WO2010024094A1 - 熱伝導性感圧接着剤組成物、熱伝導性感圧接着性シート、及び電子部品 - Google Patents
熱伝導性感圧接着剤組成物、熱伝導性感圧接着性シート、及び電子部品 Download PDFInfo
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- WO2010024094A1 WO2010024094A1 PCT/JP2009/063808 JP2009063808W WO2010024094A1 WO 2010024094 A1 WO2010024094 A1 WO 2010024094A1 JP 2009063808 W JP2009063808 W JP 2009063808W WO 2010024094 A1 WO2010024094 A1 WO 2010024094A1
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- sensitive adhesive
- conductive pressure
- heat conductive
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- adhesive composition
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- 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]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
- H01L23/3737—Organic materials with or without a thermoconductive filler
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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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
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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
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to a heat conductive pressure-sensitive adhesive composition, a heat conductive pressure-sensitive adhesive sheet formed from the heat conductive pressure-sensitive adhesive composition, and an electronic component including the heat conductive pressure-sensitive adhesive sheet.
- Patent Document 1 discloses that a heat conductive pressure sensitive adhesive composition containing a flame retardant inorganic compound, expanded graphite powder, and the like, wherein the main component is selected from a resin and the like, and the heat conductive pressure sensitive A heat conductive pressure sensitive adhesive sheet comprising an adhesive composition has been disclosed, and such a heat conductive pressure sensitive adhesive sheet has good flame retardancy, hardness, adhesive properties and thermal conductivity, and a balance of these properties. It is said to be excellent.
- Patent Document 2 discloses a technique related to a synthetic resin impregnated body made of expanded graphite and a resin.
- a material having a resin or the like as a main component such as a heat conductive pressure-sensitive adhesive sheet disclosed in Patent Document 1
- Patent Document 1 has an advantage that it is more flexible and lighter than metal.
- the present invention provides a heat conductive pressure-sensitive adhesive sheet that is light and inexpensive, having high thermal conductivity and conductivity while maintaining flexibility and sufficient strength, and the heat conductive pressure-sensitive adhesive sheet. It aims at providing the electronic component provided with the heat conductive pressure-sensitive-adhesive composition used as this, and this heat conductive pressure-sensitive-adhesive sheet.
- the present inventors have found that intensive continued research on heat-conductive and pressure-sensitive adhesive sheet, expanded graphite powder, and, dibutyl phthalate (hereinafter, referred to as "DBP".) An oil absorption of 300 cm 3/100 g or more, or BET The present inventors have found that the above problems can be solved by forming a heat conductive pressure-sensitive adhesive composition containing carbon black having a specific surface area of 500 m 2 / g or more into a sheet shape, and have completed the present invention.
- the rubber at least one polymer selected from the group consisting of elastomers and resins and (S), DBP oil absorption of 300 cm 3/100 g or more, or BET specific surface area of 500 meters 2 /
- a heat conductive pressure-sensitive adhesive composition (E) comprising g or more of carbon black (B) and expanded graphite powder (C).
- DBP oil absorption means that measured by the method defined in ASTM D2414.
- Examples of commercially available carbon black (B) that can be used in the present invention include Ketjen Black EC (manufactured by Ketjen Black International Co., Ltd.) and Ketjen Black EC-600JD (Ketjen Black International Co., Ltd.). Manufactured).
- the polymer (S) is preferably a (meth) acrylic acid ester polymer (A1). It is preferable to use the polymer (S) as the (meth) acrylic acid ester polymer (A1) because it is easy to impart adhesiveness and flexibility when used as the heat conductive pressure-sensitive adhesive sheet (F).
- the heat conductive pressure-sensitive adhesive composition (E) of the first invention when the polymer (S) is a (meth) acrylic acid ester polymer (A1), the heat conductive pressure-sensitive adhesive composition (E It is preferable to further contain a (meth) acrylic acid ester monomer (A2m).
- the thermally conductive pressure-sensitive adhesive composition (E) of the first invention comprising (meth) acrylic acid ester polymer (A1), carbon black (B), and expanded graphite powder (C).
- the heat conductive pressure-sensitive adhesive composition (E) is 2 parts by mass or more and 100 parts by mass or less of carbon black (B) with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A1), It is preferable to contain 50 parts by mass or more and 300 parts by mass or less of expanded graphite powder (C).
- the first heat-conductive and pressure-sensitive adhesive composition of the present invention in (E), carbon black (B) is, DBP oil absorption 300 cm 3/100 g or more, and, BET specific surface area of 500 meters 2 / g or more carbon black It is preferable that
- the expanded graphite powder (C) preferably has an average particle size of 30 ⁇ m to 500 ⁇ m.
- the average particle size of the expanded graphite powder (C) means that measured by a microsorting control method using a laser particle size measuring device as will be described later.
- the expanded graphite powder (C) is obtained by heat-treating acid-treated graphite at 500 ° C. to 1200 ° C. to 100 ml / g to 300 ml / g. It is preferable that the product is obtained through a process including expanding and then pulverizing.
- the heat conductive pressure-sensitive-adhesive sheet (F) formed by heat-molding the heat conductive pressure-sensitive-adhesive composition (E) of 1st this invention in a sheet form is obtained. Provided.
- the heat conductive pressure sensitive adhesive composition (E) is composed of (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester. Presence of the (meth) acrylic acid ester polymer (A1), while the body (A2m) is contained and the heat conductive pressure-sensitive adhesive composition (E) is molded into a sheet or after being molded into a sheet It is a sheet-like molded body of the solidified product (E ′) of the thermally conductive pressure-sensitive adhesive composition (E) obtained by polymerizing the (meth) acrylic acid ester monomer (A2m) below. Is preferred.
- the heat conductive pressure sensitive adhesive composition (E) is composed of (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester.
- the (meth) acrylic acid ester polymer (A1) in the heat conductive pressure-sensitive adhesive composition (E), and the heat conductive pressure-sensitive adhesive composition (E). It is preferable that it is a sheet-like molded object containing the (meth) acrylic acid ester polymer (A) obtained by polymerizing the inside (meth) acrylic acid ester monomer (A2m).
- a heat conductive pressure sensitive adhesive sheet (F) is formed by molding a heat conductive pressure sensitive adhesive composition (E) containing a (meth) acrylic acid ester polymer (A1) and a (meth) acrylic acid ester monomer (A2m). ), The (meth) acrylic acid ester monomer (A2m) in the heat conductive pressure-sensitive adhesive composition (E) is polymerized and converted into a (meth) acrylic acid ester polymer, and (meth) It is mixed and / or partially bonded to the component of the acrylic ester polymer (A1).
- (meth) acrylic acid ester polymer (A) means (meth) acrylic mixed and / or partially bonded to the components of (meth) acrylic acid ester polymer (A1) as described above. It corresponds to all the (meth) acrylic acid ester polymer components in the thermally conductive pressure-sensitive adhesive sheet (F) of the present invention, including the component of the polymer (A2) of the acid ester monomer (A2m). This is a concept that comprehensively represents all the (meth) acrylate polymer components in the heat conductive pressure-sensitive adhesive sheet (F).
- the heat conductive pressure-sensitive adhesive sheet (F) of the second aspect of the present invention comprises 1 part by mass or more and 80 parts by mass or less of carbon black (B) with respect to 100 parts by mass of the (meth) acrylic ester polymer (A).
- the expanded graphite powder (C) preferably contains 25 parts by mass or more and 250 parts by mass or less.
- carbon black (B) is, DBP oil absorption of 300 cm 3/100 g or more, and, BET specific surface area of 500 meters 2 / g or more of carbon black Preferably there is.
- the expanded graphite powder (C) preferably has an average particle size of 30 ⁇ m to 500 ⁇ m.
- the expanded graphite powder (C) is heat treated at 500 ° C. to 1200 ° C. to 100 ml / g to 300 ml / g of the acid-treated graphite. It is preferable that the product is obtained through a process including expansion and then pulverization.
- an electronic component provided with the heat conductive pressure-sensitive adhesive sheet (F) of the second aspect of the present invention is provided.
- the electronic component of the third aspect of the present invention includes an electroluminescence (EL), a device having a light emitting diode (LED) light source, an automobile power device, a fuel cell, a solar cell, a battery, a mobile phone, a personal digital assistant (PDA), a notebook A personal computer, a liquid crystal, a surface conduction electron-emitting device display (SED), a plasma display panel (PDP), or an integrated circuit (IC) can be used.
- EL electroluminescence
- LED light emitting diode
- LED light emitting diode
- SED surface conduction electron-emitting device display
- PDP plasma display panel
- IC integrated circuit
- a heat-conductive pressure-sensitive adhesive sheet having sufficient heat resistance and high heat conductivity and conductivity, and a heat-conductive pressure-sensitive adhesive composition that forms the basis of the heat-conductive pressure-sensitive adhesive sheet And an electronic component provided with the thermally conductive pressure-sensitive adhesive sheet.
- Thermally conductive pressure sensitive adhesive composition (E) Thermally conductive pressure-sensitive adhesive composition (E) of the present invention, rubber, at least one polymer selected from the group consisting of elastomers and resins and (S), DBP oil absorption of 300 cm 3/100 g or more, or the BET specific It contains carbon black (B) having a surface area of 500 m 2 / g or more and expanded graphite powder (C).
- S elastomers and resins and
- DBP oil absorption of 300 cm 3/100 g or more or the BET specific It contains carbon black (B) having a surface area of 500 m 2 / g or more and expanded graphite powder (C).
- the heat conductive pressure-sensitive adhesive composition (E) of the present invention contains carbon black (B).
