CN104553103A - Laminate - Google Patents

Laminate Download PDF

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Publication number
CN104553103A
CN104553103A CN201410315267.XA CN201410315267A CN104553103A CN 104553103 A CN104553103 A CN 104553103A CN 201410315267 A CN201410315267 A CN 201410315267A CN 104553103 A CN104553103 A CN 104553103A
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CN
China
Prior art keywords
foaming body
duplexer
mentioned
layer
heat
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410315267.XA
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Chinese (zh)
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
松下喜一郎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
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Nitto Denko Corp
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Filing date
Publication date
Priority claimed from JP2014082568A external-priority patent/JP6343478B2/en
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of CN104553103A publication Critical patent/CN104553103A/en
Pending legal-status Critical Current

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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

Landscapes

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

Abstract

The invention provides a thermal diffusion impact absorbing sheet with excellent impact absorbing performance and thermal diffusivity even if the thickness is small. A laminate of the invention is provided with a foaming body layer and a heat conductivity layer. The foaming body layer is formed by a foaming body of 30 to 500 microns in thickness, of 0.2 to 0.7g/cm <3> in density and of 10 to 150 microns in average bubble diameter. The thermal conductivity of the heat conductivity layer is more than 200W/m*k. The peak value is within the range of loss tangent (tan Delta) from above minus 30 DEG C to below 30 DEG C for the ratio of energy-storage elasticity modulus to loss elasticity modulus during dynamic viscoelasticity measurement of the above preferable forming body at angular frequency of 1 rad/s. The maximum value in the range of loss tangent (tan Delta) of the foaming body from above minus 30 DEG C to below 30 DEG C is more than 0.2.

Description

Duplexer
Technical field
Even if the present invention relates to that thickness is thin, impact absorbency and the also excellent duplexer (thermal diffusion impact-absorbing sheet) of heat diffusivity (thermal diffusivity), and employ electrical equipment or the electronic equipment of this duplexer.
Background technology
In recent years, along with the slimming of the electronic equipment such as PC (PC), dull and stereotyped PC, PDA (personal portable information terminal), mobile phone, in order to prevent the breakage of liquid crystal panel, organic EL panel etc., and employ impact-absorbing sheet at back side of panel.
In addition, along with the multifunction of electronic equipment, the heating quantitative change of the heaters such as electronic unit is large, thus in order to prevent because in inside accumulation heat, the performance that causes reduces or the scald etc. of user that is damaged and that cause because basket local reaches a high temperature, need efficiently externally diffusion heat, cool.In order to this object, and employ various radiator.
Therefore, thermal diffusion impact-absorbing sheet impact absorbing layer and heat-conducting layer combined is needed in the electronic device.Further, due to the further slimming of electronic equipment, and the further thin layer of the component being used for electronic equipment is required.
Prior art document
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2001-100216 publication
Patent document 2: Japanese Unexamined Patent Publication 2002-309198 publication
Summary of the invention
Invent problem to be solved
Thus, the object of the invention is to, even if provide that a kind of thickness is thin, impact absorbency and the also excellent thermal diffusion impact-absorbing sheet of heat diffusivity, and employ electrical equipment or the electronic equipment of such thermal diffusion impact-absorbing sheet.
For solving the means of problem
The present inventor etc. conduct in-depth research to achieve these goals, found that, for by having specific density, for the sheet that is laminated for heat-conducting layer more than particular value of foaming body layer that the foaming body of specific mean cell diameter is formed and thermal conductivity, even if be 30 ~ 500 μm of thin like this thickness, the impact absorbency of described is also obviously excellent, and heat diffusivity is also excellent, effectively the heat of inside externally can be spread, so far be completed the present invention.
That is, the invention provides a kind of duplexer, described duplexer has foaming body layer and heat-conducting layer, and the thickness of described foaming body layer is 30 ~ 500 μm, and is 0.2 ~ 0.7g/cm by density 3, mean cell diameter be 10 ~ 150 μm foaming body form, the thermal conductivity of described heat-conducting layer is more than 200W/mK.
For above-mentioned duplexer, the store elastic modulus when angular frequency of preferred above-mentioned foaming body in Measurement of Dynamic Viscoelasticity is 1rad/s and the ratio of loss elastic modulus and loss angle tangent (tan δ) are more than-30 DEG C and have peak value in the scope of less than 30 DEG C.
Loss angle tangent (tan δ) maximum more than-30 DEG C and in the scope of less than 30 DEG C of preferred above-mentioned foaming body is more than 0.2.
In addition, preferably under 23 DEG C of environment and the initial stage elastic modelling quantity that draw speed is foaming body in the tension test of 300mm/min is 5N/mm 2below.
In addition, employ pendulum type shock machine, in the impact absorbency of duplexer test (impact the weight 96g of son, put angle 30 °), the value R that the impact absorbing rate (%) defined by following formula obtains divided by the thickness (μm) of foaming body layer is preferably more than 0.15.
Impact absorbing rate (%)={ (F 0-F 1)/F 0} × 100
(in above formula, F 0for only colliding the impulsive force of impacting the period of the day from 11 p.m. to 1 a.m to support plate, F 1for the support plate to the structure be made up of support plate and above-mentioned duplexer colliding the impulsive force of impacting the period of the day from 11 p.m. to 1 a.m)
The thickness of above-mentioned heat-conducting layer is such as more than 5 μm.
Above-mentioned heat-conducting layer can be selected from least one in graphite flake and metal forming.
Foaming body can be formed by least one resin material be selected from acrylic acid series polymeric compounds, rubber, carbamate based polymer and vinyl-vinyl acetate copolymer.
Foaming body can be formed via the operation A making emulsion resin composition mechanically foam.
Foaming body can be coated on base material via the emulsion resin composition obtained mechanically foaming further and carry out dry process B and formed.
Above-mentioned process B can comprise: by the emulsion resin composition of the bubbles be coated on base material more than 50 DEG C and lower than carry out dry preparation drying process B1 at the temperature of 125 DEG C and after preparation drying process B1 further more than 125 DEG C and less than the 200 DEG C trunk drying process B2 carrying out drying.
Above-mentioned duplexer can at the single or double of foaming body layer with across adhesive phase or be not laminated with heat-conducting layer across the mode of adhesive phase.
Above-mentioned duplexer can be used as electrical equipment or electronic equipment thermal diffusion impact-absorbing sheet.
The present invention also provides a kind of electrical equipment or the electronic equipment that employ above-mentioned duplexer.
Above-mentioned electrical equipment or electronic equipment are the electrical equipment or the electronic equipment that possess display member, and described electrical equipment or electronic equipment have above-mentioned duplexer and be clamped in structure between the basket of this electrical equipment or electronic equipment and above-mentioned display member.
The effect of invention
The foaming body layer that duplexer of the present invention has by having specific density, the foaming body of specific mean cell diameter is formed and thermal conductivity are the heat-conducting layer of more than particular value, therefore, even if be 30 ~ 200 μm of thin like this thickness, impact absorbency is also very excellent, and heat diffusivity is excellent, the heat of inside externally can be spread effectively.
Accompanying drawing explanation
Fig. 1 is the signal pie graph of pendulum type shock machine (impact test apparatus).
Fig. 2 is the figure that the signal of the retaining member representing pendulum type shock machine (impact test apparatus) is formed.
Fig. 3 is the profile schematically showing the method that heat diffusivity is tested.
Fig. 4 is the top view (figure from top view) schematically showing the method that heat diffusivity is tested.
Fig. 5 is the constructed profile of the example representing duplexer of the present invention.
Detailed description of the invention
Duplexer of the present invention has the foaming body layer and heat-conducting layer that are made up of foaming body.Fig. 5 is the constructed profile of the example representing duplexer of the present invention.10 is duplexer, 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 density 3, mean cell diameter be 10 ~ 150 μm foaming body form.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, is more preferably 50 μm, and the upper limit is preferably 400 μm, is more preferably 300 μm, more preferably 200 μm.In the present invention, the thickness of foaming body layer is more than 30 μm, therefore can contain bubble equably, can give play to excellent impact absorbency.In addition, the thickness of foaming body layer is less than 500 μm, even if therefore also can easily follow for small gap.
The lower limit forming the density of the foaming body of above-mentioned foaming body layer is preferably 0.21g/cm 3, be more preferably 0.22g/cm 3, the upper limit is preferably 0.6g/cm 3, be more preferably 0.5g/cm 3, more preferably 0.4g/cm 3.Be 0.2g/cm by making the density of foaming body 3above, thus can maintain intensity, be 0.7g/cm by making the density of foaming body 3below, thus higher impact absorbency can have been given play to.In addition, by making the density of foaming body be 0.2 ~ 0.4g/cm 3scope, thus higher impact absorbency can have been given play to further.
The lower limit of the mean cell diameter of above-mentioned foaming body is preferably 15 μm, is more preferably 20 μm, and the upper limit is preferably 140 μm, is more preferably 130 μm, more preferably 100 μm.By making mean cell diameter be more than 10 μm, thus excellent impact absorbency can be given play to.In addition, because mean cell diameter is less than 100 μm, therefore compress restorative also excellent.It should be noted that, the maximum cell diameter of above-mentioned foaming body is such as 40 ~ 400 μm, and its lower limit is preferably 60 μm, is more preferably 80 μm, and the upper limit is preferably 300 μm, is more preferably 220 μm.In addition, the smallest bubbles bore dia of above-mentioned foaming body is such as 5 ~ 70 μm, and its lower limit is preferably 8 μm, is more preferably 10 μm, and the upper limit is preferably 60 μm, is more preferably 50 μm.
