CN107858114A - The manufacture method of bubble generation member, electric/electronic device and foaming body - Google Patents

The manufacture method of bubble generation member, electric/electronic device and foaming body Download PDF

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Publication number
CN107858114A
CN107858114A CN201710858132.1A CN201710858132A CN107858114A CN 107858114 A CN107858114 A CN 107858114A CN 201710858132 A CN201710858132 A CN 201710858132A CN 107858114 A CN107858114 A CN 107858114A
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CN
China
Prior art keywords
foaming body
mentioned
foaming
bubble generation
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710858132.1A
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Chinese (zh)
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CN107858114B (en
Inventor
儿玉清明
斋藤诚
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of CN107858114A publication Critical patent/CN107858114A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • 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
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • 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
    • C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • 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

Abstract

The manufacture method of a kind of bubble generation member, electric/electronic device and foaming body is provided.A kind of bubble generation member is provided, it has following foaming body：Can with good mouldability to obtain, the pick of foaming body in itself is good and is not easy to cause that foam destroys, the range of choice of such carrier band is wide in addition from carrier band when peeling off.A kind of bubble generation member, it has following foaming body：It is the foaming body of single sheet, and when above-mentioned foaming body is to be cut off to the lubricant content in region of the surface of above-mentioned foaming body untill thickness direction 50nm depth in the way of thickness halves parallel to foaming body surface, from below the 70 weight % of the lubricant content in region of the section untill thickness direction 50nm depth.

Description

The manufacture method of bubble generation member, electric/electronic device and foaming body
Technical field
The present invention relates to the bubble generation member with foaming body, the electric/electronic device with the bubble generation member and foaming body Manufacture method.
Background technology
Foamed resin uses after being punched into required shape generally according to the shape of the component using it.In recent years, by In multifunction/slimming of electronic equipment, component area diminishes, and the shape of foamed resin also further diminishes.For electricity The foamed resin of sub- equipment, its one side are pasted with fixed strong bonding band, are fixed on assigned position and carry out the group of component Dress, but the foamed resin for implementing this processing is not allowed easy to operate, therefore in order to efficiently be transported to above-mentioned assigned position, has When using carrier band.In addition, in the case of using carrier band, the state for being also pasted on carrier band with foamed resin sometimes implements various add Work (punch press process, bonding processing etc.).Thus, implemented respectively with being pasted on the state of carrier band for the foamed resin of electronic equipment Kind processing is conveyed after various processing using carrier band.
But using the low carrier band of bonding force as carrier band in the case of, bubble be present in foamed resin surface, thus Less than enough bond areas with carrier band, generation can not utilize the problem of carrier band picks up foamed resin, i.e. pick is bad. On the other hand, foam occurs in the case of using the high carrier band of bonding force, when being peeling and destroys (the foam structure in foaming body Destroy) the problem of.
In order to improve the cementability of foamed resin, sealing, it is known that set other resins on the surface of foamed resin The method of layer.For example, for the purpose for improving sealing, it is proposed that with separated foam and continuous air bubbles both bubbles One side in the upper and lower surface of foamed rubber sets the foaming body of the soft envelope softer than foamed rubber (with reference to specially Sharp document 1).It should be noted that the enhancing of foaming body, the transmission with carrier band are not considered in patent document 1.Further it is proposed that A kind of foaming body, it includes carbamate based thermoplastic polymer group by being formed on the surface of foamed polyolefin resin body The layer of compound, apply the surface-treated layer being made up of polar polymer on this layer, thus obdurability, scratch resistance, wearability Etc. excellent (with reference to patent document 2).And then, it is also proposed that surface is handled with polychlorobutadiene system adhesive composite Foaming body (with reference to patent document 3), surface be provided with the foaming body (with reference to patent document 4) of the Yishui River such as polyvinyl alcohol layer soluble layer Deng.
In addition, the interlaminar strength by improving foaming body, also may be used even for the foamed resin with high foamability To suppress or prevent to destroy from foam during carrier band stripping.Such as, it is proposed that it is excellent to be held in carrier band, processability and transporting Foamed resin (with reference to patent document 5).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 9-131822 publications
Patent document 2：Japanese Unexamined Patent Publication 2003-136647 publications
Patent document 3：Japanese Unexamined Patent Publication 5-24143 publications
Patent document 4：Japanese Unexamined Patent Publication 10-37328 publications
Patent document 5：Japanese Unexamined Patent Publication 2014-139287 publications
The content of the invention
Problems to be solved by the invention
But the foaming body proposed in patent document 1~4 has been laminated foreign material on foaming body, therefore has and cause The anxiety of required foaming body physical property reduction, in addition, its manufacturing process also becomes cumbersome.In addition, the hair proposed in patent document 5 Although foam using with specific bonding force carrier band when easily carry out various processing, the carrier band that can be used less, selection Narrow range.Therefore, it is necessary to which a kind of other layers without using for improving pick, the pick of foaming body in itself are excellent, in addition The foaming body for causing the range of choice of foam destruction and the carrier band that can be used wide is not easy when peeling off foaming body from carrier band.
The present inventors have studied the selection for the carrier band that pick to foaming body in itself is excellent, is not easy to cause foam to destroy The reason for narrow range, it is believed that although reason have it is several main reason is that the lubricant added when foaming body formed.Specifically For, it is believed that it is that the lubricant for being present in foamed resin surface causes reduction to the cohesive of carrier band.On the other hand, such as Fruit foaming does not add lubricant when body formed, then forms the mobility of the resin combination of foaming body and significantly reduce, extrusion molding Become difficult Deng shaping.By adding lubricant, the mobility of resin combination improves, and mouldability becomes good, easily carry out into Type.
Therefore, it is an object of the present invention to provide a kind of bubble generation member with following foaming body：Can be with good shaping Property to obtain, the pick of foaming body in itself is good and is not easy when peeling off from carrier band to cause foam to destroy, such carrier band in addition Range of choice it is wide.
In addition, another object of the present invention is to, there is provided there is the electric/electronic device of such bubble generation member.
In addition, another object of the present invention is to a kind of, there is provided method for manufacturing following foaming body, the foaming physical efficiency with Good mouldability is to obtain, the pick of foaming body in itself is good and is not easy to cause foam to destroy, in addition when peeling off from carrier band The range of choice of such carrier band is wide.
The solution used to solve the problem
The present inventors has made intensive studies to achieve these goals, as a result finds, by the inside for making foaming body Amounts of lubrication and surface amounts of lubrication have difference and make surface amounts of lubrication and inside amounts of lubrication be in a ratio of Below special ratios, it is hereby achieved that following foaming body：By the good forming ability of resin combination, and without using for Pick is also good when assigning other layers of pick and is not easy to cause foam destruction when peeling off from carrier band and then pick is good And it is not easy to cause the range of choice of the carrier band of foam destruction wide.The present invention is completed based on these opinions.
That is, the present invention provides a kind of bubble generation member, and it has following foaming body：For the foaming body of single sheet, and from Lubricant content in region of one surface of above-mentioned foaming body untill thickness direction 50nm depth is by above-mentioned hair It is when foam is cut off in the way of thickness halves parallel to foaming body surface, from section to thickness direction 50nm depth Below the 70 weight % of the lubricant content in region only.
In above-mentioned bubble generation member, preferably：The apparent density of above-mentioned foaming body is 0.01~0.20g/cm3, 50% compression When screen resilience be 0.1~4.0N/cm2, mean cell diameter is 10~200 μm.
In above-mentioned bubble generation member, preferably：By the said one surface of above-mentioned foaming body and the bonding force (temperature to SUS plates Degree：23 ± 2 DEG C, humidity：50 ± 5RH%, draw speed：0.3m/ minutes) pasted for the adhesive surface of 0.15N/20mm bonding sheet Close, peeling force (temperature when peeling off above-mentioned foaming body from above-mentioned bonding sheet：23 ± 2 DEG C, humidity：50 ± 5RH%, draw speed： 0.3m/ minutes) it is 0.10~2.00N/20mm.
In above-mentioned bubble generation member, preferably：By the said one surface of above-mentioned foaming body and the bonding force (temperature to SUS plates Degree：23 ± 2 DEG C, humidity：50 ± 5RH%, draw speed：0.3m/ minutes) pasted for the adhesive surface of 0.35N/20mm bonding sheet Close, peeling force (temperature when peeling off above-mentioned foaming body from above-mentioned bonding sheet：23 ± 2 DEG C, humidity：50 ± 5RH%, draw speed： 0.3m/ minutes) it is 0.10~2.00N/20mm.
Above-mentioned bubble generation member can have adhesive phase on another surface of above-mentioned foaming body.
Above-mentioned bubble generation member can be following bubble generation member：At least one side possessed in base material has the load of adhesive phase Band, above-mentioned foaming body and above-mentioned carrier band connect according to the said one surface of above-mentioned foaming body and the above-mentioned adhesive phase of above-mentioned carrier band Tactile mode is laminated.
Above-mentioned bubble generation member is preferred for electric/electronic device purposes.
In addition, the present invention provides a kind of electric/electronic device, it has above-mentioned bubble generation member.
In addition, the present invention provides a kind of manufacture method of foaming body, it includes following process：Resin and lubricant will be contained Resin combination foaming and obtain the process of the foaming body of sheet；And make lubricant at one of above-mentioned foaming body Decomposed or from the surface migration on surface, thus make the region untill thickness direction 50nm depth from said one surface In lubricant content be reduced to when above-mentioned foaming body is cut off in the way of thickness halves parallel to foaming body surface, From below the 70 weight % of the lubricant content in region of the section untill thickness direction 50nm depth process.
The effect of invention
Foaming body in the bubble generation member of the present invention is as characterized above, therefore can be obtained, picked up with good mouldability Taking property good (that is, foaming body is good to the cohesive of carrier band in itself) and it is not easy to cause foam to destroy, in addition when peeling off from carrier band The range of choice of such carrier band is wide.In addition, thus processability bubble generation member, being held under carrier band state of the invention and Transporting etc. is directed to the excellent of carrier band, and the range of choice for the carrier band that can be used is wide.
And then because the foaming body in the bubble generation member of the present invention can play the effect above, therefore need not be in foaming body On be laminated for improving foaming body relative to foreign materials such as the resin beds of the pick of carrier band, the thing of foaming body in itself will not be made Property reduce.Further, since foreign material need not be stated foaming body upper strata is stacked on, therefore manufacturing process becomes letter in this case It is single.
