JP6700563B2 - Multi-component adhesive, method for producing reaction product thereof, and method for producing laminate - Google Patents

Description

  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.

  Generally, the adhesive is classified into a dry solidification type adhesive, a chemical reaction type adhesive, a hot melt type adhesive and a pressure sensitive type adhesive depending on the solidification method. The dry solidification type adhesive is one that is cured by evaporation of water or a solvent in the adhesive. The chemical reaction type adhesive is one that is cured by a chemical reaction of a liquid compound. As the adhesive of the chemical reaction type adhesive, one that is cured by the reaction between the main agent and the curing agent, one that is cured by the reaction between the main agent and the moisture (water) on the surface of the adherend, and one that is cured by blocking the air Examples thereof include those cured by irradiation with ultraviolet rays. The hot-melt adhesive is a solid that is solid at room temperature but becomes liquid when heat is applied, and is fixed by cooling it. The pressure-sensitive adhesive is one that retains strength with an adherend due to the adhesiveness of the adhesive.

Adhesion Technology Textbook for Professionals, edited by the Japan Adhesion Society, published by Nikkan Kogyo Shimbun, June 2009

For example, a multi-component type reaction agent such as a two-component adhesive composed of a main agent and a curing agent has the following problems in terms of handleability.
(A) It cannot be touched directly when handling.
(B) It is necessary to handle each component in a completely separated state until the reaction reagent is actually used.
(C) It is difficult to selectively bond a desired place in a complicatedly complicated minute portion. For example, it is difficult to bond only the inner part of a fine tube with a normal two-component adhesive. Further, even if the inner part of the pipe can be adhered, the adhesive will adhere to the pipe before reaching the inner part.

  An object of the present invention is to provide a multi-component type reaction agent such as a two-component adhesive agent, which is excellent in handleability.

The present invention provides the following core-shell particle mixture.
[1] First core-shell particles composed of a first core containing a first substance and a first shell coating the first core,
A second core-shell particle comprising a second core containing a second substance having reactivity with the first substance, and a second shell covering the second core. ,
The core-shell particle mixture, wherein the first shell and the second shell contain solid particles.

  [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 first core-shell particles can release the first substance to the outside of the first shell by applying stress.
The core-shell particle mixture according to [1] or [2], wherein the second core-shell particles can release the second substance to the outside of the second shell by applying stress.

[4] At least one of the first substance and the second substance is a liquid substance,
The said liquid substance is a core-shell particle mixture in any one of [1]-[3] whose contact angle on the said solid particle is 90 degrees or more.

The present invention provides the adhesive shown below.
[5] An adhesive formed from the core-shell particle mixture according to any one of [1] to [4] above.

The present invention provides the following method for producing a reaction product of a first substance and a second substance.
[6] A method for producing a reaction product of a first substance and a second substance having reactivity with the first substance,
A production method, comprising a step of applying stress to the core-shell particle mixture according to any one of [1] to [4] or the adhesive according to [5].

  [7] By adjusting the number average particle diameters of the first core-shell particles and the second core-shell particles, the content ratio of the first substance and the second substance in the core-shell particle mixture is adjusted. The production method according to [6], further comprising:

  [8] The mixing ratio of the first core-shell particles and the second core-shell particles, or the content of the first substance in the first core-shell particles and the second substance in the second core-shell particles. The method according to [6] or [7], further comprising adjusting the content ratio of the first substance and the second substance in the core-shell particle mixture by adjusting the ratio with the content. Production method.

  [9] The production method according to any one of [6] to [8], wherein the reaction product is a reaction product of an adhesive.

The present invention provides the following method for producing a laminate.
[10] A step of disposing the core-shell particle mixture according to any one of [1] to [4] or the adhesive according to [5] on the surface of the first member,
Stressing the core-shell particle mixture or the adhesive;
And a step of stacking a second member on a surface of the first member on which the core-shell particles or the adhesive is arranged.

  [11] The step of applying a stress to the core-shell particle mixture or the adhesive, after applying a stress to the first core-shell particles to release the first substance to the outside of the first shell, The method for producing a laminate according to [10], including a step of applying stress to the second core-shell particles to release the second substance to the outside of the second shell.

  According to the present invention, it is possible to provide a multi-component reaction agent such as a two-component adhesive agent, which is excellent in handleability.

It is a figure which shows an example of the structure of a silicone particle.

[Core-shell particle mixture]
A core-shell particle mixture according to an embodiment of the present invention is a first core-shell particle composed of a first core containing a first substance and a first shell coating the first core, A second core-shell particle comprising a second core containing a second substance having reactivity with the first substance, and a second shell covering the second core. The first shell and the second shell contain solid particles. Hereinafter, the solid particles contained in the first shell may be referred to as “first solid particles”, and the solid particles contained in the second shell may be referred to as “second solid particles”.

  Examples of the use form of the core-shell particle mixture include a form using a mixture composed of these core-shell particles, a form using a mixture further containing other components in addition to the core-shell particle mixture. The 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 by placing it in a desired place. Hereinafter, the present invention will be described in detail.

(1) Core-shell Particles The first core-shell particles and the second core-shell particles (hereinafter, also referred to as “core-shell particles” as a term including both of them) usually have a spherical or flat spherical shape under atmospheric pressure. However, when the particle size is relatively small, the core-shell particles can be non-spherical. In the core-shell particle mixture, the first core-shell particles and the second core-shell particles do not react with each other when stress is not applied, but the stress causes the respective shells to crack or collapse. As a result, the first substance and the second substance forming the core are released outside the shell. As a result, a reaction between the first substance and the second substance can be caused.