In the present invention, from the view point of impact absorbency, the ratio of the thickness (μm) of mean cell diameter (μm) and foaming body layer (the former/the latter) is preferably in the scope of 0.2 ~ 0.9.Above-mentioned mean cell diameter (μm) is preferably 0.25 with the lower limit of the ratio of the thickness (μm) of foamed sheet, is more preferably 0.3, and the upper limit is preferably 0.85, is more preferably 0.8.
The peak value of the store elastic modulus when angular frequency of preferred above-mentioned foaming body in Measurement of Dynamic Viscoelasticity is 1rad/s and the ratio of loss elastic modulus and loss angle tangent (tan δ) is in more than-30 DEG C and the scope of less than 30 DEG C.The lower limit of the temperature range of the peak value existence of above-mentioned loss angle tangent is more preferably-25 DEG C, more preferably-20 DEG C, is particularly preferably-10 DEG C, and the upper limit is more preferably 20 DEG C, more preferably 10 DEG C.When the material of the peak value for having more than 2 loss angle tangents, wish that wherein at least one falls into above-mentioned scope.By making peak temperature be more than-30 DEG C, thus it is restorative to have given play to excellent compression.In addition, by making peak temperature be less than 30 DEG C, thus high soft right property can be demonstrated and excellent impact absorbency can have been given play to.
From the view point of impact absorbency, preferably more than-30 DEG C and peak strength (maximum) height of loss angle tangent (tan δ) in the scope of less than 30 DEG C is such as more than 0.2, preferably more than 0.3.The higher limit of above-mentioned peak strength (maximum) is such as 2.0.
Like this, the peak temperature of above-mentioned loss angle tangent (tan δ), peak strength contribute to the impact absorbency of foaming body to a great extent.If the peak value of the store elastic modulus when angular frequency of foaming body in Measurement of Dynamic Viscoelasticity is 1rad/s and the ratio of loss elastic modulus and loss angle tangent (tan δ) is present in more than-30 DEG C and the scope of less than 30 DEG C, then the impact absorbency of foaming body becomes very high, reason about this point is still not clear, but supposition is the cause owing to there is the peak value of above-mentioned loss angle tangent (tan δ) matchingly with the frequency of impacting.Namely, can infer: above-mentioned loss angle tangent (tan δ) is more than-30 DEG C and the scope of less than 30 DEG C, the scope of the frequency suitable with the drop impact of works is scaled according to the temperature-time conversion rule in determination of viscoelasticity, therefore, have the foaming body of the peak temperature of above-mentioned loss angle tangent (tan δ) more than-30 DEG C and in the scope of less than 30 DEG C, its impact absorbency uprises.In addition, store elastic modulus is the repulsion relative with the impact energy putting on foaming body, if store elastic modulus is high, then and impact of directly rebounding.On the other hand, loss elastic modulus is the physical property impact energy putting on foaming body being converted to heat, and loss elastic modulus is higher, impact energy is converted to heat muchly, therefore absorbs impact, and deformation is diminished.Can inferring thus, being converted to heat and the little foaming body of repulsion in large quantities by impacting, that is, the ratio of store elastic modulus and loss elastic modulus and the large foaming body of loss angle tangent (tan δ), its impact absorbing rate is high.
From the view point of impact absorbency, the initial stage elastic modelling quantity of preferred above-mentioned foaming body is low.This initial stage elastic modelling quantity (under 23 DEG C of environment, draw speed is in the tension test of 300mm/min, the value calculated by slope during 10% strain) is preferably 5N/mm 2below, 3N/mm is more preferably 2below.It should be noted that, the lower limit of above-mentioned initial stage elastic modelling quantity is such as 0.1N/mm 2.
As the foaming body forming above-mentioned foaming body layer, as long as have above-mentioned characteristic, then its composition, bubble structure etc. are just not particularly limited.As bubble structure, can be any one in continuous air bubbles structure, separated foam structure, semicontinuous semi-independent bubble structure.From the view point of impact absorbency, be preferably continuous air bubbles structure, semicontinuous semi-independent bubble structure.
Foaming body layer in duplexer of the present invention is thin, and has excellent impact absorbency.In addition, the impact of the size be not hit, can give play to excellent impact absorbency.
Such as, with regard to duplexer of the present invention, employ pendulum type shock machine, in the impact absorbency of this duplexer test (impact the weight 96g of son, put angle 30 °), the value R (the impact absorbing rate of per unit thickness) that the impact absorbing rate (%) that following formula defines obtains divided by the thickness (μm) of foaming body layer is such as more than 0.15, preferably more than 0.17, more preferably more than 0.19.It should be noted that, the higher limit of above-mentioned R is such as about 0.5.
Impact absorbing rate (%)={ (F 0-F 1)/F 0} × 100
(in above formula, F 0only the impulsive force of impacting the period of the day from 11 p.m. to 1 a.m is collided to support plate, F 1the support plate to the structure be made up of support plate and above-mentioned duplexer collides the impulsive force of impacting the period of the day from 11 p.m. to 1 a.m)
It should be noted that, above-mentioned impact absorbing rate is different from the thickness etc. of foaming body layer, is generally 5 ~ 70%, and lower limit is preferably 7%, the upper limit is preferably 60%.
In duplexer of the present invention, the impact absorbing rate (%) (impact the weight 96g of son, put angle 30 °) of this duplexer is preferably more than 15%, is more preferably more than 17%, more preferably more than 19%.
Signal for pendulum type shock machine (impact test apparatus) is formed, and is described by Fig. 1 and Fig. 2.As shown in Figures 1 and 2, impact test apparatus 1 (pendulum test machine 1) comprising: as with arbitrary confining force to keep the retaining member 3 of the maintaining body of test film 2 (foaming body or duplexer); Make the impact load component 4 of test film 2 load impact stress; With the pressure inductor 5 etc. as the impulsive force testing agency detected the impulsive force produced based on impact load component 4 pairs of test films 2.In addition, keep the retaining member 3 of test film 2 to be made up of stationary fixture 11 and pressing fixture 12 with arbitrary confining force, pressing fixture 12 is opposed with stationary fixture 11, and to clamp the mode that keeps test film 2 and slidably.In addition, pressing fixture 12 place is provided with press pressure governor motion 16.In addition, the impact load component 4 of the test film 2 load impact power kept by retaining member 3 is made up of support rod 23 (axle 23) and arm 21, one end 22 of support rod 23 is had in another side by the mode that can rotate relative to pillar 20 impact son 24 by axle supporting, and impacts sub 24 is lifted and remain predetermined angular by arm 21.Here, employ steel ball as impact 24, therefore, by arranging electromagnet 25 in one end of arm, thus can integratedly impact 24 be lifted as predetermined angular.In addition, the impulsive force of what impact load component 4 produced act on test film 2 carries out the pressure inductor 5 detected, and is arranged at the opposing face side of the test film contact surface of stationary fixture 11.
Impacting son 24 is steel ball (iron balls).In addition, (it a) is 30 ° ~ about 47 ° that the pendulum in Fig. 1 plays angle to impact the angles that son 24 lifts by arm 21.In embodiment described later, measure in the weight 96g of steel ball (iron ball), the condition of having put angle 30 °.
As shown in Figure 2, test film 2 (foaming body or duplexer) is clamped across the support plate 28 be made up of resinousness sheet material (acrylic board, polycarbonate plate etc.), the contour elastic plate of metal sheet material between stationary fixture 11 and pressing fixture 12.
Use above-mentioned impact test apparatus, obtain impulsive force F 0and impulsive force F 1, calculate impact absorbency by above-mentioned formula, wherein, impulsive force F 0by make stationary fixture 11 and support plate 28 closely sealed fixing after, make impact 24 impact support plates 28 and record, impulsive force F 1by between stationary fixture 11 and support plate 28, insert test film 2 and make its closely sealed fixing after, make impact 24 impact support plates 28 and record.It should be noted that, impact test apparatus is the device identical with the embodiment 1 of Japanese Unexamined Patent Publication 2006-47277 publication.
The thickness of foaming body layer large to a certain degree time, impact absorbency regulates by selecting mean cell diameter, density etc., and when the thickness of foaming body layer is very little (such as thickness is 30 ~ 500 μm), only adjustment is carried out to above-mentioned characteristic and fully cannot absorb impact.This is because following cause: when the thickness of foaming body layer is very thin, the bubble in foaming body breaks immediately because of impact, and the impact buffer function produced by bubble disappears.As mentioned above, if the peak value of the store elastic modulus when angular frequency of foaming body in Measurement of Dynamic Viscoelasticity is 1rad/s and the ratio of loss elastic modulus and loss angle tangent (tan δ) is present in more than-30 DEG C and the scope of less than 30 DEG C, even if then after bubbles burst, the constituent material of foaming body has still been given play to impacting the function cushioned.
