Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/22—Plastics; Metallised plastics
• • 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
  • C09J11/08—Macromolecular additives
• • 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
  • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
• • 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
  • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J153/02—Vinyl aromatic monomers and conjugated dienes
• • 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]
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
• • 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
  • C09J2301/308—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 tape or sheet losing adhesive strength when being stretched, e.g. stretch adhesive
• • 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
  • C09J2301/312—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 parameters being the characterizing feature
• • 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
• • 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
  • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
• • 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
  • C09J2425/00—Presence of styrenic polymer
  • C09J2425/006—Presence of styrenic polymer in the substrate
• • 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
  • C09J2453/00—Presence of block copolymer
• • 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
  • C09J2453/00—Presence of block copolymer
  • C09J2453/006—Presence of block copolymer in the substrate

Definitions

• the present invention relates to an adhesive tape.
• Adhesive tape has excellent workability and high adhesive reliability. Therefore, the adhesive tape is used as a joining means for fixing parts constituting relatively large electronic devices such as flat-screen TVs, home appliances, and OA devices, or relatively small electronic devices such as mobile electronic terminals, cameras, and personal computers. Widely used in the scene. More specifically, in each industrial field such as OA equipment, IT / home appliances, automobiles, etc., fixing of sheet metal to each other or fixing of exterior parts to housing, and to small electronic equipment constituting large electronic equipment. It is used not only for fixing parts such as exterior parts or rigid parts such as batteries, and for temporarily fixing the parts, but also for labels displaying product information.
• Patent Document 1 As a technique related to an adhesive tape that can be easily peeled off and removed, for example, Patent Document 1 can be mentioned.
• the patent document 1 is provided with an adhesive portion and a tab portion, and the tab portion can be sandwiched from an adherend attached to both sides of the adhesive portion, and the tab portion can be stretched and peeled off in a direction substantially parallel to the adhesive surface.
• Adhesive tapes that can be made are disclosed.
• Patent Document 2 discloses an adhesive tape that can be removed again by stretching it in a direction of 30 ° with respect to the adhesive surface.
• Patent Document 1 the adhesive tape is cured in an oven at 40 ° C. for 30 minutes, and then the holding power of the adhesive tape in which a weight of 1 kg is suspended is evaluated, but the removability itself has not been examined.
• Patent Document 2 examines that the adhesive article can be stretched and removed without breaking and leaving no adhesive residue.
• Patent Document 2 does not examine the removability from the state where a part of the adhesive tape is peeled off from the adherend. Generally, when the adhesive tape is stretched from the adherend and re-peeled in the 90 ° direction, the adhesive tape is peeled off while touching the adherend.
• an object of the present invention is to provide an adhesive tape having excellent removability from a state in which a part of the adhesive tape has already been peeled from the adherend.
• the present inventor has a specific relationship between the initial split adhesive force of the adhesive tape and the split adhesive force when the adhesive tape is stretched by a predetermined ratio.
• the above problems can be solved by satisfying the relationship, and have completed the present invention.
• the present invention is an adhesive tape provided with a base material layer and an adhesive layer.
• the breaking stress of the base material layer is 1 to 100 MPa, the breaking elongation is 400 to 3000%, and the breaking elongation is 400 to 3000%.
• the storage elastic modulus G'(23 ° C.) of the adhesive layer is preferably 1.0 ⁇ 10 5 to 1.0 ⁇ 10 7 Pa.
• the adhesive layer contains a filler.
• the adhesive layer contains a styrene-based block copolymer.
• the adhesive layer is (In the above general formula (1), A, B and C each independently represent a repeating unit. A and C each independently represent a methacrylic acid alkyl ester monomer unit. B represents an acrylic acid alkyl ester monomer unit and represents p, q and r independently represent the degree of polymerization of each monomer unit.
• a and C may be the same or may be methacrylic acid alkyl ester monomer units having different chemical structures.
• * is a bond representing a bond with another atom.
• the filler is a silicone resin.
• the pressure-sensitive adhesive layer further contains a pressure-sensitive adhesive resin.
• the present invention can provide an adhesive tape having excellent removability from a state in which a part of the adhesive tape has already been peeled from the adherend.
• the present embodiment embodiments of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail, but the present invention is not limited to the present embodiment.
• the adhesive tape of the present embodiment is an adhesive tape provided with a base material layer and an adhesive layer. Further, the breaking stress of the base material layer is 1 to 100 MPa.
• the adhesive tape of the present embodiment has the following relational expression (i): [Number 2] P 400 / P 0 ⁇ 0.9 (i) (In the above relational expression (i), P 0 represents the initial split adhesive force (N / cm 2 ) of the adhesive tape, and P 400 represents the split adhesive force (N / cm 2) when the adhesive tape is stretched by 400%. 2 ) is satisfied.
• the adhesive tape of the present embodiment can exhibit excellent removability from a state in which a part of the adhesive tape has already been peeled from the adherend.
• the base material layer of the adhesive tape of the present embodiment has a breaking stress of 1 to 100 MPa and a breaking elongation of 400 to 3000%, so that the initial stage when the adhesive tape is peeled off from the adherend ( In the initial stage of stretching the adhesive tape), the operator can pull it with a relatively light force, and through the peeling operation, even if the operator pulls it at a relatively high speed, it adheres to the adherend without tearing.
• the tape can be peeled off (it can be peeled off again).
• the adhesive tape of the present embodiment satisfies the above relational expression (i), it can exhibit excellent removability from a state where a part of the adhesive tape has already been peeled from the adherend.
• the initial split adhesive strength P 0 (N / cm 2 ) of the adhesive tape in the above relational expression (i) is when the adhesive tape is attached to the adherend in a normal state and then pulled under predetermined conditions.
• the initial split adhesive force P 0 (N / cm 2 ) was calculated by the following evaluation conditions and evaluation methods.
• As a test piece for convenience of evaluation, an adhesive tape having an adhesive layer and a release liner on both sides of the base material layer was used.
• the adhesive tape cut into 30 mm ⁇ 50 mm is used as a test piece, and the release liner on one side of the test piece is peeled off and attached to the surface of a stainless steel (SUS) plate having a thickness of 3 mm. After that, the release liner on the other side was peeled off, a 10 mm square surface of a test piece of 10 mm ⁇ 10 mm ⁇ length 40 mm was attached, and then pressure-bonded at 50 N / cm 2 for 10 seconds to obtain an attached material. ..
• the stainless steel piece of the test piece constituting the patch is pulled at a speed of 1000 mm / min in an atmosphere of 23 ° C. and 50% RH. was a strength stainless pieces come off the initial split ⁇ adhesive force P 0.
• the initial split adhesive force P 0 (N / cm 2 ) of the adhesive tape is preferably 0.1 to 200 N / cm 2 , more preferably 1 to 150 N / cm 2. It is preferably 50 to 130 N / cm 2 .
• the split adhesive force P 0 is 0.1 to 200 N / cm 2, it is easy to achieve both adhesiveness and dismantling property.
• the adhesive strength P 400 (N / cm 2 ) when stretched 400% in the above relational expression (i) is the adhesive tape after being attached to the adherend in a stretched state so as to have a length of 400%.
• the adhesive strength P 400 (N / cm 2 ) when stretched by 400% was calculated by the following evaluation conditions and evaluation methods.
• As a test piece for convenience of evaluation, an adhesive tape having an adhesive layer and a release liner on both sides of the base material layer was used.
• the adhesive tape cut into 30 mm ⁇ 50 mm is used as a test piece, and the release liners on both sides of the test piece are peeled off to create handles on both ends of the test piece to make stainless steel having a thickness of 2 mm.
• a strong adhesive double-sided tape that fixes the stretched tape is attached to the surface of the plate, the test piece is stretched to a length of 400%, attached to the double-sided adhesive tape on the surface of the stainless steel plate, and then on the other side.
• a 10 mm square surface of a test piece having a size of 10 mm ⁇ 10 mm ⁇ length 40 mm was attached to the tape, and then pressure-bonded at 50 N / cm 2 for 10 seconds to obtain an attached product.
• the stainless steel piece of the test piece constituting the patch is pulled at a speed of 1000 mm / min in an atmosphere of 23,50% RH.
• the adhesive strength P 400 when the strength of peeling the stainless steel piece was extended by 400% was used.
• the adhesive tape according to the present invention is not limited to a double-sided tape that indispensably has an adhesive layer on both sides of the base material layer or a (double-sided) tape that indispensably has a release liner, and at least one side of the base material layer. It suffices to have an adhesive layer on the surface. Further, the relational expression between the split adhesive force P 0 (N / cm 2 ) and the split adhesive force P 400 (N / cm 2 ) is satisfied, and an adhesive layer and / or a peeling liner is provided on both sides of the base material layer.
• the step of providing the adhesive layer on both sides of the base material layer can be appropriately changed to the step of providing the adhesive layer on only one side of the base material layer.
• the initial split adhesive force and the adhesive force when stretched by 400% are not related to the structure having the adhesive layers on both sides of the base material layer, but the characteristics of the adhesive layer and the adhesion between the adhesive layer and the base material layer. It depends mainly on power. Therefore, it goes without saying that the above relational expression (i) and the above evaluation method, which are the characteristics of the double-sided tape, can be applied to the single-sided tape.
• adhesive strength at the time of stretching 400% P 400 (N / cm 2) is preferably 0.001 ⁇ 70N / cm 2, more preferably from 0.1 ⁇ 40N / cm 2 It is more preferably 1 to 30 N / cm 2.
• P 400 / P 0 which is the above relational expression (i)
• P 400 / P 0 is 0.9 or less. It is preferably 0.001 to 0.7, more preferably 0.01 to 0.6, and even more preferably 0.01 to 0.3.
• the above relational expression (i) is 0.9 or less, an excellent effect is exhibited due to the re-peelability from the state where a part of the adhesive tape has already been peeled from the adherend.
• the storage elastic modulus G'(23 ° C.) of the adhesive layer is 1.0 ⁇ 10 5 to 1.0 ⁇ 10 7 Pa.
• the pressure-sensitive adhesive layer is a pressure-sensitive adhesive containing a styrene-based block copolymer.
• the pressure-sensitive adhesive layer is a pressure-sensitive adhesive containing an acrylic block copolymer.
• the filler contained in the pressure-sensitive adhesive layer is a silicon-based filler.
• the pressure-sensitive adhesive layer contains a tack-imparting resin.
• the restoring force of the adhesive layer after pulling the adhesive tape is low, so that the adhesive tape after being stretched by 400% is restored to the normal state. It is difficult and the adhesive strength P 400 can be lowered. Furthermore, it is easy to realize a high load holding force. Further, by satisfying the above (b), the filler in the adhesive layer is exposed on the surface when the adhesive tape is pulled, and the adhesive force P 400 in the above relational expression (i) can be reduced.
• the filler in the adhesive layer can be kept exposed on the surface for a long period of time, so that a synergistic effect is exhibited.
• re-adhesion to the adherend can be effectively suppressed, and slipperiness can be imparted to the pressure-sensitive adhesive layer at the time of re-peeling, and re-peeling property can be improved.
• the reason why "removability from a state where a part of the adhesive tape has already been peeled from the adherend" is improved by satisfying the above relational expression (i) is the requirements of the above (a) to (f). The details of the mechanism are unknown because such factors are complicatedly related. However, at present, I think as follows.
• the filler in the adhesive sticks out to the surface of the adhesive, reducing the adhesiveness. Further, by using an adhesive having an elastic modulus, the state can be maintained for a long time. Furthermore, by using a highly slippery filler such as a silicon-based filler, stretching becomes a reagent. For the above reasons, it is considered that excellent removability can be exhibited from the state where a part of the adhesive tape has already been peeled from the adherend.
• the adhesive tape according to the present invention is provided with an adhesive layer in contact with the base material layer on at least one surface of the base material layer. Further, the adhesive tape according to the present invention may be provided with two adhesive layers in contact with the base material layer on both sides of the base material layer, if necessary, and in that case, the two adhesive layers are the same. Or may be different from each other.
• the adhesive tape according to the present invention is not only a general term for a roll-shaped adhesive tape having an adhesive layer provided on one side or both sides of the base material layer, but also a plate shape having an adhesive layer provided on one side or both sides of the base material layer. Also includes those with a release liner attached.
• the pressure-sensitive adhesive tape includes at least one type of pressure-sensitive adhesive layer and a base material layer that comes into contact with the pressure-sensitive adhesive layer.
• the base material layer has a breaking stress of 1 to 100 MPa and a breaking elongation of 400 to 3000%.
• the base material layer is not particularly limited as long as it has the above characteristics, and can be appropriately selected from known materials that can be used for the adhesive tape, and includes the following base material materials. Is preferable, and other components may be further contained if necessary.
• the base material layer may have a single layer structure, or may have a multi-layer structure of two layers, three layers, or more.
• the substrate layer has a breaking stress of 1 to 100 MPa, preferably 10 to 90 MPa, more preferably 15 to 90 MPa, still more preferably 30 to 90 MPa, still more preferably 50. It is ⁇ 90 MPa.
• the breaking stress is 1 MPa or more, when the adhesive tape is peeled off from the adherend, the adhesive tape can be peeled off from the adherend without being torn even if the operator pulls it. Further, when the breaking stress is 90 MPa or less, it is possible to prevent the operator from excessively increasing the stress when pulling the adhesive tape.
• the breaking stress of the base material layer is such that the base material layer is punched into a dumbbell shape having a marked line length of 20 mm and a width of 5 mm, and the measurement atmosphere is 23 ° C. and 50% RH. (Made by A & D Co., Ltd.), which refers to the stress value measured when the material is pulled in the length direction at a tensile speed of 500 mm / min and broken.
• breaking stress can be adjusted by appropriately selecting a material and stretching the base material layer in the manufacturing process.
• the substrate layer has a breaking elongation of 400 to 3000%, preferably 500 to 2500%, more preferably 530 to 1700%, still more preferably 560 to 1300%. Even more preferably, it is 600 to 1200%.
• breaking elongation 400% or more, even when the adhesive tape is firmly adhered to the adherend, the stress when peeling off the adhesive tape does not become too large. Further, since the breaking elongation is 3000% or less, when the adhesive tape is peeled off, the stretching distance does not become too long and it is possible to work in a small space.
• the breaking elongation of the base material layer is determined by punching the base material layer into a dumbbell shape having a marked line length of 20 mm and a width of 5 mm, and under the conditions of a measurement atmosphere of 23 ° C. and 50% RH, a Tencilon tensile tester (model: RTF-1210). , A & D Co., Ltd.), pulled in the length direction at a tensile speed of 500 mm / min, and refers to the tensile elongation measured when it breaks.
• the elongation at break can be adjusted by appropriately selecting a material and stretching the base material layer in the manufacturing process.
• the base material layer preferably has a 50% modulus of 0.1 to 5 MPa, more preferably 0.5 to 4.5 MPa, and even more preferably 1 to 4 MPa.