  In the core-shell particles, the surface of the core is covered with a shell containing solid particles. The shell is usually a layer composed of a plurality of solid particles, for example, a single particle layer composed of solid particles having a single layer structure or a layer composed of an aggregate of solid particles. The shell preferably covers the core without a gap of 500 μm or more, more preferably covers the core without a gap of 100 μm or more, and more preferably the core without a gap of 5 μm or more. To cover.

  When viewing one 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 handleability. The thickness is more preferably 500 μm or more, and particularly preferably 1 mm or more. The maximum particle size 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, and is a value measured with a microscope, a ruler, or a caliper. In the case of measurement with a microscope, it can be measured by defining the equivalent circle diameter as the particle diameter and analyzing the image obtained by microscope observation with software such as a digital microscope.

  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 further preferably 500 μm or more and 40 mm, from the viewpoint of stability of the core-shell particles in atmospheric pressure. Or less, and 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, more preferably 50 μm or more and 50 mm or less, and further preferably 500 μm or more and 40 mm, from the viewpoint of stability of the core-shell particles in atmospheric pressure. Or less, and particularly preferably 800 μm or more and 30 mm or less. The number average particle diameter is obtained, for example, by a circle equivalent diameter by a microscope method, and can be measured by analyzing an image obtained by microscope observation with software such as a digital microscope. As an example of software of the digital microscope, there is, for example, Mottic Images Plus 2.2s (manufactured by Shimadzu Rika Co., Ltd.). Examples of the microscope include an electron microscope and an optical microscope, which may be appropriately selected depending on the solid particles used. The magnification at the time of observation may be appropriately selected depending on the particle diameter of the solid particles used.

  When measuring the number average particle diameter by microscope observation, a plurality of microscope observation images containing a plurality of core-shell particles are taken, and 50 core-shell particles are randomly selected from the obtained plurality of images to select these particle diameters. The average value of the particle diameters of the 50 particles at the time of measurement is defined as the number average particle diameter. When all the core-shell particles have a relatively large particle diameter of 100 μm or more, the particle diameter of the core-shell particles can also be measured using a ruler. In this case, when 50 core-shell particles are randomly selected and the particle diameters thereof are measured using a ruler, the average value of the 50 particle diameters is defined as the number average particle diameter. The core-shell particle mixture according to the present invention includes a 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 the same as in the above measuring method. “50” is defined as “core-shell particles contained in the mixture of core-shell particles (when measuring the number average particle diameter of the first core-shell particles, the number average particle diameters of the first core-shell particles and the second core-shell particles are measured. In the case of doing, the number average particle diameter is measured in the same manner as in the above measuring method except that all the numbers of the second core-shell particles are replaced.

  When looking at one 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 handleability. The volume of the core-shell particles is more preferably 40 μL or more, particularly preferably 60 μL or more. Moreover, 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 can release the first substance and the second substance, respectively, by applying stress. The magnitude of the stress is appropriately selected according to the application of the core-shell particle mixture and the general handling method. The magnitude of stress applied to the core-shell particles may be the same or different between the first core-shell particles and the second core-shell particles. Hereinafter, the stress required to release the first substance to the outside of the first shell is “first stress”, and the stress required to release the second substance to the outside of the second shell is “ It may be referred to as "second stress". The magnitudes of the first and second stresses are 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 shell It can be controlled by adjusting the average thickness and the like.

The stress applied to the core-shell particles is preferably of a magnitude that can be applied by crushing with a human finger. Specifically, the magnitude of the first and second stress is preferably 1~1000kN / ^{m 2,} and more preferably 5~100kN / ^{m 2.} Within such a range, the first substance and the second substance can be relatively easily released by, for example, arranging the core-shell particles at a desired place and then applying stress. Such a core-shell particle is easy to be crushed and is hard to be crushed when it is arranged, and thus the handleability thereof is good. If the first and second stresses are too small, the first substance and the second substance may be unintentionally released. Therefore, it is preferable that a stress of less than 1 kN/m ² does not cause cracking or collapse of the shell. When the stress is applied to the core-shell particles, a stress perpendicular to the arrangement surface of the core-shell particles may be applied, or shear stress or rotational stress may be applied. When shear stress or rotational stress is applied, the first substance and the second substance are easily released to the outside of the shell. It should be noted that the directions of shear stress and rotational stress may be selected as appropriate.

From the viewpoint of handleability, the first core-shell particles and the second core-shell particles retain the core-shell structure without collapsing the shell before applying stress or when the applied stress is less than 1 kN/m ^2. Preferably. The holding time of the core-shell structure before applying stress or when the applied stress is less than 1 kN/m ² is preferably 10 minutes or longer, more preferably 1 hour or longer, and even more preferably 24 hours or longer.

  From the viewpoint of handleability, it is preferable that the first core-shell particles and the second core-shell particles each hold the core-shell structure in a state of being in contact with each other without applying stress and without being united. The retention time of the core-shell structure when the core-shell particles are in contact with each other without applying stress is preferably 10 minutes or longer, more preferably 1 hour or longer, and further preferably 24 hours or longer.