Above-mentioned foaming body can be made up of the resin combination comprising resin material (polymer).It should be noted that, store elastic modulus when this resin combination [resin combination (solid content) when not foaming] angular frequency in Measurement of Dynamic Viscoelasticity of non-foamed state is 1rad/s and the ratio of loss elastic modulus and the peak value of loss angle tangent (tan δ) are preferably in more than-30 DEG C and the scope of less than 30 DEG C.The lower limit of the temperature range existing for the peak value of above-mentioned loss angle tangent is preferably-25 DEG C, is more preferably-20 DEG C, more preferably-10 DEG C, and the upper limit is preferably 20 DEG C, is more preferably 10 DEG C.When having the material of peak value of more than 2 loss angle tangents, preferably wherein at least one falls in above-mentioned scope.From the view point of impact absorbency, (this value is equivalent to above-mentioned foaming body more than-30 DEG C and lower than the peak strength of the loss angle tangent (tan δ) in the scope of 30 DEG C divided by the density (g/cm of foaming body to the peak strength of the preferred loss angle tangent of this resin combination (solid content) more than-30 DEG C and in the scope of less than 30 DEG C (tan δ) 3) and the value that obtains) high.Such as, the peak strength of the loss angle tangent of above-mentioned resin combination (solid content) more than-30 DEG C and in the scope of less than 30 DEG C (tan δ) is preferably 0.9 (g/cm 3) -1above, the upper limit is such as about 3.
In addition, expect that the initial stage elastic modelling quantity (23 DEG C, draw speed 300mm/min) of this resin combination (solid content) of non-foamed state is low, be preferably 50N/mm 2below, 30N/mm is more preferably 2below.It should be noted that, the lower limit of above-mentioned initial stage elastic modelling quantity is such as 0.3N/mm 2.
As the resin material (polymer) forming above-mentioned foaming body, be not particularly limited, the known and even known resin material forming foaming body can be used.As this resin material, include, for example out acrylic acid series polymeric compounds, rubber, carbamate based polymer, vinyl-vinyl acetate copolymer etc.Wherein, from the view point of impact absorbency, be preferably acrylic acid series polymeric compounds, rubber, carbamate based polymer.The resin material (polymer) forming foaming body can be independent a kind, also can be two or more.
It should be noted that, in order to store elastic modulus when making the angular frequency of above-mentioned foaming body in Measurement of Dynamic Viscoelasticity be 1rad/s and the ratio of loss elastic modulus and the peak value of loss angle tangent (tan δ) are more than-30 DEG C and the scope of less than 30 DEG C, can using the Tg of above-mentioned resin material (polymer) as index or target.Such as, as above-mentioned resin material (polymer), more than-50 DEG C can be in from Tg and select lower than the resin material (polymer) in the scope of 50 DEG C (lower limit is preferably-40 DEG C, is more preferably-30 DEG C, the upper limit is preferably 40 DEG C, is more preferably 30 DEG C).
As aforesaid propylene acid based polymer, be preferably the acrylic acid series polymeric compounds that to be the monomer of more than-10 DEG C and the Tg of homopolymers using the Tg of homopolymers formed as necessary monomer component lower than the monomer of-10 DEG C.By using such acrylic acid series polymeric compounds and adjusting with the amount ratio of the latter's monomer the former monomer, thus store elastic modulus when the angular frequency that can obtain with comparalive ease in Measurement of Dynamic Viscoelasticity is 1rad/s and the ratio of loss elastic modulus and the peak value of loss angle tangent (tan δ) are more than-30 DEG C and the foaming body of less than 30 DEG C.
It should be noted that, " forming the glass transition temperature (Tg) during homopolymers " (being sometimes only singly called " Tg of homopolymers ") in the present invention refers to " glass transition temperature (Tg) of the homopolymers of this monomer ", specifically, numerical value is enumerated in " Polymer Handbook " (the 3rd edition, John Wiley & Sons, Inc, 1987).It should be noted that, the Tg of the homopolymers of the monomer do not recorded in above-mentioned document refers to the value (with reference to Japanese Unexamined Patent Publication 2007-51271 publication) such as obtained by following assay method.Namely, to in the reactor possessing thermometer, mixer, nitrogen ingress pipe and backflow cooling tube, drop into monomer 100 weight portion, 2,2 '-azodiisobutyronitrile 0.2 weight portion and ethyl acetate 200 weight portion as polymer solvent, while importing nitrogen, stir 1 hour.Thus, by the oxygen removing in polymerization system, be then warming up to 63 DEG C and make it react 10 hours.Then, be cooled to room temperature, obtain the homopolymers solution that solid component concentration is 33 % by weight.Then, this homopolymers solution casting is coated on distance piece, carries out drying, produce the test specimen (homopolymers of sheet) of thick about 2mm.Then, this test specimen stamping-out is become diameter 7.9mm's is discoid, clamped with parallel-plate, use test for viscoelastic machine (ARES, REOMETRIX Inc.), while the shear strain of giving frequency 1Hz, temperature province-70 ~ 150 DEG C, 5 DEG C/min programming rate condition under, measure viscoplasticity by shear mode, the peak temperature of tan δ be set to the Tg of homopolymers.It should be noted that, the Tg of above-mentioned resin material (polymer) also measures by the method.
Tg for homopolymers is the monomer of more than-10 DEG C, and this Tg is such as-10 DEG C ~ 250 DEG C, is preferably 10 ~ 230 DEG C, more preferably 50 ~ 200 DEG C.
Tg as above-mentioned homopolymers is the monomer of more than-10 DEG C, can exemplify such as: (methyl) acrylonitrile; The monomer of the amide-containings such as (methyl) acrylamide, N-ethoxy (methyl) acrylamide; (methyl) acrylic acid; The Tg of the homopolymers such as methyl methacrylate, EMA is (methyl) alkyl acrylate of more than-10 DEG C; (methyl) isobornyl acrylate; NVPs etc. are containing the vinyl monomer of heterocycle; The monomer etc. of the hydroxyls such as HEMA.They can be used alone a kind or combinationally use two or more.Wherein, (methyl) acrylonitrile (especially acrylonitrile) is particularly preferably.If use (methyl) acrylonitrile (especially acrylonitrile) to be the monomer of more than-10 DEG C as the Tg of homopolymers, then intermolecular interaction is strong, therefore, it is possible to make the peak strength of the above-mentioned loss angle tangent (tan δ) of foaming body become large.
For the Tg of homopolymers lower than the monomer of-10 DEG C, this Tg be such as more than-70 DEG C and lower than-10 DEG C, be preferably-70 DEG C ~-12 DEG C, more preferably-65 DEG C ~-15 DEG C.
As the Tg of above-mentioned homopolymers lower than the monomer of-10 DEG C, the Tg that can list the homopolymers such as such as ethyl acrylate, butyl acrylate, 2-EHA is lower than (methyl) alkyl acrylate etc. of-10 DEG C.They can be used alone a kind, or combinationally use two or more.Wherein, acrylic acid C is particularly preferably 2-8arrcostab.
Relative to the whole monomer component (monomer component total amount) forming aforesaid propylene acid based polymer, the Tg of homopolymers is that the content of the monomer of more than-10 DEG C is such as 2 ~ 30 % by weight, lower limit is preferably 3 % by weight, be more preferably 4 % by weight, the upper limit is preferably 25 % by weight, is more preferably 20 % by weight.In addition, relative to the whole monomer component (monomer component total amount) forming aforesaid propylene acid based polymer, the Tg of homopolymers lower than the content of the monomer of-10 DEG C be such as 70 ~ 98 % by weight, lower limit is preferably 75 % by weight, be more preferably 80 % by weight, the upper limit is preferably 97 % by weight, is more preferably 96 % by weight.
As above-mentioned rubber, can be any one in natural rubber, synthetic rubber.As above-mentioned rubber, include, for example out acrylonitrile-butadiene rubber (NBR), methyl methacrylate butadiene rubber (MBR), SBR styrene butadiene rubbers (SBR), acrylic rubber (ACM, ANM), urethane rubber (AU), silicone rubber etc.Wherein, acrylonitrile-butadiene rubber (NBR), methyl methacrylate butadiene rubber (MBR), silicone rubber is preferably.
As above-mentioned carbamate based polymer, include, for example out polycarbonate-based polyurethane, Polyester polyurethane, polyethers system polyurethane etc.
As vinyl-vinyl acetate copolymer, known and even known vinyl-vinyl acetate copolymer can be used.
Form the foaming body of above-mentioned foaming body layer except resin material (polymer), surfactant, crosslinking agent, thickener, antirust agent, other additive can also be contained as required.
Such as in order to bubble diameter miniaturization, bubble after the stability of bubble, can arbitrary surfactant be contained.As surfactant, be not particularly limited, any one in anion system surfactant, cation system surfactant, nonionic system surfactant, amphoteric surfactant etc. can be used, the stability of the bubble after the miniaturization, foaming of bubble diameter, be preferably anion system surfactant, be especially more preferably the aliphatic acid ammonium system surfactants such as ammonium stearate.Surfactant can be used singly or in combination of two or more.In addition, can be used together different types of surfactant, such as can by anion system surfactant and nonionic system surfactant and use, anion system surfactant and amphoteric surfactant are used.
Such as relative to resin material (polymer) [solid constituent (nonvolatile component)], 100 weight portions are 0 ~ 10 weight portion to the addition [solid constituent (nonvolatile component)] of surfactant, lower limit is preferably 0.5 weight portion, the upper limit is preferably 8 weight portions.
