastic material
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/24—Presence of a foam
    • C09J2400/243—Presence of a foam in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/006—Presence of polyolefin in the substrate

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

Abstract

Provided is a flexible resin foam composite that can be used for design gaps, which have become extremely narrow as electronics have become thinner. A resin foam composite obtained by laminating a resin foam layer and an adhesive layer, wherein the apparent density of the resin foam layer is 0.03-0.30 g/cm3, the compressive stress during 50% compression is 5.0 N/cm2 or lower, the thickness of the adhesive layer is 0.0005 mm-0.06 mm, and the total thickness of the resin foam composite is 0.35 mm or less. The ratio of the thickness of the resin foam layer and the thickness of the adhesive layer (thickness of resin foam layer/thickness of adhesive layer) is preferably 2.1 or higher.

Description

Resin expanded complex body
Technical field
The present invention relates to the resin expanded complex body being laminated with foamed resin layer and binder layer.
Background technology
Foamed resin is used as sealing material, the cushioning material of the electronicss such as mobile phone, smart mobile phone, dull and stereotyped PC.Particularly in order to make its position alignment become easy when laminating operates, suitable use is provided with the resin expanded complex body of binder layer.In recent years, with the miniaturization of electronics, the maximization of picture, as sealing material, cushioning material and the area of resin expanded complex body that uses also diminishes, even if require the little flexibility that also can play sufficient stopping property, resiliency of area to resin expanded complex body.In addition, electronics is also carrying out thin layer, also requires thin layer to resin expanded complex body.
As thin foamed resin, known by implement in foaming or in subsequent handling processed compressed, stretch processing method, implement coating process after expanding method and the foamed sheet (for example, referring to patent documentation 1, patent documentation 2) that obtains.But above-mentioned foamed sheet exists the problem being difficult to improve expansion ratio, there is screen resilience (resilience stress during 25% compression) when have compressed 25% more than 3N/cm 2deng the problem that screen resilience when compressing is large.
In addition, in recent years, along with the slimming of portable equipment, use the design gaps (gap, gap) of foamed resin become very narrow (such as, the gap of below 0.1mm), consider design tolerance etc., resin expanded complex body is compressed to more than 50% to use also unrare.Such as, but during the resin expanded complex body using screen resilience during above-mentioned compression large in the very narrow design gaps of this display equipment, due to high resilience, in the liquid crystal of display part, generation display is unequal sometimes, causes display bad.
In addition, consider by using the foamed resin that thickness is thin to reduce rate of compression, thus reduce screen resilience.But as mentioned above, foamed resin is provided with the resin expanded complex body of binder layer, binder layer itself is not compressed, if therefore use thick binder layer, then screen resilience uprises and produces display inequality sometimes.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2009-190195 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2010-1407 publication
Summary of the invention
the problem that invention will solve
Therefore, the object of the invention is to, a kind of resin expanded complex body that can become the softness used in very narrow design gaps in the slimming along with electronics is provided.In addition, provide a kind of and can make the resin expanded complex body that its position alignment is easy when laminating operates.
for the scheme of dealing with problems
The present inventor etc. are in order to reach above-mentioned purpose, conduct in-depth research, found that: by using specific foamed resin layer and making the thickness of resin expanded complex body and the thickness of binder layer be the thickness of regulation, can obtain and can suppress the rising of screen resilience and the resin expanded complex body making position alignment easy.The present invention completes based on these opinions.
That is, the invention provides a kind of resin expanded complex body, it is the resin expanded complex body being laminated with foamed resin layer and binder layer, and the apparent density of above-mentioned foamed resin layer is 0.03 ~ 0.30g/cm 3, stress under compression during 50% compression is 5.0N/cm 2below, the thickness of binder layer is 0.0005mm ~ 0.06mm, and the total thickness of resin expanded complex body is below 0.35mm.
Particularly preferably be, the thickness of above-mentioned foamed resin layer is more than 2.1 with the ratio (thickness of the thickness/binder layer of foamed resin layer) of the thickness of above-mentioned binder layer.
In addition, above-mentioned binder layer is preferably acrylic adhesive layer.
And then in above-mentioned resin expanded complex body, the resin forming above-mentioned foamed resin layer is preferably thermoplastic resin, and then is more preferably polyolefin resin.
In addition, in above-mentioned resin expanded complex body, preferably have at least one mask of above-mentioned foamed resin layer the upper layer formed by heating and melting process.
In addition, in above-mentioned resin expanded complex body, preferred above-mentioned foamed resin layer through making high pressure gas be infiltrated up in resin after carry out the operation that reduces pressure and formed.
And then in above-mentioned resin expanded complex body, above-mentioned gas is preferably non-active gas, is more preferably carbonic acid gas.
And then in above-mentioned resin expanded complex body, above-mentioned high pressure gas are more preferably supercritical state.
In addition, in above-mentioned resin expanded complex body, above-mentioned foamed resin layer preferably has unicellular structure or half perforate semi-closure pore structure.
the effect of invention
Resin expanded complex body of the present invention is owing to having above-mentioned formation, therefore soft and can suppress the rising of screen resilience when compressing.Therefore, even if resin expanded complex body of the present invention uses in the very narrow gap of such as liquid crystal display, also can not cause display uneven, show bad.In addition, resin expanded complex body of the present invention especially can make its position alignment easy when laminating operates.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of serial section device.
Fig. 2 is the schematic diagram of the apparatus for continous treatment with warming mill.
Embodiment
Resin expanded complex body of the present invention at least has the formation being laminated with foamed resin layer and binder layer (pressure-sensitive adhesive layer).
[foamed resin layer]
Foamed resin layer in resin expanded complex body of the present invention is the layer be made up of foamed resin.Above-mentioned foamed resin obtains by making resin combination foam.
The apparent density of above-mentioned foamed resin layer is 0.03g/cm 3~ 0.30g/cm 3.Apparent density due to above-mentioned foamed resin layer is 0.03g/cm 3above, thus intensity can be guaranteed, in addition, because apparent density is 0.30g/cm 3below, thus good flexibility can be obtained.The apparent density of above-mentioned foamed resin layer is preferably 0.04g/cm 3~ 0.25g/cm 3, be more preferably 0.045g/cm 3~ 0.20g/cm 3.The apparent density of above-mentioned foamed resin layer can regulate expansion ratio by the amount of the whipping agent of infiltration in resin combination, pressure, controls thus.
Above-mentioned foamed resin layer 50% compression time stress under compression be 5.0N/cm 2below.Because stress under compression when 50% of above-mentioned foamed resin layer compresses is 5.0N/cm 2below, thus can obtain good flexibility, reduce by screen resilience during compression.Foamed resin layer 50% compression time stress under compression be preferably 4.0N/cm 2below, more preferably 3.0N/cm 2below.In addition, 0.1N/cm is preferably 2above, 0.2N/cm is more preferably 2above.Stress under compression during 50% compression of foamed resin layer can by adjustment expansion ratio, foam time temperature company's cell size that cause and control.Connect the degree that cell size refers to unicellular structure generation perforate (Lian Konghua) when the foaming of resin combination.
It should be noted that, stress under compression during above-mentioned 50% compression is tried to achieve in the following way: based on JISK6767, the thickness direction being determined at foamed resin layer only compresses the stress (N) during 50% of original depth, and be per unit area (cm by this EXPERIMENTAL STRAIN-STRESS CONVERSION 2).
As mentioned above, the above-mentioned foamed resin layer in resin expanded complex body of the present invention obtains by making resin combination foam.To above-mentioned foamed resin layer, there is no particular limitation, formed preferably by the thermoplastic resin composition's foaming made containing thermoplastic resin.Wherein, formed preferably by the polyolefin resin composite foaming made containing polyolefin-based resins.That is, the above-mentioned foamed resin layer in resin expanded complex body of the present invention is preferably foamed polyolefin resin body layer.It should be noted that, in above-mentioned resin combination, in addition to the resins, other composition, additive can also be comprised.In addition, above-mentioned resin, above-mentioned other composition, above-mentioned additives etc. can be used alone or combinationally use two or more.
It should be noted that, to the content of the resin in above-mentioned resin combination, there is no particular limitation, relative to resin combination total amount (100 quality %), is preferably more than 50 quality %, is more preferably more than 60 quality %.
To the bubble structure (foam structure) of the above-mentioned foamed resin layer in resin expanded complex body of the present invention, there is no particular limitation, preferred unicellular structure, the half perforate semi-closure pore structure (bubble structure that unicellular structure and open-celled structure mix, to its ratio, there is no particular limitation), more preferably half perforate semi-closure pore structure.To the ratio of the unicellular structure part of above-mentioned foamed resin layer, there is no particular limitation, from the aspect of flexibility, relative to the cumulative volume (100%) of above-mentioned foamed resin layer, is preferably less than 40%, is more preferably less than 30%.Bubble structure such as can regulate expansion ratio when foaming by the amount of the whipping agent of infiltration in resin combination, pressure, controls thus.
To the mean cell diameter (mean air bubble diameter) in the bubble structure of the above-mentioned foamed resin layer in resin expanded complex body of the present invention, there is no particular limitation, be such as preferably 10 μm ~ 150 μm, be more preferably 20 μm ~ 120 μm, more preferably 30 μm ~ 80 μm.If the mean cell diameter of above-mentioned foamed resin layer is more than 10 μm, then impact absorbency (resiliency) easily improves.In addition, if the mean cell diameter of above-mentioned foamed resin layer is less than 150 μm, then can become the foam with finer foam structure, therefore, easilier use in small gap, and then easily improve dirt resistance.
For the raw-material resin as the above-mentioned foamed resin layer in resin expanded complex body of the present invention, there is no particular limitation, is preferably thermoplastic resin (thermoplastic polymer).That is, the above-mentioned foamed resin layer in resin expanded complex body of the present invention obtains preferably by the thermoplastic resin composition's foaming made at least containing thermoplastic resin.As foamed resin layer raw-material above-mentioned thermoplastic resin (thermoplastic polymer) if for display thermoplasticity and the polymkeric substance of the high pressure gas that can infiltrate just there is no particular limitation.As this thermoplastic resin, such as, can enumerate: polyolefin-based resins (seeing below in detail); The styrene resins such as polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin); The polyamide-based resins such as 6-nylon, 66-nylon, 12-nylon; Polyamidoimide; Urethane; Polyimide; Polyetherimide; The acrylic resins such as polymethylmethacrylate; Polyvinyl chloride; Fluorinated ethylene propylene; Alkenylaromatic hydroxy-aromatic resin:; The polyester resin such as polyethylene terephthalate, polybutylene terephthalate; The polycarbonate such as Bisphenol-A based polycarbonate; Polyacetal; Polyphenylene sulfide etc.Thermoplastic resin can be used alone or combinationally uses two or more.It should be noted that, when thermoplastic resin is multipolymer, can be the multipolymer of any form in random copolymers, segmented copolymer.
