WO2020138039A1 - Composition for curing-reactive silicone adhesive agent, cured product of same, and uses for these - Google Patents

Composition for curing-reactive silicone adhesive agent, cured product of same, and uses for these Download PDF

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Publication number
WO2020138039A1
WO2020138039A1 PCT/JP2019/050529 JP2019050529W WO2020138039A1 WO 2020138039 A1 WO2020138039 A1 WO 2020138039A1 JP 2019050529 W JP2019050529 W JP 2019050529W WO 2020138039 A1 WO2020138039 A1 WO 2020138039A1
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sensitive adhesive
composition
curing
reactive silicone
group
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PCT/JP2019/050529
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French (fr)
Japanese (ja)
Inventor
一裕 西嶋
昭宏 中村
晴彦 古川
吉武　誠
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ダウ・東レ株式会社
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Priority to KR1020217022885A priority Critical patent/KR20210108427A/en
Priority to CN201980079175.7A priority patent/CN113165348A/en
Priority to JP2020563287A priority patent/JP7448486B2/en
Publication of WO2020138039A1 publication Critical patent/WO2020138039A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • 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
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to a curable reactive silicone pressure-sensitive adhesive composition and a cured product thereof, and use of the composition or a cured product thereof.
  • Silicone materials are used for various purposes because they have excellent properties such as heat resistance, chemical resistance, and electrical insulation. Silicone materials can be formed on various substrates such as plastic, metal, glass, ceramics, paper, and wood, and have various applications such as daily necessities, medical supplies, and electronic products. Silicone materials are typically obtained by crosslinking organopolysiloxanes by a hydrosilylation reaction. In particular, silicone-based pressure-sensitive adhesives that are crosslinked by heating using a hydrosilylation reaction are widely known. Since the hydrosilylation reaction proceeds even at room temperature, the entire system is hardened or gelled immediately after the addition of the hydrosilylation reaction catalyst, making it difficult to handle.
  • the hydrosilylation reaction catalyst is usually added to the liquid silicone composition just before the curing reaction and uniformly mixed, and the handling work time up to the coating work (about several hours) is secured. Therefore, it is common to add a hydrosilylation reaction inhibitor to the composition in advance.
  • Patent Document 1 discloses that a curable silicone composition that is cured by a hydrosilylation reaction contains a phosphorus-containing hydrosilylation reaction retarder. However, Patent Document 1 does not describe or suggest the adhesive composition.
  • the present inventors have found a new problem regarding a silicone-based pressure-sensitive adhesive that is cured by a hydrosilylation reaction. That is, since the hydrosilylation reaction proceeds immediately after the catalyst is added as described above, the pot life of the composition after mixing is short, and the viscosity is increased in a relatively short time even at room temperature, and gelation occurs. Have a In order to solve this problem, hydrosilylation reaction inhibitors have been used as described above, but there is room for improvement in storage stability and handling workability obtained by conventional hydrosilylation reaction inhibitors. In addition, if the composition is partially thickened or cured in a gelled state, the crosslinked state of the composition tends to be non-uniform, and in the final state of the adhesive sheet, the original adhesiveness may not be realized. is there.
  • hot melt which is a heat-meltable silicone pressure-sensitive adhesive composition or a molded product thereof, is used to fill irregularities or gaps on members to perform temporary fixing or permanent adhesion between members.
  • a heat-meltable pressure-sensitive adhesive material is non-fluid at 25° C., unlike a liquid silicone composition, a hydrosilylation reaction catalyst is used at room temperature immediately before the curing reaction. Due to its nature, it is difficult to add and uniformly disperse in the composition by mechanical force.
  • the hydrosilylation reaction catalyst in order to uniformly add the hydrosilylation reaction catalyst, a step of heating and melting the composition is necessary, but since the hydrosilylation reaction easily proceeds under heating conditions, it is necessary to add the hydrosilylation reaction catalyst. In this case, the curing reaction of the entire composition is likely to proceed in the heating and melting stage, and the resulting heat-meltable adhesive material may not be able to maintain sufficient curing reactivity and moldability. Since the same problem can occur during molding, even in a molded heat-meltable adhesive material (for example, a hot-melt adhesive sheet), the molded composition as a whole is completely cured after a few days of storage and a curing reaction occurs. In some cases, it loses its heat-melting property and heat-melting property and cannot be used as a heat-melting adhesive.
  • a molded heat-meltable adhesive material for example, a hot-melt adhesive sheet
  • the present invention has been made to solve the above problems, and is liquid or non-fluid at room temperature (including hot-melt property), even in the form of a single composition, its storage stability, handling work Property, moldability, and a curable reactive silicone pressure-sensitive adhesive composition that can be cured quickly by heating at high temperature to obtain high adhesive strength, and high adhesive strength by pressure bonding Its purpose is to provide a cured product thereof.
  • a further object of the present invention is to provide a pressure-sensitive adhesive material that is used for the above-mentioned curing reactive silicone pressure-sensitive adhesive composition and its cured product.
  • the purpose of the present invention is to (A) a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule, (B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, (C) catalyst for hydrosilylation reaction, and (D) Phosphorus-containing hydrosilylation reaction retarder, Including,
  • the content of the component (B) is such that the silicon-bonded hydrogen atoms in the component (B) are 0.5 mol or more per 1 mol of the total aliphatic unsaturated carbon-carbon bond in the composition. Achieved by a cure reactive silicone adhesive composition.
  • the phosphorus-containing hydrosilylation reaction retarder of the component (D) is selected from the group consisting of phosphine compounds, phosphoric acid compounds, phosphonic acid compounds, phosphine oxide compounds, phosphorous acid compounds, and phosphonous acid compounds. It is preferably at least one selected.
  • Component (D) includes diphenylphosphine, triphenylphosphine, dimethylphenylphosphine, diethylphenylphosphine, tripropylphosphine, dicyclohexylphenylphosphine, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1 1,2-bis(diphenylphosphino)propane,1,3-bis(diphenylphosphino)propane,1,4-bis(diphenylphosphino)butane,2,3-bis(diphenylphosphino)butane,1,5 -Bis(diphenylphosphino)pentane, 1,6-bis(diphenylphosphino)hexane, bis(2-diphenylphosphinoethyl)phenylphosphine bis(diphenylphosphino)acetylene, 1,
  • the compounding amount of the component (D) is preferably in the range of 0.01 to 1,000 moles based on 1 mole of the metal atom in the component (C). It is particularly preferable that the amount is 0.30 to 10 mol per 1 mol.
  • the curing-reactive silicone pressure-sensitive adhesive composition of the present invention comprises a siloxane unit (M) represented by (E) R 3 SiO 1/2 (wherein R independently represents a monovalent organic group) in the molecule. Unit) and an organopolysiloxane resin containing a siloxane unit (Q unit) represented by SiO 4/2 .
  • At least a part of the component (E) is (Alk)R′ 2 SiO 1/2 (wherein Alk each independently represents an aliphatic unsaturated carbon-carbon bond-containing group, and R′ are mutually independent). Curing reactivity containing at least a siloxane unit (M unit) represented by an aliphatic unsaturated carbon-carbon bond-free group) and a siloxane unit (Q unit) represented by SiO 4/2 Organopolysiloxane resins are preferred.
  • the content of the component (E) is preferably 0.1% by mass to 90% by mass of the total mass of the components (A), (B) and (E).
  • the curing reactive silicone pressure-sensitive adhesive composition of the present invention may further contain (F) a solvent.
  • the curing-reactive silicone pressure-sensitive adhesive composition of the present invention is preferably a one-component type or a single composition.
  • the cure reactive silicone pressure sensitive adhesive composition of the present invention may be fluid at 25° C. as a whole composition.
  • the above-mentioned curing-reactive silicone pressure-sensitive adhesive composition was laminated with a 50- ⁇ m-thick pressure-sensitive adhesive layer obtained by curing the composition on a SUS plate, and pulled using a 180° peel test method according to JIS Z0237.
  • the adhesive force measured at a speed of 300 mm/min is preferably 0.1 gf/inch or more.
  • the curable reactive silicone pressure-sensitive adhesive composition of the present invention is non-flowable at 25° C. as a whole and may have a softening point between 25° C. and 150° C. Furthermore, the curing-reactive silicone pressure-sensitive adhesive composition of the present invention may have tackiness in a state before the curing reaction.
  • the above-mentioned curing-reactive silicone pressure-sensitive adhesive composition was laminated with a 200- ⁇ m-thick pressure-sensitive adhesive layer obtained by curing the composition on a SUS plate, and pulled by a 180° peel test method according to JIS Z0237.
  • the adhesive force measured at a speed of 300 mm/min is preferably 0.1 gf/inch or more.
  • the present invention comprises the above-mentioned curing reactive silicone pressure-sensitive adhesive composition (preferably, the composition as a whole is non-flowable at 25° C. and has a softening point between 25° C. and 150° C.), It also relates to at least a member, component or sheet.
  • non-fluidity means that it does not flow in an unloaded state
  • the ring-and-ball method for hot melt adhesives defined in JIS K 6863-1994 “Test method for softening point of hot melt adhesives”.
  • the softening point measured by the softening point test method according to 1. is in the range of 25°C to 150°C.
  • the present invention relates to the above-mentioned cure-reactive silicone pressure-sensitive adhesive composition (preferably, the composition as a whole is non-flowable at 25°C and has a softening point between 25°C and 150°C). ) Is also a heat-meltable adhesive material consisting of.
  • the present invention also relates to a cured product of the above curing reactive silicone adhesive composition.
  • the present invention also relates to a method for producing the above-mentioned cured product, which comprises a step of applying the above-mentioned curable reactive silicone pressure-sensitive adhesive composition under a temperature condition of less than 150° C. or curing it and then heating it to 150° C. or higher for curing.
  • the present invention also relates to an adhesive material comprising a cured product of the above-mentioned curing reactive silicone adhesive composition.
  • the present invention also relates to a laminate including a layer or member made of the above-mentioned curing reactive silicone pressure-sensitive adhesive composition. Similarly, the present invention also relates to a laminate provided with a layer or member comprising a cured product of the above-mentioned curing reactive silicone adhesive composition.
  • These laminates may include at least a part of a sheet-like member having a release layer, and for example, a member, a part or a sheet made of the above composition or a cured product thereof has a release layer. It may be a peelable laminate which is arranged so as to face the sheet-shaped member and is peeled off from the peeling layer at the time of use to use the above composition or a cured product thereof as an adhesive.
  • these laminated bodies may be at least one kind selected from a display device, an electronic component or a solar cell module, and may be, for example, a display device which is a liquid crystal display or an organic EL display.
  • a display device which is a liquid crystal display or an organic EL display.
  • the above-mentioned curing reactive silicone pressure-sensitive adhesive composition or a cured product thereof may be used as a sealing material for electronic parts such as LEDs and micro LEDs.
  • the laminate of the present invention can be used in various articles together with at least one substrate.
  • the substrate may be an image display panel, a touch panel, an optical film, or a front surface or back surface protection sheet.
  • the article is preferably a display device (display).
  • the display device is a liquid crystal display or an organic EL display.
  • the substrate may be a solar cell, a sealing material layer, or a front surface or back surface protection sheet.
  • the article is preferably a solar cell module.
  • the invention also relates to the process for producing these laminates.
  • the laminate obtained by these manufacturing methods may be an intermediate material such as a peelable pressure-sensitive adhesive sheet, or a final product such as a display device having a pressure-sensitive adhesive layer or a precursor thereof.
  • the method for producing a laminate of the present invention may include the step of heating the above-mentioned curable reactive silicone pressure-sensitive adhesive composition to 80° C. or higher to melt it, and molding or filling the melt.
  • the method for producing a laminate of the present invention comprises the step of placing the curing-reactive silicone pressure-sensitive adhesive composition at 150° C. after or at the same time as disposing the curing-reactive silicone pressure-sensitive adhesive composition on or between at least one member. It may include the above heating step.
  • the method for producing a laminate of the present invention comprises a step of laminating the above-mentioned curable reactive silicone pressure sensitive adhesive composition or a cured product thereof between members, and the curing reactive silicone pressure sensitive adhesive composition or a cured product thereof. It may include a step of crimping the member.
  • the present invention is liquid or non-flowable (including hot melt) at room temperature, and even in the form of a single composition, its storage stability, handling workability, and moldability are excellent, and It is possible to provide a curing-reactive silicone pressure-sensitive adhesive composition that can be cured rapidly by heating at a high temperature to obtain high adhesive strength. Further, it is possible to provide a cured product thereof which can obtain a high adhesive force by pressure bonding.
  • a pressure-sensitive adhesive which is an application of the above-mentioned cured reactive silicone pressure-sensitive adhesive composition and a cured product thereof, and a laminate comprising a layer formed of the above-mentioned cured reactive silicone pressure-sensitive adhesive composition or a cured product thereof.
  • a body and a method for manufacturing the laminate can be provided.
  • the curable reactive silicone pressure-sensitive adhesive composition of the present invention when the curable reactive silicone pressure-sensitive adhesive composition of the present invention is in the form of a liquid composition, even a one-pack composition containing a hydrosilylation reaction catalyst does not thicken or gel in a short time. Since it can be stored for a long period of time, it has excellent storage stability and storage stability, and also has excellent handling workability. Furthermore, even under storage conditions at a relatively high temperature of about 50° C., it does not thicken or gel in a short period of time, and therefore it is excellent in storage stability and handling workability under high temperature conditions.
  • the above one-pack type composition can be designed. However, since such a composition does not require the components to be mixed at the time of use, it can be used by the user. It has an advantage that the step of preparing the composition in 1) is unnecessary and the problem of poor mixing/dispersion does not occur during the mixing. Furthermore, by using the above one-pack composition, it is possible to essentially avoid an error in the process due to an error in the component ratio due to a mistake in charging, etc. And has the advantage that the handling workability as a product, industrial productivity, and the quality of the adhesive obtained can be greatly improved.
  • the curing-reactive silicone pressure-sensitive adhesive composition of the present invention can form a pressure-sensitive adhesive layer having excellent adhesive force by curing, and when the pressure-sensitive adhesive layer is peeled from an adherend, Cohesive failure of the adhesive layer is unlikely to occur.
  • the pressure-sensitive adhesive layer is interfacially peelable from the adherend.
  • the curing-reactive silicone pressure-sensitive adhesive composition of the present invention may be non-fluid at 25° C., have a softening point between 25° C. and 150° C., and may have heat-melting property.
  • the present invention since the progress of the curing reaction is suppressed by the addition of the hydrosilylation catalyst or the heating and melting at the time of molding the composition, the present invention provides sufficient curing reactivity and moldability.
  • a meltable, curing-reactive silicone pressure-sensitive adhesive composition and a molded product thereof can be provided. Therefore, the curable reactive silicone pressure-sensitive adhesive composition of the present invention can be softened or flowable by heating.
  • the curable reactive silicone pressure-sensitive adhesive composition of the present invention can excellently fill gaps by following unevenness on a member in a molten state, and has excellent gap fill property. Further, since the curable reactive silicone pressure-sensitive adhesive composition of the present invention can have heat-melting property, the fluid in a molten state can be molded into a desired shape such as a sheet. A molded article such as a sheet made of a curing-reactive silicone pressure-sensitive adhesive composition before the curing reaction has heat-melting property, adhesive property and curing reactivity by itself, and therefore, it can be applied to a desired site by using adhesive force. By arranging and heating and melting, the fluid may be caused to flow into the irregularities of the base material. ..
  • FIG. 1 is a cross-sectional view showing an optical display of an embodiment of an article of the present invention.
  • 1 is a cross-sectional view showing an optical display of an embodiment of an article of the present invention.
  • FIG. 6 is a cross-sectional view showing an optical display of another embodiment of the article of the present invention.
  • FIG. 6 is an exploded perspective view showing an optical display of another embodiment of the article of the present invention.
  • FIG. 6 is a partial cross-sectional view showing an optical display of another embodiment of the article of the present invention.
  • the curing-reactive silicone pressure-sensitive adhesive composition of the present invention may be a liquid composition having fluidity at 25°C, is not fluid at 25°C, and has a softening point between 25°C and 150°C.
  • the composition may have a hot melt property. When designed as a hot-melt composition, the entire composition can be softened or flowed by heating.
  • the softening or fluidizing temperature is preferably 50 to 150°C, more preferably 60°C to 130°C, even more preferably 80°C to 120°C.
  • the curing reactive silicone pressure-sensitive adhesive composition of the present invention is (A) a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule, (B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, (C) catalyst for hydrosilylation reaction, and (D) Phosphorus-containing hydrosilylation reaction retarder, Including, The content of the component (B) is such that the silicon-bonded hydrogen atoms in the component (B) are 0.5 mol or more with respect to 1 mol of all the aliphatic unsaturated carbon-carbon bonds in the composition.
  • the curing-reactive silicone pressure-sensitive adhesive composition of the present invention has a siloxane unit represented by (E) R 3 SiO 1/2 (wherein R's each independently represent a monovalent organic group) in the molecule.
  • An organopolysiloxane resin containing (M unit) and a siloxane unit (Q unit) represented by SiO 4/2 may be included.
  • the component (A) is one of the main components of the curable reactive silicone pressure-sensitive adhesive composition of the present invention.
  • the component (A) may be a single organopolysiloxane or a mixture of two or more kinds of organopolysiloxane.
  • the curable reactive silicone pressure-sensitive adhesive composition of the present invention or a cured product thereof has sufficient adhesive force and, in its adhesive mode, cohesive failure upon peeling from an adherend. It is also possible to form an adhesive material layer that is less likely to generate. If permanent adhesion to an adherend is required, a composition having a high adhesive force that causes cohesive failure of the pressure-sensitive adhesive layer at the time of peeling can be designed.
  • the component (A) is a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule.
  • the siloxane polymerization degree is preferably 80 or more. When the degree of polymerization is less than the above, it becomes difficult to obtain adhesive strength.
  • the aliphatic unsaturated carbon-carbon bond-containing group is preferably the above-mentioned alkenyl group, alkenyloxyalkyl group, acryloxyalkyl group or methacryloxyalkyl group.
  • alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group and a hexenyl group. Vinyl groups are particularly preferred. Moreover, a part of these groups may be substituted with a halogen atom or the like.
  • the aliphatic unsaturated carbon-carbon bond-containing group may be present at either the terminal of the molecular chain or the side chain of the molecular chain, or may be present at both of them. Good.
  • the aliphatic unsaturated carbon-carbon bond-containing group is preferably bonded to a silicon atom.
  • the content of the aliphatic unsaturated carbon-carbon bond-containing group is preferably 0.001 to 10% by weight, and more preferably 0.005 to 5% by weight, based on the weight of the component (A).
  • the component (A) may have an aliphatic unsaturated carbon-carbon bond-free group in addition to the aliphatic unsaturated carbon-carbon bond-containing group.
  • the aliphatic unsaturated carbon-carbon bond-free group is preferably the above-mentioned alkyl group, aryl group or aralkyl group.
  • the alkyl group include a cycloalkyl group such as a cyclohexyl group and a cycloheptyl group in addition to a methyl group, an ethyl group, a propyl group, a pentyl group, a hexyl group, an octyl group and the like.
  • Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and the like.
  • Examples of the aralkyl group include a benzyl group, an ⁇ -methylstyryl group and a 2-phenylethyl group.
  • the aliphatic unsaturated carbon-carbon bond-free group is more preferably an alkyl group, and particularly preferably a methyl group. Moreover, a part of these groups may be substituted with a halogen atom or the like.
  • component (A) those having the following average composition formula (1) are preferable.
  • R 1 is an alkenyl group having 2 to 12 carbon atoms. Specific examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group, and among these, a vinyl group and an allyl group. Alternatively, a hexenyl group is preferable.
  • R 2 is a group selected from a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms which does not have an aliphatic unsaturated bond, a hydroxyl group and an alkoxy group.
  • a part of the hydrogen atoms may be replaced with a halogen atom or a hydroxyl group.
  • Examples of the monovalent saturated hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, Alkyl group such as dodecyl group, phenyl group, tolyl group, xylyl group, naphthyl group, anthracenyl group, phenanthryl group, aryl group such as pyrenyl group, benzyl group, phenethyl group, naphthylethyl group, naphthylpropyl group, anthracenylethyl group Groups, aralkyl groups such as phenanthrylethyl group and pyrenylethyl group, and hydrogen atoms of these aryl groups or aralkyl groups, alkyl groups such as methyl group
  • a and b are numbers satisfying the following conditions: 1 ⁇ a+b ⁇ 3 and 0.0001 ⁇ a/(a+b) ⁇ 0.33, and preferably the following conditions: 1.5 ⁇ a+b ⁇ 2.5 and It is a number that satisfies 0.0002 ⁇ a/(a+b) ⁇ 0.2. This is because when a+b is 1 or more, the flexibility of the cured product increases, while when a+b is 3 or less, the mechanical strength of the cured product increases. Also, if a/(a+b) is 0.0001 or more, the mechanical strength of the cured product will be high, while if it is 0.33 or less, the flexibility of the cured product will be high.
  • Such a component (A) has a general formula: R 6 3 SiO(R 6 2 SiO) m1 SiR 6 3 It is preferably a linear organopolysiloxane represented by However, the component (A) may include a branched siloxane unit represented by R 6 SiO 3/2 or SiO 4/2 in a part thereof, and may be a branched organopolysiloxane.
  • each R 6 is independently a substituted or unsubstituted monovalent hydrocarbon group, and examples thereof include the monovalent unsaturated hydrocarbon group and the monovalent saturated hydrocarbon group described above. However, at least two R 6 s in one molecule are monovalent unsaturated hydrocarbon groups, preferably alkenyl groups, and more preferably vinyl groups.
  • the organopolysiloxane having the average compositional formula (1) may be oily or raw rubber-like at room temperature, and the viscosity of the component (A) at 25° C. is 50 mPa ⁇ s or more, particularly 100 mPa ⁇ s or more. It is preferable.
  • Component (B) is one of the main components of the curable reactive silicone pressure-sensitive adhesive composition of the present invention, and functions as a crosslinking agent.
  • the component (B) may be a single organohydrogenpolysiloxane or a mixture of two or more types of organohydrogenpolysiloxane.
  • the component (B) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule.
  • the component (B) is the component (A) or, if the component (E) described later has an aliphatic unsaturated carbon-carbon bond-containing group, the component (A) and the aliphatic unsaturated carbon of the component (E)- It contains a hydrosilyl group (-SiH) that adds to the carbon bond.
  • an organopolysiloxane having the following average composition formula (2) is preferable.
  • R 3 is a group selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms which does not have an aliphatic unsaturated bond, a hydroxyl group and an alkoxy group.
  • a part of the hydrogen atoms may be replaced with a halogen atom or a hydroxyl group.
  • Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecyl group.
  • Alkyl group such as dodecyl group, phenyl group, tolyl group, xylyl group, naphthyl group, anthracenyl group, phenanthryl group, aryl group such as pyrenyl group, benzyl group, phenethyl group, naphthylethyl group, naphthylpropyl group, anthracenyl group
  • Aralkyl groups such as ethyl group, phenanthrylethyl group and pyrenylethyl group, and hydrogen atoms of these aryl groups or aralkyl groups are alkyl groups such as methyl group and ethyl group; alkoxy groups such as methoxy group and ethoxy group; chlorine; A group substituted with a halogen atom such as an atom or a bromine atom can be mentioned. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group
  • c and d are numbers satisfying the following conditions: 1 ⁇ c+d ⁇ 3 and 0.002 ⁇ c/(c+d) ⁇ 0.5, preferably the following conditions: 1.5 ⁇ c+d ⁇ 2.5 and It is a number that satisfies 0.01 ⁇ c/(c+d) ⁇ 0.5. This is because if c+d is 1 or more, the flexibility of the cured product will be high, while if it is 3 or less, the mechanical strength of the cured product will be high. Also, if c/(c+d) is 1.5 or more, the mechanical strength of the cured product will be high, while if it is 2.5 or less, the flexibility of the cured product will be high.
  • the viscosity of the organopolysiloxane having the average composition formula (2) is not limited, but the viscosity at 25° C. is preferably in the range of 0.5 to 10,000 mPa ⁇ s, particularly 1 to 1,000 mPa ⁇ s. It is preferably within the range of s.
  • organopolysiloxane having the average composition formula (2) examples include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and tris(dimethylhydrogensiloxy)methylsilane.
  • organopolysiloxane having the average composition formula (2) examples include the following organopolysiloxanes.
  • Me and Ph respectively represent a methyl group and a phenyl group
  • m2 is an integer of 1 to 100
  • n2 is an integer of 1 to 50
  • b2, c2, d2 and e2 are positive.
  • the total of b2, c2, d2 and e2 in one molecule is 1.
  • the component (B) is preferably an organohydrogenpolysiloxane represented by the following average composition formula (3).
  • R 4 is a group selected from a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, which does not have an aliphatic unsaturated bond, a hydroxyl group and an alkoxy group.
  • the monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, the hydroxyl group and the alkoxy group are the same as above.
  • R 5 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group.
  • R 5 O 1/2 which is a unit of a partial structure, is a group that is bonded to an oxygen atom in a D unit, a DH unit, a T unit, a TH unit, or a Q unit, and is a silicon atom in an organopolysiloxane.
  • the MH unit is mainly present at the molecular chain end of the organohydrogenpolysiloxane, and the DH unit is present in the molecular chain of the organohydrogenpolysiloxane.
  • the content of the component (B) is such that the amount of silicon-bonded hydrogen atoms in the component (B) is 0.5 mol or more per 1 mol of the total aliphatic unsaturated carbon-carbon bond in the composition,
  • the amount of the silicon-bonded hydrogen atoms in the component (B) is preferably 0.5 to 100 mol, and more preferably 0.5 to 60 mol, based on 1 mol of the total aliphatic unsaturated carbon-carbon bond in the composition.
  • the amount is more preferable, and the amount of 0.5 to 40 mol is even more preferable.
  • the component (C) is a catalyst for hydrosilylation reaction.
  • the component (C) may be a single hydrosilylation reaction catalyst or a mixture of two or more hydrosilylation reaction catalysts.
  • Examples of the hydrosilylation reaction catalyst include platinum-based catalysts, rhodium-based catalysts, palladium-based catalysts, nickel-based catalysts, iridium-based catalysts, ruthenium-based catalysts, and iron-based catalysts, and platinum-based catalysts are preferable.
  • platinum-based catalyst platinum-based compounds such as platinum fine powder, platinum black, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, alcohol solution of chloroplatinic acid, olefin complex of platinum, alkenylsiloxane complex of platinum, etc. Are exemplified, and an alkenylsiloxane complex of platinum is particularly preferable.
  • alkenyl siloxane 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane
  • alkenylsiloxanes in which a part of methyl groups of these alkenylsiloxanes are substituted with ethyl groups, phenyl groups and the like, and alkenylsiloxanes in which vinyl groups of these alkenylsiloxanes are substituted with allyl groups, hexenyl groups and the like.
  • 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferable because the platinum-alkenylsiloxane complex has good stability. Further, since the stability of the platinum-alkenylsiloxane complex can be improved, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,3-diallyl-1,1 are added to the complex.
  • the component (C) be active even at a relatively low temperature. Specifically, those which are active in the composition in the temperature range of 0 to 200° C. and accelerate the hydrosilylation reaction are preferable.
  • the component (C) is preferably a catalyst for hydrosilylation reaction in which the curing reaction does not substantially proceed at 80° C. or lower in the presence of the component (D), while the component (D) exists in the presence of the component (D).
  • a hydrosilylation reaction catalyst that can accelerate the hydrosilylation reaction and cure the entire composition by heating at a high temperature of 150° C. or higher.
  • the content of the component (C) varies depending on the type of catalyst and the type of composition, it is usually an amount such that the metal atom in the catalyst is within the range of 0.1 to 200 ppm in mass unit with respect to the composition. And may be in the range of 0.1 to 150 ppm, 0.1 to 100 ppm.
  • composition of the present invention contains (D) a phosphorus-containing hydrosilylation reaction retarder.
  • the phosphorus-containing hydrosilylation reaction retarder is a component that can strongly suppress the hydrosilylation reaction at low temperature and adjust the curing reaction. By selectively using such retarder, a single composition of a single composition can be obtained. Even in the form, it is possible to design a curing-reactive silicone pressure-sensitive adhesive composition having excellent storage stability, handling workability, and moldability.
  • the component (D) may be a single phosphorus-containing hydrosilylation reaction retarder or a mixture of two or more kinds.
  • the phosphorus-containing hydrosilylation reaction retarder is at least one selected from the group consisting of phosphine compounds, phosphoric acid compounds, phosphonic acid compounds, phosphine oxide compounds, phosphorous acid compounds and phosphonous acid compounds. Is preferred.
  • phosphine compound examples include diphenylphosphine, triphenylphosphine, dimethylphenylphosphine, diethylphenylphosphine, tripropylphosphine, dicyclohexylphenylphosphine, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1 1,2-bis(diphenylphosphino)propane,1,3-bis(diphenylphosphino)propane,1,4-bis(diphenylphosphino)butane,2,3-bis(diphenylphosphino)butane,1,5 -Bis(diphenylphosphino)pentane, 1,6-bis(diphenylphosphino)hexane, bis(2-diphenylphosphinoethyl)phenylphosphine bis(diphenylphosphino)acety
  • the phosphoric acid compound is preferably at least one compound selected from the group consisting of triphenyl phosphate, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tripropyl phosphate, tributyl phosphate, and diphenylmethyl phosphate. ..
  • the phosphonic acid compound is preferably at least one compound selected from the group consisting of methylphosphonic acid, dimethyl, diethyl methylphosphonate, dipropyl methylphosphonate, dibutyl methylphosphonate, diethyl phenylphosphonate, and dipropyl phenylphosphonate. ..
  • the phosphine oxide-based compound may be at least one compound selected from the group consisting of diphenylphosphine oxide, triphenylphosphine oxide, dimethylphenylphosphine oxide, diethylphenylphosphine oxide, tripropylphosphine oxide, and tributylphosphine oxide. preferable.
  • the phosphite compound is triphenyl phosphite, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, diphenyl phosphite, dimethyl phosphite, diethyl phosphite, It is preferably at least one compound selected from the group consisting of dipropyl phosphite and dibutyl phosphite.
  • the phosphonous acid-based compound is preferably at least one compound selected from the group consisting of dimethyl phenylphosphonous acid, diethyl phenylphosphonous acid, and dipropyl phenylphosphonous acid.
  • the phosphorus-containing hydrosilylation reaction retarder is preferably a phosphine compound, particularly preferably bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphine). Fino) Propane.
  • the composition of the present invention in which the phosphorus-containing hydrosilylation reaction retarder (D) is selectively used has an improved pot life and can be handled easily. Furthermore, even in the form of a single composition, it is excellent in its storage stability, handling workability, and moldability, and can be rapidly cured by heating at a high temperature to obtain high adhesive strength. It is possible. Further, since the phosphorus-containing hydrosilylation reaction retarder suppresses the progress of the curing reaction due to the addition of the hydrosilylation catalyst or the heating and melting during the molding of the composition, the present invention provides sufficient curing reactivity and moldability. It is possible to provide a heat-meltable, curing-reactive silicone pressure-sensitive adhesive composition having: When other hydrosilylation reaction retarder is used instead of the component (D), the technical effect cannot be realized.
  • the content of the (D) phosphorus-containing hydrosilylation reaction retarder is not particularly limited, but is, for example, 0.01 with respect to 1 mol of the metal atom in the component (C) in the composition, preferably 1 mol of the platinum-based metal atom.
  • the amount is preferably ⁇ 1,000 mol, more preferably 0.1 to 500 mol, particularly preferably 0.30 to 10 mol. This is because if the content of the retarder is less than the lower limit of the above range, it is difficult to obtain a single composition (such as one liquefaction) from the composition, and the viscosity increases in a relatively short time even at room temperature.
  • the curing reaction proceeds in the step of heating and melting the hot-melt adhesive sheet.
  • the temperature exceeds the upper limit of the above range, the hot-melt adhesive sheet is heated at 150°C.
  • the amount of the component (D) used is in the range of 0.30 to 10 mol per 1 mol of the metal atom in the component (C)
  • the composition of the present invention was applied in a thin film form. Even in such a case, a rapid curing reaction can be realized by heating at 150° C. or higher.
  • composition of the present invention comprises a siloxane unit (M unit) represented by R 3 SiO 1/2 (wherein R's each independently represent a monovalent organic group) in the molecule (E). And an organopolysiloxane resin containing a siloxane unit (Q unit) represented by SiO 4/2 .
  • the component (E) may be a single organopolysiloxane resin or a mixture of two or more organopolysiloxane resins.
  • the component (E) is a component that imparts pressure-sensitive adhesiveness to the curable reactive silicone pressure-sensitive adhesive composition of the present invention or a cured product thereof, and can impart high adhesion to various bases or substrates.
  • the component (E) is a siloxane unit (M unit) represented by (a) R 3 SiO 1/2 (wherein R independently represents a monovalent organic group) in the molecule, and ( b) An organopolysiloxane resin containing a siloxane unit (Q unit) represented by SiO 4/2 .
  • the range of 00 to 1.20:1.00 is more preferable, and the range of 0.60:1.00 to 1.10:1.00 is even more preferable.
  • the above molar ratio can be easily measured by 29 Si nuclear magnetic resonance.
  • the component (E) may be composed of only (a) M units and (b) Q units, but R 2 SiO 2/2 units (D units) and/or RSiO 3/2 units (T units). May be included.
  • R's each independently represent a monovalent organic group.
  • the total content of (a) M units and (b) Q units in the component (E) is preferably 50% by weight or more, more preferably 80% by weight or more, and particularly preferably 100% by weight.
  • the monovalent organic group is not particularly limited, but can be divided into, for example, an aliphatic unsaturated carbon-carbon bond-containing group and an aliphatic unsaturated carbon-carbon bond-free group.
  • the aliphatic unsaturated carbon-carbon bond-containing group and the aliphatic unsaturated carbon-carbon bond-free group respectively include a monovalent unsaturated hydrocarbon group and an oxygen atom-containing monovalent unsaturated hydrocarbon group, and A monovalent saturated hydrocarbon group and an oxygen atom-containing monovalent saturated hydrocarbon group are included.
  • the monounsaturated or saturated hydrocarbon group is, for example, a substituted or unsubstituted one having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms.
  • Examples thereof include a valent unsaturated hydrocarbon group and a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms.
  • Examples of the unsubstituted monovalent unsaturated hydrocarbon group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 6 carbon atoms include, for example, vinyl group, allyl group and propenyl group. Examples thereof include alkenyl groups such as groups, butenyl groups, pentenyl groups and hexenyl groups. Examples of the substituted monounsaturated hydrocarbon group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms include, for example, these monovalent unsaturated hydrocarbon groups.
  • a group in which a part of hydrogen atoms of the group is substituted with a halogen atom (fluorine, chlorine, bromine or iodine) and the like can be mentioned.
  • Examples of the unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, pentyl group, hexyl group and octyl group; cyclohexyl group, cycloheptyl group and the like. Examples thereof include a cycloalkyl group; an aryl group such as a phenyl group, a tolyl group and a xylyl group; and an aralkyl group such as a benzyl group, an ⁇ -methylstyryl group and a 2-phenylethyl group.
  • substituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms for example, a part of hydrogen atoms of these monovalent unsaturated hydrocarbon groups is substituted with a halogen atom (fluorine, chlorine, bromine or iodine) or the like. There are some. Specifically, fluorinated monovalent saturated hydrocarbon groups such as 3,3,3-trifluoropropyl group, 4,4,5,5,5-pentafluorolbutyl group, 3,3,4,4,4.
  • Perfluoroalkyl group such as 5,5,6,6,6-nonafluorohexyl group; chlorinated monovalent saturated hydrocarbon group, for example, chloroalkyl group such as 3-chloropropyl group, chlorophenyl group such as dichlorophenyl group Are listed.
  • a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms is preferable.
  • a methyl group is preferred as the substituted or unsubstituted alkyl group having 1 to 12 carbon atoms.
  • the monovalent unsaturated hydrocarbon group is preferably a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms.
  • a vinyl group is preferred as the substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms.
  • oxygen atom-containing monovalent unsaturated or saturated hydrocarbon group examples include, for example, a substituted or unsubstituted oxygen atom-containing monovalent unsaturated hydrocarbon group and a carbon atom number of 1 to 12 And a substituted or unsubstituted monovalent saturated hydrocarbon group containing an oxygen atom.
  • Examples of the substituted or unsubstituted monovalent unsaturated hydrocarbon group having 2 to 12 carbon atoms include an alkenyloxyalkyl group, an acryloxyalkyl group and a methacryloxyalkyl group.
  • Examples of the alkenyloxyalkyl group include an allyloxymethyl group and a 3-allyloxypropyl group.
  • Examples of the acryloxyalkyl group include an acryloxymethyl group and a 3-acryloxypropyl group.
  • Examples of the methacryloxyalkyl group include a methacryloxymethyl group and a 3-methacryloxypropyl group.
  • Examples of the substituted or unsubstituted monovalent saturated hydrocarbon group containing 1 to 12 carbon atoms include an alkoxy group containing 1 to 12 carbon atoms.
  • alkoxy group having 1 to 12 carbon atoms examples include methoxy group, ethoxy group, propoxy group, butoxy group, isopropoxy group and the like.
  • halogen atom fluorine, chlorine, bromine or iodine
  • the organopolysiloxane resin as the component (E) may contain a small amount of hydroxyl groups bonded to silicon atoms.
  • the content of hydroxyl groups is preferably 0.2 mol or less, more preferably 0.1 mol or less, based on 1 mol of all silicon atoms.
  • the organopolysiloxane resin as the component (E) contains an alkoxy group bonded to a silicon atom such as a methoxy group or an ethoxy group, the content thereof is 0.2 mol or less with respect to 1 mol of all silicon atoms. Is preferable, and 0.1 mol or less is more preferable.
  • At least a part of the component (E) is (E1) in the molecule (Alk)R′ 2 SiO 1/2 (wherein, Alk is independently of each other an aliphatic unsaturated carbon-carbon). Represents a bond-containing group, R'independently of each other represents an aliphatic unsaturated carbon-carbon bond-free group), and a siloxane unit represented by SiO 4/2. It may be a curing-reactive organopolysiloxane resin containing at least (Q unit).
  • the aliphatic unsaturated carbon-carbon bond-containing group which is Alk is preferably the alkenyl group, alkenyloxyalkyl group, acryloxyalkyl group or methacryloxyalkyl group, which has been described above.
  • the aliphatic unsaturated carbon-carbon bond-free group which is R′ is preferably the alkyl group, aryl group or aralkyl group described above. Moreover, a part of these groups may be substituted with a halogen atom or the like.
  • the aliphatic unsaturated carbon-carbon bond-containing group which is Alk may be a vinyl group, an allyl group or a hexenyl group, and the aliphatic unsaturated carbon-carbon bond-free group which is R'is It is preferably a methyl group or a phenyl group.
  • the component (E) when the component (E) other than the (E1) curing-reactive organopolysiloxane resin is present, the component (E) is preferably non-curing reactive.
  • R of the non-curing reactive component (E) is preferably the aliphatic unsaturated carbon-carbon bond-free group described above, and more preferably an alkyl group, an aryl group or an aralkyl group. Moreover, a part of these groups may be substituted with a halogen atom or the like.
  • the aliphatic unsaturated carbon-carbon bond-free group which is R is preferably a methyl group, a phenyl group or the like.
  • the proportion of the (E1) curing-reactive organopolysiloxane resin in the component (E) is not particularly limited, but in order to achieve an appropriate hardness for the composition of the present invention or the cured product thereof as an adhesive material.
  • the content of the component (E1) in the component (E) is preferably in the range of 0 to 20% by mass, particularly preferably in the range of 0 to 15% by mass, and the composition of the present invention or a cured product thereof.
  • the adhesive material made of can have appropriate hardness and flexibility as an adhesive layer of a display device, a solar cell module, or the like.
  • (E) component for example, (Me 3 SiO 1/2 ) 0.45 (SiO 4/2 ) 0.55 (HO 1/2 ) 0.05 (Me 3 SiO 1/2 ) 0.40 (SiO 4/2 ) 0.60 (HO 1/2 ) 0.10 (Me 3 SiO 1/2 ) 0.52 (SiO 4/2 ) 0.48 (HO 1/2 ) 0.01 (Me 3 SiO 1/2 ) 0.40 (Me 2 ViSiO 1/2 ) 0.05 (SiO 4/2 ) 0.55 (HO 1/2 ) 0.05 (Me 3 SiO 1/2 ) 0.45 (SiO 4/2 ) 0.55 (MeO 1/2 ) 0.10 (Me 3 SiO 1/2 ) 0.25 (Me 2 PhSiO 1/2 ) 0.20 (SiO 4/2 ) 0.55 (HO 1/2 ) 0.05 (Me 3 SiO 1/2 ) 0.40 (Me 2 SiO 2/2 ) 0.05 (SiO 4/2 ) 0.55 (HO 1/2 ) 0.05 (Me 3 SiO 1/2 ) 0.40
  • the component (E) is a component that imparts pressure-sensitive adhesiveness to the curing-reactive silicone pressure-sensitive adhesive composition of the present invention or a cured product thereof and also imparts heat-melting property, so that the blending amount thereof is selected as desired. can do.
  • the component (E) may be in the range of 0.1 mass% to 90 mass% with respect to the total mass of the component (A), the component (B), and the component (E).
  • the compounding quantity of (E) component exceeds the said upper limit, since the hardening reactive silicone adhesive composition of this invention or its hardened
  • the component (E) is the component (A), It is preferably in the range of 0.1% by mass to 40% by mass, and in the range of 0.1% by mass to 30% by mass, based on the total mass of the components (B) and (E). Good.
  • the blending amount of the component (E) is based on the total mass of the components (A), (B), and (E). Therefore, it may be designed to be 0.1 mass% or less, and is preferable. This is because the cured product can be used as a slightly tacky adhesive layer even if it does not contain the component (E).
  • the compounding amount of the (E) component is (A) component, (B) It is preferable that the amount is in the range of 35% by mass to 90% by mass based on the total mass of the component) and the component (E).
  • the blending amount of the component (E) exceeds 90% by mass, the glass transition point (Tg) of the entire composition increases, the composition becomes excessively hard, and the handling workability as an adhesive is improved. This may be difficult and is not preferable.
  • the curing-reactive silicone pressure-sensitive adhesive composition of the present invention is provided with sufficient pressure-sensitive adhesive force and heat-melting property, and the composition as a whole is non-fluid at 25° C. and has a softening point between 25° C. and 150° C.
  • the blending amount of the component (E) is 55 mass% to 90 mass% with respect to the total mass of the component (A), the component (B), and the component (E).
  • the range is preferable, and the range of 60 to 85 mass% is particularly preferable.
  • the curing-reactive silicone pressure-sensitive adhesive composition of the present invention has sufficient adhesive force as long as it is temporarily fixed before the curing reaction. Further, it is possible to design so as to provide a cured product having an adhesive force such that permanent bonding between members can be achieved by the curing reaction.
  • the composition of the present invention can be designed as a solvent-free composition or a heat-melt composition, but may further contain (F) a solvent. .. (F)
  • a solvent can reduce the viscosity and thixotropy of the entire composition to improve handling workability and coatability, and the use of a small amount of an organic solvent can improve the wettability of the composition to a substrate.
  • the cure-reactive silicone pressure-sensitive adhesive composition according to the present invention can be prepared so that it can be applied to various processes.
  • a solvent can be added to the composition of the present invention and it is preferable.
  • the solvent as the component (F) is not particularly limited in its type, and is not limited as long as it dissolves the composition of the present invention and gives a uniform solution.
  • it may be a low molecular weight siloxane solvent or an organic solvent.
  • an organic solvent and normal hexane, normal pentane, normal heptane, normal octane, isooctane, decalin or other aliphatic hydrocarbons; toluene, xylene, mesitylene or other aromatic hydrocarbons; diisopropyl ether, Examples thereof include ethers such as dibutyl ether and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; glycol esters such as propylene glycol monomethyl ether acetate and dipropylene glycol monomethyl ether acetate.
  • the blending amount of the solvent which is the component (F) is not particularly limited, but when the sum of the components (A) to (E) is 100 parts by mass, it is used in the range of 0 to 9900 parts by mass.
  • the amount of the solvent used can be appropriately designed depending on the coating conditions such as the thickness of the substrate and the coating film.
  • the sum of the above components (A) to (E) is, for example, 50 parts by mass with respect to 100 parts by mass.
  • more than one part of the solvent may be used, when the solvent is used for the purpose of improving wettability, for example, it is possible to use a relatively small amount of solvent of 20 parts by mass or less, and ,preferable.
  • Unsaturated Aliphatic Hydrocarbons may optionally further comprise unsaturated aliphatic hydrocarbons.
  • Unsaturated aliphatic hydrocarbons contain aliphatic unsaturated bonds involved in hydrosilylation reaction and the like, and therefore, they function as a crosslinking component during the curing reaction and also as the above-mentioned solvent, and should be used as a reactive diluent.
  • the unsaturated aliphatic hydrocarbon is a hydrocarbon compound having 8 to 18 carbon atoms and at least one aliphatic unsaturated moiety in the molecule.
  • the unsaturated aliphatic hydrocarbon may be linear or branched, the aliphatic unsaturated portion may be in the middle or at the end, and two or more aliphatic unsaturated hydrocarbons may be present in the molecule. It is particularly preferred to have carbon-carbon double bonds that are saturated moieties.
  • Such an unsaturated aliphatic hydrocarbon contains an alkene having 8 to 18 carbon atoms, preferably an alkene having 12 to 14 carbon atoms, which has a carbon-carbon double bond at the end of the molecular chain, and is particularly preferably a reaction product.
  • dodecene, tetradecene, hexadecene and octadecene are exemplified, and tetradecene is preferable.
  • the amount of the unsaturated aliphatic hydrocarbon used is not particularly limited, but is 0.1 to 10 parts by mass, preferably 100 parts by mass when the sum of the components (A) to (E) is 100 parts by mass. Is in the range of 0.1 to 7.5 parts by mass.
  • composition of the present invention comprises, if necessary, other organopolysiloxanes, adhesion promoters, inorganic fillers such as silica, glass, alumina and zinc oxide; organic resin fine powders such as polymethacrylate resins; It may contain a phosphor, a heat-resistant agent, a dye, a pigment, a flame retardant, a solvent and the like.
  • organopolysiloxanes such as silica, glass, alumina and zinc oxide
  • organic resin fine powders such as polymethacrylate resins
  • It may contain a phosphor, a heat-resistant agent, a dye, a pigment, a flame retardant, a solvent and the like.
  • the amount of addition of these optional components and the method thereof are known to those skilled in the art.
  • the composition of the present invention can be produced by mixing the components (A) to (D), optionally the component (E), the component (F) and/or other optional components.
  • the composition of the present invention may be prepared by mixing it at the time of use, but it is preferable to prepare it by mixing it before use.
  • the composition of the present invention can cure the hydrosilylation reaction catalyst, which is the component (C), at room temperature to heating and melting even if the catalyst for the hydrosilylation reaction coexists with the components (A) and (B). Therefore, even in the form of a single composition, the curing reaction proceeds during the mixing operation to increase the viscosity or gel, and the mixture and the molded product show the curing reactivity in several hours to several days. Loss is effectively prevented. Therefore, it is possible to stably produce the composition or a molded product thereof by a simple process.