Brief description of the drawings
Fig. 1 is the schematic diagram of one for showing the foaming body of the present invention.
Fig. 2 is the schematic diagram of one for showing the bubble generation member of the present invention.
Description of reference numerals
The foaming body of 1 present invention
11 1 surfaces
12 another surfaces
13 surface regions
14 interior zones
The bubble generation member of 2 present invention
3 carrier bands
3a base materials
3b adhesive phases
4 adhesive phases
Cut-outs of the L when the foaming body 1 of the present invention is cut off in the way of thickness halves parallel to foaming body surface Face
Embodiment
The bubble generation member of the present invention has following foaming body：For the foaming body of single sheet, from the one of above-mentioned foaming body Lubricant content in region of the individual surface untill thickness direction 50nm depth is to subtract by foregoing foaming body according to thickness When half mode is cut off parallel to foaming body surface, from the profit in region of the section untill thickness direction 50nm depth Below the 70 weight % of lubrication prescription content.It should be noted that in this manual, above-mentioned foaming body is referred to as the " present invention sometimes Foaming body ".
[foaming body]
The foaming body of the present invention is single foaming body.Here, " single foaming body " refers to be molded by one step foaming It is integrally formed go out foaming body, not include such as obtained from multiple foaming bodies are combined as being laminated, be bonded foaming body.
The present invention it is foaming body, contain from the lubricant in region of the surface untill thickness direction 50nm depth Measure for by the present invention foaming body cut off in the way of thickness halves parallel to foaming body surface when, from section to thickness Below the 70 weight % of the lubricant content in region untill degree direction 50nm depth, it is more excellent preferably below 60 weight % Select below 55 weight %, further preferred below 50 weight %.Put down by the foaming body of the present invention in the way of thickness halves Row when foaming body surface is cut off, from the lubricant content table in region of the section untill thickness direction 50nm depth Show the lubricant content of the inside of the foaming body of the present invention, be usually used in the degree that has no problem of mouldability of foaming body Lubricant content.Lubricant content on a surface of foaming body is 70 weights of the lubricant content of the inside of foaming body When measuring below %, the bonding on foaming body surface is not easy to be suppressed by lubricant, to the bonding of carrier band in the range of wider bonding force Property become good, and survivable foam when peeling off.
It should be noted that in this manual, " it is from a surface to thickness direction 50nm depth by above-mentioned sometimes Region only " is referred to as " surface region ".In addition, sometimes by it is above-mentioned " by foaming body in the way of thickness halves parallel to hair Foam surface and when cutting off, the region from section untill thickness direction 50nm depth " be referred to as " interior zone ".In addition, In the foaming body of the present invention, above-mentioned surface region and above-mentioned interior zone may have the region repeated each other.In addition, it will send out In the presence of the foaming body of 2 same thickness when foam is cut off in the way of thickness halves parallel to foaming body surface, the two Interior zone in foaming body all be present, but the lubricant content of surface region contains relative to the lubricant of at least one interior zone Measure as below 70 weight %.
The ratio of the lubricant content of surface region and the lubricant content of interior zone is always according to used lubricant And it is different, for example, time-of-flight type secondary ion mass spectrometry (TOF-SIMS) can be utilized in surface region and interior zone point The detection limit in surface region and interior zone Jian Ce not be contrasted and calculated as the compound that lubricant uses.Example When such as, using nitrogen atom compound as lubricant, the nitrogen atom of surface region and interior zone can be detected respectively The amount of compound, the detection limit in surface region and interior zone is contrasted and calculates the ratio of the amount of nitrogen atom compound Example, as the ratio of lubricant content.
In addition, to the surface (another surface) of opposite side foaming body, from said one surface of the present invention to thickness The lubricant content in region untill direction 50nm depth is not particularly limited, and can be the lubrication in above-mentioned interior zone Below the 70 weight % of agent content, can also be equal extent with the lubricant content in above-mentioned interior zone.
Fig. 1 shows the schematic diagram of one of the foaming body of the present invention.In Fig. 1, foaming body 1 of the invention has a surface 11 and another surface 12.Surface region 13 is the region untill thickness direction 50nm depth from said one surface 11.L is The section when foaming body 1 of the present invention is cut off in the way of thickness halves parallel to foaming body surface.Interior zone 14 For the region from above-mentioned section L untill thickness direction 50nm depth.It should be noted that in Fig. 1, by the hair of the present invention When foam 1 is cut off in the way of thickness halves parallel to foaming body surface, without surface region 13 foaming side Interior zone 14 is set to from regions of the above-mentioned section L untill thickness direction 50nm depth, but can also there will be surface The region from above-mentioned section L untill thickness direction 50nm depth on the foaming side in region 13 is set to interior zone.
The apparent density of the foaming body of the present invention is not particularly limited, preferably 0.01~0.20g/cm3, more preferably 0.02 ~0.10g/cm3, further preferred 0.03~0.08g/cm3.Above-mentioned apparent density is 0.01g/cm3During the above, peeled off from carrier band The survivable foams of Shi Gengjia.Furthermore, it is possible to ensure good impact absorbency, for electric/electronic device when excellent sealing Property and good dust tightness.Above-mentioned apparent density is 0.20g/cm3When following, flexibility improves, and can obtain excellent impact and inhale Receive property, for electric/electronic device when excellent gap tracing ability.
Screen resilience when being compressed to foaming body, following defined the 50% of the present invention is not particularly limited, and preferably 0.1 ~4.0N/cm2, more preferably 0.2~3.5N/cm2, further preferred 0.3~3.0N/cm2.It should be noted that in this specification In, screen resilience during following defined 50% compressions is only called " screen resilience during 50% compression " sometimes.
Screen resilience during 50% compression：In 23 DEG C of atmosphere, according to the side for reaching 50% thickness relative to original depth Formula by foaming body along thickness direction compress when confrontation load.
Screen resilience during above-mentioned 50% compression is 0.1N/cm2During the above, appropriate rigidity, processability, operation are readily obtained Property improve.Screen resilience during above-mentioned 50% compression is 4.0N/cm2When following, excellent flexibility can obtain.
The mean cell diameter of the foaming body of the present invention is not particularly limited, preferably 10~200 μm, more preferably 15~ 180 μm, further preferred 20~150 μm, particularly preferred 30~100 μm.It is soft when above-mentioned mean cell diameter is more than 10 μm Property is excellent.When above-mentioned mean cell diameter is less than 200 μm, easily suppress generation, the generation of thick abscess (hole) of pin hole, Obtain excellent dust tightness, excellent light-proofness.
The particularly preferred apparent density of foaming body of the present invention is 0.01~0.20g/cm3, 50% compression when screen resilience be 0.1~4.0N/cm2And mean cell diameter is 10~200 μm.In this case, the physical efficiency that foams is come with good mouldability Obtain, pick is good, be not easy when peeling off from carrier band to cause foam to destroy, the range of choice of such carrier band is wide, and foam The flexibility of body, dust tightness, light-proofness, processability, excellent strength.In addition, easily make the foaming body of the present invention in this case Become variously-shaped, can be consequently used for various processed goods, manufacturing procedure.It is (main additionally, there are the gas inside foaming body It is air) become more, insulating properties is excellent, therefore by that near for electronic unit, can be not easy to cause breaking caused by electrostatic It is bad.And then thermal insulation is also excellent, therefore by the inside for electronic equipment, drastically changing even if external temperature to make Internal temperature keeps uniform, can make the performance stability of electronic equipment.
The maximum cell diameter of the foaming body of the present invention is not particularly limited, preferably smaller than 200 μm, more preferably 190 μm Hereinafter, further preferred less than 175 μm.When above-mentioned maximum cell diameter is less than 200 μm, without thick abscess, bubble structure Excellent in uniformity, thus can suppress dust invaded from thick abscess, dust tightness reduce etc problem generation, be readily obtained excellent Different sealing, dust tightness.In addition, it is readily obtained excellent light-proofness.
The cell diameter of the foaming body of the present invention can be obtained as follows：For example, obtain section using digit microscope The enlarged drawing in bubble structure portion, the area of abscess is obtained by image analysis, is then convert into equivalent circle diameter.
The thickness of the foaming body of the present invention is not particularly limited, preferably 0.05~5.0mm, more preferably 0.06~3.0mm, Further preferred 0.07~1.5mm, particularly preferred 0.08~1.0mm.
By the said one surface of the foaming body of the present invention and the bonding force (temperature to SUS plates：23 ± 2 DEG C, humidity：50 ± 5RH%, draw speed：0.3m/ minutes) it is bonded for the adhesive surface of 0.15N/20mm bonding sheet, peeled off from above-mentioned bonding sheet Peeling force (the temperature during foaming body of the present invention：23 ± 2 DEG C, humidity：50 ± 5RH%, draw speed：0.3m/ minutes) do not have It is particularly limited to, preferably more than 0.10N/20mm (such as 0.10~2.00N/20mm), more preferably 0.15~1.00N/20mm, enters one Walk preferably 0.20~0.80N/20mm.It is abundant to the bonding force of micro- bonding carrier band when above-mentioned peeling force is more than 0.10N/20mm, The range of choice of the good carrier band of pick becomes wider.When above-mentioned peeling force is below 2.00N/20mm, it is not easy to cause foam The range of choice of the carrier band of destruction becomes wider.
By the said one surface of the foaming body of the present invention and the bonding force (temperature to SUS plates：23 ± 2 DEG C, humidity：50 ± 5RH%, draw speed：0.3m/ minutes) it is bonded for the adhesive surface of 0.35N/20mm bonding sheet, peeled off from above-mentioned bonding sheet Peeling force (the temperature during foaming body of the present invention：23 ± 2 DEG C, humidity：50 ± 5RH%, draw speed：0.3m/ minutes) do not have It is particularly limited to, preferably more than 0.10N/20mm (such as 0.10~2.00N/20mm), more preferably 0.15~1.00N/20mm, enters one Walk preferably 0.20~0.80N/20mm.It is abundant to the bonding force of weak bonding carrier band when above-mentioned peeling force is more than 0.10N/20mm, The range of choice of the good carrier band of pick becomes wider.When above-mentioned peeling force is below 2.00N/20mm, it is not easy to cause foam The range of choice of the carrier band of destruction becomes wider.
