WO2012102114A1 - 電気又は電子機器用の発泡積層体 - Google Patents
電気又は電子機器用の発泡積層体 Download PDFInfo
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- WO2012102114A1 WO2012102114A1 PCT/JP2012/050733 JP2012050733W WO2012102114A1 WO 2012102114 A1 WO2012102114 A1 WO 2012102114A1 JP 2012050733 W JP2012050733 W JP 2012050733W WO 2012102114 A1 WO2012102114 A1 WO 2012102114A1
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- WIPO (PCT)
- Prior art keywords
- polyolefin
- pressure
- adhesive layer
- sensitive adhesive
- foam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/26—Porous or cellular plastics
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/24—Presence of a foam
- C09J2400/243—Presence of a foam in the substrate
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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
- C09J2423/00—Presence of polyolefin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249982—With component specified as adhesive or bonding agent
- Y10T428/249983—As outermost component
Definitions
- the present invention relates to a foam laminate for electrical or electronic equipment. More specifically, it has an adhesive layer on at least one side of the foam layer, and is used for electric / electronic devices (cell phones, portable terminals, digital cameras, video movies, personal computers, LCD TVs, other household appliances, etc.)
- the present invention relates to a foam laminate suitably used as a gasket.
- a foam it is known to provide a resin layer on the surface of the foam in order to improve adhesion and sealability.
- a foam laminate in which a flexible layer or an adhesive layer is formed on a foam for the purpose of improving sealing properties has been proposed (see Patent Documents 1 and 2).
- the foam surface (refer patent document 3) by which the easily water-soluble layer (polyvinyl alcohol layer etc.) was provided in the foam surface for the purpose of waterproofing property, and a polychloroprene-type adhesive for foam surface for adhesiveness expression.
- a foam treated with the composition has also been proposed.
- foam laminates require a heating and drying step when forming a layer on the foam, and foams having low heat resistance and low density may shrink during drying. Moreover, in order to prevent the said shrinkage
- Patent Document 5 As a method that does not require a heating step when providing a resin layer on the surface of a foam, it has been proposed to provide a resin layer by co-pressing and laminating a thermoplastic elastomer on the foam (Patent Document). 5). However, the resin laminated foam obtained by such a method has anxiety about the dustproof property because there are many irregularities on the surface of the resin layer. Furthermore, it has been proposed to apply a hot melt resin to the foam surface (see Patent Document 6). However, since a high crystalline resin is added in a large amount in the hot melt resin, the physical properties of the obtained resin layer are very hard, and there is a high possibility that the layer will crack when bent.
- Japanese Unexamined Patent Publication No. 9-131822 Japanese Unexamined Patent Publication No. 2002-309198 Japanese Unexamined Patent Publication No. 10-37328 Japanese Patent Laid-Open No. 5-24143 Japanese Unexamined Patent Publication No. 2009-184181 Japanese Unexamined Patent Publication No. 2004-284575
- an object of the present invention is to provide a foamed laminate for electric or electronic equipment having excellent removability. Furthermore, the other object of this invention is to provide the foaming laminated body for electrical or electronic devices which is excellent in removability and excellent in heat resistance. Still another object of the present invention is to provide a foamed laminate for electrical or electronic equipment having excellent removability and low contamination.
- the present inventors have determined that the pressure-sensitive adhesive layer has a crystal melting energy of a specific value or less in the foamed laminate having the pressure-sensitive adhesive layer on at least one surface side of the foam layer. It has been found that when the pressure-sensitive adhesive layer has an excellent re-peelability, it can be obtained. Furthermore, when the said adhesive layer was used as the adhesive layer containing specific polyolefin, it discovered that heat resistance was obtained with the outstanding removability. Furthermore, when the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer containing a polyolefin obtained by polymerization using a metallocene as a catalyst, it has been found that excellent removability is obtained and contamination is not caused. The present invention has been completed based on these findings.
- the foamed laminate for electrical or electronic equipment of the present invention is characterized in that it has a pressure-sensitive adhesive layer having a crystal melting energy required below of 50 J / g or less on at least one surface side of the foam layer.
- Crystal melting energy Melted by heating at a heating rate of 10 ° C./min (first heating), and then cooled to ⁇ 50 ° C. by cooling at a cooling rate of 10 ° C./min (first cooling) Then, differential scanning calorimetry is performed under the condition that the temperature is raised from ⁇ 50 ° C. by heating at a temperature rising rate of 10 ° C./min (second heating), and the heat of fusion (J / g) (Conforms to JIS K 7122)
- the pressure-sensitive adhesive layer is preferably a polyolefin pressure-sensitive adhesive layer containing polyolefin.
- the polyolefin pressure-sensitive adhesive layer contains polyolefin A having a crystal melting energy of less than 50 J / g and polyolefin B having a crystal melting energy of 50 J / g or more.
- the pressure-sensitive adhesive layer is preferably 3 to 30% by weight based on the total amount of polyolefin (100% by weight).
- the polyolefin is preferably a polyolefin obtained by polymerization using a metallocene compound as a catalyst.
- At least one polyolefin of the polyolefin A and the polyolefin B is a polyolefin obtained by polymerization using a metallocene compound as a catalyst.
- the foamed laminate of the present invention is excellent in removability. Furthermore, when the foamed laminate of the present invention has a pressure-sensitive adhesive layer having a crystal melting energy of not more than a specific value and containing a specific polyolefin, it is excellent in removability and heat resistance. Furthermore, when it has a pressure-sensitive adhesive layer containing polyolefin obtained by polymerization using a metallocene compound as a catalyst, the crystal melting energy is below a specific value, it exhibits excellent removability and low contamination. To do.
- FIG. 1 is a chart (DSC curve) obtained by differential scanning calorimetry (DSC measurement) in Example 1.
- the foamed laminate for electric or electronic equipment of the present invention is a foamed laminate having an adhesive layer on at least one surface side of the foam layer.
- the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer having a crystal melting energy obtained below of 50 J / g or less.
- crystal melting energy obtained below may be simply referred to as “crystal melting energy”.
- the adhesive layer whose crystal melting energy is 50 J / g or less may be called “a specific adhesive layer”.
- the “foamed laminate for electric or electronic equipment of the present invention” may be simply referred to as “foamed laminate of the present invention”.
- the crystal melting energy means that the sample is melted by heating at a heating rate of 10 ° C./min (first heating), and then cooled at a cooling rate of 10 ° C./min to ⁇ 50 ° C.
- the differential scanning calorimetry is performed under the condition that the temperature of the sample is lowered to (first cooling), and the temperature of the sample is raised from ⁇ 50 ° C. by heating at a rate of temperature increase of 10 ° C./min (second heating) It is the heat of fusion (J / g) required during the second heating.
- the differential scanning calorimetry when obtaining the crystal melting energy conforms to JIS K 7122 (plastic transition heat measurement method).
- the foamed laminate of the present invention is not particularly limited, but preferably has a sheet shape or a tape shape. Furthermore, the foamed laminate of the present invention may be processed so as to have a desired shape in accordance with the electric / electronic device, apparatus, housing, component, etc. used in use. In addition, the adhesive layer of the foaming laminated body of this invention may be protected by the peeling film (separator) until the time of use.
- the foam laminate of the present invention is a laminate having a structure in which a specific pressure-sensitive adhesive layer is laminated directly or via another layer on at least one surface side of the foam layer.
- the foam laminate of the present invention particularly preferably has a structure in which a specific pressure-sensitive adhesive layer is directly laminated on one side or both sides of the foam layer.
- the foam laminate of the present invention may be a double-sided pressure-sensitive adhesive type having specific pressure-sensitive adhesive layers on both sides of the foam layer, or a specific pressure-sensitive adhesive only on one side of the foam layer. It may be a single-sided adhesive type having a layer.
- both pressure-sensitive adhesive layers may be a specific pressure-sensitive adhesive layer, or one surface-side pressure-sensitive adhesive layer may be a specific pressure-sensitive adhesive. It is a layer and the other surface side may be the type which is other adhesion layers (for example, well-known adhesive layers etc.).
- the foamed laminate of the present invention has a specific pressure-sensitive adhesive layer and has good removability.
- “removability” refers to the destruction of the foam layer and the contamination of the adherend when the foam laminate attached to the adherend is peeled off from the adherend in a form where the specific pressure-sensitive adhesive layer contacts. Refers to the property of being easily peelable without causing
- the specific pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer having a crystal melting energy of 50 J / g or less.
- the crystal melting energy of the said specific adhesive layer is not specifically limited as long as it is 50 J / g or less, It is preferable that it is 45 J / g or less, More preferably, it is 40 J / g or less.