  • composition of the present invention may be liquid or non-flowable at 25°C, and the preparation method thereof is not particularly limited, but may be prepared by the following method.
  • composition of the present invention is a liquid composition having fluidity at 25° C.
  • it is carried out by mechanically mixing the respective components uniformly.
  • a solvent which is the component (F) may be added, or the mixture may be prepared by mixing using a known stirrer or kneader at a temperature of 0 to less than 150°C.
  • the composition of the present invention is a composition which is non-fluid at 25° C. and has a heat-melting property
  • the components (A), (B) and (E) are added in a temperature range of 80° C. to 120° C. It can be prepared by adding and mixing a mixture in which the components (C) and (D) have been mixed in advance while kneading with heating.
  • the composition as a whole softens and the mixture of the component (C) and the component (D) can be uniformly dispersed throughout the composition. There is a real benefit of avoiding cohesive failure.
  • the softening may be insufficient, and it may be difficult to uniformly disperse the mixture of the component (C) and the component (D) even if mechanical force is used.
  • the temperature exceeds the above upper limit, the component (C) may react during mixing, resulting in a significant increase in viscosity or curing of the entire component and loss of heat-meltability, which is not preferable.
  • the mixer used in this production method is not limited, and a batch (batch) type such as a kneader, a Banbury mixer, a Henschel mixer, a planetary mixer, a two-roll mill, a three-roll mill, a Ross mixer, and a Labo Plastomill having a heating/cooling function.
  • a continuous heating and kneading device such as a single-screw extruder having a heating/cooling function or a twin-screw extruder may be used, and it is not particularly limited, and is selected according to the efficiency of processing time and the controllability of shear heat generation. It In terms of processing time, a continuous type such as a single screw extruder or a twin screw extruder may be used, or a batch type mixer such as Labo Plastomill may be used.
  • the curable reactive silicone pressure-sensitive adhesive composition of the present invention When the curable reactive silicone pressure-sensitive adhesive composition of the present invention has fluidity at 25° C., it can be formed into a coating film by coating it on a substrate, and can be heated to give a cured product.
  • the coating method include offset coating, offset gravure, roll coating, reverse roll coating, air knife coating, curtain coating, and comma coating.
  • the temperature at the time of coating is not particularly limited, but it is preferable to coat at a temperature of less than 150°C.
  • the composition of the present invention is applied in the form of a thin film, for the purpose of adjusting the overall viscosity of the composition, improving wettability, etc., for example, it is applied on a substrate in a form containing (F) a solvent. By doing so, a coating film may be formed and heated, and it is preferable.
  • the curable reactive silicone pressure-sensitive adhesive composition of the present invention When the curable reactive silicone pressure-sensitive adhesive composition of the present invention is non-fluid at 25° C. and has heat melting property, it can be molded into a desired shape and used. Such a molded product can be designed to have a sufficient adhesive force if it is about a temporary fixing, depending on the content of the component (E), and the molded product can be placed on a specific adherend. By doing so, it can be used as a heat-meltable adhesive material.
  • the composition of the present invention can be processed into objects of various shapes, preferably by heating and melting at a temperature of 80° C. or higher and lower than 150° C., and then cooling, for example, a thickness of 5 ⁇ m to 5 mm. It can be in the form of a sheet, powder, or tablet. Specifically, the composition of the present invention can be heated and melted by using an apparatus having a heating/extruding function and processed into an object having a desired shape. In addition, since the object retains the curing reactivity and the heat-melting property unless it is heated to 150° C. or higher to start the curing reaction, it can be used as a heat-melting adhesive material in the form of a member, a part, a sheet, or the like. It is particularly preferable to utilize.
  • the composition of the present invention can be designed to have sufficient adhesive force if it is about a temporary fixing, depending on the content of the component (E), and can be used as a heat-meltable adhesive material.
  • an adhesive cured product (including a semi-cured product) can be formed by heating the composition to a temperature of 150° C. or higher to cause a curing reaction. Therefore, the composition of the present invention is useful as various potting agents, sealants, adhesives/adhesives, preferably optical adhesives/adhesives, and particularly optical adhesives for displays. It is useful as an adhesive.
  • the composition of the present invention has sufficient adhesive force for temporary fixing in the state before the curing reaction and is heat-meltable, so that it easily follows irregularities and gaps of an adherend. It is possible to form an adhesive layer having excellent properties. Furthermore, since the cured product is less colored at high temperatures or under high temperature and high humidity and does not easily become turbid, it can be used as a fixing layer or an adhesive layer between members constituting a laminated body such as a display device (solar cell module). Extremely useful.
  • the composition of the present invention can be a cured product.
  • the cured product is obtained by (further) performing a hydrosilylation reaction on the composition of the present invention to cure the composition of the present invention (completely or finally).
  • the composition can be cured by heating the composition at a temperature of 150° C. or higher and performing a hydrosilylation reaction.
  • the heating time is usually 0.2 to 4 hours, preferably 0.5 to 2 hours, though it depends on the kind and blending amount of each component in the composition.
  • the cured product of the present invention can be used as various materials.
  • the cured product means that it does not flow even when heated to 200° C. or higher.
  • the hardness of this cured product is not particularly limited, but it is usually from a gel having a penetration of 70 or less to a resin having a Shore D hardness of 80.
  • the cured product of the present invention is light transmissive, and more preferably transparent.
  • a light-transmissive, particularly transparent cured product can be suitably used for optical applications.
  • the cured product of the present invention can have pressure-sensitive adhesiveness.
  • the adhesive strength of the cured product is not particularly limited, but can be measured by the method according to JIS Z0237 as follows.
  • the display unit (converted to gf/inch) is preferably 0.1 gf/inch or more, particularly preferably 0.1 gf/inch to 10 kgf/inch, and 0.2 gf/inch to 10 kgf/inch. Is more preferable. However, it goes without saying that these adhesive strengths can be designed in a desired range from slight adhesion to strong adhesion to permanent adhesion.
  • the display unit (converted to gf/inch) is preferably 0.1 gf/inch or more, particularly preferably 0.1 gf/inch to 10 kgf/inch, and 0.2 gf/inch to 10 kgf/inch. Is more preferable.
  • these adhesive strengths can be designed in a desired range from slight adhesion to strong adhesion to permanent adhesion.
  • the cured product of the present invention can have a certain elasticity or flexibility. Therefore, the cured product of the present invention can be used as an elastic adhesive member.
  • the curable reactive silicone pressure-sensitive adhesive composition of the present invention and its cured product can be used as an adhesive.
  • the pressure-sensitive adhesive material of the present invention can have a high adhesive force and can be satisfactorily adhered or adhered to various adherends. Further, the pressure-sensitive adhesive material of the present invention can form a pressure-sensitive adhesive layer in which cohesive failure is less likely to occur at the time of peeling from an adherend, but the present invention is not limited to this and may be accompanied by cohesive failure.
  • the behavior of the cured reactive silicone pressure-sensitive adhesive composition of the present invention and the cured product pressure-sensitive adhesive layer thereof when peeled from the adherend can be preferably controlled according to the application.
  • the application for example, in applications where an action as a (pressure-sensitive) pressure-sensitive adhesive is expected, there is no residue on the adherend surface, or even a small amount of residue may be present.
  • it does not pose a problem to exhibit high adhesiveness such as cohesive failure.
  • the curable reactive silicone pressure-sensitive adhesive composition of the present invention is non-flowable and hot-meltable at 25° C. as a whole composition. It can be designed as a composition.
  • the curing-reactive silicone pressure-sensitive adhesive composition of the present invention can be used as a heat-melting pressure-sensitive adhesive as a pressure-sensitive adhesive having excellent moldability, gap fill property and pressure-sensitive adhesive before the curing reaction.
  • the cured product of the curing-reactive silicone pressure-sensitive adhesive composition of the present invention can be used as a pressure-sensitive adhesive material having excellent adhesive strength, although the heat-meltability and the curing reactivity are substantially lost. Therefore, the pressure-sensitive adhesive comprising the curing-reactive silicone pressure-sensitive adhesive composition can be used to temporarily fix a member or to form a pressure-sensitive adhesive layer that makes use of the gap fill property against irregularities and gaps on an adherend, and After temporarily fixing, arranging, and pasting, the adhesive material made of the curing-reactive silicone adhesive composition is heated to 150° C. or higher to form an adhesive material made of a cured material between adherends. It may be formed.
  • the pressure-sensitive adhesive comprising the cured product of the curable reactive silicone pressure-sensitive adhesive composition of the present invention can be used as a pressure-sensitive adhesive by itself, heating of the curable reactive silicone pressure-sensitive adhesive composition of the present invention can be performed. It may be treated as a pressure-sensitive adhesive member having a desired shape by molding it after being molded into a sheet shape or the like by utilizing the meltability.
  • the curable reactive silicone adhesive composition of the present invention can form an adhesive cured product (curing reaction product) when heated at 150° C. or higher.
  • the cured product can be used as an adhesive layer, an adhesive layer, particularly a pressure-sensitive adhesive layer (PSA layer), as an adhesive material for joining members by pressure bonding.
  • PSA layer pressure-sensitive adhesive layer
  • the cured product of the curable reactive silicone adhesive composition of the present invention can be treated as an adhesive film or a pressure-sensitive adhesive film alone.
  • the curable reactive silicone adhesive composition is heated to 150° C.
  • the composition before curing is a liquid composition having fluidity at 25° C. or a non-fluidic hot-melt composition at 25° C.
  • the cured product is an adhesive material (particularly an adhesive material). Can be used as a layer).
  • Laminate It is possible to provide a laminate comprising a layer made of the curable reactive silicone pressure sensitive adhesive composition of the present invention or a layer or member made of a cured product of the composition.
  • the laminate is not particularly limited, but a pressure-sensitive adhesive sheet (including an adhesive sheet and a pressure-sensitive adhesive (PSA) sheet), a peelable sheet obtained by laminating the sheet-like member having a release layer. It may be a laminate.
  • Adhesive Sheet Next, an adhesive sheet, which is a kind of the laminate according to the present invention, will be described.
  • the adhesive sheet of the present invention At least one sheet-like substrate, Comprising at least one adhesive layer formed on the sheet-shaped substrate,
  • the adhesive layer contains the above-mentioned curing reactive silicone adhesive composition or its cured product.
  • Non-Cured Adhesive Sheet The curable reactive silicone adhesive composition contained in the adhesive layer of the adhesive sheet of the present invention may be an uncured product. Such an adhesive sheet can be easily obtained by using a non-fluidic hot-melt composition at 25°C.
  • the pressure-sensitive adhesive sheet of the present invention is, for example, a sheet-like base material on which the curable reactive silicone pressure-sensitive adhesive composition of the present invention is applied in a heat-melted state to form a pressure-sensitive adhesive layer having a predetermined thickness. Then, it can be manufactured by semi-curing the adhesive layer.
  • the type of sheet-shaped substrate is not particularly limited, and a polyester film, a polyolefin film, a polycarbonate film, an acrylic film or the like can be appropriately used.
  • the sheet-shaped substrate is preferably non-porous.
  • a coating method for a sheet-shaped substrate roll coating using an offset coat, offset gravure, offset transfer roll coater, etc., reverse roll coat, air knife coat, curtain coat using a curtain flow coater, comma coat, Mayer bar, etc.
  • Other known methods used for forming a layer can be used without limitation.
  • the sheet-shaped substrate has at least one release layer, and the release layer is in contact with the pressure-sensitive adhesive layer.
  • the release layer is sometimes called a release liner, a separator, a release layer or a release coating layer, and is preferably a release agent such as a silicone release agent, a fluorine release agent, an alkyd release agent, or a fluorosilicone release agent.
  • a release layer having a coating ability, a substrate itself which is difficult to adhere to the curing reactive silicone pressure-sensitive adhesive composition of the present invention or an adhesive layer made of the cured product, which physically forms fine irregularities on the surface of the substrate. May be Particularly in the laminate of the present invention, it is preferable to use a release layer obtained by curing a fluorosilicone release agent as the release layer.
  • the adhesive sheet of the present invention can be used, for example, by applying the adhesive layer to an adherend and then peeling the uncured adhesive sheet from the sheet-shaped substrate.
  • the adhesive sheet may be heated to 150° C. or higher to form a cured product and then peeled off before use.
  • the pressure-sensitive adhesive sheet of the present invention is a hot-melt pressure-sensitive adhesive sheet which is a molded product of a non-fluidic hot-melt composition at 25° C.
  • the adhesive sheet is softened or fluidized, and for example, even if the adherend surface of the adherend has irregularities, the adhesive layer can be filled with no gaps. ..
  • the heating means for the adhesive sheet for example, various constant temperature baths, hot plates, electromagnetic heating devices, heating rolls and the like can be used. In order to perform the bonding and the heating more efficiently, for example, an electric heat press, a diaphragm type laminator, a roll laminator, or the like is preferably used.
  • the softening temperature of the hot-melt type adhesive sheet is 50° C. or higher, the processing characteristics and the storage characteristics at room temperature can be made sufficient.
  • the softening temperature of the adhesive layer is 100° C. or lower, not only heat damage to the image display panel and the like can be suppressed, but also the adhesive layer can be prevented from flowing out and protruding. Therefore, the softening temperature of the hot-melt type adhesive sheet is preferably 50 to 100°C, more preferably 55°C or higher or 95°C or lower, and further preferably 60°C or higher or 90°C or lower.
  • the curable reactive silicone adhesive composition contained in the adhesive layer of the adhesive sheet of the present invention may be a cured product.
  • Such an adhesive sheet can be obtained by applying a fluid composition at 25°C to form an adhesive layer having a predetermined thickness, and heating and curing at a temperature of 150°C or higher. Further, such an adhesive sheet can be obtained by heating and curing the above hot-melt adhesive sheet at a temperature of 150°C.
  • the method of applying the sheet-shaped substrate and the use of the sheet-shaped substrate provided with the release layer are the same as above.
  • the pressure-sensitive adhesive sheet of the present invention is, for example, a cured reactive silicone pressure-sensitive adhesive composition contained in the pressure-sensitive adhesive layer is cured by heating after applying the pressure-sensitive adhesive layer to an adherend, and the sheet-shaped substrate is in an uncured state. It can be used by peeling off the adhesive layer.
  • the thickness of the adhesive layer is preferably 5 to 10000 ⁇ m, more preferably 10 ⁇ m or more or 8000 ⁇ m or less, and particularly preferably 20 ⁇ m or more or 5000 ⁇ m or less.
  • the pressure-sensitive adhesive sheet of the present invention At least one sheet-like substrate, It has at least one pressure-sensitive adhesive layer formed on the sheet-shaped substrate,
  • the pressure-sensitive adhesive layer contains the above-mentioned curing reactive silicone pressure-sensitive adhesive composition or a cured product thereof.
  • the curing can be carried out, for example, by performing a hydrosilylation reaction in the composition of the present invention by heating at 150° C. or higher.
  • the pressure-sensitive adhesive sheet of the present invention is, for example, a sheet-shaped substrate, the curable reactive silicone pressure-sensitive adhesive composition of the present invention is applied to form a layer having a predetermined thickness, and the layer is cured to give a pressure-sensitive adhesive sheet. It can be manufactured by using an adhesive layer.
  • the type of sheet-shaped substrate is not particularly limited, and a polyester film, a polyolefin film, a polycarbonate film, an acrylic film or the like can be appropriately used.
  • the sheet-shaped substrate is preferably non-porous. ..
  • a coating method for a sheet-shaped substrate roll coating using an offset coat, offset gravure, offset transfer roll coater, etc., reverse roll coat, air knife coat, curtain coat using a curtain flow coater, comma coat, Mayer bar, etc.
  • Other known methods used for forming a layer can be used without limitation.
  • the sheet-shaped substrate has at least one release layer, and the release layer is in contact with the pressure-sensitive adhesive layer. Thereby, the pressure-sensitive adhesive layer can be easily peeled off from the sheet-shaped substrate.
  • the release agent contained in the release layer is not particularly limited, and the above-mentioned release agents can be mentioned.
  • the number of sheet-shaped substrates may be two.
  • the pressure-sensitive adhesive sheet of the present invention A first sheet-shaped substrate, A second sheet base material, Comprising at least one pressure sensitive adhesive layer formed between a first sheet substrate and a second sheet substrate,
  • the pressure-sensitive adhesive layer may be in contact with the first sheet base material and the second sheet base material.
  • the pressure-sensitive adhesive sheet of the above-mentioned form is, for example, sandwiching the curable reactive silicone pressure-sensitive adhesive composition of the present invention between a first sheet-shaped base material and a second sheet-shaped base material, and heating it with a press or a roll. It can be produced by molding the composition to a predetermined thickness and then curing the composition.
  • the first sheet base material may be provided with a first release layer, or the first sheet base material itself may be provided with a release property.
  • the second sheet base material may be provided with a second release layer, or the second sheet base material itself may be provided with releasability.
  • the first sheet substrate and/or the second sheet substrate comprises the first release layer and/or the second release layer
  • the pressure-sensitive adhesive layer is the first release layer and/or the second release layer. It is preferable to contact the release layer.
  • the releasable sheet base material examples include a sheet base material made of a releasable material such as a fluororesin film, or a non-removable or low releasable material such as a polyolefin film such as silicone or fluororesin.
  • the sheet base material examples include a release agent added.
  • examples of the sheet substrate having a release layer include a polyolefin film coated with a release agent such as silicone and fluororesin.
  • the pressure-sensitive adhesive sheet of the present invention can be used, for example, by applying the pressure-sensitive adhesive layer to an adherend and then peeling the pressure-sensitive adhesive layer from the sheet-shaped substrate.
  • the thickness of the pressure-sensitive adhesive layer is preferably 5 to 10000 ⁇ m, more preferably 10 ⁇ m or more or 8000 ⁇ m or less, and particularly preferably 20 ⁇ m or more or 5000 ⁇ m.
  • the laminate of the present invention may be an adhesive tape, and is provided with a sheet-like member made of a fiber product such as the above-mentioned synthetic resin film/sheet, metal foil, woven cloth, non-woven cloth, paper and the above-mentioned adhesive layer.
  • a sheet-like member made of a fiber product such as the above-mentioned synthetic resin film/sheet, metal foil, woven cloth, non-woven cloth, paper and the above-mentioned adhesive layer.
  • the type of such an adhesive tape is not particularly limited, and it includes an insulating tape, a heat-resistant tape, a solder masking tape, a mica tape binder, a temporary fixing tape (including a temporary fixing tape such as a silicone rubber part), a splicing tape. (In particular, a splicing tape for silicone release paper is included).
  • insulating tape for example, a tape (base) made of a synthetic resin having an insulating property such as polyvinyl chloride and the curing reactive silicone pressure-sensitive adhesive composition of the present invention or a pressure-sensitive adhesive made of the cured product is used as a pressure-sensitive adhesive layer.
  • a tape (base) made of a synthetic resin having an insulating property such as polyvinyl chloride and the curing reactive silicone pressure-sensitive adhesive composition of the present invention or a pressure-sensitive adhesive made of the cured product is used as a pressure-sensitive adhesive layer.
  • Such an insulating tape can be suitably used, for example, in applications where electrical insulation is required, such as repairing the insulating coating of electric wires.
  • the heat-resistant tape examples include a tape (substrate) made of a heat-resistant synthetic resin such as polyimide, and the like, which is provided with the curable reactive silicone pressure-sensitive adhesive composition of the present invention or a pressure-sensitive adhesive made of the cured product as an adhesive layer. be able to.
  • a heat-resistant tape can be suitably used for applications requiring heat resistance, such as repair of mufflers of automobiles and the like. Since the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape of the present invention is made of silicone, it has excellent heat resistance.
  • the solder masking tape is a kind of insulating tape or heat resistant tape, and can be used for masking in a soldering process of a printed circuit board.
  • Mica tape is a type of insulating tape or heat-resistant tape. It can be obtained by impregnating a mica (mica) sheet (substrate) with an appropriate amount of binder and heating and compressing it as needed. It may be processed into a tape by laminating it with a reinforcing material such as a sheet.
  • the curable reactive silicone pressure-sensitive adhesive composition of the present invention or a cured product thereof can be used as the binder.
  • the mica tape may be provided with an adhesive layer, and the curable reactive silicone adhesive composition of the present invention or its cured product may be used as the adhesive layer.
  • the temporary fixing tape is a tape used for various temporary fixing applications, and includes the curable reactive silicone pressure-sensitive adhesive composition of the present invention or an adhesive layer made of a cured product thereof. Since the adhesive layer has excellent adhesiveness and peelability, the temporary fixing tape of the present invention is suitable for temporary fixing. Since the pressure-sensitive adhesive layer is made of silicone, it has a good affinity for parts made of silicone rubber, and can be particularly preferably used for temporarily fixing parts made of silicone rubber.
  • the splicing tape is a tape used for connecting films and the like, and includes a curing reactive silicone pressure-sensitive adhesive composition of the present invention or an adhesive layer made of the cured product. Since the adhesive layer has excellent adhesiveness, the splicing tape of the present invention is suitable for connecting a film or the like. Since the pressure-sensitive adhesive layer is made of silicone, it has adhesiveness even on the surface subjected to silicone release treatment, and can be particularly suitably used for connecting silicone release paper.
  • curable reactive silicone pressure-sensitive adhesive composition of the present invention or an adhesive comprising the cured product thereof can be used for adhesion of various objects.
  • the present invention is At least one substrate, An article comprising at least one adhesive component, comprising:
  • the present invention also relates to an article, wherein the pressure-sensitive adhesive component includes the curing-reactive silicone pressure-sensitive adhesive composition of the present invention or a pressure-sensitive adhesive made of a cured product thereof.
  • the shapes of the base and the adhesive component are arbitrary and can be various three-dimensional shapes.
  • the properties of the adhesive material are as described above.
  • the adhesive component can be on or in the substrate. Preferably, at least a part of the base adheres to the adhesive component.
  • the pressure-sensitive adhesive material component has a pressure-sensitive adhesive force, and can adhere well to various other substrates. Furthermore, the adhesive component may be permanently bonded to another substrate, and the adhesive component should be designed in an adhesive mode in which cohesive failure does not occur when the adhesive component is peeled from the other substrate and interfacial peeling occurs. Is also possible.
  • the present invention At least one substrate,
  • the present invention also relates to an article, wherein the pressure-sensitive adhesive layer contains the curable reactive silicone pressure-sensitive adhesive composition of the present invention or a pressure-sensitive adhesive made of a cured product thereof.
  • the shape of the substrate is a sheet or a film
  • the shape of the adhesive layer is a layer.
  • at least a part of the surface of the substrate adheres to the adhesive layer.
  • the properties of the adhesive material are as described above.
  • the adhesive layer can be present between a plurality of bases or substrates, preferably a plurality of bases or substrates are joined together.
  • the substrate or substrate may be porous or non-porous.
  • porous substrate or the porous substrate examples include woven fabric, non-woven fabric, fiber products such as paper, synthetic resin film and sheet made porous by stretching, and a combination thereof.
  • the fibers may be natural fibers, synthetic fibers or a mixture thereof.
  • the adhesive material of the present invention can be present in at least a part of the holes of the base or the substrate.
  • a porous substrate or substrate such as cloth or paper is impregnated with the composition of the present invention (including impregnation and cooling in a heated and melted state), and if necessary, heated at a higher temperature to be cured. By doing so, such an article can be manufactured.
  • non-porous substrate or non-porous substrate examples include synthetic resin films/sheets, metal foils, and combinations thereof.
  • synthetic resin films and sheets are preferable, and examples of synthetic resins include polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol (PVA), polycarbonate, polyethylene terephthalate, cyclopolyolefin, and nylon.
  • a film of heat resistant synthetic resin such as polyimide, polyether ether ketone, polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamide imide, polyether sulfone is suitable.
  • transparent materials such as polypropylene, polystyrene, polyvinylidene chloride, PVA, polycarbonate, polyethylene terephthalate, PEN, and mixtures thereof are suitable.
  • the thickness of the substrate is not particularly limited, and can be designed to have a desired thickness according to the application. Further, in order to improve the adhesion between the substrate and the pressure-sensitive adhesive layer, a substrate that has been subjected to primer treatment, corona treatment, etching treatment, and plasma treatment may be used. Further, the surface of the substrate opposite to the pressure-sensitive adhesive layer contact surface may be surface-treated to prevent scratches, stains, fingerprints, antiglare, antireflection, antistatic and the like.
  • various characteristics required for adhesion can be exhibited in a well-balanced manner.
  • the adhesive component or the adhesive layer is useful as a member of various electronic devices or electric devices.
  • the shear storage elastic modulus G′ of the pressure-sensitive adhesive material component or the pressure-sensitive adhesive material layer at ⁇ 20° C. is in the range of 0.01 to 1.0 MPa (more preferably 0.02 to 0.90 MPa, more preferably 0.03 to The range of 0.80 MPa is even more preferable, and the range of 0.04 to 0.70 MPa is further more preferable.)
  • the pressure-sensitive adhesive component or the pressure-sensitive adhesive layer is used as an elastic pressure-sensitive adhesive component or elastic pressure-sensitive adhesive layer.
  • it is useful as a member for a transducer (including a member for a sensor, a speaker, an actuator and a generator).
  • the adhesive may be opaque or transparent.
  • An opaque or low-light-transmissive adhesive material is not required to be transparent, and is a film-like or sheet-like member used for a sensor, a speaker, an actuator, etc., in which the component or layer itself is required to have a certain stretchability or flexibility. Useful for applications. It is also useful as a sealing material or an adhesive material used in a secondary battery such as a lithium-ion battery or a fuel cell.
  • the base or the substrate is preferably a member for an optical device.
  • the substrate may be an image display panel, a touch panel, a polarizing film, a retardation film, a color filter, a viewing angle widening film, a brightness enhancement film, an optical film such as a reflection sheet, or a front surface or back surface protection sheet.
  • the pressure-sensitive adhesive layer is, for example, a surface protection sheet and an optical film, an optical film and a touch panel, a surface protection sheet and an image display panel, a back protection sheet and an image display panel, a surface protection sheet and a touch panel, a touch panel and an image display panel. Can be joined together.
  • the optical device can be configured by bonding two members selected from an image display panel, a touch panel, an optical film, and a front surface or back surface protection sheet via at least one adhesive material. .. It should be noted that they may be attached one by one or two at the same time, and the attaching method and order are not limited at all.
  • the optical device constituting member side is further heated at a high temperature.
  • the composition or a semi-cured product thereof can be cured.
  • the material of the front surface or the back surface protective sheet is not particularly limited, for example, glass, or (meth) acrylic resin such as polymethyl methacrylate, polycarbonate resin, cycloolefin polymer, acetyl cellulose resin such as triacetyl cellulose, Examples thereof include polyester resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, plastics such as acyclic olefin resins such as polypropylene and polyethylene, and mixtures of these plastics.
  • acrylic resin such as polymethyl methacrylate, polycarbonate resin, cycloolefin polymer, acetyl cellulose resin such as triacetyl cellulose
  • polyester resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate
  • plastics such as acyclic olefin resins such as polypropylene and polyethylene, and mixtures of these plastics.
  • the surface protection sheet may be one in which a touch panel is integrated, and may be, for example, a touch-on lens (TOL) type or a one glass solution (OGS) type. Further, the surface protection sheet may have a print step portion printed in a frame shape on the peripheral portion thereof.
  • TOL touch-on lens
  • OGS one glass solution
  • a structure in which a surface protection sheet is laminated on a functional film such as a touch panel via an adhesive sheet is adopted. If a concealment printing section (thickness of about 5 to 80 ⁇ m) is attached, and if the adhesive does not sufficiently enter the inside corners of the step formed on the edge of the concealment printing section, bubbles will remain and the screen The visibility will be reduced. Further, there is a possibility that the film member may be bent in the vicinity of the step to cause a poor appearance, or that residual strain due to the bending of the film may serve as a starting point to cause foaming or separation between the laminated members.
  • the composition of the present invention can be applied to such a step of about 5 ⁇ m to 20 ⁇ m, and even if there is a step of about 50 ⁇ m to 80 ⁇ m, it can be applied to every corner of the step without leaving bubbles. .. Moreover, even if one of the adherends is a flexible film member, the surface of the film member can be smoothed without distortion by hot-melting the composition of the present invention.
  • the members can be bonded and integrated without causing distortion or deformation.
  • the touch panel is not particularly limited, and may be a resistive film type, an electrostatic capacitance type, an electromagnetic induction type, or a combination thereof.
  • the touch panel preferably includes at least one cover film, a transparent electrode layer such as an ITO or ATO film, or a glass substrate.
  • the touch panel may further include a decorative film or the like.
  • the image display panel is not particularly limited as long as it displays image information, and for example, in the case of a liquid crystal display, a polarizing film, a retardation film, a color filter, a viewing angle widening film, a brightness enhancement film, a reflection film. It is composed of an optical film such as a sheet, a liquid crystal material, a transparent substrate and a backlight system (usually, the surface to which the adhesive material is adhered to the image display panel is the optical film), and the STN method is used depending on the control method of the liquid crystal material. , VA system, IPS system, etc., but any system may be used.
  • the image display panel may be an in-cell type in which the touch panel function is built in the TFT-LCD, or an on-cell type in which the touch panel function is built in between the glass substrate provided with the polarizing plate and the color filter.
  • the image display panel is composed of an organic EL element substrate or a laminate of the organic EL element substrate and other optical films.
  • the article of the present invention is preferably a display, and is a CRT display, a liquid crystal display, a plasma display, an organic EL display, an inorganic EL display, an LED display, a surface conduction electron-emitting device display (SED), a field emission type.
  • a display (FED) is more preferable, and a liquid crystal display or an organic EL display is even more preferable.
  • the image display surface of the display may be flat (flat), curved or curved.
  • the display of the present invention is, for example, a communication device such as a mobile phone or a fixed line telephone; a computer device such as a tablet terminal, a desktop terminal, a notebook type terminal; a TV; a printer; an ATM (automated teller machine); an in-vehicle monitor or navigation.
  • a communication device such as a mobile phone or a fixed line telephone
  • a computer device such as a tablet terminal, a desktop terminal, a notebook type terminal
  • TV a printer
  • an ATM automated teller machine
  • System Digital camera; Video camera; Medical device; PDA (mobile terminal); Watch; Electronic paper; CD, DVD or Blue-ray disc player; Solid electronic recording medium player such as SSM or HD; E-book device; Handheld game It is applied to amusement equipment such as equipment and fixed game equipment; POS system; fish finder; automatic ticket vending machine; instrument panel.
  • the base or the substrate can be a solar cell, a sealing material layer, or a front surface or back surface protection sheet. Therefore, the pressure-sensitive adhesive layer is, for example, a surface protection sheet and a solar cell, a back surface protection sheet and a solar cell, a surface protection sheet and a sealing material layer, a back surface protection sheet and a sealing material layer, and a sealing material layer. Solar cells can be joined.
  • the article of the present invention is preferably a solar cell module.
  • the curable reactive silicone pressure-sensitive adhesive composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof has pressure-sensitive adhesiveness, and thus can be used for the construction and use of a laminated touch screen or a flat panel display.
  • a known usage method of the pressure-sensitive adhesive layer can be used without particular limitation.
  • the curable reactive silicone pressure-sensitive adhesive composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof is an optically transparent silicone pressure-sensitive adhesive disclosed in JP-A-2014-522436 or JP-A-2013-512326.
  • the adhesive film or the adhesive layer can be used for manufacturing a display device such as a touch panel.
  • the cured product obtained by curing the composition of the present invention can be used without particular limitation as the adhesive layer or the adhesive film described in JP-A-2013-512326.
  • the article of the present invention is a substrate such as a conductive plastic film having a conductive layer formed on one surface thereof, and the present invention adhered to the surface on which the conductive layer is formed or the opposite surface thereof.
  • It may be a touch panel including the curing-reactive silicone pressure-sensitive adhesive composition (1) or a pressure-sensitive adhesive made of a cured product thereof.
  • the substrate is preferably a sheet-shaped or film-shaped substrate, and a resin film or a glass plate is exemplified.
  • the conductive plastic film may be a resin film or a glass plate having an ITO layer formed on one surface thereof, particularly a polyethylene terephthalate film. These are disclosed in Japanese Patent Publication No. 2013-512326 and the like.
  • the curable reactive silicone pressure-sensitive adhesive composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof may be used as an adhesive film for a polarizing plate used for manufacturing a display device such as a touch panel, and the like.
  • JP-A-2013-065009 It may be used as a pressure-sensitive adhesive layer used for bonding between the touch panel and the display module described in 1.
  • FIG. 1 is a cross-sectional view showing a laminated body according to an embodiment of the present invention.
  • the laminate 1 of one embodiment of the present invention comprises a first member 20, a second member 21, and a curing-reactive silicone pressure-sensitive adhesive composition of the present invention arranged between two members 20, 21. And an adhesive material 15 made of the cured product.
  • the two members 20 and 21 are adhered by the adhesive material 15.
  • These optical members may be transparent or opaque, and one or both members may be a single base material, or may be an independent laminated body such as a backlight unit. It may be an optical member.
  • the member constituting the laminate of the present invention is generally provided with a plate-shaped portion having a planar spread, the plate-shaped portion or the member itself may be curved, It may have three-dimensional unevenness derived from the application.
  • the two optical members 20 and 21 can be arbitrarily combined.
  • the two optical members 20 and 21 may be the same as or different from each other.
  • the members 20 and 21 are generally used as a constituent member of an optical display. More specifically, the members 20 and 21 are optical members, for example, lenses (which may be made of resin or glass), optical sheet-shaped members (color filters, polarizing plates, retardation plates, viewing angle widening films). , A brightness enhancement film, a reflection sheet, a transparent conductive film), an optical protective material which may be transparent (a transparent protective material (transparent protective film), etc., made of glass, resin or resin coating layer), front surface It may be a display panel, a touch panel (made of glass or resin), a transparent electrode layer such as an ITO or ATO film. Needless to say, an optical protective material may be further provided on the surface of the display panel or the touch panel.
  • lenses which may be made of resin or glass
  • optical sheet-shaped members color filters, polarizing plates, retardation plates, viewing angle widening films.
  • an optical protective material which may be transparent (a transparent protective material (transparent protective
  • the optical member may be a backlight unit itself including a light emitting layer and a display surface (display panel) described below, or a component in a display device such as a component or a touch panel in which the entire optical member is an independent laminated member.
  • the optical member may further have an adhesive layer 15 made of the main cured product. That is, the concept of the optical member includes an image display panel, an optical panel, a front panel, a backlight unit, a touch panel unit, etc., which will be described later.
  • the materials of the members 20 and 21 are not particularly limited as long as they are generally used for the above-mentioned applications, but glass, an inorganic optical material such as indium tin oxide (ITO), or a polycarbonate resin, Acrylic resin, epoxy resin, polystyrene resin, polyamide resin, polyimide resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol (PVA) resin, polyethylene terephthalate (PET) resin, cyclopolyolefin resin, poly Examples of the organic optical material include ether ether ketone resin, polyethylene naphthalate (PEN) resin, liquid crystal polyarylate resin, polyamide imide resin, polyether sulfone resin, and mixtures thereof.
  • ITO indium tin oxide
  • a polycarbonate resin Acrylic resin, epoxy resin, polystyrene resin, polyamide resin, polyimide resin, polyethylene resin, polypropylene resin, polyviny
  • polyimide resin polyether ether ketone resin, polyethylene naphthalate (PEN) resin, liquid crystal polyarylate resin, polyamide imide resin, polyether sulfone resin or a mixture thereof may be used.
  • PEN polyethylene naphthalate
  • polypropylene resin polystyrene resin, polyvinylidene chloride resin, PVA resin, polycarbonate resin, PET resin, PEN resin, or a mixture thereof may be used.
  • the members 20 and 21 may be subjected to a surface treatment generally performed as a constituent member of an optical display.
  • the surface treatment may be, for example, a primer treatment or a corona treatment.
  • the two optical members may peel off at the adhesive interface due to the difference in thermal expansion coefficient between the two members.
  • the curing-reactive silicone pressure-sensitive adhesive composition of the present invention can be cured after heating and melting between members to follow gaps and irregularities on the members, and since the cured product has flexibility. The influence of the difference in the coefficient of thermal expansion can be reduced, and the two members 20 and 21 different from each other can be bonded well. Therefore, the pressure-sensitive adhesive material comprising the present invention or a cured product thereof can be suitably used for bonding members different from each other, particularly for bonding an organic material and an inorganic material having a large difference in coefficient of thermal expansion.
  • the laminated body 1 shown in FIG. 1 includes two members, but the number of members is not particularly limited as long as it includes a plurality of members, particularly an optical member.
  • the adhesive material 15 shown in FIG. 1 is formed between the two members 20 and 21 as a whole, but is formed in a part between the two members 20 and 21, for example, in the form of one or a plurality of dots. It may have been done.
  • the adhesive material 15 shown in FIG. 1 is formed between the two members 20 and 21, it may also be formed on the surface 20b opposite to the adhesive surface 20a of the member 20. It may be formed on the surface 21a opposite to the adhesive surface 21b, or may be formed on both surfaces 20b and 21a.
  • FIG. 2 is a flowchart showing a method for manufacturing a laminated body according to an embodiment of the present invention.
  • a method for producing a laminate according to an embodiment of the present invention is a method of arranging the curing-reactive silicone pressure-sensitive adhesive composition of the present invention on one surface or both surfaces of at least one of the two members, and curing the two members by the curing. And a bonding step S1 in which the composition is bonded via a hydrophilic silicone pressure-sensitive adhesive composition, and a curing step S2 in which the composition is cured by heating at a high temperature to start a hydrosilylation reaction.
  • the composition of the present invention is arranged on the member using, for example, the above-mentioned coating method.
  • the composition of the present invention may be arranged on one surface of one member.
  • the curable reactive silicone pressure-sensitive adhesive composition of the present invention arranged on both surfaces of the member or the pressure-sensitive adhesive material which is not used for bonding with other optical members is a release layer or other adhesive surface. It may be used for joining to a member.
  • composition of the present invention may be arranged on one surface of each of the two members in the arrangement step S1.
  • the “one surface” is a surface facing the other optical member.
  • the composition of the present invention may be disposed on the other surface located on the opposite side to the one surface.
  • FIG. 3 is a conceptual diagram of a method for manufacturing a laminate including a heating and melting step.
  • a pressure-sensitive adhesive material 15A made of the curable reactive silicone pressure-sensitive adhesive composition of the present invention is placed on the member 21 as shown in FIG.
  • the step of forming the adhesive material 15B having a smooth surface by molding into a specific shape or the like corresponding to the above or by filling the gap of the member 21 (not shown) is adopted. You may.
  • the pressure-sensitive adhesive material of the present invention is heat-meltable, it can be easily molded into a desired shape such as a sheet, and by having such a step, irregularities and gaps on the member can be filled, if necessary, to follow.
  • the adhesiveness is excellent and a flat adhesive surface can be formed if necessary.
  • the curable reactive silicone pressure-sensitive adhesive composition of the present invention by heating and melting.
  • an adhesive layer having higher strength can be formed by the curing step described later.
  • the curing-reactive silicone pressure-sensitive adhesive composition of the present invention is disposed on one surface or both surfaces of at least one of the two optical members, and the two optical members are It includes a disposing step S1 of laminating via a curing reactive silicone pressure sensitive adhesive composition, and a curing step S2 of curing the composition by heating at a high temperature to promote a hydrosilylation reaction of the composition.
  • step S2 it is preferable to heat at a high temperature of 150° C. or higher to obtain a cured product obtained by curing the composition of the present invention.
  • FIG. 4 is a cross-sectional view showing an optical display of one embodiment of the article of the present invention.
  • An optical display 200 as an embodiment of the present invention includes the above-mentioned laminated body 1 and an image display panel 201.
  • the laminate 1 and the image display panel 201 are adhered to each other via an adhesive layer (not shown).
  • This adhesive layer may be composed of the curable reactive silicone pressure-sensitive adhesive composition of the present invention or a cured product thereof.
  • the second optical member 21 of the laminated body 1 is in contact with the adhesive layer.
  • the first optical member 20 of the laminate 1 may be a polarizing film and the second optical member 21 may be a retardation film.
  • the 1st optical member 20 of the laminated body 1 can be a polarizing film
  • the 2nd optical member 21 can be a surface protection film, for example.
  • the image display panel 201 is not particularly limited as long as it displays image information.
  • a liquid crystal display LCD
  • a polarizing film a retardation film
  • a color filter a viewing angle widening film
  • a brightness a brightness.
  • An improvement film an optical film such as a reflection sheet, a liquid crystal material, a transparent substrate, and a backlight system (usually, the pressure-sensitive adhesive component or the pressure-sensitive adhesive layer adheres to the image display panel is the optical film)
  • the STN method, the VA method, the IPS method and the like are available depending on the control method of the liquid crystal material, but any method may be used.
  • the image display panel 201 may be an in-cell type in which a touch panel function is built in a TFT-LCD, or an on-cell type in which a touch panel function is built in between a glass substrate provided with a polarizing plate and a color filter. ..
  • the image display panel 201 is composed of an organic EL element substrate or a laminated body of an organic EL element substrate and other optical films and the like.
  • the optical display 200 can be a cathode ray tube (CRT) display or a flat panel display (FPD).
  • FPD for example, a light-receiving display device such as an LCD or an electrochromic display (ECD), or an electroluminescent display (ELD) such as an organic EL display or an inorganic EL display, a plasma display (PDP), a surface conduction electron-emitting device.
  • a field emission display (FED) such as a display (SED) and a light emitting display device such as an LED display can be mentioned.
  • FIG. 5 is a cross-sectional view showing an optical display of another embodiment of the article of the present invention.
  • An optical display 300A as another embodiment of the present invention includes an image display panel 301, an optical member 20, and a curable reactive silicone adhesive composition of the present invention disposed between the image display panel 301 and the optical member 20. And an adhesive layer 15 made of a cured product thereof.
  • the image display panel 301 may be an example of the image display panel 201 of FIG.
  • the optical display 300A is arranged, for example, on one surface 301a of the image display panel 301 with the curable layer made of the curable reactive silicone pressure-sensitive adhesive composition of the present invention, which is heated and melted, if necessary. After that, the curable layer can be obtained by curing the curable layer by heating at a high temperature.
  • a curable layer made of the curing reactive silicone pressure-sensitive adhesive composition of the present invention which is heated and melted as necessary, is provided on one side of the optical member 20. It can be obtained by forming the optical member 20 on the surface 20a, arranging the optical member 20 on one surface 301a of the image display panel 301 via the curable layer, and further curing the curable layer by heating. ..
  • FIG. 6 is a cross-sectional view showing an optical display of another embodiment of the article of the present invention.
  • An optical display 300B as another embodiment of the present invention includes an image display panel 301, a touch panel 302, and the curable reactive silicone adhesive composition of the present invention disposed between the image display panel 301 and the touch panel 302. And an adhesive layer 15 made of the cured product.
  • the touch panel 302 is not particularly limited, and may be a resistive film type, a capacitance type, an electromagnetic induction type, or a combination thereof.
  • the touch panel 302 preferably includes at least one cover film, a transparent electrode layer such as an ITO or ATO film, or a glass substrate.
  • the touch panel may further include a decorative film or the like.
  • a display unit such as a liquid crystal/organic EL and a display forming member such as a touch panel or a cover lens, or between the display forming members is provided.
  • the visibility of the optical display can be improved by adhering or sticking with the curing-reactive silicone pressure-sensitive adhesive composition or its cured product.
  • the curing-reactive silicone pressure-sensitive adhesive composition of the present invention has sufficient adhesiveness, can achieve high conformability to unevenness of a member by heating and melting, and has a property of being rapidly cured at a high temperature of 150° C. or higher. Therefore, in the optical display of the present invention, deformation and deterioration of the heat-labile material are suppressed, and further, even when exposed to high temperature and high humidity, the cured product is less likely to become turbid or colored, so that the optical display The reliability as can be improved.
  • the optical display of an embodiment of the article of the present invention further comprises Further comprising a shield substrate provided on a surface facing the display surface of the front panel and having a surface on which a transparent conductive film is formed,
  • the display device may have a structure in which the transparent conductive film and the bezel are electrically connected via a conductive material.
  • a shield substrate such as an Electro-Magnetic Interference (EMI) substrate having a conductive layer on one surface can be further inserted between the display module and the front panel. Since such a shield substrate has an electromagnetic wave shielding function, it prevents the front panel from malfunctioning due to electromagnetic waves emitted from the display module.
  • a conductive layer made of a transparent conductive film such as ITO is formed on one surface of the shield substrate uniformly or in a mesh shape. Then, in order to set the potential of the conductive layer to the GND of the display module, the adhesive member or the like arranged on the outer periphery of the bezel may be formed of a conductive adhesive member such as Ag paste.
  • the bezel of the display module is made of metal and is GND-connected inside the display module.
  • the adhesive member is made of a conductive material, the metal bezel and the conductive layer of the shield substrate can be surely GND-connected, so that a display device having a strong electromagnetic wave resistance can be provided.
  • FIG. 7 is an exploded perspective view showing an optical display of another embodiment of the article of the present invention.
  • FIG. 8 is a partial cross-sectional view showing an optical display of another embodiment of the article of the present invention.
  • a display device 400 (optical display) according to the present invention includes a display panel 110 having a display surface 111, a frame 121, and an opening end 122 inside the frame 121.
  • the bezel 120 that covers the periphery of the display panel 110 on the display surface 111 side with the frame 121, the front panel 130 that is provided on the display surface 111 side of the display panel 110 with the bezel 120 interposed therebetween, and the open end of the bezel 120.
  • a resin member 140 that fills a gap 172 formed at the overlapping portion of the bezel 120 and the display surface 111 without a gap in the direction perpendicular to the display surface 111, and the display surface 111 and the front surface.
  • an OCR 150 filled between the panel 130 and the panel 130.
  • the display surface 111 refers to the entire surface of the display panel 110 on the front panel 130 side.
  • FIG. 8 shows a so-called two-step dam structure in which a dam (resin member) 140 is further provided on the bezel 120 and a space 173 with the front panel 130 is filled with an OCR 150 made of a hardened product.
  • the resin member 140 below the bezel may be only the upper stage or the lower stage unlike the drawing.
  • the display panel 110 is mounted on the backlight unit 171, and the bezel 120 and the backlight unit 171 are fixed by a fitting structure (not shown) to form the display module 170.
  • the entire surface of the display module 170 and the front panel 130 such as a touch panel are attached via the OCR 150.
  • the curing reactivity of the present invention is applied to the inner layer of the front panel 130, the OCR 150, the resin member 140 under the bezel (which may be either the upper stage or the lower stage), and the like.
  • a silicone pressure-sensitive adhesive composition or a cured product thereof can be applied. It should be noted that the present invention is not limited to these applications, and the curing-reactive silicone pressure-sensitive adhesive composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof is used for joining and filling each member shown in FIGS. 7 and 8 and between each member. Can be used.
  • An adhesive sheet made of a cured product or a cured product thereof is a television receiver, a computer monitor, a personal digital assistant monitor, a surveillance monitor, a video camera, a digital camera, a mobile phone, a personal digital assistant, an automobile, etc.
  • the surface shape of such a display device may be a curved surface shape or a curved shape instead of a flat surface, and in addition to various flat panel displays (FPD), a curved surface display used for automobiles (including electric vehicles) and aircrafts.
