WO2009107861A1 - Microcapsule et composition de résine durcissable contenant des microcapsules - Google Patents

Microcapsule et composition de résine durcissable contenant des microcapsules Download PDF

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Publication number
WO2009107861A1
WO2009107861A1 PCT/JP2009/054110 JP2009054110W WO2009107861A1 WO 2009107861 A1 WO2009107861 A1 WO 2009107861A1 JP 2009054110 W JP2009054110 W JP 2009054110W WO 2009107861 A1 WO2009107861 A1 WO 2009107861A1
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component
compound
curable resin
microcapsule
meth
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PCT/JP2009/054110
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English (en)
Japanese (ja)
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鈴木　宏則
仁志 真舩
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株式会社スリーボンド
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Publication of WO2009107861A1 publication Critical patent/WO2009107861A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C08G59/58—Amines together with other curing agents with polycarboxylic acids or with anhydrides, halides, or low-molecular-weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a microphone mouth capsule containing a liquid amine compound that is optimal as a curing agent or curing accelerator for a curable resin, and a curable resin composition containing the microphone mouth capsule.
  • thermosetting resin compositions such as epoxy resins, which are generally used for applications such as adhesives, sealants, and coating agents
  • curing agents are used as components for crosslinking and curing reactions.
  • a curing accelerator is added as a component for improving the property.
  • epoxy adduct compounds, organophosphorus compounds, organic amine compounds, imidazole derivative compounds, and the like are known as curing agents or curing accelerators that have the potential to form a single solution.
  • organic amine compounds are preferably used as liquid curing agents or curing accelerators.
  • the epoxy adduct compound a reaction product obtained by reacting an epoxy resin typified by bisphenol A type epoxy resin and an amine compound to an intermediate stage is generally used. It is known to use a finely pulverized powder of an epoxy compound as a curing agent or curing accelerator for epoxy resin.
  • JP 7-5 7 0 8 B shows a method of forming a shell by reacting an epoxy resin on the surface of an epoxy adduct compound powder.
  • the manufacturing process is complicated and considerable accuracy is required in manufacturing. Is required.
  • the core powder is an amin compound in which an epoxy resin is already adducted, the reactivity of the amine is already lowered, and it takes a considerable time to form a shell.
  • epoxy adduct compounds are usually highly reactive and easy to handle. However, depending on the composition of the components, curing may not proceed sufficiently and satisfactory cured product characteristics may not be obtained.
  • this epoxy adduct compound is a compound having an epoxy group. When kneaded, thixotropy (thixotropy), which seems to be derived from the amine structure on the surface of the hardener, is likely to occur, and it is necessary to limit the amount of addition because it hinders handling due to its properties. Of course, if the amount added is small, there is a problem that curability is lowered.
  • Organophosphorus compounds are useful as catalysts for curing epoxy resins with phenol nopolac, but they have the disadvantage of being difficult to disperse because they are solid, and in order to improve dispersibility, they are made into fine powders. However, it is unsatisfactory as a dispersion method, and in this method, the latency of the catalyst cannot be imparted.
  • Liquid organic amine compounds or imidazole derivatives are often used as curing agents or catalysts for epoxy resins and phenol resins, but many have unique odors and toxicity. When added, the pot life is extremely short. In addition, solid materials have problems such as difficulty in dispersion. With respect to pot life, a special imidazole salt can be used to provide some latency.
  • the dispersion step, the kneading step, and the shaping step in the raw material at a temperature lower than the catalyst ability expression temperature, and the crosslinking step at a temperature higher than the catalyst ability expression temperature.
  • the effect is incomplete and has the disadvantage of slowing the curing reaction.
  • DBU 1,8-diazabicyclo [5.4.0] unde force7-en
  • DBN 1,5—diazabicyclo [4. 3. 0] nona 1-5—en
  • Curing is accelerated by amine compounds such as epoxy resins due to their strong basicity, stability, and wide range of solubility in organic solvents. It is used as a powerful curing accelerator in the system.