In addition, in order to improve intensity, heat resistance, the moisture-proof of foaming body, arbitrary crosslinking agent can be contained.Crosslinking agent is not particularly limited, oil-soluble can be used, water-soluble in any one.As crosslinking agent, include, for example out epoxy, oxazoline system, isocyanate-based, carbodiimide system, melamine series, burning system etc.Wherein, You Xuan Wei oxazoline system crosslinking agent.
Such as relative to resin material (polymer) [solid constituent (nonvolatile component)], 100 weight portions are 0 ~ 10 weight portion to the addition [solid constituent (nonvolatile component)] of crosslinking agent, lower limit is preferably 0.01 weight portion, the upper limit is preferably 9 weight portions.
In addition, in order to improve stability, the film forming of the bubble after foaming, arbitrary thickener can be contained.As thickener, be not particularly limited, acrylic acid series, carbamate system, polyethenol series etc. can be listed.Wherein, polyacrylic thickener is preferably.
Such as relative to resin material (polymer) [solid constituent (nonvolatile component)], 100 weight portions are 0 ~ 10 weight portion to the addition [solid constituent (nonvolatile component)] of thickener, lower limit is preferably 0.1 weight portion, the upper limit is preferably 5 weight portions.
In addition, in order to prevent the corrosion of the hardware adjoined with foaming body, arbitrary antirust agent can be contained.As this antirust agent, be preferably the compound containing azoles ring.If use the compound containing azoles ring, then can take into account at a high level for the anticorrosive property of metal and the adaptation with adherend.
As the above-mentioned compound containing azoles ring, as long as what contain more than one nitrogen-atoms in ring has pentacyclic compound, include, for example out the compound etc. with diazole (imidazoles, pyrazoles) ring, triazole ring, tetrazole ring, oxazole ring, isoxazole ring, thiazole ring or isothiazole ring.These rings can form condensed ring with aromatic rings generation condensations such as phenyl ring.As the above-mentioned compound with condensed ring, the compound etc. such as with benzimidazole ring, benzopyrazoles ring, BTA ring, benzoxazole ring, benzoisoxazole ring, benzothiazole ring or benzisothiazole ring can be listed.
Above-mentioned azoles ring, above-mentioned condensed ring (BTA ring, benzothiazole ring etc.) can have substituting group separately.As this substituting group, include, for example out the alkyl of the carbon numbers 1 ~ 6 (preferred carbon number 1 ~ 3) such as methyl, ethyl, propyl group, isopropyl, butyl; The alkoxyl of the carbon numbers 1 ~ 12 (preferred carbon number 1 ~ 3) such as methoxyl group, ethyoxyl, isopropoxy, butoxy; The aryl of the carbon numbers 6 ~ 10 such as phenyl, tolyl, naphthyl; Amino; Methylamino, dimethylamino etc. (list or two) C 1-10alkyl amino; Amino-the C such as amino methyl, 2-amino-ethyl 1-6alkyl; Single or the two (C such as N, N-diethylamino methyl, two (2-ethylhexyl) amino methyls of N, N- 1-10alkyl) amino-C 1-6alkyl; Sulfydryl; The alkoxy carbonyl group of the carbon number such as methoxycarbonyl group, carbethoxyl group 1 ~ 6; Carboxyl; Carboxyl-the C such as carboxymethyl 1-6alkyl; Carboxyl-the C such as 2-carboxyethyl sulfenyl 1-6alkylthio group; Two (hydroxyl-the C of N, N-such as two (methylol) amino methyls of N, N- 1-4alkyl) amino-C 1-4alkyl; Sulfo group etc.In addition, the above-mentioned compound containing azoles ring can form the salt such as sodium salt, sylvite.
From the aspect of the rust inhibition to metal, the aromatic rings such as preferred azoles ring and phenyl ring define the compound of condensed ring, wherein, BTA based compound (there is the compound of BTA ring), benzothiazole based compound (there is the compound of benzothiazole ring) is particularly preferably.
As above-mentioned BTA based compound, include, for example out 1,2,3-BTA, methylbenzotrazole, carboxyl benzotriazole, carboxymethyl BTA, 1-[N, two (2-ethylhexyl) amino methyl of N-] BTA, 1-[N, two (2-ethylhexyl) amino methyl of N-] methylbenzotrazole, 2,2 '-[[(methyl isophthalic acid H-BTA-1-base) methyl] imino group] di-methylcarbinol or their sodium salt etc.
As above-mentioned benzothiazole based compound, such as 2-mercaptobenzothiazole, 3-(2-(benzothiazolyl) sulfo-) propionic acid or their sodium salt etc. can be listed.
Compound containing azoles ring can be used singly, or in combination of two or more kinds.
The addition [solid constituent (nonvolatile component)] of antirust agent (such as the above-mentioned compound containing azoles ring) [solid constituent (nonvolatile component)] is not as long as destroying with in the scope of the characteristic of the adaptation of adherend, foaming body itself, such as relative to resin material (polymer) [solid constituent (nonvolatile component)] 100 weight portions, such as, be 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 is more preferably 3 weight portions, more preferably 2 weight portions.
In addition, not destroying in the scope of impact absorbency, other suitable arbitrarily compositions can be contained.Other compositions so only containing a kind, also can contain two or more.As these other compositions, include, for example out component of polymer other than the above, softening agent, antioxidant, age resistor, gelating agent, curing agent, plasticizer, filler, reinforcing agent, blowing agent, fire retardant, light stabilizer, ultra-violet absorber, colouring agent (pigment, dyestuff etc.), pH adjusting agent, solvent (organic solvent), thermal polymerization, Photoepolymerizationinitiater initiater etc.
As above-mentioned filler, include, for example out silica, clay (mica, talcum, terre verte etc.), aluminium oxide, titanium dioxide, 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, piezoelectric particles (titanium oxide etc.), electroconductive particle, thermal conductivity particle (boron nitride etc.), organic filler (silicone powder etc.) etc. also can be added.
Foaming body layer in duplexer of the present invention can manufacture by the resin combination comprising the resin material (polymer) forming foaming body is carried out foaming and molding.As foaming method (the formation method of bubble), normally used method in the foaming and molding such as physical method, chemical method can be adopted.In general, physical method makes the gas componant such as air, nitrogen be scattered in polymer solution, and pass through mechanical mixture and form the method for bubble.In addition, chemical method is that the gas produced by the thermal decomposition because adding the blowing agent in polymer substrate to forms abscess, thus obtains the method for foaming body.From viewpoints such as environmental problems, be preferably physical method.The bubble formed by physical method mostly is continuous air bubbles.
As the resin combination of the resin material (polymer) comprised for foaming and molding, resin material can be used to dissolve the resin solution obtained in a solvent, from the view point of bubble, preferably use the emulsion comprising resin material.As emulsion, can by used in combination for emulsion of more than two kinds.
From the view point of film forming, the solid component concentration of preferred emulsion is high.The solid component concentration of emulsion is preferably more than 30 % by weight, is more preferably more than 40 % by weight, more preferably more than 50 % by weight.
In the present invention, the operation (operation A) of preferably bubbling via making emulsion resin composition mechanically foam makes the method for foaming body.As sparger, be not particularly limited, include, for example out the device such as spray mode of high speed shear mode, mode of vibration, gas-pressurized.Wherein, from the view point of miniaturization, the Large Copacity making of bubble diameter, high speed shear mode is preferably.
Bubble when being bubbled by mechanical agitation is the bubble that gas (gas) enters into emulsion.As gas, as long as be inactive relative to emulsion, be just not particularly limited, air, nitrogen, carbon dioxide etc. can be listed.Wherein, from the view point of economy, be preferably air.
Play the emulsion resin composition of alveolation to be coated on base material via said method will be utilized and to carry out dry operation (process B), thus above-mentioned foaming body layer can be obtained.As above-mentioned base material, be not particularly limited, the plastic foil (the PETG film etc. after lift-off processing), plastic foil (PETG film etc.), heat-conducting layer (heat-conducting layer described later) etc. such as after lift-off processing can be listed.When being coated with as base material by heat-conducting layer, the adaptation of foaming body layer and heat-conducting layer can be improved, in addition, also can improve the efficiency of drying process when making foaming body layer.
In above-mentioned process B, as coating process, drying means, general method can be adopted.Process B preferably includes: by the emulsion resin composition of the bubbles be coated on base material more than 50 DEG C and lower than carry out dry preparation drying process B1 at the temperature of 125 DEG C and after preparation drying process B1 further more than 125 DEG C and less than the 200 DEG C trunk drying process B2 carrying out drying.
By arranging preparation drying process B1 and trunk drying process B2, thus can prevent temperature sharply from rising and the merging of the bubble that causes, the breaking of bubble.Especially for the foaming body layer that thickness is little, the sharply rising of Yin Wendu and cause bubble merge or break, therefore, arranges the significant of preparation drying process B1.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 such as 0.5 minute ~ 30 minutes, is preferably 1 minute ~ 15 minutes.In addition, the temperature in trunk drying process B2 be preferably more than 130 DEG C and less than 180 DEG C, be more preferably more than 130 DEG C and less than 160 DEG C.The time of trunk drying process B2 is such as 0.5 minute ~ 30 minutes, is preferably 1 minute ~ 15 minutes.
For the mean cell diameter of foaming body, maximum cell diameter and smallest bubbles bore dia, mixing speed during kind and amount, adjustment mechanical agitation by adjustment form surface-active agent and mixing time and obtain the foaming body of the mean cell diameter of 10 ~ 150 μm of scopes.