  • FPD flat panel displays
  • a curved surface display used for automobiles (including electric vehicles) and aircrafts Alternatively, a curved transmissive screen is exemplified.
  • these display devices include various icons such as icons for executing functions or programs on a screen or a display, notification display of e-mail programs, car navigation devices, membranes for speakers, audio devices, air conditioners, etc.
  • the operation buttons of the device may be displayed, and a touch panel function may be added that enables input operation by touching a finger on these icons, notification display, and operation buttons.
  • the device is a display device such as a CRT display, a liquid crystal display, a plasma display, an organic EL display, an inorganic EL display, an LED display, a surface electrolytic display (SED), a field emission display (FED), or a touch panel using these. It can be applied.
  • a display device such as a CRT display, a liquid crystal display, a plasma display, an organic EL display, an inorganic EL display, an LED display, a surface electrolytic display (SED), a field emission display (FED), or a touch panel using these. It can be applied.
  • the curing reactive silicone pressure-sensitive adhesive composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof is excellent in adhesiveness and viscoelasticity, and therefore, a member for a transducer such as a membrane for a speaker (sensor, speaker, actuator, In addition, it can be used as a film or sheet-shaped member (including a generator), and can also be used as a sealing layer or an adhesive layer used in a secondary battery, a fuel cell or a solar cell module.
  • the curing-reactive silicone pressure-sensitive adhesive composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof may be substantially transparent, and does not cause problems of poor curing or deterioration of curability, and various display devices and the like. Since it has excellent adhesion to the base material, the display device for vehicles has good visibility and operability of display contents for a long period of time, and in particular, the display for vehicles has a curved screen or curved display and optionally has a touch panel function. It can be suitably used for devices. For example, JP-A-2017-047767, JP-A-2014-182335, JP-A-2014-063064, JP-A-2013-233852 and the like disclose vehicle display devices having a curved display surface.
  • the pressure-sensitive adhesive layer of the present invention can be suitably applied or replaced as a part or all of the adhesive layer or the pressure-sensitive adhesive layer required to have transparency in these documents.
  • the curable reactive silicone pressure-sensitive adhesive composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof is an adhesive layer or pressure-sensitive adhesive layer which is currently used and is required to have transparency even in other known curved display devices.
  • the composition of the display device and the thickness of the member can be adjusted by a known method in order to further utilize the advantages of the curable reactive silicone pressure sensitive adhesive composition of the present invention or the pressure sensitive adhesive comprising the cured product.
  • the curable reactive silicone pressure sensitive adhesive composition of the present invention or the pressure sensitive adhesive comprising the cured product Preferably.
  • a transparent film-like substrate provided with a curable reactive silicone pressure-sensitive adhesive composition of the present invention or a pressure-sensitive adhesive made of a cured product thereof is used to prevent scratches, stains, fingerprints, and antistatics on the display surface. It may be used for the purpose of preventing reflection, preventing peep, etc.
  • Examples 1 to 3 and Comparative Examples 1 and 2 are experimental examples relating to a curing-reactive silicone pressure-sensitive adhesive composition that is liquid at 25° C., and its composition (parts by mass), viscosity, adhesive strength of the cured product, etc. Is shown in Table 1. In the table, the ratio of the molar amount of silicon atom-bonded hydrogen atoms to the total amount of 1 mol of alkenyl groups in the composition is described as "SiH/Vi ratio".
  • Examples 4 and 5, and Comparative Example 3 are non-fluid at 25° C., and are experimental examples relating to a curing-reactive silicone pressure-sensitive adhesive composition designed to have heat melting property (hot melt property).
  • Table 2 shows the composition (parts by mass), the adhesive strength of the uncured product, and the cured product.
  • the ratio of the molar amount of silicon atom-bonded hydrogen atoms to the total amount of 1 mol of alkenyl groups in the composition is described as "SiH/Vi ratio".
  • Me is a methyl group and Vi is a vinyl group.
  • the following components were used as the component (A).
  • a-1 ViMe 2 SiO(SiMe 2 O) 4745 (SiViMeO) 25 Me 2 Vi
  • a-2 ViMe 2 SiO(SiMe 2 O) 830 SiMe 2 Vi
  • the following components were used as the component (B).
  • d 1,3-bis(diphenylphosphino)propane.
  • d′ The following components were used as the 3,5-dimethyl-1-hexyn-3-ol (E) component.
  • e-1 (Me 3 SiO 1/2 ) 0.46 (SiO 4/2 ) 0.54 (HO 1/2 ) 0.05
  • e-2 (Me 3 SiO 1/2 ) 0.48 (SiO 4/2 ) 0.52 (HO 1/2 ) 0.04
  • e-3 (ViMe 2 SiO 1/2 ) 0.046 (Me 3 SiO 1/2 ) 0.394 (SiO 4/2 ) 0.56 (HO 1/2 ) 0.05
  • F component f-1: xylene f-2: toluene
  • Example 1 The components of Example 1 shown in Table 1 were uniformly mixed to prepare a curing reactive silicone pressure sensitive adhesive composition 1. Mixing was done at 25° C. using a batch mixer. Immediately after preparation, the viscosity of the composition at 25° C. was measured. Further, the composition was stored at 25° C. for 24 hours, and then the viscosity at 25° C. was measured. The results are shown in the columns of "Viscosity of silicone composition ⁇ immediately after preparation>" and "Viscosity of silicone composition ⁇ After preparation and after storage at 25°C for 24 hours>" in Table 1, respectively. As is clear from Table 1, no increase in viscosity with time was observed.
  • the curing-reactive silicone pressure-sensitive adhesive composition 1 was coated on a polyimide film (manufactured by Toray DuPont Co., Ltd., product name Kapton (registered trademark) 100H, thickness 25 ⁇ m) with an applicator immediately after the preparation, and 150 The solvent was removed and cured by heating at 5°C for 5 minutes. Further, it was stored at 25° C. for 1 day to prepare a cured sheet 1-1. Here, the coating amount of the composition was adjusted so that the thickness of the silicone layer after solvent removal and curing was 50 ⁇ m.
  • the sheet is cut into a width of 20 mm and a length of 300 mm, and the pressure-sensitive adhesive layer surface is pressure-bonded and bonded onto a stainless steel plate (SUS304, 50x120x2 mm) using a 2 kg rubber roller to prepare a test piece for measuring the adhesive strength. The force was measured. The results are shown in the column of "Adhesive strength of cured sheet ⁇ cured sheet prepared immediately after composition preparation>" in Table 1.
  • the curing reactive silicone pressure sensitive adhesive composition 1 was stored at 25° C. for 24 hours, and then a cured sheet 1-2 was prepared in the same manner as described above, and a test piece for measuring the adhesive strength was further prepared. It was measured. The results are shown in the column of "Adhesive strength of cured sheet ⁇ cured sheet prepared after composition was prepared and stored at 25°C for 24 hours>" in Table 1.
  • Example 2 In the same manner as in Example 1, the components of Example 2 shown in Table 1 were uniformly mixed to prepare a curing reactive silicone pressure sensitive adhesive composition 2. Immediately after preparation, the viscosity of the composition at 25° C. was measured. Further, the composition was stored at 25° C. for 24 hours, and then the viscosity at 25° C. was measured. The results are shown in the columns of "Viscosity of silicone composition ⁇ immediately after preparation>" and "Viscosity of silicone composition ⁇ After preparation and after storage at 25°C for 24 hours>" in Table 1, respectively. As is clear from Table 1, almost no increase in viscosity with time was observed.
  • a cured sheet 2-2 was prepared in the same manner as in Example 1 and the adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet ⁇ cured sheet prepared after composition was prepared and stored at 25°C for 24 hours>" in Table 1.
  • Example 3 In the same manner as in Example 1, the components of Example 3 shown in Table 1 were uniformly mixed to prepare a curable reactive silicone pressure sensitive adhesive composition 3. Immediately after preparation, the viscosity of the composition at 25° C. was measured. Further, the composition was stored at 25° C. for 24 hours, and then the viscosity at 25° C. was measured. The results are shown in the columns of "Viscosity of silicone composition ⁇ immediately after preparation>" and "Viscosity of silicone composition ⁇ After preparation and after storage at 25°C for 24 hours>" in Table 1, respectively. As is clear from Table 1, no increase in viscosity with time was observed.
  • toluene solvent
  • solvent solvent
  • a film manufactured by Toray DuPont Co., Ltd., product name Kapton (registered trademark) 100H, thickness 25 ⁇ m
  • Kapton registered trademark
  • the coating amount of the composition was adjusted so that the thickness of the silicone layer after solvent removal and curing was 50 ⁇ m.
  • the sheet is cut into a width of 20 mm and a length of 300 mm, and the pressure-sensitive adhesive layer surface is pressure-bonded and bonded onto a stainless steel plate (SUS304, 50x120x2 mm) using a 2 kg rubber roller to prepare a test piece for measuring the adhesive strength. The force was measured. The results are shown in the column of "Adhesive strength of cured sheet ⁇ cured sheet prepared immediately after composition preparation>" in Table 1.
  • the curing reactive silicone pressure-sensitive adhesive composition 3 was stored at 25° C. for 24 hours, and then a cured sheet 3-2 was prepared in the same manner as described above. It was measured. The results are shown in the column of "Adhesive strength of cured sheet ⁇ cured sheet prepared after composition was prepared and stored at 25°C for 24 hours>" in Table 1.
  • Comparative Example 1 In the same manner as in Example 1, the components shown in Table 1 were uniformly mixed to prepare a comparative silicone composition 1. Immediately after preparation, the viscosity of the composition at 25° C. was measured. The results are shown in the column of "Viscosity of silicone composition ⁇ immediately after preparation>" in Table 1.
  • Example 1 a comparative cured sheet 1-1 was prepared and the adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet ⁇ cured sheet prepared immediately after composition preparation>" in Table 1.
  • Comparative Example 2 In the same manner as in Example 3, the components shown in Table 1 were uniformly mixed to prepare a comparative silicone composition 2. Immediately after preparation, the viscosity of the composition at 25° C. was measured. The results are shown in the column of "Viscosity of silicone composition ⁇ immediately after preparation>" in Table 1.
  • Example 3 a comparative cured sheet 2-1 was prepared and the adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet ⁇ cured sheet prepared immediately after composition preparation>" in Table 1.
  • Example 4 The components of Example 4 shown in Table 2 were uniformly mixed. The mixing was performed by using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) and heating and stirring at 80° C. and 100 rpm for 10 minutes. The rotation torque during mixing showed a constant value in about 1 minute and did not change thereafter. The mixture was taken out and cooled to prepare a curing reactive silicone pressure sensitive adhesive composition 4.
  • the curable reactive silicone adhesive composition 4 was used as a polyimide film (manufactured by Toray DuPont Co., Ltd., product name Kapton (registered trademark) 100H, thickness 25 ⁇ m) and a release film (manufactured by Nipper Co., Ltd., FSC-6). Scissors were used, and a 200 ⁇ m thick polyethylene terephthalate film was used as a spacer, and press molding was performed at 70° C. to prepare an uncured sheet 4-1 having a thickness of 200 ⁇ m. By heating the sheet to 70° C., reprocessing including thickness adjustment was possible.
  • the sheet is cut into a width of 20 mm and a length of 300 mm, the release film is separated to expose the adhesive surface, and the adhesive layer surface is pressure-bonded and attached onto a stainless steel plate (SUS304, 50x120x2 mm) using a 2 kg rubber roller.
  • a test piece for measuring the adhesive strength was prepared and the adhesive strength was measured. The results are shown in the column of "Adhesive strength of uncured sheet ⁇ uncured sheet prepared immediately after composition preparation>" in Table 2.
  • the uncured sheet 4-1 was heated and cured at 150° C. for 5 minutes to prepare a cured sheet 4-1. This is cut into a width of 20 mm and a length of 300 mm, the release film is separated, the adhesive surface is exposed, and the adhesive layer surface is pressure-bonded and bonded onto a stainless steel plate (SUS304, 50x120x2 mm) using a 2 kg rubber roller. A test piece for measuring the adhesive strength was prepared and the adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet ⁇ cured sheet prepared immediately after composition preparation>" in Table 2.
  • the curing reactive silicone pressure sensitive adhesive composition 4 was stored at 25° C. for 24 hours, and then an uncured sheet 4-2 was prepared by the same method as described above. By heating the sheet to 70° C., reprocessing including thickness adjustment was possible. Next, the uncured sheet 4-2 was heated and cured at 150° C. for 5 minutes to prepare a cured sheet 4-2. This is cut into a width of 20 mm and a length of 300 mm, the release film is separated, the adhesive surface is exposed, and the adhesive layer surface is pressure-bonded and bonded onto a stainless steel plate (SUS304, 50x120x2 mm) using a 2 kg rubber roller. A test piece for measuring the adhesive strength was prepared and the adhesive strength was measured. The results are shown in the column of “Adhesive strength of cured sheet ⁇ cured sheet prepared after composition preparation and storage at 25° C. for 24 hours>” in Table 2.
  • Example 5 In the same manner as in Example 4, the components of Example 5 shown in Table 2 were uniformly mixed. The rotation torque during mixing showed a constant value in about 1 minute and did not change thereafter. The mixture was taken out and cooled to prepare a curing reactive silicone pressure sensitive adhesive composition 5.
  • Example 4 a 200 ⁇ m-thick uncured sheet 5-1 was prepared using the curing-reactive silicone pressure-sensitive adhesive composition 5. By heating the sheet to 70° C., reprocessing including thickness adjustment was possible. The adhesive force of the uncured sheet 5-1 was measured in the same manner as in Example 4. The results are shown in the column of "Adhesive strength of uncured sheet ⁇ uncured sheet prepared immediately after composition preparation>" in Table 2. Next, in the same manner as in Example 4, the uncured sheet 5-1 was heated and cured at 150° C. for 5 minutes to prepare a cured sheet 5-1 and its adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet ⁇ cured sheet prepared immediately after composition preparation>" in Table 2.
  • Example 4 the curing reactive silicone pressure-sensitive adhesive composition 5 was stored at 25° C. for 24 hours, and then an uncured sheet 5-2 was prepared by the same method as described above. By heating the sheet to 70° C., reprocessing including thickness adjustment was possible. Next, in the same manner as in Example 4, the uncured sheet 5-2 was heated and cured at 150° C. for 5 minutes to prepare a cured sheet 5-2, and the adhesive strength was measured. The results are shown in the column of “Adhesive strength of cured sheet ⁇ cured sheet prepared after composition preparation and storage at 25° C. for 24 hours>” in Table 2.
  • compositions 1 and 2 solvent type, composition 3: solventless type
  • the viscosity did not change, and the adhesive strength of the cured sheet obtained by curing the composition immediately after production/after storage was almost the same.
  • the amount of the phosphorus-based hydrosilylation reaction retarder was different in Examples 1 and 2, even a small amount (Example 2) achieved sufficient technical effects.
  • Comparative Examples 1 and 2 lacking the component (D) even if the composition was similar to that of the Example, it gelated after storage, and a one-pack type liquid curing reaction excellent in storage stability and adhesive properties. No silicone-based pressure-sensitive adhesive composition could be obtained.

Abstract

The present invention relates to a composition for a curing-reactive silicone adhesive agent, the composition comprising (A) a linear or branched organopolysiloxane having in each molecule at least two groups containing aliphatic unsaturated carbon-carbon bonds, (B) an organohydrogen polysiloxane having in each molecule at least two silicon-bonded hydrogen atoms, (C) a hydrosilylation reaction catalyst, and (D) a hydrosilylation reaction retarding agent containing phosphorus, wherein the (B) component content is an amount such that there are at least 0.5 moles of the silicon-bonded hydrogen atoms in the (B) component per one mole of all of the aliphatic unsaturated carbon-carbon bonds in the composition. The present invention makes it possible to provide a composition for a curing-reactive silicone adhesive agent, the composition having high storage stability and not thickening in a relatively short time, even as a one-component type.

Description

硬化反応性シリコーン粘着剤組成物及びその硬化物並びにそれらの用途Curing reactive silicone pressure sensitive adhesive composition, cured product thereof and uses thereof
　本発明は、硬化反応性シリコーン粘着剤組成物及びその硬化物、並びに、当該組成物又はその硬化物の用途に関する。 The present invention relates to a curable reactive silicone pressure-sensitive adhesive composition and a cured product thereof, and use of the composition or a cured product thereof.
　シリコーン材料は耐熱性、耐薬品性、電気絶縁性等の優れた性能を有することから、種々の用途に用いられている。シリコーン材料はプラスチック、金属、ガラス、セラミック、紙、木材等の様々な基材上に形成することができ、用途も日用品、医療用品、電子製品等多岐に渡る。シリコーン材料は通常、オルガノポリシロキサンをヒドロシリル化反応によって架橋させることによって得られる。特に、加熱によりヒドロシリル化反応を用いて架橋されるシリコーン系粘着剤は広く知られている。ヒドロシリル化反応は室温でも反応が進行するため、ヒドロシリル化反応触媒を添加した直後から系全体が硬化ないしゲル化して取り扱いが困難となる。このため、通常は、ヒドロシリル化反応触媒を硬化反応の直前に液状のシリコーン組成物中に添加して均一に混合しており、また、塗布作業までの取扱作業時間（数時間程度）を確保するために、ヒドロシリル化反応抑制剤を事前に当該組成物中に添加しておくことが一般的である。 -Silicone materials are used for various purposes because they have excellent properties such as heat resistance, chemical resistance, and electrical insulation. Silicone materials can be formed on various substrates such as plastic, metal, glass, ceramics, paper, and wood, and have various applications such as daily necessities, medical supplies, and electronic products. Silicone materials are typically obtained by crosslinking organopolysiloxanes by a hydrosilylation reaction. In particular, silicone-based pressure-sensitive adhesives that are crosslinked by heating using a hydrosilylation reaction are widely known. Since the hydrosilylation reaction proceeds even at room temperature, the entire system is hardened or gelled immediately after the addition of the hydrosilylation reaction catalyst, making it difficult to handle. Therefore, the hydrosilylation reaction catalyst is usually added to the liquid silicone composition just before the curing reaction and uniformly mixed, and the handling work time up to the coating work (about several hours) is secured. Therefore, it is common to add a hydrosilylation reaction inhibitor to the composition in advance.
　特許文献１には、ヒドロシリル化反応により硬化する硬化性シリコーン組成物にリン含有ヒドロシリル化反応遅延剤を含有することが開示されている。しかし、特許文献１には粘着性組成物に関して、記載も示唆もされていない。 Patent Document 1 discloses that a curable silicone composition that is cured by a hydrosilylation reaction contains a phosphorus-containing hydrosilylation reaction retarder. However, Patent Document 1 does not describe or suggest the adhesive composition.
特開２００７－３０８５４２号公報JP, 2007-308542, A
本発明者らは、ヒドロシリル化反応により硬化するシリコーン系粘着剤について、新たな課題を見出した。すなわち、ヒドロシリル化反応は、上記のとおり、触媒添加直後から進行するため、混合後の組成物のポットライフが短く、室温でも比較的短時間で増粘、ゲル化するなど、取扱作業性に問題を抱えている。この問題を解決するために、上記のとおり、ヒドロシリル化反応抑制剤が使用されているが、従来のヒドロシリル化反応抑制剤により得られる保存安定性、取扱作業性は改善の余地がある。また、部分的にでも増粘ないしゲル化した状態で硬化した場合、組成物の架橋状態が不均一になりやすく、最終的な粘着性シートの状態において、本来の粘着性が実現できなくなる場合がある。 The present inventors have found a new problem regarding a silicone-based pressure-sensitive adhesive that is cured by a hydrosilylation reaction. That is, since the hydrosilylation reaction proceeds immediately after the catalyst is added as described above, the pot life of the composition after mixing is short, and the viscosity is increased in a relatively short time even at room temperature, and gelation occurs. Have a In order to solve this problem, hydrosilylation reaction inhibitors have been used as described above, but there is room for improvement in storage stability and handling workability obtained by conventional hydrosilylation reaction inhibitors. In addition, if the composition is partially thickened or cured in a gelled state, the crosslinked state of the composition tends to be non-uniform, and in the final state of the adhesive sheet, the original adhesiveness may not be realized. is there.
更に、近年、表示装置等の製造において、部材上の凹凸や間隙を充填して、部材間の仮固定や永久接着を行う、加熱溶融性のシリコーン粘着剤組成物やその成型物であるホットメルト性粘着シートが求められているが、このような加熱溶融性粘着材は、２５℃で非流動性であるので、液状のシリコーン組成物と異なり、ヒドロシリル化反応触媒を硬化反応の直前に室温で添加し、機械力で均一に組成物中に分散させることがその性質上、困難である。このため、ヒドロシリル化反応触媒を均一に添加するためには、組成物を加熱溶融する工程が必要となるが、ヒドロシリル化反応は加熱条件下で進行しやすいので、当該ヒドロシリル化反応触媒の添加のための加熱溶融段階で組成物全体の硬化反応が進行しやすく、得られた加熱溶融性粘着材が十分な硬化反応性や成型性を維持できない場合がある。同様の問題は成型時にも発生しうるため、成型した加熱溶融性粘着材(例えば、ホットメルト性粘着シート)においても、数日の保管後に、成型した組成物全体が完全に硬化して硬化反応性や加熱溶融性を失い、加熱溶融性粘着材として使用できない結果となる場合がある。 Furthermore, in recent years, in the manufacture of display devices and the like, hot melt, which is a heat-meltable silicone pressure-sensitive adhesive composition or a molded product thereof, is used to fill irregularities or gaps on members to perform temporary fixing or permanent adhesion between members. However, since such a heat-meltable pressure-sensitive adhesive material is non-fluid at 25° C., unlike a liquid silicone composition, a hydrosilylation reaction catalyst is used at room temperature immediately before the curing reaction. Due to its nature, it is difficult to add and uniformly disperse in the composition by mechanical force. Therefore, in order to uniformly add the hydrosilylation reaction catalyst, a step of heating and melting the composition is necessary, but since the hydrosilylation reaction easily proceeds under heating conditions, it is necessary to add the hydrosilylation reaction catalyst. In this case, the curing reaction of the entire composition is likely to proceed in the heating and melting stage, and the resulting heat-meltable adhesive material may not be able to maintain sufficient curing reactivity and moldability. Since the same problem can occur during molding, even in a molded heat-meltable adhesive material (for example, a hot-melt adhesive sheet), the molded composition as a whole is completely cured after a few days of storage and a curing reaction occurs. In some cases, it loses its heat-melting property and heat-melting property and cannot be used as a heat-melting adhesive.
　本発明は上記課題を解決すべくなされたものであり、室温で液状又は非流動性（ホットメルト性を含む）であり、単一組成物の形態であっても、その保存安定性、取扱作業性、及び、成型性に優れ、且つ、高温で加熱することにより速やかに硬化して、高い接着強度を得ることが可能な硬化反応性シリコーン粘着剤組成物、及び、圧着により高い接着力が得られるその硬化物を提供することをその目的とする。更に、本発明は、前記硬化反応性シリコーン粘着剤組成物及びその硬化物の用途である粘着材を提供することを目的とする。同様に、本発明は、前記硬化反応性シリコーン粘着剤組成物又はその硬化物からなる層を備える積層体及び当該積層体の製造方法を提供することを目的とする。 The present invention has been made to solve the above problems, and is liquid or non-fluid at room temperature (including hot-melt property), even in the form of a single composition, its storage stability, handling work Property, moldability, and a curable reactive silicone pressure-sensitive adhesive composition that can be cured quickly by heating at high temperature to obtain high adhesive strength, and high adhesive strength by pressure bonding Its purpose is to provide a cured product thereof. A further object of the present invention is to provide a pressure-sensitive adhesive material that is used for the above-mentioned curing reactive silicone pressure-sensitive adhesive composition and its cured product. Similarly, it is an object of the present invention to provide a laminate including a layer of the curing reactive silicone pressure-sensitive adhesive composition or a cured product thereof, and a method for producing the laminate.
　本発明の目的は、
（Ａ）一分子中に少なくとも２個の脂肪族不飽和炭素－炭素結合含有基を有する直鎖状又は分岐鎖状オルガノポリシロキサン、
（Ｂ）一分子中に少なくとも２個のケイ素結合水素原子を有するオルガノハイドロジェンポリシロキサン、
（Ｃ）ヒドロシリル化反応用触媒、及び、
（Ｄ）リン含有ヒドロシリル化反応遅延剤、
を含み、
（Ｂ）成分の含有量が、組成物中の全脂肪族不飽和炭素－炭素結合１モルに対して、（Ｂ）成分中のケイ素結合水素原子が０．５モル以上となる量である、硬化反応性シリコーン粘着剤組成物によって達成される。 The purpose of the present invention is to
(A) a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule,
(B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule,
(C) catalyst for hydrosilylation reaction, and
(D) Phosphorus-containing hydrosilylation reaction retarder,
Including,
The content of the component (B) is such that the silicon-bonded hydrogen atoms in the component (B) are 0.5 mol or more per 1 mol of the total aliphatic unsaturated carbon-carbon bond in the composition. Achieved by a cure reactive silicone adhesive composition.
（Ｄ）成分のリン含有ヒドロシリル化反応遅延剤は、ホスフィン系化合物、リン酸系化合物、ホスホン酸系化合物、ホスフィンオキサイド系化合物、亜リン酸系化合物、及び、亜ホスホン酸系化合物からなる群から選らばれる少なくとも一種であることが好ましい。 The phosphorus-containing hydrosilylation reaction retarder of the component (D) is selected from the group consisting of phosphine compounds, phosphoric acid compounds, phosphonic acid compounds, phosphine oxide compounds, phosphorous acid compounds, and phosphonous acid compounds. It is preferably at least one selected.
（Ｄ）成分は、ジフェニルホスフィン、トリフェニルホスフィン、ジメチルフェニルホスフィン、ジエチルフェニルホスフィン、トリプロピルホスフィン、ジシクロヘキシルフェニルホスフィン、ビス(ジフェニルホスフィノ)メタン、１,２－ビス(ジフェニルホスフィノ)エタン、１,２－ビス(ジフェニルホスフィノ)プロパン、１,３－ビス(ジフェニルホスフィノ)プロパン、１,４－ビス(ジフェニルホスフィノ)ブタン、２，３－ビス(ジフェニルホスフィノ)ブタン、１,５－ビス(ジフェニルホスフィノ)ペンタン、１,６－ビス(ジフェニルホスフィノ)ヘキサン、ビス（２-ジフェニルホスフィノエチル）フェニルホスフィンビス(ジフェニルホスフィノ)アセチレン、１,１－ビス(ジフェニルホスフィノ)エチレン、１,２－ビス(ジフェニルホスフィノ)エチレン、１,１－ビス(ジフェニルホスフィノ)フェロセン、１,３－ビス(ジシクロヘキシルホスフィノ)プロパン、１,２－ビス(ジメチルホスフィノ)エタン、１,２－ビス(ジメチルホスフィノ)ベンゼン、及び、１,２－ビス(ジフェニルホスフィノ)ベンゼンからなる群から選らばれる少なくとも一種のホスフィン系化合物であることが好ましい。 Component (D) includes diphenylphosphine, triphenylphosphine, dimethylphenylphosphine, diethylphenylphosphine, tripropylphosphine, dicyclohexylphenylphosphine, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1 1,2-bis(diphenylphosphino)propane,1,3-bis(diphenylphosphino)propane,1,4-bis(diphenylphosphino)butane,2,3-bis(diphenylphosphino)butane,1,5 -Bis(diphenylphosphino)pentane, 1,6-bis(diphenylphosphino)hexane, bis(2-diphenylphosphinoethyl)phenylphosphine bis(diphenylphosphino)acetylene, 1,1-bis(diphenylphosphino) Ethylene, 1,2-bis(diphenylphosphino)ethylene, 1,1-bis(diphenylphosphino)ferrocene, 1,3-bis(dicyclohexylphosphino)propane, 1,2-bis(dimethylphosphino)ethane, It is preferably at least one phosphine compound selected from the group consisting of 1,2-bis(dimethylphosphino)benzene and 1,2-bis(diphenylphosphino)benzene.
 (Ｄ)成分の配合量は、(Ｃ)成分中の金属原子１モルに対して、０.０１～１,０００モルとなる範囲の量であることが好ましく、(Ｃ)成分中の金属原子１モルに対して、０．３０～１０モルであることが特に好ましい。 The compounding amount of the component (D) is preferably in the range of 0.01 to 1,000 moles based on 1 mole of the metal atom in the component (C). It is particularly preferable that the amount is 0.30 to 10 mol per 1 mol.
本発明の硬化反応性シリコーン粘着剤組成物は、（Ｅ）分子内にＲ３ＳｉＯ１／２（式中、Ｒは互いに独立して一価有機基を表す）で表されるシロキサン単位（Ｍ単位）及び、ＳｉＯ４／２で表されるシロキサン単位（Ｑ単位）を含むオルガノポリシロキサン樹脂を更に含むことが好ましい。 The curing-reactive silicone pressure-sensitive adhesive composition of the present invention comprises a siloxane unit (M) represented by (E) R 3 SiO 1/2 (wherein R independently represents a monovalent organic group) in the molecule. Unit) and an organopolysiloxane resin containing a siloxane unit (Q unit) represented by SiO 4/2 .
（Ｅ）成分の少なくとも一部が、分子内に（Ａｌｋ）Ｒ’２ＳｉＯ１／２（式中、Ａｌｋは互いに独立して脂肪族不飽和炭素－炭素結合含有基を表し、Ｒ’は互いに独立して脂肪族不飽和炭素－炭素結合不含基を表す）で表されるシロキサン単位（Ｍ単位）、及び、ＳｉＯ４／２で表されるシロキサン単位（Ｑ単位）を少なくとも含む硬化反応性オルガノポリシロキサン樹脂が好ましい。 At least a part of the component (E) is (Alk)R′ 2 SiO 1/2 (wherein Alk each independently represents an aliphatic unsaturated carbon-carbon bond-containing group, and R′ are mutually independent). Curing reactivity containing at least a siloxane unit (M unit) represented by an aliphatic unsaturated carbon-carbon bond-free group) and a siloxane unit (Q unit) represented by SiO 4/2 Organopolysiloxane resins are preferred.
(Ｅ)成分の含有量は、（Ａ）成分、（Ｂ）成分、及び、（Ｅ）成分の質量の総和の０．１質量％から９０質量％であることが好ましい。 The content of the component (E) is preferably 0.1% by mass to 90% by mass of the total mass of the components (A), (B) and (E).
本発明の硬化反応性シリコーン粘着剤組成物は、（Ｆ）溶剤を更に含んでいてもよい。 The curing reactive silicone pressure-sensitive adhesive composition of the present invention may further contain (F) a solvent.
本発明の硬化反応性シリコーン粘着剤組成物は、一液型又は単一の組成物であることが好ましい。 The curing-reactive silicone pressure-sensitive adhesive composition of the present invention is preferably a one-component type or a single composition.
本発明の硬化反応性シリコーン粘着剤組成物は、組成物全体として、２５℃において流動性であってよい。 The cure reactive silicone pressure sensitive adhesive composition of the present invention may be fluid at 25° C. as a whole composition.
上記の硬化反応性シリコーン粘着剤組成物は、組成物を硬化させて得られる厚み５０μｍの粘着層を、ＳＵＳ板に対して貼り合わせ、ＪＩＳ　Ｚ０２３７に準じて１８０°引き剥がし試験方法を用いて引張速度３００ｍｍ/ｍｉｎにて測定された粘着力が、０．１ｇｆ/ｉｎｃｈ以上であることが好ましい。 The above-mentioned curing-reactive silicone pressure-sensitive adhesive composition was laminated with a 50-μm-thick pressure-sensitive adhesive layer obtained by curing the composition on a SUS plate, and pulled using a 180° peel test method according to JIS Z0237. The adhesive force measured at a speed of 300 mm/min is preferably 0.1 gf/inch or more.
本発明の硬化反応性シリコーン粘着剤組成物は、組成物全体として、２５℃において非流動性であり、２５℃～１５０℃までの間に軟化点を有してもよい。更に、本発明の硬化反応性シリコーン粘着剤組成物は、硬化反応前の状態において粘着性を有するものであってよい。 The curable reactive silicone pressure-sensitive adhesive composition of the present invention is non-flowable at 25° C. as a whole and may have a softening point between 25° C. and 150° C. Furthermore, the curing-reactive silicone pressure-sensitive adhesive composition of the present invention may have tackiness in a state before the curing reaction.
上記の硬化反応性シリコーン粘着剤組成物は、組成物を硬化させて得られる厚み２００μｍの粘着層を、ＳＵＳ板に対して貼り合わせ、ＪＩＳ　Ｚ０２３７に準じて１８０°引き剥がし試験方法を用いて引張速度３００ｍｍ/ｍｉｎにて測定された粘着力が、０．１ｇｆ/ｉｎｃｈ以上であることが好ましい。 The above-mentioned curing-reactive silicone pressure-sensitive adhesive composition was laminated with a 200-μm-thick pressure-sensitive adhesive layer obtained by curing the composition on a SUS plate, and pulled by a 180° peel test method according to JIS Z0237. The adhesive force measured at a speed of 300 mm/min is preferably 0.1 gf/inch or more.
　本発明は、上記の硬化反応性シリコーン粘着剤組成物（好適には、組成物全体として、２５℃において非流動性であり、２５℃～１５０℃までの間に軟化点を有するもの）から、少なくともなる部材、部品、又は、シートにも関する。 The present invention comprises the above-mentioned curing reactive silicone pressure-sensitive adhesive composition (preferably, the composition as a whole is non-flowable at 25° C. and has a softening point between 25° C. and 150° C.), It also relates to at least a member, component or sheet.
ここで、非流動性とは、無負荷の状態で流動しないことを意味し、例えば、ＪＩＳ　Ｋ　６８６３－１９９４「ホットメルト接着剤の軟化点試験方法」で規定されるホットメルト接着剤の環球法による軟化点試験方法で測定される軟化点が、２５℃～１５０℃までの間にある状態を示す。 Here, non-fluidity means that it does not flow in an unloaded state, and for example, the ring-and-ball method for hot melt adhesives defined in JIS K 6863-1994 “Test method for softening point of hot melt adhesives”. The softening point measured by the softening point test method according to 1. is in the range of 25°C to 150°C.
　同様に、本発明は、上記の硬化反応性シリコーン粘着剤組成物（好適には、組成物全体として、２５℃において非流動性であり、２５℃～１５０℃までの間に軟化点を有するもの）からなる加熱溶融性粘着材にも関する。 Similarly, the present invention relates to the above-mentioned cure-reactive silicone pressure-sensitive adhesive composition (preferably, the composition as a whole is non-flowable at 25°C and has a softening point between 25°C and 150°C). ) Is also a heat-meltable adhesive material consisting of.
　本発明は、上記の硬化反応性シリコーン粘着剤組成物の硬化物にも関する。 The present invention also relates to a cured product of the above curing reactive silicone adhesive composition.
本発明は、上記の硬化反応性シリコーン粘着剤組成物を１５０℃未満の温度条件において塗布又は成型後 、１５０℃以上に加熱して硬化させる工程を含む、前記硬化物の製造方法にも関する。 The present invention also relates to a method for producing the above-mentioned cured product, which comprises a step of applying the above-mentioned curable reactive silicone pressure-sensitive adhesive composition under a temperature condition of less than 150° C. or curing it and then heating it to 150° C. or higher for curing.
本発明は、上記の硬化反応性シリコーン粘着剤組成物の硬化物からなる粘着材にも関する。 The present invention also relates to an adhesive material comprising a cured product of the above-mentioned curing reactive silicone adhesive composition.
本発明は、上記の硬化反応性シリコーン粘着剤組成物からなる層又は部材を備える、積層体にも関する。同様に、本発明は、上記の硬化反応性シリコーン粘着剤組成物の硬化物からなる層又は部材を備える、積層体にも関する。 The present invention also relates to a laminate including a layer or member made of the above-mentioned curing reactive silicone pressure-sensitive adhesive composition. Similarly, the present invention also relates to a laminate provided with a layer or member comprising a cured product of the above-mentioned curing reactive silicone adhesive composition.
　これらの積層体は、剥離層を備えたシート状部材を少なくとも一部に含むものであってよく、例えば、上記の組成物又はその硬化物から少なくともなる部材、部品又はシートは、剥離層を備えたシート状部材と対向するように配置され、使用時に剥離層から引き剥がすことで、上記の組成物又はその硬化物を粘着材として使用する、剥離性の積層体であってよい。 These laminates may include at least a part of a sheet-like member having a release layer, and for example, a member, a part or a sheet made of the above composition or a cured product thereof has a release layer. It may be a peelable laminate which is arranged so as to face the sheet-shaped member and is peeled off from the peeling layer at the time of use to use the above composition or a cured product thereof as an adhesive.
また、これらの積層体は、表示装置、電子部品又は太陽電池モジュールから選ばれる少なくとも１種であってよく、例えば、液晶ディスプレイ、又は、有機ＥＬディスプレイである表示装置であってよい。また、上記の硬化反応性シリコーン粘着剤組成物又はその硬化物は、ＬＥＤ、マイクロＬＥＤ等の電子部品の封止材として用いられてもよい。 In addition, these laminated bodies may be at least one kind selected from a display device, an electronic component or a solar cell module, and may be, for example, a display device which is a liquid crystal display or an organic EL display. Further, the above-mentioned curing reactive silicone pressure-sensitive adhesive composition or a cured product thereof may be used as a sealing material for electronic parts such as LEDs and micro LEDs.
好適には、本発明の積層体は、少なくとも１つの基板と共に各種の物品に使用することができる。例えば、前記基板は、画像表示パネル、タッチパネル、光学フィルム、又は、表面若しくは裏面保護シートであってもよい。この場合、前記物品は表示装置（ディスプレイ）であることが好ましい。そして、前記表示装置が、液晶ディスプレイ、又は、有機ＥＬディスプレイであることが更に好ましい。また、前記基板は、太陽電池セル、封止材層、又は、表面若しくは裏面保護シートであってもよい。この場合、前記物品は太陽電池モジュールであることが好ましい。 Suitably, the laminate of the present invention can be used in various articles together with at least one substrate. For example, the substrate may be an image display panel, a touch panel, an optical film, or a front surface or back surface protection sheet. In this case, the article is preferably a display device (display). Further, it is more preferable that the display device is a liquid crystal display or an organic EL display. Further, the substrate may be a solar cell, a sealing material layer, or a front surface or back surface protection sheet. In this case, the article is preferably a solar cell module.
本発明は、これらの積層体の製造方法にも関する。これらの製造方法で得られる積層体は、剥離性粘着材シート等の中間材であってもよく、粘着材層を備えた表示装置等の最終製品又はその前駆体であってもよい。 The invention also relates to the process for producing these laminates. The laminate obtained by these manufacturing methods may be an intermediate material such as a peelable pressure-sensitive adhesive sheet, or a final product such as a display device having a pressure-sensitive adhesive layer or a precursor thereof.
本発明の積層体の製造方法は、上記の硬化反応性シリコーン粘着剤組成物を８０℃以上に加熱して溶融させ、溶融物を成型乃至充填する工程を含むものであってよい。 The method for producing a laminate of the present invention may include the step of heating the above-mentioned curable reactive silicone pressure-sensitive adhesive composition to 80° C. or higher to melt it, and molding or filling the melt.
本発明の積層体の製造方法は、上記の硬化反応性シリコーン粘着剤組成物を少なくとも１つの部材上又は部材間に配置した後又は配置と同時に、当該硬化反応性シリコーン粘着剤組成物を１５０℃以上に加熱する工程を含むものであってよい。 The method for producing a laminate of the present invention comprises the step of placing the curing-reactive silicone pressure-sensitive adhesive composition at 150° C. after or at the same time as disposing the curing-reactive silicone pressure-sensitive adhesive composition on or between at least one member. It may include the above heating step.
　本発明の積層体の製造方法は、上記の硬化反応性シリコーン粘着剤組成物又はその硬化物を部材間に挟んで積層する工程、及び、当該硬化反応性シリコーン粘着剤組成物又はその硬化物により当該部材を圧着する工程を含むものであってよい。 The method for producing a laminate of the present invention comprises a step of laminating the above-mentioned curable reactive silicone pressure sensitive adhesive composition or a cured product thereof between members, and the curing reactive silicone pressure sensitive adhesive composition or a cured product thereof. It may include a step of crimping the member.
本発明により、室温で液状又は非流動性（ホットメルト性を含む）であり、単一組成物の形態であっても、その保存安定性、取扱作業性、及び、成型性に優れ、且つ、高温で加熱することにより速やかに硬化して、高い接着強度を得ることが可能な硬化反応性シリコーン粘着剤組成物を提供することができる。また、圧着により高い接着力が得られるその硬化物を提供することができる。更に、本発明により、前記硬化反応性シリコーン粘着剤組成物及びその硬化物の用途である粘着材を提供でき、且つ、前記硬化反応性シリコーン粘着剤組成物又はその硬化物からなる層を備える積層体及び当該積層体の製造方法を提供することができる。 According to the present invention, it is liquid or non-flowable (including hot melt) at room temperature, and even in the form of a single composition, its storage stability, handling workability, and moldability are excellent, and It is possible to provide a curing-reactive silicone pressure-sensitive adhesive composition that can be cured rapidly by heating at a high temperature to obtain high adhesive strength. Further, it is possible to provide a cured product thereof which can obtain a high adhesive force by pressure bonding. Furthermore, according to the present invention, it is possible to provide a pressure-sensitive adhesive which is an application of the above-mentioned cured reactive silicone pressure-sensitive adhesive composition and a cured product thereof, and a laminate comprising a layer formed of the above-mentioned cured reactive silicone pressure-sensitive adhesive composition or a cured product thereof. A body and a method for manufacturing the laminate can be provided.
特に、本発明の硬化反応性シリコーン粘着剤組成物が液状組成物の形態である場合、ヒドロシリル化反応触媒を含む一液型組成物であっても短時間で増粘乃至ゲル化することがなく、長期間保管することができるので、貯蔵安定性及び保存安定性に優れ、且つ、取扱作業性に優れる。更に、５０℃程度の比較的高温となる保管条件であっても、短期間で増粘乃至ゲル化しないため、高温条件における保存安定性及び取扱作業性に優れる。 In particular, when the curable reactive silicone pressure-sensitive adhesive composition of the present invention is in the form of a liquid composition, even a one-pack composition containing a hydrosilylation reaction catalyst does not thicken or gel in a short time. Since it can be stored for a long period of time, it has excellent storage stability and storage stability, and also has excellent handling workability. Furthermore, even under storage conditions at a relatively high temperature of about 50° C., it does not thicken or gel in a short period of time, and therefore it is excellent in storage stability and handling workability under high temperature conditions.
　本発明の硬化反応性シリコーン粘着剤組成物を使用することで、上記の一液型組成物が設計可能であるが、このような組成物は、使用時に成分を混合する必要がないので、ユーザーにおける組成物の調製工程が不要であり、且つ、当該混合の際に混合・分散不良の問題を生じることがないという利点を有する。更に、上記の一液型組成物を使用することで、仕込みミス等で成分量比の誤りに起因する、工程上のエラーを本質的に回避できるため、簡易なプロセスで安定的に使用することができ、製品としての取扱作業性、工業的生産性及び得られる接着剤の品質を大幅に改善できる利点がある。 By using the curable reactive silicone pressure-sensitive adhesive composition of the present invention, the above one-pack type composition can be designed. However, since such a composition does not require the components to be mixed at the time of use, it can be used by the user. It has an advantage that the step of preparing the composition in 1) is unnecessary and the problem of poor mixing/dispersion does not occur during the mixing. Furthermore, by using the above one-pack composition, it is possible to essentially avoid an error in the process due to an error in the component ratio due to a mistake in charging, etc. And has the advantage that the handling workability as a product, industrial productivity, and the quality of the adhesive obtained can be greatly improved.
本発明の硬化反応性シリコーン粘着剤組成物は硬化により優れた接着力を備える感圧接着層を形成することができ、また、被着体から当該感圧接着層を剥離する際に当該感圧接着層の凝集破壊が生じにくい。好ましくは、前記感圧接着層は被着体から界面剥離可能である。 The curing-reactive silicone pressure-sensitive adhesive composition of the present invention can form a pressure-sensitive adhesive layer having excellent adhesive force by curing, and when the pressure-sensitive adhesive layer is peeled from an adherend, Cohesive failure of the adhesive layer is unlikely to occur. Preferably, the pressure-sensitive adhesive layer is interfacially peelable from the adherend.
　また、本発明の硬化反応性シリコーン粘着剤組成物は２５℃において非流動性であり、２５℃～１５０℃までの間に軟化点を有し、加熱溶融性を備えてもよい。本発明の組成物において、ヒドロシリル化触媒の添加乃至組成物の成型時の加熱溶融によって硬化反応が進行することが抑制されるため、本発明により、十分な硬化反応性や成型性を有する、加熱溶融性の硬化反応性シリコーン粘着剤組成物及びその成型物を提供することができる。したがって、本発明の硬化反応性シリコーン粘着剤組成物は加熱により柔軟化乃至流動可能である。これにより、本発明の硬化反応性シリコーン粘着剤組成物は溶融状態で部材上の凹凸に良好に追従して段差を充填することができ、ギャップフィル性に優れている。また、本発明の硬化反応性シリコーン粘着剤組成物は加熱溶融性を有することができるので、溶融状態の流動体をシート状等の所望の形状に成型することができる。硬化反応前の硬化反応性シリコーン粘着剤組成物からなるシート等の成型物はそれ自体が加熱溶融性、粘着性及び硬化反応性を有しているので、粘着力を利用して所望の部位に配置して加熱溶融することで、その流動物を基材の凹凸に流入せしめてもよい。　 The curing-reactive silicone pressure-sensitive adhesive composition of the present invention may be non-fluid at 25° C., have a softening point between 25° C. and 150° C., and may have heat-melting property. In the composition of the present invention, since the progress of the curing reaction is suppressed by the addition of the hydrosilylation catalyst or the heating and melting at the time of molding the composition, the present invention provides sufficient curing reactivity and moldability. A meltable, curing-reactive silicone pressure-sensitive adhesive composition and a molded product thereof can be provided. Therefore, the curable reactive silicone pressure-sensitive adhesive composition of the present invention can be softened or flowable by heating. As a result, the curable reactive silicone pressure-sensitive adhesive composition of the present invention can excellently fill gaps by following unevenness on a member in a molten state, and has excellent gap fill property. Further, since the curable reactive silicone pressure-sensitive adhesive composition of the present invention can have heat-melting property, the fluid in a molten state can be molded into a desired shape such as a sheet. A molded article such as a sheet made of a curing-reactive silicone pressure-sensitive adhesive composition before the curing reaction has heat-melting property, adhesive property and curing reactivity by itself, and therefore, it can be applied to a desired site by using adhesive force. By arranging and heating and melting, the fluid may be caused to flow into the irregularities of the base material. ‥
本発明の一実施形態の積層体を示す断面図である。It is sectional drawing which shows the laminated body of one Embodiment of this invention. 本発明の一実施形態の積層体の製造方法を示すフローチャートである。It is a flow chart which shows the manufacturing method of the layered product of one embodiment of the present invention. 加熱溶融工程を含む積層体の製造方法の概念図である。It is a conceptual diagram of the manufacturing method of the laminated body including a heating melting process. 本発明の物品の一実施形態の光学ディスプレイを示す断面図である。1 is a cross-sectional view showing an optical display of an embodiment of an article of the present invention. 本発明の物品の一実施形態の光学ディスプレイを示す断面図である。1 is a cross-sectional view showing an optical display of an embodiment of an article of the present invention. 本発明の物品の別の実施形態の光学ディスプレイを示す断面図である。FIG. 6 is a cross-sectional view showing an optical display of another embodiment of the article of the present invention. 本発明の物品の別の実施形態の光学ディスプレイを示す分解斜視図である。FIG. 6 is an exploded perspective view showing an optical display of another embodiment of the article of the present invention. 本発明の物品の別の実施形態の光学ディスプレイを示す部分断面図であるFIG. 6 is a partial cross-sectional view showing an optical display of another embodiment of the article of the present invention.
