WO2014175088A1 - Adhesive sheet for roll protection purposes - Google Patents

Adhesive sheet for roll protection purposes Download PDF

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Publication number
WO2014175088A1
WO2014175088A1 PCT/JP2014/060578 JP2014060578W WO2014175088A1 WO 2014175088 A1 WO2014175088 A1 WO 2014175088A1 JP 2014060578 W JP2014060578 W JP 2014060578W WO 2014175088 A1 WO2014175088 A1 WO 2014175088A1
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WO
WIPO (PCT)
Prior art keywords
silicone resin
weight
silicone
roll
resin layer
Prior art date
Application number
PCT/JP2014/060578
Other languages
French (fr)
Japanese (ja)
Inventor
内藤　友也
倉田　直記
麻美 久保
鈴木　聡
清 中根
覚 佐原
友男 坂本
鈴木　浩之
Original Assignee
日東電工株式会社
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Filing date
Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2014175088A1 publication Critical patent/WO2014175088A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/20—Layered products comprising a layer of natural or synthetic rubber comprising silicone rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • 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
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • C09J2301/162—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer the carrier being a laminate constituted by plastic layers only
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester 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
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/006—Presence of polysiloxane in the substrate

Definitions

  • the present invention relates to a pressure-sensitive adhesive sheet for roll protection.
  • the present invention can be applied to a roll by sticking it to a roll (for example, a guide roll or a take-off roll) for transporting an adhesive substrate (for example, an adhesive tape or an elastomer sheet), for example.
  • a roll for example, a guide roll or a take-off roll
  • an adhesive substrate for example, an adhesive tape or an elastomer sheet
  • an adhesive substrate such as an adhesive tape or an elastomer sheet
  • Rolls for example, guide rolls, take-off rolls, etc.
  • the silicone rubber roll has a problem that the peelability is lowered by continuous use.
  • the silicone rubber roll whose peelability has deteriorated needs to be removed and replaced from the apparatus provided with the roll, which requires great effort and cost.
  • An object of the present invention is to provide means for obtaining a roll for transporting an adhesive base material that can maintain high peelability without being removed from the apparatus and replaced.
  • the pressure-sensitive adhesive sheet for roll protection of the present invention is A pressure-sensitive adhesive sheet comprising a silicone resin layer, a base material layer, and a pressure-sensitive adhesive layer in this order,
  • the silicone resin layer contains silicone oil in a content of 8 wt% to 70 wt%.
  • the base material layer contains at least one selected from a polyester resin and an elastomer resin.
  • the roll is a roll for transporting an adhesive substrate.
  • the pressure-sensitive adhesive sheet for roll protection according to the present invention includes a silicone resin layer, a base material layer, and an adhesive layer in this order.
  • the pressure-sensitive adhesive sheet for roll protection of the present invention includes a silicone resin layer, a base material layer, and a pressure-sensitive adhesive layer in this order, the roll protective pressure-sensitive adhesive sheet has any other appropriate layer as long as the effects of the present invention are not impaired. Also good.
  • the thickness of the pressure-sensitive adhesive sheet for roll protection of the present invention is set to any appropriate thickness within a range that does not impair the effects of the present invention, depending on the thickness of each layer included therein.
  • the thickness of the pressure-sensitive adhesive sheet for roll protection of the present invention is preferably 20 ⁇ m to 1800 ⁇ m, more preferably 30 ⁇ m to 1500 ⁇ m, still more preferably 40 ⁇ m to 1200 ⁇ m, and particularly preferably 50 ⁇ m to 1000 ⁇ m.
  • FIG. 1 shows a schematic cross-sectional view of an example of the pressure-sensitive adhesive sheet for roll protection of the present invention.
  • the pressure-sensitive adhesive sheet for roll protection 100 of the present invention includes a silicone resin layer 2, a base material layer 3, and a pressure-sensitive adhesive layer 4 in this order.
  • a release film 1 may be provided on the surface of the silicone resin layer 2 or the surface of the adhesive layer 4.
  • the surface of a roll for example, a guide roll or a take-off roll for transporting the base material (particularly, a base material having adhesiveness such as an adhesive tape or an elastomer sheet) with the pressure-sensitive adhesive sheet for roll protection of the present invention.
  • the high peelability of the pressure-sensitive adhesive sheet for roll protection of the present invention makes it difficult for the base material to adhere to the roll and become entangled.
  • the peelability of the pressure-sensitive adhesive sheet for roll protection according to the present invention has deteriorated, it is not necessary to remove and replace the roll itself from the apparatus equipped with it, and it is adhered to the surface of the roll. Since it is sufficient to replace only the pressure-sensitive adhesive sheet for roll protection of the present invention, labor and cost are not required as compared with the conventional one.
  • the silicone resin layer includes a silicone resin.
  • the content of the silicone resin in the silicone resin layer is preferably 10% to 92% by weight, more preferably 15% to 90% by weight, still more preferably 20% to 85% by weight, and particularly preferably 25% by weight. ⁇ 80 wt%.
  • the pressure-sensitive adhesive sheet for roll protection according to the present invention can maintain high peelability, and the mechanical properties of the silicone resin layer can be sufficiently exhibited. .
  • the roll protective pressure-sensitive adhesive sheet of the present invention may not exhibit sufficient peelability, and the mechanical characteristics of the silicone resin layer may not be sufficiently developed. is there.
  • the adhesive sheet for roll protection of this invention cannot maintain high peelability.
  • the thickness of the silicone resin layer any appropriate thickness can be adopted depending on the application or use environment of the pressure-sensitive adhesive sheet for roll protection of the present invention.
  • the thickness of the silicone resin layer is preferably 5 ⁇ m to 500 ⁇ m. When the thickness of the silicone resin layer falls within the above range, the effect of high releasability works effectively for a sufficiently long time and the handling property is excellent. If the thickness of the silicone resin layer is less than 5 ⁇ m, the period during which the effect of high releasability is effective is shortened and may not be practical. When the thickness of the silicone resin layer is thicker than 500 ⁇ m, the roll protective pressure-sensitive adhesive sheet of the present invention becomes thick and increases in weight, which may deteriorate handling properties.
  • any appropriate silicone resin can be adopted as long as the effects of the present invention are not impaired. Only one type of silicone resin may be used, or two or more types may be used.
  • a silicone resin may be a silicone resin that is liquid at normal temperature, or may be a silicone resin that is solid at normal temperature.
  • Such a silicone resin may be a condensation type silicone resin or an addition type silicone resin.
  • Such a silicone resin may be a one-component silicone resin that is dried alone, or a two-component silicone resin that contains a curing agent.
  • a heat curable silicone resin, a room temperature curable silicone resin, an ultraviolet curable silicone resin, or a combination of these various curable silicone resins may be used.
  • addition (hydrosilylation) cross-linking silicone resins condensation cross-linking silicone resins, organic peroxide cross-linking silicone resins, and the like may be used.
  • condensation cross-linking silicone resins condensation cross-linking silicone resins
  • organic peroxide cross-linking silicone resins and the like may be used.
  • an addition-type curable silicone resin that is liquid at room temperature and is easy to prepare a coating solution is preferable.
  • silicone resins examples include silicone rubber compounds, one-component RTV silicone rubber, and two-component RTV silicone rubber.
  • Silicone rubber compounds are generally rubber compounds based on unique silicone raw rubber that has both inorganic and organic properties and high-purity silica, and have various features not found in organic rubber. Known as being. Examples of such silicone rubber compounds include KE-655-U, KE-675-U, KE-931-U, KE-941-U, and KE-951-U manufactured by Shin-Etsu Chemical Co., Ltd.
  • One-component RTV silicone rubber can generally be operated simply by extruding it from a container such as a tube or cartridge. After curing, it becomes a rubber elastic body and adheres well to most materials at the same time as curing.
  • a container such as a tube or cartridge.
  • examples of such one-component RTV silicone rubber include KE-3423, KE-347, KE-3475, KE-3495, KE-4895, KE-4896, and KE-1830 manufactured by Shin-Etsu Chemical Co., Ltd.
  • Two-component RTV silicone rubber is generally cured by mixing and stirring the main agent and curing agent in a predetermined amount, and in the same way as one-component RTV silicone rubber, it has electrical characteristics, heat resistance, cold resistance, weather resistance, etc. It is known to have excellent properties such as deep-curability and storage stability.
  • Examples of such two-component RTV silicone rubber include KE-1800T (A / B), KE-66, KE-1031 (A / B), KE-200, and KE manufactured by Shin-Etsu Chemical Co., Ltd.
  • the silicone resin layer contains silicone oil. Only one type of silicone oil may be contained in the silicone resin layer, or two or more types may be used.
  • the silicone oil is preferably one that does not have reactivity with the silicone resin or self-condensation. As such a silicone oil, any appropriate silicone oil can be adopted as long as the effects of the present invention are not impaired.
  • Such a silicone oil is preferably incompatible with the organopolysiloxane contained in the silicone resin to some extent, and is represented by, for example, the general formula (I) in that the antifouling effect can be maintained over a long period of time. Silicone oil is preferred.
  • R 1 is the same or different and represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, a fluoroalkyl group, a polyether group, or a hydroxyl group
  • R 2 is the same or Differently, it represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, a polyether group or a fluoroalkyl group
  • n represents an integer of 0 to 150.
  • R 1 in the general formula (I) is preferably a methyl group, a phenyl group, or a hydroxyl group.
  • R 2 in the general formula (I) is preferably a methyl group, a phenyl group, or a 4-trifluorobutyl group.
  • the silicone oil represented by the general formula (I) has a number average molecular weight of preferably 180 to 20000, more preferably 1000 to 10,000.
  • the viscosity of the silicone oil represented by the general formula (I) is preferably 10 centistokes to 10000 centistokes, more preferably 100 centistokes to 5000 centistokes.
  • silicone oil represented by the general formula (I) specifically, for example, terminal hydroxyl group-containing dimethyl silicone oil R 1 at both ends or one end is a hydroxyl group, all of R 1 and R 2 is a methyl group And dimethyl silicone oils in which some of the methyl groups of these dimethyl silicone oils are substituted with phenyl groups.
  • silicone oil examples include KF-96L, KF-96A, KF-96, KF-96H, KF-99, KF-50, KF-54, and KF-965 manufactured by Shin-Etsu Chemical Co., Ltd. , KF-968, HIVAC F-4, HIVAC F-5, KF-56A, KF995, KF-69, KF-410, KF-412, KF-414, FL, manufactured by Toray Dow Corning Co., Ltd. BY16- 846, SF8416, SH200, SH203, SH230, SF8419, FS1265, SH510, SH550, SH710, FZ-2110, FZ-2203, and the like.
  • modified silicone oil may be used.
  • Modified silicone oil is generally a silicone oil in which various organic groups are introduced and new functions are added to the superior characteristics of dimethyl silicone oil. Depending on the type of organic group, solubility in water and compatibility with various organic substances can be achieved. It is known that it can impart properties such as solubility, reactivity, paintability, and lubricity.
  • modified silicone oil include, for example, side chain modified silicone oil, both end modified silicone oil, one terminal modified silicone oil, side chain both terminal modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd., Etc.
  • the content of silicone oil in the silicone resin layer is 8% to 70% by weight.
  • the lower limit of the content ratio of the silicone oil in the silicone resin layer is preferably 10% by weight or more, more preferably 15% by weight or more, still more preferably 20% by weight or more, and particularly preferably 25% by weight. That's it.
  • the upper limit of the content ratio of the silicone oil in the silicone resin layer is preferably 67% by weight or less, more preferably 65% by weight or less, still more preferably 62% by weight or less, and particularly preferably 60% by weight. It is as follows.
  • the roll protective pressure-sensitive adhesive sheet of the present invention can exhibit good peelability.
  • the base material is transported using the pressure-sensitive adhesive sheet for roll protection of the present invention, the base material is contaminated with the silicone oil. It can be effectively suppressed.
  • the silicone resin layer may contain a surface modifier such as liquid paraffin, surfactant, wax, animal fats, petrolatum, fatty acid and the like.
  • a surface modifier such as liquid paraffin, surfactant, wax, animal fats, petrolatum, fatty acid and the like.
  • surfactant examples include an anionic surfactant, a cationic surfactant, and a nonionic surfactant.
  • the content ratio of the surface modifier in the silicone resin layer is preferably 0.01% by weight to 100% by weight, more preferably 0.05% by weight to 50% by weight, and still more preferably 0.1% by weight. % By weight to 10% by weight.
  • the surface friction resistance is smaller, for example, excellent workability using a construction jig such as a squeegee, and an adhesive for roll protection. Sheets can be provided.
  • the silicone resin layer may contain any appropriate filler for improving the strength. Only one kind of such a filler may be used, or two or more kinds may be used. Examples of such fillers include reinforcing inorganic fillers, non-reinforcing inorganic fillers, and inorganic fillers obtained by treating these inorganic fillers with organosilicon compounds such as organosilanes and organopolysiloxanes. It is done.
  • the reinforcing inorganic filler examples include fumed silica, precipitated silica, calcined silica, and fumed titanium oxide.
  • a silica-based reinforcing inorganic filler can be preferably used because it can impart physical strength such as predetermined hardness and tensile strength to an addition-type curable silicone resin that is liquid at room temperature.
  • examples of such silica-based reinforcing inorganic fillers include hydrophilic silica such as fumed silica and precipitated silica; hydrophobic silica obtained by hydrophobizing these hydrophilic silicas; crystalline silica (or quartz powder) ) And the like.
  • hydrophilic silica examples include Aerosil 130, Aerosil 200, Aerosil 300 (manufactured by Aerosil Japan, manufactured by Degussa); Cabosil MS-5, Cabosil MS-7 (manufactured by Cabot); Rheorosil QS-102, Rheorosil 103 (manufactured by Tokuyama Soda); Nipsil LP (manufactured by Nippon Silica);
  • hydrophobic silica examples include Aerosil R-812, Aerosil R-812S, Aerosil R-972, Aerosil R-974, Aerosil R-976, Aerosil SRX300-5, Aerosil RX-200, Aerosil RY200, Aerosil. RY300, Aerosil R805 (manufactured by Degussa); Rheorosi1 MT-10 (manufactured by Tokuyama Soda); Nippi1 SS series (manufactured by Nippon Silica);
  • crystalline silica examples include Crystallite (manufactured by Tatsumori); Minusil, Imisil (manufactured by Illinois Mineral), and the like.
  • non-reinforcing inorganic fillers examples include pulverized quartz, diatomaceous earth, iron oxide, aluminum oxide, aluminosilicate, and calcium carbonate.
  • the content of the filler in the silicone resin layer is preferably 0 to 75% by weight, more preferably 0.5 to 70% by weight, and further preferably 1 to 65% by weight. is there.
  • the silicone resin layer may contain additives such as a heat-resistant agent, a flame retardant, a pigment, a reaction control agent, and a curing accelerator (for example, a platinum catalyst). Only one kind of such an additive may be used, or two or more kinds thereof may be used.
  • additives such as a heat-resistant agent, a flame retardant, a pigment, a reaction control agent, and a curing accelerator (for example, a platinum catalyst). Only one kind of such an additive may be used, or two or more kinds thereof may be used.
  • the silicone resin layer may contain any appropriate conductive agent in order to have conductivity.
  • a conductive agent may be only one type or two or more types.
  • the conductive agent examples include metal conductive agents such as metal powders, metal fibers, metal flakes, and conductive metal oxides; carbon black.
  • Examples of the metal used for the metal powder, metal fiber, metal flake and the like include silver, copper, nickel, stainless steel, aluminum and the like.
  • Examples of the conductive metal oxide include conductive zinc oxide and conductive titanium oxide.
  • Examples of the carbon black include acetylene black, conductive furnace black (CF), super conductive furnace black (SCF), extra conductive furnace black (XCF), conductive channel black (CC), and a furnace heat-treated at a high temperature of about 1500 ° C. Examples include black or channel black.
  • acetylene black examples include, for example, electrified acetylene black (manufactured by Electrochemical Co., Ltd.) and shaunigan acetylene black (manufactured by Shaunigan Chemical Co., Ltd.).
  • conductive furnace black examples include, for example, CONTINEX CF (manufactured by Continental Carbon Corporation), Vulcan C (manufactured by Cabot Corporation), and the like.
  • super conductive furnace black examples include, for example, Continex SCF (manufactured by Continental Carbon Corporation), Vulcan SC (manufactured by Cabot Corporation), and the like.
  • extra conductive furnace black examples include Asahi HS-500 (Asahi Carbon Co., Ltd.), Vulcan XC-72 (Cabot Co., Ltd.), and the like.
  • the conductive channel black for example, Kourax L (manufactured by Degussa Corporation) and the like can be mentioned.
  • Ketjen Black EC or Ketjen Black EC-600JD (made by Ketjen Black International Co., Ltd.), which is a kind of furnace black, can also be used.