  • JP-287 13 1 A exemplifies a technique of microencapsulating a liquid amine compound such as DBU by an interfacial precipitation method, an interfacial polymerization method, a submerged cured coating method, or the like.
  • a liquid amine compound such as DBU
  • these general encapsulation methods at least one of water and a solvent is used, and the reaction is carried out in a compatible system in which the amine compound is dissolved. Therefore, it was difficult to take out a uniform microcapsule.
  • DBN and DBU have very good compatibility with water and solvents, it was extremely difficult to take out uniform capsules with a high yield by the above-mentioned encapsulation.
  • these general encapsulation methods involve heating to synthesize capsules and long-time stirring, there is a problem that even when capsules are formed, liquid amine compounds are eluted from the micro-force cells.
  • JP 7_ 323668A, JP 2001-55473 A, and JP 8-15757 OA have reported a technique for absorbing a component that can be a curing accelerator into a microparticle to form a microcapsule.
  • the components that can be hardening accelerators are simply absorbed in the fine particles, and the capsule contents can be easily eluted with a weak stimulus. For this reason, there is a problem that a curing reaction is easily caused only by mixing with a curable resin, and a component that becomes a liquid curing accelerator is made solid to facilitate handling.
  • JP 8-1 5750 A also supports amine-based catalysts containing DBU in fine powders. Then, a technique is adopted in which the fine powder is force-pelled by coating the surface of the fine powder with a solid component. However, in this method, the surface is merely coated with a solid component, so that the solid component film is easily destroyed by the influence of heat or mechanical stimulation, and stable microcapsules cannot be obtained. Disclosure of the invention
  • An object of the present invention is to solve the above-mentioned problems, and in particular, liquid amine compounds such as DBU and DBN can be easily and microencapsulated with little variation in quality to harden curable resins or curable resins. To provide a microcapsule manufacturing technology that exhibits excellent stability when used as a curing accelerator, and as a result, can form a one-part curable resin composition with excellent storage stability. . Summary of invention
  • the following components (A) to (C) are used as constituent components, the component (A) is absorbed by the component (B), and is present on the surface of the component (B) (A It is a microcapsule formed by reacting the component (C) with the component to form a film.
  • the component (A) is at least selected from DBU, DBN, triethylenediamine, derivatives having these as main skeletons, and organic acid salts thereof.
  • the microcapsule comprising one type.
  • a third aspect of the present invention is the microcapsule, wherein the component (C) is an acid anhydride containing a plasticizer.
  • a curable resin composition comprising a curable resin containing the microcapsule as a curing agent or a curing accelerator.
  • the curable resin refers to a compound having one or more functional groups having reactivity such as epoxy group, epithio group, isocyanate group, and vinyl group in one molecule.
  • the curable resin is at least one selected from a compound having an epoxy group, a compound having an epoxy group, a compound having an isocyanate group, and a compound having a vinyl group. It is a curable resin composition.
  • the curable resin in the fourth aspect comprises at least one curable resin selected from a compound having an epoxy group and a compound having an epoxy group, and a polyamine as a curing agent.
  • the curable resin composition comprising at least one selected from a compound, a polyphenol compound, a polythiol compound, and an acid anhydride, and using the micro force capsule as a curing accelerator.
  • microcapsules of the present invention as a curing agent / curing accelerator for a curable resin, it becomes possible to provide a curable resin composition having both storage stability and curability.
  • FIG. 1 is a scanning electron micrograph of porous hollow silica powder used as the component (B) in the present invention.
  • FIG. 2 is an example of a scanning electron micrograph of the microcapsules obtained in the present invention. Best mode for carrying out the invention
  • the component (A) of the present invention is a liquid amine compound having an acid dissociation constant (p Ka) of 8.0 or more.
  • the acid dissociation constant is one of the indicators for quantitatively expressing the strength of the acid, and is represented by the negative common logarithm of the equilibrium constant (Ka) of the dissociation reaction in which protons are released from the acid. .
  • Ka equilibrium constant
  • a larger pKa value indicates a stronger base.
  • the component (A) that can be used in the present invention is not particularly limited as long as it is a liquid amine compound having a pKa of 8.0 or more.
