JPWO2017022749A1 - Adhesive tape, heat dissipation sheet, electronic device, and method for producing adhesive tape - Google Patents

Abstract

The present invention is an adhesive tape having two or more adhesive parts (B) on at least one surface (a) side of the support (A), and the adhesive part between the two or more adhesive parts (B). The present invention relates to a pressure-sensitive adhesive tape characterized in that there is a region not having (B), and the region communicates with an end of the pressure-sensitive adhesive tape. INDUSTRIAL APPLICABILITY The present invention is useful because it is possible to provide a thin pressure-sensitive adhesive tape that can quickly prevent bubbles from leaving from the interface with the adherend, prevent bubbles from remaining at the interface, and has excellent adhesive strength. .

Description

  The present invention relates to a thin adhesive tape that can be used, for example, in a manufacturing scene of an electronic device or the like.

  Adhesive tapes are widely used in the production scenes of electronic devices such as OA devices and home appliances because they are excellent in workability and have high adhesion reliability.

  In recent years, the electronic devices have been required to have high functionality, downsizing, and thinning, and in particular, portable electronic devices such as personal computers, digital video cameras, electronic notebooks, mobile phones, PHSs, smartphones, game devices, electronic books, and the like. Terminals are required to be further reduced in size and thickness. Accordingly, the adhesive tape and the like constituting the portable electronic terminal are also required to be thin.

  As the thin adhesive tape, for example, an acrylic acid ester copolymer having a weight average molecular weight of 700,000 or more and a butyl acrylate unit content of 90% by mass or more, and a tackifier are the main components, and A double-sided pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer containing 40 to 60% by mass of the tackifier on both surfaces of the core material, and the total thickness of the core material and the pressure-sensitive adhesive layers on both surfaces is 30 μm. A double-sided pressure-sensitive adhesive tape having a thickness of 2 to 10 μm is known (see, for example, Patent Document 1).

  However, when further thinning of the pressure-sensitive adhesive tape is required, when the thin pressure-sensitive adhesive tape and the adherend are bonded, air bubbles are likely to remain at the interface between them, and as a result, the pressure-sensitive adhesive tape swells. In some cases, the appearance may be deteriorated due to the above.

  Further, since the remaining bubbles become thermal resistance, when the thin adhesive tape is used for bonding the heat radiating member and the heat generating member, the heat radiating property may be lowered.

  In addition, thinning of the pressure-sensitive adhesive layer has been studied in order to realize the above-mentioned thinning, and the pressure-sensitive adhesive layer that is thin and simply provided with the bubble escape path maintains a practically sufficient adhesive force. There was a case that could not be done.

JP 2007-169327 A

  The problem to be solved by the present invention is to provide a pressure-sensitive adhesive tape that is capable of preventing bubbles from being rapidly removed from the interface with the adherend, preventing bubbles from remaining at the interface, and having excellent adhesion. .

  The present inventors are adhesive tapes having two or more adhesive parts (B) on at least one surface (a) side of the support (A), and between the two or more adhesive parts (B). The problem is solved by an adhesive tape characterized in that there is a region having no adhesive part (B), and the region communicates with an end of the adhesive tape.

  The pressure-sensitive adhesive tape of the present invention is very thin, bubbles are quickly removed from the interface with the adherend, bubbles are not easily left at the interface, and the adhesive strength is excellent. It can be suitably used for adhesion between a casing constituting a device, a heat radiating member such as a graphite sheet, and a heat generating member such as a rechargeable battery.

It is the top view which looked at the adhesive tape which has a substantially rhombus-shaped adhesion part from the adhesion part side. It is the top view which looked at the adhesive tape which has a substantially circular adhesion part from the adhesion part side. It is the top view which looked at the adhesive tape which has a substantially hexagonal adhesion part from the adhesion part side. It is the top view which looked at the adhesive tape which has a substantially square-shaped adhesion part from the adhesion part side. It is a side view of a graphite composite sheet. It is a top view of the surface which has the adhesion part of the adhesive tape obtained in Example 20. FIG. It is a top view of the surface which has the adhesion part of the adhesive tape obtained in the comparative example 2.

  The pressure-sensitive adhesive tape of the present invention is a pressure-sensitive adhesive tape having two or more pressure-sensitive adhesive parts (B) on at least one surface (a) side of the support (A), and is between the two or more pressure-sensitive adhesive parts (B). There is a region that does not have the adhesive part (B), and the region communicates with an end of the adhesive tape.

  As a specific embodiment of the pressure-sensitive adhesive tape of the present invention, the pressure-sensitive adhesive tape having two or more pressure-sensitive adhesive portions (B) directly on at least one surface (a) side of the support (A), or the support The adhesive tape which has the said adhesion part (B) through the other layer on the at least one surface (a) side of a body (A) is mentioned.

  When using a double-sided pressure-sensitive adhesive tape as the pressure-sensitive adhesive tape, the support (A) has two or more specific pressure-sensitive adhesive parts (B) on both sides (a), and the two or more pressure-sensitive adhesive parts (B). There is a region that does not have an adhesive part (B), and the double-sided adhesive tape has a configuration in which the region communicates with an end of the adhesive tape, or one side of the support (A) (a ) Side has two or more of the specific adhesive part (B), and there is an area not having the adhesive part (B) between the two or more adhesive parts (B). A double-sided pressure-sensitive adhesive tape having a configuration leading to the end and having an adhesive layer on the entire surface of the other surface of the support (A) can be used.

  Between the two or more pressure-sensitive adhesive parts (B), there is a region where the component constituting the pressure-sensitive adhesive part (B) does not exist or may exist to the extent that it does not exhibit adhesiveness. Therefore, when the adhesive tape of the present invention is observed from the side surface direction, it is observed that the adhesive part (B) forms a convex shape with respect to the surface (a) of the support (A). .

  Moreover, the adhesive tape of this invention has the structure which the area | region which does not have the adhesive part (B) between the said 2 or more adhesive parts (B) led to a part of edge part (outer edge part) of an adhesive tape. . By using the pressure-sensitive adhesive tape having the above-described structure, when the pressure-sensitive adhesive tape is attached to the adherend, air bubbles escape to the outside from the interface between the pressure-sensitive adhesive tape and the adherend through the region. It is possible to prevent poor appearance due to the above, and to maintain excellent thermal conductivity, adhesive strength and the like.

  As the pressure-sensitive adhesive tape of the present invention, it is preferable to use one having a total thickness of 50 μm or less, particularly preferably 20 μm or less, more preferably 2 μm to 15 μm, It is more preferable to use a material having a thickness of 3 μm to 10 μm, and it is particularly preferable to use a material having a thickness of 3 μm to 6 μm, for example, in order to contribute to a reduction in thickness of a portable electronic terminal or the like. Even if the pressure-sensitive adhesive tape of the present invention is very thin as described above, it retains excellent ease of air bubble removal and has excellent adhesive strength and thermal conductivity. The total thickness of the adhesive tape was measured in accordance with JIS K6783 under the condition that the dial gauge contact surface was flat, the diameter was 5 mm, and the load was 1.23 N. Refers to the thickness of the tape and does not include the thickness of the release liner. The thickness can be measured with, for example, a thickness meter TH-102 manufactured by Tester Sangyo.

  As the pressure-sensitive adhesive tape of the present invention, a tape having an adhesive strength of 1 N / 20 mm to 12 N / 20 mm is preferably used, and a tape having an adhesive strength of 1.5 N / 20 mm to 10 N / 20 mm is more preferably used. Even if it is thin, it is easy to remove bubbles from the interface between the adherend and the pressure-sensitive adhesive tape, and it has excellent adhesive strength even if it is thin and uses a material having an adhesive strength of 3N / 20mm to 8N / 20mm. It is preferable for obtaining a pressure-sensitive adhesive tape. On the other hand, when more excellent adhesiveness is required, it is more preferable to use a pressure-sensitive adhesive tape having an adhesive strength of 4 N / 20 mm to 10 N / 20 mm, and 4.5 N / 20 mm to 8 N / It is more preferable to use one having an adhesive strength of 20 mm.

  In addition, the said adhesive force refers to the value measured according to JISZ0237. Specifically, the adhesive force is obtained by overlapping a surface having an adhesive part (B) of an adhesive tape lined with a polyethylene terephthalate film having a thickness of 25 μm and a clean and smooth stainless steel plate (BA plate) on its upper surface. Is pressed by reciprocating once using a 2 kg roller, and left for 1 hour or 24 hours under the conditions of 23 ° C. and 50% RH, and then at a speed of 0.3 m / min in the 180 ° direction. It is a value measured by peeling off the adhesive tape. In addition, the said backing was performed with respect to the surface which does not have the said adhesion part (B), and was not performed with respect to the surface which has the adhesion part (B) which is a structural requirement of this invention. Moreover, when the said adhesive tape has the said adhesive part (B) on both surfaces, the surface which has any one adhesive part (B) was lined.

