TW201638281A - Core-shell particle mixture, adhesive, method for producing reactant and method for producing laminated article - Google Patents

Abstract

An objective of this invention is to provide a core-shell particle mixture containing: a first core-shell particle containing a first material as a first core and a first shell covering the first core, and a second core containing a second material with reactivity to the first material and a second shell covering the second core. The first shell and the second shell contain solid particles.

Description

Core-shell particle mixture, adhesive, method for producing reactant, and method for producing laminate

The present invention relates to a core-shell particle mixture, an adhesive, a method for producing a reactant, and a method for producing a laminate.

In general, the adhesive is classified into a dry curing type adhesive, a chemical reaction type adhesive, a hot melt type adhesive, and a pressure sensitive type adhesive according to a curing method. The dry-curing type adhesive is cured by evaporation of water or a solvent in the adhesive. The chemical reaction type adhesive is cured by a chemical reaction of a liquid compound. In the case of the adhesive of the chemical reaction type adhesive, those which are hardened by the reaction of the main agent and the curing agent, and which are hardened by the reaction of the main agent with the moisture (moisture) on the surface of the material to be bonded, by blocking Those who are hardened by air, hardened by ultraviolet irradiation, etc. The hot-melt type adhesive is a solid at normal temperature, and is liquid when it is heated, and is solidified by cooling it. The pressure-sensitive adhesive is a member that maintains strength with the substrate by adhesion of the adhesive.

[Previous Technical Literature] [Non-patent literature]

[Non-Patent Document 1] Japan continues to learn "The following technical textbook for people who aim at the profession", Nikkan Kogyo Shimbun, 2009 Issued in June

For example, in a multi-component type reaction reagent such as a two-component type binder composed of a main component and a curing agent, there are problems in handling properties as described below.

(a) When operating, it cannot be touched directly by hand.

(b) The reagents must be operated in a completely separated state until the actual use.

(c) In the intricately small parts, it is difficult to selectively follow the desired part. For example, in the case of a general two-component type adhesive, it is difficult to follow only the inside of the microtube. Furthermore, even if the inside of the tube can be carried out, the adhesive agent adheres to the tube before reaching the inside.

An object of the present invention is to provide a reaction reagent excellent in handleability, for example, a multi-component type reaction reagent of a two-liquid type adhesive.

The present invention provides a mixture of core-shell particles as shown below.

[1] A core-shell particle mixture comprising: a first core-shell particle composed of a first core containing a first substance and a first shell covering the first core; a second core particle composed of a second core containing a second substance reactive with the first substance and a second shell covering the second core; the first shell and the second shell contain a solid particle.

[2] The core-shell particle mixture according to [1], wherein the first substance contains a polymerizable compound, and the second substance contains a polymerization reagent.

[3] The core-shell particle mixture according to [1], wherein the first core-shell particle is capable of releasing the first substance to the outside of the first shell by applying a stress, and the second The core-shell particles can release the second substance to the outside of the second shell by imparting stress.

[4] The core-shell particle mixture according to any one of [1] to [3] wherein at least one of the first substance and the second substance is a liquid substance, and the liquid substance is The contact angle on the solid particles is 90 or more.

The present invention provides an adhesive as shown below.

[5] An adhesive comprising the core-shell particle mixture described in any one of the above [1] to [4].

The present invention provides a method for producing a reactant of a first substance and a second substance as shown below.

[6] A method for producing a reactant of a first substance and a second substance reactive with the first substance, comprising: the method described in any one of [1] to [4] Core-shell particle mixture Or the step of imparting stress to the adhesive described in [5].

[7] The production method according to [6], further comprising an adjustment step of adjusting the number of core-shell particles in the core-shell particle mixture by adjusting a number average particle diameter of the first core-shell particle and the second core-shell particle The step of the ratio of the content of the first substance to the second substance.

[8] The production method according to [6] or [7], further comprising an adjustment step of adjusting a mixing ratio of the first core-shell particle and the second core-shell particle or adjusting the first core shell The step of adjusting the content ratio of the first substance to the second substance in the core-shell particle mixture in the ratio of the content of the first substance in the particle to the content of the second substance in the second core-shell particle.

[9] The production method according to any one of [6] to [8] wherein the reactant is a reactant of the adhesive.

The present invention provides a method for producing a laminate as shown below.

[10] A method for producing a laminated body, comprising: a step of disposing a core-shell particle mixture described in any one of [1] to [4] on the surface of the first member or [5] a step of applying a stress to the core-shell particle mixture or the adhesive, and a step of laminating the layer of the core-shell particles or the adhesive on the first member 2 steps of the component.

[11] The method for producing a laminate according to [10], wherein the step of imparting stress to the core-shell particle mixture or the binder is The method of applying stress to the first core-shell particle, releasing the first substance to the outside of the first shell, and applying stress to the second core-shell particle, and applying the second substance to the second shell The external release step.

According to the present invention, it is possible to provide a reaction reagent which is excellent in handleability, for example, a multi-component type reaction reagent of a two-pack type adhesive.

Fig. 1 is a schematic view showing an example of the structure of the polyoxynene particles.

[core shell particle mixture]

In the core-shell particle mixture according to the embodiment of the present invention, the first core-shell particle composed of the first core containing the first substance and the first shell covering the first core is contained, and the The first substance has a second core of the second substance having reactivity and a second core particle of the second case covering the second core; and the first shell and the second shell contain solid particles. Hereinafter, the solid particles contained in the first shell are referred to as "first solid particles", and the solid particles contained in the second shell are referred to as "second solid particles".

The form of use of the core-shell particle mixture is, for example, a form in which a mixture containing the core-shell particles is used, and a mixture containing other components in addition to the core-shell particle mixture is used. The other components other than the core-shell particles may be those that do not react with the first substance and/or the second substance contained in the core-shell particles. The core-shell particle mixture can be used in a desired location. Hereinafter, the present invention is detailed Detailed description.

