WO2019044189A1 - Dampproof self-adhesive silicone rubber sheet and self-adhesive silicone rubber sheet enclosure - Google Patents

Dampproof self-adhesive silicone rubber sheet and self-adhesive silicone rubber sheet enclosure Download PDF

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Publication number
WO2019044189A1
WO2019044189A1 PCT/JP2018/026128 JP2018026128W WO2019044189A1 WO 2019044189 A1 WO2019044189 A1 WO 2019044189A1 JP 2018026128 W JP2018026128 W JP 2018026128W WO 2019044189 A1 WO2019044189 A1 WO 2019044189A1
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Prior art keywords
self
silicone rubber
rubber sheet
adhesive silicone
adhesive
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PCT/JP2018/026128
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French (fr)
Japanese (ja)
Inventor
清水　隆男
勝彦 加藤
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信越ポリマー株式会社
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Priority to JP2019539031A priority Critical patent/JP6754905B2/en
Publication of WO2019044189A1 publication Critical patent/WO2019044189A1/en

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    • 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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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

Definitions

  • the present invention relates to a moisture-proof, self-adhesive silicone rubber sheet having a moisture-proof structure and a self-adhesive silicone rubber sheet enclosure containing the same.
  • FIG. 4 shows a cross-sectional view (4A) of a conventionally known self-adhesive silicone rubber sheet before use and a cross-sectional view (4B) of a release sheet peeled off from the self-adhesive silicone rubber sheet at the time of use.
  • the self-adhesive silicone rubber sheet 10 before use is coated with release sheets 12 and 12 in the upper and lower surfaces so as not to react with moisture in the air and to be cured, And, it is enclosed in a moisture-proof bag 16.
  • the moisture-proof bag 16 is opened, the self-adhesive silicone rubber sheet 10 is taken out therefrom, and as shown in FIG.
  • the self-adhesive silicone rubber sheet The release sheets 12, 12 coated on both sides of 10 are peeled off, one surface side of the self-adhesive silicone rubber sheet 10 is attached to a target location such as an outer wall, and a tile or stone is attached to the other surface side.
  • the above conventionally known self-adhesive silicone rubber sheet 10 has a problem to be improved.
  • the self-adhesive silicone rubber sheet 10 is taken out of the moisture-proof bag 16 in order to improve the efficiency of the sticking operation, and pasting for a while There are a lot of cases to start. In such a case, the self-adhesive silicone rubber sheet 10 removed from the moisture-proof bag 16 may be left for a long time.
  • the self-adhesive silicone rubber sheet 10 which has been left can suppress moisture permeation from the upper and lower surfaces covered with the release sheets 12 and 12, it permeates moisture from the side surface of the self-adhesive silicone rubber sheet 10, gradually toward the inside By moisture permeation, the adhesive ability of the self-adhesive silicone rubber sheet 10 may be degraded. In order to prevent the problem, the self-adhesive silicone rubber sheet 10 can be sealed in the moisture-proof bag 16 until immediately before use, but the working efficiency is reduced. Furthermore, although it is conceivable to attach release sheets to both side surfaces of the self-adhesive silicone rubber sheet 10, the increase in the number of release sheets and the presence of narrow release sheets make the application work cumbersome. There will be no situation.
  • the present invention solves the above-mentioned problems, that is, a self-adhesive silicone which can suppress moisture permeation even in a state of being taken out from a moisture-proof bag without increasing the complexity of the sticking operation of a self-adhesive silicone rubber sheet. It is an object of the present invention to provide a rubber sheet and a self-adhesive silicone rubber sheet enclosure containing the rubber sheet.
  • a moisture-proof, self-adhesive silicone rubber sheet comprises at least one of a self-adhesive silicone rubber sheet in an uncured state and two wide faces of the self-adhesive silicone rubber sheet.
  • Release sheet which covers two wide sides and peels off when using a self-adhesive silicone rubber sheet, and water formed from at least one side of the self-adhesive silicone rubber sheet inward from the side of the self-adhesive silicone rubber sheet And a moisture permeation suppressing layer for suppressing permeation.
  • the moisture permeation suppressing layer is preferably a silicone-based adhesive layer.
  • the self-adhesive silicone rubber sheet is a long sheet provided with a release sheet only on the wide surface on one side thereof, and the release sheet Preferably, it is wound with the wide side not having the inside facing the inside.
  • the self-adhesive silicone rubber sheet enclosure which concerns on one Embodiment is a state which enclosed one of the above-mentioned moisture-proof self-adhesive silicone rubber sheets in a moisture-proof bag.
  • moisture permeation can be suppressed even in a state of being taken out from a moisture-proof bag without increasing the complexity of the work of attaching a self-adhesive silicone rubber sheet.
  • FIG. 1 is a cross-sectional view (1A) when the moisture-proof self-adhesive silicone rubber sheet according to the first embodiment is cut in the thickness direction, and a perspective view of the moisture-proof self-adhesive silicone rubber sheet with the release sheet removed therefrom.
  • disconnected in the thickness direction are each shown.
  • FIG. 2 shows a cross-sectional view of the moistureproof self-adhesive silicone rubber sheet according to the second embodiment, as viewed in the same manner as the front view.
  • FIG. 3 is a cross-sectional view (3A) of the moisture-proof self-adhesive silicone rubber sheet according to the third embodiment and the same view, a side view (3B) of the moisture-proof self-adhesive silicone rubber sheet, and a moisture-proof self-adhesive silicone rubber sheet
  • FIG. 3C is a partially transparent side view (3C) of the state in which the is housed in a moisture-proof bag.
  • FIG. 4 shows a cross-sectional view (4A) of a conventionally known self-adhesive silicone rubber sheet before use and a cross-sectional view (4B) of a release sheet peeled off from the self-adhesive silicone rubber sheet at the time of use.
  • FIG. 1 is a cross-sectional view (1A) when the moisture-proof, self-adhesive silicone rubber sheet according to the first embodiment is cut in the thickness direction;
  • FIG. 2 is a perspective view (1B) of the self-adhesive silicone rubber sheet enclosure according to the first embodiment and a cross-sectional view (1C) of the same in a thickness direction.
  • the moisture-proof self-adhesive silicone rubber sheet 1 is provided with a non-cured self-adhesive silicone rubber sheet 10, a moisture permeation suppressing layer 14, and release sheets 12 and 12.
  • the release sheet 12 is a sheet which covers at least one of the two wide sides of the self-adhesive silicone rubber sheet 10 and peels off when the self-adhesive silicone rubber sheet 10 is used.
  • the moisture permeation suppressing layer 14 is formed on at least one side surface of the self-adhesive silicone rubber sheet 10 and is a layer that suppresses permeation of water inward from the side surface of the self-adhesive silicone rubber sheet 10.
  • the self-adhesive silicone rubber sheet 10 with the moisture permeation suppressing layer 14 is sealed in a moisture-proof bag (hereinafter, also simply referred to as a "moisture-proof bag") 16 with the release sheets 12, 12 attached. There is.
  • a moisture-proof bag for example, a polyethylene terephthalate film laminated with aluminum can be used.
  • the self-adhesive silicone rubber sheet 10 is enclosed in the moisture-proof bag 16, so that high adhesion can be maintained even after long-term storage.
  • the self-adhesive silicone rubber sheet 10 is taken out of the moisture-proof bag 16 and, even if left for a while, the entire peripheral surface of the self-adhesive silicone rubber sheet 10 is covered with the release sheets 12 and 12 and the moisture permeation restraining layer 14 Therefore, the moisture in the air hardly penetrates into the self-adhesive silicone rubber sheet 10 through the release sheets 12 and 12 and the moisture permeation suppressing layer 14. Therefore, the curing due to moisture permeation of the self-adhesive silicone rubber sheet 10 can be suppressed.
  • the “self-adhesive silicone rubber” in this embodiment is a kind of solvent-free silicone-based adhesive and has high adhesion, heat stability, weather resistance, good water resistance, and excellent flexibility.
  • the uncured (pre-cured) self-adhesive silicone rubber can maintain a freestanding shape and is deformable according to the pressure (being a solid with plasticity). For this reason, the self-adhesive silicone rubber sheet in the uncured state can be deformed according to the unevenness and the curved surface of the place to be disposed, and can be brought into close contact with the place to be disposed, and has high adhesive strength.
  • the self-adhesive silicone rubber sheet 10 preferably has a Williams plasticity at 25 ° C. in the range of 50 to 500, more preferably in the range of 50 to 350, and in the range of 50 to 250 Even more preferred.
  • Williams plasticity is measured according to the measuring method prescribed
  • the self-adhesive silicone rubber is a condensation reaction type silicone rubber and is preferably cured by a simple means such as standing at ordinary temperature (reaction with water in the air).
  • the self-adhesive silicone rubber sheet 10 shown in FIG. 1 (1A) is obtained by forming a condensation reaction type self-adhesive silicone rubber in an uncured state into a sheet.
  • the sheet 10 may be a sheet in which an addition reaction self-adhesive silicone rubber is partially present in a condensation reaction self-adhesive silicone rubber.
  • known release sheets such as paper, cloth, glass cloth, resin and the like without particular restrictions can be used.
  • a film made of a resin such as polyethylene terephthalate, polypropylene, polyethylene, polystyrene or polyvinyl chloride can be used.
  • the release sheets 12, 12 are preferably sized such that their ends protrude from the self-adhesive silicone rubber sheet 10. This is because when peeling the release sheets 12 12, the protruding portion is gripped so that the release sheets 12 can be easily peeled.
  • Self-Adhesive Silicone Rubber Sheet a condensation reaction type self-adhesive silicone rubber that constitutes the self-adhesive silicone rubber sheet 10 that can be suitably used in this embodiment and the following embodiments will be described.
  • Condensation reaction type self-adhesive silicone rubber is mainly composed of the following components.
  • Organopolysiloxane This is a main component of condensation reaction type self-adhesive silicone rubber and is a diorganopolysiloxane represented by the following chemical formula (1) or chemical formula (2).
  • R is a monovalent hydrocarbon group.
  • an alkyl group methyl group, ethyl group, propyl group, butyl group, 2-ethylbutyl group, octyl group etc.
  • cycloalkyl group cyclohexyl group, cyclopentyl group etc.
  • alkenyl group vinyl group, propenyl group, Butenyl group, heptenyl group, hexenyl group, allyl group etc.
  • aryl group phenyl group, tolyl group, xylyl group, naphthyl group, diphenyl group etc.
  • aralkyl group benzyl group, phenylethyl group etc.
  • It is selected from those in which at least a part of hydrogen atoms bonded to carbon atoms of hydrogen groups are substituted with halogen or cyano group etc.
  • A is an oxygen atom or a polymethylene group (including a methylene group) represented by-(CH 2 ) m- (m is 1 to 8).
  • A is preferably an oxygen atom or an ethylene group.
  • n is an arbitrary number for making the kinematic viscosity at 25 ° C. of the component (a) within the range of 100 to 1,000,000 cm 2 / s.
  • the kinematic viscosity is more preferably in the range of 500 to 500,000 cm 2 / s.
  • B is a hydrolyzable group.
  • alkoxy group methoxy group, ethoxy group, propoxy group, butoxy group etc.
  • ketoxime group dimethyl ketoxime group, methyl ethyl ketoxime group etc.
  • acyloxy group acetoxy group etc.
  • alkenyloxy group isopropenyloxy group
  • isobutenyloxy group etc. can be mentioned.