  As the pressure-sensitive adhesive tape of the present invention, even if it is thin, it can be prevented from peeling off over time due to the repulsive force of the adherend and the support (A), part falling off, etc., and is used particularly at a relatively high temperature. In order to prevent the above peeling and the like, it is preferable to use one having an adhesive holding power of 2 mm or less, more preferably 0.5 mm or less, and 0.1 mm or less. It is more preferable to use what is.

  The adhesion holding force refers to a value measured according to JISZ0237. Specifically, the adhesion holding force is obtained by overlapping a surface having an adhesive portion (B) of an adhesive tape lined with an aluminum foil having a thickness of 50 μm and a clean and smooth stainless steel plate (hairline), A test piece is a sample that is pressed by reciprocating once using a 2 kg roller and left for 1 hour under conditions of 23 ° C. and 50% RH. Next, after the stainless steel plate constituting the test piece is fixed in a vertical direction in an environment of 100 ° C., and left for 24 hours with a load of 100 g applied to the lower end portion of the adhesive tape constituting the test piece. This is a value obtained by measuring the displacement distance between the stainless steel plate and the adhesive tape with a caliper.

[Support (A)]
The support (A) constituting the pressure-sensitive adhesive tape of the present invention preferably has a thickness of 1 μm to 20 μm, more preferably has a thickness of 1 μm to 10 μm, and more preferably 1 μm to 4 μm. It is preferable to use the one having a thickness of 1.5 μm to 2.5 μm, and the thickness of the adhesive tape can be reduced, and the surface having the adhesive part (B) and the surface to be covered Air bubbles can be easily removed from the interface with the adherend, and as a result, it is possible to more effectively prevent poor appearance due to swelling of the adhesive tape and performance degradation such as thermal conductivity and adhesive strength. More preferred.

  As said support body (A), the sheet-like thing obtained using resin can be used, for example.

  Examples of the resin that can be used for the production of the support (A) include polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyamide (nylon), wholly aromatic polyamide ( Amide resins such as aramid), acrylic resins such as polybutyl acrylate, polyethyl acrylate, and polymethyl methacrylate (PMMA), polystyrene, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer ( ABS resin) and other styrenic resins, polyether ether ketone (PEEK), polyether ketone ketone and other polyether ketones, polyether sulfone (PES), polysulfone, polyvinyl chloride (PVC), polyethylene Phenylene sulfide (PPS), polyimide (PI), polyamideimide, polyetherimide (PEI), polyesterimide, polycarbonate (PC), polyacetal, polyarylene ether (polyphenylene ether, etc.), polyphenylene sulfide, polyarylate, polyaryl, polyurethane, An epoxy resin etc. can be used individually or in combination of 2 or more types.

  Among them, as the support (A), it is preferable to use a polyester film because there is little variation in thickness, excellent tensile strength and workability, and economical (cost), and a polyethylene terephthalate film is used. More preferably it is used. It is preferable to use a biaxially stretched polyester film because the strength of the support (A) and the pressure-sensitive adhesive tape obtained using the support can be further increased.

  The said support body (A) can be manufactured by shape | molding above described resin in a sheet form. When using polyester as said resin, the said support body (A) can be manufactured with the following method, for example.

  First, a dry or undried polyester chip and, if necessary, a colorant or a masterbatch containing a colorant at a high concentration are melt-kneaded using a kneading extruder or the like.

  Next, the kneaded product is extruded from a die and rapidly cooled and solidified on a rotary cooling drum to obtain an unstretched polyester film that is substantially in an amorphous state.

  As a method for further improving the smoothness of the polyester film, for example, a method of shortening the residence time of the polyester in the extruder, when using a single screw extruder, the water content is preferably 50 ppm or less, more preferably When using a raw material such as polyester dried to be 30 ppm or less, or when using a twin screw extruder, a vent port is provided, preferably 40 hectopascals or less, more preferably 30 hectopascals or less, and even more preferably 20 Examples of the method include a method performed under a reduced pressure environment below hectopascal, and a method employing an electrostatic application adhesion method and a liquid application adhesion method, for example, in order to improve the adhesion between the polyester film and the rotary cooling drum.

  As a method of stretching the polyester film obtained by the above method, for example, the unstretched sheet is preferably stretched 2 to 6 times in the longitudinal direction at 70 ° C. to 145 ° C. and uniaxially stretched in the longitudinal direction. The film is stretched 2 to 6 times in the transverse direction at 90 ° C to 160 ° C, and the heat setting step is performed.

  The polyester film is preferably relaxed by 0.1% to 20% in the machine direction and / or the transverse direction in the maximum temperature zone for heat treatment and / or the cooling zone at the heat treatment outlet. The stretched polyester film obtained by the above method may be relonged and restretched as necessary.

  The support (A) obtained by the above method may be composed of a single layer, or may be composed of multiple layers made of the same or different resins.

  Moreover, as said support body (A), in order to further improve the adhesiveness with the said adhesion part (B) and another adhesion layer, etc., on one side or both surfaces, for example, chromic acid treatment, ozone exposure treatment Those having been subjected to oxidation treatment such as flame exposure treatment, high piezoelectric impact exposure treatment, ionizing radiation treatment, etc., and those having a primer layer formed by using a coating agent or the like can be used.

[Adhesive part (B)]
Next, the adhesive part (B) which comprises the adhesive tape of this invention is demonstrated.

  As described above, the adhesive part (B) is provided on one side or both sides of the support (A) directly or via another layer.

  Between the two or more pressure-sensitive adhesive parts (B), there is a region where the component constituting the pressure-sensitive adhesive part (B) does not exist or may exist to the extent that it does not exhibit adhesiveness.

  Moreover, the area | region which does not have the adhesion part (B) between the said 2 or more adhesion parts (B) has a structure connected to a part of edge part (outer edge part) of an adhesive tape. By using the pressure-sensitive adhesive tape having the above-described configuration, when the pressure-sensitive adhesive tape is applied to the adherend, air bubbles can be easily removed from the interface between them, resulting in poor appearance due to the swelling of the pressure-sensitive adhesive tape. Can be prevented, and excellent thermal conductivity, adhesive strength, and the like can be maintained.

  The shape of the pressure-sensitive adhesive part (B) is substantially square, substantially hexagonal, or substantially circular when the pressure-sensitive adhesive tape of the present invention is observed from one side (a) of the support (A). It is preferable to have a substantially circular shape because air bubbles can be easily removed from the interface with the adherend (air release property) and a good adhesive force can be maintained.

  The substantially circular shape is not particularly limited, but the ratio of the maximum diameter to the minimum diameter [maximum diameter / minimum diameter] of any one adhesive part is preferably 1 to 4. More preferably, it is 1-2, Most preferably, it is 1-1.5. An example of a substantially circular shape is a shape as shown in FIG. The adhesive portions having the above shapes are basically independent of each other, but there may be a portion where two or more adhesive portions are partially connected as shown in FIG.

  Examples of the substantially quadrangular shape include shapes such as a substantially square shape, a substantially rectangular shape, a substantially trapezoidal shape, and a substantially rhombus shape, and it is easy to remove bubbles from the interface with the adherend (air release property). In addition, it is preferable because a good adhesive force can be maintained.

  In addition, the “substantially” such as the substantially square shape and the substantially hexagonal shape is, for example, when a release liner or the like is attached to the surface of the adhesive portion (B), or when the adhesive tape is wound around a roll. By pressing the adhesive part (B), it is shown that the corners of the quadrangular and hexagonal shapes are rounded and the straight part includes a curved part.

  The substantially quadrangular corners preferably have a substantially rhombus shape in which the angle of the corners facing the flow direction of the adhesive tape is less than 90 °, and the range of 45 ° to 70 ° It is more preferable because air bubbles can be easily removed from the interface with the body (air release property) and a good adhesive force can be maintained.

  Moreover, it is preferable that the arbitrary adhesion part (b1) and adhesion part (b2) which comprise the said 2 or more adhesion part (B) are not facing with respect to the flow direction and width direction of an adhesive tape.

  Moreover, the said adhesive tape is cut | judged and used in arbitrary shapes according to a use etc. in many cases. At that time, when the adhesive part (b1) and the adhesive part (b2) are arranged so as not to face each other in the flow direction and the width direction, when the adhesive tape is cut at an arbitrary position, its end part Since the adhesive part (B) is present in a part of the adhesive tape, it is possible to suppress peeling of the adhesive tape.