(1) Core-shell particles

The first core-shell particle and the second core-shell particle (hereinafter also referred to as "core-shell particle" as a term of both) are generally spherical or flat spherical at atmospheric pressure. However, when the particle size is small, the core-shell particles may also be non-spherical. In the core-shell particle mixture, the first core-shell particle and the second core-shell particle do not react with each other when no stress is applied, and when the stress is applied, cracks occur in each of the shells, or the shell collapses to form the first core. The substance and the second substance are released to the outside, respectively. Thereby, the first substance and the second substance can be reacted.

The core-shell particle is coated on the surface of the core with a shell containing solid particles. The shell is generally a layer composed of a plurality of solid particles, for example, a single particle layer composed of solid particles of a single layer structure or a layer composed of aggregates of solid particles. The shell is preferably a core coated with a slit having no more than 500 μm, more preferably a core coated with a slit having no more than 100 μm, and more preferably a core coated with a slit having no more than 5 μm.

In view of the single core-shell particle, the maximum particle diameter of the core-shell particle is preferably 20 μm or more and 50 mm or less, and more preferably 50 μm or more and 50 mm or less from the viewpoint of workability. More preferably, it is 500 μm or more, and particularly preferably 1 mm or more. Further, the maximum particle diameter of the core-shell particles is more preferably 30 mm or less, particularly preferably 20 mm or less, and most preferably 5 mm or less. The maximum particle size means the maximum particle size of the core-shell particles, which is measured by microscopic observation, ruler or vernier scale. When measuring by a microscope, the equivalent circular diameter can be used as the particle diameter, and the image obtained by the microscope observation can be measured by analysis of a soft body of a digital microscope or the like.

The number average particle diameter of the first core-shell particles is preferably 20 μm or more and 50 mm or less, more preferably 50 μm or more and 50 mm or less, and more preferably 500 μm or more and 40 mm or less from the viewpoint of stability of the core-shell particles in the atmospheric pressure. It is particularly preferably 800 μm or more and 30 mm or less. The number average particle diameter of the second core-shell particles is preferably 20 μm or more and 50 mm or less, preferably 50 μm or more and 50 mm or less, and more preferably 500 μm or more and 40 mm or less from the viewpoint of stability of the core-shell particles at atmospheric pressure. It is particularly preferably 800 μm or more and 30 mm or less. The number average particle diameter can be measured, for example, by the equivalent circle diameter of the microscope method, and the image obtained by the microscope observation is analyzed by a soft body of a digital microscope or the like. For example, the software of the digital microscope is, for example, Motic Images Plus 2.2s (manufactured by Shimadzu Chemicals Co., Ltd.). The microscope may, for example, be an electron microscope or an optical microscope, and may be appropriately selected depending on the solid particles used. The magnification at the time of observation can be appropriately selected depending on the particle diameter of the solid particles to be used.

When the number average particle diameter is measured by microscopic observation, a plurality of microscope observation images including a plurality of core-shell particles are imaged, and 50 core-shell particles are randomly selected from the obtained plurality of images, and the particle diameters are measured, and 50 The average of the particle diameters is taken as the number average particle diameter. When the particle size of all the core-shell particles is larger than 100 μm, the particle diameter of the core-shell particles can be measured by a ruler. At this time, 50 core-shell particles were randomly selected and the particle diameters were measured using a ruler, and the average of the 50 particle diameters was taken as the number average particle diameter. Furthermore, the core-shell particle mixture according to the present invention includes the case where the number of the first core-shell particles and/or the second core-shell particles is less than 50. In this case, the number average particle diameter is determined by the above measurement method. Replace "50" in the middle with "nuclear" All of the core-shell particles contained in the shell particle mixture (the first core-shell particle when the number average particle diameter of the first core-shell particle is measured, and the second core-shell particle when the number average particle diameter of the second core-shell particle is measured) The measurement of the number average particle diameter was carried out in the same manner as the above measurement method except for the entire number.

In view of the single core-shell particle, the volume of the core-shell particle is preferably 4 fL or more and 6 mL or less, and more preferably 16 μL or more and 6 mL or less from the viewpoint of workability. The volume of the core-shell particles is more preferably 40 μL or more, and particularly preferably 60 μL or more. Further, the volume of the core-shell particles is more preferably 4 mL or less, and particularly preferably 3 mL or less.

The first core-shell particle and the second core-shell particle are each capable of releasing the first substance and the second substance by imparting stress. The magnitude of the stress can be appropriately selected depending on the use of the core-shell particle mixture and its general operation method. The magnitude of the stress imparted to the core-shell particles may be the same or different between the first core-shell particle and the second core-shell particle. In the following, the stress required to release the first substance to the outside of the first case is referred to as "first stress", and the stress required to release the second substance to the outside of the second case is referred to as "second stress". . The magnitude of the first and second stresses can be adjusted according to 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, and the average thickness of the shell. And control.

The stress imparted to the core-shell particles is preferably given to such an extent that it can be crushed by human fingers. Specifically, the magnitude of the first and second stresses is preferably from 1 to 1000 kN/m ² , more preferably from 5 to 100 kN/m ² . Within the above range, for example, after the core-shell particles are disposed in a desired place, the first substance and the second substance can be released relatively easily by imparting stress. Such core-shell particles are easily crushed and are hard to be broken during the arrangement, so that the handleability is excellent. When the first and second stresses are too small, there is a fear that the first or second substance is unpredictably released. Therefore, at a stress of less than 1 kN/m ² , it is preferred that cracking or collapse of the shell does not occur. Further, when stress is applied to the core-shell particles, vertical stress can be applied to the arrangement surface of the core-shell particles, and shear stress or rotational stress can be imparted. When the shear stress or the rotational stress is imparted, the first substance and the second substance are easily released to the outside of the shell. Furthermore, the direction of shear stress or rotational stress can be selected in an appropriate direction.

From the viewpoint of operability, it is preferred that the first core-shell particle and the second core-shell particle do not collapse before the stress is applied or the stress is less than 1 kN/m ² , and the core-shell structure is maintained. The holding time of the core-shell structure before the stress is applied or the stress is less than 1 kN/m ² is preferably 10 minutes or longer, more preferably 1 hour or longer, and still more preferably 24 hours or longer.