  • x is 2 or 3.
  • the component (a) can be produced by a known method (for example, a method by equilibrium reaction using a cyclic siloxane or linear oligomer and an acid catalyst or a base catalyst).
  • a silane or siloxane containing at least one of an SiO 3/2 unit and an SiO 4/2 unit during polymerization is routinely used.
  • a method may be used in which the diorganopolysiloxane is added so as not to gel.
  • the component (a) is preferably used after removing the low molecular weight siloxane by washing or the like in order to reduce dirt.
  • crosslinking agent a silane having two or more, preferably three or more, hydrolyzable groups in one molecule, or a partial hydrolytic condensate of the silane is used.
  • hydrolyzable groups include alkoxy (such as methoxy, ethoxy and butoxy), ketoxime (such as dimethyl ketoxime and methyl ethyl ketoxime), acyloxy (such as acetoxy), and alkenyloxy (such as iso-butyl).
  • Examples include propenyloxy group, isobutenyloxy group, etc., amino group (N-butylamino group, N, N-diethylamino group etc.), and amide group (N-methylacetamide group etc.).
  • the compounding amount of the crosslinking agent is preferably in the range of 1 to 50 parts by mass, more preferably in the range of 2 to 30 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the component (a). It is even more preferred to be in the range of parts.
  • the curing catalyst is not essential, the curing of the self-adhesive silicone rubber can be promoted by using the curing catalyst.
  • the curing catalyst include alkyl tin ester compounds (dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin dioctoate, etc.), titanate esters or titanium chelate compounds (tetraisopropoxy titanium, tetra n-butoxy titanium, tetrakis (2- Ethylhexoxy) titanium, dipropoxybis (acetylacetona) titanium, titanium isopropoxy octylene glycol etc., and other suitable organometallic compounds (zinc naphthenate, zinc stearate, zinc 2-ethyl octoate, iron-2 -Ethyl hexoate, cobalt 2-ethyl hexoate, manganese 2-ethyl hex
  • the compounding amount of the curing catalyst is preferably in the range of 0 to 20 parts by mass, more preferably in the range of 0.001 to 10 parts by mass, with respect to 100 parts by mass of the component (a). It is even more preferred to be in the range of 01-5 parts by weight.
  • filler is not essential, it can be suitably used for the purpose of reinforcement and the like.
  • fillers include reinforcing agents (fumed silica, precipitated silica, silica obtained by hydrophobizing the surface of these silicas with organic silicon compounds, quartz powder, talc, zeolite, bentonite, etc.), fibrous fillers ( Asbestos, glass fibers, organic fibers and the like), basic fillers (calcium carbonate, zinc carbonate, zinc oxide, magnesium oxide, celite and the like) can be mentioned.
  • silica, calcium carbonate and zeolite it is preferable to use silica, calcium carbonate and zeolite, and it is more preferable to use fumed silica and calcium carbonate whose surfaces have been subjected to hydrophobic treatment.
  • the blending amount of the above-mentioned filler can be selected according to the purpose and the kind of the filler, but it is in the range of 1 to 90% by volume with respect to the component (a) and in the range of 5 to 60% by volume Is preferred.
  • adhesion-imparting component is not essential but is preferably used.
  • adhesion imparting components include amino group-containing organoalkoxysilanes ( ⁇ -aminopropyltrimethoxysilane, ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane, etc.), epoxy group-containing organoalkoxysilanes ( ⁇ -gly) Mention may be made of reaction mixtures of dihydroxy-containing trimethoxysilane, etc., mercapto-containing organoalkoxysilanes ( ⁇ -mercaptopropyltrimethoxysilane, etc.), amino-containing organoalkoxysilanes and epoxy-containing organoalkoxysilanes.
  • the compounding amount of the adhesion imparting component is preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (a).
  • the self-adhesive silicone rubber sheet 10 is mainly formed into a sheet by preparing the above-mentioned condensation reaction type self-adhesive silicone rubber.
  • all side surfaces of the self-adhesive silicone rubber sheet 10 are provided with a moisture permeation suppressing layer 14 which suppresses the permeation of moisture in the air.
  • the moisture permeation suppressing layer 14 is preferably mainly formed of a tacky adhesive.
  • known pressure-sensitive adhesives for example, various pressure-sensitive adhesives such as acrylic pressure-sensitive adhesives, urethane-based and silicone-based can be used.
  • the moisture permeation suppressing layer 14 is a layer having low moisture permeability or that does not easily cure even if moisture permeation is performed.
  • the moisture permeation suppressing layer 14 is preferably made of a material that has high affinity with the self-adhesive silicone rubber sheet 10 and does not easily separate from the sheet 10 and that is integrated.
  • the moisture permeation suppressing layer 14 is more preferably a silicone-based adhesive layer mainly composed of a silicone-based adhesive.
  • the moisture permeation suppressing layer 14 (urethane adhesive layer) made of a urethane adhesive can be used because it is superior to the silicone adhesive layer in suppressing moisture permeation.
  • the self-adhesive silicone rubber sheet 10 may be provided with a moisture permeation suppressing layer 14 mainly composed of a rubber-based pressure-sensitive adhesive.
  • a rubber-based pressure-sensitive adhesive or a silicone-based pressure-sensitive adhesive is preferable because the formed moisture permeation suppressing layer 14 can follow the plastic deformation of the uncured self-adhesive silicone rubber sheet 10.
  • rubber-based pressure-sensitive adhesives include rubber (natural rubber, styrene butadiene rubber, isoprene rubber, chloroprene rubber, butyl rubber, acrylonitrile rubber, acrylic rubber, etc.), styrene butadiene copolymer, styrene isoprene block copolymer, styrene Ethylene / propylene copolymers, styrene-based block copolymers (styrene / isoprene / ethylene / propylene copolymers, etc.), and any one or a mixture of these hydrogenated products can be mentioned.
  • Rubber-based adhesives include tackifying resins (rosin, rosin derivatives, polyterpene resins, phenol resins, petroleum hydrocarbon resins, etc.), softeners (polybutene, liquid paraffin, naphthenic oils, aromatic oils, etc.), Antioxidants (amine-based, phenol-based, phosphorus-based antioxidants, etc.) and fillers (calcium carbonate, silica, clay, talc, titanium oxide, magnesium oxide, etc.) can be added.
  • tackifying resins rosin, rosin derivatives, polyterpene resins, phenol resins, petroleum hydrocarbon resins, etc.
  • softeners polybutene, liquid paraffin, naphthenic oils, aromatic oils, etc.
  • Antioxidants amine-based, phenol-based, phosphorus-based antioxidants, etc.
  • fillers calcium carbonate, silica, clay, talc, titanium oxide, magnesium oxide, etc.
  • examples of the silicone-based pressure-sensitive adhesive include those containing a silicone rubber containing an addition type organopolysiloxane having a siloxane bond as a main skeleton and an alkenyl group as a component.
  • this alkenyl group include allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group and the like.
  • it may have an organic group having no addition reactivity.
  • examples of such organic groups include alkyl groups such as methyl, ethyl and propyl, and aryl groups such as phenyl.
  • the degree of polymerization of the organopolysiloxane contained in the silicone rubber is not particularly limited, but it is preferably 500 to 10,000, and more preferably 2,000 to 8,000.
  • the platinum catalyst has a function of initiating the above addition reaction of the alkenyl group and a function of promoting the addition reaction.
  • platinum catalysts include platinum black, platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohol, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. .
  • the content of the platinum catalyst in the silicone-based pressure-sensitive adhesive is preferably 0.01 to 3 parts by mass per 100 parts by mass of the silicone rubber. The function of a platinum catalyst is stably exhibited by setting it as this range.
  • the content of the platinum catalyst in the silicone-based pressure-sensitive adhesive is more preferably 0.05 to 2.00 parts by mass per 100 parts by mass of silicone rubber, and 0 It is particularly preferable that it is 10 to 1.00 parts by mass.
  • the silicone-based pressure-sensitive adhesive preferably contains a silicone resin, that is, a branched organopolysiloxane in the molecule.
  • a silicone resin that is, a branched organopolysiloxane in the molecule.
  • the bonding strength to the self-adhesive silicone rubber sheet 10 can be enhanced.
  • the silicone resin is contained in the silicone-based pressure-sensitive adhesive, the content of the silicone resin is 10 to 100 parts by mass per 100 parts by mass of silicone rubber from the viewpoint of appropriately setting the degree of the bonding strength. Is preferable, 15 to 75 parts by mass is more preferable, and 20 to 50 parts by mass is even more preferable.
  • the silicone-based pressure-sensitive adhesive can contain various components as long as the function of suppressing water permeation can be exhibited.
  • crosslinking agents having hydrosilyl group coloring materials such as crosslinking accelerators, dyes and pigments, antioxidants such as anilides and phenols, UV absorbers such as benzophenones and benzotriazoles, talc, titanium dioxide, silica -Filler components such as starch, plasticizers, antioxidants, light stabilizers, dispersants, leveling agents and the like can be mentioned.
  • a condensation reaction type self-adhesive silicone rubber is molded to prepare a prismatic body, an adhesive is applied on all the side surfaces thereof to form the moisture permeation suppressing layer 14, and then the prismatic body is sliced to obtain a predetermined thickness. A sheet is formed, and then both upper and lower surfaces of the sheet are covered with release sheets 12. Also by such a method, the self-adhesive silicone rubber sheet 10 with the release sheets 12, 12 can be obtained.
  • the release sheets 12, 12 are attached to both upper and lower surfaces thereof. good.
  • a method of applying an adhesive to both end portions using a high viscosity dispenser such as a caulking gun may be employed. Thereafter, the release sheets 12, 12 can be attached by the method described above.
  • the self-adhesive silicone rubber sheet 10 is covered on both upper and lower sides (two wide sides) with the release sheets 12 and 12 and the moisture permeation suppressing layer 14 is provided on all sides, moisture in the air is absorbed. Entry into the self-adhesive silicone rubber sheet 10 can be suppressed. Even when the self-adhesive silicone rubber sheet 10 is taken out of the moisture-proof bag 16 and exposed to the atmosphere at the time of use, the moisture permeation from the side can be suppressed by the presence of the moisture permeation suppressing layer 14, so even if it is left for a long time, As long as the release sheets 12, 12 are not removed, there is no problem in use.
  • FIG. 2 shows a cross-sectional view of the moistureproof self-adhesive silicone rubber sheet according to the second embodiment, as viewed in the same manner as the front view.
  • the release sheet 12 is easily releasable from the self-adhesive silicone rubber sheet 10.
  • the substrate 18 can not be easily peeled off from the self-adhesive silicone rubber sheet 10.
  • the substrate 18 can be formed of, for example, paper, cloth, resin, glass cloth or the like.
  • the base 18 may be decorated in advance. All side surfaces of the self-adhesive silicone rubber sheet 10 are provided with a moisture permeation suppressing layer 14 as in the first embodiment.
  • the moisture permeation suppressing layer 14 provided on the side surface of the self-adhesive silicone rubber sheet 10 has a function of suppressing the permeation of water from the side direction of the sheet 10, and therefore contributes to maintaining the adhesive ability of the sheet 10 high.
  • FIG. 3 is a cross-sectional view (3A) of the moisture-proof self-adhesive silicone rubber sheet according to the third embodiment and the same view, a side view (3B) of the moisture-proof self-adhesive silicone rubber sheet, and a moisture-proof self-adhesive silicone rubber sheet
  • FIG. 3C is a partially transparent side view (3C) of the state in which the is housed in a moisture-proof bag.
