CN109790317A - Foamed sheet, electric/electronic device and the equipment for being installed with touch panel - Google Patents

Foamed sheet, electric/electronic device and the equipment for being installed with touch panel Download PDF

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Publication number
CN109790317A
CN109790317A CN201780060323.1A CN201780060323A CN109790317A CN 109790317 A CN109790317 A CN 109790317A CN 201780060323 A CN201780060323 A CN 201780060323A CN 109790317 A CN109790317 A CN 109790317A
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Prior art keywords
foamed sheet
thickness
weight
impact
mentioned
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Granted
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CN201780060323.1A
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CN109790317B (en
Inventor
加藤和通
德山英幸
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Nitto Denko Corp
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Nitto Denko Corp
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Priority claimed from JP2017130712A external-priority patent/JP6956544B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • 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
    • C08J9/36—After-treatment
    • C08J9/365—Coating
    • 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
    • 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
    • C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/0412—Digitisers structurally integrated in a display
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/026—Crosslinking before of after foaming
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
    • 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
    • C08J2207/00—Foams characterised by their intended use
    • 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
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • 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
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/18—Homopolymers or copolymers of nitriles
    • C08J2333/20—Homopolymers or copolymers of acrylonitrile

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

Abstract

There is provided impact absorbency excellent and excellent to the patience of repeated stock foamed sheet.Foamed sheet of the invention is characterized in that mean cell diameter is 10~200 μm, and screen resilience when by thickness reduction 50% is 6.0N/cm2Hereinafter, the caliper recovery rate being defined by the formula is 90% or more.Caliper recovery rate (%)=(thickness after uncompression state 0.5 second)/(original depth) × 100, original depth: the thickness after uncompression state 0.5 second: the thickness of the foamed sheet before applying load is applying 100g/cm to foamed sheet2Load in the state of maintain 120 seconds, uncompression, from release 0.5 second after foamed sheet thickness.

Description

Foamed sheet, electric/electronic device and the equipment for being installed with touch panel
Technical field
The present invention relates to foamed sheet, electric/electronic device and the equipment for being installed with touch panel.More specifically, this hair It is bright to be related to foamed sheet, the electric/electronic device using the foamed sheet and the equipment for being installed with touch panel using the foamed sheet.
Background technique
Back and forth, the images such as liquid crystal display, electroluminescent display, plasma scope display dress will be fixed on The image display member set, the display member for being loaded into so-called cellular phone, " smart phone ", " personal digital assistant device " etc., When the optical components such as camera, lens are fixed on defined position (for example, shell etc.), foamed material is used.As such Foamed material, in addition to by low ratio foamed and with fine cellular carbamate system foaming body, the high-foaming ammonia of independent air bubble structure Carbamate compression molding and other than winner, also use 30 times of expansion ratio or so of the polyethylene-based hair with independent air bubble Foam etc..Specifically, for example, using 0.3~0.5g/cm of density is included3Polyurethane series foaming body gasket (referring to patent Document 1), comprising mean air bubble diameter be 1~500 μm foamed structures electric/electronic sheet material (referring to patent text 2) etc. it offers.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2001-100216 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2002-309198 bulletin
Summary of the invention
Problems to be solved by the invention
Such foamed material is required to apply the characteristic (impact absorbency) absorbed when impact.For example, in order to Impact when hitting is absorbed when " smart phone " etc. is fallen to ground etc. with the electric/electronic device of display member, prevents from showing The breakage for showing component has used the foamed sheet that impact absorbency is excellent.But the excellent foamed sheet of existing impact absorbency is got over Softness more has the tendency that impact absorbency is excellent, there is flower until being restored to original thickness after releasing from impact but then Time taking tendency.Therefore, the existing foamed sheet excellent for impact absorbency is returning mostly when applying impact repeatedly It can be subjected to impact before returning to original thickness, therefore the 2nd later impact will not be fully absorbed, to the patience of repeated stock Difference.Therefore, seek impact absorbency excellent and to the patience of repeated stock also excellent foamed sheet.
In turn, in recent years, as smart phone, mobile terminal etc. are installed with the universal of the equipment of touch panel, Yong Huyong The tools such as finger, felt pen (stylus) touch, the chance of pressing picture increases.In addition, as these are installed with touch panel The slimming of equipment be in progress significantly, constitute they component (for example, using LCD panel as the display panel of representative, with contact Related touch panel in position etc.) slimming be also in progress.Therefore, when user presses picture, display panel, touch panel Become to be very easy to bending (flexure).If bending, with its bending, display panel and other internal components (for example, Circuit substrate, battery etc.) it interferes, to occur to show uneven (undulatory fuzzy pattern) in display panel sometimes.Make For the uneven occurrence cause of display, it is believed that display panel is squeezed by other internal components, so that stress is applied to display panel, The orientation disorder of liquid crystal molecule.
For sometimes through the display uneven (undulatory fuzzy pattern) generated to display panel application stress Problem proposes following scheme: gap is arranged in display panel periphery, thus even if display panel deforms, is also not easy pair Display panel applies stress；Change the design of display panel, touch panel, thus thicken, it is not flexible；Increase is installed with touch The rigidity of the shell of the equipment of panel, to be unlikely to deform.But there is the equipment for being installed with touch panel to thicken, becomes weight Disadvantage.Therefore, the equipment for being installed with touch panel, it is desirable that reply just in the slimming of remarkable break-throughs and solves sometimes The problem of display uneven (undulatory fuzzy pattern) generated and applying stress to display panel.
Therefore, hair excellent the object of the present invention is to provide impact absorbency and excellent to the patience of repeated stock Steep piece.
In addition, excellent another object of the present invention is to provide impact absorbency and excellent to the patience of repeated stock In the display unit of touch operation that is different and can highly inhibiting adjoint user in the equipment for being installed with touch panel The uneven generation of display foamed sheet.
In addition, that even if another object of the present invention is to provide thickness is very small, above-mentioned characteristic also excellent foamed sheet.
Even if in addition, another object of the present invention is to provide on the basis of above-mentioned characteristic, when other components are laminated The foamed sheet of positional shift can be also prevented without bonding adhesive layer.
The solution to the problem
The inventors of the present invention have made intensive studies in order to achieve the above objectives, as a result, it has been found that, utilize mean cell diameter For in specific range, by thickness reduction 50% when screen resilience be 6.0N/cm2Below and releasing is applied with specific load The foamed sheet that caliper recovery rate behind compressive state 0.5 second of lotus is 90% or more, impact absorbency is excellent, and to rushing repeatedly The patience hit is also excellent.The present invention is completed based on the opinion.
That is, the present invention provides a kind of foamed sheet, which is characterized in that mean cell diameter is 10~200 μm, by thickness reduction Screen resilience when 50% is 6.0N/cm2Hereinafter, the caliper recovery rate being defined by the formula is 90% or more.
Caliper recovery rate (%)=(thickness after uncompression state 0.5 second)/(original depth) × 100
Original depth: the thickness of the foamed sheet before applying load
Thickness after uncompression state 0.5 second: 100g/cm is being applied to foamed sheet2Load in the state of maintain 120 Second, uncompression, the thickness of the foamed sheet from after releasing 0.5 second
Aforementioned foamed sheet preferred thickness is 30~1000 μm, density is 0.2~0.7g/cm3。
Storage modulus and loss modulus in the aforementioned preferred Measurement of Dynamic Viscoelasticity of foamed sheet at angular frequency 1rad/s Ratio, that is, loss angle tangent (tan δ) has summit in -60 DEG C or more and 20 DEG C or less of range.
In aforementioned foamed sheet, used it is in the impact absorbency experiment of pendulum type shock machine, make impulse member with 1 second When the interval of clock strikes against for continuous 5 times in the support plate of the structural body formed by support plate and foamed sheet, the 5th shock Impact force is preferably 5% or less relative to the climbing of impact force when hitting for the first time.
Aforementioned foamed sheet preferably comprises crosslinking agent and organo-silicon compound.
The solvent insoluble component that aforementioned foamed sheet is preferably insoluble in methyl ethyl ketone is 80 weight % or more.
Maximum value of the aforementioned preferred loss angle tangent of foamed sheet (tan δ) in -60 DEG C or more and 20 DEG C or less of range be 0.2 or more.
Caliper recovery rate when the high temperature of the aforementioned preferred following definitions of foamed sheet is 50% or more.
Caliper recovery rate when high temperature: by foamed sheet, through-thickness compresses under 80 DEG C of atmosphere, so that relative to initial Thickness becomes 50% thickness, after 22 hours, places under 23 DEG C of atmosphere 2 hours, then uncompression state, compresses certainly Ratio of the thickness relative to original depth after status releasing after 24 hours
Aforementioned foamed sheet has preferably used foamed sheet of the acrylic polymer as resin material.
Shear bond power (23 DEG C, tensile speed of the aforementioned foamed sheet preferably at least face relative to SUS304BA plate 50mm/ minutes) it is 0.5N/100mm2More than.
Aforementioned foamed sheet is preferably the mechanical foaming body of emulsion resin composition.
Aforementioned foamed sheet can have adhesive phase in one or two sides.
Aforementioned foamed sheet is preferably used as electric/electronic device impact-absorbing sheet.
Aforementioned foamed sheet is preferred for being installed with the equipment of touch panel.
In addition, the present invention provides a kind of electric/electronic device, with aforementioned foamed sheet.
Aforementioned electric/electronic device is preferably provided with display member, and there is aforementioned foamed sheet to be held in the electric and electronic and set Structure between standby shell and aforementioned display member.
In addition, the present invention provides a kind of equipment for being installed with touch panel, with aforementioned foamed sheet.
The aforementioned equipment for being installed with touch panel preferably has aforementioned foamed sheet, display panel and touch panel, aforementioned The space configuration of the back side of display panel has aforementioned foamed sheet.
The effect of invention
The impact absorbency of foamed sheet of the invention is excellent and excellent to the patience of repeated stock.In addition, of the invention Foamed sheet be used for be installed with touch panel equipment when, impact absorbency it is excellent and excellent to the patience of repeated stock and The generation that can highly inhibit the display in the display unit with the touch operation of user uneven.In addition, foamed sheet of the invention Even if impact absorbency is also excellent and excellent to the patience of repeated stock in the very small situation of thickness, for installing There is the generation that can highly inhibit the display in the display unit with the touch operation of user uneven when the equipment of touch panel.
In addition, foamed sheet of the invention can using when other components be laminateds even if do not have bond adhesive layer can Prevent the composition of positional shift.
Detailed description of the invention
Fig. 1 is the schematic configuration diagram of pendulum type shock machine (impact test apparatus).
Fig. 2 is the figure for showing the schematic configuration of holding member of pendulum type shock machine (impact test apparatus).
Specific embodiment
For foamed sheet of the invention, mean cell diameter is 10~200 μm, screen resilience when by thickness reduction 50% For 6.0N/cm2Hereinafter, the caliper recovery rate being defined by the formula is 90% or more.It should be noted that in this specification, sometimes Caliper recovery rate defined in will be above-mentioned is referred to as " the caliper recovery rate after 0.5 second ".
