CN104553148B - Laminate, usage of laminate as thermal diffusion shock absorption piece and electrical equipment or electronic equipment using laminate - Google Patents

Laminate, usage of laminate as thermal diffusion shock absorption piece and electrical equipment or electronic equipment using laminate Download PDF

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Publication number
CN104553148B
CN104553148B CN201410422110.7A CN201410422110A CN104553148B CN 104553148 B CN104553148 B CN 104553148B CN 201410422110 A CN201410422110 A CN 201410422110A CN 104553148 B CN104553148 B CN 104553148B
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China
Prior art keywords
foaming body
layered product
heat
impact
layer
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CN201410422110.7A
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CN104553148A (en
Inventor
土井浩平
冈田美佳
加藤和通
德山英幸
北原纲树
高桥忠男
长崎国夫
松下喜郎
松下喜一郎
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Nitto Denko Corp
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Nitto Denko Corp
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Priority claimed from JP2014082568A external-priority patent/JP6343478B2/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/046—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/046—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0207—Materials belonging to B32B25/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0221—Vinyl resin
    • B32B2266/0235—Vinyl halide, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0242—Acrylic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0278—Polyurethane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a thermal diffusion absorption sheet which is excellent in impact absorbing and heat diffusing ability even with small thickness. The laminate is provided with a foaming body layer and a heat conduction layer. The thickness of the foaming body layer is 30-500 [mu]m and is formed by a foaming body whose density is 0.2-0.7g/cm<3> and average cell diameter is 10-150 [mu]m. The thermal conductivity of the heat conduction layer is more than 200W/m*k. Optimally, the ratio of accumulation energy elasticity modulus to loss elasticity modulus, i.e., loss tangent (tan delta) more than-30 DEG G and lower than 30 DEG G, the foaming body whose dynamic viscoelasticity is 1 rad/s during the dyanamic viscoelasticity measurement is provided with a peak value. Optimally, the maximum value of the loss tangent (tan delta) of the foaming body more than-30 DEG G and lower than 30 DEG G is more than 0.2.

Description

Layered product, it uses and has used the layered product as thermal diffusion impact-absorbing sheet Electrical equipment or electronic equipment
Technical field
Even if the present invention relates to thickness of thin, impact absorbency and the also excellent layered product (thermal expansion of heat diffusivity (thermal diffusivity) Dissipate impact-absorbing sheet), and the electrical equipment or electronic equipment for having used the layered product.
Background technology
In recent years, along with PC (PC), tablet PC, PDA (personal portable information terminal), mobile phone etc. The slimming of electronic equipment, in order to prevent the breakage of liquid crystal panel, organic EL panel etc., and has used impact to inhale in back side of panel Take up.
In addition, along with the multifunction of electronic equipment, the heating quantitative change of the heater such as electronic unit is big, thus in order to anti- The performance reduction for only being caused because internally accumulating heat or the scald of breakage and the user caused because basket locally reaches a high temperature Deng, it is necessary to efficiently to outside diffusion heat, cooled down.For the purpose, and various radiators are used.
Therefore, the thermal diffusion impact-absorbing sheet for combining impact absorbing layer and heat-conducting layer is needed in the electronic device. Also, due to the further slimming of electronic equipment, and require the further thin layer of component for electronic equipment.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2001-100216 publications
Patent document 2：Japanese Unexamined Patent Publication 2002-309198 publications
The content of the invention
Invent problem to be solved
Thus, even if it is an object of the present invention to provide a kind of thickness of thin, impact absorbency and heat diffusivity are also excellent Thermal diffusion impact-absorbing sheet, and used the electrical equipment or electronic equipment of such thermal diffusion impact-absorbing sheet.
Means for solving the problems
The present inventor etc. conduct in-depth research to achieve these goals, as a result find, for by with specific Density, specific mean cell diameter foaming body constitute foaming body layer and thermal conductivity be particular value more than heat-conducting layer For the piece being laminated, even if being 30~500 μm of so thin thickness, the impact absorbency of described is also substantially excellent, And heat diffusivity is also excellent, effectively internal heat can be spread to outside, so far be completed the present invention.
That is, the present invention provides a kind of layered product, and the layered product has foaming body layer and heat-conducting layer, the foaming body layer Thickness is 30~500 μm, and is 0.2~0.7g/cm by density3, foaming body that mean cell diameter is 10~150 μm constitute, The thermal conductivity of the heat-conducting layer is more than 200W/mK.
For above-mentioned layered product, when angular frequency of the preferably above-mentioned foaming body in Measurement of Dynamic Viscoelasticity is 1rad/s Store elastic modulus and the ratio of loss elastic modulus be loss angle tangent (tan δ) more than -30 DEG C and less than 30 DEG C In the range of have peak value.
It is preferred that maximum of the loss angle tangent (tan δ) of above-mentioned foaming body more than -30 DEG C and in less than 30 DEG C of scope Be worth is more than 0.2.
Additionally, it is preferred that under 23 DEG C of environment and draw speed for 300mm/min tension test in foaming body initial stage Elastic modelling quantity is 5N/mm2Below.
Additionally, using pendulum type shock machine, the layered product impact absorbency experiment (weight of impact 96g, put 30 ° of angle) in, the impact absorbing rate (%) being defined by the formula divided by foaming body layer thickness (μm) obtained by value R Preferably more than 0.15.
Impact absorbing rate (%)={ (F0- F1)/F0}×100
(in above formula, F0Only to collide the impulsive force of the impact period of the day from 11 p.m. to 1 a.m, F to support plate1It is to by support plate and above-mentioned layered product The impulsive force of the impact period of the day from 11 p.m. to 1 a.m is collided on the support plate of the structure of composition)
The thickness of above-mentioned heat-conducting layer is, for example, more than 5 μm.
Above-mentioned heat-conducting layer can be selected from least one in graphite flake and metal foil.
Foaming body can be by selected from acrylic acid series polymeric compounds, rubber, carbamate based polymer and ethylene-acetate second At least one resin material in enoate copolymer is formed.
Foaming body can be formed via the operation A for making emulsion resin composition mechanically foam.
Foaming body further can be coated on base material simultaneously via emulsion resin composition obtained by mechanically foaming The process B that is dried and formed.
Above-mentioned operation B can include：The emulsion resin composition of the bubbles that will be coated on base material more than 50 DEG C and The prepared drying process B1 that is dried at a temperature of less than 125 DEG C and after preparation drying process B1 further at 125 DEG C Above and less than the 200 DEG C trunk drying process B2 being dried.
Above-mentioned layered product can be in the single or double of foaming body layer with across adhesive phase or not across adhesive phase Mode is laminated with heat-conducting layer.
Above-mentioned layered product can serve as electrical equipment or electronic equipment thermal diffusion impact-absorbing sheet.
The present invention also provides a kind of electrical equipment or electronic equipment for having used above-mentioned layered product.
Above-mentioned electrical equipment or electronic equipment are the electrical equipment or electronic equipment for possessing display member, the electrical equipment Or there is electronic equipment above-mentioned layered product to be clamped between the electrical equipment or the basket and above-mentioned display member of electronic equipment Structure.
The effect of invention
Layered product of the invention has the hair being made up of the foaming body with specific density, specific mean cell diameter Blister layer and thermal conductivity are heat-conducting layer more than particular value, therefore, even if being 30~200 μm of so thin thickness, impact absorbing Property it is also very excellent, and heat diffusivity is excellent, internal heat can be effectively spread to outside.
Brief description of the drawings
Fig. 1 is the signal pie graph of pendulum type shock machine (impact test apparatus).
Fig. 2 is the figure of the signal composition of the holding member for representing pendulum type shock machine (impact test apparatus).
Fig. 3 is the profile of the method for schematically showing heat diffusivity experiment.
Fig. 4 is the top view (figure viewed from above) of the method for schematically showing heat diffusivity experiment.
Fig. 5 is the constructed profile of that represents layered product of the invention.
Specific embodiment
Layered product of the invention has the foaming body layer and heat-conducting layer being made up of foaming body.Fig. 5 is to represent layer of the invention The constructed profile of of stack.10 is layered product, and 200 is foaming body layer, and 201 is heat-conducting layer.
[foaming body layer]
The thickness of above-mentioned foaming body layer is 30~500 μm, is 0.2~0.7g/cm by density3, mean cell diameter be 10 ~150 μm of foaming body is constituted.It should be noted that in this manual, the density of foaming body refers to " apparent density ".
The lower limit of the thickness of above-mentioned foaming body layer is preferably 40 μm, more preferably 50 μm, the upper limit be preferably 400 μm, it is more excellent Elect 300 μm, more preferably 200 μm as.In the present invention, the thickness of foaming body layer is more than 30 μm, therefore can equably be contained There is bubble, excellent impact absorbency can have been given play to.In addition, the thickness of foaming body layer is less than 500 μm, therefore even for micro- Small gap also can easily follow.
Constitute the lower limit preferably 0.21g/cm of the density of the foaming body of above-mentioned foaming body layer3, more preferably 0.22g/cm3, The upper limit is preferably 0.6g/cm3, more preferably 0.5g/cm3, more preferably 0.4g/cm3.By making the density of foaming body be 0.2g/cm3More than such that it is able to intensity is maintained, by making the density of foaming body be 0.7g/cm3Below such that it is able to given play to Impact absorbency higher.In addition, by making the density of foaming body be 0.2~0.4g/cm3Scope such that it is able to further Impact absorbency higher is given play to.
The lower limit of the mean cell diameter of above-mentioned foaming body is preferably 15 μm, more preferably 20 μm, and the upper limit is preferably 140 μ M, more preferably 130 μm, more preferably 100 μm.By making mean cell diameter for more than 10 μm, so as to can give play to excellent Different impact absorbency.Further, since mean cell diameter is less than 100 μm, therefore compress restorative also excellent.Need explanation , the maximum cell diameter of above-mentioned foaming body is, for example, 40~400 μm, and its lower limit is preferably 60 μm, more preferably 80 μm, on Limit is preferably 300 μm, more preferably 220 μm.In addition, the minimum cell diameter of above-mentioned foaming body is, for example, 5~70 μm, its lower limit Preferably 8 μm, more preferably 10 μm, the upper limit is preferably 60 μm, more preferably 50 μm.
