WO2016047611A1 - 発泡シート - Google Patents
発泡シート Download PDFInfo
- Publication number
- WO2016047611A1 WO2016047611A1 PCT/JP2015/076729 JP2015076729W WO2016047611A1 WO 2016047611 A1 WO2016047611 A1 WO 2016047611A1 JP 2015076729 W JP2015076729 W JP 2015076729W WO 2016047611 A1 WO2016047611 A1 WO 2016047611A1
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- WO
- WIPO (PCT)
- Prior art keywords
- foam
- sheet according
- weight
- impact
- absorption rate
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
- C09J2433/006—Presence of (meth)acrylic polymer in the substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
- C09J2475/006—Presence of polyurethane in the substrate
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/50—Protective arrangements
- G02F2201/503—Arrangements improving the resistance to shock
Definitions
- the present invention relates to a foam sheet having excellent shock absorption and heat resistance even when the thickness is very thin, and an electric / electronic device using the foam sheet.
- an image display member fixed to an image display device such as a liquid crystal display, an electroluminescence display, a plasma display, a display member attached to a so-called “mobile phone”, “smart phone”, “portable information terminal”, camera,
- a foam material is used when an optical member such as a lens is fixed to a predetermined part (for example, a housing).
- Examples of such a foam material include a low-foam, fine-cell urethane-based foam having a closed cell structure and a product obtained by compression molding a highly foamed urethane, and a polyethylene-based foam having a closed cell and an expansion ratio of about 30 times. It was used.
- a gasket made of a polyurethane foam having an apparent density of 0.3 to 0.5 g / cm 3 , or an electrical / electric structure made of a foam structure having an average cell diameter of 1 to 500 ⁇ m.
- a sealing material for electronic devices is used.
- an object of the present invention is to provide a foamed sheet that exhibits excellent impact absorbability even when the thickness is very thin and has excellent heat resistance that does not deteriorate performance even at high temperatures.
- Another object of the present invention is to provide an electric / electronic device that is less likely to be damaged by an impact at the time of dropping, even if it is downsized and thinned, or has a heating element with a large calorific value.
- the present inventors have constituted a foam having a specific average cell diameter, a compression set at 80 ° C. of 80% or less, and a high temperature (80 ° C.).
- a foam sheet with a small difference between the shock absorption after compression and the initial shock absorption exhibits excellent shock absorption and excellent heat resistance even when the thickness is very thin. It was found that even if the installed electrical / electronic device was equipped with a heating element with a large calorific value, it was not damaged by the impact when dropped.
- the present invention has been completed through further studies based on these findings.
- the present invention is composed of a foam having an average cell diameter of 10 to 200 ⁇ m, a compression set at 80 ° C. of 80% or less, and an impact absorption change rate defined below is ⁇ 20% or less.
- a foam sheet is provided.
- Impact absorption change rate (%) ⁇ (shock absorption rate after high temperature compression b ⁇ initial impact absorption rate a) / initial impact absorption rate a ⁇ ⁇ 100
- Initial impact absorption rate a Impact absorption rate (%) of test piece A
- Impact absorption rate (%) ⁇ (F 0 -F 1 ) / F 0 ⁇ ⁇ 100 (In the above formula, F 0 is the impact force when the impactor collides only with the support plate, and F 1 impacts the impactor on the support plate of the structure consisting of the support plate and the test piece A). It is the impact force when letting
- the foamed sheet preferably has a thickness of 30 to 1000 ⁇ m and an apparent density of the foam of 0.2 to 0.7 g / cm 3 .
- the foam has a peak top in a range where a loss tangent (tan ⁇ ), which is a ratio of a storage elastic modulus and a loss elastic modulus at an angular frequency of 1 rad / s in dynamic viscoelasticity measurement, is ⁇ 30 ° C. or higher and 30 ° C. or lower. It is preferable.
- the foam can be formed of at least one resin material selected from the group consisting of acrylic polymer, rubber, urethane polymer, and ethylene-vinyl acetate copolymer.
- the foam may be formed through Step A for mechanically foaming the emulsion resin composition. Further, the foam may be formed through a step B in which a mechanically foamed emulsion resin composition is further coated on a substrate and dried. Further, the step B is a pre-drying step B1 in which the bubble-containing emulsion resin composition applied on the substrate is dried at 50 ° C. or higher and lower than 125 ° C., and then a main drying step B2 for further drying at 125 ° C. or higher and 200 ° C. May be included.
- the compression set at 80 ° C. is preferably 50% or less, more preferably 25% or less.
- the thickness is preferably 40 to 500 ⁇ m, more preferably 50 to 300 ⁇ m.
- the apparent density of the foam is preferably 0.21 to 0.6 g / cm 3 , more preferably 0.22 to 0.5 g / cm 3 .
- the foam sheet may have an adhesive layer on one side or both sides of the foam.
- It may be used as a shock absorbing sheet for electric / electronic devices.
- the present invention also provides an electric / electronic device in which the foam sheet is used.
- This electric / electronic device includes an electric / electronic device provided with a display member, wherein the foamed sheet is sandwiched between a casing of the electric or electronic device and the display member. It is.
- the foamed sheet of the present invention is made of a foam having a specific average cell diameter, has a compression set at 80 ° C. of 80% or less, and has a low impact absorption change rate of ⁇ 20% or less. Even if it is very thin, it exhibits excellent shock absorption and also has excellent heat resistance. Therefore, even when used in an electric / electronic device equipped with a heating element having a large calorific value, the performance as an impact absorbing sheet does not deteriorate and high reliability can be obtained.
- FIG. 1 It is a schematic block diagram of a pendulum type impact tester (impact test device). It is a figure which shows schematic structure of the holding member of a pendulum type impact tester (impact test apparatus).
- the foam sheet of the present invention is composed of a foam having an average cell diameter of 10 to 200 ⁇ m.
- the lower limit of the average cell diameter of the foam is preferably 15 ⁇ m, more preferably 20 ⁇ m, and the upper limit is preferably 150 ⁇ m, more preferably 130 ⁇ m, and even more preferably 100 ⁇ m.
- the maximum cell diameter of the foam is, for example, 40 to 800 ⁇ m, the lower limit is preferably 60 ⁇ m, more preferably 80 ⁇ m, and the upper limit is preferably 400 ⁇ m, more preferably 220 ⁇ m.
- the minimum cell diameter of the foam is, for example, 5 to 70 ⁇ m, and the lower limit is preferably 8 ⁇ m, more preferably 10 ⁇ m, and the upper limit is preferably 60 ⁇ m, more preferably 50 ⁇ m.
- the foamed sheet of the present invention has a compression set at 80 ° C. of 80% or less, preferably 50% or less, more preferably 25% or less, and particularly preferably 10% or less.
- the compression set test at 80 ° C. can be performed in accordance with JIS K6262.
- the compression set (%) is obtained by the following formula.
- CS ⁇ (t0 ⁇ t1) / (t0 ⁇ t2) ⁇ ⁇ 100
- CS Compression set (%)
- t0 Original thickness of the test piece (mm)
- t1 The thickness of the test piece 30 mm after removing the test piece from the compression apparatus (mm)
- t2 Test specimen thickness (mm) with compressive strain applied
- the compression set is a value when the test piece is compressed by 60%.
- the foamed sheet of the present invention has an impact absorption change rate defined below as ⁇ 20% or less, preferably ⁇ 15% or less, more preferably ⁇ 5% or less.
- Impact absorption change rate (%) ⁇ (shock absorption rate after high temperature compression b ⁇ initial impact absorption rate a) / initial impact absorption rate a ⁇ ⁇ 100
- Initial impact absorption rate a Impact absorption rate (%) of test piece A
- Impact absorption rate (%) ⁇ (F 0 -F 1 ) / F 0 ⁇ ⁇ 100 (In the above formula, F 0 is the impact force when the impactor collides only with the support plate, and F 1 impacts the impactor on the support plate of the structure consisting of the support plate and the test piece A). It is the impact force when letting
- the foamed sheet of the present invention has a low compression set at 80 ° C. and a low rate of change in shock absorption. Therefore, even when compressed at a high temperature, the foam is not easily crushed, and excellent thickness recovery is obtained. Even when subjected to an impact at a temperature, the same high shock absorption as at normal temperature is exhibited. Therefore, even when used in an electric / electronic device or the like provided with a heating element having a large calorific value, damage to the device can be prevented even if an impact is applied to the electric / electronic device when it is dropped.
- the impact test apparatus 1 (pendulum tester 1) includes a holding member 3 as a holding means for holding the test piece 2 (foamed sheet 2) with an arbitrary holding force, and the test piece 2
- An impact load member 4 for applying an impact stress to the test piece
- a pressure sensor 5 as an impact force detection means for detecting an impact force of the impact load member 4 against the test piece 2 and the like.
- the holding member 3 that holds the test piece 2 with an arbitrary holding force includes a fixing jig 11 and a holding jig 12 that is slidable so as to sandwich and hold the test piece 2 facing the fixing jig 11. It is configured.