• the 50% modulus is 0.1 MPa or more, it is possible to suppress defects due to shape deformation such as displacement when a load is applied to the adhesive tape or the adherend. Further, since the 50% modulus is 5 MPa or less, the operator can pull with a relatively light force in the initial stage of peeling the adhesive tape from the adherend.
• the 50% modulus of the base material layer punches the base material layer into a dumbbell shape with a marked line length of 20 mm and a width of 5 mm, and under the conditions of a measurement atmosphere of 23 ° C. and 50% RH, a Tencilon tensile tester (model: RTF-1210). , A & D Co., Ltd.), pulling in the length direction at a tensile speed of 500 mm / min, and refers to the stress value measured when the elongation is 50%.
• the 50% modulus can be adjusted by appropriately selecting a material and stretching the base material layer in the manufacturing process.
• the base material layer preferably has a rubber hardness of 25 to 90 A, more preferably 30 to 85 A, and further preferably 35 to 80 A.
• the rubber hardness is 25 A or more, it is possible to prevent the adhesive tape from being torn when the adhesive tape is stretched and peeled off.
• the rubber hardness is 90 A or less, the base material layer becomes soft, and for example, when the adherend to which the adhesive tape is attached is dropped, the adhesive tape easily absorbs the impact, and the adherend is squeezed. It can be protected from impact (the impact resistance of the adhesive tape can be improved).
• the rubber hardness of the base material layer is Shore A hardness, and refers to a value measured in accordance with JIS K6253 using a durometer (spring type rubber hardness tester) (model: GS-719G, manufactured by TECLOCK Co., Ltd.).
• the rubber hardness should be adjusted by appropriately selecting a material, such as changing the molecular weight of the resin or changing the monomer unit when the styrene monomer unit is contained. Can be done.
• the base material layer has an average thickness of 10 to 500 ⁇ m, preferably 30 to 250 ⁇ m, and more preferably 50 to 200 ⁇ m.
• the thickness is 10 ⁇ m or more, the strength of the adhesive tape can be ensured, and when the thickness is 500 ⁇ m or less, it is possible to avoid that the thickness is too thick and it becomes difficult to pull the adhesive tape. can.
• the "thickness of the base material layer” refers to the thickness of any five points in the base material layer as TH-104, a thickness measuring machine for paper / film (manufactured by Tester Sangyo Co., Ltd.). It is measured using and refers to the average value of those measured values.
• the ratio of the thickness of the adhesive layer to the base material layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is represented by [thickness of the adhesive layer / thickness of the base material layer].
• the ratio of the thickness of the adhesive layer to the thickness of the base material layer is preferably 1/6 to 6/1, more preferably 1/3 to 3/1, and 1/2 to 2 /. It is more preferably 1.
• excellent adhesiveness and removability (easiness of peeling) of the adhesive tape can be obtained.
• the ratio is larger than 5/1, only the adhesive layer may remain on the adherend in the removability step of the adhesive tape.
• the ratio is smaller than 1/5, there is a concern that the adhesive layer cannot follow the surface of the adherend and the adhesive strength is lowered when the surface of the adherend has an uneven shape or the like.
• the material of the base material layer is not particularly limited as long as the base material layer having the above specific physical properties can be obtained, and for example, styrene-isoprene copolymer, styrene-isoprene-styrene copolymer, styrene-isoprene- Styrene-based resins such as butadiene-styrene copolymers, styrene-butadiene-styrene copolymers, styrene-ethylene-butylene copolymers, and styrene-ethylene-propylene copolymers; polyurethane resins such as ester-based polyurethanes and ether-based polyurethanes.
• Polyethylene resin such as polyethylene and polypropylene; Polyester resin such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; Polystyrene; Polycarbonate; Polymethylpentene; Polysulfone; Polyether ether ketone; Polyether sulfone; Polyetherimide; Polyethylene film; Styrene resin; nylon; acrylic resin or the like as a main component can be mentioned. These may be used alone or in combination of two or more, but it is preferable to use two or more in combination.
• a styrene resin or a polyurethane resin is preferable because it is easy to obtain suitable breaking stress and breaking elongation, and a styrene resin is more preferable, and a styrene-isoprene copolymer and a styrene-isoprene-styrene copolymer are used. Is particularly preferable to use in combination.
• the main component of the material of the base material layer means a case where 50 mass or more is exhibited in all the materials of the base material layer.
• the styrene-based resin is a resin that exhibits thermoplasticity, it is excellent in moldability such as extrusion molding and injection molding, and it is easy to mold the base material layer. Further, the styrene-based resin can easily obtain a particularly excellent breaking elongation in the resin group generally called a thermoplastic resin, and can be suitably used as a base material layer of an adhesive sheet.
• the ratio (mass) of the styrene resin to the total resin component (or all materials) is preferably 50 to 100%, more preferably 60 to 100%, and more preferably 65 to 100. % Is more preferable, and 70 to 100% is particularly preferable.
• the ratio of the styrene resin is within the above preferable range, a base material layer having excellent breaking elongation and breaking stress can be obtained.
• styrene resin for example, a single structure having a linear structure, a branched structure, or a multi-branched structure may be used, or a mixture of different structures may be used.
• a styrene-based resin having abundant linear structures can give an excellent elongation at break to the base material layer.
• a branched structure or a multi-branched structure in which a styrene block is arranged at the molecular end can have a pseudo-crosslinked structure and can provide excellent cohesive force. Therefore, it is preferable to mix and use the styrene resin according to the required mechanical properties.
• the styrene resin it is preferable to use a resin having a structural unit represented by the following chemical formula (A) in the range of 5 to 50% by mass with respect to the total mass of the styrene resin, and 5 to 40 mass. It is more preferable to use one having a range of%, further preferably one having a range of 10 to 30% by mass, and particularly preferably one having a range of 15 to 25% by mass.
• the ratio of the structural unit represented by the following chemical formula (A) to the total mass of the styrene resin is within the above-mentioned preferable range, it becomes easy to obtain the breaking elongation and the breaking stress in the preferable range.
• * in the following chemical formula (A) is a bond representing a bond with another atom, and the same applies to the following chemical formulas (B) and chemical formulas (1) to (6).
• styrene-isoprene copolymer and a styrene-isoprene-styrene copolymer are used in combination as a styrene resin, styrene with respect to the total mass of the styrene-isoprene copolymer and the styrene-isoprene-styrene copolymer.
• the content of the isoprene copolymer is preferably 0 to 80% by mass, more preferably 0 to 70% by mass, further preferably 0 to 50% by mass, and 0 to 30%. It is particularly preferably mass%.
• the content of the styrene-isoprene copolymer is within the above-mentioned preferable range, it is possible to achieve both thermal durability while maintaining excellent breaking elongation and breaking stress.
• styrene-isoprene copolymer it is preferable to use a styrene-isoprene copolymer having a weight average molecular weight in the range of 10,000 to 800,000 measured in terms of standard polystyrene using a gel permeation chromatograph (GPC). It is more preferable to use the one in the range of 30,000 to 500,000, and further preferably to use the one in the range of 50,000 to 300,000.
• GPC gel permeation chromatograph
• the weight average molecular weight of the styrene-isoprene copolymer is within the above-mentioned preferable range, the heat fluidity and the compatibility at the time of solvent dilution can be ensured, so that the workability in the manufacturing process is good and the thermal durability is improved. It is preferable because the provided base material layer can be obtained.
• the measurement of the weight average molecular weight of the styrene-isoprene copolymer by the GPC method is a standard polystyrene-equivalent value measured using a GPC device (SC-8020, manufactured by Tosoh Corporation), and the measurement conditions are as follows. It is as follows.
• the method for producing the styrene-isoprene copolymer is not particularly limited and may be appropriately selected from conventionally known production methods.
• the styrene block and the isoprene block are sequentially produced by the anion living polymerization method. Examples include a method of polymerization.
• the method for producing the styrene-isoprene-styrene copolymer is not particularly limited and may be appropriately selected from conventionally known production methods.
• the styrene block and the isoprene block are sequentially polymerized by an anion living polymerization method. Examples thereof include a method of producing a block copolymer having a living active terminal and then reacting it with a coupling agent to produce a coupled block copolymer.
• the method for producing a mixture of the styrene-isoprene copolymer and the styrene-isoprene-styrene copolymer is not particularly limited and may be appropriately selected from conventionally known production methods.
• the method is used for production. Examples thereof include a method of mixing the styrene-isoprene copolymer and the styrene-isoprene-styrene copolymer.
• a polystyrene block having a living active terminal is formed by polymerizing a styrene monomer in a polymerization solvent using an anionic polymerization initiator by an anionic living polymerization method. ..
• isoprene is polymerized from the living-active terminal of the polystyrene block to obtain a styrene-isoprene block copolymer having a living-active terminal.
• a part of the styrene-isoprene block copolymer having a living active terminal is reacted with the coupling agent to form a coupled styrene-isoprene-styrene block copolymer.
• the rest of the styrene-isoprene block copolymer having a living active end is deactivated by using a polymerization inhibitor to deactivate the living active end of the styrene-isoprene block copolymer.
• the polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but a polyurethane resin having a softening point of 40 ° C. or higher is preferable, and a polyurethane resin having a softening point of 50 ° C. or higher is more preferable.
• the upper limit of the softening point is preferably 100 ° C. or lower.
• the softening point refers to a value measured in accordance with JIS K 2207 (ring ball type) (hereinafter, the softening point is the same measurement method).
• a reaction product of a polyol (b1-1) and a polyisocyanate (b1-2) can be preferably used.
• the polyol (b1-1) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyester polyols, polyether polyols, polycarbonate polyols and acrylic polyols. These may be used alone or in combination of two or more. Among these, as the polyol (b1-1), a polyester polyol and a polyether polyol are preferable because the mechanical properties of the base material layer can be obtained. In the base material layer, it is preferable to use a polyester polyol when heat resistance is required, and it is preferable to use a polyether polyol when water resistance and biodegradability are required.
• polyester polyol examples include a polyester obtained by esterifying a low molecular weight polyol and a polycarboxylic acid, a polyester obtained by ring-opening polymerization reaction of a cyclic ester compound such as ⁇ -caprolactone, and a copolymerization thereof.
• polyester examples include polyester.
• Examples of the low molecular weight polyol that can be used for producing the polyester polyol include ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol, which have a weight average molecular weight of about 50 to 300.
• Aliper alkylene glycols such as diethylene glycol, neopentyl glycol and 1,3-butanediol, cyclohexanedimethanol and the like can be used.
• polycarboxylic acid examples include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid; and theirs. Examples thereof include anhydrides and esterified products.
• polyether polyol examples include those obtained by addition polymerization of an alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator.
• polycarbonate polyol for example, one obtained by reacting a carbonic acid ester and / or phosgene with a low molecular weight polyol described later can be used.
• Examples of the carbonic acid ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like.
• Examples of low molecular weight polyols that can react with carbonates and / or phosgens that can be used in the production of the above polycarbonate polyols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, and 1 , 3-Propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1, , 5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1, 11-Undecanediol
• the polyisocyanate (b1-2) is not particularly limited and may be appropriately selected depending on the intended purpose.
• an alicyclic polyisocyanate, an aliphatic polyisocyanate, an aromatic polyisocyanate or the like can be used.
• Alicyclic polyisocyanate and the like may be used alone or in combination of two or more.
• alicyclic polyisocyanate examples include isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 4,4'-dicyclohexylmethanediisocyanate, 2,4-methylcyclohexanediisocyanate, and 2,6-methylcyclohexanediisocyanate.
• Cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isosianatoethyl) -4-cyclohexylene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, dimerate diisocyanate, Bicycloheptane triisocyanate and the like can be mentioned. These may be used alone or in combination of two or more.
• the method for producing the polyurethane resin (b1) by reacting the polyol (b1-1) with the polyisocyanate (b1-2) is not particularly limited, and can be appropriately selected from conventionally known production methods.
• the polyol (b1-1) charged in the reaction vessel is heated under normal pressure or reduced pressure conditions to remove water, and then the polyisocyanate (b1-2) is supplied in a lump or divided manner for reaction.
• the method etc. can be mentioned.
• the reaction between the polyol (b1-1) and the polyisocyanate (b1-2) is the equivalent of the isocyanate group (NCO) of the polyisocyanate (b1-2) and the hydroxyl group (OH) of the polyol (b1-1).
• the ratio (NCO / OH equivalent ratio) is preferably in the range of 1.0 to 20.0, more preferably in the range of 1.1 to 13.0, and in the range of 1.2 to 5.0. It is more preferable to carry out in the range of 1.5 to 3.0, and it is particularly preferable to carry out in the range of 1.5 to 3.0.
• the reaction conditions between the polyol (b1-1) and the polyisocyanate (b1-2) are not particularly limited and can be appropriately selected in consideration of various conditions such as safety, quality and cost, but the reaction temperature can be set as the reaction temperature.
• the temperature is preferably 70 to 120 ° C., and the reaction time is preferably 30 minutes to 5 hours.
• a tertiary amine catalyst, an organometallic catalyst or the like can be used as a catalyst, if necessary.
• reaction may be carried out in a solvent-free environment or in the presence of an organic solvent.
• the organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose.
• ester solvents such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate; acetone, methyl ethyl ketone, methyl butyl ketone, cyclohexanone and the like.
• Ketone-based solvent; ether ester-based solvent such as methyl cellosolve acetate and butyl cellosolve acetate; aromatic hydrocarbon-based solvent such as toluene and xylene; amide-based solvent such as dimethylformamide and dimethylacetamide.
• aromatic hydrocarbon-based solvent such as toluene and xylene
• amide-based solvent such as dimethylformamide and dimethylacetamide.
• the organic solvent may be removed during the production of the polyurethane resin (b1) or after the production of the polyurethane (b1) by an appropriate method such as heating under reduced pressure or drying at normal pressure.
• the other components in the base material layer are not particularly limited and may be appropriately selected as long as the characteristics of the pressure-sensitive adhesive tape are not impaired.
• a tackifier resin for example, a tackifier resin; a polymer component other than the material of the base material layer; a cross-linking agent, Anti-aging agents, UV absorbers, fillers, polymerization inhibitors, surface conditioners, antistatic agents, defoamers, viscosity modifiers, light-resistant stabilizers, weather-resistant stabilizers, heat-resistant stabilizers, antioxidants, leveling agents, Additives such as organic pigments, inorganic pigments, pigment dispersants, silica beads, and organic beads; inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, and antimony pentoxide can be mentioned. These may be used alone or in combination of two or more.
• the content of other components in the base material layer can be appropriately selected as long as the characteristics of the adhesive tape are not impaired.
• the tackifying resin can be used for the purpose of improving the adhesion between the adhesive layer of the adhesive tape and the base material layer and improving the heat resistance.
• the tackifier resin is not particularly limited and may be appropriately selected depending on the intended purpose.
• the softening point is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and 100 ° C. or higher. More preferably, those having a temperature of 110 ° C. or higher are particularly preferable.
• tackifier resin for example, those described in the item of "rubber-based pressure-sensitive adhesive resin" described later can be used, and the preferred embodiment is also the same.
