WO2017179579A1 - 粒状接着剤 - Google Patents
粒状接着剤 Download PDFInfo
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- WO2017179579A1 WO2017179579A1 PCT/JP2017/014840 JP2017014840W WO2017179579A1 WO 2017179579 A1 WO2017179579 A1 WO 2017179579A1 JP 2017014840 W JP2017014840 W JP 2017014840W WO 2017179579 A1 WO2017179579 A1 WO 2017179579A1
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- adhesive
- particles
- granular
- core
- shell
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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
- C09J5/08—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers using foamed adhesives
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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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/403—Adhesives in the form of films or foils characterised by release liners characterised by the structure of the release feature
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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
- C09J11/08—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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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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
- C09J7/10—Adhesives in the form of films or foils without carriers
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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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/203—Adhesives in the form of films or foils characterised by their carriers characterised by the structure of the release feature on the carrier layer
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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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- 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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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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
- C09J2301/302—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 the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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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
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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
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
Definitions
- the present invention relates to a granular adhesive.
- adhesives are classified into dry-solid adhesives, chemically-reactive adhesives, hot-melt adhesives, and pressure-sensitive adhesives depending on the solidification method.
- a dry-solidifying adhesive is one that cures by evaporation of water or a solvent in the adhesive.
- a chemically reactive adhesive is one that cures by a chemical reaction of a liquid compound. Chemically reactive adhesives include those that cure by the reaction between the main agent and the curing agent, those that cure by the reaction between the main agent and the moisture (moisture) on the surface of the substrate, and those that cure by blocking air. And those that are cured by irradiation with ultraviolet rays.
- a hot-melt adhesive is solid at room temperature, but becomes liquid when heated, and is fixed by cooling it.
- a pressure-sensitive adhesive maintains strength with an adherend due to the adhesiveness of the adhesive.
- the dry-solidifying adhesive and the chemically reactive adhesive are liquids, they could not be touched by people during handling.
- the hot melt adhesive can be touched by a person during handling, it requires heating at the time of bonding, so a heat source is required, and the adherend is required to have heat resistance.
- the pressure-sensitive adhesive can also be touched at the time of handling, but once it is touched by the person, the adhesiveness is lowered, and a support base material is necessary for use in the form of a tape.
- Patent Document 1 discloses an adhesive that does not have an adhesive force before applying a stress and is excellent in handling that expresses an adhesive force after applying the stress.
- the object of the present invention is to provide an adhesive that is further excellent in handling.
- the present invention includes the following inventions.
- a granular adhesive The particulate adhesive comprises adhesive particles;
- the adhesive particles include a core containing an adhesive composition, a shell covering the core, and an encapsulated gas.
- the shell is a granular adhesive containing solid particles.
- a step of disposing the granular adhesive according to any one of [1] to [14] on the adherend A method for producing a film, comprising: applying stress to the granular adhesive to release the adhesive composition to the outside of the shell to form a film containing the adhesive composition.
- the granular adhesive of the present invention exhibits a bonding force by applying a predetermined stress or a stress exceeding a predetermined stress, and the encapsulated gas bursts and generates a sound. Can be perceived and is excellent in handling.
- the granular adhesive of the present invention includes adhesive particles, and the adhesive particles include a core including an adhesive composition, a shell covering the core, And the shell contains solid particles.
- the number of the adhesive particles included in the present adhesive may be one or plural.
- Adhesive Particles Each adhesive particle constituting the present adhesive is usually spherical or flat in the atmosphere. However, when the particle size is relatively small, the adhesive particles can be non-spherical. Adhesive particles have shell solid particles that do not have adhesive strength on the outer surface of the core, and therefore do not have adhesive strength in a state where predetermined stress is not applied, and the shell collapses by applying predetermined stress. Only after the adhesive composition contained in the core is released to the outside of the shell, the adhesive force is developed. In addition, when the shell is collapsed, a predetermined stress or a stress exceeding the predetermined stress is applied to the adhesive composition, whereby the sealed gas bursts and generates a sound. In the present adhesive, it is possible to perceive that a predetermined stress necessary for the expression of adhesive force is applied and that no further application of stress is required by the sound generated when the sealed gas bursts. Therefore, it is excellent in handling.
- the outer surface of the core means the outermost surface of the core, that is, a critical surface with air, and may be simply referred to as “surface” in the present specification.
- FIG. 1 is a schematic diagram showing a state where adhesive particles constituting the present adhesive are placed on a table.
- w represents the maximum width of the adhesive particles 1
- b represents the ground contact width
- h represents the height.
- the maximum width w of the adhesive particles 1 is preferably 100 ⁇ m or more and 50 mm or less. More preferably, it is 500 micrometers or more, More preferably, it is 1 mm or more. Further, it is more preferably 30 mm or less, further preferably 20 mm or less, and particularly preferably 10 mm or less.
- These values adjust the type, shape and size of the solid particles constituting the shell, the viscosity of the core, the contact angle of the substance forming the core with respect to the solid particles constituting the shell, the average thickness of the shell, etc. Can be controlled.
- the contact width b and the height h may be adjusted as appropriate. However, the larger the contact width b, the larger the frictional force generated between the contact surface and the adhesive particle, and the movement of the adhesive particles on the adherence surface can be suppressed.
- the grounding width b can be 1 to 100% of the maximum width w, for example.
- the maximum width w, the contact width b, and the height h are values measured with a caliper through microscopic observation or the like.
- the volume of the adhesive particles 1 is preferably 4 ⁇ L or more and 6 mL or less. More preferably, it is 6 ⁇ L or more, and more preferably 60 ⁇ L or more. Moreover, More preferably, it is 4 mL or less, More preferably, it is 3 mL or less.
- the adhesive particles can release the adhesive composition contained in the core to the outside of the shell by applying a predetermined stress to collapse the shell.
- the magnitude of the predetermined stress is appropriately selected according to the use of the adhesive and its general handling.
- the magnitude of the predetermined stress includes the type, shape and size of solid particles constituting the shell, the viscosity of the core, the contact angle of the substance forming the core with respect to the solid particles constituting the shell, and the average thickness of the shell, etc. Can be controlled by adjusting.