- Carbon black that can be used in the present invention (B) is, DBP oil absorption of 300 cm 3/100 g or more, or BET specific surface area is more than 500m 2 / g.
- Specific examples of such commercially available carbon black (B) include Ketjen Black EC (manufactured by Ketjen Black International Co., Ltd.), Ketjen Black EC-600JD (manufactured by Ketjen Black International Co., Ltd.), and the like. Can be mentioned.
- As the carbon black (B) DBP oil absorption of 300 cm 3/100 g or more and a BET specific surface area is preferably 500 meters 2 / g or more.
- the lower limit of the amount of carbon black (B) contained in the thermally conductive pressure-sensitive adhesive composition (E) is 2 parts by mass with respect to 100 parts by mass of the (meth) acrylate polymer (A1). Is preferably 5 parts by mass, more preferably 10 parts by mass.
- the upper limit is preferably 100 parts by mass, more preferably 60 parts by mass, and even more preferably 20 parts by mass. If the amount of carbon black (B) contained in the heat conductive pressure sensitive adhesive composition (E) is less than the lower limit of the above range, the heat conductive pressure sensitive adhesive sheet (F) is brittle and surface cracks occur. Even if it does not become a sheet shape, the thermal conductivity tends to be low. On the other hand, when the upper limit of the above range is exceeded, the sol viscosity becomes high and molding becomes difficult.
- the amount of carbon black (B) contained in the heat conductive pressure-sensitive adhesive sheet (F) may be 1 part by mass with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A).
- the amount is preferably 2.5 parts by mass, more preferably 5 parts by mass.
- an upper limit is 80 mass parts, It is further more preferable that it is 50 mass parts, It is more preferable that it is 15 mass parts. If the amount of carbon black (B) contained in the heat conductive pressure sensitive adhesive sheet (F) is less than the lower limit of the above range, the heat conductive pressure sensitive adhesive sheet (F) is brittle and surface cracks occur. However, when the upper limit of the above range is exceeded, the sol viscosity of the thermally conductive pressure-sensitive adhesive composition (E) increases and it becomes difficult to mold.
- the thermally conductive pressure-sensitive adhesive composition (E) of the present invention contains expanded graphite powder (C).
- expanded graphite powder that can be used in the present invention include a process comprising heat-treating acid-treated graphite at 500 ° C. to 1200 ° C. to expand it to 100 ml / g to 300 ml / g and then pulverizing it. Can be mentioned. More preferably, the graphite is treated with a strong acid, sintered in an alkali, and then again treated with a strong acid at 500 ° C. to 1200 ° C. to remove the acid and to 100 ml / g to 300 ml / g. What was obtained through the process including expanding and then crushing can be mentioned.
- the temperature of the heat treatment is particularly preferably 800 ° C. to 1000 ° C.
- the average particle diameter of the expanded graphite powder (C) used in the present invention is preferably 30 ⁇ m to 500 ⁇ m, more preferably 100 ⁇ m to 400 ⁇ m, and further preferably 250 ⁇ m to 350 ⁇ m.
- the average particle size of the expanded graphite powder (C) is less than the lower limit of the above range, the thermal conductivity of the heat conductive pressure-sensitive adhesive composition (E) is difficult to improve, or the heat conductive pressure-sensitive adhesive sheet (F ),
- the expanded graphite powder (C) passes through the gaps between the entangled thermal conductive fibers (D), and the improvement in flame retardancy of the thermal conductive pressure-sensitive adhesive sheet (F) cannot be expected. There is a fear.
- the average particle diameter of the expanded graphite powder (C) exceeds the upper limit of the above range, the presence of large domains on the surface of the molded product makes it easy to form voids at the interface with the adherend, and thermal conductivity. In addition, there is a possibility that the adhesiveness may be lowered and the moldability may be deteriorated.
- the average particle size of the expanded graphite powder (C) is measured using a laser-type particle size measuring machine (manufactured by Seishin Enterprise Co., Ltd.) and a micro-sorting control method (measuring particles are allowed to pass only within the measurement region to ensure measurement reliability. (Measure to improve).
- a laser-type particle size measuring machine manufactured by Seishin Enterprise Co., Ltd.
- a micro-sorting control method measuring particles are allowed to pass only within the measurement region to ensure measurement reliability. (Measure to improve).
- 0.01 g to 0.02 g of the expanded graphite powder (C) to be measured is caused to flow in the cell, so that the expanded graphite powder (C) flowing into the measurement region has a semiconductor with a wavelength of 670 nm.
- the amount of the expanded graphite powder (C) contained in the heat conductive pressure-sensitive adhesive composition (E) is 50 parts by mass with respect to 100 parts by mass of the (meth) acrylate polymer (A1). Preferably, it is 100 parts by mass, more preferably 150 parts by mass.
- the upper limit is preferably 300 parts by mass, more preferably 250 parts by mass, and even more preferably 200 parts by mass. If the amount of expanded graphite powder (C) contained in the heat conductive pressure-sensitive adhesive composition (E) is less than the lower limit of the above range, the heat conductivity of the heat conductive pressure-sensitive adhesive sheet (F) is low.
- the lower limit of the amount of the expanded graphite powder (C) contained in the heat conductive pressure-sensitive adhesive sheet (F) is 25 parts by mass with respect to 100 parts by mass of the (meth) acrylate polymer (A). It is preferably 50 parts by mass, more preferably 75 parts by mass.
- the upper limit is preferably 250 parts by mass, more preferably 200 parts by mass, and even more preferably 150 parts by mass. If the amount of expanded graphite powder (C) contained in the heat conductive pressure sensitive adhesive sheet (F) is less than the lower limit of the above range, the heat conductivity of the heat conductive pressure sensitive adhesive sheet (F) tends to be low.
- the heat conductive pressure sensitive adhesive composition (E) of the present invention contains a polymer (S).
- a polymer (S) As what comprises a polymer (S), at least 1 type arbitrarily selected from rubber
- the rubber, elastomer and resin are preferably selected from those having adhesiveness and / or tackiness.
- an adhesive agent can be used in combination with rubber, elastomer and resin having no adhesiveness and / or tackiness.
- Conjugated diene polymers such as natural rubber, polybutadiene rubber, polyisoprene rubber; butyl rubber; styrene-butadiene random copolymer, styrene-isoprene random copolymer, styrene-butadiene-isoprene random copolymer, styrene-butadiene block copolymer Polymer, styrene-isoprene block copolymer, styrene-butadiene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, aromatic vinyl-conjugated diene copolymer; styrene-butadiene copolymer Hydrogenated aromatic vinyl-conjugated diene copolymer such as hydrogenated product; vinyl cyanide compound-conjugated diene copolymer such as acrylonitrile-
- Polyepichlorohydride Polyepihalohydrin rubber such as phosphorus rubber and polyepibromohydrin rubber; Polyalkylene oxide such as polyethylene oxide and polypropylene oxide; Ethylene-propylene-diene copolymer (EPDM); Silicone rubber; Silicone resin; Fluoro rubber; Fluoro resin; Polyethylene; ethylene- ⁇ -olefin copolymer such as ethylene-propylene copolymer and ethylene-butene copolymer; ⁇ -olefin polymer such as polypropylene, poly-1-butene and poly-1-octene; Polyvinyl halide resins such as polyvinyl chloride resins and polyvinyl bromide resins; Polyvinylidene chloride resins such as polyvinylidene chloride resins and polyvinylidene bromide resins; Epoxy resins; Phenol resins; Polyphenylene ether resins;
- styrene-isoprene block copolymer polyethyl acrylate, poly (n-butyl acrylate), poly (acrylic acid 2 -Ethylhexyl), poly [acrylic acid- (n-butyl acrylate)], poly [acrylic acid- (2-ethylhexyl acrylate)], poly [acrylic acid- (n-butyl acrylate)-(acrylic acid 2- Ethyl hexyl)], poly [methacrylic acid- (n-butyl acrylate)], poly [methacrylic acid- (2-ethylhexyl acrylate)], poly [methacrylic acid- (n-butyl acrylate)-(acrylic acid 2- Ethylhexyl)], poly [acrylic acid-methacrylic
- More preferable examples include poly [acrylic acid- (2-ethylhexyl acrylate)], poly [methacrylic acid- (2-ethylhexyl acrylate)], and poly [acrylic acid-methacrylic acid- (2-ethylhexyl acrylate)]. It is done.
- the above substances listed as specific examples of rubber, elastomer, and resin may be used alone or in combination of two or more.
- a (meth) acrylic acid ester polymer (A1) is preferable, and in the presence of the (meth) acrylic acid ester polymer (A1) ( Those obtained by polymerizing the (meth) acrylic acid ester monomer (A2m) are particularly preferred.
- Various known materials can be used as the adhesiveness-adhesive agent blended into the polymer (S) as desired.
- petroleum resin, terpene resin, phenol resin and rosin resin can be mentioned, and among these, petroleum resin is preferable. These may be used individually by 1 type and may use 2 or more types together.
- petroleum resins include C5 petroleum resins obtained from pentene, pentadiene, isoprene, etc .; C9 petroleum resins obtained from indene, methylindene, vinyltoluene, styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, etc .; C5-C9 copolymerized petroleum resins obtained from monomers; petroleum resins obtained from cyclopentadiene and dicyclopentadiene; hydrides of these petroleum resins; maleic anhydride, maleic acid, fumaric acid, (meth) of these petroleum resins And modified petroleum resins modified with acrylic acid, phenol, and the like.
- terpene resins examples include ⁇ -pinene resins, ⁇ -pinene resins, and aromatic-modified terpene resins obtained by copolymerizing terpenes such as ⁇ -pinene and ⁇ -pinene with aromatic monomers such as styrene. .