- the pressing jig 12 is provided with a pressing pressure adjusting means 16.
- the impact load member 4 for applying an impact force to the test piece 2 held by the holding member 3 is supported so that one end 22 is pivotally supported with respect to the column 20 and an impactor 24 is provided on the other end side. It is composed of a rod 23 (shaft 23) and an arm 21 that lifts and holds the impactor 24 at a predetermined angle.
- a steel ball is used as the impactor 24, it is possible to lift the impactor 24 integrally by a predetermined angle by providing an electromagnet 25 at one end of the arm.
- the pressure sensor 5 that detects the impact force acting on the test piece 2 by the impact load member 4 is provided on the opposite side of the surface of the fixing jig 11 that contacts the test piece.
- the impactor 24 is a steel ball (iron ball).
- the angle at which the impactor 24 is lifted by the arm 21 is 40 °.
- the weight of the steel ball (iron ball) is 28 g.
- the test piece 2 is a highly elastic plate material such as a resin plate (acrylic plate, polycarbonate plate, etc.) or a metal plate between the fixing jig 11 and the holding jig 12. It is clamped via the support plate 28 configured.
- the impact absorbability is an impact force F 0 measured by causing the impactor 24 to collide with the support plate 28 after tightly fixing the fixing jig 11 and the support plate 28 using the impact test apparatus described above.
- the impact force F 1 measured by causing the impactor 24 to collide with the support plate 28 after inserting the test piece 2 between the fixing jig 11 and the support plate 28 and fixing the test piece 2 tightly is calculated.
- the Note that the impact test apparatus is the same apparatus as that of Example 1 of JP-A-2006-47277.
- the foamed sheet of the present invention is excellent in shock absorption while being thin.
- the impact absorption rate (impactor weight 28 g, swing-up angle 40 °) is usually 5 to 70%, and the lower limit is preferably 10%, more preferably 20%, still more preferably 28%.
- the upper limit is preferably 60%.
- the thickness of the foamed sheet of the present invention is not particularly limited, but is, for example, 30 to 1000 ⁇ m.
- the lower limit is more preferably 40 ⁇ m, still more preferably 50 ⁇ m, and the upper limit is more preferably 500 ⁇ m, still more preferably 300 ⁇ m, and particularly preferably 200 ⁇ m.
- the thickness of the foamed sheet is 30 ⁇ m or more, the bubbles can be contained uniformly, and more excellent impact absorbability can be exhibited. Further, by setting the thickness of the foamed sheet to 1000 ⁇ m or less, it is possible to easily follow a minute clearance.
- the foamed sheet of the present invention is excellent in impact absorption even if the thickness is as thin as 30 to 1000 ⁇ m.
- the ratio of the average cell diameter ( ⁇ m) to the thickness of the foamed sheet ( ⁇ m) is preferably in the range of 0.1 to 0.9.
- the lower limit of the ratio of the average cell diameter ( ⁇ m) to the thickness of the foamed sheet ( ⁇ m) is preferably 0.2, more preferably 0.3, and the upper limit is preferably 0.85, more preferably 0. .8.
- the apparent density of the foam constituting the foam sheet of the present invention is not particularly limited, but is preferably 0.2 to 0.7 g / cm 3 .
- the lower limit is more preferably 0.21 g / cm 3 , further preferably 0.22 g / cm 3
- the upper limit is more preferably 0.6 g / cm 3 , still more preferably 0.5 g / cm 3 , and particularly preferably 0.4 g / cm 3 .
- the apparent density of the foam is 0.2 g / cm 3 or more, higher strength can be maintained, and when it is 0.7 g / cm 3 or less, higher impact absorbability is exhibited. Further, when the apparent density of the foam is in the range of 0.2 to 0.4 g / cm 3 , even higher impact absorbability is exhibited.
- the impact absorption can be adjusted by selecting the average cell diameter, the apparent density, etc., but when the thickness of the foam sheet is very small (for example, a thickness of 30 to 500 ⁇ m), it may not be possible to sufficiently absorb the impact only by adjusting these characteristics. This is because when the thickness of the foam sheet is very thin, the bubbles in the foam are immediately crushed by the impact and the shock buffering function by the bubbles is lost.
- the peak top of the loss tangent (tan ⁇ ) which is the ratio of the storage elastic modulus and the loss elastic modulus at an angular frequency of 1 rad / s in the dynamic viscoelasticity measurement of the foam, is ⁇ 30 ° C. or higher and 30 ° C. or lower. It is preferable that it exists in the range. By doing in this way, even after bubbles are crushed, the constituent material of the foam exerts more functions of buffering the impact.
- the lower limit of the temperature range where the loss tangent peak top is present is more preferably ⁇ 25 ° C., further preferably ⁇ 20 ° C., particularly preferably ⁇ 10 ° C., and the upper limit is more preferably 20 ° C., further preferably 10 ° C.
- the peak temperature is ⁇ 30 ° C. or higher, more excellent compression recovery is exhibited.
- the peak temperature is 30 ° C. or lower, higher flexibility is exhibited, and more excellent shock absorption is exhibited.
- the peak top strength (maximum value) of loss tangent (tan ⁇ ) in the range of ⁇ 30 ° C. or higher and 30 ° C. or lower is preferably higher from the viewpoint of shock absorption, for example, 0.2 or higher, preferably 0.3 or higher.
- the upper limit value of the peak top intensity (maximum value) is, for example, 2.0.
- the peak temperature of the loss tangent (tan ⁇ ) often contributes to the impact absorption of the foam.
- the peak top of the loss tangent (tan ⁇ ) which is the ratio of the storage elastic modulus and loss elastic modulus at the angular frequency of 1 rad / s in the dynamic viscoelasticity measurement of the foam, is in the range of ⁇ 30 ° C. or higher and 30 ° C. or lower.
- the loss tangent (tan ⁇ ) peak exists at a location that matches the frequency of impact. That is, the range where the loss tangent (tan ⁇ ) is ⁇ 30 ° C. or higher and 30 ° C.
- the storage elastic modulus is a repulsive force with respect to the impact energy applied to the foam sheet. If the storage elastic modulus is high, the impact is repelled as it is.
- the loss elastic modulus is a physical property that changes impact energy applied to the foam sheet to heat, and the higher the loss elastic modulus is, the more the impact energy is changed to heat, so the impact is absorbed and the strain is reduced.
- the foam constituting the foam sheet of the present invention is not particularly limited in its composition and cell structure as long as it has the above characteristics.
- the cell structure may be any of an open cell structure, a closed cell structure, and a semi-continuous semi-closed cell structure. From the viewpoint of impact absorption, an open cell structure and a semi-open semi-closed cell structure are preferable.
- the foam can be constituted by a resin composition containing a resin material (polymer).
- the loss which is a ratio of the storage elastic modulus and the loss elastic modulus at an angular frequency of 1 rad / s in the dynamic viscoelasticity measurement of the resin composition in an unfoamed state [resin composition when not foamed (solid matter)]
- the peak top of the tangent (tan ⁇ ) is preferably in the range of ⁇ 30 ° C. to 30 ° C.
- the lower limit of the temperature range where the loss tangent peak top is present is more preferably ⁇ 25 ° C., further preferably ⁇ 20 ° C., particularly preferably ⁇ 10 ° C., and the upper limit is more preferably 20 ° C., further preferably 10 ° C.
- the peak top strength of (tan ⁇ ) (corresponding to the value obtained by dividing the apparent density (g / cm 3 ) of the foam) is preferably higher from the viewpoint of impact absorption.
- the peak top strength of the loss tangent (tan ⁇ ) in the range of ⁇ 30 ° C. to 30 ° C. of the resin composition (solid material) is preferably 0.9 (g / cm 3 ) ⁇ 1 or more,
- the upper limit is, for example, about 3 (g / cm 3 ) ⁇ 1 .
- the resin material (polymer) constituting the foam is not particularly limited, and a known or well-known resin material constituting the foam can be used.
- the resin material include acrylic polymers, rubbers, urethane polymers, and ethylene-vinyl acetate copolymers. Among these, acrylic polymers, rubbers, and urethane polymers are preferable from the viewpoint of impact absorption.
- One type of resin material (polymer) constituting the foam may be used alone, or two or more types may be used.
- the Tg of the resin material (polymer) can be used as an index or a guide.
- the resin material (polymer) has a Tg of ⁇ 50 ° C. or more and less than 50 ° C. (lower limit is preferably ⁇ 40 ° C., more preferably ⁇ 30 ° C., upper limit is preferably 40 ° C., more preferably 30 ° C.) It can be selected from resin materials (polymers) in the range.
- the acrylic polymer is preferably an acrylic polymer formed with a monomer having a homopolymer Tg of ⁇ 10 ° C. or more and a monomer having a homopolymer Tg of less than ⁇ 10 ° C. as essential monomer components.