As said polyolefins system resin, there is no particular limitation, be preferably monomer component using alpha-olefin as necessity and formed the polymkeric substance of (formation), namely in molecule, (in 1 molecule) at least has the polymkeric substance of the Component units being derived from alpha-olefin.Said polyolefins system resin can, for the polymkeric substance be only made up of alpha-olefin, also can be both such as the polymkeric substance be made up of the monomer component beyond alpha-olefin and alpha-olefin.
Said polyolefins system resin can for homopolymer (homopolymer), maybe can for comprising the multipolymer (copolymer) of two or more monomer.In addition, when said polyolefins system resin is multipolymer, also can be random copolymers, segmented copolymer.Said polyolefins system resin both can be a kind of multipolymer, also can for the product two or more copolymer in combination obtained.
To said polyolefins system resin, there is no particular limitation, from the aspect obtaining the high foamed polyolefin resin body of expansion ratio, is preferably the polyolefine of straight-chain.
As above-mentioned alpha-olefin, such as, can enumerate: the alpha-olefin (such as ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene) of carbonatoms 2 ~ 8.It should be noted that, above-mentioned alpha-olefin can be used alone or combinationally uses two or more.
As the monomer component beyond above-mentioned alpha-olefin, such as, can enumerate: the ethylenically unsaturated monomers such as vinyl acetate, vinylformic acid, acrylate, methacrylic acid, methacrylic ester, vinyl alcohol.Monomer component beyond alpha-olefin can be used alone or combinationally uses two or more.
As said polyolefins system resin, such as, can enumerate: the multipolymer etc. of the multipolymer of the alpha-olefin beyond the multipolymer of the alpha-olefin beyond the multipolymer of the alpha-olefin beyond the multipolymer of Low Density Polyethylene, medium-density polyethylene, high density polyethylene(HDPE), wire Low Density Polyethylene, polypropylene (alfon), ethene and propylene, ethene and ethene, propylene and propylene, ethene and propylene and ethene and propylene, propylene and ethylenically unsaturated monomer.
As said polyolefins system resin, from the aspect of thermotolerance, be preferably monomer component using propylene as necessity and the polymkeric substance (polypropylene-based polymkeric substance) that formed, that is, at least there is the polymkeric substance of the Component units being derived from propylene.That is, as said polyolefins system resin, include, for example out: the polypropylene-based polymkeric substance such as multipolymer of the alpha-olefin beyond the multipolymer of polypropylene (alfon), ethene and propylene, propylene and propylene.Alpha-olefin beyond aforesaid propylene can be used alone or combinationally uses two or more.
To the content of above-mentioned alpha-olefin, there is no particular limitation, such as, relative to the monomer component total amount (100 quality %) forming said polyolefins system resin, is preferably 0.1 quality % ~ 10 quality %, is more preferably 1 quality % ~ 5 quality %.
In addition, in above-mentioned thermoplastic resin composition, except above-mentioned thermoplastic resin, " rubber and/or thermoplastic elastomer " can also be comprised as other compositions.
As above-mentioned rubber, there is no particular limitation, such as, can enumerate: the natural or synthetic rubber such as natural rubber, polyisobutene, synthetic polyisoprene, chloroprene rubber, isoprene-isobutylene rubber, paracril.Above-mentioned rubber can be used alone or combinationally uses two or more.
As above-mentioned thermoplastic elastomer, there is no particular limitation, such as, can enumerate: the thermoplastic olefin based elastomers such as ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-vinyl acetate copolymer, polybutene, polyisobutene, chlorinatedpolyethylene; Styrene-butadiene-styrene, styrene-isoprene-styrene copolymer-, styrene-isoprene-butadiene-styrene copolymer, their the thermoplastic styrene elastomerics such as hydride polymkeric substance; Thermoplastic polyester based elastomers; Thermoplastic polyurethane based elastomers; Thermoplastic propene's acids elastomerics etc.Above-mentioned thermoplastic elastomer can be used alone or combinationally uses two or more.
To the content of above-mentioned " rubber and/or the thermoplastic elastomer " in above-mentioned thermoplastic resin composition, there is no particular limitation, relative to above-mentioned thermoplastic resin composition's total amount (100 quality %), be preferably 0 quality % ~ 70 quality %, be more preferably 20 quality % ~ 60 % by weight, more preferably 20 quality % ~ 50 % by weight.
And then, in above-mentioned thermoplastic resin composition, except above-mentioned thermoplastic resin, can also containing " comprising the mixture (composition) of rubber and/or thermoplastic elastomer and tenderizer " as other compositions.It should be noted that, above-mentioned " comprising the mixture (composition) of rubber and/or thermoplastic elastomer and tenderizer " can also comprise additive as required.
As above-mentioned " comprising the mixture (composition) of rubber and/or thermoplastic elastomer and tenderizer ", such as, can enumerate: the mixture etc. at least comprising the mixture of rubber, thermoplastic elastomer and tenderizer, at least comprise the mixture of rubber and tenderizer, at least comprise thermoplastic elastomer and tenderizer.Wherein, preferably " only comprising the mixture of rubber and/or thermoplastic elastomer and tenderizer ".
As the rubber in above-mentioned " comprising the mixture of rubber and/or thermoplastic elastomer and tenderizer ", there is no particular limitation, preferably can enumerate the rubber as above-mentioned " rubber and/or thermoplastic elastomer " and the above-mentioned rubber exemplified.It should be noted that, this rubber can be used alone or combinationally uses two or more.
In addition, as the rubber in above-mentioned " comprising the mixture of rubber and/or thermoplastic elastomer and tenderizer " and/or thermoplastic elastomer, as long as just there is no particular limitation for foamable material, such as, can enumerate known usual " rubber and/or thermoplastic elastomer ".Wherein, the thermoplastic elastomer as above-mentioned " rubber and/or thermoplastic elastomer " can preferably be enumerated and the above-mentioned thermoplastic elastomer exemplified.It should be noted that, this thermoplastic elastomer can be used alone or combinationally uses two or more.
Especially, at use polyolefin-based resins as in the polyolefin resin composite of thermoplastic resin, as " rubber and/or thermoplastic elastomer " in above-mentioned " comprising the mixture of rubber and/or thermoplastic elastomer and tenderizer ", be preferably ethylene series elastomerics, be particularly preferably the ethylene series elastomerics of the structure with polyolefin component and ethylene series rubber constituent microphase-separated.There is as this ethylene series elastomerics of the structure of polyolefin component and ethylene series rubber constituent microphase-separated, the elastomerics formed can be shown preference by acrylic resin (PP) with ethylene-propylene rubber (EPM) or Ethylene-Propylene-Diene rubber (EPDM).It should be noted that, from the aspect of consistency, the mass ratio of said polyolefins composition and ethylene series rubber constituent is preferably polyolefin component/ethylene series rubber=90/10 ~ 10/90, is more preferably 80/20 ~ 20/80.
As above-mentioned tenderizer, there is no particular limitation, can preferably enumerate the tenderizer being generally used for rubber item.By containing above-mentioned tenderizer, processibility, flexibility can be improved.
As the object lesson of above-mentioned tenderizer, can enumerate: the petroleum materials such as process oil, lubricating oil, paraffin, whiteruss, petroleum pitch, Vaseline; The coal tar oils such as coal tar (coaltar), coal-tar pitch; Viscotrol C, Toenol 1140, rapeseed oil, soybean oil, coconut wet goods fatty oil; The wax classes such as Yatall MA (talloil), beeswax, carnauba wax (Carnaubawax), lanolin (lanolin); The synthetic high polymer matter such as petroleum resin, coumarone-indene resin (coumarone-indeneresin), Atactic Polypropelene (atacticpolypropylene); The ester cpds such as dioctyl phthalate (DOP), Octyl adipate, dioctyl sebacate; Microcrystalline Wax, ointment (factice), liquid polybutadiene, modified liquid polyhutadiene, liquid polysulphide rubber, liquid polyisoprene, liquid polybutene, liquid ethylene-alpha-olefin based copolymer etc.Wherein, the mineral oil of preferred paraffin series, naphthene series, fragrant family, liquid polyisoprene, liquid polybutene, liquid ethylene-alpha-olefin based copolymer, more preferably liquid polyisoprene, liquid polybutene, liquid ethylene-alpha-olefin based copolymer.It should be noted that, above-mentioned tenderizer can be used alone or combinationally uses two or more.
To the content of the tenderizer in above-mentioned " comprising the mixture of rubber and/or thermoplastic elastomer and tenderizer ", there is no particular limitation, relative to rubber and/or thermoplastic elastomer component 100 mass parts, be preferably 1 mass parts ~ 200 mass parts, be more preferably 5 mass parts ~ 100 mass parts, more preferably 10 mass parts ~ 50 mass parts.It should be noted that, if the content of tenderizer is too much, then sometimes with rubber and/or thermoplastic elastomer mixing time can cause disperse bad.
In above-mentioned " comprising the mixture of rubber and/or thermoplastic elastomer and tenderizer ", also additive can be added.As this additive, there is no particular limitation, such as, can enumerate: anti-aging agent, weather resisting agent, UV light absorber, dispersion agent, softening agent, carbon black, static inhibitor, tensio-active agent, tension modifier, mobility properties-correcting agent etc.It should be noted that, this additive can be used alone or combinationally uses two or more.
To the content of the above-mentioned additive in above-mentioned " comprising the mixture of rubber and/or thermoplastic elastomer and tenderizer ", there is no particular limitation, such as relative to rubber and/or thermoplastic elastomer component 100 mass parts, be preferably 0.01 mass parts ~ 100 mass parts, be more preferably 0.05 mass parts ~ 50 mass parts, more preferably 0.1 mass parts ~ 30 mass parts.It should be noted that, if above-mentioned content is more than 0.01 mass parts, then more easily embodies and add additive and the effect brought, therefore preferably.
To the melt flow rate (MFR) (MFR) (230 DEG C) of above-mentioned " comprising the mixture of rubber and/or thermoplastic elastomer and tenderizer ", there is no particular limitation, according to the viewpoint obtaining good formability, be preferably 3g/10 minute ~ 10g/10 minute, be more preferably 4g/10 minute ~ 9g/10 minute.
To " the JISA hardness " in above-mentioned " comprising the mixture of rubber and/or thermoplastic elastomer and tenderizer ", there is no particular limitation, is preferably 30 ° ~ 90 °, is more preferably 40 ° ~ 85 °.When above-mentioned " JISA hardness " is more than 30 °, becoming the foamed resin being easy to obtain high foamability, is preferred.In addition, when above-mentioned " JISA hardness " is below 90 °, becoming and be easy to obtain soft foamed resin, is preferred.It should be noted that, " JISA hardness " in this specification sheets refers to the hardness measured based on ISO7619 (JISK6253).