  • the moisture-proof self-adhesive silicone rubber sheet 1b includes a long self-adhesive silicone rubber sheet 10 in an uncured state.
  • the self-adhesive silicone rubber sheet 10 is provided with the release sheet 12 only on one wide surface, and is wound with the wide surface not having the release sheet 12 inside.
  • FIG. 3 (3 A) although it looks as if the release sheets 12 and 12 are provided on the upper and lower wide surfaces of the long self-adhesive silicone rubber sheet 10, the lower release sheet 12 is self overlapping in the vertical direction. It is a release sheet 12 of the adhesive silicone rubber sheet 10 itself.
  • the release sheet 12 is a sheet having substantially the same width as the width direction of the self-adhesive silicone rubber sheet 10.
  • the release sheet 12 may be one that does not protrude from the side surface of the self-adhesive silicone rubber sheet 10.
  • the self-adhesive silicone rubber sheet 10 is in the form of a band, and is provided with the moisture permeation suppressing layers 14 and 14 on both side surfaces in the width direction.
  • the self-adhesive silicone rubber sheet 10 provided with the moisture permeation suppressing layers 14 and 14 is spirally wound around the cylindrical core portion 20, as shown in FIG. 3 (3B).
  • the cylindrical core portion 20 may be omitted. Even in the spirally wound self-adhesive silicone rubber sheet 10, there is a risk that the side surface is always exposed to air.
  • the moisture permeation suppressing layer 14 on the side surface it is possible to suppress the entry of moisture into the self-adhesive silicone rubber sheet 10 from the side surface.
  • the moisture permeation suppressing layer 14 is provided on all sides or both sides in the width direction of the self-adhesive silicone rubber sheet 10, the side of a part of the whole sides or both sides in the width It may be provided only on one side of the In such a case, it is preferable that the surface not provided with the moisture permeation suppressing layer 14 be in a state where it is difficult to contact moisture in the air by some means represented by the peeling sheet 12 rather than an exposed state. .
  • the components in the various embodiments described above can be arbitrarily combined unless they can be combined with one another.
  • the base 18 used in the second embodiment may be provided in the moisture-proof self-adhesive silicone rubber sheet 1b according to the third embodiment.
  • the present invention can be used, for example, in place of a liquid adhesive.

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

Abstract

[Problem] To provide a self-adhesive silicone rubber sheet capable of suppressing moisture permeation even when extracted from a dampproof bag, without increasing the complications involved in an operation of attaching the self-adhesive silicone rubber sheet, and a self-adhesive silicone rubber enclosure enclosing the same. [Solution] The present invention pertains to a dampproof self-adhesive silicone rubber sheet 1 provided with: an uncured self-adhesive silicone rubber sheet 10; a release sheet 12 that coats at least one of two wide surfaces of the self-adhesive silicone rubber sheet 10 and is released when the self-adhesive silicone rubber sheet 10 is used; and a moisture permeation suppressing layer 14 that is formed on at least one lateral surface of the self-adhesive silicone rubber sheet 10 and suppresses inward permeation of moisture from the lateral surface of the self-adhesive silicone rubber sheet 10. The present invention pertains also to a self-adhesive silicone rubber sheet enclosure 3 in which the sheet 1 is enclosed in a dampproof bag 16.

Description

防湿性自己接着シリコーンゴムシートおよび自己接着シリコーンゴムシート封入体Moisture-proof self-adhesive silicone rubber sheet and self-adhesive silicone rubber sheet inclusion クロスリファレンスCross reference
　本出願は、２０１７年８月３１日に日本国において出願された特願２０１７－１６７０１５に基づき優先権を主張し、当該出願に記載された内容は、本明細書に援用する。また、本願において引用した特許、特許出願及び文献に記載された内容は、本明細書に援用する。 Priority is claimed on Japanese Patent Application No. 2017-167015, filed on August 31, 2017, the content of which is incorporated herein by reference. Also, the contents described in the patents, patent applications and documents cited in the present application are incorporated herein by reference.
　本発明は、防湿構造を有する防湿性自己接着シリコーンゴムシートおよびそれを封入した自己接着シリコーンゴムシート封入体に関するものである。 The present invention relates to a moisture-proof, self-adhesive silicone rubber sheet having a moisture-proof structure and a self-adhesive silicone rubber sheet enclosure containing the same.
　従来から、建造物の外壁等の装飾や保護を目的として外壁等にタイルや石材が貼られている。タイルや石材を外壁等に貼る際に、シリコーン系接着剤を用いる方法が既に知られている（例えば、特許文献１を参照）。また、液状の接着剤に代えて使用可能な半固形のシート状の自己接着シリコーンゴムシートも知られている。 BACKGROUND ART Conventionally, tiles and stones are pasted on outer walls and the like for the purpose of decoration and protection of outer walls and the like of buildings. When sticking a tile or a stone material to an outer wall etc., the method of using a silicone type adhesive is already known (for example, refer patent document 1). Also known are semisolid sheet-like self-adhesive silicone rubber sheets that can be used in place of liquid adhesives.
　図４は、従来から公知の自己接着シリコーンゴムシートの使用前の状態の断面図（４Ａ）および使用時に自己接着シリコーンゴムシートから剥離シートを剥がす状態の断面図（４Ｂ）をそれぞれ示す。図４（４Ａ）に示すように、使用前の自己接着シリコーンゴムシート１０は、空気中の水分と反応して硬化しないように、その上下面を剥離シート１２，１２にて被覆した状態で、かつ防湿性の袋１６内に封入されている。自己接着シリコーンゴムシート１０を使用する際には、防湿性の袋１６を開封して、その中から自己接着シリコーンゴムシート１０を取り出し、図４（４Ｂ）に示すように、自己接着シリコーンゴムシート１０の両面に被覆されている剥離シート１２，１２を剥離し、外壁等の目的場所に自己接着シリコーンゴムシート１０の一面側を貼着し、もう一面側にタイルや石材を貼り付ける。 FIG. 4 shows a cross-sectional view (4A) of a conventionally known self-adhesive silicone rubber sheet before use and a cross-sectional view (4B) of a release sheet peeled off from the self-adhesive silicone rubber sheet at the time of use. As shown in FIG. 4 (4A), the self-adhesive silicone rubber sheet 10 before use is coated with release sheets 12 and 12 in the upper and lower surfaces so as not to react with moisture in the air and to be cured, And, it is enclosed in a moisture-proof bag 16. When using the self-adhesive silicone rubber sheet 10, the moisture-proof bag 16 is opened, the self-adhesive silicone rubber sheet 10 is taken out therefrom, and as shown in FIG. 4 (4B), the self-adhesive silicone rubber sheet The release sheets 12, 12 coated on both sides of 10 are peeled off, one surface side of the self-adhesive silicone rubber sheet 10 is attached to a target location such as an outer wall, and a tile or stone is attached to the other surface side.
特開平８－１０８４１２号公報JP-A-8-108412
　しかし、上記従来から公知の自己接着シリコーンゴムシート１０には、改善すべき課題を有する。自己接着シリコーンゴムシート１０を建造物の所定場所に貼り付ける際に、貼付作業の効率化を図るべく、自己接着シリコーンゴムシート１０を防湿性の袋１６から取り出しておき、しばらくしてから貼付作業を開始する場合が少なくない。かかる場合、防湿性の袋１６から取り出された自己接着シリコーンゴムシート１０は、長時間、放置される場合もある。放置された自己接着シリコーンゴムシート１０は、剥離シート１２，１２で被覆された上下面からの透湿を抑制できるものの、自己接着シリコーンゴムシート１０の側面から透湿し、徐々に内部に向かって透湿することによって、自己接着シリコーンゴムシート１０の接着能が劣化するおそれがある。その問題を防止するために、自己接着シリコーンゴムシート１０を使用直前まで防湿性の袋１６の中に密封しておくこともできるが、作業効率が低下する。さらに、自己接着シリコーンゴムシート１０の両側面にも剥離シートを貼り付けておく方法も考えられるが、剥離シートの枚数の増加と幅狭の剥離シートの存在とにより、貼付作業が煩わしさに堪えない状況になる。 However, the above conventionally known self-adhesive silicone rubber sheet 10 has a problem to be improved. When affixing the self-adhesive silicone rubber sheet 10 to a predetermined place of a structure, the self-adhesive silicone rubber sheet 10 is taken out of the moisture-proof bag 16 in order to improve the efficiency of the sticking operation, and pasting for a while There are a lot of cases to start. In such a case, the self-adhesive silicone rubber sheet 10 removed from the moisture-proof bag 16 may be left for a long time. Although the self-adhesive silicone rubber sheet 10 which has been left can suppress moisture permeation from the upper and lower surfaces covered with the release sheets 12 and 12, it permeates moisture from the side surface of the self-adhesive silicone rubber sheet 10, gradually toward the inside By moisture permeation, the adhesive ability of the self-adhesive silicone rubber sheet 10 may be degraded. In order to prevent the problem, the self-adhesive silicone rubber sheet 10 can be sealed in the moisture-proof bag 16 until immediately before use, but the working efficiency is reduced. Furthermore, although it is conceivable to attach release sheets to both side surfaces of the self-adhesive silicone rubber sheet 10, the increase in the number of release sheets and the presence of narrow release sheets make the application work cumbersome. There will be no situation.
　そこで、本発明は、前記課題を解決すること、すなわち、自己接着シリコーンゴムシートの貼付作業の煩雑さを増加させることなく、防湿性の袋から取り出した状態でも透湿を抑制可能な自己接着シリコーンゴムシートおよびそれを封入した自己接着シリコーンゴムシート封入体を提供することを目的とする。 Therefore, the present invention solves the above-mentioned problems, that is, a self-adhesive silicone which can suppress moisture permeation even in a state of being taken out from a moisture-proof bag without increasing the complexity of the sticking operation of a self-adhesive silicone rubber sheet. It is an object of the present invention to provide a rubber sheet and a self-adhesive silicone rubber sheet enclosure containing the rubber sheet.
（１）前記目的を達成するための一実施形態に係る防湿性自己接着シリコーンゴムシートは、未硬化状態の自己接着シリコーンゴムシートと、自己接着シリコーンゴムシートの２つの幅広面の内の少なくとも１つの幅広面を被覆して自己接着シリコーンゴムシートの使用時に剥離する剥離シートと、自己接着シリコーンゴムシートの少なくとも１つの側面に形成されており自己接着シリコーンゴムシートの側面から内方への水分の透過を抑制する透湿抑制層と、を備える。 (1) A moisture-proof, self-adhesive silicone rubber sheet according to an embodiment for achieving the above object comprises at least one of a self-adhesive silicone rubber sheet in an uncured state and two wide faces of the self-adhesive silicone rubber sheet. Release sheet which covers two wide sides and peels off when using a self-adhesive silicone rubber sheet, and water formed from at least one side of the self-adhesive silicone rubber sheet inward from the side of the self-adhesive silicone rubber sheet And a moisture permeation suppressing layer for suppressing permeation.
（２）別の実施形態に係る防湿性自己接着シリコーンゴムシートでは、さらに、透湿抑制層は、シリコーン系粘着層であるのが好ましい。 (2) In the moistureproof self-adhesive silicone rubber sheet according to another embodiment, the moisture permeation suppressing layer is preferably a silicone-based adhesive layer.
