CN107429124A - Core-shell particles mixture, adhesive, the manufacture method of the manufacture method of reactant and layered product - Google Patents
Core-shell particles mixture, adhesive, the manufacture method of the manufacture method of reactant and layered product Download PDFInfo
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- CN107429124A CN107429124A CN201680010795.1A CN201680010795A CN107429124A CN 107429124 A CN107429124 A CN 107429124A CN 201680010795 A CN201680010795 A CN 201680010795A CN 107429124 A CN107429124 A CN 107429124A
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- Prior art keywords
- core
- shell particles
- shell
- adhesive
- stress
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
The application provides a kind of core-shell particles mixture, it contains the 1st core-shell particles and the 2nd core-shell particles, 1st core-shell particles are made up of the 1st core containing the 1st material with coating the 1st shell of the 1st core, and the 2nd core-shell particles are made up of the 2nd core containing the 2nd material to the 1st material with reactivity with coating the 2nd shell of the 2nd core；1st shell and the 2nd shell contain solids.
Description
Technical field
The present invention relates to the manufacture method of core-shell particles mixture, adhesive, the manufacture method of reactant and layered product.
Background technology
Typically, adhesive can be categorized as dry solidification type adhesive, chemical reaction type adhesive, hot melt according to curing
Melt type adhesive and Pressuresensitive Adhesive.Dry solidification type adhesive refer to by the evaporation of water or solvent in adhesive and
The adhesive solidified.Chemical reaction type adhesive refers to by the chemical reaction of liquefied compound the bonding that is solidified
Agent.As the adhesive of chemical reaction type adhesive, can enumerate by the reaction of host and curing agent the adhesive, logical that solidifies
The adhesive, viscous and what is solidified by obstructing air crossed host and solidified by the reaction of the moisture (moisture) on jointing material surface
Mixture, by irradiating ultraviolet adhesive for solidifying etc..Hot-melt type adhesive refers to be at normal temperatures solid-like, bestows heat
After be changed into liquid, the adhesive for being cooled to and fastening.Pressuresensitive Adhesive refers to keep by the cohesive of adhesive and quilt
The adhesive of the intensity of adherend.
Prior art literature
Non-patent literature
Non-patent literature 1：Bonding association of Japan writes《Towards the adhering technique reader of professional person》(プロをめざす
People め then skill Intraoperative textbooks), Nikkan Kogyo Shimbun, in June, 2009 distribution
The content of the invention
The invention problem to be solved
For example, multicomponent type reaction reagent as 2 liquid type adhesives being made up of host and curing agent, in operability side
The problem of following be present in face.
(a) directly can not be touched when operating with hand.
(b), it is necessary to which each composition is disposed with the state being kept completely separate untill when actually using reaction reagent.
(c) in complicated minute sites, it is difficult to optionally bond desired position.For example, glued with common 2 liquid type
Mixture, it is difficult to only engaged to the deep inside of microcapillary.Even if in addition, being capable of the deep internal of conjugation tube, reach inside depth
Also adhesive can be adhered on pipe before.
It is an object of the present invention to provide a kind of multicomponent type reaction reagent for example as 2 liquid type adhesives, and it is behaviour
The excellent reaction reagent of the property made.
Solves the technological means of problem
The present invention provides core-shell particles mixture as shown below.
[1] a kind of core-shell particles mixture, it contains the 1st core-shell particles and the 2nd core-shell particles, the 1st core-shell particles by containing
The 1st core for having the 1st material is formed with the 1st shell for coating the 1st core, and the 2nd core-shell particles are by containing to the 1st material
2nd core of the 2nd material with reactivity is formed with coating the 2nd shell of the 2nd core；1st shell and the 2nd shell contain
There are solids.
[2] the core-shell particles mixture described in [1], the 1st material contain polymerizable compound, and the 2nd material contains
There are poly- agents.
[3] the core-shell particles mixture described in [1] or [2], by applying stress to the 1st core-shell particles, can incite somebody to action
, can be by the 2nd material by applying stress to the 2nd core-shell particles outside 1st substance release to the 1st shell
Outside release to the 2nd shell.
[4] the core-shell particles mixture described in any one of [1]~[3], the 1st material and the 2nd material
At least any one be liquid, contact angle of the liquid on the solids be more than 90 °.
The present invention provides adhesive as shown below.
[5] a kind of adhesive formed as the core-shell particles mixture described in any 1 of [1]~[4].
The present invention provides the manufacture method of the reactant of the 1st material as shown below and the 2nd material.
The manufacture method of the reactant of [6] the 1st materials and the 2nd material, the 2nd material have reactivity to the 1st material,
The manufacture method contains to be applied to the core-shell particles mixture described in any 1 of [1]~[4] or the adhesive described in [5]
Add the process of stress.
[7] manufacture method described in [6], it further contains following process：By adjust the 1st core-shell particles and
The number average bead diameter of 2nd core-shell particles, to adjust the 1st material in the core-shell particles mixture and the 2nd thing
The containing ratio of matter.
[8] manufacture method described in [6] or [7], it further contains following process：By adjusting the 1st nucleocapsid
The content of the 1st material in the mixing ratio of particle and the 2nd core-shell particles, or the 1st core-shell particles and institute
The ratio between content of the 2nd material in the 2nd core-shell particles is stated, to adjust the 1st thing in the core-shell particles mixture
Matter and the containing ratio of the 2nd material.
[9] manufacture method described in any one of [6]~[8], the reactant are the reactants of adhesive.
The present invention provides the manufacture method of layered product as shown below.
[10] a kind of manufacture method of layered product, it contains following process：In any of surface configuration [1]~[4] of the 1st component
The process of the adhesive described in core-shell particles mixture or [5] described in 1；To the core-shell particles mixture or described
The process that adhesive applies stress；It is laminated on the core-shell particles of the 1st component or the configuration face of described adhesive
The process of 2nd component.
[11] manufacture method of the layered product described in [10], the core-shell particles mixture or described adhesive are applied
The process of stress includes following process：Stress is applied to the 1st core-shell particles, makes the 1st substance release to the 1st shell
Outside after, to the 2nd core-shell particles apply stress, make outside the 2nd substance release to the 2nd shell.
The effect of invention
According to the present invention it is possible to provide a kind of multicomponent type reaction reagent for example as 2 liquid type adhesives, it is operation
The excellent reaction reagent of property.
Brief description of the drawings
[Fig. 1] is the figure of one for showing silicone particle structure.
Embodiment
[core-shell particles mixture]
Core-shell particles mixture in one embodiment of the present invention contains the 1st core-shell particles and the 2nd core-shell particles, and the described 1st
Core-shell particles are made up of the 1st shell of the 1st core containing the 1st material and cladding the 1st core, the 2nd core-shell particles by containing
2nd core to the 1st material with the 2nd material of reactivity is formed with the 2nd shell for coating the 2nd core；1st shell with
And the 2nd shell contains solids.Hereinafter, have and the solids contained in the 1st shell are referred to as " the 1st solids ", by the 2nd
The solids contained in shell are referred to as the situation of " the 2nd solids ".