In the scope not damaging effect of the present invention, in the above-mentioned resin combination such as above-mentioned thermoplastic resin composition, also additive can be comprised.As above-mentioned additive, such as, can enumerate: bubble nucleating agent, crystallization nucleating agent, softening agent, lubricant, tinting material (pigment, dyestuff etc.), UV light absorber, antioxidant, anti-aging agent, weighting agent, toughener, static inhibitor, tensio-active agent, tension modifier, anti-shrinking medium, mobility properties-correcting agent, clay, vulcanizing agent, surface treatment agent, fire retardant etc.It should be noted that, above-mentioned additive can be used alone or combinationally uses two or more.
According to obtaining the viewpoint with the foamed resin layer of even and fine foam structure, preferably in above-mentioned resin combination, comprise bubble nucleating agent.Such as, if above-mentioned bubble nucleating agent comprises thermoplastic resin composition, then can easily obtain the foamed resin with even and fine foam structure, therefore preferably in above-mentioned thermoplastic resin composition, comprise bubble nucleating agent.
As above-mentioned bubble nucleating agent, such as, particle can be enumerated.As this particle, such as, can enumerate: the clay such as talcum, silicon-dioxide, aluminum oxide, zeolite, calcium carbonate, magnesiumcarbonate, barium sulfate, zinc oxide, titanium oxide, aluminium hydroxide, magnesium hydroxide, mica, polynite, carbon granule, glass fibre, carbon pipe etc.It should be noted that, particle can be used alone or combinationally uses two or more.
In the resin combinations such as above-mentioned thermoplastic resin composition, to the content of above-mentioned bubble nucleating agent, there is no particular limitation.Such as, above-mentioned thermoplastic resin composition is for containing above-mentioned thermoplastic resin and " comprising rubber and/or thermoplastic elastomer, and the mixture of tenderizer " resin combination time, to the content of the above-mentioned bubble nucleating agent in this resin combination, there is no particular limitation, relative to above-mentioned thermoplastic resin with " comprise rubber and/or thermoplastic elastomer, and the mixture of tenderizer (composition) " total amount (hereinafter sometimes referred to " total amount of resinous principle ") 100 mass parts, be preferably 0.5 mass parts ~ 125 mass parts, be more preferably 1 mass parts ~ 120 mass parts.
To the median size of above-mentioned particle, there is no particular limitation, is preferably 0.1 μm ~ 20 μm.When above-mentioned median size is lower than 0.1 μm, sometimes cannot play a role as foaming nucleation agent, on the other hand, when particle diameter is more than 20 μm, the reason of leaking gas when becoming foaming sometimes.
When comprising above-mentioned fire retardant in resin combination, foamed resin layer becomes flame retardant resistance, and can be used in electrically or electronics applications etc. requires the purposes of flame retardant resistance.Therefore, above-mentioned thermoplastic resin composition waits in resin combination and also can comprise fire retardant.
Above-mentioned fire retardant can be Powdered, also can be the form except Powdered.As pulverous fire retardant, preferred inorganic combustion inhibitor.As inorganic combustion inhibitor, such as, can enumerate: bromide fire retardant, chlorine-based flame retardant, phosphorus flame retardant, Sb system fire retardant, Halogen-without antimony system inorganic combustion inhibitor etc.Herein, chlorine-based flame retardant, bromide fire retardant burn time produce harmful, to equipment class, there is corrosive gaseous constituent, in addition, there is the problem such as hazardous property, explosivity in phosphorus flame retardant, Sb system fire retardant.Therefore, as inorganic combustion inhibitor, preferred Halogen-without antimony system inorganic combustion inhibitor.As Halogen-without antimony system inorganic combustion inhibitor, such as, can enumerate: the hydrated metal compounds etc. such as the hydrate of aluminium hydroxide, magnesium hydroxide, magnesium oxide nickel oxide, the hydrate of magnesium oxide zinc oxide.It should be noted that, hydrated metal oxide also can carry out surface treatment.In addition, fire retardant can be used alone or combinationally uses two or more.
From obtaining having flame retardant resistance and the aspect of the high foamed resin layer of expansion ratio, above-mentioned fire retardant preferably also has the function as bubble nucleating agent.As the fire retardant of the function had as bubble nucleating agent, such as, can enumerate: magnesium hydroxide, aluminium hydroxide etc.
In the resin combinations such as above-mentioned thermoplastic resin composition, to the content of above-mentioned fire retardant, there is no particular limitation.Such as, to the content of the above-mentioned fire retardant in above-mentioned thermoplastic resin composition, there is no particular limitation, relative to total amount 100 mass parts of above-mentioned resinous principle, is preferably 30 mass parts ~ 150 mass parts, is more preferably 60 mass parts ~ 120 mass parts.If the consumption of fire retardant is very few, then flame retardant effect is deteriorated, otherwise time too much, becomes the foam being difficult to obtain high-foaming.
In addition, when comprising above-mentioned lubricant in resin combination, the mobility of resin combination can be improved, can thermal degradation when be suppressed.Therefore, above-mentioned thermoplastic resin composition waits in resin combination and also can comprise lubricant.
As above-mentioned lubricant, there is no particular limitation, such as, can enumerate: the hydrocarbon system lubricants such as whiteruss, solid paraffin, Microcrystalline Wax, polyethylene wax; The fatty acid series lubricants such as stearic acid, behenic acid, 12-oxystearic acid; The ester base lubricants etc. such as butyl stearate, glyceryl monostearate, pentaerythritol tetrastearate, hydrogenated castor oil, stearyl stearate.It should be noted that, lubricant can be used alone or combinationally uses two or more.
In the resin combinations such as above-mentioned thermoplastic resin composition, to the content of above-mentioned lubricant, there is no particular limitation.Such as, when above-mentioned thermoplastic resin composition is the resin combination containing above-mentioned thermoplastic resin and " comprising the mixture of rubber and/or thermoplastic elastomer and tenderizer ", to the content of the above-mentioned lubricant in this resin combination, there is no particular limitation, relative to total amount 100 mass parts of above-mentioned resinous principle, be preferably 0.1 mass parts ~ 10 mass parts, be more preferably 0.5 mass parts ~ 5 mass parts.If addition is more than 10 mass parts, then mobility becomes too high and expansion ratio reduction sometimes.In addition, if lower than 0.1 mass parts, then sometimes cannot realize the raising of mobility, extensibility during foaming reduces and expansion ratio reduces.
In addition, above-mentioned anti-shrinking medium have the surface of the bubble chamber film of foam formed molecular film and effectively suppress foaming agent gas through effect.Therefore, according to the viewpoint obtaining the bubble structure of high foamability in above-mentioned foamed resin layer, in the above-mentioned resin combination such as above-mentioned thermoplastic resin composition, also anti-shrinking medium can be comprised.As above-mentioned anti-shrinking medium, as long as show suppress foaming agent gas through effect just there is no particular limitation, such as can enumerate: fatty acid metal salt aluminium, calcium, magnesium, lithium, barium, zinc, the plumbous salt etc. of lipid acid (such as stearic acid, behenic acid, the 12-oxystearic acid etc.); [carbonatoms of lipid acid is that the fatty acid amide of about 12 ~ 38 (being preferably about 12 ~ 22) (can, for any person in monoamide, bisamide, in order to obtain micro cell structure, can be suitable for using bisamide to fatty acid amide.), such as stearic amide, amine hydroxybenzene, erucicamide, methylene-bis stearic amide, ethylenebis stearic amide, lauric acid bisamide etc.] etc.It should be noted that, this anti-shrinking medium can be used alone or combinationally uses two or more.
In the resin combinations such as above-mentioned thermoplastic resin composition, to the addition (content) of above-mentioned anti-shrinking medium, there is no particular limitation.Such as, when above-mentioned thermoplastic resin composition is the resin combination containing above-mentioned thermoplastic resin and " comprising the mixture of rubber and/or thermoplastic elastomer and tenderizer ", as the addition of the above-mentioned anti-shrinking medium in this resin combination, there is no particular limitation, relative to total amount 100 mass parts of resinous principle, be preferably 0.5 mass parts ~ 10 mass parts, be more preferably 0.7 mass parts ~ 8 mass parts, more preferably 1 mass parts ~ 6 mass parts.If addition is more than 10 mass parts, then can in cell growth process, gas efficiency be reduced, the non-frothing part that therefore sometimes can obtain the less foam of cell diameter also increases, and expansion ratio reduces.In addition, if lower than 0.5 mass parts, then the formation of overlay film is insufficient sometimes, produces gas leakage and cause contraction during foaming, thus expansion ratio reduces.
It should be noted that, as additive, there is no particular limitation, such as, also can combinationally use above-mentioned lubricant and above-mentioned anti-shrinking medium.Such as also can combinationally use the lubricants such as glyceryl monostearate and the anti-shrinking medium such as erucicamide, lauric acid bisamide.
To the making method of above-mentioned resin combination, there is no particular limitation.Such as, to above-mentioned thermoplastic resin composition, there is no particular limitation, above-mentioned thermoplastic resin, other compositions as required, the additive that adds as required can be carried out mixing making.In addition, also by utilizing the known melting mixing such as single-screw intermixing extruder, twin-screw mixer extruder extrusion device carry out mixing and extrude, thus obtain.
As the shape of the above-mentioned resin combinations such as above-mentioned thermoplastic resin composition, there is no particular limitation, such as, and strand (strand) shape; Sheet; Tabular; Strand carried out water-cooled or air cooling and be cut into the particulate state etc. of suitable length.Wherein, from the view point of productivity, preferably carry out mixing and granulating in advance.
To the above-mentioned foamed resin layer in resin expanded complex body of the present invention, there is no particular limitation, foam preferably by making above-mentioned resin combination and formed, special by preferably by after making above-mentioned resin combination foam, further effects on surface carries out heating and melting process to form upper layer.Such as, formed preferably by making above-mentioned thermoplastic resin composition (such as said polyolefins based resin composition) foam.Particularly preferably by make above-mentioned thermoplastic resin composition (such as said polyolefins based resin composition) foam after, further effects on surface carries out heating and melting process to form upper layer.
As the method making the resin combination foaming such as above-mentioned thermoplastic resin composition (such as said polyolefins based resin composition), there is no particular limitation, such as, can enumerate physical foaming method, chemical foaming method.Above-mentioned physical foaming method makes low-boiling point liquid (whipping agent) infiltrate (dispersion) in resin combination, then makes whipping agent volatilize, form the method for abscess (bubble) thus.In addition, above-mentioned chemical foaming method is the method that gas by being produced by the thermolysis of the compound be added in resin combination forms abscess.Wherein, according to avoiding the viewpoint of the pollution of foamed resin layer, obtaining the viewpoint of the easy degree of fine and uniform bubble structure, preferred physical foaming method, more preferably use high pressure gas are as the physical foaming method of whipping agent.Therefore, the above-mentioned foamed resin layer in resin expanded complex body of the present invention makes it foam after particularly preferably making high pressure gas (such as non-active gas described later) infiltration in the resin combinations such as above-mentioned thermoplastic resin composition (such as said polyolefins based resin composition) and is formed.
