WO2017098919A1 - Adhesive composition and adhesive tape - Google Patents

Adhesive composition and adhesive tape Download PDF

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Publication number
WO2017098919A1
WO2017098919A1 PCT/JP2016/084638 JP2016084638W WO2017098919A1 WO 2017098919 A1 WO2017098919 A1 WO 2017098919A1 JP 2016084638 W JP2016084638 W JP 2016084638W WO 2017098919 A1 WO2017098919 A1 WO 2017098919A1
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WIPO (PCT)
Prior art keywords
sensitive adhesive
pressure
adhesive
silicone
adhesive composition
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PCT/JP2016/084638
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French (fr)
Japanese (ja)
Inventor
靖史 土屋
和樹 石川
岩本　太郎
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株式会社寺岡製作所
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Application filed by 株式会社寺岡製作所 filed Critical 株式会社寺岡製作所
Priority to KR1020187017330A priority Critical patent/KR102232802B1/en
Priority to CN201680071843.8A priority patent/CN108368413B/en
Priority to JP2017555011A priority patent/JP6626125B2/en
Publication of WO2017098919A1 publication Critical patent/WO2017098919A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • 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
    • 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
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate

Definitions

  • the present invention provides, for example, an adhesive tape used in the manufacturing process of electrical / electronic components, etc., which has excellent component fixing strength, can be peeled off without being left behind even when used in a high temperature environment, and repeats adhesion-peeling.
  • the present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape with little adhesive force change.
  • the silicone adhesive composition is excellent in heat resistance, cold resistance, weather resistance, electrical insulation, chemical resistance, and adhesiveness to various adherends. Furthermore, the adhesive tape having the silicone adhesive layer is less likely to have adhesive residue after peeling, even when used in a high temperature environment. Therefore, such an adhesive tape is widely used for applications such as component protection, masking, temporary fixing, and conveyance fixing in the manufacturing process of various components such as electric and electronic components.
  • the conventional adhesive tape was not stable when used repeatedly, and had to be replaced after each use. Specifically, the adhesive force increases due to the fact that the adhesive surface is roughened by repeating the peeling and becomes more familiar with the adherend, and the tape may not be peeled off. In addition, if the adhesive force is reduced due to the fact that the low molecular component in the adhesive and the component contributing to the expression of adhesiveness are transferred to the adherend by repeated peeling, the fixing force to the component is insufficient. Parts may fall off during the process. In addition, the adhesive may deteriorate during repeated use in a high-temperature environment, and glue may remain on the parts.
  • Patent Documents 1 to 4 Conventionally, many silicone pressure-sensitive adhesive compositions and pressure-sensitive adhesive tapes that hardly cause adhesive residue after peeling have been studied (for example, Patent Documents 1 to 4). However, no consideration has been given to the problem of stability of adhesive strength after peeling.
  • patent document 5 it is a double-sided adhesive tape for sticking a transparent protective cover on an information display screen such as a display panel, and an adsorption layer mainly composed of a silicone resin is laminated on one surface of a base film, An adhesive tape in which an adhesive layer made of an acrylic adhesive is laminated on the other surface is disclosed.
  • This silicone adsorbing layer is premised on reattachment, but in this document, there is no mention of basic adhesive physical properties such as adhesive strength as well as stability of adhesive strength when peeling is repeated.
  • this adsorption layer is a silicone resin only, and the purpose is to obtain a slight adsorption force that does not peel off the weight of the protective cover from the display panel. This is fundamentally different from those intended for applications in which some external force or force for fixing other components (ie, fixing force) is applied, such as the adhesive tape used.
  • Patent Documents 6 to 8 disclose a jig for holding and conveying a printed wiring board in which a weak adhesive resin is applied to a jig base made of a plate. These patent documents do not mention basic adhesive physical properties such as adhesive strength as well as stability of adhesive strength when peeling is repeated, and it cannot be said that sufficient verification has been made. In the patent document, a weak adhesive is used. However, if the adhesive is weak, the adhesive force is not always stable when peeling is repeated. Also, the fixing force to the parts and the adhesive residue are not verified.
  • the present inventors focused on the problem of stability of the adhesive strength after peeling, and developed an adhesive tape that can be used repeatedly for the purpose of reducing costs in the manufacturing process of various parts such as electric and electronic parts. . That is, the object of the present invention is to provide a pressure-sensitive adhesive composition and pressure-sensitive adhesive tape that have excellent component fixing strength, can be peeled off without being left behind even when used in a high-temperature environment, and have little change in adhesive strength even after repeated adhesion-peeling. Is to provide.
  • the present inventors have found that the balance between the gel fraction and the degree of swelling of the silicone pressure-sensitive adhesive layer is related to changes in adhesive strength and other performances when repeatedly used. As a result, the present invention has been completed.
  • the present invention includes a crosslinked silicone structure, the gel fraction measured by the following method is 45% or more and less than 70%, and the degree of swelling with respect to toluene measured by the following method is 290% or less. It is a silicone type adhesive composition characterized by these. (Gel fraction)
  • the gel fraction is obtained by the following formula, which is the ratio of the insoluble matter when the silicone pressure-sensitive adhesive composition is immersed in toluene at room temperature for 1 day.
  • this invention is an adhesive tape which has an adhesive layer which consists of said adhesive composition on the at least single side
  • a pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape that have excellent component fixing strength, can be peeled off without being left behind even when used in a high temperature environment, and have little change in adhesive strength even after repeated adhesion-peeling.
  • the pressure-sensitive adhesive tape of the present invention has the above-mentioned specific pressure-sensitive adhesive layer, for example, in the manufacturing process of various parts such as electrical and electronic parts at high temperatures, the parts do not peel off during the process, It is difficult to remain, and even if adhesion-peeling is repeated, the change in adhesive force is small, so that it can be used repeatedly, which is very useful in terms of cost reduction.
  • the pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition containing a silicone-based pressure-sensitive adhesive as a main component.
  • the gel fraction of the pressure-sensitive adhesive composition of the present invention is 45% or more and less than 70%, preferably 48 to 65%, more preferably 50 to 60%.
  • the swelling degree with respect to toluene of the adhesive composition of this invention is 290% or less, Preferably it is 260% or less, More preferably, it is 230% or less. Specific methods for measuring the gel fraction and the degree of swelling are described in the Examples section described below. In general, the degree of swelling depends on the crosslinking density of the pressure-sensitive adhesive composition.
  • the crosslinking density When the crosslinking density is high, the three-dimensionally crosslinked polymer chain constituting the pressure-sensitive adhesive is difficult to spread even when immersed in toluene, and the degree of swelling is low. On the other hand, when the crosslinking density is low, the polymer chain is easy to spread and the degree of swelling is high.
  • the gel fraction and the degree of swelling are within the specific ranges of the present invention, sufficient fixing force and adhesive residue prevention, and stability of adhesive strength when used repeatedly are obtained. If the gel fraction is less than 45%, the fixing force becomes stronger, but adhesive residue due to insufficient cohesion tends to occur, and the adhesive force when used repeatedly is not stable. On the other hand, if the gel fraction exceeds 70%, sufficient fixing force cannot be obtained. Even if the gel fraction is in the range of 45% or more and less than 70%, if the degree of swelling exceeds 290%, adhesive residue due to insufficient cohesion due to low crosslink density is likely to occur, and repeatedly The adhesive strength when used is not stable.
  • silicone-based pressure-sensitive adhesive used in the present invention examples include silicone raw rubber (polydimethylsiloxane long-chain polymer mainly composed of D units [(CH 3 ) 2 SiO]) and MQ resin (M units [(CH 3 ) A pressure-sensitive adhesive composed of 3 SiO 1/2 ] and a silicone resin having a three-dimensional structure composed of Q units [SiO 2 ].
  • silicone raw rubber polydimethylsiloxane long-chain polymer mainly composed of D units [(CH 3 ) 2 SiO]
  • MQ resin M units [(CH 3 )
  • Such a pressure-sensitive adhesive composed of a silicone raw rubber and an MQ resin is superior in adhesiveness compared to a silicone raw rubber alone.
  • basic adhesive properties such as adhesive strength, holding power, and tack can be controlled.
  • Silicone pressure-sensitive adhesives are roughly classified into addition-curing types and peroxide-curing types depending on the curing mechanism.
  • the addition-curable silicone pressure-sensitive adhesive is cured by heating a base agent composed of a silicone raw rubber containing an alkenyl group and a crosslinking agent comprising a polyorganosiloxane containing an SiH group, for example, under a platinum catalyst to cause a crosslinking reaction. At this time, it is possible to change the crosslinking density by appropriately adjusting the amount of the crosslinking agent.
  • the peroxide curable silicone pressure-sensitive adhesive is cured by adding a peroxide such as benzoyl peroxide as a curing agent, removing the solvent, and then heating at a high temperature, for example.
  • the pressure-sensitive adhesive composition of the present invention preferably contains a cross-linked addition-curable silicone pressure-sensitive adhesive.
  • the pressure-sensitive adhesive composition of the present invention can be obtained using a commercially available product.
  • a pressure-sensitive adhesive composition having desired physical properties can be obtained by crosslinking and curing a commercially available silicone pressure-sensitive adhesive.
  • the pressure-sensitive adhesive composition of the present invention including a crosslinked silicone structure can be obtained by crosslinking and curing the silicone-based pressure-sensitive adhesive exemplified above.
  • the crosslinking and curing reaction is usually carried out by heating, but depending on the type of pressure-sensitive adhesive or curing agent, crosslinking and curing can be performed by condensation reaction or ultraviolet irradiation.