• the anti-aging agent is not particularly limited and may be appropriately selected from known ones according to the purpose.
• a phenol-based anti-aging agent and a phosphorus-based anti-aging agent also referred to as "processing stabilizer”).
• Amine-based anti-aging agents, imidazole-based anti-aging agents, etc. may be used alone or in combination of two or more.
• phenol-based anti-aging agents and phosphorus-based anti-aging agents are preferable, and the combined use of these can effectively improve the heat-resistant stability of the base material, resulting in good results. It is preferable because an adhesive tape that maintains initial adhesiveness and has even better thermal durability can be obtained.
• the amount used should be determined in consideration of the balance between initial adhesiveness, thermal durability, and discoloration prevention. It is preferable to set it appropriately.
• a phenol-based compound having a steric hindrance group can be generally used, and monophenol type, bisphenol type, and polyphenol type are typical. Specific examples include 2,6-di-t-butyl-4-methylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 2,2'-methylenebis (4-ethyl-6).
• the amount of the phenolic antiaging agent used is not particularly limited and may be appropriately selected depending on the intended purpose, but is in the range of 0.1 part by mass to 5 parts by mass with respect to 100 parts by mass of the base material. It is preferably used, and when it is used in the range of 0.5 parts by mass to 3 parts by mass, the heat-resistant stability of the base material can be effectively improved, and as a result, good initial adhesiveness can be obtained. It is possible to obtain an adhesive tape that is maintained and has even better thermal durability.
• the pressure-sensitive adhesive layer in the present invention contains a pressure-sensitive adhesive resin, and may contain a pressure-imparting resin and / or a filler, if necessary. Further, the pressure-sensitive adhesive layer in the present invention is formed of a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive resin, which will be described later, and a pressure-sensitive adhesive resin, a filler, and / or other components added as necessary.
• the storage elastic modulus G'(23 ° C.) of the adhesive layer is preferably 1.0 ⁇ 10 5 to 1.0 ⁇ 10 7 Pa, and 1.0 ⁇ 10 5 to 1.0 ⁇ . It is more preferably 10 6 Pa, further preferably 1.5 ⁇ 10 5 to 9.0 ⁇ 10 5 Pa, and more preferably 2.0 ⁇ 10 5 to 8.0 ⁇ 10 5 Pa. More preferred.
• the storage elastic modulus G'(23 ° C.) of the adhesive layer has the effect of highly achieving both initial adhesiveness, high load holding force, and removability over time. Further, when the breaking point stress of the adhesive layer is within the above range, it is easy to follow the strain of the adherend and obtain excellent adhesive strength, and it is possible to secure the dimensional stability of the base material layer. Therefore, suitable sticking workability can be obtained.
• the stress at 25% elongation of the adhesive layer is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably 0.04 to 0.4 MPa, more preferably 0.05 to 0.1 MPa.
• an adhesive strength suitable for the adhesive tape can be obtained, and the adhesive layer can be peeled off relatively easily even when the adhesive layer is stretched and peeled off.
• the stress at 25% elongation of the adhesive layer is less than 0.04 MPa, the adhesive tape will peel off when a load is applied in the shearing direction of the adhesive tape while fixing the hard adherends to each other. If it exceeds 0.4 MPa, the force required to stretch the adhesive tape may become excessive when the adhesive tape is peeled off.
• the 25% elongation stress of the adhesive layer is obtained by punching the adhesive layer into a dumbbell shape with a marked line length of 20 mm and a width of 10 mm, and under the conditions of a measurement atmosphere of 23 ° C. and 50% RH, a Tencilon tensile tester (model: RTF-1210). , A & D Co., Ltd.), and refers to the stress value measured when the product is pulled in the length direction at a tensile speed of 300 mm / min and stretched by 25%.
• the breaking stress of the adhesive layer is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably 0.5 to 2.1 MPa, more preferably 1.0 to 2.1 MPa.
• the breaking stress of the adhesive layer is within the above-mentioned preferable range, it is possible to prevent the adhesive tape from being torn even when the adhesive tape is stretched and peeled off, and the load for stretching the adhesive tape is increased. Since it does not become excessive, the removability work by peeling becomes easy.
• the breaking stress of the adhesive layer is less than 0.5 MPa, adhesive residue may occur due to cohesive failure of the adhesive layer when the adhesive tape is stretched and peeled off, and if it exceeds 2.1 MPa, sufficient adhesion is obtained.
• the force required to stretch and deform the adhesive tape also depends on the thickness of the adhesive tape.
• the adhesive tape having a thick adhesive tape and a high breaking stress should be stretched and peeled off. Even in this case, it may not be possible to stretch it sufficiently and peel it off.
• the breaking stress of the adhesive layer is such that the adhesive layer is punched into a dumbbell shape with a marked line length of 20 mm and a width of 10 mm, and the measurement atmosphere is 23 ° C. and 50% RH.
• a & D Co., Ltd. is used to pull in the length direction at a tensile speed of 300 mm / min, and refers to the stress value measured when it breaks.
• the elongation at break of the adhesive layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 450 to 1300%, more preferably 500 to 1200%, still more preferably 600 to 1100%.
• breaking elongation of the adhesive layer is within the above-mentioned preferable range, it is possible to achieve both suitable adhesiveness and re-peelability (easiness of peeling).
• the breaking elongation of the adhesive layer is determined by punching the adhesive layer into a dumbbell shape with a marked line length of 20 mm and a width of 10 mm, and under the conditions of a measurement atmosphere of 23 ° C. and 50% RH, a Tensilon tensile tester (model: RTF-1210, stock). (Manufactured by A & D Co., Ltd.) is used to pull in the length direction at a tensile speed of 300 mm / min, and refers to the tensile elongation measured when it breaks.
• the average thickness of the adhesive layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 200 ⁇ m, more preferably 10 to 150 ⁇ m, and 30 to 120 ⁇ m. It is more preferable, and it is particularly preferable that it is 40 ⁇ m to 100 ⁇ m.
• Average thickness of adhesive layer means the thickness of the adhesive layer on one side of the adhesive tape. When the adhesive tape has adhesive layers on both sides, the average thickness of the adhesive layer on one side and the average thickness of the adhesive layer on the other side may be the same or different, but the same thickness. It is preferable that it is.
• the average thickness of the adhesive layer can be measured by the following method. That is, after immersing the adhesive tape in liquid nitrogen for 1 minute, the adhesive tape is folded and split in liquid nitrogen using a tweezers with the width direction of the adhesive tape as a crease, and a section for observing the split cross section in the thickness direction of the adhesive tape. To make. After returning the section to room temperature in a desiccator, the section is fixed on a sample table so that an electron beam is vertically incident on the fractured surface, and the fractured surface is observed using an electron microscope. Based on the scale of the electron microscope, the thickness of the adhesive layer in the adhesive tape is measured at 10 points, and the arithmetic mean value thereof is taken as the thickness of the adhesive layer. The thickness of the adhesive layer is a length measured from the surface on one side to the surface on the other side along the stacking direction.
• the pressure-sensitive adhesive resin used for the pressure-sensitive adhesive layer in the present invention is an acrylic pressure-sensitive adhesive resin containing an acrylic block copolymer or an aromatic vinyl containing a styrene-based block copolymer as the main component of the pressure-sensitive adhesive resin. It is preferable to contain a styrene adhesive resin.
• the "main component of the pressure-sensitive adhesive resin” refers to the main component of the resin component contained in the pressure-sensitive adhesive resin (typically, a component contained in an amount of more than 50% by mass).
• the acrylic block copolymer it is preferable that 30 to 100% by mass is occupied by the acrylic block copolymer, and 50 to 95% by mass is occupied by the acrylic block copolymer with respect to the entire pressure-sensitive adhesive resin used for the pressure-sensitive adhesive layer in the present invention. It is more preferable to occupy with.
• the content of the acrylic block copolymer in the adhesive layer in the present invention is 30% by mass or more, it is easy to achieve both removability and high load holding power. Further, it is preferable that 30 to 100% by mass is occupied by the styrene-based block copolymer, and 50 to 100% by mass is occupied by the styrene-based block copolymer with respect to the entire pressure-sensitive adhesive resin used for the pressure-sensitive adhesive layer in the present invention. It is more preferable to occupy with.
• the content of the styrene-based block copolymer in the adhesive layer in the present invention is 30% by mass or more, it is easy to achieve both removability and high load holding power.
• the acrylic block copolymer in the present invention has a general formula (1): (In the above general formula (1), A, B and C each independently represent a repeating unit, A and C each independently represent an alkyl methacrylate ester monomer unit, and B is an alkyl acrylate. Representing an ester monomer unit, p, q and r independently represent the degree of polymerization of each monomer unit, and A and C are alkyl methacrylates having the same or different chemical structures. It may be a monomer unit.
• * is a bonder representing a bond with another atom.
• It is a triblock copolymer having a repeating unit represented by). Is preferable.
• a and C represent a repeating unit different from B, and represent a methacrylic acid alkyl ester monomer unit. Further, A and C are independent of each other and may be the same methacrylic acid alkyl ester monomer unit or a methacrylic acid alkyl ester monomer unit having different chemical structures.
• the term "methacrylic acid alkyl ester monomer unit” as used herein refers to a structural unit derived from a methacrylate alkyl ester monomer when the methacrylate alkyl ester monomer is (co) polymerized or graft-polymerized, that is, methacryl.
• the methacrylic acid alkyl ester monomer unit in the present invention has the following general formula (2): (In the above general formula (2), R 1 represents an alkyl group having 1 to 12 carbon atoms, and one or more hydrogen atoms in the alkyl group may be substituted with the substituent R 2.
• the substituent R 2 is preferably represented by a halogen atom, an amino group, or a cyano group).
• R 1 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and carbon from the viewpoint of removability and high load holding force. Alkyl groups having 1 to 2 atoms are more preferable.
• the alkyl group having 1 to 12 carbon atoms may be linear, branched, or cyclic, and is preferably linear or branched from the viewpoint of adhesive strength. Chain form is more preferable.
• examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and an n-pentyl group.
• Linear or branched alkyl groups such as groups, isopentyl groups, hexyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups and dodecyl groups, as well as cyclobutyl groups, cyclopentyl groups, cyclohexyl groups and cycloheptyl groups.
• cyclic alkyl groups of cyclooctyl group, cyclononyl group, cyclodecyl group, dicyclopentanyl group, and adamantyl group are included.
• a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group is preferable, and a methyl group, an ethyl group, A propyl group is more preferred.
• examples of the alkyl group having 1 to 4 carbon atoms include linear chains such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group.
• examples thereof include cyclic or branched alkyl groups and cyclic alkyl groups such as cyclobutyl groups.
• the alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group from the viewpoint of removability and high load holding power. Is preferable, and a methyl group is more preferable.
• the preferred R1 in the general formula (2) is an alkyl group of any one of a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, or a cyclobutyl group.
• one or more hydrogen atoms in the alkyl group may be substituted with a halogen atom, an amino group, or a cyano group.
• the methacrylic acid alkyl ester monomer is not particularly limited, and methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and methacrylic acid are used.
• B represents a repeating unit different from A and C, and represents an acrylic acid alkyl ester monomer unit.
• the "acrylic acid alkyl ester monomer unit” in the present specification is a structural unit derived from the acrylic acid alkyl ester monomer when the acrylic acid alkyl ester monomer is (co) polymerized or graft-polymerized, that is, acrylic.
• the acrylic acid alkyl ester monomer unit in the present invention has the following general formula (3): (In the above general formula (3), R 3 represents an alkyl group having 1 to 12 carbon atoms, and one or more hydrogen atoms in the alkyl group may be substituted with the substituent R 4.
• substituent R 4 is a halogen atom, an amino group, or a cyano group.) is preferably represented by the.
• R 3 is more preferably an alkyl group having 1 to 20 carbon atoms, and further preferably an alkyl group having 4 to 8 carbon atoms, from the viewpoint of adhesiveness.
• the alkyl group having 1 to 12 carbon atoms may be linear, branched, or cyclic, and is preferably linear or branched from the viewpoint of adhesiveness. Further, the examples of the alkyl group having 1 to 12 carbon atoms and the alkyl group having 4 to 8 carbon atoms are the same as the examples of the alkyl group having 1 to 12 carbon atoms in the above general formula (2).
• preferred R 3 in the general formula (3) include methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, an isobutyl group, t- butyl group, n- pentyl group, an isopentyl group, a hexyl group , Octyl group, Nonyl group, Decyl group, Undecyl group, Dodecyl group and other linear or branched alkyl groups, or cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group.
• Cyclodecyl group, dicyclopentanyl group, or cyclic alkyl group such as adamantyl group, and one or more hydrogen atoms in the alkyl group may be substituted with halogen atom, amino group, cyano group. ..
• examples of the acrylic acid alkyl ester monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and sec acrylate.
• -Butyl, t-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate and the like can be mentioned.
• n-butyl acrylate, 2-ethylhexyl acrylate, and copolymers thereof are preferable from the viewpoint of achieving both adhesive strength and removability.
• p, q and r independently represent the degree of polymerization of each monomer unit.
• Each value of p, q and r is related to the molecular weight and the like.
• p / (p + q + r) is preferably 0.02 to 0.40, more preferably 0.05 to 0.37.
• q / (p + q + r) is preferably 0.20 to 0.95, more preferably 0.25 to 0.90.
• r / (p + q + r) is preferably 0.02 to 0.40, more preferably 0.05 to 0.37.
• the acrylic block copolymer is described by the following general formula (4):
• R 1 and R 5 each independently represent an alkyl group having 1 to 12 carbon atoms, and one or more hydrogen atoms in the alkyl group are assigned to the substituent R 2 . It may be substituted, the substituent R 2 represents a halogen atom, an amino group, or a cyano group, and R 3 represents an alkyl group having 1 to 12 carbon atoms, and one or more of the alkyl groups.
• the hydrogen atom may be substituted with a substituent R 4 , the substituent R 4 represents a halogen atom, an amino group, or a cyano group, and p, q and r are independent of each monomer unit. It is preferable to have a repeating unit represented by (representing the degree of polymerization).
• R 1 can be applied in the same manner as R 1 in the general formula (2).
• R 3 can be applied in the same manner as R 3 in the general formula (3).
• R 5 can apply the same aspect as R 1 in the general formula (2).
• p, q and r can be applied in the same manner as p, q and r in the general formula (1).
• R 1 and R 5 may be the same or different.
• R 1 is a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.
• R 3 is a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, isobutyl group, t- butyl group, n- pentyl group, an isopentyl group, a hexyl group, an octyl group, a nonyl group, be selected from the group consisting of decyl, or undecyl preferably, R 5 is a methyl group, an ethyl group , Propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and other linear or branched alkyl groups, and cyclobutyl group, preferably selected from the group consisting of p / (. It is preferable that p + q + r) is 0.02 to 0.40
• a and C in the general formula (1) are the same.
• R 1 and R 5 are the same group, and p / (p + q + r) is 0.02 to 0. It is preferably .40, q / (p + q + r) is 0.20 to 0.95, and r / (p + q + r) is 0.02 to 0.40.