To above-mentioned non-active gas, there is no particular limitation, such as, can enumerate: carbonic acid gas, nitrogen, air, helium, argon gas etc.Particularly, infiltrate fireballing aspect many from the infiltration amount in the above-mentioned resin combinations such as above-mentioned thermoplastic resin composition, above-mentioned non-active gas is preferably carbonic acid gas.It should be noted that, above-mentioned non-active gas can be used alone or combinationally uses two or more.
To the combined amount (content, infiltration amount) of above-mentioned whipping agent, there is no particular limitation, relative to the gross weight (100 quality %) of the resin combinations such as above-mentioned thermoplastic resin composition, is preferably 2 quality % ~ 10 quality %.By being in above-mentioned scope, the apparent density of the above-mentioned foamed resin layer in resin expanded complex body of the present invention can be easily made to be the scope specified.
From the aspect of the infiltration speed accelerated in the resin combinations such as thermoplastic resin composition, above-mentioned non-active gas is preferably supercritical state when infiltrating.Such as, the above-mentioned foamed resin layer in resin expanded complex body of the present invention is formed preferably by utilizing supercutical fluid to make above-mentioned thermoplastic resin composition (such as said polyolefins based resin composition) foam.When above-mentioned non-active gas is supercutical fluid (supercritical state), solubleness in the resin combinations such as thermoplastic resin composition increases, can the infiltration (being mixed into) of high density.In addition, owing to can infiltrate with high density, when therefore making pressure sharply reduce after infiltration, the generation of nuclei of bubbles increases, even if this nuclei of bubbles growth and the density of bubble that formed also can increase when void content is identical, therefore, it is possible to obtain fine bubble.It should be noted that, the critical temperature of carbonic acid gas is 31 DEG C, and emergent pressure is 7.4MPa.
For the physical foaming method using gas as whipping agent, preferably by via make high pressure gas (such as non-active gas etc.) infiltrate in thermoplastic resin composition's resin combination of etc.ing after carry out the reducing pressure operation (operation of relief pressure) of (such as until normal atmosphere) make it foam, thus the method for formation.Specifically, following method can be enumerated: by via by shaping for the resin combinations such as thermoplastic resin composition and obtain non-foaming thing, high pressure gas are infiltrated in this non-foaming thing, then the operation of decompression (such as until normal atmosphere) makes it foam, the method formed thus; Or under pressurised conditions, gas (such as non-active gas etc.) is infiltrated to wait in resin combination the thermoplastic resin composition of melting, then reduce pressure (such as until normal atmosphere) makes it foam and carries out shaping and method etc. that is that formed.
Namely, when forming the above-mentioned foamed resin layer in resin expanded complex body of the present invention, can be undertaken by intermittent mode, or also can be undertaken by continuous mode, the resin combinations such as above-mentioned thermoplastic resin composition (such as said polyolefins based resin composition) are shaped to after the suitable shapes such as sheet make non-foamex formed body (non-foaming thing) by described intermittent mode, high pressure gas are infiltrated in this non-foamex formed body, and relief pressure, it is made to foam thus, described continuous mode under elevated pressure conditions by the resin combinations such as above-mentioned thermoplastic resin composition and high pressure gas jointly mixing and shaping, meanwhile relief pressure, carry out shaping with foaming simultaneously.
In above-mentioned intermittent mode, to the method forming non-foamex formed body, there is no particular limitation, such as, can enumerate: use the forcing machine such as single screw extrusion machine, twin screw extruder by method shaping for the resin combinations such as thermoplastic resin composition; Use roller, cam, kneader, Banbury type etc. to establish vaned mixing roll that the resin combinations such as thermoplastic resin composition is evenly mixing in advance, utilize the compacting of hot plate etc. by the method for its compression moulding for the thickness of regulation; Use injection moulding machine by method etc. shaping for the resin combinations such as thermoplastic resin composition.In addition, to the shape of non-foamex formed body, there is no particular limitation, such as, can enumerate: sheet, web-like, tabular etc.In above-mentioned intermittent mode, by the appropriate means of non-foamex formed body of desired shape, thickness can be obtained, by the shaping non-foamex formed body of the resin combinations such as thermoplastic resin composition.
In above-mentioned intermittent mode, form bubble structure via following operation: gas infiltration operation, adds non-foamex formed body in pressure vessel, inject (import, be mixed into) high pressure gas, make gas infiltration in non-foamex formed body; Decompression operation, the moment relief pressure fully infiltrated making gas (usually until normal atmosphere), makes to generate nuclei of bubbles in non-foamex formed body.
On the other hand, in above-mentioned continuous mode, by following operation, thermoplastic resin composition is waited resin combination foaming: (i) mixing impregnation step, while use forcing machine (such as single screw extrusion machine, twin screw extruder etc.), injection moulding machine carries out mixing to resin combinations such as thermoplastic resin compositions, while inject (import, be mixed into) high pressure gas, high pressure gas are fully infiltrated up in the resin combinations such as thermoplastic resin composition; (ii) shaping decompression operation, waits resin combination to extrude the thermoplastic resin composition being impregnated with gas by being arranged on the mould of forcing machine front end etc., thus relief pressure (usually until normal atmosphere), carries out shaping with foaming simultaneously.
As required, above-mentioned intermittent mode, continuous mode also can be arranged through the heating process heating and nuclei of bubbles is grown.It should be noted that, also can not heating process is set and at room temperature make nuclei of bubbles grow.And then, also after making air bubble growth, cold water etc. can be utilized as required to cool rapidly, shape fixed.The importing of high pressure gas can be carried out continuously, also can discontinuously carry out.It should be noted that, there is no particular limitation for heating means when growing making nuclei of bubbles, can enumerate: the known customary ways such as water-bath, oil bath, hot-rolling, hot-air oven, far infrared rays, near infrared ray, microwave.
In the mixing impregnation step of the gas infiltration operation of above-mentioned intermittent mode, above-mentioned continuous mode, consider the kind, operability etc. of gas and be suitable for selecting pressure when making gas infiltration, such as, preferred more than 5MPa (such as 5MPa ~ 100MPa), more preferably more than 7MPa (such as 7MPa ~ 100MPa).Namely, preferably make the gas infiltration of more than pressure 5MPa (such as pressure 5MPa ~ 100MPa) in the resin combinations such as above-mentioned thermoplastic resin composition, more preferably make the non-active gas infiltration of more than pressure 7MPa (such as pressure 7MPa ~ 100MPa) in the resin combinations such as above-mentioned thermoplastic resin composition.When the pressure of gas is lower than 5MPa, air bubble growth during foaming is remarkable, and abscess becomes excessive, and easily producing the unfavorable conditions such as such as dust-proof effect reduction, is not preferred.This is because when pressure is low, the infiltration amount of gas is relatively less compared with during high pressure, nuclei of bubbles forms speed and reduces, and the bubble check figure formed reduces, and therefore the gas volume of single isolated bubbles increases on the contrary, and bubble diameter becomes very big.In addition, lower than in the pressure span of 5MPa, only make infiltration pressure change a little, cell diameter, bubble density will significantly change, and therefore easily become and are difficult to control cell diameter and bubble density.
In addition, in gas infiltration operation in above-mentioned intermittent mode, the mixing impregnation step in above-mentioned continuous mode, make the temperature (infiltration temperature) during gas infiltration different according to the kind of used gas, resin, can on a large scale in select, but when considering operability etc., be preferably 10 DEG C ~ 350 DEG C.More specifically, the infiltration temperature under intermittent mode is preferably 10 DEG C ~ 250 DEG C, be more preferably 40 DEG C ~ 240 DEG C, more preferably 60 DEG C ~ 230 DEG C.In addition, the infiltration temperature under continuous mode is preferably 60 DEG C ~ 350 DEG C, be more preferably 100 DEG C ~ 320 DEG C, more preferably 150 DEG C ~ 300 DEG C.It should be noted that, when using carbonic acid gas as high pressure gas, in order to keep supercritical state, the temperature (infiltration temperature) during infiltration is preferably more than 32 DEG C (particularly more than 40 DEG C).In addition, also can, after making gas infiltration, before foaming, resin combination be waited to be cooled to the temperature (such as 150 DEG C ~ 190 DEG C) of applicable foaming the thermoplastic resin composition being impregnated with gas.
And then, in above-mentioned intermittent mode, above-mentioned continuous mode, to the decompression rate in decompression operation (operation of relief pressure), there is no particular limitation, from the aspect obtaining the bubble structure with even and fine abscess, be preferably 5MPa/ second ~ 300MPa/ second.
When arranging heating process to make nuclei of bubbles grow, Heating temperature is such as preferably 40 DEG C ~ 250 DEG C, is more preferably 60 DEG C ~ 250 DEG C.
It should be noted that, for bubble structure, the apparent density of the above-mentioned foamed resin layer in resin expanded complex body of the present invention, according to the kind of the resin formed, such as by selecting the foaming method during resin combination foamings such as thermoplastic resin composition, foaming condition (kind of such as whipping agent, amount, temperature during foaming, pressure, time etc.) and adjusting.
Foamed resin layer in resin expanded complex body of the present invention particularly preferably carries out slice processing by effects on surface further after making thermoplastic resin composition wait resin combination foaming and is formed.Specifically, formed preferably by with under type: after making above-mentioned thermoplastic resin composition wait resin combination foaming to obtain foam (sheet foam A), slice processing is carried out to the surface of the side, two sides of this foam.Above-mentioned sheet foam A (make the resin combinations such as above-mentioned thermoplastic resin composition foam the foam obtained) has the inner high stratiform part of density ratio (expansion ratio than inner low stratiform part, table (skin) layer) near surface mostly.By slice processing, this stratiform part (top layer) can be removed, and inner bubble structure can be made to be exposed to foam surface and opening portion is set.In addition, by slice processing, the foamed resin layer of any thickness can be obtained with good thickness and precision.
As slice processing, the top layer of serial section device (slice) as shown in Figure 1 stripper surface one by one can be used.That is, in order to remove the top layer on surface, making rectangular foam reel (such as sheet foam A etc.) by twice in serial section device, forming opening portion on two surfaces thus.
The foamed resin layer used in the present invention preferably forms upper layer making the rear effects on surface further of above-mentioned resin combination foaming carry out heating and melting process.After particularly preferably making above-mentioned thermoplastic resin composition foam, further effects on surface carries out heating and melting process and forms upper layer.More specifically, after obtaining foam (sheet foam) preferably by making above-mentioned thermoplastic resin composition wait resin combination foaming, heating and melting process is carried out to the surface of this foam and forms upper layer.So, by making the melt surface of thickness direction, the thickness of foamed resin layer can be adjusted to thinner.And then flexibility reduction suppression can be inferior limit and improve the tensile strength of length direction, suppress the generation of fracture, fragmentation etc., easily the rectangular foamed resin layer of continuous acquisition.And then, non-foamed state (bulk) is returned to by making frothing part, the roughness (thickness error) on surface originally reduces further, and thickness and precision improves, even if therefore for also suppressing at a high speed the generation of gauffer (winding gauffer when batching).It should be noted that, in this specification sheets, sometimes by obtain by making above-mentioned resin combination foam, be called " foamed structures " for sheet and carrying out heating and melting foam before treatment.