- the ratio of the storage elastic modulus and loss elastic modulus at an angular frequency of 1 rad / s in dynamic viscoelasticity measurement is obtained by adjusting the amount ratio of the former monomer and the latter monomer.
- a foam having a loss tangent (tan ⁇ ) peak top of ⁇ 30 ° C. or higher and 30 ° C. or lower can be obtained relatively easily.
- glass transition temperature (Tg) when forming a homopolymer means “glass transition temperature (Tg of homopolymer of the monomer)”.
- Tg of homopolymer glass transition temperature (Tg of homopolymer of the monomer).
- the Tg of a homopolymer of a monomer not described in the above document refers to, for example, a value obtained by the following measurement method (see JP 2007-51271 A).
- this homopolymer solution is cast-coated on a separator and dried to prepare a test sample (sheet-like homopolymer) having a thickness of about 2 mm.
- This test sample was punched into a disk shape having a diameter of 7.9 mm, sandwiched between parallel plates, and subjected to a shear strain at a frequency of 1 Hz using a viscoelasticity tester (ARES, manufactured by Rheometrics). Viscoelasticity is measured in a shear mode at a heating rate of 150 ° C. and 5 ° C./min, and the peak top temperature of tan ⁇ is defined as Tg of the homopolymer.
- the Tg of the resin material (polymer) can also be measured by this method.
- the Tg is, for example, ⁇ 10 ° C. to 250 ° C., preferably 10 to 230 ° C., more preferably 50 to 200 ° C.
- Examples of the homopolymer having a Tg of ⁇ 10 ° C. or more include, for example, (meth) acrylonitrile; amide group-containing monomers such as (meth) acrylamide and N-hydroxyethyl (meth) acrylamide; (meth) acrylic acid; methacrylic acid (Meth) acrylic acid alkyl esters having homopolymers such as methyl and ethyl methacrylate having a Tg of ⁇ 10 ° C. or higher; (meth) acrylic acid isobornyl; heterocycle-containing vinyl monomers such as N-vinyl-2-pyrrolidone; Examples thereof include hydroxyl group-containing monomers such as ethyl methacrylate.
- (meth) acrylonitrile (especially acrylonitrile) is particularly preferable.
- (meth) acrylonitrile (especially acrylonitrile) is used as a monomer having a homopolymer Tg of ⁇ 10 ° C. or higher, the peak top strength of the loss tangent (tan ⁇ ) of the foam is increased because of the strong intermolecular interaction. be able to.
- the Tg is, for example, ⁇ 70 ° C. or more and less than ⁇ 10 ° C., preferably ⁇ 70 ° C. to ⁇ 12 ° C., more preferably ⁇ 65 ° C. to ⁇ 15 ° C. .
- Examples of the homopolymer having a Tg of less than ⁇ 10 ° C. include, for example, (meth) acrylic acid alkyl esters having a homopolymer Tg of less than ⁇ 10 ° C., such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. Is mentioned. These can be used individually by 1 type or in combination of 2 or more types. Among these, acrylic acid C 2-8 alkyl ester is particularly preferable.
- the content of the monomer having a Tg of -10 ° C. or more of the homopolymer is, for example, 2 to 30% by weight with respect to all the monomer components forming the acrylic polymer (total amount of monomer components), and the lower limit is preferably 3%. %, More preferably 4% by weight, and the upper limit is preferably 25% by weight, more preferably 20% by weight.
- the content of the monomer having a Tg of the homopolymer of less than ⁇ 10 ° C. with respect to all the monomer components forming the acrylic polymer (total amount of monomer components) is, for example, 70 to 98% by weight, and the lower limit is preferably The upper limit is preferably 97% by weight, more preferably 96% by weight.
- the viscosity of the composition decreases when the emulsion resin composition is foamed by applying mechanical shearing or the like. Many bubbles are likely to be taken into the emulsion, and when the emulsion resin composition containing the bubbles is applied onto a substrate and dried in a stationary state, the composition tends to aggregate and the viscosity is increased. The foam rises and the bubbles are retained in the composition and hardly diffused to the outside, so that a foam having excellent foaming characteristics can be obtained.
- nitrogen atom-containing copolymerizable monomer examples include cyano group-containing monomers such as (meth) acrylonitrile; lactam ring-containing monomers such as N-vinyl-2-pyrrolidone; (meth) acrylamide, N And amide group-containing monomers such as hydroxyethyl (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, and diacetoneacrylamide.
- cyano group-containing monomers such as acrylonitrile and lactam ring-containing monomers such as N-vinyl-2-pyrrolidone are preferable.
- a nitrogen atom containing monomer can be used individually by 1 type or in combination of 2 or more types.
- the content of the structural unit derived from the nitrogen atom-containing monomer is preferably 2 to 2 with respect to all the structural units constituting the acrylic polymer.
- the lower limit is more preferably 3% by weight, still more preferably 4% by weight, and the upper limit is more preferably 25% by weight, still more preferably 20% by weight.
- an acrylic acid C 2-18 alkyl ester (particularly acrylic acid C 2 -8 alkyl ester) is preferred.
- Acrylic acid C 2-18 alkyl ester can be used alone or in combination of two or more.
- the content of structural units derived from acrylic acid C 2-18 alkyl esters (particularly acrylic acid C 2-8 alkyl esters) is based on the total structural units constituting the acrylic polymer.
- the lower limit is more preferably 75% by weight, still more preferably 80% by weight, and the upper limit is more preferably 97% by weight, still more preferably 96% by weight. .
- the rubber may be natural rubber or synthetic rubber.
- examples of the rubber include nitrile rubber (NBR), methyl methacrylate-butadiene rubber (MBR), styrene-butadiene rubber (SBR), acrylic rubber (ACM, ANM), urethane rubber (AU), and silicone rubber.
- NBR nitrile rubber
- MRR methyl methacrylate-butadiene rubber
- SBR styrene-butadiene rubber
- ACM acrylic rubber
- AU urethane rubber
- silicone rubber silicone rubber.
- urethane polymer examples include polycarbonate polyurethane, polyester polyurethane, and polyether polyurethane.
- ethylene-vinyl acetate copolymer a known or well-known ethylene-vinyl acetate copolymer can be used.
- the foam constituting the foam sheet contains a surfactant, a crosslinking agent, a thickener, a rust inhibitor, a silicone compound, and other additives as necessary. Also good.
- an optional surfactant may be included for the purpose of reducing the bubble diameter and stabilizing the foam.
- the surfactant is not particularly limited, and any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like may be used. From the viewpoint of the stability of the foam, an anionic surfactant is preferable, and a fatty acid ammonium surfactant such as ammonium stearate is more preferable.
- Surfactant may be used individually by 1 type and may be used in combination of 2 or more type. Different surfactants may be used in combination, for example, an anionic surfactant and a nonionic surfactant, or an anionic surfactant and an amphoteric surfactant may be used in combination.
- the addition amount [solid content (nonvolatile content)] of the surfactant is, for example, 0 to 10 parts by weight with respect to 100 parts by weight of the resin material (polymer) [solid content (nonvolatile content)], and the lower limit is preferably 0.5 part by weight, the upper limit is preferably 8 parts by weight.
- an arbitrary cross-linking agent may be included.
- the crosslinking agent is not particularly limited, and any of oil-soluble and water-soluble may be used.
- examples of the crosslinking agent include epoxy, oxazoline, isocyanate, carbodiimide, melamine, and metal oxide. Among these, an oxazoline-based crosslinking agent is preferable.
- the addition amount [solid content (nonvolatile content)] of the crosslinking agent is, for example, 0 to 10 parts by weight with respect to 100 parts by weight of the resin material (polymer) [solid content (nonvolatile content)], and the lower limit is preferably 0. 0.01 parts by weight, more preferably 0.1 parts by weight, and the upper limit is preferably 9 parts by weight, more preferably 8 parts by weight.
- an optional thickener may be included.
- the thickener is not particularly limited, and examples thereof include acrylic acid type, urethane type, and polyvinyl alcohol type. Of these, polyacrylic acid thickeners and urethane thickeners are preferred.
- the addition amount of the thickener is, for example, 0 to 10 parts by weight with respect to 100 parts by weight of the resin material (polymer) [solid content (nonvolatile content)], and the lower limit is preferably 0.1 parts by weight, the upper limit is preferably 5 parts by weight.
- an arbitrary rust inhibitor may be included to prevent corrosion of the metal member adjacent to the foam sheet.
- an azole ring-containing compound is preferable. When an azole ring-containing compound is used, it is possible to achieve both high levels of corrosion prevention for metals and adhesion to adherends.
- the azole ring-containing compound may be a compound having a 5-membered ring containing one or more nitrogen atoms in the ring.
- compounds having a ring, a thiazole ring, or an isothiazole ring may be condensed with an aromatic ring such as a benzene ring to form a condensed ring.