- phenol resin a condensate of phenols and formaldehyde can be used.
- the phenols include phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin, and the like. These phenols and formaldehyde are subjected to a condensation reaction with an acid catalyst or an acid catalyst. The novolak obtained by this can be illustrated.
- the rosin phenol resin etc. which are obtained by adding phenol to an rosin with an acid catalyst and heat-polymerizing can also be illustrated.
- rosin resins include gum rosin, wood rosin or tall oil rosin, stabilized rosin or polymerized rosin disproportionated or hydrogenated using the rosin, maleic anhydride, maleic acid, fumaric acid, (meth) acrylic acid, Examples thereof include modified rosin modified with phenol and the like, and esterified products thereof.
- the alcohol used for esterification to obtain the esterified product is preferably a polyhydric alcohol, and examples thereof include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and neopentyl glycol, glycerin, trimethylolethane, Examples include trihydric alcohols such as trimethylolpropane, tetrahydric alcohols such as pentaerythritol and diglycerin, and hexahydric alcohols such as dipentaerythritol. These may be used alone or in combination of two or more. You may use together.
- the softening point of these adhesiveness-imparting agents is not particularly limited, but a liquid having a high softening point of 200 ° C. or lower can be appropriately selected and used at room temperature.
- the (meth) acrylic acid ester polymer (A1) is not particularly limited, but the (meth) acrylic acid ester monomer unit (a1) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, and It is preferable to contain a monomer unit (a2) having an organic acid group.
- the (meth) acrylate monomer (a1m) that gives the unit (a1) of the (meth) acrylate monomer that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower is not particularly limited.
- ethyl acrylate glass transition temperature of homopolymer is ⁇ 24 ° C.
- propyl acrylate propyl acrylate (-37 ° C.)
- sec-butyl acrylate (same as above) -22 ° C)
- octyl acrylate -65 ° C
- acrylic acid 2 -Methoxyethyl at -50 ° C
- 3-methoxypropyl acrylate at -75 ° C
- acrylic acid ester monomers (a1m) may be used alone or in combination of two or more.
- These (meth) acrylic acid ester monomers (a1m) are such that the monomer unit (a1) derived therefrom is preferably 80% by mass or more and 99.9% by mass in the (meth) acrylic acid ester polymer (A1). % Or less, more preferably 85% by mass or more and 99.5% by mass or less.
- the heat-sensitive pressure-sensitive adhesive sheet (F) obtained therefrom is excellent in pressure-sensitive adhesiveness around room temperature.
- the monomer (a2m) that gives the monomer unit (a2) having an organic acid group is not particularly limited, and representative examples thereof include organic acid groups such as a carboxyl group, an acid anhydride group, and a sulfonic acid group. In addition to these, monomers containing sulfenic acid groups, sulfinic acid groups, phosphoric acid groups, and the like can also be used.
- the monomer having a carboxyl group include, for example, ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and ⁇ , ⁇ such as itaconic acid, maleic acid, and fumaric acid.
- ⁇ -ethylenically unsaturated polyvalent carboxylic acid ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid partial esters such as methyl itaconate, butyl maleate and propyl fumarate can be used.
- the monomer having a sulfonic acid group examples include allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, ⁇ , ⁇ -unsaturated sulfonic acid such as acrylamide-2-methylpropane sulfonic acid, And salts thereof.
- monomers having an organic acid group monomers having a carboxyl group are more preferable, and acrylic acid and methacrylic acid are particularly preferable. These are industrially inexpensive and can be easily obtained, have good copolymerizability with other monomer components, and are preferable in terms of productivity. These monomers (a2m) having an organic acid group may be used alone or in combination of two or more.
- the monomer unit (a2) derived therefrom is 20% by mass or more and 0.1% by mass or less in the (meth) acrylic acid ester polymer (A1), Preferably, it is used in the polymerization in such an amount that it is 15% by mass or more and 0.5% by mass or less. In use within the above range, the viscosity of the polymerization system during polymerization can be maintained within an appropriate range.
- the monomer unit (a2) having an organic acid group is introduced into the (meth) acrylic acid ester polymer by polymerization of the monomer (a2m) having an organic acid group as described above.
- an organic acid group may be introduced by a known polymer reaction after the (meth) acrylic acid ester polymer is formed.
- the (meth) acrylic acid ester polymer (A1) may contain a polymer unit (a3) derived from a monomer (a3m) containing a functional group other than an organic acid group.
- Examples of functional groups other than organic acid groups include hydroxyl groups, amino groups, amide groups, epoxy groups, mercapto groups, and the like.
- Examples of the monomer having a hydroxyl group include (meth) acrylic acid hydroxyalkyl esters such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
- Examples of the monomer containing an amino group include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and aminostyrene.
- Examples of monomers having an amide group include ⁇ , ⁇ -ethylenically unsaturated carboxylic acid amide monomers such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and N, N-dimethylacrylamide. Can be mentioned.
- Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and allyl glycidyl ether.
- the monomer (a3m) containing a functional group other than the organic acid group may be used alone or in combination of two or more.
- the monomer (a3m) having a functional group other than these organic acid groups is such that the monomer unit (a3) derived therefrom is 10% by mass or less in the (meth) acrylate polymer (A1). It is preferred to be used in the polymerization in an appropriate amount. By using 10 mass% or less of monomer (a3m), the viscosity at the time of superposition
- the (meth) acrylic acid ester polymer (A1) is a (meth) acrylic acid ester monomer unit (a1) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower.
- the monomer unit (a2) and the monomer unit (a3) containing a functional group other than the organic acid group it is derived from a monomer (a4m) copolymerizable with these monomers.
- the monomer unit (a4) may be contained.
- a monomer (a4m) may be used individually by 1 type, and may use 2 or more types together.
- the amount of the monomer unit (a4) derived from the monomer (a4m) is preferably 10% by mass or less, more preferably 5% by mass or less, based on the acrylate polymer (A1).
- the monomer (a4m) is not particularly limited, and as a specific example thereof, a (meth) acrylic acid ester monomer (a1m) other than (meth) acrylate monomer (a1m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or less. ) Acrylic acid ester monomer, ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid complete ester, alkenyl aromatic monomer, conjugated diene monomer, non-conjugated diene monomer, vinyl cyanide monomer Carboxylic acid unsaturated alcohol ester, olefinic monomer and the like.
- the (meth) acrylate monomer other than the (meth) acrylate monomer (a1m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower include methyl acrylate (single The glass transition temperature of the polymer is 10 ° C., methyl methacrylate (105 ° C.), ethyl methacrylate (63 ° C.), propyl methacrylate (25 ° C.), butyl methacrylate (20 ° C.), and the like. be able to.
- ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid complete ester examples include dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate and the like.
- alkenyl aromatic monomer examples include styrene, ⁇ -methylstyrene, methyl ⁇ -methylstyrene, vinyl toluene, and divinylbenzene.
- conjugated diene monomer examples include 1,3-butadiene, 2-methyl-1,3-butadiene (synonymous with isoprene), 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene. 2-chloro-1,3-butadiene, cyclopentadiene and the like.
- non-conjugated diene monomer examples include 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene and the like.
- vinyl cyanide monomer examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile and the like.
- carboxylic acid unsaturated alcohol ester monomer examples include vinyl acetate.
- olefin monomer examples include ethylene, propylene, butene, pentene and the like.
- the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1) is preferably in the range of 100,000 to 400,000 as measured by gel permeation chromatography (GPC method). It is more preferable that it is in the range of 300 to 300,000.
- the (meth) acrylic acid ester polymer (A1) is a (meth) acrylic acid ester monomer (a1m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, and a monomer having an organic acid group (A2m), a monomer containing a functional group other than an organic acid group (a3m) used as required, and a monomer copolymerizable with these monomers used as needed ( a4m) can be obtained particularly preferably by copolymerization.
- the polymerization method is not particularly limited, and any of solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, and the like may be used.
- Solution polymerization is preferred, and among them, solution polymerization using a carboxylic acid ester such as ethyl acetate or ethyl lactate or an aromatic solvent such as benzene, toluene or xylene as the polymerization solvent is more preferred.
- the monomer may be added to the polymerization reaction vessel in a divided manner, but it is preferable to add the whole amount at once.
- the polymerization initiation method is not particularly limited, but it is preferable to use a thermal polymerization initiator as the polymerization initiator.
- the thermal polymerization initiator is not particularly limited, and may be either a peroxide or an azo compound.
- Peroxide polymerization initiators include hydroperoxides such as t-butyl hydroperoxide, peroxides such as benzoyl peroxide and cyclohexanone peroxide, and persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate. Can be mentioned. These peroxides can also be used as a redox catalyst in appropriate combination with a reducing agent.
- the usage-amount of a polymerization initiator is not specifically limited, It is preferable that it is the range of 0.01 to 50 mass parts with respect to 100 mass parts of monomers.
- polymerization conditions (polymerization temperature, pressure, stirring conditions, etc.) of these monomers are not particularly limited.
- the obtained polymer is separated from the polymerization medium if necessary.
- the separation method is not particularly limited, but in the case of solution polymerization, the (meth) acrylic acid ester polymer (A1) can be obtained by placing the polymerization solution under reduced pressure and distilling off the polymerization solvent.
- the weight average molecular weight of the (meth) acrylic acid ester polymer (A1) can be controlled by appropriately adjusting the amount of the polymerization initiator used in the polymerization and the amount of the chain transfer agent.