With regard to the density of foaming body, obtain 0.2 ~ 0.7g/cm by gas (gas) component amount entered in emulsion resin composition during adjustment mechanical agitation 3the foaming body of density.
At least one mask toughness of preferred foaming body layer.In the sticking situation of surperficial tool of foaming body layer, even if do not arrange adhesive phase between foaming body layer and heat-conducting layer, also can obtain duplexer of the present invention.As the method for the surface of foaming body layer being given to viscosity, such as following method can be listed: relative to the whole monomer components (monomer component total amount) of resin material polymer such as () acrylic acid series polymeric compounds forming above-mentioned foaming body, the Tg of homopolymers is used (to be such as more than-70 DEG C and lower than-10 DEG C lower than-10 DEG C, preferably-70 DEG C ~-12 DEG C,-65 DEG C ~-15 DEG C further preferably) monomer such as 70 ~ 98 % by weight (lower limit is preferably 75 % by weight, the upper limit is preferably 97 % by weight), as the monomer of the resin material (polymer) of the above-mentioned foaming body of formation, and suitably select the method that other monomers are used.
For by sticking for tool foaming body layer and the directly stacked and duplexer obtained of heat-conducting layer, even if do not arrange, adhesive linkage is two-layer also can not be peeled off, and can obtain high bonding reliability.In addition, due to can not adhesive linkage be arranged, therefore, the caliper portion of adhesive linkage can be used for the thickness thickening heat-conducting layer, the thermal conductivity of this duplexer can be improved.In addition, the less thick of duplexer can be made, the further slimming of the electrical equipment or electronic equipment etc. as mounting object can be contributed to.In addition, the manufacture efficiency of this duplexer can be improved, can also cost 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 the value utilizing conventional method to record.The thermal conductivity of heat-conducting layer is preferably more than 300W/mK, is more preferably more than 400W/mK.By making the thermal conductivity of heat-conducting layer be more than 200W/mK, thus excellent heat diffusivity (thermal diffusivity) can be given play to.The practical upper limit of thermal conductivity is such as 1500W/mK.It should be noted that, heat-conducting layer can be stacked more than 2 layers.
The thickness of heat-conducting layer can be adjusted to any thickness according to object.The thickness of heat-conducting layer is preferably more than 5 μm, is more preferably more than 7 μm.The upper limit of the thickness of heat-conducting layer is such as 130 μm, is preferably 120 μm, more preferably 110 μm.
As heat-conducting layer, graphite flake, metal forming can be listed.As the material of metal forming, such as aluminium, gold, silver, copper etc. can be listed.As metal forming, the aluminium foil, Copper Foil etc. with higher far infrared reflectivity and process costs cheapness can be listed.
Copper Foil has rolled copper foil, electrolytic copper foil etc.When heat-conducting layer is rolled copper foil, there is in the table of Copper Foil glassy surface and matsurface.When glassy surface is such as by being coated with stacked foaming body layer, when coiling into roll, even without protection distance piece (カ バ ー セ パ レ ー タ), also can prevent from batching dislocation.On the other hand, when matsurface is such as by being coated with stacked foaming body layer, the adaptation of foaming body layer and heat-conducting layer can be made to improve.
It should be noted that, as mentioned above, heat-conducting layer can be stacked more than 2 layers, if such as by graphite flake and metal foil laminated, then heat diffusivity improves because of the anisotropy of graphite flake.In addition, the heat-conducting layer that metal forming etc. have electric conductivity also has the function as electromagnetic wave barrier layer.
As the method for duplexer obtaining above-mentioned heat-conducting layer and foaming body layer, can list: by foamed sheet transfer printing (stickup) in the method for heat-conducting layer; Coat heat-conducting layer by playing the above-mentioned emulsion resin combination of alveolation and carry out drying and form the method etc. of foaming lamella.For the duplexer made by the method for the latter, compared with the duplexer made by the method by the former, shown higher bonding force.
[adhesive phase]
In duplexer of the present invention, above-mentioned foaming body layer and heat-conducting layer can be stacked across adhesive phase (adhesive layer).As the adhesive forming adhesive phase, being not particularly limited, can be any one in such as acrylic adhesive, elastomeric adhesive, silicone-based adhesive etc.It should be noted that, as previously mentioned, in the sticking situation of surperficial tool of foaming body layer, even if do not arrange adhesive phase, also can be stacked well with heat-conducting layer adherence.
The thickness of above-mentioned adhesive phase is such as 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 duplexer of the present invention is formed, can list such as: 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, duplexer of the present invention can carry out stacked with other functional layer (such as electromagnetic wave barrier layer, electromagnetic wave absorbing layer etc.).
Duplexer of the present invention commercially can circulate with the form of the coiling body (roll) being wound into roll.
Although the thickness of duplexer of the present invention is little, impact absorbency and heat diffusivity (thermal diffusivity) excellence.Therefore, such as in electrical equipment or electronic equipment, as various component or parts (such as optical component etc.) being installed electrical equipment that (arrangement) use when predetermined portion (such as basket etc.) or electronic device member is useful, be particularly useful as thermal diffusion impact-absorbing sheet.
As the optical component that duplexer of the present invention (sheet duplexer) can be utilized to carry out installing (arrangement), can list such as: the image display member (especially compact image display member) installed in the image display devices such as liquid crystal display, electroluminescent display, plasma scope; Be installed on the display members such as the touch panel of the device of the mobile communicating such as so-called " mobile phone ", " smart mobile phone ", " portable information terminal "; Camera, lens (especially minicam or lens) etc.
Electric/electronic of the present invention employs the duplexer of the invention described above.Electric/electronic like this, be such as the electric/electronic possessing display member, comprise and there is electrical equipment or the electronic equipment that above-mentioned duplexer (sheet duplexer) is clamped in the structure between the basket of this electrical equipment or electronic equipment and above-mentioned display member.As this electric/electronic, include, for example out the device etc. of the mobile communicating such as so-called " mobile phone ", " smart mobile phone ", " portable information terminal ".
[embodiment]
Below enumerate embodiment to be described in further detail the present invention, but the present invention is not by any restriction of embodiment.It should be noted that, unless otherwise specified, represent that " % " of content refers to % by weight.It should be noted that, cooperation number (weight portion) is the value that solid constituent (nonvolatile component) converts.
Embodiment 1
Utilize disperser (" RoboMix " PRIMIX Inc.) to acrylic emulsions solution (solid constituent amount 55%, ethyl acrylate-acrylic acid butyl ester-acrylonitrile copolymer (weight ratio 45:48:7)) 100 weight portions, the aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid constituent amount 33%) (surfactant A) 3 weight portion, oxazoline system crosslinking agent (" EPOCROS WS-500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20 % by weight), solid constituent amount 28.7%) 0.78 weight portion is uniformly mixed, it is made to play alveolation.This composition, foam is coated on the PET after lift-off processing (PETG) film (thick: 38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system), in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 120 μm, density 0.31g/cm 3, mean cell diameter 57 μm the foaming body (foamed sheet) of continuous air bubbles structure.
Fold the Copper Foil of thick 12 μm as heat-conducting layer at a surface layer of above-mentioned foamed sheet, obtain the duplexer comprising Copper Foil/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 2
Utilize disperser (" RoboMix " PRIMIX Inc.) to acrylic emulsions solution (solid constituent amount 55%, ethyl acrylate-acrylic acid butyl ester-acrylonitrile copolymer (weight ratio 45:48:7)) 100 weight portions, the aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 weight portions, oxazoline system crosslinking agent (" EPOCROS WS-500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20 % by weight), solid constituent amount 28.7%) 0.78 weight portion is uniformly mixed, it is made to play alveolation.This composition, foam is coated on the PET after lift-off processing (PETG) film (thick: 38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system), in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 150 μm, density 0.31g/cm 3, mean cell diameter 57 μm the foaming body (foamed sheet) of continuous air bubbles structure.
A surface layer in above-mentioned foamed sheet folds the Copper Foil of thick 12 μm as heat-conducting layer, obtains the duplexer comprising Copper Foil/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 3
Utilize disperser (" RoboMix " PRIMIX Inc.) to acrylic emulsions solution (solid constituent amount 55%, ethyl acrylate-acrylic acid butyl ester-acrylonitrile copolymer (weight ratio 45:48:7)) 100 weight portions, the aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 weight portions, oxazoline system crosslinking agent (" EPOCROS WS-500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20 % by weight), solid constituent amount 28.7%) 0.78 weight portion is uniformly mixed, it is made to play alveolation.This composition, foam is coated on the PET after lift-off processing (PETG) film (thick: 38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system), in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 90 μm, density 0.39g/cm 3, mean cell diameter 56 μm the foaming body (foamed sheet) of continuous air bubbles structure.