From the viewpoint of operability, the first core-shell particle and the second core-shell particle are preferably in a contact state in which no stress is applied, and each of them is a core-shell structure. The holding time of the core-shell structure when the core-shell particles are in contact with each other without stress is preferably 10 minutes or longer, more preferably 1 hour or longer, and still more preferably 24 hours or longer.

(2) Nuclear

The first core contains the first substance. The second core contains the second substance. The first substance and the second substance are reactive, and can be used in combination to form a reactant. For example, when a polymerizable compound is used as the first substance and a polymerization reagent is used as the second substance, a polymer can be obtained as a reactant. The reactant may be any of a solid, a colloid, a colloid-dried, and a viscous liquid. 1st Each of the substance and the second substance may be composed of one type of compound or two or more types of compounds.

As the polymerizable compound, a polymerizable monomer, a polymerizable oligomer, a polymerizable polymer or the like can be used. Specific examples thereof include epoxy resins (glycidyl ether type, glycidyl ester type, glycidylamine type, and alicyclic type), polyfunctional methacrylates, acrylic monomers, and polyhydric alcohols (polyester polyols). , polyether polyols, polycarbonate polyols, polytetramethylene glycols, low molecular weight diols), oleoresin containing hydroxyl groups at both ends, eucalyptus oil containing vinyl, urea, formaldehyde, melamine, phenol, isophthalic acid Phenol, phenolic resole, resorcinol, α-olefin, maleic anhydride, maleimide, vinyl acetate monomer, polyester, chloroprene rubber, acrylonitrile a butadiene copolymer, a styrene-butadiene copolymer, polyvinyl alcohol, butyl rubber, sodium alginate, natural rubber, or the like.

The polymerization reagent may be a polymerization catalyst or a reaction auxiliary agent, or may be a polymerized with the first substance.

As the reagent for polymerization, for example, a polymerization initiator, a curing agent, a crosslinking agent (containing a vulcanizing agent), or the like can be used. Specific examples thereof include polyethyleneimine, secondary amine, tertiary amine, primary amine, dicyandiamide, imidazole, tertiary amine salt, Lewis acid salt, and ketimine latent curing agent. Hydrogen peroxide, cumene hydroperoxide, benzammonium peroxide, redox initiator, acid anhydride, organic metal salt, polyisocyanate compound, hydrolyzed decane, hydrogen polyoxyalkylene, methyldimethoxy group at the end A ruthenium-based polypropylene oxide (modified polyfluorene oxide), ammonium chloride, calcium hydroxide, a vulcanizing agent (sulfur), and the like.

For the combination of the first substance and the second substance, the following The exemplified adhesives. In addition, the following "C: A/B" designation means a multi-component type reaction reagent containing a first substance and a second substance represented by C, that is, a multi-component type adhesive, which is contained as a A substance A, B as a second substance. In addition, when two or more types of substances are described in each of the fields of A and B, at least one of them can be appropriately selected from among these.

Epoxy resin adhesive: epoxy resin / polyethyleneimine, tertiary amine, secondary amine, primary amine, dicyandiamide, imidazole, tertiary amine salt, Lewis acid salt, ketimine potential hardener

Anaerobic adhesive: polyfunctional methacrylate / hydrogen peroxide

2nd generation acrylic acid (SGA) adhesive: acrylic monomer / cumene hydroperoxide, pervaporated benzamidine, organic metal salt

Polyurethane resin-based adhesive: polyol/polyisocyanate compound

Polyoxymethylene resin-based adhesive: eucalyptus oil/hydrolyzed decane containing hydroxyl groups at both ends

Polyoxymethylene resin-based adhesive: vinyl-containing eucalyptus oil/hydrogen polyoxyalkylene oxide

Modified polyoxyl resin-based adhesive: epoxy resin/polypropylene oxide with methyl dimethoxy fluorenyl group at the end (modified polyoxyl)

Urea resin based adhesive: urea, formaldehyde / ammonium chloride

Melamine resin-based adhesive: melamine, urea, phenol, formaldehyde/ammonium chloride

Phenolic resin based adhesive: phenol, formaldehyde / alkali (sodium hydroxide)

Resorcinol-based adhesive: resorcinol, formaldehyde, resol phenolic, resorcinol/alkali (sodium hydroxide)

--olefin based adhesive: α-olefin, maleic anhydride, butene Diterpenoid imide/calcium hydroxide

Vinyl acetate emulsion adhesive: vinyl acetate monomer / organic peroxide (cumene hydroperoxide, benzammonium peroxide)

Polyurethane elastomeric system adhesive: polyester / polyisocyanate

Neoprene rubber-based adhesive: chloroprene rubber/polyisocyanate

Nitrile rubber-based adhesive: acrylonitrile-butadiene copolymer/crosslinking agent (sulfur)

Styrene-butadiene rubber-based adhesive: styrene-butadiene copolymer/crosslinking agent (sulfur)

Butyl rubber based adhesive: butyl rubber / crosslinker (sulfur)

Natural rubber adhesive: natural rubber / crosslinker (sulphur)

Calcium chloride-based adhesive: sodium alginate solution / calcium chloride aqueous solution

From the viewpoint of operability and practicability, in the combination of A and B described above, it is preferred to use A/B as "epoxy resin/polyethyleneimine, tertiary amine, secondary amine, primary amine, two. An epoxy resin-based adhesive of cyanide diamine, an imidazole, a tertiary amine salt, a Lewis acid salt, a ketimine-based latent curing agent, and A/B as "acrylic acid monomer / cumene hydroperoxide, A second-generation acrylic acid (SGA)-based adhesive which is a gasified benzamidine or an organic metal salt. As described above, in the case where the combination of the first substance and the second substance is an adhesive, the core-shell particle mixture can be used as an adhesive.

When the first substance and the second substance are each a liquid, the total amount of the first core or the second core is 100% by mass, and the content of the first substance and the second substance in the core is preferably 10% by mass or more. More preferably, it is 50% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass. Here, the first substance in the nuclear or the second The content of the substance is 100%, which means that, for example, the first nucleus is composed of the first substance. When the first substance and the second substance are solid, the total amount of the first core or the second core is 100% by mass, and the content of the first substance and the second substance in the core is preferably 10% by mass or more and 90%, respectively. The mass% or less is more preferably 30% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 80% by mass or less. Here, the content of the substance when the first substance or the second substance is a solid means the total amount of water or solvent relative to the first substance or the second substance and the substance to be dissolved or dispersed, and the first The ratio of the substance or the second substance. The core may contain other components in addition to the first substance or the second substance under the restriction that the core-shell particles may be formed.