本発明者らは鋭意検討の結果、（Ａ）一分子中に少なくとも２個の脂肪族不飽和炭素－炭素結合含有基を有する直鎖状又は分岐鎖状オルガノポリシロキサン、（Ｂ）一分子中に少なくとも２個のケイ素結合水素原子を有するオルガノハイドロジェンポリシロキサン、及び、（Ｃ）ヒドロシリル化反応用触媒を所定の条件で組み合わせて含む硬化反応性シリコーン粘着剤組成物に（Ｄ）リン含有ヒドロシリル化反応遅延剤を配合することによって、単一組成物の形態であっても比較的短時間で増粘することがなく、貯蔵安定性が高い硬化反応性シリコーン粘着剤組成物を提供可能であることを見出し、本発明を完成した。 As a result of diligent studies, the present inventors have found that (A) a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule, and (B) one molecule. (D) Phosphorus-containing hydrosilyl in a curing reactive silicone pressure-sensitive adhesive composition containing an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in combination with (C) a catalyst for hydrosilylation reaction under predetermined conditions. It is possible to provide a curing-reactive silicone pressure-sensitive adhesive composition having high storage stability without thickening in a relatively short time even in the form of a single composition, by incorporating a chemical reaction retarder. The inventors have found that and completed the present invention.
本発明の硬化反応性シリコーン粘着剤組成物は、２５℃において流動性を有する液状組成物であってもよく、２５℃において非流動性であり、２５℃～１５０℃までの間に軟化点を有する、ホットメルト性の組成物であってもよい。ホットメルト性の組成物として設計する場合、組成物全体が、加熱により柔軟化乃至流動可能である。柔軟化乃至流動化する温度は、５０～１５０℃であるのが好ましく、６０℃～１３０℃がより好ましく、８０℃～１２０℃が更により好ましい。 The curing-reactive silicone pressure-sensitive adhesive composition of the present invention may be a liquid composition having fluidity at 25°C, is not fluid at 25°C, and has a softening point between 25°C and 150°C. The composition may have a hot melt property. When designed as a hot-melt composition, the entire composition can be softened or flowed by heating. The softening or fluidizing temperature is preferably 50 to 150°C, more preferably 60°C to 130°C, even more preferably 80°C to 120°C.
以下、本発明の各態様について、更に詳細に説明する。 Hereinafter, each aspect of the present invention will be described in more detail.
　まず、本発明に係る硬化反応性シリコーン粘着剤組成物について説明する。なお、本明細書中において「質量％」は「重量％」と同義であり、その基準は、特記しない限り、本発明の組成物等の全質量（全重量）である。 First, the curing reactive silicone pressure-sensitive adhesive composition according to the present invention will be described. In addition, in this specification, "mass %" is synonymous with "weight %", and the standard is the total mass (total weight) of the composition or the like of the present invention, unless otherwise specified.
［硬化反応性シリコーン粘着剤組成物］
　本発明の硬化反応性シリコーン粘着剤組成物は、
（Ａ）一分子中に少なくとも２個の脂肪族不飽和炭素－炭素結合含有基を有する直鎖状又は分岐鎖状オルガノポリシロキサン、
（Ｂ）一分子中に少なくとも２個のケイ素結合水素原子を有するオルガノハイドロジェンポリシロキサン、
（Ｃ）ヒドロシリル化反応用触媒、及び、
（Ｄ）リン含有ヒドロシリル化反応遅延剤、
を含み、
（Ｂ）成分の含有量が、組成物中の全脂肪族不飽和炭素－炭素結合１モルに対して、（Ｂ）成分中のケイ素結合水素原子が０．５モル以上となる量である。更に、本発明の硬化反応性シリコーン粘着剤組成物は、（Ｅ）分子内にＲ３ＳｉＯ１／２（式中、Ｒは互いに独立して一価有機基を表す）で表されるシロキサン単位（Ｍ単位）及び、ＳｉＯ４／２で表されるシロキサン単位（Ｑ単位）を含むオルガノポリシロキサン樹脂を含んでもよい。 [Curing reactive silicone adhesive composition]
The curing reactive silicone pressure-sensitive adhesive composition of the present invention is
(A) a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule,
(B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule,
(C) catalyst for hydrosilylation reaction, and
(D) Phosphorus-containing hydrosilylation reaction retarder,
Including,
The content of the component (B) is such that the silicon-bonded hydrogen atoms in the component (B) are 0.5 mol or more with respect to 1 mol of all the aliphatic unsaturated carbon-carbon bonds in the composition. Further, the curing-reactive silicone pressure-sensitive adhesive composition of the present invention has a siloxane unit represented by (E) R 3 SiO 1/2 (wherein R's each independently represent a monovalent organic group) in the molecule. An organopolysiloxane resin containing (M unit) and a siloxane unit (Q unit) represented by SiO 4/2 may be included.
（Ａ）成分
　（Ａ）成分は本発明の硬化反応性シリコーン粘着剤組成物の主要な成分の１つである。（Ａ）成分は単一のオルガノポリシロキサンであってもよく、２種以上のオルガノポリシロキサンの混合物でもよい。
（Ａ）成分を使用することにより、本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物は、十分な粘着力を備え、且つ、その接着モードにおいて、被着体からの剥離時に凝集破壊が生じにくい粘着材層を形成することもできる。なお、被着体との永久接着が必要であれば、剥離時に粘着材層の凝集破壊が生じる高い接着力を備える組成物も設計可能である。 Component (A) The component (A) is one of the main components of the curable reactive silicone pressure-sensitive adhesive composition of the present invention. The component (A) may be a single organopolysiloxane or a mixture of two or more kinds of organopolysiloxane.
By using the component (A), the curable reactive silicone pressure-sensitive adhesive composition of the present invention or a cured product thereof has sufficient adhesive force and, in its adhesive mode, cohesive failure upon peeling from an adherend. It is also possible to form an adhesive material layer that is less likely to generate. If permanent adhesion to an adherend is required, a composition having a high adhesive force that causes cohesive failure of the pressure-sensitive adhesive layer at the time of peeling can be designed.
（Ａ）成分は、一分子中に少なくとも２個の脂肪族不飽和炭素－炭素結合含有基を有する直鎖状又は分岐鎖状オルガノポリシロキサンである。特に、シロキサン重合度が８０以上であることが好ましい。重合度が前記以下であると、粘着力を得るのが困難になる。 The component (A) is a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule. In particular, the siloxane polymerization degree is preferably 80 or more. When the degree of polymerization is less than the above, it becomes difficult to obtain adhesive strength.
脂肪族不飽和炭素－炭素結合含有基としては、既述した、アルケニル基、アルケニルオキシアルキル基、アクリロキシアルキル基又はメタクリロキシアルキル基であることが好ましい。アルケニル基としては、例えば、ビニル基、アリル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基等が挙げられる。ビニル基が特に好ましい。また、これらの基の一部はハロゲン原子等によって置換されていてもよい。 The aliphatic unsaturated carbon-carbon bond-containing group is preferably the above-mentioned alkenyl group, alkenyloxyalkyl group, acryloxyalkyl group or methacryloxyalkyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group and a hexenyl group. Vinyl groups are particularly preferred. Moreover, a part of these groups may be substituted with a halogen atom or the like.
　（Ｂ）成分が直鎖状の場合は、脂肪族不飽和炭素－炭素結合含有基は分子鎖末端及び分子鎖側鎖のいずれに存在してもよく、或いは、これらの両方に存在してもよい。 When the component (B) is linear, the aliphatic unsaturated carbon-carbon bond-containing group may be present at either the terminal of the molecular chain or the side chain of the molecular chain, or may be present at both of them. Good.
　脂肪族不飽和炭素－炭素結合含有基はケイ素原子に結合していることが好ましい。 The aliphatic unsaturated carbon-carbon bond-containing group is preferably bonded to a silicon atom.
　脂肪族不飽和炭素－炭素結合含有基の含有量は、（Ａ）成分の重量に対して０．００１～１０重量％が好ましく、０．００５～５重量％が好ましい。 The content of the aliphatic unsaturated carbon-carbon bond-containing group is preferably 0.001 to 10% by weight, and more preferably 0.005 to 5% by weight, based on the weight of the component (A).
（Ａ）成分は、脂肪族不飽和炭素－炭素結合含有基に加えて脂肪族不飽和炭素－炭素結合不含基を有してもよい。脂肪族不飽和炭素－炭素結合不含基は、既述した、アルキル基、アリール基又はアラルキル基であることが好ましい。アルキル基としては、例えば、メチル基、エチル基、プロピル基、ペンチル基、ヘキシル基、オクチル基等の他にシクロヘキシル基、シクロヘプチル基等のシクロアルキル基が挙げられる。アリール基としては、例えば、フェニル基、トリル基、キシリル基等が挙げられる。アラルキル基としては、例えば、ベンジル基、α－メチルスチリル基及び２－フェニルエチル基等が挙げられる。脂肪族不飽和炭素－炭素結合不含基はアルキル基であることがより好ましく、メチル基が特に好ましい。また、これらの基の一部はハロゲン原子等によって置換されていてもよい。 The component (A) may have an aliphatic unsaturated carbon-carbon bond-free group in addition to the aliphatic unsaturated carbon-carbon bond-containing group. The aliphatic unsaturated carbon-carbon bond-free group is preferably the above-mentioned alkyl group, aryl group or aralkyl group. Examples of the alkyl group include a cycloalkyl group such as a cyclohexyl group and a cycloheptyl group in addition to a methyl group, an ethyl group, a propyl group, a pentyl group, a hexyl group, an octyl group and the like. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and the like. Examples of the aralkyl group include a benzyl group, an α-methylstyryl group and a 2-phenylethyl group. The aliphatic unsaturated carbon-carbon bond-free group is more preferably an alkyl group, and particularly preferably a methyl group. Moreover, a part of these groups may be substituted with a halogen atom or the like.
（Ａ）成分としては、下記平均組成式（１）を有するものが好ましい。 As the component (A), those having the following average composition formula (1) are preferable.
Ｒ１ ａＲ２ ｂＳｉＯ（４－ａ－ｂ）／２　（１） R 1 a R 2 b SiO (4-ab)/2 (1)
平均組成式（１）中、Ｒ１は炭素数２～１２のアルケニル基である。具体的には、ビニル基、アリル基、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、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基が挙げられ、これらのうちでもビニル基、アリル基又はヘキセニル基が好ましい。Ｒ２は脂肪族不飽和結合を有さない炭素数１～１２の一価飽和炭化水素基、水酸基及びアルコキシ基から選択される基である。炭素数１～１２の一価飽和炭化水素基は、その水素原子の一部がハロゲン原子又は水酸基で置換されていてもよい。炭素数１～１２の一価飽和炭化水素基の例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等のアルキル基、フェニル基、トリル基、キシリル基、ナフチル基、アントラセニル基、フェナントリル基、ピレニル基等のアリール基、ベンジル基、フェネチル基、ナフチルエチル基、ナフチルプロピル基、アントラセニルエチル基、フェナントリルエチル基、ピレニルエチル基等のアラルキル基、及び、これらのアリール基又はアラルキル基の水素原子をメチル基、エチル基等のアルキル基；メトキシ基、エトキシ基等のアルコキシ基；塩素原子、臭素原子等のハロゲン原子で置換した基が挙げられる。 In the average composition formula (1), R 1 is an alkenyl group having 2 to 12 carbon atoms. Specific examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group, and among these, a vinyl group and an allyl group. Alternatively, a hexenyl group is preferable. R 2 is a group selected from a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms which does not have an aliphatic unsaturated bond, a hydroxyl group and an alkoxy group. In the monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, a part of the hydrogen atoms may be replaced with a halogen atom or a hydroxyl group. Examples of the monovalent saturated hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, Alkyl group such as dodecyl group, phenyl group, tolyl group, xylyl group, naphthyl group, anthracenyl group, phenanthryl group, aryl group such as pyrenyl group, benzyl group, phenethyl group, naphthylethyl group, naphthylpropyl group, anthracenylethyl group Groups, aralkyl groups such as phenanthrylethyl group and pyrenylethyl group, and hydrogen atoms of these aryl groups or aralkyl groups, alkyl groups such as methyl group and ethyl group; alkoxy groups such as methoxy group and ethoxy group; chlorine atom And a group substituted with a halogen atom such as a bromine atom.
ａ及びｂは次の条件：１≦ａ＋ｂ≦３及び０．０００１≦ａ／（ａ＋ｂ）≦０．３３を満たす数であり、好ましくは、次の条件：１．５≦ａ＋ｂ≦２．５及び０．０００２≦ａ／（ａ＋ｂ）≦０．２を満たす数である。これは、ａ＋ｂが１以上であると、硬化物の柔軟性が高くなるからであり、一方ａ＋ｂが３以下であると、硬化物の機械強度が高くなるからである。また、ａ／（ａ＋ｂ）が０．０００１以上であると、硬化物の機械強度が高くなるからであり、一方０．３３以下であると、硬化物の柔軟性が高くなるからである。 a and b are numbers satisfying the following conditions: 1≦a+b≦3 and 0.0001≦a/(a+b)≦0.33, and preferably the following conditions: 1.5≦a+b≦2.5 and It is a number that satisfies 0.0002≦a/(a+b)≦0.2. This is because when a+b is 1 or more, the flexibility of the cured product increases, while when a+b is 3 or less, the mechanical strength of the cured product increases. Also, if a/(a+b) is 0.0001 or more, the mechanical strength of the cured product will be high, while if it is 0.33 or less, the flexibility of the cured product will be high.
このような（Ａ）成分としては、一般式：
Ｒ６ ３ＳｉＯ(Ｒ６ ２ＳｉＯ)ｍ１ＳｉＲ６ ３
で表される直鎖状のオルガノポリシロキサンであることが好ましい。ただし、（Ａ）成分は、その一部に、Ｒ６ＳｉＯ３／２又はＳｉＯ４／２で表される分岐シロキサン単位を含んでよく、分岐鎖状のオルガノポリシロキサンであってもよい。 Such a component (A) has a general formula:
R 6 3 SiO(R 6 2 SiO) m1 SiR 6 3
It is preferably a linear organopolysiloxane represented by However, the component (A) may include a branched siloxane unit represented by R 6 SiO 3/2 or SiO 4/2 in a part thereof, and may be a branched organopolysiloxane.
式中、各Ｒ６は独立に、置換又は非置換の、一価炭化水素基であり、既述した一価不飽和炭化水素基及び一価飽和炭化水素基が例示される。但し、一分子中、少なくとも２個のＲ６は一価不飽和炭化水素基、好ましくはアルケニル基、より好ましくはビニル基である。前記平均組成式（１）を有するオルガノポリシロキサンの室温における性状はオイル状又は生ゴム状であってもよく、（Ａ）成分の粘度は２５℃において５０ｍＰａ・ｓ以上、特に１００ｍＰａ・ｓ以上であることが好ましい。 In the formula, each R 6 is independently a substituted or unsubstituted monovalent hydrocarbon group, and examples thereof include the monovalent unsaturated hydrocarbon group and the monovalent saturated hydrocarbon group described above. However, at least two R 6 s in one molecule are monovalent unsaturated hydrocarbon groups, preferably alkenyl groups, and more preferably vinyl groups. The organopolysiloxane having the average compositional formula (1) may be oily or raw rubber-like at room temperature, and the viscosity of the component (A) at 25° C. is 50 mPa·s or more, particularly 100 mPa·s or more. It is preferable.
（Ｂ）成分
　（Ｂ）成分は本発明の硬化反応性シリコーン粘着剤組成物の主要な成分の１つであり、架橋剤として機能する。（Ｂ）成分は単一のオルガノハイドロジェンポリシロキサンであってもよく、２種以上のオルガノハイドロジェンポリシロキサンの混合物でもよい。 Component (B) Component (B) is one of the main components of the curable reactive silicone pressure-sensitive adhesive composition of the present invention, and functions as a crosslinking agent. The component (B) may be a single organohydrogenpolysiloxane or a mixture of two or more types of organohydrogenpolysiloxane.
（Ｂ）成分は、一分子中に少なくとも２個のケイ素結合水素原子を有するオルガノハイドロジェンポリシロキサンである。（Ｂ）成分は、（Ａ）成分、或いは、後述する（Ｅ）成分が脂肪族不飽和炭素－炭素結合含有基を有する場合は（Ａ）成分と（Ｅ）成分の脂肪族不飽和炭素－炭素結合に付加するヒドロシリル基（－ＳｉＨ）を含有する。 The component (B) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule. The component (B) is the component (A) or, if the component (E) described later has an aliphatic unsaturated carbon-carbon bond-containing group, the component (A) and the aliphatic unsaturated carbon of the component (E)- It contains a hydrosilyl group (-SiH) that adds to the carbon bond.
（Ｂ）成分としては、下記平均組成式（２）を有するオルガノポリシロキサンが好ましい。 As the component (B), an organopolysiloxane having the following average composition formula (2) is preferable.
ＨｃＲ３ ｄＳｉＯ（４－ｃ－ｄ）／２　（２） H c R 3 d SiO 2 (4-cd)/2 (2)
平均組成式（２）中、Ｒ３は脂肪族不飽和結合を有さない炭素数１～１２の一価炭化水素基、ヒドロキシル基及びアルコキシ基から選択される基である。炭素数１～１２の一価炭化水素基は、その水素原子の一部がハロゲン原子又は水酸基で置換されていてもよい。炭素数１～１２の一価炭化水素基は、の例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等のアルキル基、フェニル基、トリル基、キシリル基、ナフチル基、アントラセニル基、フェナントリル基、ピレニル基等のアリール基、ベンジル基、フェネチル基、ナフチルエチル基、ナフチルプロピル基、アントラセニルエチル基、フェナントリルエチル基、ピレニルエチル基等のアラルキル基、及び、これらのアリール基又はアラルキル基の水素原子をメチル基、エチル基等のアルキル基；メトキシ基、エトキシ基等のアルコキシ基；塩素原子、臭素原子等のハロゲン原子で置換した基が挙げられる。アルコキシ基の例としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンタノキシ基、ヘキサノキシ基、オクタノキシ基等が挙げられる。 In the average composition formula (2), R 3 is a group selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms which does not have an aliphatic unsaturated bond, a hydroxyl group and an alkoxy group. In the monovalent hydrocarbon group having 1 to 12 carbon atoms, a part of the hydrogen atoms may be replaced with a halogen atom or a hydroxyl group. Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecyl group. , Alkyl group such as dodecyl group, phenyl group, tolyl group, xylyl group, naphthyl group, anthracenyl group, phenanthryl group, aryl group such as pyrenyl group, benzyl group, phenethyl group, naphthylethyl group, naphthylpropyl group, anthracenyl group Aralkyl groups such as ethyl group, phenanthrylethyl group and pyrenylethyl group, and hydrogen atoms of these aryl groups or aralkyl groups are alkyl groups such as methyl group and ethyl group; alkoxy groups such as methoxy group and ethoxy group; chlorine; A group substituted with a halogen atom such as an atom or a bromine atom can be mentioned. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentanoxy group, a hexanoxy group and an octanoxy group.
ｃ及びｄは次の条件：１≦ｃ＋ｄ≦３及び０．００２≦ｃ／（ｃ＋ｄ）≦０．５を満たす数であり、好ましくは、次の条件：１．５≦ｃ＋ｄ≦２．５及び０．０１≦ｃ／（ｃ＋ｄ）≦０．５を満たす数である。これは、ｃ＋ｄが１以上であると、硬化物の柔軟性が高くなるからであり、一方３以下であると、硬化物の機械強度が高くなるからである。また、ｃ／（ｃ＋ｄ）が１．５以上であると、硬化物の機械強度が高くなるからであり、一方２．５以下であると、硬化物の柔軟性が高くなるからである。 c and d are numbers satisfying the following conditions: 1≦c+d≦3 and 0.002≦c/(c+d)≦0.5, preferably the following conditions: 1.5≦c+d≦2.5 and It is a number that satisfies 0.01≦c/(c+d)≦0.5. This is because if c+d is 1 or more, the flexibility of the cured product will be high, while if it is 3 or less, the mechanical strength of the cured product will be high. Also, if c/(c+d) is 1.5 or more, the mechanical strength of the cured product will be high, while if it is 2.5 or less, the flexibility of the cured product will be high.
前記平均組成式（２）を有するオルガノポリシロキサンの粘度は限定されないが、２５℃における粘度が０．５～１０,０００ｍＰa・ｓの範囲内であることが好ましく、特に、１～１,０００ｍＰa・ｓの範囲内であることが好ましい。 The viscosity of the organopolysiloxane having the average composition formula (2) is not limited, but the viscosity at 25° C. is preferably in the range of 0.5 to 10,000 mPa·s, particularly 1 to 1,000 mPa·s. It is preferably within the range of s.
前記平均組成式（２）を有するオルガノポリシロキサンとしては、１,１,３,３－テトラメチルジシロキサン、１,３,５,７－テトラメチルシクロテトラシロキサン、トリス(ジメチルハイドロジェンシロキシ)メチルシラン、トリス(ジメチルハイドロジェンシロキシ)フェニルシラン、１－(３－グリシドキシプロピル)－１,３,５,７－テトラメチルシクロテトラシロキサン、１,５－ジ(３－グリシドキシプロピル)－１,３,５,７－テトラメチルシクロテトラシロキサン、１－(３－グリシドキシプロピル)－５－トリメトキシシリルエチル－１,３,５,７－テトラメチルシクロテトラシロキサン、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン・ジメチルシロキサン共重合体、トリメトキシシランの加水分解縮合物、(ＣＨ３)２ＨＳiＯ１/２単位とＳiＯ４/２単位とからなる共重合体、(ＣＨ３)２ＨＳiＯ１/２単位とＳiＯ４/２単位と(Ｃ６Ｈ５)ＳiＯ３/２単位とからなる共重合体、及び、これらの２種以上の混合物が例示される。 Examples of the organopolysiloxane having the average composition formula (2) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and tris(dimethylhydrogensiloxy)methylsilane. , Tris(dimethylhydrogensiloxy)phenylsilane, 1-(3-glycidoxypropyl)-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-di(3-glycidoxypropyl)- 1,3,5,7-tetramethylcyclotetrasiloxane, 1-(3-glycidoxypropyl)-5-trimethoxysilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane, both ends of the molecular chain Trimethylsiloxy group-blocked methyl hydrogen polysiloxane, dimethylsiloxy group-capped dimethylsiloxane/methylhydrogensiloxane copolymer, both molecular chain terminals, dimethylhydrogen siloxy group-blocked dimethylpolysiloxane, both molecular chain terminals dimethylhydrogen Siloxy group-blocked dimethylsiloxane/methylhydrogensiloxane copolymer, molecular chain both ends trimethylsiloxy group-blocked methylhydrogensiloxane/diphenylsiloxane copolymer, molecular chain both ends trimethylsiloxy group-blocked methylhydrogensiloxane/diphenylsiloxane/dimethyl Siloxane copolymer, hydrolysis-condensation product of trimethoxysilane, copolymer consisting of (CH 3 ) 2 HSiO 1/2 unit and SiO 4/2 unit, (CH 3 ) 2 HSiO 1/2 unit and SiO 4 / 2 units and (C 6 H 5) consisting of SiO 3/2 units, copolymers thereof, and mixtures of two or more of these are exemplified.
前記平均組成式（２）を有するオルガノポリシロキサンとして、更に次のようなオルガノポリシロキサンも例示される。なお、式中、Ｍｅ、Ｐｈは、それぞれ、メチル基、フェニル基を示し、ｍ２は１～１００の整数であり、ｎ２は１～５０の整数であり、ｂ２、ｃ２、ｄ２、ｅ２はそれぞれ正の数であり、ただし、一分子中のｂ２、ｃ２、ｄ２、ｅ２の合計は１である。
ＨＭｅ２ＳｉＯ(Ｐｈ２ＳｉＯ)ｍ２ＳｉＭｅ２Ｈ
ＨＭｅＰｈＳｉＯ(Ｐｈ２ＳｉＯ)ｍ２ＳｉＭｅＰｈＨ
ＨＭｅＰｈＳｉＯ(Ｐｈ２ＳｉＯ)ｍ２(ＭｅＰｈＳｉＯ)ｎ２ＳｉＭｅＰｈＨ
ＨＭｅＰｈＳｉＯ(Ｐｈ２ＳｉＯ)ｍ２(Ｍｅ２ＳｉＯ)ｎ２ＳｉＭｅＰｈＨ
(ＨＭｅ２ＳｉＯ１/２)ｂ２(ＰｈＳｉＯ３/２)ｃ２
(ＨＭｅＰｈＳｉＯ１/２)ｂ２(ＰｈＳｉＯ３/２)ｃ２
(ＨＭｅＰｈＳｉＯ１/２)ｂ２(ＨＭｅ２ＳｉＯ１/２)ｃ２(ＰｈＳｉＯ３/２)ｄ２
(ＨＭｅ２ＳｉＯ１/２)ｂ２(Ｐｈ２ＳｉＯ２/２)ｃ２(ＰｈＳｉＯ３/２)ｄ２
(ＨＭｅＰｈＳｉＯ１/２)ｂ２(Ｐｈ２ＳｉＯ２/２)ｃ２(ＰｈＳｉＯ３/２)ｄ２
(ＨＭｅＰｈＳｉＯ１/２)ｂ２(ＨＭｅ２ＳｉＯ１/２)ｃ２(Ｐｈ２ＳｉＯ２/２)ｄ２(ＰｈＳｉＯ３/２)ｅ２ Examples of the organopolysiloxane having the average composition formula (2) include the following organopolysiloxanes. In the formula, Me and Ph respectively represent a methyl group and a phenyl group, m2 is an integer of 1 to 100, n2 is an integer of 1 to 50, and b2, c2, d2 and e2 are positive. However, the total of b2, c2, d2 and e2 in one molecule is 1.
HMe 2 SiO(Ph 2 SiO) m2 SiMe 2 H
HMePhSiO(Ph 2 SiO) m2 SiMePhH
HMePhSiO(Ph 2 SiO) m2 (MePhSiO) n2 SiMePhH
HMePhSiO(Ph 2 SiO) m2 (Me 2 SiO) n2 SiMePhH
(HMe 2 SiO 1/2 ) b2 (PhSiO 3/2 ) c2
(HMePhSiO 1/2 ) b2 (PhSiO 3/2 ) c2
(HMePhSiO 1/2 ) b2 (HMe 2 SiO 1/2 ) c2 (PhSiO 3/2 ) d2
(HMe 2 SiO 1 /2 ) b2 (Ph 2 SiO 2/2 ) c2 (PhSiO 3/2 ) d2
(HMePhSiO 1/2 ) b2 (Ph 2 SiO 2/2 ) c2 (PhSiO 3/2 ) d2
(HMePhSiO 1/2 ) b2 (HMe 2 SiO 1/2 ) c2 (Ph 2 SiO 2/2 ) d2 (PhSiO 3/2 ) e2
（Ｂ）成分は、更に下記平均組成式（３）で表されるオルガノハイドロジェンポリシロキサンであることが好ましい。 The component (B) is preferably an organohydrogenpolysiloxane represented by the following average composition formula (3).
(HR4 2SiO1/2)e(R4 3SiO1/2)f(HR4SiO2/2)g(R4 2SiO2/2)h(HSiO3/2)i(R4SiO3/2)j(SiO4/2)k(R5O1/2)l　(3) (HR 4 2 SiO 1/2 ) e (R 4 3 SiO 1/2 ) f (HR 4 SiO 2/2 ) g (R 4 2 SiO 2/2 ) h (HSiO 3/2 ) i (R 4 SiO 3/2 ) j (SiO 4/2 ) k (R 5 O 1/2 ) l (3)
前記平均組成式（３）中、Ｒ４は脂肪族不飽和結合を有さない炭素数１～１２の一価飽和炭化水素基、ヒドロキシル基及びアルコキシ基から選択される基である。炭素数１～１２の一価飽和炭化水素基、ヒドロキシル基及びアルコキシ基については、前記と同様である。Ｒ５は水素原子又は炭素数１～６のアルキル基であり、炭素数１～６のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基等が例示される。ｅ，ｆ、ｇ、ｈ、ｉ、ｊ、ｋ及びｌは次の条件：ｅ＋ｆ＋ｇ＋ｈ＋ｉ＋ｊ＋ｋ＝１、０≦ｌ≦０．１、０．０１≦ｅ＋ｇ＋ｉ≦０．２、０≦ｅ≦０．６、０≦ｇ≦０．６、０≦ｉ≦０．４、０．０１≦ｅ＋ｆ≦０．８、０．０１≦ｇ＋ｈ≦０．８、０≦ｉ＋ｊ≦０．６を満たす数である。 In the average composition formula (3), R 4 is a group selected from a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, which does not have an aliphatic unsaturated bond, a hydroxyl group and an alkoxy group. The monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, the hydroxyl group and the alkoxy group are the same as above. R 5 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group. e, f, g, h, i, j, k and l have the following conditions: e+f+g+h+i+j+k=1, 0≦l≦0.1, 0.01≦e+g+i≦0.2, 0≦e≦0.6, It is a number that satisfies 0≦g≦0.6, 0≦i≦0.4, 0.01≦e+f≦0.8, 0.01≦g+h≦0.8, and 0≦i+j≦0.6.
なお、前記の「HR4 2SiO1/2」、「R4 3SiO1/2」、「HR4SiO2/2」、「R4 2SiO2/2」、「HSiO3/2」、「R4SiO3/2」及び「SiO4/2」の各構成単位は、それぞれＭＨ単位，Ｍ単位、ＤＨ単位、Ｄ単位、ＴＨ単位、Ｔ単位、Ｑ単位と呼ばれるオルガノハイドロジェンポリシロキサンの部分構造の単位であり、「R5O1/2」は、Ｄ単位、ＤＨ単位、Ｔ単位、ＴＨ単位、又はＱ単位中の酸素原子と結合する基であり、オルガノポリシロキサン中のケイ素原子結合水酸基（Ｓｉ―ＯＨ）或いはオルガノポリシロキサン製造中に未反応で残った珪素原子結合アルコキシ基を意味する。ＭＨ単位は主にオルガノハイドロジェンポリシロキサンの分子鎖末端に存在し、ＤＨ単位はオルガノハイドロジェンポリシロキサンの分子鎖中に存在する。 Incidentally, the above-mentioned "HR 4 2 SiO 1/2 ", "R 4 3 SiO 1/2 ", "HR 4 SiO 2/2 ", "R 4 2 SiO 2/2 ", "HSiO 3/2 ", The constituent units of “R 4 SiO 3/2 ”and “SiO 4/2 ”are organohydrogenpolysiloxanes called MH units, M units, DH units, D units, TH units, T units, and Q units, respectively. “R 5 O 1/2 ”, which is a unit of a partial structure, is a group that is bonded to an oxygen atom in a D unit, a DH unit, a T unit, a TH unit, or a Q unit, and is a silicon atom in an organopolysiloxane. A bonded hydroxyl group (Si—OH) or a silicon atom-bonded alkoxy group that remains unreacted during the production of an organopolysiloxane. The MH unit is mainly present at the molecular chain end of the organohydrogenpolysiloxane, and the DH unit is present in the molecular chain of the organohydrogenpolysiloxane.
（Ｂ）成分の含有量は、組成物中の全脂肪族不飽和炭素－炭素結合１モルに対して、（Ｂ）成分中のケイ素結合水素原子が０．５モル以上となる量であり、組成物中の全脂肪族不飽和炭素－炭素結合１モルに対して、（Ｂ）成分中のケイ素結合水素原子が０．５～１００モルとなる量が好ましく、０．５～６０モルとなる量がより好ましく、０．５～４０モルとなる量が更により好ましい。 The content of the component (B) is such that the amount of silicon-bonded hydrogen atoms in the component (B) is 0.5 mol or more per 1 mol of the total aliphatic unsaturated carbon-carbon bond in the composition, The amount of the silicon-bonded hydrogen atoms in the component (B) is preferably 0.5 to 100 mol, and more preferably 0.5 to 60 mol, based on 1 mol of the total aliphatic unsaturated carbon-carbon bond in the composition. The amount is more preferable, and the amount of 0.5 to 40 mol is even more preferable.
（Ｃ）成分
　（Ｃ）成分はヒドロシリル化反応用触媒である。（Ｃ）成分は単一のヒドロシリル化反応用触媒であってもよく、２種以上のヒドロシリル化反応用触媒の混合物でもよい。 Component (C) The component (C) is a catalyst for hydrosilylation reaction. The component (C) may be a single hydrosilylation reaction catalyst or a mixture of two or more hydrosilylation reaction catalysts.
ヒドロシリル化反応用触媒の例としては、白金系触媒、ロジウム系触媒、パラジウム系触媒、ニッケル系触媒、イリジウム系触媒、ルテニウム系触媒及び鉄系触媒が挙げられ、好ましくは、白金系触媒である。この白金系触媒としては、白金微粉末、白金黒、白金担持シリカ微粉末、白金担持活性炭、塩化白金酸、塩化白金酸のアルコール溶液、白金のオレフィン錯体、白金のアルケニルシロキサン錯体等の白金系化合物が例示され、特に白金のアルケニルシロキサン錯体が好ましい。このアルケニルシロキサンとしては、１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン、１,３,５,７－テトラメチル－１,３,５,７－テトラビニルシクロテトラシロキサン、これらのアルケニルシロキサンのメチル基の一部をエチル基、フェニル基等で置換したアルケニルシロキサン、これらのアルケニルシロキサンのビニル基をアリル基、ヘキセニル基等で置換したアルケニルシロキサンが例示される。特に、この白金－アルケニルシロキサン錯体の安定性が良好であることから、１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンが好ましい。また、この白金－アルケニルシロキサン錯体の安定性を向上させることができることから、この錯体に１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン、１,３－ジアリル－１,１,３,３－テトラメチルジシロキサン、１,３－ジビニル－１,３－ジメチル－１,３－ジフェニルジシロキサン、１,３－ジビニル－１,１,３,３－テトラフェニルジシロキサン、１,３,５,７－テトラメチル－１,３,５,７－テトラビニルシクロテトラシロキサン等のアルケニルシロキサンやジメチルシロキサンオリゴマー等のオルガノシロキサンオリゴマーを添加することが好ましく、特に、アルケニルシロキサンを添加することが好ましい。 Examples of the hydrosilylation reaction catalyst include platinum-based catalysts, rhodium-based catalysts, palladium-based catalysts, nickel-based catalysts, iridium-based catalysts, ruthenium-based catalysts, and iron-based catalysts, and platinum-based catalysts are preferable. As the platinum-based catalyst, platinum-based compounds such as platinum fine powder, platinum black, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, alcohol solution of chloroplatinic acid, olefin complex of platinum, alkenylsiloxane complex of platinum, etc. Are exemplified, and an alkenylsiloxane complex of platinum is particularly preferable. As the alkenyl siloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples thereof include alkenylsiloxanes in which a part of methyl groups of these alkenylsiloxanes are substituted with ethyl groups, phenyl groups and the like, and alkenylsiloxanes in which vinyl groups of these alkenylsiloxanes are substituted with allyl groups, hexenyl groups and the like. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferable because the platinum-alkenylsiloxane complex has good stability. Further, since the stability of the platinum-alkenylsiloxane complex can be improved, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,3-diallyl-1,1 are added to the complex. ,3,3-Tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, 1 It is preferable to add an alkenylsiloxane such as 3,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane or an organosiloxane oligomer such as a dimethylsiloxane oligomer, and particularly, to add an alkenylsiloxane. It is preferable.
（Ｃ）成分は比較的低温でも活性を示すものが好ましい。具体的には、０～２００℃の温度範囲において組成物中で活性を示し、ヒドロシリル化反応を促進するものが好ましい。なお、（Ｃ）成分は、（Ｄ）成分の存在下、８０℃以下では硬化反応が実質的に進行しないヒドロシリル化反応用触媒であることが好ましく、一方、（Ｄ）成分の存在下であっても、１５０℃以上の高温で加熱することにより、ヒドロシリル化反応を促進し、組成物全体を硬化できるヒドロシリル化反応用触媒であることが特に好ましい。 It is preferable that the component (C) be active even at a relatively low temperature. Specifically, those which are active in the composition in the temperature range of 0 to 200° C. and accelerate the hydrosilylation reaction are preferable. The component (C) is preferably a catalyst for hydrosilylation reaction in which the curing reaction does not substantially proceed at 80° C. or lower in the presence of the component (D), while the component (D) exists in the presence of the component (D). However, it is particularly preferable to use a hydrosilylation reaction catalyst that can accelerate the hydrosilylation reaction and cure the entire composition by heating at a high temperature of 150° C. or higher.
（Ｃ）成分の含有量は、触媒の種類及び組成物の種類によって異なるが、通常は組成物に対して、この触媒中の金属原子が質量単位で０．１～２００ｐｐｍの範囲内となる量であり、０．１～１５０ｐｐｍ、０．１～１００ｐｐｍの範囲内であってもよい。 Although the content of the component (C) varies depending on the type of catalyst and the type of composition, it is usually an amount such that the metal atom in the catalyst is within the range of 0.1 to 200 ppm in mass unit with respect to the composition. And may be in the range of 0.1 to 150 ppm, 0.1 to 100 ppm.
（Ｄ）成分
　本発明の組成物は（Ｄ）リン含有ヒドロシリル化反応遅延剤を含むことを、その特徴の一つとする。リン含有ヒドロシリル化反応遅延剤は、低温におけるヒドロシリル化反応を強く抑制し、硬化反応を調整することができる成分であり、このような遅延剤を選択的に利用することで、単一組成物の形態であっても、その保存安定性、取扱作業性、及び、成型性に優れる硬化反応性シリコーン粘着剤組成物を設計可能である。また、（Ｄ）成分は単一のリン含有ヒドロシリル化反応遅延剤であってもよく、２種以上の混合物でもよい。 (D) Component One of the characteristics of the composition of the present invention is that it contains (D) a phosphorus-containing hydrosilylation reaction retarder. The phosphorus-containing hydrosilylation reaction retarder is a component that can strongly suppress the hydrosilylation reaction at low temperature and adjust the curing reaction. By selectively using such retarder, a single composition of a single composition can be obtained. Even in the form, it is possible to design a curing-reactive silicone pressure-sensitive adhesive composition having excellent storage stability, handling workability, and moldability. Further, the component (D) may be a single phosphorus-containing hydrosilylation reaction retarder or a mixture of two or more kinds.
リン含有ヒドロシリル化反応遅延剤は、ホスフィン系化合物、リン酸系化合物、ホスホン酸系化合物、ホスフィンオキサイド系化合物、亜リン酸系化合物及び亜ホスホン酸系化合物からなる群から選らばれる少なくとも一種であることが好ましい。 The phosphorus-containing hydrosilylation reaction retarder is at least one selected from the group consisting of phosphine compounds, phosphoric acid compounds, phosphonic acid compounds, phosphine oxide compounds, phosphorous acid compounds and phosphonous acid compounds. Is preferred.
　前記ホスフィン系化合物は、ジフェニルホスフィン、トリフェニルホスフィン、ジメチルフェニルホスフィン、ジエチルフェニルホスフィン、トリプロピルホスフィン、ジシクロヘキシルフェニルホスフィン、ビス(ジフェニルホスフィノ)メタン、１,２－ビス(ジフェニルホスフィノ)エタン、１,２－ビス(ジフェニルホスフィノ)プロパン、１,３－ビス(ジフェニルホスフィノ)プロパン、１,４－ビス(ジフェニルホスフィノ)ブタン、２，３－ビス(ジフェニルホスフィノ)ブタン、１,５－ビス(ジフェニルホスフィノ)ペンタン、１,６－ビス(ジフェニルホスフィノ)ヘキサン、ビス（２-ジフェニルホスフィノエチル）フェニルホスフィンビス(ジフェニルホスフィノ)アセチレン、１,１－ビス(ジフェニルホスフィノ)エチレン、１,２－ビス(ジフェニルホスフィノ)エチレン、１,１－ビス(ジフェニルホスフィノ)フェロセン、１,３－ビス(ジシクロヘキシルホスフィノ)プロパン、１,２－ビス(ジメチルホスフィノ)エタン、１,２－ビス(ジメチルホスフィノ)ベンゼン、及び、１,２－ビス(ジフェニルホスフィノ)ベンゼンからなる群から選らばれる少なくとも一種の化合物であることが好ましい。 Examples of the phosphine compound include diphenylphosphine, triphenylphosphine, dimethylphenylphosphine, diethylphenylphosphine, tripropylphosphine, dicyclohexylphenylphosphine, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1 1,2-bis(diphenylphosphino)propane,1,3-bis(diphenylphosphino)propane,1,4-bis(diphenylphosphino)butane,2,3-bis(diphenylphosphino)butane,1,5 -Bis(diphenylphosphino)pentane, 1,6-bis(diphenylphosphino)hexane, bis(2-diphenylphosphinoethyl)phenylphosphine bis(diphenylphosphino)acetylene, 1,1-bis(diphenylphosphino) Ethylene, 1,2-bis(diphenylphosphino)ethylene, 1,1-bis(diphenylphosphino)ferrocene, 1,3-bis(dicyclohexylphosphino)propane, 1,2-bis(dimethylphosphino)ethane, It is preferably at least one compound selected from the group consisting of 1,2-bis(dimethylphosphino)benzene and 1,2-bis(diphenylphosphino)benzene.
　前記リン酸系化合物は、リン酸トリフェニル、リン酸トリメチル、リン酸トリエチル、リン酸トリプロピル、リン酸トリブチル、及び、リン酸ジフェニルメチルからなる群から選らばれる少なくとも一種の化合物であることが好ましい。 The phosphoric acid compound is preferably at least one compound selected from the group consisting of triphenyl phosphate, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tripropyl phosphate, tributyl phosphate, and diphenylmethyl phosphate. ..
　前記ホスホン酸系化合物は、メチルホスホン酸、ジメチル、メチルホスホン酸ジエチル、メチルホスホン酸ジプロピル、メチルホスホン酸ジブチル、フェニルホスホン酸ジエチル、及び、フェニルホスホン酸ジプロピルからなる群から選らばれる少なくとも一種の化合物であることが好ましい。 The phosphonic acid compound is preferably at least one compound selected from the group consisting of methylphosphonic acid, dimethyl, diethyl methylphosphonate, dipropyl methylphosphonate, dibutyl methylphosphonate, diethyl phenylphosphonate, and dipropyl phenylphosphonate. ..
　前記ホスフィンオキサイド系化合物は、ジフェニルホスフィンオキサイド、トリフェニルホスフィンオキサイド、ジメチルフェニルホスフィンオキサイド、ジエチルフェニルホスフィンオキサイド、トリプロピルホスフィンオキサイド、及び、トリブチルホスフィンオキサイドからなる群から選らばれる少なくとも一種の化合物であることが好ましい。 The phosphine oxide-based compound may be at least one compound selected from the group consisting of diphenylphosphine oxide, triphenylphosphine oxide, dimethylphenylphosphine oxide, diethylphenylphosphine oxide, tripropylphosphine oxide, and tributylphosphine oxide. preferable.
　前記亜リン酸系化合物は、亜リン酸トリフェニル、亜リン酸トリメチル、亜リン酸トリエチル、亜リン酸トリプロピル、亜リン酸トリブチル、亜リン酸ジフェニル、亜リン酸ジメチル、亜リン酸ジエチル、亜リン酸ジプロピル、及び、亜リン酸ジブチルからなる群から選らばれる少なくとも一種の化合物であることが好ましい。 The phosphite compound is triphenyl phosphite, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, diphenyl phosphite, dimethyl phosphite, diethyl phosphite, It is preferably at least one compound selected from the group consisting of dipropyl phosphite and dibutyl phosphite.
前記亜ホスホン酸系化合物は、フェニル亜ホスホン酸ジメチル、フェニル亜ホスホン酸ジエチル、及び、フェニル亜ホスホン酸ジプロピルからなる群から選らばれる少なくとも一種の化合物であることが好ましい。 The phosphonous acid-based compound is preferably at least one compound selected from the group consisting of dimethyl phenylphosphonous acid, diethyl phenylphosphonous acid, and dipropyl phenylphosphonous acid.
　リン含有ヒドロシリル化反応遅延剤は、好ましくは、ホスフィン系化合物であり、特に好ましくは、ビス(ジフェニルホスフィノ)メタン、１,２－ビス(ジフェニルホスフィノ)エタン、１,３－ビス(ジフェニルホスフィノ)プロパンである。 The phosphorus-containing hydrosilylation reaction retarder is preferably a phosphine compound, particularly preferably bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphine). Fino) Propane.
（Ｄ）リン含有ヒドロシリル化反応遅延剤を選択的に使用する本発明の組成物は、ポットライフが向上し、取扱性作業性を高めることができる。更に、単一組成物の形態であっても、その保存安定性、取扱作業性、及び、成型性に優れ、且つ、高温で加熱することにより速やかに硬化して、高い接着強度を得ることが可能である。また、リン含有ヒドロシリル化反応遅延剤により、ヒドロシリル化触媒の添加乃至組成物の成型時の加熱溶融によって硬化反応が進行することが抑制されるため、本発明により、十分な硬化反応性や成型性を有する、加熱溶融性の硬化反応性シリコーン粘着剤組成物及びその成型物を提供することができる。なお、（Ｄ）成分に代えて、他のヒドロシリル化反応遅延剤を使用した場合、当該技術的効果が実現できない。 The composition of the present invention in which the phosphorus-containing hydrosilylation reaction retarder (D) is selectively used has an improved pot life and can be handled easily. Furthermore, even in the form of a single composition, it is excellent in its storage stability, handling workability, and moldability, and can be rapidly cured by heating at a high temperature to obtain high adhesive strength. It is possible. Further, since the phosphorus-containing hydrosilylation reaction retarder suppresses the progress of the curing reaction due to the addition of the hydrosilylation catalyst or the heating and melting during the molding of the composition, the present invention provides sufficient curing reactivity and moldability. It is possible to provide a heat-meltable, curing-reactive silicone pressure-sensitive adhesive composition having: When other hydrosilylation reaction retarder is used instead of the component (D), the technical effect cannot be realized.