- the crystal melting energy of the specific pressure-sensitive adhesive layer exceeds 50 J / g, there is a possibility that a problem of deterioration of removability occurs.
- voids are generated when an impact is applied to the foamed laminate, resulting in a problem that the dustproof property is lowered, and a problem that cracks occur in the adhesive layer when the foamed laminate is deformed.
- the peeling force (adhesive strength) of the specific pressure-sensitive adhesive layer to the acrylic plate is not particularly limited, but is 0.1 to 2.5 N / 20 mm. And more preferably 0.5 to 2.0 N / 20 mm. If the peeling force exceeds 2.5 N / 20 mm, sufficient removability may not be obtained.
- the haze difference (haze B-haze A) of the specific pressure-sensitive adhesive layer is not particularly limited, but is preferably less than 2.0%, more preferably less than 1.0%.
- Haze A Haze of acrylic plate.
- Haze B A haze of the acrylic plate after the specific pressure-sensitive adhesive layer was peeled off from the acrylic plate after being bonded to the acrylic plate and stored at 60 ° C. for 3 days. This is because in the specific pressure-sensitive adhesive layer, when the haze difference is 2.0% or more, it is difficult to exhibit the characteristic of low contamination.
- the said low pollution property means the characteristic which does not produce the contamination to a to-be-adhered body when it peels after sticking to a to-be-adhered body.
- the specific pressure-sensitive adhesive layer is not particularly limited, but is preferably a polyolefin pressure-sensitive adhesive layer from the viewpoint of simultaneously exhibiting good flexibility and good initial adhesion in addition to good removability. .
- the polyolefin pressure-sensitive adhesive layer contains polyolefin as an essential component.
- the ratio of the polyolefin in the polyolefin pressure-sensitive adhesive layer is not particularly limited, but is preferably 70% by weight or more (for example, 70 to 100% by weight) with respect to the total amount of the polyolefin pressure-sensitive adhesive layer (100% by weight). More preferably, it is 75% by weight or more (for example, 75 to 100% by weight).
- the polyolefin pressure-sensitive adhesive layer may contain only one type of polyolefin, or may contain a combination of two or more types of polyolefin.
- the polyolefin pressure-sensitive adhesive layer may contain a resin, an additive, and the like other than polyolefin as long as the effects of the present invention are not impaired.
- the polyolefin is preferably a polyolefin (metallocene polyolefin) polymerized using metallocene as a catalyst from the viewpoint of obtaining a low-staining polyolefin pressure-sensitive adhesive layer.
- a polyolefin obtained by polymerizing a monomer component using a metallocene as a catalyst has a narrow molecular weight distribution, so that low-molecular-component bleeding is unlikely to occur and contamination is unlikely to occur.
- the metallocene catalyst is a homogeneous catalyst, a polymer having a uniform molecular weight and composition can be obtained according to the metallocene catalyst.
- the above polyolefin is not preferably a polyolefin adjusted to a low molecular weight by thermal decomposition from the viewpoint of low contamination. This is because the polyolefin has a broad molecular weight distribution and contains a low molecular weight component, and therefore, the pressure-sensitive adhesive layer formed using the polyolefin as a raw material is likely to be contaminated by low molecular weight components (bleeding of low molecular components).
- the polyolefin pressure-sensitive adhesive layer preferably contains a polyolefin having a crystal melting energy of less than 50 J / g.
- the “polyolefin having a crystal melting energy of less than 50 J / g” may be referred to as “polyolefin A”.
- Polyolefin A is a so-called amorphous polyolefin and has almost no crystal structure.
- the polyolefin pressure-sensitive adhesive layer may contain only one type of polyolefin A, or two or more types of polyolefin A.
- Polyolefin A is a polyolefin having a crystal melting energy of less than 50 J / g (for example, 10 J / g or more and less than 50 J / g), preferably a crystal melting energy of less than 45 J / g (for example, 15 J / g or more and less than 45 J / g). More preferably, the polyolefin has a crystal melting energy of less than 40 J / g (for example, 20 J / g or more and less than 40 J / g).
- Polyolefin A is not particularly limited.
- low-density polyethylene medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, a copolymer of ethylene and propylene, and ethylene and other ⁇ -olefins.
- Copolymers, copolymers of propylene and other ⁇ -olefins, copolymers of ethylene, propylene and other ⁇ -olefins, copolymers of ethylene and other ethylenically unsaturated monomers, etc. Can be mentioned.
- the polyolefin A may be a mixture of a homopolymer and a copolymer, or a mixture of plural kinds of copolymers. Further, when the polyolefin A is a copolymer, it may be a random copolymer or a block copolymer.
- the ⁇ -olefin examples include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like. Of these, the ⁇ -olefin is preferably 1-butene, 1-hexene, 1-octene, or 4-methyl-1-pentene.
- said other ethylenically unsaturated monomer vinyl acetate, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, vinyl alcohol etc. are mentioned, for example.
- the ⁇ -olefin and the other ethylenically unsaturated monomers may be used alone or in combination of two or more.
- polyolefin A is a polypropylene resin such as polypropylene (propylene homopolymer), a copolymer of ethylene and propylene, and a copolymer of propylene and the above-mentioned other ⁇ -olefins in terms of heat resistance and flexibility. Is particularly preferred.
- the polyolefin A is more preferably a polyolefin (metallocene polyolefin) polymerized using a metallocene as a catalyst from the viewpoint of low contamination.
- the density of the polyolefin A is not particularly limited, but is preferably 0.84 to 0.89 g / cm 3 , more preferably 0.85 to 0.89 g / cm 3 . If the density exceeds 0.89 g / cm 3 , the flexibility and slight adhesiveness of the resin may be impaired. On the other hand, if the density is less than 0.84 g / cm 3 , the moldability and heat resistance may be lowered.
- polyolefin A As a commercial item of polyolefin A, for example, trade name “Tough Selenium H5002” (manufactured by Sumitomo Chemical Co., Ltd., polypropylene elastomer, crystal melting energy: 11.3 J / g, density: 0.86 g / cm 3 ), trade name “NOTIO” “PN20300” (Mitsui Chemicals, polypropylene elastomer, crystal melting energy: 23.4 J / g, density: 0.868 g / cm 3 ), trade name “Lycocene PP1502” (Clariant, polypropylene wax, crystal melting energy) : 26.0 J / g, density: 0.87 g / cm 3 ), trade name “Lycocene PP1602” (manufactured by Clariant, polypropylene wax, crystal melting energy: 26.9 J / g, density: 0.87 g / cm 3) ), “Rico
- the proportion of polyolefin A is not particularly limited, but is 70% by weight or more (for example, 70 to 70%) with respect to the total amount of polyolefin (100% by weight) contained in the polyolefin pressure-sensitive adhesive layer. 100% by weight), more preferably 75% by weight (for example, 75 to 100% by weight).
- the ratio of polyolefin A is less than 70% by weight, it may be difficult to obtain good flexibility while obtaining sufficient removability in the polyolefin pressure-sensitive adhesive layer.
- the polyolefin pressure-sensitive adhesive layer contains polyolefin A
- the polyolefin pressure-sensitive adhesive layer also contains polyolefin (polyolefin B) having a crystal melting energy of 50 J / g or more together with polyolefin A.
- polyolefin B polyolefin having a crystal melting energy of 50 J / g or more
- Polyolefin B is a so-called crystalline polyolefin and contains a large amount of crystal structure.
- the polyolefin pressure-sensitive adhesive layer may contain only one type of polyolefin B, or may contain two or more types of polyolefin B.
- Polyolefin B is not particularly limited.
- low-density polyethylene low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, a copolymer of ethylene and propylene, and ethylene and other ⁇ -olefins.
- Copolymers, copolymers of propylene and other ⁇ -olefins, copolymers of ethylene, propylene and other ⁇ -olefins, copolymers of ethylene and other ethylenically unsaturated monomers, etc. Can be mentioned.
- the polyolefin B may be a mixture of a homopolymer and a copolymer, or a mixture of a plurality of types of copolymers. Further, when the polyolefin B is a copolymer, it may be a random copolymer or a block copolymer.
- the ⁇ -olefin examples include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like. Of these, the ⁇ -olefin is preferably 1-butene, 1-hexene, 1-octene, or 4-methyl-1-pentene.
- said other ethylenically unsaturated monomer vinyl acetate, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, vinyl alcohol etc. are mentioned, for example.
- the ⁇ -olefin and the other ethylenically unsaturated monomers may be used alone or in combination of two or more.
- Polyolefin B is particularly preferably a polypropylene resin such as polypropylene (propylene homopolymer), a copolymer of ethylene and propylene, and a copolymer of propylene and the above-mentioned other ⁇ -olefin from the viewpoint of heat resistance.