（３）別の実施形態に係る防湿性自己接着シリコーンゴムシートでは、また、自己接着シリコーンゴムシートは、その片側の幅広面のみに剥離シートを備えた長尺状のシートであって、剥離シートを備えていない幅広面を内側にして巻かれているのが好ましい。 (3) In the moistureproof self-adhesive silicone rubber sheet according to another embodiment, the self-adhesive silicone rubber sheet is a long sheet provided with a release sheet only on the wide surface on one side thereof, and the release sheet Preferably, it is wound with the wide side not having the inside facing the inside.
（４）また、一実施形態に係る自己接着シリコーンゴムシート封入体は、上述のいずれかの防湿性自己接着シリコーンゴムシートを、防湿性の袋に封入した状態のものである。 (4) Moreover, the self-adhesive silicone rubber sheet enclosure which concerns on one Embodiment is a state which enclosed one of the above-mentioned moisture-proof self-adhesive silicone rubber sheets in a moisture-proof bag.
　本発明によれば、自己接着シリコーンゴムシートの貼付作業の煩雑さを増加させることなく、防湿性の袋から取り出した状態でも透湿を抑制可能となる。 According to the present invention, moisture permeation can be suppressed even in a state of being taken out from a moisture-proof bag without increasing the complexity of the work of attaching a self-adhesive silicone rubber sheet.
図１は、第１実施形態に係る防湿性自己接着シリコーンゴムシートをその厚さ方向に切断したときの断面図（１Ａ）、当該防湿性自己接着シリコーンゴムシートから剥離シートを除去した状態の斜視図（１Ｂ）及び第１実施形態に係る自己接着シリコーンゴムシート封入体をその厚さ方向に切断したときの断面図（１Ｃ）をそれぞれ示す。FIG. 1 is a cross-sectional view (1A) when the moisture-proof self-adhesive silicone rubber sheet according to the first embodiment is cut in the thickness direction, and a perspective view of the moisture-proof self-adhesive silicone rubber sheet with the release sheet removed therefrom. The figure (1B) and sectional drawing (1 C) when the self-adhesive silicone rubber sheet enclosure concerning 1st Embodiment is cut | disconnected in the thickness direction are each shown. 図２は、第２実施形態に係る防湿性自己接着シリコーンゴムシートの前示と同視の断面図を示す。FIG. 2 shows a cross-sectional view of the moistureproof self-adhesive silicone rubber sheet according to the second embodiment, as viewed in the same manner as the front view. 図３は、第３実施形態に係る防湿性自己接着シリコーンゴムシートの前示と同視の断面図（３Ａ）、防湿性自己接着シリコーンゴムシートの側面図（３Ｂ）および防湿性自己接着シリコーンゴムシートを防湿性の袋に収納した状態の一部透過側面図（３Ｃ）をそれぞれ示す。FIG. 3 is a cross-sectional view (3A) of the moisture-proof self-adhesive silicone rubber sheet according to the third embodiment and the same view, a side view (3B) of the moisture-proof self-adhesive silicone rubber sheet, and a moisture-proof self-adhesive silicone rubber sheet FIG. 3C is a partially transparent side view (3C) of the state in which the is housed in a moisture-proof bag. 図４は、従来から公知の自己接着シリコーンゴムシートの使用前の状態の断面図（４Ａ）および使用時に自己接着シリコーンゴムシートから剥離シートを剥がす状態の断面図（４Ｂ）をそれぞれ示す。FIG. 4 shows a cross-sectional view (4A) of a conventionally known self-adhesive silicone rubber sheet before use and a cross-sectional view (4B) of a release sheet peeled off from the self-adhesive silicone rubber sheet at the time of use.
１，１ａ，１ｂ　防湿性自己接着シリコーンゴムシート
３，３０　自己接着シリコーンゴムシート封入体
１０　未硬化状態の自己接着シリコーンゴムシート
１２　剥離シート
１４　透湿抑制層（一例として、シリコーン系粘着層）
１６　防湿袋（防湿性の袋） 1, 1a, 1b Moisture-proof self-adhesive silicone rubber sheet 3, 30 Self-adhesive silicone rubber sheet Encapsulated body 10 Self-adhesive silicone rubber sheet 12 in uncured state Peeling sheet 14 Moisture permeation-suppressing layer (Silicone-based adhesive layer as an example)
16 Moisture-proof bag (Damp-proof bag)
　以下、本発明の防湿性自己接着シリコーンゴムシートおよび自己接着シリコーンゴムシート封入体の各実施形態について図面を参照して説明する。なお、以下に説明する各実施形態は、特許請求の範囲に係る発明を限定するものではない。また、各実施形態の中で説明されている諸要素およびその組み合わせの全てが本発明の解決手段に必須であるとは限らない。 Hereinafter, embodiments of the moisture-proof self-adhesive silicone rubber sheet and the self-adhesive silicone rubber sheet enclosure of the present invention will be described with reference to the drawings. In addition, each embodiment described below does not limit the invention which concerns on a claim. In addition, all of the elements described in each embodiment and the combination thereof are not necessarily essential to the solution of the present invention.
（第１実施形態）
１．概略構造
　図１は、第１実施形態に係る防湿性自己接着シリコーンゴムシートをその厚さ方向に切断したときの断面図（１Ａ）、当該防湿性自己接着シリコーンゴムシートから剥離シートを除去した状態の斜視図（１Ｂ）及び第１実施形態に係る自己接着シリコーンゴムシート封入体をその厚さ方向に切断したときの断面図（１Ｃ）である。 First Embodiment
1. Schematic Structure FIG. 1 is a cross-sectional view (1A) when the moisture-proof, self-adhesive silicone rubber sheet according to the first embodiment is cut in the thickness direction; FIG. 2 is a perspective view (1B) of the self-adhesive silicone rubber sheet enclosure according to the first embodiment and a cross-sectional view (1C) of the same in a thickness direction.
　防湿性自己接着シリコーンゴムシート１は、未硬化状態の自己接着シリコーンゴムシート１０と、透湿抑制層１４と、剥離シート１２，１２とを備える。剥離シート１２，１２は、自己接着シリコーンゴムシート１０の２つの幅広面の内の少なくとも１つの幅広面を被覆して、自己接着シリコーンゴムシート１０の使用時に剥離するシートである。透湿抑制層１４は、自己接着シリコーンゴムシート１０の少なくとも１つの側面に形成されており、自己接着シリコーンゴムシート１０の側面から内方への水分の透過を抑制する層である。また、透湿抑制層１４付きの自己接着シリコーンゴムシート１０は、剥離シート１２，１２を貼り付けた状態にて防湿性の袋（以後、単に「防湿袋」ともいう。）１６に封入されている。この状態のものを、自己接着シリコーンゴムシート封入体３と称する。防湿袋１６には、例えば、アルミニウムがラミネートされたポリエチレンテレフタレートフィルム等を用いることができる。使用前には、自己接着シリコーンゴムシート１０は、防湿袋１６に封入されているので、長期間保存後でも接着能を高く維持できる。また、使用時に、防湿袋１６から自己接着シリコーンゴムシート１０を取り出し、しばらく放置しても、自己接着シリコーンゴムシート１０の全周面が剥離シート１２，１２及び透湿抑制層１４で被覆されているので、空気中の水分は剥離シート１２，１２及び透湿抑制層１４を透過して自己接着シリコーンゴムシート１０内には進入しにくい。したがって、自己接着シリコーンゴムシート１０の透湿による硬化を抑制できる。 The moisture-proof self-adhesive silicone rubber sheet 1 is provided with a non-cured self-adhesive silicone rubber sheet 10, a moisture permeation suppressing layer 14, and release sheets 12 and 12. The release sheet 12 is a sheet which covers at least one of the two wide sides of the self-adhesive silicone rubber sheet 10 and peels off when the self-adhesive silicone rubber sheet 10 is used. The moisture permeation suppressing layer 14 is formed on at least one side surface of the self-adhesive silicone rubber sheet 10 and is a layer that suppresses permeation of water inward from the side surface of the self-adhesive silicone rubber sheet 10. Further, the self-adhesive silicone rubber sheet 10 with the moisture permeation suppressing layer 14 is sealed in a moisture-proof bag (hereinafter, also simply referred to as a "moisture-proof bag") 16 with the release sheets 12, 12 attached. There is. The one in this state is referred to as a self-adhesive silicone rubber sheet enclosure 3. For the moisture-proof bag 16, for example, a polyethylene terephthalate film laminated with aluminum can be used. Before use, the self-adhesive silicone rubber sheet 10 is enclosed in the moisture-proof bag 16, so that high adhesion can be maintained even after long-term storage. Also, at the time of use, the self-adhesive silicone rubber sheet 10 is taken out of the moisture-proof bag 16 and, even if left for a while, the entire peripheral surface of the self-adhesive silicone rubber sheet 10 is covered with the release sheets 12 and 12 and the moisture permeation restraining layer 14 Therefore, the moisture in the air hardly penetrates into the self-adhesive silicone rubber sheet 10 through the release sheets 12 and 12 and the moisture permeation suppressing layer 14. Therefore, the curing due to moisture permeation of the self-adhesive silicone rubber sheet 10 can be suppressed.
　この実施形態における「自己接着シリコーンゴム」は、無溶剤のシリコーン系接着剤の一種であり、高い接着力とともに、熱安定性、耐候性、良好な耐水性、優れた可撓性を有する。未硬化状態（硬化前）の自己接着シリコーンゴムは、自立した形状を保持でき、かつ、押圧力に従って変形可能である（可塑性を有する固体状である）。このため、未硬化状態の自己接着シリコーンゴムシートは、配置する場所の凹凸や曲面に応じて変形させ、配置する場所に密着させることが可能であり、高い接着力を有する。 The “self-adhesive silicone rubber” in this embodiment is a kind of solvent-free silicone-based adhesive and has high adhesion, heat stability, weather resistance, good water resistance, and excellent flexibility. The uncured (pre-cured) self-adhesive silicone rubber can maintain a freestanding shape and is deformable according to the pressure (being a solid with plasticity). For this reason, the self-adhesive silicone rubber sheet in the uncured state can be deformed according to the unevenness and the curved surface of the place to be disposed, and can be brought into close contact with the place to be disposed, and has high adhesive strength.
　自己接着シリコーンゴムシート１０は、２５℃におけるウイリアムス可塑度が５０～５００の範囲内にあることが好ましく、５０～３５０の範囲内にあることがより好ましく、５０～２５０の範囲内にあることがさらにより好ましい。なお、ウイリアムス可塑度は、平行板可塑度計（ウイリアムスプラストメーター）を使用し、ＪＩＳ　Ｋ　６２４９「未硬化および硬化シリコーンゴムの試験方法」に規定の測定方法に準じて測定されるものである。自己接着シリコーンゴムは、縮合反応型のシリコーンゴムであり、好ましくは常温での放置（空気中の水分との反応）という手軽な手段により硬化する。 The self-adhesive silicone rubber sheet 10 preferably has a Williams plasticity at 25 ° C. in the range of 50 to 500, more preferably in the range of 50 to 350, and in the range of 50 to 250 Even more preferred. In addition, Williams plasticity is measured according to the measuring method prescribed | regulated to JISK6249 "test method of uncured and hardened silicone rubber", using a parallel plate plasticity meter (Williams plastometer). The self-adhesive silicone rubber is a condensation reaction type silicone rubber and is preferably cured by a simple means such as standing at ordinary temperature (reaction with water in the air).