　（Ｄ）リン含有ヒドロシリル化反応遅延剤の含有量は特に限定されないが、例えば、組成物中の（Ｃ）成分中の金属原子、好適には白金系金属原子１モルに対して、０．０１～１，０００モルとなる量であることが好ましくは、特に、０．１～５００モルとなる量であることが好ましく、更に０．３０～１０モルとなる量であることが特に好ましい。これは、この遅延剤の含有量が上記範囲の下限未満であると、本組成物を単一の組成物（１液化等）が困難であり、室温でも比較的短時間で増粘、本来の粘着性を示さなくなり、また、ホットメルト性粘着シートを、加熱溶融する段階で硬化反応が進行してしまう問題があるためであり、一方、上記範囲の上限を超えると、１５０℃で加熱した場合でも、硬化反応が進行しにくくなるからである。なお、（Ｄ）成分の使用量が、（Ｃ）成分中の金属原子１モルに対して０．３０～１０モルとなる範囲の量である場合、本発明の組成物を薄膜状に塗布した場合であっても、１５０℃以上で加熱することで速やかな硬化反応を実現することができる。 The content of the (D) phosphorus-containing hydrosilylation reaction retarder is not particularly limited, but is, for example, 0.01 with respect to 1 mol of the metal atom in the component (C) in the composition, preferably 1 mol of the platinum-based metal atom. The amount is preferably ˜1,000 mol, more preferably 0.1 to 500 mol, particularly preferably 0.30 to 10 mol. This is because if the content of the retarder is less than the lower limit of the above range, it is difficult to obtain a single composition (such as one liquefaction) from the composition, and the viscosity increases in a relatively short time even at room temperature. This is because there is a problem that the tackiness is not exhibited and the curing reaction proceeds in the step of heating and melting the hot-melt adhesive sheet. On the other hand, when the temperature exceeds the upper limit of the above range, the hot-melt adhesive sheet is heated at 150°C. However, it is difficult for the curing reaction to proceed. When the amount of the component (D) used is in the range of 0.30 to 10 mol per 1 mol of the metal atom in the component (C), the composition of the present invention was applied in a thin film form. Even in such a case, a rapid curing reaction can be realized by heating at 150° C. or higher.
（Ｅ）成分
本発明の組成物は、（Ｅ）分子内にＲ３ＳｉＯ１／２（式中、Ｒは互いに独立して一価有機基を表す）で表されるシロキサン単位（Ｍ単位）及び、ＳｉＯ４／２で表されるシロキサン単位（Ｑ単位）を含むオルガノポリシロキサン樹脂を更に含むことができる。（Ｅ）成分は単一のオルガノポリシロキサン樹脂であってもよく、２種以上のオルガノポリシロキサン樹脂の混合物でもよい。 Component (E) The composition of the present invention comprises a siloxane unit (M unit) represented by R 3 SiO 1/2 (wherein R's each independently represent a monovalent organic group) in the molecule (E). And an organopolysiloxane resin containing a siloxane unit (Q unit) represented by SiO 4/2 . The component (E) may be a single organopolysiloxane resin or a mixture of two or more organopolysiloxane resins.
（Ｅ）成分は、本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物に、感圧接着性を付与する成分であり、各種の基体又は基板への高密着力を付与することができる。（Ｅ）成分は、分子内に（ａ）Ｒ３ＳｉＯ１／２（式中、Ｒは、互いに独立して一価有機基を表す）で表されるシロキサン単位（Ｍ単位）、及び、（ｂ）ＳｉＯ４／２で表されるシロキサン単位（Ｑ単位）を含むオルガノポリシロキサン樹脂である。 The component (E) is a component that imparts pressure-sensitive adhesiveness to the curable reactive silicone pressure-sensitive adhesive composition of the present invention or a cured product thereof, and can impart high adhesion to various bases or substrates. The component (E) is a siloxane unit (M unit) represented by (a) R 3 SiO 1/2 (wherein R independently represents a monovalent organic group) in the molecule, and ( b) An organopolysiloxane resin containing a siloxane unit (Q unit) represented by SiO 4/2 .
（ａ）Ｍ単位と（ｂ）Ｑ単位のモル比はＭ単位：Ｑ単位＝０．５０:１．００～１．５０：１．００の範囲にあることが好ましく、０．５５：１．００～１．２０：１．００の範囲がより好ましく、０．６０：１．００～１．１０：１．００が更により好ましい。上記モル比は、２９Ｓｉ核磁気共鳴によって容易に測定することができる。 The molar ratio of (a) M unit to (b) Q unit is preferably in the range of M unit:Q unit=0.50:1.00 to 1.50:1.00, and 0.55:1. The range of 00 to 1.20:1.00 is more preferable, and the range of 0.60:1.00 to 1.10:1.00 is even more preferable. The above molar ratio can be easily measured by 29 Si nuclear magnetic resonance.
（Ｅ）成分は一般単位式：（Ｒ３ＳｉＯ１／２）ａ（ＳｉＯ４／２）ｂ（式中、Ｒは互いに独立して一価有機基であり、ａ及びｂはそれぞれ正数であり、ａ＋ｂ＝１、ａ／ｂ＝０．５～１．５である）で表されるオルガノポリシロキサン樹脂であることが好ましい。 The component (E) has a general unit formula: (R 3 SiO 1/2 ) a (SiO 4/2 ) b (In the formula, R is a monovalent organic group independently of each other, and a and b are positive numbers. And a+b=1 and a/b=0.5 to 1.5) are preferable.
（Ｅ）成分は（ａ）Ｍ単位と（ｂ）Ｑ単位のみから構成されてもよいが、Ｒ２ＳｉＯ２／２単位（Ｄ単位）、及び／又は、ＲＳｉＯ３／２単位（Ｔ単位）を含んでもよい。なお、式中、Ｒは、互いに独立して一価有機基を表す。（Ｅ）成分中の（ａ）Ｍ単位と（ｂ）Ｑ単位の合計含有量は好ましくは５０重量％以上であり、更に好ましくは８０重量％以上であり、特に好ましくは１００重量％である。 The component (E) may be composed of only (a) M units and (b) Q units, but R 2 SiO 2/2 units (D units) and/or RSiO 3/2 units (T units). May be included. In the formula, R's each independently represent a monovalent organic group. The total content of (a) M units and (b) Q units in the component (E) is preferably 50% by weight or more, more preferably 80% by weight or more, and particularly preferably 100% by weight.
一価有機基は、特に限定されるものではないが、例えば、脂肪族不飽和炭素－炭素結合含有基、及び、脂肪族不飽和炭素－炭素結合不含基に分けることができる。 The monovalent organic group is not particularly limited, but can be divided into, for example, an aliphatic unsaturated carbon-carbon bond-containing group and an aliphatic unsaturated carbon-carbon bond-free group.
脂肪族不飽和炭素－炭素結合含有基、及び、脂肪族不飽和炭素－炭素結合不含基には、それぞれ、一価不飽和炭化水素基及び酸素原子含有一価不飽和炭化水素基、並びに、一価飽和炭化水素基及び酸素原子含有一価飽和炭化水素基が含まれる。 The aliphatic unsaturated carbon-carbon bond-containing group and the aliphatic unsaturated carbon-carbon bond-free group respectively include a monovalent unsaturated hydrocarbon group and an oxygen atom-containing monovalent unsaturated hydrocarbon group, and A monovalent saturated hydrocarbon group and an oxygen atom-containing monovalent saturated hydrocarbon group are included.
一価不飽和又は飽和炭化水素基としては、例えば、炭素原子数２～１２の、好ましくは炭素原子数２～８の、より好ましくは炭素原子数２～６の、置換若しくは非置換の、一価不飽和炭化水素基、並びに、炭素原子数１～１２の、置換若しくは非置換の、一価飽和炭化水素基が挙げられる。 The monounsaturated or saturated hydrocarbon group is, for example, a substituted or unsubstituted one having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms. Examples thereof include a valent unsaturated hydrocarbon group and a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms.
炭素原子数２～１２の、好ましくは炭素原子数２～８の、より好ましくは炭素原子数２～６の、非置換一価不飽和炭化水素基としては、例えば、ビニル基、アリル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基等のアルケニル基が挙げられる。炭素原子数２～１２の、好ましくは炭素原子数２～８の、より好ましくは炭素原子数２～６の、置換一価不飽和炭化水素基としては、例えば、これらの一価不飽和炭化水素基の水素原子の一部がハロゲン原子（フッ素、塩素、臭素又はヨウ素）等によって置換されたものが挙げられる。 Examples of the unsubstituted monovalent unsaturated hydrocarbon group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 6 carbon atoms include, for example, vinyl group, allyl group and propenyl group. Examples thereof include alkenyl groups such as groups, butenyl groups, pentenyl groups and hexenyl groups. Examples of the substituted monounsaturated hydrocarbon group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms include, for example, these monovalent unsaturated hydrocarbon groups. A group in which a part of hydrogen atoms of the group is substituted with a halogen atom (fluorine, chlorine, bromine or iodine) and the like can be mentioned.
炭素原子数１～１２の非置換一価飽和炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ペンチル基、ヘキシル基、オクチル基等のアルキル基；シクロヘキシル基、シクロヘプチル基等のシクロアルキル基；フェニル基、トリル基、キシリル基等のアリール基；ベンジル基、α－メチルスチリル基及び２－フェニルエチル基等のアラルキル基が挙げられる。炭素原子数１～１２の置換一価飽和炭化水素基としては、例えば、これらの一価不飽和炭化水素基の水素原子の一部がハロゲン原子（フッ素、塩素、臭素又はヨウ素）等によって置換されたものが挙げられる。具体的には、フッ化一価飽和炭化水素基、例えば３，３，３－トリフルオロプロピル基、４，４，５，５，５－ペンタフルオロルブチル基、３，３，４，４，５，５，６，６，６－ノナフルオロヘキシル基等のパーフロロアルキル基；塩素化一価飽和炭化水素基、例えば３－クロロプロピル基のようなクロロアルキル基、ジクロロフェニル基のようなクロロフェニル基が挙げられる。 Examples of the unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, pentyl group, hexyl group and octyl group; cyclohexyl group, cycloheptyl group and the like. Examples thereof include a cycloalkyl group; an aryl group such as a phenyl group, a tolyl group and a xylyl group; and an aralkyl group such as a benzyl group, an α-methylstyryl group and a 2-phenylethyl group. As the substituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, for example, a part of hydrogen atoms of these monovalent unsaturated hydrocarbon groups is substituted with a halogen atom (fluorine, chlorine, bromine or iodine) or the like. There are some. Specifically, fluorinated monovalent saturated hydrocarbon groups such as 3,3,3-trifluoropropyl group, 4,4,5,5,5-pentafluorolbutyl group, 3,3,4,4,4. Perfluoroalkyl group such as 5,5,6,6,6-nonafluorohexyl group; chlorinated monovalent saturated hydrocarbon group, for example, chloroalkyl group such as 3-chloropropyl group, chlorophenyl group such as dichlorophenyl group Are listed.
一価飽和炭化水素基としては、炭素原子数１～１２の置換若しくは非置換のアルキル基が好ましい。炭素原子数１～１２の置換若しくは非置換のアルキル基としてはメチル基が好ましい。一価不飽和炭化水素基としては、炭素原子数２～１２の置換若しくは非置換のアルケニル基が好ましい。炭素原子数２～１２の置換若しくは非置換のアルケニル基としてはビニル基が好ましい。 As the monovalent saturated hydrocarbon group, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms is preferable. A methyl group is preferred as the substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. The monovalent unsaturated hydrocarbon group is preferably a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms. A vinyl group is preferred as the substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms.
酸素原子含有一価不飽和又は飽和炭化水素基としては、例えば、炭素原子数２～１２の、置換若しくは非置換の、酸素原子含有一価不飽和炭化水素基、並びに、炭素原子数１～１２の、置換若しくは非置換の、酸素原子含有一価飽和炭化水素基が挙げられる。 Examples of the oxygen atom-containing monovalent unsaturated or saturated hydrocarbon group include, for example, a substituted or unsubstituted oxygen atom-containing monovalent unsaturated hydrocarbon group and a carbon atom number of 1 to 12 And a substituted or unsubstituted monovalent saturated hydrocarbon group containing an oxygen atom.
　炭素原子数２～１２の、置換若しくは非置換の酸素原子含有一価不飽和炭化水素基としては、例えば、アルケニルオキシアルキル基、アクリロキシアルキル基、メタクリロキシアルキル基等が挙げられる。 Examples of the substituted or unsubstituted monovalent unsaturated hydrocarbon group having 2 to 12 carbon atoms include an alkenyloxyalkyl group, an acryloxyalkyl group and a methacryloxyalkyl group.
　アルケニルオキシアルキル基としては、例えば、アリルオキシメチル基、３－アリルオキシプロピル基等が挙げられる。アクリロキシアルキル基としては、例えば、アクリロキシメチル基、３－アクリロキシプロピル基等が挙げられる。メタクリロキシアルキル基としては、例えば、メタクリロキシメチル基、３－メタクリロキシプロピル基等が挙げられる。 Examples of the alkenyloxyalkyl group include an allyloxymethyl group and a 3-allyloxypropyl group. Examples of the acryloxyalkyl group include an acryloxymethyl group and a 3-acryloxypropyl group. Examples of the methacryloxyalkyl group include a methacryloxymethyl group and a 3-methacryloxypropyl group.
炭素原子数１～１２の、置換若しくは非置換の、酸素原子含有一価飽和炭化水素基としては、例えば、炭素原子数１～１２のアルコキシ基等が挙げられる。 Examples of the substituted or unsubstituted monovalent saturated hydrocarbon group containing 1 to 12 carbon atoms include an alkoxy group containing 1 to 12 carbon atoms.
　炭素原子数１～１２のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、イソプロポキシ基等が挙げられる。 Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, isopropoxy group and the like.
これらの基の一部はハロゲン原子（フッ素、塩素、臭素又はヨウ素）等によって置換されていてもよい。 Some of these groups may be substituted with a halogen atom (fluorine, chlorine, bromine or iodine) or the like.
（Ｅ）成分のオルガノポリシロキサン樹脂には、ケイ素原子に結合した水酸基が少量含まれていてもよい。水酸基の含有量は、全ケイ素原子１モルに対して、０．２モル以下が好ましく、０．１モル以下が更に好ましい。 The organopolysiloxane resin as the component (E) may contain a small amount of hydroxyl groups bonded to silicon atoms. The content of hydroxyl groups is preferably 0.2 mol or less, more preferably 0.1 mol or less, based on 1 mol of all silicon atoms.
なお、（Ｅ）成分のオルガノポリシロキサン樹脂が、メトキシ基、エトキシ基等のケイ素原子に結合したアルコキシ基を含む場合、その含有量は、全ケイ素原子１モルに対して、０．２モル以下が好ましく、０．１モル以下が更に好ましい。 When the organopolysiloxane resin as the component (E) contains an alkoxy group bonded to a silicon atom such as a methoxy group or an ethoxy group, the content thereof is 0.2 mol or less with respect to 1 mol of all silicon atoms. Is preferable, and 0.1 mol or less is more preferable.
（（Ｅ１）硬化反応性オルガノポリシロキサン樹脂）
本発明の一態様では、（Ｅ）成分の少なくとも一部が、（Ｅ１）分子内に（Ａｌｋ）Ｒ’２ＳｉＯ１／２（式中、Ａｌｋは互いに独立して脂肪族不飽和炭素－炭素結合含有基を表し、Ｒ’は互いに独立して脂肪族不飽和炭素－炭素結合不含基を表す）で表されるシロキサン単位（Ｍ単位）、及び、ＳｉＯ４／２で表されるシロキサン単位（Ｑ単位）を少なくとも含む硬化反応性オルガノポリシロキサン樹脂であってもよい。 ((E1) Curing Reactive Organopolysiloxane Resin)
In one embodiment of the present invention, at least a part of the component (E) is (E1) in the molecule (Alk)R′ 2 SiO 1/2 (wherein, Alk is independently of each other an aliphatic unsaturated carbon-carbon). Represents a bond-containing group, R'independently of each other represents an aliphatic unsaturated carbon-carbon bond-free group), and a siloxane unit represented by SiO 4/2. It may be a curing-reactive organopolysiloxane resin containing at least (Q unit).
上記の態様では、Ａｌｋである脂肪族不飽和炭素－炭素結合含有基は、既述した、アルケニル基、アルケニルオキシアルキル基、アクリロキシアルキル基又はメタクリロキシアルキル基であることが好ましい。また、Ｒ’である脂肪族不飽和炭素－炭素結合不含基は、既述した、アルキル基、アリール基又はアラルキル基であることが好ましい。また、これらの基の一部はハロゲン原子等によって置換されていてもよい。工業的見地からは、Ａｌｋである脂肪族不飽和炭素－炭素結合含有基は、ビニル基、アリル基又はヘキセニル基であってよく、Ｒ’である脂肪族不飽和炭素－炭素結合不含基はメチル基、フェニル基等であることが好ましい。 In the above aspect, the aliphatic unsaturated carbon-carbon bond-containing group which is Alk is preferably the alkenyl group, alkenyloxyalkyl group, acryloxyalkyl group or methacryloxyalkyl group, which has been described above. Further, the aliphatic unsaturated carbon-carbon bond-free group which is R′ is preferably the alkyl group, aryl group or aralkyl group described above. Moreover, a part of these groups may be substituted with a halogen atom or the like. From an industrial point of view, the aliphatic unsaturated carbon-carbon bond-containing group which is Alk may be a vinyl group, an allyl group or a hexenyl group, and the aliphatic unsaturated carbon-carbon bond-free group which is R'is It is preferably a methyl group or a phenyl group.
上記の態様において、（Ｅ１）硬化反応性オルガノポリシロキサン樹脂以外の（Ｅ）成分が存在する場合は当該（Ｅ）成分は非硬化反応性であることが好ましい。この場合、非硬化反応性（Ｅ）成分のＲは既述した脂肪族不飽和炭素－炭素結合不含基であることが好ましく、アルキル基、アリール基又はアラルキル基であることがより好ましい。また、これらの基の一部はハロゲン原子等によって置換されていてもよい。工業的見地からは、Ｒである脂肪族不飽和炭素－炭素結合不含基はメチル基、フェニル基等であることが好ましい。 In the above aspect, when the component (E) other than the (E1) curing-reactive organopolysiloxane resin is present, the component (E) is preferably non-curing reactive. In this case, R of the non-curing reactive component (E) is preferably the aliphatic unsaturated carbon-carbon bond-free group described above, and more preferably an alkyl group, an aryl group or an aralkyl group. Moreover, a part of these groups may be substituted with a halogen atom or the like. From an industrial point of view, the aliphatic unsaturated carbon-carbon bond-free group which is R is preferably a methyl group, a phenyl group or the like.
　（Ｅ）成分に占める（Ｅ１）硬化反応性オルガノポリシロキサン樹脂の割合は特に限定されるものではないが、本発明の組成物又はその硬化物に粘着材として適度な硬さを実現するためには、（Ｅ）成分全体を１００質量％とした場合、（Ｅ）成分の５０重量％以下が好ましく、３０重量％以下がより好ましく、２０重量％以下が更により好ましい。好適には、（Ｅ）成分中に占める（Ｅ１）成分の含有量は、０～２０質量％の範囲であり、０～１５質量％の範囲が特に好ましく、本発明の組成物又はその硬化物からなる粘着材が、表示装置や太陽電池モジュール等の接着層として適度な硬さと柔軟性を備えることができる。 The proportion of the (E1) curing-reactive organopolysiloxane resin in the component (E) is not particularly limited, but in order to achieve an appropriate hardness for the composition of the present invention or the cured product thereof as an adhesive material. When the total amount of the component (E) is 100% by mass, 50% by weight or less of the component (E) is preferable, 30% by weight or less is more preferable, and 20% by weight or less is still more preferable. The content of the component (E1) in the component (E) is preferably in the range of 0 to 20% by mass, particularly preferably in the range of 0 to 15% by mass, and the composition of the present invention or a cured product thereof. The adhesive material made of can have appropriate hardness and flexibility as an adhesive layer of a display device, a solar cell module, or the like.
　このような（Ｅ）成分として、例えば、
(Me3SiO1/2)0.45(SiO4/2)0.55(HO1/2)0.05
(Me3SiO1/2)0.40(SiO4/2)0.60(HO1/2)0.10
(Me3SiO1/2)0.52(SiO4/2)0.48(HO1/2)0.01
(Me3SiO1/2)0.40(Me２ViSiO1/2)0.05 (SiO4/2)0.55(HO1/2)0.05
(Me3SiO1/2)0.45(SiO4/2)0.55(MeO1/2)0.10
(Me3SiO1/2)0.25(Me2PhSiO1/2)0.20(SiO4/2)0.55(HO1/2)0.05
(Me3SiO1/2)0.40(Me2SiO2/2)0.05(SiO4/2)0.55(HO1/2)0.05
(Me3SiO1/2)0.40(MeSiO3/2)0.05(SiO4/2)0.55(HO1/2)0.05
(Me3SiO1/2)0.40(Me2SiO2/2)0.05(MeSiO3/2)0.05(SiO4/2)0.50(HO1/2)0.05
（Me：メチル基、Ph：フェニル基、Vi：ビニル基、MeO：メトキシ基、HO：ケイ素原子結合水酸基。なお、ケイ素原子に対する水酸基の相対量を表すために、ケイ素原子含有単位の添字の合計量を１としており、（ＨＯ）１／２単位の添字が当該相対量を示す）
を挙げることができる。 As such (E) component, for example,
(Me 3 SiO 1/2 ) 0.45 (SiO 4/2 ) 0.55 (HO 1/2 ) 0.05
(Me 3 SiO 1/2 ) 0.40 (SiO 4/2 ) 0.60 (HO 1/2 ) 0.10
(Me 3 SiO 1/2 ) 0.52 (SiO 4/2 ) 0.48 (HO 1/2 ) 0.01
(Me 3 SiO 1/2 ) 0.40 (Me 2 ViSiO 1/2 ) 0.05 (SiO 4/2 ) 0.55 (HO 1/2 ) 0.05
(Me 3 SiO 1/2 ) 0.45 (SiO 4/2 ) 0.55 (MeO 1/2 ) 0.10
(Me 3 SiO 1/2 ) 0.25 (Me 2 PhSiO 1/2 ) 0.20 (SiO 4/2 ) 0.55 (HO 1/2 ) 0.05
(Me 3 SiO 1/2 ) 0.40 (Me 2 SiO 2/2 ) 0.05 (SiO 4/2 ) 0.55 (HO 1/2 ) 0.05
(Me 3 SiO 1/2 ) 0.40 (MeSiO 3/2 ) 0.05 (SiO 4/2 ) 0.55 (HO 1/2 ) 0.05
(Me 3 SiO 1/2 ) 0.40 (Me 2 SiO 2/2 ) 0.05 (MeSiO 3/2 ) 0.05 (SiO 4/2 ) 0.50 (HO 1/2 ) 0.05
(Me: methyl group, Ph: phenyl group, Vi: vinyl group, MeO: methoxy group, HO: silicon atom-bonded hydroxyl group. In addition, in order to represent the relative amount of the hydroxyl group to the silicon atom, the total of the subscripts of the silicon atom-containing unit The quantity is 1, and the subscript of (HO) 1/2 unit indicates the relative quantity.)
Can be mentioned.
　（Ｅ）成分は、本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物に感圧接着性を付与し、且つ、加熱溶融性を付与する成分であるので、その配合量は所望により選択することができる。例えば、（Ｅ）成分は、（Ａ）成分、（Ｂ）成分、及び、（Ｅ）成分の質量の総和に対して、０．１質量％から９０質量％の範囲であってよい。なお、（Ｅ）成分の配合量が前記上限を超えると、本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物が硬くなりすぎるため、特に粘着材としての使用に適さない場合がある。 The component (E) is a component that imparts pressure-sensitive adhesiveness to the curing-reactive silicone pressure-sensitive adhesive composition of the present invention or a cured product thereof and also imparts heat-melting property, so that the blending amount thereof is selected as desired. can do. For example, the component (E) may be in the range of 0.1 mass% to 90 mass% with respect to the total mass of the component (A), the component (B), and the component (E). In addition, when the compounding quantity of (E) component exceeds the said upper limit, since the hardening reactive silicone adhesive composition of this invention or its hardened|cured material will become too hard, it may be unsuitable especially as an adhesive material.
本発明の硬化反応性シリコーン粘着剤組成物が液状であり、その硬化物が微粘着性～中程度の粘着力を有するように設計する場合には、（Ｅ）成分は、（Ａ）成分、（Ｂ）成分、及び、（Ｅ）成分の質量の総和に対して、０．１質量％から４０質量％の範囲であることが好ましく、０．１質量％から３０質量％の範囲であってよい。ただし、微粘着性の硬化反応性シリコーン粘着剤組成物においては、（Ｅ）成分の配合量を、上記の（Ａ）成分、（Ｂ）成分、及び、（Ｅ）成分の質量の総和に対して、０．１質量％以下に設計してもよく、且つ、好ましい。（Ｅ）成分を全く含まなくても、硬化物は微粘着性の粘着層として使用できるためである。 When the curable reactive silicone pressure-sensitive adhesive composition of the present invention is in a liquid state and the cured product is designed to have a slight to moderate adhesive force, the component (E) is the component (A), It is preferably in the range of 0.1% by mass to 40% by mass, and in the range of 0.1% by mass to 30% by mass, based on the total mass of the components (B) and (E). Good. However, in the slightly tacky curing-reactive silicone pressure-sensitive adhesive composition, the blending amount of the component (E) is based on the total mass of the components (A), (B), and (E). Therefore, it may be designed to be 0.1 mass% or less, and is preferable. This is because the cured product can be used as a slightly tacky adhesive layer even if it does not contain the component (E).
本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物が、ある程度強い粘着力と感圧接着性を有するように設計する場合、（Ｅ）成分の配合量は、（Ａ）成分、（Ｂ）成分、及び、（Ｅ）成分の質量の総和に対して、３５質量％～９０質量％の範囲であることが好ましい。一方、（Ｅ）成分の配合量が９０質量％を超えると、組成物全体のガラス転移点（Ｔｇ）が増大し、組成物全体が過度に硬質となって、粘着剤としての取扱作業性が困難になる場合があり、好ましくない。 When the curing-reactive silicone pressure-sensitive adhesive composition of the present invention or the cured product thereof is designed to have a certain degree of strong adhesive force and pressure-sensitive adhesive property, the compounding amount of the (E) component is (A) component, (B) It is preferable that the amount is in the range of 35% by mass to 90% by mass based on the total mass of the component) and the component (E). On the other hand, when the blending amount of the component (E) exceeds 90% by mass, the glass transition point (Tg) of the entire composition increases, the composition becomes excessively hard, and the handling workability as an adhesive is improved. This may be difficult and is not preferable.
本発明の硬化反応性シリコーン粘着剤組成物に十分な粘着力と加熱溶融性を付与し、組成物全体として、２５℃において非流動性であり、２５℃～１５０℃までの間に軟化点を有するように設計する場合には、（Ｅ）成分の配合量は、（Ａ）成分、（Ｂ）成分、及び、（Ｅ）成分の質量の総和に対して、５５質量％～９０質量％の範囲であることが好ましく、６０～８５質量％の範囲が特に好ましい。なお、２５℃において非流動性の組成物を調製する場合、後述する溶媒を使用しないことが好ましい。（Ｅ）成分の配合量が上記範囲内であれば、本発明の硬化反応性シリコーン粘着剤組成物は、硬化反応前の状態において、仮固定を行う程度であれば十分な粘着力を有し、且つ、硬化反応により部材間の永久接着が可能な程度の接着力を有する硬化物を与えるように設計することが可能である。 The curing-reactive silicone pressure-sensitive adhesive composition of the present invention is provided with sufficient pressure-sensitive adhesive force and heat-melting property, and the composition as a whole is non-fluid at 25° C. and has a softening point between 25° C. and 150° C. When it is designed to have, the blending amount of the component (E) is 55 mass% to 90 mass% with respect to the total mass of the component (A), the component (B), and the component (E). The range is preferable, and the range of 60 to 85 mass% is particularly preferable. In addition, when preparing a non-fluid composition at 25° C., it is preferable not to use a solvent described later. When the compounding amount of the component (E) is within the above range, the curing-reactive silicone pressure-sensitive adhesive composition of the present invention has sufficient adhesive force as long as it is temporarily fixed before the curing reaction. Further, it is possible to design so as to provide a cured product having an adhesive force such that permanent bonding between members can be achieved by the curing reaction.
（Ｆ）成分
本発明の組成物は、前記の通り、無溶媒型の組成物や加熱溶融型の組成物として設計することも可能であるが、更に（Ｆ）溶剤を含むものであってよい。（Ｆ）溶剤の使用により、組成物全体の粘度及びチキソトロピー性を低下させて、取扱作業性や塗工性を改善できるほか、少量の有機溶剤の使用により、組成物の基材に対する濡れ性を改善できる場合があり、本発明にかかる硬化反応性シリコーン粘着剤組成物を様々なプロセスに適用できるように調製することができる。特に、本発明の組成物を薄膜状にしたり、印刷により所望のパターンに塗布したりするために、本発明の組成物に溶剤を加えて使用することができ、且つ、好ましい。 Component (F) As described above, the composition of the present invention can be designed as a solvent-free composition or a heat-melt composition, but may further contain (F) a solvent. .. (F) The use of a solvent can reduce the viscosity and thixotropy of the entire composition to improve handling workability and coatability, and the use of a small amount of an organic solvent can improve the wettability of the composition to a substrate. In some cases, the cure-reactive silicone pressure-sensitive adhesive composition according to the present invention can be prepared so that it can be applied to various processes. In particular, in order to form the composition of the present invention into a thin film or to apply it in a desired pattern by printing, a solvent can be added to the composition of the present invention and it is preferable.
（Ｆ）成分である溶剤は、その種類において特に制限されるものではなく、本発明の組成物を溶解し、均一な溶液を与えるものであれば限定されない。たとえば、低分子シロキサン溶媒であってもよく、有機溶媒であってもよい。特に、好適には、有機溶媒の使用が好ましく、ノルマルヘキサン、ノルマルペンタン、ノルマルヘプタン、ノルマルオクタン、イソオクタン、デカリン等の脂肪族炭化水素；トルエン、キシレン、メシチレン等の芳香族炭化水素；ジイソプロピルエーテル、ジブチルエーテル、テトラヒドロフラン等のエーテル類；酢酸エチル、酢酸ブチル等のエステル類；酢酸プロピレングリコールモノメチルエーテル、酢酸ジプロピレングリコールモノメチルエーテル等のグリコールエステル類が例示される。 The solvent as the component (F) is not particularly limited in its type, and is not limited as long as it dissolves the composition of the present invention and gives a uniform solution. For example, it may be a low molecular weight siloxane solvent or an organic solvent. In particular, it is preferable to use an organic solvent, and normal hexane, normal pentane, normal heptane, normal octane, isooctane, decalin or other aliphatic hydrocarbons; toluene, xylene, mesitylene or other aromatic hydrocarbons; diisopropyl ether, Examples thereof include ethers such as dibutyl ether and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; glycol esters such as propylene glycol monomethyl ether acetate and dipropylene glycol monomethyl ether acetate.
（Ｆ）成分である溶剤の配合量は、特に制限されるものではないが、上記の（Ａ）～（Ｅ）成分の和を１００質量部とした場合、０～９９００質量部の範囲で使用することが一般的であり、基材及び塗膜の厚み等の塗工条件に応じて、溶剤の使用量は適宜、設計可能である。なお、溶剤をいわゆる分散媒として使用し、組成物全体粘度を低減して塗工性を改善する場合、上記の（Ａ）～（Ｅ）成分の和を１００質量部に対して、たとえば５０質量部以上の溶剤を使用してもよいが、溶剤を濡れ性向上等の目的で使用する場合には、たとえば、２０質量部以下の、比較的少量の溶剤を使用することも可能であり、且つ、好ましい。 The blending amount of the solvent which is the component (F) is not particularly limited, but when the sum of the components (A) to (E) is 100 parts by mass, it is used in the range of 0 to 9900 parts by mass. The amount of the solvent used can be appropriately designed depending on the coating conditions such as the thickness of the substrate and the coating film. When a solvent is used as a so-called dispersion medium to reduce the overall viscosity of the composition and improve the coating property, the sum of the above components (A) to (E) is, for example, 50 parts by mass with respect to 100 parts by mass. Although more than one part of the solvent may be used, when the solvent is used for the purpose of improving wettability, for example, it is possible to use a relatively small amount of solvent of 20 parts by mass or less, and ,preferable.
不飽和脂肪族炭化水素
本発明の組成物は、任意で、不飽和脂肪族炭化水素を更に含んでもよい。不飽和脂肪族炭化水素は、ヒドロシリル化反応等に関与する脂肪族不飽和結合を含有するため、硬化反応時の架橋成分としても、前記の溶媒としても機能する、反応性稀釈剤として利用することができる。より具体的には、不飽和脂肪族炭化水素は、炭素原子数８～１８の炭素原子を有し、分子内に少なくとも１つの脂肪族不飽和部分を有する炭化水素化合物である。当該不飽和脂肪族炭化水素は直鎖又は分岐鎖状であってよく、該脂肪族不飽和部分は途中にあっても、又は、末端にあってもよく、分子内に２以上の脂肪族不飽和部分である炭素－炭素二重結合を有することが特に好ましい。このような不飽和脂肪族炭化水素は、分子鎖末端に炭素－炭素二重結合を有する炭素原子数８～１８のアルケン、好適には、炭素原子数１２～１４のアルケンを含み、特に、反応性稀釈剤として使用する場合、ドデセン、テトラデセン、ヘキサデセン、及び、オクタデセンが例示され、テトラデセンが好ましく例示される。 Unsaturated Aliphatic Hydrocarbons The compositions of the present invention may optionally further comprise unsaturated aliphatic hydrocarbons. Unsaturated aliphatic hydrocarbons contain aliphatic unsaturated bonds involved in hydrosilylation reaction and the like, and therefore, they function as a crosslinking component during the curing reaction and also as the above-mentioned solvent, and should be used as a reactive diluent. You can More specifically, the unsaturated aliphatic hydrocarbon is a hydrocarbon compound having 8 to 18 carbon atoms and at least one aliphatic unsaturated moiety in the molecule. The unsaturated aliphatic hydrocarbon may be linear or branched, the aliphatic unsaturated portion may be in the middle or at the end, and two or more aliphatic unsaturated hydrocarbons may be present in the molecule. It is particularly preferred to have carbon-carbon double bonds that are saturated moieties. Such an unsaturated aliphatic hydrocarbon contains an alkene having 8 to 18 carbon atoms, preferably an alkene having 12 to 14 carbon atoms, which has a carbon-carbon double bond at the end of the molecular chain, and is particularly preferably a reaction product. When it is used as a sex diluent, dodecene, tetradecene, hexadecene and octadecene are exemplified, and tetradecene is preferable.
不飽和脂肪族炭化水素の使用量は、特に制限されるものではないが、上記の（Ａ）～（Ｅ）成分の和を１００質量部とした場合、０．１～１０質量部、好適には０．１～７．５質量部の範囲である。 The amount of the unsaturated aliphatic hydrocarbon used is not particularly limited, but is 0.1 to 10 parts by mass, preferably 100 parts by mass when the sum of the components (A) to (E) is 100 parts by mass. Is in the range of 0.1 to 7.5 parts by mass.
その他の成分
　本発明の組成物は、必要に応じて、他のオルガノポリシロキサン、接着性付与剤、シリカ、ガラス、アルミナ、酸化亜鉛等の無機質充填剤；ポリメタクリレート樹脂等の有機樹脂微粉末；蛍光体、耐熱剤、染料、顔料、難燃性付与剤、溶剤等を含むことができる。これらの任意成分の添加量及びその方法は、当業者に公知である。 Other Ingredients The composition of the present invention comprises, if necessary, other organopolysiloxanes, adhesion promoters, inorganic fillers such as silica, glass, alumina and zinc oxide; organic resin fine powders such as polymethacrylate resins; It may contain a phosphor, a heat-resistant agent, a dye, a pigment, a flame retardant, a solvent and the like. The amount of addition of these optional components and the method thereof are known to those skilled in the art.
［製造方法］
　本発明の組成物は、（Ａ）～（Ｄ）成分、必要に応じて（Ｅ）成分、（Ｆ）成分及び／又は他の任意成分を混合することによって製造することができる。本発明の組成物は使用時に混合して調製してもよいが、使用前に、予め混合して調製しておくことが好ましい。 [Production method]
The composition of the present invention can be produced by mixing the components (A) to (D), optionally the component (E), the component (F) and/or other optional components. The composition of the present invention may be prepared by mixing it at the time of use, but it is preferable to prepare it by mixing it before use.
　本発明の組成物は、（Ｄ）成分の使用により、（Ｃ）成分であるヒドロシリル化反応用触媒が（Ａ）、（Ｂ）成分等と共存しても、室温～加熱溶融時にその硬化反応が抑制されるため、単一組成物の形態であっても、混合操作中に硬化反応が進行して増粘乃至ゲル化したり、混合物や成型物が数時間～数日程度で硬化反応性を喪失してしまうことが効果的に防止される。このため、簡便な工程で、本組成物またはその成型物を安定して製造することが可能である。 By using the component (D), the composition of the present invention can cure the hydrosilylation reaction catalyst, which is the component (C), at room temperature to heating and melting even if the catalyst for the hydrosilylation reaction coexists with the components (A) and (B). Therefore, even in the form of a single composition, the curing reaction proceeds during the mixing operation to increase the viscosity or gel, and the mixture and the molded product show the curing reactivity in several hours to several days. Loss is effectively prevented. Therefore, it is possible to stably produce the composition or a molded product thereof by a simple process.
本発明の組成物は、２５℃において液状又は非流動性であってよく、その調製方法は特に制限されるものではないが、以下の方法で調製してよい。 The composition of the present invention may be liquid or non-flowable at 25°C, and the preparation method thereof is not particularly limited, but may be prepared by the following method.
本発明の組成物が、２５℃において流動性を有する液状組成物の場合、機械力により、それぞれの成分を均質に混合することによって行われる。必要に応じて、（Ｆ）成分である溶剤を加えてもよく、公知の攪拌機又は混練機を用いて、０～１５０℃未満の温度で混合して調製してもよい。 When the composition of the present invention is a liquid composition having fluidity at 25° C., it is carried out by mechanically mixing the respective components uniformly. If necessary, a solvent which is the component (F) may be added, or the mixture may be prepared by mixing using a known stirrer or kneader at a temperature of 0 to less than 150°C.
本発明の組成物が、２５℃において非流動性であり、加熱溶融性を有する組成物の場合、例えば、（Ａ）、（Ｂ）、（Ｅ）成分を８０℃～１２０℃の温度範囲で加熱混練しながら、あらかじめ（Ｃ）成分と（Ｄ）成分混合した混合物を、添加混合することによって調製することができる。前記温度範囲では、組成物全体が軟化し、（Ｃ）成分と（Ｄ）成分の混合物を全体に均一分散することができるので、特に、シート等の成型時に硬化不良及び接着時の部分的な凝集破壊を回避できる実益がある。一方、温度が前記下限未満では、軟化が不十分となって、機械力を用いても（Ｃ）成分と（Ｄ）成分の混合物を全体に均一分散することが困難となる場合がある。逆に、温度が前記上限を超えると、（Ｃ）成分が混合時に反応して、全体が著しい増粘又は硬化して加熱溶融性を失う場合があるため、好ましくない。本製造方法で用いる混合機は限定されず、加熱・冷却機能を備えたニーダー、バンバリーミキサー、ヘンシェルミキサー、プラネタリーミキサー、２ロールミル、３ロールミル、ロスミキサー、ラボプラストミル等の回分（バッチ）式、加熱・冷却機能を備えた単軸押出機、２軸押出機等の連続式の加熱混練装置であればよく、特に限定されないが、処理時間の効率とせん断発熱の制御能力に応じて選択される。処理時間の点で考えると、単軸押出機、２軸押出機等連続式であってもよく、ラボプラストミル等のバッチ式の混合機であってもよい。 When the composition of the present invention is a composition which is non-fluid at 25° C. and has a heat-melting property, for example, the components (A), (B) and (E) are added in a temperature range of 80° C. to 120° C. It can be prepared by adding and mixing a mixture in which the components (C) and (D) have been mixed in advance while kneading with heating. In the above temperature range, the composition as a whole softens and the mixture of the component (C) and the component (D) can be uniformly dispersed throughout the composition. There is a real benefit of avoiding cohesive failure. On the other hand, if the temperature is lower than the lower limit, the softening may be insufficient, and it may be difficult to uniformly disperse the mixture of the component (C) and the component (D) even if mechanical force is used. On the other hand, if the temperature exceeds the above upper limit, the component (C) may react during mixing, resulting in a significant increase in viscosity or curing of the entire component and loss of heat-meltability, which is not preferable. The mixer used in this production method is not limited, and a batch (batch) type such as a kneader, a Banbury mixer, a Henschel mixer, a planetary mixer, a two-roll mill, a three-roll mill, a Ross mixer, and a Labo Plastomill having a heating/cooling function. A continuous heating and kneading device such as a single-screw extruder having a heating/cooling function or a twin-screw extruder may be used, and it is not particularly limited, and is selected according to the efficiency of processing time and the controllability of shear heat generation. It In terms of processing time, a continuous type such as a single screw extruder or a twin screw extruder may be used, or a batch type mixer such as Labo Plastomill may be used.
［組成物の使用］
本発明の硬化反応性シリコーン粘着剤組成物は、２５℃で流動性を有する場合、基材上に塗工することによって塗膜を形成させ、加熱することによって硬化物とすることができる。塗工方法としては、オフセットコート、オフセットグラビア、ロールコート、リバースロールコート、エアナイフコート、カーテンコート、及びコンマコートが例示される。塗工時の温度は特に制限されるものではないが、１５０℃未満の温度で塗工することが好ましい。また、本発明の組成物を薄膜状に塗工する場合、組成物の全体粘度の調整、濡れ性の改善等の目的で、例えば、（Ｆ）溶剤を含む形態で基材上に塗工することによって塗膜を形成させ、加熱してもよく、且つ、好ましい。 [Use of composition]
When the curable reactive silicone pressure-sensitive adhesive composition of the present invention has fluidity at 25° C., it can be formed into a coating film by coating it on a substrate, and can be heated to give a cured product. Examples of the coating method include offset coating, offset gravure, roll coating, reverse roll coating, air knife coating, curtain coating, and comma coating. The temperature at the time of coating is not particularly limited, but it is preferable to coat at a temperature of less than 150°C. When the composition of the present invention is applied in the form of a thin film, for the purpose of adjusting the overall viscosity of the composition, improving wettability, etc., for example, it is applied on a substrate in a form containing (F) a solvent. By doing so, a coating film may be formed and heated, and it is preferable.
本発明の硬化反応性シリコーン粘着剤組成物が、２５℃で非流動性であり、加熱溶融性を備える場合、所望の形状に成型して使用することができる。このような成型物は、例えば、（Ｅ）成分の含有量に応じて、仮固定程度であれば十分な接着力を有するように設計することが可能であり、特定の被着体上に配置することで、加熱溶融性粘着材として使用することができる。 When the curable reactive silicone pressure-sensitive adhesive composition of the present invention is non-fluid at 25° C. and has heat melting property, it can be molded into a desired shape and used. Such a molded product can be designed to have a sufficient adhesive force if it is about a temporary fixing, depending on the content of the component (E), and the molded product can be placed on a specific adherend. By doing so, it can be used as a heat-meltable adhesive material.
本発明の組成物は、好適には８０℃以上且つ１５０℃未満の温度で加熱溶融した後に冷却することで、さまざまな形状の物体に加工することができ、例えば、厚さが５μｍ～５ｍｍのシート状、粉体状、若しくは、タブレット状とすることができる。具体的には、本発明の組成物は、加熱、押出し機能を有する装置を用いて加熱溶融し、所望の形状の物体に加工することができる。なお、１５０℃以上に加熱して硬化反応を開始させない限り、当該物体は、硬化反応性と加熱溶融性を維持しているため、加熱溶融性粘着材として、部材、部品又はシート等の形態で利用することが特に好ましい。 The composition of the present invention can be processed into objects of various shapes, preferably by heating and melting at a temperature of 80° C. or higher and lower than 150° C., and then cooling, for example, a thickness of 5 μm to 5 mm. It can be in the form of a sheet, powder, or tablet. Specifically, the composition of the present invention can be heated and melted by using an apparatus having a heating/extruding function and processed into an object having a desired shape. In addition, since the object retains the curing reactivity and the heat-melting property unless it is heated to 150° C. or higher to start the curing reaction, it can be used as a heat-melting adhesive material in the form of a member, a part, a sheet, or the like. It is particularly preferable to utilize.
　上記のとおり、本発明の組成物は例えば（Ｅ）成分の含有量に応じて、仮固定程度であれば十分な接着力を有するように設計することができ、加熱溶融性粘着材として使用できるが、当該組成物を、１５０℃以上に加熱して硬化反応を行うことによって、粘着性の硬化物（半硬化物を含む）を形成することができる。このため、本発明の組成物は、各種のポッティング剤、封止剤、接着剤・粘着剤として有用であり、好ましくは光学粘着剤・接着剤として有用であり、特に、ディスプレイ用光学粘着剤・接着剤として有用である。特に、本発明の組成物は、硬化反応前の状態において、仮固定には十分な粘着力を備え、加熱溶融性であることから、被着体の凹凸や間隙に容易に追従する、ギャップフィル性に優れた粘着材層を形成可能である。更に、その硬化物は高温又は高温・高湿下で着色が少なく、濁りを生じにくいことから、表示装置（ディスプレイ）や太陽電池モジュール等の積層体を構成する部材間の固定層、接着層として極めて有用である。 As described above, the composition of the present invention can be designed to have sufficient adhesive force if it is about a temporary fixing, depending on the content of the component (E), and can be used as a heat-meltable adhesive material. However, an adhesive cured product (including a semi-cured product) can be formed by heating the composition to a temperature of 150° C. or higher to cause a curing reaction. Therefore, the composition of the present invention is useful as various potting agents, sealants, adhesives/adhesives, preferably optical adhesives/adhesives, and particularly optical adhesives for displays. It is useful as an adhesive. In particular, the composition of the present invention has sufficient adhesive force for temporary fixing in the state before the curing reaction and is heat-meltable, so that it easily follows irregularities and gaps of an adherend. It is possible to form an adhesive layer having excellent properties. Furthermore, since the cured product is less colored at high temperatures or under high temperature and high humidity and does not easily become turbid, it can be used as a fixing layer or an adhesive layer between members constituting a laminated body such as a display device (solar cell module). Extremely useful.
（硬化物）
本発明の組成物は硬化物となることができる。硬化物は、本発明の組成物について（更に）ヒドロシリル化反応を行い本発明の組成物を（完全に又は最終的に）硬化させることによって得られる。例えば、１５０℃以上の温度で前記組成物を加熱し、ヒドロシリル化反応を行うことによって硬化させることができる。加熱時間は組成物中の各成分の種類及び配合量にもよるが、通常０．２～４時間、好ましくは０．５～２時間である。 (Cured product)
The composition of the present invention can be a cured product. The cured product is obtained by (further) performing a hydrosilylation reaction on the composition of the present invention to cure the composition of the present invention (completely or finally). For example, the composition can be cured by heating the composition at a temperature of 150° C. or higher and performing a hydrosilylation reaction. The heating time is usually 0.2 to 4 hours, preferably 0.5 to 2 hours, though it depends on the kind and blending amount of each component in the composition.
本発明の硬化物は、種々の材料として用いることができる。ここで、硬化物とは２００℃以上に加熱しても流動しないことを意味する。この硬化物の硬さは特に限定されないが、通常針入度が７０以下のゲル状から、ショアＤ硬さが８０のレジンまでである。 The cured product of the present invention can be used as various materials. Here, the cured product means that it does not flow even when heated to 200° C. or higher. The hardness of this cured product is not particularly limited, but it is usually from a gel having a penetration of 70 or less to a resin having a Shore D hardness of 80.