(3) shell

The shell contains solid particles and coats the core. The shell is preferably composed of agglomerates of solid particles. The shell is preferably a core coated with a slit having no more than 500 μm, more preferably a core coated with a slit having no more than 100 μm, and more preferably a core coated with a slit having no more than 5 μm. The content of the solid particles in the shell is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 100% by mass.

The first solid particles of the first shell are formed, and the second solid particles of the second shell are formed, and each of the fine particles having a number average particle diameter of 500 μm or less is preferably used as a main component. The first solid particles and the second solid particles preferably contain 50 to 100% by mass, more preferably 70 to 100% by mass, and particularly preferably 90 to 100% by mass, of the fine particles having a number average particle diameter of 500 μm or less.

Containing the first substance on the first solid particles aggregated The contact angle of the nucleating material and the contact angle of the nucleating material containing the second substance on the second solid particles to be aggregated are generally 90 or more, preferably 100 or more, more preferably 110 or more. More preferably, it is 120° or more. Further, the contact angle is preferably 170 or less, more preferably 160 or less. By having such a contact angle, since the adsorption between the solid particles forming the shell and the core forming material is easily formed, the shape stability of the core-shell particles is increased, which is preferable. When the contact angle is less than 90°, there is a fear that the core-forming substance containing the first substance or the second substance permeates into the plurality of solid particles of the shell material, and it is difficult to form the core-shell particles. Here, the nucleating material is a substance having the same composition as the nucleus in order to measure the contact angle. Therefore, for example, when the first core is composed of the first substance, the contact angle is the contact angle of the first substance on the first solid particle, and the first core is composed of the first substance and other components, and the contact angle is The contact angle of the first core on the first solid particle.

For the same reason as described above, when the first substance is a liquid substance, the contact angle of the first substance on the first solid particles collected is generally 90 or more, preferably 100 or more, more preferably 110 or more. More preferably, it is 120° or more. Further, the contact angle is preferably 170 or less, more preferably 160 or less. Similarly, when the second substance is a liquid substance, the contact angle of the second substance on the second solid particles collected is generally 90° or more, preferably 100° or more, more preferably 110° or more, and still more. Good is 120° or more. Further, the contact angle is preferably 170 or less, more preferably 160 or less.

The contact angle of the nucleating material on the solid particles to be aggregated can be uniformly spread in a flat shape without using a gap, and the contact angle meter ("SImage 02" manufactured by Excimer Co., Ltd.) can be used to measure the solid particles. The contact angle of the nuclear forming material is obtained.

The solid particles (the first and second solid particles) are preferably fine particles having no adhesion at 30 °C. The solid particles are more preferably at most 40 ° C, more preferably at most 50 ° C, and more preferably at a temperature below 80 ° C.

In the present specification, the adhesive force at the time of measurement by the probe viscosity test under the following conditions is not more than 0.1 N. The viscosity is the maximum stress measured by the probe viscosity test under the following conditions.

<Measurement conditions>

Probe viscosity tester: TE-6002 (manufactured by TESTER Industries, Ltd.), the speed at which the solid particles were brought into contact with the probe: 10 mm/s, contact time: 30 seconds, and peeling speed: 10 mm/s.

The glass transition temperature (Tg) of the solid particles (the first and second solid particles) is preferably 40 ° C or higher, more preferably 50 ° C or higher, and still more preferably 80 ° C or higher. When the Tg is lower than the above value, the shell may exhibit an adhesive force due to a change in the external environment, which may cause the operation to be defective. The glass transition temperature (Tg) of the solid particles (the first and second solid particles) can be measured using a differential scanning calorimeter.

The softening temperature of the solid particles (the first and second solid particles) is preferably 40 ° C or higher, more preferably 50 ° C or higher, and still more preferably 80 ° C or higher. When the softening temperature is lower than the above value, the shell may exhibit an adhesive force due to a change in the external environment, which may cause the operation to be defective. Solid particles (1st and 2nd) The softening temperature of the solid particles can be measured using an automatic dropping point/softening point measuring system (for example, manufactured by METTLER TOLEDO Co., Ltd.).

The decomposition temperature of the solid particles (the first and second solid particles) is preferably 40 ° C or higher, more preferably 50 ° C or higher, and still more preferably 80 ° C or higher. When the decomposition temperature is lower than the above value, the core-shell particles may exhibit an adhesion force due to a change in the external environment, which may cause the operation to be defective. The decomposition temperature of the solid particles (the first and second solid particles) can be measured using a thermogravimetric measuring device.

The number average particle diameter of the fine particles as a main component contained in the solid particles is generally 50 nm or more and 500 μm or less, preferably 10 nm or more and 500 μm or less, more preferably 10 nm or more and 100 μm or less, and still more preferably 20 nm or more and 50 μm or less. When the number average particle diameter of the fine particles is within the above range, the stability of the particulate binder in the atmosphere is preferably high. The number average particle diameter can be measured by microscopic observation using Motic Images Plus 2.2s (manufactured by Shimadzu Chemicals Co., Ltd.). The specific measurement method of the number average particle diameter of the above-mentioned fine particles observed by a microscope is the same as the method of measuring the number average particle diameter of the core-shell particles.

As the solid particles, various kinds of fine particles such as polyfluorene oxide particles, inorganic fine particles, and organic fine particles can be used. The solid particles may be a combination of two or more kinds of fine particles.

The polysiloxane particles are, for example, particles having a three-dimensional network structure in which a siloxane coupling is formed as shown in Fig. 1 and an inorganic and organic intermediate structure in which a ruthenium atom is bonded to one methyl group.

As the fine particles of the inorganic substance, talc, Clay, kaolin, vermiculite, 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, cerium oxide, aluminum oxide, mica, zeolite, glass, zirconia, calcium phosphate, metal (gold, silver, copper, iron), carbon material (nanocarbon tube, fullerene, graphene, Graphite) and so on. Further, the surface of the fine particles may be surface-modified with a surface modifier such as a decane coupling agent or a surfactant.