Caliper recovery rate (%)=(thickness after uncompression state 0.5 second)/(original depth) × 100
Original depth: the thickness of the foamed sheet before applying load
Thickness after uncompression state 0.5 second: 100g/cm is being applied to foamed sheet2Load in the state of maintain 120 Second, uncompression, the thickness of the foamed sheet from after releasing 0.5 second
The mean cell diameter of foamed sheet of the invention is 10~200 μm as described above.Preferably 15 μm of its lower limit, more preferably It is preferably 180 μm, more preferably 150 μm, further preferably 100 μm for 20 μm, the upper limit.By making mean cell diameter 10 μm or more, to play superior impact absorbency.In addition, by making 200 μm of mean cell diameter hereinafter, to compress It is restorative also excellent, in addition, can be restored to after being impacted with the short time near original thickness, therefore to repeated stock Patience is excellent.It should be noted that the maximum cell diameter of above-mentioned foamed sheet is, for example, 40~400 μm, preferably 60 μm of lower limit, More preferable 80 μm, the upper limit is preferably 300 μm, more preferably 220 μm.In addition, the minimum cell diameter of above-mentioned foamed sheet is, for example, 5 ~70 μm, preferably 8 μm of lower limit, 10 μm more preferable, the upper limit is preferably 60 μm, more preferably 50 μm, further preferably 30 μm.
Screen resilience when by the thickness reduction of foamed sheet of the invention 50% is 6.0N/cm as described above2Hereinafter, it is preferred that For 4.0N/cm2Below, it is more preferably 2.9N/cm2It below, is more preferably 2.5N/cm2Below.By making above-mentioned screen resilience For 6.0N/cm2Hereinafter, to which the impact absorbency of foamed sheet of the invention is more excellent.The lower limit of above-mentioned screen resilience is not special It limits, preferably 0.1N/cm2.It should be noted that above-mentioned screen resilience when having compressed 50% can be according to remembering in JIS K 6767 The compressive hardness measuring method of load measures.
Caliper recovery rate behind 0.5 second of foamed sheet of the invention is 90% or more as described above, preferably 90.5% with Above, more preferably 91% or more.Foamed sheet of the invention by making above-mentioned 90% or more caliper recovery rate, so as to by It is restored near original thickness after to impact with the short time, therefore excellent to the patience of repeated stock.In addition, dust tightness, close Envelope property is also excellent.Caliper recovery rate after above-mentioned 0.5 second applies load to foamed sheet for area to some degree to compress Come the recovery rate measured, apply load from part to which the so-called recess recovery rate for only making a part be recessed and measuring is different.
The thickness of foamed sheet of the invention is not particularly limited, and preferably 30~1000 μm.Its lower limit is preferably 40 μm, more Preferably 50 μm, the upper limit is preferably 700 μm, more preferably 500 μm, further preferably 300 μm.Foamed sheet with a thickness of 30 μm It when above, can equably contain bubble, superior impact absorbency can be played.In addition, foamed sheet with a thickness of 1000 μ When m or less, can easily it be followed to small gap.Foamed sheet with a thickness of in the case where in above range, to the greatest extent Tube thickness is thin, and impact absorbency is also excellent.
The density of foamed sheet of the invention is not particularly limited, preferably 0.2~0.7g/cm3.Its lower limit is preferably 0.21g/cm3, more preferably 0.22g/cm3, the upper limit is preferably 0.50g/cm3, more preferably 0.40g/cm3, further preferably 0.35g/cm3.Above-mentioned density is 0.2g/cm3When above, it is easy to maintain the intensity of foamed sheet.Above-mentioned density is 0.7g/cm3Below When, play higher impact absorbency.In addition, above-mentioned density is 0.2~0.7g/cm3In the range of when, and then play it is higher Impact absorbency.It should be noted that the density of foamed sheet (foaming body) refers to " apparent density " in this specification.
In the present invention, from the viewpoint of impact absorbency, the thickness (μm) of mean cell diameter (μm) and foamed sheet Than (the former/the latter) it is preferably in the range of 0.1~0.8.The thickness (μm) of above-mentioned mean cell diameter (μm) and foamed sheet Ratio lower limit be preferably 0.15, more preferably 0.2, the upper limit is preferably 0.75, more preferably 0.6.
Foamed sheet of the invention, storage modulus and loss modulus in Measurement of Dynamic Viscoelasticity at angular frequency 1rad/s The summit of ratio, that is, loss angle tangent (tan δ) be not particularly limited, be preferably in -60 DEG C or more and 20 DEG C of ranges below It is interior.It is preferably -50 DEG C, more preferably -40 DEG C there are the lower limit of the temperature range of the summit of above-mentioned loss angle tangent, further excellent Be selected as -30 DEG C, the upper limit be preferably 10 DEG C, more preferably 0 DEG C, further preferably -10 DEG C, particularly preferably -15 DEG C (such as - 20℃).In the case where the material of summit with 2 or more loss angle tangents, it is generally desirable to which wherein at least 1 falls into above-mentioned model In enclosing.When summit is in above range, the temperature dependency of foamed sheet is low, can also play even in a high temperature environment superior It compresses restorative, in addition, showing high flexibility, plays excellent impact absorbency.If summit is high, there is flexibility reduction Tendency have the tendency that the restorative reduction of compression if summit is low.The summit temperature of especially above-mentioned loss angle tangent (tan δ) When in the range of -50~-10 DEG C, especially -30~-15 DEG C, it is easier to separately design the following characteristic of foamed sheet and say In bright book record in the range of, that is, the characteristic be it is above-mentioned by thickness reduction 50% when screen resilience, it is 0.5 second above-mentioned after The various characteristics such as caliper recovery rate when caliper recovery rate and aftermentioned high temperature.
From the viewpoint of impact absorbency, the loss angle tangent (tan δ) in -60 DEG C or more and 20 DEG C or less of range Summit intensity (maximum value) it is higher be it is preferred, for example, 0.2 or more, preferably 0.3 or more.Above-mentioned summit intensity is (maximum Value) upper limit value be, for example, 2.0.
For foamed sheet of the invention, the ratio of the summit intensity of above-mentioned loss angle tangent (tan δ) and above-mentioned density (the former/ The latter) it is preferably in the range of 1~5.The lower limit of the ratio of the summit intensity and above-mentioned density of above-mentioned loss angle tangent (tan δ) Preferably 1.5,2 are more preferably, the upper limit is preferably 4.5, more preferably 4, further preferably 3.Above-mentioned loss angle tangent (tan When the ratio of summit intensity and above-mentioned density δ) is in above range, superior impact absorbency is played.
From the viewpoint of impact absorbency, it is ideal that the initial elastic modulus of foamed sheet of the invention is lower.Initially Elasticity modulus (by under 23 DEG C of environment, initial sample dimension 10mm width × 40mm length, the drawing under tensile speed 300mm/ minutes The value that slope when stretching 10% strain in test calculates) it is preferably 5N/mm2Below, it is more preferably 3N/mm2Below, further Preferably 1N/mm2Below.It should be noted that the lower limit value of above-mentioned initial elastic modulus is, for example, 0.1N/mm2。
From the viewpoint of impact absorbency, it is ideal that the initial elastic modulus of foamed sheet of the invention is lower.Initially Elasticity modulus (by under 0 DEG C of environment, initial sample dimension 10mm width × 40mm length, the drawing under tensile speed 300mm/ minutes The value that slope when stretching 10% strain in test calculates) it is preferably 5N/mm2Below, it is more preferably 3N/mm2Below, further Preferably 1N/mm2Below.It should be noted that the lower limit value of above-mentioned initial elastic modulus is, for example, 0.1N/mm2.Under 0 DEG C of environment Initial elastic modulus it is high when, the tendency being easily reduced by flexibility has compression when the initial elastic modulus under 0 DEG C of environment is low Restorative reduced tendency.
As long as foamed sheet of the invention has above-mentioned characteristic, it is formed, bubble structure etc. is not particularly limited.Make It can be any one of continuous air bubbles structure, independent air bubble structure, semicontinuous and semi-independent bubble structure for bubble structure.From From the perspective of impact absorbency, preferably continuous air bubbles structure, semicontinuous and semi-independent bubble structure.
Foamed sheet of the invention has excellent impact absorbency.In addition, also there is height even for very weak impact Impact absorbency, the size no matter impacted plays excellent impact absorbency.For example, having used impact test pendulum type In the impact absorbency experiment of machine, the impact absorbing rate (%) being defined by the formula finds out unit divided by the thickness (μm) of foamed sheet The impact absorbing rate R of thickness.
Impact absorbing rate (%)={ (F0-F1)/F0}×100
(in above-mentioned formula, F0Impact force when to make impulse member only hit support plate, F1To strike against impulse member by supporting Impact force when in the support plate for the structural body that plate and foamed sheet are formed)
It is illustrated using schematic configuration of the Fig. 1 and Fig. 2 to pendulum type shock machine (impact test apparatus).Such as Fig. 1 And shown in Fig. 2, impact test apparatus 1 (pendulum test machine 1) is made of such as lower member etc.: keeping testing as with any retentivity The holding member 3 of the holding means of piece 2 (foamed sheet 2), to the impact load component 4 of 2 load impact stress of test film, as inspection Impact load component 4 is surveyed to the pressure sensor 5 of the impact force detection means of impact force caused by test film 2.In addition, with any Retentivity keeps the holding member 3 of test film 2 to be made of stationary fixture 11 and holding jig 12, and the holding jig 12 can be slided It is dynamic, so as to which opposite with stationary fixture 11 keep test film 2 to clamp.In turn, holding jig 12 is provided with holding Pressure adjusts means 16.In turn, to the impact load component 4 of the 2 load impact power of test film kept by holding member 3 by supporting Stick 23 (axis 23) and arm 21 are constituted, one end 22 of the support stick 23 pivot support in a manner of it can rotate relative to pillar 20, And there is impulse member 24 in another side, the arm 21 is for being raised up to predetermined angular for impulse member 24 and keeping.It is used herein as Impulse member 24 can be integrally raised up to regulation as impulse member 24, therefore by the way that electromagnet 25 is arranged in one end of arm by steel ball Angle.In turn, the pressure sensor 5 for detecting the impact force for acting on test film 2 by impact load component 4 is arranged in stationary fixture The opposite side in the face of 11 contact test piece.
Impulse member 24 is steel ball (iron ball).In addition, angle (the upward pendulum in Fig. 1 that impulse member 24 is lifted using arm 21 Dynamic angle a) is 40 °.The weight of steel ball (iron ball) is 66g.
As shown in Fig. 2, test film 2 (foamed sheet 2) is by by resinousness plate (acrylic board, polycarbonate plate etc.), gold Belong to the support plate 28 that the elastomeric plate such as panel is constituted to be held between stationary fixture 11 and holding jig 12.