• a and C are the same (ABA type triblock copolymer)
• a higher elastic modulus can be secured. Therefore, it becomes easier to secure a high load holding force, a removability over time, and an adhesive force having excellent storage stability.
• the general formula (5) (In the above general formula (5), D and E each independently represent a repeating unit, D represents a methacrylic acid alkyl ester monomer unit, and E represents an acrylic acid alkyl ester monomer unit. s and t independently represent the degree of polymerization of each monomer unit.
• * is a bonder representing a bond with another atom), which is a repeating unit. It is preferable that it is a diblock copolymer having.
• the acrylic block copolymer used for the pressure-sensitive adhesive resin comprises a triblock copolymer represented by the general formula (1) and a triblock copolymer represented by the general formula (5). It is preferably at least one selected from the group.
• a triblock copolymer and a diblock copolymer are used in combination with the pressure-sensitive adhesive resin, it becomes easier to secure a high elastic modulus and initial adhesiveness, so that high load holding force, removability over time, and initial adhesiveness can be obtained. It becomes easier to secure power.
• the adhesive layer contains a filler
• the filler in the adhesive layer can be maintained exposed on the surface for a long period of time as compared with the form in which the filler does not exist in the adhesive layer. Combined with it, it exerts an excellent synergistic effect.
• the methacrylic acid alkyl ester monomer unit and the acrylic acid alkyl ester monomer unit in the general formula (5) are the methacrylic acid alkyl ester monomer unit and the acrylic acid alkyl ester single amount in the general formula (1). The same morphology as the body unit can be applied.
• the diblock polymer in the present invention has the following general formula (6).
• R 6 represents an alkyl group having 1 to 12 carbon atoms, and one or more hydrogen atoms in the alkyl group may be substituted with the substituent R 8.
• Substituent R 8 represents a halogen atom, an amino group, or a cyano group
• R 7 represents an alkyl group having 1 to 12 carbon atoms
• one or more hydrogen atoms in the alkyl group are substituent R. It may be substituted with 9, and the substituent R 9 represents a halogen atom, an amino group, or a cyano group, and s and t each independently represent the degree of polymerization of each monomer unit). It is preferable to have a repeating unit.
• R 6 can apply the same embodiment as R 1 in the general formula (2).
• R 7 can apply the same form as R 3 in the general formula (3).
• s and t can be applied in the same manner as p and q in the general formula (1).
• the weight average molecular weight Mw of the diblock copolymer is 50,000 to 300,000 and the number average molecular weight Mn is 50,000 to 300,000.
• the method for measuring the weight average molecular weight of the triblock copolymer in the present invention can be incorporated.
• p, q and r independently represent the degree of polymerization of each monomer unit.
• Each value of s and t is related to the molecular weight and the like.
• s / (s + t) is preferably 0.01 to 0.99, more preferably 0.1 to 0.9.
• t / (s + t) is preferably 0.01 to 0.99, more preferably 0.1 to 0.9.
• the content of the diblock copolymer is not particularly limited and can be appropriately selected depending on the intended purpose.
• the diblock copolymer is preferably contained in an amount of 0 to 100 parts by mass, more preferably 1 to 50 parts by mass, and 10 to 50 parts by mass with respect to 100 parts by mass of the triblock copolymer. It is more preferably contained in parts by mass.
• the weight average molecular weight Mw of the acrylic block copolymer is 50,000 to 300,000 and the number average molecular weight Mn is 50,000 to 300,000. More preferably, the weight average molecular weight Mw of the block copolymer is 100,000 to 250,000, and the number average molecular weight Mn is 100,000 to 250,000, and even more preferably, the weight average molecular weight of the block copolymer.
• the Mw is 130,000 to 230,000, and the number average molecular weight Mn is 130,000 to 230,000.
• the preferred ranges of the weight average molecular weight Mw and the number average molecular weight Mn of the triblock copolymer represented by the general formula (1) are also the same as the above ranges.
• the weight average molecular weight Mw of the acrylic block copolymer is in the above range, it is preferable from the viewpoint of removability, and when the number average molecular weight Mn of the acrylic block copolymer is in the above range, it is preferable from the viewpoint of removability.
• the triblock copolymer and / or the partial structure (for example, block) of the triblock copolymer in the present invention has any stereoregularity of isotactic, syndiotactic and atactic. It may have a plurality of blocks having any of these stereoregularities.
• the ratio of rr triplets in which the syndiotacticity of the polymer block in the "-(A) p-" portion in the general formula (1) is 65% or more is 65% or more. Is preferable, and the ratio of rr triplets is more preferably 75 to 95%.
• the ratio of rr triplets in which the syndiotacticity of the polymer block in the "-(C) r-" portion in the general formula (1) is 65% or more is 65% or more. Is preferable, and the ratio of rr triplets is more preferably 75 to 95%.
• the triblock copolymer in the present invention has a polymer block in the "-(A) p- " portion in which the proportion of rr triplets is 65% or more, the removability and the holding power at high temperature are good. It has the effect of being there.
• the syndiotacticity of a polymer is expressed by the ratio in which the chain (triplet) composed of three monomer units is rr. In this specification, it is calculated by NMR measurement of a polymer. Specifically, since the signal peak representing the triplet sequence in 13 C-NMR differs depending on the conditions such as the type of polymer, the measurement solvent, or the measurement temperature, the signal is identified according to each measurement condition. ⁇ It is necessary to quantify. In this specification, a sample dissolved in deuterated chloroform is measured at 50 ° C.
• Preferred forms of the triblock copolymer in the present invention include polymethylmethacrylate block-n-butylblock polyacrylate-methylpolymethacrylate, ethyl block polymethacrylate-n-butylblock polyacrylate-polymethacrylic acid.
• Ethyl, polypropyl methacrylate block-n-butyl block polyacrylic acid-propyl poly methacrylate, methyl methyl methacrylate block-t-butyl block polyacrylic acid-methyl poly methacrylate, methyl methyl methacrylate block-propyl polyacrylate Block-polymethyl methacrylate can be mentioned.
• the overall molecular weight distribution of the triblock copolymer is preferably in the range of 0.8 to 2.3 in terms of the weight average molecular weight / number average molecular weight ratio. It is more preferably in the range of .00 to 1.50.
• the ratio of the "-" part to the total weight of the polymer block is preferably in the range of 5/95 to 80/20 in terms of the mass ratio of a / b from the viewpoint of adhesive properties, and is preferably 10/90 to 75 /. It is more preferably in the range of 25.
• the polymer block of the "-(A) p-" portion contained in the molecule of the triblock copolymer in the present invention is referred to as a
• the ratio of the total weight of the polymer block in the q ⁇ ”part to b) is preferably in the range of 2/98 to 67/33 in terms of the mass ratio of a / b from the viewpoint of adhesive properties. More preferably, it is in the range of 5/95 to 60/40.
• the polymer block of the "-(C) r-" portion contained in the molecule of the triblock copolymer in the present invention when A and C in the general formula (1) are different repeating units, the polymer block of the "-(C) r-" portion contained in the molecule of the triblock copolymer in the present invention.
• the ratio of the total weight of the polymer block in the "-(C) p- " part (referred to as c) to the total weight of the polymer block in the "-(B) q-" part is the adhesive property.
• the mass ratio of c / b is preferably in the range of 2/98 to 67/33, and more preferably in the range of 5/95 to 60/40.
• the ratio of (.) To the total weight (referred to as b) of the polymer block in the "-(B) q- " part is 5/95 to 80/20 in terms of the mass ratio of d / b from the viewpoint of adhesive properties. It is preferably in the range of 10/90 to 75/25, and more preferably in the range of 10/90 to 75/25.
• the triblock copolymer in the present invention contains a hydroxyl group, a carboxyl group, an acid anhydride group, an amino group, and a tri, as required, in the side chain of the molecule or at the end of the main chain of the molecule, as long as the effects of the present invention are not impaired. It may be modified to a functional group such as a methoxysilyl group.
• the method for producing the triblock copolymer used in the present embodiment is not particularly limited, and can be appropriately selected from conventionally known production methods.
• an anion living polymerization method and a cation living polymerization method examples thereof include a method of sequentially polymerizing block copolymers.
• a known method using an organometallic complex may be used.
• a polymerization initiator is used to polymerize a methacrylic acid alkyl ester monomer as a main component in an inert polymerization solvent, and the main component is used.
• a triblock copolymer is prepared by a method consisting of sequentially polymerizing a certain acrylic acid alkyl ester monomer and / or a monomer containing a methacrylate alkyl ester monomer as a main component in a desired block bonding order. Can be manufactured.
• a methacrylic acid alkyl ester monomer is polymerized in a polymerization solvent using a polymerization initiator by an anion living polymerization method, and living.
• a polymethacrylic acid alkyl ester block having a sex active terminal (corresponding to the "-(A) p- " moiety in the general formula (1)) is formed.
• a methacrylic acid alkyl ester-acrylic acid alkyl ester binary block copolymer having an acrylic acid alkyl ester monomer polymerized from the living active terminal of the polymethacrylic acid alkyl ester and having a living active terminal.
• Examples of the above-mentioned polymerization initiator include organometallic compounds such as organolithium compounds and organometallic complexes.
• organic metal complex examples include rare earth metal complexes having a pentamethylcyclopentadienyl group as a ligand, for example, bis (pentamethylcyclopentadienyl) samarium methyltetrahydrofuranate and bis (pentamethylcyclopentadienyl) ittriummethyl. Examples include tetrahydrofuranate. Further, these organometallic complexes may be used in combination with alkylaluminums such as trimethylaluminum.
• organic lithium compound examples include alkyllithium such as t-butyllithium and a compound obtained by reacting alkyllithium with 1,1-diphenylethylene, diphenylmethane and the like.
• these organolithium compounds for example, an inorganic salt such as lithium chloride, a lithium salt of alcoholide such as lithium 2- (2-methoxyethoxy) ethoxide, and diisobutyl (2,6-di-t-butyl-4-methylphenoxy). It may be used in combination with an organoaluminum compound such as aluminum. ..
• a hydrocarbon solvent such as benzene, toluene and xylene
• a halogenated hydrocarbon solvent such as chloroform, methylene chloride and carbon tetrachloride
• an ether solvent such as tetrahydrofuran and diethyl ether
• the acrylic pressure-sensitive adhesive resin containing the acrylic block copolymer it is preferable that 30 to 100% by mass is occupied by the acrylic pressure-sensitive adhesive resin containing the acrylic block copolymer, and 50 to 95% by mass is based on the total pressure-sensitive adhesive resin used for the pressure-sensitive adhesive layer in the present invention. It is more preferable to occupy an acrylic pressure-sensitive adhesive resin containing an acrylic block copolymer.
• the main component of the pressure-sensitive adhesive resin used for the pressure-sensitive adhesive layer in the present invention preferably contains an acrylic block copolymer, and more preferably contains a tri-block copolymer represented by the above general formula (1).
• the acrylic pressure-sensitive adhesive resin other than the triblock copolymer represented by the general formula (1) is not particularly limited, and the following acrylic pressure-sensitive adhesive resin, the following rubber-based pressure-sensitive adhesive resin, and the like can be used. It may be included.
• the acrylic pressure-sensitive adhesive resin other than the above-mentioned acrylic-based triblock copolymer is not particularly limited and may be appropriately selected depending on the intended purpose.
• an acrylic polymer and a pressure-imparting resin or a cross-linked resin can be used as necessary.
• examples thereof include those containing additives such as agents.
• the acrylic polymer has a chemical structure other than the triblock copolymer represented by the general formula (1), and can be produced, for example, by polymerizing a (meth) acrylate monomer.
• a (meth) acrylate monomer for example, an alkyl (meth) acrylate having an alkyl group having 1 to 12 carbon atoms can be used.
• alkyl (meth) acrylate having an alkyl group having 1 to 12 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-.
• alkyl (meth) acrylate having an alkyl group having 1 to 12 carbon atoms it is preferable to use an alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms, and an alkyl having 4 to 8 carbon atoms is preferable. It is more preferable to use an alkyl (meth) acrylate having a group, and it is particularly preferable to use an n-butyl acrylate in order to ensure excellent adhesion to an adherend.
• the alkyl (meth) acrylate having an alkyl group having 1 to 12 carbon atoms is preferably used in the range of 0 to 50% by mass with respect to the total amount of the monomers used in the production of the acrylic polymer, and is 0. It is more preferable to use it in the range of about 30% by mass.
• a highly polar vinyl monomer can be used if necessary.
• Examples of the highly polar vinyl monomer include (meth) acrylic monomers having a hydroxyl group, (meth) acrylic monomers having a carboxyl group, and (meth) acrylic monomers having an amide group.
• examples thereof include acrylic monomers, vinyl acetates, ethylene oxide-modified amber acid acrylates, and sulfonic acid group-containing monomers such as 2-acrylamide-2-methylpropansulphonic acid. These may be used alone or in combination of two or more.
• vinyl monomer having a hydroxyl group examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate.
• examples include (meth) acrylic monomers.
• the vinyl monomer having a hydroxyl group is preferably used when a pressure-sensitive adhesive resin containing an isocyanate-based cross-linking agent is used.
• a pressure-sensitive adhesive resin containing an isocyanate-based cross-linking agent is used as the vinyl monomer having a hydroxyl group.
• 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate are preferably used.
• the vinyl monomer having a hydroxyl group is preferably used in the range of 0.01 to 1.0% by mass with respect to the total amount of the monomers used in the production of the acrylic polymer, and is 0.03 to 0. It is more preferable to use it in the range of 3% by mass.
• vinyl monomer having a carboxyl group examples include (meth) acrylics such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, (meth) acrylic acid dimer, crotonic acid, and ethylene oxide-modified amber acid acrylate. Examples include monomers. Of these, acrylic acid is preferable.
• vinyl having an amide group examples include (meth) acrylic monomers such as N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, acrylamide, N, N-dimethylacrylamide and the like.
• the highly polar vinyl monomer is preferably used in the range of 1.5 to 20% by mass, preferably in the range of 1.5 to 10% by mass, based on the total amount of the monomers used in the production of the acrylic polymer. It is more preferable to use it in the range of 2 to 8% by mass because an adhesive layer having a good balance in terms of cohesive force, holding power and adhesiveness can be formed.
• the method for producing the above-mentioned acrylic polymer is not particularly limited, and can be appropriately selected from known methods according to the intended purpose.
• the monomer is selected by a solution polymerization method, a massive polymerization method, or a suspension weight.
• examples thereof include a method of polymerizing by a polymerization method such as a legal method or an emulsion polymerization method.
• the acrylic polymer is preferably produced by a solution polymerization method or a bulk polymerization method.
• a peroxide-based thermal polymerization initiator such as benzoyl peroxide or lauroyl peroxide, an azo thermal polymerization initiator such as azobisisobutylnitrile, an acetophenone-based photopolymerization initiator, or benzoin.
• Ether-based photopolymerization initiators, benzylketal-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzophenone-based photopolymerization initiators, and the like can be used.