  • DBU pKa 12.7
  • DBN pKa 12.5
  • Diorthotrilguanidine pKa l O. 8
  • Laurylamine pKa l O. 6
  • Diphenyldanidine pKa l O. 1
  • Diventramine pKa 9.7
  • Triethylenediamine pKa 8.8
  • DBU, DBN, and triethylenediamine have strong nucleophilicity and can easily react with the component (C) described later to form the shell of the capsule.
  • amines or derivatives of these compounds are used alone, or DBU, DBN or triethylenediamine is used as a salt of an organic acid such as carboxylic acid, sulfonic acid or phenol.
  • the component (B) that can be used in the present invention is not particularly limited as long as it is a porous fine particle powder that can absorb the component (A).
  • the average particle size is preferably 20 m or less.
  • Specific examples of materials include carbon black, colloidal silica, fumed silica, wet silica, silicates such as magnesium, calcium, and barium, oxides such as copper, zinc, aluminum, titanium, tin, iron, cobalt, and nickel.
  • Examples thereof include porous inorganic fine particles such as nitrides. Especially porous with an average particle size of 20 m or less Silica powder is preferred.
  • porous silica powders having an average particle size of 20 / m or less examples include God Ball (silica spherical powder, hollow spherical powder) (manufactured by Suzuki Oil & Fat Co., Ltd.), Mizu Force Ace (Kay Acid shaped powder) (manufactured by Mizusawa Chemical Industry Co., Ltd.), etc., and the particle size can be appropriately selected according to the application.
  • the average particle size of the porous fine particles exceeds 2.0 / im, the viscosity of the capsule of the present invention becomes too high when mixed with the curable resin, so that the applicability of the curable resin composition is reduced and stored. Separation ⁇ There is a risk of becoming settled easily.
  • an index of absorptivity of the porous fine particle powder which is the component (B) of the present invention it is in the range of 50 to 500 ml / 100 g in the oil absorption measurement specified in JIS-K-5101. preferable.
  • the purpose of using the component (B) is to use the component (A) for imitating solidification.
  • the component (C) that can be used in the present invention is not particularly limited as long as it is a liquid at room temperature and can be polymerized with the component (A) to form a capsule film.
  • compounds having one or more carboxylic acid anhydride groups such as acid, benzophenone tetracarboxylic anhydride, and tetrabromofuranic anhydride.
  • Specific examples of products based on acid anhydrides with such functions include HN-2200, HN-2000, HN-5500, MHAC-P made by Hitachi Chemical Co., Ltd. and Shin Nippon Rika Co., Ltd. Ricacid TH, HT-1A, MH-700, MH-700 G, HNA-100, TMEG-S, T MEG-100, TMEG200, TMEG-500, TMEG-600, TM TA-TMA-15, DDSA HF-08, SA, DSDA, TMEG-100, TDA-100, BT-100, EP I CLON B-570, B-650, B-4400 manufactured by Dainippon Ink & Chemicals, Inc.
  • an acid anhydride that is solid at room temperature can be used if it is dissolved in a liquid acid anhydride at room temperature and finally made liquid at room temperature.
  • the object of the present invention can be achieved by combining the component (A) and the component (C).
  • the component (A) remains on the surface of the porous fine particle powder of the component (B) that has absorbed the component (A) in the present invention.
  • the component (C) is brought into contact with each other, they react to form a capsule shell on the surface of the component (B).
  • the brittleness of the capsule can also be controlled by using an acid anhydride containing a plasticizer as the component (C). That is, the capsule can be made brittle by increasing the amount of plasticizer, and stiffened by decreasing the amount.
  • the plasticizer that can be used here is preferably a plasticizer that is easily compatible with an acid anhydride, and in particular, plasticizers such as phthalic ester, adipic ester, and polyester are preferred.
  • the content of the plasticizer in the component (C) is preferably 0.1 to 50 parts by weight of the plasticizer with respect to 100 parts by weight of the component (C).
  • (Ii) Isolate ingredients. This isolation is performed, for example, by adding a cleaning solvent to the mixture and further stirring, then filtering the solid content by suction filtration or the like and volatilizing the solvent in a hot air drying furnace or the like to recover the powder. be able to.