　好ましくは、本発明の硬化物は光透過性であり、より好ましくは透明である。光透過性、特に透明の硬化物は光学用途に好適に使用することができる。 Preferably, the cured product of the present invention is light transmissive, and more preferably transparent. A light-transmissive, particularly transparent cured product can be suitably used for optical applications.
本発明の硬化物は感圧接着性を有することができる。硬化物の粘着力は特には限定されないが、ＪＩＳ　Ｚ０２３７に準じた方法で、以下の通り測定可能である。 The cured product of the present invention can have pressure-sensitive adhesiveness. The adhesive strength of the cured product is not particularly limited, but can be measured by the method according to JIS Z0237 as follows.
＜２５℃で液状組成物の場合＞
組成物を硬化させて得られる厚み５０μｍの粘着層を、ＳＵＳ鋼板に対して貼り合わせ、１８０°引き剥がし試験方法を用いて引張速度３００ｍｍ/ｍｉｎにて測定した粘着力（２０ｍｍ幅での測定を表示単位ｇｆ/インチに換算）が、０．１ｇｆ/ｉｎｃｈ以上であることが好ましく、０．１ｇｆ／インチ～１０ｋｇｆ／インチであることが特に好ましく、０．２ｇｆ／インチ～１０ｋｇｆ／インチであることが更に好ましい。ただし、これらの粘着力は、微粘着～強粘着乃至永久接着まで、所望の範囲で設計可能であることは言うまでもない。 <For liquid compositions at 25°C>
An adhesive layer having a thickness of 50 μm obtained by curing the composition was adhered to a SUS steel plate, and the adhesive force measured at a pulling speed of 300 mm/min using a 180° peeling test method (measurement in a width of 20 mm was performed. The display unit (converted to gf/inch) is preferably 0.1 gf/inch or more, particularly preferably 0.1 gf/inch to 10 kgf/inch, and 0.2 gf/inch to 10 kgf/inch. Is more preferable. However, it goes without saying that these adhesive strengths can be designed in a desired range from slight adhesion to strong adhesion to permanent adhesion.
＜２５℃で非流動性の加熱溶融性組成物の場合＞
組成物を硬化させて得られる厚み２００μｍの粘着層を、ＳＵＳ鋼板に対して貼り合わせ、１８０°引き剥がし試験方法を用いて引張速度３００ｍｍ/ｍｉｎにて測定した粘着力（２０ｍｍ幅での測定を表示単位ｇｆ/インチに換算）が、０．１ｇｆ/ｉｎｃｈ以上であることが好ましく、０．１ｇｆ／インチ～１０ｋｇｆ／インチであることが特に好ましく、０．２ｇｆ／インチ～１０ｋｇｆ／インチであることが更に好ましい。ただし、これらの粘着力は、微粘着～強粘着乃至永久接着まで、所望の範囲で設計可能であることは言うまでもない。 <In the case of a heat-meltable composition which is non-fluid at 25°C>
An adhesive layer having a thickness of 200 μm obtained by curing the composition was adhered to an SUS steel plate, and the adhesive force measured at a pulling rate of 300 mm/min using a 180° peeling test method (measurement in a width of 20 mm was performed. The display unit (converted to gf/inch) is preferably 0.1 gf/inch or more, particularly preferably 0.1 gf/inch to 10 kgf/inch, and 0.2 gf/inch to 10 kgf/inch. Is more preferable. However, it goes without saying that these adhesive strengths can be designed in a desired range from slight adhesion to strong adhesion to permanent adhesion.
　本発明の硬化物は、一定の伸縮性若しくは柔軟性を有することができる。したがって、本発明の硬化物を弾性粘着部材として使用することができる。 The cured product of the present invention can have a certain elasticity or flexibility. Therefore, the cured product of the present invention can be used as an elastic adhesive member.
（粘着剤）
　本発明の硬化反応性シリコーン粘着剤組成物及びその硬化物は粘着材として利用することができる。 (Adhesive)
The curable reactive silicone pressure-sensitive adhesive composition of the present invention and its cured product can be used as an adhesive.
本発明の粘着材は、高い接着力を備えることができ、各種の被着体と良好に粘着又は接着可能である。また、本発明の粘着材は、被着体からの剥離時に凝集破壊が生じにくい粘着層を形成可能であるが、用途によってはこの限りではなく、凝集破壊を伴うものであってもよい The pressure-sensitive adhesive material of the present invention can have a high adhesive force and can be satisfactorily adhered or adhered to various adherends. Further, the pressure-sensitive adhesive material of the present invention can form a pressure-sensitive adhesive layer in which cohesive failure is less likely to occur at the time of peeling from an adherend, but the present invention is not limited to this and may be accompanied by cohesive failure.
したがって、本発明の硬化反応性シリコーン粘着剤組成物及びその硬化物粘着材層を被着体から剥離する際の挙動は用途の応じて好ましく制御することが可能である。例えば、（感圧）粘着剤としての作用が期待される用途においては、被着体表面の残留物が無いか、若しくは、あっても僅かとすることができる。一方、用途のよっては凝集破壊を示すような高接着性を示すことも問題とはならない。 Therefore, the behavior of the cured reactive silicone pressure-sensitive adhesive composition of the present invention and the cured product pressure-sensitive adhesive layer thereof when peeled from the adherend can be preferably controlled according to the application. For example, in applications where an action as a (pressure-sensitive) pressure-sensitive adhesive is expected, there is no residue on the adherend surface, or even a small amount of residue may be present. On the other hand, depending on the application, it does not pose a problem to exhibit high adhesiveness such as cohesive failure.
加熱溶融性粘着材としての使用
例えば、上記の（Ｅ）成分の配合量により、本発明の硬化反応性シリコーン粘着剤組成物は、組成物全体として、２５℃において非流動性且つホットメルト性の組成物として設計可能である。この場合、本発明の硬化反応性シリコーン粘着剤組成物は、硬化反応前においては、加熱溶融性粘着材として、成形性、ギャップフィル性及び粘着力に優れる粘着材として使用することができる。また、本発明の硬化反応性シリコーン粘着剤組成物の硬化物は、加熱溶融性と硬化反応性を実質的に失うが、粘着力に優れる粘着材として使用することができる。このため、硬化反応性シリコーン粘着剤組成物からなる粘着材は、部材を仮固定したり、凹凸や間隙に対するギャップフィル性を生かした粘着材層を被着体に形成して、被着体間の仮固定、配置、及び、貼り合わせを行ったうえで、当該硬化反応性シリコーン粘着剤組成物からなる粘着材を１５０℃以上に加熱して、被着体間に硬化物からなる粘着材を形成させてもよい。また、本発明の硬化反応性シリコーン粘着剤組成物の硬化物からなる粘着材は、それ自体が感圧接着材として使用することができるため、本発明の硬化反応性シリコーン粘着剤組成物の加熱溶融性を利用してシート状等に成型してから硬化させ、所望の形状を有する粘着部材として単独で取り扱ってもよい。 Use as a heat-meltable pressure-sensitive adhesive material For example, depending on the blending amount of the above-mentioned component (E), the curable reactive silicone pressure-sensitive adhesive composition of the present invention is non-flowable and hot-meltable at 25° C. as a whole composition. It can be designed as a composition. In this case, the curing-reactive silicone pressure-sensitive adhesive composition of the present invention can be used as a heat-melting pressure-sensitive adhesive as a pressure-sensitive adhesive having excellent moldability, gap fill property and pressure-sensitive adhesive before the curing reaction. Further, the cured product of the curing-reactive silicone pressure-sensitive adhesive composition of the present invention can be used as a pressure-sensitive adhesive material having excellent adhesive strength, although the heat-meltability and the curing reactivity are substantially lost. Therefore, the pressure-sensitive adhesive comprising the curing-reactive silicone pressure-sensitive adhesive composition can be used to temporarily fix a member or to form a pressure-sensitive adhesive layer that makes use of the gap fill property against irregularities and gaps on an adherend, and After temporarily fixing, arranging, and pasting, the adhesive material made of the curing-reactive silicone adhesive composition is heated to 150° C. or higher to form an adhesive material made of a cured material between adherends. It may be formed. In addition, since the pressure-sensitive adhesive comprising the cured product of the curable reactive silicone pressure-sensitive adhesive composition of the present invention can be used as a pressure-sensitive adhesive by itself, heating of the curable reactive silicone pressure-sensitive adhesive composition of the present invention can be performed. It may be treated as a pressure-sensitive adhesive member having a desired shape by molding it after being molded into a sheet shape or the like by utilizing the meltability.
硬化物からなる粘着材としての使用
本発明の硬化反応性シリコーン粘着剤組成物は、１５０℃以上で加熱することで、粘着性の硬化物（硬化反応物）を形成することができる。当該硬化物は、粘着層、接着層、特に感圧接着層（ＰＳＡ層）として、圧着により部材間を接合する粘着材として利用することができる。後述するように、硬化物は、単独で粘着材として使用することができるため、本発明の硬化反応性シリコーン粘着剤組成物の硬化物を粘着性フィルム又は感圧接着性フィルムとして単独で取り扱ってもよく、液状又は上記の加熱溶融性粘着材の形態で部材上に配置した後又は配置と同時に、当該硬化反応性シリコーン粘着剤組成物を１５０℃以上に加熱して硬化させ、粘着材を形成してもよい。なお、硬化前の状態が２５℃において流動性を有する液状組成物であっても、２５℃において非流動性のホットメルト性の組成物であっても、その硬化物は、粘着材（特に粘着層）として使用可能である。 Use as an Adhesive Material Consisting of Cured Product The curable reactive silicone adhesive composition of the present invention can form an adhesive cured product (curing reaction product) when heated at 150° C. or higher. The cured product can be used as an adhesive layer, an adhesive layer, particularly a pressure-sensitive adhesive layer (PSA layer), as an adhesive material for joining members by pressure bonding. As will be described later, since the cured product can be used alone as an adhesive material, the cured product of the curable reactive silicone adhesive composition of the present invention can be treated as an adhesive film or a pressure-sensitive adhesive film alone. Alternatively, after being placed on the member in the form of a liquid or the above heat-meltable adhesive material, or simultaneously with the arrangement, the curable reactive silicone adhesive composition is heated to 150° C. or higher to be cured to form an adhesive material. You may. Whether the composition before curing is a liquid composition having fluidity at 25° C. or a non-fluidic hot-melt composition at 25° C., the cured product is an adhesive material (particularly an adhesive material). Can be used as a layer).
［積層体］
本発明の硬化反応性シリコーン粘着剤組成物からなる層又は当該組成物の硬化物からなる層又は部材を備える積層体を提供することができる。前記積層体は、特に制限されるものではないが、粘着性シート（接着性シート感圧接着（PSA）性シートを含む）、それらが剥離層を備えたシート状部材に積層された剥離性の積層体であってよい。 [Laminate]
It is possible to provide a laminate comprising a layer made of the curable reactive silicone pressure sensitive adhesive composition of the present invention or a layer or member made of a cured product of the composition. The laminate is not particularly limited, but a pressure-sensitive adhesive sheet (including an adhesive sheet and a pressure-sensitive adhesive (PSA) sheet), a peelable sheet obtained by laminating the sheet-like member having a release layer. It may be a laminate.
粘着性シート
　次に、本発明に係る積層体の一種である粘着性シートについて説明する。 Adhesive Sheet Next, an adhesive sheet, which is a kind of the laminate according to the present invention, will be described.
　本発明の粘着性シートは、
　少なくとも１つのシート状基材、
　前記シート状基材上に形成された少なくとも１つの粘着性層
を備えており、
　前記粘着性層が上記の硬化反応性シリコーン粘着剤組成物又はその硬化物を含む。 The adhesive sheet of the present invention,
At least one sheet-like substrate,
Comprising at least one adhesive layer formed on the sheet-shaped substrate,
The adhesive layer contains the above-mentioned curing reactive silicone adhesive composition or its cured product.
未硬化状態の粘着性シート
　本発明の粘着性シートの粘着性層に含まれる硬化反応性シリコーン粘着剤組成物は未硬化物であってもよい。このような粘着性シートは、２５℃において非流動性のホットメルト性の組成物を用いることで容易に得ることができる。 Non-Cured Adhesive Sheet The curable reactive silicone adhesive composition contained in the adhesive layer of the adhesive sheet of the present invention may be an uncured product. Such an adhesive sheet can be easily obtained by using a non-fluidic hot-melt composition at 25°C.
　本発明の粘着性シートは、例えば、シート状基材上に、本発明の硬化反応性シリコーン粘着剤組成物を加熱溶融状態で塗布して所定の厚みの粘着性層を形成し、必要に応じて、当該粘着性層を半硬化させることによって製造することができる。 The pressure-sensitive adhesive sheet of the present invention is, for example, a sheet-like base material on which the curable reactive silicone pressure-sensitive adhesive composition of the present invention is applied in a heat-melted state to form a pressure-sensitive adhesive layer having a predetermined thickness. Then, it can be manufactured by semi-curing the adhesive layer.
　シート状基材の種類は特には限定されるものではなく、ポリエステルフィルム、ポリオレフィンフィルム、ポリカーボネートフィルム、アクリルフィルム等を適宜使用することができる。シート状基材は非多孔性であることが好ましい。 The type of sheet-shaped substrate is not particularly limited, and a polyester film, a polyolefin film, a polycarbonate film, an acrylic film or the like can be appropriately used. The sheet-shaped substrate is preferably non-porous.
シート状基材への塗布方法としては、オフセットコート、オフセットグラビア、オフセット転写ロールコーター等を用いたロールコート、リバースロールコート、エアナイフコート、カーテンフローコーター等を用いたカーテンコート、コンマコート、マイヤーバー、その他公知の、層を形成する目的で使用される方法が制限なく使用できる。 As a coating method for a sheet-shaped substrate, roll coating using an offset coat, offset gravure, offset transfer roll coater, etc., reverse roll coat, air knife coat, curtain coat using a curtain flow coater, comma coat, Mayer bar, etc. Other known methods used for forming a layer can be used without limitation.
　本発明の粘着性シートでは、シート状基材が少なくとも１つの剥離層を備えており、当該剥離層が粘着材層と接触していることが好ましい。これにより、粘着材層をシート状基材から容易に剥離することができる。剥離層は剥離ライナー、セパレーター、離型層或いは剥離コーティング層と呼ばれることもあり、好適には、シリコーン系剥離剤、フッ素系剥離剤、アルキド系剥離剤、又は、フルオロシリコーン系剥離剤等の剥離コーティング能を有する剥離層、基材表面に物理的に微細な凹凸を形成させたり、本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる接着材層と付着しにくい基材それ自体であってもよい。特に本発明の積層体においては、剥離層として、フルオロシリコーン系剥離剤を硬化させてなる剥離層の使用が好ましい。 In the pressure-sensitive adhesive sheet of the present invention, it is preferable that the sheet-shaped substrate has at least one release layer, and the release layer is in contact with the pressure-sensitive adhesive layer. Thereby, the adhesive layer can be easily peeled off from the sheet-shaped substrate. The release layer is sometimes called a release liner, a separator, a release layer or a release coating layer, and is preferably a release agent such as a silicone release agent, a fluorine release agent, an alkyd release agent, or a fluorosilicone release agent. A release layer having a coating ability, a substrate itself which is difficult to adhere to the curing reactive silicone pressure-sensitive adhesive composition of the present invention or an adhesive layer made of the cured product, which physically forms fine irregularities on the surface of the substrate. May be Particularly in the laminate of the present invention, it is preferable to use a release layer obtained by curing a fluorosilicone release agent as the release layer.
　本発明の粘着性シートは、例えば、粘着性層を被着体に適用後に、当該未硬化状態の粘着性シートを、シート状基材から剥離することにより使用することができる。なお、後述するように、粘着性シートを１５０℃以上に加熱して硬化物を形成させてから剥離して使用してもよい。 The adhesive sheet of the present invention can be used, for example, by applying the adhesive layer to an adherend and then peeling the uncured adhesive sheet from the sheet-shaped substrate. As will be described later, the adhesive sheet may be heated to 150° C. or higher to form a cured product and then peeled off before use.
　本発明の粘着性シートが、２５℃において非流動性のホットメルト性の組成物の成型物である、ホットメルト型の粘着性シートの場合、当該粘着性シートを被着体に適用後、最終硬化前に、粘着性シートを加熱することで、粘着性シートは柔軟化乃至流動化し、例えば、被着体の被着面に凹凸があっても、隙間なく粘着性層を充填することができる。粘着性シートの加熱手段としては、例えば各種の恒温槽や、ホットプレート、電磁加熱装置、加熱ロール等を用いることができる。より効率的に貼合と加熱を行うためには、例えば電熱プレス機や、ダイアフラム方式のラミネータ、ロールラミネータなどが好ましく用いられる。 When the pressure-sensitive adhesive sheet of the present invention is a hot-melt pressure-sensitive adhesive sheet which is a molded product of a non-fluidic hot-melt composition at 25° C., after applying the pressure-sensitive adhesive sheet to an adherend, the final By heating the adhesive sheet before curing, the adhesive sheet is softened or fluidized, and for example, even if the adherend surface of the adherend has irregularities, the adhesive layer can be filled with no gaps. .. As the heating means for the adhesive sheet, for example, various constant temperature baths, hot plates, electromagnetic heating devices, heating rolls and the like can be used. In order to perform the bonding and the heating more efficiently, for example, an electric heat press, a diaphragm type laminator, a roll laminator, or the like is preferably used.
この際、ホットメルト型の粘着性シートの軟化温度が５０℃以上であれば、加工特性や常温での保管特性を十分にすることができる。一方、粘着性層の軟化温度が１００℃以下であれば、画像表示パネル等に対する熱損傷を抑制することができるばかりか、粘着性層が流動し過ぎてはみだしたりするのを防ぐことができる。よって、ホットメルト型の粘着性シートの軟化温度は、５０～１００℃であるのが好ましく、中でも５５℃以上或いは９５℃以下、その中でも６０℃以上或いは９０℃以下であるのが更に好ましい。 At this time, if the softening temperature of the hot-melt type adhesive sheet is 50° C. or higher, the processing characteristics and the storage characteristics at room temperature can be made sufficient. On the other hand, if the softening temperature of the adhesive layer is 100° C. or lower, not only heat damage to the image display panel and the like can be suppressed, but also the adhesive layer can be prevented from flowing out and protruding. Therefore, the softening temperature of the hot-melt type adhesive sheet is preferably 50 to 100°C, more preferably 55°C or higher or 95°C or lower, and further preferably 60°C or higher or 90°C or lower.
硬化物を含む粘着性シート
本発明の粘着性シートの粘着性層に含まれる硬化反応性シリコーン粘着剤組成物は硬化物であってもよい。このような粘着性シートは、２５℃において流動性の組成物を塗布して所定の厚みの粘着性層を形成し、１５０℃以上の温度で加熱硬化させて得ることができる。また、このような粘着性シートは、上記のホットメルト型の粘着性シートを１５０℃の温度で加熱硬化させて得ることができる。なお、シート状基材への塗布方法及び剥離層を備えたシート状基材の使用は上記同様である。 Adhesive Sheet Containing Cured Product The curable reactive silicone adhesive composition contained in the adhesive layer of the adhesive sheet of the present invention may be a cured product. Such an adhesive sheet can be obtained by applying a fluid composition at 25°C to form an adhesive layer having a predetermined thickness, and heating and curing at a temperature of 150°C or higher. Further, such an adhesive sheet can be obtained by heating and curing the above hot-melt adhesive sheet at a temperature of 150°C. The method of applying the sheet-shaped substrate and the use of the sheet-shaped substrate provided with the release layer are the same as above.
　本発明の粘着性シートは、例えば、粘着性層を被着体に適用後に加熱等により当該粘着性層に含まれる硬化反応性シリコーン粘着剤組成物を硬化させ、シート状基材から未硬化状態の粘着性層を剥離することにより使用することができる。 The pressure-sensitive adhesive sheet of the present invention is, for example, a cured reactive silicone pressure-sensitive adhesive composition contained in the pressure-sensitive adhesive layer is cured by heating after applying the pressure-sensitive adhesive layer to an adherend, and the sheet-shaped substrate is in an uncured state. It can be used by peeling off the adhesive layer.
粘着性層については、厚みを薄くすることで、薄肉化要求に応えることができる一方、厚みを薄くし過ぎると、たとえば被着面に凹凸部あった場合に充分に凹凸に追従できなかったり、十分な接着力を発揮できなかったりする可能性がある。かかる観点から、粘着性層の厚みは５～１００００μｍであるのが好ましく、中でも１０μｍ以上或いは８０００μｍ以下、その中でも２０μｍ以上或いは５０００μｍ以下であるのが特に好ましい。 Regarding the adhesive layer, by making the thickness thin, it is possible to meet the demand for thinning, while if the thickness is too thin, for example, if there is an uneven portion on the adherend, it may not be possible to follow the unevenness sufficiently, There is a possibility that it may not exhibit sufficient adhesive strength. From this viewpoint, the thickness of the adhesive layer is preferably 5 to 10000 μm, more preferably 10 μm or more or 8000 μm or less, and particularly preferably 20 μm or more or 5000 μm or less.
感圧接着シート
　次に、上記粘着性シートの一種である感圧接着シートについて説明する。 Pressure-Sensitive Adhesive Sheet Next, a pressure-sensitive adhesive sheet that is a kind of the above-mentioned adhesive sheet will be described.
　本発明の感圧接着シートは、
　少なくとも１つのシート状基材、
　前記シート状基材上に形成された少なくとも１つの感圧接着層
を備えており、
　前記感圧接着層が上記の硬化反応性シリコーン粘着剤組成物又はその硬化物を含む。 The pressure-sensitive adhesive sheet of the present invention,
At least one sheet-like substrate,
It has at least one pressure-sensitive adhesive layer formed on the sheet-shaped substrate,
The pressure-sensitive adhesive layer contains the above-mentioned curing reactive silicone pressure-sensitive adhesive composition or a cured product thereof.
　硬化は、例えば、１５０℃以上での加熱等により、本発明の組成物においてヒドロシリル化反応を行うことで実施することができる。 The curing can be carried out, for example, by performing a hydrosilylation reaction in the composition of the present invention by heating at 150° C. or higher.
　本発明の感圧接着シートは、例えば、シート状基材上に、本発明の硬化反応性シリコーン粘着剤組成物を塗布して所定の厚みの層を形成し、当該層を硬化させて感圧接着層とすることによって製造することができる。 The pressure-sensitive adhesive sheet of the present invention is, for example, a sheet-shaped substrate, the curable reactive silicone pressure-sensitive adhesive composition of the present invention is applied to form a layer having a predetermined thickness, and the layer is cured to give a pressure-sensitive adhesive sheet. It can be manufactured by using an adhesive layer.
　シート状基材の種類は特には限定されるものではなく、ポリエステルフィルム、ポリオレフィンフィルム、ポリカーボネートフィルム、アクリルフィルム等を適宜使用することができる。シート状基材は非多孔性であることが好ましい。　 The type of sheet-shaped substrate is not particularly limited, and a polyester film, a polyolefin film, a polycarbonate film, an acrylic film or the like can be appropriately used. The sheet-shaped substrate is preferably non-porous. ‥
シート状基材への塗布方法としては、オフセットコート、オフセットグラビア、オフセット転写ロールコーター等を用いたロールコート、リバースロールコート、エアナイフコート、カーテンフローコーター等を用いたカーテンコート、コンマコート、マイヤーバー、その他公知の、層を形成する目的で使用される方法が制限なく使用できる。 As a coating method for a sheet-shaped substrate, roll coating using an offset coat, offset gravure, offset transfer roll coater, etc., reverse roll coat, air knife coat, curtain coat using a curtain flow coater, comma coat, Mayer bar, etc. Other known methods used for forming a layer can be used without limitation.
　本発明の感圧接着シートでは、シート状基材が少なくとも１つの剥離層を備えており、当該剥離層が感圧接着層と接触していることが好ましい。これにより、感圧接着層をシート状基材から容易に剥離することができる。剥離層に含まれる剥離剤は特には限定されるものではなく、上記の剥離剤を挙げることができる。 In the pressure-sensitive adhesive sheet of the present invention, it is preferable that the sheet-shaped substrate has at least one release layer, and the release layer is in contact with the pressure-sensitive adhesive layer. Thereby, the pressure-sensitive adhesive layer can be easily peeled off from the sheet-shaped substrate. The release agent contained in the release layer is not particularly limited, and the above-mentioned release agents can be mentioned.
　本発明の感圧接着シートの一態様では、シート状基材は２つであってもよい。 In one aspect of the pressure-sensitive adhesive sheet of the present invention, the number of sheet-shaped substrates may be two.
例えば、本発明の感圧接着シートは、
第１のシート状基材、
第２のシート基材、
第１のシート基材及び第２のシート基材の間に形成された少なくとも１つの感圧接着層
を備え、
前記感圧接着層が前記第１のシート基材及び前記第２のシート基材に接触する形態であってもよい。 For example, the pressure-sensitive adhesive sheet of the present invention,
A first sheet-shaped substrate,
A second sheet base material,
Comprising at least one pressure sensitive adhesive layer formed between a first sheet substrate and a second sheet substrate,
The pressure-sensitive adhesive layer may be in contact with the first sheet base material and the second sheet base material.
上記の形態の感圧接着シートは、例えば、本発明の硬化反応性シリコーン粘着剤組成物を第１のシート状基材及び第２のシート状基材に挟み、加熱しつつ、プレス又はロールで一定の厚みに成形した後、前記組成物を硬化させることによって製造することができる。 The pressure-sensitive adhesive sheet of the above-mentioned form is, for example, sandwiching the curable reactive silicone pressure-sensitive adhesive composition of the present invention between a first sheet-shaped base material and a second sheet-shaped base material, and heating it with a press or a roll. It can be produced by molding the composition to a predetermined thickness and then curing the composition.
　第１のシート基材は第１の剥離層を備えていてもよく、或いは、第１のシート基材自体が剥離性を備えるものであってもよい。同様に、第２のシート基材は第２の剥離層を備えていてもよく、或いは、第２のシート基材自体が剥離性を備えるものであってもよい。第１のシート基材及び／又は第２のシート基材が第１の剥離層及び／又は第２の剥離層を備える場合は、感圧接着層は第１の剥離層及び／又は第２の剥離層に接触することが好ましい。 The first sheet base material may be provided with a first release layer, or the first sheet base material itself may be provided with a release property. Similarly, the second sheet base material may be provided with a second release layer, or the second sheet base material itself may be provided with releasability. When the first sheet substrate and/or the second sheet substrate comprises the first release layer and/or the second release layer, the pressure-sensitive adhesive layer is the first release layer and/or the second release layer. It is preferable to contact the release layer.
　剥離性を有するシート基材としては、例えば、フッ素樹脂製フィルム等の剥離性を有する材質からなるシート基材、或いは、ポリオレフィンフィルム等の剥離性がないか若しくは低い材質にシリコーン、フッ素樹脂等の剥離剤を添加したものからなるシート基材が挙げられる。一方、剥離層を備えるシート基材としては、例えば、シリコーン、フッ素樹脂等の剥離剤をコーティングしたポリオレフィンフィルム等が挙げられる。 Examples of the releasable sheet base material include a sheet base material made of a releasable material such as a fluororesin film, or a non-removable or low releasable material such as a polyolefin film such as silicone or fluororesin. Examples of the sheet base material include a release agent added. On the other hand, examples of the sheet substrate having a release layer include a polyolefin film coated with a release agent such as silicone and fluororesin.
　本発明の感圧接着シートは、例えば、感圧接着層を被着体に適用後に、シート状基材から感圧接着層を剥離することにより使用することができる。 The pressure-sensitive adhesive sheet of the present invention can be used, for example, by applying the pressure-sensitive adhesive layer to an adherend and then peeling the pressure-sensitive adhesive layer from the sheet-shaped substrate.
感圧接着層の厚みは、５～１００００μｍであるのが好ましく、中でも１０μｍ以上或いは８０００μｍ以下、その中でも２０μｍ以上或いは５０００μｍであるのが特に好ましい。 The thickness of the pressure-sensitive adhesive layer is preferably 5 to 10000 μm, more preferably 10 μm or more or 8000 μm or less, and particularly preferably 20 μm or more or 5000 μm.
粘着テープとしての使用
以下、本発明の積層体の具体例について更に説明する。 Use as Adhesive Tape Hereinafter, specific examples of the laminate of the invention will be further described.
例えば、本発明の積層体は、粘着テープであってよく、上記の合成樹脂フィルム・シート、金属箔、織布、不織布、紙等の繊維製品からなるシート状部材と上記の粘着層を備えることを特徴とする。このような粘着テープの種類は、特に制限されるものではなく、絶縁テープ、耐熱テープ、ハンダマスキングテープ、マイカテープバインダー、仮止めテープ（シリコーンゴム部品等の仮止めテープを特に含む）、スプライシングテープ（シリコーン剥離紙用スプライシングテープを特に含む）があげられる。 For example, the laminate of the present invention may be an adhesive tape, and is provided with a sheet-like member made of a fiber product such as the above-mentioned synthetic resin film/sheet, metal foil, woven cloth, non-woven cloth, paper and the above-mentioned adhesive layer. Is characterized by. The type of such an adhesive tape is not particularly limited, and it includes an insulating tape, a heat-resistant tape, a solder masking tape, a mica tape binder, a temporary fixing tape (including a temporary fixing tape such as a silicone rubber part), a splicing tape. (In particular, a splicing tape for silicone release paper is included).
絶縁テープとしては、例えば、ポリ塩化ビニル等の絶縁性を備える合成樹脂からなるテープ（基体）に本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着材を粘着層として備えるものを挙げることができる。そのような絶縁テープは、例えば、電線の絶縁被覆の補修等の電気絶縁性が求められる用途に好適に使用することができる。 As the insulating tape, for example, a tape (base) made of a synthetic resin having an insulating property such as polyvinyl chloride and the curing reactive silicone pressure-sensitive adhesive composition of the present invention or a pressure-sensitive adhesive made of the cured product is used as a pressure-sensitive adhesive layer. Can be mentioned. Such an insulating tape can be suitably used, for example, in applications where electrical insulation is required, such as repairing the insulating coating of electric wires.
　耐熱テープとしては、例えば、ポリイミド等の耐熱性を有する合成樹脂からなるテープ（基体）に本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着材を粘着層として備えるものを挙げることができる。そのような耐熱テープは、例えば、自動車等のマフラーの補修等の耐熱性が求められる用途に好適に使用することができる。本発明の粘着テープの粘着層はシリコーン系であるので耐熱性に優れている。 Examples of the heat-resistant tape include a tape (substrate) made of a heat-resistant synthetic resin such as polyimide, and the like, which is provided with the curable reactive silicone pressure-sensitive adhesive composition of the present invention or a pressure-sensitive adhesive made of the cured product as an adhesive layer. be able to. Such a heat-resistant tape can be suitably used for applications requiring heat resistance, such as repair of mufflers of automobiles and the like. Since the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape of the present invention is made of silicone, it has excellent heat resistance.
ハンダマスキングテープは絶縁テープ又は耐熱テープの一種であり、プリント基板のはんだ付け工程でのマスキングに使用することができる。 The solder masking tape is a kind of insulating tape or heat resistant tape, and can be used for masking in a soldering process of a printed circuit board.
マイカテープは絶縁テープ又は耐熱テープの一種であり、マイカ（雲母）製シート（基体）に適量のバインダーを含浸させて必要に応じて加熱圧縮して得ることができ、また、これを更にガラスクロスシート等の補強材と貼り合わせてテープ状に加工してもよい。本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物を上記バインダーとして使用することができる。更に、マイカテープは粘着層を備えていてもよく、本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物を当該粘着層として使用してもよい。 Mica tape is a type of insulating tape or heat-resistant tape. It can be obtained by impregnating a mica (mica) sheet (substrate) with an appropriate amount of binder and heating and compressing it as needed. It may be processed into a tape by laminating it with a reinforcing material such as a sheet. The curable reactive silicone pressure-sensitive adhesive composition of the present invention or a cured product thereof can be used as the binder. Further, the mica tape may be provided with an adhesive layer, and the curable reactive silicone adhesive composition of the present invention or its cured product may be used as the adhesive layer.
仮止めテープは、各種の仮止め用途に使用されるテープであり、本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着層を備える。前記粘着層は優れた粘着性及び剥離性を備えるので本発明の仮止めテープは仮止めに好適である。前記粘着層はシリコーン系であるのでシリコーンゴム製の部品に対する親和性に優れており、シリコーンゴム製の部品の仮止めに特に好適に使用することができる。 The temporary fixing tape is a tape used for various temporary fixing applications, and includes the curable reactive silicone pressure-sensitive adhesive composition of the present invention or an adhesive layer made of a cured product thereof. Since the adhesive layer has excellent adhesiveness and peelability, the temporary fixing tape of the present invention is suitable for temporary fixing. Since the pressure-sensitive adhesive layer is made of silicone, it has a good affinity for parts made of silicone rubber, and can be particularly preferably used for temporarily fixing parts made of silicone rubber.
　スプライシングテープはフィルム等の接続に使用されるテープであり、本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着層を備える。前記粘着層は優れた粘着性を備えるので本発明のスプライシングテープはフィルム等の接続に好適である。前記粘着層はシリコーン系であるのでシリコーン剥離処理された面にも接着性を備えており、シリコーン剥離紙の接続に特に好適に使用することができる。 The splicing tape is a tape used for connecting films and the like, and includes a curing reactive silicone pressure-sensitive adhesive composition of the present invention or an adhesive layer made of the cured product. Since the adhesive layer has excellent adhesiveness, the splicing tape of the present invention is suitable for connecting a film or the like. Since the pressure-sensitive adhesive layer is made of silicone, it has adhesiveness even on the surface subjected to silicone release treatment, and can be particularly suitably used for connecting silicone release paper.
物品
　本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着材は様々な物体の接着に使用することができる。 Articles The curable reactive silicone pressure-sensitive adhesive composition of the present invention or an adhesive comprising the cured product thereof can be used for adhesion of various objects.
　斯くして、本発明は、
　少なくとも１つの基体、
　少なくとも１つの粘着材部品
を備える物品であって、
　前記粘着材部品が本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着材を含む、物品にも関する。 Thus, the present invention is
At least one substrate,
An article comprising at least one adhesive component, comprising:
The present invention also relates to an article, wherein the pressure-sensitive adhesive component includes the curing-reactive silicone pressure-sensitive adhesive composition of the present invention or a pressure-sensitive adhesive made of a cured product thereof.
　前記基体及び前記粘着材部品の形状は任意であり、各種の三次元形状とすることができる。前記粘着材の性質は上記のとおりである。 The shapes of the base and the adhesive component are arbitrary and can be various three-dimensional shapes. The properties of the adhesive material are as described above.
　前記粘着材部品は基体上又は基体中に存在することができる。好ましくは、前記基体の少なくとも一部が前記粘着材部品と接着する。 The adhesive component can be on or in the substrate. Preferably, at least a part of the base adheres to the adhesive component.
前記粘着材部品は、粘着力を備えており、他の各種の基体と良好に接着することができる。更に、前記粘着材部品により他の基体に永久接着してもよく、また、前記粘着材部品を他の基体から剥離する際には凝集破壊が生じず、界面剥離となる接着モードに設計することも可能である。 The pressure-sensitive adhesive material component has a pressure-sensitive adhesive force, and can adhere well to various other substrates. Furthermore, the adhesive component may be permanently bonded to another substrate, and the adhesive component should be designed in an adhesive mode in which cohesive failure does not occur when the adhesive component is peeled from the other substrate and interfacial peeling occurs. Is also possible.
　同様に、本発明は、
　少なくとも１つの基板、
　少なくとも１つの粘着材層
を備える積層体を含む物品であって、
　前記粘着材層が本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着材を含む、物品にも関する。 Similarly, the present invention
At least one substrate,
An article comprising a laminate comprising at least one adhesive layer, comprising:
The present invention also relates to an article, wherein the pressure-sensitive adhesive layer contains the curable reactive silicone pressure-sensitive adhesive composition of the present invention or a pressure-sensitive adhesive made of a cured product thereof.
　前記基板の形状はシート状又はフィルム状であり、また、前記粘着材層の形状は層状である。好ましくは、前記基板の表面の少なくとも一部が前記粘着材層と接着する。前記粘着材の性質は上記のとおりである。 The shape of the substrate is a sheet or a film, and the shape of the adhesive layer is a layer. Preferably, at least a part of the surface of the substrate adheres to the adhesive layer. The properties of the adhesive material are as described above.
　前記基体又は前記基板は複数存在することができる。この場合、前記粘着材層は複数の基体又は基板の間に存在することができ、好ましくは、複数の基体又は基板を相互に接合する。 There can be a plurality of the bases or the substrates. In this case, the adhesive layer can be present between a plurality of bases or substrates, preferably a plurality of bases or substrates are joined together.
前記基体又は前記基板は多孔性又は非多孔性のいずれでもよい。 The substrate or substrate may be porous or non-porous.
　多孔性基体又は多孔性基板としては、例えば、織布、不織布、紙等の繊維製品、延伸等により多孔化した合成樹脂フィルム・シート、これらの組合せが挙げられる。繊維としては、天然繊維、合成繊維又はこれらの混合物のいずれであってもよい。 Examples of the porous substrate or the porous substrate include woven fabric, non-woven fabric, fiber products such as paper, synthetic resin film and sheet made porous by stretching, and a combination thereof. The fibers may be natural fibers, synthetic fibers or a mixture thereof.
　多孔性基体又は多孔性基板を備える本発明の物品では、当該基体又は基板の少なくとも一部の孔内に本発明の粘着材が存在可能である。この場合、例えば、布又は紙等の多孔性の基体又は基板に本発明の組成物を含浸（加熱溶融状態における含浸及び冷却を含む）して、必要に応じて更に高温で加熱して硬化させることにより、そのような物品を製造することができる。 In an article of the present invention including a porous base or a porous substrate, the adhesive material of the present invention can be present in at least a part of the holes of the base or the substrate. In this case, for example, a porous substrate or substrate such as cloth or paper is impregnated with the composition of the present invention (including impregnation and cooling in a heated and melted state), and if necessary, heated at a higher temperature to be cured. By doing so, such an article can be manufactured.
　非多孔性基体又は非多孔性基板としては、例えば、合成樹脂フィルム・シート、金属箔、これらの組合せが挙げられる。 Examples of the non-porous substrate or non-porous substrate include synthetic resin films/sheets, metal foils, and combinations thereof.
特に、合成樹脂フィルム・シートが好ましく、合成樹脂として、ポリイミド、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコール（ＰＶＡ）、ポリカーボネート、ポリエチレンテレフタレート、シクロポリオレフィン、ナイロンが例示される。特に耐熱性が要求される場合には、ポリイミド、ポリエーテルエーテルケトン、ポリエチレンナフタレート（ＰＥＮ）、液晶ポリアリレート、ポリアミドイミド、ポリエーテルスルフォン等の耐熱性合成樹脂のフィルムが好適である。一方、表示デバイス等視認性が求められる用途においては、ポリプロピレン、ポリスチレン、ポリ塩化ビニリデン、ＰＶＡ、ポリカーボネート、ポリエチレンテレフタレート、ＰＥＮ又はこれらの混合物等の透明材料が好適である。 In particular, synthetic resin films and sheets are preferable, and examples of synthetic resins include polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol (PVA), polycarbonate, polyethylene terephthalate, cyclopolyolefin, and nylon. Especially when heat resistance is required, a film of heat resistant synthetic resin such as polyimide, polyether ether ketone, polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamide imide, polyether sulfone is suitable. On the other hand, in applications such as display devices where visibility is required, transparent materials such as polypropylene, polystyrene, polyvinylidene chloride, PVA, polycarbonate, polyethylene terephthalate, PEN, and mixtures thereof are suitable.
　前記基板の厚さは特に制限されず、用途に応じて所望の厚さで設計することができる。また、基板と感圧接着層の密着性を向上させるために、プライマー処理、コロナ処理、エッチング処理、プラズマ処理された基板を用いてもよい。更に、基板の感圧接着層接触面と反対側の面には、傷つき防止、汚れ防止、指紋付着防止、防眩、反射防止、帯電防止等の表面処理がされてもよい。 The thickness of the substrate is not particularly limited, and can be designed to have a desired thickness according to the application. Further, in order to improve the adhesion between the substrate and the pressure-sensitive adhesive layer, a substrate that has been subjected to primer treatment, corona treatment, etching treatment, and plasma treatment may be used. Further, the surface of the substrate opposite to the pressure-sensitive adhesive layer contact surface may be surface-treated to prevent scratches, stains, fingerprints, antiglare, antireflection, antistatic and the like.
　前記粘着材部品又は前記粘着材層は複数存在することができる。複数の粘着材部品又は粘着材層を使用することによって、接着に求められる各種の特性をバランスよく発揮することができる。 There can be a plurality of the adhesive component or the adhesive layer. By using a plurality of adhesive material parts or adhesive material layers, various characteristics required for adhesion can be exhibited in a well-balanced manner.
前記粘着材部品又は前記粘着材層は各種の電子機器又は電気的装置の部材として有用である。特に、前記粘着材部品又は前記粘着材層の－２０℃におけるせん断貯蔵弾性率Ｇ’が０．０１～１．０ＭＰａの範囲（０．０２～０．９０ＭＰａの範囲がより好ましく、０．０３～０．８０ＭＰａの範囲が更により好ましく、０．０４～０．７０ＭＰａの範囲が更により好ましい）にある場合、前記粘着材部品又は前記粘着材層は、弾性粘着部品又は弾性粘着層として、電子部品又はトランスデューサー用部材（センサ、スピーカー、アクチュエーター及びジェネレーター用を含む）として有用である。 The adhesive component or the adhesive layer is useful as a member of various electronic devices or electric devices. In particular, the shear storage elastic modulus G′ of the pressure-sensitive adhesive material component or the pressure-sensitive adhesive material layer at −20° C. is in the range of 0.01 to 1.0 MPa (more preferably 0.02 to 0.90 MPa, more preferably 0.03 to The range of 0.80 MPa is even more preferable, and the range of 0.04 to 0.70 MPa is further more preferable.), the pressure-sensitive adhesive component or the pressure-sensitive adhesive layer is used as an elastic pressure-sensitive adhesive component or elastic pressure-sensitive adhesive layer. Alternatively, it is useful as a member for a transducer (including a member for a sensor, a speaker, an actuator and a generator).
前記粘着材は不透明又は透明のいずれであってもよい。 The adhesive may be opaque or transparent.
不透明乃至低光透過性の粘着材は、透明性が要求されず、前記部品又は層自体に一定の伸縮性若しくは柔軟性が求められるセンサ、スピーカー、アクチュエーター等に用いられるフィルム状又はシート状部材の用途に有用である。また、リチウムイオン電池等の二次電池、又は、燃料電池に使用される封止材又は接着材としても有用である。 An opaque or low-light-transmissive adhesive material is not required to be transparent, and is a film-like or sheet-like member used for a sensor, a speaker, an actuator, etc., in which the component or layer itself is required to have a certain stretchability or flexibility. Useful for applications. It is also useful as a sealing material or an adhesive material used in a secondary battery such as a lithium-ion battery or a fuel cell.
透明乃至高光透過性の粘着材は光学装置用途に有用である。この場合、前記基体又は前記基板は光学装置用の部材であることが好ましい。例えば、前記基板は、画像表示パネル、タッチパネル、偏光フィルム、位相差フィルム、カラーフィルタ、視野角拡大フィルム、輝度向上フィルム、反射シート等の光学フィルム、又は、表面若しくは裏面保護シートであることができる。したがって、前記感圧接着層は、例えば、表面保護シート及び光学フィルム、光学フィルム及びタッチパネル、表面保護シート及び画像表示パネル、裏面保護シートと画像表示パネル、表面保護シートとタッチパネル、タッチパネルと画像表示パネルを接合することができる。 A transparent or highly light-transmissive adhesive material is useful for optical device applications. In this case, the base or the substrate is preferably a member for an optical device. For example, the substrate may be an image display panel, a touch panel, a polarizing film, a retardation film, a color filter, a viewing angle widening film, a brightness enhancement film, an optical film such as a reflection sheet, or a front surface or back surface protection sheet. .. Therefore, the pressure-sensitive adhesive layer is, for example, a surface protection sheet and an optical film, an optical film and a touch panel, a surface protection sheet and an image display panel, a back protection sheet and an image display panel, a surface protection sheet and a touch panel, a touch panel and an image display panel. Can be joined together.
より具体的には、少なくとも１つの粘着材を介して、画像表示パネル、タッチパネル、光学フィルム、表面若しくは裏面保護シートから選択される２つの部材を貼り合わせることにより、光学装置を構成することができる。なお、１つずつ貼り合わせても２つ同時に貼り合わせてもよく、貼り合わせ方法・順序はなんら制限されない。また、２つの光学装置構成用部材を本発明の硬化反応性シリコーン粘着剤組成物又はその半硬化物を介して貼り合わせた後に、かかる光学装置構成用部材側から、更に、高温で加熱することにより、かかる組成物又はその半硬化物を硬化させることもできる。このような方法を採用することで、硬化前の本発明の組成物の優れた段差吸収性能によって、凹凸を有する光学装置構成用部材であっても平滑に貼合し易い、或いは、貼合後の信頼性に優れる等の利点がある。 More specifically, the optical device can be configured by bonding two members selected from an image display panel, a touch panel, an optical film, and a front surface or back surface protection sheet via at least one adhesive material. .. It should be noted that they may be attached one by one or two at the same time, and the attaching method and order are not limited at all. In addition, after bonding two optical device constituting members via the curable reactive silicone pressure-sensitive adhesive composition of the present invention or a semi-cured product thereof, the optical device constituting member side is further heated at a high temperature. Thus, the composition or a semi-cured product thereof can be cured. By adopting such a method, due to the excellent step absorption performance of the composition of the present invention before curing, even an optical device constituting member having irregularities can be easily bonded smoothly, or after bonding Has advantages such as excellent reliability.
表面若しくは裏面保護シートの材質は、特に限定されるものではなく、例えば、ガラス、又は、ポリメチルメタクリレート等の（メタ）アクリル樹脂、ポリカーボネート樹脂、シクロオレフィンポリマー、トリアセチルセルロース等のアセチルセルロース樹脂、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート等のポリエステル系樹脂、ポリプロピレン、ポリエチレン等の非環状オレフィン系樹脂等のプラスチック若しくはこれらのプラスチックの混合物が挙げられる。 The material of the front surface or the back surface protective sheet is not particularly limited, for example, glass, or (meth) acrylic resin such as polymethyl methacrylate, polycarbonate resin, cycloolefin polymer, acetyl cellulose resin such as triacetyl cellulose, Examples thereof include polyester resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, plastics such as acyclic olefin resins such as polypropylene and polyethylene, and mixtures of these plastics.
表面保護シートは、タッチパネルが一体化したものであってもよく、例えば、タッチオンレンズ（ＴＯＬ）型やワンガラスソリューション（ＯＧＳ）型であってもよい。また、表面保護シートは、その周縁部に枠状に印刷された印刷段差部を有していてもよい。 The surface protection sheet may be one in which a touch panel is integrated, and may be, for example, a touch-on lens (TOL) type or a one glass solution (OGS) type. Further, the surface protection sheet may have a print step portion printed in a frame shape on the peripheral portion thereof.