  • the content of the conductive agent in the silicone resin layer is preferably 0% by weight to 90% by weight, more preferably 0.1% by weight to 80% by weight when the conductive agent is a metal-based conductivity imparting agent. More preferably, it is 1 to 75% by weight. If the content ratio of such a conductive agent in the silicone resin layer is too large, there is a possibility that the effect of the conductive agent corresponding to the content ratio may not be obtained, and the mechanical strength of the silicone resin layer may be reduced. is there.
  • the content of the conductive agent in the silicone resin layer is preferably 0% by weight to 60% by weight, more preferably 0.1% by weight to 50% by weight, and still more preferably Is 1 to 40% by weight. If the content ratio of such a conductive agent in the silicone resin layer is too large, there is a possibility that the effect of the conductive agent corresponding to the content ratio may not be obtained, and the mechanical strength of the silicone resin layer may be reduced. is there.
  • At least one selected from a silicone resin layer and a base material layer includes at least one selected from a silane coupling agent, silicone powder, and silica particles.
  • the adhesion between the silicone resin layer and the base material layer is improved. be able to.
  • silane coupling agent Only one type of silane coupling agent may be used, or two or more types may be used.
  • silane coupling agent examples include vinyl group-containing silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyl Epoxy group-containing silane coupling agents such as dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; p-styryltrimethoxysilane, etc.
  • vinyl group-containing silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane
  • 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 3-glycidoxypropylmethyl Epoxy group-containing silane coupling agents such as dimethoxysilane, 3-glycidoxypropyl
  • Styryl group-containing silane coupling agent 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxy Methacrylic group-containing silane coupling agent such as silane; Acrylic group-containing silane coupling agent such as 3-acryloxypropyltrimethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N Amino group-containing silane coupling agents such as phenyl-3-a
  • silane coupling agents include KBM5103, KBM1003, KBM903, KBM403, and KBM802 manufactured by Shin-Etsu Chemical Co., Ltd.
  • silicone powder Only one type of silicone powder may be used, or two or more types may be used.
  • the average particle size of the silicone powder is preferably 1 nm to 100 ⁇ m, more preferably 10 nm to 70 ⁇ m, still more preferably 100 nm to 50 ⁇ m, and particularly preferably 500 nm to 20 ⁇ m.
  • silicone powder examples include silicone rubber particles having a structure in which linear dimethylpolysiloxane is crosslinked, and a silicone resin that is a cured product of polyorganosilsesquioxane having a structure in which siloxane bonds are crosslinked in a three-dimensional network.
  • silicone resin examples include particles and silicone composite particles in which the surface of silicone rubber particles is coated with a silicone resin.
  • silicone powders that are commercially available include, for example, silicone composite powders (KMP-600, KMP-601, KMP-602, KMP-605, X-52-7030, etc.) manufactured by Shin-Etsu Chemical Co., Ltd. Silicone rubber powder (KMP-597, KMP-598, KMP-594, X-52-875, etc.), silicone resin powder (KMP-590, KMP-701, X-52-854, X-52-1621, etc.) Can be mentioned.
  • silicone composite powders KMP-600, KMP-601, KMP-602, KMP-605, X-52-7030, etc.
  • Silicone rubber powder KMP-597, KMP-598, KMP-594, X-52-875, etc.
  • silicone resin powder KMP-590, KMP-701, X-52-854, X-52-1621, etc.
  • the silica particles may be only one kind or two or more kinds.
  • the average particle diameter of the silica particles is preferably 1 nm to 100 ⁇ m, more preferably 2 nm to 70 ⁇ m, still more preferably 3 nm to 50 ⁇ m, and particularly preferably 5 nm to 30 ⁇ m.
  • silica particles examples include silicon dioxide (SiO 2 ) particles or particles composed of silicon dioxide (SiO 2 ), and examples include hydrophobic silica particles and hydrophilic silica particles.
  • examples of the silica particles include particles whose surface has been subjected to a hydrophobic treatment and particles whose surface has been subjected to a hydrophilic treatment.
  • silica particles include Aerosil series (produced by Nippon Aerosil Co., Ltd.). More specifically, in hydrophobicity, Aerosil R8200 (primary average particle size: 12 nm, hexamethyldisilazane treatment), Aerosil R104 (Primary average particle size: 12 nm, octamethylcyclotetrasiloxane treatment), Aerosil R972 (Primary average particle size: 16 nm, dimethyldichlorosilane treatment), Aerosil R974 (Primary average particle size: 12 nm, dimethyldichlorosilane treatment), Aerosil R812 (Primary average particle size: 7 nm, hexamethyldisilazane treatment), etc. Examples of hydrophilicity include Aerosil 200 (primary average particle size: 12 nm), Aerosil 300 (primary average particle size: 7 nm), and the like.
  • the total content of the silane coupling agent, the silicone powder, and the silica particles with respect to the total of the silicone resin layer and the base material layer is preferably 0.01% by weight to 100% by weight, and more preferably 0.5% by weight. % To 30% by weight, more preferably 0.1% to 10% by weight, and particularly preferably 1% to 5% by weight.
  • the content ratio so as to be within the above range, high adhesion between the silicone resin layer and the base material layer can be expressed more effectively.
  • the said content rate is less than 0.01 weight%, there exists a possibility that sufficient adhesiveness cannot be expressed between a base material layer and a silicone resin layer.
  • the upper limit of the content ratio of the silane coupling agent relative to the total of the silicone resin layer and the base material layer is preferably 30% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less. is there.
  • the silane coupling agent becomes a crosslinking point and contains the silane coupling agent. Can be suppressed from becoming too hard.
  • a primer may be applied to the base material layer in advance.
  • any appropriate material can be adopted as long as the effects of the present invention are not impaired.
  • Such a material for the base material layer is preferably excellent in water resistance, strength, flexibility and tearability.
  • the material for the base material layer include polyurethane resin, polyurethane acrylic resin, rubber resin, vinyl chloride resin, polyester resin, silicone resin, elastomers, fluororesin, polyamide resin, polyolefin resin (polyethylene, polypropylene, etc.) ) And the like.
  • the material of such a base material layer may be only one type or two or more types.
  • the base material layer preferably contains at least one selected from polyester resins and elastomer resins.
  • the base material layer contains at least one selected from polyester resin and elastomer resin, it can be easily attached to parts other than flat surfaces such as curved surfaces and acute angle surfaces with good workability, and wrinkles and floats on the surface after application.
  • the pressure-sensitive adhesive sheet for roll protection of the present invention can be easily attached to the roll surface.
  • the base material layer is a polyester resin from the viewpoint that the effects of the present invention can be further exhibited, and that high adhesiveness and high durability are provided.
  • the polyester resin is preferably polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the polyester resin that can be contained in the base material layer may be only one kind or two or more kinds.
  • any appropriate elastomer resin can be adopted as long as the effects of the present invention are not impaired.
  • elastomer resins include vulcanized rubber and thermoplastic elastomer.
  • thermoplastic elastomer examples include styrene elastomers, olefin elastomers, vinyl chloride elastomers, urethane elastomers, ester elastomers, amide elastomers, and the like.
  • the elastomer resin that can be included in the base material layer may be only one type or two or more types.
  • the content ratio of at least one selected from the polyester resin and the elastomer resin in the base material layer is preferably 50% by weight or more, more preferably 60% by weight to 100% by weight, and still more preferably 70% by weight. It is ⁇ 99% by weight, particularly preferably 80% by weight to 98% by weight, and most preferably 90% by weight to 97% by weight.
  • the elastomer resin is preferably a urethane elastomer.
  • the urethane elastomer is preferably at least one selected from polyurethane acrylic resins and polyurethane resins.
  • the polyurethane resin include carbonate-based polyurethane, ester-based polyurethane, and ether-based polyurethane.
  • the base material layer may contain any appropriate additive as long as the effects of the present invention are not impaired.
  • additives include olefin resins, silicone polymers, liquid acrylic copolymers, tackifiers, anti-aging agents, hindered amine light stabilizers, ultraviolet absorbers, antioxidants, and antistatic agents. , Polyethyleneimine, fatty acid amide, fatty acid ester, phosphate ester, lubricant, surfactant, filler and pigment (for example, calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide, carbon black, etc.).
  • the thickness of the base material layer is preferably 1 ⁇ m to 1000 ⁇ m, more preferably 10 ⁇ m to 800 ⁇ m, and still more preferably 20 ⁇ m to 500 ⁇ m.
  • the pressure-sensitive adhesive sheet for roll protection of the present invention has excellent adhesion between the silicone resin layer and the base material layer, and can be applied to parts other than flat surfaces such as curved surfaces and acute angle surfaces. It can be easily applied with good workability, and it is difficult for appearance defects such as wrinkles and floats to occur on the surface after application. Therefore, it can be easily attached to the roll surface. Therefore, the pressure-sensitive adhesive sheet for roll protection of the present invention can be easily attached to the roll surface.
  • any appropriate adhesive layer can be adopted as long as the effects of the present invention are not impaired.
  • the material for such an adhesive layer include acrylic resin adhesives, epoxy resin adhesives, amino resin adhesives, vinyl resin (vinyl acetate polymers, etc.) adhesives, and curable acrylic resin adhesives. Agents, silicone resin adhesives, and the like.
  • the material of the adhesive layer may be only one type or two or more types.
  • the thickness of the pressure-sensitive adhesive layer is preferably 10 ⁇ m or more.
  • the thickness of the pressure-sensitive adhesive layer is within the above range, the shape of the adherend can be sufficiently followed, the adhesion area can be sufficiently secured, and sufficient adhesive force can be expressed.
  • the thickness of the pressure-sensitive adhesive layer is less than 10 ⁇ m, it is impossible to sufficiently follow the shape of the adherend, the adhesion area is reduced, and there is a possibility that sufficient pressure-sensitive adhesive force cannot be expressed.
  • the upper limit of the thickness of the pressure-sensitive adhesive layer is preferably 300 ⁇ m or less from the viewpoint of handleability.
  • the roll protective pressure-sensitive adhesive sheet of the present invention can be produced by any appropriate method.
  • a method for example, a method of forming a silicone resin layer by applying a silicone resin layer forming material on a substrate layer after pasting a separately prepared substrate layer and an adhesive layer, one of the substrate layers
  • Examples include a method of forming a silicone resin layer by applying a silicone resin layer forming material on a base material layer after co-extrusion of the forming material to form a base material layer / adhesive layer laminate.
  • Examples of the method for applying the silicone resin layer forming material on the base material layer include a coater, spray, brush coating, roller, curtain flow, roll, and dip.
  • the silicone resin layer forming material is applied onto the base material layer by these methods, and the silicone resin layer is formed, for example, by drying at a temperature from room temperature to 250 ° C. (preferably a temperature from room temperature to 180 ° C.). can do.
  • variable angle peel tester product
  • the force required for peeling was measured at a peeling angle of 30 ° (Tensile speed: 3 m / min) with the name “Yamamoto-type bending angle measuring machine YM-121” manufactured by Asahi Seiko Co., Ltd.).
  • Peeling was performed at a peeling angle of 180 ° with a testing machine (trade name “Autograph AG-X 200N”, manufactured by Shimadzu Corporation) (pulling speed: 300 mm / min).
  • the peeled No. 31B was pressure-bonded to a SUS304 plate polished with abrasive paper of particle size 280 by reciprocating a 2 kg heavy rubber roller once, and stored for 30 minutes under conditions of a temperature of 23 ° C. and a humidity of 65% RH, then a tensile tester (Trade name “Autograph AG-X 200N”, manufactured by Shimadzu Corporation) was peeled at a peeling angle of 180 ° (pulling speed: 300 mm / min).
  • the contamination state of the SUS404 plate after peeling was confirmed visually.
  • ⁇ Contamination cannot be visually confirmed
  • ⁇ Contamination can be visually confirmed
  • 1,6-hexanediol diacrylate (HDDA): 0.08 part by weight is added as a crosslinking agent, and this is added to a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc.). , 50 ⁇ m thick) with an applicator, and a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., 38 ⁇ m thick) is bonded with a hand roller, and ultraviolet rays are emitted from an ultraviolet lamp (BL type).
  • BL type ultraviolet lamp
  • Example 1 50 parts by weight of KE-1950-A (manufactured by Shin-Etsu Chemical Co., Ltd.) as liquid silicone rubber, 50 parts by weight of KE-1950-B (manufactured by Shin-Etsu Chemical Co., Ltd.), and KF-96-100Cs as silicone oil 10 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd.) was added, 32 parts by weight of toluene was added, and the mixture was stirred and mixed to prepare a coating solution.
  • KE-1950-A manufactured by Shin-Etsu Chemical Co., Ltd.
  • KF-96-100Cs silicone oil
  • This coating solution is applied on a PET base material (trade name “Lumirror S10”, manufactured by Toray Industries, Inc., thickness 38 ⁇ m) so as to have a thickness of 100 ⁇ m after drying with an applicator, and heated in an oven at 130 ° C. for 5 minutes.
  • a PET base material trade name “Lumirror S10”, manufactured by Toray Industries, Inc., thickness 38 ⁇ m
  • the pressure-sensitive adhesive sheet (1) having a laminated structure of silicone resin layer / base material layer / pressure-sensitive adhesive layer is obtained by bonding the pressure-sensitive adhesive layer obtained in Production Example 1 and the base material with the silicone resin layer (1) with a hand roller. Obtained.
  • the content ratio of the silicone oil in the silicone resin layer of the pressure-sensitive adhesive sheet (1) was 9.1% by weight.
  • Various evaluation results are shown in Table 1.
  • Example 2 The same procedure as in Example 1 was repeated, except that KF-96-100Cs (manufactured by Shin-Etsu Chemical Co., Ltd.) of Example 1 was changed to 30 parts by weight and toluene was changed to 16 parts by weight. / The adhesive sheet (2) which has the laminated structure of the adhesion layer was obtained. The content ratio of the silicone oil in the silicone resin layer of the pressure-sensitive adhesive sheet (2) was 23.1% by weight. Various evaluation results are shown in Table 1.
  • Example 3 The same procedure as in Example 1 was repeated except that KF-96-100Cs (manufactured by Shin-Etsu Chemical Co., Ltd.) in Example 1 was changed to 50 parts by weight and toluene was changed to 0 parts by weight. / The adhesive sheet (3) which has the laminated structure of the adhesion layer was obtained. The content ratio of the silicone oil in the silicone resin layer of the pressure-sensitive adhesive sheet (3) was 33.3% by weight. Various evaluation results are shown in Table 1.
  • Example 4 The same procedure as in Example 1 was repeated except that KF-96-100Cs (manufactured by Shin-Etsu Chemical Co., Ltd.) in Example 1 was changed to 90 parts by weight and toluene was changed to 0 parts by weight. / The adhesive sheet (4) which has the laminated structure of an adhesion layer was obtained. The content ratio of the silicone oil in the silicone resin layer of the pressure-sensitive adhesive sheet (4) was 47.4% by weight. Various evaluation results are shown in Table 1.
  • Example 5 The same procedure as in Example 1 was repeated except that KF-96-100Cs (manufactured by Shin-Etsu Chemical Co., Ltd.) in Example 1 was changed to 90 parts by weight and toluene was changed to 0 parts by weight. / The adhesive sheet (5) which has the laminated structure of an adhesion layer was obtained. The content ratio of the silicone oil in the silicone resin layer of the pressure-sensitive adhesive sheet (5) was 60.0% by weight. Various evaluation results are shown in Table 1.
  • This coating solution is applied on a PET base material (trade name “Lumirror S10”, manufactured by Toray Industries, Inc., thickness 38 ⁇ m) so as to have a thickness of 100 ⁇ m after drying with an applicator, and heated in an oven at 130 ° C.
  • a pressure-sensitive adhesive sheet (C2) having a laminated structure of silicone resin layer / base material layer / pressure-sensitive adhesive layer is obtained by bonding the pressure-sensitive adhesive layer obtained in Production Example 1 and the base material with silicone resin layer (C2) with a hand roller. Obtained.
  • the content ratio of the silicone oil in the silicone resin layer of the pressure-sensitive adhesive sheet (C2) was 75.0% by weight.
  • the pressure-sensitive adhesive sheet for roll protection of the present invention is, for example, attached to a roll (for example, a guide roll or a take-off roll) for transporting a substrate having adhesiveness (for example, a pressure-sensitive adhesive tape or an elastomer sheet), It can utilize suitably for the adhesive sheet for roll protection which can prevent the base material which has adhesiveness from being wound in a roll.
  • a roll for example, a guide roll or a take-off roll
  • a substrate having adhesiveness for example, a pressure-sensitive adhesive tape or an elastomer sheet

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

Abstract

Provided is a means for producing a roll for delivering an adhesive base material, which can keep the detachability thereof at a high level without the need of removing the means from a device and replacing the means with a new one. An adhesive sheet for roll protection purposes according to the present invention comprises a silicone resin layer, a base material layer and an adhesive layer arranged in this order, wherein the silicone resin layer contains a silicone oil at a content of 8 to 70 wt%.