Examples of the organic fine particles include fine particles of a resin, fine particles derived from natural materials, and the like.

Examples of the component of the resin fine particles include a homopolymer of a monomer such as a styrene type, an acrylic type, a methacryl type, an olefin type, a vinyl ketone or an acrylonitrile, or a copolymer which polymerizes two or more types of monomers. ; PTFE resin such as polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride; melamine resin; urea resin; polydimethyl siloxane polymer ; polyester; polyamine and the like. Further, the surface of the fine particles may be surface-modified with a surface modifier such as a decane coupling agent or a surfactant.

The solid particles as described above may be a combination of two or more kinds of fine particles, and the combination is preferred. Examples of the combination include a combination of two or more types of fine particles having different materials, a combination of two or more types of fine particles having the same material size and different particle size distributions.

The Tg of the above resin can be adjusted depending on polymerization conditions such as a molar ratio.

For the above-mentioned microparticles derived from natural substances, the spores of plants can be cited. Seeds, pollen, or microparticles derived from natural wax. Further, the surface of the fine particles may be surface-modified with a surface modifier such as a decane coupling agent or a surfactant.

Microparticles are commercially available. The commercially available products include polyoxynene particles ("Tospearl 2000B" manufactured by MOMENTIVE Co., Ltd., "Tospearl 1110A", "Tospearl 145A", "Tospearl 150KA"), and cerium oxide particles (manufactured by Japan AEROSIL Co., Ltd.). "RX-300", "RY-300"), poly(tetrafluoroethylene) ("poly(tetrafluoroethylene)" manufactured by Sigma-Aldrich Japan Co., Ltd.).

The average thickness of the first and second shells is preferably 10 nm or more and 500 μm or less, and more preferably 100 nm or more and 500 μm or less. Within the above range, since the shape stability of the core-shell particle mixture is high, it is preferable to cause the shell to collapse by imparting appropriate stress. The average thickness of the first and second shells can be measured by observation with an electron microscope (transmission electron microscope, scanning electron microscope). More specifically, the average thickness of the shell was observed by electron microscopy, and the thickness of the shell was measured for 10 randomly selected places. The average thickness of the shell is the average of the 10 measurements.

(4) Method for producing core-shell particles

The core-shell particle system can be produced by, for example, the following steps (1) to (3).

(1) a step of bringing droplets containing the first substance or the second substance into contact with the solid particles (the first solid particles or the second solid particles), and (2) containing the droplets of the first substance or the second substance. a step of coating all of the surrounding solid particles, (3) Optionally, the step of drying the droplets containing the first substance or the second substance, which are coated with solid particles in their entirety, is dried.

In the liquid droplet containing the first substance or the second substance, the first substance or the second substance may be used as it is, or the first substance or the second substance may be dissolved in water or a solvent, and the first substance may be used. Or the second substance is dispersed in water or a solvent, and the first substance or the second substance may be diluted with water or a solvent.

The content of the first substance or the second substance in the droplet containing the first substance or the second substance when the solid particles are brought into contact is usually 5 to 100% by mass, preferably 10 to 80% by mass, more preferably 20 It is 70% by mass, and more preferably 40 to 60% by mass. When the content is within the above range, it is preferred because the core-shell particles are easily produced. The content of the first substance or the second substance in the droplet containing the first substance or the second substance is the ratio of the first substance or the second substance in the droplet, and is generally the solvent contained in the droplet and Concentration of ingredients other than water.

The volume of the droplet containing the first substance or the second substance is preferably 4 fL or more and 5 mL or less, more preferably 15 μL or more and 5 mL or less. The volume of the droplets is more preferably 30 μL or more, and particularly preferably 50 μL or more. Further, the volume of the droplets is more preferably 3 mL or less, and particularly preferably 2 mL or less. The number average particle diameter of the core-shell particles can be adjusted by adjusting the volume of the droplet containing the first substance or the second substance.

The method of bringing the droplet containing the first substance or the second substance into contact with the solid particles may be carried out by spraying a droplet containing the first substance or the second substance by a spray or the like, or may be dripping.

The entire periphery of the liquid droplet containing the first substance or the second substance is generally coated with solid particles by rolling a droplet containing the first substance or the second substance onto the solid particles.

Further, the droplets containing the first substance or the second substance and the solid particles may be brought into contact with each other by stirring using a stirrer or the like to coat the periphery of the liquid droplets with solid particles.

The droplets containing the first substance or the second substance, which are coated with solid particles in their entirety, can be dried. In the case where the droplet containing the first substance or the second substance contains a solvent or water, the droplet is preferably dried. By "drying" in the present specification, it means that water or a solvent is removed from the droplet containing the first substance or the second substance coated with the solid particles. At this time, water or a solvent is preferably completely removed, but may remain if it does not impair the effects of the present invention. The drying method may be a method of standing at a temperature at which the chemical and physical properties of the first substance or the second substance and the solid particles are not changed; exposure to warm air, hot air or low humidity Method; vacuum drying method; freeze drying method; method of irradiating infrared rays, far infrared rays or electron beams, and the like. The drying temperature is preferably from 10 to 200 ° C, more preferably from 20 to 100 ° C.

The content of the first substance or the second substance contained in the core-shell particles after drying is generally 10 to 99.9% by mass, preferably 10 to 99% by mass, more preferably 20 to 98% by mass, still more preferably 40. It is 98% by mass, and more preferably 60 to 95% by mass.

(5) Method for producing core-shell particle mixture

The core-shell particle mixture can be obtained by using the first core-shell particle and the second core-shell particle The product is produced by mixing at a desired mixing ratio. The desired mixing ratio is preferably a mixing ratio in which the reaction between the first substance and the second substance can be efficiently performed.

The core-shell particle mixture can be used as a reaction component of, for example, a two-component type binder or a two-component type coating.