  • the ( ⁇ ) component remains on the surface as well as the ( ⁇ ) component.
  • the ( ⁇ ) component is added to the liquid phase of the (C) component and mixed with a stirrer or the like to react the ( ⁇ ) component with the (C) component. By doing so, the ( ⁇ ) component remaining on the surface of the ( ⁇ ) component reacts with the (C) component to form a film.
  • the ( ⁇ ) component existing inside the ( ⁇ ) component remains as it is.
  • the microcapsules are then isolated from this mixture. This isolation is, for example, the mixture After adding a washing solvent to the compound and further stirring, the solid content is filtered by suction filtration or the like, and the remaining solid content is recovered by volatilizing the solvent with a hot air drying furnace or the like.
  • This solid component is a liquid amin compound in which the microcapsules are encapsulated.
  • the component (A) and the component (C) form a capsule film have not been completely elucidated, the component (A) present on the porous fine particle powder as a capsule carrier, ie, p K
  • a liquid amine compound of a strong base with a of 8.0 or more opens the acid anhydride, and the resulting carboxylamide reacts with another component (C) to form a structure as shown in the following formula (3). It is thought that it will become a polymer.
  • a compound having an epoxy group such as the following formula (4), a compound having an epoxide group such as the following formula (5), a compound having an isocyanate group, a compound having a vinyl group, etc., is an amine compound. Because it is a compound that reacts as an accelerator,
  • the amine compound as the component (B) can be used as a curing agent or a curing accelerator for the curable resin.
  • the microcapsules of the present invention can be used as a curing agent or a curing accelerator having a latent property with respect to the curable resin.
  • a curable resin is a compound that has one or more reactive functional groups such as epoxy group, epithio group, isocyanate group, and vinyl group in the molecule. There are no particular restrictions on the type or molecular weight, and it may have other functional groups in the molecule.
  • the curable resin when using a compound having an epoxy group, a compound having an epithio group, or a compound having an isocyanate group,
  • the component (B) can be used as a curing agent.
  • the mechanism is that the amine compound in component (B) becomes an anion and plays a role in ring-opening polymerization of reactive functional groups such as epoxy groups.
  • the amine compound when a compound having an epoxy group or a compound having an epoxy group is combined with a polyamine compound, polyphenol compound, polythiol compound, or acid anhydride as a curing agent, the amine compound can be used as a curing accelerator.
  • the mechanism is that the amine compound liberates active hydrogen such as a polyamine compound or a polyphenol compound, and reacts these with a plurality of epoxy groups or epoxy groups.
  • the amine compound can be used as a curing agent for anionic polymerization, and can be used for radical polymerization as a curing accelerator in combination with an organic peroxide.
  • the mechanism is that the amine compound facilitates the decomposition of organic peroxides and facilitates the generation of radical species.
  • epoxy resins for example, those obtained by condensation of epichlorohydrin with polyhydric phenols such as bisphenols and polyhydric alcohols.
  • specific examples include bisphenol A type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, bisphenol S type, bisphenol AF type, biphenyl type, and naphthylene type.
  • examples thereof include tan-type daricidyl ether-type epoxy resins.
  • Glycidyl ester type epoxy resin obtained by condensation of epichlorohydrin with forceful sulfonic acids such as phthalic acid derivatives and fatty acids, obtained by reaction of epichlorohydrin with amines, cyanuric acids and hydantoins
  • forceful sulfonic acids such as phthalic acid derivatives and fatty acids
  • Examples include, but are not limited to, daricidylamine type epoxy resins and epoxy resins modified by various methods.
  • a compound having an epithio group is often described as a thiirane compound in publications and patent documents.