To heating and melting process, there is no particular limitation, according to the generation of the gauffer suppressed when batching, the generation of the gauffer particularly during high speed wind-up and obtain the better viewpoint of batching stability and improve the viewpoint of thickness and precision, is preferably at least one side whole implementation heating and melting process to above-mentioned foamed structures.Namely, by make above-mentioned thermoplastic resin composition foam after, and then effects on surface is when carrying out heating and melting process and form the foamed resin layer used in the present invention, preferably by make above-mentioned thermoplastic resin composition foam and after obtaining foamed structures, heating and melting process is implemented to the single or double of this foamed structures, is formed thus.In addition, the heating and melting process of more than twice also can be implemented to the same face.
And then, also can carry out heating and melting process with the form of the resin expanded complex body being laminated with binder layer described later.Also after making the resin expanded complex body being laminated with foamed structures and binder layer, heating and melting process can be carried out to foamed structures and forms upper layer.
As above-mentioned heating and melting process, there is no particular limitation, such as, can enumerate: utilize the pressing treatment of hot-rolling, laser radiation process, through heating roller on contact melting treatment, flame treating etc.When utilizing the pressing treatment of hot-rolling, heat-laminator etc. can be used suitably to process.It should be noted that, as the material of roller, rubber, metal, fluorine resin (such as, Teflon (registered trademark)) etc. can be listed.
To temperature during above-mentioned heating and melting process, there is no particular limitation, be preferably the temperature of more than the softening temperature of resin or the temperature (being more preferably the softening temperature of the resin comprised than foamed structures or the temperature of low 12 DEG C of fusing point) of low 15 DEG C of fusing point comprised than foamed structures, in addition, the softening temperature of resin comprised than foamed structures or temperature (being more preferably the softening temperature of the resin comprised than foamed structures or the temperature of high 10 DEG C of the fusing point) temperature below of high 20 DEG C of fusing point is preferably.
In addition, when carrying out heating and melting process with the form of the resin expanded complex body being laminated with binder layer, temperature during heating and melting process being not particularly limited, being preferably than more than the softening temperature of resin or the temperature of high 40 DEG C of fusing point.
Such as, be preferably more than the softening temperature of thermoplastic resin (such as said polyolefins system resin etc.) or the temperature (being more preferably the softening temperature of the thermoplastic resin comprised than foamed structures or the temperature of low 12 DEG C of fusing point) of low 15 DEG C of fusing point comprised than foamed structures, in addition, the temperature (being more preferably the softening temperature of the thermoplastic resin comprised than foamed structures or the temperature of high 10 DEG C of fusing point) of the softening temperature of the thermoplastic resin comprised than foamed structures or high 20 DEG C of fusing point is preferably below.When temperature during heating and melting process is higher than temperature than the softening temperature of the resin such as thermoplastic resin formed or low 15 DEG C of fusing point, be preferred from the aspect effectively can implementing heating and melting process.In addition, when temperature during heating and melting process is lower than temperature than the softening temperature of the resin such as thermoplastic resin formed or high 20 DEG C of fusing point, can suppresses to shrink and produce gauffer etc., be preferred.
In addition, as the treatment time of heating and melting process, relevant to treatment temp, be such as preferably 0.1 second ~ about 10 seconds, be preferably 0.5 second ~ about 7 seconds.This is because if the time is too short, melting sometimes cannot be carried out, in addition, if overlong time, shrink and produce gauffer etc.
Especially, produce according to the gauffer suppressed when batching, particularly batching at high speeds time gauffer produce and obtain the viewpoint of the better viewpoint of batching stability and further raising thickness and precision, above-mentioned heating and melting process preferably uses the heating and melting treatment unit by gap (gap, interval) that can regulate foamed structures.
As this heating and melting treatment unit, such as, can enumerate the apparatus for continous treatment of the warming mill (hot dielectric roller) 23 with adjustable clearance of Fig. 2.Namely, make to pass through in warming mill (hot dielectric roller) 23 with the gap of cooling roller 24 from the foamed structures of conveying roller 21, utilize hot-rolling (hot dielectric roller) 23 to carry out contact melting treatment, and utilize winding roller 25 to reel to be formed with the foamed resin layer of upper layer by heat fusing process.
The apparent density forming the foamed resin of the foamed resin layer in resin expanded complex body of the present invention is low, thin and soft, stability (batching stability) when batching is excellent.Therefore, it is possible to obtain the wide and longer rectangular volume of width.In addition, the foamed resin forming above-mentioned foamed resin layer is thinner, can improve thickness and precision.
When foamed resin layer in resin expanded complex body of the present invention arranges upper layer, being preferably surface-coated rate is the face of more than 40%.That is, above-mentioned foamed resin layer preferably has the upper layer that surface-coated rate is more than 40%.
Above-mentioned surface-coated rate is preferably more than 40%, is more preferably more than 45%, more preferably more than 50%.
Above-mentioned surface-coated rate is the index of the ratio in the non-hole portion (what surface existed is not the part in hole, the part of block, non-foamed state) that display surface exists, and defines by following formula (1).It should be noted that if surface-coated rate is 100%, then on this face, to there is not hole portion.
Surface-coated rate (%)=[(area on surface)-(area in the hole that surface exists)]/(area on surface) × 100 (1)
For the thickness of the foamed resin layer in resin expanded complex body of the present invention, as long as design to make the mode that the thickness of resin expanded complex body is below 0.35mm, then there is no particular limitation, is preferably 0.03mm ~ 0.34mm, is more preferably 0.04mm ~ 0.28mm, more preferably 0.05mm ~ 0.20mm.If the thickness of foamed resin layer is in above-mentioned scope, then has and keep HI high impact absorptivity and the advantage inserted in narrow gap can be compressed.On the other hand, if the thickness of foamed resin is lower than 0.03mm, then sometimes reduce as the impact absorbency of main application, on the other hand, if the thickness of foamed resin is more than 0.34mm, then sometimes cannot be inserted in the such narrow gap of 0.1mm.It should be noted that, in resin expanded complex body of the present invention, the thickness of foamed resin layer refers to the thickness comprising above-mentioned upper layer.
To the value obtained by following formula (2) of the foamed resin layer in resin expanded complex body of the present invention, there is no particular limitation, is preferably less than 25%, is more preferably less than 15%, more preferably less than 10%.If " value obtained by formula (2) " is within 25%, then can suppress the generation of gauffer when batching, the generation of gauffer when particularly batching at high speeds obtain and better batch stability, be preferred.In addition, can obtaining high thickness and precision, therefore preventing the generation of gauffer when fitting with binder layer, be preferred.It should be noted that, in this specification sheets, high speed when batching refers to the speed of such as 10 ~ 40m/ minute.
(thickness deviation)/(central value of thickness) × 100 (2)
Thickness deviation refers to the value obtained as follows: at 1 place of length direction, thickness is measured to the other end every 10mm in the width direction from an end, and then measure thickness to the other end every 10mm from an end in the width direction, the difference of the maxima and minima of whole measured values of gained at 1 some place moving 1m along its length by above-mentioned length direction.
The central value of thickness refers to the value obtained as follows: at 1 place of length direction, thickness is measured to the other end every 10mm in the width direction from an end, and then measure thickness to the other end every 10mm from an end in the width direction at 1 some place moving 1m along its length by above-mentioned length direction, be in the value of middle position when whole measured values of gained being arranged according to order from small to large.
In foamed resin layer in resin expanded complex body of the present invention, the foamed resin used in foamed resin layer can be flap, also can be taken up and be web-like (coiling body).
In foamed resin layer in resin expanded complex body of the present invention, when making with flap the foamed resin used in foamed resin layer, to its width, there is no particular limitation, is preferably more than 300mm (such as 300mm ~ 1500mm), is more preferably more than 400mm (such as 400mm ~ 1200mm), more preferably more than 500mm (such as 500mm ~ 1000mm).Because above-mentioned width is more than 300mm, therefore, it is possible to carry out the high design of degree of freedom, processing, be preferred.
In addition, in foamed resin layer in resin expanded complex body of the present invention, when making with flap the foamed resin used in foamed resin layer, to its length, there is no particular limitation, is preferably more than 5m (such as 5m ~ 1000m), is more preferably more than 30m (such as 30m ~ 500m), more preferably more than 50m (such as 50m ~ 300m).
[binder layer]
In resin expanded complex body of the present invention, binder layer refers to be provided the adhesive face of above-mentioned foamed resin layer and the nonwoven fabric from filaments to the adhesive face of clung body.Such as, the binder layer in resin expanded complex body of the present invention comprises without base material double-sided adhesive sheet (adhesive sheet be only made up of a binder layer), the band double-sided adhesive sheet (having the adhesive sheet of binder layer at the double-face side of base material) of base material, the binder layer etc. of band base material described later.
To the binder layer in resin expanded complex body of the present invention, there is no particular limitation, such as, can be formed by following tackiness agent: the tackiness agent such as acrylic adhesives, elastomeric adhesive (natural rubber system tackiness agent, synthetic rubber system tackiness agent etc.), silicon-type tackiness agent, Polyester tackiness agent, carbamate system tackiness agent, polyamide-based tackiness agent, epoxy adhesive, vinyl alkyl ethers system tackiness agent, fluorine system tackiness agent.Especially, from the aspect with high adhesion characteristic and thermotolerance, preferably acrylic adhesives is used.Above-mentioned tackiness agent can be used alone or combinationally uses two or more.It should be noted that, above-mentioned tackiness agent can be the tackiness agent of any form in emulsion system tackiness agent, solvent system tackiness agent, Hotmelt Adhesive, oligomeric system tackiness agent, solid system tackiness agent etc.
Particularly, because the transparency is high, thermotolerance, excellent in light-resistance, the tackiness agent therefore forming the binder layer in resin expanded complex body of the present invention is preferably acrylic adhesives.That is, the binder layer in resin expanded complex body of the present invention is preferably acrylic adhesive layer.
Above-mentioned tackiness agent contains the suitable additive such as base polymer and linking agent as required, tackifier, tenderizer, softening agent, weighting agent, anti-aging agent, tinting material.Such as, aforesaid propylene acrylic binder using acrylic polymers as binding property composition (base polymer) or host, and wherein as required containing the additive that linking agent, tackifier, tenderizer, softening agent, weighting agent, anti-aging agent, tinting material etc. are suitable.