As the occupation mode of core-shell particles mixture, the mixture being for example made up of using these core-shell particles can be enumerated
Mode, use further mode of the mixture containing other compositions etc. in addition to these core-shell particles mixtures.Nucleocapsid
Other compositions beyond particle can be not the 1st material and/or the thing of the 2nd substance reaction with containing in core-shell particles
Matter.Core-shell particles mixture can be configured to desired place and be used.The present invention is described in detail below.
(1) core-shell particles
1st core-shell particles and the 2nd core-shell particles (below as this word is included, being also denoted as " core-shell particles ") are generally
It is spherical in atmospheric pressure or oblate spheroid.But particle diameter it is relatively small when, core-shell particles can be non-spherical.Core-shell particles
In mixture, the 1st core-shell particles and the 2nd core-shell particles do not react each other when not being applied in stress, but by being applied
Add stress, respective shell produces crack or shell avalanche, form the 1st material of core and the 2nd material be released into respectively shell it
Outside.Accordingly, can produce the reaction between the 1st material and the 2nd material.
In core-shell particles, the surface of core is coated by the shell containing solids.Shell is typically by multiple solids structures
Into layer, the monolayer being e.g. made up of the solids of a Rotating fields or be made up of the agglutination body of solids
Layer.Shell preferably coats core without more than 500 μm of gap, more preferably without more than 100 μm of gap by core bag
Cover, further preferably coat core without more than 5 μm of gap.
When observing 1 core-shell particles, based on the viewpoint of operability, maximum particle diameter preferably more than the 20 μm 50mm of core-shell particles
Hereinafter, more preferably more than 50 μm below 50mm.Further preferred more than 500 μm, particularly preferred more than 1mm.In addition, core-shell particles
Maximum particle diameter further preferred below 30mm, most preferably particularly preferred below 20mm, below 5mm.Maximum particle diameter refers to nucleocapsid
The maximum particle diameter of particle, it is the value determined by micro- sem observation, ruler or slide measure., can during using measurement microscope
So that using equivalent diameter as particle diameter, the image as obtained from micro- sem observation to be solved with software of digit microscope etc.
Analyse and determine.
The viewpoint of stability based on the core-shell particles in atmospheric pressure, preferably 20 μm of the number average bead diameters of the 1st core-shell particles with
Upper below 50mm, more preferably more than 50 μm below 50mm, further preferred more than 500 μm below 40mm, particularly preferred 800 μm with
Upper below 30mm.The viewpoint of stability based on the core-shell particles in atmospheric pressure, preferably 20 μm of the number average bead diameter of the 2nd core-shell particles
Below above 50mm, more preferably more than 50 μm below 50mm, further preferred more than 500 μm below 40mm, particularly preferred 800 μm
Below above 30mm.The value that number average bead diameter is e.g. tried to achieve by the equivalent diameter obtained via microscopic method, Ke Yitong
Cross and determined being parsed as the image obtained by micro- sem observation with software of digit microscope etc..As digit microscope
The example of software, such as have Motic Images Plus 2.2s ((strain) Shimadzu physics and chemistry system).As microscope, electronics can be enumerated
Microscope or light microscope etc., as long as being properly selected according to the solids used.As long as multiplying power root during observation
According to the particle diameter of the solids used, properly select.
During by microscope Observe and measure number average bead diameter, multiple micro- sem observation figures for including multiple core-shell particles are shot
Picture, 50 core-shell particles are randomly choosed from the multiple images obtained, are averaged when determining these particle diameters, 50 particle diameters
Value is used as number average bead diameter.When the particle diameter of all core-shell particles is larger more than 100 μm, the particle diameter of core-shell particles can also make
Determined with ruler.It is when now, to determine the particle diameter of randomly selected 50 core-shell particles using ruler, 50 particle diameters flat
Average is number average bead diameter.In addition, core-shell particles mixture involved in the present invention includes the 1st core-shell particles and/or the 2nd nucleocapsid
The number of particle is less than the situation of 50, but the number average bead diameter of the situation, except " 50 " in said determination method are replaced
For " core-shell particles that contain in core-shell particles mixture (the 1st core-shell particles of measure number average bead diameter when be the 1st core-shell particles, survey
Be the 2nd core-shell particles during the number average bead diameter of fixed 2nd core-shell particles) sum " outside, determine number identically with said determination method
Equal particle diameter.
Observe 1 core-shell particles when, based on operability viewpoint, preferred more than 4fL below the 6mL of volume of core-shell particles,
More preferably below 16 μ L above 6mL.Volume further preferred more than the 40 μ L, particularly preferred more than 60 μ L of core-shell particles.In addition,
Volume further preferred below the 4mL, particularly preferred below 3mL of core-shell particles.
By applying stress to the 1st core-shell particles and the 2nd core-shell particles, the 1st material and the 2nd thing can be discharged respectively
Matter.Stress intensity properly selects according to the purposes of core-shell particles mixture or its general processing method.Put on nucleocapsid
The stress intensity of particle, it can be the same or different for the 1st core-shell particles and the 2nd core-shell particles.Below sometimes will be to the 1st
Stress necessary to the 1st material is discharged outside shell is referred to as " the 1st stress ", will be required to the 2nd material institute is discharged outside the 2nd shell
Stress be referred to as " the 2nd stress ".The size of 1st and the 2nd stress can pass through species, the shape of the solids for adjusting composition shell
Shape and size, the viscosity of core, the material of core is formed relative to the contact angle of solids and the average thickness of shell for forming shell
Degree etc. controls.
The stress for putting on core-shell particles is preferably the size that applied degree is crushed with the finger of the mankind.Specifically,
1st and the 2nd stress is preferably sized to 1~1000kN/m2, more preferably 5~100kN/m2.If such scope, such as
After core-shell particles are configured at into desired place, by applying stress, it is possible to relatively easily discharge the 1st material and the
2 materials.Such core-shell particles are easy to crush, and are difficult to crush when configuring, and its operability becomes good.Above-mentioned 1st and
When 2nd stress is too small, there is the worry for discharging the 1st material or the 2nd material unintentionally.It is therefore preferable that it is less than 1kN/m2Stress
When crack or the avalanche of shell do not occur.In addition, when applying stress to core-shell particles, the configuration face of core-shell particles can be applied and hung down
Straight stress, it can also apply shear stress or rotation stress.When applying shear stress or rotation stress, the 1st material and the 2nd thing
Matter is easy to be released into outside shell.In addition, the direction that the set direction of shear stress or rotation stress is appropriate.
Based on the viewpoint of operability, the 1st core-shell particles and the 2nd core-shell particles are preferably before stress is applied, Huo Zheshi
The stress added is less than 1kN/m2When, shell will not avalanche and keep core shell structure.Before applying stress, or the stress applied is less than
1kN/m2When core shell structure preferably more than 10 minutes retention time, more preferably more than 1 hour, further preferred 24 hours with
On.
Based on the viewpoint of operability, the 1st core-shell particles are with the 2nd core-shell particles preferably in the state for not applying stress and contacting
Under, do not integrate, keep core shell structure respectively.Core-shell particles keep nucleocapsid when being contacted between each other not being applied in stress
The time of structure, preferably more than 10 minutes, more preferably more than 1 hour, further preferred more than 24 hours.