For impact absorbing rate, using above-mentioned impact test apparatus, find out by by stationary fixture 11 and support plate 28 The impact force F for making impulse member 24 hit support plate 28 after closely sealed fixation and measuring0And by stationary fixture 11 and support plate 28 Between be inserted into test film 2 and closely sealed fixation after so that impulse member 24 is hit support plate 28 and the impact force F that measures1, according to above-mentioned formula It calculates.It should be noted that impact test apparatus is similarly to fill with the embodiment 1 of Japanese Unexamined Patent Publication 2006-47277 bulletin It sets.
The weight of above-mentioned impulse member is 66g, is swung up angle be 40 ° in the case where F1, used punching pendulum type The support plate for making impulse member strike against the structural body formed by support plate and foamed sheet is hit in the impact absorbency experiment of testing machine The preferred 1000N or less of impact force when upper, more preferably 900N or less, further preferably 800N or less, particularly preferably 750N or less.When above-mentioned impact force is 1000N or less, the impact absorbing power of foamed sheet is more excellent.The lower limit of above-mentioned impact force can Think 0N or more, 100N or more, 300N or more or 500N or more.It should be noted that above-mentioned impact force is to be not affected by big rush The impact force of the initial foamed sheet hit.
By it is in the impact absorbency experiment for having used pendulum type shock machine, connect impulse member with 1 second interval When striking against in the support plate of the structural body formed by support plate and foamed sheet for continuous 5 times, number of shocks is as x-axis, impact force (N) it is used as y-axis, draws at 5 points, the slope of the linear approximation straight line obtained by this 5 points by least square method is not particularly limited, It is preferred that 10 or less, more preferably 5 or less, further preferably 1 or less, particularly preferably 0.5 or less.Above-mentioned slope is 10 or less When, it is more excellent to the patience of repeated stock.The lower limit of above-mentioned slope is, for example, -5.
Used it is in the impact absorbency experiment of pendulum type shock machine, make impulse member with 1 second interval continuous 5 Impact force when in the secondary support plate for striking against the structural body formed by support plate and foamed sheet, the 5th is hit relative to The climbing (%) [(impact force of the impact force-when hitting for the first time when the 5th is hit)/for the first time of impact force when hitting for the first time Impact force × 100 when shock] preferably 5% or less, more preferably 3.5% or less, further preferably 2% or less.On above-mentioned It is more excellent to the patience of repeated stock when the rate of liter is 5% or less.The lower limit of above-mentioned climbing is, for example, -10%.
For foamed sheet of the invention, caliper recovery rate preferably 50% the or more when high temperature of following definitions, more preferably It 70%, is more preferably 80%, further preferably 90% or more, particularly preferably 94% or more.It should be noted that this In specification, sometimes by the high temperature of following definitions when caliper recovery rate be referred to as " caliper recovery rate when high temperature ".
Caliper recovery rate when high temperature: by foamed sheet, through-thickness compresses so that relative to initial thickness under 80 DEG C of atmosphere Degree becomes 50% thickness, after 22 hours, places under 23 DEG C of atmosphere 2 hours, then uncompression state, compresses shape certainly Ratio of the thickness relative to original depth after state releasing after 24 hours
When caliper recovery rate when the high temperature of foamed sheet of the invention is 50% or more, it is not only under normal temperature environment, and And even in a high temperature environment (such as under 40~120 DEG C of temperature environment), the resume speed for applying the thickness after impact is also fast, It is more excellent to the patience of the repeated stock under hot environment.
Foamed sheet of the invention can be made of the resin combination comprising resin material (polymer).It needs to illustrate It is, in the Measurement of Dynamic Viscoelasticity of the resin combination [resin combination (solid matter) when unexpanded] of unexpanded state The summit of ratio, that is, loss angle tangent (tan δ) of storage modulus and loss modulus at angular frequency 1rad/s is preferably in -60 DEG C or more and 20 DEG C or less of range in.There are the lower limit of the temperature range of the summit of above-mentioned loss angle tangent be preferably -50 DEG C, More preferably -40 DEG C, further preferably -30 DEG C, the upper limit is preferably 10 DEG C, more preferably 0 DEG C, further preferably -10 DEG C, Particularly preferably -15 DEG C (such as -20 DEG C).In the case where the material of summit with 2 or more loss angle tangents, it is generally desirable to Wherein at least 1 falls within the above-described range.From the viewpoint of impact absorbency, the resin combination (solid matter) is -60 DEG C or more and loss angle tangent (tan δ) in 20 DEG C or less of range summit intensity (value be equivalent to above-mentioned foamed sheet- The summit intensity of 60 DEG C or more and the loss angle tangent (tan δ) in 20 DEG C or less of range divided by foamed sheet density (g/cm3) Resulting value) it is higher be preferred.For example, above-mentioned resin combination (solid matter) is in -60 DEG C or more and 20 DEG C of models below The summit intensity of loss angle tangent (tan δ) in enclosing is preferably 0.9 (g/cm3)-1More than, the upper limit is, for example, 3 or so.
In addition, initial elastic modulus (23 DEG C, the initial sample ruler of the resin combination (solid matter) of unexpanded state Very little 10mm width × 40mm length, tensile speed 300mm/ minutes) it is lower be ideal, preferably 50N/mm2Below, more preferably For 30N/mm2Below.It should be noted that the lower limit value of above-mentioned initial elastic modulus is, for example, 0.3N/mm2。
In addition, initial elastic modulus (0 DEG C, the initial sample ruler of the resin combination (solid matter) of unexpanded state Very little 10mm width × 40mm length, tensile speed 300mm/ minutes) it is lower be ideal, preferably 50N/mm2Below, more preferably For 30N/mm2Below.It should be noted that the lower limit value of above-mentioned initial elastic modulus is, for example, 0.3N/mm2.Under 0 DEG C of environment When initial elastic modulus is high, have the tendency that flexibility is easily reduced, when the initial elastic modulus under 0 DEG C of environment is low, has compression extensive The tendency that renaturation reduces.
The solvent insoluble component (gel fraction) insoluble in methyl ethyl ketone of foamed sheet of the invention is not particularly limited, preferably 80 weight % or more, more preferably 90 weight % or more.It should be noted that the above-mentioned solvent insoluble component insoluble in methyl ethyl ketone Usually 100 weight % or less.
Find out the above-mentioned solvent insoluble component (gel fraction) insoluble in methyl ethyl ketone as follows.About 0.2g is obtained by foamed sheet Sample, the weight obtained by accurate weighing is set as " weight (g) before saving " by the accurate weighing sample.Then, by the sample Product are put into the methyl ethyl ketone of 50g (MEK), are saved 5 days at room temperature.Then, sample is taken out from methyl ethyl ketone, makes to take Sample out is 1 hour dry at 130 DEG C.It after drying, at room temperature places 30 minutes, then accurate weighing sample.It will " weight (g) after preservation " is set as by the weight that the accurate weighing obtains.Then, it is calculated by following formula insoluble in the molten of methyl ethyl ketone Agent insoluble component.
Solvent insoluble component (weight %)=(weight after preservation)/(weight before saving) × 100 insoluble in methyl ethyl ketone
It as the resin material (polymer) for constituting foamed sheet of the invention, is not particularly limited, composition hair can be used The known or even known resin material of foam.As the resin material, for example, can enumerate acrylic polymer, rubber, Carbamate based polymer, vinyl-vinyl acetate copolymer etc..It is (right from reduction permanent strain, heat resistance in these The patience of deformation strain) it is excellent, can be easy to reduce compressive load, impact absorbency it is more excellent from the perspective of, preferred propylene Acids polymers.The resin material (polymer) for constituting foamed sheet can be independent a kind, or two or more.
It should be noted that in order to make storage modulus of the foamed sheet in Measurement of Dynamic Viscoelasticity at angular frequency 1rad/s In the range that summit with ratio, that is, loss angle tangent (tan δ) of loss modulus is -60 DEG C or more and 20 DEG C or less, it can incite somebody to action The Tg of above-mentioned resin material (polymer) is as index or standard.For example, as above-mentioned resin material (polymer), it can be from Tg In -60 DEG C or more and 20 DEG C or less (preferably -50 DEG C, more preferably -30 DEG C of lower limit, preferably 10 DEG C of the upper limit, it is 0 DEG C more preferable, into one Step preferably -10 DEG C, particularly preferably -15 DEG C (such as -20 DEG C)) in the range of resin material (polymer) among select.
Storage modulus and damage of the above-mentioned resin material (polymer) in Measurement of Dynamic Viscoelasticity at angular frequency 1rad/s The summit intensity for consuming ratio, that is, loss angle tangent (tan δ) of modulus is preferably 0.8 or more, is more preferably 1 or more, is further excellent It is selected as 1.5 or more, particularly preferably 1.7 or more.When summit intensity is big, impact absorbency becomes better.
As above-mentioned acrylic polymer, preferably by the Tg of the Tg of the homopolymer monomer for being -10 DEG C or more and homopolymer Insufficient -10 DEG C of monomer is as must monomer component and the acrylic polymer that is formed.By using such acrylic compounds Polymer and adjust the former monomer and the latter monomer amount ratio, so as to relatively easily obtain in Measurement of Dynamic Viscoelasticity The summit of ratio, that is, loss angle tangent (tan δ) of storage modulus and loss modulus at angular frequency 1rad/s be in -60 DEG C with Upper and 20 DEG C of foamed sheets below.
It should be noted that " forming the glass transition temperature (Tg) when homopolymer " in the present invention is (sometimes referred to simply as " Tg of homopolymer ") refer to " glass transition temperature (Tg) of the homopolymer of the monomer ", specifically, can enumerate Numerical value in " Polymer Handbook " (the 3rd edition, John Wiley&Sons, Inc, 1987).On it should be noted that The Tg for stating the homopolymer for the monomer that do not record in document for example refers to that the value obtained by measuring method below is (special referring to Japan Open 2007-51271 bulletin).That is, being thrown in the reactor for having thermometer, blender, nitrogen ingress pipe and reflux condensing tube Enter 100 parts by weight of monomer, 2,2 '-azobis isobutyronitrile, 0.2 parts by weight and 200 parts by weight of ethyl acetate as polymer solvent, It is stirred when importing nitrogen 1 hour.After eliminating the oxygen in polymerization system in this way, 63 DEG C are warming up to, is reacted 10 hours.Then, It is cooled to room temperature, obtains the homopolymer solution of 33 weight % of solid component concentration.Then, which is coated on It on isolation film, is dried, manufactures the test specimen (homopolymer of sheet) of thickness about 2mm.Then, which is punched It for the discoid of diameter 7.9mm, is clamped with parallel-plate, uses test for viscoelastic machine (ARES, Rheometrics, Inc. system) side The shear strain for applying frequency 1Hz, while passing through shear mode in temperature region -70~150 DEG C, with 5 DEG C/min of heating rate Viscoplasticity is measured, using the summit temperature of tan δ as the Tg of homopolymer.It should be noted that above-mentioned resin material (polymer) Tg can also be measured by this method.