In the present invention, from from the viewpoint of impact absorbency, the thickness (μ of mean cell diameter (μm) and foaming body layer The ratio between m) (the former/the latter) it is preferably in 0.2~0.9 scope.Above-mentioned mean cell diameter (μm) and the thickness (μ of foamed sheet The ratio between m) lower limit is preferably 0.25, more preferably 0.3, and the upper limit is preferably 0.85, more preferably 0.8.
It is preferred that store elastic modulus and damage when angular frequency of the above-mentioned foaming body in Measurement of Dynamic Viscoelasticity is 1rad/s The ratio for consuming elastic modelling quantity is the peak value of loss angle tangent (tan δ) in more than -30 DEG C and less than 30 DEG C of scope.Above-mentioned damage Consume angle tangent peak value exist temperature range lower limit be more preferably -25 DEG C, more preferably -20 DEG C, particularly preferably It it is -10 DEG C, the upper limit is more preferably 20 DEG C, more preferably 10 DEG C.For with more than 2 peak values of loss angle tangent In the case of material, it is desirable to which wherein at least one is fallen into above range.By making peak temperature for more than -30 DEG C, so that can Excellent compression is given play to restorative.In addition, by making peak temperature for less than 30 DEG C, thus can show the soft right property of height and Excellent impact absorbency can have been given play to.
From from the viewpoint of impact absorbency, the loss angle tangent in preferably more than -30 DEG C and less than 30 DEG C of scope The peak strength (maximum) of (tan δ) is high, and for example, more than 0.2, preferably more than 0.3.Above-mentioned peak strength (maximum) Higher limit is, for example, 2.0.
So, the peak temperature of above-mentioned loss angle tangent (tan δ), peak strength largely contribute to foaming body Impact absorbency.If store elastic modulus and loss when angular frequency of the foaming body in Measurement of Dynamic Viscoelasticity is 1rad/s The ratio of elastic modelling quantity is that the peak value of loss angle tangent (tan δ) is present in the scope of more than -30 DEG C and less than 30 DEG C, then foam The impact absorbency of body becomes very high, is still not clear the reasons why on this point, but the frequency phase for being presumably due to and impacting Matchingly there is the reason of the peak value of above-mentioned loss angle tangent (tan δ).That is, can speculate：Above-mentioned loss angle tangent (tan δ) It is more than -30 DEG C and less than 30 DEG C of scope, the temperature-time in determination of viscoelasticity converts regular and is scaled and knot The scope of the suitable frequency of the drop impact of structure thing, therefore, there is above-mentioned damage more than -30 DEG C and in less than 30 DEG C of scope The foaming body of the peak temperature of consumption angle tangent (tan δ), its impact absorbency is uprised.In addition, store elastic modulus are and put on The relative repulsion of the impact energy of foaming body, if store elastic modulus are high, impact of directly rebounding.On the other hand, elasticity is lost Modulus is that the impact energy that will put on foaming body is converted to hot physical property, and loss elastic modulus is higher, then more will impact Energy is converted to heat, therefore absorbs impact, deformation is diminished.Thus it could be speculated that in large quantities by impact be converted to heat and repulsion is small Foaming body, i.e. the ratio of store elastic modulus and loss elastic modulus is the big foaming body of loss angle tangent (tan δ), its punching Hit absorptivity high.
From from the viewpoint of impact absorbency, the initial stage elastic modelling quantity of preferably above-mentioned foaming body is low.The initial stage elastic modelling quantity (under 23 DEG C of environment, in the tension test that draw speed is 300mm/min, the value that slope when being strained by 10% is calculated) is excellent Elect 5N/mm as2Below, it is more preferably 3N/mm2Below.It should be noted that the lower limit of above-mentioned initial stage elastic modelling quantity is, for example, 0.1N/mm2。
Used as the foaming body for constituting above-mentioned foaming body layer, as long as having above-mentioned characteristic, then its composition, bubble structure etc. just do not have Have specifically limited.Can be continuous air bubbles structure, separated foam structure, semicontinuous semi-independent bubble structure as bubble structure In any one.From from the viewpoint of impact absorbency, preferably continuous air bubbles structure, semicontinuous semi-independent bubble structure.
Foaming body layer in layered product of the invention is thin, and with excellent impact absorbency.In addition, be not hit The influence of size, can give play to excellent impact absorbency.
For example, for layered product of the invention, being inhaled pendulum type shock machine, layered product impact has been used In the property received experiment (impact the weight 96g of son, put 30 ° of angle), impact absorbing rate (%) is divided by foaming body defined in following formula Value R (the impact absorbing rate of per unit thickness) obtained by the thickness (μm) of layer is, for example, more than 0.15, is preferably more than 0.17, enters One step is preferably more than 0.19.It should be noted that the higher limit of above-mentioned R is, for example, 0.5 or so.
Impact absorbing rate (%)={ (F0- F1)/F0}×100
(in above formula, F0It is the impulsive force that the impact period of the day from 11 p.m. to 1 a.m is only collided to support plate, F1It is to by support plate and above-mentioned stacking The impulsive force of the impact period of the day from 11 p.m. to 1 a.m is collided on the support plate of the structure that body is constituted)
It should be noted that above-mentioned impact absorbing rate is different because of thickness etc. of foaming body layer, usually 5~70%, lower limit Preferably 7%, the upper limit is preferably 60%.
In layered product of the invention, the impact absorbing rate (%) of the layered product (is impacted the weight 96g of son, has put angle 30 °) it is preferably more than 15%, more preferably more than 17%, more preferably more than 19%.
For the signal of pendulum type shock machine (impact test apparatus) is constituted, said by Fig. 1 and Fig. 2 It is bright.As shown in Figures 1 and 2, impact test apparatus 1 (pendulum test machine 1) include：As keeping with arbitrary confining force experiment The holding member 3 of the maintaining body of piece 2 (foaming body or layered product)；Make the impact load component of the load impact stress of test film 2 4；With the pressure as the impact tension detection mechanism to being detected to the impulsive force that test film 2 is produced based on impact load component 4 Power inductor 5 etc..In addition, keeping the holding member 3 of test film 2 with arbitrary confining force by stationary fixture 11 and pressing fixture 12 constitute, pressing fixture 12 it is opposed with stationary fixture 11, and to clamp to keep test film 2 in the way of and slidably.Additionally, Press pressure governor motion 16 is provided with pressing fixture 12.Additionally, rushing the load of test film 2 kept by holding member 3 The impact load component 4 for hitting power is made up of support rod 23 (axle 23) and arm 21, and one end 22 of support rod 23 is by with relative to pillar 20 modes that can be rotated have impact 24 by e axle supporting and in another side, and arm 21 is lifted son 24 is impacted and remained Predetermined angular.Here, steel ball has been used as impact 24, therefore, by one end of arm, electromagnet 25 is set, so as to Enough integratedly lifting impact 24 is predetermined angular.Additionally, acting on test film 2 produced by impact load component 4 The pressure inductor 5 that impulsive force is detected, is arranged at the opposite surface side of the test film contact surface of stationary fixture 11.
Impact 24 is steel ball (iron ball).In addition, angle (the pendulum angle in Fig. 1 that impact 24 is lifted by arm 21 Degree is a) 30 °~47 ° or so.In embodiment described later, weight 96g in steel ball (iron ball), the condition for having put 30 ° of angle are entered Row is determined.
As shown in Fig. 2 test film 2 (foaming body or layered product) stationary fixture 11 and pressing fixture 12 between across by setting The support plate 28 that the elastic plate high such as lipid sheet material (acrylic board, polycarbonate plate etc.), metal panel is constituted is clamped.
Using above-mentioned impact test apparatus, impulsive force F is obtained0And impulsive force F1, impact absorbing is calculated by above-mentioned formula Property, wherein, impulsive force F0After making stationary fixture 11 and the closely sealed fixation of support plate 28, make impact son 24 impact support plate 28 and Measure, impulsive force F1By inserting test film 2 between stationary fixture 11 and support plate 28 and after making its closely sealed fixation, making impact Son 24 impacts support plate 28 and measures.It should be noted that impact test apparatus are and Japanese Unexamined Patent Publication 2006-47277 publications The identical device of embodiment 1.
The thickness of foaming body layer it is big to a certain degree when, impact absorbency can be by selecting mean cell diameter, density Etc. being adjusted, and in the thickness very hour (such as thickness is 30~500 μm) of foaming body layer, only above-mentioned characteristic is adjusted Save and impact cannot be fully absorbed.Because following reason：When the thickness of foaming body layer is very thin, the bubble in foaming body Ruptured immediately because of impact, the impact buffer function produced by bubble disappears.If as described above, foaming body is surveyed in dynamic viscoelastic The ratio of store elastic modulus and loss elastic modulus when the angular frequency in fixed is 1rad/s is loss angle tangent (tan δ) Peak value is present in the scope of more than -30 DEG C and less than 30 DEG C, even if then after bubbles burst, the constituent material of foaming body is still sent out Shoot the function of being buffered to impact.
Above-mentioned foaming body can be made up of the resin combination comprising resin material (polymer).It should be noted that not sending out The angular frequency of the resin combination [resin combination (solid content) when unexpanded] in Measurement of Dynamic Viscoelasticity of blister state The ratio of store elastic modulus and loss elastic modulus during for 1rad/s is that the peak value of loss angle tangent (tan δ) is preferably located In more than -30 DEG C and less than 30 DEG C of scope.The lower limit of the temperature range existing for the peak value of above-mentioned loss angle tangent is preferred It it is -25 DEG C, more preferably -20 DEG C, more preferably -10 DEG C, the upper limit is preferably 20 DEG C, more preferably 10 DEG C.Have During the material of more than 2 peak values of loss angle tangent, at least one fall within the above-described range preferably wherein.From impact absorbency Viewpoint is set out, preferably the loss angle tangent of the resin combination (solid content) more than -30 DEG C and in less than 30 DEG C of scope (tan δ) peak strength (value equivalent to above-mentioned foaming body -30 DEG C less than the loss angle in the range of 30 DEG C just Cut the density (g/cm of the peak strength divided by foaming body of (tan δ)3) obtained by be worth) it is high.For example, above-mentioned resin combination (solid Thing) peak strength of loss angle tangent (tan δ) more than -30 DEG C and in less than 30 DEG C of scope is preferably 0.9 (g/cm3 )-1Above, the upper limit is, for example, 3 or so.