  • Specific examples of a compound having an epicio group include 2,2-bis (4 — (2,3-epithiopropoxy) phenyl) propane, bis (4- (2,3-epitipropoxy) phenyl) methane, 1 , 6-Di (2,3-Epiciopropoxy) Naphthalene, 1, 1, 1-Tris (4- (2,3-Epiciopropoxy) phenyl) ethane, 2, 2-bis (4- 2, 3-Epiciopropoxy) cyclohexyl) propane, bis (4 ((2,3-Epiciopropoxy) cyclohexyl) methane, 1,1,1,1-tris ((4 2,3-Epithiopropoxy) Cyclohexyl) Ethane, 1,5-pentenediol 2,3-Epithiocyclohexyl) Ether, 1,6-Hexaned
  • the compound having an isocyanate group include aromatic diisocyanate: 2,4 monotolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, polyphenylenepolyethylenepolyisocyanate, 1,5-naphthylene diisocyanate, 1,4-naphthyl Examples include range isocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, o_xylylene diisocyanate, m-xylylene diisocyanate, and aliphatic diisocyanate includes tetramethylene.
  • Alicyclic diisocyanates include 1-methylcyclohexane-1,4-diisocyanate, isophorone diisocyanate, Examples include oral hexylmethane 1,4′-diisocyanate, but are not particularly limited.
  • a compound having an acrylic group, a methyl chloride group or a vinyl ether group is preferable.
  • Monofunctional, bifunctional, trifunctional, and polyfunctional monomers and oligomers are compounds having an acrylic group, a methacrylic group, or a vinyl ether group.
  • the monomer or oligomer is polymerized by anionic polymerization reaction with the amine compound.
  • a radical species is generated by an organic peroxide and an amine compound and a radical polymerization reaction is carried out to form a polymer.
  • acrylic and methacrylic are collectively called (meth) acrylic
  • Monofunctional compounds having (meth) acrylic groups include lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, force prolactone modified tetrahydrofurfuryl (meth) acrylate, Hexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Isoponyl (meth) acrylate, Benzyl (meth) acrylate, Phenyl (meth) acrylate, Phenoxetyl (meth) acrylate, Phenoxyethylene Glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, nonylphenoxychetyl (meth) acrylate, nonylphenoloxyethylene glycol (meth) acrylate , Methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, but
  • Bifunctional compounds include 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, neopentyl glycol di
  • trifunctional compounds include trimethylolpropane tri (meth) acrylate, pentylerythritol tri (meth) acrylate, E ⁇ modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, Examples include, but are not limited to, ECH-modified trimethylolpropane tri (meth) acrylate, ECH-modified glycerol tri (meth) acrylate, tris (acryloyloxychetyl) isocyanurate, and the like.
  • Polyfunctional compounds include ditrimethylolpropane tetra (meth) acrylate, pen erythritol tetra (meth) acrylate, dipentaerythritol monohydroxy pen meth (acrylate), alkyl-modified dipentyl erythritol benzoyl acrylate, and dipentaerythritol.
  • Examples include, but are not limited to, oxa (meth) acrylate, force prolactone-modified dipenyl erythritol hexyl (meth) acrylate, and the like.
  • oligomers examples include bisphenol A type, novolak type, polyhydric alcohol type, polybasic acid type, polybutadiene type epoxy (meth) acrylate, polyester type, polyether type urethane (meth) acrylate, etc. It is not limited to.
  • Examples of the compound having a vinyl ether group include ethylene dallicol divinyl ether, 1,3-propanediol divinyl ether, propylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,3-butanediol divinyl ether.
  • organic peroxide used for radical polymerization of the (meth) acrylic compound examples include methyl ethyl ketone peroxide, cyclohexanone peroxide.
  • Ketone peroxides such as oxide, 3, 3, 5-trimethylcyclohexanone peroxide, methyl hexanone peroxide, methyl acetoacetate peroxide, acetyl acetone peroxide; Butyl peroxy) — 3, 3, 5, 5-trimethylcyclohexane, 1, 1 bis (t-butylperoxy) cyclohexane, 2, 2-bis (t-butyl peroxy) octane, n-butyl-4, 4-bis (t-butylperoxy) valerate, 2, 2_bis (t-butylperoxy) butanes and other paraketals; t-butylhydride peroxide, cumene hydroperoxide, diisopropylbenzene hydropoxide, p —Mentan o
  • the microcapsules of the present invention can be used as a curing agent or a curing accelerator for each of the curable resins listed above, and are particularly preferably used as a curing accelerator for a compound having an epoxy group or a compound having an epoxy group. be able to.