　図１（１Ａ）に示す自己接着シリコーンゴムシート１０は、未硬化状態の縮合反応型の自己接着シリコーンゴムをシート状に成形したものである。ただし、当該シート１０を、縮合反応型の自己接着シリコーンゴムに付加反応型の自己接着シリコーンゴムを部分的に存在せしめたシートとしても良い。自己接着シリコーンゴムシート１０の上下面を被覆する剥離シート１２，１２には、紙、布、ガラスクロス、樹脂等の特に制約のない公知の剥離シートを使用できるが、好ましくは、樹脂、とりわけ、ポリエチレンテレフタレート、ポリプロピレン、ポリエチレン、ポリスチレン、ポリ塩化ビニル等の樹脂からなるフィルムを用いることができる。剥離シート１２，１２は、好ましくは、その端部を自己接着シリコーンゴムシート１０からはみ出すような大きさである。これは、剥離シート１２，１２を剥離する際に、当該はみ出している部分を把持して、剥離シート１２，１２を簡単に剥離できるようにするためである。 The self-adhesive silicone rubber sheet 10 shown in FIG. 1 (1A) is obtained by forming a condensation reaction type self-adhesive silicone rubber in an uncured state into a sheet. However, the sheet 10 may be a sheet in which an addition reaction self-adhesive silicone rubber is partially present in a condensation reaction self-adhesive silicone rubber. As the release sheets 12 and 12 covering the upper and lower surfaces of the self-adhesive silicone rubber sheet 10, known release sheets such as paper, cloth, glass cloth, resin and the like without particular restrictions can be used. A film made of a resin such as polyethylene terephthalate, polypropylene, polyethylene, polystyrene or polyvinyl chloride can be used. The release sheets 12, 12 are preferably sized such that their ends protrude from the self-adhesive silicone rubber sheet 10. This is because when peeling the release sheets 12 12, the protruding portion is gripped so that the release sheets 12 can be easily peeled.
２．自己接着シリコーンゴムシート
　以下、この実施形態および以後の実施形態にて好適に使用可能な自己接着シリコーンゴムシート１０を構成する縮合反応型の自己接着シリコーンゴムについて説明する。 2. Self-Adhesive Silicone Rubber Sheet Hereinafter, a condensation reaction type self-adhesive silicone rubber that constitutes the self-adhesive silicone rubber sheet 10 that can be suitably used in this embodiment and the following embodiments will be described.
縮合反応型の自己接着シリコーンゴム
　縮合反応型の自己接着シリコーンゴムは、主に以下の成分から構成される。 Condensation reaction type self-adhesive silicone rubber The condensation reaction type self-adhesive silicone rubber is mainly composed of the following components.
（ａ）オルガノポリシロキサン
　縮合反応型の自己接着シリコーンゴムの主剤成分であり、下記の化学式（１）または化学式（２）により表されるジオルガノポリシロキサンである。 (A) Organopolysiloxane This is a main component of condensation reaction type self-adhesive silicone rubber and is a diorganopolysiloxane represented by the following chemical formula (1) or chemical formula (2).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　上記の化学式（１），（２）において、Ｒは一価の炭化水素基である。Ｒとしては、アルキル基（メチル基、エチル基、プロピル基、ブチル基、２－エチルブチル基、オクチル基等）、シクロアルキル基（シクロヘキシル基、シクロペンチル基等）、アルケニル基（ビニル基、プロペニル基、ブテニル基、ヘプテニル基、ヘキセニル基、アリル基等）、アリール基（フェニル基、トリル基、キシリル基、ナフチル基、ジフェニル基等）、アラルキル基（ベンジル基、フェニルエチル基等）、および、上記炭化水素基の炭素原子に結合している水素原子の少なくとも一部をハロゲンやシアノ基等で置換したもの（クロロメチル基、トリフルオロプロピル基、２－シアノエチル基、３－シアノプロピル基等）から選択される一または複数の炭化水素基を挙げることができる。Ｒの炭素数としては、１～１２であることが好ましく、１～１０であることが一層好ましい。上記の化学式（１），（２）においては、Ａは酸素原子または－（ＣＨ２）ｍ－（ｍは１～８）で表されるポリメチレン基（メチレン基を含む）である。Ａは、酸素原子またはエチレン基であることが好ましい。 In the above chemical formulas (1) and (2), R is a monovalent hydrocarbon group. As R, an alkyl group (methyl group, ethyl group, propyl group, butyl group, 2-ethylbutyl group, octyl group etc.), cycloalkyl group (cyclohexyl group, cyclopentyl group etc.), alkenyl group (vinyl group, propenyl group, Butenyl group, heptenyl group, hexenyl group, allyl group etc., aryl group (phenyl group, tolyl group, xylyl group, naphthyl group, diphenyl group etc.), aralkyl group (benzyl group, phenylethyl group etc.), It is selected from those in which at least a part of hydrogen atoms bonded to carbon atoms of hydrogen groups are substituted with halogen or cyano group etc. (chloromethyl group, trifluoropropyl group, 2-cyanoethyl group, etc.) And one or more hydrocarbon groups can be mentioned. The carbon number of R is preferably 1 to 12, and more preferably 1 to 10. In the above chemical formulas (1) and (2), A is an oxygen atom or a polymethylene group (including a methylene group) represented by-(CH 2 ) m- (m is 1 to 8). A is preferably an oxygen atom or an ethylene group.
　上記の化学式（１），（２）において、ｎは（ａ）成分の２５℃における動粘度を１００～１００００００ｃｍ２／ｓの範囲内とする任意の数である。当該動粘度は、５００～５０００００ｃｍ２／ｓの範囲内とすることが一層好ましい。 In the above chemical formulas (1) and (2), n is an arbitrary number for making the kinematic viscosity at 25 ° C. of the component (a) within the range of 100 to 1,000,000 cm 2 / s. The kinematic viscosity is more preferably in the range of 500 to 500,000 cm 2 / s.
　上記の化学式（１），（２）において、Ｂは加水分解性基である。Ｂとしては、アルコキシ基（メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等）、ケトオキシム基（ジメチルケトオキシム基、メチルエチルケトオキシム基等）、アシルオキシ基（アセトキシ基等）、アルケニルオキシ基（イソプロペニルオキシ基、イソブテニルオキシ基等）を挙げることができる。なお、上記の化学式（１），（２）におけるｘは２または３である。 In the above chemical formulas (1) and (2), B is a hydrolyzable group. As B, alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group etc.), ketoxime group (dimethyl ketoxime group, methyl ethyl ketoxime group etc.), acyloxy group (acetoxy group etc.), alkenyloxy group (isopropenyloxy group) Group, isobutenyloxy group etc. can be mentioned. In the above chemical formulas (1) and (2), x is 2 or 3.
　上記（ａ）成分は、公知の方法（例えば、環状シロキサンまたは線状オリゴマーと酸触媒または塩基触媒とを用いた平衡反応による方法）により製造することができる。 The component (a) can be produced by a known method (for example, a method by equilibrium reaction using a cyclic siloxane or linear oligomer and an acid catalyst or a base catalyst).
　なお、（ａ）成分であるジオルガノポリシロキサンに分岐構造を導入する場合には、常法として、重合中にＳｉＯ３／２単位およびＳｉＯ４／２単位のうち少なくとも一方を含むシランまたはシロキサンをジオルガノポリシロキサンがゲル化しない程度に添加する方法を用いることができる。（ａ）成分については、汚れを低減するため、洗浄等により低分子シロキサンを除去してから用いることが好ましい。 When a branched structure is introduced into the diorganopolysiloxane which is the component (a), a silane or siloxane containing at least one of an SiO 3/2 unit and an SiO 4/2 unit during polymerization is routinely used. A method may be used in which the diorganopolysiloxane is added so as not to gel. The component (a) is preferably used after removing the low molecular weight siloxane by washing or the like in order to reduce dirt.
（ｂ）架橋剤
　架橋剤としては、加水分解性基を１分子中に２個以上、好ましくは３個以上有するシラン、または、当該シランの部分加水分解縮合物を用いる。加水分解性基の例としては、アルコキシ基（メトキシ基、エトキシ基、ブトキシ基等）、ケトオキシム基（ジメチルケトオキシム基、メチルエチルケトオキシム基等）、アシルオキシ基（アセトキシ基等）、アルケニルオキシ基（イソプロペニルオキシ基、イソブテニルオキシ基等）、アミノ基（Ｎ－ブチルアミノ基、Ｎ，Ｎ－ジエチルアミノ基等）、アミド基（Ｎ－メチルアセトアミド基等）を挙げることができる。これらの中では、アルコキシ基、ケトオキシム基、アシルオキシ基、アルケニルオキシ基を用いることが好ましい。架橋剤の配合量は、（ａ）成分１００質量部に対して１～５０質量部の範囲内にあることが好ましく、２～３０質量部の範囲内にあることが一層好ましく、５～２０質量部の範囲内にあることがより一層好ましい。 (B) Crosslinking agent As the crosslinking agent, a silane having two or more, preferably three or more, hydrolyzable groups in one molecule, or a partial hydrolytic condensate of the silane is used. Examples of hydrolyzable groups include alkoxy (such as methoxy, ethoxy and butoxy), ketoxime (such as dimethyl ketoxime and methyl ethyl ketoxime), acyloxy (such as acetoxy), and alkenyloxy (such as iso-butyl). Examples include propenyloxy group, isobutenyloxy group, etc., amino group (N-butylamino group, N, N-diethylamino group etc.), and amide group (N-methylacetamide group etc.). Among these, it is preferable to use an alkoxy group, a ketoxime group, an acyloxy group or an alkenyloxy group. The compounding amount of the crosslinking agent is preferably in the range of 1 to 50 parts by mass, more preferably in the range of 2 to 30 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the component (a). It is even more preferred to be in the range of parts.
