WO2020138055A1 - 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 - Google Patents
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 Download PDFInfo
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- WO2020138055A1 WO2020138055A1 PCT/JP2019/050558 JP2019050558W WO2020138055A1 WO 2020138055 A1 WO2020138055 A1 WO 2020138055A1 JP 2019050558 W JP2019050558 W JP 2019050558W WO 2020138055 A1 WO2020138055 A1 WO 2020138055A1
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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
- 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]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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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
- 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
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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
- 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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
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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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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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
- 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
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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
- 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. However, even if the hydrosilylation reaction inhibitor is added, gelation or curing reaction proceeds in a relatively short time, and thus long-term storage is difficult.
- Patent Document 1 discloses a hydrosilylation reaction-curable silicone composition containing platinum-based catalyst-containing thermoplastic resin fine particles.
- Patent Document 1 does not describe the adhesive composition.
- Patent Document 2 a silicone pressure-sensitive adhesive using thermoplastic resin fine particles containing a platinum-based catalyst is disclosed, but the silicone pressure-sensitive adhesive is imparted with thixotropy. Therefore, a considerable amount of silica particles is used.
- 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.
- thermoplastic resin fine particles containing the platinum-based catalyst when used, the hydrosilylation reaction can be suppressed for a relatively long period of time, and the storage stability and handling workability of the silicone-based adhesive are improved.
- solid particle component such as silica
- 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, and (C) Thermoplastic resin fine particles containing a catalyst for hydrosilylation reaction, Including,
- the content of the component (B) is such that the silicon-bonded hydrogen atom in the component (B) is 0.5 mol or more per 1 mol of the total aliphatic unsaturated carbon-carbon bond in the composition, And it is achieved by the curable reactive silicone adhesive composition in which the content of solid particles in the entire composition is 0.50% by mass or less.
- thermoplastic resin forming the catalyst-containing thermoplastic resin fine particles for the hydrosilylation reaction is preferably 75° C. or higher.
- the curing-reactive silicone pressure-sensitive adhesive composition of the present invention has a siloxane unit (M) represented by R 3 SiO 1/2 (wherein R's each independently represent a monovalent organic group) in the molecule (D). Unit) and an organopolysiloxane resin containing a siloxane unit (Q unit) represented by SiO 4/2 .
- M siloxane unit
- Q unit organopolysiloxane resin containing a siloxane unit represented by SiO 4/2 .
- At least a part of the component (D) 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).
- the content of the component (D) is preferably 0.1% by mass to 90% by mass of the total mass of the components (A), (B), and (D).
- the curable reactive silicone pressure-sensitive adhesive composition of the present invention may further contain (E) unsaturated aliphatic hydrocarbon.
- the curing reactive silicone pressure-sensitive adhesive composition of the present invention may further contain (F) a curing retarder.
- the curable reactive silicone pressure-sensitive adhesive composition of the present invention may further contain (G) 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. Further, the curing-reactive silicone pressure-sensitive adhesive composition of the present invention may be such that the composition has tackiness 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 present inventors have (A) a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule, and (B) one.
- (C) Platinum-based catalyst-containing thermoplastic resin fine particles are added to a curing-reactive silicone pressure-sensitive adhesive composition containing a combination of organohydrogenpolysiloxanes having at least two silicon-bonded hydrogen atoms in the molecule under predetermined conditions,
- the curable reactive silicone pressure-sensitive adhesive composition containing 0.50% by mass or less of solid particles in the entire composition thickens in a relatively short time even in the form of a single composition.
- the present invention has been completed by finding that it is possible to provide a curing-reactive silicone pressure-sensitive adhesive composition that has no storage stability, high storage stability, and excellent adhesive properties.
- 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, and (C) Thermoplastic resin fine particles containing a catalyst for hydrosilylation reaction, Including, The content of the component (B) is such that the silicon-bonded hydrogen atom in the component (B) is 0.5 mol or more per 1 mol of the total aliphatic unsaturated carbon-carbon bond in the composition, In addition, the content of solid particles in the entire composition is 0.50% by mass or less.
- the curing-reactive silicone pressure-sensitive adhesive composition of the present invention has a siloxane unit represented by (D) 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 an alkenyl group, an alkenyloxyalkyl group, an acryloxyalkyl group or a 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 thermoplastic resin fine particle containing a catalyst for hydrosilylation reaction.
- the component (C) is a catalyst for promoting curing of the composition of the present invention by a hydrosilylation reaction, and fine particles in which a hydrosilylation reaction catalyst such as a platinum-based catalyst is dissolved or dispersed in a thermoplastic resin.
- a hydrosilylation reaction catalyst such as a platinum-based catalyst is dissolved or dispersed in a thermoplastic resin.
- it may be any of microcapsule fine particles having a structure in which a catalyst for hydrosilylation reaction such as a platinum catalyst is contained in the shell of a thermoplastic resin as a nucleus.
- the hydrosilylation reaction catalyst contained in the component (C) may be a single kind or a mixture of two or more kinds of hydrosilylation reaction catalysts.