(2) Core The first core contains the first substance. The second core contains a second substance. The first substance and the second substance can be used in combination as long as they have reactivity and generate a reaction product. 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 reaction product. The reactant may be a solid, a gel, a dried gel, or a viscous liquid. The first substance and the second substance may each be composed of one kind of compound, or may be composed of two or more kinds of compounds.

  As the polymerizable compound, a polymerizable monomer, a polymerizable oligomer, a polymerizable polymer or the like can be used. Specifically, epoxy resin (glycidyl ether type, glycidyl ester type, glycidyl amine type, alicyclic), polyfunctional methacrylic acid ester, acrylic monomer, polyols (polyester polyol, polyether polyol, polycarbonate polyol, polytetramethylene) Glycol, low-molecular diol), silicone oil containing hydroxyl groups at both ends, vinyl oil containing vinyl group, urea, formaldehyde, melamine, phenol, resorcinol, phenol resole, resorcinol, α-olefin, maleic anhydride, maleic anhydride, vinyl acetate Examples thereof include monomers, polyesters, chloroprene rubber, acrylonitrile-butadiene copolymers, styrene-butadiene copolymers, polyvinyl alcohol, butyl rubbers, sodium alginate, and natural rubbers.

  The polymerization reagent may be a polymerization catalyst or a reaction aid, or may be one that polymerizes with the first substance.

  As the polymerization reagent, for example, a polymerization initiator, a curing agent, a crosslinking agent (including a vulcanizing agent), or the like can be used. Specifically, polyethyleneimine, secondary amine, tertiary amine, primary amine, dicyandiamide, imidazoles, tertiary amine salt, Lewis acid salt, ketimine-based latent curing agent, hydroperoxide, cumene hydroperoxide, benzoyl Peroxides, redox initiators, acid anhydrides, organic metal salts, polyisocyanate compounds, hydrolyzable silanes, hydrogen polysiloxanes, polypropylene oxide (modified silicone) having a methyldimethoxysilyl group at the end, ammonium chloride, hydroxylation Examples include calcium and a vulcanizing agent (sulfur).

  As an example of the combination of the first substance and the second substance, an adhesive will be described below as an example. In addition, the following notation “C:A/B” means that a multi-component type reaction agent containing a first substance and a second substance represented by C, that is, a multi-component adhesive is the first It is meant to include A as a substance and B as a second substance. Further, when two or more kinds of substances are described in the respective columns of A and B, at least one of them can be appropriately selected and used.

Epoxy resin adhesive: Epoxy resin/polyethyleneimine, tertiary amine, secondary amine, primary amine, dicyandiamide, imidazoles, tertiary amine salt, Lewis acid salt, ketimine latent curing agent Anaerobic adhesive: multifunctional Methacrylic acid ester/hydroperoxide Second generation acrylic (SGA) adhesive: acrylic monomer/cumene hydroperoxide, benzoyl peroxide, organic metal salt Polyurethane resin adhesive: polyols/polyisocyanate compound Silicone resin adhesive : Silicone oil containing hydroxyl groups at both ends/hydrolyzable silane Silicone resin adhesive: Vinyl group containing silicone oil/hydrogen polysiloxane Modified silicone resin adhesive: Epoxy resin/Methyldimethoxysilyl group-terminated polypropylene oxide (modified silicone)
Urea resin adhesive: Urea, formaldehyde/ammonium chloride Melamine resin adhesive: Melamine, urea, phenol, formaldehyde/ammonium chloride Phenolic resin adhesive: phenol, formaldehyde/alkali (sodium hydroxide)
Resorcinol adhesive: resorcinol, formaldehyde, phenol resole, resorcinol/alkali (sodium hydroxide)
α-Olefin adhesive: α-Olefin, maleic anhydride, maleic anhydride imide/calcium hydroxide Vinyl acetate emulsion adhesive: Vinyl acetate monomer/organic peroxide (cumene hydroperoxide, benzoyl peroxide)
Urethane elastomer adhesives: polyester/polyisocyanate chloroprene rubber adhesives: chloroprene rubber/polyisocyanate nitrile rubber adhesives: acrylonitrile-butadiene copolymer/crosslinking agent (sulfur)
Styrene-butadiene rubber adhesive: styrene-butadiene copolymer/crosslinking agent (sulfur)
Butyl Rubber Adhesive: Butyl Rubber/Crosslinking Agent (Sulfur)
Natural rubber adhesive: Natural rubber/crosslinking agent (sulfur)
Calcium chloride adhesive: sodium alginate aqueous solution/calcium chloride aqueous solution Among the above combinations A and B, A/B is “epoxy resin/polyethyleneimine, tertiary amine, secondary amine, primary amine, dicyandiamide, imidazoles, Epoxy resin adhesive that is "tertiary amine salt, Lewis acid salt, ketimine-based latent curing agent", and second that A/B is "acrylic monomer/cumene hydroperoxide, benzoyl peroxide, organometallic salt" It is preferable to use a next-generation acrylic (SGA) adhesive from the viewpoint of handleability and practicality. Thus, when the combination of the first substance and the second substance is the adhesive, the core-shell particle mixture can be used as the adhesive.