[adhesive agent]

In one embodiment of the invention, the core-shell particle mixture is an adhesive. The adhesive is preferably a multi-component type adhesive, and corresponds to a case where, for example, a combination of the first substance and the second substance becomes an adhesive. In the adhesive agent of the present invention, for example, by stressing the core-shell particle mixture, each of the shells collapses, and the released first substance and the second substance react to express the form of the bonding force. The adhesive of the present invention does not have an adhesive force in a state where no stress is applied, and the adhesive force is expressed by the above specified stress.

The subsequent agent contains a mixture of core-shell particles and other components typically used in the adhesive. Examples of the other components include metal fine particles, metal oxide fine particles, conductive fine particles, an ion conductive composition, an ionic compound having an organic cation or an anion, a decane coupling agent, a crosslinking catalyst, a weathering stabilizer, and the like. Adhesives, plasticizers, softeners, dyes, pigments, inorganic fillers, resins other than the above polymers, and light-diffusing fine particles such as organic beads. The other component may be contained in at least one of the first core-shell particle and the second core-shell particle. Alternatively, the other component may be a constituent component of another adhesive different from the first core-shell particle and the second core-shell particle.

Since the core-shell particle mixture does not release the first substance and the second substance from the core-shell particles until the stress is applied, it is easy to uniformly fill the gap between the two or more member to be joined. When the core-shell particle mixture can uniformly fill the gap between the member to be bonded, stress is applied to the core-shell particle mixture, and the first substance and the second substance can be uniformly spread between the slits, and can be obtained well in the desired region. The force of the next.

The adhesive formed from the mixture of core-shell particles can be applied to automotive adhesives, adhesives for building materials, bearing mounting, pipeline fixing, screw locking, gear and propeller fixing, and furniture assembly.

[Method for Producing Reactant]

The method for producing a reactant of the first substance and the second substance includes a step of imparting stress to the core-shell particle mixture or the above-mentioned adhesive. When stress is applied to the core-shell particle mixture or the above-mentioned adhesive, the shell is cracked or collapsed, and the first and second substances are released from each of the first and second core-shell particles, and the first substance and the second substance are brought into contact with each other. Thereby, the first substance reacts with the second substance to generate a reactant. If necessary, in order to promote the reaction, heating, light irradiation, or the like may be performed after stress is applied to the core-shell particle mixture. The above reactant is preferably a reactant of an adhesive (a multi-component type of adhesive or the like).

The mixing ratio of the first substance to the second substance in the core-shell particle mixture (content ratio, therefore, the ratio of the reaction amount of the first substance and the second substance) can be adjusted by adjusting the first core-shell particle and the second core-shell particle The average particle diameter was adjusted to adjust the number. The adjustment of the number average particle diameter of the core-shell particles can be adjusted by the first or second substance in the manufacturing step of the core-shell particles. The size of the droplets proceeds.

Further, the mixing ratio (content ratio) of the first substance and the second substance in the core-shell particle mixture can be adjusted by adjusting the mixing ratio of the first core-shell particle and the second core-shell particle.

Further, the mixing ratio (content ratio) of the first substance and the second substance in the core-shell particle mixture may be adjusted by adjusting the content of the first substance in the first core-shell particle and the second substance in the second core-shell particle. Adjusted by the ratio of the contents.

[Manufacturing method of laminated body]

The laminate system can be produced by the following steps (1) to (3).

(1) a step of disposing the core-shell particle mixture or the above-mentioned adhesive agent on the surface of the first member (hereinafter also referred to as "arrangement step"), and (2) imparting stress to the core-shell particle mixture or the above-mentioned adhesive agent Step (hereinafter also referred to as "stress applying step"), (3) a step of laminating a second member on the arrangement surface of the core-shell particles or the adhesive agent of the first member (hereinafter, also referred to as "layering step" ").

The order of the stress imparting step and the laminating step is not limited, and the step of laminating may be performed after the stress imparting step, or the stress imparting step may be performed after the laminating step.

In the disposing step, the method of disposing the core-shell particle mixture on the surface of the first member is not particularly limited. For example, it may be manually operated (arranged by hand or tweezers), or may be configured by air supply or by inflow of a funnel or the like.

For the lamination step after the stress imparting step The shape is explained. It is preferable to provide a stress to the core-shell particle mixture or the adhesive disposed on the surface of the first member, preferably a release material is disposed on the core-shell particle mixture or the adhesive, and a stress is applied from the release material. When the stress is applied, the shell is cracked, and the first substance and the second substance are released from each of the first and second core-shell particles, and the first substance reacts with the second substance. That is, the reactants of the first substance and the second substance can be developed on the surface of the first member. Next, after removing the release material, the second member is laminated on the arrangement surface of the core-shell particle mixture or the adhesive of the first member (that is, the arrangement surface of the reactants). Thereby, the first member and the second member are laminated via the reactants. In the case where the reactant is a reactant of the adhesive, the first member and the second member are well fixed. Further, after the release material is removed, a film composed of a reactant can be formed on the surface of the first member without laminating the second member.

Here, the reactant of the first substance and the second substance may be a reaction product after the reaction between the first substance and the second substance, a mixture of the reactant and the unreacted first substance and the second substance, the first substance and the first 2 Any of a mixture of substances (state before the reaction is carried out).

The case where the stress imparting step is performed after the lamination step will be described. After the second member is laminated on the arrangement surface of the core-shell particle mixture or the adhesive of the first member, the first member and the second member apply stress so as to face each other in contact with each other, and the core-shell particle mixture or the like The agent imparts stress. Thereby, the shell is cracked, and the first substance and the second substance are released from each of the first and second core-shell particles, and the first substance reacts with the second substance. That is, the first member and the second member can be deployed between the first member and the second member. 1 substance and the reactant of the second substance. In the case where the reactant is a reactant of the adhesive, the first member and the second member are well fixed.

The solid particles forming the shell of the core-shell particles generally maintain shape and size in the reactants. Therefore, the particle diameter of the solid particles corresponds to the minimum value of the thickness of the layer formed of the reactant formed on the surface of the first member. Therefore, the thickness of the reactant layer formed on the surface of the first member can be adjusted by adjusting the number average particle diameter of the solid particles.