  • the pressure-sensitive adhesive composition having a specific gel fraction and swelling degree according to the present invention can be obtained by using, for example, a mixture of two or more types of commercially available silicone pressure-sensitive adhesives. Specifically, for example, a silicone pressure-sensitive adhesive having a relatively high gel fraction and swelling degree and a silicone pressure-sensitive adhesive having a relatively low gel fraction and swelling degree are mixed at an appropriate ratio and crosslinked and cured. A pressure-sensitive adhesive composition having a gel fraction and a swelling degree within the range of the present invention can be obtained. However, the pressure-sensitive adhesive composition of the present invention is not limited to that obtained by such a method.
  • An additive may be added to the pressure-sensitive adhesive composition of the present invention for the purpose of improving various properties.
  • additives include inorganic fillers such as carbon black and silica; polyorganosiloxanes such as silicone resin, polydimethylsiloxane and polydimethylphenylsiloxane; and antioxidants such as phenolic antioxidants and amine antioxidants. Agents; silane coupling agents.
  • the type and amount of the additive must be appropriately selected so as not to impair the effects of the invention.
  • the pressure-sensitive adhesive tape of the present invention is a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition of the present invention described above on at least one side of a base material, and typically the pressure-sensitive adhesive is applied to one side or both sides of a base film. It is an adhesive tape having an agent layer.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 2 to 150 ⁇ m, more preferably 5 to 100 ⁇ m, and particularly preferably 10 to 75 ⁇ m.
  • the pressure-sensitive adhesive layer can be formed by cross-linking and curing reaction of the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition can be applied on a base material and crosslinked and cured by heating or condensation reaction or ultraviolet irradiation to form a pressure-sensitive adhesive layer on the base material.
  • the pressure-sensitive adhesive composition is applied onto a release paper or other film, and is subjected to crosslinking and curing by heating or condensation reaction or ultraviolet irradiation to form a pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer is applied to one or both sides of the substrate. It can also be combined.
  • a solvent may be added.
  • the solvent include aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, octane and isoparaffin; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and isobutyl acetate.
  • ether solvents such as diisopropyl ether and 1,4-dioxane.
  • the coating method is not particularly limited, and a known method may be used. Specific examples thereof include coating using a comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater or gravure coater; screen coating; dip coating; cast coating. It is done.
  • the substrate is not particularly limited, but a film-like substrate is preferable.
  • a resin film having high heat resistance that can be processed at a high temperature is preferable.
  • Specific examples thereof include polyimide (PI), polyetheretherketone (PEEK), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyamideimide (PAI), polyethersulfone (PES). ), And a resin film such as polytetrafluoroethylene (PTFE).
  • PI polyimide
  • PEEK polyetheretherketone
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PPS polyphenylene sulfide
  • PAI polyamideimide
  • PES polyethersulfone
  • PTFE polytetrafluoroethylene
  • the thickness of the substrate is not particularly limited, but is preferably 2 to 180 ⁇ m, more preferably 5 to 100 ⁇ m, and particularly
  • the surface on which the pressure-sensitive adhesive layer of the substrate is provided may be subjected to an easy adhesion treatment as necessary.
  • the easy adhesion treatment include primer treatment, corona treatment, etching treatment, plasma treatment, and sandblast treatment.
  • a release liner may be provided on the adhesive tape of the present invention.
  • the release liner is for protecting the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape, and is peeled off immediately before application, and the pressure-sensitive adhesive is exposed and the pressure-sensitive adhesive tape is attached to the adherend.
  • the kind of release liner is not particularly limited, and a known release liner can be used. Specific examples thereof include those obtained by subjecting the surface of a base material such as fine paper, glassine paper, and synthetic resin film to a release agent treatment.
  • a release agent using a fluorine-substituted alkyl-modified silicone resin or the like may be used.
  • the release liner to be laminated on the silicone-based pressure-sensitive adhesive layer is preferably one obtained by releasing the surface of the polyethylene terephthalate film with a fluorine-substituted alkyl-modified silicone resin.
  • part means “part by mass”.
  • Example 1 Addition-curing silicone adhesive stock solution (trade name SD-4560, manufactured by Toray Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass, and addition-curing silicone adhesive stock solution having a solid content concentration of 40% by mass (product name SD) -4587L, manufactured by Toray Dow Corning Co., Ltd.) 30 parts, 54 parts of toluene as a diluting solvent, and platinum part (trade name NC-25, manufactured by Toray Dow Corning Co., Ltd.) as a curing catalyst were mixed uniformly. A pressure-sensitive adhesive liquid (1) was obtained.
  • the pressure-sensitive adhesive liquid (1) was applied on one side of a primer-treated polyimide (PI) film having a thickness of 25 ⁇ m so that the thickness of the pressure-sensitive adhesive layer after drying was 30 ⁇ m.
  • the adhesive layer was formed by curing and drying in 2 minutes.
  • a release liner 50 ⁇ m thick PET film which had been subjected to a release treatment with a fluorine-substituted alkyl-modified silicone resin
  • Example 2 Addition-curing silicone adhesive stock solution (trade name SD-4560, manufactured by Toray Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass, and addition-curing silicone adhesive stock solution having a solid content concentration of 40% by mass (product name SD) -4587L, 50 parts of Toray Dow Corning Co., Ltd., 43 parts of toluene as diluent solvent, and 0.3 parts of platinum catalyst as a curing catalyst (trade name NC-25, produced by Toray Dow Corning Co., Ltd.) are uniformly mixed. A pressure-sensitive adhesive liquid (2) was obtained. And the adhesive tape was obtained by the method similar to Example 1 except having used the adhesive liquid (2).
  • Example 3 Addition-curing silicone adhesive stock solution (trade name SD-4560, manufactured by Toray Dow Corning Co., Ltd.) with a solid content concentration of 60% by mass, addition-curing silicone adhesive stock solution with a solid content concentration of 40% by mass (product name SD) -4587L, manufactured by Toray Dow Corning Co., Ltd.) 80 parts, 26 parts of toluene as a diluting solvent, and 0.3 parts of a platinum catalyst (trade name NC-25, manufactured by Toray Dow Corning Co., Ltd.) as a curing catalyst are uniformly mixed. An adhesive liquid (3) was obtained. And the adhesive tape was obtained by the method similar to Example 1 except having used the adhesive liquid (3).
  • ⁇ Comparative Example 9 100 parts of a peroxide curable silicone adhesive stock solution (trade name SH-4280, manufactured by Toray Dow Corning Co., Ltd.) with a solid content concentration of 60% by weight, 71 parts of toluene as a diluent, and a curing agent (trade name Nyper (registered trademark)) ) BMT-40 (manufactured by NOF Corporation) (3.0 parts) was mixed uniformly to obtain an adhesive liquid (12).
  • a peroxide curable silicone adhesive stock solution trade name SH-4280, manufactured by Toray Dow Corning Co., Ltd.
  • a curing agent trade name Nyper (registered trademark)
  • the pressure-sensitive adhesive liquid (12) was applied on one side of a primer-treated polyimide (PI) film having a thickness of 25 ⁇ m so that the thickness of the pressure-sensitive adhesive layer after drying was 30 ⁇ m.
  • the solvent was removed at 60 ° C. for 1 minute in a drying furnace, and further cured and dried at 180 ° C. for 2 minutes to form an adhesive layer.
  • a release liner 50 ⁇ m thick PET film which had been subjected to a release treatment with a fluorine-substituted alkyl-modified silicone resin
  • ⁇ Comparative Example 10 100 parts of a peroxide curable silicone adhesive stock solution (trade name KR-100, manufactured by Shin-Etsu Chemical Co., Ltd.) with a solid content concentration of 60% by weight, 71 parts of toluene as a diluent solvent, a curing agent (trade name Nyper (registered trademark)) 3.0 parts of BMT-40 (manufactured by NOF Corporation) were uniformly mixed to obtain a pressure-sensitive adhesive liquid (13). And the adhesive tape was obtained by the method similar to the comparative example 9 except having used the adhesive liquid (13).
  • a peroxide curable silicone adhesive stock solution trade name KR-100, manufactured by Shin-Etsu Chemical Co., Ltd.
  • a curing agent trade name Nyper (registered trademark)
  • BMT-40 manufactured by NOF Corporation
  • the pressure-sensitive adhesive liquids (1) to (13) obtained in Examples and Comparative Examples were applied on the release liner so that the thickness after drying was 50 to 200 ⁇ m. Subsequently, it was heated in a drying oven, cured and dried to obtain an adhesive composition, which was used as a sample. The heating temperature at this time was set to the same temperature as each example and comparative example. That is, in the case of the adhesive liquids (1) to (11), the temperature was 130 ° C. for 2 minutes, and in the case of the adhesive liquids (12) and (13), the temperature was 60 ° C., 1 minute and 180 ° C., 2 minutes.
  • the obtained sample was cut into 50 mm ⁇ 50 mm, the release liner was peeled off, and a measurement sample comprising a sheet-like pressure-sensitive adhesive composition was obtained.
  • the peeled adhesive tape was affixed to a polished SUS plate again, and the adhesive strength after heating was measured in the same manner as the first time. Thereafter, the adhesive strength was repeatedly measured until the tenth heating. Moreover, the adhesive residue property at the time of peeling in each time was confirmed visually, and evaluated according to the following criteria. ⁇ : No glue residue ⁇ : There is glue residue
  • Rate of change (%) Adhesive strength after each heating / Adhesive strength after the first heating ⁇ 100%
  • ⁇ Fixing force test> As shown in FIG. 2, a 75 g weight 2 is attached to the adhesive layer 1b side (lower side) of the adhesive tape 1 with both ends fixed (attachment area 20 mm ⁇ 25 mm) and left in a dryer at 200 ° C. for 1 hour. Then, the presence or absence of the weight 2 was confirmed, and the fixing force was evaluated according to the following criteria. ⁇ : The weight did not fall ⁇ : The weight fell
  • Tables 1 to 3 show the results of the above measurements. Furthermore, the graph which put together the comprehensive evaluation of an Example and a comparative example in the correlation of a gel fraction and a swelling degree is shown in FIG.