（ｃ）硬化触媒
　硬化触媒は必須ではないが、硬化触媒を用いることにより、自己接着シリコーンゴムの硬化を促進することができる。硬化触媒の例としては、アルキル錫エステル化合物（ジブチル錫ジアセテート、ジブチル錫ジラウレート、ジブチル錫ジオクトエート等）、チタン酸エステルまたはチタンキレート化合物（テトライソプロポキシチタン、テトラｎ－ブトキシチタン、テトラキス（２－エチルヘキソキシ）チタン、ジプロポキシビス（アセチルアセトナ）チタン、チタニウムイソプロポキシオクチレングリコール等）、その他の適切な有機金属化合物（ナフテン酸亜鉛、ステアリン酸亜鉛、亜鉛－２－エチルオクトエート、鉄－２－エチルヘキソエート、コバルト－２－エチルヘキソエート、マンガン－２－エチルヘキソエート、ナフテン酸コバルト、アルコキシアルミニウム化合物等）、アミノアルキル基置換アルコキシシラン（３－アミノプロピルトリエトキシシラン、Ｎ－β（アミノエチル）γ－アミノプロピルトリメトキシシラン等）、アミン化合物またはその塩（ヘキシルアミン、リン酸ドデシルアミン等）、第４級アンモニウム塩（ベンジルトリエチルアンモニウムアセテート等）、アルカリ金属の低級脂肪酸塩（酢酸カリウム、酢酸ナトリウム、シュウ酸リチウム等）、のアルカリ金属の低級脂肪酸塩、ジアルキルヒドロキシルアミン（ジメチルヒドロキシルアミン、ジエチルヒドロキシルアミン等）、グアニジル基を有するシランまたはシロキサン（テトラメチルグアニジルプロピルトリメトキシシラン、テトラメチルグアニジルプロピルメチルジメトキシシラン、テトラメチルグアニジルプロピルトリス（トリメチルシロキシ）シラン等）を挙げることができる。これらは、１種のみで用いてもよいし、２種以上の混合物として用いてもよい。硬化触媒の配合量は、（ａ）成分１００質量部に対して０～２０質量部の範囲内にあることが好ましく、０．００１～１０質量部の範囲内にあることが一層好ましく、０．０１～５質量部の範囲内にあることがより一層好ましい。 (C) Curing Catalyst Although the curing catalyst is not essential, the curing of the self-adhesive silicone rubber can be promoted by using the curing catalyst. Examples of the curing catalyst include alkyl tin ester compounds (dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin dioctoate, etc.), titanate esters or titanium chelate compounds (tetraisopropoxy titanium, tetra n-butoxy titanium, tetrakis (2- Ethylhexoxy) titanium, dipropoxybis (acetylacetona) titanium, titanium isopropoxy octylene glycol etc., and other suitable organometallic compounds (zinc naphthenate, zinc stearate, zinc 2-ethyl octoate, iron-2 -Ethyl hexoate, cobalt 2-ethyl hexoate, manganese 2-ethyl hexoate, cobalt naphthenate, alkoxy aluminum compound etc., aminoalkyl substituted alkoxysilane (3-aminopropyl trie (Xylsilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, etc.), amine compounds or salts thereof (hexylamine, dodecylamine phosphate, etc.), quaternary ammonium salts (benzyltriethylammonium acetate, etc.), alkali metals Lower fatty acid salts (potassium acetate, sodium acetate, lithium oxalate etc.) of lower metals, alkali metal lower fatty acid salts, dialkylhydroxylamines (dimethylhydroxylamine, diethylhydroxylamine etc.), silanes or siloxanes with guanidyl group (tetramethyl Anidyl propyl trimethoxysilane, tetramethyl guanidyl propyl methyl dimethoxysilane, tetramethyl guanidyl propyl tris (trimethylsiloxy) silane, etc. can be mentioned. These may be used alone or as a mixture of two or more. The compounding amount of the curing catalyst is preferably in the range of 0 to 20 parts by mass, more preferably in the range of 0.001 to 10 parts by mass, with respect to 100 parts by mass of the component (a). It is even more preferred to be in the range of 01-5 parts by weight.
（ｄ）充填剤
　充填剤は、必須ではないが、補強等の目的で好適に用いることができる。充填剤の例としては、補強剤（ヒュームドシリカ、沈降性シリカ、これらのシリカの表面を有機珪素化合物で疎水化処理したシリカ、石英粉末、タルク、ゼオライト、ベントナイト等）、繊維質充填剤（アスベスト、ガラス繊維、有機繊維等）、塩基性充填剤（炭酸カルシウム、炭酸亜鉛、酸化亜鉛、酸化マグネシウム、セライト等）を挙げることができる。これらの中では、シリカ、炭酸カルシウムおよびゼオライトを用いることが好ましく、表面を疎水化処理したヒュームドシリカおよび炭酸カルシウムを用いることが一層好ましい。上記充填剤の配合量は、目的や充填剤の種類により選択することができるが、（ａ）成分に対して１～９０体積％の範囲内にあり、５～６０体積％の範囲内にあることが好ましい。 (D) Filler Although the filler is not essential, it can be suitably used for the purpose of reinforcement and the like. Examples of fillers include reinforcing agents (fumed silica, precipitated silica, silica obtained by hydrophobizing the surface of these silicas with organic silicon compounds, quartz powder, talc, zeolite, bentonite, etc.), fibrous fillers ( Asbestos, glass fibers, organic fibers and the like), basic fillers (calcium carbonate, zinc carbonate, zinc oxide, magnesium oxide, celite and the like) can be mentioned. Among these, it is preferable to use silica, calcium carbonate and zeolite, and it is more preferable to use fumed silica and calcium carbonate whose surfaces have been subjected to hydrophobic treatment. The blending amount of the above-mentioned filler can be selected according to the purpose and the kind of the filler, but it is in the range of 1 to 90% by volume with respect to the component (a) and in the range of 5 to 60% by volume Is preferred.
（ｅ）接着性付与成分
　接着性付与成分は必須ではないが好適に用いられる。接着性付与成分の例としては、アミノ基含有オルガノアルコキシシラン（γ－アミノプロピルトリメトキシシラン、γ－（２－アミノエチル）アミノプロピルトリメトキシシラン等）、エポキシ基含有オルガノアルコキシシラン（γ－グリシドキシプロピルトリメトキシシラン等）、メルカプト含有オルガノアルコキシシラン（γ－メルカプトプロピルトリメトキシシラン等）、アミノ基含有オルガノアルコキシシランとエポキシ基含有オルガノアルコキシシランとの反応混合物を挙げることができる。接着性付与成分の配合量は、（ａ）成分１００質量部に対して０．１～５質量部の範囲内にあることが好ましい。 (E) Adhesion-imparting component The adhesion-imparting component is not essential but is preferably used. Examples of adhesion imparting components include amino group-containing organoalkoxysilanes (γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, etc.), epoxy group-containing organoalkoxysilanes (γ-gly) Mention may be made of reaction mixtures of dihydroxy-containing trimethoxysilane, etc., mercapto-containing organoalkoxysilanes (γ-mercaptopropyltrimethoxysilane, etc.), amino-containing organoalkoxysilanes and epoxy-containing organoalkoxysilanes. The compounding amount of the adhesion imparting component is preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (a).
　自己接着シリコーンゴムシート１０は、主として、上記の縮合反応型の自己接着シリコーンゴムを調製し、シート状に形成したものである。 The self-adhesive silicone rubber sheet 10 is mainly formed into a sheet by preparing the above-mentioned condensation reaction type self-adhesive silicone rubber.
３．透湿抑制層
　次に、自己接着シリコーンゴムシート１０の側面に備える透湿抑制層１４について説明する。 3. Next, the moisture permeation restraining layer 14 provided on the side surface of the self-adhesive silicone rubber sheet 10 will be described.
　図１（１Ｂ）に示すように、この実施形態では、自己接着シリコーンゴムシート１０の全側面は、空気中の水分の透過を抑制する透湿抑制層１４を備える。透湿抑制層１４は、好ましくは、粘着性を有する粘着剤から主として形成されている。粘着剤としては、公知の粘着剤、例えば、アクリル系粘着剤、ウレタン系、シリコーン系の各種粘着剤を用いることができる。透湿抑制層１４は、先に説明した自己接着シリコーンゴム１０と異なり、透湿性が低いか、若しくは透湿しても容易に硬化しない層である。透湿抑制層１４は、自己接着シリコーンゴムシート１０との親和性が高く、当該シート１０から容易に分離せずに、一体的になる材料から成るのが好ましい。この点では、透湿抑制層１４を、シリコーン系粘着剤から主として構成されるシリコーン系粘着層とするのがより好ましい。一方、ウレタン系粘着剤から成る透湿抑制層１４（ウレタン系粘着層）は、透湿を抑制する点で上記シリコーン系粘着層に勝るので使用可能である。また、ゴム系粘着剤から主に構成される透湿抑制層１４を自己接着シリコーンゴムシート１０に備えても良い。 As shown in FIG. 1 (1 B), in this embodiment, all side surfaces of the self-adhesive silicone rubber sheet 10 are provided with a moisture permeation suppressing layer 14 which suppresses the permeation of moisture in the air. The moisture permeation suppressing layer 14 is preferably mainly formed of a tacky adhesive. As the pressure-sensitive adhesive, known pressure-sensitive adhesives, for example, various pressure-sensitive adhesives such as acrylic pressure-sensitive adhesives, urethane-based and silicone-based can be used. Unlike the self-adhesive silicone rubber 10 described above, the moisture permeation suppressing layer 14 is a layer having low moisture permeability or that does not easily cure even if moisture permeation is performed. The moisture permeation suppressing layer 14 is preferably made of a material that has high affinity with the self-adhesive silicone rubber sheet 10 and does not easily separate from the sheet 10 and that is integrated. In this respect, the moisture permeation suppressing layer 14 is more preferably a silicone-based adhesive layer mainly composed of a silicone-based adhesive. On the other hand, the moisture permeation suppressing layer 14 (urethane adhesive layer) made of a urethane adhesive can be used because it is superior to the silicone adhesive layer in suppressing moisture permeation. Further, the self-adhesive silicone rubber sheet 10 may be provided with a moisture permeation suppressing layer 14 mainly composed of a rubber-based pressure-sensitive adhesive.
　ゴム系粘着剤やシリコーン系粘着剤は、形成した透湿抑制層１４が未硬化の自己接着シリコーンゴムシート１０の塑性変形に追随できるので好ましい。ゴム系粘着剤としては、例えばゴム（天然ゴム、スチレン・ブタジエンゴム、イソプレンゴム、クロロプレンゴム、ブチルゴム、アクリロニトリルゴム、アクリルゴム等）、スチレン・ブタジエン共重合体、スチレン・イソプレンブロック共重合体、スチレン・エチレン・プロピレン共重合体、スチレン系ブロック共重合体（スチレン・イソプレン・エチレン・プロピレン共重合体等）、及びこれらの水添物のいずれか又は混合物を挙げることができる。ゴム系粘着剤中には、粘着付与樹脂（ロジン、ロジン誘導体、ポリテルペン樹脂、フェノール樹脂、石油系炭化水素樹脂等）、軟化剤（ポリブテン、流動パラフィン、ナフテン系オイル、芳香族系オイル等）、酸化防止剤（アミン系、フェノール系、リン系の酸化防止剤等）、充填材（炭酸カルシウム、シリカ、クレー、タルク、酸化チタン、酸化マグネシウム等）を添加することができる。 A rubber-based pressure-sensitive adhesive or a silicone-based pressure-sensitive adhesive is preferable because the formed moisture permeation suppressing layer 14 can follow the plastic deformation of the uncured self-adhesive silicone rubber sheet 10. Examples of rubber-based pressure-sensitive adhesives include rubber (natural rubber, styrene butadiene rubber, isoprene rubber, chloroprene rubber, butyl rubber, acrylonitrile rubber, acrylic rubber, etc.), styrene butadiene copolymer, styrene isoprene block copolymer, styrene Ethylene / propylene copolymers, styrene-based block copolymers (styrene / isoprene / ethylene / propylene copolymers, etc.), and any one or a mixture of these hydrogenated products can be mentioned. Rubber-based adhesives include tackifying resins (rosin, rosin derivatives, polyterpene resins, phenol resins, petroleum hydrocarbon resins, etc.), softeners (polybutene, liquid paraffin, naphthenic oils, aromatic oils, etc.), Antioxidants (amine-based, phenol-based, phosphorus-based antioxidants, etc.) and fillers (calcium carbonate, silica, clay, talc, titanium oxide, magnesium oxide, etc.) can be added.