- Examples of the hydrosilylation reaction catalyst in the component (C) include platinum catalysts, rhodium catalysts, palladium catalysts, nickel catalysts, iridium catalysts, ruthenium catalysts and iron catalysts, and preferably, It is a platinum-based catalyst.
- 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 catalyst for hydrosilylation reaction in the component (C) is preferably one which exhibits activity 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 thermoplastic resin that constitutes the component (C) is a wall material that encloses a hydrosilylation reaction catalyst such as a platinum-based catalyst, and by taking the form of the above-mentioned fine particles or microcapsule fine particles, the hydrosilylation reaction is performed at low temperatures.
- the catalyst for use is inactivated by the wall material so as not to disperse in the system, but at high temperature, the thermoplastic resin that is the wall material melts and the catalyst for hydrosilylation reaction is dispersed in the system. , And the curing reaction based on the hydrosilylation reaction proceeds.
- thermoplastic resin does not substantially permeate a hydrosilylation reaction catalyst such as a platinum-based catalyst at least during storage, and is substantially dissolved in components such as the organopolysiloxane in the composition of the present invention.
- a hydrosilylation reaction catalyst such as a platinum-based catalyst at least during storage
- components such as the organopolysiloxane in the composition of the present invention.
- silicone resin, polysilane resin, acrylic resin, methyl cellulose, and polycarbonate resin are preferred.
- the glass transition point (Tg) of these thermoplastic resins is preferably 75° C. or higher, more preferably 80° C. or higher, particularly preferably 100 to less than 250° C.
- Such thermoplastic resins may be used alone or in combination, but it is particularly preferable that at least a part of the component (C) of the present invention is a polycarbonate resin.
- the storage stability of the composition of the present invention tends to be remarkably reduced, and when the catalyst is added to the hot melt form in a heated and melted state, When the composition is heated and melt-molded, curing may proceed.
- the glass transition point of the thermoplastic resin is 250° C. or higher, a sufficient heat-curing rate tends to be not obtained unless the entire composition is heated at a high temperature exceeding 250° C. to cure the composition of the present invention. Therefore, from the viewpoint of industrial production efficiency, the thermoplastic resin constituting the component (C) preferably has a glass transition point of less than 250°C. Further, when it is desired to cure the composition of the present invention at 150° C., it is possible to select a material having a glass transition point of less than 150° C. as the thermoplastic resin constituting the component (C), and It is preferable in practice.
- the average particle diameter of the catalyst-containing thermoplastic resin fine particles for hydrosilylation reaction is not limited, but is preferably in the range of 0.1 to 500 ⁇ m, and more preferably 0.3 to 100 ⁇ m. This is because it is difficult to prepare the catalyst-containing thermoplastic resin fine particles for the hydrosilylation reaction having an average particle diameter of less than the lower limit of the above range, while on the other hand, when the average particle diameter exceeds the upper limit of the above range, the curable silicone resin This is because the dispersibility in the composition decreases.
- the method for preparing the thermoplastic resin fine particles containing the catalyst for the hydrosilylation reaction is not limited, and may be a chemical method such as a conventionally known interfacial polymerization method or an in-situ polymerization method, or a physical method such as a coacervation method or a submerged drying method.
- -A mechanical method is illustrated.
- the in-liquid drying method and the gas phase drying method are preferable because microcapsule fine particles having a narrow particle size distribution can be obtained relatively easily.
- the fine particles obtained by these methods can be used as they are, but it is preferable to wash the fine particles with an appropriate washing solvent to remove the platinum-based catalyst adhering to the surface of the fine curable silicone. It is desirable to obtain a resin composition.
- a suitable washing solvent is one that does not dissolve the thermoplastic resin but has the property of dissolving the hydrosilylation reaction catalyst.
- a cleaning solvent include alcohols such as methyl alcohol and ethyl alcohol, and low molecular weight organopolysiloxanes such as hexamethyldisiloxane.
- the ratio of the catalyst for hydrosilylation reaction to the thermoplastic resin varies greatly depending on the method for producing the granular material, and therefore it is not particularly limited, but the content of the catalyst for hydrosilylation reaction to the thermoplastic resin is 0.01% by mass or more. It is preferable that
- the composition of the present invention Due to the presence of the component (C), the composition of the present invention has improved storage stability at low temperatures, and suppresses activation of the hydrosilylation reaction catalyst even when other components are softened or melted by heating.
- the component (C) can be uniformly dispersed in the composition and the composition can be molded without proceeding the curing reaction.
- heating at high temperature melts the catalyst-containing thermoplastic resin fine particles for hydrosilylation reaction, and the hydrosilylation reaction catalyst released from the fine particles accelerates the hydrosilylation reaction, so that rapid curing is possible.
- a curable reactive silicone pressure-sensitive adhesive composition having excellent storage stability, handling workability, and moldability. Can be designed.
- the content of the component (C) is not particularly limited, for example, when the hydrosilylation reaction catalyst is a platinum-based catalyst, 0.1 to 200 ppm by mass of platinum metal in the fine particles is contained in the composition of the present invention.
- the amount is within the range of 0.1 to 150 ppm, and may be within the range of 0.1 to 100 ppm.