Description

ロール保護用粘着シートRoll protection adhesive sheet
　本発明は、ロール保護用粘着シートに関する。詳細には、本発明は、例えば、粘着性を有する基材（例えば、粘着テープやエラストマーシートなど）を搬送するためのロール（例えば、ガイドロールやテイクオフロールなど）に貼り付けることによって、ロールに粘着性を有する基材が巻き込まれることを防止し得る、ロール保護用粘着シートに関する。 The present invention relates to a pressure-sensitive adhesive sheet for roll protection. Specifically, the present invention can be applied to a roll by sticking it to a roll (for example, a guide roll or a take-off roll) for transporting an adhesive substrate (for example, an adhesive tape or an elastomer sheet), for example. It is related with the adhesive sheet for roll protection which can prevent that the base material which has adhesiveness is caught.
　塗工機、印刷機、ラミネーター、巻き替え機、ロール加工装置（スリッターなど）、貼り合わせ機などの各種加工装置には、一般に、粘着性を有する基材（例えば、粘着テープやエラストマーシートなど）を搬送するためのロール（例えば、ガイドロールやテイクオフロールなど）が備えられている。 In various processing apparatuses such as a coating machine, a printing machine, a laminator, a rewinding machine, a roll processing apparatus (such as a slitter), and a laminating machine, in general, an adhesive substrate (such as an adhesive tape or an elastomer sheet) is used. Rolls (for example, guide rolls, take-off rolls, etc.) are provided.
　上記のような各種加工装置において、粘着性を有する基材を搬送する場合には、ガイドロールやテイクオフロールなどのロールに該基材が接着してしまって巻き込まれてしまうという問題が生じるおそれがある。このような問題を回避するため、粘着性を有する基材を搬送するためのロールとして、従来、通常、シリコーンゴムロールが広く用いられている。このようなシリコーンゴムロールには、高い剥離性が求められるため、例えば、表面に微細な凹凸を設けることによって高い剥離性を発現させるシリコーンゴムロールなどが従来提案されている（例えば、特許文献１参照）。 In various processing apparatuses such as those described above, when transporting a substrate having adhesiveness, there is a risk that the substrate will be attached to a roll such as a guide roll or a take-off roll and become entangled. is there. In order to avoid such a problem, conventionally, a silicone rubber roll has been widely used as a roll for transporting an adhesive substrate. Since such a silicone rubber roll is required to have high peelability, for example, a silicone rubber roll that exhibits high peelability by providing fine irregularities on the surface has been conventionally proposed (for example, see Patent Document 1). .
　しかし、シリコーンゴムロールは、連続使用することによって剥離性が低下してしまうという問題がある。剥離性が低下してしまったシリコーンゴムロールは、それが備えられている装置から取り外して交換する必要があり、大きな労力とコストがかかってしまう。 However, the silicone rubber roll has a problem that the peelability is lowered by continuous use. The silicone rubber roll whose peelability has deteriorated needs to be removed and replaced from the apparatus provided with the roll, which requires great effort and cost.
特許第４３１７８２７号公報Japanese Patent No. 4317828
　本発明の課題は、装置から取り外して交換しなくても高い剥離性を維持できる、粘着性を有する基材を搬送するためのロールを得るための手段を提供することにある。 An object of the present invention is to provide means for obtaining a roll for transporting an adhesive base material that can maintain high peelability without being removed from the apparatus and replaced.
　本発明のロール保護用粘着シートは、
　シリコーン樹脂層と基材層と粘着層をこの順に含む粘着シートであって、
　該シリコーン樹脂層がシリコーンオイルを８重量％～７０重量％の含有割合で含む。 The pressure-sensitive adhesive sheet for roll protection of the present invention is
A pressure-sensitive adhesive sheet comprising a silicone resin layer, a base material layer, and a pressure-sensitive adhesive layer in this order,
The silicone resin layer contains silicone oil in a content of 8 wt% to 70 wt%.
　好ましい実施形態においては、上記基材層が、ポリエステル樹脂およびエラストマー樹脂から選ばれる少なくとも１種を含む。 In a preferred embodiment, the base material layer contains at least one selected from a polyester resin and an elastomer resin.
　好ましい実施形態においては、上記ロールが、粘着性を有する基材を搬送するためのロールである。 In a preferred embodiment, the roll is a roll for transporting an adhesive substrate.
　本発明によれば、装置から取り外して交換しなくても高い剥離性を維持できる、粘着性を有する基材を搬送するためのロールを得るための手段を提供することができる。 According to the present invention, it is possible to provide a means for obtaining a roll for transporting an adhesive substrate that can maintain high peelability without being removed from the apparatus and replaced.
本発明のロール保護用粘着シートの一例の概略断面図である。It is a schematic sectional drawing of an example of the adhesive sheet for roll protection of this invention.
　本発明のロール保護用粘着シートは、シリコーン樹脂層と基材層と粘着層をこの順に含む。本発明のロール保護用粘着シートは、シリコーン樹脂層と基材層と粘着層をこの順に含んでいれば、本発明の効果を損なわない範囲で、任意の適切な他の層を有していても良い。 The pressure-sensitive adhesive sheet for roll protection according to the present invention includes a silicone resin layer, a base material layer, and an adhesive layer in this order. As long as the pressure-sensitive adhesive sheet for roll protection of the present invention includes a silicone resin layer, a base material layer, and a pressure-sensitive adhesive layer in this order, the roll protective pressure-sensitive adhesive sheet has any other appropriate layer as long as the effects of the present invention are not impaired. Also good.
　本発明のロール保護用粘着シートの厚みは、それに含まれる各層の厚みによって、本発明の効果を損なわない範囲で、任意の適切な厚みに設定される。本発明のロール保護用粘着シートの厚みは、好ましくは２０μｍ～１８００μｍであり、より好ましくは３０μｍ～１５００μｍであり、さらに好ましくは４０μｍ～１２００μｍであり、特に好ましくは５０μｍ～１０００μｍである。 The thickness of the pressure-sensitive adhesive sheet for roll protection of the present invention is set to any appropriate thickness within a range that does not impair the effects of the present invention, depending on the thickness of each layer included therein. The thickness of the pressure-sensitive adhesive sheet for roll protection of the present invention is preferably 20 μm to 1800 μm, more preferably 30 μm to 1500 μm, still more preferably 40 μm to 1200 μm, and particularly preferably 50 μm to 1000 μm.
　図１に、本発明のロール保護用粘着シートの一例の概略断面図を示す。本発明のロール保護用粘着シート１００は、シリコーン樹脂層２と基材層３と粘着層４をこの順に含む。図１に示すように、シリコーン樹脂層２の表面や、粘着層４の表面には、剥離フィルム１が設けられていても良い。このような本発明のロール保護用粘着シートを基材（特に、粘着テープやエラストマーシートなどの、粘着性を有する基材）を搬送するためのロール（例えば、ガイドロールやテイクオフロールなど）の表面に貼着すれば、本発明のロール保護用粘着シートが有する高い剥離性により、ロールに該基材が接着してしまって巻き込まれてしまうという問題が起こり難くなり、また、連続使用することによって本発明のロール保護用粘着シートが有する剥離性が低下してしまった際には、ロールそのものをそれが備えられている装置から取り外して交換する必要はなく、ロールの表面に貼着されている本発明のロール保護用粘着シートのみを交換すれば足りるので、従来に比べて労力がかからずコストもかからない。 FIG. 1 shows a schematic cross-sectional view of an example of the pressure-sensitive adhesive sheet for roll protection of the present invention. The pressure-sensitive adhesive sheet for roll protection 100 of the present invention includes a silicone resin layer 2, a base material layer 3, and a pressure-sensitive adhesive layer 4 in this order. As shown in FIG. 1, a release film 1 may be provided on the surface of the silicone resin layer 2 or the surface of the adhesive layer 4. The surface of a roll (for example, a guide roll or a take-off roll) for transporting the base material (particularly, a base material having adhesiveness such as an adhesive tape or an elastomer sheet) with the pressure-sensitive adhesive sheet for roll protection of the present invention. By sticking to the roll, the high peelability of the pressure-sensitive adhesive sheet for roll protection of the present invention makes it difficult for the base material to adhere to the roll and become entangled. When the peelability of the pressure-sensitive adhesive sheet for roll protection according to the present invention has deteriorated, it is not necessary to remove and replace the roll itself from the apparatus equipped with it, and it is adhered to the surface of the roll. Since it is sufficient to replace only the pressure-sensitive adhesive sheet for roll protection of the present invention, labor and cost are not required as compared with the conventional one.
　シリコーン樹脂層は、シリコーン樹脂を含む。シリコーン樹脂層中のシリコーン樹脂の含有割合は、他の成分の含有割合によって、任意の適切な含有割合を採用し得る。シリコーン樹脂層中のシリコーン樹脂の含有割合は、好ましくは１０重量％～９２重量％、より好ましくは１５重量％～９０重量％、さらに好ましくは２０重量％～８５重量％、特に好ましくは２５重量％～８０重量％である。シリコーン樹脂層中のシリコーン樹脂の含有割合が上記範囲内に収まることにより、本発明のロール保護用粘着シートが高い剥離性を維持し得るとともに、シリコーン樹脂層の機械的特性も十分に発現し得る。シリコーン樹脂層中のシリコーン樹脂の含有割合が少なすぎると、本発明のロール保護用粘着シートが十分な剥離性を発現できないおそれがあるとともに、シリコーン樹脂層の機械的特性も十分に発現できないおそれがある。シリコーン樹脂層中のシリコーン樹脂の含有割合が多すぎると、本発明のロール保護用粘着シートが高い剥離性を維持できないおそれがある。 The silicone resin layer includes a silicone resin. Arbitrary appropriate content rates can be employ | adopted for the content rate of the silicone resin in a silicone resin layer by the content rate of another component. The content of the silicone resin in the silicone resin layer is preferably 10% to 92% by weight, more preferably 15% to 90% by weight, still more preferably 20% to 85% by weight, and particularly preferably 25% by weight. ~ 80 wt%. When the content ratio of the silicone resin in the silicone resin layer falls within the above range, the pressure-sensitive adhesive sheet for roll protection according to the present invention can maintain high peelability, and the mechanical properties of the silicone resin layer can be sufficiently exhibited. . If the content ratio of the silicone resin in the silicone resin layer is too small, the roll protective pressure-sensitive adhesive sheet of the present invention may not exhibit sufficient peelability, and the mechanical characteristics of the silicone resin layer may not be sufficiently developed. is there. When there is too much content rate of the silicone resin in a silicone resin layer, there exists a possibility that the adhesive sheet for roll protection of this invention cannot maintain high peelability.
　シリコーン樹脂層の厚みは、本発明のロール保護用粘着シートの用途や使用環境などによって、任意の適切な厚みを採用し得る。シリコーン樹脂層の厚みは、好ましくは５μｍ～５００μｍである。シリコーン樹脂層の厚みが上記範囲内に収まることにより、高い剥離性の効果が十分に長く有効に働くとともに、ハンドリング性に優れる。シリコーン樹脂層の厚みが５μｍより薄いと、高い剥離性の効果が有効に働く期間が短くなり、実用的ではなくなるおそれがある。シリコーン樹脂層の厚みが５００μｍより厚いと、本発明のロール保護用粘着シートが分厚くなって重量が大きくなるため、ハンドリング性が悪くなるおそれがある。 As the thickness of the silicone resin layer, any appropriate thickness can be adopted depending on the application or use environment of the pressure-sensitive adhesive sheet for roll protection of the present invention. The thickness of the silicone resin layer is preferably 5 μm to 500 μm. When the thickness of the silicone resin layer falls within the above range, the effect of high releasability works effectively for a sufficiently long time and the handling property is excellent. If the thickness of the silicone resin layer is less than 5 μm, the period during which the effect of high releasability is effective is shortened and may not be practical. When the thickness of the silicone resin layer is thicker than 500 μm, the roll protective pressure-sensitive adhesive sheet of the present invention becomes thick and increases in weight, which may deteriorate handling properties.
　シリコーン樹脂としては、本発明の効果を損なわない範囲で、任意の適切なシリコーン樹脂を採用し得る。シリコーン樹脂は、１種のみであっても良いし、２種以上であっても良い。このようなシリコーン樹脂としては、常温で液状のシリコーン樹脂であっても良いし、常温で固体状のシリコーン樹脂であっても良い。また、このようなシリコーン樹脂としては、縮合型のシリコーン樹脂であっても良いし、付加型のシリコーン樹脂であっても良い。また、このようなシリコーン樹脂としては、単独で乾燥させる１液型のシリコーン樹脂であっても良いし、硬化剤を配合する２液型のシリコーン樹脂であっても良い。また、加熱硬化型のシリコーン樹脂、室温硬化型のシリコーン樹脂、紫外線硬化型のシリコーン樹脂、これらの各種硬化型のシリコーン樹脂を組み合わせたものなどでも良い。さらに、付加（ヒドロシリル化）架橋型のシリコーン樹脂、縮合架橋型のシリコーン樹脂、有機過酸化物架橋型のシリコーン樹脂などでも良い。これらの様々なシリコーン樹脂の中でも、本発明においては、シート作製時の作業性の観点からは、塗布液の調製が容易な、常温で液状の付加型の硬化型シリコーン樹脂が好ましい。 As the silicone resin, any appropriate silicone resin can be adopted as long as the effects of the present invention are not impaired. Only one type of silicone resin may be used, or two or more types may be used. Such a silicone resin may be a silicone resin that is liquid at normal temperature, or may be a silicone resin that is solid at normal temperature. Such a silicone resin may be a condensation type silicone resin or an addition type silicone resin. Such a silicone resin may be a one-component silicone resin that is dried alone, or a two-component silicone resin that contains a curing agent. Further, a heat curable silicone resin, a room temperature curable silicone resin, an ultraviolet curable silicone resin, or a combination of these various curable silicone resins may be used. Furthermore, addition (hydrosilylation) cross-linking silicone resins, condensation cross-linking silicone resins, organic peroxide cross-linking silicone resins, and the like may be used. Among these various silicone resins, in the present invention, from the viewpoint of workability during sheet preparation, an addition-type curable silicone resin that is liquid at room temperature and is easy to prepare a coating solution is preferable.
　このようなシリコーン樹脂としては、例えば、シリコーンゴムコンパウンド、１液型ＲＴＶシリコーンゴム、２液型ＲＴＶシリコーンゴムなどが挙げられる。 Examples of such silicone resins include silicone rubber compounds, one-component RTV silicone rubber, and two-component RTV silicone rubber.
　シリコーンゴムコンパウンドは、一般に、無機と有機の両方の性質を兼ね備えた特異なシリコーン生ゴムと高純度のシリカを主成分とするゴムコンパウンドであり、有機系ゴムにはない優れた特徴を多様に備えているものとして知られている。このようなシリコーンゴムコンパウンドとしては、例えば、信越化学工業（株）製の、ＫＥ－６５５－Ｕ、ＫＥ－６７５－Ｕ、ＫＥ－９３１－Ｕ、ＫＥ－９４１－Ｕ、ＫＥ－９５１－Ｕ、ＫＥ－９６１－Ｕ、ＫＥ－９７１－Ｕ、ＫＥ－９８１－Ｕ、ＫＥ－９６１Ｔ－Ｕ、ＫＥ－９７１Ｔ－Ｕ、ＫＥ－９４１０－Ｕ、ＫＥ－９５１０－Ｕ、ＫＥ－９６１０－Ｕ、ＫＥ－９７１０－Ｕ、ＫＥ－７４２－Ｕ、ＫＥ－７５２－Ｕ、ＫＥ－７６２－Ｕ、ＫＥ－７７２－Ｕ、ＫＥ－７８２－Ｕ、ＫＥ－８５０－Ｕ、ＫＥ－８７０－Ｕ、ＫＥ－８８０－Ｕ、ＫＥ－８９０－Ｕ、ＫＥ－９５９０－Ｕ、ＫＥ－５５９０－Ｕ、ＫＥ－５５２－Ｕ、ＫＥ－５８２－Ｕ、ＫＥ－５５２Ｂ－Ｕ、ＫＥ－５５５－Ｕ、ＫＥ－５７５－Ｕ、ＫＥ－５４１－Ｕ、ＫＥ－５５１－Ｕ、ＫＥ－５６１－Ｕ、ＫＥ－５７１－Ｕ、ＫＥ－５８１－Ｕ、ＫＥ－５９４、ＫＥ－５９７、ＫＥ－５２０－Ｕ、ＫＥ－５３０Ｂ－２－Ｕ、ＫＥ－５４０Ｂ－２－Ｕ、ＫＥ－１５５１－Ｕ、ＫＥ－１５７１－Ｕ、ＫＥ－１５３－Ｕ、ＫＥ－１７４－Ｕ、ＫＥ－３６０１ＳＢ－Ｕ、ＫＥ－３７１１－Ｕ、ＫＥ－３８０１Ｍ－Ｕ、ＫＥ－５６１２Ｇ－Ｕ、ＫＥ－５６２０ＢＬ－Ｕ、ＫＥ－５６２０Ｗ－Ｕ、ＫＥ－５６３４－Ｕ、ＫＥ－７５１１－Ｕ、ＫＥ－７６１１－Ｕ、ＫＥ－７７１１－Ｕ、ＫＥ－７６５－Ｕ、ＫＥ－７８５－Ｕ、ＫＥ－７００８－Ｕ、ＫＥ－７００５－Ｕ、ＫＥ－５０３－Ｕ、ＫＥ－５０４２－Ｕ、ＫＥ－５０５－Ｕ、ＫＥ－６８０１－Ｕ、ＫＥ－１３６Ｙ－Ｕ、ＦＥ－２５１－Ｕ、ＦＥ－２６１－Ｕ、ＦＥ－２７１－Ｕ、ＦＥ－３５１－Ｕ、ＦＥ－３６１－Ｕ、ＦＥ－４５１－Ｕ、ＳＥＰ－１７１１－Ｕ、ＳＥＰ－１７２１－Ｕ、ＳＥＰ－１７３１－Ｕ、ＳＥＰ－３６３－Ｕなどが挙げられる。 Silicone rubber compounds are generally rubber compounds based on unique silicone raw rubber that has both inorganic and organic properties and high-purity silica, and have various features not found in organic rubber. Known as being. Examples of such silicone rubber compounds include KE-655-U, KE-675-U, KE-931-U, KE-941-U, and KE-951-U manufactured by Shin-Etsu Chemical Co., Ltd. KE-961-U, KE-971-U, KE-981-U, KE-961T-U, KE-971T-U, KE-9410-U, KE-9510-U, KE-9610-U, KE- 9710-U, KE-742-U, KE-752-U, KE-762-U, KE-772-U, KE-782-U, KE-850-U, KE-870-U, KE-880- U, KE-890-U, KE-9590-U, KE-5590-U, KE-552-U, KE-582-U, KE-552B-U, KE-555-U, KE-575-U, KE-541-U, KE-551 U, KE-561-U, KE-571-U, KE-581-U, KE-594, KE-597, KE-520-U, KE-530B-2-U, KE-540B-2-U, KE-1551-U, KE-1571-U, KE-153-U, KE-174-U, KE-3601SB-U, KE-3711-U, KE-3801M-U, KE-5612G-U, KE- 5620BL-U, KE-5620W-U, KE-5634-U, KE-7511-U, KE-7611-U, KE-7711-U, KE-765-U, KE-785-U, KE-7008- U, KE-7005-U, KE-503-U, KE-5042-U, KE-505-U, KE-6801-U, KE-136Y-U, FE-251-U, FE-261-U, FE-271 , FE-351-U, FE-361-U, FE-451-U, SEP-1711-U, SEP-1721-U, SEP-1731-U, and the like SEP-363-U.