Additionally, it is desirable to initial stage elastic modelling quantity (23 DEG C, the draw speed of the resin combination (solid content) of unexpanded state It is 300mm/min) low, preferably 50N/mm2Below, it is more preferably 30N/mm2Below.It should be noted that above-mentioned initial stage springform The lower limit of amount is, for example, 0.3N/mm2。
As the resin material (polymer) for constituting above-mentioned foaming body, it is not particularly limited, can be used and constitute foaming body Known or even known resin material.As the resin material, for example, can include acrylic acid series polymeric compounds, rubber, amino first Acid esters based polymer, vinyl-vinyl acetate copolymer etc..Wherein, from from the viewpoint of impact absorbency, preferably propylene Sour based polymer, rubber, carbamate based polymer.The resin material (polymer) for constituting foaming body can be independent a kind, Can also be two or more.
It should be noted that in order that angular frequency of the above-mentioned foaming body in Measurement of Dynamic Viscoelasticity be 1rad/s when storage The ratio of energy elastic modelling quantity and loss elastic modulus is that the peak value of loss angle tangent (tan δ) is more than -30 DEG C and less than 30 DEG C Scope, can be using the Tg of above-mentioned resin material (polymer) as index or target.For example, as the (polymerization of above-mentioned resin material Thing), can from Tg be in -50 DEG C less than 50 DEG C (lower limit be preferably -40 DEG C, more preferably -30 DEG C, the upper limit it is preferred Be 40 DEG C, more preferably 30 DEG C) in the range of resin material (polymer) in selected.
As aforesaid propylene acid based polymer, preferably by monomer and homopolymers that the Tg of homopolymers is more than -10 DEG C Tg less than the acrylic acid series polymeric compounds that -10 DEG C of monomer is formed as necessary monomer component.By using such third Olefin(e) acid based polymer is simultaneously adjusted to the former monomer with the amount ratio of the latter's monomer, so that comparable be readily derived in dynamic The ratio of store elastic modulus and loss elastic modulus when the angular frequency in determination of viscoelasticity is 1rad/s is loss angle tangent The peak value of (tan δ) is the foaming body of more than -30 DEG C and less than 30 DEG C.
It should be noted that " forming the glass transition temperature (Tg) during homopolymers " in the present invention is (sometimes only single to claim It is " Tg of homopolymers ") refer to " glass transition temperature (Tg) of the homopolymers of the monomer ", specifically, in " Polymer Numerical value is enumerated in Handbook " (the 3rd edition, John Wiley＆Sons, Inc, 1987).It should be noted that above-mentioned text The Tg for offering the homopolymers of the monomer do not recorded refers to (with reference to Japanese Unexamined Patent Publication for example by value obtained by following assay method 2007-51271 publications).That is, in the reactor for possessing thermometer, mixer, nitrogen ingress pipe and backflow cooling tube, throw Enter the weight portion of monomer 100,2, the weight portion of 2 '-azodiisobutyronitrile 0.2 and the weight portion of ethyl acetate 200 as polymer solvent, While nitrogen is imported, stir 1 hour.Thus, the oxygen in polymerization system is removed, then heating to 63 DEG C makes its reaction 10 Hour.Then, room temperature is cooled to, the homopolymers solution that solid component concentration is 33 weight % is obtained.Then, it is the homopolymers is molten Liquid cast coat is dried on distance piece, produces the test specimen (homopolymers of sheet) of thickness about 2mm.Then, by this Test specimen is punched into the discoid of diameter 7.9mm, is clamped with parallel-plate, using test for viscoelastic machine (ARES, REOMETRIX company systems), while the shear strain of frequency 1Hz is assigned, temperature province -70~150 DEG C, 5 DEG C/min Programming rate under conditions of, viscoplasticity is determined by shear mode, the peak temperature of tan δ is set to the Tg of homopolymers.Need It is noted that the Tg of above-mentioned resin material (polymer) can be also measured by the method.
For the monomer that the Tg of homopolymers is more than -10 DEG C, the Tg is, for example, -10 DEG C~250 DEG C, is preferably 10 ~230 DEG C, more preferably 50~200 DEG C.
As the monomer that the Tg of above-mentioned homopolymers is more than -10 DEG C, can exemplify for example：(methyl) acrylonitrile；(methyl) The monomer of the amide-containings such as acrylamide, N- ethoxys (methyl) acrylamide；(methyl) acrylic acid；Methyl methacrylate, The Tg of the homopolymers such as EMA is more than -10 DEG C (methyl) alkyl acrylate；(methyl) isobomyl acrylate Ester；The vinyl monomer containing heterocycle such as NVP；The hydroxyls such as HEMA Monomer etc..They can be used alone or are applied in combination two or more.Wherein, particularly preferably (methyl) acrylonitrile is (especially It is acrylonitrile).If using (methyl) acrylonitrile (especially acrylonitrile) as the monomer that the Tg of homopolymers is more than -10 DEG C, Intermolecular interaction is strong, and the peak strength therefore, it is possible to make the above-mentioned loss angle tangent (tan δ) of foaming body becomes big.
For the Tg of homopolymers is less than -10 DEG C of monomer, the Tg be, for example, -70 DEG C less than -10 DEG C, Preferably -70 DEG C~-12 DEG C, more preferably -65 DEG C~-15 DEG C.
As the Tg of above-mentioned homopolymers less than -10 DEG C of monomer, can include for example ethyl acrylate, butyl acrylate, (methyl) alkyl acrylates of the Tg of the homopolymers such as 2-EHA less than -10 DEG C etc..They can individually make With a kind, or it is applied in combination two or more.Wherein, particularly preferably acrylic acid C2-8Arrcostab.
Relative to the whole monomer component (monomer component total amount) for forming aforesaid propylene acid based polymer, the Tg of homopolymers For the content of more than -10 DEG C of monomer be, for example, 2~30 weight %, lower limit be preferably 3 weight %, more preferably 4 weight %, The upper limit is preferably 25 weight %, more preferably 20 weight %.In addition, whole relative to formation aforesaid propylene acid based polymer Monomer component (monomer component total amount), the content of the monomer of the Tg of homopolymers less than -10 DEG C be, for example, 70~98 weight %, under Limit is preferably 75 weight %, more preferably 80 weight %, the upper limit and is preferably 97 weight %, more preferably 96 weight %.
Can be any one in natural rubber, synthetic rubber as above-mentioned rubber.As above-mentioned rubber, for example, can arrange Enumerate nitrile rubber (NBR), methyl methacrylate butadiene rubber (MBR), SBR styrene butadiene rubberses (SBR), third Olefin(e) acid class rubber (ACM, ANM), urethane rubber (AU), silicone rubber etc..Wherein, preferably nitrile rubber (NBR), first Base methylacrylate-butadiene rubber (MBR), silicone rubber.
As above-mentioned carbamate based polymer, can for example include polycarbonate-based polyurethane, Polyester polyurethane, Polyethers system polyurethane etc..
As vinyl-vinyl acetate copolymer, known or even known ethylene-vinyl acetate c can be used Thing.
The foaming body of above-mentioned foaming body layer is constituted in addition to resin material (polymer), can also be contained as needed Surfactant, crosslinking agent, thickener, antirust agent, other additives.
For example for the stability of the bubble after miniaturization, the foaming of bubble diameter, arbitrary surfactant can be contained. As surfactant, be not particularly limited, can be used anion system surfactant, cation system surfactant, it is non-from Any one in subsystem surfactant, amphoteric surfactant etc., the stabilization of the bubble after miniaturization, foaming from bubble diameter Property from the viewpoint of, preferably anion system surfactant, especially more preferably the aliphatic acid ammonium system such as ammonium stearate surface is lived Property agent.Surfactant can be used singly or in combination of two or more.Furthermore it is possible to simultaneously with different types of , for example, can be used in combination for anion system surfactant and nonionic surfactants by surfactant, by anion system table Face activating agent is used in combination with amphoteric surfactant.
The addition [solid constituent (nonvolatile component)] of surfactant for example relative to resin material (polymer) [Gu Body composition (nonvolatile component)] 100 weight portions are that 0~10 weight portion, lower limit are preferably 0.5 weight portion, the upper limit and are preferably 8 weight Part.
In addition, intensity, heat resistance, moisture-proof in order to improve foaming body, can contain arbitrary crosslinking agent.Crosslinking agent does not have Have specifically limited, it is possible to use oil-soluble, water solubility in any one.As crosslinking agent, for example, can include epoxy, oxazoles Quinoline system, isocyanates system, carbodiimide system, melamine series, metal oxide system etc..Wherein, You Xuan Wei oxazolines system crosslinking Agent.
The addition [solid constituent (nonvolatile component)] of crosslinking agent for example relative to resin material (polymer) [solid into Point (nonvolatile component)] 100 weight portions are that 0~10 weight portion, lower limit are preferably 0.01 weight portion, the upper limit and are preferably 9 weight portions.
Additionally, stability, film forming in order to improve the bubble after foaming, can contain arbitrary thickener.As thickening Agent, is not particularly limited, and can include acrylic acid series, carbamate system, polyethenol series etc..Wherein, preferably polypropylene Acid is thickener.
The addition [solid constituent (nonvolatile component)] of thickener for example relative to resin material (polymer) [solid into Point (nonvolatile component)] 100 weight portions are that 0~10 weight portion, lower limit are preferably 0.1 weight portion, the upper limit and are preferably 5 weight portions.
In addition, in order to prevent the corrosion with the hardware of foaming body adjoining, arbitrary antirust agent can be contained.As this Antirust agent, preferably containing the compound of azoles ring.If using the compound containing azoles ring, can take into account at a high level for metal Anticorrosive property and the adaptation with adherend.