In the monomer that the Tg of homopolymer is -10 DEG C or more, for example, -10 DEG C~250 DEG C of the Tg, preferably 10~230 DEG C, Further preferably 50~200 DEG C, particularly preferably 100~200 DEG C.
The monomer that Tg as above-mentioned homopolymer is -10 DEG C or more, for example, (methyl) acrylonitrile can be enumerated；(methyl) The amide-containings monomers such as acrylamide, N- hydroxyethyl (methyl) acrylamide；The Tg of the homopolymers such as (methyl) acrylic acid is -10 DEG C or more carboxylic (methyl) acrylate；The Tg of the homopolymers such as methyl methacrylate, ethyl methacrylate is -10 DEG C or more (methyl) alkyl acrylate；The homopolymers such as (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate (methyl) acrylic acid alicyclic ester that Tg is -10 DEG C or more；(methyl) third that the Tg such as (methyl) benzyl acrylate are -10 DEG C or more Olefin(e) acid aromatic ester；The vinyl monomer containing heterocycle such as n-vinyl-2-pyrrolidone, acryloyl morpholine；Methacrylic acid Hydroxyls monomer such as 2- hydroxy methacrylate etc..These can be used alone or two or more is applied in combination.Wherein, preferably there is carboxylic The functional groups such as the group of the nitrogen atoms such as base, hydroxyl, itrile group monomer (especially (methyl) acrylonitrile, (methyl) acrylic acid, (methyl) acrylic acid 2- hydroxy methacrylate), particularly preferred acrylonitrile, acrylic acid.If the list that the Tg using homopolymer is -10 DEG C or more Body, then intermolecular interaction enhances or is capable of increasing the summit intensity of the above-mentioned loss angle tangent (tan δ) of foamed sheet.
- 10 DEG C of monomer insufficient for the Tg of homopolymer, the Tg are, for example, -70 DEG C or more and insufficient -10 DEG C, preferably -70 DEG C~-12 DEG C, more preferably -65 DEG C~-15 DEG C.
Insufficient -10 DEG C of Tg of the monomer as above-mentioned homopolymer, for example, can enumerate ethyl acrylate, butyl acrylate, (methyl) alkyl acrylate etc. of -10 DEG C of the Tg deficiency of the homopolymers such as 2-EHA.These can be used alone 1 Two or more is applied in combination in kind.In these, preferably acrylic acid C2-8Arrcostab, particularly preferred acrylic acid C4-8Arrcostab.
Relative to the whole monomer components (monomer component total amount) for forming above-mentioned acrylic polymer, the Tg of homopolymer Content for -10 DEG C or more of monomer is, for example, 2~30 weight %, and lower limit is preferably 3 weight %, is more preferably 4 weight %, on Limit is preferably 25 weight %, more preferably 20 weight %.In addition, relative to the whole monomers for forming above-mentioned acrylic polymer The content of ingredient (monomer component total amount), the monomer of -10 DEG C of the Tg deficiency of homopolymer is, for example, 70~98 weight %, and lower limit is preferred It is preferably 97 weight %, more preferably 96 weight % for 75 weight %, more preferably 80 weight %, the upper limit.
As above-mentioned acrylic polymer, especially as the monomer component for forming acrylic polymer, preferably phase For whole monomer components, having comprising 50 weight % or more (preferably 70 weight % or more, more preferable 80 weight % or more) (methyl) alkyl acrylate of the alkyl of the carbon number 4~8 of straight or branched and 2~20 weight % (preferably 3~15 weights Measure %, more preferable 5~10 weight %) the Tg of homopolymer be 10 DEG C or more and there are the nitrogen atoms such as carboxyl, hydroxyl, itrile group The monomer of the functional groups such as group.
It as above-mentioned rubber, can be any one of natural rubber, synthetic rubber.As above-mentioned rubber, for example, can arrange Enumerate nitrile rubber (NBR), methyl methacrylate butadiene rubber (MBR), SBR styrene butadiene rubbers (SBR), acrylic acid Class rubber (ACM, ANM), urethane rubber (AU), silicon rubber etc..In these, preferably nitrile rubber (NBR), metering system Sour methyl esters-butadiene rubber (MBR), silicon rubber.
As above-mentioned carbamate based polymer, for example, the poly- ammonia of polycarbonate-based polyurethane, Polyester can be enumerated Ester, polyether system polyurethane etc..
As vinyl-vinyl acetate copolymer, known or even known ethylene-vinyl acetate c can be used Object.
Foamed sheet of the invention is other than resin material (polymer), as needed, may include surfactant, hands over Join the additives such as agent, thickener, antirust agent, silicon-type compound.Wherein, above-mentioned by thickness reduction from that can be readily derived Screen resilience when 50% is 6.0N/cm2Below, the sight for the foamed sheet that the caliper recovery rate after above-mentioned 0.5 second is 90% or more Point sets out, and preferably comprises crosslinking agent, silicon-type compound.In turn, it is easier to the hair such as caliper recovery rate when by above-mentioned high temperature The various characteristics of bubble piece separately design in the range of record in the description.
For example, may include arbitrary surfaces activity for the stability of bubble made of the miniaturization of bubble diameter, blistering Agent.As surfactant, be not particularly limited, can be used anionic surfactant, cationic system surfactant, Any one of nonionic surfactants, amphoteric surfactant etc., from the miniaturization, blistering of bubble diameter made of steep Stability from the perspective of, the fatty acid ammonium such as preferred anionic system surfactant, particularly more preferable ammonium stearate system table Face activating agent.Surfactant can be used singly or in combination of two or more.Furthermore it is possible to be applied in combination not Surfactant of the same race, for example, can be applied in combination anionic surfactant and nonionic surfactants, yin from Subsystem surfactant and amphoteric surfactant.
In the case where surfactant, additive amount [solid component (nonvolatile component)] such as phase of surfactant For resin material (polymer) [solid component (nonvolatile component)] 100 parts by weight be more than 0 parts by weight and for 10 parts by weight with Under, lower limit is preferably 0.5 parts by weight, and the upper limit is preferably 8 parts by weight.
For foamed sheet of the invention, due to be easy to get it is above-mentioned by thickness reduction 50% when screen resilience be 6.0N/ cm2Below, the caliper recovery rate after above-mentioned 0.5 second be 90% or more foamed sheet, therefore in turn be easy by above-mentioned high temperature when The various characteristics of the foamed sheets such as caliper recovery rate are set in the range of recording in specification, in addition, in order to improve foamed sheet Intensity, heat resistance, moisture-proof, may include any crosslinking agent.Crosslinking agent is not particularly limited, and oil-soluble, water can be used Any one of dissolubility.As crosslinking agent, for example, can enumerate epoxy, oxazoline system, isocyanates system, carbodiimide system, Melamine series, organic silicon-type (for example, silane coupling agent etc.), metal oxide system etc..As above-mentioned crosslinking agent, can only make With a kind, two or more also can be used.It wherein, preferably at least include oxazoline system crosslinking agent.
In the case where crosslinking agent, the additive amount [solid component (nonvolatile component)] of crosslinking agent is for example relative to resin Material (polymer) [solid component (nonvolatile component)] 100 parts by weight are more than 0 parts by weight and are 10 parts by weight hereinafter, lower limit is excellent 0.01 parts by weight are selected as, the upper limit is preferably 9 parts by weight.
In turn, in order to improve the stability of bubble made of blistering, film forming, it may include any thickener.As thickening Agent is not particularly limited, and can enumerate acrylic acid series, carbamate system, polyethenol series etc..Wherein, preferred polyacrylic acid It is thickener, carbamate system thickener.
In the case where thickener, the additive amount [solid component (nonvolatile component)] of thickener is for example relative to resin Material (polymer) [solid component (nonvolatile component)] 100 parts by weight are more than 0 parts by weight and are 10 parts by weight hereinafter, lower limit is excellent 0.1 parts by weight are selected as, the upper limit is preferably 5 parts by weight.
In addition, may include any antirust agent for the anticorrosion of the metal component adjacent with foamed sheet.As the antirust Agent, the preferably compound of the ring containing azoles.Using the ring containing azoles compound when, can be taken into account with high level to the anticorrosive property of metal and To the adaptation of adherend.
As the compound of the above-mentioned ring containing azoles, as long as the chemical combination with 5 member rings in ring including 1 or more nitrogen-atoms Object, for example, can enumerate with diazole (imidazoles, pyrazoles) ring, triazole ring, tetrazole ring, oxazole ring, isozole ring, thiazole Ring or the compound of isothiazole ring etc..These rings can condense with aromatic rings such as phenyl ring and form condensed ring.It is such as having The compound of condensed ring, for example, can enumerate with benzimidazole ring, benzopyrazoles ring, benzotriazole ring, benzoxazoles ring, benzene And isozole ring, benzothiazole ring or compound of benzisothiazole ring etc..
Above-mentioned azoles ring, above-mentioned condensed ring (benzotriazole ring, benzothiazole ring etc.) respectively can have substituent group.It is taken as this Dai Ji, for example, the alkyl of the carbon numbers such as methyl, ethyl, propyl, isopropyl, butyl 1~6 (preferably carbon number 1~3) can be enumerated；First The alkoxy of the carbon numbers such as oxygroup, ethyoxyl, isopropoxy, butoxy 1~12 (preferably carbon number 1~3)；Phenyl, tolyl, naphthalene The aryl of equal carbon numbers 6~10；Amino；Methylamino, dimethylamino etc. (list or two) C1-10Alkyl amino；Amino methyl, 2- The amino such as amino-ethyl-C1-6Alkyl；N, N- diethylamino methyl, N, the list such as bis- (2- ethylhexyl) amino methyls of N- or two (C1-10Alkyl) amino-C1-6Alkyl；Sulfydryl；The alkoxy carbonyl of the carbon numbers such as methoxycarbonyl, ethoxy carbonyl 1~6；Carboxyl； The carboxyls such as carboxymethyl group-C1-6Alkyl；The carboxyls such as 2- carboxylethylthio-C1-6Alkylthio group；Bis- (hydroxymethyl) amino methyls of N, N- Equal N, the bis- (hydroxyl-C of N-1-4Alkyl) amino-C1-4Alkyl；Sulfo group etc..In addition, the compound of the above-mentioned ring containing azoles can form sodium The salt such as salt, sylvite.
It sets out from the anti-rust action aspect to metal, preferably the compound of the aromatic rings such as azoles ring and phenyl ring formation condensed ring, Wherein, particularly preferred benzotriazole based compound (compound with benzotriazole ring), benzothiazole based compound (have benzene And the compound of thiazole ring).
As above-mentioned benzotriazole based compound, for example, 1,2,3- benzotriazole, methylbenzotrazole, carboxylic can be enumerated Base benzotriazole, carboxymethyl group benzotriazole, 1- [bis- (2- ethylhexyl) amino methyls of N, N-] benzotriazole, [N, N- are bis- by 1- (2- ethylhexyl) amino methyl] methylbenzotrazole, 2,2 '-[[(methyl-1 H- benzotriazole -1- base) methyl] imino groups] Di-methylcarbinol or their sodium salt etc..