- composition of the present invention comprises (D) a siloxane unit (M unit) represented by R 3 SiO 1/2 (wherein R independently represents a monovalent organic group) in the molecule. And an organopolysiloxane resin containing a siloxane unit (Q unit) represented by SiO 4/2 .
- the component (D) may be a single organopolysiloxane resin or a mixture of two or more organopolysiloxane resins.
- the component (D) 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 (D) is a siloxane unit (M unit) represented by (a) R 3 SiO 1/2 (wherein R is independently 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 (D) 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 (D) 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 (D) 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 part of the component (D) is (D1) 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 (D) when the component (D) other than the (D1) curing-reactive organopolysiloxane resin is present, the component (D) is preferably non-curing reactive.
- R of the non-curing reactive component (D) 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 (D1) curing-reactive organopolysiloxane resin in the component (D) is not particularly limited, but in order to achieve an appropriate hardness as an adhesive in the composition of the present invention or the cured product thereof. Is preferably 50% by weight or less, more preferably 30% by weight or less, still more preferably 20% by weight or less, based on 100% by weight of the entire component (D).
- the content of the component (D1) in the component (D) 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 its cured product.
- 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.
- a component (D) 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 )
- the component (D) 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 compounding amount thereof is selected as desired. can do.
- the component (D) 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 (D). If the amount of the component (D) exceeds the above upper limit, the curable reactive silicone pressure-sensitive adhesive composition of the present invention or its cured product becomes too hard, and therefore it may not be particularly suitable for use as an adhesive.
- the component (D) 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 (D). Good.
- the blending amount of the component (D) is based on the total mass of the components (A), (B), and (D). Therefore, it may be designed to be 0.1% by 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 (D).
- the compounding amount of the component (D) is as follows: It is preferable that the amount is in the range of 35% by mass to 90% by mass with respect to the total mass of the component) and the component (D).
- 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 content of the component (D) is 55% by mass to 90% by mass based on the total mass of the components (A), (B), and (D).
- 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 strength 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.
- composition of the present invention may further contain (E) an unsaturated aliphatic hydrocarbon.
- 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 component (E) used is not particularly limited, but is 0.1 to 10 parts by mass, preferably 0 when the sum of the components (A) to (D) is 100 parts by mass. It is in the range of 1 to 7.5 parts by mass.
- composition of the present invention may further contain (F) a curing retarder.
- the (F) curing retardant can suppress the hydrosilylation reaction and delay the curing reaction.
- the component (F) may be a single set retarder or a mixture of two or more set retarders. Since the present invention uses the above-mentioned component (C), there is an advantage that a sufficiently long storage stability and a pot life during handling can be realized in practical use without using the component (F). In some cases, more stable storage stability and the like can be realized as a one-pack type composition by using F) a curing retarder together.
- composition (F) contains a curing retarder
- the composition of the present invention has a further improved pot life and can be more easily handled.
- the content of the (F) curing retarder is not particularly limited, but is, for example, 0.01 to 1,000 mol with respect to 1 mol of metal atom in the metal catalyst for hydrosilylation reaction in the composition. It is preferable that the amount is 0.1 to 500 mol.
- the content of the (E) curing retardant is not limited to the composition even in the form of a single composition (for example, a one-pack composition). The amount may be less than 0.1 mol, and is preferable, with respect to 1 mol of the metal atom in the metal catalyst for hydrosilylation reaction in the product.
- the curable reactive silicone pressure-sensitive adhesive composition of the present invention is characterized in that the content of solid particles in the composition is less than 0.50% by mass from the viewpoint of improving the adhesive strength of itself or a cured product thereof. To do.
- the content of solid particles in the composition is less than 0.50% by mass based on the solid content (components (A) to (D), which form a non-volatile cured product by a curing reaction). It is preferably 0.40 mass% or less, and particularly preferably 0.30 mass% or less.
- the “solid particles” in the present invention do not include the catalyst-containing thermoplastic resin fine particles for hydrosilylation reaction, which are the above-mentioned component (C), and its constituent components.
- the solid particles in the present invention are particle components that are solid at room temperature, and examples thereof include inorganic fillers such as silica, glass, alumina, and zinc oxide; organic resin fine powders such as polymethacrylate resins, phosphors, and pigments. To be done. If a large amount of these components is contained, the adhesive strength of the cured product may be significantly deteriorated and sufficient adhesive strength may not be realized.
- composition of the present invention can be designed as a solvent-free composition or a heat-melting composition as described above, but within a range that does not impair the technical effects of the present invention, It may optionally include (G) a solvent.
- a solvent can reduce the viscosity and thixotropy of the entire composition to improve the handling workability and coatability, and the use of a small amount of an organic solvent can improve the wettability of the composition with respect to the 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 (G) when the solvent (G) is selected, it should be a solvent that does not dissolve the thermoplastic resin constituting the component (C) or penetrate into the wall material to elute the hydrosilylation reaction catalyst. is necessary. If a solvent having high solubility and permeability with respect to the thermoplastic resin constituting the component (C) is used, the technical effects of the present invention may not be sufficiently exhibited.
- the solvent (G) 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 (G) is not particularly limited, but when the sum of the components (A) to (F) is 100 parts by mass, it may be used in the range of 0 to 9900 parts by mass. In general, the amount of 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 coatability, the sum of the components (A) to (F) is 100 parts by mass, for example, 50 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.