- the predetermined stress is preferably large enough to be given by crushing with a human finger. Specifically, it is preferably 1 to 1000 kN / m 2 , more preferably 5 to 200 kN / m 2 , and still more preferably 5 to 100 kN / m 2 . If it is this range, after arrange
- the shell of the adhesive particle does not collapse at a stress of less than 1 kN / m 2 .
- the adhesive composition is easily released to the outside of the shell by adding a twist.
- the adhesive particles are ruptured by the encapsulated gas when a predetermined stress or a stress exceeding the predetermined stress is applied to the adhesive composition, thereby generating sound.
- the magnitude of the sound generated by the burst of the sealed gas can be controlled by adjusting the number of sealed gases, the volume of each sealed gas, the sealed pressure, and the like.
- the volume of sound generated when a shell is collapsed by applying a predetermined stress to one adhesive particle and the enclosed gas is ruptured is from the adhesive particle in the environment of a quiet room (32 to 33 dB). It is preferably 35 dB or more, more preferably 40 dB or more, measured at a position 1.5 cm away. If it is this range, the user who is applying stress can fully perceive, and it can be used as a standard for ending the work of applying the stress.
- the core contains an adhesive composition.
- the core is the adhesive composition itself, or when the core is a droplet containing the adhesive composition described later, the core is a part of which water or solvent contained in the droplet is partially removed.
- the adhesive composition includes a dry-solidifying adhesive, a chemically reactive adhesive, or a pressure-sensitive adhesive.
- the adhesive composition may be the adhesive itself.
- Dry solidified adhesives are classified into solvent-based adhesives, water-based adhesives, and emulsion-based adhesives.
- the solvent-based adhesive is a type of adhesive that is solidified by dissolving a polymer in an organic solvent and evaporating the organic solvent.
- the polymer include chloroprene rubber, styrene butadiene rubber, nitrile rubber, natural rubber, vinyl chloride resin, vinyl acetate resin, acrylic resin, and urethane resin.
- organic solvent examples include toluene, normal hexane, ethyl acetate, methyl ethyl ketone, acetone, methanol, tetrahydrofuran, xylene, cyclohexanone, and the like.
- Water-based adhesive is a type of adhesive that is solidified by dissolving a water-soluble polymer in water and evaporating the water.
- the water-soluble polymer include natural polymers such as starch and glue, dextrin, polyvinyl alcohol resin, and polyvinyl pyrrolidone resin.
- the water may be pure water or may contain impurities as much as tap water.
- the emulsion adhesive is a type of adhesive in which polymer particles stabilized by an electrostatic stabilizing effect or a steric stabilizing effect are dispersed in a dispersion medium and solidified by evaporating the dispersion medium.
- polymers constituting the polymer particles include vinyl acetate resins, (meth) acrylic resins, vinylidene chloride resins, epoxy resins, urethane resins, olefin resins, polyester resins, natural rubber resins, and styrene butadiene. Resin, chloroprene rubber resin and the like.
- the dispersion medium include water and an organic solvent, and examples of the organic solvent include the same ones as described above.
- a chemical reaction type adhesive is one in which one or more types of adhesive components are solidified by a chemical reaction caused by an external stimulus such as heat or light.
- Chemically reactive adhesives include epoxy adhesives containing epoxy resins and curing agents, polyurethane adhesives containing polyisocyanates and polyols, urea resin adhesives containing urea and formaldehyde, melamine and formaldehyde. Examples thereof include melamine resin-based adhesives and phenol resin-based adhesives including phenol and formaldehyde.
- photocurable epoxy adhesives acrylic resin adhesives, anaerobic acrylic adhesives, two-component curable acrylic adhesives called SGA (Second generation of acrylic adhesives), and cyanoacrylate adhesives
- SGA Syncond generation of acrylic adhesives
- cyanoacrylate adhesives Moisture curable adhesives and the like can also be cited as chemically reactive adhesives.
- the two-component curable adhesive is an adhesive that cures when the main agent and the curing agent come into contact with each other, and is configured so that the main agent and the curing agent are included in different adhesive particles.
- the chemical reaction type adhesive may contain water or a solvent together with these adhesives, and these adhesives may be dissolved or dispersed in water or an organic solvent. Examples of the organic solvent are the same as those described above.
- a pressure-sensitive adhesive expresses adhesive force due to the tackiness of the adhesive, and the pressure-sensitive adhesive usually contains a polymer such as a (meth) acrylic resin, a rubber resin, or a silicone resin. It is.
- the pressure-sensitive adhesive may contain water or an organic solvent together with these adhesives, and these adhesives may be dissolved or dispersed in water or an organic solvent. Examples of the organic solvent are the same as those described above.
- the adhesive composition may contain other components.
- Other components include metal fine particles, metal oxide fine particles, conductive fine particles, ionic conductive compositions, ionic compounds having organic cations or anions, silane coupling agents, crosslinking catalysts, weathering stabilizers, tackifiers, Examples include plasticizers, softeners, dyes, pigments, fragrances, inorganic fillers, resins other than the above polymers, and light diffusing fine particles such as organic beads.
- the volume of the core containing the adhesive composition is preferably 3 ⁇ L or more and 5 mL or less. More preferably, it is 30 ⁇ L or more, and more preferably 50 ⁇ L or more. Moreover, More preferably, it is 3 mL or less, More preferably, it is 2 mL or less.
- the shell in the present invention is formed from solid particles and covers the core. Preferably, it is formed from an aggregate of solid particles.
- the shell preferably covers the core without having a gap of 500 ⁇ m or more, more preferably covers the core without having a gap of 100 ⁇ m or more, and more preferably has no gap of 5 ⁇ m or more. It covers. 90 mass% or more is preferable, as for content of the solid particle in a shell, 95 mass% or more is more preferable, and 100 mass% is further more preferable.
- the solid particles forming the shell in the present adhesive have a number average particle diameter of 500 ⁇ m or less.
- the number average particle diameter is preferably 10 nm to 500 ⁇ m, more preferably 10 nm to 800 nm, and still more preferably 20 nm to 500 nm. It is preferable that the number average particle diameter of the fine particles is within the above range because the stability of the granular adhesive in the air is further increased.