- the heat conductive pressure-sensitive adhesive composition (E) of the present invention may further contain a (meth) acrylic acid ester monomer (A2m) in addition to the (meth) acrylic acid ester polymer (A1). More preferred.
- a (meth) acrylic acid ester monomer (A2m) is formed into a heat conductive pressure-sensitive adhesive sheet (F), (meth) in the heat conductive pressure-sensitive adhesive composition (E).
- Acrylic acid ester monomer (A2m) is polymerized and converted to (meth) acrylic acid ester polymer (A2), mixed with components of (meth) acrylic acid ester polymer (A1) and / or partially bonded.
- the (meth) acrylic acid ester polymer (A) corresponds to all the (meth) acrylic acid ester polymer components in the heat conductive pressure-sensitive adhesive sheet (F) of the present invention, and the heat conductive feeling of the present invention. It is a concept that comprehensively represents all the (meth) acrylic acid ester polymer components in the pressure-adhesive sheet (F).
- the (meth) acrylic acid ester monomer (A2m) is not particularly limited as long as it contains a (meth) acrylic acid ester monomer, but a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower. It is preferable to contain the (meth) acrylic acid ester monomer (a5m) to form.
- a (meth) acrylate monomer (a5m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, it is used for the synthesis of a (meth) acrylate polymer (A1) (meth) )
- a (meth) acrylic acid ester monomer (a5m) may be used individually by 1 type, and may use 2 or more types together.
- the (meth) acrylic acid ester monomer (A2m) may be used as a mixture of the (meth) acrylic acid ester monomer (a5m) and a monomer copolymerizable therewith.
- Particularly preferred (meth) acrylate monomer (A2m) includes (meth) acrylate monomer (a5m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, and an organic acid group. It consists of a monomer (a6m) having
- the monomer (a6m) having an organic acid group a monomer having an organic acid group similar to that exemplified as the monomer (a2m) used for the synthesis of the (meth) acrylic acid ester polymer (A1).
- a polymer can be mentioned.
- the monomer having an organic acid group (a6m) one type may be used alone, or two or more types may be used in combination.
- the ratio of the (meth) acrylate monomer (a5m) in the (meth) acrylate monomer (A2m) is preferably 70% by mass or more and 99.9% by mass or less, more preferably 75% by mass or more. 99% by mass or less.
- the ratio of the (meth) acrylic acid ester monomer (a5m) is in the above range, the pressure-sensitive adhesiveness and flexibility of the heat conductive pressure-sensitive adhesive sheet (F) are excellent.
- the ratio of the monomer (a6m) having an organic acid group in the (meth) acrylic acid ester monomer (A2m) is preferably 30% by mass or more and 0.1% by mass or less, more preferably 25% by mass or more and 1%. It is below mass%.
- the ratio of the monomer having an organic acid group (a6m) is in the above range, the hardness of the heat conductive pressure sensitive adhesive sheet is appropriate, and the pressure sensitive adhesive property at high temperature (100 ° C.) is good. It becomes.
- the (meth) acrylic acid ester monomer (A2m) is a monomer capable of copolymerizing with the (meth) acrylic acid ester monomer (a5m) and the monomer having an organic acid group (a6m).
- a body (a7m) can be contained in 20 mass% or less.
- Examples of the monomer (a7m) include a monomer (a3m), a monomer (a4m) used in the synthesis of the (meth) acrylic acid ester polymer (A1), or a polyfunctional monomer shown below.
- the monomer similar to what is illustrated as a body can be mentioned.
- a polyfunctional monomer having two or more polymerizable unsaturated bonds can also be used.
- intramolecular and / or intermolecular crosslinking can be introduced into the copolymer to increase the cohesive force as a pressure-sensitive adhesive.
- Polyfunctional monomers include 1,6-hexanediol di (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate ) Acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pen erythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri Multifunctional (meth) acrylates such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 2,4-bis (trichloromethyl) -6-p-other substituted tria
- pen erythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate are preferable.
- the (meth) acrylic acid ester monomer (A2m) preferably contains the above polyfunctional monomer.
- the polyfunctional monomer is preferably 0.5% by mass or more and 5% by mass or less, more preferably 1% by mass or more and 3% by mass with respect to 100% by mass of the (meth) acrylic acid ester monomer (A2m). It is desirable to contain the following.
- the amount of the (meth) acrylate monomer (A2m) contained in the heat conductive pressure-sensitive adhesive composition (E) is the lower limit with respect to 100 parts by weight of the (meth) acrylate polymer (A1). Is preferably 20 parts by mass, more preferably 30 parts by mass, and even more preferably 50 parts by mass.
- the upper limit is preferably 100 parts by mass, more preferably 80 parts by mass, and even more preferably 70 parts by mass.
- (Meth) acrylate monomer (A2m) in the heat conductive pressure sensitive adhesive composition (E) is polymerized when the heat conductive pressure sensitive adhesive sheet (F) is formed.
- the thermally conductive pressure-sensitive adhesive composition (E) is added to the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer (A2m), It preferably contains a polymerization initiator.
- the polymerization initiator examples include a photopolymerization initiator, an azo thermal polymerization initiator, an organic peroxide thermal polymerization initiator, and the like. From the viewpoint of the adhesive strength of the obtained heat conductive pressure-sensitive adhesive sheet (F). Therefore, an organic peroxide thermal polymerization initiator is preferably used.
- the photopolymerization initiator various known photopolymerization initiators can be used. Among these, a phosphine oxide compound is preferable. Examples of the phosphine oxide compound that is a preferred photopolymerization initiator include bis (2,4,6-trimethylbenzyl) phenylphosphine oxide and 2,4,6-trimethylbenzyldiphenylphosphine oxide.
- azo-based thermal polymerization initiator 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile) ) And the like.
- organic peroxide thermal polymerization initiator examples include hydroperoxides such as t-butyl hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, 1,6-bis (t-butylperoxycarbonyloxy) hexane, 1,1-bis ( Examples thereof include peroxides such as (t-butylperoxy) -3,3,5-trimethylcyclohexanone, but it is preferable not to release volatile substances that cause odor during thermal decomposition.
- the organic peroxide thermal polymerization initiators those having a one-minute half-life temperature of 120 ° C. or more and 170 ° C. or less are preferable.
- the lower limit of the amount of the polymerization initiator such as the organic peroxide thermal polymerization initiator used is preferably 0.1 parts by mass, more preferably 0 with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A1). 0.3 parts by mass, more preferably 0.5 parts by mass, and the upper limit is preferably 10 parts by mass, more preferably 5 parts by mass, and even more preferably 3 parts by mass.
- the polymerization conversion rate of the (meth) acrylic acid ester monomer (A2m) is preferably 95% by mass or more. If the polymerization conversion rate is too low, a monomer odor remains in the obtained heat conductive pressure-sensitive adhesive sheet (F), which is not preferable.
- the heat-conductive pressure-sensitive adhesive composition (E) of the present invention further includes various known additions such as a foaming agent, an external cross-linking agent, a pigment, other fillers, an anti-aging agent, and a thickener, if necessary.
- An agent can be contained in the range which does not impair the effect of this invention.
- a foaming agent can also be added to the heat conductive pressure sensitive adhesive composition (E) of the present invention in order to foam the heat conductive pressure sensitive adhesive sheet (F) obtained therefrom.
- a thermally decomposable organic foaming agent is preferable.
- a thermally decomposable organic foaming agent what has a decomposition start temperature of 80 degreeC or more and 200 degrees C or less is preferable.
- thermally decomposable organic foaming agents include 4,4′-oxybis (benzenesulfonyl hydrazide).
- foaming aid examples include zinc stearate, a mixture of stearic acid and zinc white (zinc oxide), zinc laurate, a mixture of lauric acid and zinc white, zinc palmitate, a mixture of palmitic acid and zinc white, stearin Examples include sodium acid, sodium laurate, sodium palmitate, potassium stearate, potassium laurate, and potassium palmitate.
- an external cross-linking agent is added to the heat conductive pressure-sensitive adhesive composition (E) of the present invention in order to increase the cohesive force as a pressure-sensitive adhesive and improve heat resistance, and (meth) A crosslinked structure can be introduced into the polymer obtained by polymerizing the (meth) acrylate monomer (A2m) in the presence of the acrylate polymer (A1).
- external crosslinking agents include polyfunctional isocyanate crosslinking agents such as tolylene diisocyanate, trimethylolpropane diisocyanate, diphenylmethane triisocyanate; epoxy crosslinking such as diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether Melamine resin crosslinking agent; amino resin crosslinking agent; metal salt crosslinking agent; metal chelate crosslinking agent; peroxide crosslinking agent;
- polyfunctional isocyanate crosslinking agents such as tolylene diisocyanate, trimethylolpropane diisocyanate, diphenylmethane triisocyanate
- epoxy crosslinking such as diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether Melamine resin crosslinking agent; amino resin crosslinking agent; metal salt crosslinking agent; metal chelate crosslink
- the external crosslinking agent is obtained by polymerizing the (meth) acrylic acid ester monomer (A2m) in the presence of the (meth) acrylic acid ester polymer (A1), and then added to this. By performing heat treatment or radiation irradiation treatment, a cross-link is formed within and / or between the molecules of the copolymer.
- pigment As a pigment, it can be used regardless of organic type or inorganic type, such as carbon black excluding the carbon black (B) and the expanded graphite powder (C) defined in the present application, and titanium dioxide.
- examples of other fillers include inorganic compounds such as clay.
- Antioxidants such as polyphenols, hydroquinones, and hindered amines can be used as the anti-aging agent because they are likely to inhibit radical polymerization and are not usually used.