The foaming body of the present invention has bubble structure (foam structure).To the bubble structure (bubble in the foaming body of the present invention Pore structure) be not particularly limited, from the viewpoint of excellent flexibility is obtained, preferably semicontinuous semi-independent bubble structure (for The bubble structure of separated foam structure and continuous air bubbles mixing up of structure, its ratio is not particularly limited).The particularly preferably present invention Foaming body have separated foam structural portion be less than 40% (more preferably less than 30%) bubble structure.
The foaming body of the present invention preferably comprises resin.As above-mentioned resin, preferred thermoplastic resin.Above-mentioned resin can be only Using one kind, can also use two or more.
As above-mentioned thermoplastic resin, can enumerate for example：Polyolefin-based resins, phenylethylene resin series, polyamide-based tree Fat, polyamidoimide, polyurethane, polyimides, PEI, acrylic resin, polyvinyl chloride, polyvinyl fluoride, alkene Base aromatic resin, polyester based resin, makrolon, polyacetals, polyphenylene sulfide etc..
Said polyolefins system resin can be homopolymer (homopolymer), or contain two or more monomers Copolymer (copolymer).Can be random copolymer, block copolymerization in addition, when said polyolefins system resin is copolymer Thing.One kind can be used only in said polyolefins system resin, can also use two or more.
As said polyolefins system resin, be not particularly limited, preferably using alpha-olefin as must monomer component and formed At least there is the polymer of the construction unit from alpha-olefin in the polymer of (formation), i.e. molecule (in 1 molecule).Above-mentioned polyene Hydrocarbon system resin for example both can be the polymer being only made up of alpha-olefin, or by the monomer beyond alpha-olefin and alpha-olefin The polymer that composition is formed.
As above-mentioned alpha-olefin, can enumerate for example：Alpha-olefin (such as ethene, propylene, 1- butylene, the 1- of carbon number 2~8 Amylene, 1- hexenes, 4-methyl-1-pentene, 1- heptene, 1- octenes etc.).One kind can be used only in above-mentioned alpha-olefin, can also make With two or more.
As the monomer component beyond above-mentioned alpha-olefin, can enumerate for example：Vinyl acetate, acrylic acid, acrylate, The ethylenically unsaturated monomers such as methacrylic acid, methacrylate, vinyl alcohol.Monomer component beyond above-mentioned alpha-olefin can be only Using one kind, can also use two or more.
As said polyolefins system resin, can enumerate for example：Low density polyethylene (LDPE), medium density polyethylene, high density are gathered Beyond ethene, linear low density of polyethylene, polypropylene (Noblen), the copolymer of ethene and propylene, ethene and ethene Copolymer, ethene and the propylene of alpha-olefin beyond the copolymer of alpha-olefin, propylene and propylene with addition to ethene and propylene Copolymer of the copolymer of alpha-olefin, propylene and ethylenically unsaturated monomer etc..
Said polyolefins system resin is not particularly limited, from obtaining the high foamed polyolefin resin body of expansion ratio Viewpoint is set out, preferably the polyolefin of straight-chain.
As said polyolefins system resin, from the viewpoint of heat resistance, preferably using propylene as required monomer component The polymer (polypropylene-based resin) of composition, i.e., preferably at least there is the polymer of the construction unit from propylene.As above-mentioned Polypropylene-based resin, it can enumerate for example：Copolymer, propylene and the propylene of polypropylene (Noblen), ethene and propylene with Copolymer of outer alpha-olefin etc..One kind can be used only in alpha-olefin beyond aforesaid propylene, can also use two or more.
The content of alpha-olefin in said polyolefins system resin is not particularly limited, for example, above-mentioned poly- relative to forming Monomer component total amount (100 weight %) preferably 0.1~10 weight %, more preferably 1~5 weight % of olefin-based resin.
As above-mentioned polyester based resin, can enumerate for example：Polyethylene terephthalate, poly terephthalic acid the third two Alcohol ester, mutual-phenenyl two acid bromide two alcohol ester, PEN, PBN, poly terephthalic acid ring The polyalkylene terephthalate such as hexane diformazan alcohol ester system resin etc..Further, it is also possible to enumerate make it is two or more above-mentioned poly- Copolymer obtained from the resin copolymerization of terephthalic acid (TPA) alkane diol ester system.Above-mentioned copolymer can be that random copolymer, block are common The copolymer of any form in polymers, graft copolymer.
As above-mentioned thermoplastic resin, the elastomer components such as rubber, thermoplastic elastomer (TPE) can be additionally enumerated.Contain bullet Property body composition when, the elasticity raising of foaming body, impact absorbency easily improves.
As above-mentioned rubber, can enumerate for example：Natural rubber, polyisobutene, isoprene rubber, neoprene, fourth The natural or synthetic rubber such as base rubber, nitrile rubber.One kind can be used only in above-mentioned rubber, can also use two or more.
As above-mentioned thermoplastic elastomer (TPE), can enumerate for example：Ethylene-propylene copolymer elastomer, ethylene-propylene-two Alkene copolymer elastomer, vinyl-vinyl acetate copolymer elastomer, polybutylene elastomer, polyisobutene elastomer, chlorination gather The thermoplastic olefin based elastomers such as ethylene elastomer；Styrene-butadiene-styrene elastomer, styrene-isoamyl two Alkene-styrenic copolymer elastomers, styrene-isoprene-BS elastomer, their hydride Deng thermoplastic styrene elastomer；Thermoplastic poly ester based elastomers；Thermoplastic polyurethane based elastomers；Thermoplastic acrylic Elastomer etc..One kind can be used only in above-mentioned thermoplastic elastomer (TPE), can also use two or more.
As above-mentioned resin, thermoplastic resin preferably wherein, more preferably polyolefin-based resins, polyester based resin are (especially It is thermoplastic poly ester based elastomers).In the case of using polyester based resin, the narrow processing of progress (such as it is processed as 1mm's or so Line width etc.) when easily suppress the generation that ruptures, crush.In addition, shape retention is excellent, and then it is preferred for the seal that foams. Polyester based resin also has high intensity, high elastic modulus in thermoplastic resin.
As above-mentioned thermoplastic poly ester based elastomers, it is not particularly limited, preferably comprises aromatic dicarboxylic acid and glycol is made For the Polyester thermoplastic elastomer (TPE) of monomeric unit.One kind can be used only in above-mentioned thermoplastic poly ester based elastomers, can also make With two or more.
As above-mentioned aromatic dicarboxylic acid, can enumerate for example：Terephthalic acid (TPA), M-phthalic acid, phthalic acid, naphthalene Carboxylic acid (such as 2,6 naphthalene dicarboxylic acid, 1,4- naphthalene dicarboxylic acids etc.), diphenyl ether dicarboxylic acids, 4,4 '-diphenyl dicarboxylic acid etc..Above-mentioned virtue One kind can be used only in fragrant race's dicarboxylic acids, can also use two or more.
As above-mentioned glycol, can enumerate for example：(four is sub- for ethylene glycol, propane diols, trimethylene, 1,4- butanediols Methyl glycol), 2- methyl-1,3-propanediols, 1,5- pentanediols, 2,2- dimethyl -1,3- propane diols (neopentyl glycol), 1,6- oneself Glycol, 3- methyl isophthalic acids, 5- pentanediols, 2- methyl -2,4-PD, 1,7- heptandiols, 2,2- diethyl -1,3- propane diols, 2- Methyl-2-propyl -1,3- propane diols, 2- methyl isophthalic acids, 6- hexylene glycols, 1,8- ethohexadiols, 2-butyl-2-ethyl-1,3-propanediol, 1,3,5- trimethyl -1,3- pentanediols, 1,9- nonanediols, 2,4- diethyl -1,5- pentanediols, 2- methyl isophthalic acids, 8- ethohexadiols, 1, The aliphatic two such as 10- decanediols, 2- methyl isophthalic acids, 9- nonanediols, 1,18- octacosanols, dimer diol (dimerdiol) Alcohol；1,4- cyclohexanediols, 1,3- cyclohexanediols, 1,2- cyclohexanediols, 1,4 cyclohexane dimethanol, 1,3- cyclohexanedimethanols, The ester ring type glycol such as 1,2- cyclohexanedimethanols；Bisphenol-A, the ethylene oxide adduct of bisphenol-A, bisphenol S, the epoxy second of bisphenol S The aromatic diols such as alkane addition product, benzene dimethanol, naphthalene glycol；Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropyl Ether glycol such as glycol etc..It should be noted that as the polymer morphology such as glycol or PTMEG, polyester-diol Diol component.As above-mentioned PTMEG, can enumerate for example：Make the ring-opening polymerisations such as oxirane, expoxy propane, tetrahydrofuran The polyethylene glycol that forms, polypropylene glycol, polytetramethylene glycol and make copolyether that these copolymerization form etc..Above-mentioned glycol can Using only one kind, can also use two or more.
And then as above-mentioned thermoplastic poly ester based elastomers, particularly preferable as the block copolymerization of hard segment and soft chain segment The polyester-based elastomer of thing.In this case modulus of elasticity is big and flexibility is excellent, therefore screen resilience during 50% compression is excellent In the range of choosing, in addition, impact absorbency is also excellent.
For the Polyester thermoplastic elastomer (TPE) as hard segment and the block copolymer of soft chain segment, do not limit especially It is fixed, preferably following (i)~(iii), the copolymer of the polyester and polyether type of more preferably following (ii).
(i) using the glycol that the carbon number of the main chain used between aromatic dicarboxylic acid and 2 hydroxyls is 2~4 as monomeric unit Polyester as hard segment, using the carbon number of the main chain used between aromatic dicarboxylic acid and 2 hydroxyls be more than 5 glycol as singly Copolymer of the polyester of body unit as polyester/polyester-type of soft chain segment
(ii) polyester that will be same with above-mentioned (i) is as hard segment and by polyethers such as above-mentioned PTMEG, aliphatic polyethers Copolymer as the polyester and polyether type of soft chain segment
(iii) polyester/poly- of polyester that will be same with above-mentioned (i) as hard segment and using aliphatic polyester as soft chain segment The copolymer of ester type
In addition, as above-mentioned resin, further preferably polyolefin-based resins and above-mentioned elastomer components are applied in combination.In polyene When elastomer components are added in hydrocarbon system resin, the elasticity raising of foaming body, impact absorbency easily improves.