- the number average particle diameter is obtained from the equivalent circle diameter by microscopy, and can be measured by analyzing an image obtained by microscopic observation with software of a digital microscope.
- An example of digital microscope software is the product name “Motic Images Plus 2.2s” manufactured by Shimadzu Rika Co., Ltd.
- Examples of the microscope include an electron microscope and an optical microscope, and may be appropriately selected depending on the solid particles to be used. What is necessary is just to select the magnification at the time of observation suitably according to the particle diameter of the solid particle to be used.
- the number average particle size of the solid particles is the number average particle size of 100 randomly selected solid particles.
- the contact angle of the substance forming the core on the aggregated solid particles is usually 90 ° or more, preferably 100 ° or more, more preferably 110 ° or more, and further preferably 120 ° or more.
- the contact angle is usually 170 ° or less, and may be 160 ° or less.
- the solid particles forming the shell and the core-forming substance can be easily adsorbed, and the form stability of the adhesive particles is increased, which is preferable.
- the contact angle is less than 90 °, the substance forming the core may permeate into the plurality of solid particles that are the shell material, making it difficult to form adhesive particles.
- the solid particles preferably include fine particles having a hydrophobic surface. Although depending on the type of substance forming the core, the contact angle described above can be 90 ° or more by using fine particles having a hydrophobic surface.
- the solid particles are preferably fine particles having no adhesive force in an atmosphere at a temperature of 30 ° C. More preferably, the fine particles have no adhesive force in an atmosphere at a temperature of 40 ° C. or lower, more preferably at a temperature of 50 ° C. or lower, and even more preferably at a temperature of 80 ° C. or lower.
- having no adhesive force means an adhesive force with a tack of 0.02 MPa or less when measured by a probe tack test under the following conditions using a commercially available device. Tack is the maximum stress measured by the probe tack test under the following conditions.
- a commercially available device for example, there is a probe tack tester with a thermostat (product name “TE-6002”) manufactured by Tester Sangyo Co., Ltd.
- Probe tack tester Probe tack tester with thermostatic chamber, Speed at which the adhesive is brought into contact with the probe: 10 mm / second, Contact time: 30 seconds, Peeling speed: 10 mm / second.
- the glass transition temperature (Tg) of the solid particles is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 80 ° C. or higher. If Tg is lower than the above value, the shell may exhibit adhesive force due to a change in the external environment, which may be unsatisfactory in handling.
- the softening temperature of the fine particles is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 80 ° C. or higher. If the softening temperature is lower than the above value, the shell may exhibit an adhesive force due to a change in the external environment, and handling may be poor.
- the decomposition temperature of the solid particles is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 80 ° C. or higher. If the decomposition temperature is lower than the above value, the adhesive may exhibit an adhesive force due to a change in the external environment, resulting in poor handling.
- fine particles such as inorganic fine particles and organic fine particles can be preferably used.
- the solid particles may be a combination of two or more kinds of fine particles.
- Inorganic fine particles include talc, clay, kaolin, silica, hydrotalcite, diatomaceous earth, magnesium carbonate, barium carbonate, calcium sulfate, calcium carbonate, magnesium sulfate, barium sulfate, barium titanate, aluminum hydroxide, magnesium hydroxide, Calcium oxide, magnesium oxide, titanium oxide, zinc oxide, silicon oxide, alumina, mica, zeolite, glass, zirconia, calcium phosphate, metal (gold, silver, copper, iron), carbon material (carbon nanotube, fullerene, graphene, graphite) ) And the like. Further, the surface of these fine particles may be surface-modified with a surface modifier such as a silane coupling agent or a surfactant.
- a surface modifier such as a silane coupling agent or a surfactant.
- organic fine particles examples include resin fine particles and fine particles derived from natural products.
- resin fine particles examples include resin fine particles and fine particles derived from natural products.
- homopolymers such as styrene, vinyl ketone, acrylonitrile, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, and methyl (meth) acrylate, or two or more types of monomers were polymerized.
- Fluorine resin such as polytetrafluoroethylene, tetrafluoroethylene-6-propylene copolymer, tetrafluoroethylene-ethylene copolymer, and polyvinylidene fluoride; melamine resin; urea resin; polyethylene Polypropylene, polydimethylsiloxane polymer, polyester, polyamide, and the like.
- the surface of these fine particles may be surface-modified with a surface modifier such as a silane coupling agent or a surfactant.
- the solid particles may be a combination of two or more kinds of fine particles.
- the combination include a combination of two or more kinds of fine particles having different materials, and a combination of two or more kinds of fine particles having the same material and different particle size distributions.
- the Tg of the resin can be adjusted by polymerization conditions such as the monomer ratio.
- the fine particles derived from natural products include plant spores, pollen, or fine particles derived from natural wax. Further, the surface of these fine particles may be surface-modified with a surface modifier such as a silane coupling agent or a surfactant.
- the fine particles are preferably fine particles having a hydrophobic surface. If the surface is hydrophobic, it tends to cover the entire surface of the droplets described later, and a granular adhesive can be easily produced.
- the fine particles having a hydrophilic surface can be rendered hydrophobic by subjecting the surface to a hydrophobic treatment.
- the fine particles are preferably silica, lycopodium, polytetrafluoroethylene, or calcium carbonate particles that have been subjected to a hydrophobic treatment.
- Such particles can be obtained from the market.
- Commercially available products include silica particles (“RX-300” and “RY-300” manufactured by Nippon Aerosil Co., Ltd.), calcium carbonate particles (manufactured by Shiraishi Kogyo Co., Ltd., hydrophobized), polytetrafluoroethylene ( Sigma Aldrich Japan Co., Ltd.), silicone particles (“Tospearl 2000B”, “Tospearl 1110A”, “Tospearl 145A”, “Tospearl 150KA” manufactured by Momentive) and the like.
- the thickness of the shell can be obtained from the number average particle diameter of the solid particles, but the shell may be a single layer or a plurality of layers of the solid particles partially, and there are variations. It is preferable to determine the thickness.
- the average thickness of the shell is preferably 2 mm or less, more preferably 10 nm or more and 500 ⁇ m or less, and further preferably 100 nm or more and 500 ⁇ m or less. Such a range is preferable because the shape stability of the adhesive particles is high and the shell can be collapsed by applying an appropriate stress.