- inorganic polymer fine particles such as acrylic polymer particles and fine silica, and reactive inorganic compounds such as magnesium oxide can be used.
- Thermally conductive pressure sensitive adhesive sheet (F) The heat conductive pressure sensitive adhesive sheet (F) of the present invention is formed by molding a heat conductive pressure sensitive adhesive composition (E) into a sheet shape.
- the heat conductive pressure-sensitive adhesive composition (E) is a (meth) acrylate polymer (A1) and a (meth) acrylate ester. Presence of the (meth) acrylic acid ester polymer (A1), while the body (A2m) is contained and the heat conductive pressure-sensitive adhesive composition (E) is molded into a sheet or after being molded into a sheet A sheet-like molded body of the solidified product (E ′) of the heat conductive pressure-sensitive adhesive composition (E) obtained by polymerizing the (meth) acrylic acid ester monomer (A2m) below.
- the heat conductive pressure-sensitive adhesive composition (E) can be regarded as substantially equivalent to the solidified product (E ′).
- the heat conductive pressure-sensitive adhesive composition (E) that does not contain a liquid component such as a (meth) acrylic acid ester monomer (A2m) is considered to be equivalent to the solidified product (E ′). it can.
- the heat conductive pressure-sensitive adhesive composition (E) when the content of a liquid component represented by a monomer or the like in the heat conductive pressure-sensitive adhesive composition (E) is 5% by mass or less.
- the heat conductive pressure-sensitive adhesive composition (E) is molded as it is without solidifying the liquid component (for example, polymerization of the monomer), and the heat conductive pressure-sensitive adhesive sheet ( F).
- the heat conductive pressure-sensitive adhesive sheet (F) of the present invention may be composed of only the heat conductive pressure-sensitive adhesive composition (E) or its solidified product (E ′). It may be a composite comprising a thermally conductive pressure-sensitive adhesive composition (E) or a solidified product (E ′) layer formed on both sides.
- the thickness of the layer of the heat conductive pressure-sensitive adhesive composition (E) or its solidified product (E ′) in the heat conductive pressure-sensitive adhesive sheet (F) of the present invention is not particularly limited, but is usually 50 ⁇ m to 3 mm. is there. If it is thinner than 50 ⁇ m, air is likely to be involved when affixing to the heat generator and the heat radiating body, and as a result, sufficient thermal conductivity may not be obtained. On the other hand, if it is thicker than 3 mm, the thermal resistance in the thickness direction of the heat conductive pressure-sensitive adhesive sheet (F) becomes large, and there is a possibility that the heat dissipation is impaired.
- the base material is not particularly limited.
- the substrate include metals having excellent thermal conductivity such as aluminum, copper, stainless steel, and beryllium copper, and foils of alloys and polymers having excellent thermal conductivity such as thermal conductive silicone.
- a sheet-like material, a heat conductive plastic film containing a heat conductive filler, various nonwoven fabrics, glass cloth, a honeycomb structure, or the like can be used.
- Plastic films include polyimide, polyethylene terephthalate, polyethylene naphthalate, polytetrafluoroethylene, polyether ketone, polyethersulfone, polymethylpentene, polyetherimide, polysulfone, polyphenylene sulfide, polyamideimide, polyesterimide, aromatic polyamide, etc.
- a film made of a heat-resistant polymer can be used.
- the method for forming the heat conductive pressure-sensitive adhesive composition (E) or its solidified product (E ′) into a sheet is not particularly limited. Suitable methods include, for example, a casting method in which the heat conductive pressure-sensitive adhesive composition (E) is applied onto process paper such as a polyester film subjected to a release treatment, the heat conductive pressure-sensitive adhesive composition (E) or The solidified product (E ′) is sandwiched between two exfoliated process papers if necessary and passed between rolls, and the thickness is controlled through a die when extruding using an extruder. And the like.
- the pressurizing condition is usually 10 MPa or less, preferably 1 MPa or less. Pressurization exceeding 10 MPa is not preferable because the foamed cell may be crushed when the thermally conductive pressure-sensitive adhesive sheet (F) is foamed.
- the pressurization time may be selected in accordance with the temperature conditions and the type and amount of the polymerization initiator to be used, but is preferably within 1 hour in view of productivity.
- the heat conductive pressure-sensitive adhesive composition (E) is suitably obtained by heating the heat conductive pressure-sensitive adhesive composition (E) with hot air, an electric heater, infrared rays, or the like. be able to.
- the heating temperature at this time is preferably such that the organic peroxide thermal polymerization initiator decomposes efficiently and the polymerization of the (meth) acrylic acid ester monomer (A2m) proceeds.
- the temperature range varies depending on the type of organic peroxide thermal polymerization initiator used, but is preferably 100 ° C. to 200 ° C., more preferably 130 ° C. to 180 ° C.
- the heat conductive pressure-sensitive adhesive sheet (F) is obtained by forming the heat conductive pressure-sensitive adhesive composition (E) into a sheet shape and heating it to a temperature of 100 ° C. or higher and 200 ° C. or lower. It is preferable that it is a sheet-like molded object formed by forming the pressure-adhesive composition (E) into a sheet and polymerizing the (meth) acrylic acid ester monomer (A2m).
- the above-described heat conductive pressure-sensitive adhesive sheet (F) of the present invention can be used as a part of an electronic component. In that case, it can also form directly on base materials, such as a heat radiator, and can also provide as a part of electronic component.
- Specific examples of the electronic component include components around a heat generating part in a device having an electroluminescence (EL) light emitting diode (LED) light source, components around a power device such as an automobile, a fuel cell, a solar cell, a battery, and a mobile phone.
- EL electroluminescence
- LED light emitting diode
- PDA personal digital assistant
- notebook computer liquid crystal
- SED surface conduction electron-emitting device display
- PDP plasma display panel
- IC integrated circuit
- thermo conductive pressure-sensitive adhesive sheet (hereinafter sometimes simply referred to as “strength”)
- the pressure-sensitive adhesive surface of the heat conductive pressure-sensitive adhesive sheet (F) is sandwiched with release paper or release PET (cut plate) and left in a constant temperature and humidity room at 23 ° C. and 50% RH for 1 hour or longer. Then, the following measurements were performed. First, the heat conductive pressure-sensitive adhesive sheet (F) was cut using an SD type lever type sample cutter (trade name “SDL-100” manufactured by Dumbbell Co., Ltd.), and the width was 4 mm ⁇ length 100 mm ⁇ thickness 1 mm. A test piece was prepared.
- the longitudinal direction was made to be the MD direction (direction along the film forming direction) of the heat conductive pressure-sensitive adhesive sheet (F).
- a marked line was written on the surface and side surface of the test piece using a marked ruler (for a distance between marked lines of 40 mm).
- the test piece on which the marked line is written is set in a tensile tester (trade name “Autograph AGIS-20kN”, manufactured by Shimadzu Corporation), load cell: 1 kN, test speed: 300 mm / min. Was measured as strength.
- a test piece was prepared by cutting a heat conductive pressure-sensitive adhesive sheet (F) having a thickness of 1 mm into a size of 50 mm width ⁇ 110 mm length with scissors.
- the release PET of this test piece was peeled off, and a wrap film was affixed to the surface where the release PET was peeled off so as not to enter air.
- the size of the wrap film may be larger than the adhesive surface of the test piece.
- the heat conductivity was measured using the test piece which stuck this wrap film.
- the thermal conductivity (unit: W / m ⁇ K) was measured by an unsteady hot wire comparison method using a rapid thermal conductivity meter (trade name “QTM-500”, manufactured by Kyoto Electronics Industry Co., Ltd.).
- a rapid thermal conductivity meter (trade name “QTM-500”, manufactured by Kyoto Electronics Industry Co., Ltd.).
- quartz current value: 4A
- zirconia current value: 6A
- mullite current value: 9A
- a test piece was prepared by cutting a heat conductive pressure-sensitive adhesive sheet (F) having a thickness of 1 mm into a size of 30 mm width ⁇ 100 mm length with scissors.
- a flat ceramic heater having a contact area of 25 mm ⁇ 25 mm was placed on the test piece.
- the test piece was placed so that one end on the short side of the test piece and one end face of the ceramic heater were aligned.
- a voltage of 15 V was applied to the ceramic heater in an atmosphere of 23 ° C., and after 15 minutes, the ceramic heater and the test piece were photographed from the upper surface side by thermovision.
- the highest temperature portion of the ceramic heater was confirmed, and the difference from the temperature of the ceramic heater when the test piece was not in contact with the ceramic heater was defined as the temperature reduction degree. It can be said that the greater the value of the temperature reduction degree, the higher the heat dissipation performance.
- a test piece was prepared by cutting a heat conductive pressure-sensitive adhesive sheet (F) having a thickness of 1 mm into a size of 50 mm width ⁇ 50 mm length with scissors. A current was passed through both ends of the test piece in the width direction, and the electrical resistance value was confirmed. About the same test piece, the resistance value was measured 3 times by the said method, and the average value was calculated
- a test piece was prepared by cutting a heat conductive pressure-sensitive adhesive sheet (F) having a thickness of 1 mm into a size of 30 mm ⁇ 50 mm. The test piece was sandwiched between clamps, placed on a hook of a balance on the top of an automatic hydrometer (trade name “DENSIMETER-H”, manufactured by Toyo Seiki Seisakusho), measured, and the measured value was read.