- a polypropylene resin such as polypropylene (propylene homopolymer), a copolymer of ethylene and propylene, and a copolymer of propylene and the above-mentioned other ⁇ -olefin from the viewpoint of heat resistance.
- the polyolefin B is more preferably a polyolefin (metallocene polyolefin) polymerized using a metallocene as a catalyst from the viewpoint of low contamination.
- the said polyolefin-type adhesive layer contains both polyolefin A and polyolefin B, it is preferable that both polyolefin A and polyolefin B are metallocene-type polyolefin from the point of low pollution property.
- the density of the polyolefin B is not particularly limited, but is preferably 0.90 to 0.91 g / cm 3 . If the density is less than 0.90 g / cm 3 , the heat resistance may decrease. Polyolefin B having a density exceeding 0.91 g / cm 3 is difficult to obtain.
- polyolefin B As a commercially available product of polyolefin B, for example, trade name “High Wax NP055” (manufactured by Mitsui Chemicals, polypropylene wax, crystal melting energy: 89.1 J / g, density: 0.90 g / cm 3 ), trade name “ Ricocene PP6502 "(manufactured by Clariant, polypropylene wax, crystal melting energy: 87.2 J / g, density: 0.90 g / cm 3 , metallocene polyolefin).
- High Wax NP055 manufactured by Mitsui Chemicals, polypropylene wax, crystal melting energy: 89.1 J / g, density: 0.90 g / cm 3
- Ricocene PP6502 trade name “(manufactured by Clariant, polypropylene wax, crystal melting energy: 87.2 J / g, density: 0.90 g / cm 3 , metallocene polyolef
- the ratio of polyolefin B is not particularly limited, but is based on the total amount of polyolefin (100% by weight) included in the specific polyolefin pressure-sensitive adhesive layer. It is preferably 3 to 30% by weight, more preferably 4 to 28% by weight, and even more preferably 5 to 25% by weight. If the ratio of polyolefin B exceeds 30% by weight, the polyolefin pressure-sensitive adhesive layer becomes too hard, and the flexibility and fine-tackiness of the foamed laminate may be impaired, or the polyolefin pressure-sensitive adhesive layer may become brittle. On the other hand, if the proportion of polyolefin B is less than 3% by weight, sufficient heat resistance may not be obtained in the polyolefin pressure-sensitive adhesive layer.
- the polyolefin-based pressure-sensitive adhesive layer has a tackifier (tackifier resin), an antioxidant, an anti-aging agent, a plasticizer, a colorant, a filler, and other resins as long as the effects of the present invention are not impaired.
- tackifier resin tackifier resin
- antioxidant antioxidant
- anti-aging agent e.g., sodium bicarbonate
- plasticizer e.g., sodium bicarbonate
- colorant e.g., sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium
- the polyolefin pressure-sensitive adhesive layer preferably contains a tackifier (tackifier resin).
- tackifier resin tackifier resin
- the adhesive strength of the adhesive layer can be improved, and for example, the slip resistance and dust resistance of the foamed laminate of the present invention can be improved.
- the tackifier may be used individually or in combination of 2 or more types.
- the tackifier is a resin having a softening point (conforming to JIS K 2207) of 70 to 180 ° C., more preferably a resin having a softening point of 80 to 160 ° C., and still more preferably a softening point. Is a resin having a temperature of 90 to 150 ° C. In addition, when the softening point is too high, the removability may be lowered or the flexibility of the resin may be lowered. On the other hand, if the softening point is too low, heat resistance may be lowered.
- the tackifier is not particularly limited as long as it has the softening point.
- an aliphatic petroleum resin a fully hydrogenated aliphatic petroleum resin, a partially hydrogenated aliphatic petroleum resin, an aromatic petroleum
- resins include resins, fully hydrogenated aromatic petroleum resins, and partially hydrogenated aromatic petroleum resins.
- the content of the tackifier in the polyolefin-based pressure-sensitive adhesive layer is not particularly limited, but if the content of the tackifier is too large, the removability may be lost, while the content of the tackifier is too small. And the tackifier contained therein may not provide the expected effect (for example, further improvement in dustproofness).
- the content of the tackifier in the polyolefin pressure-sensitive adhesive layer is 100 parts by weight of polyolefin (when polyolefin A and polyolefin B are included, the total amount of polyolefin A and polyolefin B is 100 parts by weight),
- the amount is preferably 25 parts by weight or less (for example, 1 to 25 parts by weight), more preferably 20 parts by weight or less (for example, 3 to 20 parts by weight).
- the foam laminate of the present invention has the specific pressure-sensitive adhesive layer (particularly, the polyolefin-based pressure-sensitive adhesive layer) on at least one surface side of the foam layer, and the thickness of the specific pressure-sensitive adhesive layer (particularly the polyolefin layer).
- the thickness of the system pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 50 ⁇ m, more preferably 2 to 40 ⁇ m. There exists a possibility that sufficient adhesiveness may not be acquired as the said thickness is less than 1 micrometer. On the other hand, if the thickness exceeds 50 ⁇ m, the flexibility of the foam laminate may be reduced.
- the specific pressure-sensitive adhesive layer may have a single layer structure or a laminated structure.
- the foam laminate of the present invention has a foam layer. For this reason, the foamed laminate of the present invention is excellent in flexibility and impact absorption.
- the foam layer is formed by foaming and molding the resin composition.
- the resin composition is a composition obtained by mixing a resin as a raw material and an additive or the like added as necessary.
- the foam layer has a cell structure.
- the cell structure is not particularly limited, but is a closed cell structure, a semi-continuous semi-closed cell structure (a cell structure in which a closed cell structure and an open cell structure are mixed, and the ratio between the closed cell structure and the open cell structure is It is not particularly limited, and any of open cell structures may be used.
- the foam layer preferably has a cell structure of an open cell structure or a semi-continuous semi-closed cell structure from the viewpoint of obtaining better flexibility.
- Examples of the semi-continuous semi-closed cell structure include a cell structure in which the closed cell structure part in the cell structure is 40% (volume%) or less (preferably 30% (volume%) or less).
- the density (apparent density) of the foam layer can be appropriately set according to the purpose of use, but is preferably 0.02 to 0.20 g / cm 3 , more preferably 0.03 to 0. .17 g / cm 3 , and still more preferably 0.04 to 0.15 g / cm 3 .
- the density of the foam layer exceeds 0.20 g / cm 3 , foaming may be insufficient and flexibility may be impaired.
- it is less than 0.02 g / cm 3 , the strength of the foam layer may be remarkably lowered, which is not preferable.
- the density of the foam layer is determined as follows.
- the foam layer is punched with a 40 mm ⁇ 40 mm punching blade mold, and the dimensions (vertical and horizontal) of the punched sample are measured. Further, the thickness of the sample is measured with a 1/100 dial gauge having a measurement terminal diameter ( ⁇ ) of 20 mm.
- the volume of the sample is calculated from the dimensions of the sample and the thickness values of the sample.
- the weight of the sample is measured with an upper pan balance having a minimum scale of 0.01 g or more.
- the density (g / cm 3 ) of the foam layer is calculated from the volume of the sample and the value of the weight of the sample.
- the thickness of the foam layer is not particularly limited, and is, for example, 0 from the viewpoint of dustproof performance and shock absorption, and from the viewpoint of applicability to electronic or electric devices having shapes such as thin, small, and narrow.
- the thickness is preferably 1 to 5 mm, more preferably 0.2 to 3 mm.
- the foam layer is made of resin.
- the resin constituting the foam layer is not particularly limited as long as it shows thermoplasticity and can be impregnated with gas (gas forming gas), but a thermoplastic resin is preferable.
- the said foam layer may be comprised only with 1 type of resin, and may be comprised with 2 or more types of resin.
- thermoplastic resin examples include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, copolymers of ethylene and propylene, ethylene or propylene and other ⁇ -olefins (for example, Copolymer with butene-1, pentene-1, hexene-1,4-methylpentene-1, etc.), ethylene and other ethylenically unsaturated monomers (for example, vinyl acetate, acrylic acid, acrylic ester, Polyolefin resins such as copolymers with methacrylic acid, methacrylic acid esters, vinyl alcohol, etc.); styrene resins such as polystyrene, acrylonitrile-butadiene-styrene copolymers (ABS resins); 6-nylon, 66-nylon, Polyamide resin such as 12-nylon; polyamide Polyimide; Polyetherimide; Acrylic resin such as polymethyl methacrylate; Polyvinyl chloride;
- the polyolefin resin is preferable.
- the polyolefin resin is preferably a resin having a broad molecular weight distribution and having a shoulder on the high molecular weight side, a finely cross-linked resin (a slightly cross-linked resin), a long-chain branched resin, or the like.