  The content of the first substance and the second substance in the core is such that when the first substance and the second substance are liquids, the total amount of the first core or the second core is 100% by mass, respectively. 10 mass% or more is preferable, 50 mass% or more is more preferable, 80 mass% or more is further preferable, 90 mass% or more is especially preferable, and 100 mass% is the most preferable. Here, that the content of the first substance or the second substance in the core is 100% by mass means that, for example, the first core is composed of the first substance. When the first substance and the second substance are solid, the contents of the first substance and the second substance in the core are respectively 100% by mass of the total amount of the first core or the second core, The content is preferably 10% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 90% by mass or less, and further preferably 50% by mass or more and 80% by mass or less. Here, the contents of these substances when the first substance and the second substance are solid are the first substance or the second substance and water or a solvent in which the substance is dissolved or dispersed. Means the ratio of the first substance or the second substance to the total amount of. The core may contain other components in addition to the first substance or the second substance as long as the core-shell particles can be formed.

(3) Shell The shell contains solid particles and covers the core. The shell preferably comprises an aggregate of solid particles. The shell preferably covers the core without a gap of 500 μm or more, more preferably covers the core without a gap of 100 μm or more, and more preferably the core without a gap of 5 μm or more. To cover. The content of the solid particles in the shell is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 100% by mass.

  Each of the first solid particles forming the first shell and the second solid particles forming the second shell preferably contains fine particles having a number average particle diameter of 500 μm or less as a main component. The first solid particles and the second solid particles more preferably contain 50 to 100% by mass of fine particles having a number average particle diameter of 500 μm or less, further preferably 70 to 100% by mass, and particularly preferably 90 to 100% by mass. % Included.

  The contact angle of the core-forming substance containing the first substance on the aggregated first solid particles and the contact angle of the core-forming substance containing the second substance on the aggregated second solid particles are usually 90. Or more, preferably 100° or more, more preferably 110° or more, still more preferably 120° or more. The contact angle is preferably 170° or less, more preferably 160° or less. Such a contact angle is preferable because the solid particles forming the shell and the core-forming substance are easily adsorbed and the shape stability of the core-shell particles is increased. When the contact angle is less than 90°, the core-forming substance containing the first substance or the second substance may penetrate into the plurality of solid particles as the shell material, which may make it difficult to form the core-shell particles. is there. Here, the core forming substance is a substance having the same composition as the core, which is used for measuring 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 particles, and the first core is the first substance and other substances. When it is composed of the above component, the contact angle is the contact angle of the first core on the first solid particles.

  For the same reason as above, when the first substance is a liquid substance, the contact angle of the first substance on the aggregated first 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 preferably 170° or less, more preferably 160° or less. For the same reason, when the second substance is a liquid substance, the contact angle of the second substance on the aggregated second solid particles is usually 90° or more, preferably 100° or more, and It is preferably 110° or more, and more preferably 120° or more. The contact angle is preferably 170° or less, more preferably 160° or less.

  The contact angle of the core-forming substance on the aggregated solid particles is determined by uniformly expanding the solid particles in a plane without a gap and using a contact angle meter (“SIimage 02” manufactured by Excimer) to form the core on the solid particles. It can be determined by measuring the contact angle of the substance.

  The solid particles (first and second solid particles) are preferably fine particles having no adhesive force at 30°C. The solid particles are fine particles having no adhesive force at 40° C. or lower, more preferably 50° C. or lower, and further preferably 80° C. or lower.

In the present specification, having no adhesive force means an adhesive force with which the tack is 0.1 N or less when measured by the probe tack test under the following conditions. The tack is the maximum stress measured by the probe tack test under the following conditions.
<Measurement conditions>
Probe tack tester: TE-6002 (manufactured by Tester Sangyo Co., Ltd.),
Speed of contacting the solid particles with the probe: 10 mm/s,
Contact time: 30 seconds,
Peeling speed: 10 mm/s.

  The glass transition temperature (Tg) of the solid particles (first and second solid particles) is preferably 40° C. or higher, more preferably 50° C. or higher, even more preferably 80° C. or higher. If the Tg is lower than the above value, the shell may develop an adhesive force due to changes in the external environment, resulting in poor handling. The glass transition temperature (Tg) of the solid particles (first and second solid particles) can be measured using a differential scanning calorimeter.

  The softening temperature of the solid particles (first and second solid particles) is preferably 40° C. or higher, more preferably 50° C. or higher, even more preferably 80° C. or higher. If the softening temperature is lower than the above value, the shell may develop an adhesive force due to a change in the external environment, resulting in poor handling. The softening temperature of solid particles (first and second solid particles) can be measured using an automatic dropping point/softening point measuring system (for example, manufactured by METTLER TOLEDO).

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

The number average particle diameter of the above-mentioned fine particles contained as a main component in the solid particles is usually 5 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 further preferably 20 nm or more. It is 50 μm or less. When the number average particle size of the fine particles is within the above range, the stability of the granular adhesive in the air is further increased, which is preferable. For the number average particle size, the image obtained by microscopic observation is
It can be measured by analysis using Images Plus 2.2s (manufactured by Shimadzu Rika Co., Ltd.). A more specific method of measuring the number average particle diameter of the fine particles by microscopic observation is the same as the method of measuring the number average particle diameter of the core-shell particles.

  As the solid particles, various fine particles such as silicone 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.

  As shown in FIG. 1, for example, a silicone particle has a network structure formed by three-dimensionally connecting siloxane bonds, and an intermediate structure between inorganic and organic in which one methyl group is bonded to a silicon atom. It is a particle which shows.