例えば、携帯電話の表示画面等では、一般に、タッチパネル等の機能性フィルム上に粘着シートを介して表面保護シートを積層する構成が採用されているところ、該保護シートの裏面には、周縁部に隠蔽用印刷部（厚さ５μｍ～８０μｍ程度）が付設され、隠蔽用印刷部の縁に形成される段差部の入隅部内にまで粘着剤が十分に入り込まないと、気泡が残留して画面の視認性が低下することになる。また、段差近傍でフィルム部材が屈曲して外観不良となったり、フィルムの屈曲による残留歪が起点となって、積層した部材間に発泡や剥離が起こったりするおそれがあった。本発明の組成物は、このような５μｍ～２０μｍ程度の段差はもちろん、５０μｍ～８０μｍ程度の段差があっても、段差の隅々まで充填して気泡を残留させることなく貼着することができる。しかも、たとえ被着体の一方が屈曲性をもつフィルム部材であったとしても、本発明の組成物をホットメルトさせることで、表面を歪みなく平滑に均すことが可能であるため、フィルム部材に歪や変形を生じさせずに、部材を貼合一体化することができる。 For example, in a display screen of a mobile phone or the like, generally, a structure in which a surface protection sheet is laminated on a functional film such as a touch panel via an adhesive sheet is adopted. If a concealment printing section (thickness of about 5 to 80 μm) is attached, and if the adhesive does not sufficiently enter the inside corners of the step formed on the edge of the concealment printing section, bubbles will remain and the screen The visibility will be reduced. Further, there is a possibility that the film member may be bent in the vicinity of the step to cause a poor appearance, or that residual strain due to the bending of the film may serve as a starting point to cause foaming or separation between the laminated members. The composition of the present invention can be applied to such a step of about 5 μm to 20 μm, and even if there is a step of about 50 μm to 80 μm, it can be applied to every corner of the step without leaving bubbles. .. Moreover, even if one of the adherends is a flexible film member, the surface of the film member can be smoothed without distortion by hot-melting the composition of the present invention. The members can be bonded and integrated without causing distortion or deformation.
タッチパネルは、特に限定されるものではなく、抵抗膜方式、静電容量方式、電磁誘導方式又はこれらの組み合わせ等のいずれであってもよい。タッチパネルは、少なくとも１つの、カバーフィルム、ＩＴＯ又はＡＴＯ膜等の透明電極層、又は、ガラス基板を備えるものが好ましい。なお、タッチパネルは装飾フィルム等を更に含んでもよい。 The touch panel is not particularly limited, and may be a resistive film type, an electrostatic capacitance type, an electromagnetic induction type, or a combination thereof. The touch panel preferably includes at least one cover film, a transparent electrode layer such as an ITO or ATO film, or a glass substrate. The touch panel may further include a decorative film or the like.
　画像表示パネルは、画像情報を表示するものであれば特には限定されるものではなく、例えば、液晶ディスプレイの場合、偏光フィルム、位相差フィルム、カラーフィルタ、視野角拡大フィルム、輝度向上フィルム、反射シート等の光学フィルム、液晶材料、透明基板及びバックライトシステムから構成される（通常、粘着材の画像表示パネルに対する被着面は光学フィルムとなる）ものであり、液晶材料の制御方式によりＳＴＮ方式やＶＡ方式やＩＰＳ方式等があるが、何れの方式であってもよい。また、画像表示パネルは、タッチパネル機能をＴＦＴ－ＬＣＤ内に内蔵したインセル型であっても、偏光板とカラーフィルタを設けたガラス基板の間にタッチパネル機能を内蔵したオンセル型であってもよい。一方、有機ＥＬディスプレイの場合、画像表示パネルは有機ＥＬ素子基板或いは有機ＥＬ素子基板とその他の光学フィルム等の積層体から構成される。 The image display panel is not particularly limited as long as it displays image information, and for example, in the case of a liquid crystal display, a polarizing film, a retardation film, a color filter, a viewing angle widening film, a brightness enhancement film, a reflection film. It is composed of an optical film such as a sheet, a liquid crystal material, a transparent substrate and a backlight system (usually, the surface to which the adhesive material is adhered to the image display panel is the optical film), and the STN method is used depending on the control method of the liquid crystal material. , VA system, IPS system, etc., but any system may be used. Further, the image display panel may be an in-cell type in which the touch panel function is built in the TFT-LCD, or an on-cell type in which the touch panel function is built in between the glass substrate provided with the polarizing plate and the color filter. On the other hand, in the case of an organic EL display, the image display panel is composed of an organic EL element substrate or a laminate of the organic EL element substrate and other optical films.
　この場合、本発明の物品は、ディスプレイであることが好ましく、ＣＲＴディスプレイ、液晶ディスプレイ、プラズマディスプレイ、有機ＥＬディスプレイ、無機ＥＬディスプレイ、ＬＥＤディスプレイ、表面伝導型電子放出素子ディスプレイ（ＳＥＤ）、電界放出型ディスプレイ（ＦＥＤ）がより好ましく、液晶ディスプレイ又は有機ＥＬディスプレイであることが更により好ましい。 In this case, the article of the present invention is preferably a display, and is a CRT display, a liquid crystal display, a plasma display, an organic EL display, an inorganic EL display, an LED display, a surface conduction electron-emitting device display (SED), a field emission type. A display (FED) is more preferable, and a liquid crystal display or an organic EL display is even more preferable.
　ディスプレイの画像表示面はフラット（平面）でもよく、曲面乃至湾曲した形状でもよい。 The image display surface of the display may be flat (flat), curved or curved.
本発明のディスプレイは、例えば、携帯電話、固定電話等の通信機器；タブレット端末、デスクトップ端末、ノート型端末等のコンピュータ機器；ＴＶ；プリンタ；ＡＴＭ（現金自動預け払い機）；車載用モニター又はナビゲーションシステム；デジタルカメラ；ビデオカメラ；医療機器；ＰＤＡ（モバイル端末）；時計；電子ペーパー；ＣＤ、ＤＶＤ又はＢｌｕｅ－ｒａｙディスクプレーヤー；ＳＳＭやＨＤ等の固体電子記録媒体再生機；電子書籍機器；携帯ゲーム機器、固定ゲーム機器等の遊戯機器；ＰＯＳシステム；魚群探知機；自動券売機；計器盤等の用途に適用される。 The display of the present invention is, for example, a communication device such as a mobile phone or a fixed line telephone; a computer device such as a tablet terminal, a desktop terminal, a notebook type terminal; a TV; a printer; an ATM (automated teller machine); an in-vehicle monitor or navigation. System; Digital camera; Video camera; Medical device; PDA (mobile terminal); Watch; Electronic paper; CD, DVD or Blue-ray disc player; Solid electronic recording medium player such as SSM or HD; E-book device; Handheld game It is applied to amusement equipment such as equipment and fixed game equipment; POS system; fish finder; automatic ticket vending machine; instrument panel.
　一方、前記基体又は前記基板は、太陽電池セル、封止材層、表面若しくは裏面保護シートであることができる。したがって、前記感圧接着層は、例えば、表面保護シート及び太陽電池セル、裏面保護シートと太陽電池セル、表面保護シートと封止材層、裏面保護シートと封止材層、封止材層と太陽電池セルを接合することができる。 On the other hand, the base or the substrate can be a solar cell, a sealing material layer, or a front surface or back surface protection sheet. Therefore, the pressure-sensitive adhesive layer is, for example, a surface protection sheet and a solar cell, a back surface protection sheet and a solar cell, a surface protection sheet and a sealing material layer, a back surface protection sheet and a sealing material layer, and a sealing material layer. Solar cells can be joined.
この場合、本発明の物品は、太陽電池モジュールであることが好ましい。 In this case, the article of the present invention is preferably a solar cell module.
　以下、本発明の具体的な利用例について更に説明する。 The following will further explain specific examples of use of the present invention.
［表示パネル又はディスプレイ用の部材］
本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着材は、感圧接着性を備えることから、積層タッチスクリーン又はフラットパネルディスプレイの構築及び利用に使用することができ、その具体的な使用方法としては、感圧接着剤層（特に、シリコーンＰＳＡ）の公知の使用方法を特に制限なく用いることができる。 [Display panel or display member]
The curable reactive silicone pressure-sensitive adhesive composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof has pressure-sensitive adhesiveness, and thus can be used for the construction and use of a laminated touch screen or a flat panel display. As a typical usage method, a known usage method of the pressure-sensitive adhesive layer (particularly, silicone PSA) can be used without particular limitation.
例えば、本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着材は、特表２０１４－５２２４３６号又は特表２０１３－５１２３２６等で開示された光学的に透明なシリコーン系感圧接着剤フィルム或いは粘着剤層として、タッチパネル等の表示デバイスの製造に用いることができる。具体的には、本発明の組成物を硬化してなる硬化物は、特表２０１３－５１２３２６に記載の粘着層又は粘着フィルムとして、特に制限なく用いることができる。 For example, the curable reactive silicone pressure-sensitive adhesive composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof is an optically transparent silicone pressure-sensitive adhesive disclosed in JP-A-2014-522436 or JP-A-2013-512326. The adhesive film or the adhesive layer can be used for manufacturing a display device such as a touch panel. Specifically, the cured product obtained by curing the composition of the present invention can be used without particular limitation as the adhesive layer or the adhesive film described in JP-A-2013-512326.
一例として、本発明の物品は、一面に導電層が形成されている伝導性プラスチックフィルム等の基材、及び、当該導電層が形成された側又はその反対側の面に付着されている本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着材を含むタッチパネルであってよい。前記基材は、シート状又はフィルム状基材であることが好ましく樹脂フィルム又はガラス板が例示される。また、前記伝導性プラスチックフィルムは、一面にＩＴＯ層が形成されている樹脂フィルム又はガラス板、特に、ポリエチレンテレフタレートフィルムであってよい。これらは、特表２０１３－５１２３２６等に開示されている。 As an example, the article of the present invention is a substrate such as a conductive plastic film having a conductive layer formed on one surface thereof, and the present invention adhered to the surface on which the conductive layer is formed or the opposite surface thereof. It may be a touch panel including the curing-reactive silicone pressure-sensitive adhesive composition (1) or a pressure-sensitive adhesive made of a cured product thereof. The substrate is preferably a sheet-shaped or film-shaped substrate, and a resin film or a glass plate is exemplified. Further, the conductive plastic film may be a resin film or a glass plate having an ITO layer formed on one surface thereof, particularly a polyethylene terephthalate film. These are disclosed in Japanese Patent Publication No. 2013-512326 and the like.
その他、本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着材は、タッチパネル等の表示デバイスの製造に用いる偏光板用接着フィルムとして用いてもよく、特開２０１３－０６５００９号公報に記載のタッチパネルとディスプレイモジュール間の貼合に用いる感圧接着層として用いてもよい。 In addition, the curable reactive silicone pressure-sensitive adhesive composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof may be used as an adhesive film for a polarizing plate used for manufacturing a display device such as a touch panel, and the like. JP-A-2013-065009 It may be used as a pressure-sensitive adhesive layer used for bonding between the touch panel and the display module described in 1.
積層体の製造及び構造
図１は、本発明の一実施形態の積層体を示す断面図である。本発明の一実施形態の積層体１は、第１の部材２０と、第２の部材２１と、２つの部材２０、２１の間に配置された本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着材１５と、を備えている。積層体１では、２つの部材２０、２１が粘着材１５により接着されている。これらの光学部材は透明であっても、不透明であってもよく、一方又は両方の部材が、単独の基材であってもよく、バックライトユニットのようにそれ自体が独立した積層体である光学部材であってもよい。なお、本発明の積層体を構成する部材は、平面状の広がりを有する板状部分を備えていることが一般的であり、当該板状部分又は部材自身が湾曲していてもよく、部材の用途に由来する三次元的な凹凸を備えていてもよい。 Manufacturing and Structure of Laminated Body FIG. 1 is a cross-sectional view showing a laminated body according to an embodiment of the present invention. The laminate 1 of one embodiment of the present invention comprises a first member 20, a second member 21, and a curing-reactive silicone pressure-sensitive adhesive composition of the present invention arranged between two members 20, 21. And an adhesive material 15 made of the cured product. In the laminated body 1, the two members 20 and 21 are adhered by the adhesive material 15. These optical members may be transparent or opaque, and one or both members may be a single base material, or may be an independent laminated body such as a backlight unit. It may be an optical member. Incidentally, the member constituting the laminate of the present invention is generally provided with a plate-shaped portion having a planar spread, the plate-shaped portion or the member itself may be curved, It may have three-dimensional unevenness derived from the application.
　２つの光学部材２０、２１は、任意で組み合わせることができる。２つの光学部材２０、２１は、互いに同一であってもよいし、異なっていてもよい。 The two optical members 20 and 21 can be arbitrarily combined. The two optical members 20 and 21 may be the same as or different from each other.
　好適には、部材２０、２１は、光学ディスプレイの構成部材として一般的に使用されるものである。より具体的には、部材２０、２１は光学部材であり、例えば、レンズ（樹脂製又はガラス製であってよい）、光学シート状部材（カラーフィルタ、偏光板、位相差板、視野角拡大フィルム、輝度向上フィルム、反射シート、透明導電性フィルムを含む）、透明であってもよい光学保護材（透明保護材（透明保護フィルム）等であり、ガラス製、樹脂製又は樹脂コーティング層）、前面表示パネル、タッチパネル（ガラス製又は樹脂製）、ＩＴＯ又はＡＴＯ膜等の透明電極層であり得る。いうまでもなく、表示パネル又はタッチパネル表面には、光学保護材を更に備えてもよい。また、光学部材は、後述する発光層及び表示面（表示パネル）を含むバックライトユニットそれ自体であってもよく、光学部材全体が独立した積層部材からなる部品又はタッチパネル等の表示装置内のモジュールであってもよく、当該光学部材内に、本硬化物からなる接着層１５を更に有していてもよい。すなわち、光学部材の概念には、後述する画像表示パネル、光学パネル、前面パネル、バックライトユニット、タッチパネルユニット等が、包含される。 Preferably, the members 20 and 21 are generally used as a constituent member of an optical display. More specifically, the members 20 and 21 are optical members, for example, lenses (which may be made of resin or glass), optical sheet-shaped members (color filters, polarizing plates, retardation plates, viewing angle widening films). , A brightness enhancement film, a reflection sheet, a transparent conductive film), an optical protective material which may be transparent (a transparent protective material (transparent protective film), etc., made of glass, resin or resin coating layer), front surface It may be a display panel, a touch panel (made of glass or resin), a transparent electrode layer such as an ITO or ATO film. Needless to say, an optical protective material may be further provided on the surface of the display panel or the touch panel. Further, the optical member may be a backlight unit itself including a light emitting layer and a display surface (display panel) described below, or a component in a display device such as a component or a touch panel in which the entire optical member is an independent laminated member. Alternatively, the optical member may further have an adhesive layer 15 made of the main cured product. That is, the concept of the optical member includes an image display panel, an optical panel, a front panel, a backlight unit, a touch panel unit, etc., which will be described later.
　部材２０、２１の材質は、上記の用途で一般的に使用されるものであれば特に制限されないが、ガラス、酸化インジウムスズ（Ｉｎｄｉｕｍ　Ｔｉｎ　Ｏｘｉｄｅ、ＩＴＯ）等の無機光学材料、又は、ポリカーボネート樹脂、アクリル樹脂、エポキシ樹脂、ポリスチレン樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリ塩化ビニル樹脂、ポリ塩化ビニリデン樹脂、ポリビニルアルコール（ＰＶＡ）樹脂、ポリエチレンテレフタレート（ＰＥＴ）樹脂、シクロポリオレフィン樹脂、ポリエーテルエーテルケトン樹脂、ポリエチレンナフタレート（ＰＥＮ）樹脂、液晶ポリアリレート樹脂、ポリアミドイミド樹脂、ポリエーテルスルフォン樹脂又はこれらの混合物等の有機光学材料が例示される。 The materials of the members 20 and 21 are not particularly limited as long as they are generally used for the above-mentioned applications, but glass, an inorganic optical material such as indium tin oxide (ITO), or a polycarbonate resin, Acrylic resin, epoxy resin, polystyrene resin, polyamide resin, polyimide resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol (PVA) resin, polyethylene terephthalate (PET) resin, cyclopolyolefin resin, poly Examples of the organic optical material include ether ether ketone resin, polyethylene naphthalate (PEN) resin, liquid crystal polyarylate resin, polyamide imide resin, polyether sulfone resin, and mixtures thereof.
　特に耐熱性が要求される場合には、ポリイミド樹脂、ポリエーテルエーテルケトン樹脂、ポリエチレンナフタレート（ＰＥＮ）樹脂、液晶ポリアリレート樹脂、ポリアミドイミド樹脂、ポリエーテルスルフォン樹脂又はこれらの混合物等であり得る。 When heat resistance is particularly required, polyimide resin, polyether ether ketone resin, polyethylene naphthalate (PEN) resin, liquid crystal polyarylate resin, polyamide imide resin, polyether sulfone resin or a mixture thereof may be used.
　一方、表示デバイス等視認性が求められる用途においては、ポリプロピレン樹脂、ポリスチレン樹脂、ポリ塩化ビニリデン樹脂、ＰＶＡ樹脂、ポリカーボネート樹脂、ＰＥＴ樹脂、ＰＥＮ樹脂又はこれらの混合物等であり得る。 On the other hand, for applications requiring visibility such as display devices, polypropylene resin, polystyrene resin, polyvinylidene chloride resin, PVA resin, polycarbonate resin, PET resin, PEN resin, or a mixture thereof may be used.
　部材２０、２１は、光学ディスプレイの構成部材として一般的に施される表面処理が行われていてもよい。表面処理は、例えばプライマー処理又はコロナ処理等であり得る。 The members 20 and 21 may be subjected to a surface treatment generally performed as a constituent member of an optical display. The surface treatment may be, for example, a primer treatment or a corona treatment.
　２つの部材が互いに異なる場合、例えば２つの部材の熱膨張率差に起因して２つの光学部材が接着界面で剥がれることがある。しかしながら、本発明の硬化反応性シリコーン粘着剤組成物は部材間で加熱溶融して部材上のギャップや凹凸に追従した上で、硬化させることができ、また、その硬化物は柔軟性を有するので、熱膨張率差の影響を小さくすることができ、互いに異なる２つの部材２０、２１を良好に接着することができる。したがって、本発明又はその硬化物からなる粘着材は、互いに異なる部材の接着、特に熱膨張率差の大きい有機材料と無機材料との接着に好適に使用することができる。 If the two members are different from each other, for example, the two optical members may peel off at the adhesive interface due to the difference in thermal expansion coefficient between the two members. However, the curing-reactive silicone pressure-sensitive adhesive composition of the present invention can be cured after heating and melting between members to follow gaps and irregularities on the members, and since the cured product has flexibility. The influence of the difference in the coefficient of thermal expansion can be reduced, and the two members 20 and 21 different from each other can be bonded well. Therefore, the pressure-sensitive adhesive material comprising the present invention or a cured product thereof can be suitably used for bonding members different from each other, particularly for bonding an organic material and an inorganic material having a large difference in coefficient of thermal expansion.
　なお、図１に示す積層体１は、２つの部材を備えているが、複数の部材、特に光学部材を備えていれば部材の数は特に制限されない。 The laminated body 1 shown in FIG. 1 includes two members, but the number of members is not particularly limited as long as it includes a plurality of members, particularly an optical member.
　また、図１に示す粘着材１５は、２つの部材２０、２１の間に全体にわたって形成されているが、２つの部材２０、２１の間の一部、例えば、一又は複数の点状に形成されていてもよい。また、図１に示す粘着材１５は、２つの部材２０、２１の間に形成されているが、部材２０の接着面２０ａの反対側の面２０ｂにも形成されていてもよく、部材２１の接着面２１ｂの反対側の面２１ａにも形成されていてもよく、両方の面２０ｂ及び２１ａに形成されていてもよい。 Further, the adhesive material 15 shown in FIG. 1 is formed between the two members 20 and 21 as a whole, but is formed in a part between the two members 20 and 21, for example, in the form of one or a plurality of dots. It may have been done. Although the adhesive material 15 shown in FIG. 1 is formed between the two members 20 and 21, it may also be formed on the surface 20b opposite to the adhesive surface 20a of the member 20. It may be formed on the surface 21a opposite to the adhesive surface 21b, or may be formed on both surfaces 20b and 21a.
　以下、本発明の一実施形態における積層体の製造方法について説明する。 Hereinafter, a method for manufacturing a laminate according to an embodiment of the present invention will be described.
　図２は、本発明の一実施形態の積層体の製造方法を示すフローチャートである。本発明の一実施形態の積層体の製造方法は、本発明の硬化反応性シリコーン粘着剤組成物を二つの部材のうち少なくとも一方の部材の一面又は両面に配置し、当該二つの部材を当該硬化性シリコーン粘着剤組成物を介して貼り合わせる配置及び貼り合わせ工程Ｓ１、並びに、高温で加熱することによりヒドロシリル化反応を開始させ、当該組成物を硬化させる硬化工程Ｓ２を含む。 FIG. 2 is a flowchart showing a method for manufacturing a laminated body according to an embodiment of the present invention. A method for producing a laminate according to an embodiment of the present invention is a method of arranging the curing-reactive silicone pressure-sensitive adhesive composition of the present invention on one surface or both surfaces of at least one of the two members, and curing the two members by the curing. And a bonding step S1 in which the composition is bonded via a hydrophilic silicone pressure-sensitive adhesive composition, and a curing step S2 in which the composition is cured by heating at a high temperature to start a hydrosilylation reaction.
　上記の配置工程Ｓ１では、例えば上述した塗工方法を用いて本発明の組成物を部材上に配置する。上記の配置工程Ｓ１では、一方の部材の一面に本発明の組成物を配置してもよい。また、部材の両面に配置された本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物であって他の光学部材との貼り合わせに使用されない粘着材は、接着面として剥離層や他の部材への接合に用いてもよい。 In the arranging step S1, the composition of the present invention is arranged on the member using, for example, the above-mentioned coating method. In the arranging step S1, the composition of the present invention may be arranged on one surface of one member. Further, the curable reactive silicone pressure-sensitive adhesive composition of the present invention arranged on both surfaces of the member or the pressure-sensitive adhesive material which is not used for bonding with other optical members, is a release layer or other adhesive surface. It may be used for joining to a member.
　また、別の実施形態において、上記の配置工程Ｓ１では、二つの部材のそれぞれの一面に本発明の組成物を配置してもよい。 In another embodiment, the composition of the present invention may be arranged on one surface of each of the two members in the arrangement step S1.
　上記の実施形態において、「一面」とは、他方の光学部材と対向する面である。 In the above embodiment, the “one surface” is a surface facing the other optical member.
　更に、別の実施形態において、上記の配置工程Ｓ１では、上記の一面とは反対側に位置する他面にも本発明の組成物を配置してもよい。 Further, in another embodiment, in the disposing step S1, the composition of the present invention may be disposed on the other surface located on the opposite side to the one surface.
図３は加熱溶融工程を含む積層体の製造方法の概念図である。上記の配置工程Ｓ１において、部材２１が凹凸を有し、且つ、本発明の硬化反応性シリコーン粘着剤組成物をシート状等の形状に成型して粘着材１５として使用する場合、図３（Ａ）のように部材２１上に加熱溶融前の本発明の硬化反応性シリコーン粘着剤組成物からなる粘着材１５Ａを配置した後に、８０℃以上に加熱して溶融させ、溶融物を部材２１の凹部に対応する特定の形状等に成型したり、或いは、図示を省略する部材２１の間隙に充填する等して、平滑な表面を有する粘着材１５Ｂとする工程（図３（Ｂ）参照）を採用してもよい。本発明の粘着材は加熱溶融性であるため、容易にシート状等の所望の形状に成型でき、かかる工程を有することで、必要に応じて、部材上の凹凸や間隙を充填して、追従性に優れ、且つ、必要に応じて平坦な粘着面を形成できる利点がある。特に、部材の材質、凹凸や間隙に由来して難接着性となっている部材であっても、本発明の硬化反応性シリコーン粘着剤組成物を加熱溶融して配置することで、容易に接着でき、且つ、後述する硬化工程により、更に強度の高い粘着材層を形成できる場合がある。 FIG. 3 is a conceptual diagram of a method for manufacturing a laminate including a heating and melting step. In the arrangement step S1 described above, when the member 21 has irregularities and the curable reactive silicone pressure-sensitive adhesive composition of the present invention is molded into a sheet shape or the like and used as the pressure-sensitive adhesive material 15, FIG. ), a pressure-sensitive adhesive material 15A made of the curable reactive silicone pressure-sensitive adhesive composition of the present invention is placed on the member 21 as shown in FIG. The step of forming the adhesive material 15B having a smooth surface by molding into a specific shape or the like corresponding to the above or by filling the gap of the member 21 (not shown) (see FIG. 3B) is adopted. You may. Since the pressure-sensitive adhesive material of the present invention is heat-meltable, it can be easily molded into a desired shape such as a sheet, and by having such a step, irregularities and gaps on the member can be filled, if necessary, to follow. There is an advantage that the adhesiveness is excellent and a flat adhesive surface can be formed if necessary. In particular, even if the material of the member is difficult to adhere due to unevenness or gaps due to the material of the member, it can be easily bonded by arranging the curable reactive silicone pressure-sensitive adhesive composition of the present invention by heating and melting. In some cases, an adhesive layer having higher strength can be formed by the curing step described later.
　本発明の実施形態における積層体の製造方法は、本発明の硬化反応性シリコーン粘着剤組成物を二つの光学部材のうち少なくとも一方の部材の一面又は両面に配置し、前記二つの光学部材を当該硬化反応性シリコーン粘着剤組成物を介して貼り合わせる配置工程Ｓ１、及び高温で加熱することにより当該組成物のヒドロシリル化反応を進行させて当該組成物を硬化させる硬化工程Ｓ２を含む。 The method for producing a laminate according to the embodiment of the present invention, the curing-reactive silicone pressure-sensitive adhesive composition of the present invention is disposed on one surface or both surfaces of at least one of the two optical members, and the two optical members are It includes a disposing step S1 of laminating via a curing reactive silicone pressure sensitive adhesive composition, and a curing step S2 of curing the composition by heating at a high temperature to promote a hydrosilylation reaction of the composition.
　上記の硬化工程Ｓ２では、好適には、１５０℃以上の高温で加熱することり、本発明の組成物を硬化させた硬化物を得る。 In the above curing step S2, it is preferable to heat at a high temperature of 150° C. or higher to obtain a cured product obtained by curing the composition of the present invention.
光学ディスプレイ
　図４は、本発明の物品の一実施形態の光学ディスプレイを示す断面図である。本発明の一実施形態としての光学ディスプレイ２００は、上記の積層体１と、画像表示パネル２０１と、を備えている。 Optical Display FIG. 4 is a cross-sectional view showing an optical display of one embodiment of the article of the present invention. An optical display 200 as an embodiment of the present invention includes the above-mentioned laminated body 1 and an image display panel 201.
　積層体１と、画像表示パネル２０１とは接着剤層（図示なし）を介して接着されている。この接着剤層は、本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物で構成されていてもよい。 The laminate 1 and the image display panel 201 are adhered to each other via an adhesive layer (not shown). This adhesive layer may be composed of the curable reactive silicone pressure-sensitive adhesive composition of the present invention or a cured product thereof.
　図４に示す光学ディスプレイ２００では、積層体１の第２の光学部材２１が接着剤層に接している。図４に示す光学ディスプレイ２００において、例えば積層体１の第１の光学部材２０は偏光フィルムであり、第２の光学部材２１は位相差フィルムであり得る。また、別の実施形態においては、例えば積層体１の第１の光学部材２０は偏光フィルムであり、第２の光学部材２１は表面保護フィルムであり得る。 In the optical display 200 shown in FIG. 4, the second optical member 21 of the laminated body 1 is in contact with the adhesive layer. In the optical display 200 shown in FIG. 4, for example, the first optical member 20 of the laminate 1 may be a polarizing film and the second optical member 21 may be a retardation film. Moreover, in another embodiment, the 1st optical member 20 of the laminated body 1 can be a polarizing film, and the 2nd optical member 21 can be a surface protection film, for example.
　画像表示パネル２０１は、画像情報を表示するものであれば特には限定されるものではなく、例えば、液晶ディスプレイ（ＬＣＤ）の場合、偏光フィルム、位相差フィルム、カラーフィルタ、視野角拡大フィルム、輝度向上フィルム、反射シート等の光学フィルム、液晶材料、透明基板及びバックライトシステムから構成される（通常、感圧接着部品又は感圧接着層の画像表示パネルに対する被着面は光学フィルムとなる）ものであり、液晶材料の制御方式によりＳＴＮ方式やＶＡ方式やＩＰＳ方式等があるが、何れの方式であってもよい。また、画像表示パネル２０１は、タッチパネル機能をＴＦＴ－ＬＣＤ内に内蔵したインセル型であっても、偏光板とカラーフィルタを設けたガラス基板の間にタッチパネル機能を内蔵したオンセル型であってもよい。一方、有機ＥＬディスプレイの場合、画像表示パネル２０１は有機ＥＬ素子基板又は有機ＥＬ素子基板とその他の光学フィルム等の積層体から構成される。 The image display panel 201 is not particularly limited as long as it displays image information. For example, in the case of a liquid crystal display (LCD), a polarizing film, a retardation film, a color filter, a viewing angle widening film, a brightness. An improvement film, an optical film such as a reflection sheet, a liquid crystal material, a transparent substrate, and a backlight system (usually, the pressure-sensitive adhesive component or the pressure-sensitive adhesive layer adheres to the image display panel is the optical film) The STN method, the VA method, the IPS method and the like are available depending on the control method of the liquid crystal material, but any method may be used. Further, the image display panel 201 may be an in-cell type in which a touch panel function is built in a TFT-LCD, or an on-cell type in which a touch panel function is built in between a glass substrate provided with a polarizing plate and a color filter. .. On the other hand, in the case of an organic EL display, the image display panel 201 is composed of an organic EL element substrate or a laminated body of an organic EL element substrate and other optical films and the like.
　光学ディスプレイ２００は、ブラウン管（Cathode Ray Tube、ＣＲＴ）ディスプレイ、又はフラットパネルディスプレイ（ＦＰＤ）であり得る。ＦＰＤとしては、例えば、ＬＣＤ、エレクトロクロミックディスプレイ（ＥＣＤ）等の受光型表示装置、又は有機ＥＬディスプレイ、無機ＥＬディスプレイ等の電界発光ディスプレイ（ＥＬＤ）、プラズマディスプレイ（ＰＤＰ）、表面伝導型電子放出素子ディスプレイ（ＳＥＤ）等の電界放出型ディスプレイ（ＦＥＤ）、ＬＥＤディスプレイ等の発光型表示装置が挙げられる。 The optical display 200 can be a cathode ray tube (CRT) display or a flat panel display (FPD). As the FPD, for example, a light-receiving display device such as an LCD or an electrochromic display (ECD), or an electroluminescent display (ELD) such as an organic EL display or an inorganic EL display, a plasma display (PDP), a surface conduction electron-emitting device. A field emission display (FED) such as a display (SED) and a light emitting display device such as an LED display can be mentioned.
　図５は、本発明の物品の別の実施形態の光学ディスプレイを示す断面図である。本発明の別の実施形態としての光学ディスプレイ３００Ａは、画像表示パネル３０１と、光学部材２０と、画像表示パネル３０１と光学部材２０との間に配置された本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる接着層１５と、を備えている。 FIG. 5 is a cross-sectional view showing an optical display of another embodiment of the article of the present invention. An optical display 300A as another embodiment of the present invention includes an image display panel 301, an optical member 20, and a curable reactive silicone adhesive composition of the present invention disposed between the image display panel 301 and the optical member 20. And an adhesive layer 15 made of a cured product thereof.
　画像表示パネル３０１は、図４の画像表示パネル２０１について例示したものであり得る。 The image display panel 301 may be an example of the image display panel 201 of FIG.
　光学ディスプレイ３００Ａは、例えば、光学部材２０を画像表示パネル３０１の一方の面３０１ａに、必要に応じて加熱溶融させた本発明の硬化反応性シリコーン粘着剤組成物からなる硬化性層を介して配置した後、当該硬化性層を高温で加熱することにより硬化させることにより得ることができる。 The optical display 300A is arranged, for example, on one surface 301a of the image display panel 301 with the curable layer made of the curable reactive silicone pressure-sensitive adhesive composition of the present invention, which is heated and melted, if necessary. After that, the curable layer can be obtained by curing the curable layer by heating at a high temperature.
　図５に示す本発明の物品の実施形態の光学ディスプレイは、例えば、必要に応じて加熱溶融させた本発明の硬化反応性シリコーン粘着剤組成物からなる硬化性層を、光学部材２０の一方の面２０ａに形成させた後、光学部材２０を画像表示パネル３０１の一方の面３０１ａに当該硬化性層を介して配置し、更に、硬化性層を加熱することにより硬化させることにより得ることができる。 In the optical display of the embodiment of the article of the present invention shown in FIG. 5, for example, a curable layer made of the curing reactive silicone pressure-sensitive adhesive composition of the present invention, which is heated and melted as necessary, is provided on one side of the optical member 20. It can be obtained by forming the optical member 20 on the surface 20a, arranging the optical member 20 on one surface 301a of the image display panel 301 via the curable layer, and further curing the curable layer by heating. ..
　図６は、本発明の物品の別の実施形態の光学ディスプレイを示す断面図である。本発明の別の実施形態としての光学ディスプレイ３００Ｂは、画像表示パネル３０１と、タッチパネル３０２と、画像表示パネル３０１とタッチパネル３０２との間に配置された本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる接着層１５と、を備えている。 FIG. 6 is a cross-sectional view showing an optical display of another embodiment of the article of the present invention. An optical display 300B as another embodiment of the present invention includes an image display panel 301, a touch panel 302, and the curable reactive silicone adhesive composition of the present invention disposed between the image display panel 301 and the touch panel 302. And an adhesive layer 15 made of the cured product.
　タッチパネル３０２は、特に制限されるものではなく、抵抗膜方式、静電容量方式、電磁誘導方式又はこれらの組み合わせ等のいずれであってもよい。タッチパネル３０２は、少なくとも１つの、カバーフィルム、ＩＴＯ又はＡＴＯ膜等の透明電極層、又は、ガラス基板を備えるものが好ましい。なお、タッチパネルは装飾フィルム等を更に含んでもよい。 The touch panel 302 is not particularly limited, and may be a resistive film type, a capacitance type, an electromagnetic induction type, or a combination thereof. The touch panel 302 preferably includes at least one cover film, a transparent electrode layer such as an ITO or ATO film, or a glass substrate. The touch panel may further include a decorative film or the like.
　図６に示す本発明の物品の実施形態の光学ディスプレイでは、液晶・有機ＥＬ等の表示部と、タッチパネル、カバーレンズ等のディスプレイ形成部材との間、或いは、ディスプレイ形成部材間を、本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物により接着若しくは粘着することにより、光学ディスプレイの視認性を向上させることができる。 In the optical display of the embodiment of the article of the present invention shown in FIG. 6, a display unit such as a liquid crystal/organic EL and a display forming member such as a touch panel or a cover lens, or between the display forming members is provided. The visibility of the optical display can be improved by adhering or sticking with the curing-reactive silicone pressure-sensitive adhesive composition or its cured product.
本発明の硬化反応性シリコーン粘着剤組成物は、十分な粘着性を備え、加熱溶融により部材の凹凸に対する高い追従性を実現でき、且つ、１５０℃以上の高温下で速やかに硬化する性質を備える、このため、本発明の光学ディスプレイでは、熱に不安定な材料の変形や劣化が抑制され、更には、高温高湿下に曝されても硬化物に濁りや着色を生じ難いので、光学ディスプレイとしての信頼性を向上させることができる。 The curing-reactive silicone pressure-sensitive adhesive composition of the present invention has sufficient adhesiveness, can achieve high conformability to unevenness of a member by heating and melting, and has a property of being rapidly cured at a high temperature of 150° C. or higher. Therefore, in the optical display of the present invention, deformation and deterioration of the heat-labile material are suppressed, and further, even when exposed to high temperature and high humidity, the cured product is less likely to become turbid or colored, so that the optical display The reliability as can be improved.
　本発明の物品の実施形態の光学ディスプレイは、更に、
　前面パネルの表示面に対向する面に設けられ、透明導電膜が形成された面を有するシールド基板を更に備え、
　前記透明導電膜とベゼルとが導電性材料を介して電気的に接続された構造を備えた表示装置であってよい。 The optical display of an embodiment of the article of the present invention further comprises
Further comprising a shield substrate provided on a surface facing the display surface of the front panel and having a surface on which a transparent conductive film is formed,
The display device may have a structure in which the transparent conductive film and the bezel are electrically connected via a conductive material.
　例えば、表示装置において、表示モジュールと前面パネルとの間に、更に、片面に導電層を備えた電磁妨害（Ｅｌｅｃｔｒｏ－Ｍａｇｎｅｔｉｃ　Ｉｎｔｅｒｆｅｒｅｎｃｅ、ＥＭＩ）基板等のシールド基板を挿入することができる。このようなシールド基板は電磁波遮蔽機能を有するので、表示モジュールから放射される電磁波によって前面パネルが誤動作することを防ぐ。また、前記シールド基板の片面には、ＩＴＯ等の透明導電膜からなる導電層が一様に又はメッシュ状に形成されている。そして、前記導電層の電位を表示モジュールのＧＮＤに設定するため、ベゼルの外周に配置する接着部材等を、例えばＡｇペースト等の導電性接着部材で形成することもできる。なお、表示モジュールのベゼルは、金属製であり、表示モジュール内でＧＮＤ接続されている。ここで、接着部材を導電性材料とすることで、金属製のベゼルと前記のシールド基板の導電層とを確実にＧＮＤ接続できるため、電磁波耐性の強い表示装置を提供することができる。 For example, in a display device, a shield substrate such as an Electro-Magnetic Interference (EMI) substrate having a conductive layer on one surface can be further inserted between the display module and the front panel. Since such a shield substrate has an electromagnetic wave shielding function, it prevents the front panel from malfunctioning due to electromagnetic waves emitted from the display module. A conductive layer made of a transparent conductive film such as ITO is formed on one surface of the shield substrate uniformly or in a mesh shape. Then, in order to set the potential of the conductive layer to the GND of the display module, the adhesive member or the like arranged on the outer periphery of the bezel may be formed of a conductive adhesive member such as Ag paste. The bezel of the display module is made of metal and is GND-connected inside the display module. When the adhesive member is made of a conductive material, the metal bezel and the conductive layer of the shield substrate can be surely GND-connected, so that a display device having a strong electromagnetic wave resistance can be provided.
　図７は、本発明の物品の別の実施形態の光学ディスプレイを示す分解斜視図である。また、図８は、本発明の物品の別の実施形態の光学ディスプレイを示す部分断面図である。 FIG. 7 is an exploded perspective view showing an optical display of another embodiment of the article of the present invention. Further, FIG. 8 is a partial cross-sectional view showing an optical display of another embodiment of the article of the present invention.
　図７及び図８に示すように、本発明にかかる表示装置４００（光学ディスプレイ）は、表示面１１１を有する表示パネル１１０と、枠部１２１と枠部１２１の内側の開口端１２２とを有し、表示パネル１１０の表示面１１１側の周縁を枠部１２１で覆うベゼル１２０と、表示パネル１１０の表示面１１１側にベゼル１２０を挟んだ状態で設けられた前面パネル１３０と、ベゼル１２０の開口端１２２の直下であって、ベゼル１２０と表示面１１１との重なり部位に生じた間隙１７２を表示面１１１に対して垂直方向に空隙を有さずに充填する樹脂部材１４０と、表示面１１１と前面パネル１３０との間に充填されたＯＣＲ１５０と、を備えている。ここで、表示面１１１とは、表示パネル１１０の前面パネル１３０側の面全域を指す。 As shown in FIGS. 7 and 8, a display device 400 (optical display) according to the present invention includes a display panel 110 having a display surface 111, a frame 121, and an opening end 122 inside the frame 121. The bezel 120 that covers the periphery of the display panel 110 on the display surface 111 side with the frame 121, the front panel 130 that is provided on the display surface 111 side of the display panel 110 with the bezel 120 interposed therebetween, and the open end of the bezel 120. Immediately below 122, a resin member 140 that fills a gap 172 formed at the overlapping portion of the bezel 120 and the display surface 111 without a gap in the direction perpendicular to the display surface 111, and the display surface 111 and the front surface. And an OCR 150 filled between the panel 130 and the panel 130. Here, the display surface 111 refers to the entire surface of the display panel 110 on the front panel 130 side.
　図８において、ベゼル１２０上に更にダム（樹脂部材）１４０を設け、前面パネル１３０との空間１７３を本硬化物からなるＯＣＲ１５０で充填した構造、いわゆる二段ダム構造が示されている。なお、ベゼル下の樹脂部材１４０は図と異なり上段又は下段のみであってもよい。バックライトユニット１７１上に表示パネル１１０が搭載され、ベゼル１２０とバックライトユニット１７１とが嵌合構造（図示せず）により固定されることにより、表示モジュール１７０が構成されている。表示モジュール１７０とタッチパネル等の前面パネル１３０とは、ＯＣＲ１５０を介して全面が貼り合されている。 FIG. 8 shows a so-called two-step dam structure in which a dam (resin member) 140 is further provided on the bezel 120 and a space 173 with the front panel 130 is filled with an OCR 150 made of a hardened product. Note that the resin member 140 below the bezel may be only the upper stage or the lower stage unlike the drawing. The display panel 110 is mounted on the backlight unit 171, and the bezel 120 and the backlight unit 171 are fixed by a fitting structure (not shown) to form the display module 170. The entire surface of the display module 170 and the front panel 130 such as a touch panel are attached via the OCR 150.
　図７及び図８に示す本発明の物品の実施形態では、前面パネル１３０の内層、ＯＣＲ１５０、ベゼル下の樹脂部材１４０（上段及び下段のいずれであってもよい）等に本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物を適用可能である。なお、これらの用途に限定されず、図７及び図８に示す各部材内又は各部材間の接合に及び充填に本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着材を使用することができる。 In the embodiment of the article of the present invention shown in FIGS. 7 and 8, the curing reactivity of the present invention is applied to the inner layer of the front panel 130, the OCR 150, the resin member 140 under the bezel (which may be either the upper stage or the lower stage), and the like. A silicone pressure-sensitive adhesive composition or a cured product thereof can be applied. It should be noted that the present invention is not limited to these applications, and the curing-reactive silicone pressure-sensitive adhesive composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof is used for joining and filling each member shown in FIGS. 7 and 8 and between each member. Can be used.
本発明の硬化反応性のシリコーン（オルガノポリシロキサン）組成物、それを硬化してなる硬化物の用途としては、上記に開示した他に何ら制約はなく、本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着材を備えてなる粘着性シートはテレビ受像機、コンピューター用モニター、携帯情報端末用モニター、監視用モニター、ビデオカメラ、デジタルカメラ、携帯電話、携帯情報端末、自動車等の計器盤用ディスプレイ、種々の設備・装置・機器の計器盤用ディスプレイ、自動券売機、現金自動預け払い機、車載用表示装置、車載用透過型スクリーン等、文字や記号、画像を表示するための種々の表示装置に利用可能である。このような表示装置の表面形状は、平面ではなく曲面状ないし湾曲した形状であってもよく、各種フラットパネルディスプレイ（ＦＰＤ）のほか、自動車（電気自動車含む）や航空機等に利用される曲面ディスプレイ又は曲面透過型スクリーンが例示される。更に、これらの表示装置は、スクリーンやディスプレイ上に機能又はプログラムを実行するためのアイコンや、電子メール・プログラム等の通知表示、カーナビゲーション装置、スピーカー用のメンブレン、オーディオ装置、空調装置等の各種装置の操作ボタンを表示することができ、これらのアイコンや通知表示、操作ボタンに指を触れることで、入力操作が可能となるタッチパネル機能が付加されていてもよい。装置としては、ＣＲＴディスプレイ、液晶ディスプレイ、プラズマディスプレイ、有機ＥＬディスプレイ、無機ＥＬディスプレイ、ＬＥＤディスプレイ、表面電解ディスプレイ（ＳＥＤ）、電界放出型ディスプレイ（ＦＥＤ）等の表示装置や、これらを利用したタッチパネルに応用が可能である。また、本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着材は、接着性と粘弾性特性に優れるため、スピーカー用のメンブレン等のトランスデューサー用部材（センサ、スピーカー、アクチュエーター、及び、ジェネレーター用を含む）であるフィルム又はシート状部材として利用できるほか、更に、二次電池、燃料電池又は太陽電池モジュールに用いる封止層又は接着剤層として利用することができる。 The use of the curing-reactive silicone (organopolysiloxane) composition of the present invention and the cured product obtained by curing the same is not limited to the above-mentioned ones, and the curing-reactive silicone pressure-sensitive adhesive composition of the present invention is used. An adhesive sheet made of a cured product or a cured product thereof is a television receiver, a computer monitor, a personal digital assistant monitor, a surveillance monitor, a video camera, a digital camera, a mobile phone, a personal digital assistant, an automobile, etc. To display characters, symbols, images, such as instrument panel displays, instrument panel displays for various equipment, devices and equipment, automatic ticket vending machines, automated teller machines, in-vehicle display devices, in-vehicle transparent screens, etc. Can be used for various display devices. The surface shape of such a display device may be a curved surface shape or a curved shape instead of a flat surface, and in addition to various flat panel displays (FPD), a curved surface display used for automobiles (including electric vehicles) and aircrafts. Alternatively, a curved transmissive screen is exemplified. Further, these display devices include various icons such as icons for executing functions or programs on a screen or a display, notification display of e-mail programs, car navigation devices, membranes for speakers, audio devices, air conditioners, etc. The operation buttons of the device may be displayed, and a touch panel function may be added that enables input operation by touching a finger on these icons, notification display, and operation buttons. The device is a display device such as a CRT display, a liquid crystal display, a plasma display, an organic EL display, an inorganic EL display, an LED display, a surface electrolytic display (SED), a field emission display (FED), or a touch panel using these. It can be applied. Further, the curing reactive silicone pressure-sensitive adhesive composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof is excellent in adhesiveness and viscoelasticity, and therefore, a member for a transducer such as a membrane for a speaker (sensor, speaker, actuator, In addition, it can be used as a film or sheet-shaped member (including a generator), and can also be used as a sealing layer or an adhesive layer used in a secondary battery, a fuel cell or a solar cell module.