- composition of the present invention may contain other organopolysiloxane, an adhesiveness-imparting agent, a heat-resistant agent, a dye, a flame retardant-imparting agent, etc., if necessary.
- an adhesiveness-imparting agent e.g., a heat-resistant agent
- a dye e.g., a flame retardant-imparting agent
- a flame retardant-imparting agent e.g., etc., etc.
- the amount of addition of these optional components and the method thereof are known to those skilled in the art.
- composition of the present invention the components (A) to (C), and if necessary, the components (D), (E), (F), (G) and/or other optional components are mixed. Can be manufactured by.
- 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 allows the curing reaction during room temperature to heating and melting even if the hydrosilylation reaction catalyst in the component (C) 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 manufacture the present 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 may be added, or a known stirrer or kneader may be used to mix and prepare 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 (D) are added in a temperature range of 80° C. to 120° C. It can be prepared by adding and mixing the component (C) while heating and kneading. In the above temperature range, the composition as a whole is softened and the component (C) can be uniformly dispersed throughout the composition. Therefore, there is a practical advantage that curing failure during molding of a sheet or the like and partial cohesive failure during bonding can be avoided. is there.
- the softening may be insufficient, and it may be difficult to uniformly disperse the component (C) even if mechanical force is used.
- the temperature exceeds the upper limit, the component (C) reacts at the time of mixing depending on the melting temperature of the thermoplastic resin (wall material) constituting the component (C), and the entire composition remarkably thickens or cures. Therefore, the heating and melting property may be lost, 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 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 so as to have sufficient adhesive force if it is about a temporary fixing, depending on the content of the component (D), and the molded product can be arranged 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 so as to have sufficient adhesive force if it is about temporary fixing, depending on the content of the component (D), 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 material 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.
- the adhesiveness is high enough to cause cohesive failure.
- the curable reactive silicone pressure-sensitive adhesive composition of the present invention can be designed as a non-flowable and hot-melt composition at 25° C. as a whole by adjusting the blending amount of the above-mentioned component (D).
- 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.
- 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 curing-reactive silicone pressure-sensitive adhesive composition of the present invention can form an adhesive cured product (curing reaction product) by heating 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. or higher to be cured to form an adhesive material.
- 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, the 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.
- the curing reactive silicone pressure-sensitive adhesive composition contained in the pressure-sensitive adhesive layer of the pressure-sensitive 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 curing reactive silicone pressure-sensitive adhesive composition contained in the pressure-sensitive adhesive layer of the pressure-sensitive 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.
- the curable reactive silicone pressure-sensitive adhesive composition of the present invention or the pressure-sensitive 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 heating and melting state), and high energy rays such as ultraviolet rays are further added if necessary. Irradiation and curing can produce such articles.
- 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 properties 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 pressure-sensitive adhesive may be used for optical devices, and the substrate is an optical film such as 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, and a reflection sheet. Alternatively, it may be a front or back protective sheet.
- 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. It is possible to bond and integrate members without causing distortion or deformation in the
- 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.
- FIG. 1 is a cross-sectional view showing a laminated body of one 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.
- the method for producing a laminate according to an 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 member of the two members, and the two members are subjected to the curing.
- a bonding step S1 for bonding via a hydrophilic silicone adhesive composition and a curing step S2 for curing the composition by initiating a hydrosilylation reaction by irradiation with high energy rays such as ultraviolet rays.
- 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.
- 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 and 2 and Comparative Examples 1 and 2 relate to a curable reactive silicone pressure-sensitive adhesive composition designed to be non-fluid at 25° C. and have a heat-melting property (hot melt property). It is an experimental example, and its composition (parts by mass), adhesive strength of uncured product and cured product, etc. are 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 3 and 4 and Comparative Examples 3 to 5 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 2.
- Comparative Examples 4 and 5 are experimental examples in the case where the comparative component g (silica) was blended in the composition similar to that of Example 3. 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".
- 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) 830 SiMe 2 Vi
- a-2 ViMe 2 SiO(SiMe 2 O) 150 SiMe 2 Vi
- the following components were used as the component (B).
- c Master batch containing platinum catalyst-containing fine particles prepared by the method shown in the following reference example (platinum metal concentration is 0.16% by mass)
- c′ Platinum (0-valent) divinyltetramethyldisiloxane complex solution in divinyltetramethyldisiloxane (platinum metal concentration is 4% by weight)
- platinum metal concentration is 4% by weight
- This solution was sprayed and dried using a spray dryer in which nitrogen gas was used as a hot stream to obtain 450 g of spherical platinum catalyst-containing fine particles (average particle size 1.1 ⁇ m).
- 40 parts by mass of the platinum catalyst-containing fine particles are mixed with 60 parts by mass of dimethylpolysiloxane having a viscosity of 350 mPa ⁇ s with both ends of the molecular chain blocked by dimethylvinylsiloxy groups and a vinyl group content of 0.47% by mass.
- a master batch containing the platinum catalyst-containing fine particles was prepared.
- the platinum metal concentration in the masterbatch was 0.16% by mass.