- Examples of the compound having such a condensed ring include a compound having a benzimidazole ring, a benzopyrazole ring, a benzotriazole ring, a benzoxazole ring, a benzoisoxazole ring, a benzothiazole ring, or a benzoisothiazole ring.
- the azole ring and the condensed ring each may have a substituent.
- substituents include alkyl groups having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms) such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; methoxy group, ethoxy group, isopropyloxy
- a compound in which an azole ring forms a condensed ring with an aromatic ring such as a benzene ring is preferable.
- a benzotriazole compound (a compound having a benzotriazole ring), a benzothiazole compound ( A compound having a benzothiaazole ring) is particularly preferred.
- benzotriazole compounds include 1,2,3-benzotriazole, methylbenzotriazole, carboxybenzotriazole, carboxymethylbenzotriazole, and 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole.
- 1- [N, N-bis (2-ethylhexyl) aminomethyl] methylbenzotriazole, 2,2 ′-[[(methyl-1H-benzotriazol-1-yl) methyl] imino] bisethanol, or these A sodium salt etc. are mentioned.
- benzothiazole compound examples include 2-mercaptobenzothiazole, 3- (2- (benzothiazolyl) thio) propionic acid, or a sodium salt thereof.
- the azole ring-containing compound may be used alone or in combination of two or more.
- the addition amount [solid content (nonvolatile content)] of the rust inhibitor (for example, the azole ring-containing compound) [solid content (nonvolatile content)] is within a range that does not impair the adhesion to the adherend and the original properties of the foam.
- 0.2 to 5 parts by weight is preferable with respect to 100 parts by weight of the resin material (polymer) [solid content (nonvolatile content)].
- the lower limit is more preferably 0.3 parts by weight, still more preferably 0.4 parts by weight, and the upper limit is more preferably 3 parts by weight, still more preferably 2 parts by weight.
- a silicone compound may be added in order to improve the thickness recoverability and recovery speed of the foamed sheet after being compressed.
- a silicone-modified polymer for example, a silicone-modified acrylic polymer, a silicone-modified urethane polymer, etc.
- a silicone-modified urethane polymer may be used as at least a part of the resin material (polymer). These can be used alone or in combination of two or more.
- the silicone compound is preferably a silicone compound having a siloxane bond of 2000 or less.
- examples of the silicone compound include silicone oil, modified silicone oil, and silicone resin.
- silicone oil straight silicone oil
- examples of silicone oil include dimethyl silicone oil and methylphenyl silicone oil.
- modified silicone oil examples include polyether-modified silicone oil (polyether-modified dimethyl silicone oil, etc.), alkyl-modified silicone oil (alkyl-modified dimethyl silicone oil, etc.), aralkyl-modified silicone oil (aralkyl-modified dimethyl silicone oil, etc.), higher fatty acids
- modified silicone oil examples include ester-modified silicone oil (higher fatty acid ester-modified dimethyl silicone oil and the like), fluoroalkyl-modified silicone oil (fluoroalkyl-modified dimethyl silicone oil and the like), and the like.
- polyether-modified silicone is preferred.
- examples of commercially available polyether-modified silicone oils include “PEG11 methyl ether dimethicone”, “PEG / PPG-20 / 22 butyl ether dimethicone”, “PEG-9 methyl ether dimethicone”, “PEG-32 methyl ether dimethicone”, “ Linear type such as “PEG-9 dimethicone”, “PEG-3 dimethicone”, “PEG-10 dimethicone”; branched such as “PEG-9 polydimethylsiloxyethyl dimethicone”, “lauryl PEG-9 polydimethylsiloxyethyl dimethicone” Examples include the type (manufactured by Shin-Etsu Silicone).
- the silicone resin includes straight silicone resin and modified silicone resin.
- the straight silicone resin include methyl silicone resin and methylphenyl silicone resin.
- the modified silicone resin include alkyd-modified silicone resin, epoxy-modified silicone resin, acrylic-modified silicone resin, and polyester-modified silicone resin.
- the total content of the silicone compound and the silicone chain part present in the silicone-modified polymer in the foam is in terms of non-volatile content (in terms of solid content) with respect to 100 parts by weight of the resin material (polymer) in the foam. ), For example, 0.01 to 5 parts by weight.
- the lower limit of the total content is preferably 0.05 parts by weight, more preferably 0.1 parts by weight, and the upper limit is preferably 4 parts by weight, more preferably 3 parts by weight.
- the total content of the silicone compound and the silicone chain portion present in the silicone-modified polymer in the foam is, for example, 0.01 to 5% by weight in terms of nonvolatile content (in terms of solid content).
- the lower limit of the total content is preferably 0.05% by weight, more preferably 0.1% by weight, and the upper limit is preferably 4% by weight, more preferably 3% by weight.
- the foam constituting the foam sheet may contain any appropriate other component within a range not impairing the impact absorbability.
- Such other components may contain only 1 type and may contain 2 or more types.
- the other components include polymer components other than those described above, softeners, antioxidants, anti-aging agents, gelling agents, curing agents, plasticizers, fillers, reinforcing agents, foaming agents (such as baking soda), micro Capsules (thermally expandable microspheres, etc.), flame retardants, light stabilizers, UV absorbers, colorants (pigments, dyes, etc.), pH adjusters, solvents (organic solvents), thermal polymerization initiators, photopolymerization initiators, etc. Is mentioned.
- the addition amount [solid content (nonvolatile content)] of these components may be in a range that does not impair the adhesion to the adherend and the original properties of the foam.
- resin material (polymer) solid content (nonvolatile content)
- a range of 0.2 to 60 parts by weight per 100 parts by weight is preferable.
- the amount of foaming agent (such as baking soda) added [solid content (nonvolatile content)] is more preferably 0.5 to 20 parts by weight relative to 100 parts by weight of the resin material (polymer) [solid content (nonvolatile content)]. It is.
- the addition amount [solid content (nonvolatile content)] of microcapsules (thermally expandable microspheres, etc.) is more preferably 0.2 parts per 100 parts by weight of resin material (polymer) [solid content (nonvolatile content)]. ⁇ 10 parts by weight.
- the addition amount [solid content (nonvolatile content)] of the filler is more preferably 0.3 to 50 parts by weight with respect to 100 parts by weight of the resin material (polymer) [solid content (nonvolatile content)].
- the filler examples include silica, clay (mica, talc, smectite, etc.), alumina, aluminum hydroxide, alkaline earth metal hydroxide (magnesium hydroxide, etc.), and alkaline earth metal carbonate (carbonic acid). Calcium, etc.), titania, zinc oxide, tin oxide, zeolite, graphite, carbon black, carbon nanotube, inorganic fiber (carbon fiber, glass fiber, potassium titanate fiber, etc.), organic fiber, metal powder (silver, copper, etc.), Examples thereof include wax (polyethylene wax, polypropylene wax, etc.).
- piezoelectric particles titanium oxide, barium titanate, etc.
- conductive particles conductive carbon black, conductive titanium oxide, tin oxide, etc.
- thermally conductive particles boron nitride, etc.
- organic filler Silicone powder, polyethylene powder, polypropylene powder, etc.
- silica is used as the filler, the amount added is particularly preferably in the range of 0.5 to 40 parts by weight with respect to 100 parts by weight of the thermoplastic resin [solid content (nonvolatile content)].
- the addition amount is particularly preferably in the range of 0.3 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin [solid content (nonvolatile content)].
- the addition amount thereof is particularly preferably in the range of 5 to 40 parts by weight with respect to 100 parts by weight of the thermoplastic resin [solid content (nonvolatile content)].
- the addition amount thereof is particularly preferably in the range of 5 to 40 parts by weight with respect to 100 parts by weight of the thermoplastic resin [solid content (nonvolatile content)].
- the foam sheet of the present invention can be produced by subjecting a resin composition containing a resin material (polymer) constituting the foam to foam molding.
- foaming method bubble forming method
- methods usually used for foam molding such as physical methods and chemical methods, can be employed.
- the physical method is to disperse a gas component such as air or nitrogen in a polymer solution and form bubbles by mechanical mixing.
- the chemical method is a method of obtaining a foam by forming cells with a gas generated by thermal decomposition of a foaming agent added to a polymer base. From the viewpoint of environmental problems, a physical method is preferable. Bubbles formed by physical methods are often open cells.
- a resin composition containing a resin material (polymer) to be subjected to foam molding a resin solution in which a resin material is dissolved in a solvent may be used. From the viewpoint of foaming properties, an emulsion containing a resin material may be used. preferable. As an emulsion, you may blend and use 2 or more types of emulsion.
- the solid content concentration of the emulsion is preferably higher from the viewpoint of film formability.
- the solid content concentration of the emulsion is preferably 30% by weight or more, more preferably 40% by weight or more, and further preferably 50% by weight or more.
- a method of producing a foam through a step of foaming the emulsion resin composition mechanically (Step A) is preferable.
- the foaming device is not particularly limited, and examples thereof include a high-speed shearing method, a vibration method, and a pressurized gas discharge method. Among these, the high-speed shearing method is preferable from the viewpoint of finer bubble diameter and production of a large capacity.