As above-mentioned elastomer components when being applied in combination with polyolefin-based resins, thermoplastic olefin system bullet preferably wherein Property body, the olefin-based bullet of the structure of microphase-separated particularly preferably occurs with polyolefin-based resins composition and olefin-based rubber constituent Property body.There is polyolefin-based resins composition and the olefin-based elasticity of the structure of olefin-based rubber constituent generation microphase-separated as this Body, the elasticity preferably formed by polypropylene (PP) and ethylene-propylene rubber (EPM) or Ethylene-Propylene-Diene rubber (EPDM) Body.But the above-mentioned polyolefin-based resins composition having in the olefin-based elastomer that the scattered structure of microfacies occurs is considered as and included Composition in elastomer components.On the weight ratio of said polyolefins system resin component and olefin-based rubber constituent, from compatible From the viewpoint of property, preferred polyolefm system resin component/olefin-based rubber constituent=90/10~10/90, more preferably 80/20~ 20/80。
Melt flow rate (MFR) (MFR) at 230 DEG C of above-mentioned resin is not particularly limited, preferably 1.5~4.0g/10 points Clock, more preferably 1.5~3.8g/10 minutes, further preferred 1.5~3.5g/10 minutes.Above-mentioned MFR is 1.5g/10 more than minute When, the mouldability of resin combination improves.Such as it can not occur with desired shape easily to enter with blocking from extruder Row extrusion.When above-mentioned MFR is below 4.0g/10 minutes, the deviation of cell diameter is not likely to produce after formation bubble structure, it is easy to obtain To uniform foam structure.It should be noted that in this manual, MFR at 230 DEG C is set to be based on ISO1133 (JIS K 7210) MFR determined under 230 DEG C of temperature, load 2.16kgf.
The content of above-mentioned resin in the foaming body of the present invention is not particularly limited, relative to the weight (100 of foaming body Weight %) preferably more than 70 weight %, more preferably more than 80 weight %, further preferred more than 90 weight %.To above-mentioned content The upper limit be not particularly limited, less than 100 weight %.
When above-mentioned resin contains said polyolefins system resin, the content of polyolefin-based resins is not particularly limited, relatively In the weight (100 weight %) preferably more than 10 weight % of foaming body, more preferably more than 20 weight %, further preferred 30 weight Measure more than %.The upper limit of above-mentioned content is not particularly limited, it is more excellent preferably below 80 weight % less than 100 weight % Select below 50 weight %.
When above-mentioned resin contains said polyolefins system resin and above-mentioned elastomer components, do not have to the content of elastomer components It is particularly limited to, 0 weight % and below 70 weight % is preferably greater than relative to the weight (100 weight %) of foaming body, more preferably 20 ~60 weight %, further preferred 20~50 weight %.
As described above, the foaming body of the present invention contains lubricant.By containing lubricant, the hair of the present invention will be molded The mouldability of the resin combination of foam improves.Specifically, the slickness of resin combination becomes good, for example, extrusion molding When, do not occur easily easily to be extruded with desired shape with blocking from extruder, in addition, when interval is molded, easily The mobility of resin combination is improved, resin combination is deployed into the corner of mould and makes it have smooth surface.On One kind can be used only by stating lubricant, can also be used two or more.
As above-mentioned lubricant, the body formed middle known usual lubricant used that foams can be used.As above-mentioned profit Lubrication prescription, it can enumerate for example：The hydrocarbon system lubricant such as atoleine, solid paraffin, microwax, Tissuemat E；Stearic acid, behenyl The fatty acid series lubricants such as acid, 12- hydroxy stearic acids；The higher alcohol base lubricant such as stearyl alcohol；Fatty acid carboxylate and its derivative； The fatty acid amide base lubricant such as stearic amide, oleamide, erucyl amide；Di-2-ethylhexylphosphine oxide stearic amide, ethylenebis The alkylidene fatty acid amide base lubricant such as stearic amide；Butyl stearate, glyceryl monostearate, pentaerythrite four are stearic The ester base lubricant such as acid esters, rilanit special, stearyl stearate；Acrylic acid series lubricant etc..
As the derivative of above-mentioned aliphatic carboxylic acid, can enumerate for example：The alkali gold of aliphatic carboxylic acid acid anhydride, aliphatic carboxylic acid Belong to alkali salt of salt, aliphatic carboxylic acid etc..As above-mentioned aliphatic carboxylic acid and its derivative, laurate preferably wherein, The fatty acid carboxylate and its derivative of the carbon numbers such as stearic acid, crotonic acid, oleic acid, maleic acid, glutaric acid, behenic acid, montanic acid 3~30 Thing.In addition, in the fatty acid carboxylate and its derivative of carbon number 3~30, from the dispersiveness, dissolubility, surface to resin combination The viewpoints such as outward appearance improved effect are set out, preferably stearic acid and its derivative, montanic acid and its derivative, particularly preferably stearic Alkali metal salt, stearic alkali salt.And then in stearic alkali metal salt, stearic alkali salt, it is more excellent Select zinc stearate, calcium stearate.
In addition, as above-mentioned lubricant, preferably at least using nitrogen atom compound.In this case, due to by dividing Lubricant can be calculated by not determining the amount of the nitrogen atom compound in the surface region and interior zone of the foaming body of the present invention The ratio of content, therefore calculating for the ratio of the lubricant content of surface region and interior zone becomes easy.Therefore, as upper Lubricant is stated, fatty acid amide base lubricant preferably wherein.Fatty acid amide base lubricant be not susceptible to from interior zone to The migration of surface region, therefore the ratio of the lubricant content for further reducing surface region is useful.In addition, lubricant exists Migration inside foaming body is not easy to occur, and lubricant is not easy to separate out on foaming body surface, therefore is not easy to make to be bonded a variety of Adhesive phase changes property, also has the advantages of increasing the option of available adhesive phase.
Therefore, the content of the nitrogen atom compound in the surface region of the foaming body of the present invention is not particularly limited, It is preferred that below the 70 weight % of the content of nitrogen atom compound in interior zone, more preferably below 60 weight %, further It is preferred that below 55 weight %, particularly preferred below 50 weight %.
Lubricant content in the interior zone of the foaming body of the present invention is not particularly limited, relative in the region The parts by weight of resin 100 preferably 0.1~20 parts by weight, more preferably 0.3~10 parts by weight, further preferred 0.5~8 parts by weight.On When stating lubricant content to be more than 0.1 parts by weight, by containing above-mentioned lubricant, being readily obtained obtained effect.Above-mentioned profit When lubrication prescription content is below 20 parts by weight, bubble vagus escape when resin combination is foamed is inhibited, easy alveolation occurred frequently.Need It is noted that the content in above-mentioned interior zone is set to identical with the content in the resin combination for forming foaming body.
, can also be in the scope for the effect for not damaging the present invention in addition to above-mentioned each composition in the foaming body of the present invention Inside contain additive.As above-mentioned additive, can enumerate for example：Softening agent, crosslinking agent, antirust agent, age resistor, weather resisting agent, Ultra-violet absorber, dispersant, plasticizer, colouring agent (pigment, dyestuff etc.), antistatic additive, surfactant, modification Agent, mobility modifying agent, antioxidant, filler, reinforcing agent, surface conditioning agent, anti-shrinking medium, vulcanizing agent, fire retardant etc..On One kind can be used only by stating additive, can also be used two or more.
When above-mentioned resin contains polyolefin-based resins, foaming body of the invention preferably also contains softening agent.Particularly preferred one Rise and contain above-mentioned elastomer components and softening agent.It during containing softening agent, can improve the processability of foaming body, flexibility.On One kind can be used only by stating softening agent, can also be used two or more.
As above-mentioned softening agent, it is not particularly limited, softening agent usually used in rubber can be enumerated.As upper The specific example of softening agent is stated, can be enumerated：The mineral oil such as paraffin series, naphthene series, fragrant family；Operate oil, lubricating oil, liquid The petroleum material such as paraffin, asphalt, vaseline；The coal tar oils such as coal tar (coaltar), coal tar asphalt；Castor oil, The fat oils such as Linseed oil, rapeseed oil, soybean oil, coconut oil；Tall oil (talloil), beeswax, Brazil wax, lanolin Etc. wax class；Petropols, coumarone-indene resin (coumarone-indeneresin), atactic polypropylene etc. synthesize high score Sub- material；The ester compounds such as dioctyl phthalate, dioctyl adipate, di-n-octyl sebacate；Microwax, ointment (factice), liquid polybutadiene, modified liquid polybutadiene, liquid polysulphide rubber, liquid polyisoprene, the poly- fourth of liquid Alkene, liquid ethylene-alpha-olefin based copolymer etc..Mineral oil preferably wherein, liquid polyisoprene, liquid polybutene, liquid Ethene-alpha-olefin based copolymer, more preferably liquid polyisoprene, liquid polybutene, liquid ethylene-alpha-olefin based copolymer.
When the foaming body of the present invention contains softening agent, the content of the above-mentioned softening agent in foaming body is not particularly limited, Relative to the parts by weight of resin 100 preferably 1~200 parts by weight, more preferably 5~100 parts by weight, further preferred 10~50 weight Part.When above-mentioned content is more than 1 parts by weight, there is the processability of foaming body, flexibility improves.Above-mentioned content is 100 weights When measuring below part, have the tendency of to improve with the dispersiveness of resin.
When the foaming body of the present invention contains elastomer components and softening agent together, to containing for the above-mentioned softening agent in foaming body Amount is not particularly limited, relative to the parts by weight of elastomer components 100 preferably 1~200 parts by weight, more preferably 5~100 parts by weight, Further preferred 10~50 parts by weight.When above-mentioned content is more than 1 parts by weight, there are the processability of foaming body, flexibility to improve Tendency.When above-mentioned content is below 100 parts by weight, dispersiveness improves when having the tendency of to be kneaded with elastomer components.
It should be noted that in this manual, each composition included in foaming body of the invention (such as resin, profit Lubrication prescription, additive etc.) content can be appropriate out of described scope respectively in the way of adding up to below 100 weight % Selection.
The foaming body of the present invention is shaped as sheet (banding).Furthermore, it is possible to be processed into according to application target it is appropriate Shape.For example, linear, circular or polygon, frame shape (frame shape) etc. can be processed into by cutting off processing, punch press process etc..