- Example 1 The components of Example 1 shown in Table 1 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 1.
- the curable reactive silicone adhesive composition 1 was composed of a polyethylene terephthalate film (Toray Co., Ltd., product name Lumirror (registered trademark) S10, thickness 50 ⁇ m) and a release film (Nippa Co., Ltd. FSC-6). Scissors and a polyethylene terephthalate film having a thickness of 200 ⁇ m were used as spacers and press-molded at 70° C. to prepare an uncured sheet 1-1 having a thickness of 200 ⁇ m. By heating the sheet to 70° C., reprocessing including thickness adjustment was possible.
- a polyethylene terephthalate film Toray Co., Ltd., product name Lumirror (registered trademark) S10, thickness 50 ⁇ m
- a release film Nippa Co., Ltd. FSC-6.
- 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 1.
- the uncured sheet 1-1 was heated and cured at 150° C. for 5 minutes to prepare a cured sheet 1-1. 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 1.
- the curing-reactive silicone pressure-sensitive adhesive composition 1 was stored at 25° C. for 24 hours, and then an uncured sheet 1-2 was prepared by the same method as above. By heating the sheet to 70° C., reprocessing including thickness adjustment was possible. Next, the uncured sheet 1-2 was heated and cured at 150° C. for 5 minutes to prepare a cured sheet 1-2. 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 was prepared and stored at 25°C for 24 hours>" in Table 1.
- Example 2 As in Example 1, the components of Example 2 shown in Table 1 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 2.
- Example 2 In the same manner as in Example 1, a 200 ⁇ m thick uncured sheet 2-1 was prepared using the curable reactive silicone pressure sensitive adhesive composition 2. By heating the sheet to 70° C., reprocessing including thickness adjustment was possible. The adhesive force of the uncured sheet 2-1 was measured in the same manner as in Example 1. The results are shown in the column of "Adhesive strength of uncured sheet ⁇ uncured sheet prepared immediately after composition preparation>" in Table 1.
- Example 1 the uncured sheet 2-1 was heated and cured at 150° C. for 5 minutes to prepare a cured sheet 2-1, 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 1 the curing reactive silicone pressure sensitive adhesive composition 2 was stored at 25° C. for 24 hours, and then an uncured sheet 2-2 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 1, the uncured sheet 2-2 was heated and cured at 150° C. for 5 minutes to prepare a cured sheet 2-2, and the adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet ⁇ cured sheet prepared after composition was prepared and stored at 25°C for 24 hours>" in Table 1.
- Example 3 The components of Example 3 shown in Table 2 were uniformly mixed to prepare a curing reactive silicone pressure sensitive adhesive composition 3. 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 50° C. for 5 days, 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 50°C for 5 days>" in Table 2, respectively. As is clear from Table 2, no increase in viscosity was observed over time.
- the curing-reactive silicone pressure-sensitive adhesive composition 3 was coated on a polyethylene terephthalate film (manufactured by Toray Co., Ltd., product name Lumirror (registered trademark) S10, thickness 50 ⁇ m) with an applicator immediately after preparation, and 150° C. It was cured by heating for 5 minutes. 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 cured silicone layer 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 2.
- the curing reactive silicone pressure sensitive adhesive composition 3 was stored at 50° C. for 5 days, and then a cured sheet 3-2 was prepared in the same manner as described above, and a test piece for measuring the adhesive strength was further prepared to determine the adhesive strength. It was measured. The results are shown in the column of “Adhesion of cured sheet ⁇ Cured sheet prepared after storage of composition for 5 days at 50° C.>” in Table 2.
- Example 4 In the same manner as in Example 3, the components of Example 4 shown in Table 2 were uniformly mixed to prepare a curing reactive silicone pressure sensitive adhesive composition 4. Immediately after preparation, the viscosity of the composition at 25° C. was measured. Further, the composition was stored at 50° C. for 5 days, 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 50°C for 5 days>" in Table 2, respectively. As is clear from Table 2, no increase in viscosity was observed over time.
- heptane solvent
- a film manufactured by Toray Co., Ltd., product name Lumirror (registered trademark) S10, thickness 50 ⁇ m
- 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 2.
- the curing-reactive silicone pressure-sensitive adhesive composition 4 was stored at 50° C. for 5 days, and then a cured sheet 4-2 was prepared in the same manner as described above, and a test piece for measuring the adhesive strength was further prepared, and the adhesive strength was measured. It was measured. The results are shown in the column of "Adhesion of cured sheet ⁇ Cured sheet prepared after storage of composition for 5 days at 50°C>" in Table 2.
- Example 3 In the same manner as in Example 3, the components shown in Table 2 were uniformly mixed to prepare a comparative silicone composition 3. 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 2.
- Example 3 a comparative cured sheet 3-1 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 2.
- Comparative Example 4 In the same manner as in Example 3, the components shown in Table 2 were uniformly mixed to prepare a comparative silicone composition 4. Immediately after preparation, the viscosity of the composition at 25° C. was measured. Further, the composition was stored at 50° C. for 5 days, 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 50°C for 5 days>" in Table 2, respectively.