  • Comparative Example 8 (weakly sticky pressure-sensitive adhesive), the gel fraction was high and the degree of swelling was high, so that adhesive residue was likely to occur, and the stability of the adhesive strength when repeatedly used was poor. Moreover, due to the high gel fraction, the fixing force of the parts was also inferior.
  • the pressure-sensitive adhesive composition of the present invention is particularly useful as a material for forming a pressure-sensitive adhesive layer of a pressure-sensitive adhesive tape, for example.
  • the pressure-sensitive adhesive tape of the present invention is very useful for applications such as component protection, masking, temporary fixing, and conveyance fixing in the manufacturing process of various components such as electric and electronic components.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Disclosed are: an adhesive composition including a crosslinked silicone component, the gel fraction (ratio of insoluble content when immersed for 1 day in toluene at normal temperature) of the adhesive composition being 45% to less than 70%, and the degree of swelling thereof with respect to toluene (ratio of swelling due to toluene absorption when immersed for 1 day) being 290% or less; and an adhesive tape having an adhesive layer comprising the adhesive composition. The adhesive composition and the adhesive tape have excellent part fixing force and can be peeled without adhesive transfer even when used in a high-temperature environment, and have minimal change in bonding strength despite repeated bonding and peeling.

Description

粘着剤組成物及び粘着テープAdhesive composition and adhesive tape
　本発明は、例えば、電気・電子部品等の製造工程で使用される粘着テープにおいて、部品の固定力に優れ、高温環境下で使用しても糊残りせず剥離でき、かつ接着－剥離を繰返しても接着力の変化が少ない粘着剤組成物及び粘着テープに関する。 The present invention provides, for example, an adhesive tape used in the manufacturing process of electrical / electronic components, etc., which has excellent component fixing strength, can be peeled off without being left behind even when used in a high temperature environment, and repeats adhesion-peeling. However, the present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape with little adhesive force change.
　シリコーン粘着剤組成物は、耐熱性、耐寒性、耐候性、電気絶縁性、耐薬品性、各種被着体に対する粘着性に優れている。さらにシリコーン粘着剤層を有する粘着テープは、特に高温環境下で使用しても剥離後に糊残りしにくい。したがって、そのような粘着テープは、電気・電子部品等の各種部品の製造工程において部品の保護、マスキング、仮固定、搬送用固定等の用途に広く利用されている。 The silicone adhesive composition is excellent in heat resistance, cold resistance, weather resistance, electrical insulation, chemical resistance, and adhesiveness to various adherends. Furthermore, the adhesive tape having the silicone adhesive layer is less likely to have adhesive residue after peeling, even when used in a high temperature environment. Therefore, such an adhesive tape is widely used for applications such as component protection, masking, temporary fixing, and conveyance fixing in the manufacturing process of various components such as electric and electronic components.
　従来の粘着テープは繰り返し使用したときの接着性が安定せず、約１回使用するごとに交換する必要があった。具体的には、剥離を繰り返すことで粘着面が荒れて被着体によりなじみやすくなる等の理由により接着力が上昇し、テープを剥離できないことがある。また、剥離を繰り返すことで粘着剤中の低分子成分や接着性の発現に寄与する成分が被着体に移行する等の理由で接着力が低下した場合、部品への固定力が不足して工程中で部品が剥がれ落ちることがある。また、高温環境下で繰り返し使用するうちに粘着剤が劣化し、部品に糊残りすることもある。 The conventional adhesive tape was not stable when used repeatedly, and had to be replaced after each use. Specifically, the adhesive force increases due to the fact that the adhesive surface is roughened by repeating the peeling and becomes more familiar with the adherend, and the tape may not be peeled off. In addition, if the adhesive force is reduced due to the fact that the low molecular component in the adhesive and the component contributing to the expression of adhesiveness are transferred to the adherend by repeated peeling, the fixing force to the component is insufficient. Parts may fall off during the process. In addition, the adhesive may deteriorate during repeated use in a high-temperature environment, and glue may remain on the parts.
　従来は、剥離後に糊残りしにくいシリコーン粘着剤組成物や粘着テープが数多く研究されてきた（例えば特許文献１～４）。しかし、剥離後の接着力の安定性という課題についてはなんら検討されていない。 Conventionally, many silicone pressure-sensitive adhesive compositions and pressure-sensitive adhesive tapes that hardly cause adhesive residue after peeling have been studied (for example, Patent Documents 1 to 4). However, no consideration has been given to the problem of stability of adhesive strength after peeling.
　特許文献５では、ディスプレイパネル等の情報表示画面に透明保護カバーを貼着するための両面粘着テープであって、基材フィルムの一方の面にシリコーン樹脂を主成分とする吸着層を積層し、もう一方の面にアクリル系粘着剤からなる粘着剤層を積層した粘着テープが開示されている。このシリコーン吸着層は貼り直しを前提としたものであるが、この文献内に剥離を繰り返したときの接着力の安定性はもとより、粘着力等の基本的な粘着物性について言及されていない。また、この吸着層はあくまでシリコーン樹脂であり、該保護カバー程度の重量のものがディスプレイパネルから剥落しない程度の僅かな吸着力を得ることを目的としているため、電気・電子部品等の製造工程で使用される粘着テープのように、何らかの外力や他の部品を固定する力（即ち固定力）が加わる用途を目的としたものとは根本的に異なるものである。 In patent document 5, it is a double-sided adhesive tape for sticking a transparent protective cover on an information display screen such as a display panel, and an adsorption layer mainly composed of a silicone resin is laminated on one surface of a base film, An adhesive tape in which an adhesive layer made of an acrylic adhesive is laminated on the other surface is disclosed. This silicone adsorbing layer is premised on reattachment, but in this document, there is no mention of basic adhesive physical properties such as adhesive strength as well as stability of adhesive strength when peeling is repeated. In addition, this adsorption layer is a silicone resin only, and the purpose is to obtain a slight adsorption force that does not peel off the weight of the protective cover from the display panel. This is fundamentally different from those intended for applications in which some external force or force for fixing other components (ie, fixing force) is applied, such as the adhesive tape used.
　特許文献６～８では、板体よりなる治具ベースに弱粘着性樹脂を塗布したプリント配線基板の保持搬送用の治具について開示されている。これらの特許文献にも剥離を繰り返したときの接着力の安定性はもとより、粘着力等の基本的な粘着物性について言及されておらず、十分な検証がなされているとはいえない。特許文献内では弱粘着性の粘着剤が用いられているが、弱粘着性であれば必ずしも剥離を繰り返したときの接着力が安定するわけではない。また部品への固定力や糊残り性も検証されていない。 Patent Documents 6 to 8 disclose a jig for holding and conveying a printed wiring board in which a weak adhesive resin is applied to a jig base made of a plate. These patent documents do not mention basic adhesive physical properties such as adhesive strength as well as stability of adhesive strength when peeling is repeated, and it cannot be said that sufficient verification has been made. In the patent document, a weak adhesive is used. However, if the adhesive is weak, the adhesive force is not always stable when peeling is repeated. Also, the fixing force to the parts and the adhesive residue are not verified.
特開２００２－２７５４５０号公報JP 2002-275450 A 特開２００３－９６４２９号公報JP 2003-96429 A 特開２００３－１９３２２６号公報JP 2003-193226 A 特開２００４－１６８８０８号公報JP 2004-168808 A 特開２０１５－１９９８７８号公報Japanese Patent Application Laid-Open No. 2015-199878 特開２００１－１４４４３０号公報JP 2001-144430 A 特開２００３－３３２７９５号公報JP 2003-332895 A 特開２００４－３５９２７０号公報JP 2004-359270 A
　本発明者らは、剥離後の接着力の安定性という課題に着目し、電気・電子部品等の各種部品の製造工程でのコスト削減を目的として繰返し使用が可能な粘着テープに関して開発を行った。すなわち本発明の目的は、部品の固定力に優れ、高温環境下で使用しても糊残りせず剥離でき、かつ接着－剥離を繰返しても接着力の変化が少ない粘着剤組成物及び粘着テープを提供することにある。 The present inventors focused on the problem of stability of the adhesive strength after peeling, and developed an adhesive tape that can be used repeatedly for the purpose of reducing costs in the manufacturing process of various parts such as electric and electronic parts. . That is, the object of the present invention is to provide a pressure-sensitive adhesive composition and pressure-sensitive adhesive tape that have excellent component fixing strength, can be peeled off without being left behind even when used in a high-temperature environment, and have little change in adhesive strength even after repeated adhesion-peeling. Is to provide.
　本発明者らは上記目的を達成すべく鋭意検討した結果、シリコーン粘着剤層のゲル分率と膨潤度のバランスが、繰り返し使用したときの接着力の変化及びその他の諸性能と関係していることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have found that the balance between the gel fraction and the degree of swelling of the silicone pressure-sensitive adhesive layer is related to changes in adhesive strength and other performances when repeatedly used. As a result, the present invention has been completed.
　すなわち本発明は、架橋されたシリコーン構造を含み、下記方法により測定されるゲル分率が４５％以上７０％未満であり、かつ下記方法により測定されるトルエンに対する膨潤度が２９０％以下であることを特徴とするシリコーン系粘着剤組成物である。
（ゲル分率）
　トルエンにシリコーン系粘着剤組成物を常温で１日間浸漬したときの不溶解分の比率である、下記式によってゲル分率を得る。
　ゲル分率（％）＝（Ｃ／Ａ）×１００
　　Ａ：シリコーン系粘着剤組成物の初期質量
　　Ｃ：トルエン浸漬後のシリコーン系粘着剤組成物の乾燥質量（乾燥条件：１３０℃、２時間）
（膨潤度）
　トルエンにシリコーン系粘着剤組成物を常温で１日間浸漬したときのトルエン吸収による膨潤比率である、下記式によって膨潤度を得る。
　　膨潤度（％）＝（（Ｂ―Ａ）／Ａ）×１００％
　　Ａ：シリコーン系粘着剤組成物の初期質量
　　Ｂ：トルエン浸漬後のシリコーン系粘着剤組成物の膨潤質量 That is, the present invention includes a crosslinked silicone structure, the gel fraction measured by the following method is 45% or more and less than 70%, and the degree of swelling with respect to toluene measured by the following method is 290% or less. It is a silicone type adhesive composition characterized by these.