(manufacture method of foaming body of the invention)
The foaming body of the present invention can be manufactured by the method comprising following process, and the process is：Resin will be contained The process (foaming process) of foaming body is obtained with the resin combination foaming of lubricant；And lubricant is set to exist Decompose or from the surface migration from a surface of above-mentioned foaming body, thus make from said one surface to thickness direction The lubricant content in region untill 50nm depth be reduced to by above-mentioned foaming body in the way of thickness halves it is parallel When foaming body surface is cut off, from 70 of the lubricant content in region of the section untill thickness direction 50nm depth Below weight % process (lubricant reduction process).It should be noted that in this manual, above-mentioned hair will be made sometimes The method of bright foaming body is referred to as " manufacture method of foaming body of the invention ".
Above-mentioned resin combination can also contain above-mentioned additive etc. as needed.Above-mentioned resin combination can also contain Bubble nucleating agent (foaming nucleation agent), crystallization nucleating agent.Wherein, above-mentioned resin combination preferably comprises bubble nucleating agent.Contain During bubble nucleating agent, by making above-mentioned resin combination foam, the foaming with uniform, fine foam structure is readily obtained Body.
As above-mentioned bubble nucleating agent, such as particle can be enumerated.As the particle, can enumerate for example：Talcum, dioxy SiClx, aluminum oxide, zeolite, calcium carbonate, magnesium carbonate, barium sulfate, zinc oxide, titanium oxide, aluminium hydroxide, magnesium hydroxide, mica, illiteracy The clays such as de- soil, carbon particle, glass fibre, carbon pipe etc..One kind can be used only in above-mentioned bubble nucleating agent, can also use two kinds More than.Particularly, the clay such as magnesium hydroxide, montmorillonite can assign anti-flammability to resulting foaming body, thus preferably.
The average grain diameter (particle diameter) of particle as above-mentioned bubble nucleating agent is not particularly limited, preferably 0.1~20 μm. When above-mentioned average grain diameter is more than 0.1 μm, have the tendency of more fully to play the function as bubble nucleating agent.Above-mentioned average grain When footpath is less than 20 μm, gas is less susceptible to vagus escape when having the tendency of foaming.
When above-mentioned resin combination contains bubble nucleating agent, to the no spy of content of the bubble nucleating agent in resin combination Do not limit, relative to the parts by weight of resin 100 preferably 0.5~125 parts by weight, more preferably 1~120 parts by weight.
Above-mentioned resin combination can by by above-mentioned resin, above-mentioned lubricant, the above-mentioned bubble that uses as needed into Core agent and above-mentioned additive etc. are kneaded and made.Squeezed for example, above-mentioned resin combination can be kneaded by using single screw rod (single shaft) Go out melting mixing extrusion device known to machine, twin-screw mixer extruder etc. to be kneaded, extruded and obtained.
During using above-mentioned elastomer components and softening agent, after being pre-mixed above-mentioned elastomer components and softening agent Material (mixture of elastomer components and softening agent) and other resin components etc. mix.To above-mentioned elastomer components and softening The content of softening agent in the mixture of agent is not particularly limited, relative to resin component (such as the polyene in elastomer components Hydrocarbon system resin component) 100 parts by weight preferably 1~200 parts by weight, more preferably 5~100 parts by weight, further preferred 10~50 weight Measure part.It should be noted that when the content of softening agent is below 200 parts by weight, there is dispersiveness change when being kneaded with elastomer components Obtain better tendency.
Above-mentioned additive (particularly age resistor, weather-proof can be contained in the mixture of above-mentioned elastomer components and softening agent Agent, ultra-violet absorber, dispersant, plasticizer, colouring agent, antistatic additive, surfactant, tension modifier, mobility change Property agent).
The content of additive in the mixture of above-mentioned elastomer components and softening agent is not particularly limited, relative to bullet Resin component (such as polyolefin-based resins composition) 100 parts by weight preferably 0.01~100 parts by weight in property body composition, more preferably 0.05~50 parts by weight, further preferred 0.1~30 parts by weight.It should be noted that above-mentioned content is more than 0.01 parts by weight When, it is easier to show effect caused by the addition of additive.
The melt flow rate (MFR) of above-mentioned elastomer components and the mixture of softening agent (MFR) (230 DEG C) is not limited especially It is fixed, from the viewpoint of good mouldability is obtained, preferably 3~10g/10 minutes, more preferably 4~9g/10 minutes.
" the JIS A hardness " of the mixture of above-mentioned elastomer components and softening agent is not particularly limited, preferably 30~ 90 °, more preferably 40~85 °.When above-mentioned " JIS A hardness " is more than 30 °, the foaming body of high foamability is readily obtained.In addition, When above-mentioned " JIS A hardness " is less than 90 °, the foaming body of softness is readily obtained.It should be noted that " the JIS in this specification A hardness " refers to the hardness based on ISO7619 (JIS K6253) measure.
Above-mentioned resin combination, which can enumerate such as strand form, sheet, tabular, graininess, (such as will be extruded as strand The resin combination water cooling or air cooling of shape simultaneously cut into graininess obtained by appropriate length) etc..Wherein, from the viewpoint of productivity ratio Set out, preferably graininess.
In above-mentioned foaming process, as the method for making above-mentioned resin combination foaming, physical blowing can be enumerated Method, chemical blowing method.Above-mentioned physical foaming method is to make low-boiling point liquid (foaming agent) infiltration (scattered) in resin combination In thing, then foaming agent is set to volatilize, the method for being consequently formed abscess (bubble).In addition, above-mentioned chemical blowing method be by by Gas caused by the thermal decomposition of the compound in resin combination is added to form the method for abscess.Wherein, according to avoiding sending out The viewpoint of foam pollution, obtain fine and uniform bubble structure easy degree viewpoint and it is preferred that physical foaming method, more It is preferred that use physical foaming method of the gases at high pressure as foaming agent.
As the above-mentioned foaming agent used in physical foaming method, it is not particularly limited, from obtaining, fine and abscess is close Spend from the viewpoint of the easy degree of high bubble structure, preferably gas, particularly preferably relative to form foaming body resin (on State the resin that resin combination is included) it is inert gas (non-active gas).
Above-mentioned non-active gas can be enumerated for example：Carbon dioxide, nitrogen, air, helium, argon gas etc..From in resin group Infiltration amount in compound is more, the fireballing viewpoint of infiltration is set out, the above-mentioned particularly preferred carbon dioxide of non-active gas.It is above-mentioned non-live Property gas can be used only one kind, can also use two or more.
The combined amount (content, infiltration amount) of above-mentioned foaming agent is not particularly limited, relative to above-mentioned resin combination Gross weight (100 weight %) preferably 2~10 weight %.
From the viewpoint of the infiltration speed to resin combination is accelerated, above-mentioned non-active gas are super preferably in infiltration Critical condition.That is, in foaming process, preferably above-mentioned resin combination is foamed with supercritical fluid and form foaming body. When above-mentioned non-active gas are supercritical fluid (supercriticality), the solubility increase in resin combination can be highly concentrated Degree ground infiltration (being mixed into).Further, since can be infiltrated with high concentration, therefore when after infiltration drastically reducing pressure, nuclei of bubbles Generation increase, the bubble nucleus growth and the density of the bubble that is formed, the porosity also increase even if identical, therefore can obtained micro- Thin bubble.It should be noted that the critical-temperature of carbon dioxide is 31 DEG C, critical pressure 7.4MPa.
For using physical foaming method of the gas as foaming agent, method is preferably as follows：Via make gases at high pressure (such as Non-active gas etc.) be infiltrated up in resin combination after depressurized (such as until atmospheric pressure) process (release pressure Process) make its foaming, it is consequently formed.Specifically, method can be listed below：By the way that resin combination is molded to obtain not Foaming thing, gases at high pressure are made to be infiltrated up in the unexpanded article shaped, then decompression (such as until atmospheric pressure), via as above The method that process makes it foam and formed；Gas (such as non-active gas etc.) is set to be infiltrated up to the resin of melting under pressurised conditions In composition, then decompression (such as until atmospheric pressure) makes it foam and simultaneously for shaping, method being consequently formed etc..
That is, when foaming body is formed in foaming process, can carry out in the following manner：By above-mentioned resin combination The suitable shape such as sheet is shaped to after unexpanded resin-formed body (unexpanded article shaped) is made, is infiltrated up to gases at high pressure In the unexpanded resin-formed body, discharge pressure and it is foamed (intermittent mode), can additionally enter in the following manner OK：Above-mentioned resin combination is kneaded together with gases at high pressure under elevated pressure conditions, pressure is discharged while shaping so as to same Shi Jinhang is molded and the mode (continuation mode) of foaming.
In above-mentioned intermittent mode, forming the method for unexpanded resin-formed body can enumerate for example：Squeezed using single screw rod Go out the method that resin combination is molded by the extruders such as machine, double screw extruder；Use roller, cam, kneader, Banbury type etc. By its punch forming it is specific thickness using hot plate pressurization etc. if resin combination is kneaded uniformly by vaned kneading machine in advance Method；Method for being molded resin combination using injection (mo(u)lding) machine etc..In addition, the shape of unexpanded resin-formed body can be with Enumerate for example：Sheet, web-like, tabular etc..In above-mentioned intermittent mode, by can obtain desired shape, thickness it is unexpanded The proper method of resin-formed body, forming processes are carried out to resin combination.
In above-mentioned intermittent mode, bubble structure is formed via following process：Gas infiltration process, add in pressure vessel Enter unexpanded resin-formed body, inject (import, be mixed into) gases at high pressure, make gas infiltration into unexpanded resin-formed body；Subtract Process is pressed, pressure (usually until atmospheric pressure) is discharged at the time of gas is fully infiltrated, makes to produce bubble in resin combination Core.
In above-mentioned continuation mode, the foaming that resin combination is carried out by following process is handled：It is kneaded infiltration work Sequence, while being carried out using extruder (such as single screw extrusion machine, double screw extruder etc.), injection (mo(u)lding) machine to resin combination It is kneaded, while injection (import, be mixed into) gases at high pressure, make gases at high pressure fully be infiltrated up in resin combination；Shaping decompression work Sequence, the mould by being arranged on extruder front end etc. extrudes resin combination, thus discharges pressure (usually until atmospheric pressure) And it is molded and is foamed simultaneously.