In aforesaid propylene acrylic binder, for aforesaid propylene acids polymers, preferably by (methyl) alkyl acrylate as monomer main component, as required use can carry out the monomer (co-polymerized monomer) of copolymerization as other monomer component with above-mentioned (methyl) alkyl acrylate.As above-mentioned (methyl) alkyl acrylate, such as, can enumerate: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Ethyl acrylate, (methyl) heptylacrylate, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid pentadecyl ester, (methyl) aliphatic acrylate, (methyl) vinylformic acid heptadecyl ester, (methyl) octadecyl acrylate, (methyl) vinylformic acid nonadecyl ester, (methyl) vinylformic acid eicosyl ester etc. has (methyl) alkyl acrylate that carbonatoms is the straight-chain of 1 ~ 20 or the alkyl of branched and (is sometimes referred to as " (methyl) vinylformic acid C 1-20alkyl ester ").As above-mentioned (methyl) alkyl acrylate, wherein, preferably can enumerate and there is (methyl) alkyl acrylate that carbonatoms is the straight-chain of 4 ~ 18 or the alkyl of branched (be sometimes referred to as " (methyl) vinylformic acid C 4-18alkyl ester ").Above-mentioned (methyl) alkyl acrylate can suitablely according to target binding property etc. be selected.In addition, above-mentioned (methyl) alkyl acrylate can be used alone or combinationally use two or more.
In addition, as the above-mentioned co-polymerized monomer in aforesaid propylene acids polymers, such as, can enumerate: carboxylic monomer or its acid anhydrides such as (methyl) vinylformic acid, methylene-succinic acid, toxilic acid, fumaric acid, β-crotonic acid, iso-crotonic acid; Sodium vinyl sulfonates etc. are containing sulfonic monomer; The aromatic ethenyl compound such as vinylbenzene, substituted phenylethylene; The monomer of the cyano-containings such as vinyl cyanide; The olefines such as ethene, propylene, divinyl; The vinyl esters such as vinyl-acetic ester; Vinylchlorid; The monomer of the amide-containings such as acrylamide, Methacrylamide, NVP, N, N-dimethyl (methyl) acrylamide; The monomer of hydroxyl such as (methyl) hydroxyalkyl acrylates, glycerine dimethacrylate etc.; (methyl) acrylate, (methyl) acryloyl morpholine etc. are containing amino monomer; Cyclohexyl maleic acid ester imines, isopropylmaleimide etc. are containing the monomer of imide; (methyl) glycidyl acrylate, (methyl) vinylformic acid methylglycidyl esters etc. are containing the monomer of epoxy group(ing); 2-methacryloxyethyl isocyanic ester etc. are containing the monomer etc. of isocyanate group.In addition, also can enumerate: triethylene glycol two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, TEG two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, the co-polymerized monomer (polyfunctional monomer) etc. that Vinylstyrene etc. are multi-functional.Above-mentioned co-polymerized monomer can be used alone or combinationally uses two or more.As co-polymerized monomer, can preferably enumerate the modification monomer with functional groups such as carboxyls.
Base polymer in above-mentioned tackiness agent can utilize usual polymerization process to be prepared.Such as, aforesaid propylene acids polymers can utilize the usual polymerization process such as solution polymerization process, emulsion polymerization, uviolizing polymerization to be prepared.
Binder layer can utilize known or usual formation method to be formed, such as can enumerate: on the position or face of regulation coating adhesive method (coating process), on the stripping films such as release liner coating adhesive and after forming bonding coat, this binder layer is transferred to the method (printing transferring method) etc. on the position of regulation or face.It should be noted that, when the formation of binder layer, can be suitable for utilizing known usual coating process (casting method, roller coating machine method, reverse roll coater method, doctor blade method etc.).
Binder layer in resin expanded complex body of the present invention can be individual layer, also can be duplexer.In addition, the binder layer in resin expanded complex body of the present invention also can for comprising the binder layer in the binder layer of the band base material of suitable base material.The binder layer of above-mentioned band base material such as also can for having the double-sided adhesive mould assembly of binder layer at the double-face side of base material.It should be noted that, when binder layer in resin expanded complex body of the present invention is the binder layer in the binder layer of band base material, the total thickness (thickness) of above-mentioned resin expanded complex body comprises the thickness of the thickness of foamed resin and the binder layer of band base material.
That is, resin expanded complex body of the present invention also can for being laminated with the resin expanded complex body of the binder layer of above-mentioned foamed resin layer and above-mentioned band base material.Such as, resin expanded complex body of the present invention can have the formation sequentially laminated with the binder layer in the binder layer of the base material in the binder layer of the binder layer in the binder layer of above-mentioned foamed resin layer, above-mentioned band base material, above-mentioned band base material, above-mentioned band base material.It should be noted that, this formation is equivalent to the formation of the binder layer of the band base material being laminated with above-mentioned foamed resin layer and double-sided adhesive mould assembly.
The binder layer of above-mentioned band base material also can for the plastics system base materials such as paper system base material, fiber system base material, metal system base material, PET film etc. two-sided on be provided with the binder layer of the band base material of the binder layer formed by above-mentioned tackiness agent.It should be noted that, when the binder layer of band base material is double-sided adhesive mould assembly, the composition of two binder layers can be the same or different.In addition, the thickness of two binder layers can be the same or different.
As the material of the base material in the binder layer of above-mentioned band base material, there is no particular limitation, and plastic material is suitable.As this plastic material (material of plastic film), various engineering plastic materials can be enumerated aptly.As plastic material, such as, can enumerate: polyester [polyethylene terephthalate (PET), PEN (PEN), polybutylene terephthalate (PBT) etc.]; Ethylene series resin [the ethylene series resin etc. using alpha-olefin as monomer component such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, vinyl-vinyl acetate copolymer (EVA)]; Polyethersulfone (PES) (polyethersulfone); Polysulfones; Polyvinyl chloride (PVC); Polyphenylene sulfide (PPS); Acid amides system resin [polymeric amide (nylon), fully aromatic polyamide (aromatic poly amide) etc.], polyimide (PI), polyamidoimide, polyetherimide (PEI), polyester-imide, methacrylate ester resin [polymethylmethacrylate (PMMA) etc.]; Phenylethylene resin series [polystyrene, acrylonitritrile-styrene resin (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin) etc.]; Polycarbonate (PC); Polyacetal; Poly (arylene ether) (polyphenylene oxide etc.); Polyphenylene sulfide; Polyarylester; Poly-aryl compound; Polyurethanes; Polyethers ketone [polyether-ether-ketone (PEEK), PEKK etc.]; Polyacrylate(s) [butyl polyacrylate, polyethyl acrylate etc.]; Epoxy system resin etc.These starting material (plastic material) can be used alone or combinationally use two or more.
As above-mentioned plastic material, according to viewpoints such as thickness and precision, economy (cost), tensile strength, processibilities, polyester (especially polyethylene terephthalate) can be enumerated especially aptly.That is, as the base material in the binder layer of above-mentioned band base material, polyester film (especially pet film) can be enumerated especially aptly.
It should be noted that, above-mentioned base material also can have individual layer, stacked in any form, not by structural restriction.
As the thickness of above-mentioned base material, there is no particular limitation, is preferably 0.0005mm ~ 0.038mm, is more preferably 0.001mm ~ 0.025mm, more preferably 0.002mm ~ 0.012mm.
In addition, above-mentioned binder layer also can pass through stripping film (isolated body) (such as interleaving paper, stripping film etc.) protection adhesive face.It should be noted that, stripping film (isolated body) is not included in the total thickness (thickness) of resin expanded complex body of the present invention.
The thickness of the above-mentioned binder layer in resin expanded complex body of the present invention is 0.0005mm ~ 0.06mm, is preferably 0.0007mm ~ 0.05mm, is more preferably 0.001mm ~ 0.04mm, more preferably 0.002mm ~ 0.04mm.If the thickness of binder layer is in above-mentioned scope, then exists and maintain suitable bounding force, and also can compress the advantage of foam.On the other hand, if the thickness of binder layer is lower than 0.0005mm, then cannot obtain sufficient bounding force, on the other hand, if the thickness of binder layer is more than 0.06mm, even if then through-thickness compression binder layer sometimes, the thickness of the binder layer after compression also can not fully diminish, even if sometimes compress foam also can not become the size being less than the gap that will apply.Its result, when resin expanded complex body being applied to gap, is difficult to use sometimes.It should be noted that, in resin expanded complex body of the present invention, when binder layer is the binder layer in the binder layer of band base material, the thickness of binder layer refers to the thickness comprising base material.Such as, when the binder layer in resin expanded complex body of the present invention is the binder layer in the bonding coat of the band base material of double-sided adhesive mould assembly, the thickness that the thickness of above-mentioned binder layer comprises base material and the thickness of two binder layers had at the double-face side of base material.
[resin expanded complex body]
Resin expanded complex body of the present invention is the formation being laminated with above-mentioned foamed resin layer and above-mentioned binder layer.If have binder layer, be then conducive to clung body fixing, temporarily fix, from the aspect of assembleability, be favourable.It should be noted that, to the shape of resin expanded complex body of the present invention, there is no particular limitation, can be sheet (membranaceous), web-like, in addition, also can according to purposes Punching Technology, be cut into different shape.
To the making method of resin expanded complex body of the present invention, there is no particular limitation.Such as, resin expanded complex body of the present invention can by arranging above-mentioned binder layer to make on above-mentioned foamed resin layer.When above-mentioned foamed resin layer arranges above-mentioned binder layer, to reduce as far as possible, the mode of the tension force that foamed resin layer and binder layer apply is adjusted, even if the thickness of foamed resin layer and binder layer is very thin thus, also can not produce gauffer etc., thus resin expanded complex body can be manufactured with good state, particularly good apparent condition.As tension force when applying tension force for the purpose of the resin expanded complex body manufacturing good state, particularly good apparent condition, there is no particular limitation, such as, when the width of foamed resin layer and binder layer is 500mm, is preferably 1 ~ 100N, is more preferably 1 ~ 90N, more preferably 2 ~ 80N.In addition, when the width of foamed resin layer and binder layer is 1000mm, tension force is preferably 2 ~ 200N, is more preferably 2 ~ 180N, more preferably 4 ~ 160N.Such as, more than 100N is applied, when applying the tension force of more than 200N when width 1000mm when width 500mm, if the thickness of foamed resin layer and binder layer is thin, then foamed resin layer and binder layer become the state of elongation because of tension force, in operation thereafter, if eliminate the tension force applied foamed resin layer and binder layer, then foamed resin layer and binder layer become original state from state contraction (reducing) of extending, and easily produce gauffer etc. when arranging binder layer being waited by laminating on foamed resin layer.It should be noted that, for the tension force applied foamed resin layer and binder layer, such as, when obtaining the resin expanded complex body of strip, adjusting with the form of coiling tension during wound into rolls.