As above-mentioned benzothiazole based compound, for example, 2-mercaptobenzothiazole, 3- (2- (benzothiazole can be enumerated Base) thio) propionic acid or their sodium salt etc..
The compound of the ring containing azoles can be used singly or in combination of two or more.
In the case where antirust agent, antirust agent (for example, compound of the above-mentioned ring containing azoles) [solid component (and it is non-volatile at Point)] additive amount [solid component (nonvolatile component)] if in the range of not damaging foaming body original characteristic, example Such as, relative to resin material (polymer) [solid component (nonvolatile component)] 100 parts by weight, such as preferably 0.2~5 weight Part.Its lower limit be more preferably 0.3 parts by weight, further preferably 0.4 parts by weight, the upper limit be more preferably 3 parts by weight, further Preferably 2 parts by weight.
In addition, following the restorative of thickness for improving compressed foamed sheet, resume speed are (above-mentioned especially for making Caliper recovery rate after 0.5 second is 90% or more), in turn, the foamed sheets such as caliper recovery rate when being easy above-mentioned high temperature it is each Kind characteristic is set in the range of recording in specification, preferably addition silicon-type compound.In addition, for same mesh , silicone modified polymers can be used (for example, organosilicon at least part as above-mentioned resin material (polymer) Modified acroleic acid quasi polymer, organic-silicon-modified carbamate based polymer etc.).These can be used a kind, also can be used Two or more.
As above-mentioned silicon-type compound, preferably siloxanes key is 2000 silicon-type compounds below.As having Machine silicon systems compound, for example, silicone oil, modified silicon oil, silicone resin etc. can be enumerated.
As silicone oil (common silicone oil (straight silicone oil)), for example, dimethicone, first can be enumerated Base phenyl silicone oil etc..
As modified silicon oil, for example, polyether modified silicon oil (polyether-modified dimethicone etc.), alkyl-modified can be enumerated Silicone oil (alkyl-modified dimethicone etc.), aralkyl modified silicone oil (aralkyl modified dimethicone etc.), higher fatty acids Ester modified silicone oil (ester modified dimethicone of higher fatty acids etc.), fluoroalkyl silicone oil (fluoroalkyl dimethicone Deng) etc..
In these, preferred, polyethers modified organic silicon.As the commercially available product of polyether modified silicon oil, for example, can enumerate " PEG11 methyl ether dimethicone ", " PEG/PPG-20/22 butyl ether dimethyl silicone polymer ", " the poly- diformazan of PEG-9 methyl ether Radical siloxane ", " PEG-32 methyl ether dimethicone ", " PEG-9 dimethyl silicone polymer ", " PEG-3 polydimethylsiloxanes The straight chain types such as alkane ", " PEG-10 Polydimethylsiloxane "；" PEG-9 Polydimethylsiloxyethyl Dimethicone ", " moon (the above are Shin-Etsu Chemial Co., Ltd for the branched chain types such as osmanthus base PEG-9 Polydimethylsiloxyethyl Dimethicone " System) etc..
Silicone resin includes normal silicone (straight silicone resin), modified silicone resin.As ordinary silicon tree Rouge, for example, methyl silicon resin, methyl phenyl silicone resin etc. can be enumerated.In addition, as modified silicone resin, for example, can enumerate Alkyd modified silicone resin, epoxy-modified silicone resin, acrylic modified silicone resin, polyester modification silicone resin etc..
For silicon-type compound in foamed sheet of the invention, above-mentioned and it is present in above-mentioned silicone modified polymers In organosilicon chain portion total content, relative to 100 parts by weight of resin material (polymer) in foamed sheet of the invention, with not Volatile ingredient conversion (solid component conversion) meter for example, 0.01~5 parts by weight.The lower limit of above-mentioned total content is preferably 0.05 weight Part, further preferably 0.1 parts by weight are measured, the upper limit is preferably 4 parts by weight, further preferably 3 parts by weight.Foaming of the invention The total content of silicone ingredients and organosilicon chain portion in piece is to be easy to improve compressed extensive in the case that above-mentioned range is interior Renaturation and resume speed are without damaging the characteristic as foamed sheet.
In addition, for silicon-type compound in foamed sheet of the invention, above-mentioned and being present in above-mentioned organic-silicon-modified The total content in the organosilicon chain portion in polymer is, for example, 0.01~5 weight in terms of nonvolatile component conversion (solid component conversion) Measure %.The lower limit of above-mentioned total content is preferably 0.05 weight %, further preferably 0.1 weight %, and the upper limit is preferably 4 weights Measure %, further preferably 3 weight %.The total content of silicone ingredients and organosilicon chain portion in foamed sheet of the invention is upper In the case where in the range of stating, it is easy to further increase compressed restorative and resume speed without damaging as foamed sheet Characteristic.
In addition, may include any suitable other compositions in the range of not damaging impact absorbency.It is such other Ingredient can only include a kind, also may include two or more.As the other compositions, for example, can enumerate than that described above Component of polymer, softening agent, antioxidant, antiaging agent, gelating agent, curing agent, plasticizer, filler, hardening agent, foaming Agent, fire retardant, light stabilizer, ultraviolet absorbing agent, colorant (pigment, dyestuff etc.), pH adjusting agent, solvent (organic solvent), Thermal polymerization, Photoepolymerizationinitiater initiater etc..
As above-mentioned filler, for example, can enumerate silica, clay (mica, talcum, montmorillonite etc.), aluminium oxide, Titanium oxide, tin oxide, zeolite, calcium carbonate, graphite, carbon nanotube, inorfil (carbon fiber, glass fibre etc.), has zinc oxide Machine fiber, metal powder (silver, copper etc.) etc..In addition, piezoelectricity particle (titanium oxide etc.), electric conductivity can also be added as filler Particle, thermal conductive particle (boron nitride etc.), organic filler (organosilicon powder etc.) etc..
As above-mentioned filler, wherein preferred silica, calcium carbonate.Use silica or calcium carbonate as above-mentioned When filler, caliper recovery rate when high temperature can be further increased.In addition, be easy to further increase it is compressed restorative and Resume speed.
In the case that foamed sheet of the invention includes filler, the content of above-mentioned filler is relative to foamed sheet of the invention In 100 parts by weight of resin material (polymer) preferably 0.5~10 parts by weight, more preferably 0.8~6 parts by weight, further it is excellent It is selected as 0.9~5 parts by weight.When above-mentioned content is 0.5 parts by weight or more, caliper recovery when high temperature can be further improved Rate.In addition, being easy further to improve compressed restorative and resume speed.When above-mentioned content is 10 parts by weight or less, hold The softness of caliper recovery rate, compressed restorative and resume speed without reducing foamed sheet when easily further increasing high temperature Property.
Foamed sheet of the invention can by will include constitute its resin material (polymer) resin combination for Foaming and molding manufactures.As foaming method (forming method of bubble), can be foamed into using physical method, chemical method etc. Commonly used approach in shape.That is, foamed sheet of the invention can be foam the foaming body to be formed by physical method (physical blowing body), or foam the foaming body to be formed (chemical blowing body) is carried out by chemical method.Usual physics Method is to be scattered in the gas componants such as air, nitrogen in polymer solution, forms bubble (mechanical foaming by mechanical mixture Body) method.In addition, chemical method is to utilize the gas generated by the pyrolysis for the foaming agent being added in polymer base The method for forming abscess, obtaining foaming body.It sets out from the viewpoint such as environmental problem, preferably physical method.It is formed by physical method Bubble be mostly continuous air bubbles.
As can be used for the resin combination comprising resin material (polymer) of foaming and molding by resinous wood Material is dissolved in resin solution made of solvent, from the viewpoint of bubble, it is preferable to use the lotion comprising resin material.That is, Foamed sheet of the invention is preferably the foaming body of emulsion resin composition.As lotion, two or more lotion can be mixed to make With.In addition, above-mentioned resin combination can by without crosslinking agent resin combination in the form of pre-save, will for hair Mixed cross-linker before foam forming.
From the viewpoint of film forming, the solid component concentration height of lotion is preferred.The solid component concentration of lotion is excellent It is selected as 30 weight % or more, more preferably 40 weight % or more, further preferably 50 weight % or more.
In the present invention, preferably through make emulsion resin composition mechanical foaming to which the process (process A) of alveolation is made Make the method for foaming body.That is, foamed sheet of the invention is preferably the mechanical foaming body of emulsion resin composition.It is filled as blistering It sets, is not particularly limited, for example, the devices such as high speed shear mode, mode of vibration, the discharge mode of gas-pressurized can be enumerated. In these, from the viewpoint of the miniaturization of bubble diameter, large capacity production, preferred high speed shear mode.
Bubble when being blistered by mechanical stirring is made of gas (gas) is involved in lotion.As gas, as long as right Lotion is just not particularly limited to be nonactive, can enumerate air, nitrogen, carbon dioxide etc..Wherein, go out from the viewpoint of economy Hair, preferably air.
By the way that foamed sheet of the invention can be obtained by following process: the lotion tree of alveolation will be played by the above method Oil/fat composition is coated on process (process B) on substrate and dry.As above-mentioned base material, it is not particularly limited, for example, can enumerate Plastic film (pet film etc. for having carried out lift-off processing), the plastics for having carried out lift-off processing out are thin Film (pet film etc.), heat-conducting layer (aftermentioned heat-conducting layer) etc..Feelings of the coated with thermally conductive layer as substrate Under condition, the adaptation of foamed sheet and heat-conducting layer can be improved, in addition, can also improve the effect of drying process when foamed sheet production Rate.
In above-mentioned operation B, as coating method, drying means, usual way can be used.Process B preferably include by The emulsion resin composition of the bubbles on substrate is coated at 50 DEG C or more and less than 125 DEG C at dry preparation drying process The B1 and formal drying process B2 being then dried in turn at 125 DEG C or more and 200 DEG C or less.
By the way that preparation drying process B1 and formal drying process B2 is arranged, so as to prevent temperature rising sharply from causing The unification of bubble, bubble rupture.The especially small foamed sheet of thickness causes bubble to close because of the rising sharply of temperature One, it ruptures, therefore the meaning that preparation drying process B1 is arranged is very big.Temperature in preparation drying process B1 is preferably 50 DEG C or more And 100 DEG C or less.The time of preparation drying process B1 is, for example, 0.5 minute~30 minutes, preferably 1 minute~15 minutes.Separately Outside, the temperature in formal drying process B2 is preferably 130 DEG C or more and 180 DEG C or less, more preferably 130 DEG C or more and 160 DEG C Below.The time of formal drying process B2 is, for example, 0.5 minute~30 minutes, preferably 1 minute~15 minutes.
The foamed sheet of the mean cell diameter of 10~200 μm of range can lead to type, the amount, tune of adjustment surfactant Mixing speed, mixing time when whole mechanical stirring obtain.