As needed, above-mentioned intermittent mode, continuation mode may also set up the heating process for making bubble nucleus growth by heating. It should be noted that heating process can also be not provided with and make bubble nucleus growth at room temperature.And then bubble can also be given birth to After length, rapidly cooled down using cold water etc. as needed, fix shape.The importing of gases at high pressure can be carried out continuously, can also It is discontinuous to carry out.It should be noted that there is no particular limitation for heating means during to making bubble nucleus growth, can enumerate：Water Customary way known in bath, oil bath, hot-rolling, hot-air oven, far infrared, near infrared ray, microwave etc..
Gas infiltration process in above-mentioned intermittent mode, in the mixing impregnation step of above-mentioned continuation mode, consider gas Species, operability etc. and pressure when suitably selecting to make gas infiltration, for example, it is preferable to more than 5MPa (such as 5~100MPa), more It is preferred that more than 7MPa (such as 7~100MPa).That is, soak preferably more than pressure 5MPa the gas of (such as 5~100MPa of pressure) It is seeped into above-mentioned resin combination, more preferably infiltrates more than pressure 7MPa the non-active gas of (such as 7~100MPa of pressure) Into above-mentioned resin combination.When the pressure of gas is more than 5MPa, moderately suppress air bubble growth during foaming, having to press down Abscess processed excessively becomes big tendency.This is because, when pressure is high, the infiltration amount of gas when low pressure compared with relative become more, bubble Karyomorphism is fast into speed, the bubble check figure increase formed, therefore reduces the gas flow in each bubble, and bubble diameter is not easy pole Degree becomes big.In addition, in more than 5MPa pressure span, even if infiltration pressure change is a little, cell diameter, bubble density are not easy to Significantly change, it is easily controlled cell diameter and bubble density.
In addition, in mixing impregnation step in gas infiltration process, above-mentioned continuation mode in above-mentioned intermittent mode, make gas Temperature (infiltration temperature) when body infiltrates used in gas, the species of resin and it is different, can carry out in a wide range Selection, but in the case of consideration operability etc., preferably 10~350 DEG C.More specifically, the infiltration temperature under intermittent mode is preferred 10~250 DEG C, more preferably 40~240 DEG C, further preferred 60~230 DEG C.In addition, the infiltration temperature preferably 60 under continuation mode ~350 DEG C, more preferably 100~320 DEG C, further preferred 150~300 DEG C.It should be noted that it is used as height using carbon dioxide Calm the anger in the case of body, in order to keep supercriticality, preferably more than 32 DEG C of the temperature (infiltration temperature) (particularly 40 during infiltration More than DEG C).In addition, the resin combination for being impregnated with gas can be also cooled to suitable after making gas infiltration, before foaming The temperature (such as 150~190 DEG C) of foaming.
And then in above-mentioned intermittent mode, above-mentioned continuation mode, to the decompression speed in decompression process (process of release pressure) There is no particular limitation for degree, from obtaining the bubble structure aspect with uniform and fine abscess, preferably 5~ The 300MPa/ seconds.
In order that bubble nucleus growth and when heating process is set, such as preferably 40~250 DEG C of heating-up temperature, more preferably 60~ 250℃。
It should be noted that on the bubble structure of the foaming body of the present invention, density, relative density, can be set according to forming The species of fat come select by foaming method during resin combination foaming, foaming condition (such as the species of foaming agent, amount, Temperature, pressure, time during foaming etc.), thus it is adjusted.
The foaming body obtained by above-mentioned foaming process can before process is reduced for above-mentioned lubricant for Other processes such as slice processing process, heat fusing treatment process.
In the case that the manufacture method of the foaming body of the present invention includes slice processing process, to being obtained by foaming process The foaming body arrived implements slice processing.Specifically, above-mentioned resin combination is foamed and after obtaining foaming body, to the foaming The surface of two surface sides of body carries out slice processing.Above-mentioned foaming body has superimposed portions high inside density ratio near surface mostly Divide (expansion ratio is than internal low stratiform part, table (skin) layer).By slice processing, the stratiform part can be removed, and The bubble structure of inside can be made to expose on foaming body surface and opening portion is set.In addition, pass through slice processing, it is possible to achieve thick The raising of precision is spent, thus thickness and precision improves.
In the case that the manufacture method of the foaming body of the present invention includes heat fusing treatment process, the further foaming to obtaining The surface of body carries out heat fusing processing (surface heat melt process).Specifically, obtain making above-mentioned resin combination foam After foaming body (after implementing slice processing as needed), heat fusing processing is carried out to the surface of the foaming body.Thus, by making thickness Spend the melt surface in direction and the reduction of flexibility is suppressed to bottom line, and improve the tensile strength of long side direction, suppress The generation of fracture, tear etc., easily can continuously obtain foaming body.In addition, by making frothing part recover to non-foamed State (bulk), the roughness (thickness error) on surface diminish, and thickness and precision improves.
As the processing of above-mentioned heat fusing, can enumerate for example：Using the stamping process of hot-rolling, laser treatment with irradiation, through adding Contact melt process, flame treatment on the roller of heat etc..When using the stamping process of hot-rolling, heat-laminator etc. can be used to enter Row processing.It should be noted that the material as roller, rubber, metal, fluorine resin (such as Teflon (registrar can be enumerated Mark)) etc..
Temperature when handling above-mentioned heat fusing is not particularly limited, preferably the softening than the resin included in foaming body Point or low 15 DEG C of fusing point temperature more than (more preferably than the resin included in foaming body low 12 DEG C of softening point or fusing point temperature It is more than degree), furthermore it is preferred that than below the temperature of high 20 DEG C of the softening point or fusing point of the resin included in foaming body (more preferably Below temperature than high 10 DEG C of the softening point or fusing point of the resin included in foaming body).Heat fusing processing when temperature be than It is preferable in terms of heat fusing processing is efficiently implemented when forming more than the softening point of resin or the temperature of low 15 DEG C of fusing point. And sufficient heat fusing processing can be carried out, the thickness and precision for having the tendency of foaming body further improves.In addition, at heat fusing When temperature during reason is than forming below the softening point of resin or the temperature of high 20 DEG C of fusing point, having can suppress to shrink and produce pleat The tendency such as wrinkle.
In the case that resin included in foaming body is polyolefin-based resins, temperature when above-mentioned heat fusing is handled is specific It is preferred that 100~300 DEG C, more preferably 150~250 DEG C, further preferred 170~230 DEG C.
In addition, the processing time as heat fusing processing, although also depending on treatment temperature, preferably such as 0.1 second~ 10 seconds or so, preferably 0.5 second~7 seconds or so.Processing time within the above range when, it can be ensured that when melting required sufficient Between, in addition, there is the caused tendency that can suppress the caused fold of excessive heating etc..And it is possible to carry out sufficient heat fusing Processing, the thickness and precision of foaming body improve.
In above-mentioned heat fusing processing, preferably use can adjust the gap (gap, interval) that foamed structures pass through Heat fusing processing unit.As such heat fusing processing unit, can enumerate for example：With the heating roller that can adjust gap The apparatus for continuous treatment of (hot dielectric roller).
Above-mentioned lubricant is reduced in process, in order that the lubricant content in above-mentioned surface region is reduced to above-mentioned inner area Below the 70 weight % of lubricant content in domain, make the lubricant breakdown on a surface of foaming body or make lubricant from hair One surface migration of foam.
As the means for decomposing lubricant, can enumerate for example：Cut off using the high material (such as active oxygen) of reactivity Form the method for the chemical bond of lubricant, irradiate high-power electron beam to cut off the method for the chemical bond for forming lubricant.
As the method for producing active oxygen, known customary way can be enumerated.It can enumerate for example：Enter in the presence of oxygen The method of row ultraviolet irradiation, method of corona discharge etc. is carried out in the presence of oxygen.Wherein, ultraviolet photograph is carried out in the presence of oxygen The method penetrated can be efficiently obtained active oxygen, therefore preferably.In the method for carrying out ultraviolet irradiation in the presence of oxygen, it is specific and When speech is using the UV lamp near 185nm and near 254nm with strong emission wavelength, oxygen molecule receives the energy of 185nm wavelength And be decomposed, produce oxygen atom, the oxygen atom and oxygen molecule with reference to and produce ozone.Then, ozone receives the energy of 254nm wavelength Measure and be decomposed, produce active oxygen.Particularly, 185nm is nearby not easy cut-out and forms foaming body with the emission wavelength near 254nm Molecule, therefore preferably.
In the method for irradiating electron beam, (handed over crosslinking resin, crosslinking agent in foaming body after so-called Connection) degree, the low energy for the degree that the physical property of foaming body changes is carried out irradiating electron beam in addition.
The irradiation of above-mentioned ultraviolet and electron beam irradiation can be carried out by intermittent mode, can also by continuation mode come Carry out.
As the means for migrating lubricant, can enumerate for example：By heating and make method that it is evaporate into air, Method, coating adhesive and the stripping in the solvent that can dissolve lubricant are eluted to so that it moves to the adhesive In method etc..
It is set to evaporate into the method in air above by heating, not make resin, the crosslinking agent in foaming body Crosslink the degree of (so-called post-crosslinking), the low in calories of the degree that in addition changes the physical property of foaming body is added Heat.
As the above-mentioned method being eluted in solvent, can enumerate for example：To foaming body surface ejection of solvent and quiet Put certain time, then remove the method for solvent on surface etc..
In above-mentioned coating adhesive and stripping so that it is moved in the method in the adhesive, it can use to have and glue Mixture known usual and the adhesive tape that can be peeled off.Specifically, by adhesive tape joining foaming body said one table On face and kept for certain time, then peeled off, it is possible thereby to make lubricant move in adhesive.As above-mentioned adhesive, only There is cohesive to foaming body and can peel off again and be not particularly limited, such as acrylic acid series, rubber series can be used, had Usual adhesive known in machine silicon systems etc..In addition, other characteristics such as thickness are also not particularly limited.Stripping on adhesive tape From, continuous a large amount of processing due to be easier to make for than intermittent mode and it is preferred that.In addition, acrylic adhesive and fatty acid amide The compatibility of base lubricant is high, thus the absorption of the fatty acid amide base lubricant of the surface region to being present in foaming body or Absorbability is excellent, therefore preferably.
Method, above-mentioned be eluted to that it is evaporate into air is set to dissolve the molten of lubricant above by heating Method and above-mentioned coating adhesive and stripping in agent was so that its method moved in the adhesive both can be with interval Mode is carried out can also be in a continuous manner.