(2) core
1st core contains the 1st material.2nd core contains the 2nd material.1st material and the 2nd material can be applied in combination with reactivity
And the material of reaction of formation thing.For example, using polymerizable compound as the 1st material, the 2nd material is used as using poly- agents
When, it can obtain polymer as reactant.Reactant can be solid, gel, gel drying thing, thick liquid it is any.
1st material and the 2nd material can be made up of a kind of compound respectively, can also be made up of compound of more than two kinds.
As polymerizable compound, polymerizable monomer, polyreactive oligomerses, polymerizable polymer etc. can be used.Specifically
Ground, epoxy resin (diglycidyl ether type, glycidyl ester type, glycidic amine type, ester ring type), multifunctional methyl-prop can be enumerated
Olefin(e) acid ester, acrylic monomers, polyalcohols (PEPA, PPG, polycarbonate polyol, polytetramethylene two
Alcohol, low-molecular-weight diol), two end hydroxyl silicone oil, containing vinyl silicone oil, urea, formaldehyde, melamine, phenol, isophthalic two
Phenol, resol, resorcinol, alpha-olefin, maleic anhydride, maleic anhydride imide, vinyl acetate monomer, polyester,
Neoprene, acrylonitrile-butadiene copolymer, SB, polyvinyl alcohol, butyl rubber, sodium alginate,
Natural rubber etc..
Poly- agents can be polymerization catalyst or reaction promoter or the material with the 1st polymerization.
As poly- agents, can use such as polymerization initiator, curing agent, crosslinking agent (including vulcanizing agent).Tool
Body, polyethyleneimine, secondary amine, tertiary amine, primary amine, dicyandiamide, imidazoles, tertiary ammonium salt, lewis acid, ketimide type can be enumerated
Latent curing agent, hydrogen peroxide, cumyl hydroperoxide, dibenzoyl peroxide, redox type initiator, acid anhydrides, have
Machine metal salt, polyisocyanate compounds, hydrolysable silanes, hydrogen containing siloxane, end have methyl dimethoxy epoxide silicon substrate
PPOX (modified silicone), ammonium chloride, calcium hydroxide, vulcanizing agent (sulphur) etc..
As the example of the combination of the 1st material and the 2nd material, citing below shows adhesive.In addition, following " C：A/B”
Symbol refer to containing containing the 1st material and the multicomponent type reaction reagent of the 2nd material, i.e. multicomponent type adhesive shown in C
A as the 1st material, the B as the 2nd material.In addition, when recording materials more than 2 species in A and B respective column, can
Suitably to select at least one use therein.
Epoxy resin adhesive：Epoxy resin/polyethyleneimine, tertiary amine, secondary amine, primary amine, dicyandiamide, imidazoles, uncle
Amine salt, lewis acid, ketimide type latent curing agent
Anaerobic adhesive：Multifunctional methacrylate/hydrogen peroxide
2nd generation acrylic acid (SGA) is adhesive：Acrylic monomers/cumyl hydroperoxide, dibenzoyl peroxide, You Jijin
Belong to salt
Polyurethane resin system adhesive：Polyalcohols/polyisocyanate compounds
Silicone resin system adhesive：Two end hydroxyl silicone oil/hydrolysable silanes
Silicone resin system adhesive：Containing vinyl silicone oil/hydrogen containing siloxane
Modified silicone resin system adhesive：Epoxy resin/end has the PPOX (modified silicon of methyl dimethoxy epoxide silicon substrate
Ketone)
Urea resin system adhesive：Urea, formaldehyde/ammonium chloride
Melmac system adhesive：Melamine, urea, phenol, formaldehyde/ammonium chloride
Phenolic resin system adhesive：Phenol, formaldehyde/alkali (sodium hydroxide)
Resorcinol system adhesive：Resorcinol, formaldehyde, resol, resorcinol/alkali (sodium hydroxide)
Alpha-olefin system adhesive：Alpha-olefin, maleic anhydride, maleic anhydride imide/calcium hydroxide
Vinyl acetate emulsion adhesive：Vinyl acetate monomer/organic peroxide (cumyl hydroperoxide, peroxidating two
Benzoyl)
Urethane elastomers system adhesive：Polyester/PIC
Neoprene system adhesive：Neoprene/PIC
Itrile group elastomeric adhesive：Acrylonitrile-butadiene copolymer/crosslinking agent (sulphur)
SBR styrene butadiene rubberses system adhesive：SB/crosslinking agent (sulphur)
Butyl rubber system adhesive：Butyl rubber/crosslinking agent (sulphur)
Natural rubber system adhesive：Natural rubber/crosslinking agent (sulphur)
Calcium chloride system adhesive：Sodium alginate aqueous solution/calcium chloride water
In above-mentioned A and B combination, the viewpoint based on operability and practicality, is " epoxy resin/poly- second preferably using A/B
Alkene imines, tertiary amine, secondary amine, primary amine, dicyandiamide, imidazoles, tertiary ammonium salt, lewis acid, ketimide type latent curing agent "
Epoxy resin adhesive, and A/B are " acrylic monomers/cumyl hydroperoxide, dibenzoyl peroxide, organic metal
The 2nd generation acrylic acid (SGA) of salt " is adhesive.In this way, when the 1st material and when being combined as adhesive of the 2nd material, can make
Adhesive is used as by the use of core-shell particles mixture.
When 1st material and the 2nd material are respectively liquid, using the total amount of the 1st core or the 2nd core as 100 mass %, in core
The content of 1st material and the 2nd material difference is preferably more than 10 mass %, more preferably more than 50 mass %, further preferred 80 matter
Measure more than %, most preferably particularly preferred more than 90 mass %, 100 mass %.Herein, the 1st material in core or the 2nd material contain
Measure and refer to for 100 mass %, such as the 1st core is made up of the 1st material.When 1st material and the 2nd material are solid, with the 1st core or
The total amount of 2nd core is 100 mass %, the content of the 1st material and the 2nd material in core 90 matter preferably more than 10 mass % respectively
Measure below %, more preferably more than 30 mass % below 90 mass %, further preferred below the mass % of more than 50 mass % 80.This
Place, the content of these materials when the 1st material and the 2nd material are solid refer to that the 1st material or the 2nd material are relative to the 1st
Material either the 2nd material and makes these materials dissolve or the ratio of the total amount of scattered etc. water or solvent.As long as core can be formed
Shell particles, it can also contain other compositions in addition to the 1st material or the 2nd material in core.
(3) shell
Shell is the thing containing solids and cladding core.Shell is preferably made up of the agglutination body of solids.It is preferred that shell with without
More than 500 μm of cladding core with gap, more preferably without more than 100 μm of cladding core with gap, further preferably without 5
Cladding core with gap more than μm.The content of solids in shell is preferably more than 90 mass %, more preferably more than 95 mass %,
Further preferred 100 mass %.