- thermoplastic resin includes a thermoplastic elastomer (for example, the following thermoplastic elastomer).
- a thermoplastic elastomer included as the resin constituting the foam layer, the glass transition temperature of the thermoplastic elastomer is not higher than room temperature (for example, 20 ° C. or lower), and therefore the flexibility and shape following property of the foam layer are high. It will be significantly better.
- thermoplastic elastomer is not particularly limited.
- natural or synthetic rubber such as natural rubber, polyisobutylene, polyisoprene, chloroprene rubber, butyl rubber, nitrile butyl rubber; ethylene-propylene copolymer, ethylene-propylene-diene copolymer Olefin-based elastomers such as polymers, ethylene-vinyl acetate copolymers, polybutene, chlorinated polyethylene; styrene-based styrene-butadiene-styrene copolymers, styrene-isoprene-styrene copolymers, and hydrogenated products thereof
- elastomers such as elastomers, polyester elastomers, polyamide elastomers, and polyurethane elastomers.
- a thermoplastic elastomer is used individually or in combination of 2 or more types.
- the thermoplastic elastomer is preferably the olefin elastomer.
- the olefin elastomer has a structure in which an olefin resin component such as polyethylene or polypropylene and an olefin rubber component such as ethylene-propylene rubber or ethylene-propylene-diene rubber are microphase-separated.
- the olefin-based elastomer may be a type in which each component is physically dispersed or a type in which heat treatment is performed dynamically in the presence of a crosslinking agent.
- the olefin elastomer has good compatibility with the polyolefin resin exemplified as the thermoplastic resin.
- the foam layer is preferably composed of the thermoplastic resin (the thermoplastic resin excluding the thermoplastic elastomer) and the thermoplastic elastomer.
- the ratio of the thermoplastic resin (the thermoplastic resin excluding the thermoplastic elastomer) and the thermoplastic elastomer is not particularly limited, but if the ratio of the thermoplastic elastomer is too small, the cushioning property of the foam layer On the other hand, if the ratio of the thermoplastic elastomer is too large, outgassing is likely to occur when the cell structure is formed, and a highly foamed cell structure may not be obtained in the foam layer.
- the foam layer is composed of the polyolefin resin such as polypropylene (the polyolefin resin excluding the olefin elastomer) and the olefin elastomer
- the polyolefin resin and the olefin resin are used.
- the ratio (weight basis) with the elastomer is preferably 1/99 to 99/1 in the former / the latter, more preferably 10/90 to 90/10, and even more preferably 20/80 to 80/20.
- the melt flow rate (MFR) of the resin composition constituting the foam layer is preferably 0.1 to 30 g / 10 min, more preferably 0.2 to 15 g / 10 min. It is particularly preferably 0.3 to 10 g / 10 min. If the MFR is higher than 30 g / 10 min, the resin composition may be soft and gas may easily escape during foaming. If the MFR is lower than 0.1 g / 10 min, the resin composition may become too hard to be extruded. .
- MFR indicates a measured value at “230 ° C., 98 N” unless otherwise specified.
- the foam layer may contain various additives as necessary.
- the additive is not particularly limited.
- cell nucleating agent particles described later
- crystal nucleating agent plasticizer
- lubricant colorant (pigment, dye, etc.)
- ultraviolet absorber antioxidant, anti-aging Agent
- filler reinforcing agent
- antistatic agent surfactant
- tension modifier tension modifier
- shrinkage inhibitor fluidity modifier
- clay vulcanizing agent
- flame retardant flame retardant in various forms other than powder, etc.
- flame retardants in various forms other than powder, etc. The amount of the additive is appropriately selected within a range that does not impair the formation of bubbles.
- the foam layer contains particles. Since the particles can function as a cell nucleating agent (foaming nucleating agent) at the time of foam molding of the resin composition, if the resin composition contains particles, the foam layer has good foamed cells. A structure is obtained.
- the particles include clays such as talc, silica, alumina, zeolite, calcium carbonate, magnesium carbonate, barium sulfate, zinc oxide, titanium oxide, aluminum hydroxide, magnesium hydroxide, mica, montmorillonite, carbon particles, and glass fiber. And carbon tubes.
- grains are used individually or in combination of 2 or more types.
- particles having an average particle size (particle size) of 0.1 to 20 ⁇ m are particularly preferable. This is because if the average particle size of the particles is less than 0.1 ⁇ m, the particles may not function sufficiently as a nucleating agent, whereas if the particle size exceeds 20 ⁇ m, they may cause outgassing during foam molding.
- the content of the particles in the foam layer is not particularly limited.
- the content is preferably 0.1 to 150 parts by weight, more preferably 1 to 130 parts by weight with respect to 100 parts by weight of the total resin. More preferably, it is 2 to 50 parts by weight. If it is less than 0.1 part by weight, the function as a cell nucleating agent cannot be sufficiently exhibited during foam molding of the resin composition, and there is a possibility that a uniform cell structure cannot be obtained in the foam layer. When the amount exceeds parts by weight, the viscosity of the resin composition is remarkably increased, and gas escape occurs during foam formation, which may impair foaming characteristics and fail to provide a highly foamed cell structure.
- the foam layer contains a flame retardant (powdered flame retardant, various forms of flame retardant other than powder, etc.).
- a flame retardant such as electrical or electronic equipment.
- the foam layer is composed of a thermoplastic resin, it easily burns. It is because it has the characteristic.
- the powdery flame retardant is preferably an inorganic flame retardant.
- the inorganic flame retardant include bromine-based flame retardant, chlorine-based flame retardant, phosphorus-based flame retardant, antimony-based flame retardant, and non-halogen-non-antimony-based inorganic flame retardant.
- chlorinated flame retardants and brominated flame retardants generate gas components that are harmful to the human body and corrosive to equipment during combustion
- phosphorous flame retardants and antimony flame retardants are There are problems such as toxicity and explosiveness. Therefore, the inorganic flame retardant is preferably a non-halogen / non-antimony inorganic flame retardant.
- non-halogen-nonantimony inorganic flame retardant examples include hydrated metal compounds such as aluminum hydroxide, magnesium hydroxide, magnesium oxide / nickel oxide hydrate, magnesium oxide / zinc oxide hydrate, and the like. .
- the hydrated metal oxide may be surface treated.
- a powdery flame retardant is used individually or in combination of 2 or more types.
- the content of the flame retardant in the foam layer is not particularly limited, but if the amount is too small, the flame retarding effect may not be obtained, and conversely if too large, it is difficult to obtain a highly foamed cell structure. There is a risk.
- the content of the powdery flame retardant in the resin composition is preferably 5 to 130 parts by weight, more preferably 10 to 120 parts by weight with respect to 100 parts by weight of the total resin.
- the powdery flame retardant may function as a bubble nucleating agent.
- the foam layer is more suitable as a bubble nucleating agent than both a bubble nucleating agent and a flame retardant from the viewpoint of achieving both sufficient flame retardancy and highly foamed cell structure. It is preferred that only a functioning powdery flame retardant is included.
- the foam layer is formed by foam molding a resin composition, which is a composition obtained by mixing a resin as a raw material and an additive added as necessary.
- the foaming method used when foam-molding the composition is not particularly limited. For example, a physical method (low boiling liquid (foaming agent) is dispersed in the resin composition and then heated to volatilize the foaming agent. And a chemical method (method of forming bubbles with a gas generated by thermal decomposition of a compound (foaming agent) added to the resin composition).
- the foaming method used when foam-molding the resin composition is preferably a physical foaming method.
- a high-pressure foaming agent is used.
- a physical foaming method using gas is more preferable.
- the gas as the foaming agent is more preferably an inert gas which is an inert gas with respect to the resin in the resin composition. That is, the foam layer is preferably formed by foaming and molding a resin composition by a physical foaming method using a high-pressure inert gas as a foaming agent.
- the inert gas is not particularly limited as long as it is inert to the resin constituting the foam layer and can be impregnated, and examples thereof include carbon dioxide, nitrogen gas, and air.
- the inert gas is preferably carbon dioxide from the viewpoint that the amount of impregnation into the resin is large and the impregnation speed is high.
- the inert gas may be a mixed gas.
- the high-pressure gas (particularly inert gas, and further carbon dioxide) is preferably a gas in a supercritical state.
- the solubility of the gas in the resin is increased and high concentration can be mixed.
- the generation of bubble nuclei increases, and the density of bubbles formed by the growth of the bubble nuclei has a porosity. Even if they are the same, they become larger, so that fine bubbles can be obtained.
- Carbon dioxide has a critical temperature of 31 ° C. and a critical pressure of 7.4 MPa.
- the physical foaming method using a high-pressure gas as the foaming agent is preferably a method in which a resin composition is impregnated with a high-pressure gas and then subjected to a decompression step.