　１液型ＲＴＶシリコーンゴムは、一般に、チューブやカートリッジなどの容器から押し出すだけで作業することができ、硬化後はゴム弾性体となり、硬化と同時にほとんどの材料とよく接着するため、様々な用途に用いられるものとして知られている。このような１液型ＲＴＶシリコーンゴムとしては、例えば、信越化学工業（株）製の、ＫＥ－３４２３、ＫＥ－３４７、ＫＥ－３４７５、ＫＥ－３４９５、ＫＥ－４８９５、ＫＥ－４８９６、ＫＥ－１８３０、ＫＥ－１８８４、ＫＥ－３４７９、ＫＥ－３４８、ＫＥ－４８９７、ＫＥ－４８９８、ＫＥ－１８２０、ＫＥ－１８２５、ＫＥ－１８３１、ＫＥ－１８３３、Ｘ－３２－１９４７、ＫＥ－１０５６、ＫＥ－１１５１、ＫＥ－１８４２、Ｘ－３２－１９６４、ＫＥ－３４２４Ｇ、ＫＥ－３４９４、ＫＥ－３４９０、ＫＥ－４０ＲＴＶ、ＫＥ－４８９０、ＫＥ－３４９７、ＫＥ－３４９８、ＫＥ－３４９３、ＫＥ－３４６６、ＫＥ－３４６７、ＫＥ－１８６２、Ｘ－３２－２０２０、ＫＥ－１８６７、ＫＥ－３４９１、ＫＥ－３４９２、ＫＥ－３４１７、ＫＥ－３４１８、ＦＥ－１２３、ＦＥ－６１、ＦＥ－５７、Ｘ－３２－１６１９、ＫＥ－３４２７、ＫＥ－３４２８、ＫＥ－４１、ＫＥ－４２、ＫＥ－４４、ＫＥ－４５、ＫＥ－４４１、ＫＥ－４４５、ＫＥ－４５Ｓなどが挙げられる。 One-component RTV silicone rubber can generally be operated simply by extruding it from a container such as a tube or cartridge. After curing, it becomes a rubber elastic body and adheres well to most materials at the same time as curing. Known to be used. Examples of such one-component RTV silicone rubber include KE-3423, KE-347, KE-3475, KE-3495, KE-4895, KE-4896, and KE-1830 manufactured by Shin-Etsu Chemical Co., Ltd. KE-1884, KE-3479, KE-348, KE-4897, KE-4898, KE-1820, KE-1825, KE-1831, KE-1833, X-32-1947, KE-1056, KE-1151 , KE-1842, X-32-1964, KE-3424G, KE-3494, KE-3490, KE-40RTV, KE-4890, KE-3497, KE-3498, KE-3466, KE-3466, KE-3467 , KE-1862, X-32-2020, KE-1867, KE-3491, KE-3492, E-3417, KE-3418, FE-123, FE-61, FE-57, X-32-1619, KE-3427, KE-3428, KE-41, KE-42, KE-44, KE-45, Examples thereof include KE-441, KE-445, and KE-45S.
　２液型ＲＴＶシリコーンゴムは、一般に、主剤と硬化剤を所定量で混合・撹拌することにより硬化し、１液型ＲＴＶシリコーンゴムと同様に、電気特性、耐熱性、耐寒性、耐候性などに優れ、深部硬化性や保存性といった性質を兼ね備えているものとして知られている。このような２液型ＲＴＶシリコーンゴムとしては、例えば、信越化学工業（株）製の、ＫＥ－１８００Ｔ（Ａ／Ｂ）、ＫＥ－６６、ＫＥ－１０３１（Ａ／Ｂ）、ＫＥ－２００、ＫＥ－１１８、ＫＥ－１０３、ＫＥ－１０８、ＫＥ－１１９、ＫＥ－１０９（Ａ／Ｂ）、ＫＥ－１０５１Ｊ（Ａ／Ｂ）、ＫＥ－１０５２（Ａ／Ｂ）、ＫＥ－１０６、ＫＥ－１８００（Ａ／Ｂ／Ｃ）、ＫＥ－１８０１（Ａ／Ｂ／Ｃ）、ＫＥ－１８０２（Ａ／Ｂ／Ｃ）、ＫＥ－１２８１（Ａ／Ｂ）、ＫＥ－１２０４（Ａ／Ｂ）、ＫＥ－１２０４（ＡＬ／ＢＬ）、ＫＥ－５１３（Ａ／Ｂ）、ＫＥ－５２１（Ａ／Ｂ）、ＫＥ－１８６１、ＳＣＲ－１０１１（Ａ／Ｂ）、ＳＣＲ－１０１２（Ａ／Ｂ）、ＳＣＲ－１０１６（Ａ／Ｂ）、ＫＥＲ－２５００（Ａ／Ｂ）、ＫＥＲ－２６００（Ａ／Ｂ）、ＡＳＰ－１０１０（Ａ／Ｂ）、ＡＳＰ－１０２０（Ａ／Ｂ）、ＫＥＲ－３０００－Ｍ２、ＫＥＲ－３１００－Ｕ２、ＫＥＲ－３２００－Ｔ１、ＫＥ－１２、ＫＥ－１４、ＫＥ－１７、ＫＥ－１１１、ＫＥ－１２２２（Ａ／Ｂ）、ＫＥ－１２４１、ＫＥ－１１３、ＫＥ－２４、ＫＥ－２６、ＫＥ－１４１４、ＫＥ－１４１５、ＫＥ－１４１６、ＫＥ－１４１７、ＫＥ－１３００Ｔ、ＫＥ－１３１０ＳＴ、ＫＥ－１３１４－２、ＫＥ－１６００、ＫＥ－１６０３（Ａ／Ｂ）、ＫＥ－１６０６、ＳＩＭ－２６０、ＳＩＭ－２４０、ＳＩＭ－３６０などが挙げられる。 Two-component RTV silicone rubber is generally cured by mixing and stirring the main agent and curing agent in a predetermined amount, and in the same way as one-component RTV silicone rubber, it has electrical characteristics, heat resistance, cold resistance, weather resistance, etc. It is known to have excellent properties such as deep-curability and storage stability. Examples of such two-component RTV silicone rubber include KE-1800T (A / B), KE-66, KE-1031 (A / B), KE-200, and KE manufactured by Shin-Etsu Chemical Co., Ltd. -118, KE-103, KE-108, KE-119, KE-109 (A / B), KE-1051J (A / B), KE-1052 (A / B), KE-106, KE-1800 ( A / B / C), KE-1801 (A / B / C), KE1802 (A / B / C), KE-1281 (A / B), KE-1204 (A / B), KE-1204 (AL / BL), KE-513 (A / B), KE-521 (A / B), KE-1861, SCR-1011 (A / B), SCR-1012 (A / B), SCR-1016 ( A / B), KER-2500 (A / B), KER-26 0 (A / B), ASP-1010 (A / B), ASP-1020 (A / B), KER-3000-M2, KER-3100-U2, KER-3200-T1, KE-12, KE-14 KE-17, KE-111, KE-1222 (A / B), KE-1241, KE-113, KE-24, KE-26, KE-1414, KE-1415, KE-1416, KE-1417, Examples thereof include KE-1300T, KE-1310ST, KE-1314-2, KE-1600, KE-1603 (A / B), KE-1606, SIM-260, SIM-240, and SIM-360.
　シリコーン樹脂層は、シリコーンオイルを含む。シリコーン樹脂層に含まれるシリコーンオイルは１種のみであっても良いし、２種以上であっても良い。シリコーンオイルとしては、シリコーン樹脂との反応性や自己縮合性を有さないものが好ましい。このようなシリコーンオイルとしては、本発明の効果を損なわない範囲で、任意の適切なシリコーンオイルを採用し得る。このようなシリコーンオイルとしては、シリコーン樹脂に含まれるオルガノポリシロキサンとある程度不相溶であるものが好ましく、長期間にわたって防汚効果を持続できる点で、例えば、一般式（Ｉ）で表されるシリコーンオイルが好ましい。 The silicone resin layer contains silicone oil. Only one type of silicone oil may be contained in the silicone resin layer, or two or more types may be used. The silicone oil is preferably one that does not have reactivity with the silicone resin or self-condensation. As such a silicone oil, any appropriate silicone oil can be adopted as long as the effects of the present invention are not impaired. Such a silicone oil is preferably incompatible with the organopolysiloxane contained in the silicone resin to some extent, and is represented by, for example, the general formula (I) in that the antifouling effect can be maintained over a long period of time. Silicone oil is preferred.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　一般式（Ｉ）中、Ｒ１は、同一または異なって、炭素数１～１０のアルキル基、アリール基、アラルキル基、フルオロアルキル基、ポリエーテル基、または水酸基を表し、Ｒ２は、同一または異なって、炭素数１～１０のアルキル基、アリール基、アラルキル基、ポリエーテル基、フルオロアルキル基を表し、ｎは０～１５０の整数を表す。 In general formula (I), R 1 is the same or different and represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, a fluoroalkyl group, a polyether group, or a hydroxyl group, and R 2 is the same or Differently, it represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, a polyether group or a fluoroalkyl group, and n represents an integer of 0 to 150.
　一般式（Ｉ）中のＲ１としては、好ましくは、メチル基、フェニル基、水酸基である。一般式（Ｉ）中のＲ２としては、好ましくは、メチル基、フェニル基、４－トリフルオロブチル基である。 R 1 in the general formula (I) is preferably a methyl group, a phenyl group, or a hydroxyl group. R 2 in the general formula (I) is preferably a methyl group, a phenyl group, or a 4-trifluorobutyl group.
　一般式（Ｉ）で表されるシリコーンオイルは、数平均分子量が、好ましくは１８０～２００００、より好ましくは１０００～１００００である。 The silicone oil represented by the general formula (I) has a number average molecular weight of preferably 180 to 20000, more preferably 1000 to 10,000.
　一般式（Ｉ）で表されるシリコーンオイルは、粘度が、好ましくは１０センチストークス～１００００センチストークス、より好ましくは１００センチストークス～５０００センチストークスである。 The viscosity of the silicone oil represented by the general formula (I) is preferably 10 centistokes to 10000 centistokes, more preferably 100 centistokes to 5000 centistokes.
　一般式（Ｉ）で表されるシリコーンオイルとしては、具体的には、例えば、両末端または片末端のＲ１が水酸基である末端水酸基含有ジメチルシリコーンオイル、Ｒ１およびＲ２の全てがメチル基であるジメチルシリコーンオイル、これらのジメチルシリコーンオイルのメチル基の一部がフェニル基に置換されたフェニルメチルシリコーンオイルなどが挙げられる。 As the silicone oil represented by the general formula (I), specifically, for example, terminal hydroxyl group-containing dimethyl silicone oil R 1 at both ends or one end is a hydroxyl group, all of R 1 and R 2 is a methyl group And dimethyl silicone oils in which some of the methyl groups of these dimethyl silicone oils are substituted with phenyl groups.
　シリコーンオイルの市販品としては、例えば、信越化学工業（株）製の、ＫＦ－９６Ｌ、ＫＦ－９６Ａ、ＫＦ－９６、ＫＦ－９６Ｈ、ＫＦ－９９、ＫＦ－５０、ＫＦ－５４、ＫＦ－９６５、ＫＦ－９６８、ＨＩＶＡＣ　Ｆ－４、ＨＩＶＡＣ　Ｆ－５、ＫＦ－５６Ａ、ＫＦ９９５、ＫＦ－６９、ＫＦ－４１０、ＫＦ－４１２、ＫＦ－４１４、ＦＬ、東レダウコーニング（株）製の、ＢＹ１６－８４６、ＳＦ８４１６、ＳＨ２００、ＳＨ２０３、ＳＨ２３０、ＳＦ８４１９、ＦＳ１２６５、ＳＨ５１０、ＳＨ５５０、ＳＨ７１０、ＦＺ－２１１０、ＦＺ－２２０３などが挙げられる。 Examples of commercially available silicone oil include KF-96L, KF-96A, KF-96, KF-96H, KF-99, KF-50, KF-54, and KF-965 manufactured by Shin-Etsu Chemical Co., Ltd. , KF-968, HIVAC F-4, HIVAC F-5, KF-56A, KF995, KF-69, KF-410, KF-412, KF-414, FL, manufactured by Toray Dow Corning Co., Ltd. BY16- 846, SF8416, SH200, SH203, SH230, SF8419, FS1265, SH510, SH550, SH710, FZ-2110, FZ-2203, and the like.
　シリコーンオイルとして、変性シリコーンオイルを用いても良い。変性シリコーンオイルは、一般に、各種有機基を導入してジメチルシリコーンオイルの優れた特徴に新たな機能を付加したシリコーンオイルであり、有機基の種類により、水への溶解性、各種有機物との相溶性や反応性、ペインタブル性、潤滑性などの特性を付与できるものとして知られている。このような変性シリコーンオイルとしては、例えば、信越化学工業（株）製の、側鎖型変性シリコーンオイル、両末端型変性シリコーンオイル、片末端型変性シリコーンオイル、側鎖両末端型変性シリコーンオイル、などが挙げられる。 As the silicone oil, modified silicone oil may be used. Modified silicone oil is generally a silicone oil in which various organic groups are introduced and new functions are added to the superior characteristics of dimethyl silicone oil. Depending on the type of organic group, solubility in water and compatibility with various organic substances can be achieved. It is known that it can impart properties such as solubility, reactivity, paintability, and lubricity. Examples of such modified silicone oil include, for example, side chain modified silicone oil, both end modified silicone oil, one terminal modified silicone oil, side chain both terminal modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd., Etc.
　シリコーン樹脂層中のシリコーンオイルの含有割合は８重量％～７０重量％である。シリコーン樹脂層中のシリコーンオイルの含有割合の下限値は、好ましくは１０重量％以上であり、より好ましくは１５重量％以上であり、さらに好ましくは２０重量％以上であり、特に好ましくは２５重量％以上である。シリコーン樹脂層中のシリコーンオイルの含有割合の上限値は、好ましくは６７重量％以下であり、より好ましくは６５重量％以下であり、さらに好ましくは６２重量％以下であり、特に好ましくは６０重量％以下である。 The content of silicone oil in the silicone resin layer is 8% to 70% by weight. The lower limit of the content ratio of the silicone oil in the silicone resin layer is preferably 10% by weight or more, more preferably 15% by weight or more, still more preferably 20% by weight or more, and particularly preferably 25% by weight. That's it. The upper limit of the content ratio of the silicone oil in the silicone resin layer is preferably 67% by weight or less, more preferably 65% by weight or less, still more preferably 62% by weight or less, and particularly preferably 60% by weight. It is as follows.
　シリコーン樹脂層中のシリコーンオイルの含有割合の下限値を上記範囲内に調整することにより、本発明のロール保護用粘着シートは良好な剥離性を発現し得る。 By adjusting the lower limit of the content ratio of the silicone oil in the silicone resin layer within the above range, the roll protective pressure-sensitive adhesive sheet of the present invention can exhibit good peelability.
　シリコーン樹脂層中のシリコーンオイルの含有割合の上限値を上記範囲内に調整することにより、本発明のロール保護用粘着シートを用いて基材を搬送する場合に、シリコーンオイルによる基材の汚染を効果的に抑制し得る。 By adjusting the upper limit of the content ratio of the silicone oil in the silicone resin layer within the above range, when the base material is transported using the pressure-sensitive adhesive sheet for roll protection of the present invention, the base material is contaminated with the silicone oil. It can be effectively suppressed.
　シリコーン樹脂層には、流動パラフィン、界面活性剤、ワックス、動物脂類、ペトロラタム、脂肪酸などの表面改質剤が含有されていても良い。シリコーン樹脂層がこのような表面改質剤を含むことにより、表面摩擦抵抗が小さく、施工性に優れる、ロール保護用粘着シートを提供することができる。このような表面改質剤は、１種のみであっても良いし、２種以上であっても良い。 The silicone resin layer may contain a surface modifier such as liquid paraffin, surfactant, wax, animal fats, petrolatum, fatty acid and the like. By including such a surface modifier in the silicone resin layer, it is possible to provide a roll protective pressure-sensitive adhesive sheet having low surface friction resistance and excellent workability. Such a surface modifier may be only one kind, or may be two or more kinds.
　界面活性剤としては、例えば、アニオン系界面活性剤、カチオン系界面活性剤、ノニオン系界面活性剤などが挙げられる。 Examples of the surfactant include an anionic surfactant, a cationic surfactant, and a nonionic surfactant.
　シリコーン樹脂層中の上記表面改質剤の含有割合は、好ましくは０．０１重量％～１００重量％であり、より好ましくは０．０５重量％～５０重量％であり、さらに好ましくは０．１重量％～１０重量％である。シリコーン樹脂層中の上記表面改質剤の含有割合を上記範囲内に調整することにより、表面摩擦抵抗がより小さく、例えば、スキージなどの施工治具を用いた施工性に優れる、ロール保護用粘着シートを提供することができる。 The content ratio of the surface modifier in the silicone resin layer is preferably 0.01% by weight to 100% by weight, more preferably 0.05% by weight to 50% by weight, and still more preferably 0.1% by weight. % By weight to 10% by weight. By adjusting the content ratio of the surface modifier in the silicone resin layer within the above range, the surface friction resistance is smaller, for example, excellent workability using a construction jig such as a squeegee, and an adhesive for roll protection. Sheets can be provided.
　シリコーン樹脂層には、強度向上のために、任意の適切な充填剤を含有させても良い。このような充填剤は、１種のみであっても良いし、２種以上であっても良い。このような充填剤としては、例えば、補強性無機質充填剤、非補強性無機質充填剤、これらの無機質充填剤をオルガノシラン、オルガノポリシロキサンなどの有機珪素化合物で処理した無機質充填剤、などが挙げられる。 The silicone resin layer may contain any appropriate filler for improving the strength. Only one kind of such a filler may be used, or two or more kinds may be used. Examples of such fillers include reinforcing inorganic fillers, non-reinforcing inorganic fillers, and inorganic fillers obtained by treating these inorganic fillers with organosilicon compounds such as organosilanes and organopolysiloxanes. It is done.
　補強性無機質充填剤としては、例えば、ヒュームドシリカ、沈降シリカ、焼成シリカ、ヒュームド酸化チタンなどが挙げられる。特に、シリカ系の補強性無機質充填剤は、常温で液状の付加型の硬化型シリコーン樹脂に所定の硬度や引張り強さなどの物理的強度を付与し得るので、好ましく用い得る。このようなシリカ系の補強性無機質充填剤としては、例えば、ヒュームドシリカ、沈降性シリカ等の親水性シリカ；これらの親水性シリカを疎水化処理した疎水性シリカ；結晶性シリカ（または石英粉末）などが挙げられる。 Examples of the reinforcing inorganic filler include fumed silica, precipitated silica, calcined silica, and fumed titanium oxide. In particular, a silica-based reinforcing inorganic filler can be preferably used because it can impart physical strength such as predetermined hardness and tensile strength to an addition-type curable silicone resin that is liquid at room temperature. Examples of such silica-based reinforcing inorganic fillers include hydrophilic silica such as fumed silica and precipitated silica; hydrophobic silica obtained by hydrophobizing these hydrophilic silicas; crystalline silica (or quartz powder) ) And the like.