- the collapse of the shell means that the adhesive composition contained in the core is released to the outside of the shell due to the stress applied to the adhesive particles.
- the average thickness of the shell is determined by dividing the adhesive particles at a temperature below the glass transition point of the adhesive composition forming the core, and observing the cross section with an electron microscope (transmission electron microscope, scanning electron microscope) The thickness of the shell is measured at 10 points, and the number is averaged. When the adhesive particle is too large, it can be measured by preparing an ultrathin section.
- Enclosed gas examples include oxygen, carbon dioxide, nitrogen, helium, and combinations thereof.
- the sealed gas may be air whose composition is not particularly adjusted. Further, the sealed gas may contain water vapor.
- the sealed gas is preferably enclosed in the core, and in this case, the substance forming the core is adjusted so that the gas is held in the core.
- the number of encapsulated gases in the adhesive particles may be one or plural.
- the volume fraction of the enclosed gas in each adhesive particle is, for example, 3% to 80%, preferably 10% to 70%, more preferably 15 to 60%, based on the volume of the entire core.
- This adhesive can be produced by the following steps (1) to (3) and a step of enclosing gas. (1) a step of bringing a droplet containing an adhesive composition into contact with solid particles; (2) a step of covering the entire surface of the droplet containing the adhesive composition with the solid particles, and (3) optionally drying the droplet including the adhesive composition whose entire surface is covered with the solid particles. Process.
- the method for enclosing the gas is not particularly limited, and the air is encapsulated by entraining the air when preparing the droplet containing the adhesive composition before the step (1).
- the adhesive composition may be used as it is, or the adhesive composition dissolved in water or a solvent may be used, or the adhesive composition may be water or What was disperse
- the adhesive composition containing the pressure-sensitive adhesive those obtained by dissolving or dispersing the pressure-sensitive adhesive in water or a solvent are usually used.
- the solvent include organic solvents, and examples thereof include the same ones as described above.
- the solid content concentration of the droplet containing the adhesive composition when contacting the solid particles is usually 5 to 100% by mass, preferably 10 to 80% by mass, more preferably 20 to 70% by mass. More preferably, it is 40 to 60% by mass. It is preferable for the solid content concentration to fall within such a range because the present adhesive can be easily produced.
- solid content concentration means the density
- the size (volume of the core) of the droplet containing the adhesive composition is preferably 3 ⁇ L or more and 5 mL or less. More preferably, it is 30 ⁇ L or more, and more preferably 50 ⁇ L or more. Moreover, More preferably, it is 3 mL or less, More preferably, it is 2 mL or less.
- the size of the droplet By adjusting the size of the droplet, the number average particle diameter of the adhesive particles can be adjusted.
- the droplet containing the adhesive composition may be sprayed on the aggregate of solid particles by spraying or the like, or may be dropped.
- the entire surface of the droplet containing the adhesive composition only needs to be covered with solid particles, and is usually covered with the solid particles by rolling the droplet containing the adhesive composition on the solid particles.
- the droplets and the solid particles may be mixed with each other using a mixer or the like to contact each other and the periphery of the droplets may be covered with the solid particles.
- the droplets containing the adhesive composition whose entire surface is covered with solid particles may be dried.
- the droplet containing the adhesive composition contains a solvent or water, it is preferably dried. Drying may be performed before applying the stress or after applying the stress.
- drying means removing water or a solvent from a droplet containing the adhesive composition covered with the solid particles. Water or the solvent may be completely removed, but may remain as long as the adhesiveness of the adhesive is not lowered.
- drying method a method of standing at a temperature at which the chemical and physical properties of the adhesive composition and solid particles do not change; a method of exposing to hot air, hot air, or low humidity; a method of vacuum drying; a method of freeze drying A method of irradiating infrared rays, far infrared rays, electron beams or the like.
- the drying temperature is preferably 10 to 200 ° C, more preferably 20 to 100 ° C.
- the solid content concentration of the adhesive composition contained in the present adhesive after drying is, for example, 10 to 100% by mass, preferably 50 to 100% by mass, more preferably 80 to 100% by mass, Preferably, it is 90 to 100% by mass.
- the adhesive particles may be sieved or washed with water or the like.
- the adhesive of the present invention can be used by being sandwiched between adherends.
- adherend A one adherend
- adherend B another adherend
- adherend A and the adherend B can be bonded.
- adherend A and the adherend B may be the same or different.
- the adhesive can be applied, for example, by sandwiching the adhesive between the adherend A and the release material, pressing the adherend A and the release material, and applying stress to the adhesive.
- the adhesive composition can be released on the surface of the dressing A. Thereafter, the release material can be removed. After removing the release agent, the adherend B may be adhered.
- the present adhesive can be developed into a planar shape, and stress can be applied to the present adhesive to release the adhesive composition to the outside of the shell to form a film containing the adhesive composition.
- this adhesive agent is normally arrange
- An adherend B may be further bonded onto the film.
- a coating film can also be formed by curing the film.
- the surface of the adherend can be coated with a cured product of the adhesive composition.
- Example 1 Preparation of adhesive composition> A mixed solution of 0.6 g of ammonium peroxide and 5 mL of ion-exchanged water was added to a mixed solution of 195 mL of ion-exchanged water, 60 g of purified butyl acrylate (BA), and 0.6 g of acrylic acid. Thereafter, the polymerization reaction was carried out by stirring at 65 ° C. for 24 hours (stirring speed: 250 rpm). The obtained mixture was put into a dialysis membrane (fractionated molecular weight: 100,000) and purified by dialysis to obtain a polybutyl acrylate emulsion (1).
- BA purified butyl acrylate
- the resulting polybutyl acrylate emulsion (1) has a solid content concentration of 49.4% by mass, and the dispersoid measured using a laser diffraction particle size distribution analyzer (product name “Mastersizer2000” manufactured by Malvern).
- the volume average particle diameter (Dv) was 540 ⁇ 200 nm.
- the solid content concentration was measured by a gravimetric method.