  The distance between an arbitrary adhesive part (b1) selected from the two or more adhesive parts (B) and another adhesive part (b2) close to (adjacent to) the adhesive part (b1) is: It is preferably 0.5 mm or less, more preferably 0.05 mm to 0.2 mm, further preferably 0.06 mm to 0.15 mm, and 0.08 mm to 0.13 mm. It is particularly preferable because air bubbles can be easily removed from the interface with the adherend (air release property) and can maintain a good adhesive force.

The adhesive portion (B) any adhesive portion selected from (b1) size per piece is preferably an area 0.001 mm ² 100 mm ^2, it is 0.01 mm 2 25 mm ² more ^preferably, more preferably from 0.015mm ² ~16mm 2, it is 0.02 mm ² to 5 mm ² is easily escape bubbles from the interface between the adherend (the air removability), and a good This is particularly preferable because the adhesive strength can be maintained.

  The pressure-sensitive adhesive part (B) is preferably present in the range of 10 to 1,000,000, and 1,000 to 50,000 in the area of the pressure-sensitive adhesive tape of the present invention (square of 5 cm in the flow direction and 5 cm in the width direction). More preferably, the presence of 5,000 to 40,000 is particularly preferable because air bubbles can be easily removed from the interface with the adherend (air release property) and good adhesive force can be maintained.

In addition, as the adhesive tape, bubbles can be easily removed from the interface with the adherend during application (air release property), can maintain a good adhesive force, and the adherend such as a graphite sheet can be made thinner. Even if it is made into a case, from the viewpoint of effectively preventing poor appearance due to the shape of the adhesive part, 120 to a predetermined area of the adhesive tape (1 cm in the flow direction and 1 cm in the width direction) It is preferable to use those having 2000 adhesive parts, more preferably using 280 to 1600 adhesive parts, and more preferably using 520 to 1200 adhesive parts. Further preferred.
In addition, the number of the above-mentioned adhesion parts is any by observing and counting an arbitrary range (1 cm in the flow direction and 1 cm in the width direction) or (a square in the flow direction of 5 cm and 5 cm in the width direction) with an electron microscope. Can be sought.

  It is preferable that the ratio of the area | region which has the said adhesion part (B) to occupy for the area of said one surface (a) is 10%-99%. More preferably, it is 20% to 90%, more preferably 30% to 80%, and most preferably 35% to 80%. It is possible to form a substantially circular pressure-sensitive adhesive portion, which will be described later, to be in the above range, and as a result, it is easy for air bubbles to escape from the interface with the adherend (air release property) and to maintain a good adhesive force. It is particularly preferable because an adhesive tape can be produced efficiently. In addition, the ratio of the said area | region is an area ratio of the said adhesion part (B) in the area of a square tape of the flow direction 5cm and the width direction 5cm.

  The peak temperature of the loss tangent based on the dynamic viscoelastic spectrum measured at a frequency of 1 Hz of the adhesive part (B) is not particularly limited, but is preferably −30 ° C. to 20 ° C., It is more preferable that the temperature is 20 ° C to 10 ° C, and that the temperature is -10 ° C to 5 ° C is easy to remove air bubbles from the interface with the adherend (air release property) and can maintain a good adhesive force. As a result, it is more preferable because it is possible to more effectively prevent poor appearance due to swelling of the pressure-sensitive adhesive tape and the like, and performance degradation such as thermal conductivity, heat resistance, and adhesive strength.

  In the dynamic viscoelasticity measurement, a viscoelasticity tester (manufactured by Rheometrics, trade name: Ares 2KSTD) is used, and a test piece is sandwiched between parallel disks which are measurement units of the tester and stored at a frequency of 1 Hz. An elastic modulus (G ′) and a loss elastic modulus (G ″) are measured. The loss tangent is calculated by an expression represented by tan δ = (G ″) / (G ′). The peak temperature refers to the peak temperature confirmed by the spectrum of tan δ with respect to the measurement temperature region (−50 ° C. to 150 ° C.).

  As the test piece, a pressure-sensitive adhesive layer having a thickness of 0.5 mm to 2.5 mm formed using a pressure-sensitive adhesive used for forming the pressure-sensitive adhesive part (B) can be used.

  Moreover, as the said test piece, the thing whose total thickness of an adhesive layer is 0.5 mm-2.5 mm among what laminated | stacked the adhesive tape of this invention in multiple numbers can be used. When the test piece having the different configuration is used, the value of the tan δ changes, but when the total thickness of the pressure-sensitive adhesive layer (B) in the test piece is the same, the peak temperature is substantially It does not change. Therefore, any test piece may be used in the measurement of the peak temperature.

  As the adhesive part (B), those having a gel fraction of 10% by mass to 60% by mass are preferably used, and those having a gel fraction of 20% by mass to 55% by mass are more preferably used. Preferably, using a material having a gel fraction of 30% by mass to 50% by mass prevents the change over time because the surface shape of the adhesive part (B) is easily maintained even if it is thin. Air bubbles can be easily removed from the interface between the adherend and the adhesive part (B). As a result, poor appearance due to swelling of the adhesive tape, thermal conductivity, heat resistance and adhesive strength. It is more preferable because it is possible to more effectively prevent such performance degradation. In addition, the said gel fraction points out the value measured with the following method.

  In addition, the said gel fraction points out the value measured by the method shown below.

  The release liner (C) having a release treatment surface coated with the pressure-sensitive adhesive so that the thickness after drying becomes 50 μm is dried in an environment of 100 ° C. for 3 minutes, and then an environment of 40 ° C. A pressure-sensitive adhesive layer was formed by aging under for 2 days.

  A test piece was prepared by cutting the pressure-sensitive adhesive layer into a square of 50 mm length and 50 mm width.

  After measuring the mass (G1) of the test piece, the test piece was immersed in toluene for 24 hours in an environment of 23 ° C.

  After the immersion, the mixture of the test piece and toluene was filtered using a 300 mesh wire net to extract insoluble components in toluene. The mass (G2) of the insoluble component dried at 110 ° C. for 1 hour was measured.

  The gel fraction was calculated based on the mass (G1), the mass (G2), and the following formula.

    Gel fraction (mass%) = (G2 / G1) × 100

  As the adhesive part (B), one having a thickness of 1 μm to 6 μm is preferably used, and one having a thickness of 2 μm to 5 μm can be used from the interface between the adherend and the adhesive part (B). Can be easily removed, and as a result, poor appearance due to swelling of the pressure-sensitive adhesive tape and performance degradation such as thermal conductivity, heat resistance and adhesive strength can be more effectively prevented. The thickness of the adhesive part (B) is measured by a method using a dial gauge in accordance with JIS K6783 under the condition that the contact surface of the dial gauge is flat, the diameter thereof is 5 mm, and the load is 1.23N. Refers to the thickness of double-sided adhesive tape.

  The adhesive part (B) is, for example, an acrylic adhesive, a rubber adhesive, a silicone adhesive, a urethane adhesive, a polyester adhesive, a styrene-diene block copolymer adhesive, a vinyl alkyl ether adhesive. It can be formed using a known pressure-sensitive adhesive such as a polyamide-based pressure-sensitive adhesive, a fluorine-based pressure-sensitive adhesive, a creep property-improving pressure-sensitive adhesive, or a radiation curable pressure-sensitive adhesive. Especially, as said adhesive part (B), since it is excellent in adhesive reliability, it is preferable to use the adhesive part obtained using an acrylic adhesive.

  When using the pressure-sensitive adhesive tape of the present invention having a pressure-sensitive adhesive portion or a pressure-sensitive adhesive layer on both sides of the support, the pressure-sensitive adhesive portion or pressure-sensitive adhesive layer has the same composition or gel fraction, but has a different composition or gel content. You may use the adhesion part or adhesion layer which is rate.

  As said acrylic adhesive, what contains an acrylic polymer can be used.

  As said acrylic polymer, what is obtained by polymerizing the monomer component containing (meth) acryl monomers, such as a (meth) acrylic-acid alkylester, can be used.

  Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth ) Isobutyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylic acid Undecyl, dodecyl (meth) acrylate, tridecyl (meth) acrylate, Tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate alone Or two or more types can be combined. Especially, as a (meth) acrylic-acid alkylester, it is preferable to use the (meth) acrylic-acid alkylester whose carbon atom number of the said alkyl group is 1-20, and the carbon atom number of the said alkyl group is 4-18. It is more preferable to use (meth) acrylic acid alkyl ester. Examples of the alkyl group include linear or branched alkyl groups.

  As the (meth) acrylic acid alkyl ester having 4 to 18 carbon atoms for the acrylic group, it is easy to maintain the surface shape of the pressure-sensitive adhesive layer (B) by using butyl (meth) acrylate, It is preferable for obtaining a pressure-sensitive adhesive tape that can easily prevent a change with time, can easily remove bubbles from the interface with the adherend (air release property), and can maintain a good adhesive force.