- the foam layer is prepared by molding a resin composition in an appropriate shape such as a sheet in advance to obtain an unfoamed resin molded body (unfoamed molded product). It may be obtained by a batch method in which gas is impregnated and foamed by releasing pressure, and the resin composition is kneaded with high-pressure gas under pressure, and simultaneously molded and released, and simultaneously molded and foamed. It may be obtained in a continuous manner.
- the method for forming the unfoamed resin molded body is not particularly limited.
- the resin composition is molded using an extruder such as a single screw extruder or a twin screw extruder; A method in which a product is uniformly kneaded using a kneader equipped with blades such as a roller, a cam, a kneader, a banbari type, and press-molded to a predetermined thickness using a hot plate press; resin composition The method etc. which shape
- the shape of the unfoamed resin molded body is not particularly limited, and examples thereof include a sheet shape, a roll shape, and a plate shape.
- the resin composition is molded by an appropriate method for obtaining an unfoamed resin molded body having a desired shape and thickness.
- a non-foamed resin molded body is placed in a pressure-resistant container, a high-pressure gas is injected (introduced), and the non-foamed resin molded body is impregnated with a high-pressure gas.
- the pressure is released at the time of impregnating (usually up to atmospheric pressure), and bubbles are formed through a decompression step for generating bubble nuclei in the resin.
- the resin composition is kneaded using an extruder (for example, a single screw extruder, a twin screw extruder, etc.) or an injection molding machine, and a high-pressure gas is injected (introduced) sufficiently.
- the resin composition is impregnated with a high-pressure gas in a kneading impregnation process, the resin composition is extruded through a die provided at the tip of the extruder, etc., to release the pressure (usually up to atmospheric pressure), and molding and foaming simultaneously
- the resin composition is foam-molded by the molding decompression step.
- a heating step for growing bubble nuclei by heating may be provided as necessary.
- bubble nuclei may be grown at room temperature without providing a heating step.
- the shape may be fixed rapidly by cooling with cold water or the like.
- the high-pressure gas may be introduced continuously or discontinuously.
- the heating method for growing the cell nuclei is not particularly limited, and examples thereof include known or conventional methods such as a water bath, an oil bath, a hot roll, a hot air oven, far infrared rays, near infrared rays, and microwaves.
- the amount of gas mixture is not particularly limited, but is, for example, 2 to 10% by weight with respect to the total amount of resin in the resin composition.
- the pressure when impregnating the gas is appropriately selected in consideration of the type of gas, operability, etc.
- the pressure is preferably 6 MPa or more (for example, 6 to 100 MPa), more preferably 8 MPa or more (for example, 8 to 100 MPa).
- the gas pressure is lower than 6 MPa, the bubble growth during foaming is remarkable, the bubble diameter becomes too large, and disadvantages such as, for example, a reduction in the dustproof effect are likely to occur, which is not preferable.
- the temperature at which the gas is impregnated varies depending on the type of gas and resin used and can be selected in a wide range. In consideration of the above, it is preferably 10 to 350 ° C. More specifically, the impregnation temperature in the batch method is preferably 10 to 250 ° C, more preferably 40 to 240 ° C, and still more preferably 60 to 230 ° C. In the continuous method, the impregnation temperature is preferably 60 to 350 ° C., more preferably 100 to 320 ° C., and still more preferably 150 to 300 ° C. When carbon dioxide is used as the high-pressure gas, the temperature during impregnation (impregnation temperature) is preferably 32 ° C. or higher (particularly 40 ° C. or higher) in order to maintain a supercritical state.
- the pressure reduction rate in the pressure reduction step is not particularly limited, but is preferably 5 to 300 MPa / second in order to obtain uniform fine bubbles.
- the heating temperature in the heating step is preferably, for example, 40 to 250 ° C., more preferably 60 to 250 ° C.
- a physical foaming method using a high-pressure gas as the foaming agent when foaming / molding the resin composition, a highly foamed cell structure can be obtained, and the thickness of the foam layer can be increased.
- a foam layer having a thickness of 0.50 to 5.00 mm can be obtained.
- the thickness of the foam layer is not particularly limited, but is preferably 0.1 mm to 5 mm, more preferably 0.2 mm to 3 mm. If the thickness is less than 0.1 mm, the foamed laminate of the present invention may be deteriorated in dustproof performance or cushion performance. On the other hand, when the thickness exceeds 5 mm, it may be difficult to apply the foamed laminate of the present invention to an electronic or electrical device having a shape such as a thin shape, a small size, and a small width. The thickness of the foam layer may be adjusted by obtaining a thick foam layer in advance and then slicing it to a desired thickness.
- relative density density after foaming / density in unfoamed state (for example, resin composition) And the density of the unfoamed molded product
- relative density are preferably 0.02 to 0.30, and more preferably 0.03 to 0.25.
- the relative density exceeds 0.30, foaming becomes insufficient, and the flexibility of the foam layer may be lowered.
- the relative density is less than 0.02, the strength of the foam layer may be remarkably lowered.
- the cell structure, density, and relative density of the foam layer are determined according to the foaming method and foaming conditions (for example, the type of foaming agent and the like) when foaming the resin composition according to the type of resin constituting the foam layer. Volume, temperature, pressure, time, etc. during foaming).
- a foam layer having a density (apparent density) of 0.02 to 0.20 g / cm 3 is 10 MPa under a temperature atmosphere of 150 to 190 ° C. in a physical foaming method using a high-pressure gas as the foaming agent. It can be easily obtained by impregnating the resin composition with a gas as a blowing agent (preferably an inert gas, more preferably carbon dioxide) under a pressure of ⁇ 30 MPa.
- a gas as a blowing agent preferably an inert gas, more preferably carbon dioxide
- the foam laminate of the present invention may have other layers in addition to the polyolefin pressure-sensitive adhesive layer and the foam layer.
- an intermediate layer provided between the foam layer and the polyolefin pressure-sensitive adhesive layer for example, an undercoat layer that improves adhesion, a base material layer that functions as a core material (for example, a film layer, Non-woven fabric layer, etc.), and other pressure-sensitive adhesive layers (other pressure-sensitive adhesive layers) than the polyolefin-based pressure-sensitive adhesive layer.
- the production method of the foam laminate of the present invention is not particularly limited, and for example, it is produced by providing a specific pressure-sensitive adhesive layer on one side or both sides of the foam layer.
- a foam laminate having a polyolefin pressure-sensitive adhesive layer on at least one side of a foam layer is coated with a polyolefin pressure-sensitive adhesive composition and cured on at least one side of the foam layer, It is produced by forming.
- the polyolefin pressure-sensitive adhesive composition is a composition that forms a polyolefin pressure-sensitive adhesive layer, and includes a composition that forms a polyolefin pressure-sensitive adhesive.
- the polyolefin-based pressure-sensitive adhesive composition can be obtained by mixing raw materials such as polyolefins such as polyolefin A and polyolefin B and additives added as necessary. In addition, when mixing the raw materials, heat may be applied.
- the melt viscosity of the polyolefin-based pressure-sensitive adhesive composition is not particularly limited, for example, at a temperature of 200 ° C. from the viewpoint of obtaining a high-precision coating property such as forming a pressure-sensitive adhesive layer by accurately coating the foam layer.
- the melt viscosity is preferably 1 to 30 Pa ⁇ s, more preferably 2 to 20 Pa ⁇ s. If it exceeds 30 Pa ⁇ s, the viscosity may be high and it may be difficult to apply uniformly.
- the melt viscosity of the polyolefin pressure-sensitive adhesive composition is also the melt viscosity of the polyolefin pressure-sensitive adhesive layer.
- the thickness of the foamed laminate of the present invention is not particularly limited, but is preferably 0.1 mm to 5 mm, more preferably 0, from the viewpoint of application to an electronic or electrical device having a shape such as a thin shape, a small size, and a narrow width. .2 mm to 3 mm.
- the foamed laminate of the present invention preferably has good heat resistance evaluated by the following (heat resistance evaluation method). If the heat resistance evaluated below is poor, the adhesive layer in the foam laminate incorporated inside melts and protrudes out of the foam laminate during use of the electrical / electronic device. May cause problems such as failure of the display or adversely affect the visibility of the display part of the electric / electronic device.
- Evaluation method of heat resistance A sample compressed in the thickness direction so that the thickness is 50% before compression is stored for 72 hours in a 60 ° C temperature atmosphere, and the adhesive layer protrudes outside the foamed laminate. It is confirmed visually whether it is. And the case where the protrusion of an adhesive layer has not arisen is evaluated as favorable, and the case where the protrusion of an adhesive layer has arisen is evaluated as bad.