• the weight average molecular weight of the acrylic polymer obtained by the above method is the weight average molecular weight measured in terms of standard polystyrene using a gel permeation chromatograph (GPC) under the same method and conditions as for the triblock copolymer. , 300,000 to 3 million, and more preferably 500,000 to 2.5 million.
• GPC gel permeation chromatograph
• the acrylic pressure-sensitive adhesive resin other than the above-mentioned acrylic-based triblock copolymer it is preferable that 0 to 40% by mass is occupied by the acrylic pressure-sensitive adhesive resin other than the above-mentioned acrylic-based triblock copolymer, and 0 to 1% by mass is , It is more preferable to occupy an acrylic pressure-sensitive adhesive resin other than the above-mentioned acrylic triblock copolymer.
• the content of the acrylic pressure-sensitive adhesive resin other than the acrylic-based triblock copolymer in the pressure-sensitive adhesive layer in the present invention is within the above range, the initial adhesiveness is improved while maintaining removability and high load holding force. Easy to make.
• the rubber-based pressure-sensitive adhesive resin is not particularly limited, and includes rubber materials that can be generally used as pressure-sensitive adhesive resins such as synthetic rubber-based pressure-sensitive adhesive resins and natural rubber-based pressure-sensitive adhesive resins, and, if necessary, tack-imparting resins and the like. Examples include those containing additives.
• the rubber material examples include a block copolymer of an aromatic vinyl compound and a conjugated diene compound, specifically, a styrene-isoprene copolymer, a styrene-isoprene-styrene copolymer, and a styrene-isoprene-butadiene-styrene.
• styrene-based resins such as copolymers, styrene-butadiene-styrene copolymers, styrene-ethylene-butylene copolymers, styrene-ethylene-propylene copolymers and their hydrogenated additives.
• styrene resins may be used alone or in combination of two or more.
• the styrene resin for example, a single structure having a linear structure, a branched structure, or a multi-branched structure may be used, or a mixture of different structures may be used.
• the adhesive tape can be provided with excellent adhesive performance.
• a branched structure or a multi-branched structure in which a styrene block is arranged at the molecular end can have a pseudo-crosslinked structure and can give an excellent cohesive force, so that a high holding force can be given. can. Therefore, it is preferable to mix and use the styrene resin according to the required characteristics.
• the styrene resin it is preferable to use a resin having a structural unit represented by the following chemical formula (B) in the range of 10 to 80% by mass with respect to the total mass of the styrene resin, and 12 to 60. It is more preferable to use one having a mass in the range of 15 to 40% by mass, further preferably to use one having a range of 15 to 40% by mass, and particularly preferably to use one having a range of 17 to 35% by mass. .. Thereby, excellent adhesiveness and heat resistance can be obtained.
• B chemical formula
• the entire pressure-sensitive adhesive resin used for the pressure-sensitive adhesive layer in the present invention it is preferable that 0 to 50% by mass is occupied by the rubber-based pressure-sensitive adhesive resin, and 0 to 30% by mass is occupied by the rubber-based pressure-sensitive adhesive resin. More preferred.
• the content of the rubber-based pressure-sensitive adhesive resin in the pressure-sensitive adhesive layer of the present invention is within the above range, it is easy to achieve both adhesiveness, dismantability, and high load holding force.
• Aromatic vinyl adhesive resin containing styrene block copolymer is not particularly limited, and is generally used as a synthetic rubber-based pressure-sensitive adhesive resin or a natural rubber-based pressure-sensitive adhesive resin. Examples thereof include a rubber material that can be used as a pressure-sensitive adhesive resin, and a material containing an additive such as a pressure-sensitive adhesive resin, if necessary.
• the aromatic vinyl-based pressure-sensitive adhesive resin other than the styrene-based block copolymer preferably contains, for example, a block copolymer of a monovinyl-substituted aromatic compound and a conjugated diene compound as a base polymer.
• the monovinyl-substituted aromatic compound refers to a compound in which one functional group having a vinyl group is bonded to an aromatic ring.
• a typical example of the aromatic ring is a benzene ring (which may be a benzene ring substituted with a functional group having no vinyl group (for example, an alkyl group)).
• the monovinyl-substituted aromatic compound examples include styrene, ⁇ -methylstyrene, vinyltoluene, vinylxylene and the like.
• the conjugated diene compound examples include 1,3-butadiene, isoprene and the like. Such block copolymers can be used alone or in combination of two or more as a base polymer.
• the copolymerization ratio of the monovinyl-substituted aromatic compound (two or more thereof can be used in combination) is 70% by mass or more (more preferably 90% by mass or more). It may be substantially 100% by mass.).
• the copolymerization ratio of the conjugated diene compound (two or more thereof can be used in combination) is 70% by mass or more (more preferably 90% by mass or more), which is substantially the same. It may be 100% by mass.). According to such a block copolymer, a higher performance adhesive tape can be realized.
• the block copolymer may be in the form of a diblock body, a triblock body, a radial body, a mixture thereof, or the like.
• the A segment for example, styrene block
• the A-segments arranged at the ends of the polymer chains are likely to gather to form a domain, thereby forming a pseudo-crosslinked structure and improving the cohesiveness of the pressure-sensitive adhesive.
• the diblock ratio is 30% by mass or more (more preferably 40% by mass) from the viewpoint of adhesive strength (peeling strength) to the adherend and repulsion resistance.
• adhesive strength peeling strength
• those having a diblock body ratio of 90% by mass or less can be preferably used.
• the base polymer is a styrene-based block copolymer.
• the base polymer contains at least one of a styrene isoprene block copolymer and a styrene butadiene block copolymer.
• the proportion of styrene-isoprene block copolymer is 70% by mass or more, the proportion of styrene-butadiene block copolymer is 70% by mass or more, or
• the total ratio of the styrene-isoprene block copolymer and the styrene-butadiene block copolymer is preferably 70% by mass or more.
• substantially all (eg, 95-100% by weight) of the styrene-based block copolymer is a styrene isoprene block copolymer.
• substantially all (eg, 95-100% by weight) of the styrene-based block copolymer is a styrene-butadiene block copolymer. According to such a composition, an adhesive tape having excellent repulsion resistance and a good balance with other adhesive properties can be preferably realized.
• the styrene-based block copolymer may be in the form of a diblock body, a triblock body, a radial body, a mixture thereof, or the like.
• the styrene block is arranged at the end of the polymer chain. This is because the styrene blocks arranged at the ends of the polymer chains are likely to gather to form a styrene domain, thereby forming a pseudo-crosslinked structure and improving the cohesiveness of the pressure-sensitive adhesive.
• the diblock ratio is 30% by mass or more (more preferably) from the viewpoint of adhesive strength (peeling strength) to the adherend and repulsion resistance. Is 40% by mass or more, more preferably 50% by mass or more, particularly preferably 60% by mass or more, and typically 65% by mass or more). A styrene-based block copolymer having a diblock ratio of 70% by mass or more (for example, 75% by mass or more) may be used.
• a styrene-based block copolymer having a diblock compound ratio of 90% by mass or less (more preferably 85% by mass or less, for example, 80% by mass or less) can be preferably used.
• a styrene-based block copolymer having a diblock ratio of 60 to 85% by mass can be preferably adopted.
• the styrene content of the styrene-based block copolymer can be, for example, 5 to 40% by mass. From the viewpoint of repulsion resistance and holding power, a styrene-based block copolymer having a styrene content of 10% by mass or more (more preferably larger than 10% by mass, for example, 12% by mass or more) is usually preferable. Further, from the viewpoint of adhesive strength to the adherend, the copolymer weight of the styrene-based block having a styrene content of 35% by mass or less (typically 30% by mass or less, more preferably 25% by mass or less, for example, less than 20% by mass). Coalescence is preferred. For example, a styrene-based block copolymer having a styrene content of 12% by mass or more and less than 20% by mass can be preferably adopted.
• the aromatic vinyl pressure-sensitive adhesive resin containing a styrene-based block copolymer it is more preferable to occupy the aromatic vinyl pressure-sensitive adhesive resin containing a styrene-based block copolymer.
• the content of the aromatic vinyl pressure-sensitive adhesive resin containing the styrene-based block copolymer in the pressure-sensitive adhesive layer of the present invention is 50% by mass or more, it is easy to maintain removability and high load holding power.
• the content of the acrylic pressure-sensitive adhesive resin containing the acrylic block copolymer is 50% by mass or more, it is easy to maintain removability and high load holding force.
• a styrene-based block copolymer as the main component of the pressure-sensitive adhesive resin used for the pressure-sensitive adhesive layer in the present invention.
• the aromatic vinyl-based pressure-sensitive adhesive resin other than the styrene-based block copolymer is not particularly limited, and may include the above-mentioned acrylic-based pressure-sensitive adhesive resin, the above-mentioned rubber-based pressure-sensitive adhesive resin, and the like.
• the pressure-sensitive adhesive layer of the present embodiment contains a pressure-imparting resin.
• the tackifier resin is preferably used in order to improve the adhesion to the adherend and the surface adhesive strength.
• the tackifier resin of the present embodiment preferably has a softening point of 95 ° C. or higher. More preferably, the softening point is 95 ° C. to 180 ° C., and more preferably 95 ° C. to 140 ° C. for forming an adhesive layer having high adhesive performance.
• the glass transition temperature thereof is preferably 30 ° C. to 200 ° C., more preferably 50 ° C. to 160 ° C.
• tackifier resin examples include rosin-based tackifier resin, polymerized rosin-based tackifier resin, polymerized rosin ester-based tackifier resin, rosinphenol-based tackifier resin, stabilized rosin ester-based tackifier resin, and disproportionate.
• examples thereof include a rosin ester-based tackifier resin, a hydrogenated rosin ester-based tackifier resin, a terpene-based tackifier resin, a terpenphenol-based tackifier resin, a petroleum resin-based tackifier resin, and a (meth) acrylate-based tackifier resin.
• the tackifier resins are polymerized rosin ester-based tackifier resins, rosinphenol-based tackifier resins, disproportionate rosin ester-based tackifier resins, hydrogenated rosin ester-based tackifier resins, terpenphenol resins, (meth). ) Phenolic resins are preferred.
• rosin-based tackifier resin examples include unmodified rosins (raw rosins) such as gum rosin, wood rosin, and tall oil rosin; modified rosins obtained by modifying these unmodified rosins by hydrogenation, disproportionation, polymerization, or the like. (Hydrogenized rosin, disproportionated rosin, polymerized rosin, other chemically modified rosin, etc. The same shall apply hereinafter.); Other various rosin derivatives; etc. may be mentioned.
• rosin derivatives examples include rosins in which unmodified rosin is esterified with alcohols (that is, rosin esterified product) and modified rosin is esterified with alcohols (that is, modified rosin esterified product).
• Esters Unmodified rosins and unsaturated fatty acid-modified rosins obtained by modifying modified rosins with unsaturated fatty acids; Unsaturated fatty acid-modified rosin esters modified from rosin esters with unsaturated fatty acids; Unmodified rosins, modified rosins, unsaturated Rosin alcohols obtained by reducing the carboxy group in fatty acid-modified rosins or unsaturated fatty acid-modified rosin esters; metal salts of rosins (particularly rosin esters) such as unmodified rosins, modified rosins, and various rosin derivatives; rosins.
• Examples thereof include a rosin phenol resin obtained by adding phenol to (unmodified rosin, modified rosin, various rosin derivatives, etc.) with an acid catalyst and thermally polymerizing the rosin.
• a rosin-based tackifier resin When an acrylic polymer is used as the base polymer, it is preferable to use a rosin-based tackifier resin. From the viewpoint of improving the adhesive properties such as adhesive strength, it is more preferable to use two or three or more kinds of the rosin-based tackifying resins having different types and characteristics (for example, softening points) in combination.
• terpene resins such as ⁇ -pinene polymer, ⁇ -pinene polymer, and dipentene polymer; these terpene resins are modified (phenolic modification, aromatic modification, hydrogenation modification, hydrocarbonation). Modified terpene resin (hydrocarbon-modified, etc.); etc.
• modified terpene resin include terpene-modified phenolic resin, styrene-modified terpene resin, aromatic-modified terpene resin, hydrogenated terpene resin and the like.
• a krill polymer When a krill polymer is used as the base polymer, it is preferable to use a terpene-based tackifier resin (for example, a terpene-modified phenol resin).
• a terpene-based tackifier resin for example, a terpene-modified phenol resin
• one or more of the above terpene-based tackifying resins for example, terpene-modified phenolic resins
• characteristics for example, softening points
• hydrocarbon-based tackifier resins examples include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic / aromatic petroleum resins (styrene-olefin copolymers, etc.) ), Various hydrocarbon-based resins such as aliphatic / alicyclic petroleum resins, hydrogenated hydrocarbon resins, kumaron-based resins, and kumaron-inden-based resins.
• tackifier resin As the tackifier resin, a tackifier resin having a softening point (softening temperature) of 95 ° C. or higher can be preferably used. According to the pressure-sensitive adhesive containing the pressure-sensitive adhesive resin having a softening point equal to or higher than the above-mentioned lower limit value, a pressure-sensitive adhesive tape having more excellent adhesive strength can be realized.
• a terpene-based tackifier resin having the above softening point for example, a terpene-modified phenol resin
• a rosin-based tackifier resin for example, an esterified product of a polymerized rosin
• the upper limit of the softening point of the tackifier resin is not particularly limited, and can be, for example, about 200 ° C. or lower.
• the softening point of the tackifier resin referred to here is defined as a value measured by the softening point test method (ring ball method) specified in any of JIS K 5902 and JIS K 2207.
• the amount of the tackifier resin used is not particularly limited and may be appropriately selected depending on the intended purpose, but it is preferably used in the range of 5 to 65 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive resin. , 8 to 55 parts by mass is more preferable because it is easy to secure the adhesion with the adherend.
• the pressure-sensitive adhesive resin containing the acrylic block copolymer or the styrene-based block copolymer of the present embodiment it is preferable to use a pressure-sensitive adhesive resin containing a cross-linking agent in order to further improve the cohesive force of the pressure-sensitive adhesive layer. ..
• the above-mentioned cross-linking agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, metal chelate-based cross-linking agents, and aziridine-based cross-linking agents. These may be used alone or in combination of two or more.
• the cross-linking agent is preferably a type of cross-linking agent that is mixed after the production of the acrylic polymer to allow the cross-linking reaction to proceed, and an isocyanate-based cross-linking agent and an epoxy-based cross-linking agent having high reactivity with the acrylic polymer are used. Is more preferable.
• Examples of the isocyanate-based cross-linking agent include tolylene diisocyanate, triphenylmethane isocyanate, naphthylene-1,5-diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and trimethylolpropane-modified tolylene diisocyanate. These may be used alone or in combination of two or more. Among these, tolylene diisocyanate, which is a trifunctional polyisocyanate compound, trimethylolpropane adduct thereof, and triphenylmethane isocyanate are particularly preferable.