The acrylic adhesive layer double-faced adhesive tape (trade name " No.5603 ") of the Dong electrician Inc. (, thick 30 μm) is formed in face of above-mentioned foamed sheet, on this adhesive phase, the Copper Foil of stacked thick 35 μm is as heat-conducting layer, obtains the duplexer comprising Copper Foil/adhesive phase/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 4
Utilize disperser (" RoboMix " PRIMIX Inc.) to acrylic emulsions solution (solid constituent amount 55%, ethyl acrylate-acrylic acid butyl ester-acrylonitrile copolymer (weight ratio 45:48:7)) 100 weight portions, the aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 weight portions, oxazoline system crosslinking agent (" EPOCROS WS-500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20 % by weight), solid constituent amount 28.7%) 0.78 weight portion is uniformly mixed, it is made to play alveolation.This composition, foam is coated on the PET after lift-off processing (PETG) film (thick: 38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system), in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 120 μm, density 0.31g/cm 3, maximum cell diameter 94 μm, smallest bubbles bore dia 30 μm, mean cell diameter 57 μm the foaming body (foamed sheet) of continuous air bubbles structure.
A surface layer in above-mentioned foamed sheet folds the Copper Foil of thick 35 μm as heat-conducting layer, obtains the duplexer comprising Copper Foil/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 5
Utilize disperser (" RoboMix " PRIMIX Inc.) to acrylic emulsions solution (solid constituent amount 55%, ethyl acrylate-acrylic acid butyl ester-acrylonitrile copolymer (weight ratio 45:48:7)) 100 weight portions, the aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 weight portions, oxazoline system crosslinking agent (" EPOCROS WS-500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20 % by weight), solid constituent amount 28.7%) 0.78 weight portion is uniformly mixed, it is made to play alveolation.This composition, foam is coated on the PET after lift-off processing (PETG) film (thick: 38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system), in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 120 μm, density 0.31g/cm 3, mean cell diameter 57 μm the foaming body (foamed sheet) of continuous air bubbles structure.
The acrylic adhesive layer double-faced adhesive tape (trade name " No.5603 ") of the Dong electrician Inc. (, thick 30 μm) is formed in face of above-mentioned foamed sheet, on this adhesive phase, the Copper Foil of stacked thick 12 μm is as heat-conducting layer, obtains the duplexer comprising Copper Foil/adhesive phase/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 6
Utilize disperser (" RoboMix " PRIMIX Inc.) to be uniformly mixed acrylic emulsions solution (" LX-852B " Japanese ZEON Inc., solid constituent amount 45%) 100 weight portions, aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid constituent 33%) 3.7 weight portions, polyacrylic thickener (copolymer (acrylic acid 20 % by weight) of ethyl acrylate-acrylic acid, solid constituent 28.7%) 0.96 weight portion, make it play alveolation.This composition, foam is coated on the PET after lift-off processing (PETG) film (thick: 38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system), in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 150 μm, density 0.37g/cm 3, mean cell diameter 43 μm the foaming body (foamed sheet) of continuous air bubbles structure.
A surface layer in above-mentioned foamed sheet folds the Copper Foil of thick 12 μm as heat-conducting layer, obtains the duplexer comprising Copper Foil/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Comparative example 1
Utilize the twin shaft mixing roll of JSW (JSW) Inc. in the temperature of 200 DEG C to polypropylene [melt flow rate (MFR) (MFR): 0.35g/10min]: 45 weight portions, the mixture (MFR (230 DEG C): 6g/10 minute of polyolefin elastomer and softening agent (paraffin series extend oil (extension oil)), JIS A hardness: 79 °, softening agent 30 mass parts is coordinated relative to polyolefin elastomer 100 mass parts): 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 carry out mixing after, be extruded into wire harness shape, water-cooled postforming is graininess.This particle is put into the single axle extruding machine of Inc. of JSW, under the atmosphere of 220 DEG C, inject carbon dioxide under the pressure of 13 (inject after 12) MPa.Carbon dioxide injects according to the ratio relative to particle total amount being 5.6 % by weight.After making carbon dioxide fully saturated, be cooled to the temperature being suitable for foaming, then mould is utilized to be extruded into cylindrical shape, make it by between the axle (マ Application De リ Le) that cools the inner surface of foaming body and the foaming body cooling air-flow cooled the outer surface of the foaming body of the cylindrical shape that the annular die from extruder is extruded, the some of diameter is cut off, be launched into sheet, obtain the former material of rectangular foaming body.For the former material of this rectangular foaming body, mean cell diameter is 55 μm, apparent density is 0.041g/cm 3.
The former material of this rectangular foaming body cut into the width (slit processing) of regulation, use serial section device (section production line), the low ratio foamed layer on surface is peeled off by each face one by one, obtains foamed resin (thick 0.30mm, wide 550mm).
Make above-mentioned foamed resin by the temperature of induction heat generating roller is set to 160 DEG C, is set in gap in the above-mentioned apparatus for continous treatment of 0.20mm, utilize heat to carry out melt process to one side, carry out slice processing, then batch, obtain coiling body.It should be noted that, (draw I and get り) speed of drawing is set to 20m/min.
Then, by above-mentioned coiling body uncoiling, make it by the temperature of induction heat generating roller is set to 160 DEG C, is set in gap in the above-mentioned apparatus for continous treatment of 0.10mm, heat is utilized to carry out melt process to the face (untreated face) of not carrying out melt process thus, carry out slice processing, then batch, obtain the two-sided resin expanded body piece through heat fusing process.It should be noted that, hauling speed is set to 20m/min.
The acrylic adhesive layer double-faced adhesive tape (trade name " No.5603 ") of the Dong electrician Inc. (, thick 30 μm) is formed in face of above-mentioned foaming body piece, on this adhesive phase, the Copper Foil of stacked thick 12 μm is as heat-conducting layer, obtains the duplexer comprising Copper Foil/adhesive phase/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Comparative example 2
Utilize the twin shaft mixing roll of JSW (JSW) Inc. in the temperature of 200 DEG C to polypropylene [melt flow rate (MFR) (MFR): 0.35g/10min]: 45 weight portions, the mixture (MFR (230 DEG C): 6g/10 minute of polyolefin elastomer and softening agent (paraffin series extend oil), JISA hardness: 79 °, softening agent 30 mass parts is coordinated relative to polyolefin elastomer 100 mass parts): 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 carry out mixing after, be extruded into wire harness shape, water-cooled postforming is graininess.This particle is put in the single axle extruding machine of Inc. of JSW, under the atmosphere of 220 DEG C, inject carbon dioxide under the pressure of 13 (inject after 12) MPa.Carbon dioxide injects according to the ratio relative to particle total amount being 5.6 % by weight.After making carbon dioxide fully saturated, be cooled to the temperature being suitable for foaming, then mould is utilized to be extruded into cylindrical shape, make it by between the axle that cools the inner surface of foaming body and the foaming body cooling air-flow cooled the outer surface of the foaming body of the cylindrical shape that the annular die from extruder is extruded, the some of diameter is cut off, be launched into sheet, obtain the former material of rectangular foaming body.For the former material of this rectangular foaming body, mean cell diameter is 55 μm, apparent density is 0.041g/cm 3.
The former material of this rectangular foaming body is cut into the width (slice processing) of regulation, use serial section device (section production line), the low ratio foamed layer on surface is peeled off by each face one by one, obtains foamed resin (thick 0.30mm, wide 550mm).
Make above-mentioned foamed resin by the temperature of induction heat generating roller is set to 160 DEG C, is set in gap in the above-mentioned apparatus for continous treatment of 0.20mm, utilize heat to carry out melting to one side and dissolve process, carry out slice processing, then batch, obtain coiling body.It should be noted that, hauling speed is set to 20m/min.
Then, by above-mentioned coiling body uncoiling, make it by the temperature of induction heat generating roller is set to 160 DEG C, is set in gap in the above-mentioned apparatus for continous treatment of 0.10mm, heat is utilized to carry out melt process to the face (untreated face) of not carrying out melt process, carry out slice processing, then batch, obtain the two-sided resin expanded body piece through heat fusing process.It should be noted that, hauling speed is set to 20m/min.
Wish that a surface layer in above-mentioned foaming body piece folds the Copper Foil of thick 12 μm as heat-conducting layer.But, due to Copper Foil and foaming body layer not closely sealed and peel off immediately, therefore cannot carry out impact absorbency test.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Comparative example 3
Utilize disperser (" RoboMix " PRIMIX Inc.) to acrylic emulsions solution (solid constituent amount 55%, ethyl acrylate-acrylic acid butyl ester-acrylonitrile copolymer (weight ratio 45:48:7)) 100 weight portions, the aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 weight portions, oxazoline system crosslinking agent (" EPOCROS WS-500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20 % by weight), solid constituent amount 28.7%) 0.78 weight portion is uniformly mixed, it is made to play alveolation.This foaming body is coated on the PET after lift-off processing (PETG) film (thick: 38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system), in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 120 μm, density 0.31g/cm 3, mean cell diameter 57 μm the foaming body (foamed sheet) of continuous air bubbles structure.
Non-laminated copper foil on above-mentioned foamed sheet.
Comparative example 4
Utilize disperser (" RoboMix " PRIMIX Inc.) to be uniformly mixed acrylic emulsions solution (solid constituent amount 60%, methyl acrylate-Methyl Methacrylate-acrylonitrile Copolymer (acrylonitrile 5 % by weight)) 100 weight portions, aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 2.8 weight portions, polyacrylic thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20 % by weight), solid constituent amount 28.7%) 0.48 weight portion, make it play alveolation.This composition, foam is coated on the PET after lift-off processing (PETG) film (thick: 38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system), in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 150 μm, density 0.45g/cm 3, mean cell diameter 69 μm the foaming body (foamed sheet) of continuous air bubbles structure.