- F heat conductive pressure-sensitive adhesive sheet
- Example 1 A reactor was charged with 100 parts of a monomer mixture composed of 94% 2-ethylhexyl acrylate and 6% acrylic acid, 0.03 parts 2,2′-azobisisobutyronitrile and 700 parts ethyl acetate. Then, after substitution with nitrogen, a polymerization reaction was carried out at 80 ° C. for 6 hours. The polymerization conversion rate was 97%. The obtained polymer was dried under reduced pressure to evaporate ethyl acetate to obtain a viscous solid (meth) acrylate polymer (A1).
- the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1) was 270,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 3.1.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined in terms of standard polystyrene by gel permeation chromatography using tetrahydrofuran as an eluent.
- 2EHA 2-ethylhexyl
- MAA methacrylic acid
- tBCH 1,6-bis (t —Butylperoxycarbonyloxy) hexane
- the (meth) acrylic acid ester polymer (A1) 70 parts of carbon black (B) (trade name “Ketjenblack EC”, Ketjen Black International Co., DBP oil absorption: 360 cm 3/100 g , 5 parts of BET surface area: 800 m 2 / g, particle size: 38 nm), 130 parts of expanded graphite powder (C) (trade name “EC-50”, manufactured by Ito Graphite Industries Co., Ltd., average particle size 250 ⁇ m),
- B carbon black
- C expanded graphite powder
- E1 heat conductive pressure-sensitive adhesive composition
- the mixing was performed using a Hobart mixer (trade name “ACM-5LVT type, capacity: 5 L”) manufactured by Kodaira Seisakusho under the following conditions.
- Mixing conditions Using a thermostatic bath (trade name “Viscomate 150III”, manufactured by Toki Sangyo Co., Ltd.), the temperature control of the Hobart container was set to 40 ° C. 1.
- Mix in the rotation speed memory 3 ⁇ 10 minutes 2.
- a polyester film with a release agent is laid on the bottom of the mold having a length of 400 mm, a width of 400 mm, and a depth of 1 mm, and then the heat conductive pressure-sensitive adhesive composition (E1) is poured into the mold. Then, it was covered with a polyester film with a release agent. This was taken out of the mold and polymerized in a hot air oven at 155 ° C. for 30 minutes to obtain a heat conductive pressure sensitive adhesive sheet (F1) whose both surfaces were covered with a polyester film with a release agent.
- the polymerization conversion rate of the (meth) acrylic acid ester monomer mixture (A2m) was calculated from the residual monomer amount in the heat conductive pressure-sensitive adhesive sheet (F1) and found to be 99.9%. Each characteristic was evaluated about this heat conductive pressure sensitive adhesive sheet (F1). The results are shown in Table 2.
- Example 2 As shown in Table 1, the heat-conductive pressure-sensitive adhesive composition (E2) and the heat-conductive pressure-sensitive adhesive were the same as in Example 1 except that the content of ketjen black EC was changed from 5 parts to 15 parts. Sheet (F2) was obtained. Each characteristic was evaluated about this heat conductive pressure sensitive adhesive sheet (F2). The results are shown in Table 2.
- Example 3 As shown in Table 1, the heat-conductive pressure-sensitive adhesive composition (E3) and the heat-conductive pressure-sensitive adhesive were the same as in Example 1 except that the content of ketjen black EC was changed from 5 parts to 10 parts. Sheet (F3) was obtained. Each characteristic was evaluated about this heat conductive pressure sensitive adhesive sheet (F3). The results are shown in Table 2.
- Example 4 As shown in Table 1, the heat-conductive pressure-sensitive adhesive composition (E4) and the heat-conductive pressure-sensitive adhesive were the same as in Example 1 except that the content of ketjen black EC was changed from 5 parts to 50 parts. Sex sheet (F4) was obtained. Each characteristic was evaluated about this heat conductive pressure sensitive adhesive sheet (F4). The results are shown in Table 2.
- Example 5 As shown in Table 1, the content of the expanded graphite powder (C) was changed from 130 parts to 90 parts, and the content of the ketjen black EC was changed from 5 parts to 10 parts. Thus, a heat conductive pressure sensitive adhesive composition (E5) and a heat conductive pressure sensitive adhesive sheet (F5) were obtained. Each characteristic was evaluated about this heat conductive pressure sensitive adhesive sheet (F5). The results are shown in Table 2.
- Example 6 As shown in Table 1, the content of the expanded graphite powder (C) was changed from 130 parts to 150 parts, and the content of the ketjen black EC was changed from 5 parts to 10 parts. Thus, a heat conductive pressure sensitive adhesive composition (E6) and a heat conductive pressure sensitive adhesive sheet (F6) were obtained. Each characteristic was evaluated about this heat conductive pressure sensitive adhesive sheet (F6). The results are shown in Table 2.
- Example 2 As shown in Table 1, in the same manner as in Example 2 except that 300 parts of artificial graphite (average particle size 0.5 mm, manufactured by Ito Graphite Industries Co., Ltd.) was included instead of expanded graphite powder (C). Thus, a heat conductive pressure sensitive adhesive composition (EC2) and a heat conductive pressure sensitive adhesive sheet (FC2) were obtained. Each characteristic was evaluated about this heat conductive pressure sensitive adhesive sheet (FC2). The results are shown in Table 2.
- Table 1 shows the compositions of the thermally conductive pressure-sensitive adhesive compositions prepared in Examples and Comparative Examples.
- the state after the sheet indicates whether or not the shape could be maintained even when touched after being formed into a sheet.
- ⁇ means that the material has been maintained, and “ ⁇ ” means that the material is destroyed when touched.
- - in Table 2 means that measurement was impossible.
- “11.5 ⁇ ” means that a place exceeding 11.5 W / m ⁇ K could not be measured due to a problem of the performance of the thermal conductivity meter. That is, it means that the actual thermal conductivity was higher than 11.5 W / m ⁇ K.
- the heat conductive pressure-sensitive adhesive sheets of Examples 1 to 6 containing specific carbon black and expanded graphite have sufficient strength as a sheet, and have high thermal conductivity and a high degree of temperature reduction. The electrical resistance value was low.
- the heat conductive pressure-sensitive adhesive sheet of Comparative Example 1 containing no carbon black was broken when touched, and the sheet shape could not be maintained.
- the thermally conductive pressure-sensitive adhesive sheet of Comparative Example 4 containing carbon black (MA8) whose DBP oil absorption amount and BET surface area are outside the specified ranges of the present invention should be destroyed when touched and the sheet shape maintained. I could not.
- the heat conductive pressure-sensitive adhesive sheet of Comparative Example 2 containing artificial graphite instead of the expanded graphite powder (C) has sufficient strength as a sheet, the thermal conductivity and the temperature reduction degree are low. The electrical resistance value was very high.
- the thermally conductive pressure-sensitive adhesive sheet of Comparative Example 3 containing copper fibers in place of the expanded graphite powder (C) and carbon black has sufficient strength as a sheet, but the thermal conductivity and temperature. The degree of reduction was low, the electrical resistance value was very high, and the specific gravity was the highest compared to the others.