• the value of the gel fraction for measuring the insoluble content after immersing the adhesive layer in toluene for 24 hours is used.
• the gel fraction of the adhesive layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 to 70% by mass, more preferably 25 to 65% by mass, and 35 to 60% by mass. It is more preferable to obtain an adhesive layer having good cohesiveness and adhesiveness.
• the gel fraction refers to the value measured by the following method.
• An adhesive resin containing an adhesive resin and, if necessary, an additive is applied onto the release sheet so that the thickness after drying is 50 ⁇ m, dried at 100 ° C. for 3 minutes, and dried at 40 ° C. Aged for 2 days is cut into 50 mm squares and used as a sample.
• the mass (G1) of the sample before immersion in toluene was measured in advance, and the toluene-insoluble component of the sample after being immersed in a toluene solution at 23 ° C. for 24 hours was separated by filtering with a 300 mesh wire net.
• the mass (G2) of the residue after drying at 110 ° C. for 1 hour is measured, and the gel fraction is determined according to the following formula (4).
• the mass (G3) of the conductive fine particles in the sample is calculated from the mass (G1) of the sample and the composition of the pressure-sensitive adhesive composition.
• Gel fraction (mass%) (G2-G3) / (G1-G3) x 100 ...
• the other components in the pressure-sensitive adhesive layer of the present embodiment are not particularly limited and may be appropriately selected as long as the characteristics of the pressure-sensitive adhesive tape are not impaired.
• a polymer component other than the pressure-sensitive adhesive resin, a cross-linking agent, and an anti-aging agent for example, a polymer component other than the pressure-sensitive adhesive resin, a cross-linking agent, and an anti-aging agent.
• UV absorbers fillers, polymerization inhibitors, surface modifiers, antistatic agents, defoamers, viscosity modifiers, light stabilizers, weather stabilizers, heat stabilizers, antioxidants, leveling agents, organic pigments, Additives such as inorganic pigments, pigment dispersants, plasticizers, softeners, flame retardants, metal defoamers, silica beads, organic beads, etc .; Inorganic fillings such as silicon oxide, aluminum oxide, titanium oxide, zirconia, antimony pentoxide, etc. Examples include agents. These may be used alone or in combination of two or more.
• the content of other components in the adhesive layer of the present embodiment can be appropriately selected as long as the characteristics of the adhesive tape are not impaired.
• the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape of the present embodiment preferably contains a filler, a pressure-imparting resin, and a pressure-sensitive adhesive resin.
• the pressure-sensitive adhesive composition which is a precursor of the pressure-sensitive adhesive layer preferably contains a filler.
• the filler is exposed from the pressure-sensitive adhesive layer when the pressure-sensitive adhesive tape is stretched, whereby the adhesive area between the pressure-sensitive adhesive layer and the adherend is small. Become. Therefore, the extension direction of the adhesive tape is at a relatively large angle with respect to the attachment surface of the adherend (hereinafter, also referred to as "adhesive surface"), for example, the vertical direction (sometimes referred to as "90 ° direction"). Even when the adhesive tape is stretched at a high speed, the adhesive tape can be peeled off more easily and more quickly.
• the type of the above filler is not particularly limited and may be appropriately selected as long as the effect of the present invention is not impaired, and may be an inorganic filler or an organic filler. These may be used alone or in combination of two or more.
• the inorganic filler examples include aluminum hydroxide, magnesium hydroxide, aluminum oxide, silicon oxide, magnesium oxide, zinc oxide, titanium oxide, zirconium oxide, iron oxide, silicon carbide, boron nitride, aluminum nitride, titanium nitride, and the like.
• silicon nitride titanium boring, carbon, nickel, copper, aluminum, titanium, gold, silver, zirconium hydroxide, basic magnesium carbonate, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, tin oxide, tin oxide Hydrate, borosand, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate-calcium, calcium carbonate, barium carbonate, molybdenum oxide, antimony oxide, red phosphorus, mica, clay, kaolin, talc, zeolite , Wollastonite, smectite, silica (quartz, fumed silica, precipitated silica, silicic anhydride, molten silica, crystalline silica, ultrafine atypical silica, etc.), potassium titanate, magnesium sulfate, sepiolite, zonolite, hoe Aluminum oxide, barium sulfate, barium titanate, zirconia oxide,
• the inorganic filler may be subjected to a surface treatment such as a silane coupling treatment or a stearic acid treatment in order to improve the dispersibility in the pressure-sensitive adhesive resin.
• organic fillers include polystyrene-based fillers, benzoguanamine-based fillers, polyethylene-based fillers, polypropylene-based fillers, silicone-based fillers, urea-formalin-based fillers, styrene / methacrylic acid copolymers, fluorine-based fillers, and acrylic-based fillers.
• the silicone-based filler is specifically a silicone rubber particle obtained by three-dimensionally cross-linking a linear organopolysiloxane (Japanese Patent Laid-Open No. 63-77942, JP-A-3-). 93834 (see JP-A-04-198324), powdered silicone rubber (see US Pat. No. 3,843,601, JP-A-62-270660, JP-A-59-96,122). ) Etc. can be used. Further, the surface of the silicone rubber particles obtained by the above method is formed into a three-dimensional network represented by (R'SiO 3/2 ) n (R'represents a substituted or unsubstituted monovalent hydrocarbon group). Silicone composite particles having a structure coated with a silicone resin, which is a cured product of polyorganosylsesquioxane having a crosslinked structure (see JP-A-7-196815) can also be used.
• silicone particles examples include Trefil E-500, Trefil E-600, Trefil E-601, and Trefil E-850 from Toray Dow Corning Silicone Co., Ltd. under the above trade names, and KMP-600, respectively.
• KMP-601, KMP-602, KMP-605 and the like commercially available from Shin-Etsu Chemical Co., Ltd. can be used.
• acrylic-modified silicone particles can be used as another silicone-based filler.
• acrylic-modified silicone particles include a polyorganosiloxane represented by the following general formula (C), an acrylic acid-based ester monomer and / or a methacrylic acid-based ester monomer, and a functional group-containing simple copolymer capable of copolymerizing the polyorganosiloxane.
• examples thereof include an emulsified graft polymer with a monomer.
• R 5 and R 6 independently represent substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms or aryl groups having 6 to 20 carbon atoms, and X 1 and X 2 respectively.
• X 3 , X 4 , X 5 , and X 6 are independently substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and alkoxy groups having 1 to 20 carbon atoms, respectively.
• Y 1 and Y 2 independently indicate a group represented by X 1 or-[O-Si (X 7 ) (X 8 )] c- X 9 , X 7 , X 8 , and X 9 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group or a hydroxyl group having 1 to 20 carbon atoms, X 1, At least two groups in X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , and X 9 and Y 1 and Y 2 are hydroxyl groups, where a, b, and c are respectively.
• the alkyl group of R 5 or 1 to 20 carbon atoms represented by R 6 is a straight-chain It may be in the form of a branched chain, or in the form of a ring.
• alkyl groups may be substituted with a halogen atom, an acryloxy group, a metharoxy group, a carboxy group, an alkoxy group, an alkenyloxy group, an amino group, an alkyl, an alkoxy or a (meth) acryloxy-substituted amino group.
• Examples of the aryl group having 6 to 20 carbon atoms represented by R 5 or R 6 include a phenyl group, a tolyl group, a naphthyl group and the like.
• R 5 or R 6 is preferably a methyl group.
• the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by X 1 to X 9 are the alkyl group and the aryl group exemplified by R 5 or R 6. Similar groups can be mentioned for each.
• Examples of the alkoxy group having 1 to 20 carbon atoms represented by X 1 to X 9 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a tetradecyloxy group.
• the group etc. can be mentioned.
• a, b and c are positive numbers of 0 ⁇ a ⁇ 1,000, 100 ⁇ b ⁇ 10,000, and 1 ⁇ c ⁇ 1,000. Is preferably a positive number from 0 to 200. When a becomes larger than 1,000, the strength of the obtained film becomes insufficient.
• b is preferably a positive number from 1,000 to 5,000. If b is less than 100, the flexibility of the film becomes poor, and if it is larger than 10,000, it becomes difficult to become a solid like particles.
• c is preferably a positive number from 1 to 200.
• the polyorganosiloxane represented by the general formula (C) has at least two, preferably 2 to 4 hydroxyl groups in one molecule from the viewpoint of crosslinkability, and the hydroxyl groups are located at both ends of the molecular chain. It is preferable to have.
• acrylic acid-based ester monomer or methacrylic acid-based ester monomer examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, and methacrylic. Cyclohexyl acid acid and the like can be mentioned.
• the functional group-containing monomer copolymerizable with the acrylic acid-based ester monomer and / or the methacrylate-based ester monomer does not contain a carboxyl group, an amide group, a hydroxyl group, a vinyl group, an allyl group, or the like. Examples thereof include monomers having a saturated bond.
• the acrylic-modified silicone powder contains 10 to 100 parts by mass of an acrylic acid ester monomer and / or a methacrylic acid ester monomer with respect to 100 parts by mass of the polyorganosiloxane represented by the general formula (4). It is preferable that 0.01 to 20 parts by mass of a copolymerizable functional group-containing monomer is mixed and obtained by emulsifying graft polymerization.
• the conditions in the emulsified graft polymerization are not particularly limited, and as the initiator used in the polymerization, a known radical initiator usually used for an acrylic polymer can be used. Further, as the emulsifier, a known anionic surfactant or nonionic surfactant can be used.
• the above-mentioned acrylic-modified silicone particles are granulated and powdered by the methods listed below. That is, spray-dry drying, air-flow drying, and the like can be mentioned, but a spray dryer is preferable in consideration of productivity.
• the powdering is preferably hot-dried and preferably treated at 80 to 150 ° C.
• acrylic-modified silicone particles for example, commercially available products such as Charine R-170S and Charine R-200 (all manufactured by Nisshin Kagaku Kogyo Co., Ltd.) can be used.
• the shape of the filler of the present embodiment is not particularly limited and may be appropriately selected depending on the intended purpose, and may be a regular shape or an irregular shape.
• Specific examples of the shape of the filler include polygonal shape, cubic shape, elliptical shape, spherical shape, needle shape, flat plate shape, and scale shape.
• the fillers having these shapes may be used alone or in combination of two or more. Further, the fillers having these shapes may be aggregated.
• the shape of the filler is preferably elliptical, spherical, or polygonal. When the filler shape is elliptical, spherical, polygonal, or the like, when the adhesive tape is stretched, the adhesive layer slides well to the adherend, and the adhesive tape can be peeled off more easily and more quickly. Can be done.
• the particle size distribution (D90 / D10) of the filler of the present embodiment is not particularly limited and may be appropriately selected depending on the intended purpose, but 2.5 to 20 is preferable, and in terms of impact resistance, 2. 5 to 15 is more preferable, and 2.5 to 5 is even more preferable.
• the adhesive tape can be peeled off more easily and more quickly, and it is difficult to tear even when the thickness of the base material of the adhesive tape is thin. Moreover, it is excellent in impact resistance, shear adhesive strength, and split adhesive strength.
• the particle size distribution (D90 / D10) of the filler is less than 2.5, the elongation peelability may be impaired, and if it exceeds 20, the adhesive performance such as impact resistance, shear adhesive force, and split adhesive force may be impaired. May be damaged.
• the particle size distribution (D90 / D10) of the filler of the present embodiment is converted into a particle size distribution by measuring the average particle size of the filler by using, for example, a measuring machine (microtrack) using a laser diffraction / scattering method. It can be obtained by.
• the average particle size of the filler of the present embodiment is 0.1 to 40 ⁇ m, preferably 5 to 40 ⁇ m, more preferably 10 to 35 ⁇ m, still more preferably 10 to 30 ⁇ m, and particularly preferably 10 to 10 to 30 ⁇ m. It is 25 ⁇ m.
• the adhesive tape can be peeled off more easily and more quickly, and even if the thickness of the base material of the adhesive tape is thin, it is difficult to tear and is resistant to tearing. Excellent impact resistance, shear adhesive strength, and split adhesive strength.
• the particle size of the filler is less than 0.1 ⁇ m, the elongation peelability may be impaired, and if it exceeds 40 ⁇ m, the adhesive performance such as impact resistance, shear adhesive force, and split adhesive force may be impaired. ..
• the average particle size of the filler of the present embodiment refers to the volume average particle size, and can be measured by using, for example, a measuring machine (microtrack) using a laser diffraction / scattering method.
• the average particle size of the silicone rubber particles or the silicone composite particles is preferably 0.1 to 40 ⁇ m, more preferably 0.1 to 40 ⁇ m. It is 5 to 40 ⁇ m. If the average particle size is less than 0.1 ⁇ m, the effect of reducing the adhesive area by the filler when the adhesive tape is stretched tends to decrease, and if it is larger than 40 ⁇ m, the adhesive force of the adhesive tape tends to decrease. be.
• the average particle size of the acrylic-modified silicone particles is preferably 0.1 to 40 ⁇ m, more preferably 5 to 40 ⁇ m. It is more preferably 5 to 30 ⁇ m, and even more preferably 10 to 25 ⁇ m. If the average particle size is less than 0.1 ⁇ m, the effect of reducing the adhesive area by the filler when the adhesive tape is stretched tends to decrease, and if it is larger than 40 ⁇ m, the adhesive force of the adhesive tape tends to decrease. be.
• the ratio of the average particle size of the filler of the present embodiment to the average thickness of the adhesive layer is not particularly limited and may be appropriately selected depending on the intended purpose.
• the ratio of the average particle size of the filler to the average thickness of the adhesive layer represented by [average thickness] is preferably 5/100 or more, and more preferably 5/100 to 95/100. 10/100 to 75/100 is more preferable, and 20/100 to 60/100 is particularly preferable.
• the ratio is 5/100 or more, the adhesive tape can be peeled off more easily and more quickly, and even when the thickness of the base material of the adhesive tape is thin, it is difficult to tear. Further, it is advantageous in that the ratio is 95/100 or less, and the adhesive performance such as impact resistance, shear adhesive force, and split adhesive force is more excellent.
• the content of the filler in the pressure-sensitive adhesive layer of the present embodiment is preferably 0 to 300% by mass, more preferably 1 to 100% by mass, and 10 to 70% by mass with respect to 100% by mass of the pressure-sensitive adhesive resin. It is preferably%, and more preferably 20 to 50% by mass.
• the content of the filler with respect to 100% by mass of the pressure-sensitive adhesive resin is 1% by mass or more, the pressure-sensitive adhesive tape can be peeled off more easily and more quickly.
• the content of the filler with respect to 100% by mass of the pressure-sensitive adhesive resin is 50% by mass or less, the pressure-sensitive adhesive composition may remain on the adherend, the impact resistance may be deteriorated, and the shear adhesive strength may be increased. It is possible to prevent the split adhesive strength from being weakened.
• the content of the filler in the pressure-sensitive adhesive layer of the present embodiment can be appropriately adjusted when preparing the pressure-sensitive adhesive composition which is a precursor of the pressure-sensitive adhesive layer.