  As the (meth) acrylic monomer, in addition to those described above, a monomer having a carboxyl group such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, or the anhydride thereof A monomer having a sulfonic acid group such as sodium vinyl sulfonate; a monomer having a cyano group such as acrylonitrile; an amide group such as acrylamide, methacrylamide, N-vinylpyrrolidone, N, N-dimethyl (meth) acrylamide; A monomer having a hydroxyl group such as hydroxyalkyl (meth) acrylate and glycerin dimethacrylate; a monomer having an amino group such as aminoethyl (meth) acrylate and (meth) acryloylmorpholine; Imido groups such as cyclohexylmaleimide and isopropylmaleimide Monomers having an epoxy group such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; Monomers having an isocyanate group such as 2-methacryloyloxyethyl isocyanate, triethylene glycol di ( (Meth) acrylate, diethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tri Use monomers such as methylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinylbenzene, etc. alone or in combination of two or more. It can be.

  In addition to the (meth) acrylic monomer, the monomer includes aromatic vinyl compounds such as styrene and substituted styrene; olefins such as ethylene, propylene, and butadiene; vinyl esters such as vinyl acetate; Vinyl chloride or the like can also be used.

  The acrylic polymer can be produced by polymerizing the monomer by a method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, or an emulsion polymerization method, and a solution polymerization method may be employed. It is preferable for improving the production efficiency of the acrylic polymer.

  Examples of the solution polymerization method include a method of radical polymerization by mixing and stirring the monomer, a polymerization initiator, and an organic solvent, preferably at a temperature of 40 ° C. to 90 ° C.

  Examples of the polymerization initiator include peroxides such as benzoyl peroxide and lauryl peroxide, azo thermal polymerization initiators such as azobisisobutylnitrile, acetophenone photopolymerization initiators, benzoin ether photopolymerization initiators, benzyl A ketal photopolymerization initiator, an acyl phosphine oxide photopolymerization initiator, a benzoin photopolymerization initiator, a benzophenone photopolymerization initiator, or the like can be used.

  The acrylic polymer obtained by the above method may be in a state dissolved or dispersed in an organic solvent, for example, when it is produced by a solution polymerization method.

  As the acrylic polymer obtained by the above method, those having a weight average molecular weight of 300,000 to 1,200,000 are preferably used, and those having a weight average molecular weight of 400,000 to 1,100,000 are more preferably used. It is preferable to use a material having a weight average molecular weight of 500,000 to 1,000,000 in order to obtain a pressure-sensitive adhesive tape having even better adhesive strength and ease of air bubble removal even if it is thin.

  The weight average molecular weight is a value measured by gel permeation chromatography (GPC method) and calculated in terms of standard polystyrene. Specifically, the weight average molecular weight can be measured under the following conditions using a GPC apparatus (HLC-8329GPC) manufactured by Tosoh Corporation.

Sample concentration: 0.5% by mass (tetrahydrofuran solution)
Sample injection volume: 100 μl
Eluent: Tetrahydrofuran Flow rate: 1.0 ml / min Measuring temperature: 40 ° C
This column: TSKgel GMHHR-H (20) 2 Guard column: TSKgel HXL-H
Detector: Differential refractometer Weight average molecular weight of standard polystyrene: 10,000 to 20 million (manufactured by Tosoh Corporation)

  As the pressure-sensitive adhesive that can be used for forming the pressure-sensitive adhesive part (B), a pressure-sensitive adhesive containing a tackifying resin is used to form a pressure-sensitive adhesive part having even better adhesive strength, tensile strength, and tensile breaking strength. It is preferable.

  Examples of the tackifying resin include a rosin tackifying resin, a polymerized rosin tackifying resin, a polymerized rosin ester tackifying resin, a rosin phenol tackifying resin, a stabilized rosin ester tackifying resin, and a disproportionated rosin ester. It is possible to use petroleum resin-based tackifiers such as styrene-based tackifier resins, hydrogenated rosin ester-based tackifier resins, terpene-based tackifier resins, terpene phenol-based tackifier resins, and styrene-based tackifier resins.

  As the tackifying resin, a combination of a rosin-based tackifying resin and a petroleum resin-based tackifying resin is used, and the pressure-sensitive adhesive tape has an even better adhesive force and ease of removing bubbles. Is preferable in obtaining. The rosin-based tackifying resin and petroleum resin-based tackifying resin are particularly preferably used in combination with the acrylic polymer, and an acrylic polymer obtained by polymerizing a monomer containing butyl (meth) acrylate; Use in combination is preferable in order to obtain a pressure-sensitive adhesive tape having even better adhesive strength and ease of air bubble removal even if it is thin.

  In addition, as the tackifier resin, it is preferable to use a tackifier resin that is liquid at room temperature in order to further improve the initial adhesive force of the pressure-sensitive adhesive portion (B). Examples of the tackifying resin that is liquid at room temperature include low-molecular-weight liquid rubbers such as process oil, polyester plasticizer, and polybutene, and terpene phenol resins can be used. Commercially available YP manufactured by Yashara Chemical Co., Ltd. -90L etc. are mentioned.

  The tackifying resin is preferably used in the range of 20 to 60 parts by mass, more preferably in the range of 30 to 55 parts by mass, with respect to 100 parts by mass of the acrylic polymer. It is more preferable for obtaining a pressure-sensitive adhesive tape having a high adhesive strength.

  Moreover, as an adhesive which comprises the said adhesion part (B), what contains a softener, a plasticizer, a filler, anti-aging agent, a coloring agent etc. as needed other than the said acrylic polymer Can be used.

  Among them, the use of a crosslinking agent can adjust the gel fraction of the adhesive part (B) to a suitable range, and as a result, the shape of the adhesive part (B) is easily maintained. This is preferable because it is easy to prevent a change, air bubbles can be easily removed from the interface between the adherend and the pressure-sensitive adhesive layer (B), and a pressure-sensitive adhesive tape with excellent adhesive strength can be obtained. .

  As the crosslinking agent, for example, an isocyanate crosslinking agent or an epoxy crosslinking agent is preferably used.

  Examples of the isocyanate crosslinking agent include tolylene diisocyanate, naphthylene-1,5-diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, trimethylolpropane-modified tolylene diisocyanate, and the like. It is preferable to use a toluene diisocyanate adduct such as trimethylolpropane-modified tolylene diisocyanate. The toluene diisocyanate adduct has a structure derived from toluene diisocyanate in the molecule, and examples of commercially available products include Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd.).

  When the isocyanate crosslinking agent is used, it is preferable to use an acrylic polymer having a hydroxyl group as the acrylic polymer. The acrylic polymer having a hydroxyl group is, for example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, etc. It is more preferable to use 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

  Moreover, as an epoxy crosslinking agent, for example, Tetrad X and Tetrad C manufactured by Mitsubishi Gas Chemical Co., Ltd., or E-05X manufactured by Soken Chemical Co., Ltd. can be used.

  When the epoxy crosslinking agent is used, it is preferable to use an acrylic polymer having an acid group as the acrylic polymer. The acrylic polymer having an acid group preferably uses, for example, (meth) acrylic acid, acrylic acid dimer, itaconic acid, crotonic acid, maleic acid, maleic anhydride, etc. It is more preferable to use (meth) acrylic acid.

  As the pressure-sensitive adhesive that can be used for forming the pressure-sensitive adhesive part (B), it is preferable to use a pressure-sensitive adhesive containing a solvent as necessary. As the pressure-sensitive adhesive, it is preferable to use one whose viscosity is adjusted to a range of 0.1 mPa · s to 1000 mPa · s, and one whose viscosity is adjusted to a range of 1 mPa · s to 200 mPa · s is used. It is more preferable to use a material adjusted to a range of 10 mPa · s to 100 mPa · s because it is easy to form the adhesive portion (B) having a predetermined shape.

[Production method of adhesive tape]
The pressure-sensitive adhesive tape of the present invention is produced, for example, by applying the pressure-sensitive adhesive intermittently on at least one surface (a) side of the support (A) and drying it to form a pressure-sensitive adhesive part (B). Can do.

  Moreover, the said adhesive tape can also be manufactured by apply | coating the said adhesive to the both surfaces side of the said support body (A) intermittently, respectively, and making it dry.

  The pressure-sensitive adhesive is preferably applied intermittently to at least one surface (a) of the support (A) by a coating method such as a gravure coating method or a slot die coating method. It is preferable to apply by a coating method.

  In addition, the pressure-sensitive adhesive tape may be formed by, for example, applying the pressure-sensitive adhesive on the surface of a release liner and drying the pressure-sensitive adhesive portion (B), and then forming the pressure-sensitive adhesive portion (B) on at least one of the supports (A). It can manufacture by transferring to the surface (a) side.