As the above-mentioned compound containing azoles ring, as long as ring be contained within more than one nitrogen-atoms with pentacyclicization Compound, for example, can include with diazole (imidazoles, pyrazoles) ring, triazole ring, tetrazole ring, oxazole ring, isoxazole rings, thiazole Compound of ring or isothiazole ring etc..These rings can occur condensation and form condensed ring with the aromatic rings such as phenyl ring.As above-mentioned Compound with condensed ring, can include for example has benzimidazole ring, benzopyrazoles ring, BTA ring, benzoxazole Compound of ring, benzoisoxazole ring, benzothiazole ring or benzisothiazole ring etc..
Above-mentioned azoles ring, above-mentioned condensed ring (BTA ring, benzothiazole ring etc.) can each have substitution base.As this Substitution base, for example, can include the carbon numbers such as methyl, ethyl, propyl group, isopropyl, butyl 1~6 (preferably carbon number 1~3) Alkyl；The alcoxyl of the carbon numbers such as methoxyl group, ethyoxyl, isopropoxy, butoxy 1~12 (preferably carbon number 1~3) Base；The aryl of the carbon numbers such as phenyl, tolyl, naphthyl 6~10；Amino；Methylamino, dimethylamino etc. (list or two) C1-10Alkyl amino；Amino-the C such as amino methyl, 2- amino-ethyls1-6Alkyl；N, N- diethylamino methyl, N, N- are double The list such as (2- ethylhexyls) amino methyl or two (C1-10Alkyl) amino-C1-6Alkyl；Sulfydryl；Methoxycarbonyl group, carbethoxyl group etc. The alkoxy carbonyl group of carbon number 1~6；Carboxyl；The carboxyl such as carboxymethyl-C1-6Alkyl；Carboxyl-the C such as 2- carboxyethyl sulfenyls1-6Alkane Sulfenyl；Double (hydroxyl-the C of the N such as double (methylol) amino methyls of N, N-, N-1-4Alkyl) amino-C1-4Alkyl；Sulfo group etc..Separately Outward, the above-mentioned compound containing azoles ring can form the salt such as sodium salt, sylvite.
From the anti-rust action aspect to metal, the preferably aromatic rings such as azoles ring and phenyl ring forms the chemical combination of condensed ring Thing, wherein, particularly preferably the BTA based compound compound of BTA ring (have), benzothiazole based compound (there is the compound of benzothiazole ring).
As above-mentioned BTA based compound, for example, can include 1,2,3- BTAs, methylbenzotrazole, carboxylic Base BTA, carboxymethyl BTA, 1- [double (2- ethylhexyls) amino methyls of N, N-] BTA, 1- [N, N- Double (2- ethylhexyls) amino methyls] methylbenzotrazole, 2,2 '-[[(methyl isophthalic acid H- BTA -1- bases) methyl] Imino group] di-methylcarbinol or their sodium salt etc..
As above-mentioned benzothiazole based compound, such as 2-mercaptobenzothiazole, 3- (2- (benzothiazoles can be included Base) thio) propionic acid or their sodium salt etc..
Compound containing azoles ring can be used singly, or in combination of two or more kinds.
Addition [the solid constituent of antirust agent (such as the above-mentioned compound containing azoles ring) [solid constituent (nonvolatile component)] (nonvolatile component)] if do not destroy with the range of adaptation, the foaming body of adherend characteristic in itself, such as phase For resin material (polymer) [solid constituent (nonvolatile component)] 100 weight portions, such as preferably 0.2~5 weight portion.Its Lower limit is more preferably 0.3 weight portion, more preferably 0.4 weight portion, its upper limit and is more preferably 3 weight portions, further preferably It is 2 weight portions.
In addition, not destroying in the range of impact absorbency, any appropriate other compositions can be contained.It is such other Composition can only contain a kind, it is also possible to contain two or more.As the other compositions, for example, can include polymerization other than the above It is thing composition, softening agent, antioxidant, age resistor, gelating agent, curing agent, plasticizer, filler, reinforcing agent, foaming agent, fire-retardant Agent, light stabilizer, ultra-violet absorber, colouring agent (pigment, dyestuff etc.), pH adjusting agent, solvent (organic solvent), thermal polymerization are drawn Hair agent, Photoepolymerizationinitiater initiater etc..
As above-mentioned filler, for example, can include silica, clay (mica, talcum, terre verte etc.), aluminum oxide, two Titanium oxide, zinc oxide, tin oxide, zeolite, graphite, CNT, inorfil (carbon fiber, glass fibre etc.), organic fiber, Metal powder (silver, copper etc.) etc..In addition, as filler, can also add piezoelectric particles (titanium oxide etc.), electroconductive particle, heat conduction Property particle (boron nitride etc.), organic filler (silicone powder etc.) etc..
Foaming body layer in layered product of the invention can be by by comprising the resin material (polymer) for constituting foaming body Resin combination carry out foaming and molding and manufacture.As foaming method (forming method of bubble), can be using physical method, change Commonly used approach in the foaming and moldings such as method.In general, physical method is to disperse the gas componants such as air, nitrogen In polymer solution, and the method that bubble is formed by mechanical mixture.In addition, chemical method is by because being added to polymer The thermal decomposition of the foaming agent in matrix and the gas that produces form abscess, the method so as to obtain foaming body.From environmental problem Set out etc. viewpoint, preferably physical method.The bubble formed by physical method is generally continuous air bubbles.
As the resin combination comprising the resin material (polymer) for foaming and molding, it is possible to use make resin material Resin solution obtained by dissolving in a solvent, from from the viewpoint of bubble, preferably uses the emulsion comprising resin material.As , can be used in mixed way for emulsion of more than two kinds by emulsion.
From from the viewpoint of film forming, the solid component concentration of preferred emulsion is high.The solid component concentration of emulsion is preferably More than 30 weight %, more preferably more than 40 weight %, more preferably more than 50 weight %.
In the present invention, it is preferred to for via the operation (operation A) for making emulsion resin composition mechanically foam and bubbling Method to make foaming body.As sparger, it is not particularly limited, for example, can includes high speed shear mode, vibration side The devices such as formula, the spray mode of gas-pressurized.Wherein, from bubble diameter from the viewpoint of miniaturization, Large Copacity make, preferably It is high speed shear mode.
Bubble when being bubbled by mechanical agitation is the bubble that gas (gas) is entered into emulsion.As gas, As long as being inactive relative to emulsion, just it is not particularly limited, air, nitrogen, carbon dioxide etc. can be included.Wherein, from From the viewpoint of economy, preferably air.
It is coated on base material and carries out dry work via by the emulsion resin composition that alveolation is played using the above method Sequence (process B), such that it is able to obtain above-mentioned foaming body layer.As above-mentioned base material, it is not particularly limited, can includes for example through stripping Plastic foil (polyethylene terephthalate film after release-treated etc.) after treatment, plastic foil (poly terephthalic acid Glycol ester film etc.), heat-conducting layer (heat-conducting layer described later) etc..When heat-conducting layer is coated as base material, foaming can be improved Body layer and the adaptation of heat-conducting layer, in addition, can also improve the efficiency of drying process when making foaming body layer.
In above-mentioned operation B, as coating method, drying means, general method can be used.Process B is preferably included：Will The emulsion resin composition of the bubbles being coated on base material 50 DEG C less than 125 DEG C at a temperature of be dried it is pre- Standby drying process B1 and after preparation drying process B1 further more than 125 DEG C and less than the 200 DEG C trunks being dried Drying process B2.
By setting preparation drying process B1 and trunk drying process B2 such that it is able to prevent temperature drastically from rising and cause The rupture of the mergingization, bubble of bubble.For especially for the small foaming body layer of thickness, cause because of steeply rising for temperature Bubble merges or ruptures, therefore, the significant of preparation drying process B1 is set.Temperature in preparation drying process B1 is preferably More than 50 DEG C and less than 100 DEG C.The time of preparation drying process B1 is, for example, 0.5 minute~30 minutes, is preferably 1 minute~15 Minute.In addition, the temperature in trunk drying process B2 be preferably more than 130 DEG C and less than 180 DEG C, more preferably more than 130 DEG C and Less than 160 DEG C.The time of trunk drying process B2 is, for example, 0.5 minute~30 minutes, is preferably 1 minute~15 minutes.
For mean cell diameter, maximum cell diameter and minimum cell diameter for foaming body, can be by adjusting table Mixing speed and mixing time when the species of face activating agent and amount, adjustment mechanical agitation and obtain the flat of 10~150 μ ms The foaming body of equal cell diameters.
For the density of foaming body, can be by adjusting the gas entered in emulsion resin composition during mechanical agitation (gas) component amount and obtain 0.2~0.7g/cm3Density foaming body.
It is preferred that at least one mask toughness of foaming body layer.In the case where the surface of foaming body layer has viscosity, i.e., Make to be not provided with adhesive phase between foaming body layer and heat-conducting layer, can also obtain layered product of the invention.As to foaming body layer Surface assign viscosity method, for example following methods can be included：Relative to the resin material for constituting above-mentioned foaming body Whole monomer components (monomer component total amount) of (polymer such as acrylic acid series polymeric compounds), -10 DEG C are less than using the Tg of homopolymers (for example, -70 DEG C less than -10 DEG C, preferably -70 DEG C~-12 DEG C, further preferably -65 DEG C~-15 DEG C) Monomer such as 70~98 weight % (lower limit is preferably 75 weight %, the upper limit and is preferably 97 weight %), it is above-mentioned as constituting The monomer of the resin material (polymer) of foaming body, and the method that suitably selection other monomers are used.
For layered product obtained by having sticking foaming body layer and heat-conducting layer and being directly laminated, even if being not provided with gluing Connecing layer two-layer will not also peel off, and can obtain bonding reliability high.Further, since adhesive linkage can be not provided with, therefore, it can by The caliper portion of adhesive linkage is used to thicken the thickness of heat-conducting layer, can improve the thermal conductivity of the layered product.In addition, stacking can be made The thickness of body diminishes, and can aid in the further slimming as the electrical equipment or electronic equipment of mounting object etc..Separately Outward, it is possible to increase the manufacture efficiency of the layered product, cost can also be cut down.