- Bubbles when foamed by mechanical stirring are gas (gas) taken into the emulsion.
- the gas is not particularly limited as long as it is inert to the emulsion, and examples thereof include air, nitrogen, carbon dioxide and the like. Among these, air is preferable from the viewpoint of economy.
- the foamed sheet of the present invention can be obtained through a step (Step B) in which the emulsion resin composition foamed by the above method is applied onto a substrate and dried.
- a step (Step B) in which the emulsion resin composition foamed by the above method is applied onto a substrate and dried.
- the peeled plastic film peeleling-treated polyethylene terephthalate film etc.
- the plastic film polyethylene terephthalate film etc.
- a heat conductive layer etc. are mentioned.
- the adhesion between the foam layer and the heat conductive layer can be improved, and the efficiency of the drying process when the foam layer is produced can also be improved.
- Step B a general method can be adopted as a coating method and a drying method.
- Step B includes a preliminary drying step B1 for drying the bubble-containing emulsion resin composition applied on the substrate at 50 ° C. or higher and lower than 125 ° C., and then a main drying step B2 for further drying at 125 ° C. or higher and 200 ° C. or lower. Preferably it is.
- the temperature in the preliminary drying step B1 is preferably 50 ° C. or higher and 100 ° C. or lower.
- the time of the preliminary drying step B1 is, for example, 0.5 minutes to 30 minutes, preferably 1 minute to 15 minutes. Moreover, the temperature in this drying process B2 becomes like this.
- the main drying step B2 is, for example, 0.5 minutes to 30 minutes, preferably 1 minute to 15 minutes.
- the average cell diameter, maximum cell diameter, and minimum cell diameter of the foam can be controlled by adjusting the type and amount of the surfactant, or by adjusting the stirring speed and stirring time during mechanical stirring. .
- the apparent density of the foam can be controlled by adjusting the amount of gas (gas) component taken into the emulsion resin composition during mechanical stirring.
- the value of the compression set at 80 ° C. and the value of the change rate of shock absorption can be controlled by adjusting, for example, the degree of crosslinking and Tg of the resin material (polymer) constituting the foam. More specifically, for example, by adjusting the amount of the crosslinking agent added, or by adjusting the ratio of the monomer having a Tg of -10 ° C. or more in the total monomer component forming the resin material (polymer), The value of the compression set at 80 ° C. and the value of the shock absorption change rate can be controlled within a predetermined range. The compression set at 80 ° C.
- the value of the shock absorption change rate can be reduced.
- the foamed sheet of the present invention may have an adhesive layer (adhesive layer) on one or both sides of the foam. It does not specifically limit as an adhesive which comprises an adhesive layer, For example, any of an acrylic adhesive, a rubber adhesive, a silicone adhesive, etc. may be sufficient. Moreover, when providing an adhesive layer, you may laminate
- the foamed sheet of the present invention may be distributed on the market as a wound body (rolled material) wound in a roll shape.
- the foamed sheet of the present invention is excellent in impact absorption even if the thickness is small. In addition, it has excellent heat resistance and possesses the ability to recover to its original shape (thickness) even when subjected to compression or impact at high temperatures (for example, about 80 ° C.).
- the foam sheet of the present invention has an 80 ° C. stress retention defined below as 68% or more.
- the conventional foamed sheet generally has a low 80 ° C. stress retention rate, and the stress is relaxed at 80 ° C., and the restoring force is attenuated. ⁇ 80 ° C stress retention> After holding the test piece (foamed sheet) in an atmosphere of 80 ° C.
- 80 ° C stress retention rate (%) [Load after 120 seconds (N) / Maximum load (N)] ⁇ 100
- the foamed sheet of the present invention is excellent in shock absorption and heat resistance even when it is thin, it has high mounting (adhesion) reliability even at high temperatures.
- various members or parts for example, optical members are useful as members for electric / electronic devices used for attaching (mounting) to a predetermined part (for example, a housing), particularly as a shock absorbing sheet. is there.
- an image display member attached to an image display device such as a liquid crystal display, an electroluminescence display, a plasma display (particularly, a small image display).
- display members such as touch panels attached to mobile communication devices such as so-called “mobile phones”, “smartphones” and “portable information terminals”, cameras and lenses (particularly small cameras and lenses), etc.
- mobile communication devices such as so-called “mobile phones”, “smartphones” and “portable information terminals”, cameras and lenses (particularly small cameras and lenses), etc.
- the electrical / electronic device of the present invention uses the foam sheet of the present invention.
- Such an electric / electronic device is, for example, an electric / electronic device provided with a display member, in which the foamed sheet is sandwiched between a housing of the electric or electronic device and the display member.
- Electric and electronic equipment having Examples of the electric / electronic devices include mobile communication devices such as so-called “mobile phones”, “smartphones”, and “portable information terminals”.
- % representing the content means% by weight.
- all the compounding parts are values in terms of solid content (non-volatile content).
- Example 1 100 parts by weight of acrylic emulsion solution (solid content 55%, ethyl acrylate-butyl acrylate-acrylonitrile copolymer (weight ratio 45: 48: 7)), silicone compound A (dimethylsilicone oil, number average molecular weight Mn: 7 .16 ⁇ 10 3 , weight average molecular weight Mw: 1.71 ⁇ 10 4 , solid content (nonvolatile content) 100%) 1 part by weight, fatty acid ammonium surfactant (aqueous dispersion of ammonium stearate, solid content 33) %) 3 parts by weight, oxazoline-based crosslinking agent ("Epocross WS-500" manufactured by Nippon Shokubai Co., Ltd., solid content 39%) 2.0 parts by weight, benzotriazole sodium salt (solid content 40%) (rust inhibitor) 1 weight Part, polyacrylic acid thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20% by weight), solid content 28.7%
- This foamed composition was applied onto a release-treated PET (polyethylene terephthalate) film (thickness: 38 ⁇ m, trade name “MRF # 38” manufactured by Mitsubishi Plastics), 70 ° C. for 4.5 minutes, and 140 ° C. It is dried for 4.5 minutes, and has an open cell structure with a thickness of 100 ⁇ m, an apparent density of 0.34 g / cm 3 , a bubble rate of 65.7%, a maximum cell diameter of 72.5 ⁇ m, a minimum cell diameter of 28.5 ⁇ m, and an average cell diameter of 45 ⁇ m. A foam (foamed sheet) was obtained.
- Example 2 100 parts by weight of acrylic emulsion solution (solid content 55%, ethyl acrylate-butyl acrylate-acrylonitrile copolymer (weight ratio 45: 48: 7)), silicone compound A (dimethylsilicone oil, number average molecular weight Mn: 7 .16 ⁇ 10 3 , weight average molecular weight Mw: 1.71 ⁇ 10 4 , solid content (nonvolatile content) 100%) 1 part by weight, fatty acid ammonium surfactant (aqueous dispersion of ammonium stearate, solid content 33) %) 3 parts by weight, oxazoline-based crosslinking agent (Epocross WS-500, manufactured by Nippon Shokubai Co., Ltd., solid content 39%) 0.35 parts by weight, benzotriazole sodium salt (solid content 40%) (rust inhibitor) 1 weight Parts, polyacrylic acid thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20% by weight), solid content 28
- This foamed composition was applied onto a release-treated PET (polyethylene terephthalate) film (thickness: 38 ⁇ m, trade name “MRF # 38” manufactured by Mitsubishi Plastics), 70 ° C. for 4.5 minutes, and 140 ° C. It is dried for 4.5 minutes, and has an open cell structure with a thickness of 100 ⁇ m, an apparent density of 0.45 g / cm 3 , a bubble rate of 54.5%, a maximum cell diameter of 87.5 ⁇ m, a minimum cell diameter of 48.5 ⁇ m, and an average cell diameter of 65 ⁇ m. A foam (foamed sheet) was obtained.
- Example 3 100 parts by weight of acrylic emulsion solution (solid content 55%, ethyl acrylate-butyl acrylate-acrylonitrile copolymer (weight ratio 45: 48: 7)), silicone compound A (dimethylsilicone oil, number average molecular weight Mn: 7 .16 ⁇ 10 3 , weight average molecular weight Mw: 1.71 ⁇ 10 4 , solid content (nonvolatile content) 100%) 1 part by weight, fatty acid ammonium surfactant (aqueous dispersion of ammonium stearate, solid content 33) %) 3 parts by weight, oxazoline-based crosslinking agent (Epocross WS-500, manufactured by Nippon Shokubai Co., Ltd., solid content 39%) 0.35 parts by weight, benzotriazole sodium salt (solid content 40%) (rust inhibitor) 1 weight Parts, polyacrylic acid thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20% by weight), solid content 28
- This foamed composition was applied onto a release-treated PET (polyethylene terephthalate) film (thickness: 38 ⁇ m, trade name “MRF # 38” manufactured by Mitsubishi Plastics), 70 ° C. for 4.5 minutes, and 140 ° C. It was dried for 4.5 minutes and had an open cell structure with a thickness of 120 ⁇ m, an apparent density of 0.26 g / cm 3 , a bubble rate of 73.7%, a maximum cell diameter of 57.5 ⁇ m, a minimum cell diameter of 15.3 ⁇ m, and an average cell diameter of 30 ⁇ m. A foam (foamed sheet) was obtained.