- ⁇ Preparation of adhesive particles Calcium carbonate particles having a number average particle size of 120 nm (hydrophobized, manufactured by Shiroishi Kogyo Co., Ltd.) were spread thinly on a petri dish. The calcium carbonate particles did not have adhesive strength at a temperature of 80 ° C. or lower. 15 ⁇ L of polybutyl acrylate emulsion (1) (solid content concentration 49.4% by mass) was dropped onto the calcium carbonate particles. After dripping, the tip of the pipetter was inserted into the polybutyl acrylate emulsion, and air was injected.
- the polybutyl acrylate emulsion (1) containing the dropped air is rolled on the calcium carbonate particles for 30 seconds, and the entire outer surface of the droplets of the polybutyl acrylate emulsion is covered with the calcium carbonate particles. (1) was obtained.
- the adhesive particles (1) are dried at room temperature for 24 hours to remove water, and flat spherical adhesive particles in which the entire outer surface of butyl polyacrylate particles is covered with calcium carbonate particles ( 2) was obtained.
- Adhesive particles (2) were sandwiched from above and below by two pieces of release paper (laminated release paper manufactured by Lintec Corporation). From above, two glass slides (MICRO SLIDE GLASS S7213, size: 76 ⁇ 26mm, thickness: 0.9-0.12mm, Pre-Cleaned: 100Pcs, Matsunami Glass Industry Co., Ltd.), scissors, vertical, horizontal Kneading was performed by reciprocating 30 times in the direction, and stress was applied to the adhesive particles (2). The adhesive strength of the obtained adhesive particles (2) was evaluated by the following method using a probe tack tester (product name “TE-6002”, Tester Sangyo Co., Ltd.) in an atmosphere at a temperature of 30 ° C.
- a probe tack tester product name “TE-6002”, Tester Sangyo Co., Ltd.
- a granular adhesive (2) was placed at the tip of the probe. Further, a bobbin-like weight (200 g: bobbin 10 g + weight 190 g) to which the cover glass was fixed was arranged so that the cover glass faced the adhesive particles (2). By lowering the bobbin-like weight with the cover glass fixed at a constant speed (10 mm / second), the probe on which the adhesive particles (2) are arranged pushes up the cover glass, and the adhesive particles (with a constant load (200 g)) ( 2) was brought into contact with the tip of the cover glass (contact time: 30 seconds). Thereafter, the adhesive particles (2) were separated from the cover glass by raising the bobbin-like weight to which the cover glass was fixed at a constant speed (10 mm / second).
- the tack was calculated from the maximum stress of the stress-displacement curve measured at this time, and the peel energy was calculated from the area of the curve.
- the average value of the tack of the five adhesive particles (2) was 0.115 MPa, and the average value of the peeling energy was 157 J / m 2 .
- ⁇ Measurement of volume of adhesive particles The volume of sound generated when the encapsulated gas burst when stress was applied to the granular adhesive (2) was measured with a digital sound level meter (digital sound level meter, manufactured by 3322-165-120 Shiraimatsu Kikai Co., Ltd.). . The distance between the granular adhesive (2) and the microphone was 1.5 cm, and the measurement was performed in a quiet room (32 to 33 dB). As a result of measuring the five adhesive particles (2), the minimum value was 43.9 dB, the maximum value was 49.2 dB, and the average value was 46.4 dB.
- Example 2 Preparation of adhesive particles> A flat spherical adhesive under the same conditions as those obtained for the adhesive particles (2) of Example 1, except that 180 ⁇ L of polybutyl acrylate emulsion (1) was dropped onto the calcium carbonate particles. Particles (3) were obtained.
- volume fraction of enclosed gas was calculated in the same manner as for the adhesive particles (2).
- the minimum value was 8.5%
- the maximum value was 41.3%
- the average value was 18. It was 5%.
- Adhesive particles (3) that collapsed the shell by applying a predetermined stress had adhesive strength in an atmosphere at a temperature of 30 ° C.
- the adhesive particles (3) that did not give a predetermined stress did not have adhesive strength in an atmosphere at a temperature of 30 ° C.
- Adhesive particles (3) that collapsed the shell by applying a predetermined stress had adhesive strength in an atmosphere at a temperature of 30 ° C. Note that the sound of bursting of the sealed gas did not occur even when a predetermined stress was applied. On the other hand, the adhesive particles (3) that did not give a predetermined stress (the shell did not collapse) did not have adhesive strength in an atmosphere at a temperature of 30 ° C.
- the present adhesive before applying stress has no adhesive force, and an adhesive that exhibits adhesive force and produces sound when given stress is obtained. . That is, since the user can perceive that the adhesive force is expressed by the generation of sound, this adhesive is an adhesive that is excellent in handling. Moreover, the adhesive force can be controlled in a wide range.
- the granular adhesive of the present invention is useful because it is easier to handle than conventional adhesives and has excellent handleability.