[heat-conducting layer]
In the present invention, the thermal conductivity of above-mentioned heat-conducting layer is more than 200W/mK.Above-mentioned thermal conductivity is to utilize conventional method The value for measuring.The thermal conductivity of heat-conducting layer is preferably more than 300W/mK, more preferably more than 400W/mK.By making heat-conducting layer Thermal conductivity be more than 200W/mK, so as to excellent heat diffusivity (thermal diffusivity) can have been given play to.The practical upper limit example of thermal conductivity Such as it is 1500W/mK.It should be noted that heat-conducting layer can be laminated more than 2 layers.
The thickness of heat-conducting layer can be adjusted to any thickness according to purpose.The thickness of heat-conducting layer be preferably more than 5 μm, more preferably It is more than 7 μm.The upper limit of the thickness of heat-conducting layer is, for example, 130 μm, is preferably 120 μm, is more preferably 110 μm.
As heat-conducting layer, graphite flake, metal foil can be included.As the material of metal foil, can include for example aluminium, gold, Silver, copper etc..As metal foil, can include with far infrared reflectivity higher and the cheap aluminium foil of process costs, Copper Foil Deng.
Copper Foil has rolled copper foil, electrolytic copper foil etc..In the case where heat-conducting layer is rolled copper foil, there is light in the table of Copper Foil Damp face and mat surface.In the case where glassy surface is for example laminated foaming body layer by being coated with, when roll is coiled into, even if not having Have protection interval part (カ バ ー セ パ レ ー タ), it is also possible to prevent from batching dislocation.On the other hand, in mat surface for example by applying In the case that cloth is to be laminated foaming body layer, foaming body layer can be made to be improved with the adaptation of heat-conducting layer.
It should be noted that as described above, heat-conducting layer can be laminated more than 2 layers, if for example by graphite flake with it is metal foil laminated, Then heat diffusivity is improved because of the anisotropy of graphite flake.In addition, the conductive heat-conducting layer such as metal foil also has conduct The function of electromagnetic wave barrier layer.
Method as above-mentioned heat-conducting layer and the layered product of foaming body layer is obtained, can include：Foamed sheet transfer is (viscous Patch) in the method for heat-conducting layer；The above-mentioned emulsion resin combination for playing alveolation is coated into heat-conducting layer and is dried and is formed hair Steep method of lamella etc..For the layered product made by the method as the latter, with the layer made by the method by the former Stack is compared, and shows bonding force higher.
[adhesive phase]
In layered product of the invention, above-mentioned foaming body layer and heat-conducting layer can be across adhesive phase (adhesive layer) and tegillums It is folded.As the adhesive for constituting adhesive phase, it is not particularly limited, can is such as acrylic adhesive, rubber series bonding Any one in agent, silicone-based adhesive etc..It should be noted that as it was previously stated, sticking in the surface tool of foaming body layer In the case of, even if being not provided with adhesive phase, also can be well laminated with heat-conducting layer adherence.
The thickness of above-mentioned adhesive phase is, for example, 4~100 μm, and its lower limit is preferably 5 μm, and its upper limit is preferably 50 μm.
As the example that the layer of layered product of the invention is constituted, can include for example：Heat-conducting layer/foaming body layer, heat-conducting layer/ Adhesive phase/foaming body layer, foaming body layer/heat-conducting layer/foaming body layer, foaming body layer/adhesive phase/heat-conducting layer/adhesive phase/ Foaming body layer, heat-conducting layer/foaming body layer/heat-conducting layer, heat-conducting layer/adhesive phase/foaming body layer/adhesive phase/heat-conducting layer etc..
In addition, layered product of the invention can be with other functional layers (such as electromagnetic wave barrier layer, electromagnetic wave absorbing layer etc.) It is laminated.
Layered product of the invention can commercially be circulated in the form of being wound into the coiling body of roll (roll).
The thickness of layered product of the invention is although small, but impact absorbency and heat diffusivity (thermal diffusivity) are excellent.Therefore, example Such as in electrical equipment or electronic equipment, (placement) is installed in regulation as by various components or part (such as optical component etc.) The electrical equipment or electronic device member used during position (such as basket etc.) are useful, especially as thermal diffusion punching It is useful to hit absorbing sheet.
As the optical component that (placement) can be installed using layered product of the invention (sheet layered product), can enumerate Go out for example：The image installed in the image display devices such as liquid crystal display, electroluminescent display, plasma scope shows Show component (especially compact image display member)；It is installed on so-called " mobile phone ", " smart mobile phone ", " mobile information end The display members such as the touch panels of the device of mobile communicating such as end "；Camera, lens (especially minicam or lens) Deng.
Electric/electronic of the invention has used the layered product of the invention described above.With regard to such electric/electronic Speech, e.g. possesses the electric/electronic of display member, including be clamped in this with above-mentioned layered product (sheet layered product) The electrical equipment or electronic equipment of the structure between electrical equipment or the basket and above-mentioned display member of electronic equipment.As the electricity The sub- equipment of gas-to-electric, for example, can include the moving body such as so-called " mobile phone ", " smart mobile phone ", " portable information terminal " and lead to Device of letter etc..
【Embodiment】
Embodiment is exemplified below to illustrate the present invention in further detail, but the present invention is not by any of embodiment Limitation.It should be noted that unless otherwise specified, " % " for representing content refers to weight %.It should be noted that coordinating Number (weight portion) is the value of solid constituent (nonvolatile component) conversion.
Embodiment 1
Using disperser (" RoboMix " PRIMIX company systems) to acrylic emulsions solution (solid constituent amount 55%, third (weight compares 45 to olefin(e) acid ethylacrylate-acrylic acid butyl ester-acrylonitrile copolymer：48：7)) 100 weight portions, aliphatic acid ammonium system surface are lived Property agent (aqueous dispersions of ammonium stearate, solid constituent amount 33%) (surfactant A) 3 weight portion, oxazolines system crosslinking agent (" EPOCROS WS-500 " Japan catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate-acrylic acid copolymer (the weight % of acrylic acid 20), solid constituent amount 28.7%) 0.78 weight portion is stirred Mixing, makes it play alveolation.By the composition, foam coat it is release-treated after PET (polyethylene terephthalate) film It is (thick：38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system) on, in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of 4.5 points of dryings Clock, obtains thickness 120 μm, density 0.31g/cm3, 57 μm of mean cell diameter continuous air bubbles structure foaming body (foamed sheet).
Thick 12 μm Copper Foil is folded as heat-conducting layer in a surface layer of above-mentioned foamed sheet, is obtained comprising Copper Foil/foaming body layer Layered product.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 2
Using disperser (" RoboMix " PRIMIX company systems) to acrylic emulsions solution (solid constituent amount 55%, third (weight compares 45 to olefin(e) acid ethylacrylate-acrylic acid butyl ester-acrylonitrile copolymer：48：7)) 100 weight portions, aliphatic acid ammonium system surface are lived Weight portion, oxazolines system crosslinking agent (" the EPOCROS WS- of property agent (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate- Acrylic copolymer (the weight % of acrylic acid 20), solid constituent amount 28.7%) 0.78 weight portion is stirred mixing, it is bubbled Change.By the composition, foam coat it is release-treated after PET (polyethylene terephthalate) film it is (thick：38 μm, commodity Name " MRF#38 " Mitsubishi Resins Corporation system) on, in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 150 μ M, density 0.31g/cm3, 57 μm of mean cell diameter continuous air bubbles structure foaming body (foamed sheet).
Thick 12 μm Copper Foil is folded as heat-conducting layer in a surface layer of above-mentioned foamed sheet, is obtained comprising Copper Foil/foaming body layer Layered product.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 3
Using disperser (" RoboMix " PRIMIX company systems) to acrylic emulsions solution (solid constituent amount 55%, third (weight compares 45 to olefin(e) acid ethylacrylate-acrylic acid butyl ester-acrylonitrile copolymer：48：7)) 100 weight portions, aliphatic acid ammonium system surface are lived Weight portion, oxazolines system crosslinking agent (" the EPOCROS WS- of property agent (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate- Acrylic copolymer (the weight % of acrylic acid 20), solid constituent amount 28.7%) 0.78 weight portion is stirred mixing, it is bubbled Change.By the composition, foam coat it is release-treated after PET (polyethylene terephthalate) film it is (thick：38 μm, commodity Name " MRF#38 " Mitsubishi Resins Corporation system) on, in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 90 μ M, density 0.39g/cm3, 56 μm of mean cell diameter continuous air bubbles structure foaming body (foamed sheet).
In a face of above-mentioned foamed sheet formed acrylic adhesive layer (day east electrician company system double-faced adhesive tape It is (trade name " No.5603 "), thick 30 μm), in thick 35 μm Copper Foil is laminated on the adhesive phase as heat-conducting layer, obtain comprising copper The layered product of paper tinsel/adhesive phase/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 4
Using disperser (" RoboMix " PRIMIX company systems) to acrylic emulsions solution (solid constituent amount 55%, third (weight compares 45 to olefin(e) acid ethylacrylate-acrylic acid butyl ester-acrylonitrile copolymer：48：7)) 100 weight portions, aliphatic acid ammonium system surface are lived Weight portion, oxazolines system crosslinking agent (" the EPOCROS WS- of property agent (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate- Acrylic copolymer (the weight % of acrylic acid 20), solid constituent amount 28.7%) 0.78 weight portion is stirred mixing, it is bubbled Change.By the composition, foam coat it is release-treated after PET (polyethylene terephthalate) film it is (thick：38 μm, commodity Name " MRF#38 " Mitsubishi Resins Corporation system) on, in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 120 μ M, density 0.31g/cm3, maximum 94 μm of cell diameter, minimum 30 μm of cell diameter, the continuous air bubbles of 57 μm of mean cell diameter The foaming body (foamed sheet) of structure.