- Example 4 100 parts by weight of acrylic emulsion solution (solid content 55%, ethyl acrylate-butyl acrylate-acrylonitrile copolymer (weight ratio 45: 48: 7)), silicone compound A (dimethylsilicone oil, number average molecular weight Mn: 7 .16 ⁇ 10 3 , weight average molecular weight Mw: 1.71 ⁇ 10 4 , solid content (nonvolatile content) 100%) 1 part by weight, fatty acid ammonium surfactant (aqueous dispersion of ammonium stearate, solid content 33) %) 3 parts by weight, benzotriazole sodium salt (solid content 40%) (rust inhibitor) 1 part by weight, polyacrylic acid thickener (ethyl acrylate-acrylic acid copolymer (acrylic acid 20% by weight), 0.8 parts by weight of a solid content of 28.7% was stirred and mixed with a disper (“Robomix” manufactured by Primics) to form a foam.
- silicone compound A dimethyl
- This foamed composition was applied onto a release-treated PET (polyethylene terephthalate) film (thickness: 38 ⁇ m, trade name “MRF # 38” manufactured by Mitsubishi Plastics), 70 ° C. for 4.5 minutes, and 140 ° C. It is dried for 4.5 minutes, and has an open cell structure with a thickness of 130 ⁇ m, an apparent density of 0.37 g / cm 3 , a bubble rate of 62.6%, a maximum cell diameter of 82.5 ⁇ m, a minimum cell diameter of 43.5 ⁇ m, and an average cell diameter of 60 ⁇ m A foam (foamed sheet) was obtained.
- This long foam original fabric was cut into a predetermined width (slit processing), and using a continuous slicing device (slice line), the low foam layer on the surface was peeled off one by one to obtain a resin foam.
- a resin foam By passing the resin foam through the continuous processing apparatus in which the temperature of the induction heating roll is set to 160 ° C. and the gap is set to 0.20 mm, one side is melt-processed with heat, slitted, and then wound up. Thus, a wound body was obtained. The take-up speed was 20 m / min. Next, the wound body is rewound, and is passed through the continuous processing apparatus in which the temperature of the induction heating roll is set to 160 ° C. and the gap is set to 0.10 mm.
- An average cell diameter ( ⁇ m) was obtained by capturing an enlarged image of the foam cross section with a low vacuum scanning electron microscope (“S-3400N scanning electron microscope” manufactured by Hitachi High-Tech Science Systems) and analyzing the image. The number of bubbles analyzed is about 10 to 20. Similarly, the minimum cell diameter ( ⁇ m) and the maximum cell diameter ( ⁇ m) of the foam sheet were determined.
- a foam (foamed sheet) is punched with a 100 mm ⁇ 100 mm punching blade mold, and the dimensions of the punched sample are measured. Further, the thickness is measured with a 1/100 dial gauge having a measurement terminal diameter ( ⁇ ) of 20 mm. The volume of the foam was calculated from these values. Next, the weight of the foam is measured with an upper pan balance having a minimum scale of 0.01 g or more. From these values, the apparent density (g / cm 3 ) of the foam was calculated.
- compression set test The foamed sheets (sample size: 30 mm ⁇ 30 mm) obtained in the examples and comparative examples were used as test pieces. Using this test piece, a compression set test was performed at 80 ° C. (according to JIS K6262). More specifically, the test piece is compressed in an atmosphere of 80 ° C. (the compressed test piece is compressed until the thickness of the compressed test piece becomes 40% of the original thickness), and the state is maintained for 24 hours. After being held, the test piece was released from the compressed state, left at 23 ° C. for 30 minutes, and the thickness of the test piece was measured at 23 ° C. The compression set (%) at 80 ° C. was determined by the following formula.
- CS ⁇ (t0 ⁇ t1) / (t0 ⁇ t2) ⁇ ⁇ 100 CS: Compression set (%) t0: Original thickness of the test piece (mm) t1: The thickness of the test piece 30 mm after removing the test piece from the compression apparatus (mm) t2: Test specimen thickness (mm) with compressive strain applied
- shock absorption change rate For the foamed sheets (sample size: 20 mm ⁇ 20 mm) (test piece A) obtained in Examples and Comparative Examples, the above pendulum type impact tester (impact test device) (see FIGS. 1 and 2) was used. The impact absorption test was conducted under the conditions of °C, impactor weight 28 g, and swing angle 40 °. The shock absorption rate obtained at this time is defined as an initial shock absorption rate a. Next, after the test piece A was stored at 80 ° C. for 72 hours in a compressed state of 60% with respect to the initial thickness of the test piece A, the compressed state was released, and then after 23 ° C.
- Impact absorption change rate (%) ⁇ (shock absorption rate after high temperature compression b ⁇ initial impact absorption rate a) / initial impact absorption rate a ⁇ ⁇ 100
- the impact absorption rate is a value defined by the following formula.
- Impact absorption rate (%) ⁇ (F 0 ⁇ F 1 ) / F 0 ⁇ ⁇ 100 (In the above equation, F 0 is the impact force when the impactor collides only with the support plate, and F 1 is when the impactor collides with the support plate of the structure consisting of the support plate and the test piece A. Impact force)
- the foamed sheet of the present invention is excellent in shock absorption even when it is thin, and also has excellent heat resistance, so it has high mounting (adhesion) reliability even at high temperatures.
- it is useful as a member for an electric / electronic device, particularly an impact absorbing sheet, used when a component (for example, an optical member) is attached (attached) to a predetermined part (for example, a housing).
- an optical member that can be attached (attached) using the foam sheet of the present invention for example, an image display member attached to an image display device such as a liquid crystal display, an electroluminescence display, a plasma display (particularly, a small image display).
- the foam sheet of the present invention is used for the electrical / electronic device of the present invention.
- Such an electric / electronic device is, for example, an electric / electronic device provided with a display member, in which the foamed sheet is sandwiched between a housing of the electric or electronic device and the display member.
- Electric and electronic equipment having Examples of the electric / electronic devices include mobile communication devices such as so-called “mobile phones”, “smartphones”, and “portable information terminals”.