Wish that a surface layer in above-mentioned foamed sheet folds the Copper Foil of thick 12 μm as heat-conducting layer.But, due to Copper Foil and foaming body layer not closely sealed and peel off immediately, therefore cannot carry out impact absorbency test.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 7
Utilize disperser (" RoboMix " PRIMIX Inc.) to acrylic emulsions solution (solid constituent amount 55%, ethyl acrylate-acrylic acid butyl ester-acrylonitrile copolymer (weight ratio 45:48:7)) 100 weight portions, the aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid constituent amount 33%) (surfactant A) 1.5 weight portion, carboxy betaine type amphoteric surfactant (" Amogen CB-H ", first industrial pharmaceutical Inc.) (surfactant B) 1 weight portion, oxazoline system crosslinking agent (" EPOCROS WS-500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20 % by weight), solid constituent amount 28.7%) 0.78 weight portion, BTA system antirust agent " SEETEC BT-NA ", SHIPRO changes into Inc.) 0.5 weight portion is uniformly mixed, it is made to play alveolation.This composition, foam is coated on the PET after lift-off processing (PETG) film (thick: 38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system), in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 130 μm, density 0.33g/cm 3, maximum cell diameter 110 μm, smallest bubbles bore dia 20 μm, mean cell diameter 45 μm the foaming body (foamed sheet) of continuous air bubbles structure.
A surface layer in above-mentioned foamed sheet folds the Copper Foil of thick 35 μm as heat-conducting layer, obtains the duplexer comprising Copper Foil/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 8
Utilize disperser (" RoboMix " PRIMIX Inc.) to acrylic emulsions solution (solid constituent amount 55%, ethyl acrylate-acrylic acid butyl ester-acrylonitrile copolymer (weight ratio 45:48:7)) 100 weight portions, the aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 weight portions, oxazoline system crosslinking agent (" EPOCROS WS-500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20 % by weight), solid constituent amount 28.7%) 0.78 weight portion, BTA system antirust agent (" SEETEC BT-NA ", SHIPRO changes into Inc.) 0.5 weight portion is uniformly mixed, it is made to play alveolation.This composition, foam is coated on the PET after lift-off processing (PETG) film (thick: 38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system), in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 130 μm, density 0.43g/cm 3, maximum cell diameter 160 μm, smallest bubbles bore dia 41 μm, mean cell diameter 101 μm the foaming body (foamed sheet) of continuous air bubbles structure.
A surface layer in above-mentioned foamed sheet folds the Copper Foil of thick 35 μm as heat-conducting layer, obtains the duplexer comprising Copper Foil/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 9
Utilize disperser (" RoboMix " PRIMIX Inc.) to acrylic emulsions solution (solid constituent amount 55%, ethyl acrylate-acrylic acid butyl ester-acrylonitrile copolymer (weight ratio 45:48:7)) 100 weight portions, the aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 weight portions, oxazoline system crosslinking agent (" EPOCROS WS-500 " Japanese catalyst Co. system, solid constituent amount 39%) 2 weight portions, polyacrylic thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20 % by weight), solid constituent amount 28.7%) 0.78 weight portion, BTA system antirust agent (" SEETEC BT-NA ", SHIPRO changes into Inc.) 0.5 weight portion is uniformly mixed, it is made to play alveolation.This composition, foam is coated on the PET after lift-off processing (PETG) film (thick: 38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system), in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 130 μm, density 0.24g/cm 3, maximum cell diameter 69.5 μm, smallest bubbles bore dia 15 μm, mean cell diameter 34 μm the foaming body (foamed sheet) of continuous air bubbles structure.
A surface layer in above-mentioned foamed sheet folds the Copper Foil of thick 35 μm as heat-conducting layer, obtains the duplexer comprising Copper Foil/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 10
Utilize disperser (" RoboMix " PRIMIX Inc.) to be uniformly mixed acrylic emulsions solution (solid constituent amount 55%, ethyl acrylate-acrylic acid butyl ester-acrylonitrile copolymer (weight ratio 40:45:15)) 100 weight portions, aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 weight portions, polyacrylic thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20 % by weight), solid constituent amount 28.7%) 0.58 weight portion, make it play alveolation.This composition, foam is coated on the PET after lift-off processing (PETG) film (thick: 38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system), in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 150 μm, density 0.31g/cm 3, maximum cell diameter 187 μm, smallest bubbles bore dia 21 μm, mean cell diameter 72 μm the foaming body (foamed sheet) of continuous air bubbles structure.
A surface layer in above-mentioned foamed sheet folds the Copper Foil of thick 35 μm as heat-conducting layer, obtains the duplexer comprising Copper Foil/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 11
Utilize disperser (" RoboMix " PRIMIX Inc.) to acrylic emulsions solution (solid constituent amount 55%, ethyl acrylate-acrylic acid butyl ester-acrylonitrile copolymer (weight ratio 45:48:7)) 100 weight portions, the aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 weight portions, oxazoline system crosslinking agent (" EPOCROS WS-500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20 % by weight), solid constituent amount 28.7%) 0.78 weight portion, BTA system antirust agent (" SEETEC BT-NA ", SHIPRO changes into Inc.) 0.5 weight portion is uniformly mixed, it is made to play alveolation.This composition, foam is coated on the PET after lift-off processing (PETG) film (thick: 38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system), in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 450 μm, density 0.25g/cm 3, maximum cell diameter 199 μm, smallest bubbles bore dia 24 μm, mean cell diameter 84 μm the foaming body (foamed sheet) of continuous air bubbles structure.
A surface layer in above-mentioned foamed sheet folds the Copper Foil of thick 35 μm as heat-conducting layer, obtains the duplexer comprising Copper Foil/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 12
Utilize disperser (" RoboMix " PRIMIX Inc.) to acrylic emulsions solution (solid constituent amount 55%, ethyl acrylate-acrylic acid butyl ester-acrylonitrile copolymer (weight ratio 45:48:7)) 100 weight portions, the aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 weight portions, oxazoline system crosslinking agent (" EPOCROS WS-500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20 % by weight), solid constituent amount 28.7%) 0.78 weight portion, BTA system antirust agent (" SEETEC BT-NA ", SHIPRO changes into Inc.) 0.5 weight portion is uniformly mixed, it is made to play alveolation.This composition, foam is coated on the PET after lift-off processing (PETG) film (thick: 38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system), in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 300 μm, density 0.25g/cm 3, maximum cell diameter 149 μm, smallest bubbles bore dia 19 μm, mean cell diameter 76 μm the foaming body (foamed sheet) of continuous air bubbles structure.
A surface layer in above-mentioned foamed sheet folds the Copper Foil of thick 35 μm as heat-conducting layer, obtains the duplexer comprising Copper Foil/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 13
Utilize disperser (" RoboMix " PRIMIX Inc.) to acrylic emulsions solution (solid constituent amount 55%, ethyl acrylate-acrylic acid butyl ester-acrylonitrile copolymer (weight ratio 45:48:7)) 100 weight portions, the aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 weight portions, oxazoline system crosslinking agent (" EPOCROS WS-500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20 % by weight), solid constituent amount 28.7%) 0.78 weight portion is uniformly mixed, it is made to play alveolation.This composition, foam is coated on the Copper Foil (heat-conducting layer) of thick 35 μm, in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, formed thick 130 μm, maximum cell diameter 102 μm, smallest bubbles bore dia 23 μm, mean cell diameter 56 μm the foaming body layer of continuous air bubbles structure, obtain the duplexer comprising Copper Foil/foaming body layer.The thermal conductivity of above-mentioned Copper Foil is 400W/mK.
Embodiment 14
Utilize disperser (" RoboMix " PRIMIX Inc.) to acrylic emulsions solution (solid constituent amount 55%, ethyl acrylate-acrylic acid butyl ester-acrylonitrile copolymer (weight ratio 45:48:7)) 100 weight portions, the aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 weight portions, oxazoline system crosslinking agent (" EPOCROS WS-500 " Japanese catalyst Co. system, solid constituent amount 39%) 0.35 weight portion, polyacrylic thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20 % by weight), solid constituent amount 28.7%) 0.78 weight portion is uniformly mixed, it is made to play alveolation.This composition, foam is coated on the PET after lift-off processing (PETG) film (thick: 38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system), in 70 DEG C of dryings 4.5 minutes and in 140 DEG C of dryings 4.5 minutes, obtain thick 130 μm, density 0.31g/cm 3, maximum cell diameter 94 μm, smallest bubbles bore dia 30 μm, mean cell diameter 57 μm the foaming body (foamed sheet) of continuous air bubbles structure.
A surface layer in above-mentioned foamed sheet folds the graphite flake (GRAF TECH Inc.) of thick 40 μm as heat-conducting layer, obtains the duplexer 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 obtained in embodiment 1 ~ 14 and comparative example 1 ~ 4, duplexer.Show the result in table 1 ~ 3.It should be noted that, the cooperation number (weight portion) [solid constituent (nonvolatile component) conversion] of each composition in each embodiment, comparative example shown in table 1." Em " represents acrylic emulsions solution.
(mean cell diameter, maximum cell diameter, smallest bubbles bore dia)
Utilizing low vacuum SEM (Hightech Science Systems Inc. of " S-3400N type SEM " Hitachi) to obtain the expanded view picture of foaming body section, obtaining mean cell diameter (μm), maximum cell diameter (μm), smallest bubbles bore dia (μm) by carrying out image analysis.It should be noted that, the number of bubbles parsed is about 10 ~ 20.