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Abstract
Description
〔1〕 粒状接着剤であって、
前記粒状接着剤は接着剤粒子を含み、
前記接着剤粒子は、接着剤組成物を含むコアと、前記コアを被覆するシェルと、封入気体とを含み、
前記シェルは固形粒子を含む、粒状接着剤。
〔3〕 前記封入気体の体積分率が、前記コアの全体の体積を基準として、3%~80%である、〔1〕又は〔2〕に記載の粒状接着剤。
前記粒状接着剤に応力を与えることにより、前記接着剤組成物を前記シェルの外側に放出させて前記接着剤組成物を含む膜を形成する工程、を備える膜の製造方法。
本発明の粒状接着剤(以下、「本接着剤」ということがある)は、接着剤粒子を含み、前記接着剤粒子は、接着剤組成物を含むコアと、前記コアを被覆するシェルと、封入気体とを含み、前記シェルは固形粒子を含む。本接着剤が含む接着剤粒子の数は、一つであっても複数であってもよい。
本接着剤を構成する各接着剤粒子は、通常、大気中では球形状又は扁平した球形状である。ただし、粒子径が比較的小さいとき、接着剤粒子は、非球形状であり得る。接着剤粒子は、コアの外表面に接着力を有しないシェルの固形粒子を有するため、所定の応力を与えない状態では接着力を有さず、所定の応力を与えてシェルが崩壊することによりコアに含まれる接着剤組成物がシェルの外側に放出されて初めて接着力を発現する。また、シェル崩壊時に、接着剤組成物にも所定の応力又は所定の応力を超える応力が印加されることにより、封入気体が破裂して音を発する。本接着剤においては、封入気体の破裂時に発生する音により、接着力の発現に必要な所定の応力が印加されたこと、そして応力のさらなる印加が不要であることを知覚することができる。したがって、取扱いに優れたものである。
本発明の粒状接着剤において、コアは接着剤組成物を含むものである。その例として、コアが接着剤組成物そのものである場合、コアが後述する接着剤組成物を含む液滴である場合、コアが前記液滴に含まれる水又は溶剤が一部除去されたものである場合などがある。接着剤組成物には、乾燥固化型接着剤、化学反応型接着剤又は、感圧型接着剤が含まれる。接着剤組成物は、接着剤そのものであってもよい。
本発明におけるシェルは、固形粒子から形成されるものであり、コアを覆うものである。好ましくは固形粒子の凝集体から形成されるものである。シェルは、好ましくは500μm以上の隙間を有することなくコアを覆うものであり、より好ましくは100μm以上の隙間を有することなくコアを覆うものであり、さらに好ましくは5μm以上の隙間を有することなくコアを覆うものである。シェル中の固形粒子の含有量は、90質量%以上が好ましく、95質量%以上がより好ましく、100質量%がさらに好ましい。
プローブタック試験機:恒温槽付プローブタックテスター、
粘着剤をプローブに接触させる速度:10mm/秒、
接触時間:30秒、
剥離速度:10mm/秒。
封入気体としては、例えば、酸素、二酸化炭素、窒素、ヘリウム、又はこれらの組み合わせを挙げることができる。封入気体は、特に組成を調整していない空気であってもよい。また、封入気体は、水蒸気を含んでいてもよい。
本接着剤は、以下の工程(1)~(3)と、気体を封入する工程によって製造することができる。
(1)接着剤組成物を含む液滴を、固形粒子に接触させる工程、
(2)前記接着剤組成物を含む液滴の表面全体を前記固形粒子で覆う工程、及び
(3)任意に、表面全体が固形粒子で覆われた接着剤組成物を含む液滴を乾燥させる工程。
本接着剤は、自動車用接着剤、建材用接着剤、ベアリングのはめ合い、配管の固定、ねじの緩み止め、ギアやプロペラの固定、家具の組み立て、転倒防止部材(地震対策)、展示品の仮止め材、衣類の仮止め材、文房具などに用いることができる。
前記膜を硬化させることによりコーティング膜を形成することもできる。例えば、被着材の表面を接着剤組成物の硬化物によってコーティングすることができる。
<接着剤組成物の作製>
過酸化アンモニウム0.6gと、イオン交換水5mLとの混合溶液を、イオン交換水195mLと、精製したアクリル酸ブチル(BA)60g、アクリル酸0.6gとの混合液に加えた。その後、65℃で24時間攪拌(攪拌速度:250rpm)して重合反応を行った。得られた混合物を、透析膜(分画分子量:10万)に入れ透析を行うことで精製し、ポリアクリル酸ブチルエマルション(1)を得た。得られたポリアクリル酸ブチルエマルション(1)の固形分濃度は49.4質量%であり、レーザー回折式粒度分布測定装置(Malvern社製の製品名“Mastersizer2000”)を用いて測定した分散質の体積平均粒子径(Dv)は540±200nmであった。固形分濃度は重量法により測定した。
数平均粒子径が120nmの炭酸カルシウム粒子(疎水化処理済、白石工業(株)製)を、シャーレ上に薄く広げた。炭酸カルシウム粒子は、80℃以下の温度において接着力を有しなかった。ポリアクリル酸ブチルエマルション(1)15μL(固形分濃度49.4質量%)を前記炭酸カルシウム粒子の上に滴下した。滴下後、ポリアクリル酸ブチルエマルション内部にピペッターの先端を突き差し空気の注入を行った。滴下された空気を含んだポリアクリル酸ブチルエマルション(1)を、炭酸カルシウム粒子の上で30秒間転がし、ポリアクリル酸ブチルエマルションの液滴の外表面全体が炭酸カルシウム粒子で覆われた接着剤粒子(1)を得た。接着剤粒子(1)を、室温で24時間乾燥することで、水を除去し、ポリアクリル酸ブチルの粒の外表面全体が炭酸カルシウム粒子で覆われた、扁平した球形状の接着剤粒子(2)を得た。
10個の接着剤粒子(1)(乾燥前)及び接着剤粒子(2)(乾燥後)の大きさをノギスで測定したところ、以下のとおりであった。
最大幅(w):4.0~4.9mm(平均4.5±0.3mm)、
接地幅(b):3.1~3.9mm(平均3.5±0.3mm)、
高さ(h):3.2~4.0mm(平均3.7±0.2mm)。
最大幅(w):3.4~4.2mm(平均3.9±0.3mm)、
接地幅(b):2.5~3.1mm(平均2.9±9.2mm)、
高さ(h):2.9~3.6mm(平均3.3±0.3mm)。
pH2に調整した硝酸水溶液に、接着剤粒子(2)を1つ加え撹拌することで炭酸カルシウムの除去を行った。炭酸カルシウム除去後のAPS-P(BA-AA)粘着性粒子乾燥体をデジタルカメラ(Moticam 2000,株式会社島津理化製)を搭載した光学顕微鏡(Motic BA200,島津理化器械株式会社)及び実体顕微鏡(TG300PCマイクロスコープ(300万画素))で観察した。撮影した写真から、5個の接着剤粒子(2)について、コア全体の体積を基準とした、封入気体の体積分率の計算を行った。結果、最小値48.6%、最大値76.8%、平均値58.2%であった。