　また、シリコーン系粘着剤には、例えば、シロキサン結合を主骨格としアルケニル基を有する付加型のオルガノポリシロキサンを構成成分として含むシリコーンゴムを含有するものを挙げることができる。このアルケニル基の具体例として、アリル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基等が挙げられる。更に、付加反応性を有さない有機基を有していても良い。このような有機基の具体例としては、メチル基、エチル基、プロピル基等のアルキル基、フェニル基等などのアリール基等を挙げることができる。上記のシリコーンゴムに含まれるオルガノポリシロキサンの重合度は特に制限されないが、通常、５００～１００００、更には２０００～８０００であることが好ましい。 Further, examples of the silicone-based pressure-sensitive adhesive include those containing a silicone rubber containing an addition type organopolysiloxane having a siloxane bond as a main skeleton and an alkenyl group as a component. Specific examples of this alkenyl group include allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group and the like. Furthermore, it may have an organic group having no addition reactivity. Specific examples of such organic groups include alkyl groups such as methyl, ethyl and propyl, and aryl groups such as phenyl. The degree of polymerization of the organopolysiloxane contained in the silicone rubber is not particularly limited, but it is preferably 500 to 10,000, and more preferably 2,000 to 8,000.
　また、上記シリコーン系粘着剤には、白金触媒を含有することが好ましい。白金触媒は、上記のアルケニル基の付加反応を開始させる機能や当該付加反応を促進する機能を有する。白金触媒の種類として、白金黒、塩化第２白金、塩化白金酸、塩化白金酸と１価アルコールとの反応物、塩化白金酸とオレフィン類との錯体、白金ビスアセトアセテート等を挙げることができる。白金触媒のシリコーン系粘着剤中の含有量は、シリコーンゴム１００質量部当たり０．０１～３質量部とすることが好ましい。かかる範囲とすることで、白金触媒の機能が安定的に発揮される。白金触媒の機能をより安定的に発揮させる観点から、シリコーン系粘着剤中の白金触媒の含有量は、シリコーンゴム１００質量部あたり０．０５～２．００質量部であることがより好ましく、０．１０～１．００質量部であることが特に好ましい。 Moreover, it is preferable to contain a platinum catalyst in the said silicone type adhesive. The platinum catalyst has a function of initiating the above addition reaction of the alkenyl group and a function of promoting the addition reaction. Examples of platinum catalysts include platinum black, platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohol, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. . The content of the platinum catalyst in the silicone-based pressure-sensitive adhesive is preferably 0.01 to 3 parts by mass per 100 parts by mass of the silicone rubber. The function of a platinum catalyst is stably exhibited by setting it as this range. From the viewpoint of exhibiting the function of the platinum catalyst more stably, the content of the platinum catalyst in the silicone-based pressure-sensitive adhesive is more preferably 0.05 to 2.00 parts by mass per 100 parts by mass of silicone rubber, and 0 It is particularly preferable that it is 10 to 1.00 parts by mass.
　シリコーン系粘着剤には、シリコーンレジン、すなわち、分子中に分岐状オルガノポリシロキサンを含有することが好ましい。このようなシリコーンレジンを含有することにより、自己接着シリコーンゴムシート１０に対する結合力を高めることができる。当該結合力の程度を適切に設定する観点から、シリコーン系粘着剤中に上記シリコーンレジンを含有する場合には、シリコーンレジンの含有量は、シリコーンゴム１００質量部当たり１０～１００質量部とすることが好ましく、１５～７５質量部とすることがより好ましく、２０～５０質量部とすることがさらにより好ましい。 The silicone-based pressure-sensitive adhesive preferably contains a silicone resin, that is, a branched organopolysiloxane in the molecule. By containing such silicone resin, the bonding strength to the self-adhesive silicone rubber sheet 10 can be enhanced. When the silicone resin is contained in the silicone-based pressure-sensitive adhesive, the content of the silicone resin is 10 to 100 parts by mass per 100 parts by mass of silicone rubber from the viewpoint of appropriately setting the degree of the bonding strength. Is preferable, 15 to 75 parts by mass is more preferable, and 20 to 50 parts by mass is even more preferable.
　シリコーン系粘着剤は、水分透過の抑制機能を発揮できる限り、各種の成分を含有できる。例えば、ヒドロシリル基を有する架橋剤、架橋促進剤・染料・顔料等の着色材料、アニリド系・フェノール系等の酸化防止剤、ベンゾフェノン系・ベンゾトリアゾール系等の紫外線吸収剤、タルク・二酸化チタン・シリカ・でんぷん等のフィラー成分、可塑剤、酸化防止剤、光安定剤、分散剤、レベリング剤等を挙げることができる。 The silicone-based pressure-sensitive adhesive can contain various components as long as the function of suppressing water permeation can be exhibited. For example, crosslinking agents having hydrosilyl group, coloring materials such as crosslinking accelerators, dyes and pigments, antioxidants such as anilides and phenols, UV absorbers such as benzophenones and benzotriazoles, talc, titanium dioxide, silica -Filler components such as starch, plasticizers, antioxidants, light stabilizers, dispersants, leveling agents and the like can be mentioned.
４．製法
　以上、説明してきた未硬化状態の縮合反応型の自己接着シリコーンゴム、粘着剤及び剥離シート１２を用いて、図１（１Ａ）に示す防湿構造を有する自己接着シリコーンゴムシート１０を製造する場合には、インサート成形を適用可能である。例えば、以下の要領にて製造可能である。まず、自己接着シリコーンゴム用の硬化性組成物を成形して所定厚さのシート体を得た後、このシート体を金型に入れて、シート体の全側面領域に粘着剤を供給する。その後、金型成形を行って、側面全面に透湿抑制層１４を備えた自己接着シリコーンゴムシート１０を得る。その後、当該シート１０の上下両面に剥離シート１２，１２を貼り付ける。 4. Manufacturing Method In the case of producing the self-adhesive silicone rubber sheet 10 having a moisture-proof structure shown in FIG. 1 (1A) using the condensation reaction type self-adhesive silicone rubber, adhesive and release sheet 12 in the uncured state described above. In the above, insert molding is applicable. For example, it can be manufactured in the following manner. First, a curable composition for a self-adhesive silicone rubber is molded to obtain a sheet having a predetermined thickness, and the sheet is put in a mold to supply an adhesive to the entire side surface area of the sheet. Thereafter, molding is performed to obtain the self-adhesive silicone rubber sheet 10 provided with the moisture permeation suppressing layer 14 on the entire side surface. Thereafter, the release sheets 12, 12 are attached to the upper and lower surfaces of the sheet 10.
　また、縮合反応型の自己接着シリコーンゴムを成形して角柱体を作製し、その全側面に粘着剤を塗布して透湿抑制層１４を形成した後、角柱体をスライスして所定厚さのシートとし、次いでシートの上下両面を剥離シート１２，１２で被覆する。このような方法によっても、剥離シート１２，１２付きの自己接着シリコーンゴムシート１０を得ることができる。 In addition, a condensation reaction type self-adhesive silicone rubber is molded to prepare a prismatic body, an adhesive is applied on all the side surfaces thereof to form the moisture permeation suppressing layer 14, and then the prismatic body is sliced to obtain a predetermined thickness. A sheet is formed, and then both upper and lower surfaces of the sheet are covered with release sheets 12. Also by such a method, the self-adhesive silicone rubber sheet 10 with the release sheets 12, 12 can be obtained.
　また、金型成形以外の成形、例えば、押出成形によって、全側面に透湿抑制層１４を備えた自己接着シリコーンゴムシート１０を得て、その上下両面に剥離シート１２，１２を貼り付けても良い。また、自己接着シリコーンゴムシート１０を押出あるいはカレンダーロールにてシート状に成形後、その両端部分にコーキングガンのような高粘度ディスペンサを使って粘着剤を塗布する方法を採用しても良い。その後、先に述べた方法にて剥離シート１２，１２を貼り付けることができる。 Further, even if the self-adhesive silicone rubber sheet 10 provided with the moisture permeation suppressing layer 14 on all side surfaces is obtained by molding other than molding, for example, extrusion molding, the release sheets 12, 12 are attached to both upper and lower surfaces thereof. good. Alternatively, after the self-adhesive silicone rubber sheet 10 is extruded or formed into a sheet by a calender roll, a method of applying an adhesive to both end portions using a high viscosity dispenser such as a caulking gun may be employed. Thereafter, the release sheets 12, 12 can be attached by the method described above.
５．作用・効果
　自己接着シリコーンゴムシート１０は、その上下両面（２つの幅広面）を剥離シート１２，１２に覆われ、全側面に透湿抑制層１４が備えられているので、空気中の水分が自己接着シリコーンゴムシート１０内に進入することを抑制できる。自己接着シリコーンゴムシート１０は、使用時に防湿袋１６から出されて大気に晒されても、透湿抑制層１４の存在により側面からの透湿を抑制できるので、そのまま長時間放置しても、剥離シート１２，１２を剥がさない限り、使用に際して支障が無い。 5. Since the self-adhesive silicone rubber sheet 10 is covered on both upper and lower sides (two wide sides) with the release sheets 12 and 12 and the moisture permeation suppressing layer 14 is provided on all sides, moisture in the air is absorbed. Entry into the self-adhesive silicone rubber sheet 10 can be suppressed. Even when the self-adhesive silicone rubber sheet 10 is taken out of the moisture-proof bag 16 and exposed to the atmosphere at the time of use, the moisture permeation from the side can be suppressed by the presence of the moisture permeation suppressing layer 14, so even if it is left for a long time, As long as the release sheets 12, 12 are not removed, there is no problem in use.
（第２実施形態）
　次に、本発明の第２実施形態について説明する。ただし、第２実施形態において、第１実施形態と共通する構成については同一の符号を付し、重複した説明を省略する。 Second Embodiment
Next, a second embodiment of the present invention will be described. However, in the second embodiment, the same reference numerals are given to the same components as in the first embodiment, and the redundant description will be omitted.
　図２は、第２実施形態に係る防湿性自己接着シリコーンゴムシートの前示と同視の断面図を示す。 FIG. 2 shows a cross-sectional view of the moistureproof self-adhesive silicone rubber sheet according to the second embodiment, as viewed in the same manner as the front view.
　第２実施形態に係る防湿性自己接着シリコーンゴムシート１ａは、自己接着シリコーンゴムシート１０の上下の幅広面の内の一方の面のみを剥離シート１２に被覆される一方、他方の面を基材１８にて覆われている。剥離シート１２は、自己接着シリコーンゴムシート１０から容易に剥離可能である。しかし、基材１８は、自己接着シリコーンゴムシート１０から容易に剥離できない。基材１８は、例えば、紙、布、樹脂、ガラスクロス等にて形成可能である。基材１８には予め装飾を施しておいても良い。自己接着シリコーンゴムシート１０の全側面は、第１実施形態と同様、透湿抑制層１４を備えている。このため、防湿袋１６から取り出した自己接着シリコーンゴムシート１０を空気中に放置しても、剥離シート１２を剥離しない限り、同シート１０の内部への空気中の水分の透過を抑制できる。自己接着シリコーンゴムシート１０の側面に備える透湿抑制層１４は、同シート１０の側面方向からの水分の透過を抑える機能を有するので、同シート１０の接着能を高く維持するのに寄与する。 In the moisture-proof self-adhesive silicone rubber sheet 1a according to the second embodiment, only one of the upper and lower wide surfaces of the self-adhesive silicone rubber sheet 10 is covered with the release sheet 12, while the other surface is a substrate Covered at 18 The release sheet 12 is easily releasable from the self-adhesive silicone rubber sheet 10. However, the substrate 18 can not be easily peeled off from the self-adhesive silicone rubber sheet 10. The substrate 18 can be formed of, for example, paper, cloth, resin, glass cloth or the like. The base 18 may be decorated in advance. All side surfaces of the self-adhesive silicone rubber sheet 10 are provided with a moisture permeation suppressing layer 14 as in the first embodiment. Therefore, even if the self-adhesive silicone rubber sheet 10 taken out of the moisture-proof bag 16 is left in the air, permeation of moisture in the air into the air of the sheet 10 can be suppressed as long as the release sheet 12 is not peeled off. The moisture permeation suppressing layer 14 provided on the side surface of the self-adhesive silicone rubber sheet 10 has a function of suppressing the permeation of water from the side direction of the sheet 10, and therefore contributes to maintaining the adhesive ability of the sheet 10 high.