　親水性シリカの市販品としては、例えば、Ａｅｒｏｓｉｌ　１３０、Ａｅｒｏｓｉｌ　２００、Ａｅｒｏｓｉｌ　３００（日本アエロジル社製、Ｄｅｇｕｓｓａ社製）；Ｃａｂｏｓｉｌ　ＭＳ－５、Ｃａｂｏｓｉｌ　ＭＳ－７（Ｃａｂｏｔ社製）；Ｒｈｅｏｒｏｓｉｌ　ＱＳ－１０２、Ｒｈｅｏｒｏｓｉｌ　１０３（徳山曹達社製）；Ｎｉｐｓｉｌ　ＬＰ（日本シリカ社製）；などが挙げられる。 Examples of commercially available products of hydrophilic silica include Aerosil 130, Aerosil 200, Aerosil 300 (manufactured by Aerosil Japan, manufactured by Degussa); Cabosil MS-5, Cabosil MS-7 (manufactured by Cabot); Rheorosil QS-102, Rheorosil 103 (manufactured by Tokuyama Soda); Nipsil LP (manufactured by Nippon Silica);
　疎水性シリカの市販品としては、例えば、Ａｅｒｏｓｉｌ　Ｒ－８１２、Ａｅｒｏｓｉｌ　Ｒ－８１２Ｓ、Ａｅｒｏｓｉｌ　Ｒ－９７２、Ａｅｒｏｓｉｌ　Ｒ－９７４、Ａｅｒｏｓｉｌ　Ｒ－９７６、Ａｅｒｏｓｉｌ　ＳＲＸ３００－５、Ａｅｒｏｓｉｌ　ＲＸ－２００、Ａｅｒｏｓｉｌ　ＲＹ２００、Ａｅｒｏｓｉｌ　ＲＹ３００、Ａｅｒｏｓｉｌ　Ｒ８０５（Ｄｅｇｕｓｓａ社製）；Ｒｈｅｏｒｏｓｉ１　ＭＴ－１０（徳山曹達社製）；Ｎｉｐｓｉ１　ＳＳシリーズ（日本シリカ社製）；などが挙げられる。 Examples of commercially available hydrophobic silica include Aerosil R-812, Aerosil R-812S, Aerosil R-972, Aerosil R-974, Aerosil R-976, Aerosil SRX300-5, Aerosil RX-200, Aerosil RY200, Aerosil. RY300, Aerosil R805 (manufactured by Degussa); Rheorosi1 MT-10 (manufactured by Tokuyama Soda); Nippi1 SS series (manufactured by Nippon Silica);
　結晶性シリカの市販品としては、例えば、クリスタライト（（株）龍森製）；Ｍｉｎｕｓｉｌ、Ｉｍｉｓｉｌ（Ｉｌｌｉｎｏｉｓ　Ｍｉｎｅｒａｌ社製）；などが挙げられる。 Examples of commercially available crystalline silica include Crystallite (manufactured by Tatsumori); Minusil, Imisil (manufactured by Illinois Mineral), and the like.
　非補強性無機質充填剤としては、例えば、粉砕石英、ケイ藻土、酸化鉄、酸化アルミニウム、アルミノケイ酸、炭酸カルシウムなどが挙げられる。 Examples of non-reinforcing inorganic fillers include pulverized quartz, diatomaceous earth, iron oxide, aluminum oxide, aluminosilicate, and calcium carbonate.
　シリコーン樹脂層中の充填剤の含有割合は、好ましくは０重量％～７５重量％であり、より好ましくは０．５重量％～７０重量％であり、さらに好ましくは１重量％～６５重量％である。 The content of the filler in the silicone resin layer is preferably 0 to 75% by weight, more preferably 0.5 to 70% by weight, and further preferably 1 to 65% by weight. is there.
　シリコーン樹脂層には、耐熱剤、難燃剤、顔料、反応制御剤、硬化促進剤（例えば、白金触媒など）などの添加剤を含有させても良い。このような添加剤は、１種のみであっても良いし、２種以上であっても良い。 The silicone resin layer may contain additives such as a heat-resistant agent, a flame retardant, a pigment, a reaction control agent, and a curing accelerator (for example, a platinum catalyst). Only one kind of such an additive may be used, or two or more kinds thereof may be used.
　シリコーン樹脂層には、導電性を持たせるために、任意の適切な導電剤を含有させても良い。このような導電剤は、１種のみであっても良いし、２種以上であっても良い。シリコーン樹脂層に導電性を持たせることによって、剥離帯電による静電気の発生を抑制し得る。 The silicone resin layer may contain any appropriate conductive agent in order to have conductivity. Such a conductive agent may be only one type or two or more types. By imparting conductivity to the silicone resin layer, generation of static electricity due to peeling charging can be suppressed.
　導電剤としては、例えば、金属粉末、金属繊維、金属フレーク、導電性金属酸化物等の金属系導電剤；カーボンブラック；などが挙げられる。 Examples of the conductive agent include metal conductive agents such as metal powders, metal fibers, metal flakes, and conductive metal oxides; carbon black.
　金属粉末、金属繊維、金属フレークなどに用いられる金属としては、例えば、銀、銅、ニッケル、ステンレス、アルミニウムなどが挙げられる。 Examples of the metal used for the metal powder, metal fiber, metal flake and the like include silver, copper, nickel, stainless steel, aluminum and the like.
　導電性金属酸化物としては、例えば、導電性酸化亜鉛、導電性酸化チタンなどが挙げられる。 Examples of the conductive metal oxide include conductive zinc oxide and conductive titanium oxide.
　カーボンブラックとしては、例えば、アセチレンブラック、コンダクティブファーネスブラック（ＣＦ）、スーパーコンダクティブファーネスブラック（ＳＣＦ）、エクストラコンダクティブファーネスブラック（ＸＣＦ）、コンダクティブチャンネルブラック（ＣＣ）、１５００℃程度の高温で熱処理されたファーネスブラックまたはチャンネルブラックなどが挙げられる。 Examples of the carbon black include acetylene black, conductive furnace black (CF), super conductive furnace black (SCF), extra conductive furnace black (XCF), conductive channel black (CC), and a furnace heat-treated at a high temperature of about 1500 ° C. Examples include black or channel black.
　アセチレンブラックの具体例としては、例えば、電化アセチレンブラック（電気化学株式会社製）、シャウニガンアセチレンブラック（シャウニガンケミカル株式会社製）などが挙げられる。 Specific examples of acetylene black include, for example, electrified acetylene black (manufactured by Electrochemical Co., Ltd.) and shaunigan acetylene black (manufactured by Shaunigan Chemical Co., Ltd.).
　コンダクティブファーネスブラックの具体例としては、例えば、コンチネックスＣＦ（コンチネンタルカーボン株式会社製）、バルカンＣ（キャボット株式会社製）などが挙げられる。 Specific examples of conductive furnace black include, for example, CONTINEX CF (manufactured by Continental Carbon Corporation), Vulcan C (manufactured by Cabot Corporation), and the like.
　スーパーコンダクティブファーネスブラックの具体例としては、例えば、コンチネックスＳＣＦ（コンチネンタルカーボン株式会社製）、バルカンＳＣ（キャボット株式会社製）などが挙げられる。 Specific examples of super conductive furnace black include, for example, Continex SCF (manufactured by Continental Carbon Corporation), Vulcan SC (manufactured by Cabot Corporation), and the like.
　エクストラコンダクティブファーネスブラックの具体例としては、例えば、旭ＨＳ－５００（旭カーボン株式会社製）、バルカンＸＣ－７２（キャボット株式会社製）などが挙げられる。 Specific examples of extra conductive furnace black include Asahi HS-500 (Asahi Carbon Co., Ltd.), Vulcan XC-72 (Cabot Co., Ltd.), and the like.
　コンダクティブチャンネルブラックの具体例としては、例えば、コウラックスＬ（デグッサ株式会社製）などが挙げられる。 As a specific example of the conductive channel black, for example, Kourax L (manufactured by Degussa Corporation) and the like can be mentioned.
　カーボンブラックとして、ファーネスブラックの一種であるケッチェンブラックＥＣやケッチェンブラックＥＣ－６００ＪＤ（ケッチェンブラックインターナショナル株式会社製）を用いることもできる。 As carbon black, Ketjen Black EC or Ketjen Black EC-600JD (made by Ketjen Black International Co., Ltd.), which is a kind of furnace black, can also be used.
　シリコーン樹脂層中の導電剤の含有割合は、導電剤が金属系導電付与剤の場合は、好ましくは０重量％～９０重量％であり、より好ましくは０．１重量％～８０重量％であり、さらに好ましくは１重量％～７５重量％である。シリコーン樹脂層中のこのような導電剤の含有割合が多すぎると、含有割合に見合うだけの導電剤の効果が得られないおそれがあり、また、シリコーン樹脂層の機械的強度が低下するおそれがある。 The content of the conductive agent in the silicone resin layer is preferably 0% by weight to 90% by weight, more preferably 0.1% by weight to 80% by weight when the conductive agent is a metal-based conductivity imparting agent. More preferably, it is 1 to 75% by weight. If the content ratio of such a conductive agent in the silicone resin layer is too large, there is a possibility that the effect of the conductive agent corresponding to the content ratio may not be obtained, and the mechanical strength of the silicone resin layer may be reduced. is there.
　シリコーン樹脂層中の導電剤の含有割合は、導電剤がカーボンブラックの場合は、好ましくは０重量％～６０重量％であり、より好ましくは０．１重量％～５０重量％であり、さらに好ましくは１重量％～４０重量％である。シリコーン樹脂層中のこのような導電剤の含有割合が多すぎると、含有割合に見合うだけの導電剤の効果が得られないおそれがあり、また、シリコーン樹脂層の機械的強度が低下するおそれがある。 When the conductive agent is carbon black, the content of the conductive agent in the silicone resin layer is preferably 0% by weight to 60% by weight, more preferably 0.1% by weight to 50% by weight, and still more preferably Is 1 to 40% by weight. If the content ratio of such a conductive agent in the silicone resin layer is too large, there is a possibility that the effect of the conductive agent corresponding to the content ratio may not be obtained, and the mechanical strength of the silicone resin layer may be reduced. is there.
　本発明のロール保護用粘着シートにおいては、好ましくは、シリコーン樹脂層および基材層から選ばれる少なくとも１種が、シランカップリング剤、シリコーンパウダー、およびシリカ粒子から選ばれる少なくとも１種を含む。シリコーン樹脂層および基材層から選ばれる少なくとも１種が、シランカップリング剤、シリコーンパウダー、およびシリカ粒子から選ばれる少なくとも１種を含むことにより、シリコーン樹脂層と基材層との密着性を高めることができる。 In the pressure-sensitive adhesive sheet for roll protection of the present invention, preferably, at least one selected from a silicone resin layer and a base material layer includes at least one selected from a silane coupling agent, silicone powder, and silica particles. When at least one selected from the silicone resin layer and the base material layer includes at least one selected from a silane coupling agent, a silicone powder, and silica particles, the adhesion between the silicone resin layer and the base material layer is improved. be able to.
　シランカップリング剤は、１種のみであっても良いし、２種以上であっても良い。 Only one type of silane coupling agent may be used, or two or more types may be used.
　シランカップリング剤としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン等のビニル基含有シランカップリング剤；２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン等のエポキシ基含有シランカップリング剤；ｐ－スチリルトリメトキシシラン等のスチリル基含有シランカップリング剤；３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリエトキシシラン等のメタクリル基含有シランカップリング剤；３－アクリロキシプロピルトリメトキシシラン等のアクリル基含有シランカップリング剤；Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチル－ブチリデン）プロピルアミン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、Ｎ－（ビニルベンジル）－２－アミノエチル－３－アミノプロピルトリメトキシシランの塩酸塩等のアミノ基含有シランカップリング剤；３－ウレイドプロピルトリエトキシシラン等のウレイド基含有シランカップリング剤；３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキシシラン等のメルカプト基含有シランカップリング剤；ビス（トリエトキシシリルプロピル）テトラスルフィド等のスルフィド基含有シランカップリング剤；３－イソシアネートプロピルトリエトキシシラン等のイソシアネート基含有シランカップリング剤；などが挙げられる。 Examples of the silane coupling agent include vinyl group-containing silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyl Epoxy group-containing silane coupling agents such as dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; p-styryltrimethoxysilane, etc. Styryl group-containing silane coupling agent: 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxy Methacrylic group-containing silane coupling agent such as silane; Acrylic group-containing silane coupling agent such as 3-acryloxypropyltrimethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N Amino group-containing silane coupling agents such as phenyl-3-aminopropyltrimethoxysilane and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; 3-ureidopropyltriethoxysilane Silane coupling containing ureido groups such as A mercapto group-containing silane coupling agent such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; a sulfide group-containing silane coupling agent such as bis (triethoxysilylpropyl) tetrasulfide; 3-isocyanatopropyltri And isocyanate group-containing silane coupling agents such as ethoxysilane.
　市販されている具体的なシランカップリング剤としては、例えば、信越化学工業（株）製のＫＢＭ５１０３、ＫＢＭ１００３、ＫＢＭ９０３、ＫＢＭ４０３、ＫＢＭ８０２などが挙げられる。 Specific examples of commercially available silane coupling agents include KBM5103, KBM1003, KBM903, KBM403, and KBM802 manufactured by Shin-Etsu Chemical Co., Ltd.
　シリコーンパウダーは、１種のみであっても良いし、２種以上であっても良い。 Only one type of silicone powder may be used, or two or more types may be used.
　シリコーンパウダーの平均粒径は、好ましくは１ｎｍ～１００μｍであり、より好ましくは１０ｎｍ～７０μｍであり、さらに好ましくは１００ｎｍ～５０μｍであり、特に好ましくは５００ｎｍ～２０μｍである。シリコーンパウダーの平均粒径を上記範囲内に調整することによって、シリコーン樹脂層と基材層との高い密着性をより効果的に発現することができる。 The average particle size of the silicone powder is preferably 1 nm to 100 μm, more preferably 10 nm to 70 μm, still more preferably 100 nm to 50 μm, and particularly preferably 500 nm to 20 μm. By adjusting the average particle size of the silicone powder within the above range, high adhesion between the silicone resin layer and the base material layer can be expressed more effectively.
　シリコーンパウダーとしては、例えば、直鎖状のジメチルポリシロキサンを架橋した構造を持つシリコーンゴム粒子や、シロキサン結合が三次元網目状に架橋した構造を持つポリオルガノシルセスキオキサン硬化物であるシリコーンレジン粒子や、シリコーンゴム粒子の表面をシリコーンレジンで被膜したシリコーン複合粒子などが挙げられる。 Examples of the silicone powder include silicone rubber particles having a structure in which linear dimethylpolysiloxane is crosslinked, and a silicone resin that is a cured product of polyorganosilsesquioxane having a structure in which siloxane bonds are crosslinked in a three-dimensional network. Examples include particles and silicone composite particles in which the surface of silicone rubber particles is coated with a silicone resin.
　市販されている具体的なシリコーンパウダーとしては、例えば、信越化学工業（株）製のシリコーン複合パウダー（ＫＭＰ－６００、ＫＭＰ－６０１、ＫＭＰ－６０２、ＫＭＰ－６０５、Ｘ－５２－７０３０など）、シリコーンゴムパウダー（ＫＭＰ－５９７、ＫＭＰ－５９８、ＫＭＰ－５９４、Ｘ－５２－８７５など）、シリコーンレジンパウダー（ＫＭＰ－５９０、ＫＭＰ－７０１、Ｘ－５２－８５４、Ｘ－５２－１６２１など）が挙げられる。 Specific silicone powders that are commercially available include, for example, silicone composite powders (KMP-600, KMP-601, KMP-602, KMP-605, X-52-7030, etc.) manufactured by Shin-Etsu Chemical Co., Ltd. Silicone rubber powder (KMP-597, KMP-598, KMP-594, X-52-875, etc.), silicone resin powder (KMP-590, KMP-701, X-52-854, X-52-1621, etc.) Can be mentioned.
　シリカ粒子は、１種のみであっても良いし、２種以上であっても良い。 The silica particles may be only one kind or two or more kinds.
　シリカ粒子の平均粒径は、好ましくは１ｎｍ～１００μｍであり、より好ましくは２ｎｍ～７０μｍであり、さらに好ましくは３ｎｍ～５０μｍであり、特に好ましくは５ｎｍ～３０μｍである。シリカ粒子の平均粒径を上記範囲内に調整することによって、シリコーン樹脂層と基材層との高い密着性をより効果的に発現することができる。 The average particle diameter of the silica particles is preferably 1 nm to 100 μm, more preferably 2 nm to 70 μm, still more preferably 3 nm to 50 μm, and particularly preferably 5 nm to 30 μm. By adjusting the average particle diameter of the silica particles within the above range, high adhesion between the silicone resin layer and the base material layer can be expressed more effectively.
　シリカ粒子としては、例えば、二酸化ケイ素（ＳｉＯ２）の粒子もしくは二酸化ケイ素（ＳｉＯ２）によって構成された粒子が挙げられ、例えば、疎水性のシリカ粒子や親水性のシリカ粒子が挙げられる。シリカ粒子としては、例えば、表面が疎水処理された粒子や表面が親水処理された粒子も挙げられる。 Examples of the silica particles include silicon dioxide (SiO 2 ) particles or particles composed of silicon dioxide (SiO 2 ), and examples include hydrophobic silica particles and hydrophilic silica particles. Examples of the silica particles include particles whose surface has been subjected to a hydrophobic treatment and particles whose surface has been subjected to a hydrophilic treatment.