  As the inorganic fine particles, 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.

The organic fine particles include resin fine particles and natural product-derived fine particles.
As the component of the fine particles of the resin, a homopolymer of a monomer such as styrene-based, acrylic-based, methacrylic-based, olefin-based, vinyl ketone and acrylonitrile, or a copolymer obtained by polymerizing two or more kinds of monomers; polytetrafluoroethylene, 4 Fluorinated ethylene-6-fluorinated propylene copolymer, fluorinated ethylene-ethylene copolymer, polyvinylidene fluoride and other fluorine-based resins; melamine resins; urea resins; polydimethylsiloxane-based polymers; polyesters; polyamides, etc. Can be mentioned. Further, the surface of these fine particles may be surface-modified with a surface modifier such as a silane coupling agent or a surfactant.

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

The Tg of the resin can be adjusted by the polymerization conditions such as the monomer ratio.
Examples of the above-mentioned fine particles derived from natural products include fine particles derived from plant spores, pollen, or 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.

  Microparticles are available on the market. Examples of commercially available products include silicone particles ("Tospearl 2000B", "Tospearl 1110A", "Tospearl 145A", "Tospearl 150KA" manufactured by Momentive Co., Ltd.), silica particles ("RX-300" manufactured by Nippon Aerosil Co., Ltd., " RY-300"), Poly(tetrafluoroethylene) ("Poly(tetrafluoroethylene"" manufactured by Sigma-Aldrich Japan KK), and the like.

  The average thickness of the first and second shells is preferably 10 nm or more and 500 μm or less, more preferably 100 nm or more and 500 μm or less. Within such a range, the shape stability of the core-shell particle mixture is high, and the shell can be collapsed by applying an appropriate stress, which is preferable. 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 is obtained by observing the cross section of the core-shell particles with an electron microscope and measuring the shell thickness at 10 randomly selected locations. The average thickness of the shell is the average value of the 10 measured values.

(4) Method for producing core-shell particles The core-shell particles can be produced, for example, by the following steps (1) to (3).
(1) A step of bringing a droplet containing a first substance or a second substance into contact with solid particles (first solid particles or second solid particles),
(2) A step of covering the entire periphery of the droplet containing the first substance or the second substance with the solid particles,
(3) optionally drying the droplets containing the first substance or the second substance whose entire periphery is covered with solid particles.

  For the 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. What was used may be used, what disperse|distributed the 1st substance or the 2nd substance in water or a solvent may be used, and what diluted the 1st substance or the 2nd substance with water or a solvent You may use.

  The content of the first substance or the second substance in the droplet containing the first substance or the second substance when contacting the solid particles is usually 5 to 100% by mass, preferably 10 to 80% by mass. It is mass%, more preferably 20 to 70 mass%, still more preferably 40 to 60 mass%. When the content is within the above range, the core-shell particles are easily produced, which is preferable. The content of the first substance or the second substance in the droplet containing the first substance or the second substance is the proportion of the first substance or the second substance in the droplet, and is usually It is the concentration of components other than the solvent and water contained in the droplet.

  The volume of the droplet containing the first substance or the second substance is preferably 4 fL or more and 5 mL or less, and more preferably 15 μL or more and 5 mL or less. The volume of the droplet is more preferably 30 μL or more, and particularly preferably 50 μL or more. Moreover, the volume of the droplet 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 liquid droplets containing the first substance or the second substance into contact with the solid particles may be performed by spraying the liquid droplets containing the first substance or the second substance by atomization or the like. Good.

  The entire circumference of the droplet containing the first substance or the second substance is usually covered with the solid particles by rolling the droplet containing the first substance or the second substance on the solid particles.

  Alternatively, the droplets containing the first substance or the second substance and the solid particles may be mixed with each other by using a mixer or the like to bring them into contact with each other, and the periphery of the droplets may be covered with the solid particles.

  The droplets containing the first substance or the second substance whose entire circumference is covered with solid particles may be dried. When the droplet containing the first substance or the second substance contains the solvent or water, the droplet is preferably dried. As used herein, “drying” means removing water or a solvent from the droplets containing the first substance or the second substance covered with the solid particles. In this case, the water or the solvent is preferably completely removed, but may remain as long as the effect of the present invention is not impaired. As the drying method, a method in which the first substance or the second substance and the solid particles are allowed to stand at a temperature at which the chemical and physical properties do not change; a method in which they are exposed to hot air, hot air or low humidity air; A method of lyophilizing; a method of irradiating infrared rays, far infrared rays, an electron beam, or the like. The drying temperature is preferably 10 to 200°C, more preferably 20 to 100°C.

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

(5) Method for producing core-shell particle mixture The core-shell particle mixture can be produced by mixing the first core-shell particles and the second core-shell particles in a desired mixing ratio. The desired mixing ratio is preferably a mixing ratio with 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 multi-component type reaction agent such as a two-component adhesive or a two-component paint.

[adhesive]
In one embodiment of the invention, the core shell particle mixture is an adhesive. The adhesive is preferably a multi-component adhesive, and this form corresponds to, for example, the case where the combination of the first substance and the second substance is the adhesive. The adhesive is, for example, a form in which stress is applied to the core-shell particle mixture so that the respective shells collapse and the released first substance reacts with the second substance to develop an adhesive force. Is mentioned. The present adhesive does not have an adhesive force in a state where no stress is applied, but exerts an adhesive force by applying the above-mentioned predetermined stress.