In the stress imparting step, it is preferable to apply stress to the first core-shell particles to release the first substance to the outside of the first shell, and then apply stress to the second core-shell particles to release the second substance to the outside of the second shell. Thereby, the first substance and the second substance can be easily and uniformly mixed. For example, when the average particle diameter of the first core-shell particles is larger than the average particle diameter of the second core-shell particles, the first core shell may be first compared to the second core-shell particles in the core-shell particle mixture. The particles impart stress.

Of course, stress may be simultaneously applied to the first core-shell particle and the second core-shell particle, and stress may be applied to the first core-shell particle after stress is applied to the second core-shell particle.

Further, the laminate may be produced by the following steps (4) to (8).

(4) separating the first core-shell particles from the second core-shell particles from the core-shell particle mixture, disposing the first core-shell particles on the surface of the first member, and (5) applying stress to the first core-shell particles. a step of releasing the first substance to the outside of the first shell, and (6) arranging the second core shell on the surface of the first member from which the first substance is released (7) a step of laminating a second member on a surface on which the first member is released from the first member, and (8) applying stress to the second core-shell particle to cause the second substance to be outside the second member The steps to release.

The order of the step (7) and the step (8) is not limited, and the step (8) may be performed after the step (7), or the step (7) may be performed after the step (8).

[Examples]

Hereinafter, the present invention will be further specifically described by showing the examples and comparative examples, but the present invention is not limited by the examples.

<Production of Core Shell Particles>

The reagents used in the preparation of core-shell particles are as follows.

Epoxy resin: "Denacol EX-810" (ethylene glycol diglycidyl ether, viscosity 20mPa‧s) manufactured by Nagase ChemteX Co., Ltd., hardener: "polyethyleneimine" manufactured by Wako Pure Chemical Industries Co., Ltd. (weight average molecular weight: 600, hereinafter also referred to as "PEI"), polytetrafluoroethylene particles: "poly(tetrafluoroethylene)" manufactured by Sigma-Aldrich Japan Co., Ltd. (number average particle diameter: 1 μm, agglomerated state, below "Tospearl 2000B" (a spherical shape, a number average particle diameter of 6.0 μm) and a polysiloxane particle B: "Tospearl 1110A" manufactured by MOMENTIVE Co., Ltd., manufactured by MOMENTIVE Co., Ltd. (Positive spherical shape, number average particle diameter 11.0 μm), Polysiloxane particles C: "Tospearl 145A" manufactured by MOMENTIVE Co., Ltd. (positive spherical shape, number average particle diameter: 4.5 μm), and polyoxynium particle D: "Tospearl 150KA" manufactured by MOMENTIVE Co., Ltd. A number average particle diameter of 5.0 μm), Shisong: Sigma-Aldrich Japan Co., Ltd. (spherical shape having irregularities on the surface, number average particle diameter: 40 μm), and cerium oxide particles A: AEROSIL RX-300, manufactured by Japan AEROSIL Co., Ltd. Trimethylhydrazine surface, area average particle size of about 14 to 17 nm), cerium oxide particles B: manufactured by AEROSIL RY-300, Japan (AEROSIL RY-300, polydimethyl siloxane surface, area average particle size of about 21 to 27 nm ),

[Manufacturing Example 1]

As a shell material, PTFE particles are spread thinly on a petri dish. As a core material, 15 μL of an epoxy resin was dropped onto a PTFE particle in a petri dish using a micropipette (Michipet, manufactured by NICHIRYO Co., Ltd.). After the dropping, the petri dish was shaken in an in-plane parallel to the ground for 30 seconds to roll the droplets, and the PTFE particles were adsorbed onto the surface of the droplets of the epoxy resin to prepare core-shell particles. Further, the liquid droplets were rolled using a plastic spatula for the droplets which were only shaken by the Petri dish, and the core-shell particles were produced.

[Manufacturing Example 2]

In Production Example 2, a nucleus was produced in the same manner as in Production Example 1 except that the PTFE particles of Production Example 1 were changed to the polysiloxane particles A. Shell particles.

[Manufacturing Example 3]

In the production example 3, core-shell particles were produced in the same manner as in Production Example 1, except that the PTFE particles of Production Example 1 were changed to the polysiloxane particles D.

[Manufacturing Example 4]

In Production Example 4, core-shell particles were produced in the same manner as in Production Example 1, except that the epoxy resin of Production Example 1 was changed to PEI.

[Manufacturing Example 5]

In the production example 5, the core-shell particles were produced in the same manner as in Production Example 4 except that the PTFE particles of Production Example 4 were changed to the polysiloxane particles A.

[Manufacturing Example 6]

In the production example 6, the core-shell particles were produced in the same manner as in Production Example 4 except that the PTFE particles of Production Example 4 were changed to the polysiloxane particles B.

[Manufacturing Example 7]

In the production example 7, the core-shell particles were produced in the same manner as in Production Example 4 except that the PTFE particles of Production Example 4 were changed to the polyfluorene oxide particles C.

[Manufacturing Example 8]

In the production example 8, the core-shell particles were produced in the same manner as in Production Example 4 except that the PTFE particles of Production Example 4 were changed to the polysiloxane particles D.

[Manufacturing Example 9]

In the production example 9, except that the PTFE particles of Production Example 1 were changed to stone pine, core-shell particles were produced in the same manner as in Production Example 1.

[Manufacturing Example 10]

2.8 g of RX-300 was weighed in an agitated vessel of a blender (Model: 1500 rpm, Osaka Chemical Co., Ltd.) with an electronic balance, and 25 g of an epoxy resin solution (epoxy resin concentration: 20) The mass%) was added thereto, and the core-shell particles were produced by stirring for 5 seconds by a stirrer.

[Manufacturing Example 11]

In the production example 11, except that the RX-300 of Production Example 10 was changed to RY-300, core-shell particles were produced in the same manner as in Production Example 10.

[Manufacturing Example 12]

In the production example 12, the core-shell particles were produced in the same manner as in Production Example 10 except that the epoxy resin of Production Example 10 was changed to PEI.

[Manufacturing Example 13]

In the production example 13, except that the RX-300 of Production Example 12 was changed to RY-300, core-shell particles were produced in the same manner as in Production Example 12.

Evaluation of the stability of core-shell particles)

The core-shell particles of each of the production examples were transferred to a glass plate using a plastic spatula, and the stability was confirmed at room temperature (23 ° C). The results are shown in Table 1.