（第３実施形態）
　次に、本発明の第３実施形態について説明する。ただし、第３実施形態において、先の各実施形態と共通する構成については同一の符号を付し、重複した説明を省略する。 Third Embodiment
Next, a third embodiment of the present invention will be described. However, in the third embodiment, the same reference numerals are assigned to configurations common to the previous embodiments, and redundant description will be omitted.
　図３は、第３実施形態に係る防湿性自己接着シリコーンゴムシートの前示と同視の断面図（３Ａ）、防湿性自己接着シリコーンゴムシートの側面図（３Ｂ）および防湿性自己接着シリコーンゴムシートを防湿性の袋に収納した状態の一部透過側面図（３Ｃ）をそれぞれ示す。 FIG. 3 is a cross-sectional view (3A) of the moisture-proof self-adhesive silicone rubber sheet according to the third embodiment and the same view, a side view (3B) of the moisture-proof self-adhesive silicone rubber sheet, and a moisture-proof self-adhesive silicone rubber sheet FIG. 3C is a partially transparent side view (3C) of the state in which the is housed in a moisture-proof bag.
　第３実施形態に係る防湿性自己接着シリコーンゴムシート１ｂは、未硬化状態の長尺状の自己接着シリコーンゴムシート１０を備える。当該自己接着シリコーンゴムシート１０は、その片側の幅広面のみに剥離シート１２を備え、剥離シート１２を備えていない幅広面を内側にして巻かれている。図３（３Ａ）では、長尺状の自己接着シリコーンゴムシート１０の上下両幅広面に剥離シート１２，１２を備えているように見えるが、下側の剥離シート１２は、上下方向に重なる自己接着シリコーンゴムシート１０自身の剥離シート１２である。なお、剥離シート１２は、この実施形態では、自己接着シリコーンゴムシート１０の幅方向とほぼ同じ幅のシートである。このように、剥離シート１２は、自己接着シリコーンゴムシート１０の側面からはみ出さないものであっても良い。 The moisture-proof self-adhesive silicone rubber sheet 1b according to the third embodiment includes a long self-adhesive silicone rubber sheet 10 in an uncured state. The self-adhesive silicone rubber sheet 10 is provided with the release sheet 12 only on one wide surface, and is wound with the wide surface not having the release sheet 12 inside. In FIG. 3 (3 A), although it looks as if the release sheets 12 and 12 are provided on the upper and lower wide surfaces of the long self-adhesive silicone rubber sheet 10, the lower release sheet 12 is self overlapping in the vertical direction. It is a release sheet 12 of the adhesive silicone rubber sheet 10 itself. In this embodiment, the release sheet 12 is a sheet having substantially the same width as the width direction of the self-adhesive silicone rubber sheet 10. Thus, the release sheet 12 may be one that does not protrude from the side surface of the self-adhesive silicone rubber sheet 10.
　この実施形態では、自己接着シリコーンゴムシート１０は、帯状であって、その幅方向両側面に透湿抑制層１４，１４を備える。透湿抑制層１４，１４を備える自己接着シリコーンゴムシート１０は、図３（３Ｂ）に示すように、筒状芯部２０に対してスパイラル状に巻かれている。ただし、筒状芯部２０は無くとも良い。スパイラル状に巻かれた状態の自己接着シリコーンゴムシート１０でも、その側面は常に空気に晒される危険性がある。しかし、当該側面に透湿抑制層１４を備えることによって、当該側面から自己接着シリコーンゴムシート１０内への水分の進入を抑制することができる。スパイラル状に巻かれた状態の自己接着シリコーンゴムシート１０を保管する場合、図３（３Ｂ）に示すように、防湿袋１６内に封入することが好ましい。この状態のものを、自己接着シリコーンゴムシート封入体３０と称する。 In this embodiment, the self-adhesive silicone rubber sheet 10 is in the form of a band, and is provided with the moisture permeation suppressing layers 14 and 14 on both side surfaces in the width direction. The self-adhesive silicone rubber sheet 10 provided with the moisture permeation suppressing layers 14 and 14 is spirally wound around the cylindrical core portion 20, as shown in FIG. 3 (3B). However, the cylindrical core portion 20 may be omitted. Even in the spirally wound self-adhesive silicone rubber sheet 10, there is a risk that the side surface is always exposed to air. However, by providing the moisture permeation suppressing layer 14 on the side surface, it is possible to suppress the entry of moisture into the self-adhesive silicone rubber sheet 10 from the side surface. When storing the self-adhesive silicone rubber sheet 10 in a spirally wound state, it is preferable to enclose it in the moisture-proof bag 16, as shown in FIG. 3 (3B). This state is referred to as a self-adhesive silicone rubber sheet enclosure 30.
（その他の実施形態）
　以上、本発明の好適な各実施形態について説明したが、本発明は上記各実施形態に限定されることなく、種々変更して実施可能である。 (Other embodiments)
The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above-described embodiments and can be implemented with various modifications.
　例えば、透湿抑制層１４は、自己接着シリコーンゴムシート１０の全側面あるいは幅方向にある両側面に備えられるのが好ましいが、当該全側面の内の一部の側面あるいは上記幅方向の両側面の内の一方の面のみに備えられていても良い。そのような場合、透湿抑制層１４を備えていない面は、露出した状態よりは、剥離シート１２に代表される何らかの手段によって空気中の水分に接触困難な状況におかれている方が望ましい。 For example, although it is preferable that the moisture permeation suppressing layer 14 is provided on all sides or both sides in the width direction of the self-adhesive silicone rubber sheet 10, the side of a part of the whole sides or both sides in the width It may be provided only on one side of the In such a case, it is preferable that the surface not provided with the moisture permeation suppressing layer 14 be in a state where it is difficult to contact moisture in the air by some means represented by the peeling sheet 12 rather than an exposed state. .
　また、上述の各種実施形態における構成要素は、互いに組み合わせられない場合を除き、任意に組み合わせ可能である。例えば、第２実施形態において用いられる基材１８は、第３実施形態に係る防湿性自己接着シリコーンゴムシート１ｂに備えられていても良い。 In addition, the components in the various embodiments described above can be arbitrarily combined unless they can be combined with one another. For example, the base 18 used in the second embodiment may be provided in the moisture-proof self-adhesive silicone rubber sheet 1b according to the third embodiment.
　本発明は、例えば、液状の接着剤の代わりに用いることができる。 The present invention can be used, for example, in place of a liquid adhesive.

Claims (4)

  1. 　未硬化状態の自己接着シリコーンゴムシートと、
    　前記自己接着シリコーンゴムシートの２つの幅広面の内の少なくとも１つの幅広面を被覆して、前記自己接着シリコーンゴムシートの使用時に剥離する剥離シートと、
    　前記自己接着シリコーンゴムシートの少なくとも１つの側面に形成されており前記自己接着シリコーンゴムシートの側面から内方への水分の透過を抑制する透湿抑制層と、
    を備える防湿性自己接着シリコーンゴムシート。     Uncured self-adhesive silicone rubber sheet,
    A release sheet which covers at least one of the two wide sides of the self-adhesive silicone rubber sheet and which is released when the self-adhesive silicone rubber sheet is used;
    A moisture permeation suppressing layer which is formed on at least one side surface of the self-adhesive silicone rubber sheet, and which suppresses permeation of water inward from the side surface of the self-adhesive silicone rubber sheet;
    Moisture-proof self-adhesive silicone rubber sheet with.
  2. 　前記透湿抑制層は、シリコーン系粘着層であることを特徴とする請求項１に記載の防湿性自己接着シリコーンゴムシート。 The moistureproof self-adhesive silicone rubber sheet according to claim 1, wherein the moisture permeation suppressing layer is a silicone-based adhesive layer.
  3. 　前記自己接着シリコーンゴムシートは、その片側の前記幅広面のみに前記剥離シートを備えた長尺状のシートであって、前記剥離シートを備えていない前記幅広面を内側にして巻かれていることを特徴とする請求項１または２に記載の防湿性自己接着シリコーンゴムシート。 The self-adhesive silicone rubber sheet is a long sheet provided with the release sheet only on the wide surface on one side thereof, and is wound with the wide surface not including the release sheet inside. The moisture-proof self-adhesive silicone rubber sheet according to claim 1 or 2, characterized in that
  4. 　請求項１から３のいずれか１項に記載の防湿性自己接着シリコーンゴムシートを、防湿性の袋に封入した状態の自己接着シリコーンゴムシート封入体。 The self-adhesive silicone rubber sheet enclosure in the state which enclosed the moisture-proof self-adhesive silicone rubber sheet of any one of Claim 1 to 3 in the moisture-proof bag.
PCT/JP2018/026128 2017-08-31 2018-07-11 Dampproof self-adhesive silicone rubber sheet and self-adhesive silicone rubber sheet enclosure WO2019044189A1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01245079A (en) * 1988-03-25 1989-09-29 Toyoda Gosei Co Ltd Adhesive tape
JPH01245078A (en) * 1988-03-25 1989-09-29 Toyoda Gosei Co Ltd Adhesive tape
JPH1161100A (en) * 1997-08-26 1999-03-05 Shin Etsu Polymer Co Ltd Silicone sealing material
JPH11106738A (en) * 1997-09-30 1999-04-20 Shin Etsu Polymer Co Ltd Silicone sealing material
JP2004175959A (en) * 2002-11-28 2004-06-24 Shin Etsu Polymer Co Ltd Curable regular size silicone rubber composition
WO2010134485A1 (en) * 2009-05-18 2010-11-25 株式会社タイカ Optical transparent pressure-sensitive adhesive material, optical transparent pressure-sensitive adhesive laminate, and process for producing same
JP2015512960A (en) * 2012-02-03 2015-04-30 エルジー・ケム・リミテッド Adhesive film

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01245079A (en) * 1988-03-25 1989-09-29 Toyoda Gosei Co Ltd Adhesive tape
JPH01245078A (en) * 1988-03-25 1989-09-29 Toyoda Gosei Co Ltd Adhesive tape
JPH1161100A (en) * 1997-08-26 1999-03-05 Shin Etsu Polymer Co Ltd Silicone sealing material
JPH11106738A (en) * 1997-09-30 1999-04-20 Shin Etsu Polymer Co Ltd Silicone sealing material
JP2004175959A (en) * 2002-11-28 2004-06-24 Shin Etsu Polymer Co Ltd Curable regular size silicone rubber composition
WO2010134485A1 (en) * 2009-05-18 2010-11-25 株式会社タイカ Optical transparent pressure-sensitive adhesive material, optical transparent pressure-sensitive adhesive laminate, and process for producing same
JP2015512960A (en) * 2012-02-03 2015-04-30 エルジー・ケム・リミテッド Adhesive film

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