- Example 3 a comparative cured sheet 4-2 was prepared and the adhesive strength was measured. The results are shown in the column of “Adhesion of cured sheet ⁇ Cured sheet prepared after storage of composition for 5 days at 50° C.>” in Table 2.
- the adhesive strengths of the comparative cured sheets 4-1 and 4-2 are significantly lower than those of the cured sheets 3-1 and 3-2 obtained in Example 3, respectively, and the function as an adhesive is impaired. there were. It is clear that the addition of the comparative component g is an adverse effect.
- Comparative Example 5 In the same manner as in Example 3, the components shown in Table 2 were uniformly mixed to prepare a comparative silicone composition 5. Immediately after preparation, the viscosity of the composition at 25° C. was measured. Further, the composition was stored at 50° C. for 5 days, 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 50°C for 5 days>" in Table 2, respectively.
- Example 3 a comparative cured sheet 5-2 was prepared and the adhesive strength was measured. The results are shown in the column of “Adhesion of cured sheet ⁇ Cured sheet prepared after storage of composition for 5 days at 50° C.>” in Table 2.
- the adhesive strengths of the comparative cured sheets 5-1 and 5-2 are significantly lower than those of the cured sheets 3-1 and 3-2 obtained in Example 3, respectively, impairing the function as an adhesive. there were. From this result, it was confirmed that even if the composition was similar to that of Example 3, the addition of the comparative component g (silica) significantly impaired the adhesive property.
- a catalyst-containing thermoplastic resin fine particle (c) for hydrosilylation reaction is used, and a solid particle component is used.
- a hot-melt curable reactive silicone pressure-sensitive adhesive composition can be actually prepared, and the composition has excellent storage stability and is prepared from the composition. It was confirmed that the obtained sheet was excellent in both the adhesive property, the curability at 150° C. and the adhesive property after curing.
- Example 3 relating to a liquid curing reactive silicone adhesive composition
- the catalyst-containing thermoplastic resin fine particles (c) for a hydrosilylation reaction and not using a solid particle component, storage stability
- Example 3 is a composition design with strong adhesive force
- Example 4 is a composition design with slight adhesion.
- Comparative Example 3 using the usual catalyst for hydrosilylation reaction (c'), a one-pack type liquid curable reactive silicone pressure-sensitive adhesive composition excellent in storage stability and adhesive properties, which gelated after storage.
- the catalyst-containing thermoplastic resin fine particles (c) for hydrosilylation reaction were used in a composition similar to that of Example 3, the silica component (g) was used (Comparative Examples 4 and 5).
- the adhesive strength was significantly inferior and sufficient adhesive strength could not be realized. Therefore, it was confirmed that if the amount of solid particles is not controlled, the adhesive property after curing in the curing-reactive silicone pressure-sensitive adhesive composition is significantly impaired, which is a serious obstacle particularly in the formulation design of high-adhesiveness.
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Abstract
Description
(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含有熱可塑性樹脂微粒子、
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り、且つ、組成物全体に占める固体粒子の含有量が0.50質量%以下である、硬化性反応性シリコーン粘着剤組成物によって達成される。
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、及び、
(C)ヒドロシリル化反応用触媒含有熱可塑性樹脂微粒子、
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り、且つ、組成物全体に占める固体粒子の含有量が0.50質量%以下である。更に、本発明の硬化反応性シリコーン粘着剤組成物は、(D)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。
(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。
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。
(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。
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
(C)成分はヒドロシリル化反応用触媒含有熱可塑性樹脂微粒子である。(C)成分は、本発明の組成物のヒドロシリル化反応による硬化を促進するための触媒であり、白金系触媒等のヒドロシリル化反応用触媒が熱可塑性樹脂の中に溶解又は分散している微粒子、或いは、熱可塑性樹脂の殻の中に白金系触媒等のヒドロシリル化反応用触媒が核として含有されている構造のマイクロカプセル微粒子のいずれであってもよい。(C)成分中に含まれるヒドロシリル化反応用触媒は単一種類であってもよく、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。
本発明の組成物は、(D)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。(D)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。
本発明の一態様では、(D)成分の少なくとも一部が、(D1)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。
(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。