接着剤粒子(2)を、2枚の剥離紙(リンテック(株)製ラミネート剥離紙)で上下から挟んだ。さらにその上から、2枚のスライドガラス(MICRO SLIDE GLASS S7213、大きさ:76×26mm、厚さ:0.9~0.12mm、Pre-Cleaned:100Pcs、松浪硝子工業(株))ではさみ、縦、横方向に30往復させることで混練を行い、接着剤粒子(2)に応力を加えた。得られた接着剤粒子(2)の接着力を、温度30℃の雰囲気で、プローブタック試験機(製品名“TE-6002”、テスター産業(株))を用いて以下の方法によって評価した。粒状接着剤(2)をプローブの先端に配置した。また、カバーガラスを固定したボビン状の重り(200g:ボビン10g + 重り190g)を、カバーガラスが接着剤粒子(2)に向き合うように配置した。カバーガラスを固定したボビン状の重りを一定速度(10mm/秒)で下降させることで、該接着剤粒子(2)を配置したプローブがカバーガラスを突き上げ、一定荷重(200g)で接着剤粒子(2)とカバーガラスの先を接触させた(接触時間:30秒)。その後、カバーガラスを固定したボビン状の重りを一定速度(10mm/秒)で上昇させることで、接着剤粒子(2)をカバーガラスから引き離した。このときに測定された応力-変位曲線の、最大応力からタックを算出し、曲線の面積から剥離エネルギーを算出した。結果、5個の接着剤粒子(2)のタックの平均値は0.115MPa、剥離エネルギーの平均値は157J/m2であった。
粒状接着剤(2)に応力を与えて封入気体が破裂したときに発生する音の大きさを、デジタル騒音計(デジタル騒音計、3223-165-120白井松機器(株)製)で測定した。粒状接着剤(2)とマイクロホンの距離は1.5cmとし、静かな室内(32~33dB)で測定を行った。5個の接着剤粒子(2)について測定したところ、最小値43.9dB、最大値49.2dB、平均値46.4dBであった。
<接着剤粒子の作製>
ポリアクリル酸ブチルエマルション(1)180μLを炭酸カルシウム粒子の上に滴下した用いた以外は、実施例1の接着剤粒子(2)を得たのと同様の条件で、扁平した球形状の接着剤粒子(3)を得た。
10個の接着剤粒子(3)(乾燥前、乾燥後)について、接着剤粒子(2)と同様にしてその大きさを測定した。
最大幅(w):8.2~9.8mm(平均9.1±0.4mm)、
接地幅(b):7.0~8.2mm(平均7.9±0.3mm)、
高さ(h):5.5~7.0mm(平均6.3±0.5mm)。
最大幅(w):7.8~8.4mm(平均8.1±0.2mm)、
接地幅(b):6.2~7.2mm(平均6.9±0.3mm)、
高さ(h):5.8~6.2mm(平均6.1±0.1mm)。
5個の接着剤粒子(3)について、接着剤粒子(2)と同様にして封入気体の体積分率を計算したところ、最小値8.5%、最大値41.3%、平均値18.5%であった。
所定の応力を印加してシェルを崩壊させた接着剤粒子(3)は、温度30℃の雰囲気で接着力を有していた。一方、所定の応力を与えていない(シェルが崩壊していない)接着剤粒子(3)は、温度30℃の雰囲気で接着力を有さなかった。
5個の接着剤粒子(3)について、接着剤粒子(2)と同様にして、応力を与えて封入気体が破裂したときに発生する音の大きさを測定したところ、最小値42.9dB、最大値45.9dB、平均値43.9dBであった。
<接着剤粒子の作製>
ポリアクリル酸ブチルエマルション(1)15μLを炭酸カルシウム粒子の上に滴下し、ポリアクリル酸ブチルエマルション内部にピペッターの先端を突き差し空気の注入を行わなかった以外は、実施例1の接着剤粒子(2)を得たのと同様の条件で、扁平した球形状の接着剤粒子(4)を得た。
10個の接着剤粒子(4)(乾燥前、乾燥後)について、接着剤粒子(2)と同様にしてその大きさを測定した。
最大幅(w):2.8~3.5mm(平均3.2±0.2mm)、
接地幅(b):2.7~3.1mm(平均2.9±0.1mm)、
高さ(h):2.3~3.0mm(平均2.7±0.2mm)。
最大幅(w):2.6~2.9mm(平均2.8±0.1mm)、
接地幅(b):1.9~2.1mm(平均2.0±0.1mm)、
高さ(h):2.1~2.7mm(平均2.4±0.2mm)。
5個の接着剤粒子(4)について、接着剤粒子(2)と同様にして、所定の応力を与えてシェルを崩壊させて接着性を評価したところ、タックの平均値は0.0885N、剥離エネルギーの平均値は112J/m2であった。なお、所定の応力を与えても封入気体が破裂する音は発生しなかった。
<接着剤粒子の作製>
ポリアクリル酸ブチルエマルション(1)180μLを炭酸カルシウム粒子の上に滴下し、ポリアクリル酸ブチルエマルション内部にピペッターの先端を突き差し空気の注入を行わなかった以外は、実施例1の接着剤粒子(2)を得たのと同様の条件で、扁平した球形状の接着剤粒子(5)を得た。
10個の接着剤粒子(5)(乾燥前、乾燥後)について、接着剤粒子(2)と同様にしてその大きさを測定した。
最大幅(w):8.3~9.2mm(平均9.0±0.3mm)、
接地幅(b):7.3~8.3mm(平均7.9±0.3mm)、
高さ(h):4.0~4.9mm(平均4.6±0.2mm)。
最大幅(w):6.9~8.0mm(平均7.8±0.3mm)、
接地幅(b):5.7~6.8mm(平均6.4±0.3mm)、
高さ(h):3.8~4.2mm(平均4.0±0.1mm)。
所定の応力を印加してシェルを崩壊させた接着剤粒子(3)は、温度30℃の雰囲気で接着力を有していた。なお、所定の応力を与えても封入気体が破裂する音は発生しなかった。一方、所定の応力を与えていない(シェルが崩壊していない)接着剤粒子(3)は、温度30℃の雰囲気で接着力を有さなかった。
Claims (16)
- 粒状接着剤であって、
前記粒状接着剤は接着剤粒子を含み、
前記接着剤粒子は、接着剤組成物を含むコアと、前記コアを被覆するシェルと、封入気体とを含み、
前記シェルは固形粒子を含む、粒状接着剤。 - 前記コアが前記封入気体を内包する、請求項1に記載の粒状接着剤。
- 前記封入気体の体積分率が、前記コアの全体の体積を基準として、3%~80%である、請求項1又は2に記載の粒状接着剤。
- 前記固形粒子が、疎水性の表面を有する微粒子を含む、請求項1~3のいずれか1項に記載の粒状接着剤。
- 前記固形粒子の数平均粒子径が500μm以下である、請求項1~4のいずれか1項に記載の粒状接着剤。
- 前記固形粒子の数平均粒子径が10nm以上500μm以下である、請求項5に記載の粒状接着剤。
- 前記固形粒子が、温度30℃の雰囲気において接着力を有しない、請求項1~6のいずれか1項に記載の粒状接着剤。
- 前記接着剤粒子の最大幅が100μm以上50mm以下である、請求項1~7のいずれか1項に記載の粒状接着剤。
- 前記コアの体積が3μL以上5mL以下である、請求項1~8のいずれか1項に記載の粒状接着剤。
- 前記固形粒子が、無機物の微粒子を含む、請求項1~9のいずれか1項に記載の粒状接着剤。
- 前記固形粒子が、有機物の微粒子を含む、請求項1~10のいずれか1項に記載の粒状接着剤。
- 固形分濃度が50~100質量%である、請求項1~11のいずれか1項に記載の粒状接着剤。
- 応力を与えることにより接着力が発現する、請求項1~12のいずれか1項に記載の粒状接着剤。
- 応力を与えることにより前記封入気体が破裂して音が発せられる、請求項1~13のいずれか1項に記載の粒状接着剤。
- 請求項1~14のいずれか1項に記載の粒状接着剤を被着材上に配置する工程、