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Abstract
Description
本発明の他の目的は、小型化、薄型化されていても、また発熱量の大きい発熱体を備えていても、落下時の衝撃により破損しにくい電気・電子機器を提供することにある。
衝撃吸収変化率(%)={(高温圧縮後の衝撃吸収率b-初期の衝撃吸収率a)/初期の衝撃吸収率a}×100
初期の衝撃吸収率a:試験片Aの衝撃吸収率(%)
高温圧縮後の衝撃吸収率b(%):試験片Aの初期厚みに対して60%圧縮した状態で試験片Aを80℃×72時間保存した後、圧縮状態を解除し、その後23℃×24時間経過後に測定した衝撃吸収率(%)
衝撃吸収率:振り子型衝撃試験機を用いた衝撃吸収性試験(衝撃子の重さ28g、振り上げ角度40°)(23℃)において、下記式で定義される値
衝撃吸収率(%)={(F0-F1)/F0}×100
(上記式において、F0は支持板のみに衝撃子を衝突させた時の衝撃力のことであり、F1は支持板と試験片Aとからなる構造体の支持板上に衝撃子を衝突させた時の衝撃力のことである)
CS={(t0-t1)/(t0-t2)}×100
CS:圧縮永久歪み(%)
t0:試験片の元の厚さ(mm)
t1:試験片を圧縮装置から取り外し、30分後の試験片の厚さ(mm)
t2:圧縮歪みを加えた状態での試験片の厚さ(mm)
なお、本発明において、圧縮永久歪みは、試験片を60%圧縮したときの値である。
衝撃吸収変化率(%)={(高温圧縮後の衝撃吸収率b-初期の衝撃吸収率a)/初期の衝撃吸収率a}×100
初期の衝撃吸収率a:試験片Aの衝撃吸収率(%)
高温圧縮後の衝撃吸収率b(%):試験片Aの初期厚みに対して60%圧縮した状態で試験片Aを80℃×72時間保存した後、圧縮状態を解除し、その後23℃×24時間経過後に測定した衝撃吸収率(%)
衝撃吸収率:振り子型衝撃試験機を用いた衝撃吸収性試験(衝撃子の重さ28g、振り上げ角度40°)(23℃)において、下記式で定義される値
衝撃吸収率(%)={(F0-F1)/F0}×100
(上記式において、F0は支持板のみに衝撃子を衝突させた時の衝撃力のことであり、F1は支持板と試験片Aとからなる構造体の支持板上に衝撃子を衝突させた時の衝撃力のことである)
<80℃応力保持率>
試験片(発泡シート)を80℃の雰囲気下に30分間保持した後、引張試験機を用い、80℃で、チャック間距離40mmにてセットし、引張速度500mm/minで50%延伸後、120秒間保持する操作を行い、最大荷重と120秒後の荷重を計測し、下記式により80℃応力保持率を求める
80℃応力保持率(%)=[120秒後の荷重(N)/最大荷重(N)]×100
アクリルエマルション溶液(固形分量55%、アクリル酸エチル-アクリル酸ブチル-アクリロニトリル共重合体(重量比45:48:7))100重量部、シリコーン系化合物A(ジメチルシリコーンオイル、数平均分子量Mn:7.16×103、重量平均分子量Mw:1.71×104、固形分(不揮発分)量100%)1重量部、脂肪酸アンモニウム系界面活性剤(ステアリン酸アンモニウムの水分散液、固形分量33%)3重量部、オキサゾリン系架橋剤(「エポクロスWS-500」日本触媒社製、固形分量39%)2.0重量部、ベンゾトリアゾールナトリウム塩(固形分40%)(防錆剤)1重量部、ポリアクリル酸系増粘剤(アクリル酸エチル-アクリル酸共重合体(アクリル酸20重量%)、固形分量28.7%)0.8重量部をディスパー(「ロボミックス」プライミクス社製)で撹拌混合して起泡化した。この発泡組成物を、剥離処理をしたPET(ポリエチレンテレフタレート)フィルム(厚さ:38μm、商品名「MRF♯38」三菱樹脂社製)上に塗布し、70℃で4.5分、140℃で4.5分乾燥させ、厚さ100μm、見掛け密度0.34g/cm3、気泡率65.7%、最大セル径72.5μm、最小セル径28.5μm、平均セル径45μmの連続気泡構造の発泡体(発泡シート)を得た。
アクリルエマルション溶液(固形分量55%、アクリル酸エチル-アクリル酸ブチル-アクリロニトリル共重合体(重量比45:48:7))100重量部、シリコーン系化合物A(ジメチルシリコーンオイル、数平均分子量Mn:7.16×103、重量平均分子量Mw:1.71×104、固形分(不揮発分)量100%)1重量部、脂肪酸アンモニウム系界面活性剤(ステアリン酸アンモニウムの水分散液、固形分量33%)3重量部、オキサゾリン系架橋剤(「エポクロスWS-500」日本触媒社製、固形分量39%)0.35重量部、ベンゾトリアゾールナトリウム塩(固形分40%)(防錆剤)1重量部、ポリアクリル酸系増粘剤(アクリル酸エチル-アクリル酸共重合体(アクリル酸20重量%)、固形分量28.7%)0.8重量部をディスパー(「ロボミックス」プライミクス社製)で撹拌混合して起泡化した。この発泡組成物を、剥離処理をしたPET(ポリエチレンテレフタレート)フィルム(厚さ:38μm、商品名「MRF♯38」三菱樹脂社製)上に塗布し、70℃で4.5分、140℃で4.5分乾燥させ、厚さ100μm、見掛け密度0.45g/cm3、気泡率54.5%、最大セル径87.5μm、最小セル径48.5μm、平均セル径65μmの連続気泡構造の発泡体(発泡シート)を得た。
アクリルエマルション溶液(固形分量55%、アクリル酸エチル-アクリル酸ブチル-アクリロニトリル共重合体(重量比45:48:7))100重量部、シリコーン系化合物A(ジメチルシリコーンオイル、数平均分子量Mn:7.16×103、重量平均分子量Mw:1.71×104、固形分(不揮発分)量100%)1重量部、脂肪酸アンモニウム系界面活性剤(ステアリン酸アンモニウムの水分散液、固形分量33%)3重量部、オキサゾリン系架橋剤(「エポクロスWS-500」日本触媒社製、固形分量39%)0.35重量部、ベンゾトリアゾールナトリウム塩(固形分40%)(防錆剤)1重量部、ポリアクリル酸系増粘剤(アクリル酸エチル-アクリル酸共重合体(アクリル酸20重量%)、固形分量28.7%)0.8重量部をディスパー(「ロボミックス」プライミクス社製)で撹拌混合して起泡化した。この発泡組成物を、剥離処理をしたPET(ポリエチレンテレフタレート)フィルム(厚さ:38μm、商品名「MRF♯38」三菱樹脂社製)上に塗布し、70℃で4.5分、140℃で4.5分乾燥させ、厚さ120μm、見掛け密度0.26g/cm3、気泡率73.7%、最大セル径57.5μm、最小セル径15.3μm、平均セル径30μmの連続気泡構造の発泡体(発泡シート)を得た。
アクリルエマルション溶液(固形分量55%、アクリル酸エチル-アクリル酸ブチル-アクリロニトリル共重合体(重量比45:48:7))100重量部、シリコーン系化合物A(ジメチルシリコーンオイル、数平均分子量Mn:7.16×103、重量平均分子量Mw:1.71×104、固形分(不揮発分)量100%)1重量部、脂肪酸アンモニウム系界面活性剤(ステアリン酸アンモニウムの水分散液、固形分量33%)3重量部、ベンゾトリアゾールナトリウム塩(固形分40%)(防錆剤)1重量部、ポリアクリル酸系増粘剤(アクリル酸エチル-アクリル酸共重合体(アクリル酸20重量%)、固形分量28.7%)0.8重量部をディスパー(「ロボミックス」プライミクス社製)で撹拌混合して起泡化した。この発泡組成物を、剥離処理をしたPET(ポリエチレンテレフタレート)フィルム(厚さ:38μm、商品名「MRF♯38」三菱樹脂社製)上に塗布し、70℃で4.5分、140℃で4.5分乾燥させ、厚さ130μm、見掛け密度0.37g/cm3、気泡率62.6%、最大セル径82.5μm、最小セル径43.5μm、平均セル径60μmの連続気泡構造の発泡体(発泡シート)を得た。
ポリプロピレン[メルトフローレート(MFR):0.35g/10min]:45重量部、ポリオレフィン系エラストマーと軟化剤(パラフィン系伸展油)の混合物(MFR(230℃):6g/10分、JIS A硬度:79°、軟化剤をポリオレフィン系エラストマー100質量部に対して30質量部配合):55重量部、水酸化マグネシウム:10重量部、カーボン(商品名「旭♯35」旭カーボン株式会社製):10重量部、ステアリン酸モノグリセリド:1重量部、及び脂肪酸アミド(ラウリン酸ビスアミド):1.5重量部を、日本製鋼所(JSW)社製の二軸混練機にて、200℃の温度で混練した後、ストランド状に押出し、水冷後ペレット状に成形した。このペレットを、日本製鋼所社製の単軸押出機に投入し、220℃の雰囲気下、13(注入後12)MPaの圧力で、二酸化炭素ガスを注入した。二酸化炭素ガスは、ペレット全量に対して5.6重量%の割合で注入した。二酸化炭素ガスを十分飽和させた後、発泡に適した温度まで冷却後、ダイから円筒状に押出して、発泡体の内側表面を冷却するマンドレルと、押出機の環状ダイから押し出された円筒状の発泡体の外側表面を冷却する発泡体冷却用エアリングの間を通過させ、直径の一部を切断してシート状に展開して長尺発泡体原反を得た。この長尺発泡体原反において、平均セル径は55μm、見掛け密度は0.041g/cm3であった。
この長尺発泡体原反を所定の幅に切断し(スリット加工)、連続スライス装置(スライスライン)を用いて、1面ずつ表面の低発泡層を剥がしとり、樹脂発泡体を得た。
上記樹脂発泡体を、誘導発熱ロールの温度を160℃、ギャップを0.20mmにセットした上記連続処理装置内を通過させることにより、片面を熱で溶融処理して、スリット加工し、その後巻き取って、巻回体を得た。なお、引き取り速度は、20m/minとした。
次に、上記巻回体を巻き戻して、誘導発熱ロールの温度を160℃、ギャップを0.10mmにセットした上記連続処理装置内を通過させることにより、溶融処理がされていない面(未処理面)を熱で溶融処理して、スリット加工し、その後巻き取って、両面が熱溶融処理された厚さ100μm、見掛け密度0.12g/cm3、気泡率88%、最大セル径90μm、最小セル径30μm、平均セル径60μmの連続気泡構造の発泡体(発泡シート)を得た。