  The pressure-sensitive adhesive tape of the present invention may be produced, for example, using a release liner as described above, and then, if necessary, the release liner is peeled off and another release liner is affixed.

  Since the pressure-sensitive adhesive tape of the present invention has an excellent adhesive force even if it is very thin, it can be suitably used, for example, in the production scene of electronic devices such as portable electronic terminals that are required to be thin. In particular, even if the clearance between adherends (adhesive site of the adhesive tape) is in a very narrow range with a width of 20 μm or less, the adherends can be firmly bonded.

  Moreover, since the said adhesive tape is easy to remove | eliminate a bubble from the interface of a to-be-adhered body and an adhesion part (B), the fixation use of the thermal radiation sheet | seat which is concerned about the fall of the performance resulting from the said bubble remaining, fixation of a magnetic sheet It can be suitably used for applications and the like.

(Use for fixing heat dissipation sheet)
Many electronic devices such as portable electronic terminals are equipped with a member that generates heat when used. Examples of the heat generating member include a rechargeable battery and a circuit board.

  It is preferable to avoid a part of the electronic device from being locally heated due to the heat generated by the member in order to prevent malfunction of the electronic device. Therefore, the heat-generating member or a member adjacent to the heat-generating member (for example, a metal member that is a frame material used for imparting rigidity to the electronic device) is radiated by a heat-dissipating sheet or the like for the purpose of diffusing the heat. Members are often affixed.

  As the heat radiating member, for example, a graphite sheet or a graphene sheet is preferably used.

  Examples of the graphite sheet include two types: an artificial graphite sheet and a natural graphite sheet.

  Examples of the artificial graphite sheet include a pyrolytic graphite sheet obtained by pyrolyzing an organic film such as a polyimide film in a high-temperature inert gas atmosphere.

  Examples of the natural graphite sheet include those obtained by acid-treating natural graphite and then pressurizing and expanding the graphite powder heated and expanded.

  As the graphite sheet, it is preferable to use a sheet having less wrinkles from the standpoint of further improving heat dissipation, and it is more preferable to use an artificial graphite sheet having less wrinkles.

  The thickness of the graphite sheet is preferably 10 μm to 100 μm, and more preferably 15 μm to 50 μm, in order to contribute to thinning of electronic devices such as portable electronic terminals.

  On the other hand, since the graphite sheet is relatively brittle, it is generally used in the form of a graphite composite sheet having an adhesive tape attached to one or both sides thereof.

  As the graphite composite sheet, for example, as shown in FIG. 5, it is possible to use a graphite composite sheet having a configuration sealed with a single-sided adhesive tape and a double-sided adhesive tape, to increase the strength and insulation of the graphite sheet. It is preferable to achieve both.

  As the graphite composite sheet, use of what is sealed (pouched) with an adhesive tape having a larger area than the graphite sheet can prevent the graphite sheet from causing interlaminar breakage, powder falling, etc. This is preferable because it is easy to realize suitable workability.

  The pressure-sensitive adhesive tape of the present invention can be suitably used when pouching the graphite sheet. In that case, it is preferable to use the said adhesive tape in the state which the surface which has the adhesion part (B) faces the outer side (direction which is not a graphite sheet side). Thereby, when bonding a graphite composite sheet and heat generating members, such as a rechargeable battery, or a member adjacent to it, it can prevent effectively that air bubbles remain in those interfaces.

  The bonding of the graphite composite sheet and the member is performed, for example, by placing the graphite composite sheet on the surface of the member and temporarily bonding them by lightly pressing them, after the temporary bonding, using a roller or the like. It can be carried out through a step of pressing and firmly bonding them. In the temporary adhering step, bubbles are usually present at the interface between the member and the graphite composite sheet. However, if it is a graphite composite sheet using the adhesive tape of this invention, when it pressurizes with the said roller etc., the said bubble will be removed from the said interface rapidly.

  In addition, a surface protective film is often attached to the graphite composite sheet for the purpose of preventing scratches on the surface thereof. The surface protective film is usually removed after attaching the graphite composite sheet and the member.

  If the pressure-sensitive adhesive tape of the present invention is used, it is possible to firmly adhere to an adherend such as a member after the bubbles are removed. Therefore, when removing the surface protective film from the graphite composite sheet, the member of the graphite composite sheet Difficult to cause floating or peeling off.

  As described above, the graphite composite sheet obtained using the pressure-sensitive adhesive tape of the present invention can prevent air bubbles from existing at the interface with the adherend such as a member. Therefore, the thermal resistance of the pressure-sensitive adhesive tape due to the presence of the air bubbles The increase in value can be effectively prevented, and as a result, the thermal conductivity in the thickness direction of the adhesive tape can be improved.

(Use for fixing magnetic sheets)
The magnetic sheet is used to block the leakage of electromagnetic waves emitted from the members constituting the electronic device to the outside, and to prevent the electromagnetic waves generated outside from affecting the electronic device. It is often affixed to.

  Examples of the magnetic sheet include Ni-based ferrite magnetic powder, Mg-based ferrite magnetic powder, Mn-based ferrite magnetic powder, Ba-based ferrite magnetic powder, Sr-based ferrite magnetic powder, Fe-Si alloy powder, Fe- Sheets obtained using Ni alloy powder, Fe-Co alloy powder, Fe-Si-Al alloy powder, Fe-Si-Cr alloy powder, iron powder, Fe-based amorphous, Co-based amorphous, Fe-based nanocrystals, etc. Can be used.

  In general, it is preferable to use a relatively thick sheet as the magnetic sheet in order to impart good electromagnetic wave shielding characteristics.

  Since the pressure-sensitive adhesive tape of the present invention is very thin as described above, a magnetic sheet having a maximum thickness can be used as the magnetic sheet.

  The magnetic sheet is preferably used in the form of a magnetic composite sheet in which an adhesive tape is attached to one or both sides for the purpose of imparting good insulation and high strength.

  Examples of the present invention will be described below in more detail.

(Preparation Example 1) Adhesive a
N-butyl acrylate 97.98 parts by mass, acrylic acid 2 parts by mass, 4-hydroxybutyl acrylate 0.02 parts by mass, azobisisobutyronitrile 0.2 part by mass as a polymerization initiator, ethyl acetate An acrylic polymer having a weight average molecular weight of 900,000 was obtained by solution polymerization in solution at 80 ° C. for 8 hours.

  5 parts by mass of “D-135” (manufactured by Arakawa Chemical Industries, Ltd., polymerized rosin ester) and “KE-100” (manufactured by Arakawa Chemical Industries, Ltd., disproportionated rosin with respect to 100 parts by mass of the acrylic polymer. Ester) 20 parts by mass and “FTR6100” (manufactured by Mitsui Chemicals, petroleum resin) 25 parts by mass were mixed, and further an ethyl acetate was added to obtain a pressure-sensitive adhesive solution adjusted to a solid content of 40% by mass. .

  By mixing and stirring the pressure-sensitive adhesive solution and 2.0 parts by mass of “NC40” (manufactured by DIC Corporation, isocyanate crosslinking agent), pressure-sensitive adhesive a was obtained.

  The peak temperature of tan δ of the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive a was 0 ° C., and the gel fraction thereof was 40% by mass.

(Preparation Example 2) Adhesive b
Ethyl acetate using 97.98 parts by mass of n-butyl acrylate, 2 parts by mass of acrylic acid, 0.02 parts by mass of 4-hydroxybutyl acrylate, 0.3 parts by mass of azobisisobutyronitrile as a polymerization initiator An acrylic polymer having a weight average molecular weight of 500,000 was obtained by solution polymerization in solution at 90 ° C. for 6 hours.

  With respect to 100 parts by mass of the acrylic polymer, 5 parts by mass of “D-135” (Arakawa Chemical Industries, Ltd., polymerized rosin ester) and “KE-100” (Arakawa Chemical Industries, Ltd., disproportionated rosin ester) ) 20 parts by mass and 25 parts by mass of “FTR6100” (manufactured by Mitsui Chemicals, petroleum resin) were mixed, and further an ethyl acetate was added to obtain an adhesive solution adjusted to a solid content of 40% by mass.

  The pressure-sensitive adhesive solution and “NC40” (manufactured by DIC Corporation, isocyanate cross-linking agent) 0.6 parts by mass were mixed and stirred to obtain pressure-sensitive adhesive b.

  The peak temperature of tan δ of the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive b was 0 ° C., and the gel fraction thereof was 10% by mass.