• the content of the silicone rubber particles or the silicone composite particles is preferably 20 to 70% by mass with respect to 100% by mass of the adhesive layer.
• the content of the acrylic-modified silicone particles is preferably 20 to 70% by mass with respect to 100% by mass of the adhesive layer.
• the volume ratio of the filler to the total volume of the adhesive layer of the present embodiment is preferably 4 to 40%, more preferably 5 to 30%, further preferably 5 to 20%, and most preferably 5 to 15%.
• the volume ratio of the filler is 4% or more, the adhesive tape can be peeled off more easily and more quickly. Further, when the volume ratio of the filler is 40% or less, the adhesive layer remains on the adherend, the impact resistance is deteriorated, and the shear adhesive force and the split adhesive force are weakened. Can be prevented.
• the volume ratio of the filler to the adhesive layer can be calculated from the following formulas (1) to (3).
• Adhesive resin * 1 mass A (g) / adhesive resin * 1 Density A (g / cm 3) adhesive resin * 1 volume A (cm 3) ⁇ ⁇ ⁇ Equation (1)
• Filler mass B (g) / Filler density B (g / cm 3 ) Filler volume B (cm 3 ) ⁇ ⁇ ⁇ Formula (2)
• x 100 Filler volume ratio (%) ...
• the pressure-sensitive adhesive resin represented by * 1 in the above formulas (1) and (3) may contain other components described later.
• the density is a value measured according to JIS Z 8804.
• the adhesive tape of the present embodiment may be provided with one or more layers as appropriate depending on the purpose.
• the other layer include a primer layer, an antistatic layer, a non-combustible layer, a decorative layer, a conductive layer, a heat conductive layer, and a release layer.
• the shape and dimensions of the adhesive tape of the present embodiment are not particularly limited as long as it includes a base material layer and an adhesive layer on at least one surface of the base material layer.
• a predetermined adherend for example, Adhesive tape with a shape and dimensions suitable for sticking to (for example, adhesive tape in the state after punching), and long sheet-like adhesive tape (for example, adhesive tape before being processed into a specific shape) ) Is included.
• the adhesive tape of the present embodiment can optionally be provided with a non-adhesive gripping area for, for example, attachment to or peeling from the adherend.
• the (average) thickness of the adhesive tape is not particularly limited and may be appropriately selected depending on the (average) thickness of the adhesive layer and the base material layer, but is preferably 15 to 800 ⁇ m, and is preferably 30. It is more preferably ⁇ 540 ⁇ m, further preferably 60 to 320 ⁇ m, and particularly preferably 70 to 250 ⁇ m.
• the "thickness of the adhesive tape” means that the adhesive tape is cut at 5 points in the length direction at 100 mm intervals and 5 points in the width direction, and 5 points at 100 mm intervals in the width direction on each cut surface.
• the thickness of the adhesive layer is measured using a TH-104 paper / film thickness measuring machine (manufactured by Tester Sangyo Co., Ltd.), and refers to the average value of a total of 25 points.
• the hardness of the adhesive tape (type A hardness (shore A hardness)) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 to 90, more preferably 20 to 85, and 64 to 85. More preferred.
• the removability work by peeling off the adhesive tape becomes easy.
• the Shore A hardness is less than 10
• the adhesive tape may be torn when the adhesive tape is stretched and peeled off, and if it exceeds 90, the adhesive tape is stretched to try to be peelable again.
• the stress for stretching may become too high to be removable.
• the rubber hardness of the adhesive tape is Shore A hardness, and refers to a value measured in accordance with JIS K 6253 using a durometer (spring type rubber hardness tester) (model: GS-719G, manufactured by TECLOCK Co., Ltd.).
• the stress at 25% elongation of the adhesive tape is preferably 0.15 MPa to 82 MPa, more preferably 0.16 to 10 MPa, further preferably 0.17 to 5 MPa, and most preferably 0.18 to 4.5 MPa.
• the 25% elongation stress of the adhesive tape is 0.15 MPa to 82 MPa, it is possible to obtain an adhesive strength suitable for the adhesive tape, and it is possible to peel it off relatively easily even when the adhesive tape is stretched and peeled off.
• the adhesive tape may be peeled off when a load is applied in the shearing direction of the adhesive tape while fixing the hard adherends to each other. be.
• the stress at 25% elongation of the adhesive tape exceeds 82 MPa, the force required to extend the adhesive tape tends to be excessive when the adhesive tape is peeled off.
• the 25% elongation stress of the adhesive tape is obtained by punching the adhesive tape into a dumbbell shape with a marked line length of 20 mm and a width of 5 mm, and under the conditions of a measurement atmosphere of 23 ° C. and 50% RH, a Tencilon tensile tester (model: RTF-1210). , A & D Co., Ltd.), and refers to the stress value measured when the product is pulled in the length direction at a tensile speed of 500 mm / min and stretched by 25%.
• the breaking stress of the adhesive tape is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 to 100.0 MPa, more preferably 15 to 90.0 MPa, still more preferably 30 to 90.0 MPa. 40-90.0 MPa is particularly preferable.
• the breaking stress of the adhesive tape is within the above-mentioned preferable range, it is possible to prevent the adhesive tape from being torn even when the adhesive tape is quickly stretched and peeled off, and a load for stretching the adhesive tape. Is not excessive, so that the removability work by peeling becomes easy.
• the breaking stress of the adhesive tape is less than 10 MPa, the adhesive tape may be torn when the adhesive tape is stretched and peeled off quickly, and if it exceeds 100.0 MPa, the adhesive tape is stretched and peeled off again. If you try to get rid of it, you may not be able to stretch it sufficiently and you may not be able to re-peel it.
• the force required to stretch and deform the adhesive tape also depends on the thickness of the adhesive tape. For example, the adhesive tape having a thick adhesive tape and a high breaking stress is stretched and re-peeled. Even when trying to sexualize, it may not be sufficiently stretched and may not be removable.
• the breaking stress of the adhesive tape is such that the adhesive tape is punched into a dumbbell shape with a marked line length of 20 mm and a width of 5 mm, and the measurement atmosphere is 23 ° C. and 50% RH.
• a & D Co., Ltd. is used to pull in the length direction at a tensile speed of 500 mm / min, and refers to the stress value measured when it breaks.
• the breaking elongation of the adhesive tape is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 400% to 2000%, more preferably 500% to 1800%, still more preferably 600% to 1200%. ..
• the breaking elongation of the adhesive tape is 400% or more, even if the adhesive tape is firmly adhered to the adherend, when the adhesive tape is re-peelable, it is applied to the surface to which the adherend is attached. The stress for stretching in the horizontal direction to the vertical direction does not become too large, and the adhesive tape can be easily peeled off without being excessively stretched.
• the breaking elongation is 2000% or less
• the adhesive tape when the adhesive tape is re-peelable, the stretching distance in the horizontal direction to the vertical direction with respect to the attachment surface of the adherend does not become too long and in a small space. Work becomes possible.
• the elongation at break is less than 500%, the adhesive tape can be peeled off with breakage when it is stretched from the horizontal direction to the vertical direction with respect to the sticking surface of the adherend when the adhesive tape is re-peelable. If it exceeds 1300%, when the adhesive tape is re-peelable, the stretching distance from the horizontal direction to the vertical direction with respect to the sticking surface of the adherend becomes too long, resulting in poor workability. There is.
• the breaking elongation of the adhesive tape is determined by punching the adhesive tape into a dumbbell shape with a marked line length of 20 mm and a width of 5 mm, and under the conditions of a measurement atmosphere of 23 ° C. and 50% RH, a Tencilon tensile tester (model: RTF-1210, stock). (Manufactured by A & D Co., Ltd.) is used to pull in the length direction at a tensile speed of 500 mm / min, and refers to the tensile elongation measured when it breaks.
• the storage elastic modulus G'(23 ° C.) of the adhesive tape is preferably 1.0 ⁇ 10 4 to 1.0 ⁇ 10 8 Pa, preferably 5.0 ⁇ 10 4 to 5.0 ⁇ 10 7 Pa. More preferably, it is more preferably 1.0 ⁇ 10 5 to 1.0 ⁇ 10 7 Pa, and even more preferably 3.0 ⁇ 10 5 to 8.0 ⁇ 10 6 Pa.
• the breaking point stress of the adhesive tape is within the above range, it is easy to follow the strain of the adherend and obtain excellent adhesive strength, and the dimensional stability of the adhesive tape can be ensured. Suitable sticking workability can be obtained.
• the adherend is a hard material such as metal or plastic but has a large area. In general, the larger the area of the adherend, the more difficult it is to suppress distortion and mold it. If the adhesive tape has the storage elastic modulus range, the strain of the adherend as described above can be followed by the adhesive tape, and a suitable adhesive force can be obtained.
• the 180 ° peel adhesive force of the adhesive tape is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3N / 20mm to 50N / 20mm, more preferably 10N / 20mm to 50N / 20mm, and 15N / 20 mm to 45 N / 20 mm is more preferable.
• the 180 ° peel adhesive force is within the above-mentioned preferable range, the adhesive tape is applied in the horizontal direction with respect to the attachment surface of the adherend while having an appropriate adhesive force without causing peeling or displacement from the adherend. -It can be easily peeled off when it is stretched in the vertical direction and re-peeled.
• the 180 ° peel adhesive strength of the adhesive tape refers to the value measured and measured in accordance with JIS Z 0237.
• the adhesive tape of the present embodiment preferably has an initial split adhesive force of 10 to 200 N / cm 2 , more preferably 30 to 150 N / cm 2, and even more preferably 50 to 100 N / cm 2 .
• the split adhesive force is within the above-mentioned preferable range, it is easy to achieve both removability and adhesiveness.
• the split adhesive strength of the adhesive tape refers to a value measured by the method described in Examples described later.
• the method for producing the adhesive tape is not particularly limited, and can be appropriately selected from known methods.
• the method for producing an adhesive tape of the present embodiment preferably includes an adhesive layer forming step, a base material layer forming step, and a laminating step, and further includes other layer forming steps, if necessary. Further, it can also be produced by a multi-layer simultaneous forming step in which the adhesive layer forming step and the base material layer forming step are simultaneously performed.
• the pressure-sensitive adhesive layer forming step is not particularly limited as long as the pressure-sensitive adhesive layer can be formed, and can be appropriately selected depending on the intended purpose.
• Examples thereof include a method of forming an adhesive layer by a method such as a uniaxial stretching method, a sequential secondary stretching method, a simultaneous biaxial stretching method, an inflation method, a tube method, a calendar method, and a solution method.
• the casting method and the solution method by extrusion molding are preferable.
• the release sheet is not particularly limited and may be appropriately selected depending on the intended purpose.
• paper such as kraft paper, glassin paper, high-quality paper; polyethylene, polypropylene (biaxially stretched polypropylene (OPP), uniaxially stretched polypropylene). (CPP)), resin film such as polyethylene terephthalate (PET); laminated paper in which the paper and the resin film are laminated, and the paper coated with clay or polyvinyl alcohol, and one or both sides of the paper are silicone-based. Examples thereof include those that have been subjected to a peeling treatment such as resin. These may be used alone or in combination of two or more.
• the base material layer forming step is not particularly limited as long as the base material layer can be formed, and can be appropriately selected depending on the intended purpose.
• a heat press method for example, a calendar method by extrusion molding, a uniaxial stretching method, etc.
• Examples thereof include a sequential secondary stretching method, a simultaneous biaxial stretching method, an inflation method, a tube method, a calendar method, and a solution method. These methods may be used alone or in combination of two or more.
• the cast method by extrusion molding, the inflation method, the tube method, the calendar method, and the solution method are preferable in order to impart suitable flexibility and extensibility to the base material layer.
• the base material layer may be surface-treated for the purpose of further improving the adhesion to the adhesive layer.
• the surface treatment method is not particularly limited and can be appropriately selected from known methods as long as the characteristics of the adhesive tape are not impaired.
• sandblasting method surface polishing / friction method, corona discharge treatment method, etc.
• examples include a chromic acid treatment method, a flame treatment method, a hot air treatment method, an ozone treatment method, an ultraviolet irradiation treatment method, and an oxidation treatment method.
• the laminating step is a step of laminating the base material layer and the adhesive layer.
• the method of laminating the base material layer and the adhesive layer is not particularly limited and may be appropriately selected from known methods.
• the adhesive layer in a state of being attached to the release sheet formed in the adhesive layer forming step.
• a method of pressurizing and laminating the substrate layer and the substrate layer can be mentioned.
• the adhesive tape according to the present invention can be used for fixing sheets of sheets constituting relatively large electronic devices such as flat-screen TVs, home appliances, and OA devices, fixing exterior parts and housings, portable electronic terminals, cameras, personal computers, and the like. Suitable for fixing parts in various industrial fields such as fixing exterior parts and rigid parts such as batteries to relatively small electronic devices, temporarily fixing the parts, and labels displaying product information. can.
• the adhesive tape according to the present invention is not limited to the above example, and can be appropriately modified.
• the base material layer and adhesive layer are cut at 5 points in the length direction at 100 mm intervals and 5 points in the width direction, and 5 points at 100 mm intervals in the width direction on each cut surface.
• the average particle size (primary particle size) of the filler was measured by using a measuring machine (microtrack) using a laser diffraction / scattering method.
• each adhesive tape was cut into a length of 150 mm and a width of 20 mm, and one surface of the adhesive tape was lined with a PET film having a thickness of 25 ⁇ m.
• the other surface of the adhesive tape is attached to a stainless steel plate (length 100 mm, width 30 mm, thickness 3 mm) under the conditions of an atmosphere of 23 ° C. and 50% RH, and the adhesive tape and the stainless steel plate are attached.
• the adhesive tape in the test piece is subjected to a Tensilon tensile tester (model: RTF-1210, manufactured by A & D Co., Ltd.) in the 180 ° direction (horizontal direction) under the conditions of an atmosphere of 23 ° C. and 50% RH.
• the adhesive tape was stretched at a tensile speed of 300 mm / min, and the 180 ° peel adhesive force of the adhesive tape was measured.
• the removability is such that the gripper portion provided at one end in the longitudinal direction of the adhesive tape is stretched in the direction of 90 ° with respect to the longitudinal direction.
• Two types of evaluations were performed: a case where the evaluation was left for 1 minute (removability 1) and a case where the evaluation was left for 30 minutes (removability 2). Details will be described below.
• the gripping part was stretched by hand in the direction of 90 ° with respect to the longitudinal direction of the adhesive tape at a speed of about 300 mm / min. .. After peeling off 30 mm, it was left for 1 minute, and the gripping part was stretched by hand again at a speed of about 300 mm / min in the 90 ° direction.
• the adhesive tape was cut and the cover after the adhesive tape was peeled off. The degree of adhesive residue on the body was visually evaluated according to the following criteria. ⁇ : All 10 times, the adhesive tape could be peeled off cleanly without any breakage or adhesive residue. ⁇ : The adhesive tape was peeled off without breaking in all 10 times, but the adhesive residue was generated more than once.