(density)
Utilize the blanking knife model tool of 100mm × 100mm to carry out stamping-out to foaming body (foamed sheet), the size of the sample determined that liquidates measures.In addition, the diameter measuring terminal is utilized for 1/100 dial ga(u)ge of 20mm measures thickness.These values are utilized to calculate the volume of foaming body.
Then, the upper ware Libra of more than minimum scale 0.01g is utilized to measure the weight of foaming body.Density (the g/cm of foaming body is calculated according to these values 3).
(dynamic viscoelastic)
Utilize the film stretching mode determination of determination of viscoelasticity device (" ARES2KFRTN1-FCO " TA Instruments Japan Inc.), carry out temperature dispersion test when angular frequency is 1rad/s.To store elastic modulus E ' now and loss elastic modulus E " ratio and the temperature (DEG C) of peak value of loss angle tangent (tan δ) and intensity (maximum) measure.
" tan δ temperature " hurdle 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, calculate initial stage elastic modelling quantity (N/mm by slope during 10% strain 2), this initial stage elastic modelling quantity is evaluated.
(shear bond power)
By made foaming body (embodiment 3,5, in comparative example 1, double-faced adhesive tape (trade name " No.5603 ", Dong electrician Inc., thick 30 μm) is made to be pasted on the two-sided of foaming body) cut into 25mm × 25mm, respectively at the double faced adhesive SUS304BA plate of foaming body, thus make mensuration sample.The roller of 5kg is made a round trip on the mensuration sample of horizontal positioned crimp.After crimping, place 30 minutes under normal temperature (23 DEG C), then according to making the vertical mode of mensuration sample be fixed in stenter (Tensilon), stretching with draw speed 50mm/ minute, determining the shear bond power that it is the most central.Mensuration sample is determined, using its mean value as shear bond power (N/100mm in the mode of n=2 2).
(impact absorbency test)
Above-mentioned pendulum type shock machine (impact test apparatus) (with reference to Fig. 1 and Fig. 2) is used to carry out impact absorbency test.
For the duplexer (sample size: 20mm × 20mm) obtained in embodiment 1 ~ 14 and comparative example 1,3, tilt under the impact condition of 30 ° making the iron ball of 96g and carry out impact test, obtain impact absorbing rate (%).It should be noted that, become according to foaming side the mode that iron ball carries out the side impacted and arrange.Then, with the thickness (μm) of this impact absorbing rate (%) divided by foamed sheet, the impact absorbing rate R of per unit thickness is obtained.It should be noted that, for embodiment and the comparative example 1,3 that can implement impact absorbency test, even if after impact absorbing test, Copper Foil and foaming body layer still can maintain duplexer and form, and bonding reliability is good.
(heat diffusivity test)
Be used in hot box the device of the ceramic heater being provided with band thermocouple, carry out heat diffusivity test.As shown in Figures 3 and 4, on ceramic heater 103 (size on surface: horizontal 20mm × vertical 40mm), double-faced adhesive tape (trade name " No.5603 ", Dong electrician Inc., thick 30 μm) 102 is utilized by the duplexer (comparative example 3 is foaming body) 104 (horizontal 75mm × vertical 45mm) of embodiment or comparative example to be fixed (when having Copper Foil, the mode becoming heater side according to Copper Foil side is arranged), and the temperature (surface temperature) of the center on foaming body layer surface is measured.In addition, make heater wattage output constant, measure the heter temperature after 10 minutes.
(copper closing force)
When embodiment 4: make adhesive tape (No.31B, Dong electrician Inc.) fit in the foaming body (foamed sheet of gained; At the stacked stripping film of one side) a face.Be cut to the size of 20mm × 100mm, as assess sample.Stripping film is peeled, makes another face of foaming body at 25 DEG C, be pasted on Copper Foil as adherend, make the roller of 5Kg make a round trip to crimp.Take out after it is placed 1 day at 80 DEG C, 2 hours are put in ambient temperatare, then under the condition of peel angle 180 °, draw speed 300mm/ minute, implement disbonded test, determine bonding force (bonding force relative to Copper Foil) (N/20mm).
When embodiment 13: make adhesive tape (No.31B, Dong electrician Inc.) fit in the foamed sheet side of the duplexer of gained, cut into the size of 20mm × 100mm, as assess sample.Take out after it is placed 1 day at 80 DEG C, put 2 hours in ambient temperatare, then utilize two-sided tape that acrylic board is fixed in Copper Foil side.According to the mode that foamed sheet is peeled off from Copper Foil, under the condition of peel angle 180 °, draw speed 300mm/ minute, implement disbonded test, determine bonding force (bonding force relative to Copper Foil) (N/20mm).
Table 1
Symbol description
1, pendulum type shock machine (impact test apparatus)
2, test film [foaming body layer (foamed sheet) or duplexer]
3, retaining member
4, impact load component
5, pressure sensor
10, duplexer
11, stationary fixture
12, fixture is pressed
16, pressure regulating mechanism
20, pillar
21, arm
22, one end of support rod (axle)
23, support rod (axle)
24, son is impacted
25, electromagnet
28, support plate
A, put angle
100, foaming body layer
101, Copper Foil
102, adhesive tape
103, ceramic heater
104, sample (sample)
200, foaming body layer
201, heat-conducting layer

Claims (15)

1. a duplexer, it has foaming body layer and heat-conducting layer, and the thickness of described foaming body layer is 30 ~ 500 μm, and is 0.2 ~ 0.7g/cm by density 3, mean cell diameter be 10 ~ 150 μm foaming body form, the thermal conductivity of described heat-conducting layer is more than 200W/mK.
2. duplexer according to claim 1, wherein, the store elastic modulus when angular frequency of described foaming body in Measurement of Dynamic Viscoelasticity is 1rad/s and the ratio of loss elastic modulus and losstangenttanδ are more than-30 DEG C and have peak value in the scope of less than 30 DEG C.
3. duplexer according to claim 1 and 2, wherein, the maximum of the losstangenttanδ of described foaming body more than-30 DEG C and in the scope of less than 30 DEG C is more than 0.2.
4. the duplexer according to any one of claims 1 to 3, wherein, under 23 DEG C of environment and draw speed is in the tension test of 300mm/min, the initial stage elastic modelling quantity of foaming body is 5N/mm 2below.
5. the duplexer according to any one of Claims 1 to 4, wherein, in the impact absorbency test of duplexer employing pendulum type shock machine, when impacting sub weight 96g, having put angle 30 °, the value R that the impact absorbing rate that following formula defines obtains divided by the thickness of foaming body layer is more than 0.15, described impact absorbing rate is in %, and the unit of the thickness of described foaming body layer is μm
Impact absorbing rate (%)={ (F 0-F 1)/F 0} × 100
In above-mentioned formula, F 0for only colliding the impulsive force of impacting the period of the day from 11 p.m. to 1 a.m to support plate, F 1for the support plate to the structure be made up of support plate and described duplexer colliding the impulsive force of impacting the period of the day from 11 p.m. to 1 a.m.
6. the duplexer according to any one of Claims 1 to 5, wherein, the thickness of described heat-conducting layer is more than 5 μm.
7. the duplexer according to any one of claim 1 ~ 6, wherein, described heat-conducting layer is be selected from least one in graphite flake and metal forming.
8. the duplexer according to any one of claim 1 ~ 7, wherein, foaming body is formed by least one resin material be selected from acrylic acid series polymeric compounds, rubber, carbamate based polymer and vinyl-vinyl acetate copolymer.
9. the duplexer according to any one of claim 1 ~ 8, wherein, foaming body is formed via operation A, and described operation A is the operation that emulsion resin composition is mechanically foamed.
10. duplexer according to claim 9, wherein, foaming body is formed via process B further, and described process B is coated on by the emulsion resin composition obtained through mechanically foaming on base material and carries out dry operation.
11. duplexers according to claim 10, wherein, described process B comprises: by the emulsion resin composition of the bubbles be coated on base material more than 50 DEG C and lower than carry out dry preparation drying process B1 at the temperature of 125 DEG C and after preparation drying process B1 further more than 125 DEG C and less than the 200 DEG C trunk drying process B2 carrying out drying.
12. duplexers according to any one of claim 1 ~ 11, wherein, at the single or double of foaming body layer with across adhesive phase or be not laminated with heat-conducting layer across the mode of adhesive phase.
13. duplexers according to any one of claim 1 ~ 12, it is used as electrical equipment or electronic equipment thermal diffusion impact-absorbing sheet.
14. 1 kinds of electrical equipments or electronic equipment, it use the duplexer according to any one of claim 1 ~ 13.
15. electrical equipment according to claim 14 or electronic equipments, it is the electrical equipment or the electronic equipment that possess display member, and described electrical equipment or the electronic equipment duplexer had according to any one of claim 1 ~ 13 is clamped in the structure between the basket of this electrical equipment or electronic equipment and described display member.
CN201410315267.XA 2013-10-29 2014-07-03 Laminate Pending CN104553103A (en)

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CN106497523A (en) * 2016-09-27 2017-03-15 清华大学深圳研究生院 A kind of graphite composite material and preparation method thereof
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CN115298279B (en) * 2020-03-19 2024-01-09 三井化学株式会社 Self-adhesive sheet

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