(Measurement of contact angle)

The shell material used in each of the production examples was spread out in a plane on a flat surface, and droplets were dropped thereon by using the core material used in each of the production examples. After 1 to 2 minutes, the contact angle of the core material on the shell material was measured using a contact angle meter ("SImage 02" manufactured by Excimer Co., Ltd.). The results are shown in Table 1.

(Evaluation of contact stability of core-shell particles)

One of the core-shell particles of Production Example 2 was brought into contact with one of the core-shell particles of Production Example 5 on a glass plate, and left to stand at room temperature (23 ° C). The two core-shell particles were combined into one in 5 minutes.

One of the core-shell particles of Production Example 2 was brought into contact with one of the core-shell particles of Production Example 6 on a glass plate, and left to stand at room temperature (23 ° C). After 24 hours, the two core-shell particles were not combined and existed steadily, and were well separated. Further, after cutting the two core-shell particles with a bamboo stick, it was confirmed that the inner nuclear material was in a liquid state. This epoxy resin showing the core material was not in contact with PEI.

<Manufacture of core-shell particle mixture and evaluation of its stability)

[Example 1]

The core-shell particles of Production Example 2 and the core-shell particles of Production Example 5 were mixed at a ratio of 1: to obtain a core-shell particle mixture.

[Embodiment 2]

The number of core-shell particles of Production Example 2 and the core-shell particles of Production Example 6 were counted. A mixture of core-shell particles is obtained by mixing in a manner other than 1:.

[Example 3]

The core-shell particles of Production Example 10 and the core-shell particles of Production Example 13 were mixed at a mass ratio of 1:1 to obtain a core-shell particle mixture. This core-shell particle mixture is a well-flowing powdery core particle aggregate (dry liquid). This core-shell particle mixture was placed at room temperature (23 ° C), and the fluidity did not change even after 24 hours, and it was stably present.

(Adhesion evaluation of core-shell particle mixture)

The core-shell particle mixture of Example 1 was sandwiched between glass plates ("S7213" manufactured by Matsunaga Glass Industry Co., Ltd.), and stress was applied from the upper side of the glass plate to collapse the core-shell particles, and the internal epoxy resin was mixed with PEI. . The mixed liquid is a white paste-like liquid. When the upper glass plate was pulled after standing at room temperature (23 ° C) for 1 hour, the glass plate was slightly moved but fixed. When the upper glass plate was pulled after standing for 4 hours, the glass plate could not move at all and was completely fixed.

The core-shell particle mixture of Example 2 was sandwiched between glass plates ("S7213" manufactured by Matsunaga Glass Industry Co., Ltd.), and stress was applied from the upper side of the glass plate to collapse the core-shell particles, and the internal epoxy resin was mixed with PEI. . The mixed liquid is a translucent liquid. When the upper glass plate was pulled after standing at room temperature (23 ° C) for 1 hour, the glass plate was slightly moved but fixed. When the upper glass plate was pulled after standing for 4 hours, the glass plate could not move at all and was completely fixed.

The core-shell particle mixture of Example 3 was sandwiched between glass plates ("S7213" manufactured by Matsunaga Glass Industry Co., Ltd.) from the glass plate. The upper side is stressed to cause the core-shell particles to collapse, and the internal epoxy resin is mixed with the PEI. The mixed liquid is a white paste-like liquid. After standing at room temperature (23 ° C) for 1 hour, the upper glass plate was pulled, and the glass plate was fixed while being slightly moved. After standing for 4 hours, the upper glass plate was pulled, and the glass plate could not be moved at all, and was completely fixed.

Since the figure in the present case is a schematic diagram of an example of a structure of polyoxynene particles, it is not a representative figure of the present case. Therefore, there is no designated representative map in this case.

Claims (11)

A core-shell particle mixture comprising: a first core-shell particle composed of a first core containing a first substance and a first shell covering the first core; and containing a reactivity with the first substance The second core of the second substance and the second core of the second core coated with the second core; the first shell and the second shell contain solid particles. The core-shell particle mixture according to claim 1, wherein the first substance contains a polymerizable compound, and the second substance contains a polymerization reagent. The core-shell particle mixture according to claim 1 or 2, wherein the first core-shell particle is capable of releasing the first substance to the outside of the first shell by applying a stress, and the second core shell The particles can be released to the outside of the second shell by applying stress. The core-shell particle mixture according to any one of claims 1 to 3, wherein at least one of the first substance and the second substance is a liquid substance, and the liquid substance is in the solid particle The upper contact angle is 90° or more. An adhesive comprising an adhesive formed from a mixture of core-shell particles according to any one of claims 1 to 4. A manufacturing method for producing a first substance and the first substance A method for producing a reactant of a reactive second substance, comprising: a core-shell particle mixture according to any one of claims 1 to 4, or an adhesive agent as described in claim 5 The step of stress. The production method according to claim 6, further comprising an adjustment step of adjusting the core-shell particle mixture by adjusting a number average particle diameter of the first core-shell particle and the second core-shell particle The step of the ratio of the content of the first substance to the second substance. The manufacturing method according to claim 6 or 7, further comprising an adjusting step of adjusting a mixing ratio of the first core-shell particle and the second core-shell particle or adjusting the first core-shell particle The ratio of the content of the first substance to the content of the second substance in the second core-shell particle is adjusted to adjust the content ratio of the first substance to the second substance in the core-shell particle mixture. The production method according to any one of claims 6 to 8, wherein the reactant is a reactant of the adhesive. A method for producing a laminate comprising: a step of disposing, a surface of the first member, a core-shell particle mixture according to any one of claims 1 to 4, or a scope of claim 5 a step of applying a stress to the core-shell particle mixture or the adhesive, and a step of laminating the layer of the core-shell particles or the adhesive on the first member 2 steps of the component. The method for producing a layered product according to the above aspect of the invention, wherein the step of applying a stress to the core-shell particle mixture or the adhesive agent includes: stressing the first core-shell particle to cause the first After the substance is released to the outside of the first case, stress is applied to the second core-shell particles to release the second substance to the outside of the second case.