(Gel fraction)
The gel fraction is obtained by the following formula, which is the ratio of the insoluble matter when the silicone pressure-sensitive adhesive composition is immersed in toluene at room temperature for 1 day.
Gel fraction (%) = (C / A) × 100
A: Initial mass of silicone-based pressure-sensitive adhesive composition C: Dry mass of silicone-based pressure-sensitive adhesive composition after immersion in toluene (drying conditions: 130 ° C., 2 hours)
(Swelling degree)
The degree of swelling is obtained by the following formula, which is the swelling ratio due to toluene absorption when the silicone-based pressure-sensitive adhesive composition is immersed in toluene at room temperature for 1 day.
Swelling degree (%) = ((B−A) / A) × 100%
A: Initial mass of silicone pressure-sensitive adhesive composition B: Swelling mass of silicone-based pressure-sensitive adhesive composition after immersion in toluene
　さらに本発明は、基材の少なくとも片面に上記粘着剤組成物からなる粘着剤層を有する粘着テープである。 Furthermore, this invention is an adhesive tape which has an adhesive layer which consists of said adhesive composition on the at least single side | surface of a base material.
　本発明によれば、部品の固定力に優れ、高温環境下で使用しても糊残りせず剥離でき、かつ接着－剥離を繰返しても接着力の変化が少ない粘着剤組成物及び粘着テープが提供される。特に、本発明の粘着テープは上記特定の粘着剤層を有するので、例えば高温下での電気・電子部品等の各種部品の製造工程において、工程中で部品が剥がれ落ちることがなく、剥離後に糊残りしにくく、かつ接着－剥離を繰返しても接着力の変化が少ないので繰返し使用が可能であり、コスト削減の点で非常に有用である。 According to the present invention, there are provided a pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape that have excellent component fixing strength, can be peeled off without being left behind even when used in a high temperature environment, and have little change in adhesive strength even after repeated adhesion-peeling. Provided. In particular, since the pressure-sensitive adhesive tape of the present invention has the above-mentioned specific pressure-sensitive adhesive layer, for example, in the manufacturing process of various parts such as electrical and electronic parts at high temperatures, the parts do not peel off during the process, It is difficult to remain, and even if adhesion-peeling is repeated, the change in adhesive force is small, so that it can be used repeatedly, which is very useful in terms of cost reduction.
実施例及び比較例の総合評価を、ゲル分率と膨潤度の相関関係においてまとめたグラフである。It is the graph which put together comprehensive evaluation of an Example and a comparative example in the correlation of a gel fraction and swelling degree. 実施例及び比較例における固定力試験を説明する為の模式図である。It is a schematic diagram for demonstrating the fixing force test in an Example and a comparative example.
　＜粘着剤組成物＞
　本発明の粘着剤組成物は、シリコーン系粘着剤を主成分として含む粘着剤組成物である。本発明の粘着剤組成物のゲル分率は４５％以上７０％未満であり、好ましくは４８～６５％、より好ましくは５０～６０％である。また、本発明の粘着剤組成物のトルエンに対する膨潤度は２９０％以下であり、好ましくは２６０％以下、より好ましくは２３０％以下である。ゲル分率及び膨潤度の具体的な測定方法は、後述する実施例の欄に記載する。一般に、膨潤度は粘着剤組成物の架橋密度に依存する。架橋密度が高い場合はトルエンに浸漬しても粘着剤を構成する三次元に架橋されたポリマー鎖が広がりにくく、膨潤度は低くなる。一方、架橋密度が低い場合はポリマー鎖が広がりやすく膨潤度は高くなる。 <Adhesive composition>
The pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition containing a silicone-based pressure-sensitive adhesive as a main component. The gel fraction of the pressure-sensitive adhesive composition of the present invention is 45% or more and less than 70%, preferably 48 to 65%, more preferably 50 to 60%. Moreover, the swelling degree with respect to toluene of the adhesive composition of this invention is 290% or less, Preferably it is 260% or less, More preferably, it is 230% or less. Specific methods for measuring the gel fraction and the degree of swelling are described in the Examples section described below. In general, the degree of swelling depends on the crosslinking density of the pressure-sensitive adhesive composition. When the crosslinking density is high, the three-dimensionally crosslinked polymer chain constituting the pressure-sensitive adhesive is difficult to spread even when immersed in toluene, and the degree of swelling is low. On the other hand, when the crosslinking density is low, the polymer chain is easy to spread and the degree of swelling is high.
　ゲル分率と膨潤度が本発明の特定の範囲であれば、十分な固定力と糊残り防止性、繰り返し使用したときの接着力の安定性が得られる。ゲル分率が４５％未満であると、固定力はより強固になる反面、凝集力不足による糊残りが発生しやすくなり、繰り返し使用した時の接着力は安定しない。一方、ゲル分率が７０％を超えると、十分な固定力が得られない。また、ゲル分率が４５％以上７０％未満の範囲内であっても、膨潤度が２９０％を超えると、架橋密度が低いことに起因した凝集力不足による糊残りが発生しやすくなり、繰り返し使用したときの接着力は安定しない。 If the gel fraction and the degree of swelling are within the specific ranges of the present invention, sufficient fixing force and adhesive residue prevention, and stability of adhesive strength when used repeatedly are obtained. If the gel fraction is less than 45%, the fixing force becomes stronger, but adhesive residue due to insufficient cohesion tends to occur, and the adhesive force when used repeatedly is not stable. On the other hand, if the gel fraction exceeds 70%, sufficient fixing force cannot be obtained. Even if the gel fraction is in the range of 45% or more and less than 70%, if the degree of swelling exceeds 290%, adhesive residue due to insufficient cohesion due to low crosslink density is likely to occur, and repeatedly The adhesive strength when used is not stable.
　本発明に用いるシリコーン系粘着剤の具体例としては、主にシリコーン生ゴム（Ｄ単位［(CH3)2SiO］からなるポリジメチルシロキサンの長鎖の重合体）とＭＱレジン（Ｍ単位［(CH3)3SiO1/2］とＱ単位［SiO2］からなる３次元構造のシリコーンレジンの重合体）からなる粘着剤が挙げられる。このようなシリコーン生ゴムとＭＱレジンからなる粘着剤は、シリコーン生ゴム単体に比較べて粘着性に優れる。また、粘着剤中のシリコーン生ゴムとＭＱレジンの比率を変えることで粘着力・保持力・タック等の基本的な粘着物性をコントロールすることができる。シリコーン系粘着剤としては、その硬化機構により、付加硬化型、過酸化物硬化型に大別される。付加硬化型シリコーン粘着剤は、アルケニル基を含有するシリコーン生ゴムからなる主剤とＳｉＨ基を含有するポリオルガノシロキサンからなる架橋剤を例えば白金触媒下で加熱して架橋反応させることにより硬化する。このとき架橋剤の量を適宜調整することで架橋密度を変えることが可能である。また、過酸化物硬化型シリコーン粘着剤は、硬化剤として過酸化ベンゾイル等の過酸化物を添加し、溶媒を除去した後、例えば高温で加熱することで硬化する。このとき、添加する過酸化物の量を適宜調整することで粘着剤の架橋密度を変えることが可能である。シリコーン系粘着剤は２種以上を組み合わせて使用しても良い。特に、本発明の粘着剤組成物は架橋硬化された付加硬化型シリコーン粘着剤を含むことが好ましい。 Specific examples of the silicone-based pressure-sensitive adhesive used in the present invention include silicone raw rubber (polydimethylsiloxane long-chain polymer mainly composed of D units [(CH 3 ) 2 SiO]) and MQ resin (M units [(CH 3 ) A pressure-sensitive adhesive composed of 3 SiO 1/2 ] and a silicone resin having a three-dimensional structure composed of Q units [SiO 2 ]. Such a pressure-sensitive adhesive composed of a silicone raw rubber and an MQ resin is superior in adhesiveness compared to a silicone raw rubber alone. In addition, by changing the ratio of silicone raw rubber and MQ resin in the adhesive, basic adhesive properties such as adhesive strength, holding power, and tack can be controlled. Silicone pressure-sensitive adhesives are roughly classified into addition-curing types and peroxide-curing types depending on the curing mechanism. The addition-curable silicone pressure-sensitive adhesive is cured by heating a base agent composed of a silicone raw rubber containing an alkenyl group and a crosslinking agent comprising a polyorganosiloxane containing an SiH group, for example, under a platinum catalyst to cause a crosslinking reaction. At this time, it is possible to change the crosslinking density by appropriately adjusting the amount of the crosslinking agent. Further, the peroxide curable silicone pressure-sensitive adhesive is cured by adding a peroxide such as benzoyl peroxide as a curing agent, removing the solvent, and then heating at a high temperature, for example. At this time, it is possible to change the crosslinking density of the pressure-sensitive adhesive by appropriately adjusting the amount of peroxide to be added. Two or more silicone pressure-sensitive adhesives may be used in combination. In particular, the pressure-sensitive adhesive composition of the present invention preferably contains a cross-linked addition-curable silicone pressure-sensitive adhesive.