本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着材は、実質的に透明であってよく、硬化不良や硬化性の低下の問題を生じることなく、且つ、各種表示デバイス等の基材への密着性に優れることから、長期間にわたって表示内容の視認性及び操作性が良好な車両用表示装置、特に、曲面スクリーン又は曲面ディスプレイを備え、任意でタッチパネル機能を有する車両用表示装置に好適に利用できる。例えば、特開2017-047767号公報、特開2014-182335号公報、特開2014-063064号公報、特開2013-233852号公報等には曲面状の表示面を備えた車両用表示装置が開示されているが、本発明の感圧接着層は、これらの文献中の透明性が求められる接着層又は粘着層の一部又は全部として好適に適用乃至置き換えが可能である。更に、本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着材は、他の公知の曲面状の表示装置についても、現在使用されている透明性が求められる接着層又は粘着層を置き換えて利用できることは言うまでもなく、本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着材の利点を更に活用するために表示装置の設計や部材の厚みを公知の手法により調整することが好ましい。 The curing-reactive silicone pressure-sensitive adhesive composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof may be substantially transparent, and does not cause problems of poor curing or deterioration of curability, and various display devices and the like. Since it has excellent adhesion to the base material, the display device for vehicles has good visibility and operability of display contents for a long period of time, and in particular, the display for vehicles has a curved screen or curved display and optionally has a touch panel function. It can be suitably used for devices. For example, JP-A-2017-047767, JP-A-2014-182335, JP-A-2014-063064, JP-A-2013-233852 and the like disclose vehicle display devices having a curved display surface. However, the pressure-sensitive adhesive layer of the present invention can be suitably applied or replaced as a part or all of the adhesive layer or the pressure-sensitive adhesive layer required to have transparency in these documents. Further, the curable reactive silicone pressure-sensitive adhesive composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof is an adhesive layer or pressure-sensitive adhesive layer which is currently used and is required to have transparency even in other known curved display devices. Needless to say, the composition of the display device and the thickness of the member can be adjusted by a known method in order to further utilize the advantages of the curable reactive silicone pressure sensitive adhesive composition of the present invention or the pressure sensitive adhesive comprising the cured product. Preferably.
なお、本発明の硬化反応性シリコーン粘着剤組成物又はその硬化物からなる粘着材を備えた透明なフィルム状基材を、これらの、ディスプレイ表面の傷つき防止、汚れ防止、指紋付着防止、帯電防止、反射防止、のぞき見防止等の目的で使用してもよい。 In addition, a transparent film-like substrate provided with a curable reactive silicone pressure-sensitive adhesive composition of the present invention or a pressure-sensitive adhesive made of a cured product thereof is used to prevent scratches, stains, fingerprints, and antistatics on the display surface. It may be used for the purpose of preventing reflection, preventing peep, etc.
以下、本発明を実施例に基づいて更に詳細に説明するが、本発明はこれらの実施例によってなんら限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
［液状組成物の実験例］
実施例１～３、並びに、比較例１及び２は、２５℃において液状である硬化反応性シリコーン粘着剤組成物に関する実験例であり、その組成（質量部）、粘度、硬化物の粘着力等を表１に示す。なお、表中、組成物中のアルケニル基の総量１モルに対するケイ素原子結合水素原子のモル量の比率を「ＳｉＨ／Ｖｉ比」として記載した。 [Experimental example of liquid composition]
Examples 1 to 3 and Comparative Examples 1 and 2 are experimental examples relating to a curing-reactive silicone pressure-sensitive adhesive composition that is liquid at 25° C., and its composition (parts by mass), viscosity, adhesive strength of the cured product, etc. Is shown in Table 1. In the table, the ratio of the molar amount of silicon atom-bonded hydrogen atoms to the total amount of 1 mol of alkenyl groups in the composition is described as "SiH/Vi ratio".
［非流動性組成物の実験例］
実施例４及び５、並びに、比較例３は、２５℃において非流動性であり、加熱溶融性（ホットメルト性）を有することを意図して設計した硬化反応性シリコーン粘着剤組成物に関する実験例であり、その組成（質量部）、未硬化物及び硬化物の粘着力等を表２に示す。なお、表中、組成物中のアルケニル基の総量１モルに対するケイ素原子結合水素原子のモル量の比率を「ＳｉＨ／Ｖｉ比」として記載した。 [Experimental example of non-fluid composition]
Examples 4 and 5, and Comparative Example 3 are non-fluid at 25° C., and are experimental examples relating to a curing-reactive silicone pressure-sensitive adhesive composition designed to have heat melting property (hot melt property). Table 2 shows the composition (parts by mass), the adhesive strength of the uncured product, and the cured product. In the table, the ratio of the molar amount of silicon atom-bonded hydrogen atoms to the total amount of 1 mol of alkenyl groups in the composition is described as "SiH/Vi ratio".
　以下に本実施例で用いた成分を示す。各構造式中、Ｍｅはメチル基であり、Ｖｉはビニル基である。
（Ａ）成分として、次の成分を用いた。
ａ－１：　ＶｉＭｅ２ＳｉＯ（ＳｉＭｅ２Ｏ）４７４５（ＳｉＶｉＭｅＯ）２５Ｍｅ２Ｖｉ
ａ－２：　ＶｉＭｅ２ＳｉＯ（ＳｉＭｅ２Ｏ）８３０ＳｉＭｅ２Ｖｉ
（Ｂ）成分として、次の成分を用いた。
ｂ－１：　Ｍｅ３ＳｉＯ（ＳｉＭｅＨＯ）５０ＳｉＭｅ３
ｂ－２：　Ｍｅ３ＳｉＯ（ＳｉＭｅ２Ｏ）２５（ＳｉＭｅＨＯ）５４ＳｉＭｅ３
ｂ－３：　Ｍｅ２ＨＳｉＯ（ＳｉＭｅ２Ｏ）２４ＳｉＭｅ３Ｈ
ｂ－４：　Ｍｅ３ＳｉＯ（ＳｉＭｅ２Ｏ）３０（ＳｉＭｅＨＯ）３０ＳｉＭｅ３
（Ｃ）成分として、次の成分を用いた。
ｃ：　白金（０価）ジビニルテトラメチルジシロキサン錯体のジビニルテトラメチルジシロキサン溶液（白金金属濃度は４質量％）。
（Ｄ）成分及び比較成分として、それぞれ、次の成分を用いた。
ｄ：　　１,３－ビス(ジフェニルホスフィノ)プロパン。
ｄ’：　 ３、５－ジメチル－１－ヘキシン－３－オール
（Ｅ）成分として、次の成分を用いた。
ｅ－１：　（Ｍｅ３ＳｉＯ１／２）０．４６（ＳｉＯ４／２）０．５４（ＨＯ１／２）０．０５
ｅ－２：　（Ｍｅ３ＳｉＯ１／２）０．４８（ＳｉＯ４／２）０．５２（ＨＯ１／２）０．０４
ｅ－３：　（ＶｉＭｅ２ＳｉＯ１／２）０．０４６（Ｍｅ３ＳｉＯ１／２）０．３９４（ＳｉＯ４／２）０．５６（ＨＯ１／２）０．０５
（Ｆ成分）として、次の成分を用いた。
ｆ－１：　キシレン
ｆ－２：　トルエン The components used in this example are shown below. In each structural formula, Me is a methyl group and Vi is a vinyl group.
The following components were used as the component (A).
a-1: ViMe 2 SiO(SiMe 2 O) 4745 (SiViMeO) 25 Me 2 Vi
a-2: ViMe 2 SiO(SiMe 2 O) 830 SiMe 2 Vi
The following components were used as the component (B).
b-1: Me 3 SiO(SiMeHO) 50 SiMe 3
b-2: Me 3 SiO(SiMe 2 O) 25 (SiMeHO) 54 SiMe 3
b-3: Me 2 HSiO(SiMe 2 O) 24 SiMe 3 H
b-4: Me 3 SiO(SiMe 2 O) 30 (SiMeHO) 30 SiMe 3
The following components were used as the component (C).
c: Divinyltetramethyldisiloxane solution of platinum (0-valent) divinyltetramethyldisiloxane complex (platinum metal concentration is 4% by mass).
The following components were used as the component (D) and the comparative component, respectively.
d: 1,3-bis(diphenylphosphino)propane.
d′: The following components were used as the 3,5-dimethyl-1-hexyn-3-ol (E) component.
e-1: (Me 3 SiO 1/2 ) 0.46 (SiO 4/2 ) 0.54 (HO 1/2 ) 0.05
e-2: (Me 3 SiO 1/2 ) 0.48 (SiO 4/2 ) 0.52 (HO 1/2 ) 0.04
e-3: (ViMe 2 SiO 1/2 ) 0.046 (Me 3 SiO 1/2 ) 0.394 (SiO 4/2 ) 0.56 (HO 1/2 ) 0.05
The following components were used as (F component).
f-1: xylene f-2: toluene
　また、実験例中の測定、評価は次のようにして行った。
〔粘度の測定〕
　ＪＩＳ　Ｋ７１１７－１に準拠した回転粘度計を用いて、「粘度（ｍＰａ・ｓ）」を測定した。
〔粘着力の測定〕
引張試験機（オリエンテック社製ＲＴＣ－１２１０）を用い、ＪＩＳ　Ｚ０２３７に準じた１８０°引き剥がし試験方法で、３００ｍｍ／ｍｉｎの引張速度で引き剥がし「粘着力（ｇｆ／ｉｎｃｈ）」を測定した。ここで、測定は２５℃で行った。 The measurement and evaluation in the experimental examples were performed as follows.
[Measurement of viscosity]
“Viscosity (mPa·s)” was measured by using a rotational viscometer according to JIS K7117-1.
[Measurement of adhesive strength]
Using a tensile tester (RTC-1210 manufactured by Orientec Co., Ltd.), the "peel strength (gf/inch)" was measured by peeling at a tensile speed of 300 mm/min by a 180° peel test method according to JIS Z0237. Here, the measurement was performed at 25°C.
〔実施例１〕
表１に示す実施例１の各成分を均一に混合し、硬化反応性シリコーン粘着剤組成物１を調製した。混合は、２５℃でバッチミキサーを使用して行った。調製後、直ちに前記組成物の２５℃での粘度を測定した。また、前記組成物を２５℃で２４時間保管後、２５℃での粘度を測定した。結果を表１の「シリコーン組成物の粘度＜調製直後＞」及び「シリコーン組成物の粘度＜調製後、２５℃で２４時間保管後＞」の欄にそれぞれ示す。
表１から明らかなように、経時での粘度上昇は見られなかった。 [Example 1]
The components of Example 1 shown in Table 1 were uniformly mixed to prepare a curing reactive silicone pressure sensitive adhesive composition 1. Mixing was done at 25° C. using a batch mixer. Immediately after preparation, the viscosity of the composition at 25° C. was measured. Further, the composition was stored at 25° C. for 24 hours, and then the viscosity at 25° C. was measured. The results are shown in the columns of "Viscosity of silicone composition <immediately after preparation>" and "Viscosity of silicone composition <After preparation and after storage at 25°C for 24 hours>" in Table 1, respectively.
As is clear from Table 1, no increase in viscosity with time was observed.
次に、硬化反応性シリコーン粘着剤組成物１を、調製後直ちにポリイミドフィルム（株式会社東レ・デュポン製、製品名カプトン（登録商標）１００Ｈ、厚さ２５μｍ）上に、アプリケーターで塗工し、１５０℃で５分間加熱することにより、溶剤除去・硬化させた。更に、２５℃で１日間保管し、硬化シート１－１を作成した。ここで、組成物の塗工量は、溶剤除去・硬化後のシリコーン層の厚みが５０μｍとなるように調整した。
前記シートを幅２０ｍｍ、長さ３００ｍｍに切断し、２ｋｇのゴムローラーを用いて、その粘着層面をステンレス板（ＳＵＳ３０４、５０ｘ１２０ｘ２ｍｍ）上に圧着・貼り合わせて粘着力測定用試験片を作成し、粘着力を測定した。結果を表１の「硬化シートの粘着力＜組成物調製直後に調製した硬化シート＞」の欄に示す。 Next, the curing-reactive silicone pressure-sensitive adhesive composition 1 was coated on a polyimide film (manufactured by Toray DuPont Co., Ltd., product name Kapton (registered trademark) 100H, thickness 25 μm) with an applicator immediately after the preparation, and 150 The solvent was removed and cured by heating at 5°C for 5 minutes. Further, it was stored at 25° C. for 1 day to prepare a cured sheet 1-1. Here, the coating amount of the composition was adjusted so that the thickness of the silicone layer after solvent removal and curing was 50 μm.
The sheet is cut into a width of 20 mm and a length of 300 mm, and the pressure-sensitive adhesive layer surface is pressure-bonded and bonded onto a stainless steel plate (SUS304, 50x120x2 mm) using a 2 kg rubber roller to prepare a test piece for measuring the adhesive strength. The force was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared immediately after composition preparation>" in Table 1.
更に、硬化反応性シリコーン粘着剤組成物１を、２５℃で２４時間保管後、上記と同様の方法で硬化シート１－２を作成し、更に粘着力測定用試験片を作成し、粘着力を測定した。結果を表１の「硬化シートの粘着力＜組成物調製後、２５℃で２４時間保管後に調製した硬化シート＞」の欄に示す。 Further, the curing reactive silicone pressure sensitive adhesive composition 1 was stored at 25° C. for 24 hours, and then a cured sheet 1-2 was prepared in the same manner as described above, and a test piece for measuring the adhesive strength was further prepared. It was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared after composition was prepared and stored at 25°C for 24 hours>" in Table 1.
両者の粘着力に大きな差異は見られず、共に良好な粘着性を有していた。 No significant difference was found in the adhesive strength between the two, and both had good adhesiveness.
〔実施例２〕
実施例１と同様に、表１に示す実施例２の各成分を均一に混合し、硬化反応性シリコーン粘着剤組成物２を調製した。調製後、直ちに前記組成物の２５℃での粘度を測定した。また、前記組成物を２５℃で２４時間保管後、２５℃での粘度を測定した。結果を表１の「シリコーン組成物の粘度＜調製直後＞」及び「シリコーン組成物の粘度＜調製後、２５℃で２４時間保管後＞」の欄にそれぞれ示す。
表１から明らかなように、経時での粘度上昇はほぼ見られなかった。 [Example 2]
In the same manner as in Example 1, the components of Example 2 shown in Table 1 were uniformly mixed to prepare a curing reactive silicone pressure sensitive adhesive composition 2. Immediately after preparation, the viscosity of the composition at 25° C. was measured. Further, the composition was stored at 25° C. for 24 hours, and then the viscosity at 25° C. was measured. The results are shown in the columns of "Viscosity of silicone composition <immediately after preparation>" and "Viscosity of silicone composition <After preparation and after storage at 25°C for 24 hours>" in Table 1, respectively.
As is clear from Table 1, almost no increase in viscosity with time was observed.
次に、実施例１と同様に、硬化シート２－１を作成し、粘着力を測定した。結果を表１の「硬化シートの粘着力＜組成物調製直後に調製した硬化シート＞」の欄に示す。 Next, in the same manner as in Example 1, a cured sheet 2-1 was prepared and the adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared immediately after composition preparation>" in Table 1.
更に、実施例１と同様に、硬化シート２－２を作成し、粘着力を測定した。結果を表１の「硬化シートの粘着力＜組成物調製後、２５℃で２４時間保管後に調製した硬化シート＞」の欄に示す。 Further, a cured sheet 2-2 was prepared in the same manner as in Example 1 and the adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared after composition was prepared and stored at 25°C for 24 hours>" in Table 1.
両者の粘着力に大きな差異は見られず、共に良好な粘着性を有していた。 No significant difference was found in the adhesive strength between the two, and both had good adhesiveness.
〔実施例３〕
実施例１と同様に、表１に示す実施例３の各成分を均一に混合し、硬化反応性シリコーン粘着剤組成物３を調製した。調製後、直ちに前記組成物の２５℃での粘度を測定した。また、前記組成物を２５℃で２４時間保管後、２５℃での粘度を測定した。結果を表１の「シリコーン組成物の粘度＜調製直後＞」及び「シリコーン組成物の粘度＜調製後、２５℃で２４時間保管後＞」の欄にそれぞれ示す。
表１から明らかなように、経時での粘度上昇は見られなかった。 [Example 3]
In the same manner as in Example 1, the components of Example 3 shown in Table 1 were uniformly mixed to prepare a curable reactive silicone pressure sensitive adhesive composition 3. Immediately after preparation, the viscosity of the composition at 25° C. was measured. Further, the composition was stored at 25° C. for 24 hours, and then the viscosity at 25° C. was measured. The results are shown in the columns of "Viscosity of silicone composition <immediately after preparation>" and "Viscosity of silicone composition <After preparation and after storage at 25°C for 24 hours>" in Table 1, respectively.
As is clear from Table 1, no increase in viscosity with time was observed.
次に、硬化反応性シリコーン粘着剤組成物３を調製後、直ちにトルエン（溶剤）を更に加え（該組成物１００部に対し、５質量部）、均一に混合し、得られた混合物を、ポリイミドフィルム（株式会社東レ・デュポン製、製品名カプトン（登録商標）１００Ｈ、厚さ２５μｍ）上に、アプリケーターで塗工し、１５０℃で５分間加熱することにより、溶剤除去・硬化させた。更に、２５℃で１日間保管し、硬化シート３－１を作成した。ここで、組成物の塗工量は、溶剤除去・硬化後のシリコーン層の厚みが５０μｍとなるように調整した。
前記シートを幅２０ｍｍ、長さ３００ｍｍに切断し、２ｋｇのゴムローラーを用いて、その粘着層面をステンレス板（ＳＵＳ３０４、５０ｘ１２０ｘ２ｍｍ）上に圧着・貼り合わせて粘着力測定用試験片を作成し、粘着力を測定した。結果を表１の「硬化シートの粘着力＜組成物調製直後に調製した硬化シート＞」の欄に示す。 Next, immediately after the curing reactive silicone pressure sensitive adhesive composition 3 is prepared, toluene (solvent) is further added (5 parts by mass relative to 100 parts of the composition) and uniformly mixed, and the resulting mixture is treated with polyimide. A film (manufactured by Toray DuPont Co., Ltd., product name Kapton (registered trademark) 100H, thickness 25 μm) was applied with an applicator and heated at 150° C. for 5 minutes to remove and cure the solvent. Further, it was stored at 25° C. for 1 day to prepare a cured sheet 3-1. Here, the coating amount of the composition was adjusted so that the thickness of the silicone layer after solvent removal and curing was 50 μm.
The sheet is cut into a width of 20 mm and a length of 300 mm, and the pressure-sensitive adhesive layer surface is pressure-bonded and bonded onto a stainless steel plate (SUS304, 50x120x2 mm) using a 2 kg rubber roller to prepare a test piece for measuring the adhesive strength. The force was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared immediately after composition preparation>" in Table 1.
更に、硬化反応性シリコーン粘着剤組成物３を、２５℃で２４時間保管後、上記と同様の方法で硬化シート３－２を作成し、更に粘着力測定用試験片を作成し、粘着力を測定した。結果を表１の「硬化シートの粘着力＜組成物調製後、２５℃で２４時間保管後に調製した硬化シート＞」の欄に示す。 Further, the curing reactive silicone pressure-sensitive adhesive composition 3 was stored at 25° C. for 24 hours, and then a cured sheet 3-2 was prepared in the same manner as described above. It was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared after composition was prepared and stored at 25°C for 24 hours>" in Table 1.
両者の粘着力に差異は見られず、保護材料としての使用に適した粘着力を有していた。 There was no difference in the adhesive strength between the two, and the adhesive strength was suitable for use as a protective material.
〔比較例１〕
実施例１と同様に、表１に示す各成分を均一に混合し、比較用シリコーン組成物１を調製した。調製後、直ちに前記組成物の２５℃での粘度を測定した。結果を表１の「シリコーン組成物の粘度＜調製直後＞」の欄に示す。 [Comparative Example 1]
In the same manner as in Example 1, the components shown in Table 1 were uniformly mixed to prepare a comparative silicone composition 1. Immediately after preparation, the viscosity of the composition at 25° C. was measured. The results are shown in the column of "Viscosity of silicone composition <immediately after preparation>" in Table 1.
また、実施例１と同様に、比較用硬化シート１－１を作成し、粘着力を測定した。結果を表１の「硬化シートの粘着力＜組成物調製直後に調製した硬化シート＞」の欄に示す。 Further, in the same manner as in Example 1, a comparative cured sheet 1-1 was prepared and the adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared immediately after composition preparation>" in Table 1.
一方、比較用シリコーン組成物１を２５℃で２４時間保管したところ、試料全体がゲル化し、粘度の測定や粘着力の測定は出来なかった。 On the other hand, when the comparative silicone composition 1 was stored at 25° C. for 24 hours, the entire sample gelled, and the viscosity and adhesive strength could not be measured.
〔比較例２〕
実施例３と同様に、表１に示す各成分を均一に混合し、比較用シリコーン組成物２を調製した。調製後、直ちに前記組成物の２５℃での粘度を測定した。結果を表１の「シリコーン組成物の粘度＜調製直後＞」の欄に示す。 [Comparative Example 2]
In the same manner as in Example 3, the components shown in Table 1 were uniformly mixed to prepare a comparative silicone composition 2. Immediately after preparation, the viscosity of the composition at 25° C. was measured. The results are shown in the column of "Viscosity of silicone composition <immediately after preparation>" in Table 1.
また、実施例３と同様に、比較用硬化シート２－１を作成し、粘着力を測定した。結果を表１の「硬化シートの粘着力＜組成物調製直後に調製した硬化シート＞」の欄に示す。 In addition, similarly to Example 3, a comparative cured sheet 2-1 was prepared and the adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared immediately after composition preparation>" in Table 1.
一方、比較用シリコーン組成物２を２５℃で２４時間保管したところ、試料全体がゲル化し、粘度の測定や粘着力の測定は出来なかった。 On the other hand, when the comparative silicone composition 2 was stored at 25° C. for 24 hours, the entire sample gelled, and the viscosity and the adhesive strength could not be measured.
〔実施例４〕
表２に示す実施例４の各成分を均一に混合した。混合はラボプラストミル（東洋精機製）を使用し、８０℃、１００ｒｐｍの条件で１０分間、加熱・攪拌することで行った。混合中の回転トルクは１分程度で一定値を示し、それ以降は変化しなかった。混合物を取り出して冷却し、硬化反応性シリコーン粘着剤組成物４を調製した。 [Example 4]
The components of Example 4 shown in Table 2 were uniformly mixed. The mixing was performed by using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) and heating and stirring at 80° C. and 100 rpm for 10 minutes. The rotation torque during mixing showed a constant value in about 1 minute and did not change thereafter. The mixture was taken out and cooled to prepare a curing reactive silicone pressure sensitive adhesive composition 4.
調製直後の硬化反応性シリコーン粘着剤組成物４をポリイミドフィルム（株式会社東レ・デュポン製、製品名カプトン（登録商標）１００Ｈ、厚さ２５μｍ）と剥離フィルム（ニッパ株式会社製、ＦＳＣ－６）とではさみ、厚さ２００μｍのポリエチレンテレフタレートフィルムをスペーサにして、７０℃でプレス成型し、厚さ２００μｍの未硬化シート４－１を調製した。
前記シートは、７０℃に加熱することで、厚み調整を含む再加工が可能であった。
前記シートを幅２０ｍｍ、長さ３００ｍｍに切断し、剥離フィルムを分離して粘着面を露出させ、２ｋｇのゴムローラーを用いて、その粘着層面をステンレス板（ＳＵＳ３０４、５０ｘ１２０ｘ２ｍｍ）上に圧着・貼り合わせて粘着力測定用試験片を作成し、粘着力を測定した。結果を表２の「未硬化シートの粘着力＜組成物調製直後に調製した未硬化シート＞」の欄に示す。 Immediately after the preparation, the curable reactive silicone adhesive composition 4 was used as a polyimide film (manufactured by Toray DuPont Co., Ltd., product name Kapton (registered trademark) 100H, thickness 25 μm) and a release film (manufactured by Nipper Co., Ltd., FSC-6). Scissors were used, and a 200 μm thick polyethylene terephthalate film was used as a spacer, and press molding was performed at 70° C. to prepare an uncured sheet 4-1 having a thickness of 200 μm.
By heating the sheet to 70° C., reprocessing including thickness adjustment was possible.
The sheet is cut into a width of 20 mm and a length of 300 mm, the release film is separated to expose the adhesive surface, and the adhesive layer surface is pressure-bonded and attached onto a stainless steel plate (SUS304, 50x120x2 mm) using a 2 kg rubber roller. A test piece for measuring the adhesive strength was prepared and the adhesive strength was measured. The results are shown in the column of "Adhesive strength of uncured sheet <uncured sheet prepared immediately after composition preparation>" in Table 2.
次に、未硬化シート４－１を１５０℃で５分間加熱・硬化し、硬化シート４－１を作成した。これを幅２０ｍｍ、長さ３００ｍｍに切断し、剥離フィルムを分離して粘着面を露出させ、２ｋｇのゴムローラーを用いて、その粘着層面をステンレス板（ＳＵＳ３０４、５０ｘ１２０ｘ２ｍｍ）上に圧着・貼り合わせて粘着力測定用試験片を作成し、粘着力を測定した。結果を表２の「硬化シートの粘着力＜組成物調製直後に調製した硬化シート＞」の欄に示す。 Next, the uncured sheet 4-1 was heated and cured at 150° C. for 5 minutes to prepare a cured sheet 4-1. This is cut into a width of 20 mm and a length of 300 mm, the release film is separated, the adhesive surface is exposed, and the adhesive layer surface is pressure-bonded and bonded onto a stainless steel plate (SUS304, 50x120x2 mm) using a 2 kg rubber roller. A test piece for measuring the adhesive strength was prepared and the adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared immediately after composition preparation>" in Table 2.
一方、硬化反応性シリコーン粘着剤組成物４を、２５℃で２４時間保管後、上記と同様の方法で未硬化シート４－２を作成した。
前記シートは、７０℃に加熱することで、厚み調整を含む再加工が可能であった。
次に、未硬化シート４－２を１５０℃で５分間加熱・硬化し、硬化シート４－２を作成した。これを幅２０ｍｍ、長さ３００ｍｍに切断し、剥離フィルムを分離して粘着面を露出させ、２ｋｇのゴムローラーを用いて、その粘着層面をステンレス板（ＳＵＳ３０４、５０ｘ１２０ｘ２ｍｍ）上に圧着・貼り合わせて粘着力測定用試験片を作成し、粘着力を測定した。結果を表２の「硬化シートの粘着力＜組成物調製後、２５℃で２４時間保管後に調製した硬化シート＞」の欄に示す。 On the other hand, the curing reactive silicone pressure sensitive adhesive composition 4 was stored at 25° C. for 24 hours, and then an uncured sheet 4-2 was prepared by the same method as described above.
By heating the sheet to 70° C., reprocessing including thickness adjustment was possible.
Next, the uncured sheet 4-2 was heated and cured at 150° C. for 5 minutes to prepare a cured sheet 4-2. This is cut into a width of 20 mm and a length of 300 mm, the release film is separated, the adhesive surface is exposed, and the adhesive layer surface is pressure-bonded and bonded onto a stainless steel plate (SUS304, 50x120x2 mm) using a 2 kg rubber roller. A test piece for measuring the adhesive strength was prepared and the adhesive strength was measured. The results are shown in the column of “Adhesive strength of cured sheet <cured sheet prepared after composition preparation and storage at 25° C. for 24 hours>” in Table 2.
硬化シート４－１と硬化シート４－２の間で粘着力に差異は見られず、共に良好な粘着性を有していた。 There was no difference in the adhesive strength between the cured sheet 4-1 and the cured sheet 4-2, and both had good adhesiveness.
〔実施例５〕
実施例４と同様に、表２に示す実施例５の各成分を均一に混合した。混合中の回転トルクは１分程度で一定値を示し、それ以降は変化しなかった。混合物を取り出して冷却し、硬化反応性シリコーン粘着剤組成物５を調製した。 [Example 5]
In the same manner as in Example 4, the components of Example 5 shown in Table 2 were uniformly mixed. The rotation torque during mixing showed a constant value in about 1 minute and did not change thereafter. The mixture was taken out and cooled to prepare a curing reactive silicone pressure sensitive adhesive composition 5.
実施例４と同様に、硬化反応性シリコーン粘着剤組成物５を用いて厚さ２００μｍの未硬化シート５－１を調製した。
前記シートは、７０℃に加熱することで、厚み調整を含む再加工が可能であった。
実施例４と同様に、未硬化シート５－１の粘着力を測定した。結果を表２の「未硬化シートの粘着力＜組成物調製直後に調製した未硬化シート＞」の欄に示す。
次に、実施例４と同様に、未硬化シート５－１を１５０℃で５分間加熱・硬化し、硬化シート５－１を作成し、粘着力を測定した。結果を表２の「硬化シートの粘着力＜組成物調製直後に調製した硬化シート＞」の欄に示す。 In the same manner as in Example 4, a 200 μm-thick uncured sheet 5-1 was prepared using the curing-reactive silicone pressure-sensitive adhesive composition 5.
By heating the sheet to 70° C., reprocessing including thickness adjustment was possible.
The adhesive force of the uncured sheet 5-1 was measured in the same manner as in Example 4. The results are shown in the column of "Adhesive strength of uncured sheet <uncured sheet prepared immediately after composition preparation>" in Table 2.
Next, in the same manner as in Example 4, the uncured sheet 5-1 was heated and cured at 150° C. for 5 minutes to prepare a cured sheet 5-1 and its adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared immediately after composition preparation>" in Table 2.
一方、実施例４と同様に、硬化反応性シリコーン粘着剤組成物５を、２５℃で２４時間保管後、上記と同様の方法で未硬化シート５－２を作成した。
前記シートは、７０℃に加熱することで、厚み調整を含む再加工が可能であった。
次に、実施例４と同様に、未硬化シート５－２を１５０℃で５分間加熱・硬化し、硬化シート５－２を作成し、粘着力を測定した。結果を表２の「硬化シートの粘着力＜組成物調製後、２５℃で２４時間保管後に調製した硬化シート＞」の欄に示す。 On the other hand, similarly to Example 4, the curing reactive silicone pressure-sensitive adhesive composition 5 was stored at 25° C. for 24 hours, and then an uncured sheet 5-2 was prepared by the same method as described above.
By heating the sheet to 70° C., reprocessing including thickness adjustment was possible.
Next, in the same manner as in Example 4, the uncured sheet 5-2 was heated and cured at 150° C. for 5 minutes to prepare a cured sheet 5-2, and the adhesive strength was measured. The results are shown in the column of “Adhesive strength of cured sheet <cured sheet prepared after composition preparation and storage at 25° C. for 24 hours>” in Table 2.
硬化シート５－１と硬化シート５－２の間で粘着力に差異は見られず、共に良好な粘着性を有していた。 No difference was found in the adhesive force between the cured sheet 5-1 and the cured sheet 5-2, and both had good adhesiveness.
〔比較例３〕
　表２に示す各成分を均一に混合すべく、ラボプラストミル（東洋精機製）を使用し、８０℃、１００ｒｐｍの条件で加熱・攪拌を行ったところ、攪拌直後から回転トルクが上昇し、目的とするシリコーン組成物を得ることができなかった。 [Comparative Example 3]
Using Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) to uniformly mix the components shown in Table 2, heating and stirring were performed at 80° C. and 100 rpm. Could not be obtained.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
［総括］
実施例１～３に示すとおり、本発明の硬化反応性シリコーン粘着剤組成物１～３（組成物１及び２：溶剤型、組成物３：無溶剤型）は、長期間保管してもその粘度が変化せず、且つ、製造直後／保管後に組成物を硬化させて得られる硬化シートの粘着力もほぼ同じであった。なお、実施例１及び２はリン系ヒドロシリル化反応遅延剤の量が異なるが、少量（実施例２）でも十分な技術的効果を実現するものであった。一方、成分（Ｄ）を欠いた比較例１及び２においては、実施例と類似組成であっても、保存後にゲル化してしまい、貯蔵安定性及び粘着特性に優れる一液型の液状の硬化反応性シリコーン粘着剤組成物を得ることはできなかった。 [Summary]
As shown in Examples 1 to 3, the curing-reactive silicone pressure sensitive adhesive compositions 1 to 3 (compositions 1 and 2: solvent type, composition 3: solventless type) of the present invention are The viscosity did not change, and the adhesive strength of the cured sheet obtained by curing the composition immediately after production/after storage was almost the same. Although the amount of the phosphorus-based hydrosilylation reaction retarder was different in Examples 1 and 2, even a small amount (Example 2) achieved sufficient technical effects. On the other hand, in Comparative Examples 1 and 2 lacking the component (D), even if the composition was similar to that of the Example, it gelated after storage, and a one-pack type liquid curing reaction excellent in storage stability and adhesive properties. No silicone-based pressure-sensitive adhesive composition could be obtained.
実施例４及び５に示すとおり、本発明の硬化反応性シリコーン粘着剤組成物４及び５からは、非流動性且つ加熱溶融性粘着剤として使用可能な未硬化シートを得ることができ、且つ、当該組成物の製造直後／保管後に当該組成物を硬化させて得られる硬化シートの粘着力もほぼ同じであった。一方、成分（Ｄ）を欠いた比較例３からは、非流動性且つ加熱溶融性粘着剤として使用可能な未硬化シートを得ることができなかった。 As shown in Examples 4 and 5, from the curing-reactive silicone pressure-sensitive adhesive compositions 4 and 5 of the present invention, uncured sheets usable as non-fluidic and heat-meltable pressure-sensitive adhesives can be obtained, and The adhesive force of the cured sheet obtained by curing the composition immediately after the production/after storage of the composition was almost the same. On the other hand, from Comparative Example 3 lacking the component (D), it was not possible to obtain an uncured sheet that was non-fluid and could be used as a heat-meltable adhesive.

Claims (26)

  1. （Ａ）一分子中に少なくとも２個の脂肪族不飽和炭素－炭素結合含有基を有する直鎖状又は分岐鎖状オルガノポリシロキサン、
    （Ｂ）一分子中に少なくとも２個のケイ素結合水素原子を有するオルガノハイドロジェンポリシロキサン、
    （Ｃ）ヒドロシリル化反応用触媒、及び、
    （Ｄ）リン含有ヒドロシリル化反応遅延剤、
    を含み、
    （Ｂ）成分の含有量が、組成物中の全脂肪族不飽和炭素－炭素結合１モルに対して、（Ｂ）成分中のケイ素結合水素原子が０．５モル以上となる量である、硬化反応性シリコーン粘着剤組成物。     (A) a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule,
    (B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule,
    (C) catalyst for hydrosilylation reaction, and
    (D) Phosphorus-containing hydrosilylation reaction retarder,
    Including,
    The content of the component (B) is such that the silicon-bonded hydrogen atoms in the component (B) are 0.5 mol or more per 1 mol of the total aliphatic unsaturated carbon-carbon bond in the composition. Curing reactive silicone adhesive composition.
  2. （Ｄ）成分のリン含有ヒドロシリル化反応遅延剤が、ホスフィン系化合物、リン酸系化合物、ホスホン酸系化合物、ホスフィンオキサイド系化合物、亜リン酸系化合物、及び、亜ホスホン酸系化合物からなる群から選らばれる少なくとも一種である、請求項１記載の硬化反応性シリコーン粘着剤組成物。 The phosphorus-containing hydrosilylation reaction retarder of the component (D) is selected from the group consisting of phosphine compounds, phosphoric acid compounds, phosphonic acid compounds, phosphine oxide compounds, phosphorous acid compounds, and phosphonous acid compounds. The curable reactive silicone pressure-sensitive adhesive composition according to claim 1, which is at least one selected.
  3. （Ｄ）成分が、ジフェニルホスフィン、トリフェニルホスフィン、ジメチルフェニルホスフィン、ジエチルフェニルホスフィン、トリプロピルホスフィン、ジシクロヘキシルフェニルホスフィン、ビス(ジフェニルホスフィノ)メタン、１,２－ビス(ジフェニルホスフィノ)エタン、１,２－ビス(ジフェニルホスフィノ)プロパン、１,３－ビス(ジフェニルホスフィノ)プロパン、１,４－ビス(ジフェニルホスフィノ)ブタン、２，３－ビス(ジフェニルホスフィノ)ブタン、１,５－ビス(ジフェニルホスフィノ)ペンタン、１,６－ビス(ジフェニルホスフィノ)ヘキサン、ビス（２-ジフェニルホスフィノエチル）フェニルホスフィンビス(ジフェニルホスフィノ)アセチレン、１,１－ビス(ジフェニルホスフィノ)エチレン、１,２－ビス(ジフェニルホスフィノ)エチレン、１,１－ビス(ジフェニルホスフィノ)フェロセン、１,３－ビス(ジシクロヘキシルホスフィノ)プロパン、１,２－ビス(ジメチルホスフィノ)エタン、１,２－ビス(ジメチルホスフィノ)ベンゼン、及び、１,２－ビス(ジフェニルホスフィノ)ベンゼンからなる群から選らばれる少なくとも一種のホスフィン系化合物である、請求項１又は２記載の硬化反応性シリコーン粘着剤組成物。 Component (D) is diphenylphosphine, triphenylphosphine, dimethylphenylphosphine, diethylphenylphosphine, tripropylphosphine, dicyclohexylphenylphosphine, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1 ,2-bis(diphenylphosphino)propane,1,3-bis(diphenylphosphino)propane,1,4-bis(diphenylphosphino)butane,2,3-bis(diphenylphosphino)butane,1,5 -Bis(diphenylphosphino)pentane, 1,6-bis(diphenylphosphino)hexane, bis(2-diphenylphosphinoethyl)phenylphosphine bis(diphenylphosphino)acetylene, 1,1-bis(diphenylphosphino) Ethylene, 1,2-bis(diphenylphosphino)ethylene, 1,1-bis(diphenylphosphino)ferrocene, 1,3-bis(dicyclohexylphosphino)propane, 1,2-bis(dimethylphosphino)ethane, The curing reactivity according to claim 1 or 2, which is at least one phosphine-based compound selected from the group consisting of 1,2-bis(dimethylphosphino)benzene and 1,2-bis(diphenylphosphino)benzene. Silicone adhesive composition.
  4. (Ｄ)成分の配合量が、(Ｃ)成分中の金属原子１モルに対して、０.０１～１,０００モルとなる範囲の量である、請求項１乃至３のいずれか１項に記載の硬化反応性シリコーン粘着剤組成物。 The compounding amount of the component (D) is in the range of 0.01 to 1,000 mols per 1 mol of the metal atom in the component (C), according to any one of claims 1 to 3. A curable reactive silicone adhesive composition as described.
  5. (Ｄ)成分の配合量が、(Ｃ)成分中の金属原子１モルに対して、０．３０～１０モルとなる範囲の量である、請求項１乃至４のいずれか１項に記載の硬化反応性シリコーン粘着剤組成物。 5. The composition according to claim 1, wherein the amount of the component (D) compounded is in the range of 0.30 to 10 mol per 1 mol of the metal atom in the component (C). Curing reactive silicone adhesive composition.
  6. （Ｅ）分子内にＲ３ＳｉＯ１／２（式中、Ｒは互いに独立して一価有機基を表す）で表されるシロキサン単位（Ｍ単位）及び、ＳｉＯ４／２で表されるシロキサン単位（Ｑ単位）を含むオルガノポリシロキサン樹脂を更に含む請求項１乃至５のいずれか１項に記載の硬化反応性シリコーン粘着剤組成物。 (E) A siloxane unit (M unit) represented by R 3 SiO 1/2 (wherein R independently represents a monovalent organic group) in the molecule and a siloxane represented by SiO 4/2. The curable reactive silicone pressure sensitive adhesive composition according to any one of claims 1 to 5, further comprising an organopolysiloxane resin containing units (Q units).
  7. （Ｅ）成分の少なくとも一部が、分子内に（Ａｌｋ）Ｒ’２ＳｉＯ１／２（式中、Ａｌｋは互いに独立して脂肪族不飽和炭素－炭素結合含有基を表し、Ｒ’は互いに独立して脂肪族不飽和炭素－炭素結合不含基を表す）で表されるシロキサン単位（Ｍ単位）、及び、ＳｉＯ４／２で表されるシロキサン単位（Ｑ単位）を少なくとも含む硬化反応性オルガノポリシロキサン樹脂である、請求項６記載の硬化反応性シリコーン粘着剤組成物。 At least a part of the component (E) is (Alk)R′ 2 SiO 1/2 (wherein Alk each independently represents an aliphatic unsaturated carbon-carbon bond-containing group, and R′ are mutually independent). Curing reactivity containing at least a siloxane unit (M unit) represented by an aliphatic unsaturated carbon-carbon bond-free group) and a siloxane unit (Q unit) represented by SiO 4/2 The curing-reactive silicone pressure-sensitive adhesive composition according to claim 6, which is an organopolysiloxane resin.
  8. (Ｅ)成分の含有量が、（Ａ）成分、（Ｂ）成分、（Ｅ）成分の質量の総和の０．１質量％から９０質量％である、請求項６又は７記載の硬化反応性シリコーン粘着剤組成物。 The curing reactivity according to claim 6 or 7, wherein the content of the component (E) is 0.1% by mass to 90% by mass of the total mass of the components (A), (B) and (E). Silicone adhesive composition.
  9. （Ｆ）溶剤を更に含む、請求項１乃至８のいずれか１項に記載の硬化反応性シリコーン粘着剤組成物。 The curing-reactive silicone pressure-sensitive adhesive composition according to any one of claims 1 to 8, further comprising (F) a solvent.
  10. 一液型又は単一の組成物である、請求項１乃至９のいずれか１項に記載の硬化反応性シリコーン粘着剤組成物。 The curable reactive silicone pressure-sensitive adhesive composition according to any one of claims 1 to 9, which is a one-pack type or a single composition.
  11. 　２５℃において流動性である、請求項１乃至１０のいずれか１項に記載の硬化反応性シリコーン粘着剤組成物。 The curing-reactive silicone pressure-sensitive adhesive composition according to any one of claims 1 to 10, which is fluid at 25°C.
  12. 　組成物を硬化させて得られる厚み５０μｍの粘着層を、ＳＵＳ板に対して貼り合わせ、ＪＩＳ　Ｚ０２３７に準じて１８０°引き剥がし試験方法を用いて引張速度３００ｍｍ/ｍｉｎにて測定された粘着力が、０．１ｇｆ/ｉｎｃｈ以上である、請求項１１記載の硬化反応性シリコーン粘着剤組成物。 An adhesive layer with a thickness of 50 μm obtained by curing the composition was attached to a SUS plate, and the adhesive force measured at a pulling speed of 300 mm/min using a 180° peel test method according to JIS Z0237. The curing-reactive silicone pressure-sensitive adhesive composition according to claim 11, which is 0.1 gf/inch or more.
  13. ２５℃において非流動性であり、２５℃～１５０℃までの間に軟化点を有する、請求項１乃至１０のいずれか１項に記載の硬化反応性シリコーン粘着剤組成物。 The curing-reactive silicone pressure-sensitive adhesive composition according to any one of claims 1 to 10, which is non-flowable at 25°C and has a softening point between 25°C and 150°C.
  14. 　組成物を硬化させて得られる厚み２００μｍの粘着層を、ＳＵＳ板に対して貼り合わせ、ＪＩＳ　Ｚ０２３７に準じて１８０°引き剥がし試験方法を用いて引張速度３００ｍｍ/ｍｉｎにて測定された粘着力が、０．１ｇｆ/ｉｎｃｈ以上である、請求項１３記載の硬化反応性シリコーン粘着剤組成物。 An adhesive layer with a thickness of 200 μm obtained by curing the composition was attached to a SUS plate, and the adhesive force measured at a pulling speed of 300 mm/min using a 180° peel test method according to JIS Z0237. , 0.1 gf/inch or more, The curable reactive silicone pressure-sensitive adhesive composition according to claim 13.
  15. 　硬化反応前の状態において粘着性を有する、請求項１３又は１４記載の硬化反応性シリコーン粘着剤組成物。 The curing-reactive silicone pressure-sensitive adhesive composition according to claim 13 or 14, which has tackiness in a state before curing reaction.
  16. 請求項１３乃至１５のいずれか１項に記載の硬化反応性シリコーン粘着剤組成物から少なくともなる部材、部品、又は、シート。 A member, component, or sheet comprising at least the curable reactive silicone pressure-sensitive adhesive composition according to any one of claims 13 to 15.
  17. 請求項１３乃至１５のいずれか１項に記載の硬化反応性シリコーン粘着剤組成物からなる加熱溶融性粘着材。 A heat-meltable pressure-sensitive adhesive material comprising the curing-reactive silicone pressure-sensitive adhesive composition according to any one of claims 13 to 15.
  18. 請求項１乃至１５のいずれか１項に記載の硬化反応性シリコーン粘着剤組成物の硬化物。 A cured product of the curable reactive silicone pressure-sensitive adhesive composition according to any one of claims 1 to 15.
  19. 請求項１乃至１５のいずれか１項に記載の硬化反応性シリコーン粘着剤組成物を１５０℃未満の温度条件において塗布又は成型後、１５０℃以上に加熱して硬化させる工程を含む、請求項１８記載の硬化物の製造方法。 The method according to any one of claims 1 to 15, further comprising a step of applying or molding the curing-reactive silicone pressure-sensitive adhesive composition under a temperature condition of less than 150°C, followed by heating at 150°C or higher to cure the composition. A method for producing the cured product described.
  20. 請求項１乃至１５のいずれか１項に記載の硬化反応性シリコーン粘着剤組成物の硬化物からなる粘着材。 An adhesive material comprising a cured product of the curable reactive silicone adhesive composition according to any one of claims 1 to 15.
  21. 請求項１乃至１５のいずれか１項に記載の硬化反応性シリコーン粘着剤組成物からなる層又は部材を備える、積層体。 A laminate comprising a layer or member comprising the curable reactive silicone pressure sensitive adhesive composition according to any one of claims 1 to 15.
  22. 請求項１乃至１５のいずれか１項に記載の硬化反応性シリコーン粘着剤組成物の硬化物からなる層又は部材を備える、積層体。 A laminate comprising a layer or a member made of a cured product of the curable reactive silicone pressure-sensitive adhesive composition according to any one of claims 1 to 15.
  23. 剥離層を備えたシート状部材を少なくとも一部に含む、請求項２１又は２２記載の積層体。 The laminated body according to claim 21 or 22, which comprises a sheet-like member provided with a release layer in at least a part thereof.
  24. 表示装置、電子部品又は太陽電池モジュールから選ばれる少なくとも１種である、請求項２１又は２２記載の積層体。 The laminate according to claim 21 or 22, which is at least one kind selected from a display device, an electronic component, and a solar cell module.
  25. 請求項１３乃至１５のいずれか１項に記載の硬化反応性シリコーン粘着剤組成物を８０℃以上に加熱して溶融させ、溶融物を成型乃至充填する工程を含む、請求項２１乃至２４のいずれか１項に記載の積層体の製造方法。 The method according to any one of claims 21 to 24, which includes a step of heating the curing-reactive silicone pressure-sensitive adhesive composition according to any one of claims 13 to 15 to 80°C or higher to melt the composition and molding or filling the melt. 2. The method for producing a laminate according to Item 1.
  26. 　請求項１乃至１５のいずれか１項に記載の硬化反応性シリコーン粘着剤組成物又はその硬化物を部材間に挟んで積層する工程、及び、前記硬化反応性シリコーン粘着剤組成物又はその硬化物により前記部材を圧着する工程を含む、請求項２１乃至２４のいずれか１項に記載の積層体の製造方法。 A step of laminating the curable reactive silicone pressure sensitive adhesive composition according to any one of claims 1 to 15 or a cured product thereof between members, and the curable reactive silicone pressure sensitive adhesive composition or a cured product thereof. The method for manufacturing a laminate according to any one of claims 21 to 24, comprising a step of pressure-bonding the member by.
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