本発明の組成物は、(E)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。
本発明の組成物は(F)硬化遅延剤を更に含むことができる。(F)硬化遅延剤は、ヒドロシリル化反応を抑制し、硬化反応を遅らせることができる。(F)成分は単一の硬化遅延剤であってもよく、2種以上の硬化遅延剤の混合物でもよい。なお、本発明は前記の(C)成分を使用しているので、(F)成分を用いることなく、実用上十分に長い保存安定性及び取扱時のポットライフを実現できる利点があるが、(F)硬化遅延剤を併用することで、一液型組成物として、より安定した保存安定性等を実現できる場合がある。
本発明の硬化反応性シリコーン粘着剤組成物は、それ自体又はその硬化物の粘着力を改善する見地から、組成物中の固体粒子の含有量が0.50質量%未満であることを特徴とする。特に、組成物中の固形分((A)~(D)成分を含み、硬化反応により不揮発性の硬化物を形成する成分)対する固体粒子の含有量が0.50質量%未満であることが好ましく、0.40質量%以下、0.30質量%以下であることが特に好ましい。固体粒子成分の含有量が前記上限未満であると、硬化反応性シリコーン粘着剤組成物又はその硬化物の粘着力を維持することができる。
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、本発明の技術的効果を損なわない範囲で、任意で、(G)溶剤を含むものであってよい。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。
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、耐熱剤、染料、難燃性付与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。
本発明の組成物は、(A)~(C)成分、必要に応じて(D)成分、(E)成分、(F)成分、(G)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。
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。
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。
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。
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。
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。
例えば、上記の(D)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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
実施例1及び2、並びに、比較例1及び2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。
実施例3及び4、及び、比較例3~5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2に示す。比較例4及び5は、実施例3と類似組成において、比較成分g(シリカ)を配合した場合の実験例である。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。
(A)成分として、次の成分を用いた。
a-1: ViMe2SiO(SiMe2O)830SiMe2Vi
a-2: ViMe2SiO(SiMe2O)150SiMe2Vi
(B)成分として、次の成分を用いた。
b-1: Me2HSiO(SiMe2O)24SiMe3H
b-2: Me3SiO(SiMe2O)30(SiMeHO)30SiMe3
b-3: Me3SiO(SiMe2O)5(SiMeHO)5SiMe3
(C)成分、及び比較成分として、次の成分を用いた。
c: 下記の参考例に示す方法によって調製した白金触媒含有微粒子を含むマスターバッチ(白金金属濃度は0.16質量%)
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重量%)
(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: (Me3SiO1/2)0.46(SiO4/2)0.54(HO1/2)0.05
d-2: (Me3SiO1/2)0.48(SiO4/2)0.52(HO1/2)0.04
d-3: (ViMe2SiO1/2)0.046(Me3SiO1/2)0.394(SiO4/2)0.56(HO1/2)0.05
(E)成分として、次の成分を用いた。
e: エチニルシクロヘキサノール
(F成分)として、次の成分を用いた。
f-1: 1-テトラデセン
比較成分として、次の成分を用いた。
g: 乾式シリカ(比表面積が200m2/g)
攪拌機付フラスコにビスフェノールA型の熱可塑性ポリカーボネート樹脂(ガラス転移温度(Tg)145℃)900gとトルエン500gとジクロロメタン4600gを投入し均一に混合した。これに白金(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5質量%)44.4gを加えて混合し、均一な溶液を得た。この溶液を、窒素ガスを熱気流としたスプレードライヤーを用いて噴霧・乾燥することで、球状の白金触媒含有微粒子(平均粒子径は1.1μm)、450gを得た。
次に、上記の白金触媒含有微粒子40質量部と、分子鎖両末端がジメチルビニルシロキシ基で封鎖された粘度350mPa・s、ビニル基含有量0.47質量% のジメチルポリシロキサン60質量部を混合し、白金触媒含有微粒子を含むマスターバッチを調製した。前記マスターバッチ中の白金金属の濃度は0.16質量%であった。
〔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。
表1に示す実施例1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1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。
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1-2を150℃で5分間加熱・硬化し、硬化シート1-2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。
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2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1と同様に、未硬化シート2-1の粘着力を測定した。結果を表1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。
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1と同様に、未硬化シート2-2を150℃で5分間加熱・硬化し、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。
表1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。
表2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。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50℃で5日間保管後、25℃での粘度を測定した。結果を表2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、50℃で5日間保管後>」の欄にそれぞれ示す。表2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。
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。
実施例3と同様に、表2に示す実施例4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4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50℃で5日間保管後、25℃での粘度を測定した。結果を表2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、50℃で5日間保管後>」の欄にそれぞれ示す。表2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。
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。
実施例3と同様に、表2に示す各成分を均一に混合し、比較用シリコーン組成物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。結果を表2の「シリコーン組成物の粘度<調製直後>」の欄に示す。
実施例3と同様に、表2に示す各成分を均一に混合し、比較用シリコーン組成物4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50℃で5日間保管後、25℃での粘度を測定した。結果を表2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、50℃で5日間保管後>」の欄にそれぞれ示す。
実施例3と同様に、表2に示す各成分を均一に混合し、比較用シリコーン組成物5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50℃で5日間保管後、25℃での粘度を測定した。結果を表2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、50℃で5日間保管後>」の欄にそれぞれ示す。
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おいて、ヒドロシリル化反応用触媒含有熱可塑性樹脂微粒子(c)を使用し、且つ、固体粒子成分を使用しないことで、実施例1及び2において、実際にホットメルト性の硬化反応性シリコーン粘着剤組成物を調製することができ、且つ、当該組成物は保存安定性に優れ、当該組成物から作製されたシートの粘着特性並びに150℃における硬化性及び硬化後の粘着特性においていずれも優れていることが確認された。