  • a compound having an epoxy group, a polyamine compound having two or more amino groups in the molecule as a curing agent for curing the compound having an epoxy group, a polyphenol compound having two or more phenol groups in the molecule, molecule
  • polyamine compound to be used in combination examples include diethylene / polyamine, triethylenetetramine, metaxylylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, diaminodiphenylmethane, and metaphenylenediamine. , Diaminodiphenylsulfone, dicyandiamide, organic acid dihydrazide, piperidine and the like, but are not limited thereto.
  • polyphenol compound examples include nopolac-type phenol resins obtained by reacting phenols such as phenol and alkylphenol with aldehydes such as formaldehyde and paraformaldehyde, and zylog type which are these modified phenol nopolac resins.
  • Polyphenolic resins such as phenol resin, dicyclopentene type phenolic resin, multifunctional type phenolic resin, etc. It is not limited. A polyphenol compound that is liquid at room temperature is particularly preferred.
  • polythiol compound examples include 3-methoxybutyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, tridecyl 3-mercaptopropionate, trimethylolpropane tristhiopropionate, pen Erythrol tetrakisthiopropionate, Methylthioglycolate, 2-Ethylhexylthioglycolate, Ethylene glycol bisthiodallicolate, 1,4-Butanediol bisthioglycolate, Trimethylolpropane tristiodalycolate Monotetrakisthioglycolate, di (2_mercaptoethyl) ether, 1-butanethiol, 1-hexanethiol, cyclohexylmercaptan, 1,4_butanedithiol, 3 —mercapto 2 —butanol , Ermercaptopropyl trimethoxys
  • the acid anhydride examples include dodecenyl succinic anhydride, polyazeline acid anhydride, hexahydrohydrofuranic acid, tetrahydroanhydrofuranic acid, methyltetrahydroanhydrofuranic acid anhydride, methylnadic acid anhydride, Cyclic acid anhydrides such as merit acid, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, tetrabromofuranic acid anhydride, and head acid anhydride are preferred, but are not limited thereto.
  • the amount of the microphone mouth capsule of the present invention in the curable resin composition of the present invention is an effective amount in which the amine compound in the microcapsule functions as a curing agent or a curing accelerator, and is the same as the amount used in the prior art. It is determined appropriately according to the purpose of use. General Specifically, it is preferable to add 0.1 to 50 parts by mass of the microcapsules of the present invention with respect to 100 parts by mass of the reactive functional group.
  • a colorant such as pigment and dye, an inorganic filler such as metal powder, calcium carbonate, talc, silica, alumina, and aluminum hydroxide
  • Additives such as flame retardants, organic fillers, plasticizers, antioxidants, antifoaming agents, silane coupling agents, leveling agents, rheology control agents, and solvents may be blended in appropriate amounts. With these additions, a composition excellent in resin strength, adhesive strength, workability, preservation, etc. and a cured product thereof can be obtained.
  • DBU (manufactured by SanPro Corporation) 200 g and B-6C (manufactured by Suzuki Yushi Kogyo Co., Ltd., porous / hollow silica type) 100 g are placed in a beaker and stirred for 30 minutes. Since it generates heat during absorption, leave it at room temperature for 2 hours after stirring. Add 300 g of methyl ethyl ketone (hereinafter referred to as MEK) and stir for 30 minutes. Suction filtration is performed with a No. 3 filter paper on a Kiriyama Mfg. Co., Ltd. (commonly known as Kiriyama funnel), and excess DBU that has not been absorbed and MEK added for cleaning are filtered. Spread the filtrate thinly on a pallet bowl and dry at 40 for 2 hours in a hot air drying oven. (Hereafter, the powder processed in the first step is called the processed powder)
  • MEK methyl ethyl ketone
  • Example 2 100 g of treated powder 3 or 4-methyl-1,2,3,6-tetrahydrohydrofuranic acid (NH-2200 R, manufactured by Hitachi Chemical Co., Ltd.) 200 g is added for 30 minutes Stir. After stirring, add 300 g of MEK and stir for another 30 minutes. Suction-filter the Kiriyama funnel with No. 3 filter paper. Spread the filtrate on a pallet and dry it for 40 x 2 hours in a hot air drying oven. [Example 2, Example 3, Comparative Example 1]
  • the following three methods were used to make the liquid amine compound absorbed in the porous fine powder latent.