　本発明の粘着剤組成物は、市販品を用いて得ることができる。例えば、市販のシリコーン系粘着剤を架橋硬化させることにより所望の物性の粘着剤組成物が得られる。具体的には、先に例示したシリコーン系粘着剤を架橋硬化させることにより、架橋されたシリコーン構造を含む本発明の粘着剤組成物を得ることができる。架橋硬化反応は通常は加熱によって行うが、粘着剤や硬化剤の種類によっては縮合反応や紫外線照射でも架橋硬化が可能である。 The pressure-sensitive adhesive composition of the present invention can be obtained using a commercially available product. For example, a pressure-sensitive adhesive composition having desired physical properties can be obtained by crosslinking and curing a commercially available silicone pressure-sensitive adhesive. Specifically, the pressure-sensitive adhesive composition of the present invention including a crosslinked silicone structure can be obtained by crosslinking and curing the silicone-based pressure-sensitive adhesive exemplified above. The crosslinking and curing reaction is usually carried out by heating, but depending on the type of pressure-sensitive adhesive or curing agent, crosslinking and curing can be performed by condensation reaction or ultraviolet irradiation.
　本発明の特定のゲル分率及び膨潤度を有する粘着剤組成物は、例えば、２種以上の市販のシリコーン系粘着剤の混合物を用いて得ることができる。具体的には、例えばゲル分率及び膨潤度が比較的高いシリコーン系粘着剤と、ゲル分率及び膨潤度が比較的低いシリコーン系粘着剤とを適当な比率で混合して架橋硬化することにより、ゲル分率及び膨潤度が本発明の範囲内となる粘着剤組成物を得ることができる。ただし本発明の粘着剤組成物は、このような方法で得たものに限定されるものではない。 The pressure-sensitive adhesive composition having a specific gel fraction and swelling degree according to the present invention can be obtained by using, for example, a mixture of two or more types of commercially available silicone pressure-sensitive adhesives. Specifically, for example, a silicone pressure-sensitive adhesive having a relatively high gel fraction and swelling degree and a silicone pressure-sensitive adhesive having a relatively low gel fraction and swelling degree are mixed at an appropriate ratio and crosslinked and cured. A pressure-sensitive adhesive composition having a gel fraction and a swelling degree within the range of the present invention can be obtained. However, the pressure-sensitive adhesive composition of the present invention is not limited to that obtained by such a method.
　本発明の粘着剤組成物には、各種特性の向上を目的として添加剤を添加しても良い。添加剤の具体例としては、カーボンブラック、シリカ等の無機充填剤；シリコーンレジン、ポリジメチルシロキサン、ポリジメチルフェニルシロキサン等のポリオルガノシロキサン；フェノール系酸化防止剤、アミン系酸化防止剤等の酸化防止剤；シランカップリング剤が挙げられる。ただし添加剤の種類や量は、発明の効果が損なわれないよう適宜選定する必要がある。 An additive may be added to the pressure-sensitive adhesive composition of the present invention for the purpose of improving various properties. Specific examples of additives include inorganic fillers such as carbon black and silica; polyorganosiloxanes such as silicone resin, polydimethylsiloxane and polydimethylphenylsiloxane; and antioxidants such as phenolic antioxidants and amine antioxidants. Agents; silane coupling agents. However, the type and amount of the additive must be appropriately selected so as not to impair the effects of the invention.
　＜粘着テープ＞
　本発明の粘着テープは、基材の少なくとも片面に以上説明した本発明の粘着剤組成物からなる粘着剤層を有する粘着テープであり、代表的には、基材フィルムの片面又は両面にその粘着剤層を有する粘着テープである。粘着剤層の厚さは特に限定されないが、好ましくは２～１５０μｍ、より好ましくは５～１００μｍ、特に好ましくは１０～７５μｍである。 <Adhesive tape>
The pressure-sensitive adhesive tape of the present invention is a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition of the present invention described above on at least one side of a base material, and typically the pressure-sensitive adhesive is applied to one side or both sides of a base film. It is an adhesive tape having an agent layer. The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 2 to 150 μm, more preferably 5 to 100 μm, and particularly preferably 10 to 75 μm.
　粘着剤層は、粘着剤組成物を架橋硬化反応させることにより形成できる。例えば、粘着剤組成物を基材上に塗布し、加熱又は縮合反応や紫外線照射により架橋硬化させて基材上に粘着剤層を形成できる。また、粘着剤組成物を離型紙又はその他のフィルム上に塗布し、加熱又は縮合反応や紫外線照射により架橋硬化させて粘着剤層を形成し、この粘着剤層を基材の片面又は両面に貼り合せることもできる。 The pressure-sensitive adhesive layer can be formed by cross-linking and curing reaction of the pressure-sensitive adhesive composition. For example, the pressure-sensitive adhesive composition can be applied on a base material and crosslinked and cured by heating or condensation reaction or ultraviolet irradiation to form a pressure-sensitive adhesive layer on the base material. In addition, the pressure-sensitive adhesive composition is applied onto a release paper or other film, and is subjected to crosslinking and curing by heating or condensation reaction or ultraviolet irradiation to form a pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer is applied to one or both sides of the substrate. It can also be combined.
　塗布の際の粘着剤組成物の粘度を下げる為に、溶剤を添加しても良い。溶剤の具体例としては、トルエン、キシレン等の芳香族系溶剤；ヘキサン、オクタン、イソパラフィン等の脂肪族系溶剤；メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤；酢酸エチル、酢酸イソブチル等のエステル系溶剤；ジイソプロピルエーテル、１,４－ジオキサン等のエーテル系溶剤が挙げられる。 In order to reduce the viscosity of the pressure-sensitive adhesive composition during application, a solvent may be added. Specific examples of the solvent include aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, octane and isoparaffin; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and isobutyl acetate. And ether solvents such as diisopropyl ether and 1,4-dioxane.
　塗工方法は特に限定されず、公知の方法を用いれば良い。その具体例としては、コンマコーター、リップコーター、ロールコーター、ダイコーター、ナイフコーター、ブレードコーター、ロッドコーター、キスコーター又はグラビアコーターを用いた塗工；スクリーン塗工；浸漬塗工；キャスト塗工が挙げられる。 The coating method is not particularly limited, and a known method may be used. Specific examples thereof include coating using a comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater or gravure coater; screen coating; dip coating; cast coating. It is done.
　基材は特に限定されないが、フィルム状の基材が好ましい。特に、高温下で処理可能な耐熱性の高い樹脂フィルムが好ましい。その具体例としては例えば、ポリイミド（ＰＩ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリフェニレンサルファイド（ＰＰＳ）、ポリアミドイミド（ＰＡＩ）、ポリエーテルスルフォン（ＰＥＳ）、ポリテトラフルオロエチレン（ＰＴＦＥ）等の樹脂フィルムが挙げられる。これらのフィルムを単層、または２層以上の積層フィルムとして使用することができる。中でも、ポリイミドフィルムが好ましい。基材の厚さは特に限定されないが、好ましくは２～１８０μｍ、より好ましくは５～１００μｍ、特に好ましくは１２～７５μｍである。 The substrate is not particularly limited, but a film-like substrate is preferable. In particular, a resin film having high heat resistance that can be processed at a high temperature is preferable. Specific examples thereof include polyimide (PI), polyetheretherketone (PEEK), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyamideimide (PAI), polyethersulfone (PES). ), And a resin film such as polytetrafluoroethylene (PTFE). These films can be used as a single layer or a laminated film of two or more layers. Among these, a polyimide film is preferable. The thickness of the substrate is not particularly limited, but is preferably 2 to 180 μm, more preferably 5 to 100 μm, and particularly preferably 12 to 75 μm.
　さらに、基材の粘着剤層を設ける面には、必要に応じて易接着処理を施しても良い。易接着処理としては、例えば、プライマー処理、コロナ処理、エッチング処理、プラズマ処理、サンドブラスト処理などが挙げられる。 Furthermore, the surface on which the pressure-sensitive adhesive layer of the substrate is provided may be subjected to an easy adhesion treatment as necessary. Examples of the easy adhesion treatment include primer treatment, corona treatment, etching treatment, plasma treatment, and sandblast treatment.
　本発明の粘着テープには剥離ライナーを設けても良い。剥離ライナーとは、粘着テープの粘着剤層を保護する為のものであり、貼り付け直前に剥離し、粘着剤を露出させて被着体に粘着テープを貼り付ける。剥離ライナーの種類は特に限定されず、公知の剥離ライナーを使用できる。その具体例としては、上質紙、グラシン紙、合成樹脂フィルム等の基材の表面に離型剤処理を施したものが挙げられる。離型剤処理には、例えばフッ素置換アルキル変性シリコーン樹脂等による離型剤を用いれば良い。特に、シリコーン系粘着剤層に積層する剥離ライナーとしては、ポリエチレンタレフタレートフィルムの表面をフッ素置換アルキル変性シリコーン樹脂で離型処理したものが好ましい。 A release liner may be provided on the adhesive tape of the present invention. The release liner is for protecting the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape, and is peeled off immediately before application, and the pressure-sensitive adhesive is exposed and the pressure-sensitive adhesive tape is attached to the adherend. The kind of release liner is not particularly limited, and a known release liner can be used. Specific examples thereof include those obtained by subjecting the surface of a base material such as fine paper, glassine paper, and synthetic resin film to a release agent treatment. For the release agent treatment, for example, a release agent using a fluorine-substituted alkyl-modified silicone resin or the like may be used. In particular, the release liner to be laminated on the silicone-based pressure-sensitive adhesive layer is preferably one obtained by releasing the surface of the polyethylene terephthalate film with a fluorine-substituted alkyl-modified silicone resin.
　以下、実施例により本発明をさらに詳細に説明する。ただし、本発明はこれら実施例に限定されるものではない。以下の記載において「部」は「質量部」を意味する。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In the following description, “part” means “part by mass”.