　市販されている具体的なシリカ粒子としては、例えば、アエロジルシリーズ（日本アエロジル（株）製）が用いられる。より具体的には、疎水性においては、アエロジルＲ８２００（１次平均粒子径：１２ｎｍ、ヘキサメチルジシラザン処理）、アエロジルＲ１０４（１次平均粒子径：１２ｎｍ、オクタメチルシクロテトラシロキサン処理）、アエロジルＲ９７２（１次平均粒子径：１６ｎｍ、ジメチルジクロロシラン処理）、アエロジルＲ９７４（１次平均粒子径：１２ｎｍ、ジメチルジクロロシラン処理）、アエロジルＲ８１２（１次平均粒子径：７ｎｍ、ヘキサメチルジシラザン処理）などが挙げられ、親水性においては、アエロジル２００（１次平均粒子径：１２ｎｍ）、アエロジル３００（１次平均粒子径：７ｎｍ）などが挙げられる。 Specific examples of commercially available silica particles include Aerosil series (produced by Nippon Aerosil Co., Ltd.). More specifically, in hydrophobicity, Aerosil R8200 (primary average particle size: 12 nm, hexamethyldisilazane treatment), Aerosil R104 (Primary average particle size: 12 nm, octamethylcyclotetrasiloxane treatment), Aerosil R972 (Primary average particle size: 16 nm, dimethyldichlorosilane treatment), Aerosil R974 (Primary average particle size: 12 nm, dimethyldichlorosilane treatment), Aerosil R812 (Primary average particle size: 7 nm, hexamethyldisilazane treatment), etc. Examples of hydrophilicity include Aerosil 200 (primary average particle size: 12 nm), Aerosil 300 (primary average particle size: 7 nm), and the like.
　シリコーン樹脂層および基材層の合計に対する、シランカップリング剤、シリコーンパウダー、およびシリカ粒子の合計の含有割合は、好ましくは０．０１重量％～１００重量％であり、より好ましくは０．５重量％～３０重量％であり、さらに好ましくは０．１重量％～１０重量％であり、特に好ましくは１重量％～５重量％である。上記含有割合を上記範囲内に収まるように調整することにより、シリコーン樹脂層と基材層との高い密着性をより効果的に発現することができる。上記含有割合が０．０１重量％未満の場合、基材層とシリコーン樹脂層との間に十分な密着性が発現できないおそれがある。 The total content of the silane coupling agent, the silicone powder, and the silica particles with respect to the total of the silicone resin layer and the base material layer is preferably 0.01% by weight to 100% by weight, and more preferably 0.5% by weight. % To 30% by weight, more preferably 0.1% to 10% by weight, and particularly preferably 1% to 5% by weight. By adjusting the content ratio so as to be within the above range, high adhesion between the silicone resin layer and the base material layer can be expressed more effectively. When the said content rate is less than 0.01 weight%, there exists a possibility that sufficient adhesiveness cannot be expressed between a base material layer and a silicone resin layer.
　なお、シリコーン樹脂層および基材層の合計に対するシランカップリング剤の含有割合の上限は、好ましくは３０重量％以下であり、さらに好ましくは１０重量％以下であり、特に好ましくは５重量％以下である。シリコーン樹脂層および基材層の合計に対するシランカップリング剤の含有割合の上限を上記範囲内に収まるように調整することにより、シランカップリング剤が架橋点となって該シランカップリング剤を含む層が硬くなり過ぎることを抑制できる。 The upper limit of the content ratio of the silane coupling agent relative to the total of the silicone resin layer and the base material layer is preferably 30% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less. is there. By adjusting the upper limit of the content ratio of the silane coupling agent relative to the total of the silicone resin layer and the base material layer so as to be within the above range, the silane coupling agent becomes a crosslinking point and contains the silane coupling agent. Can be suppressed from becoming too hard.
　基材層には、シリコーン樹脂層との密着性をさらに向上させるために、プライマーをあらかじめ塗工しておいても良い。 In order to further improve the adhesion with the silicone resin layer, a primer may be applied to the base material layer in advance.
　基材層の材料としては、本発明の効果を損なわない範囲で、任意の適切な材料を採用し得る。このような基材層の材料としては、好ましくは、耐水性、強度、柔軟性、裂け性に優れるものである。このような基材層の材料としては、例えば、ポリウレタン樹脂、ポリウレタンアクリル樹脂、ゴム系樹脂、塩化ビニル樹脂、ポリエステル樹脂、シリコーン樹脂、エラストマー類、フッ素樹脂、ポリアミド樹脂、ポリオレフィン樹脂（ポリエチレン、ポリプロピレンなど）などが挙げられる。このような基材層の材料は、１種のみであっても良いし、２種以上であっても良い。 As the material of the base material layer, any appropriate material can be adopted as long as the effects of the present invention are not impaired. Such a material for the base material layer is preferably excellent in water resistance, strength, flexibility and tearability. Examples of the material for the base material layer include polyurethane resin, polyurethane acrylic resin, rubber resin, vinyl chloride resin, polyester resin, silicone resin, elastomers, fluororesin, polyamide resin, polyolefin resin (polyethylene, polypropylene, etc.) ) And the like. The material of such a base material layer may be only one type or two or more types.
　基材層は、好ましくは、ポリエステル樹脂およびエラストマー樹脂から選ばれる少なくとも１種を含む。基材層がポリエステル樹脂およびエラストマー樹脂から選ばれる少なくとも１種を含むことにより、曲面や鋭角面など、平面以外の部位にも容易に作業性良く貼着でき、貼着後の表面にしわや浮きなどの外観不良が生じ難い、ロール保護用粘着シートを提供することができる。したがって、本発明のロール保護用粘着シートをロール表面に容易に貼着することができる。特に、本発明のロール保護用粘着シートにおいては、本発明の効果をより一層発現できるとともに、高い貼着性や高い耐久性を有する点で、基材層がポリエステル樹脂であることがより好ましい。 The base material layer preferably contains at least one selected from polyester resins and elastomer resins. When the base material layer contains at least one selected from polyester resin and elastomer resin, it can be easily attached to parts other than flat surfaces such as curved surfaces and acute angle surfaces with good workability, and wrinkles and floats on the surface after application. Thus, it is possible to provide a pressure-sensitive adhesive sheet for roll protection that hardly causes poor appearance. Therefore, the pressure-sensitive adhesive sheet for roll protection of the present invention can be easily attached to the roll surface. In particular, in the pressure-sensitive adhesive sheet for roll protection of the present invention, it is more preferable that the base material layer is a polyester resin from the viewpoint that the effects of the present invention can be further exhibited, and that high adhesiveness and high durability are provided.
　ポリエステル樹脂としては、好ましくは、ポリエチレンテレフタレート（ＰＥＴ）が挙げられる。基材層中に含まれ得るポリエステル樹脂は、１種のみであっても良いし、２種以上であっても良い。 The polyester resin is preferably polyethylene terephthalate (PET). The polyester resin that can be contained in the base material layer may be only one kind or two or more kinds.
　エラストマー樹脂としては、本発明の効果を損なわない範囲で任意の適切なエラストマー樹脂を採用し得る。このようなエラストマー樹脂としては、例えば、加硫ゴム、熱可塑性エラストマーなどが挙げられる。熱可塑性エラストマーとしては、例えば、スチレン系エラストマー、オレフィン系エラストマー、塩ビ系エラストマー、ウレタン系エラストマー、エステル系エラストマー、アミド系エラストマーなどが挙げられる。基材層中に含まれ得るエラストマー樹脂は、１種のみであっても良いし、２種以上であっても良い。 As the elastomer resin, any appropriate elastomer resin can be adopted as long as the effects of the present invention are not impaired. Examples of such elastomer resins include vulcanized rubber and thermoplastic elastomer. Examples of the thermoplastic elastomer include styrene elastomers, olefin elastomers, vinyl chloride elastomers, urethane elastomers, ester elastomers, amide elastomers, and the like. The elastomer resin that can be included in the base material layer may be only one type or two or more types.
　基材層中の、ポリエステル樹脂およびエラストマー樹脂から選ばれる少なくとも１種の含有割合は、好ましくは５０重量％以上であり、より好ましくは６０重量％～１００重量％であり、さらに好ましくは７０重量％～９９重量％であり、特に好ましくは８０重量％～９８重量％であり、最も好ましくは９０重量％～９７重量％である。 The content ratio of at least one selected from the polyester resin and the elastomer resin in the base material layer is preferably 50% by weight or more, more preferably 60% by weight to 100% by weight, and still more preferably 70% by weight. It is ˜99% by weight, particularly preferably 80% by weight to 98% by weight, and most preferably 90% by weight to 97% by weight.
　エラストマー樹脂としては、好ましくは、ウレタン系エラストマーである。ウレタン系エラストマーとしては、好ましくは、ポリウレタンアクリル樹脂およびポリウレタン樹脂から選ばれる少なくとも１種である。ポリウレタン樹脂としては、例えば、カーボネート系ポリウレタン、エステル系ポリウレタン、エーテル系ポリウレタンなどが挙げられる。エラストマー樹脂としてウレタン系エラストマーを採用することにより、曲面や鋭角面など、平面以外の部位にも一層容易に作業性良く貼着でき、貼着後の表面にしわや浮きなどの外観不良が一層生じ難い、ロール保護用粘着シートを提供することができる。したがって、本発明のロール保護用粘着シートをロール表面に容易に貼着することができる。 The elastomer resin is preferably a urethane elastomer. The urethane elastomer is preferably at least one selected from polyurethane acrylic resins and polyurethane resins. Examples of the polyurethane resin include carbonate-based polyurethane, ester-based polyurethane, and ether-based polyurethane. By using urethane elastomer as the elastomer resin, it can be easily applied to areas other than flat surfaces, such as curved surfaces and acute angles, with better workability, resulting in further appearance defects such as wrinkles and floats on the surface after application. It is difficult to provide a pressure-sensitive adhesive sheet for roll protection. Therefore, the pressure-sensitive adhesive sheet for roll protection of the present invention can be easily attached to the roll surface.
　基材層は、本発明の効果を損なわない範囲で、任意の適切な添加剤を含んでいても良い。このような添加剤としては、例えば、オレフィン系樹脂、シリコーン系ポリマー、液状アクリル系共重合体、粘着付与剤、老化防止剤、ヒンダードアミン系光安定剤、紫外線吸収剤、酸化防止剤、帯電防止剤、ポリエチレンイミン、脂肪酸アミド、脂肪酸エステル、リン酸エステル、滑剤、界面活性剤、充填剤や顔料（例えば、酸化カルシウム、酸化マグネシウム、シリカ、酸化亜鉛、酸化チタン、カーボンブラックなど）などが挙げられる。 The base material layer may contain any appropriate additive as long as the effects of the present invention are not impaired. Examples of such additives include olefin resins, silicone polymers, liquid acrylic copolymers, tackifiers, anti-aging agents, hindered amine light stabilizers, ultraviolet absorbers, antioxidants, and antistatic agents. , Polyethyleneimine, fatty acid amide, fatty acid ester, phosphate ester, lubricant, surfactant, filler and pigment (for example, calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide, carbon black, etc.).
　基材層の厚みは、目的に応じて、任意の適切な厚みを採用し得る。基材層の厚みは、好ましくは１μｍ～１０００μｍであり、より好ましくは１０μｍ～８００μｍであり、さらに好ましくは２０μｍ～５００μｍである。基材層の厚みを上記範囲内に収めることにより、本発明のロール保護用粘着シートは、シリコーン樹脂層と基材層との密着性に優れ、曲面や鋭角面など、平面以外の部位にも容易に作業性良く貼着でき、貼着後の表面にしわや浮きなどの外観不良が生じ難い。したがって、ロール表面に容易に貼着することができる。したがって、本発明のロール保護用粘着シートをロール表面に容易に貼着することができる。 Any appropriate thickness can be adopted as the thickness of the base material layer according to the purpose. The thickness of the base material layer is preferably 1 μm to 1000 μm, more preferably 10 μm to 800 μm, and still more preferably 20 μm to 500 μm. By keeping the thickness of the base material layer within the above range, the pressure-sensitive adhesive sheet for roll protection of the present invention has excellent adhesion between the silicone resin layer and the base material layer, and can be applied to parts other than flat surfaces such as curved surfaces and acute angle surfaces. It can be easily applied with good workability, and it is difficult for appearance defects such as wrinkles and floats to occur on the surface after application. Therefore, it can be easily attached to the roll surface. Therefore, the pressure-sensitive adhesive sheet for roll protection of the present invention can be easily attached to the roll surface.
　粘着層としては、本発明の効果を損なわない範囲で、任意の適切な粘着層を採用し得る。このような粘着層の材料としては、例えば、アクリル樹脂系粘着剤、エポキシ樹脂系粘着剤、アミノ樹脂系粘着剤、ビニル樹脂（酢酸ビニル系重合体など）系粘着剤、硬化型アクリル樹脂系粘着剤、シリコーン樹脂系粘着剤などが挙げられる。粘着層の材料は、１種のみであっても良いし、２種以上であっても良い。 As the adhesive layer, any appropriate adhesive layer can be adopted as long as the effects of the present invention are not impaired. Examples of the material for such an adhesive layer include acrylic resin adhesives, epoxy resin adhesives, amino resin adhesives, vinyl resin (vinyl acetate polymers, etc.) adhesives, and curable acrylic resin adhesives. Agents, silicone resin adhesives, and the like. The material of the adhesive layer may be only one type or two or more types.
　粘着層の厚みは、本発明のロール保護用粘着シートの用途や使用環境などによって、任意の適切な厚みを採用し得る。粘着層の厚みは、好ましくは１０μｍ以上である。粘着層の厚みが上記範囲内に収まることにより、被着体の形状に十分に追従でき、接着面積を十分に確保でき、十分な粘着力が発現できる。粘着層の厚みが１０μｍより薄いと、被着体の形状に十分に追従できなくなり、接着面積が減少してしまい、十分な粘着力が発現できないおそれがある。粘着層の厚みの上限は、取扱性の観点から、好ましくは３００μｍ以下である。 Any appropriate thickness can be adopted as the thickness of the pressure-sensitive adhesive layer depending on the application or use environment of the pressure-sensitive adhesive sheet for roll protection of the present invention. The thickness of the adhesive layer is preferably 10 μm or more. When the thickness of the pressure-sensitive adhesive layer is within the above range, the shape of the adherend can be sufficiently followed, the adhesion area can be sufficiently secured, and sufficient adhesive force can be expressed. When the thickness of the pressure-sensitive adhesive layer is less than 10 μm, it is impossible to sufficiently follow the shape of the adherend, the adhesion area is reduced, and there is a possibility that sufficient pressure-sensitive adhesive force cannot be expressed. The upper limit of the thickness of the pressure-sensitive adhesive layer is preferably 300 μm or less from the viewpoint of handleability.
　本発明のロール保護用粘着シートは、任意の適切な方法によって製造し得る。このような方法としては、例えば、別途準備した基材層と粘着層を貼付した後にシリコーン樹脂層形成材料を基材層上に塗布してシリコーン樹脂層を形成する方法、基材層の一方の面に粘着層形成材料を塗布して粘着層を形成し、基材層のもう一方の面にシリコーン樹脂層形成材料を塗布してシリコーン樹脂層を形成する方法、基材層形成材料と粘着層形成材料を共押出しして基材層／粘着層の積層体を形成させた後にシリコーン樹脂層形成材料を基材層上に塗布してシリコーン樹脂層を形成する方法、などが挙げられる。 The roll protective pressure-sensitive adhesive sheet of the present invention can be produced by any appropriate method. As such a method, for example, a method of forming a silicone resin layer by applying a silicone resin layer forming material on a substrate layer after pasting a separately prepared substrate layer and an adhesive layer, one of the substrate layers A method for forming a silicone resin layer by applying an adhesive layer forming material on the surface to form an adhesive layer, and applying a silicone resin layer forming material on the other surface of the base material layer, the base material layer forming material and the adhesive layer Examples include a method of forming a silicone resin layer by applying a silicone resin layer forming material on a base material layer after co-extrusion of the forming material to form a base material layer / adhesive layer laminate.
　シリコーン樹脂層形成材料を基材層上に塗布する方法としては、例えば、コーター、スプレー、ハケ塗り、ローラー、カーテンフロー、ロール、ディップなどが挙げられる。これらの方法でシリコーン樹脂層形成材料を基材層上に塗布して、例えば、室温から２５０℃までの温度（好ましくは、室温から１８０℃の温度）で乾燥させることにより、シリコーン樹脂層を形成することができる。 Examples of the method for applying the silicone resin layer forming material on the base material layer include a coater, spray, brush coating, roller, curtain flow, roll, and dip. The silicone resin layer forming material is applied onto the base material layer by these methods, and the silicone resin layer is formed, for example, by drying at a temperature from room temperature to 250 ° C. (preferably a temperature from room temperature to 180 ° C.). can do.
　以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例になんら限定されるものではない。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.