実施例及び比較例で得られた発泡体(発泡シート)について、以下の評価を行った。結果を表1及び表2に示す。なお、表1に、各実施例、比較例における各成分の配合部数(重量部)[固形分(不揮発分)換算]を示す。「Em」はエマルションを示す。
低真空走査電子顕微鏡(「S-3400N型走査電子顕微鏡」日立ハイテクサイエンスシステムズ社製)により、発泡体断面の拡大画像を取り込み、画像解析することにより平均セル径(μm)を求めた。なお解析した気泡数は10~20個程度である。同様にして、発泡シートの最小セル径(μm)及び最大セル径(μm)を求めた。
100mm×100mmの打抜き刃型にて発泡体(発泡シート)を打抜き、打抜いた試料の寸法を測定する。また、測定端子の直径(φ)20mmである1/100ダイヤルゲージにて厚さを測定する。これらの値から発泡体の体積を算出した。
次に、発泡体の重量を最小目盛り0.01g以上の上皿天秤にて測定する。これらの値より発泡体の見掛け密度(g/cm3)を算出した。
粘弾性測定装置(「ARES2KFRTN1-FCO」TA Instruments Japan社製)のフィルム引張り測定モードにて、角振動数1rad/sで温度分散性試験を行った。その際の貯蔵弾性率E'と損失弾性率E''の比率である損失正接(tanδ)のピークトップの温度(℃)と強度(最大値)を測定した。
表2の「tanδ温度」の欄に、発泡体の損失正接(tanδ)のピークトップの温度(℃)を記載し、「tanδ最大値」の欄に、該ピークトップの強度(最大値)を記載した。
実施例及び比較例で得られた発泡シート(サンプルサイズ:30mm×30mm)を試験片とした。この試験片を用い、80℃で、圧縮永久歪み試験を行った(JIS K6262の規定に準じる)。より具体的には、試験片を80℃の雰囲気下で圧縮し(圧縮された試験片の厚さが、元の厚さの40%の厚さになるまで圧縮する)、その状態を24時間保持した後、試験片を圧縮状態から解放し、23℃で30分放置し、23℃で試験片の厚さを測定した。そして、80℃での圧縮永久歪み(%)を下記式により求めた。
CS={(t0-t1)/(t0-t2)}×100
CS:圧縮永久歪み(%)
t0:試験片の元の厚さ(mm)
t1:試験片を圧縮装置から取り外し、30分後の試験片の厚さ(mm)
t2:圧縮歪みを加えた状態での試験片の厚さ(mm)
実施例及び比較例で得られた発泡シート(サンプルサイズ:20mm×20mm)(試験片A)について、前記の振り子型衝撃試験機(衝撃試験装置)(図1及び図2参照)を用い、23℃、衝撃子の重さ28g、振り上げ角度40°の条件で衝撃吸収性試験を行った。このとき得られた衝撃吸収率を初期の衝撃吸収率aとする。
次に、試験片Aの初期厚みに対して60%圧縮した状態で試験片Aを80℃×72時間保存した後、圧縮状態を解除し、その後23℃×24時間経過後に、上記と同様、23℃、衝撃子の重さ28g、振り上げ角度40°の条件で衝撃吸収性試験を行った。このとき得られた衝撃吸収率を高温圧縮後の衝撃吸収率bとする。
そして、下記式により、衝撃吸収変化率(%)を求めた。
衝撃吸収変化率(%)={(高温圧縮後の衝撃吸収率b-初期の衝撃吸収率a)/初期の衝撃吸収率a}×100
なお、衝撃吸収率は下記式で定義される値である。
衝撃吸収率(%)={(F0-F1)/F0}×100
(上記式において、F0は支持板のみに衝撃子を衝突させた時の衝撃力、F1は支持板と試験片Aとからなる構造体の支持板上に衝撃子を衝突させた時の衝撃力である)
実施例及び比較例で得られた発泡シート[サンプルの形状及びサイズ:ダンベル1号(JIS K6251参照)]を80℃の雰囲気下に30分間保持した後、引張試験機を用い、80℃で、チャック間距離40mmにてセットし、引張速度500mm/minで50%延伸後、120秒間保持する操作を行い、最大荷重と120秒後の荷重を計測し、下記式により80℃応力保持率を求めた。
80℃応力保持率(%)=[120秒後の荷重(N)/最大荷重(N)]×100
2 試験片(発泡シート)
3 保持部材
4 衝撃負荷部材
5 圧力センサー
11 固定治具
12 押さえ治具
16 圧力調整手段
20 支柱
21 アーム
22 支持棒(シャフト)の一端
23 支持棒(シャフト)
24 衝撃子
25 電磁石
28 支持板
a 振り上げ角度
Claims (17)
- 平均セル径が10~200μmの発泡体で構成され、80℃での圧縮永久歪みが80%以下であり、下記で定義される衝撃吸収変化率が±20%以下である発泡シート。
衝撃吸収変化率(%)={(高温圧縮後の衝撃吸収率b-初期の衝撃吸収率a)/初期の衝撃吸収率a}×100
初期の衝撃吸収率a:試験片Aの衝撃吸収率(%)
高温圧縮後の衝撃吸収率b(%):試験片Aの初期厚みに対して60%圧縮した状態で試験片Aを80℃×72時間保存した後、圧縮状態を解除し、その後23℃×24時間経過後に測定した衝撃吸収率(%)
衝撃吸収率:振り子型衝撃試験機を用いた衝撃吸収性試験(衝撃子の重さ28g、振り上げ角度40°)(23℃)において、下記式で定義される値
衝撃吸収率(%)={(F0-F1)/F0}×100
(上記式において、F0は支持板のみに衝撃子を衝突させた時の衝撃力のことであり、F1は支持板と試験片Aとからなる構造体の支持板上に衝撃子を衝突させた時の衝撃力のことである) - 厚さが30~1000μmであり、前記発泡体の見掛け密度が0.2~0.7g/cm3である請求項1記載の発泡シート。
- 前記発泡体が、動的粘弾性測定における角振動数1rad/sでの貯蔵弾性率と損失弾性率の比率である損失正接(tanδ)が-30℃以上30℃以下の範囲にピークトップを有する請求項1又は2記載の発泡シート。
- 発泡体が、アクリル系ポリマー、ゴム、ウレタン系ポリマー、及びエチレン-酢酸ビニル共重合体からなる群より選択された少なくとも1種の樹脂材料で形成されている請求項1~3の何れか1項に記載の発泡シート。
- 発泡体が、エマルション樹脂組成物を機械的に発泡させる工程Aを経て形成される請求項1~4の何れか1項に記載の発泡シート。
- 発泡体が、さらに、機械的に発泡させたエマルション樹脂組成物を基材上に塗工して乾燥する工程Bを経て形成される請求項5に記載の発泡シート。
- 前記工程Bが、基材上に塗布した気泡含有エマルション樹脂組成物を50℃以上125℃未満で乾燥する予備乾燥工程B1と、その後さらに125℃以上200℃以下で乾燥する本乾燥工程B2を含んでいる請求項6記載の発泡シート。
- 前記80℃での圧縮永久歪みが50%以下である請求項1~7の何れか1項に記載の発泡シート。
- 前記80℃での圧縮永久歪みが25%以下である請求項8に記載の発泡シート。
- 厚さが40~500μmである請求項2~9の何れか1項に記載の発泡シート。
- 厚さが50~300μmである請求項10に記載の発泡シート。
- 前記発泡体の見掛け密度が0.21~0.6g/cm3である請求項2~11の何れか1項に記載の発泡シート。
- 前記発泡体の見掛け密度が0.22~0.5g/cm3である請求項12に記載の発泡シート。
- 発泡体の片面又は両面に粘着剤層を有する請求項1~13の何れか1項に記載の発泡シート。
- 電気・電子機器用衝撃吸収シートとして用いられる請求項1~14の何れか1項に記載の発泡シート。
- 請求項1~15の何れか1項に記載の発泡シートが用いられている電気・電子機器。
- 表示部材を備えた電気・電子機器であって、請求項1~14の何れか1項に記載の発泡シートが該電気又は電子機器の筐体と前記表示部材との間に挟持された構造を有する請求項16記載の電気・電子機器。
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WO2018025568A1 (ja) * | 2016-08-01 | 2018-02-08 | 日東電工株式会社 | 発泡シート、電気電子機器、及びタッチパネル搭載機器 |
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KR20170063530A (ko) | 2017-06-08 |
CN111690165B (zh) | 2023-02-28 |
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CN105745263B (zh) | 2020-08-28 |
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CN105745263A (zh) | 2016-07-06 |
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JP2021008636A (ja) | 2021-01-28 |
US20160303822A1 (en) | 2016-10-20 |
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WO2016047610A1 (ja) | 2016-03-31 |
CN111690165A (zh) | 2020-09-22 |
WO2016047612A1 (ja) | 2016-03-31 |
US10316156B2 (en) | 2019-06-11 |
JP6693881B2 (ja) | 2020-05-13 |
CN106660305B (zh) | 2019-06-18 |
JPWO2016047611A1 (ja) | 2017-07-06 |
CN105745262A (zh) | 2016-07-06 |
JPWO2016047612A1 (ja) | 2017-04-27 |
KR102441216B1 (ko) | 2022-09-06 |
JPWO2016047610A1 (ja) | 2017-07-06 |
KR20170058882A (ko) | 2017-05-29 |
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