The 1st solids for being preferably formed as the 1st shell, the 2nd solids for forming the 2nd shell contain the μ of number average bead diameter 500 respectively
Below m particulate is as principal component.1st solids and the 2nd solids further preferably 50~100 mass % number are equal
Particulate below 500 μm of particle diameter, further preferably 70~100 mass %, particularly preferably containing 90~100 mass %.
The contact angle of core forming material on 1st solids of set, containing the 1st material, and the 2nd of set are solid
The contact angle of core forming material on body particle, containing the 2nd material, usually more than 90 °, preferably more than 100 ° are more excellent
Elect more than 110 °, more preferably more than 120 ° as.In addition, the contact angle is preferably less than 170 °, more preferably 160 ° with
Under.By the way that with such contact angle, forming the solids of shell and the absorption of core forming material becomes easy, in addition, nucleocapsid
The dimensional stability of particle improves, so it is preferred that.When contact angle is less than 90 °, the core containing the 1st material or the 2nd material be present
Forming material is infiltrated through in multiple shell material solids so that the formation of core-shell particles becomes difficult worry.Herein, karyomorphism into
Material refers to, for determining used in contact angle, with the material with core same composition.Thus, for example the 1st core is by the 1st thing
Texture into when, the contact angle is the contact angle of the 1st material on the 1st solids, and the 1st core is by the 1st material and other compositions structure
Cheng Shi, the contact angle are the contact angles of the 1st core on the 1st solids.
Based on it is same as described above the reasons why, when the 1st material is liquid, the 1st material on the 1st solids of set
Contact angle be usually more than 90 °, preferably more than 100 °, more preferably more than 110 °, more preferably more than 120 °.This
Outside, the contact angle is preferably less than 170 °, more preferably less than 160 °.Based on it is identical the reasons why, when the 2nd material is liquid,
The contact angle of the 2nd material on 2nd solids of set is usually more than 90 °, preferably more than 100 °, more preferably 110 °
More than, more preferably more than 120 °.In addition, the contact angle is preferably less than 170 °, more preferably less than 160 °.
It is on the solids of set, core forming material contact angle to be determined as follows：By solids equably continuously
Unoccupied place expand into it is plane, using contact angle meter (エ キ シ マ societies " SImage 02 "), measure try to achieve karyomorphism thereon into
The contact angle of material.
Solids (the 1st and the 2nd solids) are preferably the particulate for not having at 30 DEG C bonding force.Solids are more
Preferably less than 40 DEG C, more preferably less than 50 DEG C, do not have the particulate of bonding force more preferably below 80 DEG C.
In this specification, refer to without bonding force, tested and surveyed by the probe initial bonding strength (Probe Tack) of following conditions
The initial bonding strength (Tack) of timing is below 0.1N bonding force.Initial bonding strength, which refers to be tested by the probe initial bonding strength of following conditions, to be carried out
The maximum stress of measure.
＜ condition determinations ＞
Probe initial bonding strength tester：TE-6002 (テ ス タ ー Industry Co., Ltd system)
Make the speed of solids contact detector：10mm/s
Time of contact：30 seconds
Peeling rate：10mm/s
The glass transition temperature (Tg) of solids (the 1st and the 2nd solids) is preferably more than 40 DEG C, more preferably
For more than 50 DEG C, more preferably more than 80 DEG C.When Tg is less than above-mentioned value, exists and cause shell to show by the change of external environment condition
Go out bonding force, operability becomes bad situation.The glass transition temperature (Tg) of solids (the 1st and the 2nd solids)
Means of differential scanning calorimetry measure device can be used to be measured.
The softening temperature of solids (the 1st and the 2nd solids) is preferably more than 40 DEG C, more preferably 50 DEG C with
On, more preferably more than 80 DEG C.When softening temperature is less than above-mentioned value, exists and cause shell to show by the change of external environment condition
Bonding force, operability become bad situation.The softening temperature of solids (the 1st and the 2nd solids) can use automatic
Titration softening point measurement system (such as Mettler Toledo Inc.'s product) is measured.
The decomposition temperature of solids (the 1st and the 2nd solids) is preferably more than 40 DEG C, more preferably 50 DEG C with
On, more preferably more than 80 DEG C.When decomposition temperature is less than above-mentioned value, exists and cause shell to show by the change of external environment condition
Bonding force, and then operability becomes bad situation.The decomposition temperature of solids (the 1st and the 2nd solids) can use
Thermogravimetric measure device is measured.
The number average bead diameter of the above-mentioned particulate contained in solids as principal component generally below 500 μm of more than 5nm,
It is preferred that below 500 μm of more than 10nm, more preferably below 100 μm of more than 10nm, further preferred below 50 μm of more than 20nm.Particulate
Number average bead diameter within the above range when, the stability of the binder granules in air more improves, so it is preferred that.Number average bead diameter
The image obtained by micro- sem observation can be entered by using Motic Images Plus 2.2s ((strain) Shimadzu physics and chemistry system)
Row is parsed and determined.Pass through the more specifically assay method and core-shell particles of the number average bead diameter of the above-mentioned particulate of microscope Observe and measure
Number average bead diameter assay method it is identical.
As solids, the various particulates such as silicone particle, mineral particulates, organic matter particulate can be used.Solid grain
Son can be the combination of particulate of more than two kinds.
Silicone particle refers to, such as particle as shown in Figure 1, and it has the network structure that silicon oxygen bond is connected as three-dimensional shape,
Show be connected with silicon atom 1 methyl between inorganic with organic intermediate structure.
As mineral particulates, can enumerate talcum, clay, kaolin, silica, hydrotalcite, Gui diatomaceous earths, magnesium carbonate,
Barium carbonate, calcium sulfate, calcium carbonate, magnesium sulfate, barium sulfate, barium titanate, aluminium hydroxide, magnesium hydroxide, calcium oxide, magnesia, oxygen
Change titanium, zinc oxide, silica, aluminum oxide, mica, zeolite, glass, zirconium oxide, calcium phosphate, metal (gold, silver, copper, iron), carbon materials
Expect (CNT, fullerene, graphene, graphite) etc..In addition, the surface of these particulates can pass through the surfaces such as silane coupler
Dressing agent, surfactant etc. carry out surface modification.
As organic matter particulate, resin particle, and particulate from natural goods etc. can be enumerated.
As resin particle composition, polystyrene, acrylic acid series, metha crylic, olefin-based, vinyl ketone, third can be enumerated
The copolymer that the autopolymer of the monomers such as alkene nitrile or two or more monomer are polymerized；Polytetrafluoroethylene (PTFE), hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)
The fluorine resins such as copolymer, tetrafluoroethylene-ethylene copolymer, polyvinyladine floride；Melmac；Urea resin；Poly- diformazan
Radical siloxane system macromolecule；Polyester；Polyamide etc..In addition, the surface of these particulates can be repaiied by surfaces such as silane couplers
Adorn agent, surfactant etc. and carry out surface modification.
As described above, solids can be particulate combinations of more than two kinds, it is preferably the combination.The example of combination can arrange
Lift, different combination of particulate of more than two kinds of the combination of the different particulate of more than two kinds of material, material same particle size distribution etc..