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Abstract
Description
本発明の熱伝導性感圧接着剤組成物(E)は、ゴム、エラストマー及び樹脂よりなる群から選ばれる少なくとも一種の重合体(S)と、DBP吸油量が300cm3/100g以上、又はBET比表面積が500m2/g以上のカーボンブラック(B)と、膨張化黒鉛粉(C)と、を含有している。以下にこれらの各物質について詳細に説明する。
本発明の熱伝導性感圧接着剤組成物(E)には、カーボンブラック(B)が含有される。本発明に用いることができるカーボンブラック(B)は、DBP吸油量が300cm3/100g以上、又はBET比表面積が500m2/g以上のものである。このようなカーボンブラック(B)で市販されているもの具体例としては、ケッチェンブラックEC(ケッチェンブラックインターナショナル株式会社製)、ケッチェンブラックEC-600JD(ケッチェンブラックインターナショナル株式会社製)などを挙げることができる。カーボンブラック(B)としては、DBP吸油量が300cm3/100g以上でかつBET比表面積が500m2/g以上のものが好ましい。
本発明の熱伝導性感圧接着剤組成物(E)には、膨張化黒鉛粉(C)が含有される。本発明に用いることができる膨張化黒鉛粉の例としては、酸処理した黒鉛を500℃~1200℃にて熱処理して100ml/g~300ml/gに膨張させ、次いで、粉砕することを含む工程を経て得られたものを挙げることができる。より好ましくは、黒鉛を強酸で処理した後アルカリ中で焼結し、その後再度強酸で処理したものを500℃~1200℃にて熱処理して、酸を除去すると共に100ml/g~300ml/gに膨張させ、次いで、粉砕することを含む工程を経て得られたものを挙げることができる。上記熱処理の温度は、特に好ましくは800℃~1000℃である。
本発明の熱伝導性感圧接着剤組成物(E)には、重合体(S)が含有されている。重合体(S)を構成するものとしては、ゴム、エラストマー及び樹脂の中から任意に選んだ少なくとも一種を挙げることができる。そして、本発明の熱伝導性感圧接着剤組成物(E)をシート状に成形して、熱伝導性感圧接着性シート(F)として用いるためには、重合体(S)に接着性及び/又は粘着性を備えさせることが好ましい。重合体(S)に、接着性及び/又は粘着性を備えさせるためには、ゴム、エラストマー及び樹脂は、接着性及び/又は粘着性を有するものの中から選ぶことが好ましい。しかしながら、接着性及び/又は粘着性を有しないゴム、エラストマー及び樹脂に、粘接着性付与剤を組み合わせて用いることもできる。
重合体(S)を構成するものとしては、(メタ)アクリル酸エステル重合体(A1)が好ましい。
酸、ビニルスルホン酸、スチレンスルホン酸、アクリルアミド-2-メチルプロパンスル
ホン酸などのα,β-不飽和スルホン酸、及び、これらの塩を挙げることができる。
本発明の熱伝導性感圧接着剤組成物(E)は、(メタ)アクリル酸エステル重合体(A1)に加えて、さらに、(メタ)アクリル酸エステル単量体(A2m)を含有することがより好ましい。本発明の熱伝導性感圧接着剤組成物(E)を成形して、熱伝導性感圧接着性シート(F)とする際に、熱伝導性感圧接着剤組成物(E)中の(メタ)アクリル酸エステル単量体(A2m)は、重合して(メタ)アクリル酸エステル重合体(A2)に変換し、(メタ)アクリル酸エステル重合体(A1)の成分と混合及び/又は一部結合して、(メタ)アクリル酸エステル重合体(A)となる。前記(メタ)アクリル酸エステル重合体(A)とは、本発明の熱伝導性感圧接着性シート(F)中の(メタ)アクリル酸エステル重合体成分全てに相当し、本発明の熱伝導性感圧接着性シート(F)中の(メタ)アクリル酸エステル重合体成分全てを包括的に表す概念である。
本発明の熱伝導性感圧接着剤組成物(E)には、さらに、必要により、発泡剤、外部架橋剤、顔料、その他の充填材、老化防止剤、増粘剤、などの公知の各種添加剤を、本発明の効果を損なわない範囲で含有することができる。
本発明の熱伝導性感圧接着剤組成物(E)には、それから得られる熱伝導性感圧接着性シート(F)を発泡させるために、発泡剤を添加することもできる。発泡剤としては、熱分解性有機発泡剤が好ましい。さらに、熱分解性有機発泡剤としては、80℃以上かつ200℃以下の分解開始温度を有するものが好ましい。
また、本発明の熱伝導性感圧接着剤組成物(E)には、感圧接着剤としての凝集力を高め、耐熱性などを向上させるために、外部架橋剤を添加して、(メタ)アクリル酸エステル重合体(A1)の存在下に(メタ)アクリル酸エステル単量体(A2m)を重合してなる重合体に架橋構造を導入することができる。
顔料としては、本願規定のカーボンブラック(B)と膨張化黒鉛粉(C)とを除くカーボンブラックや、二酸化チタンなど、有機系、無機系を問わず使用できる。その他の充填材としては、クレーなどの無機化合物などが挙げられる。フラーレンやカーボンナノチューブなどのナノ粒子を添加してもよい。老化防止剤としては、ラジカル重合を阻害する可能性が高いため通常は使用しないが、必要に応じてポリフェノール系、ハイドロキノン系、ヒンダードアミン系などの酸化防止剤を使用することができる。増粘剤としては、アクリル系ポリマー粒子、微粒シリカなどの無機化合物微粒子、酸化マグネシウムなどのような反応性無機化合物を使用することできる。
本発明の熱伝導性感圧接着性シート(F)は、熱伝導性感圧接着剤組成物(E)をシート状に成形してなる。
熱伝導性感圧接着性シート(F)の粘着面を、離形紙又は離形PETではさんだ状態(カット板)にして、23℃、50%RHの恒温恒湿室に1時間以上放置してから、以下の測定を行った。
まず、SD型レバー式試料裁断器(商品名「SDL-100」、株式会社ダンベル製)を用いて熱伝導性感圧接着性シート(F)を裁断し、幅4mm×長さ100mm×厚さ1mmの試験片を作製した。
このとき、長手方向が熱伝導性感圧接着性シート(F)のMD方向(製膜方向に沿った方向)となるようにした。その後、標線定規(標線間距離40mm用)を用いて試験片の表面と側面に標線を書き込んだ。さらに、標線を書き込んだ試験片を引っ張り試験機(商品名「オートグラフ AGIS-20kN」、株式会社島津製作所製)にセットし、ロードセル:1kN、試験速度:300mm/分の条件で、破断応力を測定し、強度とした。
厚さ1mmの熱伝導性感圧接着性シート(F)をはさみで幅50mm×長さ110mmの大きさに裁断した試験片を用意した。この試験片の離形PETを剥がし、離形PETを剥がした面に、空気が入らないようにラップフィルムを貼った。このラップフィルムの大きさは、試験片の粘着面より大きいものであれば良い。そして、このラップフィルムを貼った試験片を用いて熱伝導率を測定した。熱伝導率(単位:W/m・K)測定には、迅速熱伝導率計(商品名「QTM-500」、京都電子工業株式会社製)を用いて、非定常熱線比較法により行った。なお、リファレンスプレートには、石英(電流値:4A)、ジルコニア(電流値:6A)、及び、ムライト(電流値:9A)をこの順で使用した。同一の試験片について2回、熱伝導率を測定し、その平均値を求めた。
厚さ1mmの熱伝導性感圧接着性シート(F)をはさみで幅30mm×長さ100mmの大きさに裁断した試験片を用意した。
この試験片の上に、接触面積が25mm×25mmとなる平板状のセラミックヒータを載せた。このとき、試験片の短辺側の一端とセラミックヒータの一端面とを揃えるようにして載せた。その後、23℃雰囲気下で、セラミックヒータに15Vの電圧を付加し、15分後にセラミックヒータと試験片とを上面側からサーモビジョンで撮影した。セラミックヒータの最も温度が高い部分を確認し、セラミックヒータに試験片を接触させてない場合のセラミックヒータの温度との差分を温度低減度とした。この温度低減度の値が大きいほど、放熱性能が高いと言える。
厚さ1mmの熱伝導性感圧接着性シート(F)をはさみで幅50mm×長さ50mmの大きさに裁断した試験片を用意した。試験片の幅方向の両端に電流を流し、その電気抵抗値を確認した。同一の試験片について、上記方法で3回、抵抗値を測定し、その平均値を求めた。
厚さ1mmの熱伝導性感圧接着性シート(F)を30mm×50mmの大きさに裁断した試験片を用意した。試験片をクランプに挟み、自動比重計(商品名「DENSIMETER-H」、東洋精機製作所製)上部の天秤のフックに掛け、測定を行い、測定値を読み取った。
反応器に、アクリル酸2-エチルヘキシル94%とアクリル酸6%とからなる単量体混合物100部、2,2’-アゾビスイソブチロニトリル0.03部及び酢酸エチル700部を入れて均一に溶解し、窒素置換後、80℃で6時間重合反応を行った。重合転化率は97%であった。得られた重合体を減圧乾燥して酢酸エチルを蒸発させ、粘性のある固体状の(メタ)アクリル酸エステル重合体(A1)を得た。(メタ)アクリル酸エステル重合体(A1)の重量平均分子量(Mw)は270,000、重量平均分子量(Mw)/数平均分子量(Mn)は3.1であった。重量平均分子量(Mw)及び数平均分子量(Mn)は、テトラヒドロフランを溶離液とするゲルパーミエーションクロマトグラフィーにより、標準ポリスチレン換算で求めた。
混合条件:
恒温槽(商品名「ビスコメイト 150III」、東機産業株式会社製)を用いて、ホバート容器の温調を40℃に設定。
1.回転数メモリ3×10分で混合
2.回転数メモリ5×20分で混合
3.回転数メモリ3×10分、-0.1MPaで真空脱泡しながら混合
これを金型から取り出し、155℃の熱風炉で30分間、重合を行わせ、両面を離型剤付きポリエステルフィルムで覆われた、熱伝導性感圧接着性シート(F1)を得た。
熱伝導性感圧接着性シート(F1)中の残存単量体量から(メタ)アクリル酸エステル単量体混合物(A2m)の重合転化率を計算したところ、99.9%であった。
この熱伝導性感圧接着性シート(F1)について各特性を評価した。その結果を表2に示す。
表1に示すように、ケッチェンブラックECの含有量を5部から15部に変更した以外は実施例1と同様にして、熱伝導性感圧接着剤組成物(E2)及び熱伝導性感圧接着性シート(F2)を得た。この熱伝導性感圧接着性シート(F2)について各特性を評価した。その結果を表2に示す。
表1に示すように、ケッチェンブラックECの含有量を5部から10部に変更した以外は実施例1と同様にして、熱伝導性感圧接着剤組成物(E3)及び熱伝導性感圧接着性シート(F3)を得た。この熱伝導性感圧接着性シート(F3)について各特性を評価した。その結果を表2に示す。
表1に示すように、ケッチェンブラックECの含有量を5部から50部に変更した以外は実施例1と同様にして、熱伝導性感圧接着剤組成物(E4)及び熱伝導性感圧接着性シート(F4)を得た。この熱伝導性感圧接着性シート(F4)について各特性を評価した。その結果を表2に示す。
表1に示すように、膨張化黒鉛粉(C)の含有量を130部から90部に変更し、ケッチェンブラックECの含有量を5部から10部に変更した以外は実施例1と同様にして、熱伝導性感圧接着剤組成物(E5)及び熱伝導性感圧接着性シート(F5)を得た。この熱伝導性感圧接着性シート(F5)について各特性を評価した。その結果を表2に示す。