0.2~0.7g/cm3The foamed sheet of density be involved in emulsion resin composition when can be by adjusting mechanical stirring In gas (gas) component amount obtain.
Foamed sheet of the invention can have adhesive phase (adhesive layer) in the one or two sides of foamed sheet.It is viscous as constituting The adhesive of mixture layer, is not particularly limited, for example, can be viscous for acrylic adhesives, elastomeric adhesive, organic silicon-type Any one of mixture etc..In addition, can be laminated on its surface for protecting adhesive phase in the case where setting adhesive phase Release liner is until use.It should be noted that constituting the foamed sheet of foamed sheet of the invention has the case where microviscosity Under, component etc. is capable of fixing being not provided with adhesive phase.
For foamed sheet of the invention, for shear bond power of at least one face relative to SUS304BA plate of foamed sheet (determination condition: 23 DEG C, tensile speed 50mm/ minutes) is 0.5N/100mm2For the above person, by the foamed sheet and other components (such as heat-conducting layer etc.) is laminated in the case where use, even if bonding adhesive layer is not arranged in foamed sheet, also can get can prevent Only effect of the positional shift without removing other above-mentioned components.In addition, can subtract since bonding adhesive layer can be not provided with The thickness of the laminated body of small foamed sheet and other components, can aid in electric/electronic device of the object as installation etc. into The slimming of one step.In turn, it can be improved the manufacture efficiency of the laminated body, can also reduce cost.It should be noted that conduct The example that the layer of the laminated body of foamed sheet and other components (such as heat-conducting layer etc.) of the invention is constituted, for example, it can be enumerated His component/foamed sheet, other component/adhesive phase/foamed sheets, foamed sheet/other component/foamed sheets, foamed sheet/adhesive Layer/other component/adhesive phase/foamed sheets etc..
In the case that foamed sheet of the invention has viscosity, foamed sheet of the invention is viscous relative to the shearing of SUS304BA plate Relay can for example be made up of the type and its composition of the monomer of the resin material (polymer) of foamed sheet of the invention selection Than adjusting.For example, as the resin material (polymer such as acrylic polymer) for constituting foamed sheet of the invention is formed Monomer, can relative to constitute above-mentioned resin material (polymer such as acrylic polymer) whole monomer components (monomer at Point total amount), using such as 70~98 weight % (lower limit preferably 75 weight %, the upper limit preferably 97 weight %) homopolymer Tg not The list of -10 DEG C of foot (such as -70 DEG C or more -10 DEG C, preferably -70 DEG C~-12 DEG C of deficiencies, further preferably -65 DEG C~-15 DEG C) Body, and be suitable for the type and amount for selecting other monomers, thus the shear bond power by foamed sheet relative to SUS304BA plate is set as 0.5N/100mm2More than.
Foamed sheet of the invention is preferably 0.5N/100mm relative to the lower limit of the shear bond power of SUS304BA plate2, into One step is preferably 0.7N/100mm2.In addition, the upper limit of above-mentioned shear bond power is not particularly limited, for example, being 100N/ 100mm2。
Foamed sheet of the invention can circulate on the market in the form of the coiling body (roll) of wound into rolls.
The impact absorbency of foamed sheet of the invention is excellent, and excellent to the patience of repeated stock.Thus, for example conduct By various components or component (such as optical component etc.) installation (loading) in defined position (such as shell in electric/electronic device Deng) when the electric/electronic device component that uses, particularly impact-absorbing sheet it is useful.Electric/electronic device of the invention uses Foamed sheet of the invention, therefore be not easy the impact when falling due to is damaged, in addition, also not cracky when by repeated stock. In addition, for foamed sheet of the invention, even if impact absorbency is also excellent and to repeatedly in the case where thickness is very thin The patience of impact is excellent, even if therefore electric/electronic device of the invention carried out miniaturization, slimming, when being also not easy because falling Impact and it is damaged, in addition, also not cracky when by repeated stock.It should be noted that " electric/electronic device " refers to The equipment for being equivalent at least either in electrical equipment or electronic equipment.
As the optical component using foamed sheet mountable (loading) of the invention, liquid crystal is loaded into for example, can enumerate Image display member in the image display devices such as display, electroluminescent display, plasma scope is (especially small-sized Image display member), be loaded into the dresses of the mobile communication such as so-called cellular phone, " smart phone ", " personal digital assistant device " The display members such as the touch panel in setting, camera, lens (especially small-sized camera, lens) etc..
Electric/electronic device of the invention has used foamed sheet of the invention.Such electric/electronic device includes for example making For have the electric/electronic device of display member and with above-mentioned foamed sheet be clamped in the shell of the electric/electronic device with it is upper State the electric/electronic device of the structure between display member.As the electric/electronic device, for example, can enumerate so-called " mobile Device of mobile communication such as phone ", " smart phone ", " personal digital assistant device " etc..
In addition, foamed sheet of the invention is in the equipment for being installed with touch panel, even if the touch with user is grasped Make and display panel, touch panel have occurred bending, deformation, also can effectively by the power generated with the deformation dispersion suction It receives.Therefore, foamed sheet of the invention can highly inhibit to apply in the display unit that stress generates sometimes through to display panel Display uneven (undulatory fuzzy pattern) generation.Therefore, foamed sheet of the invention can be preferred for being installed with touch The equipment of panel.
The above-mentioned equipment for being installed with touch panel refers to display panel and the equipment that is installed with touch panel.As dress Equipment equipped with touch panel, is not particularly limited, for example, mobile phone can be enumerated；Smart phone；Personal digital assistant device (PDA)；Tablet computer；The various personal computers such as desktop type, notebook type, plate (computer)；Plasma scope, liquid The various displays (monitor) such as crystal display, electroluminescent display (organic el display)；Portable game machine；Digital sound Frequency player；Electronic book reader (e-book reading equipment, e-book special-purpose terminal)；Wearable computer (wearable device)；Digital signage (electronic bill-board)；ATM (ATM)；Ticket, various convertible notes, beverage, food, perfume (or spice) Cigarette, magazine, newspaper etc. sell used in automatic machine/automatic vending machine；Television receiver (TV)；Electronic blackboard (is handed over Mutual formula blank) etc..
The equipment for being installed with touch panel of the invention has used foamed sheet of the invention.Touch is installed with as such The equipment of panel, for example, can enumerate with above-mentioned foamed sheet, display panel and touch panel, and in above-mentioned display panel The space configuration of back side has above-mentioned foamed sheet person.The equipment for being installed with touch panel of the invention has used foaming of the invention Piece, therefore be not easy the impact when falling due to is damaged, in addition, also not cracky when by repeated stock.In addition, of the invention Even if foamed sheet, in the case where thickness is very thin, impact absorbency is also excellent and excellent to the patience of repeated stock, therefore Even if the equipment for being installed with touch panel of the invention has carried out miniaturization, slimming, the impact being also not easy when falling due to, is broken Damage, in addition, also not cracky when by repeated stock.In turn, inhibit to the device height for being installed with touch panel of the invention The uneven generation of display in the display unit for the touch operation for attending by user.
Embodiment
Hereinafter, enumerating embodiment, the present invention will be described in more detail, but the present invention is not by any of these embodiments Limitation.It should be noted that unless otherwise specified, then it represents that " % " of content refers to weight %.It should be noted that matching The value of mixed number (parts by weight) all solid components (nonvolatile component) conversion.
Embodiment 1
By acrylic emulsions solution (solid content 57%, butyl acrylate-methyl ester-acrylonitrile-the third Olefin(e) acid copolymer (weight ratio 91:4:3:2)) 100 parts by weight, fatty acid ammonium system surfactant (aqueous dispersions of ammonium stearate, Solid content 33%) (surfactant A) 1.5 parts by weight, carboxy betaine type amphoteric surfactant (" AMOGEN CB- H ", Di-ichi Kogyo Seiyaku Co., Ltd.'s system) (surfactant B) 1.0 parts by weight, oxazoline system crosslinking agent (" EPOCROS WS- 500 ", Nippon Shokubai Co., Ltd's system, solid content 39%) 0.35 parts by weight, polyacrylic thickener (acrylic acid second Ester-acrylic copolymer (acrylic acid 20%), solid content 28.7%) 0.78 parts by weight, lubricant (modified silicon oil, " X- 22-163C ", Shin-Etsu Chemial Co., Ltd's system) 1.0 parts by weight dispersion machine (" ROBOMIX ", PRIMIX Corporation system) it is stirred, make its blistering.The composition, foam is coated on to (poly- pair of PET for having carried out lift-off processing Ethylene terephthalate) on film (thickness: 38 μm, trade name " MRF#38 ", Mitsubishi Plastics Inc's system), at 80 DEG C It is 5 minutes dry at 5 minutes, 140 DEG C dry, obtain 150 μm of thickness, density 0.31g/cm3, it is maximum 110 μm of cell diameter, minimum 20 μm of cell diameter, 45 μm of mean cell diameter continuous air bubbles structure foaming body (foamed sheet).
Embodiment 2
By acrylic emulsions solution (solid content 57%, butyl acrylate-methyl ester-acrylonitrile-the third Olefin(e) acid copolymer (weight ratio 91:4:3:2)) 100 parts by weight, fatty acid ammonium system surfactant (aqueous dispersions of ammonium stearate, Solid content 33%) (surfactant A) 1.5 parts by weight, carboxy betaine type amphoteric surfactant (" AMOGEN CB- H ", Di-ichi Kogyo Seiyaku Co., Ltd.'s system) (surfactant B) 1.0 parts by weight, oxazoline system crosslinking agent (" EPOCROS WS- 500 ", Nippon Shokubai Co., Ltd's system, solid content 39%) 2.0 parts by weight, polyacrylic thickener (ethyl acrylate- Acrylic copolymer (acrylic acid 20%), solid content 28.7%) 1.5 parts by weight, lubricant (modified silicon oil, " X-22- 163C ", Shin-Etsu Chemial Co., Ltd's system) 1.0 parts by weight dispersion machine (" ROBOMIX ", PRIMIX Corporation System) it is stirred, make its blistering.The composition, foam is coated on to PET (the poly terephthalic acid second two for having carried out lift-off processing Alcohol ester) on film (thickness: 38 μm, trade name " MRF#38 ", Mitsubishi Plastics Inc's system), 5 minutes dry at 80 DEG C, It is 5 minutes dry at 140 DEG C, obtain 200 μm of thickness, density 0.25g/cm3, maximum 110 μm of cell diameter, minimum cell diameter 20 μm, the foaming body (foamed sheet) of 40 μm of mean cell diameter of continuous air bubbles structure.