Thus, in foaming process, the resin combination foaming containing resin and lubricant is foamed Body, slice processing, heat fusing processing are carried out as needed, then the profit in above-mentioned surface region is made during lubricant reduces process Lubrication prescription content is reduced to below 70 weight % of the lubricant content in above-mentioned interior zone, it can thus be concluded that the foaming to the present invention Body.
[bubble generation member]
The bubble generation member of the present invention comprises at least the foaming body of the present invention.The bubble generation member of the present invention can be only by the present invention Foaming body form, it is possible to have other components beyond foaming body of the invention.As above-mentioned other components, can enumerate Adhesive phase, substrate layer, bonding sheet (such as carrier band) etc..
The present invention foaming body pick it is good, and from carrier band peel off when be not easy to cause foam to destroy.Therefore, this hair In bright bubble generation member, foaming body of the invention uses preferably in the way of said one surface mount is on carrier band.By This, as the bubble generation member of the invention of other components beyond the foaming body with the present invention, can enumerate for example：In this hair There is the bubble generation member of carrier band on the said one surface of bright foaming body.
The bonding sheets such as above-mentioned carrier band can be the bonding sheet that is made up of adhesive phase or with base material and positioned at this The bonding sheet of the adhesive phase of at least one side of base material.In addition, both can be one side bonding sheet or two sides bonding sheet. As above-mentioned carrier band, preferably with base material and positioned at the base material one side adhesive phase carrier band.Therefore, as with carrier band Bubble generation member of the invention, it is preferred that at least one side possessed in base material have the carrier band of adhesive phase and the present invention The side that foaming body and above-mentioned carrier band contact according to the said one surface of the foaming body of the present invention with the adhesive phase of above-mentioned carrier band The bubble generation member that formula is laminated.
In addition, in the bubble generation member of the present invention, foaming body of the invention can have adhesive phase in one or two sides.It is special Preferably not there is adhesive phase on above-mentioned another surface.And then bubble generation member of the invention is in the above-mentioned of foaming body of the invention In the case that one surface has carrier band, particularly preferably there is adhesive phase on above-mentioned another surface of the foaming body of the present invention. When the bubble generation member of the present invention has adhesive phase, such as it can set and add via adhesive phase on the bubble generation member of the present invention Work lining paper, and then it is first-class to fix or be temporarily fixed at adherend (such as housing, part etc.).
As above-mentioned adhesive phase is formed, (one or two sides of adhesive phase and foaming body in carrier band can have viscous Mixture layer) adhesive, can enumerate for example：Acrylic adhesive, elastomeric adhesive (natural rubber system adhesive, close Into elastomeric adhesive etc.), silicon-type adhesive, Polyester adhesive, carbamate system adhesive, polyamide-based bonding Agent, epoxy adhesive, vinyl alkyl ethers system adhesive, fluorine system adhesive etc..One kind can be used only in adhesive, can also Using two or more.In addition, adhesive can be emulsion system adhesive, solvent system adhesive, heat-fusible adhesive, oligomer system Adhesive, be admittedly any form in adhesive etc. adhesive.As above-mentioned adhesive, from preventing from polluting the viewpoints such as adherend Set out, acrylic adhesive preferably wherein.
The thickness of above-mentioned adhesive phase is not particularly limited, preferably 2~100 μm, more preferably 10~100 μm.Adhesive Layer is more thin, prevents that the effect of the attachment of the waste, dust of end is higher, therefore the mode that preferred thickness is thin.Need what is illustrated It is that adhesive phase can have any of individual layer, layered product form.
Above-mentioned adhesive phase can be arranged on by other layers (lower floor) on the foaming body of the present invention.Under this Layer, can be enumerated for example：Other adhesive phases, intermediate layer, priming coat, substrate layer (particularly film layer, nonwoven layer etc.) etc..Enter And above-mentioned adhesive phase can be stripped the stripping films such as paper, stripping film (barrier film) protection.
Fig. 2 shows the schematic diagram of one of the bubble generation member of the present invention.In Fig. 2, bubble generation member 2 of the invention includes this hair Bright foaming body 1.On a surface 11 of the foaming body 1 of the present invention, according to a surface 11 and adhesive phase 3b bonding The one side that the mode of face contact is laminated with base material 3a has adhesive phase 3b carrier band 3.In addition, the foaming body 1 of the present invention Adhesive phase 4 is laminated with another surface 12.
The bubble generation member of the present invention is preferred for electric/electronic device purposes.It is particularly preferably close as electric/electronic device Sealing, dust guard.Furthermore it is preferred that inhaled as bolster, the bolster of shock absorber, particularly electric/electronic device, impact Addressee.It should be noted that " electric/electronic device " refers to set equivalent to electrical equipment or at least any of of electronic equipment It is standby.In addition, by the way that the bubble generation member of the present invention is used for into above-mentioned electric/electronic device, the electric and electronic that the present invention can be made is set It is standby.The electric/electronic device of the present invention comprises at least the bubble generation member of the present invention.
As above-mentioned electric/electronic device, portable electric electronic equipment is especially enumerated.As such portable electric Electronic equipment, it can enumerate for example：Mobile phone, PHS, smart phone, tablet personal computer (plate computer), mobile computer are (mobile PC), the portable broadcasting receiver such as personal digital assistant device (PDA), electronic memo, portable television and portable radio, The cameras such as portable game machine, portable audio player, Portable DVD player, digital camera, camera type are taken the photograph Camera etc..It should be noted that as the electric/electronic device beyond above-mentioned portable electric/electronic device, example can be enumerated Such as：Family's electrical article, personal computer etc..
Particularly, for the bubble generation member of the present invention, as (installation) can be assembled in above-mentioned electric/electronic device Various components (part), can enumerate for example：Shown installed in liquid crystal display (LCD), electroluminescent display, plasma Image display member (display part) (particularly small-sized image display member) in the image display devices such as device；Installed in hand The optical components such as the cameras of the mobile communicating devices such as machine, personal digital assistant device, lens (particularly small-sized camera, lens) or Optical component etc..
As the preferred occupation mode of the bubble generation member of the present invention, can enumerate for example：For dust-proof, shading, buffering etc. Purpose and the mode inserted between LCD etc. display part periphery, LCD etc. display part and housing (window portion).
Embodiment
It is exemplified below embodiment and the present invention is described in more detail, but the present invention is not by these embodiment any restrictions.
(Production Example 1 of foaming body)
Using the block copolymer (commodity of the polybutylene terephthalate (PBT) as hard segment and the polyethers as soft chain segment " Co. Ltd. system, 230 DEG C of melt flow rate (MFR) are spun to name by Pelprene P-90BD02 ", Japan：2.4g/10 minute) 100 weights Measure part, (trade name " Metablen L-1000 ", Mitsubishi Rayon Co., Ltd's system, contains nitrogen atom to acrylic acid series lubricant Compound) 5 parts by weight, batt (trade name " ST-301 ", Shiraishi Calcium Kaisha Ltd.'s system, carried out at surface with silane coupler Reason processing) 1 parts by weight, carbon black (trade name " rising sun #35 ", Asahi Carbon Co. Ltd. systems) 5 parts by weight and epoxy be modified Agent (epoxy-modified acrylic acid based polymer, weight average molecular weight (Mw)：50000th, epoxide equivalent：1200g/eq, viscosity： 2850mPa/s) 1.5 parts by weight are extruded as strand form after being kneaded with twin screw compounder with 220 DEG C of temperature, are cut to after water cooling Graininess, thus it is molded.And obtain granular polyester resin composition.
The granular polyester resin composition is put into tandem type single screw extrusion machine (Japan of Co., Ltd. steel It is made), carbon dioxide is injected with 17 (13 after injection) MPa pressure in 240 DEG C of atmosphere.Fill carbon dioxide After dividing saturation, the temperature for being adapted to foaming is cooled to, is extruded from die head, the polyester based resin for obtaining the sheet that thickness is 2.0mm is sent out Foam.
Obtained foaming body is cut into slices, obtains the foaming body that thickness is 1.1mm.Use the heat-laminator that can adjust roll gap (device name " MRK-6504 ", M Co., Ltd.'s CK systems), 0.95mm, 190 DEG C of roll temperature, processing speed 12m/ minutes in gap Under the conditions of to above-mentioned foaming body carry out surface heat melt process, thus obtain foaming body A.
(Production Example 2 of foaming body)
By polypropylene [melt flow rate (MFR) (MFR)：0.35g/10 minutes] 35 parts by weight, composition for thermoplastic elastomer [blend (the cross-linking type alkene of polypropylene (PP) and ethylene/propene/5- ethidine -2- norbornene terpolymers (EPT) Based thermoplastic elastomer, TPV), PP and EPT ratio are calculated as 25/75 with weight basis, the carbon black containing 15.0 weight %] 60 Parts by weight, lubricant (compounded with the masterbatch of the parts by weight of polyethylene 10 in the parts by weight of glycerol stearate monoesters 1) 5 parts by weight, into Core agent (magnesium hydroxide, average grain diameter：0.8 μm) 10 parts by weight, lubricant (80~85 DEG C of erucyl amide, fusing point) 2 parts by weight use Twin screw compounder is extruded as strand form after being kneaded with 200 DEG C of temperature, and graininess is cut to after water cooling, is thus molded.
The particle is put into single screw extrusion machine, with 17 (13 after injection) MPa/cm in 240 DEG C of atmosphere2Pressure note Enter carbon dioxide.After making the abundant saturation of carbon dioxide, it is cooled to after being adapted to the temperature of foaming and is extruded from die head, obtained Polypropylene resin foam.
Using dielectric heat generating roller (TOKUDEN Co., Ltd.s system), in 170 DEG C of roll temperature, the bar of processing speed 12m/ minutes Surface heat melt process is carried out to obtained foaming body under part, thus obtains foaming body B.
(embodiment 1)
For the foaming body A obtained in the Production Example 1 of foaming body, in the presence of the air, from implementing at the heat fusing of surface The surface side of reason is with low pressure mercury lamp (trade name " QGL400U-3 ", Iwasaki Electric Co., Ltd.'s system) with illumination 90mW/cm2, light quantity 1000mJ/cm2Condition carry out UV irradiations.
(embodiment 2)
The foaming body A obtained in the Production Example 1 of foaming body the surface for implementing surface heat melt process fitting propylene Acid system adhesive tape (trade name " ECT755 ", Nitto Denko Corp's system), peeled off after carrying out the curing of 24 hours at normal temperatures Adhesive tape.