The Tg of above-mentioned resin can be adjusted according to the polymerizing condition of monomer ratio etc..
The above-mentioned particulate from natural goods can be enumerated, plant spore, pollen or particulate from native paraffin etc..In addition, these
The surface of particulate can carry out surface modification by the coating materials such as silane coupler, surfactant etc..
Particulate can obtain from market.As commercially available product, can enumerating silicone particle, (Mai Tugao new companies produce
" TOSPEARL 2000B ", " TOSPEARL 1110A ", " TOSPEARL 145A ", " TOSPEARL 150KA "), silica
Particle (" RX-300 ", " RY-300 " of Japanese AEROSIL (strain) production), poly- (tetrafluoroethene) (Sigma-Aldrich companies day
" poly- (tetrafluoroethene) " of this (strain) production etc..
Below 500 μm of preferred more than the 10nm of average thickness of 1st and the 2nd shell, more preferably below 500 μm of more than 100nm.If
Such scope, then the dimensional stability of core-shell particles mixture is high, in addition, shell avalanche can be made by applying appropriate stress,
So it is preferred that.The average thickness of 1st and the 2nd shell can (transmission electron microscope, scanning electron show by electron microscope
Micro mirror) observation be measured.More specifically, the average thickness of shell can cutting by using electron microscope observation core-shell particles
Face, the thickness to determining shell at randomly selected 10.The average thickness of shell refers to the average value of 10 measured values.
(4) manufacture method of core-shell particles
Core-shell particles can be manufactured for example, by following process (1)~(3).
(1) drop containing the 1st material or the 2nd material is made, with solids (the 1st solids or the 2nd solids)
The process of contact；
(2) work for being coated the whole surrounding of the above-mentioned drop containing the 1st material or the 2nd material with above-mentioned solids
Sequence；
(3) arbitrarily make to coat the droplet drying containing the 1st material or the 2nd material formed by solids around whole
Process.
In drop containing the 1st material or the 2nd material, the 1st material or the 2nd material can be directly used, can also be made
With by the 1st material, either the 2nd material is dissolved in the drop that water or solvent form, it is possible to use by the 1st material or the 2nd material
The drop that water or solvent form is scattered in, can also use that either solvent dilutes what the 1st material or the 2nd material formed with water
Drop.
It is when being contacted with solids, contain the 1st material or the 2nd material in the 1st the material either drop of the 2nd material
Content be usually 5~100 mass %, preferably 10~80 mass %, more preferably 20~70 mass %, more preferably
40~60 mass %.Content within the range when, easy to manufacture core-shell particles so it is preferred that.Contain the 1st material or the 2nd material
Drop in the 1st material or the content of the 2nd material refer to, the ratio of the 1st shared material or the 2nd material in the drop
Example, it is typically the concentration of the composition beyond the solvent and water contained in the drop.
The volume of drop containing the 1st material or the 2nd material is preferably more than 4fL below 5mL, more preferably 15 μ L with
Upper below 5mL.The volume of the drop is more preferably more than 30 μ L, particularly preferably more than 50 μ L.In addition, the body of the drop
Product is more preferably below 3mL, particularly preferably below 2mL.By adjusting the drop containing the 1st material or the 2nd material
Volume, the number average bead diameters of core-shell particles can be adjusted.
The method for alloing the drop containing the 1st material or the 2nd material to be contacted with solids is by containing the 1st material
Or the 2nd material the injection such as drop sprayer, or can be added dropwise.
The whole surrounding of drop containing the 1st material or the 2nd material, generally by making containing the 1st material or the 2nd thing
The drop of matter rolls on solids, so as to be coated by solids.
In addition it is also possible to the drop containing the 1st material or the 2nd material is set to be mixed with solids by using agitator etc.
Close and contact with each other, thus with around solids cladding drop.
The drop containing the 1st material or the 2nd material formed around whole by solids cladding, can be allowed to dry
It is dry.When drop containing the 1st material either the 2nd material contains solvent or water, preferably make the droplet drying.In this specification,
" drying " refers to, from by above-mentioned solids cladding form containing in the 1st the material either drop of the 2nd material remove water or
Solvent.Now, water or solvent are preferably completely removed, if but the degree of the effect of the present invention will not be damaged, it can also remain
A little.As drying means, can enumerate in the chemistry and physical property of the 1st material or the 2nd material and solids not
The method stood at a temperature of changing；It is positioned over the method for warm air, hot blast or low wet wind；Vacuum drying method；It is cold
Lyophilized dry method；Irradiate method of infrared ray, far infrared or electron ray etc. etc..Preferably 10~200 DEG C of drying temperature,
More preferably 20~100 DEG C.
The 1st material or the content of the 2nd material contained in dried core-shell particles, usually 10~99.9 matter
% is measured, preferably 10~99 mass %, more preferably 20~98 mass %, more preferably 40~98 mass %, separately enters one
Step is preferably 60~95 mass %.
(5) manufacture method of core-shell particles mixture
Core-shell particles mixture can be by the way that the 1st core-shell particles be mixed to manufacture with the 2nd core-shell particles with desired mixing ratio.
So-called desired mixing ratio is suitably the mixing ratio that the reaction of the 1st material and the 2nd material can be made effectively to carry out.
Multicomponent type reaction examination as core-shell particles mixture can be used as such as 2 liquid type adhesives or 2 liquid type coating
Agent uses.
[adhesive]
One embodiment of the present invention is that core-shell particles mixture is adhesive.The adhesive is preferably multicomponent type adhesive,
Which is equivalent to such as situation for being combined as adhesive of the 1st material and the 2nd material.As the adhesive, such as can enumerate
By applying stress, respective shell avalanche, the 1st material and the 2nd substance reaction discharged and body to core-shell particles mixture
Reveal the mode of bonding force.The adhesive does not have bonding force in the state of no application stress, by applying above-mentioned regulation
Stress and embody bonding force.
Adhesive can while containing core-shell particles mixture also containing adhesive in the other compositions that typically use.
As other compositions, metal particle, metal oxide microparticle can be enumerated, electrically conductive microparticle, ionic conductivity composition, had
The ionic compound of machine cation or anion, silane coupler, crosslinking catalyst, weathering stabilizers, tackifier, plasticising
The light diffusing particulates such as resin and organic bead beyond agent, softening agent, dyestuff, pigment, inorganic filler, above-mentioned polymer
Deng.Other compositions can contain at least any one party in the 1st core-shell particles and the 2nd core-shell particles.Or other into
It point can be the constituent of another adhesive different from the 1st core-shell particles and the 2nd core-shell particles.
Because core-shell particles mixture is untill stress is applied in, do not discharged from core-shell particles the 1st material and
2nd material, therefore be easy to fill uniformly with the gap of the engaged component of more than 2.Can be uniform by core-shell particles mixture
, can be by the 1st material and the 2nd when applying stress to core-shell particles mixture when ground is filled in the gap between engaged component
Material is unrolled evenly among gap, in desired engagement field, can obtain good bonding force.