Embodiment 3
By acrylic emulsions solution (solid content 57%, butyl acrylate-methyl ester-acrylonitrile-the third Olefin(e) acid copolymer (weight ratio 91:4:3:2)) 100 parts by weight, fatty acid ammonium system surfactant (aqueous dispersions of ammonium stearate, Solid content 33%) (surfactant A) 1.5 parts by weight, carboxy betaine type amphoteric surfactant (" AMOGEN CB- H ", Di-ichi Kogyo Seiyaku Co., Ltd.'s system) (surfactant B) 1.0 parts by weight, oxazoline system crosslinking agent (" EPOCROS WS- 500 ", Nippon Shokubai Co., Ltd's system, solid content 39%) 1.0 parts by weight, polyacrylic thickener (ethyl acrylate- Acrylic copolymer (acrylic acid 20%), solid content 28.7%) 1.0 parts by weight, lubricant (modified silicon oil, " X-22- 163C ", Shin-Etsu Chemial Co., Ltd's system) 1.0 parts by weight dispersion machine (" ROBOMIX ", PRIMIX Corporation System) it is stirred, make its blistering.The composition, foam is coated on to PET (the poly terephthalic acid second two for having carried out lift-off processing Alcohol ester) on film (thickness: 38 μm, trade name " MRF#38 ", Mitsubishi Plastics Inc's system), 5 minutes dry at 80 DEG C, It is 5 minutes dry at 140 DEG C, obtain 80 μm of thickness, density 0.35g/cm3, maximum 60 μm of cell diameter, 20 μ of minimum cell diameter M, the foaming body (foamed sheet) of 40 μm of mean cell diameter of continuous air bubbles structure.
Embodiment 4
By acrylic emulsions solution (solid content 57%, butyl acrylate-methyl ester-acrylonitrile-the third Olefin(e) acid copolymer (weight ratio 91:4:3:2)) 100 parts by weight, fatty acid ammonium system surfactant (aqueous dispersions of ammonium stearate, Solid content 33%) (surfactant A) 1.5 parts by weight, carboxy betaine type amphoteric surfactant (" AMOGEN CB- H ", Di-ichi Kogyo Seiyaku Co., Ltd.'s system) (surfactant B) 1.0 parts by weight, oxazoline system crosslinking agent (" EPOCROS WS- 500 ", Nippon Shokubai Co., Ltd's system, solid content 39%) 1.0 parts by weight, polyacrylic thickener (ethyl acrylate- Acrylic copolymer (acrylic acid 20%), solid content 28.7%) 1.0 parts by weight, lubricant (modified silicon oil, " X-22- 163C ", Shin-Etsu Chemial Co., Ltd's system) 1.0 parts by weight dispersion machine (" ROBOMIX ", PRIMIX Corporation System) it is stirred, make its blistering.The composition, foam is coated on to PET (the poly terephthalic acid second two for having carried out lift-off processing Alcohol ester) on film (thickness: 38 μm, trade name " MRF#38 ", Mitsubishi Plastics Inc's system), 5 minutes dry at 80 DEG C, It is 5 minutes dry at 140 DEG C, obtain 300 μm of thickness, density 0.24g/cm3, maximum 120 μm of cell diameter, minimum cell diameter 30 μm, the foaming body (foamed sheet) of 50 μm of mean cell diameter of continuous air bubbles structure.
Embodiment 5
By acrylic emulsions solution (solid content 57%, butyl acrylate-methyl ester-acrylonitrile-the third Olefin(e) acid copolymer (weight ratio 91:4:3:2)) 100 parts by weight, fatty acid ammonium system surfactant (aqueous dispersions of ammonium stearate, Solid content 33%) (surfactant A) 1.5 parts by weight, carboxy betaine type amphoteric surfactant (" AMOGEN CB- H ", Di-ichi Kogyo Seiyaku Co., Ltd.'s system) (surfactant B) 1.0 parts by weight, oxazoline system crosslinking agent (" EPOCROS WS- 500 ", Nippon Shokubai Co., Ltd's system, solid content 39%) 1.0 parts by weight, polyacrylic thickener (ethyl acrylate- Acrylic copolymer (acrylic acid 20%), solid content 28.7%) 1.0 parts by weight, lubricant (modified silicon oil, " X-22- 163C ", Shin-Etsu Chemial Co., Ltd's system) 1.0 parts by weight, filler (silica dioxide granule, average grain diameter: 1 μm) 0.9 weight Amount part is stirred with dispersion machine (" ROBOMIX ", PRIMIX Corporation system), makes its blistering.By the composition, foam Be coated on carried out lift-off processing PET (polyethylene terephthalate) film (thickness: 38 μm, trade name " MRF#38 ", Mitsubishi Plastics Inc's system) on, it is 5 minutes dry at 5 minutes, 140 DEG C dry at 80 DEG C, obtain 150 μm of thickness, density 0.30g/cm3, maximum 110 μm of cell diameter, minimum 20 μm of cell diameter, 45 μm of mean cell diameter continuous air bubbles structure Foaming body (foamed sheet).
Embodiment 6
By acrylic emulsions solution (solid content 57%, butyl acrylate-methyl ester-acrylonitrile-the third Olefin(e) acid copolymer (weight ratio 91:4:3:2)) 100 parts by weight, fatty acid ammonium system surfactant (aqueous dispersions of ammonium stearate, Solid content 33%) (surfactant A) 1.5 parts by weight, carboxy betaine type amphoteric surfactant (" AMOGEN CB- H ", Di-ichi Kogyo Seiyaku Co., Ltd.'s system) (surfactant B) 1.0 parts by weight, oxazoline system crosslinking agent (" EPOCROS WS- 500 ", Nippon Shokubai Co., Ltd's system, solid content 39%) 1.0 parts by weight, polyacrylic thickener (ethyl acrylate- Acrylic copolymer (acrylic acid 20%), solid content 28.7%) 1.0 parts by weight, lubricant (modified silicon oil, " X-22- 163C ", Shin-Etsu Chemial Co., Ltd's system) 1.0 parts by weight, filler (silica dioxide granule, average grain diameter: 1 μm) 5 weight Part is stirred with dispersion machine (" ROBOMIX ", PRIMIX Corporation system), makes its blistering.The composition, foam is applied Cloth is in PET (polyethylene terephthalate) film (thickness: 38 μm, trade name " MRF#38 ", three for carrying out lift-off processing Water chestnut resin Co. Ltd. system) on, it is 5 minutes dry at 5 minutes, 140 DEG C dry at 80 DEG C, obtain 150 μm of thickness, density 0.30g/cm3, maximum 110 μm of cell diameter, minimum 20 μm of cell diameter, 45 μm of mean cell diameter continuous air bubbles structure Foaming body (foamed sheet).
Comparative example 1
By acrylic emulsions solution (solid content 55%, ethyl acrylate-acrylic acid butyl ester-acrylonitrile copolymer (weight ratio 45:48:7)) 100 parts by weight, fatty acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid content 33%) (surfactant A) 1.5 parts by weight, (" AMOGEN CB-H ", the first industry of carboxy betaine type amphoteric surfactant Pharmaceutical Co., Ltd's system) (surfactant B) 1.0 parts by weight, (" EPOCROS WS-500 ", the strain formula meeting of oxazoline system crosslinking agent Community day this catalyst system, solid content 39%) 0.35 parts by weight, (the ethyl acrylate-acrylic acid copolymerization of polyacrylic thickener Object (acrylic acid 20%), solid content 28.7%) 0.78 parts by weight dispersion machine (" ROBOMIX ", PRIMIX Corporation system) it is stirred, make its blistering.The composition, foam is coated on to (poly- pair of PET for having carried out lift-off processing Ethylene terephthalate) on film (thickness: 38 μm, trade name " MRF#38 ", Mitsubishi Plastics Inc's system), at 80 DEG C It is 5 minutes dry at 5 minutes, 140 DEG C dry, obtain 150 μm of thickness, density 0.32g/cm3, it is maximum 110 μm of cell diameter, minimum 20 μm of cell diameter, 45 μm of mean cell diameter continuous air bubbles structure foaming body (foamed sheet).
Comparative example 2
By acrylic emulsions solution (solid content 55%, ethyl acrylate-acrylic acid butyl ester-acrylonitrile copolymer (weight ratio 45:48:7)) 100 parts by weight, fatty acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid content 33%) (surfactant A) 1.5 parts by weight, (" AMOGEN CB-H ", the first industry of carboxy betaine type amphoteric surfactant Pharmaceutical Co., Ltd's system) (surfactant B) 1.0 parts by weight, (" EPOCROS WS-500 ", the strain formula meeting of oxazoline system crosslinking agent Community day this catalyst system, solid content 39%) 0.35 parts by weight, filler (silica dioxide granule, average grain diameter: 5 μm) 25 weights Amount part is stirred with dispersion machine (" ROBOMIX ", PRIMIX Corporation system), makes its blistering.By the composition, foam Be coated on carried out lift-off processing PET (polyethylene terephthalate) film (thickness: 38 μm, trade name " MRF#38 ", Mitsubishi Plastics Inc's system) on, it is 5 minutes dry at 5 minutes, 140 DEG C dry at 80 DEG C, obtain 150 μm of thickness, density 0.31g/cm3, maximum 110 μm of cell diameter, minimum 20 μm of cell diameter, 45 μm of mean cell diameter continuous air bubbles structure Foaming body (foamed sheet).
Comparative example 3
By 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): 3.0g/10 minutes, fusing point: 204 are spun by name " Pelprene P-90BD ", Japan DEG C): 100 parts by weight, acrylic compounds lubricant (trade name " METABLEN L-1000 ", MITSUBISHI RAYON CO., LTD. make): 5 parts by weight, batt (trade name " ST-301 ", shiraishi calcium that surface treatment processing has been carried out with silane coupling agent Co. Ltd. system): 1 parts by weight, carbon black (trade name " rising sun #35 ", Asahi Carbon Co.Ltd. system): 5 parts by weight and epoxy Be modification agent (epoxy-modified acrylic acid quasi polymer, weight average molecular weight (Mw): 50000, epoxide equivalent: 1200g/eq, viscosity: 2850mPas): 2 parts by weight with twin shaft kneading machine 220 DEG C at a temperature of be kneaded after, with strands shape extrusion, cut off after water cooling It is configured to partical.The pellet is put into single screw extrusion machine, in 240 DEG C of atmosphere, 17 (13 after injection) MPa's Carbon dioxide gas is injected under pressure.After being saturated carbon dioxide gas sufficiently, after being cooled to the temperature suitable for foaming, from mold Middle extrusion obtains the polyester-based elastomer foaming body of the sheet with a thickness of 2.0mm.Gained foaming body is sliced, thickness is obtained Spend 200 μm, density 0.07g/cm3, maximum 80 μm of cell diameter, minimum 20 μm of cell diameter, 30 μm of mean cell diameter company The foaming body (foamed sheet) of continuous bubble structure.
<evaluation>
Foaming body obtained in Examples and Comparative Examples (foamed sheet) is conducted the following evaluation.Show the result in table 1.It needs It is noted that showing each embodiment in table 1, the compounding number (parts by weight) of each ingredient in comparative example [(do not wave by solid component Send out ingredient) conversion].