In resin expanded complex body of the present invention, above-mentioned binder layer only can be arranged at the one side side of above-mentioned foamed resin layer, also can be arranged at double-face side.In addition, when above-mentioned foamed resin layer has the upper layer formed by heating and melting process, above-mentioned binder layer can be arranged at the face with upper layer in above-mentioned foamed resin layer, also can be arranged at the face without upper layer in above-mentioned foamed resin layer, be preferably disposed on the face without upper layer of foamed resin layer.It should be noted that, in resin expanded complex body of the present invention, the mode that also directly can contact with foamed resin layer and binder layer is formed, but in order to improve adaptation, also can arrange the middle layer of undercoat and so on.
The total thickness (thickness) of resin expanded complex body of the present invention is below 0.35mm.As long as the total thickness of resin expanded complex body is that just there is no particular limitation for below 0.35mm, is preferably 0.06mm ~ 0.33mm, is more preferably 0.07mm ~ 0.30mm, more preferably 0.08mm ~ 0.25mm.Because above-mentioned total thickness is below 0.35mm, even if the gap of therefore applying resin composite foam is less, the function (such as stopping property, flexibility, impact absorbency etc.) of foamed resin also can be played.In addition, if the total thickness of resin expanded complex body (thickness) is more than 0.05mm, then required intensity is easily guaranteed.
In resin expanded complex body of the present invention, to the ratio (thickness of the thickness/binder layer of foamed resin layer) of the thickness of above-mentioned foamed resin layer and the thickness of above-mentioned binder layer, there is no particular limitation, preferably to be the mode determination foamed resin layer of more than 2.1 and the thickness of binder layer.The thickness of above-mentioned foamed resin layer is more preferably more than 3.0, more preferably more than 5.0 with the ratio (thickness of the thickness/binder layer of foamed resin layer) of the thickness of above-mentioned binder layer.In addition, the thickness of above-mentioned foamed resin layer and the ratio (thickness of the thickness/binder layer of foamed resin layer) of the thickness of above-mentioned binder layer are generally less than 13, are preferably less than 11.If the ratio of above-mentioned thickness is more than 2.1, then there is the advantage also compressing foam within the scope of suitable bounding force.That is, foam can be compressed while guaranteeing sufficient bounding force, therefore also can apply resin composite foam aptly for less gap.
Resin expanded complex body of the present invention is preferred for various component or parts to install (assembling) in the purposes at the position of regulation.Especially, in electric or electronics, can will to form electrically or the parts of electronics are installed (assembling) when the position of regulation and used aptly.That is, resin expanded complex body of the present invention is preferably electrically or electronics use.
As above-mentioned various component or parts, there is no particular limitation, such as, can preferably enumerate electrically or various component in electronics class or parts etc.As this electrically or the component of electronics or parts, such as can enumerate: be arranged on optical component or the opticses etc. such as the image display member (display part) (particularly small-sized image display member) in the image display devices such as liquid-crystal display, electroluminescent display, plasma display, the photographic camera be arranged in the mobile communications device such as so-called " mobile phone ", " personal digital assistant device ", lens (particularly small-sized photographic camera, lens).
More specifically, in order to dust-proof, shading, buffering etc., use around the display part that resin expanded complex body of the present invention can be clipped in LCD (liquid-crystal display) etc., between the display part of LCD (liquid-crystal display) etc. and housing (window portion).
In addition, resin expanded complex body of the present invention is thin and soft, and then can improve thickness and precision.Therefore, even if what the smart mobile phone that resin expanded complex body of the present invention is used for being provided with touch panel was such be laminated with a large amount of parts, component electrically or electronics, also can not produce high screen resilience, display such as the liquid-crystal display of display part uneven grade can not be caused bad.
Embodiment
Below, illustrate in greater detail the present invention according to embodiment, but the present invention is not limited to the examples.
[embodiment]
Use the twin screw compounder that JSW (JSW) Co., Ltd. manufactures, at the temperature of 200 DEG C, by polypropylene [melt flow rate (MFR) (MFR): 0.35g/10 minute]: 45 mass parts, the mixture [MFR (230 DEG C): 6g/10 minute of polyolefin elastomerics and tenderizer (paraffin series filling oil), JISA hardness: 79 °, relative to 100 mass parts polyolefin elastomer 30 mass parts tenderizers]: 55 mass parts, magnesium hydroxide: 10 mass parts, carbon (trade(brand)name " rising sun #35 " AsahiCarbonCo., Ltd. manufacture): 10 mass parts, glyceryl monostearate: 1 mass parts, and fatty acid amide (lauric acid bisamide): after 1.5 mass parts are mixing, be extruded into strand form, water-cooled aftershaping is particulate state.This particle is fed in the single screw extrusion machine of Japan Steel Co., Ltd's manufacture, under the atmosphere of 220 DEG C, with the pressure injecting carbon dioxide gas of 13 (after injecting 12) MPa.Carbon dioxide is with the ratio injection relative to particle total amount being 5.7 quality %.After making carbon dioxide fully saturated, be cooled to the temperature of suitable foaming, then cylindrical shape is extruded into from mould, make between the foam cooling of the outer surface of the foam of its cylindrical shape extruded from the annular die of forcing machine by plug and cooling of cooling the inner surface of foam ventilated, the partial cutoff of diameter is launched into sheet, obtains rectangular foam reel.
This rectangular foam reel is cut into width (the joint-cutting processing of regulation, slitprocessing), use the serial section device (slicing line shown in Fig. 1, sliceline), by the low ratio foamed layer of face stripper surface, obtain thickness different foamed resin layer A, foamed resin layer B and foamed resin layer C.In addition, in foamed resin layer A, foamed resin layer B and foamed resin layer C, mean cell diameter is 60 μm, and apparent density is 0.047g/cm 3.
Foamed resin layer A: thickness 0.20mm
Foamed resin layer B: thickness 0.30mm
Foamed resin layer C: thickness 0.40mm
(embodiment 1)
On the one side of above-mentioned foamed resin layer A, laminating double-faced adhesive tape (trade(brand)name " No.5603 ", Nitto Denko Corp manufactures, PET base material two-sided on be provided with the self adhesive tape of acrylic adhesive layer, tape thickness (thickness): 0.03mm), obtain resin expanded complex body.The total thickness of this resin expanded complex body is 0.23mm.
(embodiment 2)
On the one side of above-mentioned foamed resin layer B, laminating double-faced adhesive tape (trade(brand)name " No.5603 ", Nitto Denko Corp manufactures, PET base material two-sided on be provided with the self adhesive tape of acrylic adhesive layer, tape thickness (thickness): 0.03mm), obtain resin expanded complex body.The total thickness of this resin expanded complex body is 0.33mm.
(embodiment 3)
Make above-mentioned foamed resin layer A by the temperature of induction heat generating roller is set to 160 DEG C, is set in gap in the above-mentioned apparatus for continous treatment of 0.10mm, utilize heat to carry out melting treatment to one side thus, obtain the foamed resin layer that one side has carried out the thickness 0.10mm of heat fusing process.The surface-coated rate of having carried out the upper layer of heat fusing process is 89.1%.Then, on the face of not carrying out heat fusing process, laminating double-faced adhesive tape (trade(brand)name " No.5603 ", Nitto Denko Corp manufactures, PET base material two-sided on be provided with the self adhesive tape of acrylic adhesive layer, tape thickness (thickness): 0.03mm), obtain resin expanded complex body.The total thickness of this resin expanded complex body is 0.13mm.
(embodiment 4)
On the one side of above-mentioned foamed resin layer A, laminating double-faced adhesive tape (trade(brand)name " No.5603 ", Nitto Denko Corp manufactures, PET base material two-sided on be provided with the self adhesive tape of acrylic adhesive layer, tape thickness (thickness): 0.03mm).The total thickness of the works of gained is 0.23mm.Under the state remaining the PET release liner (thickness 0.075mm) being pasted with protection tackiness agent aspect; make said structure thing by the temperature of induction heat generating roller is set to 220 DEG C, is set in gap in the above-mentioned apparatus for continous treatment of 0.15mm and passes through; utilize heat to carry out melting treatment to the face not attaching double-faced adhesive tape in said structure thing thus, obtain resin expanded complex body.In this resin expanded complex body, the thickness that one side has carried out the foamed resin layer of heat fusing process is 0.07mm, and the thickness of binder layer is 0.03mm, and total thickness is 0.10mm.In addition, the surface-coated rate of having carried out the upper layer of heat fusing process is 88.4%.
(embodiment 5)
Make above-mentioned foamed resin layer A by the temperature of induction heat generating roller is set to 160 DEG C, is set in gap in the above-mentioned apparatus for continous treatment of 0.10mm, utilize heat to carry out melting treatment to one side thus, obtain the foamed resin layer that one side has carried out the thickness 0.10mm of heat fusing process.The surface-coated rate of the upper layer of the heat fusing process of the carrying out in this foamed resin layer is 89.1%.Then, on the face of not carrying out heat fusing process of above-mentioned foamed resin layer, laminating double-faced adhesive tape (trade(brand)name " No.5601 ", Nitto Denko Corp manufactures, PET base material two-sided on be provided with the self adhesive tape of acrylic adhesive layer, tape thickness (thickness): 0.01mm), obtain resin expanded complex body.The total thickness of this resin expanded complex body is 0.11mm.
(embodiment 6)
On the one side of above-mentioned foamed resin layer A, laminating double-faced adhesive tape (trade(brand)name " No.5601 ", Nitto Denko Corp manufactures, PET base material two-sided on be provided with the self adhesive tape of acrylic adhesive layer, tape thickness (thickness): 0.01mm).The total thickness of the works of gained is 0.21mm.Under the state remaining the PET release liner (thickness 0.075mm) being pasted with protection tackiness agent aspect; make said structure thing by the temperature of induction heat generating roller is set to 220 DEG C, is set in gap in the above-mentioned apparatus for continous treatment of 0.15mm; utilize heat to carry out melting treatment to the face not attaching double-faced adhesive tape thus, obtain resin expanded complex body.In this resin expanded complex body, the thickness that one side has carried out the foamed resin layer of heat fusing process is 0.07mm, and the thickness of binder layer is 0.01mm, and total thickness is 0.08mm.In addition, the surface-coated rate of having carried out the upper layer of heat fusing process is 94.1%.
(embodiment 7)
Make above-mentioned foamed resin layer A by the temperature of induction heat generating roller is set to 160 DEG C, is set in gap in the above-mentioned apparatus for continous treatment of 0.10mm, utilize heat to carry out melting treatment to one side thus, obtain the foamed resin layer that one side has carried out the thickness 0.10mm of heat fusing process.The surface-coated rate of the upper layer of the heat fusing process of the carrying out in this foamed resin is 89.1%.Then, on the face of not carrying out heat fusing process in above-mentioned foamed resin layer, laminating double-faced adhesive tape (trade(brand)name " No.5600 ", Nitto Denko Corp manufactures, PET base material two-sided on be provided with the self adhesive tape of acrylic adhesive layer, tape thickness (thickness): 0.005mm), obtain resin expanded complex body.The total thickness of this resin expanded complex body is 0.105mm.