(Preparation Example 3) Adhesive c
Ethyl acetate using 97.98 parts by mass of n-butyl acrylate, 2 parts by mass of acrylic acid, 0.02 parts by mass of 4-hydroxybutyl acrylate, 0.3 parts by mass of azobisisobutyronitrile as a polymerization initiator An acrylic polymer having a weight average molecular weight of 500,000 was obtained by solution polymerization in solution at 90 ° C. for 6 hours.

  5 parts by mass of “D-135” (Arakawa Chemical Industries, Ltd., polymerized rosin ester) and “KE-100” (Arakawa Chemical Industries, Ltd., disproportionated rosin ester) with respect to 100 parts by mass of the acrylic polymer. ) 20 parts by mass and 25 parts by mass of “FTR6100” (manufactured by Mitsui Chemicals, petroleum resin) were mixed, and further an ethyl acetate was added to obtain an adhesive solution adjusted to a solid content of 40% by mass.

  The pressure-sensitive adhesive c was obtained by mixing and stirring the pressure-sensitive adhesive solution and 3.3 parts by mass of “NC40” (manufactured by DIC Corporation, isocyanate crosslinking agent).

  The peak temperature of tan δ of the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive c was 0 ° C., and the gel fraction thereof was 46% by mass.

(Preparation Example 4) Adhesive d
Ethyl acetate using 97.98 parts by mass of n-butyl acrylate, 2 parts by mass of acrylic acid, 0.02 parts by mass of 4-hydroxybutyl acrylate, 0.3 parts by mass of azobisisobutyronitrile as a polymerization initiator An acrylic polymer having a weight average molecular weight of 500,000 was obtained by solution polymerization in solution at 90 ° C. for 6 hours.

  5 parts by mass of “D-135” (Arakawa Chemical Industries, Ltd., polymerized rosin ester) and “KE-100” (Arakawa Chemical Industries, Ltd., disproportionated rosin ester) with respect to 100 parts by mass of the acrylic polymer. ) 20 parts by mass and 25 parts by mass of “FTR6100” (manufactured by Mitsui Chemicals, petroleum resin) were mixed, and further an ethyl acetate was added to obtain an adhesive solution adjusted to a solid content of 40% by mass.

  The pressure-sensitive adhesive d was obtained by mixing and stirring the pressure-sensitive adhesive solution and 1.2 parts by mass of “NC40” (manufactured by DIC Corporation, isocyanate-based crosslinking agent).

  The peak temperature of tan δ of the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive d was 0 ° C., and the gel fraction thereof was 20% by mass.

(Preparation Example 5) Adhesive e
96.4 parts by mass of n-butyl acrylate, 3.5 parts by mass of acrylic acid, 0.1 part by mass of 4-hydroxy-ethyl acrylate, 0.2 part by mass of azobisisobutyronitrile as a polymerization initiator Then, an acrylic polymer having a weight average molecular weight of 800,000 was obtained by solution polymerization in an ethyl acetate solution at 80 ° C. for 8 hours.

  10 parts by weight of “D-135” (Arakawa Chemical Industries, Ltd., polymerized rosin ester) and “A100” (disproportionated rosin ester, Arakawa Chemical Industries, Ltd.) 10 with respect to 100 parts by mass of the acrylic polymer. A pressure-sensitive adhesive solution adjusted to a solid content of 40% by mass was obtained by mixing with parts by mass and further adding ethyl acetate.

  The pressure-sensitive adhesive e was obtained by mixing and stirring the pressure-sensitive adhesive solution and 1.3 parts by mass of “NC40” (manufactured by DIC Corporation, isocyanate crosslinking agent).

  The peak temperature of tan δ of the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive e was −15 ° C., and the gel fraction thereof was 40% by mass.

(Preparation Example 6) Adhesive f
44.9 parts by mass of n-butyl acrylate, 50 parts by mass of 2-ethylhexyl acrylate, 3 parts by mass of vinyl acetate, 2 parts by mass of acrylic acid, and 0.1 part by mass of 4-hydroxybutyl acrylate were mixed with azobisiso An acrylic polymer having a weight average molecular weight of 800,000 was obtained by performing solution polymerization at 70 ° C. for 10 hours in an ethyl acetate solution using 0.1 part by mass of butyronitrile as a polymerization initiator.

  100 parts by mass of the acrylic polymer was mixed with 10 parts by mass of “D-135” (manufactured by Arakawa Chemical Industries, Ltd., polymerized rosin ester), and further adjusted to a solid content of 40% by mass by adding ethyl acetate. An adhesive solution was obtained.

  Adhesive f was obtained by mixing and stirring the pressure-sensitive adhesive solution and 1.3 parts by mass of “NC40” (manufactured by DIC Corporation, isocyanate cross-linking agent).

  The peak temperature of tan δ of the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive f was −25 ° C., and the gel fraction thereof was 40% by mass.

Example 1
“PET25 × 1J0L” (manufactured by Nipper Co., Ltd., coated with the pressure-sensitive adhesive a using a roll coater on a release liner having a silicone release surface on the surface of a smooth PET film, and then at 100 ° C. for 1 minute. By drying, an adhesive layer having a thickness of 1 μm was produced.

  Next, a single-sided tape was obtained by transferring the pressure-sensitive adhesive layer onto one surface of “K100-2.0W” (Mitsubishi Resin Co., Ltd., polyester film, thickness 2 μm) as a support.

  Next, the pressure-sensitive adhesive a is dot-printed on the other surface of the support constituting the single-sided tape using a gravure coater and dried at 100 ° C. for 1 minute, thereby forming a substantially rhombus shape shown in FIG. An adhesive tape with a total thickness of 6 μm having an adhesive part with a thickness of 3 μm was obtained. In addition, the distance of the arbitrary adhesion part and the adhesion part adjacent to it was 0.1 mm among the said adhesion parts.

  “PET25 × 1J0L” (manufactured by Nipper Co., Ltd., release liner having a silicone-based release treatment surface on the surface of a smooth PET film) is laminated on the surface of the adhesive tape obtained above with a laminator. Affixed at 3 N / mm.

(Examples 2 to 12)
An adhesive tape was produced in the same manner as in Example 1 except that the shape and area of the adhesive part (B) and the thickness of the adhesive part (B) were changed to those shown in Tables 1 to 3.

(Example 13)
“PET25 × 1J0L” (manufactured by Nipper Co., Ltd., release liner having a silicone-based release treatment surface on the surface of a smooth PET film) is dot-printed with the adhesive a using a gravure coater, and 100 ° C. for 1 minute. By drying, an adhesive part having a thickness of 3 μm and a substantially rhombus shape (the angle of the corner part facing the flow direction of the adhesive tape was 60 °) shown in FIG. 1 was formed. In addition, the distance of the arbitrary adhesion part and the adhesion part adjacent to it was 0.1 mm among the said adhesion parts.

  Next, the single-sided tape was obtained by transcribe | transferring the said adhesion part to one side of "K100-2.0W" (Mitsubishi resin Co., Ltd. make, polyester film, thickness 2 micrometers) which is a support body.

  Next, the pressure-sensitive adhesive a is dot-printed on the other surface of the support constituting the single-sided tape using a gravure coater and dried at 100 ° C. for 1 minute, thereby forming a substantially rhombus shape ( A pressure-sensitive adhesive portion having a thickness of 3 μm was formed, with the angle of the corner facing the flow direction of the pressure-sensitive adhesive tape being 60 °. In addition, the distance of the arbitrary adhesion part and the adhesion part adjacent to it was 0.1 mm among the said adhesion parts.

  By the above method, a pressure-sensitive adhesive tape having a total thickness of 8 μm having a substantially rhombus-shaped pressure-sensitive adhesive portion having a thickness of 3 μm shown in FIG. 1 was obtained on both surfaces of the support.

(Example 14)
An adhesive tape was obtained in the same manner as in Example 1 except that the adhesive b was used instead of the adhesive a.

(Example 15)
An adhesive tape was obtained in the same manner as in Example 1 except that the adhesive c was used instead of the adhesive a.

(Example 16)
An adhesive tape was obtained in the same manner as in Example 1 except that the adhesive d was used instead of the adhesive a.

(Example 17)
An adhesive tape was obtained in the same manner as in Example 1 except that adhesive e was used instead of adhesive a.

(Example 18)
An adhesive tape was obtained in the same manner as in Example 1 except that the adhesive f was used in place of the adhesive a.

(Examples 19 to 25)
An adhesive tape was prepared in the same manner as in Example 1 except that the shape and area of the adhesive part (B) and the thickness of the adhesive part (B) were changed to those shown in Tables 4 and 5. Moreover, the surface which has a substantially circular adhesion part of the adhesive tape obtained in Example 20 was observed at 200-times multiplication factor using the optical microscope (FIG. 6).