(mean cell diameter)
With low vacuum scanning electron microscope (" S-3400N type scanning electron microscope ", Hitachi High-Tech Science Systems Co., Ltd. system), the enlarged drawing of foaming body section is obtained, image analysis is carried out, it is straight thus to find out Average Cell Diameter (μm).It should be noted that the number of bubbles of analysis is 10~20 or so.In addition, by same as mean cell diameter Method finds out the minimum cell diameter (μm) and maximum cell diameter (μm) of foamed sheet.
(density)
Foaming body (foamed sheet) is punched with the blanking knife model of 100mm × 100mm, measures the ruler of the sample through being punched It is very little.In addition, with the diameter of measurement terminalThickness is measured for 1/100 amesdial (dial gauge) of 20mm.According to these Value calculates the volume of foaming body.
Then, the weight of foaming body is measured with the counter balance of minimum scale 0.01g or more.It is calculated by these values Density (the g/cm of foaming body3)。
(dynamic viscoelastic)
In the film of determination of viscoelasticity device (" ARES2KFRTN1-FCO ", TA Instruments Japan corporation) It stretches and carries out temperature dispersion test under mode determination, under angular frequency 1rad/s, 5 DEG C/min of heating rate.It measures at this time The temperature (DEG C) and intensity (maximum value) of the summit of ratio, that is, loss angle tangent (tan δ) of storage modulus E ' and loss modulus E ".
Described in the column of " the tan δ temperature " of table 1 summit of the loss angle tangent (tan δ) of foaming body temperature (DEG C), The intensity (maximum value) of the summit is described in the column of " tan δ maximum value ", is described in the column of " tan δ maximum value/density " The intensity (maximum value) of summit is stated [to be equivalent to divided by the resulting value of density of foaming body and constitute the material itself of foaming body and (do not wrap Include bubble) tan δ summit intensity (maximum value)].
(initial elastic modulus (under 0 DEG C of environment))
Foaming body is cut to width: the test film of sheet is made in 10mm, length: 40mm.To the test film viscoplasticity Measurement device (" RSA-III ", TA Instruments Japan corporation), in 0 DEG C of measuring temperature, tensile speed 300mm/ points Tension test is carried out under conditions of clock, slope when by 10% strain calculates initial elastic modulus (N/mm2).Evaluation result is remembered It is loaded in the column of " initial elastic modulus " of table 1.
(caliper recovery rate)
Foaming body is cut to width: the test film of sheet is made in 25mm, length: 40mm.To the test film electromagnetic force Decline small test machine (micro- servo) (trade name " MMT-250 ", society, Shimadzu Scisakusho Ltd system), under 23 DEG C of atmosphere, edge Thickness direction applies 1kg (every 1cm2For the load of 100g), 120 seconds compressive states are maintained.Under 23 DEG C of atmosphere, uncompression State, (thickness change, thickness are extensive for the recovery movement with high-speed camera (high speed camera) to the thickness of foaming body It is multiple) it is shot, according to the image of shooting, find out the thickness of the foaming body after uncompression state after 0.5 second.Then, pass through Following formula finds out recovery rate.Evaluation result is recorded in the column of " caliper recovery rate " of table 1.
Caliper recovery rate (%)=(thickness after uncompression state 0.5 second)/(original depth) × 100
(screen resilience (anti-rebound load, 50% compressive load when 50% compression) when 50% compression)
It is measured according to the compressive hardness measuring method recorded in JIS K 6767.
Foaming body is cut to width: the test film of sheet is made in 30mm, length: 30mm.It then, will be to the test film With compression speed: 10mm/ minutes, through-thickness, carry out compress until compression ratio becomes 50% until when stress (N) by singly Plane accumulates (1cm2) convert, as screen resilience (N/cm2).Evaluation result is recorded in the column of " 50% compressive load " of table 1 In.
(impact absorbency experiment)
Impact absorbency is carried out using above-mentioned pendulum type shock machine (impact test apparatus) (referring to FIG. 1 and FIG. 2) Test.To foamed sheet obtained in Examples and Comparative Examples (sample size: 20mm × 20mm), 40 ° are tilted in the iron ball for making 66g Under conditions of, make iron balls impact for continuous 5 times with 1 second interval, carry out impact test, measure the impact force (N) when each shock. Evaluation result is recorded in the column of " impact absorbing test " of table 1.
In addition, the impact force (N) when for each shock, is 5 points of y-axis drafting as x-axis, with impact force (N) using number of shocks, The linear approximation straight line obtained by this 5 points by least square method is obtained, its slope is found out.Evaluation result is recorded in table 1 In the column of " slope of repeated stock power ".
(caliper recovery rate when high temperature)
Foaming body is cut to width: the test film of sheet is made in 30mm, length: 30mm.Correctly measure the test film Thickness is denoted as thickness a.Then, to test film, using fixture with 2 compression plates (aluminium sheet) from the two sides of test film along thickness side To by relative to initial thickness as 50% thickness in a manner of using spacer (the thickness c) of spacer compressed (that is, 50% compressive state), the compressive state is maintained, is taken care of 22 hours under conditions of humidity 50%, 80 DEG C of temperature.By 22 hours Afterwards, it is taken care of under 23 DEG C of atmosphere 2 hours, then releases the compressive state of test film, placed 24 hours.After placement, Accurate Determining The thickness of test film is denoted as thickness b.
By thickness a, thickness b and thickness c, the caliper recovery rate (%) when high temperature is calculated by following formula.Evaluation result is remembered It is loaded in the column of " caliper recovery rate when high temperature " of table 1.
Caliper recovery rate (%)=(1- (thickness a- thickness b)/(thickness a- thickness c)) × 100 when high temperature
It should be noted that for thickness a and thickness b, in the environment of 23 ± 2 DEG C of temperature, relative humidity 50 ± 5% into Row measurement.
[table 1]
As shown in table 1, for the foamed sheet of embodiment, mean cell diameter is 10~200 μm, by thickness reduction 50% When screen resilience be 6.0N/cm2Below, the caliper recovery rate after above-mentioned 0.5 second is 90% or more, shows high impact and inhales The property received, and the impact absorbency of same degree when hitting with the 1st time is shown when the 5th is hit.In contrast, for The foamed sheet of comparative example 1~3, the caliper recovery rate after above-mentioned 0.5 second are not up to 90% or more, and when the 5th is hit, impact is inhaled The property received when the 1st shock than being greatly reduced.
Description of symbols
1 pendulum type shock machine (impact test apparatus)
2 test films (foamed sheet)
3 holding members
4 impact load components
5 pressure sensors
11 stationary fixtures
12 holding jigs
16 pressure adjustment means
20 pillars
21 arms
One end of 22 support sticks (axis)
23 support sticks (axis)
24 impulse members
25 electromagnets
28 support plates
A is swung up angle

Claims (18)

1. a kind of foamed sheet, which is characterized in that mean cell diameter is 10~200 μm, rebound when by thickness reduction 50% Power is 6.0N/cm2Hereinafter, the caliper recovery rate being defined by the formula is 90% or more,
Caliper recovery rate (%)=(thickness after uncompression state 0.5 second)/(original depth) × 100
Original depth: the thickness of the foamed sheet before applying load
Thickness after uncompression state 0.5 second: 100g/cm is being applied to foamed sheet2Load in the state of maintain 120 seconds, Uncompression, the thickness of the foamed sheet from after releasing 0.5 second.
2. foamed sheet according to claim 1, with a thickness of 30~1000 μm, density is 0.2~0.7g/cm3。
3. foamed sheet according to claim 1 or 2, wherein the storage in Measurement of Dynamic Viscoelasticity at angular frequency 1rad/s Ratio, that is, loss angle tangent (tan δ) of energy modulus and loss modulus has peak in -60 DEG C or more and 20 DEG C or less of range Top.
4. foamed sheet described in any one of claim 1 to 3, wherein used the impact of pendulum type shock machine It is in absorbent test, so that impulse member is struck against the structural body formed by support plate and foamed sheet continuous 5 times with 1 second interval Support plate on when, the 5th hit when impact force relative to for the first time hit when impact force climbing be 5% or less.
5. foamed sheet according to any one of claims 1 to 4 is comprising crosslinking agent and organo-silicon compound.
6. foamed sheet according to any one of claims 1 to 5, wherein the solvent insoluble component insoluble in methyl ethyl ketone is 80 weight % or more.
7. foamed sheet described according to claim 1~any one of 6, wherein loss angle tangent (tan δ) at -60 DEG C or more and Maximum value in 20 DEG C or less of range is 0.2 or more.
8. foamed sheet according to any one of claims 1 to 7, wherein the caliper recovery rate when high temperature of following definitions It is 50% or more,
Caliper recovery rate when high temperature: by foamed sheet, through-thickness compresses under 80 DEG C of atmosphere, so that relative to original depth As 50% thickness, after 22 hours, 2 hours are placed under 23 DEG C of atmosphere, then uncompression state, from compressive state Ratio of the thickness relative to original depth after releasing after 24 hours.
9. foamed sheet described according to claim 1~any one of 8, wherein used acrylic polymer as resin Material.
10. foamed sheet described according to claim 1~any one of 9, wherein at least one face is relative to SUS304BA plate Shear bond power (23 DEG C, tensile speed 50mm/ minutes) is 0.5N/100mm2More than.
11. foamed sheet described according to claim 1~any one of 10 is the mechanical foaming body of emulsion resin composition.
12. foamed sheet described according to claim 1~any one of 11 has adhesive phase in one or two sides.
13. foamed sheet described according to claim 1~any one of 12 is used as electric/electronic device impact-absorbing sheet.
14. foamed sheet described according to claim 1~any one of 13, the equipment for being used to be installed with touch panel.
15. a kind of electric/electronic device, with foamed sheet described in any one of claim 1~14.
16. electric/electronic device according to claim 15 has display member, and has the foamed sheet clamped Structure between the shell and the display member of the electric/electronic device.
17. a kind of equipment for being installed with touch panel, with the foamed sheet described in claim 14.
18. the equipment according to claim 17 for being installed with touch panel, with the foamed sheet, display panel and Touch panel has the foamed sheet in the space configuration of the back side of the display panel.
CN201780060323.1A 2016-08-01 2017-07-06 Foam sheet, electric and electronic device, and device with touch panel Active CN109790317B (en)

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JP2016-151180 2016-08-01
JP2016151180 2016-08-01
JP2017-130712 2017-07-03
JP2017130712A JP6956544B2 (en) 2016-08-01 2017-07-03 Foam sheet, electrical and electronic equipment, and touch panel-equipped equipment
PCT/JP2017/024785 WO2018025568A1 (en) 2016-08-01 2017-07-06 Foam sheet, electrical and electronic apparatus, and touch-panel-equipped apparatus

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JP2019167484A (en) * 2018-03-26 2019-10-03 日東電工株式会社 Foam sheet
KR20210031683A (en) * 2018-07-11 2021-03-22 세키스이가가쿠 고교가부시키가이샤 Shock absorbing sheet
JP7552584B2 (en) * 2019-03-27 2024-09-18 日本ゼオン株式会社 Composition for self-adhesive foam sheet and self-adhesive foam laminate sheet

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