  The adhesive may include the core shell particle mixture as well as other components commonly used in adhesives. Other components include metal fine particles, metal oxide fine particles, conductive fine particles, ion conductive compositions, ionic compounds having organic cations or anions, silane coupling agents, crosslinking catalysts, weathering stabilizers, tackifiers, Examples thereof include 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 particles and the second core-shell particles. Alternatively, the other component may be a component of another adhesive different from the first core-shell particles and the second core-shell particles.

  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, and thus it is easy to uniformly fill the gap between the two or more adherend members. If the core-shell particle mixture can be uniformly filled in the gaps between the members to be adhered, when stress is applied to the core-shell particle mixture, the first substance and the second substance can be uniformly spread in the gap, Good adhesion can be obtained over the desired adhesion area.

  The adhesive formed from the core-shell particle mixture is suitable for automobile adhesives, building adhesives, bearing fittings, pipe fixing, screw locking, gear and propeller fixing, and furniture assembly. Can be used.

[Method for producing reaction product]
A method for producing a reaction product of a first substance and a second substance includes a step of applying a stress to the above core-shell particle mixture or the above adhesive. When stress is applied to the core-shell particle mixture or the adhesive, the shell cracks or collapses to release the first substance and the second substance from the first and second core-shell particles, respectively. Then, the first substance and the second substance come into contact with each other. As a result, the first substance and the second substance react with each other to generate a reactant. If necessary, in order to accelerate the reaction, the core-shell particle mixture may be subjected to stress and then heated, irradiated with light, or the like. The reaction product is preferably a reaction product of an adhesive (multi-component adhesive, etc.).

  The mixing ratio of the first substance and the second substance in the core-shell particle mixture (content ratio, therefore, the reaction amount ratio of the first substance and the second substance) is determined by the first core-shell particles and the second core-shell. It can be adjusted by adjusting the number average particle size of the particles. The number average particle diameter of the core-shell particles can be adjusted by adjusting the size of the droplet containing the first substance or the second substance in the manufacturing process of the core-shell particles.

  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 particles and the second core-shell particles. ..

  In addition, the mixing ratio (content ratio) of the first substance and the second substance in the core-shell particle mixture is the content of the first substance in the first core-shell particles and the second substance in the second core-shell particles. It can also be adjusted by adjusting the ratio with the content.

[Method of manufacturing laminated body]
The laminate can be manufactured by the following steps (1) to (3).
(1) A step of disposing the core-shell particle mixture or the adhesive on the surface of the first member (hereinafter, also referred to as “arrangement step”),
(2) a step of applying stress to the core-shell particle mixture or the adhesive (hereinafter, also referred to as “stress applying step”),
(3) A step of laminating the second member on the surface of the first member on which the core-shell particles or the adhesive are arranged (hereinafter, also referred to as a “laminating step”).

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

  In the arranging step, the method of arranging the core-shell particle mixture on the surface of the first member is not particularly limited. Alternatively, they may be arranged by pouring using a funnel or the like.

  A case where the laminating step is performed after the stress applying step will be described. The application of stress to the core-shell particle mixture or adhesive placed on the surface of the first member is a method in which a release material is placed on the core-shell particle mixture or adhesive and stress is applied from above the release material. It is preferable. By applying stress, the shell is cracked, the first substance and the second substance are released from the first and second core-shell particles, respectively, and the first substance and the second substance react with each other. . That is, the reaction product of the first substance and the second substance can be spread on the surface of the first member. Next, after removing the release material, the second member is laminated on the surface on which the core-shell particle mixture or the adhesive of the first member is arranged (that is, the surface on which the reactant is arranged). As a result, the first member and the second member are laminated with the reaction product in between. When the reaction product is the reaction product of the adhesive, the first member and the second member are well fixed. In addition, when the second member is not laminated after removing the release material, a film made of the reaction product can be formed on the surface of the first member.

  Here, the reaction product of the first substance and the second substance means the reaction product of the first substance and the second substance, the first substance and the second substance which have not reacted with the reaction substance. And a mixture of the first substance and the second substance (state before the reaction proceeds).

  A case where the stress applying step is performed after the laminating step will be described. After laminating the second member on the surface of the first member on which the core-shell particle mixture or the adhesive is arranged, stress is applied so that the first member and the second member come into contact with each other on the surfaces facing each other, and the core shell Stress is applied to the particle mixture or the adhesive containing it. Thereby, a crack is generated in the shell, the first substance and the second substance are released from the first and second core-shell particles, respectively, and the first substance and the second substance react with each other. That is, a reaction product of the first substance and the second substance can be spread between the first member and the second member. When the reaction product is the reaction product of the adhesive, the first member and the second member are well fixed.

  The solid particles forming the shell of the core-shell particles are usually maintained in shape and size in the reactants. Therefore, the particle size of the solid particles may correspond to the minimum value of the thickness of the layer formed of the reactant 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 applying step, stress is applied to the first core-shell particles to release the first substance outside the first shell, and then stress is applied to the second core-shell particles outside the second shell. Preferably, the step of releasing the second substance is included. According to this, it becomes easy to uniformly mix the first substance and the second substance. For example, by making the average particle diameter of the first core-shell particles larger than the average particle diameter of the second core-shell particles, stress is applied to the first core-shell particles in the core-shell particle mixture prior to the stress of the second core-shell particles. Can be given.