＜粘着テープ剥離力の測定＞
　実施例および比較例で得られた粘着シートを幅５０ｍｍ×長さ１００ｍｍに切断し、粘着層側を平滑なＡＢＳ樹脂板（幅５０ｍｍ×長さ１００ｍｍ、厚さ３ｍｍ）にハンドローラーにて貼り合せた。粘着シートのシリコーン樹脂層側に粘着テープとしてＮｏ．３１Ｂ（アクリル系粘着剤、日東電工（株）製、幅２０ｍｍ×長さ８０ｍｍ）をハンドローラーにて圧着し、温度２３℃、湿度６５％ＲＨの条件下にて、変角度ピール試験機（商品名「山本式変角ピール測定機　ＹＭ－１２１」、旭精工（株）製）にて、３０°の剥離角度で剥離に要する力を測定した（引っ張り速度：３ｍ／分）。 <Measurement of adhesive tape peeling force>
The pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were cut into a width of 50 mm and a length of 100 mm, and the pressure-sensitive adhesive layer side was bonded to a smooth ABS resin plate (width 50 mm × length 100 mm, thickness 3 mm) with a hand roller. It was. No. as an adhesive tape on the silicone resin layer side of the adhesive sheet. 31B (acrylic pressure-sensitive adhesive, manufactured by Nitto Denko Corporation, width 20 mm x length 80 mm) is pressure-bonded with a hand roller, and under a condition of a temperature of 23 ° C. and a humidity of 65% RH, a variable angle peel tester (product) The force required for peeling was measured at a peeling angle of 30 ° (Tensile speed: 3 m / min) with the name “Yamamoto-type bending angle measuring machine YM-121” manufactured by Asahi Seiko Co., Ltd.).
＜汚染性評価＞
　実施例および比較例で得られた粘着シートを幅５０ｍｍ×長さ１００ｍｍに切断し、粘着層側を平滑なＡＢＳ樹脂板（幅５０ｍｍ×長さ１００ｍｍ、厚さ３ｍｍ）にハンドローラーにて貼り合せた。粘着シートのシリコーン樹脂層側に粘着テープとしてＮｏ．３１Ｂ（アクリル系粘着剤、日東電工（株）製、幅２０ｍｍ×長さ８０ｍｍ）をハンドローラーにて圧着し、温度２３℃、湿度６５％ＲＨの条件下で３０分保管後、粘着テープを引張試験機（商品名「Ａｕｔｏｇｒａｐｈ　ＡＧ－Ｘ　２００Ｎ」、（株）島津製作所製）にて１８０°の剥離角度で剥離した（引っ張り速度：３００ｍｍ／分）。剥離したＮｏ．３１Ｂを粒度２８０番の研磨紙で磨いたＳＵＳ３０４板に重さ２ｋｇ重のゴムローラーを１往復させる方法によって圧着し、温度２３℃、湿度６５％ＲＨの条件下で３０分保管後、引張試験機（商品名「Ａｕｔｏｇｒａｐｈ　ＡＧ－Ｘ　２００Ｎ」、（株）島津製作所製）にて１８０°の剥離角度で剥離した（引っ張り速度：３００ｍｍ／分）。剥離後のＳＵＳ４０４板の汚染状況を目視にて確認した。
〇：汚染が目視で確認できない
×：汚染が目視で確認できる <Contamination evaluation>
The pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were cut into a width of 50 mm and a length of 100 mm, and the pressure-sensitive adhesive layer side was bonded to a smooth ABS resin plate (width 50 mm × length 100 mm, thickness 3 mm) with a hand roller. It was. No. as an adhesive tape on the silicone resin layer side of the adhesive sheet. 31B (acrylic pressure-sensitive adhesive, manufactured by Nitto Denko Corporation, width 20 mm x length 80 mm) is pressure-bonded with a hand roller and stored for 30 minutes under conditions of a temperature of 23 ° C. and a humidity of 65% RH, and then the adhesive tape is pulled. Peeling was performed at a peeling angle of 180 ° with a testing machine (trade name “Autograph AG-X 200N”, manufactured by Shimadzu Corporation) (pulling speed: 300 mm / min). The peeled No. 31B was pressure-bonded to a SUS304 plate polished with abrasive paper of particle size 280 by reciprocating a 2 kg heavy rubber roller once, and stored for 30 minutes under conditions of a temperature of 23 ° C. and a humidity of 65% RH, then a tensile tester (Trade name “Autograph AG-X 200N”, manufactured by Shimadzu Corporation) was peeled at a peeling angle of 180 ° (pulling speed: 300 mm / min). The contamination state of the SUS404 plate after peeling was confirmed visually.
○: Contamination cannot be visually confirmed ×: Contamination can be visually confirmed
〔製造例１〕：粘着層の作製
　冷却管、窒素導入管、温度計、および攪拌機を備えた反応容器に、（メタ）アクリル系モノマーとして、２－エチルヘキシルアクリレート（２ＥＨＡ、東亜合成（株）製）：９０重量部、アクリル酸（ＡＡ）：１０重量部、光重合開始剤として２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（商品名「イルガキュア６５１」、ＢＡＳＦ製）：０．１重量部を投入して分散させ、攪拌しながら窒素気流下にて上部よりＵＶ照射することにより、一部のモノマーをポリマーに転化させて塗工可能な粘度に調整し、（メタ）アクリル系モノマー混合物を得た。この（メタ）アクリル系モノマー混合物に、架橋剤として１，６－ヘキサンジオールジアクリレート（ＨＤＤＡ）：０．０８重量部を添加し、これをセパレーター（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み５０μｍ）の表面にアプリケーターにて塗布し、カバーセパレーター（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）をハンドローラーにて貼り合わせ、さらに紫外線ランプ（ＢＬタイプ）により紫外線を照射（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：２０００ｍＪ／ｃｍ２）することにより、厚み５０μｍの粘着層を得た。 [Production Example 1]: Preparation of adhesive layer 2-ethylhexyl acrylate (2EHA, manufactured by Toagosei Co., Ltd.) was used as a (meth) acrylic monomer in a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer. ): 90 parts by weight, acrylic acid (AA): 10 parts by weight, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”, manufactured by BASF) as a photopolymerization initiator: 0 .1 part by weight is added and dispersed, and UV irradiation is performed from above in a nitrogen stream while stirring to convert some of the monomer to a polymer to adjust the viscosity so that it can be applied to (meth) acrylic. A monomer mixture was obtained. To this (meth) acrylic monomer mixture, 1,6-hexanediol diacrylate (HDDA): 0.08 part by weight is added as a crosslinking agent, and this is added to a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc.). , 50 μm thick) with an applicator, and a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., 38 μm thick) is bonded with a hand roller, and ultraviolet rays are emitted from an ultraviolet lamp (BL type). By irradiation (ultraviolet ray illuminance: 3.4 mW / cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ), an adhesive layer having a thickness of 50 μm was obtained.
〔実施例１〕
　液状シリコーンゴムとしてＫＥ－１９５０－Ａ（信越化学工業（株）製）を５０重量部、ＫＥ－１９５０－Ｂ（信越化学工業（株）製）を５０重量部、シリコーンオイルとしてＫＦ－９６－１００Ｃｓ（信越化学工業（株）製）を１０重量部添加し、トルエンを３２重量部加えて撹拌混合することで塗布液を調整した。この塗布液をアプリケーターにて乾燥後厚み１００μｍとなるようにＰＥＴ基材（商品名「ルミラーＳ１０」、東レ（株）製、厚み３８μｍ）上に塗布し、オーブンにて１３０℃×５分加熱することにより、シリコーン樹脂層付き基材（１）を得た。製造例１において得られた粘着層とシリコーン樹脂層付き基材（１）をハンドローラーにて貼り合わせることにより、シリコーン樹脂層／基材層／粘着層の積層構造を有する粘着シート（１）を得た。粘着シート（１）のシリコーン樹脂層中のシリコーンオイルの含有割合は９．１重量％であった。
　各種評価結果を表１に示す。 [Example 1]
50 parts by weight of KE-1950-A (manufactured by Shin-Etsu Chemical Co., Ltd.) as liquid silicone rubber, 50 parts by weight of KE-1950-B (manufactured by Shin-Etsu Chemical Co., Ltd.), and KF-96-100Cs as silicone oil 10 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd.) was added, 32 parts by weight of toluene was added, and the mixture was stirred and mixed to prepare a coating solution. This coating solution is applied on a PET base material (trade name “Lumirror S10”, manufactured by Toray Industries, Inc., thickness 38 μm) so as to have a thickness of 100 μm after drying with an applicator, and heated in an oven at 130 ° C. for 5 minutes. This obtained the base material (1) with a silicone resin layer. The pressure-sensitive adhesive sheet (1) having a laminated structure of silicone resin layer / base material layer / pressure-sensitive adhesive layer is obtained by bonding the pressure-sensitive adhesive layer obtained in Production Example 1 and the base material with the silicone resin layer (1) with a hand roller. Obtained. The content ratio of the silicone oil in the silicone resin layer of the pressure-sensitive adhesive sheet (1) was 9.1% by weight.
Various evaluation results are shown in Table 1.
〔実施例２〕
　実施例１のＫＦ－９６－１００Ｃｓ（信越化学工業（株）製）を３０重量部に、トルエンを１６重量部に変更した以外は、実施例１と同様に行い、シリコーン樹脂層／基材層／粘着層の積層構造を有する粘着シート（２）を得た。粘着シート（２）のシリコーン樹脂層中のシリコーンオイルの含有割合は２３．１重量％であった。
　各種評価結果を表１に示す。 [Example 2]
The same procedure as in Example 1 was repeated, except that KF-96-100Cs (manufactured by Shin-Etsu Chemical Co., Ltd.) of Example 1 was changed to 30 parts by weight and toluene was changed to 16 parts by weight. / The adhesive sheet (2) which has the laminated structure of the adhesion layer was obtained. The content ratio of the silicone oil in the silicone resin layer of the pressure-sensitive adhesive sheet (2) was 23.1% by weight.
Various evaluation results are shown in Table 1.
〔実施例３〕
　実施例１のＫＦ－９６－１００Ｃｓ（信越化学工業（株）製）を５０重量部に、トルエンを０重量部に変更した以外は、実施例１と同様に行い、シリコーン樹脂層／基材層／粘着層の積層構造を有する粘着シート（３）を得た。粘着シート（３）のシリコーン樹脂層中のシリコーンオイルの含有割合は３３．３重量％であった。
　各種評価結果を表１に示す。 Example 3
The same procedure as in Example 1 was repeated except that KF-96-100Cs (manufactured by Shin-Etsu Chemical Co., Ltd.) in Example 1 was changed to 50 parts by weight and toluene was changed to 0 parts by weight. / The adhesive sheet (3) which has the laminated structure of the adhesion layer was obtained. The content ratio of the silicone oil in the silicone resin layer of the pressure-sensitive adhesive sheet (3) was 33.3% by weight.
Various evaluation results are shown in Table 1.
〔実施例４〕
　実施例１のＫＦ－９６－１００Ｃｓ（信越化学工業（株）製）を９０重量部に、トルエンを０重量部に変更した以外は、実施例１と同様に行い、シリコーン樹脂層／基材層／粘着層の積層構造を有する粘着シート（４）を得た。粘着シート（４）のシリコーン樹脂層中のシリコーンオイルの含有割合は４７．４重量％であった。
　各種評価結果を表１に示す。 Example 4
The same procedure as in Example 1 was repeated except that KF-96-100Cs (manufactured by Shin-Etsu Chemical Co., Ltd.) in Example 1 was changed to 90 parts by weight and toluene was changed to 0 parts by weight. / The adhesive sheet (4) which has the laminated structure of an adhesion layer was obtained. The content ratio of the silicone oil in the silicone resin layer of the pressure-sensitive adhesive sheet (4) was 47.4% by weight.
Various evaluation results are shown in Table 1.
〔実施例５〕
　実施例１のＫＦ－９６－１００Ｃｓ（信越化学工業（株）製）を９０重量部に、トルエンを０重量部に変更した以外は、実施例１と同様に行い、シリコーン樹脂層／基材層／粘着層の積層構造を有する粘着シート（５）を得た。粘着シート（５）のシリコーン樹脂層中のシリコーンオイルの含有割合は６０．０重量％であった。
　各種評価結果を表１に示す。 Example 5
The same procedure as in Example 1 was repeated except that KF-96-100Cs (manufactured by Shin-Etsu Chemical Co., Ltd.) in Example 1 was changed to 90 parts by weight and toluene was changed to 0 parts by weight. / The adhesive sheet (5) which has the laminated structure of an adhesion layer was obtained. The content ratio of the silicone oil in the silicone resin layer of the pressure-sensitive adhesive sheet (5) was 60.0% by weight.
Various evaluation results are shown in Table 1.
〔比較例１〕
　液状シリコーンゴムとしてＫＥ－１９５０－Ａ（信越化学工業（株）製）を５０重量部、ＫＥ－１９５０－Ｂ（信越化学工業（株）製）を５０重量部添加し、トルエンを５０重量部加えて撹拌混合することで塗布液を調整した。この塗布液をアプリケーターにて乾燥後厚み１００μｍとなるようにＰＥＴ基材（商品名「ルミラーＳ１０」、東レ（株）製、厚み３８μｍ）上に塗布し、オーブンにて１３０℃×５分加熱することにより、シリコーン樹脂層付き基材（Ｃ１）を得た。製造例１において得られた粘着層とシリコーン樹脂層付き基材（Ｃ１）をハンドローラーにて貼り合わせることにより、シリコーン樹脂層／基材層／粘着層の積層構造を有する粘着シート（Ｃ１）を得た。粘着シート（Ｃ１）のシリコーン樹脂層中のシリコーンオイルの含有割合は０重量％であった。
　各種評価結果を表１に示す。 [Comparative Example 1]
50 parts by weight of KE-1950-A (manufactured by Shin-Etsu Chemical Co., Ltd.), 50 parts by weight of KE-1950-B (manufactured by Shin-Etsu Chemical Co., Ltd.) are added as liquid silicone rubber, and 50 parts by weight of toluene is added. The coating solution was adjusted by stirring and mixing. This coating solution is applied on a PET substrate (trade name “Lumirror S10”, manufactured by Toray Industries, Inc., thickness 38 μm) so as to have a thickness of 100 μm after drying with an applicator, and heated in an oven at 130 ° C. for 5 minutes. This obtained the base material (C1) with a silicone resin layer. By sticking the adhesive layer obtained in Production Example 1 and the base material with a silicone resin layer (C1) with a hand roller, the adhesive sheet (C1) having a laminated structure of silicone resin layer / base material layer / adhesive layer is obtained. Obtained. The content ratio of the silicone oil in the silicone resin layer of the pressure-sensitive adhesive sheet (C1) was 0% by weight.
Various evaluation results are shown in Table 1.
〔比較例２〕
　液状シリコーンゴムとしてＫＥ－１９５０－Ａ（信越化学工業（株）製）を５０重量部、ＫＥ－１９５０－Ｂ（信越化学工業（株）製）を５０重量部、シリコーンオイルとしてＫＦ－９６－１００Ｃｓ（信越化学工業（株）製）を２５０重量部添加し、撹拌混合することで塗布液を調整した。この塗布液をアプリケーターにて乾燥後厚み１００μｍとなるようにＰＥＴ基材（商品名「ルミラーＳ１０」、東レ（株）製、厚み３８μｍ）上に塗布し、オーブンにて１３０℃×５分加熱することにより、シリコーン樹脂層付き基材（Ｃ２）を得た。製造例１において得られた粘着層とシリコーン樹脂層付き基材（Ｃ２）をハンドローラーにて貼り合わせることにより、シリコーン樹脂層／基材層／粘着層の積層構造を有する粘着シート（Ｃ２）を得た。粘着シート（Ｃ２）のシリコーン樹脂層中のシリコーンオイルの含有割合は７５．０重量％であった。
　各種評価結果を表１に示す。 [Comparative Example 2]
50 parts by weight of KE-1950-A (manufactured by Shin-Etsu Chemical Co., Ltd.) as liquid silicone rubber, 50 parts by weight of KE-1950-B (manufactured by Shin-Etsu Chemical Co., Ltd.), and KF-96-100Cs as silicone oil 250 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed by stirring to prepare a coating solution. This coating solution is applied on a PET base material (trade name “Lumirror S10”, manufactured by Toray Industries, Inc., thickness 38 μm) so as to have a thickness of 100 μm after drying with an applicator, and heated in an oven at 130 ° C. for 5 minutes. This obtained the base material (C2) with a silicone resin layer. A pressure-sensitive adhesive sheet (C2) having a laminated structure of silicone resin layer / base material layer / pressure-sensitive adhesive layer is obtained by bonding the pressure-sensitive adhesive layer obtained in Production Example 1 and the base material with silicone resin layer (C2) with a hand roller. Obtained. The content ratio of the silicone oil in the silicone resin layer of the pressure-sensitive adhesive sheet (C2) was 75.0% by weight.
Various evaluation results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　本発明のロール保護用粘着シートは、例えば、粘着性を有する基材（例えば、粘着テープやエラストマーシートなど）を搬送するためのロール（例えば、ガイドロールやテイクオフロールなど）に貼り付けることによって、ロールに粘着性を有する基材が巻き込まれることを防止し得る、ロール保護用粘着シートに好適に利用できる。 The pressure-sensitive adhesive sheet for roll protection of the present invention is, for example, attached to a roll (for example, a guide roll or a take-off roll) for transporting a substrate having adhesiveness (for example, a pressure-sensitive adhesive tape or an elastomer sheet), It can utilize suitably for the adhesive sheet for roll protection which can prevent the base material which has adhesiveness from being wound in a roll.
　　１　　　　　　剥離フィルム
　　２　　　　　　シリコーン樹脂層
　　３　　　　　　基材層
　　４　　　　　　粘着層
１００　　　　　　ロール保護用粘着シート DESCRIPTION OF SYMBOLS 1 Release film 2 Silicone resin layer 3 Base material layer 4 Adhesive layer 100 Adhesive sheet for roll protection