(Comparative Example 1)
After applying the pressure-sensitive adhesive a to “PET25 × 1J0L” (manufactured by Nipper Co., Ltd., release liner having a silicone-type release treatment surface on the surface of a smooth PET film) using a roll coater, 1 at 100 ° C. By drying for 1 minute, an adhesive layer having a thickness of 1 μm was produced.

  Next, a single-sided tape was obtained by transferring the pressure-sensitive adhesive layer onto one surface of “K100-2.0W” (Mitsubishi Resin Co., Ltd., polyester film, thickness 2 μm) as a support.

  Next, after applying the pressure-sensitive adhesive a to the other surface of the support constituting the single-sided tape using a roll coater, the pressure-sensitive adhesive layer having a thickness of 3 μm is formed by drying at 100 ° C. for 1 minute. Produced.

  “PET25 × 1J0L” (manufactured by Nipper Co., Ltd., with a release liner having a silicone release treatment surface on the surface of a smooth surface PET film is laminated on the surface of the pressure-sensitive adhesive tape obtained above with a laminator. Affixed at / mm.

(Comparative Example 2)
After applying the pressure-sensitive adhesive a to “PET25 × 1J0L” (manufactured by Nipper Co., Ltd., release liner having a silicone-type release treatment surface on the surface of a smooth PET film) using a roll coater, 1 at 100 ° C. By drying for 2 minutes, a pressure-sensitive adhesive layer having a thickness of 2 μm was produced.
Next, the adhesive layer was transferred to one side of “K100-2.0W” (Mitsubishi Resin Co., Ltd., polyester film, thickness 2 μm) as a support to obtain a single-sided tape.
Further, the pressure-sensitive adhesive a was coated on a single-sided tape support using a roll coater, and then dried at 100 ° C. for 1 minute to prepare a pressure-sensitive adhesive layer having a thickness of 2 μm. The pressure of the laminator used when transferring the pressure-sensitive adhesive layer to the support was set to a linear pressure of 3 N / mm.
Thereafter, the release paper subjected to the grid-like embossing treatment is bonded to the pressure-sensitive adhesive layer and cured at 40 ° C. for 2 days to provide a pressure-sensitive adhesive layer having an uneven shape as shown in FIG. 7 on the surface of the pressure-sensitive adhesive layer. An adhesive tape was obtained. FIG. 7 shows the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape obtained in Comparative Example 2 observed using an optical microscope at a magnification of 100 times.

(Comparative Example 3)
After applying the pressure-sensitive adhesive a to “PET25 × 1J0L” (manufactured by Nipper Co., Ltd., release liner having a silicone-type release treatment surface on the surface of a smooth PET film) using a roll coater, 1 at 100 ° C. By drying for 2 minutes, a pressure-sensitive adhesive layer having a thickness of 2 μm was produced.
Next, a single-sided tape was obtained by transferring the pressure-sensitive adhesive layer onto one surface of “K100-2.0W” (Mitsubishi Resin Co., Ltd., polyester film, thickness 2 μm) as a support.
Next, a roll coater is used for “PSM100GS” (manufactured by Lintec Corporation, a release liner having a silicone-based release treatment surface on the surface of a PET film that has been sand-matted, centerline average surface roughness Ra = 0.36 μm). After coating the pressure-sensitive adhesive a, the pressure-sensitive adhesive layer having a thickness of 2 μm was prepared by drying at 100 ° C. for 1 minute. Next, the pressure-sensitive adhesive layer was transferred to the other surface of the support to obtain a pressure-sensitive adhesive tape having a total thickness of 6 μm. The pressure of the laminator used when transferring the pressure-sensitive adhesive layer to the support was set to a linear pressure of 3 N / mm.

(Measurement method of gel fraction of adhesive part)
Each of the pressure-sensitive adhesives a to f was coated on the release treatment surface of the release liner so that the thickness after drying was 50 μm, and was dried in an environment of 100 ° C. for 3 minutes. Thereafter, an adhesive layer was formed by aging in an environment of 40 ° C. for 2 days. A test piece was prepared by cutting the pressure-sensitive adhesive layer into a square of 50 mm length and 50 mm width.

  After measuring the mass (G1) of the test piece, the test piece was immersed in toluene for 24 hours in an environment of 23 ° C. After the immersion, the mixture of the test piece and toluene was filtered using a 300 mesh wire net to extract insoluble components in toluene. The mass (G2) of the insoluble component dried at 110 ° C. for 1 hour was measured.

  The gel fraction was calculated based on the mass (G1), the mass (G2), and the following formula.

    Gel fraction (mass%) = (G2 / G1) × 100

(Measurement of dynamic viscoelasticity)
Each of the pressure-sensitive adhesives a to f was applied to the surface of the release liner so as to have a dry thickness of 50 μm and dried to form a pressure-sensitive adhesive layer, and was cured in an environment of 40 ° C. for 2 days. A test piece was prepared by laminating the adhesive layer after curing until the total thickness was 2 mm.

  Next, using a viscoelasticity tester (trade name: Ares 2KSTD, manufactured by Rheometrix Co., Ltd.), the test piece was sandwiched between parallel disk-shaped measuring parts having a diameter of 7.9 mm, a frequency of 1 Hz, and a heating time of 1 ° C./1. The storage elastic modulus (G ′) and loss elastic modulus (G ″) from −50 ° C. to 150 ° C. were measured under the condition of min. The loss tangent tan δ was calculated from the following calculation formula.

  Loss tangent tan δ = G ″ / G ′

(Production of graphite composite sheet)
A single-sided adhesive tape “IL-05G” (manufactured by DIC Corporation) having a length of 104 mm × width of 104 mm × thickness of 5 μm is bonded to one surface of a graphite sheet having a length of 100 mm × width of 100 mm × thickness of 25 μm. On the other surface, the adhesive tapes obtained in Examples and Comparative Examples were cut into a size of 104 mm length × 104 mm width, and bonded together.

  At that time, among the pressure-sensitive adhesive layers constituting the pressure-sensitive adhesive tape, the pressure-sensitive adhesive layer having a smooth surface was in contact with the graphite sheet.

  Next, a fine composite single-sided tape “CPF50 (25) -SP” (manufactured by Nipper Co., Ltd.) having a thickness of 62 μm was bonded to the surface of the single-sided adhesive tape “IL-05G” to obtain a graphite composite sheet. .

(Adhesive strength (1 hour after application))
The pressure-sensitive adhesive tapes obtained in Examples and Comparative Examples were cut into a width of 20 mm, and a test piece was prepared by backing one side of the pressure-sensitive adhesive layer with a polyethylene terephthalate film having a thickness of 25 μm. The backing is performed on the surface of the pressure-sensitive adhesive layer having a smooth surface, and is not performed on the pressure-sensitive adhesive layer corresponding to the pressure-sensitive adhesive portion (B) which is a constituent of the present invention.

  The test piece was affixed to the surface of a clean and smooth stainless steel plate and pressurized by reciprocating a 2 kg roller on its upper surface under conditions of 23 ° C. and 50% RH according to JISZ-0237. After leaving for 1 hour, peel adhesion (peeling direction: 180 °, tensile speed: 0.3 m / min) was measured using a Tensilon tensile tester in an atmosphere of 23 ° C. and 50% RH. The measurement results are shown in the column of “Adhesive strength (1 hour after sticking)” in the table.

(Adhesive strength (24 hours after application))
The pressure-sensitive adhesive tapes obtained in Examples and Comparative Examples were cut into a width of 20 mm, and a test piece was prepared by backing one side of the pressure-sensitive adhesive layer with a polyethylene terephthalate film having a thickness of 25 μm. The backing is performed on the surface of the pressure-sensitive adhesive layer having a smooth surface, and is not performed on the pressure-sensitive adhesive layer corresponding to the pressure-sensitive adhesive portion (B) which is a constituent of the present invention.

  The test piece was affixed to the surface of a clean and smooth stainless steel plate and pressurized by reciprocating once using a 2 kg roller on the upper surface, under conditions of 23 ° C. and 50% RH according to JISZ-0237. After being left for 24 hours, peel adhesion (peeling direction: 180 °, tensile speed: 0.3 m / min) was measured using a Tensilon tensile tester in an atmosphere of 23 ° C. and 50% RH. The measurement results are shown in the column of “Adhesive strength (24 hours after application)” in the table.

(Holding power)
The pressure-sensitive adhesive tapes obtained in Examples and Comparative Examples were cut to a width of 20 mm, and a test piece was prepared by backing the pressure-sensitive adhesive layer on one side with an aluminum foil having a thickness of 50 μm. The backing is performed on the surface of the pressure-sensitive adhesive layer having a smooth surface, and is not performed on the pressure-sensitive adhesive layer corresponding to the pressure-sensitive adhesive portion (B) which is a constituent of the present invention.