　＜実施例１＞
　固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＳＤ－４５６０、東レ・ダウコーニング株式会社製）７０部、固形分濃度４０質量％の付加硬化型シリコーン粘着剤原液（商品名ＳＤ－４５８７Ｌ、東レ・ダウコーニング株式会社製）３０部、希釈溶剤としてトルエン５４部、硬化触媒として白金触媒（商品名ＮＣ－２５、東レ・ダウコーニング株式会社製）０.３部を均一に混合し、粘着剤液（１）を得た。 <Example 1>
Addition-curing silicone adhesive stock solution (trade name SD-4560, manufactured by Toray Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass, and addition-curing silicone adhesive stock solution having a solid content concentration of 40% by mass (product name SD) -4587L, manufactured by Toray Dow Corning Co., Ltd.) 30 parts, 54 parts of toluene as a diluting solvent, and platinum part (trade name NC-25, manufactured by Toray Dow Corning Co., Ltd.) as a curing catalyst were mixed uniformly. A pressure-sensitive adhesive liquid (1) was obtained.
　次に、プライマー処理した厚さ２５μｍのポリイミド（ＰＩ）フィルムの片面に、粘着剤液（１）を乾燥後の粘着剤層の厚さが３０μｍになるように塗布し、乾燥炉内で１３０℃、２分にて硬化・乾燥して粘着剤層を形成した。そして剥離ライナー（フッ素置換アルキル変性シリコーン樹脂で離型処理を施した厚さ５０μｍのＰＥＴフィルム）を粘着剤層に貼り合わせ、粘着テープを得た。 Next, the pressure-sensitive adhesive liquid (1) was applied on one side of a primer-treated polyimide (PI) film having a thickness of 25 μm so that the thickness of the pressure-sensitive adhesive layer after drying was 30 μm. The adhesive layer was formed by curing and drying in 2 minutes. Then, a release liner (50 μm thick PET film which had been subjected to a release treatment with a fluorine-substituted alkyl-modified silicone resin) was bonded to the adhesive layer to obtain an adhesive tape.
　＜実施例２＞
　固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＳＤ－４５６０、東レ・ダウコーニング株式会社製）５０部、固形分濃度４０質量％の付加硬化型シリコーン粘着剤原液（商品名ＳＤ－４５８７Ｌ、東レ・ダウコーニング株式会社製）５０部、希釈溶剤としてトルエン４３部、硬化触媒として白金触媒（商品名ＮＣ－２５、東レ・ダウコーニング株式会社製）０.３部を均一に混合し、粘着剤液（２）を得た。そして、粘着剤液（２）を用いたこと以外は実施例１と同様の方法で、粘着テープを得た。 <Example 2>
Addition-curing silicone adhesive stock solution (trade name SD-4560, manufactured by Toray Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass, and addition-curing silicone adhesive stock solution having a solid content concentration of 40% by mass (product name SD) -4587L, 50 parts of Toray Dow Corning Co., Ltd., 43 parts of toluene as diluent solvent, and 0.3 parts of platinum catalyst as a curing catalyst (trade name NC-25, produced by Toray Dow Corning Co., Ltd.) are uniformly mixed. A pressure-sensitive adhesive liquid (2) was obtained. And the adhesive tape was obtained by the method similar to Example 1 except having used the adhesive liquid (2).
　＜実施例３＞
　固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＳＤ－４５６０、東レ・ダウコーニング株式会社製）２０部、固形分濃度４０質量％の付加硬化型シリコーン粘着剤原液（商品名ＳＤ－４５８７Ｌ、東レ・ダウコーニング株式会社製）８０部、希釈溶剤としてトルエン２６部、硬化触媒として白金触媒（商品名ＮＣ－２５、東レ・ダウコーニング株式会社製）０.３部を均一に混合し、粘着剤液（３）を得た。そして、粘着剤液（３）を用いたこと以外は実施例１と同様の方法で、粘着テープを得た <Example 3>
Addition-curing silicone adhesive stock solution (trade name SD-4560, manufactured by Toray Dow Corning Co., Ltd.) with a solid content concentration of 60% by mass, addition-curing silicone adhesive stock solution with a solid content concentration of 40% by mass (product name SD) -4587L, manufactured by Toray Dow Corning Co., Ltd.) 80 parts, 26 parts of toluene as a diluting solvent, and 0.3 parts of a platinum catalyst (trade name NC-25, manufactured by Toray Dow Corning Co., Ltd.) as a curing catalyst are uniformly mixed. An adhesive liquid (3) was obtained. And the adhesive tape was obtained by the method similar to Example 1 except having used the adhesive liquid (3).
　＜比較例１＞
　固形分濃度４０質量％の付加硬化型シリコーン粘着剤原液（商品名ＳＤ－４５８７Ｌ、東レ・ダウコーニング株式会社製）１００部、希釈溶剤としてトルエン３３部、硬化触媒として白金触媒（商品名ＮＣ－２５、東レ・ダウコーニング株式会社製）０.３部を均一に混合し、粘着剤液（４）を得た。そして、粘着剤液（４）を用いたこと以外は実施例１と同様の方法で、粘着テープを得た。 <Comparative Example 1>
Addition-curing silicone adhesive stock solution with a solid content of 40% by mass (trade name SD-4487L, manufactured by Toray Dow Corning Co., Ltd.), 33 parts of toluene as a diluting solvent, platinum catalyst as a curing catalyst (trade name NC-25) 0.3 parts of Toray Dow Corning Co., Ltd.) were uniformly mixed to obtain a pressure-sensitive adhesive liquid (4). And the adhesive tape was obtained by the method similar to Example 1 except having used the adhesive liquid (4).
　＜比較例２＞
　固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＳＤ－４５８０、東レ・ダウコーニング株式会社製）１００部、希釈溶剤としてトルエン７１部、硬化触媒として白金触媒（商品名ＮＣ－２５、東レ・ダウコーニング株式会社製）０.３部を均一に混合し、粘着剤液（５）を得た。そして、粘着剤液（５）を用いたこと以外は実施例１と同様の方法で、粘着テープを得た。 <Comparative Example 2>
Addition-curing silicone pressure-sensitive adhesive stock solution (trade name SD-4580, manufactured by Toray Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass, 71 parts of toluene as a diluting solvent, and a platinum catalyst (trade name NC-25 as a curing catalyst) 0.3 parts of Toray Dow Corning Co., Ltd.) were uniformly mixed to obtain a pressure-sensitive adhesive liquid (5). And the adhesive tape was obtained by the method similar to Example 1 except having used the adhesive liquid (5).
　＜比較例３＞
　固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＳＤ－４５８４、東レ・ダウコーニング株式会社製）１００部、希釈溶剤としてトルエン７１部、硬化触媒として白金触媒（商品名ＮＣ－２５、東レ・ダウコーニング株式会社製）０.３部を均一に混合し、粘着剤液（６）を得た。そして、粘着剤液（６）を用いたこと以外は実施例１と同様の方法で、粘着テープを得た。 <Comparative Example 3>
Addition-curing silicone adhesive stock solution (trade name SD-4484, manufactured by Toray Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass, 71 parts of toluene as a diluting solvent, and a platinum catalyst (trade name NC-25 as a curing catalyst) 0.3 parts of Toray Dow Corning Co., Ltd.) were uniformly mixed to obtain an adhesive liquid (6). And the adhesive tape was obtained by the method similar to Example 1 except having used the adhesive liquid (6).
　＜比較例４＞
　固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＳＤ－４５６０、東レ・ダウコーニング株式会社製）１００部、希釈溶剤としてトルエン７１部、硬化触媒として白金触媒（商品名ＮＣ－２５、東レ・ダウコーニング株式会社製）０.３部を均一に混合し、粘着剤液（７）を得た。そして、粘着剤液（７）を用いたこと以外は実施例１と同様の方法で、粘着テープを得た。 <Comparative Example 4>
Addition-curing silicone adhesive stock solution (trade name SD-4560, manufactured by Toray Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass, toluene 71 parts as a diluting solvent, platinum catalyst (trade name NC-25) 0.3 parts of Toray Dow Corning Co., Ltd.) was uniformly mixed to obtain an adhesive liquid (7). And the adhesive tape was obtained by the method similar to Example 1 except having used the adhesive liquid (7).
　＜比較例５＞
　固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＳＤ－４５７０、東レ・ダウコーニング株式会社製）１００部、希釈溶剤としてトルエン７１部、硬化触媒として白金触媒（商品名ＮＣ－２５、東レ・ダウコーニング株式会社製）０.３部を均一に混合し、粘着剤液（８）を得た。そして、粘着剤液（８）を用いたこと以外は実施例１と同様の方法で、粘着テープを得た。 <Comparative Example 5>
Addition-curing silicone adhesive stock solution (trade name SD-4570, manufactured by Toray Dow Corning Co., Ltd.) having a solid concentration of 60% by mass, toluene 71 parts as a diluting solvent, platinum catalyst (trade name NC-25) And 0.3 part of Toray Dow Corning Co., Ltd.) were uniformly mixed to obtain a pressure-sensitive adhesive liquid (8). And the adhesive tape was obtained by the method similar to Example 1 except having used the adhesive liquid (8).
　＜比較例６＞
　固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＫＲ－３７００、信越化学工業株式会社製）１００部、希釈溶剤としてトルエン７１部、硬化触媒として白金触媒（商品名ＣＡＴ－ＰＬ－５０Ｔ、信越化学工業株式会社製）０.５部を均一に混合し、粘着剤液(９)を得た。そして、粘着剤液(９)を用いたこと以外は実施例１と同様の方法で、粘着テープを得た。 <Comparative Example 6>
Addition-curing silicone adhesive stock solution (trade name KR-3700, manufactured by Shin-Etsu Chemical Co., Ltd.) having a solid concentration of 60% by mass, toluene 71 parts as a diluent solvent, platinum catalyst (trade name CAT-PL-) 0.5 part (50T, manufactured by Shin-Etsu Chemical Co., Ltd.) was uniformly mixed to obtain an adhesive liquid (9). And the adhesive tape was obtained by the method similar to Example 1 except having used the adhesive liquid (9).