(embodiment 3)
For the foaming body B obtained in the Production Example 2 of foaming body, in the presence of air, from implementing surface heat fusing The surface side of processing is with low pressure mercury lamp (trade name " QGL400U-3 ", Iwasaki Electric Co., Ltd.'s system) with illumination 90mW/cm2, light quantity 1000mJ/cm2Condition carry out UV irradiations.
(embodiment 4)
The foaming body B obtained in the Production Example 2 of foaming body the surface for implementing surface heat melt process fitting propylene Acid system adhesive tape (trade name " SPV-C-600 ", Nitto Denko Corp's system), shelled after carrying out the curing of 24 hours at normal temperatures From adhesive tape.
(comparative example 1)
Directly using the foaming body A obtained in the Production Example 1 of foaming body.
(comparative example 2)
Directly using the foaming body B obtained in the Production Example 2 of foaming body.
＜ evaluates ＞
Following evaluation is carried out to the foaming body (foamed sheet) obtained in embodiment and comparative example.Show the result in table 1.
(the presence ratio of nitrogen atom compound)
Determine the presence ratio of nitrogen atom compound, the ratio as lubricant content.
Using TOF-SIMS (ION-TOF company systems, trade name " TOF-SIMS5 "), make conduct under accelerating potential 25kV The Bi of primary ions3 2+The surface of the foaming body of 400 μm of thickness is irradiated to, obtains positive and negative SIMS.By nitrogen atom Mass spectral intensities and standard specimen (C7H5O-) mass spectral intensities be used for relative intensity.Nitrogen atom is determined along depth direction The relative intensity of compound, measure are present in the nitrogen atom compound of surface region (from the 50nm of surface internally region) Relative intensity and be present in interior zone and (cut foaming body parallel to foaming body surface in the way of thickness halves It is disconnected, from the section internally 50nm region) nitrogen atom compound relative intensity, calculate these relative intensities it Than the presence ratio as surface region relative to the nitrogen atom compound of interior zone.
Also, because the foaming body obtained in embodiment and comparative example uses nitrogen atom compound as lubricant, because This is used as surface region relative to interior using surface region relative to the relative ratios of the nitrogen atom compound of interior zone The ratio of the lubricant content in portion region.
(mean cell diameter)
Putting for foaming body bubble portion is read by digit microscope (trade name " VHX-500 ", KEYENCE Co. Ltd. systems) Big image, image analysis is carried out with the analysis software of the Measuring Device, the bubble diameter (μm) of each abscess is thus obtained, obtains flat Equal cell diameters (μm).The number of bubbles of the enlarged drawing read is 200 or so.It should be noted that cell diameter is to ask Go out the area of abscess and be scaled the value of equivalent circle diameter.
(apparent density)
The density (apparent density) of foaming body calculates as follows.By the foaming body of each embodiment and comparative example be punched into 20mm × 20mm sizes with the size of slide calliper rule determination test piece and calculate the volume of test film as test film.Then, surveyed with electronic balance Determine the quality of test film.Then calculated by following formula.
Apparent density (g/cm3The volume of quality/test film of)=test film
(screen resilience (confrontation load, 50% compressive load during 50% compression) during 50% compression)
Determined based on the compressive hardness determination method described in JIS K 6767.
Foaming body is cut into width 30mm × length 30mm, thus makes the test film of sheet.Then by the test film with Compression speed 10mm/ minutes are compressed to compression ratio as untill 50%, the stress (N) when carrying out the compression is changed along thickness direction It is counted as unit area (1cm2) stress, as screen resilience (N/cm2)。
(to the peeling force of carrier band)
Foaming body (width 20mm × length 120mm) is taken care of in 23 ± 2 DEG C of temperature, 50 ± 5RH% of humidity atmosphere It is viscous with carrying according to the face for implementing surface heat melt process after more than 24 hours (Pretreatment is based on JIS Z 0237) The form of mixture layer surface contact 2kg rollers, 1 time it is reciprocal under conditions of be crimped on width 30mm × length 120mm micro- bonding Carry (trade name " 3164S ", Kern company systems, the single-sided adhesive tape with base material, base material：PET base material, SUS bonding forces (are drawn Stretch speed：0.3m/ minutes)：0.15N/20mm) or weak bonding carries (trade name " 3165S ", Kern company systems, the list with base material Face adhesive tape, base material：PET base material, to SUS bonding force (draw speeds：0.3m/ minutes)：Adhesive phase table 0.35N/20mm) Face, place 24 hours, as test sample.
In order to float and peel off from support plate (thickness 2mm phenolic resin plate) in measure, by test sample The face of carrier band substrate side be fixed on via strong bonding two-sided tape (trade name " No.500 ", Nitto Denko Corp's system) It is (draw speed in stripping conditions under 23 ± 2 DEG C of temperature, 50 ± 5RH% of humidity atmosphere on support plate：0.3m/ minutes) Under conditions of measure from carrier band peel off foaming body when the power that needs, obtain bonding force (N/20mm).
, to carrying peeling force as " to micro- bonding carrier band peeling force ", it will will be used upper when using above-mentioned micro- bonding to carry " to weak bonding carrier band peeling force " is used as to carrier band peeling force when stating weak bonding carrier band, is documented in table 1.
(pick)
Foaming body (width 10mm × length 120mm) is taken care of under 23 ± 2 DEG C of temperature, 50 ± 5RH% of humidity atmosphere After more than 24 hours (Pretreatment is based on JIS Z 0237), with width 10mm × length 120mm two-sided tape (trade name " No.5603 ", Nitto Denko Corp's system, the two-sided tape with base material, base material：PET base material) it is fixed on and has carried out organosilicon On the peeling paper of processing, the bonding of (trade name " 3164S ", Kern company systems) is carried with micro- bonding according to the opposing face of foaming body The form of oxidant layer surface contact 2kg rollers, 1 time it is reciprocal under conditions of crimped, place 24 hours, as test sample.
When available hand picks up the carrier band of said determination sample, pick is recited as "○", carry it is peeling-off, When can not pick up, pick is evaluated as "×".
(foam destruction)
Foaming body (width 10mm × length 120mm) is taken care of under 23 ± 2 DEG C of temperature, 50 ± 5RH% of humidity atmosphere After more than 24 hours (Pretreatment is based on JIS Z 0237), with width 10mm × length 120mm two-sided tape (trade name " No.5603 ", Nitto Denko Corp's system) it is fixed on SUS plates, carry (business according to the opposing face and weak bonding of foaming body The name of an article " 3165S ", Kern company systems) adhesive layer surface contact form 2kg rollers, 1 time it is reciprocal under conditions of pressed Connect, place 24 hours, as test sample.
With quick-moving speed above-mentioned carrier band is peeled off, the state for visually confirming to peel off evaluates whether that the surface there occurs foaming body is broken It is bad.
"○" is recited as in table 1, during the surface breakdown that foaming body does not occur, there occurs remember during the surface breakdown of foaming body Carry as "×".
【Table 1】
(table 1)
As shown in table 1, the pick that the foaming physical efficiency of embodiment is carried with good mouldability to obtain, to micro- bonding Well, not only micro- bonding is carried in addition, also big to the peeling force of weak bonding carrier band, cohesive is good.And then using weak viscous Will not also foam be caused to destroy when closing carrier band, during stripping.Therefore, the foaming body of embodiment can use micro- bonding carrier band to be glued with weak Both carrier bands are closed, therefore the range of choice carried is wide.On the other hand, in the foaming body of comparative example 1 and 2, surface region is relative It is 100 weight % in content, the i.e. lubricant content of the nitrogen atom compound of interior zone, micro- bonding is carried and weak bonding The peeling force of carrier band is smaller, and cohesive is weak.In addition, pick is also bad.

Claims (9)

1. a kind of bubble generation member, it has following foaming body：For the foaming body of single sheet, and from one of the foaming body Lubricant content in region of the surface untill thickness direction 50nm depth is to halve by the foaming body according to thickness Mode when being cut off parallel to foaming body surface, from the lubrication in region of the section untill thickness direction 50nm depth Below the 70 weight % of agent content.
2. bubble generation member according to claim 1, wherein, the apparent density of the foaming body is 0.01~0.20g/cm3, Screen resilience during 50% compression is 0.1~4.0N/cm2, mean cell diameter is 10~200 μm.
3. bubble generation member according to claim 1 or 2, wherein, by one surface of the foaming body and to SUS plates Bonding force (temperature：23 ± 2 DEG C, humidity：50 ± 5RH%, draw speed：0.3m/ minutes) be 0.15N/20mm bonding sheet Adhesive surface fitting, from the bonding sheet peel off the foaming body when peeling force (temperature：23 ± 2 DEG C, humidity：50± 5RH%, draw speed：0.3m/ minutes) it is 0.10~2.00N/20mm.
4. the bubble generation member according to any one of claims 1 to 3, wherein, by one table of the foaming body Face and the bonding force (temperature to SUS plates：23 ± 2 DEG C, humidity：50 ± 5RH%, draw speed：0.3m/ minutes) it is 0.35N/ The adhesive surface fitting of 20mm bonding sheet, peeling force (temperature when peeling off the foaming body from the bonding sheet：23 ± 2 DEG C, it is wet Degree：50 ± 5RH%, draw speed：0.3m/ minutes) it is 0.10~2.00N/20mm.
5. the bubble generation member according to any one of Claims 1 to 4, wherein, on another surface of the foaming body With adhesive phase.
6. the bubble generation member according to any one of Claims 1 to 5, wherein, at least one side possessed in base material has The carrier band of adhesive phase, the foaming body and the carrier band are according to one surface of the foaming body and the institute of the carrier band The mode for stating adhesive phase contact is laminated.
7. the bubble generation member according to any one of claim 1~6, it is used for electric/electronic device purposes.
8. a kind of electric/electronic device, it has the bubble generation member described in any one of claim 1~7.
9. a kind of manufacture method of foaming body, it includes following process：Resin combination containing resin and lubricant is foamed It is molded and obtains the process of the foaming body of sheet；And lubricant is set to be decomposed on a surface of the foaming body or from institute Surface migration is stated, so that from the lubricant content drop in region of one surface untill thickness direction 50nm depth It is low for when the foaming body is cut off in the way of thickness halves parallel to foaming body surface, from section to thickness side To 50nm depth untill region in lubricant content below 70 weight % process.
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KR20180032182A (en) 2018-03-29

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