The adhesive formed by core-shell particles mixture goes for automobile using adhesive, building materials adhesive, bearing
Installation, pipe arrangement is fixed, screw locks, gear or propeller are fixed and the assembling of furniture etc..
[manufacture method of reactant]
The manufacture method of the reactant of 1st material and the 2nd material, comprising to above-mentioned core-shell particles mixture or above-mentioned adhesive
Apply the process of stress.When applying stress to above-mentioned core-shell particles mixture or above-mentioned adhesive, shell produces crack or collapsed
Collapse, discharge the 1st material and the 2nd material respectively from the 1st and the 2nd core-shell particles, and then the 1st material contacts with the 2nd material.
Accordingly, the 1st material and the 2nd substance reaction, reaction of formation thing.As needed, in order to promote to react, core-shell particles mixture is applied
After adding stress, it can also be heated, light irradiation etc..Above-mentioned reactant is preferably the anti-of adhesive (multicomponent type adhesive etc.)
Answer thing.
Blending ratio (containing ratio namely the 1st material and of the 1st material and the 2nd material in core-shell particles mixture
The reacting dose ratio of 2 materials) it can be adjusted by adjusting the number average bead diameter of the 1st core-shell particles and the 2nd core-shell particles.Core
The adjustment of the number average bead diameter of shell particles, the 1st material or the 2nd thing can be contained by being adjusted in the manufacturing process of core-shell particles
The size of the drop of matter is carried out.
In addition, the blending ratio (containing ratio) of the 1st material and the 2nd material in core-shell particles mixture, can pass through
The mixing ratios of the 1st core-shell particles and the 2nd core-shell particles is adjusted to be adjusted.
In addition, the blending ratio (containing ratio) of the 1st material and the 2nd material in core-shell particles mixture, can also lead to
The ratio between content and the content of the 2nd material in the 2nd core-shell particles of the 1st material crossed in the 1st core-shell particles of adjustment is adjusted
It is whole.
[manufacture method of layered product]
Layered product can be manufactured by following process (1)~(3).
(1) (it is also denoted as below in the above-mentioned core-shell particles mixture of surface configuration of the 1st component or the process of above-mentioned adhesive
" arrangement step ")；
(2) process for applying stress to above-mentioned core-shell particles mixture or above-mentioned adhesive (is also denoted as " stress application work below
Sequence ")；
(3) process of the 2nd component is laminated on the above-mentioned core-shell particles of above-mentioned 1st component or the configuration face of above-mentioned adhesive
(being also denoted as below " lamination process ").
Stress applying step and the order of lamination process are not limited, and stacking work can be carried out after stress applying step
Sequence, stress applying step can be also carried out after lamination process.
In arrangement step, it is not particularly limited in the method for the surface configuration core-shell particles mixture of the 1st component, such as can be with
It is manually operated (being configured by hand, tweezers), can also be configured using air-supply, it is possible to use the inflow such as funnel is carried out
Configuration.
The situation that lamination process is carried out after stress applying step is illustrated.To being configured on the surface of the 1st component
Core-shell particles mixture or adhesive apply stress, preferably on core-shell particles mixture or adhesive configure peel off
Material, apply the method for stress from the stripping material.By applying stress, shell produces crack, respectively from the 1st and the 2nd nucleocapsid grain
Son discharges the 1st material and the 2nd material, the 1st material immediately with the 2nd substance reaction.I.e., it is possible on the surface of the 1st component
Deploy the reactant of the 1st material and the 2nd material.Then, remove after peeling off material, in the core-shell particles mixture of the 1st component
Or the 2nd component is laminated on the configuration face (that is, the configuration face of reactant) of adhesive.Accordingly, the 1st component and the 2nd component across
Reactant and be laminated.When reactant is the reactant of adhesive, the 1st component is well secured with the 2nd component.In addition, remove stripping
After material, when not being laminated 2 component, the film being made up of reactant can be formed on the surface of the 1st component.
Herein, the reactant with the 1st material and the 2nd material refers to, reactant after the 1st material and the 2nd substance reaction,
Mixture (reaction of the reactant with the mixture of unreacted 1st material and the 2nd material, with the 1st material and the 2nd material
State before progress) in arbitrary substance.
The situation that stress applying step is carried out after lamination process is illustrated.Mixed in the core-shell particles of the 1st component
It is laminated on the configuration face of thing or adhesive after the 2nd component, the 1st component is connect with the 2nd component with face facing each other
Contact to earth and apply stress, apply stress to core-shell particles mixture or containing its adhesive.Accordingly, shell produces crack, respectively
Discharge the 1st material and the 2nd material from the 1st and the 2nd core-shell particles, the 1st material immediately with the 2nd substance reaction.I.e., it is possible to
Between the 1st component and the 2nd component, deploy the reactant of the 1st material and the 2nd material.Reactant is the reactant of adhesive
When, the 1st component is fixed well with the 2nd component.
The solids of the formation shell of core-shell particles generally maintain shape and size in reactant.Accordingly, there exist
Feelings of the particle diameter of solids equivalent to the minimum value of the thickness for the layer that the reactant by being formed on the surface of the 1st component is formed
Condition.Therefore, by adjusting the number average bead diameter of solids, the thickness of the reaction layer formed on the surface of the 1st component can be adjusted
Degree.
Stress applying step preferably comprises following process：Stress is applied to the 1st core-shell particles, makes the 1st substance release to the 1st
After outside shell, stress is applied to the 2nd core-shell particles, the 2nd substance release is gone out to outside the 2nd shell.Accordingly, it is easy to equably mix
1st material and the 2nd material.Such as by making the average grain diameter of the 1st core-shell particles be more than the average grain diameter of the 2nd core-shell particles, can
To apply stress to the 1st core-shell particles in core-shell particles mixture prior to the 2nd core-shell particles.
Of course, it is possible to apply stress to the 1st core-shell particles and the 2nd core-shell particles simultaneously, can also be applied to the 2nd core-shell particles
After adding stress, then stress is applied to the 1st core-shell particles.
In addition, layered product can also be manufactured by following process (4)~(8).
(4) separated from core-shell particles mixture by the 1st core-shell particles and the 2nd core-shell particles, the 1st core-shell particles are configured the 1st
Process in component surface；
(5) stress is applied to the 1st core-shell particles, makes the process outside the 1st substance release to the 1st shell；
(6) on the face for discharging the 1st material of the 1st component, the process of the 2nd core-shell particles of configuration；
(7) on the face for discharging the 1st material of the 1st component, the process of the 2nd component of stacking；
(8) stress is applied to above-mentioned 2nd core-shell particles, makes the process outside the 2nd substance release to the 2nd shell.
The order of process (7) and process (8) is not particularly limited, and process (8) can be carried out after process (7), also may be used
To carry out process (7) after process (8).
Embodiment
It is described below to cross embodiment and comparative example, the present invention is described in further detail, but the present invention is not
It is defined in these examples.
The making ＞ of ＜ core-shell particles
The reagent used in the making of core-shell particles is as follows.