　＜比較例７＞
　固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＫＲ－３７０１、信越化学工業株式会社製）１００部、希釈溶剤としてトルエン７１部、硬化触媒として白金触媒（商品名ＣＡＴ－ＰＬ－５０Ｔ、信越化学工業株式会社製）０.５部を均一に混合し、粘着剤液(１０)を得た。そして、粘着剤液(１０)を用いたこと以外は実施例１と同様の方法で、粘着テープを得た。 <Comparative Example 7>
Addition-curing silicone adhesive stock solution (trade name KR-3701, manufactured by Shin-Etsu Chemical Co., Ltd.) with a solid content concentration of 60% by mass, toluene 71 parts as a diluting solvent, platinum catalyst (trade name CAT-PL-) 0.5 part (50T, manufactured by Shin-Etsu Chemical Co., Ltd.) was uniformly mixed to obtain an adhesive liquid (10). And the adhesive tape was obtained by the method similar to Example 1 except having used the adhesive liquid (10).
　＜比較例８＞
　固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＫＲ－３７０４、信越化学工業株式会社製）１００部、希釈溶剤としてトルエン７１部、硬化触媒として白金触媒（商品名ＣＡＴ－ＰＬ－５０Ｔ、信越化学工業株式会社製）０.５部を均一に混合し、粘着剤液(１１)を得た。そして、粘着剤液(１１)を用いたことと、剥離ライナーとして厚さ３８μｍの未処理のＰＥＴフィルムを用いたこと以外は実施例１と同様の方法で、粘着テープを得た。 <Comparative Example 8>
Addition-curing silicone adhesive stock solution (trade name KR-3704, manufactured by Shin-Etsu Chemical Co., Ltd.) having a solid content concentration of 60% by mass, toluene 71 parts as a diluting solvent, platinum catalyst (trade name CAT-PL-) 0.5 part (50T, manufactured by Shin-Etsu Chemical Co., Ltd.) was uniformly mixed to obtain an adhesive liquid (11). Then, an adhesive tape was obtained in the same manner as in Example 1 except that the adhesive liquid (11) was used and an untreated PET film having a thickness of 38 μm was used as the release liner.
　＜比較例９＞
　固形分濃度６０質量％の過酸化物硬化型シリコーン粘着剤原液（商品名ＳＨ－４２８０、東レ・ダウコーニング株式会社製）１００部、希釈溶剤としてトルエン７１部、硬化剤（商品名ナイパー（登録商標）ＢＭＴ－４０、日油株式会社製）３.０部を均一に混合し、粘着剤液（１２）を得た。 <Comparative Example 9>
100 parts of a peroxide curable silicone adhesive stock solution (trade name SH-4280, manufactured by Toray Dow Corning Co., Ltd.) with a solid content concentration of 60% by weight, 71 parts of toluene as a diluent, and a curing agent (trade name Nyper (registered trademark)) ) BMT-40 (manufactured by NOF Corporation) (3.0 parts) was mixed uniformly to obtain an adhesive liquid (12).
　次に、プライマー処理した厚さ２５μｍのポリイミド（ＰＩ）フィルムの片面に、粘着剤液（１２）を乾燥後の粘着剤層の厚さが３０μｍになるように塗布した。これを乾燥炉内で６０℃、１分で溶媒を除去し、さらに１８０℃、２分で硬化・乾燥して粘着剤層を形成した。そして剥離ライナー（フッ素置換アルキル変性シリコーン樹脂で離型処理を施した厚さ５０μｍのＰＥＴフィルム）を粘着剤層に貼り合せて、粘着テープを得た。 Next, the pressure-sensitive adhesive liquid (12) was applied on one side of a primer-treated polyimide (PI) film having a thickness of 25 μm so that the thickness of the pressure-sensitive adhesive layer after drying was 30 μm. The solvent was removed at 60 ° C. for 1 minute in a drying furnace, and further cured and dried at 180 ° C. for 2 minutes to form an adhesive layer. Then, a release liner (50 μm thick PET film which had been subjected to a release treatment with a fluorine-substituted alkyl-modified silicone resin) was bonded to the adhesive layer to obtain an adhesive tape.
　＜比較例１０＞
　固形分濃度６０質量％の過酸化物硬化型シリコーン粘着剤原液（商品名ＫＲ－１００、信越化学工業株式会社製）１００部、希釈溶剤としてトルエン７１部、硬化剤（商品名ナイパー（登録商標）ＢＭＴ－４０、日油株式会社製）３.０部を均一に混合し、粘着剤液（１３）を得た。そして、粘着剤液（１３）を用いたこと以外は比較例９と同様の方法で、粘着テープを得た。 <Comparative Example 10>
100 parts of a peroxide curable silicone adhesive stock solution (trade name KR-100, manufactured by Shin-Etsu Chemical Co., Ltd.) with a solid content concentration of 60% by weight, 71 parts of toluene as a diluent solvent, a curing agent (trade name Nyper (registered trademark)) 3.0 parts of BMT-40 (manufactured by NOF Corporation) were uniformly mixed to obtain a pressure-sensitive adhesive liquid (13). And the adhesive tape was obtained by the method similar to the comparative example 9 except having used the adhesive liquid (13).
　＜粘着剤組成物のゲル分率及び膨潤度＞
　実施例及び比較例で得た粘着剤液（１）～（１３）を、剥離ライナー上に乾燥後の厚さが５０～２００μｍになるように塗布した。続いて、乾燥炉で加熱し硬化・乾燥して粘着剤組成物とし、これをサンプルとした。この際の加熱温度は各実施例及び比較例と同じ温度とした。すなわち、粘着剤液（１）～（１１）の場合は１３０℃、２分、粘着剤液（１２）及び（１３）の場合は６０℃、１分及び１８０℃、２分とした。 <Gel fraction and swelling degree of pressure-sensitive adhesive composition>
The pressure-sensitive adhesive liquids (1) to (13) obtained in Examples and Comparative Examples were applied on the release liner so that the thickness after drying was 50 to 200 μm. Subsequently, it was heated in a drying oven, cured and dried to obtain an adhesive composition, which was used as a sample. The heating temperature at this time was set to the same temperature as each example and comparative example. That is, in the case of the adhesive liquids (1) to (11), the temperature was 130 ° C. for 2 minutes, and in the case of the adhesive liquids (12) and (13), the temperature was 60 ° C., 1 minute and 180 ° C., 2 minutes.
　得られたサンプルを５０ｍｍ×５０ｍｍに断裁し、剥離ライナーを剥離し、シート状の粘着剤組成物からなる測定用サンプルを得た。この測定用サンプルの初期質量（Ａ）（＝膨潤前の粘着剤組成物の質量）を測定した。そしてこの測定用サンプルを、初期質量（Ａ）の２５０倍量以上のトルエンに常温（２３℃）で１日間浸漬し膨潤させた。浸漬後に測定用サンプルを取り出して膨潤質量（Ｂ）（＝トルエンで膨潤した粘着剤組成物の質量）を測定した。さらにこの測定用サンプルを、１３０℃の乾燥機で２時間乾燥させて吸収した溶媒を除去し、乾燥質量（Ｃ）（＝乾燥した粘着剤組成物の質量）を測定した。粘着剤組成物のゲル分率及び膨潤度を下記式によって得た。
　ゲル分率（％）＝（Ｃ／Ａ）×１００
　膨潤度（％）＝（（Ｂ―Ａ）／Ａ）×１００％ The obtained sample was cut into 50 mm × 50 mm, the release liner was peeled off, and a measurement sample comprising a sheet-like pressure-sensitive adhesive composition was obtained. The initial mass (A) of this measurement sample (= mass of the pressure-sensitive adhesive composition before swelling) was measured. Then, this measurement sample was immersed and swollen in toluene at 250 times the initial mass (A) at room temperature (23 ° C.) for 1 day. The sample for measurement was taken out after immersion, and swelling mass (B) (= mass of the adhesive composition swollen with toluene) was measured. Further, this measurement sample was dried with a dryer at 130 ° C. for 2 hours to remove the absorbed solvent, and the dry mass (C) (= the mass of the dried pressure-sensitive adhesive composition) was measured. The gel fraction and swelling degree of the pressure-sensitive adhesive composition were obtained by the following formula.
Gel fraction (%) = (C / A) × 100
Swelling degree (%) = ((B−A) / A) × 100%
　＜常温（２３℃）の対ＳＵＳ粘着力＞
　２０ｍｍ幅に裁断した粘着テープを研磨したＳＵＳ板に貼り付け、重さ２ｋｇのゴム層で被覆されたローラーで１往復させて圧着し、２３℃環境下で２０～４０分放置した。その後、引張試験機を用いて３００ｍｍ／分の速度で１８０°の角度でテープを剥離するのに要する力を測定した。 <Normal temperature (23 ° C.) resistance to SUS>
The pressure-sensitive adhesive tape cut to a width of 20 mm was attached to a polished SUS plate, pressed once by a roller covered with a rubber layer having a weight of 2 kg, and left in a 23 ° C. environment for 20 to 40 minutes. Thereafter, the force required to peel the tape at an angle of 180 ° at a speed of 300 mm / min was measured using a tensile tester.
　＜加熱（２００℃及び２３０℃）後の繰り返し対ＳＵＳ粘着力・糊残り性＞
　２０ｍｍ幅に裁断した粘着テープを研磨したＳＵＳ板に貼り付け、重さ２ｋｇのゴム層で被覆されたローラーで１往復させて圧着し、２００℃及び２３０℃の乾燥機中に３０分放置した。これを取り出して室温で放冷した。その後、引張試験機を用いて３００ｍｍ／分の速度で１８０°の角度でテープを剥離するのに要する力（１回目の加熱後粘着力）を測定した。この剥離後の粘着テープを再び研磨したＳＵＳ板に貼り付け、１回目と同様にして２回目の加熱後粘着力を測定した。以降、１０回目の加熱後粘着力まで繰り返し測定した。また、各回における剥離したときの糊残り性を目視で確認し、以下の基準で評価した。
　○：糊残りなし
　×：糊残りあり <Repeating vs. SUS adhesive strength and adhesive residue after heating (200 ° C. and 230 ° C.)>
The pressure-sensitive adhesive tape cut to a width of 20 mm was attached to a polished SUS plate, pressed once by a roller covered with a rubber layer having a weight of 2 kg, and left in a dryer at 200 ° C. and 230 ° C. for 30 minutes. This was taken out and allowed to cool at room temperature. Then, the force (adhesive force after the first heating) required to peel off the tape at an angle of 180 ° at a speed of 300 mm / min was measured using a tensile tester. The peeled adhesive tape was affixed to a polished SUS plate again, and the adhesive strength after heating was measured in the same manner as the first time. Thereafter, the adhesive strength was repeatedly measured until the tenth heating. Moreover, the adhesive residue property at the time of peeling in each time was confirmed visually, and evaluated according to the following criteria.