Thick 35 μm Copper Foil is folded as heat-conducting layer in a surface layer of above-mentioned foamed sheet, is obtained comprising Copper Foil/foaming body layer Layered product.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 5
Using disperser (" RoboMix " PRIMIX company systems) to acrylic emulsions solution (solid constituent amount 55%, third (weight compares 45 to olefin(e) acid ethylacrylate-acrylic acid butyl ester-acrylonitrile copolymer：48：7)) 100 weight portions, aliphatic acid ammonium system surface are lived Weight portion, oxazolines system crosslinking agent (" the EPOCROS WS- of property agent (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate- Acrylic copolymer (the weight % of acrylic acid 20), solid constituent amount 28.7%) 0.78 weight portion is stirred mixing, it is bubbled Change.By the composition, foam coat it is release-treated after PET (polyethylene terephthalate) film it is (thick：38 μm, commodity Name " MRF#38 " Mitsubishi Resins Corporation system) on, in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 120 μ M, density 0.31g/cm3, 57 μm of mean cell diameter continuous air bubbles structure foaming body (foamed sheet).
In a face of above-mentioned foamed sheet formed acrylic adhesive layer (day east electrician company system double-faced adhesive tape It is (trade name " No.5603 "), thick 30 μm), in thick 12 μm Copper Foil is laminated on the adhesive phase as heat-conducting layer, obtain comprising copper The layered product of paper tinsel/adhesive phase/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 6
Using disperser (" RoboMix " PRIMIX company systems) to acrylic emulsions solution (" LX-852B " Japan ZEON company systems, solid constituent amount 45%) 100 weight portions, aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, Solid constituent 33%) 3.7 weight portions, the polyacrylic thickener (copolymer (weight of acrylic acid 20 of ethyl acrylate-acrylic acid Amount %), solid constituent 28.7%) 0.96 weight portion is stirred mixing, it is played alveolation.By the composition, foam coat through PET (polyethylene terephthalate) film after lift-off processing is (thick：38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system) On, in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thickness 150 μm, density 0.37g/cm3, Average Cell The foaming body (foamed sheet) of the continuous air bubbles structure of 43 μm of diameter.
Thick 12 μm Copper Foil is folded as heat-conducting layer in a surface layer of above-mentioned foamed sheet, is obtained comprising Copper Foil/foaming body layer Layered product.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Comparative example 1
Using JSW (JSW) company system twin shaft kneading machine in 200 DEG C temperature to polypropylene [melt flows speed Rate (MFR)：0.35g/10min]：45 weight portions, polyolefin elastomer and softening agent (paraffin series filling is oily (extension oil)) Mixture (MFR (230 DEG C)：6g/10 minutes, JIS A hardness：79 °, relative to the mass parts of polyolefin elastomer 100 coordinate it is soft The mass parts of agent 30)：55 weight portions, magnesium hydroxide：10 weight portions, carbon (trade name " rising sun #35 " ASAHI CARBON Co., Ltd. System)：10 weight portions, glyceryl monostearate：1 weight portion and fatty acid amide (laurate bisamide)：1.5 weight portions are carried out After mixing, wire harness shape is extruded into, water-cooled postforming is graininess.The single shaft that the particle puts into JSW's company system is squeezed Go out machine, in injecting carbon dioxide under 220 DEG C of atmosphere and under the pressure of 13 (12 after injection) MPa.Carbon dioxide is pressed Take a picture and injected for the ratio that particle total amount is 5.6 weight %.After making the abundant saturation of carbon dioxide, it is cooled to and is suitable to foaming Temperature, be then extruded into cylindrical shape using mould, be passed to heart axle (the マ Application cooled down to the inner surface of foaming body De リ Le) and the foaming body that is cooled down of outer surface of cylindric foaming body to being extruded from the annular die of extruder it is cold But between air-flow, by some cut-outs of diameter, launch slabbing, obtain strip foaming body former material.Foamed for the strip For body former material, mean cell diameter is 55 μm, apparent density is 0.041g/cm3。
The strip foaming body former material is cut into the width (slit processing) of regulation, (the section life of serial section device is used Producing line), the low ratio foamed layer on surface is peeled off one by one for each face, obtain foamed resin (thick 0.30mm, width 550mm).
Make above-mentioned foamed resin by the temperature of heat generating roller will be induced to be set to 160 DEG C, gap is set into 0.20mm's In above-mentioned apparatus for continuous treatment, melt process is carried out to one side using heat, carry out slice processing, then batched, rolled up Around body.It should be noted that traction (draw I and take り) speed is set into 20m/min.
Then, by above-mentioned coiling body uncoiling, it is passed to induce the temperature of heat generating roller to be set to 160 DEG C, be set to gap In the above-mentioned apparatus for continuous treatment of 0.10mm, the face (untreated face) for not carrying out melt process is carried out at melting using heat thus Reason, carries out slice processing, is then batched, and obtains the two-sided foamed resin piece processed through heat fusing.It should be noted that Hauling speed is set to 20m/min.
In a face of above-mentioned foaming body piece formed acrylic adhesive layer (day east electrician company system double-faced adhesive tape It is (trade name " No.5603 "), thick 30 μm), in thick 12 μm Copper Foil is laminated on the adhesive phase as heat-conducting layer, obtain comprising copper The layered product of paper tinsel/adhesive phase/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Comparative example 2
Using JSW (JSW) company system twin shaft kneading machine in 200 DEG C temperature to polypropylene [melt flows speed Rate (MFR)：0.35g/10min]：The mixture of 45 weight portions, polyolefin elastomer and softening agent (paraffin series filling oil) (MFR(230℃)：6g/10 minutes, JIS A hardness：79 °, relative to the mass parts of polyolefin elastomer 100 coordinate softening agent 30 Mass parts)：55 weight portions, magnesium hydroxide：10 weight portions, carbon (trade name " rising sun #35 " ASAHI CARBON Co. Ltd. systems)：10 Weight portion, glyceryl monostearate：1 weight portion and fatty acid amide (laurate bisamide)：After 1.5 weight portions are kneaded, Wire harness shape is extruded into, water-cooled postforming is graininess.During the particle put into the single axle extruding machine of JSW's company system, In injecting carbon dioxide under 220 DEG C of atmosphere and under the pressure of 13 (12 after injection) MPa.Carbon dioxide is according to relative In the ratio injection that particle total amount is 5.6 weight %.After making the abundant saturation of carbon dioxide, the temperature for being suitable to foaming is cooled to Degree, is then extruded into cylindrical shape using mould, is passed to the heart axle that is cooled down to the inner surface of foaming body and to from squeezing Between the foaming body cooling air-flow that is cooled down of outer surface of the cylindric foaming body for going out the annular die extrusion of machine, will The a part of cut-out of diameter, launches slabbing, obtains strip foaming body former material.For the strip foaming body former material, averagely Cell diameter is 55 μm, apparent density is 0.041g/cm3。
The strip foaming body former material is cut into the width (slice processing) of regulation, (the section life of serial section device is used Producing line), the low ratio foamed layer on surface is peeled off one by one for each face, obtain foamed resin (thick 0.30mm, width 550mm).
Make above-mentioned foamed resin by the temperature of heat generating roller will be induced to be set to 160 DEG C, gap is set to the upper of 0.20mm State in apparatus for continuous treatment, carrying out melting to one side using heat dissolves treatment, carries out slice processing, is then batched, and obtains Coiling body.It should be noted that hauling speed is set into 20m/min.
Then, by above-mentioned coiling body uncoiling, it is passed to induce the temperature of heat generating roller to be set to 160 DEG C, be set to gap In the above-mentioned apparatus for continuous treatment of 0.10mm, melt process is carried out to the face (untreated face) for not carrying out melt process using heat, Slice processing is carried out, is then batched, obtain the two-sided foamed resin piece processed through heat fusing.It should be noted that will Hauling speed is set to 20m/min.
The surface layer wished in above-mentioned foaming body piece folds thick 12 μm Copper Foil as heat-conducting layer.But, due to Copper Foil with Foaming body layer is not closely sealed and peel off immediately, therefore cannot carry out impact absorbency experiment.The thermal conductivity of above-mentioned Copper Foil is 400W/m·K。
Comparative example 3
Using disperser (" RoboMix " PRIMIX company systems) to acrylic emulsions solution (solid constituent amount 55%, third (weight compares 45 to olefin(e) acid ethylacrylate-acrylic acid butyl ester-acrylonitrile copolymer：48：7)) 100 weight portions, aliphatic acid ammonium system surface are lived Weight portion, oxazolines system crosslinking agent (" the EPOCROS WS- of property agent (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate- Acrylic copolymer (the weight % of acrylic acid 20), solid constituent amount 28.7%) 0.78 weight portion is stirred mixing, it is bubbled Change.By the foaming body coat it is release-treated after PET (polyethylene terephthalate) film it is (thick：38 μm, trade name Resins Corporation of " MRF#38 " Mitsubishi system) on, in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain it is thick 120 μm, Density 0.31g/cm3, 57 μm of mean cell diameter continuous air bubbles structure foaming body (foamed sheet).
The non-laminated copper foil on above-mentioned foamed sheet.
Comparative example 4
Using disperser (" RoboMix " PRIMIX company systems) to acrylic emulsions solution (solid constituent amount 60%, third E pioic acid methyl ester-Methyl Methacrylate-acrylonitrile Copolymer (the weight % of acrylonitrile 5)) 100 weight portions, aliphatic acid ammonium system table Face activating agent (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 2.8 weight portions, polyacrylic thickener (acrylic acid Ethylacrylate-acrylic acid copolymer (the weight % of acrylic acid 20), solid constituent amount 28.7%) 0.48 weight portion is stirred mixing, makes It plays alveolation.By the composition, foam coat it is release-treated after PET (polyethylene terephthalate) film it is (thick：38μ M, Resins Corporation of trade name " MRF#38 " Mitsubishi system) on, in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain Thickness 150 μm, density 0.45g/cm3, 69 μm of mean cell diameter continuous air bubbles structure foaming body (foamed sheet).