Epoxy resin：Nagase ChemteX (strain) productions " Denacol EX-810 " (ethylene glycol diglycidylether,
Viscosity 20mPas)
Curing agent：With " polyethyleneimine " (weight average molecular weight of Wako Pure Chemical Industries (strain) production：600th, it is also denoted as below
“PEI”。)
Polytetrafluoroethylparticle particle：" poly- (the tetrafluoro ethylene) " of Japan of Sigma-Aldrich companies (strain) production
(1 μm of number average bead diameter, state of aggregation, it is also denoted as below " PTFE particles ".)
Silicone particle A：" the TOSPEARL 2000B " (just spherical, 6.0 μm of number average bead diameter) of Mai Tugao new companies production
Silicone particle B：" the TOSPEARL 1110A " (just spherical, 11.0 μm of number average bead diameter) of Mai Tugao new companies production
Silicone particle C：" the TOSPEARL 145A " (just spherical, 4.5 μm of number average bead diameter) of Mai Tugao new companies production
Silicone particle D：" TOSPEARL 150KA " (the irregular star sugar shape of surface tool, the number of Mai Tugao new companies production
Equal 5.0 μm of particle diameter)
Lycopod (リ U Port デ ィ ウ system)：(the irregular spherical, number of surface tool is for Japan of Sigma-Aldrich companies (strain) production
About 40 μm of particle diameter)
Silicon dioxide granule A：(AEROSIL RX-300, trimethyl silicane surface, area are average for Japanese Aeronnell (strain) production
Particle diameter about 14~17nm)
Silicon dioxide granule B：Japanese Aeronnell (strain) produces (AEROSIL RY-300, dimethyl silicone polymer surface, face
Product average grain diameter about 21~27nm)
[Production Example 1]
As shell material, PTFE particles are thinly spread out on shallow chassis.As nuclear material, the μ L of epoxy resin 15 are used micro-
Amount dropper (Michipet of (strain) Nichiryo productions) is added drop-wise on the PTFE particles in shallow chassis.After completion of dropwise addition, make shallow
Chassis is vibrated in face parallel to the ground, drop is rolled 30 seconds, is made PTFE particle absorptions in the drop of epoxy resin
Surface, make core-shell particles.In addition, for only vibrating shallow chassis without the drop of rolling, make liquid using plastic medicine spoon
Drop rolls, and makes core-shell particles.
[Production Example 2]
In Production Example 2, the PTFE particles of Production Example 1 are changed to silicone particle A, in addition with the identical side of Production Example 1
Legal system makees core-shell particles.
[Production Example 3]
In Production Example 3, the PTFE particles of Production Example 1 are changed to silicone particle D, in addition with the identical side of Production Example 1
Legal system makees core-shell particles.
[Production Example 4]
In Production Example 4, the epoxy resin of Production Example 1 is changed to PEI, made in addition of with the identical method of Production Example 1
Core-shell particles.
[Production Example 5]
In Production Example 5, the PTFE particles of Production Example 4 are changed to silicone particle A, in addition with the identical side of Production Example 4
Legal system makees core-shell particles.
[Production Example 6]
In Production Example 6, the PTFE particles of Production Example 4 are changed to silicone particle B, in addition with the identical side of Production Example 4
Legal system makees core-shell particles.
[Production Example 7]
In Production Example 7, the PTFE particles of Production Example 4 are changed to silicone particle C, in addition with the identical side of Production Example 4
Legal system makees core-shell particles.
[Production Example 8]
In Production Example 8, the PTFE particles of Production Example 4 are changed to silicone particle D, in addition with the identical side of Production Example 4
Legal system makees core-shell particles.
[Production Example 9]
In Production Example 9, the PTFE particles of Production Example 1 are changed to lycopod, made in addition of with the identical method of Production Example 1
Core-shell particles.
[Production Example 10]
With electronics Libra weigh 2.8g RX-300 to agitator (model Labo Milser LM-PLUS rotating speeds 20,000rpm,
Osaka KCC) stirring container in, thereto add the 25g epoxy resin aqueous solution (epoxy resin concentration：20 matter
Measure %), stirred 5 seconds in agitator, thus make core-shell particles.
[Production Example 11]
In Production Example 11, the RX-300 of Production Example 10 is changed to RY-300, in addition with the identical method of Production Example 10
Make core-shell particles.
[Production Example 12]
In Production Example 12, the epoxy resin of Production Example 10 is changed to PEI, in addition with the identical method system of Production Example 10
Make core-shell particles.
[Production Example 13]
In Production Example 13, the RX-300 of Production Example 12 is changed to RY-300, in addition with the identical method of Production Example 12
Make core-shell particles.
[table 1]
(estimation of stabilitys of core-shell particles)
The core-shell particles of each Production Example are moved on on glass plate with plastics pharmacy spoon, stabilization when confirming to stand under room temperature (23 DEG C)
Property.As a result it is shown in table 1.
(measure of contact angle)
The shell material used in each Production Example is equably seamlessly deployed in the plane, to being added dropwise thereon in each Production Example to make
Nuclear material, make drop.After 1~2 minute, shell material is determined using contact angle meter (" SImage02 " of エ キ シ マ societies)
The contact angle of nuclear material on material.As a result it is shown in table 1.
(the contact stabilization evaluations of core-shell particles)
The core-shell particles of 1 Production Example 2, the core-shell particles of 1 Production Example 5 is contacted on a glass, be statically placed in room temperature (23
DEG C), within 5 minutes, the core-shell particles of two sides integrate.
The core-shell particles of 1 Production Example 2, the core-shell particles of 1 Production Example 6 is contacted on a glass, be statically placed in room temperature
(23℃).After 24 hours, the core-shell particles of two sides do not integrate and stably existed, and can separate well.In addition, make
The core-shell particles of two sides are cut open with bamboo stick, the nuclear material for confirming inside is liquid.This represents that nuclear material epoxy resin does not have
Contacted with PEI.
The making of ＜ core-shell particles mixtures and its estimation of stability ＞
[embodiment 1]
By the core-shell particles of Production Example 2 and the core-shell particles of Production Example 5 with number than 1：1 is mixed, and is obtained core-shell particles and is mixed
Compound.
[embodiment 2]
By the core-shell particles of Production Example 2 and the core-shell particles of Production Example 6 with number than 1：1 is mixed, and is obtained core-shell particles and is mixed
Compound.
[embodiment 3]
By the core-shell particles of Production Example 10 and the core-shell particles of Production Example 13 with mass ratio 1：1 is mixed, and obtains core-shell particles
Mixture.The core-shell particles mixture is the powdery core-shell particles aggregate (dry liquids) that can be flowed well.By the nucleocapsid grain
Sub- mixture is statically placed in room temperature (23 DEG C), and after 24 hours, mobility does not also change, and stably exists.
(the cohesive evaluation of core-shell particles mixture)
The core-shell particles mixture of embodiment 1 is clamped with glass plate (" S7213 " that unrestrained nitre of pine industrial (strain) produces), from glass
Side applies stress crushing core-shell particles above glass plate, the epoxy resin of inside is mixed with PEI.Mixed liquor is the paste of white
Liquid.After 1 hour being stood under room temperature (23 DEG C), when pulling open the glass plate on top, though glass plate has a little movement to be fixed.