  Of course, stress may be applied simultaneously to the first core-shell particles and the second core-shell particles, or stress may be applied to the first core-shell particles after applying stress to the second core-shell particles.

The laminated body can also be manufactured by the following steps (4) to (8).
(4) a step of separating the first core-shell particles and the second core-shell particles from the core-shell particle mixture, and arranging the first core-shell particles on the surface of the first member,
(5) applying a stress to the first core-shell particles to release the first substance outside the first shell,
(6) disposing the second core-shell particles on the surface of the first member from which the first substance is released,
(7) stacking a second member on the surface of the first member from which the first substance is released,
(8) A step of applying stress to the second core-shell particles to release the second substance to the outside of the second shell.

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

  Hereinafter, the present invention will be described more specifically by showing Examples and Comparative Examples, but the present invention is not limited to these Examples.

<Preparation of core-shell particles>
The reagents used for producing the core-shell particles are shown below.

Epoxy resin: "Denacol EX-810" (Ethylene manufactured by Nagase Chemtex Co., Ltd.)
Glycol Diglycidyl Ether, viscosity 20mPa・s)
Curing agent: "Polyethyleneimine" manufactured by Wako Pure Chemical Industries, Ltd. (weight average molecular weight: 600, hereinafter also referred to as "PEI")
Polytetrafluoroethylene particles: "Poly(tetrafluoro ethylene)" manufactured by Sigma-Aldrich Japan Co., Ltd. (number average particle diameter 1 μm, aggregated state, hereinafter also referred to as "PTFE particles"),
Silicone particles A: "Tospearl 2000B" manufactured by Momentive Co. (true sphere, number average particle diameter 6.0 μm),
Silicone particles B: "Tospearl 1110A" manufactured by Momentive Co. (spherical, number average particle diameter 11.0 μm),
Silicone particles C: "Tospearl 145A" manufactured by Momentive Co. (true sphere, number average particle diameter 4.5 μm),
Silicone particles D: "Tospearl 150KA" manufactured by Momentive Co., Ltd. (shape of sugar flat sugar having irregularities on the surface, number average particle diameter 5.0 μm),
Lycopodium: manufactured by Sigma-Aldrich Japan Co., Ltd. (spherical surface having irregularities, number average particle diameter of about 40 μm),
Silica particles A: manufactured by Nippon Aerosil Co., Ltd. (AEROSIL RX-300, trimethylsilyl surface, area average particle diameter of about 14 to 17 nm),
Silica particles B: Nippon Aerosil Co., Ltd. product (AEROSIL RY-300, polydimethylsiloxane surface, area average particle diameter of about 21 to 27 nm).

[Production Example 1]
As a shell material, PTFE particles were spread thinly on a petri dish. As a core material, 15 μL of epoxy resin was dropped onto the PTFE particles in the petri dish using a micropipette (Michipet manufactured by Nichiryo Co., Ltd.). After the dropping, the petri dish was vibrated in a plane parallel to the ground to roll the droplets for 30 seconds, and the PTFE particles were adsorbed on the droplet surface of the epoxy resin to prepare core-shell particles. For droplets that did not roll only by vibrating the petri dish, the droplets were rolled using a plastic spoon and core-shell particles were produced.

[Production Example 2]
In Production Example 2, 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 silicone particles A.

[Production Example 3]
In 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 silicone particles D.

[Production 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.

[Production Example 5]
In Production Example 5, 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 silicone particles A.

[Production Example 6]
In Production Example 6, 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 silicone particles B.

[Production Example 7]
In Production Example 7, 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 silicone particles C.

[Production Example 8]
In Production Example 8, 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 silicone particles D.

[Production Example 9]
In Production Example 9, 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 lycopodium.

[Production Example 10]
2.8 g of RX-300 was weighed with an electronic balance in a stirring vessel of a mixer (type Labo Milser LM-PLUS rotation speed 20,000 rpm, Osaka Chemical Co., Ltd.), and an epoxy resin aqueous solution (epoxy resin concentration: 20% by mass) was placed therein. Core shell particles were prepared by adding 25 g and stirring with a mixer for 5 seconds.

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

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

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

(Stability evaluation of core-shell particles)
The stability of the core-shell particles of each production example was confirmed when the core-shell particles were transferred onto a glass plate with a plastic spoon and allowed to stand at room temperature (23°C). The results are shown in Table 1.

(Measurement of contact angle)
The shell material used in each production example was uniformly spread on a flat surface without a gap, and the core material used in each production example was dropped onto the shell material to form a droplet. After 1 to 2 minutes, the contact angle of the core material on the shell material was measured using a contact angle meter (“SIimage02” manufactured by Excimer). The results are shown in Table 1.

(Evaluation of contact stability of core-shell particles)
When one core-shell particle of Production Example 2 and one core-shell particle of Production Example 5 were brought into contact with each other on a glass plate and allowed to stand at room temperature (23° C.), both core-shell particles were found within 5 minutes. United.

  One core-shell particle of Production Example 2 and one core-shell particle of Production Example 6 were brought into contact with each other on a glass plate and allowed to stand at room temperature (23°C). After 24 hours, both core-shell particles existed stably without coalescence and could be separated well. Also, when both core-shell particles were split with a bamboo skewer, it was confirmed that the core material inside was liquid. This indicates that the epoxy resin as the core material and the PEI are not in contact with each other.