前記粒状接着剤に応力を与えることにより、前記接着剤組成物を前記シェルの外側に放出させて前記接着剤組成物を含む膜を形成する工程、を備える膜の製造方法。 - 前記膜を硬化させる工程をさらに備える、請求項15に記載の製造方法。
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JP2018512022A JP6989784B2 (ja) | 2016-04-12 | 2017-04-11 | 粒状接着剤 |
EP17782392.9A EP3444312A4 (en) | 2016-04-12 | 2017-04-11 | GRANULAR ADHESIVE |
KR1020187032545A KR20190004290A (ko) | 2016-04-12 | 2017-04-11 | 입상 접착제 |
CN201780023181.1A CN109196071A (zh) | 2016-04-12 | 2017-04-11 | 粒状粘接剂 |
US16/093,053 US20190119532A1 (en) | 2016-04-12 | 2017-04-11 | Granular adhesive |
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EP (1) | EP3444312A4 (ja) |
JP (1) | JP6989784B2 (ja) |
KR (1) | KR20190004290A (ja) |
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KR20220089792A (ko) | 2020-12-21 | 2022-06-29 | 엘지디스플레이 주식회사 | 점착제 조성물 및 이를 포함하는 표시 장치 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS48103635A (ja) * | 1972-04-12 | 1973-12-26 | ||
JPH08507567A (ja) * | 1993-03-09 | 1996-08-13 | ミネソタ・マイニング・アンド・マニュファクチュアリング・カンパニー | 感圧接着ビーズを磁気的および/または静電気的に配置する方法および磁気的に配置可能な感圧接着ビーズ |
JP2005232390A (ja) * | 2004-02-23 | 2005-09-02 | Tombow Pencil Co Ltd | 感圧性接着剤 |
WO2015129903A1 (ja) * | 2014-02-25 | 2015-09-03 | 住友化学株式会社 | 粒状接着剤 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62174284A (ja) * | 1985-09-25 | 1987-07-31 | Toray Ind Inc | エポキシ系球状粒子状接着剤及びその製造方法 |
JP2625275B2 (ja) * | 1990-06-08 | 1997-07-02 | 積水化学工業株式会社 | 粘着テープもしくはシート及びその表面加工方法 |
JPH11236541A (ja) * | 1998-02-23 | 1999-08-31 | Toshiba Chem Corp | シート積層造形用接着剤 |
JP2016027066A (ja) | 2014-07-01 | 2016-02-18 | 公立大学法人大阪市立大学 | 共重合体の製造方法 |
-
2017
- 2017-04-11 WO PCT/JP2017/014840 patent/WO2017179579A1/ja active Application Filing
- 2017-04-11 JP JP2018512022A patent/JP6989784B2/ja active Active
- 2017-04-11 CN CN201780023181.1A patent/CN109196071A/zh active Pending
- 2017-04-11 KR KR1020187032545A patent/KR20190004290A/ko unknown
- 2017-04-11 US US16/093,053 patent/US20190119532A1/en not_active Abandoned
- 2017-04-11 EP EP17782392.9A patent/EP3444312A4/en not_active Withdrawn
- 2017-04-12 TW TW106112181A patent/TW201807132A/zh unknown
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS48103635A (ja) * | 1972-04-12 | 1973-12-26 | ||
JPH08507567A (ja) * | 1993-03-09 | 1996-08-13 | ミネソタ・マイニング・アンド・マニュファクチュアリング・カンパニー | 感圧接着ビーズを磁気的および/または静電気的に配置する方法および磁気的に配置可能な感圧接着ビーズ |
JP2005232390A (ja) * | 2004-02-23 | 2005-09-02 | Tombow Pencil Co Ltd | 感圧性接着剤 |
WO2015129903A1 (ja) * | 2014-02-25 | 2015-09-03 | 住友化学株式会社 | 粒状接着剤 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3444312A4 * |
Cited By (2)
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JPWO2019054361A1 (ja) * | 2017-09-15 | 2020-10-15 | 株式会社スリーボンド | 粒状接着剤及びその製造方法 |
JP7168861B2 (ja) | 2017-09-15 | 2022-11-10 | 株式会社スリーボンド | 粒状接着剤及びその製造方法 |
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US20190119532A1 (en) | 2019-04-25 |
TW201807132A (zh) | 2018-03-01 |
JPWO2017179579A1 (ja) | 2019-02-21 |
CN109196071A (zh) | 2019-01-11 |
KR20190004290A (ko) | 2019-01-11 |
EP3444312A4 (en) | 2019-11-27 |
EP3444312A1 (en) | 2019-02-20 |
JP6989784B2 (ja) | 2022-01-12 |
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