The surface layer wished in above-mentioned foamed sheet folds thick 12 μm Copper Foil as heat-conducting layer.But, due to Copper Foil and hair Blister layer does not have closely sealed and peels off immediately, therefore cannot carry out impact absorbency experiment.The thermal conductivity of above-mentioned Copper Foil is 400W/m·K。
Embodiment 7
Using disperser (" RoboMix " PRIMIX company systems) to acrylic emulsions solution (solid constituent amount 55%, third (weight compares 45 to olefin(e) acid ethylacrylate-acrylic acid butyl ester-acrylonitrile copolymer：48：7)) 100 weight portions, aliphatic acid ammonium system surface are lived Property agent (aqueous dispersions of ammonium stearate, solid constituent amount 33%) (surfactant A) 1.5 weight portion, carboxy betaine type two Property surfactant (" Amogen CB-H ", the first industrial pharmaceutical company system) (surfactant B) 1 weight portion, oxazolines system Crosslinking agent (" EPOCROS WS-500 " Japan catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic Thickener (ethyl acrylate-acrylic acid copolymer (the weight % of acrylic acid 20), solid constituent amount 28.7%) 0.78 weight portion, Enumerate BTA system antirust agent " SEETEC BT-NA ", SHIPRO chemical conversions company system) 0.5 weight portion is stirred mixing, plays it Alveolation.By the composition, foam coat it is release-treated after PET (polyethylene terephthalate) film it is (thick：38 μm, business Resins Corporation of the name of an article " MRF#38 " Mitsubishi system) on, in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thickness 130 μm, density 0.33g/cm3, maximum 110 μm of cell diameter, minimum 20 μm of cell diameter, 45 μm of mean cell diameter it is continuous The foaming body (foamed sheet) of bubble structure.
Thick 35 μm Copper Foil is folded as heat-conducting layer in a surface layer of above-mentioned foamed sheet, is obtained comprising Copper Foil/foaming body layer Layered product.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 8
Using disperser (" RoboMix " PRIMIX company systems) to acrylic emulsions solution (solid constituent amount 55%, third (weight compares 45 to olefin(e) acid ethylacrylate-acrylic acid butyl ester-acrylonitrile copolymer：48：7)) 100 weight portions, aliphatic acid ammonium system surface are lived Weight portion, oxazolines system crosslinking agent (" the EPOCROS WS- of property agent (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate- Acrylic copolymer (the weight % of acrylic acid 20), solid constituent amount 28.7%) 0.78 weight portion, enumerate BTA system antirust agent (" SEETEC BT-NA ", SHIPRO are melted into company system) 0.5 weight portion is stirred mixing, it is played alveolation.By the foaming group Compound coat it is release-treated after PET (polyethylene terephthalate) film it is (thick：38 μm, trade name " MRF#38 " three Water chestnut Resins Corporation system) on, in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thickness 130 μm, density 0.43g/ cm3, maximum 160 μm of cell diameter, minimum 41 μm of cell diameter, the foaming of the continuous air bubbles structure of 101 μm of mean cell diameter Body (foamed sheet).
Thick 35 μm Copper Foil is folded as heat-conducting layer in a surface layer of above-mentioned foamed sheet, is obtained comprising Copper Foil/foaming body layer Layered product.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 9
Using disperser (" RoboMix " PRIMIX company systems) to acrylic emulsions solution (solid constituent amount 55%, third (weight compares 45 to olefin(e) acid ethylacrylate-acrylic acid butyl ester-acrylonitrile copolymer：48：7)) 100 weight portions, aliphatic acid ammonium system surface are lived Weight portion, oxazolines system crosslinking agent (" the EPOCROS WS- of property agent (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 500 " Japanese catalyst Co. system, solid constituent amount 39%) 2 weight portions, polyacrylic thickener (ethyl acrylate-propylene Acid copolymer (the weight % of acrylic acid 20), solid constituent amount 28.7%) 0.78 weight portion, enumerate BTA system antirust agent (" SEETEC BT-NA ", SHIPRO are melted into company system) 0.5 weight portion is stirred mixing, it is played alveolation.By composition, foam coating PET (polyethylene terephthalate) film after release-treated is (thick：38 μm, trade name " MRF#38 " Mitsubishi resin public affairs Department's system) on, in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thickness 130 μm, density 0.24g/cm3, it is maximum 69.5 μm of cell diameter, minimum 15 μm of cell diameter, the foaming body (foaming of the continuous air bubbles structure of 34 μm of mean cell diameter Piece).
Thick 35 μm Copper Foil is folded as heat-conducting layer in a surface layer of above-mentioned foamed sheet, is obtained comprising Copper Foil/foaming body layer Layered product.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 10
Using disperser (" RoboMix " PRIMIX company systems) to acrylic emulsions solution (solid constituent amount 55%, third (weight compares 40 to olefin(e) acid ethylacrylate-acrylic acid butyl ester-acrylonitrile copolymer：45：15)) 100 weight portions, aliphatic acid ammonium system surface are lived Property agent (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 weight portions, polyacrylic thickener (ethyl acrylate- Acrylic copolymer (the weight % of acrylic acid 20), solid constituent amount 28.7%) 0.58 weight portion is stirred mixing, it is bubbled Change.By the composition, foam coat it is release-treated after PET (polyethylene terephthalate) film it is (thick：38 μm, commodity Name " MRF#38 " Mitsubishi Resins Corporation system) on, in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 150 μ M, density 0.31g/cm3, maximum 187 μm of cell diameter, minimum 21 μm of cell diameter, the continuous air bubbles of 72 μm of mean cell diameter The foaming body (foamed sheet) of structure.
Thick 35 μm Copper Foil is folded as heat-conducting layer in a surface layer of above-mentioned foamed sheet, is obtained comprising Copper Foil/foaming body layer Layered product.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 11
Using disperser (" RoboMix " PRIMIX company systems) to acrylic emulsions solution (solid constituent amount 55%, third (weight compares 45 to olefin(e) acid ethylacrylate-acrylic acid butyl ester-acrylonitrile copolymer：48：7)) 100 weight portions, aliphatic acid ammonium system surface are lived Weight portion, oxazolines system crosslinking agent (" the EPOCROS WS- of property agent (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate- Acrylic copolymer (the weight % of acrylic acid 20), solid constituent amount 28.7%) 0.78 weight portion, enumerate BTA system antirust agent (" SEETEC BT-NA ", SHIPRO are melted into company system) 0.5 weight portion is stirred mixing, it is played alveolation.By the foaming group Compound coat it is release-treated after PET (polyethylene terephthalate) film it is (thick：38 μm, trade name " MRF#38 " three Water chestnut Resins Corporation system) on, in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thickness 450 μm, density 0.25g/ cm3, maximum 199 μm of cell diameter, minimum 24 μm of cell diameter, the foaming body of the continuous air bubbles structure of 84 μm of mean cell diameter (foamed sheet).
Thick 35 μm Copper Foil is folded as heat-conducting layer in a surface layer of above-mentioned foamed sheet, is obtained comprising Copper Foil/foaming body layer Layered product.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 12
Using disperser (" RoboMix " PRIMIX company systems) to acrylic emulsions solution (solid constituent amount 55%, third (weight compares 45 to olefin(e) acid ethylacrylate-acrylic acid butyl ester-acrylonitrile copolymer：48：7)) 100 weight portions, aliphatic acid ammonium system surface are lived Weight portion, oxazolines system crosslinking agent (" the EPOCROS WS- of property agent (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate- Acrylic copolymer (the weight % of acrylic acid 20), solid constituent amount 28.7%) 0.78 weight portion, enumerate BTA system antirust agent (" SEETEC BT-NA ", SHIPRO are melted into company system) 0.5 weight portion is stirred mixing, it is played alveolation.By the foaming group Compound coat it is release-treated after PET (polyethylene terephthalate) film it is (thick：38 μm, trade name " MRF#38 " three Water chestnut Resins Corporation system) on, in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thickness 300 μm, density 0.25g/ cm3, maximum 149 μm of cell diameter, minimum 19 μm of cell diameter, the foaming body of the continuous air bubbles structure of 76 μm of mean cell diameter (foamed sheet).
Thick 35 μm Copper Foil is folded as heat-conducting layer in a surface layer of above-mentioned foamed sheet, is obtained comprising Copper Foil/foaming body layer Layered product.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 13
Using disperser (" RoboMix " PRIMIX company systems) to acrylic emulsions solution (solid constituent amount 55%, third (weight compares 45 to olefin(e) acid ethylacrylate-acrylic acid butyl ester-acrylonitrile copolymer：48：7)) 100 weight portions, aliphatic acid ammonium system surface are lived Weight portion, oxazolines system crosslinking agent (" the EPOCROS WS- of property agent (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate- Acrylic copolymer (the weight % of acrylic acid 20), solid constituent amount 28.7%) 0.78 weight portion is stirred mixing, it is bubbled Change.The composition, foam is coated on thick 35 μm of Copper Foil (heat-conducting layer), in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, formed thick 130 μm, maximum 102 μm of cell diameter, minimum 23 μm of cell diameter, 56 μm of mean cell diameter it is continuous The foaming body layer of bubble structure, obtains the layered product comprising Copper Foil/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 14
Using disperser (" RoboMix " PRIMIX company systems) to acrylic emulsions solution (solid constituent amount 55%, third (weight compares 45 to olefin(e) acid ethylacrylate-acrylic acid butyl ester-acrylonitrile copolymer：48：7)) 100 weight portions, aliphatic acid ammonium system surface are lived Weight portion, oxazolines system crosslinking agent (" the EPOCROS WS- of property agent (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate- Acrylic copolymer (the weight % of acrylic acid 20), solid constituent amount 28.7%) 0.78 weight portion is stirred mixing, it is bubbled Change.By the composition, foam coat it is release-treated after PET (polyethylene terephthalate) film it is (thick：38 μm, commodity Name " MRF#38 " Mitsubishi Resins Corporation system) on, in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 130 μ M, density 0.31g/cm3, maximum 94 μm of cell diameter, minimum 30 μm of cell diameter, the continuous air bubbles of 57 μm of mean cell diameter The foaming body (foamed sheet) of structure.
Thick 40 μm graphite flake (GRAF TECH company systems) is folded in a surface layer of above-mentioned foamed sheet, as heat-conducting layer, to obtain To the layered product comprising Copper Foil/foaming body layer.The thermal conductivity of above-mentioned graphite is 1400W/mK.