(comparative example 1)
On the one side of above-mentioned foamed resin layer A, laminating double-faced adhesive tape (trade(brand)name " No.5610 ", Nitto Denko Corp manufactures, PET base material two-sided on be provided with the self adhesive tape of acrylic adhesive layer, tape thickness (thickness): 0.10mm), obtain resin expanded complex body.The total thickness of this resin expanded complex body is 0.30mm.
(comparative example 2)
On the one side of above-mentioned foamed resin layer C, laminating double-faced adhesive tape (trade(brand)name " No.5603 ", Nitto Denko Corp manufactures, PET base material two-sided on be provided with the self adhesive tape of acrylic adhesive layer, tape thickness (thickness): 0.03mm), obtain resin expanded complex body.The total thickness of this resin expanded complex body is 0.43mm.
(comparative example 3)
Make above-mentioned foamed resin layer A by the temperature of induction heat generating roller is set to 160 DEG C, is set in gap in the above-mentioned apparatus for continous treatment of 0.10mm, utilize heat to carry out melting treatment to one side thus, obtain the foamed resin layer that one side has carried out the thickness 0.10mm of heat fusing process.The surface-coated rate of the upper layer of the heat fusing process of the carrying out in this foamed resin layer is 87.2%.Then, on the face of not carrying out heat fusing process in above-mentioned foamed resin layer, laminating double-faced adhesive tape (trade(brand)name " No.5608 ", Nitto Denko Corp manufactures, PET base material two-sided on be provided with the self adhesive tape of acrylic adhesive layer, tape thickness (thickness): 0.08mm), obtain resin expanded complex body.The total thickness of this resin expanded complex body is 0.18mm.
(comparative example 4)
At polyurethane foam (trade(brand)name " PORONSR-S-32P ", thickness 0.20mm, foam layer density 0.32g/cm that one side is supported by PET film 3rOGERSINOACCORPORATION manufacture) side, PET face, laminating double-faced adhesive tape (trade(brand)name " No.5603 ", Nitto Denko Corp manufactures, PET base material two-sided on be provided with the self adhesive tape of acrylic adhesive layer, tape thickness (thickness): 0.03mm), obtain resin expanded complex body.The total thickness of this resin expanded complex body is 0.23mm.
(comparative example 5)
In polyolefin foam (trade(brand)name " VOLARAWF03 ", Sekisui Chemical Co., Ltd's system, thickness 0.30mm, density: 0.20g/cm 3, sheet) on, laminating double-faced adhesive tape (trade(brand)name " No.5603 ", Nitto Denko Corp manufactures, PET base material two-sided on be provided with the self adhesive tape of acrylic adhesive layer, tape thickness (thickness): 0.03mm), obtain resin expanded complex body.The total thickness of this resin expanded complex body is 0.33mm.
[evaluation]
(apparent density)
The cutting die of foamed resin layer width 40mm × length 40mm is carried out stamping-out, obtains the test sample of sheet.Then utilize said determination sample, try to achieve apparent density (g/cm according to JISK6767 3).
Specifically, measure width, the length of said determination sample, measure the thickness (mm) of test sample with 1/100 dial gauge (dialgauge) that mensuration terminal diameter (φ) is 20mm.Volume (the cm of foamed resin layer is calculated by these measured values 3).Then, the quality (g) of test sample is measured with the upper ware Libra of more than minimum scale 0.01g.Apparent density (g/cm is calculated by the measured value of above-mentioned volume and quality 3).
(mean cell diameter)
Digit microscope (trade(brand)name " VHX-500 " KEYENCECORPORATION system) is utilized to obtain the enlarged image in foam bubble portion, use image analysis software (manufacture of trade(brand)name " WinROOF " three paddy business Co., Ltd.) to carry out image analysis, obtain mean cell diameter (μm) thus.It should be noted that, the number of bubbles of the enlarged image of acquisition is about 100.
(surface-coated rate)
The utilization heat measuring foamed resin layer has carried out the surface-coated rate in the face of melting treatment, using the surface-coated rate of this value as foamed resin layer.
Surface-coated rate is obtained by following formula (1).
Surface-coated rate (%)=[(area on surface)-(area in the hole that surface exists)]/(area on surface) × 100 (1)
The image that the area in the hole that the area on surface and surface exist passes through the mensuration face using microscope (device name " VHX600 ", KEYENCECORPORATION manufactures) to obtain is obtained.
Utilize microscopical observation to adopt side to penetrate illumination as means of illumination, its illumination is set to 17000 luxs.In addition, multiplying power is set to 500 times.
As the double photographic camera of illumination, use internal illumination lens cameras (device name " 0P72404 ", KEYENCECORPORATION manufactures), and use zoom lens (trade(brand)name " VH-Z100 ", KEYENCECORPORATION manufactures) as lens.
It should be noted that, illumination uses luxmeter (trade(brand)name " VHX600 ", CUSTOMCORPORATION manufactures) to regulate.
(compressive load during 50% compression)
According to JISK6767, after the thickness direction of foamed resin layer only compresses 50% of initial foam thickness, measure the stress (N) through 10 seconds time, this EXPERIMENTAL STRAIN-STRESS CONVERSION is become per unit area (cm 2), as stress under compression (N/cm during 50% compression 2).Show the result in table 1, table 2.
(inserting compressive load during 0.10mm)
According to JISK6767, to the resin expanded complex body of embodiment and comparative example, in a thickness direction with after making mode that thickness is 0.10mm compress, measure the stress (N) through 10 seconds time, this EXPERIMENTAL STRAIN-STRESS CONVERSION is become per unit area (cm 2), as compressive load (N/cm during insertion 0.10mm 2).If compressive load when inserting 0.10mm is 3.5N/cm 2below, in the narrow like this gap of 0.1mm, the flexibility that also can not cause distortion etc. is used even if be then judged as having.Show the result in table 1, table 2.
(inserting compressive load during 0.05mm)
According to JISK6767, to the resin expanded complex body of embodiment and comparative example, in a thickness direction with after making mode that thickness is 0.05mm compress, measure the stress (N) through 10 seconds time, this EXPERIMENTAL STRAIN-STRESS CONVERSION is become per unit area (cm 2), as compressive load (N/cm during insertion 0.05mm 2).If compressive load when inserting 0.05mm is 3.5N/cm 2below, in the narrow like this gap of 0.05mm, the flexibility that also can not cause distortion etc. is used even if be then judged as having.Show the result in table 1, table 2.
(bounding force)
By resin expanded complex body (width: 20mm × length: 120mm) in temperature: 23 ± 2 DEG C, keeping 24 hours more than is afterwards (Pretreatment is based on JISZ0237) under the atmosphere of humidity: 50 ± 5%RH, under the form that adherend (SUS) contacts with the adhesive layer surface of resin expanded complex body, carry out crimping with 2kg roller, the condition of reciprocal 1 time and place 30 minutes, making test sample.Then, utilize universal tensile testing machine (device name " TCN-1kNB ", MinebeaCo., Ltd. manufacture), in temperature: 23 ± 2 DEG C, under the atmosphere of humidity: 50 ± 5%RH, measure with draw speed 300mm/ minute, the one-sided end of resin expanded complex body is peeled off by peel angle 90 ° time bounding force.If bounding force is more than 2N/20mm, be then judged as that there is the bounding force of position alignment when operating laminating without impact.Show the result in table 1, table 2.
[table 1]
Table 1
[table 2]
Table 2
In embodiment, use apparent density is 0.03 ~ 0.30g/cm 3, 50% compression time stress under compression be 5.0N/cm 2following foamed resin layer, the binder layer being 0.005mm ~ 0.06mm with thickness combines, make the resin expanded complex body that total thickness becomes below 0.35mm, thus in the evaluation of situation being equivalent to the gap being inserted into 0.1mm, can obtain compressive load is 3.5N/cm 2following good result.And then can be made into the resin expanded complex body in the gap that also can adapt to 0.05mm.In addition, for bounding force now, also can be judged as that there is the bounding force of position alignment when operating laminating without impact.
On the other hand, known: in comparative example 1, comparative example 3, the thickness of binder layer is the thickness of more than specified range, in addition, in comparative example 2, the total thickness of resin expanded complex body is the thickness of more than specified range, and compressive load value when therefore inserting 0.1mm uprises.In addition known: in the comparative example 4 of foam as apparent density being more than particular value, lack resiliency, compressive load value when inserting 0.1mm uprises.And then known: in the comparative example 5 that the stress under compression when use 50% is compressed is foam more than particular value, also lack resiliency, compressive load value when inserting 0.1mm uprises.
utilizability in industry
Resin expanded complex body of the present invention may be used for the purposes such as dust-proof material, sealing material, sound-proof material, cushioning material used when such as various component or parts being arranged on the position of regulation.
description of reference numerals
1 serial section device (slicing line)
11 conveying rollers
12 pinch rolls
13 cutters (section cutting tool)
14 deflector rolls
15 winding rollers
16 foamed resins
2 apparatus for continous treatment with warming mill
21 conveying rollers
22 deflector rolls
23 warming mills (hot dielectric roller)
24 cooling rollers
25 winding rollers
26 foamed resins
A flow direction

Claims (11)

1. a resin expanded complex body, it is the resin expanded complex body being laminated with foamed resin layer and binder layer,
The apparent density of described foamed resin layer is 0.03 ~ 0.30g/cm 3, stress under compression during 50% compression is 5.0N/cm 2below,
The thickness of described binder layer is 0.0005mm ~ 0.06mm,
The total thickness of resin expanded complex body is below 0.35mm.
2. resin expanded complex body according to claim 1, wherein, the thickness of described foamed resin layer is more than 2.1 with the ratio (thickness of the thickness/binder layer of foamed resin layer) of the thickness of described binder layer.
3. resin expanded complex body according to claim 1 and 2, wherein, described binder layer is acrylic adhesive layer.
4. the resin expanded complex body according to any one of claims 1 to 3, wherein, the resin forming described foamed resin layer is thermoplastic resin.
5. the resin expanded complex body according to any one of Claims 1 to 4, wherein, described thermoplastic resin is polyolefin resin.
6. the resin expanded complex body according to any one of Claims 1 to 5, wherein, has at least one mask of described foamed resin layer the upper layer formed by heating and melting process.
7. the resin expanded complex body according to any one of claim 1 ~ 6, wherein, described foamed resin layer be through make high pressure gas to be infiltrated up in resin after the operation of carrying out reducing pressure formed.
8. resin expanded complex body according to claim 7, wherein, described gas is non-active gas.
9. resin expanded complex body according to claim 8, wherein, described non-active gas is carbonic acid gas.
10. the resin expanded complex body according to any one of claim 7 ~ 9, wherein, described high pressure gas are supercritical state.
11. resin expanded complex bodys according to any one of claim 1 ~ 10, wherein, described foamed resin layer has unicellular structure or half perforate semi-closure pore structure.
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