  The test piece was affixed to the surface of a clean and smooth stainless steel plate so as to have a sticking area of 20 mm × 20 mm, and pressed by reciprocating once using a 2 kg roller on the upper surface thereof to JISZ-0237. Similarly, after being left for 1 hour under conditions of 23 ° C. and 50% RH, a load of 100 g was applied in the shear direction under an atmosphere of 100 ° C., and the deviation distance of the tape after 24 hours was measured. The measurement results are shown in the “holding force” column of the table.

[Evaluation Method for Ease of Bubble Removal 1 (Ease of Removal)]
The release liner of the graphite composite sheet is peeled off, and an aluminum plate measuring 200 mm in length and 200 mm in width is placed on the surface of the adhesive part in an atmosphere of 23 ° C. and 50% RH, and left for 5 seconds under a load of 10 N from the top of the aluminum plate. By doing so, a temporary patch was obtained.

  Next, after reversing the temporary patch, a laminate was obtained by pressing them by reciprocating a 2 kg roller from the surface of the graphite composite sheet side.

  Ten laminates were produced by the above method. Whether or not bubbles exist between the pressure-sensitive adhesive layer of the graphite composite sheet constituting the laminate and the aluminum plate was confirmed by visually observing the swelling of the graphite sheet. The ease of bubble removal was evaluated based on the number of laminates for which the presence of bubbles could not be confirmed by the above method.

[Evaluation Method for Ease of Bubble Removal 2 (Ease of Removal)]
A “PET25X1J0L” (manufactured by Nipper Co., Ltd., release liner with a smooth release treatment surface, Ra = 0.03 μm) is pasted on the surface of the adhesive part that appears by peeling off the release liner of the graphite composite sheet, and a laminator -Was used under the condition of a linear pressure of 3 N / mm and then left in an environment at 23 ° C for 1 day.

  Thereafter, the “PET25X1J0L” was peeled off, and an aluminum plate having a length of 200 mm × width of 200 mm was placed on the surface of the adhesive part that appeared by the peeling under an atmosphere of 23 ° C. and 50% RH, and 10 N was loaded from above the aluminum plate Was left for 5 seconds to obtain a temporary patch.

  Next, after reversing the temporary patch, a laminate was obtained by pressing them by reciprocating a 2 kg roller from the surface of the graphite composite sheet side.

  Ten laminates were produced by the above method. It was confirmed by visually observing the swelling of the graphite sheet whether air bubbles exist between the adhesive part of the graphite composite sheet constituting the laminate and the aluminum plate. The ease of bubble removal was evaluated based on the number of laminates for which the presence of bubbles could not be confirmed by the above method.

(Whether or not the graphite composite sheet floats when the slightly adhesive film is peeled off)
On the surface of the single-sided adhesive tape “IL-05G” (manufactured by DIC Corporation) constituting the graphite composite sheet, a fine-adhesive film (one having a silicone-based fine-adhesive layer on one side of a 75 μm-thick PET film: adhesive strength = The laminated product with 0.05 N / 20 mm) was placed on an aluminum plate and pasted by reciprocating the surface once with a 2 kg roller.

  1 minute after the sticking, whether or not the graphite composite sheet floats off the surface of the aluminum plate after peeling the fine adhesive film at a speed of 5 m / min in the direction of 180 ° with respect to the surface of the graphite composite sheet Was visually evaluated. Ten laminates were produced for each of the graphite composite sheets obtained in the examples and comparative examples, and the above test was performed. The number of laminates for which the graphite composite sheet was not lifted from the surface of the aluminum plate by the above test is shown in the table below.

(Appearance evaluation method)
When the graphite composite sheet is affixed to an aluminum plate and observed from a position 30 cm above the top of the graphite composite sheet under a fluorescent lamp, can the shape of the adhesive part (such as the above approximate rhombus shape, substantially round shape) be visually recognized? Evaluation was based on whether or not. The case where the shape of the adhesive part was not visible at all was evaluated as “◎”, the part of the shape slightly visible as “◯”, and the case where the shape was clearly visible was evaluated as “X”. did. In addition, as shown in Comparative Example 1, in the case where the pressure-sensitive adhesive was applied to the entire surface of the support and the pressure-sensitive adhesive layer was formed, the pressure-sensitive adhesive portion did not form a predetermined shape. Since it was not visually recognizable, it was evaluated as “−”.
[Number of adhesive parts]
The number of adhesive parts was determined by observing and counting an arbitrary range (5 cm in the flow direction and 5 cm width) or (a square in the flow direction 1 cm and 1 cm width) range of the adhesive tape.

  The “substantially rhombus 1” in the table refers to a rhombus-shaped pressure-sensitive adhesive portion in which the angle of the corner portion facing the flow direction of the adhesive tape is 60 ° (the angle of the corner portion facing the width direction is 120 °) ( Fig. 1), "substantially rhombus 2" refers to a rhombus-shaped adhesive portion in which the angle of the corner portion facing the flow direction of the adhesive tape is 30 ° (the angle of the corner portion facing the width direction is 150 °). , “Substantially square shape” refers to a square-shaped adhesive portion having an angle of 90 ° in the flow direction of the adhesive tape (an angle of the corner portion in the width direction is 90 °). “Shape” refers to the adhesive portion having the shape shown in FIG. 2, “substantially hexagonal (hatched)” refers to the adhesive portion having the shape illustrated in FIG. 3, and “substantially square (hatched)” refers to the adhesive portion having the shape illustrated in FIG. Point to.

  Since the adhesive tapes of the examples all have a plurality of independent adhesive layers on one surface, they are excellent in easy removal of bubbles. On the other hand, since the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape of Comparative Example 1 is smooth, there is no bubble passage and the ease of bubble removal is extremely poor. Even in the pressure-sensitive adhesive tapes of Comparative Examples 2 and 3, since the pressure-sensitive adhesive layer has irregularities, it is excellent in the ease of air bubble removal at the beginning. descend.

DESCRIPTION OF SYMBOLS 1 Support body 2 Adhesive part 3 Adhesive tape 4 Graphite sheet 5 Single-sided adhesive tape 6 Double-sided adhesive tape

Claims (12)

An adhesive tape having two or more adhesive parts (B) on at least one surface (a) side of the support (A), wherein the adhesive part (B) is interposed between the two or more adhesive parts (B). There is a region that does not have, and the region communicates with an end of the adhesive tape. The shape of the adhesive part (B) when the adhesive part (B) is observed from the one surface (a) side of the support (A) is a substantially circular shape, a substantially square shape, or a substantially hexagonal shape. Item 2. The pressure-sensitive adhesive tape according to item 1. The distance between an arbitrary adhesive part (b1) selected from the two or more adhesive parts (B) and an adhesive part (b2) adjacent to the adhesive part (b1) is 0.5 mm or less. 2. The adhesive tape according to 2. The ratio of the area | region which has the said adhesion part (B) which occupies for the area of the one surface (a) of the said support body (A) is 10%-99%. Adhesive tape. The pressure-sensitive adhesive tape according to any one of claims 1 to 4, wherein 120 to 2000 of the pressure-sensitive adhesive portions (B) are present in a range of 1 cm in the flow direction and 1 cm in the width direction of the pressure-sensitive adhesive tape. The pressure-sensitive adhesive tape according to any one of claims 1 to 5, wherein the total thickness is 20 µm or less. It is obtained by placing a smooth stainless steel plate on the surface having the adhesive part (B), reciprocating it once using a 2 kg roller, and allowing them to stand for 1 hour at 23 ° C. and 50% RH. The pressure-sensitive adhesive tape according to any one of claims 1 to 6, wherein a 180 ° peel adhesive force measured using the test piece is in a range of 2N / 20mm to 12N / 20mm. The pressure-sensitive adhesive tape according to any one of claims 1 to 7, which is used for bonding a heat generating member and a heat radiating member, or for bonding a metal member in contact with the heat generating member and a heat radiating member. The pressure-sensitive adhesive tape according to claim 8, wherein the heat radiating member is a graphite sheet or a graphene sheet. The heat-radiation sheet by which arbitrary single-sided adhesive tape was affixed on the one surface side of the heat radiating member, and the adhesive tape of any one of Claims 1-8 was affixed on the other surface side of the said heat radiating member. It is an electronic device which has the composition by which the heat dissipation sheet according to claim 10 is stuck to the heat generating member or the metal member in contact with the heat generating member, and the surface having the adhesive portion (B) of the heat dissipation sheet is An electronic device having a structure attached to a heat generating member or the metal member. By applying an adhesive to at least one surface (a) of the support by a gravure coating method or a slot die coating method, two or more adhesive portions having a substantially circular shape, a substantially rectangular shape or a substantially hexagonal shape ( B) A method for producing a pressure-sensitive adhesive tape characterized by forming.

Images