＜ evaluates ＞
Following evaluation is carried out for the foaming body that is obtained in embodiment 1~14 and comparative example 1~4, layered product.By result It is shown in table 1~3.It should be noted that the cooperation number (weight portion) of each composition during each embodiment, comparative example are shown in table 1 [solid constituent (nonvolatile component) conversion]." Em " represents acrylic emulsions solution.
(mean cell diameter, maximum cell diameter, minimum cell diameter)
Using low vacuum SEM (" S-3400N types SEM " Hitachi Hightech Science Systems company systems) the expanded view picture of foaming body section is obtained, by carrying out image analysis, to obtain Average Cell straight Footpath (μm), maximum cell diameter (μm), minimum cell diameter (μm).It should be noted that the number of bubbles for parsing is 10~20 It is individual or so.
(density)
Foaming body (foamed sheet) is punched using the blanking knife model tool of 100mm × 100mm, to the sample that is punched out Size is measured.In addition, using the diameter for determining terminalFor 1/100 dial ga(u)ge of 20mm is surveyed to thickness It is fixed.The volume of foaming body is calculated using these values.
Then, the weight of foaming body is determined using the upper ware Libra of more than minimum scale 0.01g.Calculated according to these values Density (the g/cm of foaming body3)。
(dynamic viscoelastic)
Using the film of determination of viscoelasticity device (" ARES 2KFRTN1-FCO " TA Instruments Japan company systems) Stretching mode determination, temperature dispersion experiment is carried out when angular frequency is 1rad/s.To store elastic modulus E ' now and damage The ratio of consumption elastic modulus E " is that the temperature (DEG C) and intensity (maximum) of the peak value of loss angle tangent (tan δ) are measured.
" tan δ temperature " column of table 1 describes the temperature (DEG C) of the peak value of the loss angle tangent (tan δ) of foaming body.
(initial stage elastic modelling quantity)
Under 23 DEG C of environment and in the tension test of draw speed 300mm/min, slope when being strained by 10% is calculated just Phase elastic modelling quantity (N/mm2), the initial stage elastic modelling quantity is evaluated.
(shear bond power)
By made foaming body (in embodiment 3,5, comparative example 1, make double-faced adhesive tape (trade name " No.5603 ", It is day eastern electrician's company system, thick 30 μm) it is pasted on the two-sided of foaming body) 25mm × 25mm is cut into, respectively in the two-sided of foaming body SUS304BA plates are pasted, so as to be made measure sample.The roller of 5kg is set to make a round trip to carry out on the measure sample of horizontal positioned Crimping.After crimping, placed 30 minutes under normal temperature (23 DEG C), be then fixed in drawing according to the mode for making measure sample vertical Width machine (Tensilon), was stretched with draw speed 50mm/ minutes, determined its most central shear bond power.With n=2 Mode determine measure sample, be averaged value as shear bond power (N/100mm2)。
(impact absorbency experiment)
Impact absorbency is carried out using above-mentioned pendulum type shock machine (impact test apparatus) (reference picture 1 and Fig. 2) Experiment.
For the layered product (sample size obtained in embodiment 1~14 and comparative example 1,3：20mm × 20mm), make Impact test is carried out under the conditions of the impact of 30 ° of the iron ball inclination of 96g, impact absorbing rate (%) is obtained.It should be noted that according to The mode of the side that foaming side is impacted as iron ball is set.Then, with the impact absorbing rate (%) divided by hair The thickness (μm) of piece is steeped, the impact absorbing rate R of per unit thickness is obtained.It should be noted that for impact absorbency can be implemented For the embodiment and comparative example 1,3 of experiment, even if after impact absorbing experiment, Copper Foil can still maintain layered product with foaming body layer Constitute, and bonding reliability is good.
(heat diffusivity experiment)
Using in hot box be provided with the ceramic heater with thermocouple device, carry out heat diffusivity experiment.Such as Fig. 3 And shown in Fig. 4, in (the size on surface of ceramic heater 103：Horizontal 20mm × vertical 40mm) on, by the stacking of embodiment or comparative example Body (comparative example 3 is foaming body) 104 (horizontal 75mm × vertical 45mm) is using double-faced adhesive tape (trade name " No.5603 ", day east electrician It is company system, thick 30 μm) 102 fix (in the case of with Copper Foil, to enter according to mode of the Copper Foil side as heater side Row is set), and the temperature (surface temperature) of the center to foaming body layer surface is measured.In addition, exporting heater Power invariability, determines by the heter temperature after 10 minutes.
(copper closing force)
In the case of embodiment 4：Adhesive tape (No.31B, day east electrician company system) is set to fit in the foaming body of gained (foamed sheet；One side be laminated stripping film) a face.The size of 20mm × 100mm is cut to, as evaluation sample.Will Stripping film is peeled, and makes another face of foaming body in being pasted on as the Copper Foil of adherend at 25 DEG C, the roller of 5Kg is made a round trip To be crimped.It is taken out after being placed 1 day at 80 DEG C, is placed at room temperature 2 hours, then in 180 ° of peel angle, drawing Implement disbonded test under conditions of stretching speed 300mm/ minutes, determine bonding force (relative to the bonding force of Copper Foil) (N/ 20mm)。
In the case of embodiment 13：Adhesive tape (No.31B, day east electrician company system) is set to fit in the layered product of gained Foamed sheet side, cut into the size of 20mm × 100mm, as evaluate sample.It is taken out after being placed 1 day at 80 DEG C, Place 2 hours at room temperature, acrylic board is then fixed in Copper Foil side using two-sided tape.Shelled from Copper Foil according to by foamed sheet From mode, implement disbonded test under conditions of 180 ° of peel angle, draw speed 300mm/ minutes, determine bonding force (relative to the bonding force of Copper Foil) (N/20mm).
Table 1
Symbol description
1st, pendulum type shock machine (impact test apparatus)
2nd, test film [foaming body layer (foamed sheet) or layered product]
3rd, holding member
4th, impact load component
5th, pressure sensor
10th, layered product
11st, stationary fixture
12nd, fixture is pressed
16th, pressure regulating mechanism
20th, pillar
21st, arm
22nd, one end of support rod (axle)
23rd, support rod (axle)
24th, son is impacted
25th, electromagnet
28th, support plate
A, angle is put
100th, foaming body layer
101st, Copper Foil
102nd, adhesive tape
103rd, ceramic heater
104th, sample (sample)
200th, foaming body layer
201st, heat-conducting layer

Claims (14)

1. a kind of layered product, it has foaming body layer and heat-conducting layer, and the thickness of the foaming body layer is 30~500 μm, and by close It is 0.2~0.7g/cm to spend3, foaming body that mean cell diameter is 10~150 μm constitute, the thermal conductivity of the heat-conducting layer is More than 200W/mK,
Store elastic modulus and loss springform when angular frequency of the foaming body in Measurement of Dynamic Viscoelasticity is 1rad/s The ratio of amount is that losstangenttanδ has peak value more than -30 DEG C and in less than 30 DEG C of scope.
2. layered product according to claim 1, wherein, the losstangenttanδ of the foaming body more than -30 DEG C and Maximum in less than 30 DEG C of scope is more than 0.2.
3. layered product according to claim 1 and 2, wherein, under 23 DEG C of environment and draw speed is the drawing of 300mm/min Stretch in experiment, the initial stage elastic modelling quantity of foaming body is 5N/mm2Below.
4. layered product according to claim 1 and 2, wherein, in rushing for the layered product using pendulum type shock machine Hit in absorbent test, weight 96g in impact, when having put 30 ° of angle, impact absorbing rate is divided by foaming defined in following formula Value R obtained by the thickness of body layer is more than 0.15, and in terms of %, the unit of the thickness of the foaming body layer is the impact absorbing rate μm,
Impact absorbing rate (%)={ (F0- F1)/F0}×100
In above-mentioned formula, F0Only to collide the impulsive force of the impact period of the day from 11 p.m. to 1 a.m, F to support plate1It is to being made up of support plate and the layered product Structure support plate on collide impact the period of the day from 11 p.m. to 1 a.m impulsive force.
5. layered product according to claim 1 and 2, wherein, the thickness of the heat-conducting layer is more than 5 μm.
6. layered product according to claim 1 and 2, wherein, the heat-conducting layer be selected from graphite flake and metal foil extremely Few one kind.
7. layered product according to claim 1 and 2, wherein, foaming body is by selected from acrylic acid series polymeric compounds, rubber, amino At least one resin material in formic acid esters based polymer and vinyl-vinyl acetate copolymer is formed.
8. layered product according to claim 1 and 2, wherein, foaming body is formed via operation A, and the operation A is to make breast The operation that liquid resin combination mechanically foams.
9. layered product according to claim 8, wherein, foaming body is further formed via process B, and the process B is To be coated on base material and carry out dry operation through emulsion resin composition obtained by mechanically foaming.
10. layered product according to claim 9, wherein, the process B includes：The bubbles that will be coated on base material Emulsion resin composition 50 DEG C less than 125 DEG C at a temperature of the prepared drying process B1 that is dried and in preparation After drying process B1 further more than 125 DEG C and less than the 200 DEG C trunk drying process B2 being dried.
11. layered products according to claim 1 and 2, wherein, foaming body layer single or double with across adhesive phase Or across the mode of adhesive phase it is not laminated with heat-conducting layer.
Layered product described in 12. claims 1 or 2 makes as electrical equipment or electronic equipment thermal diffusion impact-absorbing sheet With.
A kind of 13. electrical equipments or electronic equipment, it use the layered product described in claim 1 or 2.
14. electrical equipments according to claim 13 or electronic equipment, it is the electrical equipment or electricity for possessing display member There is the layered product to be clamped in the basket of the electrical equipment or electronic equipment for sub- equipment, the electrical equipment or electronic equipment With the structure between the display member.
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KR101922938B1 (en) * 2017-09-29 2018-11-29 일진머티리얼즈 주식회사 Multi-functional composite sheet having function of controlling electromagnetic wave, thermal radiation, and absorbing impact
JP7434527B2 (en) * 2020-03-19 2024-02-20 三井化学株式会社 self adhesive sheet
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