- the foamed laminate of the present invention is excellent in dimensional stability (characteristic that the dimensional change is small even if the temperature and time are changed) if the heat resistance is good.
- the foamed laminate of the present invention is often incorporated in an electric / electronic device, and a temperature atmosphere of 60 to 100 ° C. is assumed inside the electric / electronic device due to the use of the electric / electronic device. If the heat resistance is good, the performance does not deteriorate or deteriorate under the temperature atmosphere.
- the foamed laminate of the present invention has a polyolefin-based pressure-sensitive adhesive layer obtained by polymerization using metallocene as a pressure-sensitive adhesive layer, it exhibits low contamination in addition to removability. Furthermore, the foamed laminate of the present invention comprises, as an adhesive layer, a polyolefin-based adhesive layer formed by polyolefin A obtained by polymerization using metallocene as a catalyst and polyolefin B obtained by polymerization using metallocene as a catalyst. If it has, in addition to removability, it is excellent in heat resistance and further exhibits low contamination.
- the foamed laminate of the present invention has low contamination, for example, when disassembling an electrical or electronic device in which the foamed laminate is incorporated, or during rework in the case of incorporating the foamed laminate into an electrical or electronic device, the foamed laminate When the body is peeled off from the resin surface or metal surface of the device housing, the glass surface of the image display unit, or the like, the resin surface or metal surface of the device housing or the glass surface of the image display unit is hardly contaminated. For this reason, it is advantageous at the time of rework when the foam laminate is incorporated in an electric or electronic device if the foam laminate of the present invention has low contamination, and the components, members, and casings constituting the electric or electronic device It is advantageous for recycling.
- the foamed laminate of the present invention has the specific pressure-sensitive adhesive layer as the pressure-sensitive adhesive layer, it has excellent removability (reworkability). In addition, since the foaming laminated body of this invention is excellent in removability, it can promote recycling of a member and resource saving.
- the foamed laminate of the present invention is preferably used for, for example, a mobile phone, a mobile terminal, a digital camera, a video movie, a personal computer, a liquid crystal television, and other home appliances. More specifically, the foamed laminate of the present invention is preferably used as a gasket for use in attaching (attaching) various members or parts constituting an electric or electronic device to a predetermined site in an electric or electronic device. Used.
- Various members or parts constituting the electrical or electronic device that can be attached (mounted) using the foamed laminate of the present invention are not particularly limited.
- a liquid crystal display, an electroluminescence display, a plasma display, and the like Cameras and lenses (especially, a camera or lens mounted on a mobile communication device such as an image display member (particularly a small image display member) or a so-called “mobile phone” or “portable information terminal”)
- An optical member such as a small camera or lens
- an optical component such as a small camera or lens
- the foam laminate of the present invention electrical or electronic devices including a foam laminate for electrical or electronic equipment can be obtained.
- the electrical or electronic equipment has a configuration in which members or parts for electrical or electronic equipment are attached (attached) to a predetermined site via the foamed laminate for electrical or electronic equipment. .
- Examples of the electric or electronic devices include image display devices such as liquid crystal displays, electroluminescence displays, and plasma displays as optical members or components (particularly, image display devices in which small image display members are mounted as optical members). ), Or an electric or electronic device (for example, so-called “portable”) having a configuration in which a camera or a lens (particularly, a small camera or lens) is mounted via the foamed laminate for the electric or electronic device.
- image display devices such as liquid crystal displays, electroluminescence displays, and plasma displays as optical members or components (particularly, image display devices in which small image display members are mounted as optical members).
- an electric or electronic device for example, so-called “portable” having a configuration in which a camera or a lens (particularly, a small camera or lens) is mounted via the foamed laminate for the electric or electronic device.
- Mobile communication devices such as “telephone” and “portable information terminal”).
- Such electric or electronic devices may be products thinner than conventional ones, and the thickness and shape thereof are not particularly limited.
- the softening point of the pellet was 155 ° C.
- This pellet was put into a single screw extruder manufactured by Japan Steel Works (JSW), and carbon dioxide gas was injected at a pressure of 22 (19 after injection) MPa while kneading in an atmosphere of 220 ° C. After sufficiently saturating the carbon dioxide gas, it was cooled to a temperature suitable for foaming and then extruded from a die to obtain a foam having a semi-continuous semi-independent structure.
- This foam had a sheet-like shape, a density of 0.05 g / cm 3 , and a thickness of 2.0 mm. And this foam was sliced and the foam layer (foam layer A) (sheet-like foam) of thickness 0.5mm was obtained.
- Examples 1 to 4 The materials of each Example shown in the following Table 1 are put into a lab plast mill (kneading extruder) manufactured by Toyo Seiki Seisakusho Co., Ltd., kneaded for 5 minutes under the conditions of rotation speed: 30 rpm, temperature: 140 ° C., and further the temperature : It heated up at 200 degreeC and knead
- the pressure-sensitive adhesive composition was coated on the foam layer A with a thickness of 30 ⁇ m using a coating machine (device name “GPD-300”, manufactured by Yuri Roll Machinery Co., Ltd.) under a melting temperature of 200 ° C.
- the foamed laminate of each example was produced by coating with a thickness.
- this foaming laminated body has a sheet-like shape, and has a layer structure of a foam layer / adhesive layer.
- Tough Selenium H5002 is a polypropylene elastomer (trade name “Tough Selenium H5002”, manufactured by Sumitomo Chemical Co., Ltd., crystal melting energy: 11.3 J / g)
- “Notio PN20300” is a polypropylene elastomer (trade name).
- “Lycocene PP1502” is a polypropylene wax (trade name “Lycocene PP1502”, manufactured by Clariant, Inc., crystal melting energy: 26.
- “Lycocene PP2602” is a polypropylene wax (trade name “Lycocene PP2602”, manufactured by Clariant, crystal melting energy: 39.8 J / g), and “Lycocene PP6502” is a metallocene-based polypro Len wax (trade name “Ricosen PP6502”, manufactured by Clariant, crystal melting energy: 89.1 J / g), “High Wax NP055” is a polypropylene wax (trade name “High Wax NP055”, Mitsui Chemicals, Inc.) “Calcon P125” is a hydrogenated petroleum resin (trade name “Arcon P125”, manufactured by Arakawa Chemical Industries, Ltd., softening point: 125 ° C.).
- Crystal melting energy of the adhesive layer 3.0 mg of the pressure-sensitive adhesive layer of the foam laminate was sampled and used as a sample. Using this sample, differential scanning calorimetry (DSC measurement) was performed under the following conditions to obtain a DSC curve (for example, FIG. 1). In addition, it measured based on JISK7122. And the sum total of the melting energy at the time of 2nd Run heating was calculated, and it was set as the crystal melting energy.
- FIG. 1 shows a chart (DSC curve) obtained by differential scanning calorimetry (DSC measurement) of Example 1.
- the sample was melted by raising the temperature from ⁇ 50 ° C. to 200 ° C. by heating at a heating rate of 10 ° C./min.
- the molten sample was cooled from 200 ° C. to ⁇ 50 ° C. by solidification by cooling at a temperature decreasing rate of 10 ° C./min.
- the solidified sample was again melted by heating from ⁇ 50 ° C. to 200 ° C. by heating at a heating rate of 10 ° C./min.
- the melting peak baselines are the low temperature side base line (base line E in FIG. 1) and the high temperature side base when the glass transition temperature is determined from the step change part (step change part D in FIG. 1) of the DSC curve.
- baseline F in FIG. 1 it is a high-temperature side baseline (baseline F).
- the foam laminate was cut into a width: 20 mm and a length: 100 mm to obtain a test piece.
- the test piece was bonded to an acrylic plate (trade name “Acrylite (Part No. 001)”, manufactured by Mitsubishi Rayon Co., Ltd.) under the conditions of 1 kg roller and one reciprocation, and bonded together at room temperature (23 ⁇ 2 ° C.). For 30 minutes.
- Comparative Example 2 and 3 did not exhibit adhesiveness even if it crimped
- melt viscosity of adhesive layer 20 g of the pressure-sensitive adhesive layer of the foam laminate was sampled to obtain a test piece. Next, the test piece was dissolved in a sample chamber at 200 ° C. and stirred with a rotor for 30 minutes to obtain a melt. And the viscosity of the melt was measured and melt viscosity was calculated
- Melt viscosity apparatus “DV-II + VISCOMETER” (manufactured by BROOK FILD) Sample chamber: HT-2DB Rotor: SC4-27
- haze difference The haze of an acrylic plate (trade name “Acrylite”, manufactured by Mitsubishi Rayon Co., Ltd.) was measured and designated as haze A.