Claims (25)
- (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含有熱可塑性樹脂微粒子、
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り、且つ、
組成物全体に占める固体粒子の含有量が0.50質量%以下である、硬化性反応性シリコーン粘着剤組成物。 - (C)ヒドロシリル化反応用触媒含有熱可塑性樹脂微粒子を構成する熱可塑性樹脂のTgが75℃以上である、請求項1記載の硬化性反応性シリコーン粘着剤組成物。
- (D)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又は2記載の硬化性反応性シリコーン粘着剤組成物。
- (D)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3記載の硬化反応性シリコーン粘着剤組成物。
- (D)成分の含有量が、(A)成分、(B)成分、及び、(D)成分の質量の総和の0.1質量%から90質量%である、請求項3又は4記載の硬化性反応性シリコーン粘着剤組成物。
- (E)不飽和脂肪族炭化水素を更に含む、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。
- (F)硬化遅延剤を更に含む、請求項1乃至6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。
- (G)溶剤を更に含む、請求項1乃至7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。
- 一液型又は単一の組成物である、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。
- 25℃において流動性である、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。
- 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10記載の硬化反応性シリコーン粘着剤組成物。
- 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。
- 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12記載の硬化反応性シリコーン粘着剤組成物。
- 硬化反応前の状態において粘着性を有する、請求項12又は13記載の硬化反応性シリコーン粘着剤組成物。
- 請求項10乃至14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。
- 請求項10乃至14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。
- 請求項1乃至14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。
- 請求項1乃至14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17記載の硬化物の製造方法。
- 請求項1乃至14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。
- 請求項1乃至14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。
- 請求項1乃至14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。
- 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20又は21記載の積層体。
- 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20又は請求項21に記載の積層体。
- 請求項10乃至14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20乃至23のいずれか1項に記載の積層体の製造方法。
- 請求項1乃至14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20乃至23のいずれか1項に記載の積層体の製造方法。
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KR (1) | KR20210105408A (ja) |
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Cited By (2)
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WO2023282270A1 (ja) * | 2021-07-05 | 2023-01-12 | ダウ・東レ株式会社 | トランスデューサー用オルガノポリシロキサン組成物、その硬化物フィルムからなる積層体、その用途、およびその製造方法 |
WO2023120347A1 (ja) * | 2021-12-21 | 2023-06-29 | ダウ・東レ株式会社 | ホットメルト性を有する硬化性シリコーン組成物、その硬化生成物、及び前記組成物を含む積層体 |
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JP2001081436A (ja) * | 1999-09-07 | 2001-03-27 | Dow Corning Corp | シリコーン組成物及びそれから形成したシリコーン感圧性接着剤 |
JP2006274007A (ja) * | 2005-03-29 | 2006-10-12 | Dow Corning Toray Co Ltd | ホットメルト型シリコーン系接着剤 |
WO2007055176A1 (ja) * | 2005-11-11 | 2007-05-18 | Hisamitsu Pharmaceutical Co., Inc. | 粘着基剤および経皮吸収型貼付剤 |
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JP5420141B2 (ja) | 2006-03-01 | 2014-02-19 | 東レ・ダウコーニング株式会社 | 硬化性シリコーンレジン組成物および硬化物 |
JP5377846B2 (ja) * | 2007-11-09 | 2013-12-25 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | 熱硬化性シリコーンゴム組成物 |
KR20150112851A (ko) | 2014-03-28 | 2015-10-07 | 신에쓰 가가꾸 고교 가부시끼가이샤 | 실리콘 점착제 조성물, 그의 제조 방법 및 점착 필름 |
EP3159369A4 (en) * | 2014-06-20 | 2018-02-14 | Dow Corning Toray Co., Ltd. | Silicone exhibiting hot-melt properties, and curable hot-melt composition |
JP6678388B2 (ja) * | 2014-12-25 | 2020-04-08 | 信越化学工業株式会社 | 硬化性シリコーン樹脂組成物 |
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- 2019-12-24 WO PCT/JP2019/050558 patent/WO2020138055A1/ja active Application Filing
- 2019-12-24 CN CN201980082349.5A patent/CN113195222B/zh active Active
- 2019-12-24 JP JP2020563294A patent/JP7534061B2/ja active Active
Patent Citations (3)
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JP2001081436A (ja) * | 1999-09-07 | 2001-03-27 | Dow Corning Corp | シリコーン組成物及びそれから形成したシリコーン感圧性接着剤 |
JP2006274007A (ja) * | 2005-03-29 | 2006-10-12 | Dow Corning Toray Co Ltd | ホットメルト型シリコーン系接着剤 |
WO2007055176A1 (ja) * | 2005-11-11 | 2007-05-18 | Hisamitsu Pharmaceutical Co., Inc. | 粘着基剤および経皮吸収型貼付剤 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2023282270A1 (ja) * | 2021-07-05 | 2023-01-12 | ダウ・東レ株式会社 | トランスデューサー用オルガノポリシロキサン組成物、その硬化物フィルムからなる積層体、その用途、およびその製造方法 |
WO2023120347A1 (ja) * | 2021-12-21 | 2023-06-29 | ダウ・東レ株式会社 | ホットメルト性を有する硬化性シリコーン組成物、その硬化生成物、及び前記組成物を含む積層体 |
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CN113195222A (zh) | 2021-07-30 |
JPWO2020138055A1 (ja) | 2021-11-25 |
KR20210105408A (ko) | 2021-08-26 |
JP7534061B2 (ja) | 2024-08-14 |
CN113195222B (zh) | 2023-05-09 |
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