• the gripping part was stretched by hand in the direction of 90 ° with respect to the longitudinal direction of the adhesive tape at a speed of about 300 mm / min. .. After peeling off by 30 mm, it was left to stand for 30 minutes, and again, the gripper portion was stretched by hand at a speed of about 300 mm / min in the 90 ° direction.
• the degree of adhesive tape breakage and adhesive residue on the adherend after the adhesive tape was peeled off was visually evaluated according to the following criteria. ⁇ : All 10 times, the adhesive tape could be peeled off cleanly without any breakage or adhesive residue. ⁇ : The adhesive tape was peeled off without breaking in all 10 times, but the adhesive residue was generated more than once. ⁇ : 6 to 9 times, the adhesive tape was peeled off cleanly without any breakage of the adhesive tape and adhesive residue. X: The adhesive tape was cut or the adhesive residue was generated 5 to 10 times, or the adhesive tape could not be stretched and peeled off.
• the stainless steel piece of the test piece constituting the patch is pulled at a speed of 1000 mm / min in an atmosphere of 23 ° C. and 50% RH to make stainless steel. The peeling strength of the piece was measured.
• styrene-based base material (1) As the material for the base material used for the styrene-based base material (1), a resin composition (1) of a styrene-ethylenebutylene-styrene copolymer and a styrene-ethylenebutylene copolymer was used.
• the resin composition (1) has a structural unit derived from styrene represented by the chemical formula (A) of 29% by mass, and the ratio of the styrene-ethylenebutylene copolymer to the total amount of the resin composition is 1% by mass.
• a base material (1) having a thickness of 50 ⁇ m was prepared by heat pressing (pressure 0.5 MPa, press plate temperature 130 ° C., pressing time 2 minutes).
• the breaking stress of the base material (1) was 78 MPa.
• the elongation at break was 650%.
• the stress (modulus) at the time of 50% elongation was 3 MPa.
• ⁇ Base material (2) Styrene-based base material (2)>
• a resin composition (2) of a styrene-isoprene copolymer and a styrene-isoprene-styrene copolymer was used as the material for the base material used for the styrene-based base material (2).
• the resin composition (2) has a structural unit derived from styrene represented by the chemical formula (A) of 26% by mass, and the ratio of the styrene-isoprene copolymer to the total amount of the resin composition (2) is 16% by mass. I used the one.
• the resin composition (2) was heat-pressed (pressure 0.5 MPa, press plate temperature 130 ° C., press time 2 minutes) to prepare a base material (2) having a thickness of 50 ⁇ m.
• the breaking stress of the base material (2) was 11 MPa.
• the elongation at break was 1100%.
• the stress (modulus) at the time of 50% elongation was 1 MPa.
• the pressure-sensitive adhesive composition used for the pressure-sensitive adhesive layer in the present invention contains the following filler and pressure-sensitive adhesive resin.
• Silicone particles (1) particles having a surface made of silicone resin and an inside made of silicone rubber (manufactured by Shin-Etsu Chemical Co., Ltd., KMP-602, volume average particle size: 30 ⁇ m, particle size distribution (D 90 / D 10 ): 5.2) was used.
• Silicone particles (2) particles having a surface made of silicone resin and an inside made of silicone rubber (manufactured by Shin-Etsu Chemical Co., Ltd., KMP-600, volume average particle size: 5 ⁇ m, particle size distribution (D 90 / D 10 ): 3.2) was used.
• Acrylic particles (1) particles that are polymethyl methacrylate (manufactured by Japan Exlan Co., Ltd., FH-S010, volume average particle size: 10 ⁇ m, particle size distribution (D 90 / D 10 ): 2.8) are used. did.
• the syndiotacticity of the PMMA block portion of the triblock copolymer (PMMA-b-PnBA-b-PMMA, hereinafter referred to as acrylic block copolymer (1)) is 71%, which is the same block.
• the glass transition temperature of the part is 113.7 ° C.
• the glass transition temperature of the PnBA block part is ⁇ 46.8 ° C.
• the Mn of the entire copolymer is 95936
• the distribution) was 1.09, and it was confirmed that the proportion of each polymer block was PMMA (11% by mass) -PnBA (78% by mass) -PMMA (11% by mass).
• NMR measurement, DSC measurement, and GPC (gel permeation chromatography) measurement were performed. Then, based on the measurement result, the number average molecular weight (Mn), PMMA / PnBA / P2EHA (polymethyl methacrylate / n-butyl polyacrylic acid / -2 ethylhexyl polyacrylic acid) ratio and the like were determined.
• the white precipitate of is a triblock copolymer of polymethylmethacrylate (PMMA) block-n-butyl polyacrylate (PnBA) / polyacrylic acid-2 ethylhexyl (2EHA) block-polymethyl methacrylate (PMMA) block.
• the syndiotacticity of the PMMA block portion of the triblock copolymer (PMMA-b-PnBA / 2EHA-b-PMMA, hereinafter referred to as acrylic block copolymer (2)) is 75%.
• the glass transition temperature of the block portion is 105.8 ° C.
• the glass transition temperature of the PnBA block portion is ⁇ 53.6 ° C.
• the Mn of the entire copolymer is 51370
• the Mw / Mn of the entire copolymer is Mw / Mn.
• (Molecular weight distribution) is 1.15, and it is confirmed that the ratio of each polymer block is PMMA (10% by mass) -PnBA (44% by mass) / 2EHA (36% by mass) -PMMA (10% by mass).
• SIS rubber As the pressure-sensitive adhesive resin, SIS rubber (styrene-based triblock copolymer) (Quintac 3270 manufactured by Zeon, styrene amount 24%, SI diblock amount 67%) was used.
• the Mw of the styrene-based triblock copolymer was 175,000, and the Mw / Mn (molecular weight distribution) was 1.05.
• the Mw of the diblock copolymer was 84,000, and the Mw / Mn (molecular weight distribution) was 1.05.
• -Adhesive composition (1) 50 parts by mass of terpenphenol-based tackifier resin (Tamanol T-803L, Arakawa Chemical Industry Co., Ltd., softening point 150 ° C.) with respect to 100 parts by mass of the acrylic block copolymer (1) obtained in Synthesis Example 1 described above. The parts were mixed and stirred, and then ethyl acetate was added to obtain a pressure-sensitive adhesive resin solution (1) having a solid content of 35% by mass.
• terpenphenol-based tackifier resin Temanol T-803L, Arakawa Chemical Industry Co., Ltd., softening point 150 ° C.
• -Adhesive composition (2) 50 parts by mass of a terpene phenol-based tackifier resin (YS Polystar T130, Yasuhara Chemical Co., Ltd., softening point 130 ° C.) is mixed with 100 parts by mass of the acrylic block copolymer (1) obtained in Synthesis Example 1 described above. After stirring, ethyl acetate was added to obtain a pressure-sensitive adhesive resin solution (2) having a solid content of 35% by mass. Next, 38 parts by mass of the silicone particles (1) and ethyl acetate were added to 100 parts by mass of the solid content of the pressure-sensitive adhesive resin solution (2), and the mixture was stirred and mixed so as to be uniform, so that the solid content was 40% by mass. The pressure-sensitive adhesive composition (2) was obtained.
• a terpene phenol-based tackifier resin (YS Polystar T130, Yasuhara Chemical Co., Ltd., softening point 130 ° C.)
• -Adhesive composition (3) 50 parts by mass of a terpene phenol-based tackifier resin (YS Polystar T130, Yasuhara Chemical Co., Ltd., softening point 130 ° C.) is mixed with 100 parts by mass of the acrylic block copolymer (1) obtained in Synthesis Example 1 described above. After stirring, ethyl acetate was added to obtain a pressure-sensitive adhesive resin solution (3) having a solid content of 35% by mass. Next, 38 parts by mass of the silicone particles (2) and ethyl acetate were added to 100 parts by mass of the solid content of the pressure-sensitive adhesive resin solution (3), and the mixture was stirred and mixed so as to be uniform, so that the solid content was 40% by mass. The pressure-sensitive adhesive composition (3) was obtained.
• a terpene phenol-based tackifier resin (YS Polystar T130, Yasuhara Chemical Co., Ltd., softening point 130 ° C.)
• -Adhesive composition (4) 50 parts by mass of a terpene phenol-based tackifier resin (YS Polystar T130, Yasuhara Chemical Co., Ltd., softening point 130 ° C.) is mixed with 100 parts by mass of the acrylic block copolymer (2) obtained in Synthesis Example 2 described above. After stirring, ethyl acetate was added to obtain a pressure-sensitive adhesive resin solution (4) having a solid content of 35% by mass. Next, 38 parts by mass of the silicone particles (1) and ethyl acetate were added to 100 parts by mass of the solid content of the pressure-sensitive adhesive resin solution (4), and the mixture was stirred and mixed so as to be uniform, so that the solid content was 40% by mass. The pressure-sensitive adhesive composition (4) was obtained.
• a terpene phenol-based tackifier resin (YS Polystar T130, Yasuhara Chemical Co., Ltd., softening point 130 ° C.)
• -Adhesive composition (5) 50 parts by mass of a terpene phenol-based tackifier resin (YS Polystar T130, Yasuhara Chemical Co., Ltd., softening point 130 ° C.) is mixed with 100 parts by mass of the acrylic block copolymer (1) obtained in Synthesis Example 1 described above. After stirring, ethyl acetate was added to obtain a pressure-sensitive adhesive resin solution (5) having a solid content of 35% by mass. Next, 38 parts by mass of the acrylic particles (1) and ethyl acetate were added to 100 parts by mass of the solid content of the pressure-sensitive adhesive resin solution (5), and the mixture was stirred and mixed so as to be uniform to have a solid content of 40% by mass. The pressure-sensitive adhesive composition (5) was obtained.
• a terpene phenol-based tackifier resin (YS Polystar T130, Yasuhara Chemical Co., Ltd., softening point 130 ° C.)
• -Adhesive composition (6) 50 parts by mass of a terpene phenol-based tackifier resin (YS Polystar T130, Yasuhara Chemical Co., Ltd., softening point 130 ° C.) is mixed with 100 parts by mass of the acrylic block copolymer (1) obtained in Synthesis Example 1 described above. After stirring, ethyl acetate was added to obtain a pressure-sensitive adhesive resin solution (6) having a solid content of 35% by mass. Next, 70 parts by mass of the silicone particles (1) and ethyl acetate were added to 100 parts by mass of the solid content of the pressure-sensitive adhesive resin solution (4), and the mixture was stirred and mixed so as to be uniform, so that the solid content was 40% by mass. The pressure-sensitive adhesive composition (6) was obtained.
• a terpene phenol-based tackifier resin (YS Polystar T130, Yasuhara Chemical Co., Ltd., softening point 130 ° C.)
• a rosin-based pressure-sensitive adhesive resin (Superester A-) is applied to 100 parts by mass of a styrene-based triblock copolymer (Quintac 3270 manufactured by Nippon Zeon Co., Ltd., styrene content 24%, SI diblock content 67%). 100, Arakawa Chemical Co., Ltd., softening point 100 ° C.) 50 parts by mass was mixed and stirred, and then toluene was added to obtain a pressure-sensitive adhesive resin solution (7) having a solid content of 35% by mass.
• a pressure-sensitive adhesive having a solid content of 40% by mass by adding 38 parts by mass of silicone particles (1) and toluene and stirring and mixing them uniformly with respect to 100 parts by mass of the solid content of the pressure-sensitive adhesive resin solution (7).
• the composition (7) was obtained.
• -Adhesive composition 8 5 parts by mass of rosin-based tackifier resin (Haritac PCJ, Harima Kasei Co., Ltd., softening point 135 ° C.), petroleum-based tackifier resin with respect to 100 parts by mass of the acrylic random copolymer obtained in Synthesis Example 3 described above. (FTR6125, Mitsui Kagaku Co., Ltd., softening point 125 ° C.) After mixing and stirring 45 parts by mass, ethyl acetate was added to obtain a pressure-sensitive adhesive resin solution (8) having a solid content of 35% by mass.
• rosin-based tackifier resin Harditac PCJ, Harima Kasei Co., Ltd., softening point 135 ° C.
• FSR6125 Mitsui Kagaku Co., Ltd., softening point 125 ° C.
• Example 1 The above pressure-sensitive adhesive composition (1) is applied on a release liner (film binar 75E-0010GT, manufactured by Fujimori Kogyo Co., Ltd., the same applies hereinafter) so that the thickness after drying becomes 50 ⁇ m with an applicator, and 3 at 80 ° C. An adhesive layer was prepared by drying for minutes. Next, as a base material layer, both sides of the base material (1) are subjected to corona treatment so that the wet tension becomes 52 mN / m, and then the pressure-sensitive adhesive layer is bonded to both sides, and the base material layer and the pressure-sensitive adhesive layer are combined.
• the adhesive tape of Example 1 was produced by pressurizing and laminating the laminated structure at 0.2 MPa. The obtained adhesive tape was evaluated by the above method, and the results are shown in Table 1.
• Example 2 In the production of the adhesive tape of Example 1, the adhesive tape of Example 2 was produced by the same method as in Example 1 except that the pressure-sensitive adhesive composition (1) was changed to the pressure-sensitive adhesive composition (2). .. The obtained adhesive tape was evaluated by the above method, and the results are shown in Table 1.
• Example 3 In the production of the adhesive tape of Example 1, the adhesive tape of Example 3 was produced by the same method as in Example 1 except that the pressure-sensitive adhesive composition (1) was changed to the pressure-sensitive adhesive composition (3). .. The obtained adhesive tape was evaluated by the above method, and the results are shown in Table 1.
• Example 4 In the production of the adhesive tape of Example 1, the adhesive tape of Example 4 was produced by the same method as in Example 1 except that the pressure-sensitive adhesive composition (1) was changed to the pressure-sensitive adhesive composition (4). .. The obtained adhesive tape was evaluated by the above method, and the results are shown in Table 1.
• Example 5 In the production of the adhesive tape of Example 1, the adhesive tape of Example 5 was produced by the same method as in Example 1 except that the pressure-sensitive adhesive composition (1) was changed to the pressure-sensitive adhesive composition (5). .. The obtained adhesive tape was evaluated by the above method, and the results are shown in Table 1.
• Example 6 In the production of the adhesive tape of Example 1, the adhesive tape of Example 6 was produced by the same method as in Example 1 except that the pressure-sensitive adhesive composition (1) was changed to the pressure-sensitive adhesive composition (6). .. The obtained adhesive tape was evaluated by the above method, and the results are shown in Table 1.
• Example 7 In the production of the adhesive tape of Example 1, the adhesive tape of Example 7 was produced by the same method as in Example 1 except that the pressure-sensitive adhesive composition (1) was changed to the pressure-sensitive adhesive composition (7). .. The obtained adhesive tape was evaluated by the above method, and the results are shown in Table 1.
• Example 8 In the production of the adhesive tape of Example 1, the adhesive tape of Example 8 was produced by the same method as in Example 1 except that the base material (1) was changed to the base material (2). The obtained adhesive tape was evaluated by the above method, and the results are shown in Table 1.

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