- the foam laminate was cut into a width: 20 mm and a length: 100 mm to obtain a test piece. Next, the test piece was bonded to the acrylic plate by pressure bonding under a condition of 1 kg roller and one reciprocation, and left to stand for 72 hours in a temperature atmosphere at 60 ° C. and stored.
- a tensile tester (device name “TG-1kN”, manufactured by Minebea Co., Ltd.), in an atmosphere of temperature: 23 ⁇ 2 ° C., humidity: 50 ⁇ 5 RH, tensile speed: 0.3 m / min, peeling
- the test piece was peeled off from the acrylic plate under an angle of 180 °.
- the haze of the acrylic board after peeling was measured, and it was set as haze B.
- a haze difference (haze B ⁇ haze A) was determined from haze A and haze B.
- the haze was measured according to JIS K 7105, and a haze meter (device name “HM-150”, manufactured by Murakami Color Research Laboratory Co., Ltd.) was used as a measuring device.
- HM-150 manufactured by Murakami Color Research Laboratory Co., Ltd.
- the comparative example 1 does not have an adhesive layer.
- the haze difference was similarly applied except that it was pressed on the acrylic plate after being positioned on the acrylic plate, and was removed from the acrylic plate by hand after storage. Asked.
- the foamed laminate was cut into a width: 30 mm ⁇ length: 30 mm to obtain a measurement sample.
- the measurement sample was uniformly compressed in the thickness direction using a jig so that the thickness was 50% before compression.
- the measurement sample was stored for 72 hours in a temperature atmosphere at 80 ° C. while maintaining a state compressed by 50% in the thickness direction.
- save was observed, and the adhesive layer in a foaming laminated body flowed, and it was confirmed visually whether the adhesive layer protruded out of the foaming laminated body.
- the foam layer did not break upon peeling from the acrylic plate at the time of the above measurement (adhesive strength to the acrylic plate).
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Abstract
Description
さらに、本発明の他の目的は、再剥離性に優れるとともに、耐熱性に優れる電気又は電子機器用の発泡積層体を提供することにある。
さらにまた、本発明の他の目的は、再剥離性に優れ、低汚染性の電気又は電子機器用の発泡積層体を提供することにある。
結晶融解エネルギー:10℃/minの昇温速度での加熱により溶融させ(第一の加熱)、次に10℃/minの降温速度での冷却により-50℃まで降温させ(第一の冷却)、そして10℃/minの昇温速度での加熱により-50℃から昇温させる(第二の加熱)という条件で示差走査熱量測定を行い、前記第二の加熱時に求められる融解熱(J/g)(JIS K 7122に準拠)
上記特定の粘着剤層は、結晶融解エネルギーが50J/g以下である粘着剤層である。上記特定の粘着剤層の結晶融解エネルギーは、50J/g以下である限り特に限定されないが、45J/g以下であることが好ましく、より好ましくは40J/g以下である。上記特定の粘着剤層の結晶融解エネルギーが50J/gを超えると、再剥離性の低下という問題が生じるおそれがある。さらに、発泡積層体に衝撃が加わった際に空隙が発生し防塵性が低下するという問題や発泡積層体を変形させた際に粘着剤層で亀裂が生じるという問題が生じるおそれがある。
ヘイズA:アクリル板のヘイズ。
ヘイズB:特定の粘着剤層を上記アクリル板に貼り合わせ、60℃で3日間保存してから、特定の粘着剤層を上記アクリル板から剥離した後の上記アクリル板のヘイズ。
上記特定の粘着剤層において、上記ヘイズ差が2.0%以上であると、低汚染性という特性を発揮することが困難となるためである。なお、上記低汚染性とは、被着体に貼付してから剥離する際に被着体への汚染を生じない特性をいう。
本発明の発泡積層体は、発泡体層を有する。このため、本発明の発泡積層体は、柔軟性、衝撃吸収性に優れる。なお、上記発泡体層は、樹脂組成物を発泡させて成形することにより形成される。該樹脂組成物は、原料としての樹脂と、必要に応じて添加される添加剤等とを、混合することにより得られる組成物である。
本発明の発泡積層体は、上記ポリオレフィン系粘着剤層や発泡体層以外に、その他の層を有していてもよい。その他の層としては、例えば、発泡体層とポリオレフィン系粘着剤層との間に設けられる中間層(例えば、密着性を向上させる下塗り層、芯材として作用する基材層(例えば、フィルム層、不織布層など)、上記ポリオレフィン系粘着剤層以外の粘着層(その他の粘着層)が挙げられる。
厚さが圧縮前の50%となるように厚さ方向に圧縮したサンプルを、60℃の温度雰囲気下で72時間保存し、粘着剤層の発泡積層体外へのはみ出しが生じているか否かを目視で確認する。そして、粘着剤層のはみ出しが生じていない場合を良好と評価し、一方、粘着剤層のはみ出しが生じている場合を不良と評価する。
本発明の発泡積層体により、電気又は電子機器用の発泡積層体を含む電気又は電子機器類を得ることができる。該電気又は電子機器類は、電気又は電子機器用の部材又は部品が、上記電気又は電子機器用の発泡積層体を介して所定の部位に取り付けられた(装着された)構成を有している。
ポリプロピレン(メルトフローレート(MFR):0.35g/10min):50重量部、ポリオレフィン系エラストマー(メルトフローレート(MFR):6g/10min、JIS A硬度:79°):55重量部、カーボンブラック(商品名「旭♯35」、旭カーボン株式会社製):6重量部、及び、水酸化マグネシウム(平均粒子径:0.7μm):10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。なお、ペレットの軟化点は155℃であった。
このペレットを、日本製鋼所(JSW)社製の単軸押出機に投入し、220℃の雰囲気下、混練しながら、22(注入後19)MPaの圧力で、二酸化炭素ガスを注入した。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、ダイから押し出して、半連続半独立構造を有する発泡体を得た。なお、この発泡体は、シート状の形状を有し、密度は0.05g/cm3であり、厚さは2.0mmであった。
そして、この発泡体をスライスして、厚さが0.5mmの発泡体層(発泡体層A)(シート状の発泡体)を得た。
東洋精機製作所社製のラボプラストミル(混練押出機)に、下記表1に示す各実施例の材料を投入し、回転数:30rpm、温度:140℃の条件で5分間混練して、さらに温度:200℃に昇温して10分間混練し、各実施例の粘着剤組成物を得た。
次に、該粘着剤組成物を、溶融温度:200℃の条件下、コーティングマシン(装置名「GPD-300」、由利ロール機械株式会社製)を用いて、上記発泡体層A上に30μmの厚さで塗工して、各実施例の発泡積層体を作製した。なお、この発泡積層体は、シート状の形状を有し、発泡体層/粘着剤層の層構成を有する。
上記発泡体層の製造例1で得た発泡体層を、そのまま使用した。
東洋精機製作所社製のラボプラストミル(混練押出機)に、下記表1に示す各比較例の材料を投入し、回転数:30rpm、温度:140℃の条件で5分間混練して、さらに温度:200℃に昇温して10分間混練し、各比較例の粘着剤組成物を得た。
次に、該粘着剤組成物を、溶融温度:200℃の条件下、コーティングマシン(装置名「GPD-300」、由利ロール機械株式会社製)を用いて、上記発泡体層A上に30μmの厚さで塗工して、各比較例の発泡積層体を作製した。なお、この発泡積層体は、シート状の形状を有し、発泡体層/粘着剤層の層構成を有する。
実施例及び比較例について、粘着剤層の結晶融解エネルギー、アクリル板に対する粘着力、粘着剤層の溶融粘度、ヘイズ差、汚染性、耐熱性を測定又は評価した。その結果を表2にまとめた。
発泡積層体の粘着剤層を3.0mgサンプリングし、試料とした。
該試料を用いて、下記条件で示差走査熱量測定(DSC測定)を行い、DSC曲線を得た(例えば、図1)。なお、JIS K 7122に準拠して測定を行った。
そして、2nd Run heating時の融解エネルギーの総和を算出し、結晶融解エネルギーとした。