○: No glue residue ×: There is glue residue
　＜接着力の変化率＞
　加熱後粘着力を１０回繰り返し測定した際、以下の式に従い接着力の変化率を算出し（表１及び２）、最大・最小の変化率を記載した（表３）。
　変化率（％）＝各回の加熱後粘着力／１回目の加熱後粘着力×１００％ <Change rate of adhesive strength>
When the adhesive strength after heating was measured 10 times repeatedly, the change rate of the adhesive force was calculated according to the following formula (Tables 1 and 2), and the maximum and minimum change rates were listed (Table 3).
Rate of change (%) = Adhesive strength after each heating / Adhesive strength after the first heating × 100%
　＜固定力試験＞
　図２に示すとおり、両端を固定した粘着テープ１の粘着層１ｂ側（下側）に７５ｇのおもり２を貼り付け（貼り付け面積２０ｍｍ×２５ｍｍ）、２００℃の乾燥機中で１時間放置して、おもり２の落下の有無を確認し、以下の基準で固定力を評価した。
　○：おもりが落下しなかった
　×：おもりが落下した <Fixing force test>
As shown in FIG. 2, a 75 g weight 2 is attached to the adhesive layer 1b side (lower side) of the adhesive tape 1 with both ends fixed (attachment area 20 mm × 25 mm) and left in a dryer at 200 ° C. for 1 hour. Then, the presence or absence of the weight 2 was confirmed, and the fixing force was evaluated according to the following criteria.
○: The weight did not fall ×: The weight fell
　以上の各測定の結果を表１～３に示す。さらに、実施例及び比較例の総合評価をゲル分率と膨潤度の相関関係においてまとめたグラフを図１に示す。 Tables 1 to 3 show the results of the above measurements. Furthermore, the graph which put together the comprehensive evaluation of an Example and a comparative example in the correlation of a gel fraction and a swelling degree is shown in FIG.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　＜評価結果＞
　表３に示すように、実施例１～３では２００℃及び２３０℃で１０回繰り返し使用しても、加熱後の粘着力の変化は初期の±１５％以内に収まり、繰り返し使用したときの接着力は非常に安定していた。また糊残りもなく部品の固定力も十分であった。 <Evaluation results>
As shown in Table 3, in Examples 1 to 3, even after repeated use at 200 ° C. and 230 ° C. 10 times, the change in adhesive strength after heating was within ± 15% of the initial value, and adhesion when repeatedly used The force was very stable. Moreover, there was no adhesive residue and the fixing force of the parts was sufficient.
　比較例１では、ゲル分率は低くないが膨潤度が高い（すなわち架橋密度が低い）ので、糊残りはなかったが、２３０℃で繰り返し使用すると著しく粘着力が上昇し、繰り返し使用したときの接着力は不安定であった。 In Comparative Example 1, the gel fraction was not low, but the degree of swelling was high (that is, the crosslinking density was low), so there was no adhesive residue, but when used repeatedly at 230 ° C., the adhesive strength increased significantly, and when used repeatedly. The adhesive force was unstable.
　比較例２～３及び比較例６～７では、ゲル分率が低くかつ膨潤度が高いので、２３０℃で繰り返し使用すると糊残りが発生した。また繰り返し使用したときの接着力の変化が大きかった。 In Comparative Examples 2 to 3 and Comparative Examples 6 to 7, since the gel fraction was low and the degree of swelling was high, adhesive residue was generated after repeated use at 230 ° C. Moreover, the change of the adhesive force when repeatedly used was large.
　比較例４～５では、膨潤度は高くないので糊残りはなかったが、ゲル分率が低いので繰り返し使用したときの接着力の安定性が劣っていた。 In Comparative Examples 4 to 5, since the degree of swelling was not high, there was no adhesive residue, but the gel fraction was low, so the stability of the adhesive strength when repeatedly used was poor.
　比較例８（弱粘着性の粘着剤）では、ゲル分率が高くかつ膨潤度が高いので、糊残りが発生しやすく、繰り返し使用したときの接着力の安定性が劣っていた。また、ゲル分率が高いことに起因して、部品の固定力も劣っていた。 In Comparative Example 8 (weakly sticky pressure-sensitive adhesive), the gel fraction was high and the degree of swelling was high, so that adhesive residue was likely to occur, and the stability of the adhesive strength when repeatedly used was poor. Moreover, due to the high gel fraction, the fixing force of the parts was also inferior.
　比較例９～１０（過酸化物硬化型の粘着剤）では、ゲル分率が低くかつ膨潤度が高いので、糊残りが発生しやすく、繰り返し使用したときの接着力の安定性が劣っていた。 In Comparative Examples 9 to 10 (peroxide curable pressure-sensitive adhesive), the gel fraction was low and the degree of swelling was high, so that adhesive residue was likely to occur, and the stability of the adhesive strength when used repeatedly was poor. .
　本発明の粘着剤組成物は、例えば粘着テープの粘着剤層を形成する為の材料として特に有用である。本発明の粘着テープは、例えば電気・電子部品等の各種部品の製造工程において、部品の保護、マスキング、仮固定、搬送用固定等の用途に非常に有用である。 The pressure-sensitive adhesive composition of the present invention is particularly useful as a material for forming a pressure-sensitive adhesive layer of a pressure-sensitive adhesive tape, for example. The pressure-sensitive adhesive tape of the present invention is very useful for applications such as component protection, masking, temporary fixing, and conveyance fixing in the manufacturing process of various components such as electric and electronic components.
　１　粘着テープ
　１ａ　基材
　１ｂ　粘着剤層
　２　おもり DESCRIPTION OF SYMBOLS 1 Adhesive tape 1a Base material 1b Adhesive layer 2 Weight

Claims (7)

  1. 　架橋されたシリコーン構造を含み、下記方法により測定されるゲル分率が４５％以上７０％未満であり、かつ下記方法により測定されるトルエンに対する膨潤度が２９０％以下であることを特徴とするシリコーン系粘着剤組成物。
    （ゲル分率）
    　トルエンにシリコーン系粘着剤組成物を常温で１日間浸漬したときの不溶解分の比率である、下記式によってゲル分率を得る。
    　ゲル分率（％）＝（Ｃ／Ａ）×１００
    　　Ａ：シリコーン系粘着剤組成物の初期質量
    　　Ｃ：トルエン浸漬後のシリコーン系粘着剤組成物の乾燥質量（乾燥条件：１３０℃、２時間）
    （膨潤度）
    　トルエンにシリコーン系粘着剤組成物を常温で１日間浸漬したときのトルエン吸収による膨潤比率である、下記式によって膨潤度を得る。
    　　膨潤度（％）＝（（Ｂ―Ａ）／Ａ）×１００％
    　　Ａ：シリコーン系粘着剤組成物の初期質量
    　　Ｂ：トルエン浸漬後のシリコーン系粘着剤組成物の膨潤質量     A silicone comprising a crosslinked silicone structure, having a gel fraction measured by the following method of 45% or more and less than 70%, and a swelling degree with respect to toluene measured by the following method of 290% or less -Based pressure-sensitive adhesive composition.
    (Gel fraction)
    The gel fraction is obtained by the following formula, which is the ratio of the insoluble matter when the silicone pressure-sensitive adhesive composition is immersed in toluene at room temperature for 1 day.
    Gel fraction (%) = (C / A) × 100
    A: Initial mass of silicone-based pressure-sensitive adhesive composition C: Dry mass of silicone-based pressure-sensitive adhesive composition after immersion in toluene (drying conditions: 130 ° C., 2 hours)
    (Swelling degree)
    The degree of swelling is obtained by the following formula, which is the swelling ratio due to toluene absorption when the silicone-based pressure-sensitive adhesive composition is immersed in toluene at room temperature for 1 day.
    Swelling degree (%) = ((B−A) / A) × 100%
    A: Initial mass of silicone pressure-sensitive adhesive composition B: Swelling mass of silicone-based pressure-sensitive adhesive composition after immersion in toluene
  2. 　ゲル分率が４８～６５％である請求項１記載のシリコーン系粘着剤組成物。 The silicone pressure-sensitive adhesive composition according to claim 1, wherein the gel fraction is 48 to 65%.
  3. 　膨潤度が２６０％以下である請求項１記載のシリコーン系粘着剤組成物。 The silicone pressure-sensitive adhesive composition according to claim 1, wherein the degree of swelling is 260% or less.
  4. 　架橋硬化された付加硬化型シリコーン粘着剤を含む請求項１記載のシリコーン系粘着剤組成物。 The silicone pressure-sensitive adhesive composition according to claim 1, comprising an addition-curable silicone pressure-sensitive adhesive that has been crosslinked and cured.
  5. 　基材の少なくとも片面に請求項１記載の粘着剤組成物からなる粘着剤層を有する粘着テープ。 A pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition according to claim 1 on at least one side of a substrate.
  6. 　基材が樹脂フィルムである請求項５記載の粘着テープ。 6. The adhesive tape according to claim 5, wherein the substrate is a resin film.
  7. 　樹脂フィルムがポリイミドフィルムである請求項６記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 6, wherein the resin film is a polyimide film.
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