<Preparation of core-shell particle mixture and its stability evaluation>
[Example 1]
The core-shell particles of Production Example 2 and the core-shell particles of Production Example 5 were mixed at a number ratio of 1:1 to obtain a core-shell particle mixture.

[Example 2]
The core-shell particles of Production Example 2 and the core-shell particles of Production Example 6 were mixed at a number ratio of 1:1 to obtain a core-shell particle mixture.

[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 was a powdery core-shell particle aggregate (dry liquid) that satisfactorily flows. When this core-shell particle mixture was allowed to stand at room temperature (23° C.), there was no change in fluidity even after 24 hours, and it existed stably.

(Adhesion evaluation of core-shell particle mixture)
The core-shell particle mixture of Example 1 was sandwiched between glass plates (“S7213” manufactured by Matsunami Glass Industry Co., Ltd.), stress was applied from the upper surface side of the glass plates to crush the core-shell particles, and the internal epoxy resin and PEI were added. Were mixed. The mixed liquid was a white paste-like liquid. When the glass plate on the upper side was pulled after standing for 1 hour at room temperature (23° C.), the glass plate moved a little but was fixed. When the upper glass plate was pulled after standing for 4 hours, the glass plate did not move at all and was completely fixed.

  The core-shell particle mixture of Example 2 was sandwiched between glass plates (“S7213” manufactured by Matsunami Glass Industry Co., Ltd.), stress was applied from the upper surface side of the glass plates to crush the core-shell particles, and the internal epoxy resin and PEI were added. Were mixed. The mixture was a translucent liquid. When the glass plate on the upper side was pulled after standing for 1 hour at room temperature (23° C.), the glass plate moved a little but was fixed. When the upper glass plate was pulled after standing for 4 hours, the glass plate did not move at all and was completely fixed.

  The core-shell particle mixture of Example 3 was sandwiched between glass plates (“S7213” manufactured by Matsunami Glass Industry Co., Ltd.), stress was applied from the upper surface side of the glass plates to crush the core-shell particles, and the internal epoxy resin and PEI were added. Were mixed. The mixed liquid was 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 moved a little but was fixed. When the upper glass plate was pulled after standing for 4 hours, the glass plate did not move at all and was completely fixed.

Claims (14)

A multi-component adhesive formed from a core-shell particle mixture,
The core-shell particle mixture is
First core-shell particles composed of a first core containing a first substance and a first shell coating the first core;
A second core-shell particle composed of a second core containing a second substance having reactivity with the first substance and a second shell covering the second core ; Including,
The first substance includes a polymerizable compound,
The second substance includes a polymerization reagent,
A multi-component adhesive, wherein the first shell and the second shell are layers composed only of a plurality of solid particles. The adhesive is an epoxy resin adhesive,
The multi-component adhesive according to claim 1, wherein the solid particles are one or more selected from the group consisting of silicone particles, inorganic fine particles, and fluorine-based resin fine particles. The multi-component adhesive according to claim 2, wherein the inorganic fine particles are silica particles. The polymerizable compound is an epoxy resin,
The multi-component adhesive according to any one of claims 1 to 3, wherein the polymerization reagent is a curing agent. The first shell and the second shell are layers composed of aggregates of the solid particles,
The multi-component adhesive according to claim 1, wherein the solid particles include fine particles having a number average particle diameter of 5 nm or more and 500 μm or less. The multi-component adhesive according to any one of claims 1 to 5, wherein the multi-component adhesive is a two-component adhesive. The first core-shell particle is capable of releasing the first substance to the outside of the first shell by applying a stress,
The multi-component according to claim 1, wherein the second core-shell particles can release the second substance to the outside of the second shell by applying stress. Mold adhesive . At least one of the first substance and the second substance is a liquid substance,
The multi-component adhesive according to any one of claims 1 to 7 , wherein the liquid substance has a contact angle on the solid particles of 90° or more. A reaction between a first substance and a second substance having reactivity with the first substance , which is contained in the multi-component adhesive according to any one of claims 1 to 8. A method of manufacturing a product,
A method of manufacturing, comprising the step of applying stress to the multi-component adhesive . The stress is 1 to 1000 kN/m ^Two The manufacturing method according to claim 9, wherein A step of adjusting the content ratio of the first substance and the second substance in the core-shell particle mixture by adjusting the number average particle diameters of the first core-shell particles and the second core-shell particles. The manufacturing method according to claim 9 or 10 , further comprising: A mixing ratio of the first core-shell particles and the second core-shell particles, or a content of the first substance in the first core-shell particles and a content of the second substance in the second core-shell particles The method according to any one of claims 9 to 11 , further comprising a step of adjusting a content ratio of the first substance and the second substance in the core-shell particle mixture by adjusting a ratio of. The manufacturing method described. Arranging the multi-component adhesive according to any one of claims 1 to 8 on the surface of the first member,
And the step of providing a stress before Symbol adhesive,
And a step of laminating the second member onto the placement plane before SL adhesive of said first member, the manufacturing method of the laminate. Step of providing a stress before SL adhesive, giving a stress to the first core-shell particles, after to release the first of the first material out of the shell, the stress on the second core-shell particles The method for manufacturing a laminate according to claim 13 , further comprising the step of: supplying the second substance to release the second substance to the outside of the second shell.

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