表1に示すように、膨張化黒鉛粉(C)の含有量を130部から150部に変更し、ケッチェンブラックECの含有量を5部から10部に変更した以外は実施例1と同様にして、熱伝導性感圧接着剤組成物(E6)及び熱伝導性感圧接着性シート(F6)を得た。この熱伝導性感圧接着性シート(F6)について各特性を評価した。その結果を表2に示す。
表1に示すように、ケッチェンブラックECを含有させないこと以外は実施例1と同様にして、熱伝導性感圧接着剤組成物(EC1)及び熱伝導性感圧接着性シート(FC1)を得た。この熱伝導性感圧接着性シート(FC1)について各特性を評価した。その結果を表2に示す。
表1に示すように、膨張化黒鉛粉(C)にかえて、人造黒鉛(平均粒径0.5mm、伊藤黒鉛工業株式会社製)300部を含有させたこと以外は実施例2と同様にして、熱伝導性感圧接着剤組成物(EC2)及び熱伝導性感圧接着性シート(FC2)を得た。この熱伝導性感圧接着性シート(FC2)について各特性を評価した。その結果を表2に示す。
表1に示すように、膨張化黒鉛粉(C)及びケッチェンブラックECにかえて、銅繊維(商品名「KCメタルファイバー」、長さ3cm、虹技株式会社製)を130部含有させたこと以外は実施例1と同様にして、熱伝導性感圧接着剤組成物(EC3)及び熱伝導性感圧接着性シート(FC3)を得た。この熱伝導性感圧接着性シート(FC3)について各特性を評価した。その結果を表2に示す。
表1に示すように、ケッチェンブラックECにかえて、他のカーボンブラック(商品名「MA8」、三菱化学株式会社製、DBP吸油量:57cm3/100g、BET表面積:120m2/g、粒径:24nm)5部を含有させたこと以外は実施例1と同様にして、熱伝導性感圧接着剤組成物(EC4)及び熱伝導性感圧接着性シート(FC4)を得た。この熱伝導性感圧接着性シート(FC4)について各特性を評価した。その結果を表2に示す。
上記で作製した熱伝導性感圧接着性シートを評価した。その結果を表2に示す。
一方、カーボンブラックを含有しない比較例1の熱伝導性感圧接着性シートは、触ると破壊し、シート状を維持することができなかった。DBP吸油量及びBET表面積が本発明の規定範囲外であるカーボンブラック(MA8)を含有させた比較例4の熱伝導性感圧接着性シートも同様に、触ると破壊し、シート状を維持することができなかった。また、膨張化黒鉛粉(C)にかえて人造黒鉛を含有させた比較例2の熱伝導性感圧接着性シートは、シートとしての強度は十分に備えるものの、熱伝導率及び温度低減度が低く、電気抵抗値が非常に高かった。さらに、膨張化黒鉛粉(C)及びカーボンブラックにかえて、銅繊維を含有させた比較例3の熱伝導性感圧接着性シートは、シートとしての強度は十分に備えるものの、熱伝導率及び温度低減度が低く、電気抵抗値が非常に高かったうえ、比重が他のものに比べて最も大きくなった。
Claims (16)
- ゴム、エラストマー及び樹脂よりなる群から選ばれる少なくとも一種の重合体(S)と、DBP吸油量が300cm3/100g以上、又はBET比表面積が500m2/g以上のカーボンブラック(B)と、膨張化黒鉛粉(C)と、を含有してなる、熱伝導性感圧接着剤組成物(E)。
- 前記重合体(S)が(メタ)アクリル酸エステル重合体(A1)である、請求の範囲第1項に記載の熱伝導性感圧接着剤組成物(E)。
- さらに、(メタ)アクリル酸エステル単量体(A2m)を含有する、請求の範囲第2項に記載の熱伝導性感圧接着剤組成物(E)。
- 前記(メタ)アクリル酸エステル重合体(A1)100質量部に対して、前記カーボンブラック(B)2質量部以上100質量部以下と、前記膨張化黒鉛粉(C)50質量部以上300質量部以下と、を含有してなる、請求の範囲第2項又は第3項に記載の熱伝導性感圧接着剤組成物(E)。
- 前記カーボンブラック(B)が、DBP吸油量が300cm3/100g以上、かつ、BET比表面積が500m2/g以上のカーボンブラックである、請求の範囲第1項~第4項のいずれか1項に記載の熱伝導性感圧接着剤組成物(E)。
- 前記膨張化黒鉛粉(C)の平均粒径が30μm~500μmである、請求の範囲第1項~第5項のいずれか1項に記載の熱伝導性感圧接着剤組成物(E)。
- 前記膨張化黒鉛粉(C)が、酸処理した黒鉛を500℃~1200℃にて熱処理して100ml/g~300ml/gに膨張させ、次いで、粉砕することを含む工程を経て得られたものである、請求の範囲第1項~第6項のいずれか1項に記載の熱伝導性感圧接着剤組成物(E)。
- 請求の範囲第1項~第7項のいずれか1項に記載の熱伝導性感圧接着剤組成物(E)を加熱及びシート状に形成してなる、熱伝導性感圧接着性シート(F)。
- 請求の範囲第3項又は第4項に記載の熱伝導性感圧接着剤組成物(E)をシート状に成形しながら、又はシート状に成形した後、該熱伝導性感圧接着剤組成物(E)中の(メタ)アクリル酸エステル重合体(A1)の存在下に該熱伝導性感圧接着剤組成物(E)中の(メタ)アクリル酸エステル単量体(A2m)を重合することにより得られる、該熱伝導性感圧接着剤組成物(E)の固化物(E’)のシート状成形体である、熱伝導性感圧接着性シート(F)。
- 請求の範囲第3項又は第4項に記載の熱伝導性感圧接着剤組成物(E)中の前記(メタ)アクリル酸エステル重合体(A1)の存在下に、該熱伝導性感圧接着剤組成物(E)中の前記(メタ)アクリル酸エステル単量体(A2m)を重合させることにより得られる(メタ)アクリル酸エステル重合体(A)を含む、熱伝導性感圧接着性シート(F)。
- 前記(メタ)アクリル酸エステル重合体(A)100質量部に対して、前記カーボンブラック(B)1質量部以上80質量部以下と、前記膨張化黒鉛粉(C)25質量部以上250質量部以下と、を含有する、請求の範囲第10項に記載の熱伝導性感圧接着性シート(F)。
- 前記カーボンブラック(B)が、DBP吸油量が300cm3/100g以上、かつ、BET比表面積が500m2/g以上のカーボンブラックである、請求の範囲第8項~第11項のいずれか1項に記載の熱伝導性感圧接着性シート(F)。
- 前記膨張化黒鉛粉(C)の、平均粒径が30μm~500μmである、請求の範囲第8項~第12項のいずれか1項に記載の熱伝導性感圧接着性シート(F)。
- 前記膨張化黒鉛粉(C)が、酸処理した黒鉛を500℃~1200℃にて熱処理して100ml/g~300ml/gに膨張させ、次いで、粉砕することを含む工程を経て得られたものである、請求の範囲第8項~第13項のいずれか1項に記載の熱伝導性感圧接着性シート(F)。
- 請求の範囲第8項~第14項のいずれか1項に記載の熱伝導性感圧接着性シート(F)を備えた電子部品。
- エレクトロルミネッセンス(EL)、発光ダイオード(LED)光源を有する機器、自動車のパワーデバイス、燃料電池、太陽電池、バッテリー、携帯電話、携帯情報端末(PDA)、ノートパソコン、液晶、表面伝導型電子放出素子ディスプレイ(SED)、プラズマディスプレイパネル(PDP)、又は集積回路(IC)である、請求の範囲第15項に記載の電子部品。
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JP2010526636A JPWO2010024094A1 (ja) | 2008-08-25 | 2009-08-04 | 熱伝導性感圧接着剤組成物、熱伝導性感圧接着性シート、及び電子部品 |
KR1020117003666A KR20110044869A (ko) | 2008-08-25 | 2009-08-04 | 열전도성 감압 접착제 조성물, 열전도성 감압 접착성 시트, 및 전자 부품 |
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Cited By (7)
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WO2012014794A1 (ja) * | 2010-07-30 | 2012-02-02 | 国立大学法人東北大学 | 光電変換部材 |
JP2012158695A (ja) * | 2011-02-01 | 2012-08-23 | Hitachi Chemical Co Ltd | 熱伝導シート及び放熱装置 |
JP2013187451A (ja) * | 2012-03-09 | 2013-09-19 | Mitsubishi Cable Ind Ltd | 搬送パッド、およびそれを用いてなる搬送アーム |
JP2014167061A (ja) * | 2013-02-28 | 2014-09-11 | Nippon Zeon Co Ltd | 熱伝導性感圧接着剤組成物、熱伝導性感圧接着性シート状成形体、これらの製造方法、及び電子機器 |
JP2014167060A (ja) * | 2013-02-28 | 2014-09-11 | Nippon Zeon Co Ltd | 熱伝導性感圧接着剤組成物、熱伝導性感圧接着性シート状成形体、これらの製造方法、及び電子機器 |
CN105479843A (zh) * | 2016-01-06 | 2016-04-13 | 李忠诚 | 一种无硅导热材料及其制备方法 |
JP2017126614A (ja) * | 2016-01-12 | 2017-07-20 | 日立化成株式会社 | 熱伝導シート、熱伝導シートの製造方法及び放熱装置 |
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KR20140074869A (ko) * | 2011-09-28 | 2014-06-18 | 제온 코포레이션 | 열전도성 감압 접착제 조성물, 열전도성 감압 접착성 시트상 성형체, 이들의 제조 방법, 및 전자 부품 |
JP5582553B1 (ja) * | 2014-05-02 | 2014-09-03 | 清二 加川 | 高熱伝導率の放熱シート及びその製造方法 |
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WO2012014794A1 (ja) * | 2010-07-30 | 2012-02-02 | 国立大学法人東北大学 | 光電変換部材 |
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JP2017126614A (ja) * | 2016-01-12 | 2017-07-20 | 日立化成株式会社 | 熱伝導シート、熱伝導シートの製造方法及び放熱装置 |
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CN102131879A (zh) | 2011-07-20 |
KR20110044869A (ko) | 2011-05-02 |
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