When pulling open the glass plate on top after standing 4 hours, glass plate is motionless, is fixed completely.
The core-shell particles mixture of embodiment 2 is clamped with glass plate (" S7213 " that unrestrained nitre of pine industrial (strain) is made), from
Side applies stress crushing core-shell particles above glass plate, the epoxy resin of inside is mixed with PEI.Mixed liquor is translucent
Liquid.After 1 hour being stood under room temperature (23 DEG C), when pulling open the glass plate on top, though glass plate has a little movement to be fixed.
When pulling open the glass plate on top after standing 4 hours, glass plate is motionless, is fixed completely.
The core-shell particles mixture of embodiment 3 is clamped with glass plate (" S7213 " that unrestrained nitre of pine industrial (strain) is made), from
Side applies stress crushing core-shell particles above glass plate, the epoxy resin of inside is mixed with PEI.Mixed liquor is the cream of white
Shape liquid.After 1 hour being stood under room temperature (23 DEG C), when pulling open the glass plate on top, though glass plate has a little movement to be fixed
Firmly.When pulling open the glass plate on top after standing 4 hours, glass plate is motionless, is fixed completely.
Claims (11)
1. a kind of core-shell particles mixture, it contains the 1st core-shell particles and the 2nd core-shell particles, the 1st core-shell particles by containing
1st core of the 1st material is formed with coating the 1st shell of the 1st core,
2nd core-shell particles are by the 2nd core containing the 2nd material to the 1st material with reactivity and cladding the described 2nd
2nd shell of core is formed；
1st shell and the 2nd shell contain solids.
2. core-shell particles mixture according to claim 1, the 1st material contains polymerizable compound, the 2nd thing
Matter contains poly- agents.
3. according to the core-shell particles mixture described in claim 1 or claim 2, by being applied to the 1st core-shell particles
Add stress, can by outside the 1st substance release to the 1st shell,
, can be by outside the 2nd substance release to the 2nd shell by applying stress to the 2nd core-shell particles.
4. according to the core-shell particles mixture described in any 1 of 1~claim 3 of claim, the 1st material and institute
State the 2nd material at least any one be liquid,
Contact angle of the liquid on the solids is more than 90 °.
A kind of 5. adhesive that core-shell particles mixture as described in any 1 of 1~claim 4 of claim is formed.
6. the manufacture method of the reactant of the 1st material and the 2nd material, the 2nd material has reactivity to the 1st material,
The manufacture method contains to the core-shell particles mixture or power described in any 1 of 1~claim 4 of claim
Profit requires that the adhesive described in 5 applies the process of stress.
7. manufacture method according to claim 6, it further contains following process：By adjusting the 1st nucleocapsid grain
The number average bead diameter of sub and described 2nd core-shell particles, come adjust the 1st material in the core-shell particles mixture with it is described
The containing ratio of 2nd material.
8. according to the manufacture method described in claim 6 or claim 7, it further contains following process：Pass through adjustment
The 1st material in the mixing ratio of 1st core-shell particles and the 2nd core-shell particles, or the 1st core-shell particles
Content and the 2nd core-shell particles in the ratio between the content of the 2nd material, to adjust in the core-shell particles mixture
The containing ratio of 1st material and the 2nd material.
9. according to the manufacture method described in any 1 of 6~claim 8 of claim, the reactant is the anti-of adhesive
Answer thing.
10. a kind of manufacture method of layered product, it contains following process：
In the core-shell particles mixture described in any 1 of the surface configuration 1~claim 4 of claim of the 1st component or
The process of adhesive described in claim 5；
Apply the process of stress to the core-shell particles mixture or described adhesive；
The process of the 2nd component is laminated on the core-shell particles of the 1st component or the configuration face of described adhesive.
11. the manufacture method of layered product according to claim 10, to the core-shell particles mixture or the bonding
The process that agent applies stress includes following process：Stress is applied to the 1st core-shell particles, makes the 1st substance release to institute
After stating outside the 1st shell, stress is applied to the 2nd core-shell particles, made outside the 2nd substance release to the 2nd shell.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015031879 | 2015-02-20 | ||
| JP2015-031879 | 2015-02-20 | ||
| PCT/JP2016/054522 WO2016133104A1 (en) | 2015-02-20 | 2016-02-17 | Core-shell particle mixture, adhesive, reaction product manufacturing method, and laminate manufacturing method |
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| Publication Number | Publication Date |
|---|---|
| CN107429124A true CN107429124A (en) | 2017-12-01 |
Family
ID=56692259
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680010795.1A Pending CN107429124A (en) | 2015-02-20 | 2016-02-17 | Core-shell particles mixture, adhesive, the manufacture method of the manufacture method of reactant and layered product |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6700563B2 (en) |
| CN (1) | CN107429124A (en) |
| TW (1) | TW201638281A (en) |
| WO (1) | WO2016133104A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114127217A (en) * | 2019-03-25 | 2022-03-01 | 斯皮拉技术有限公司 | Multi-component system and method for producing a multi-component system |
| CN115245799A (en) * | 2021-12-21 | 2022-10-28 | 兰州理工大学 | Preparation method and application of double-shell core-shell structure particles BT @ SSMWNT @ PANI |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7184874B2 (en) * | 2018-03-28 | 2022-12-06 | 株式会社カネカ | adhesive composition |
| JP7540226B2 (en) | 2019-07-31 | 2024-08-27 | 株式会社リコー | Composite particles, composite particles for forming liquid-encapsulated particles, liquid-encapsulated particles, and method for producing liquid-encapsulated particles |
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2016
- 2016-02-17 WO PCT/JP2016/054522 patent/WO2016133104A1/en active Application Filing
- 2016-02-17 CN CN201680010795.1A patent/CN107429124A/en active Pending
- 2016-02-17 JP JP2017500699A patent/JP6700563B2/en active Active
- 2016-02-19 TW TW105104893A patent/TW201638281A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63273680A (en) * | 1987-04-30 | 1988-11-10 | Kyocera Corp | Capsule type adhesive and bonding process using same |
| EP1221470A2 (en) * | 2001-01-03 | 2002-07-10 | Exchem Plc | Glass particles as detackifying agent in adhesive/sealant material and process for packaging the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114127217A (en) * | 2019-03-25 | 2022-03-01 | 斯皮拉技术有限公司 | Multi-component system and method for producing a multi-component system |
| CN115245799A (en) * | 2021-12-21 | 2022-10-28 | 兰州理工大学 | Preparation method and application of double-shell core-shell structure particles BT @ SSMWNT @ PANI |
| CN115245799B (en) * | 2021-12-21 | 2023-09-19 | 兰州理工大学 | Preparation method and application of double-shell core-shell structure particle BT@SSMWNT@PANI |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016133104A9 (en) | 2017-07-06 |
| TW201638281A (en) | 2016-11-01 |
| WO2016133104A1 (en) | 2016-08-25 |
| JPWO2016133104A1 (en) | 2017-11-30 |
| JP6700563B2 (en) | 2020-05-27 |
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