DSC測定条件
サンプル量:3.0mg
パン:Tzeroパン(ティー・エイ・インスツルメント社製)(直径:4mm)、Tzeroフタ(ティー・エイ・インスツルメント社製)
昇温速度:10℃/min
降温速度:10℃/min
温度条件
1st Run heating(第一の加熱):-50℃から200℃に昇温
1st Run cooling(第一の冷却):200℃から-50℃に降温
2nd Run heating(第二の加熱):-50℃から200℃に昇温
なお、比較例1は、粘着剤層を有しないので、粘着剤層の結晶融解エネルギーの測定を行わなかった。
最初に、試料を、昇温速度:10℃/minでの加熱により、-50℃から200℃まで昇温させて、溶融させた。次に、該溶融した試料を、降温速度:10℃/minでの冷却により、200℃から-50℃まで降温させて、固化させた。次に、該固化した試料を、再度、昇温速度:10℃/minでの加熱により、-50℃から200℃まで昇温させて、溶融させた。そして、示差走査熱量測定(DSC測定)によるDSC曲線を得た(図1のチャート参照)。
次に、このDSC曲線から、融解ピーク(図1のピークC(図1の斜線のピーク))前後のベースラインから離れる点(図1の点A)とベースラインに戻る点(図1の点B)とを結ぶことに得られる直線と融解ピークとに囲まれている部分の面積(図1の斜線のピークの面積)から、結晶融解エネルギーを求めた。
なお、融解ピークのベースラインは、DSC曲線の階段状変化部(図1の階段状変化部D)からガラス転移温度を決める際の低温側ベースライン(図1のベースラインE)と高温側ベースライン(図1のベースラインF)のうち、高温側ベースライン(ベースラインF)である。
発泡積層体を、幅:20mm、長さ:100mmに裁断し、試験片とした。
該試験片を、1kgローラー、一往復の条件で、アクリル板(商品名「アクリライト(品番001)」、三菱レイヨン株式会社製)に圧着することにより、貼り合わせ、室温(23±2℃)で30分間放置した。
放置後、引張試験機(装置名「TG-1kN」、ミネベア社製)を使用して、温度:23±2℃、湿度:50±5RHの雰囲気下、引張速度:0.3m/min、剥離角度:180°の条件で剥離試験(JIS Z 0237に準拠)を行い、アクリル板に対する粘着力(アクリル板に対する引き剥がし接着強さ)を測定した。
なお、比較例1は、粘着剤層を有しないので、アクリル板に対する粘着力の測定を行わなかった。また、比較例2及び3は、アクリル板に圧着しても密着性を発揮せず、アクリル板に対する粘着力の測定を行うことができなかったので、「密着せず」と評価した。
発泡積層体の粘着剤層を20gサンプリングして、試験片とした。次に、該試験片をサンプルチャンバー内で200℃で溶解させ、30分間ローターで攪拌し、溶融物を得た。そして、その溶融物の粘度を測定し、溶融粘度を求めた。
なお、比較例1は、粘着剤層を有しないので、粘着剤層の溶融粘度の測定を行わなかった。
溶融粘度装置:「DV-II+ VISCOMETER」(BROOK FILD社製)
サンプルチャンバー:HT-2DB
ローター:SC4-27
アクリル板(商品名「アクリライト」、三菱レイヨン株式会社製)のヘイズを測定し、ヘイズAとした。
発泡積層体を、幅:20mm、長さ:100mmに裁断し、試験片とした。次に、該試験片を、1kgローラー、一往復の条件で、上記アクリル板に圧着することにより貼り合わせ、60℃の温度雰囲気下で72時間放置し、保存した。保存後、引張試験機(装置名「TG-1kN」、ミネベア社製)を使用して、温度:23±2℃、湿度:50±5RHの雰囲気下、引張速度:0.3m/min、剥離角度:180°の条件で、アクリル板から試験片を引き剥がした。そして、引き剥がした後のアクリル板のヘイズを測定し、ヘイズBとした。
そして、ヘイズA及びヘイズBより、ヘイズ差(ヘイズB-ヘイズA)を求めた。
また、ヘイズの測定はJIS K 7105に準拠して行い、また、測定装置として、ヘイズメーター(装置名「HM-150」、村上色彩技術研究所社製)を使用した。
なお、比較例1は、粘着剤層を有しない。このため、比較例1では、アクリル板上に位置させてから、1kgローラー、一往復の条件で圧着させたこと、及び、保存後に手でアクリル板から除いたこと以外は、同様にヘイズ差を求めた。
上記ヘイズ差(ヘイズA-ヘイズB)から、下記基準により、低汚染性を評価した。
とても良好(◎):上記ヘイズ差が1.0%未満の場合、見かけ汚染がないとして、低汚染性はとても良好と評価した。
良好(○):上記ヘイズが1.0%以上であり2.0%未満である場合、実用上、見かけ汚染がないと判断できるので、低汚染性は良好と評価した。
不良(×):上記ヘイズが2.0%以上の場合、見かけ汚染があるとして、低汚染性は不良と評価した。
発泡積層体を幅:30mm×長さ:30mmに切断し、測定用サンプルとした。測定用サンプルを、治具を使用して、厚さが圧縮前の50%となるように厚さ方向に均一に圧縮した。次に、測定用サンプルを、厚さ方向に50%圧縮した状態を維持しつつ、80℃の温度雰囲気下で72時間保存した。そして、保存後の測定用サンプルを観察し、発泡積層体中の粘着剤層が流動し、粘着剤層が発泡積層体外にはみ出している否かを目視で確認した。
粘着剤層のはみ出しが生じていない場合を耐熱性良好(○)と評価し、一方、粘着剤層のはみ出しが生じている場合を耐熱性不良(×)と評価した。
なお、何れにおいても、保存前に厚さ方向に50%圧縮した段階で、発泡積層体外に粘着剤層のはみ出しが生じることはなかった。
また、比較例1は、粘着剤層を有しない。このため、比較例1では、保存後に構造の変化が生じているか否かにより耐熱性を評価した。
Claims (5)
- 発泡体層の少なくとも一方の面側に、下記で求められる結晶融解エネルギーが50J/g以下である粘着剤層を有することを特徴とする電気又は電子機器用の発泡積層体。
結晶融解エネルギー:10℃/minの昇温速度での加熱により溶融させ(第一の加熱)、次に10℃/minの降温速度での冷却により-50℃まで降温させ(第一の冷却)、そして10℃/minの昇温速度での加熱により-50℃から昇温させる(第二の加熱)という条件で示差走査熱量測定を行い、前記第二の加熱時に求められる融解熱(J/g)(JIS K 7122に準拠) - 前記粘着剤層が、ポリオレフィンを含むポリオレフィン系粘着剤層である請求項1記載の電気又は電子機器用の発泡積層体。
- 前記ポリオレフィン系粘着剤層が、結晶融解エネルギーが50J/g未満であるポリオレフィンA及び結晶融解エネルギーが50J/g以上であるポリオレフィンBを含み、ポリオレフィンBの割合がポリオレフィン全量(100重量%)に対して3~30重量%である粘着剤層である請求項2記載の電気又は電子機器用の発泡積層体。
- 前記ポリオレフィンが、メタロセン化合物を触媒とする重合により得られたポリオレフィンである請求項2記載の電気又は電子機器用の発泡積層体。
- ポリオレフィンA及びポリオレフィンBのうち少なくとも1つのポリオレフィンが、メタロセン化合物を触媒とする重合により得られたポリオレフィンである請求項3記載の電気又は電子機器用の発泡積層体。
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CN2012800063620A CN103338923A (zh) | 2011-01-24 | 2012-01-16 | 电气或电子器件用发泡层压体 |
KR1020137019538A KR101905929B1 (ko) | 2011-01-24 | 2012-01-16 | 전기 또는 전자 기기용 발포 적층체 |
US13/981,374 US20130309483A1 (en) | 2011-01-24 | 2012-01-16 | Foam laminated body for electrical or electronic equipment |
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JP2011012250A JP5731835B2 (ja) | 2011-01-24 | 2011-01-24 | 電気又は電子機器用の発泡積層体 |
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JP (1) | JP5731835B2 (ja) |
KR (1) | KR101905929B1 (ja) |
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US10580090B2 (en) | 2012-05-25 | 2020-03-03 | Microsoft Technology Licensing, Llc | Batch-computed activity stream updates |
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JP5666926B2 (ja) * | 2011-01-24 | 2015-02-12 | 日東電工株式会社 | 電気又は電子機器用の発泡積層体 |
JP5299596B1 (ja) | 2011-12-26 | 2013-09-25 | Dic株式会社 | 粘着テープ |
US10316221B2 (en) | 2012-03-22 | 2019-06-11 | Dic Corporation | Adhesive tape |
TWI468485B (zh) * | 2012-05-21 | 2015-01-11 | Dainippon Ink & Chemicals | 黏膠帶 |
JP6054692B2 (ja) * | 2012-09-27 | 2016-12-27 | 日本プラスト株式会社 | ステアリング装置 |
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US20130309483A1 (en) | 2013-11-21 |
JP5731835B2 (ja) | 2015-06-10 |
TW201235214A (en) | 2012-09-01 |
KR20140002717A (ko) | 2014-01-08 |
TWI569968B (zh) | 2017-02-11 |
CN103338923A (zh) | 2013-10-02 |
KR101905929B1 (ko) | 2018-10-08 |
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