Claims (3)

  1. 　シリコーン樹脂層と基材層と粘着層をこの順に含む粘着シートであって、
    　該シリコーン樹脂層がシリコーンオイルを８重量％～７０重量％の含有割合で含む、
    　ロール保護用粘着シート。     A pressure-sensitive adhesive sheet comprising a silicone resin layer, a base material layer, and a pressure-sensitive adhesive layer in this order,
    The silicone resin layer contains silicone oil in a content of 8 wt% to 70 wt%;
    Adhesive sheet for roll protection.
  2. 　前記基材層が、ポリエステル樹脂およびエラストマー樹脂から選ばれる少なくとも１種を含む、請求項１に記載のロール保護用粘着シート。 2. The pressure-sensitive adhesive sheet for roll protection according to claim 1, wherein the base material layer contains at least one selected from a polyester resin and an elastomer resin.
  3. 　前記ロールが、粘着性を有する基材を搬送するためのロールである、請求項１または２に記載のロール保護用粘着シート。
     
     
          The pressure-sensitive adhesive sheet for roll protection according to claim 1 or 2, wherein the roll is a roll for conveying a substrate having adhesiveness.


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JPS60133051A (en) * 1983-12-21 1985-07-16 Dow Corning Kk Releasable film-forming composition
JPH01110461A (en) * 1987-10-19 1989-04-27 Sekisui Chem Co Ltd Pressure sensitive tacky tape winding structure
JPH03114845U (en) * 1990-03-07 1991-11-26
JPH10158594A (en) * 1996-11-27 1998-06-16 Matsushita Electric Works Ltd Silicone-transfer film and transfer constituent
JP2002120424A (en) * 2000-10-16 2002-04-23 Nitto Denko Corp Method for forming printing sheet and device therefor
JP2003041216A (en) * 2001-08-02 2003-02-13 Nitto Denko Corp Surface protecting sheet and method for manufacturing the same

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Publication number Priority date Publication date Assignee Title
JPS60133051A (en) * 1983-12-21 1985-07-16 Dow Corning Kk Releasable film-forming composition
JPH01110461A (en) * 1987-10-19 1989-04-27 Sekisui Chem Co Ltd Pressure sensitive tacky tape winding structure
JPH03114845U (en) * 1990-03-07 1991-11-26
JPH10158594A (en) * 1996-11-27 1998-06-16 Matsushita Electric Works Ltd Silicone-transfer film and transfer constituent
JP2002120424A (en) * 2000-10-16 2002-04-23 Nitto Denko Corp Method for forming printing sheet and device therefor
JP2003041216A (en) * 2001-08-02 2003-02-13 Nitto Denko Corp Surface protecting sheet and method for manufacturing the same

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