  • the raw materials used for each method are listed in Table 2.
  • the raw materials in Table 2 are raw materials used in place of the acid anhydrides referred to in Example 1.
  • Dry encapsulation was performed with a hybrid system NHS-0 manufactured by Nara Machinery Co., Ltd. Add 10 g of the raw material used in Comparative Example 1 1-13 to 10 g of the treated powder and treat with 970 OmZs for 1 minute. The processed product is scraped and collected.
  • Second step Place 200 g of DBU and 100 g of B-6 C in a beaker and stir for 30 minutes. Since it generates heat during absorption, leave it at room temperature for 2 hours after stirring. Add 300 g ME K and stir for 30 minutes. Suction-filter with a No. 3 filter paper through a funnel made by Kiriyama Seisakusho, and filter the excess DBU that was not absorbed and MEK added for cleaning. The filtered material is spread thinly on a pallet and dried in a hot air drying oven for 40 x 2 hours. Second step
  • a curable resin composition was produced using the microcapsules produced in Example 1, Example 4, and Example 5 as a curing accelerator. According to Table 5, using Epiclone EXA—835 LV as the compound having an epoxy group, j ER Cure QX40 as the polythiol compound, MEH—8005 (manufactured by Meiwa Kasei Co., Ltd.) as the polyphenol compound, and Guatemalacid MH-700 as the acid anhydride. Blended. Each compound was stirred with a stirrer for 15 minutes to prepare a curable resin composition.
  • Measurement mode Oscillation distortion control
  • a curable resin composition was produced using the microcapsules produced in Example 1 as a curing agent.
  • Hydrogenated bisphenol A type Epicoat YL 700 7 (manufactured by Japan Epoxy Resin Co., Ltd.) as a compound having an epoxide group as a curable resin, or Millionate MR-2200 (manufactured by Nippon Polyurethane Co., Ltd.) as a compound having an isocyanate group
  • Penyu Erythritol Tetraclay® light acrylate PE-4A manufactured by Kyoeisha Chemical Co., Ltd.
  • Each compound was stirred with a stirrer for 15 minutes to prepare a curable resin composition.
  • a curable resin composition using the microcapsules produced in Example 1 as a curing accelerator was produced.
  • curable resins dimethyl methacrylate / tricyclodecane diacrylate (light acrylate DCP—A manufactured by Kyoeisha Chemical Co., Ltd.) and t-butylperoxy 2-ethyl hexyl monocarbonate (perbutyl E NOF Corporation) were used. Used and formulated according to Table 8. Each compound was stirred with a stirrer for 15 minutes to prepare a curable resin composition.
  • the reactivity varies depending on the type of curing agent, it can be cured at a low temperature of 90 if the microcapsules of the present invention are used as a curing accelerator even for polyphenol compounds and acid anhydrides that are generally low reactivity curing agents. It turns out that we can do it. It was also confirmed that the reactivity could be further improved by using a plasticizer. Although this method causes a decrease in storage stability, it can also be stored commercially at low temperatures and is an effective method for controlling reactivity. Furthermore, the microcapsules of the present invention have a storage stability comparable to that of the Epoxy duck type compound, and it has been recognized that a tougher shear adhesive force is exhibited in the resin composition also used. Therefore, the curable resin composition containing the microcapsule of the present invention can exhibit excellent reactivity derived from the microencapsulated strong basic liquid amine compound, and also has good storage stability. It was confirmed that Industrial applicability
  • a curable resin composition having both reactivity and storage stability By using the micro force pushell of the present invention as a curing agent or curing accelerator for a curable resin, it is possible to prepare a curable resin composition having both reactivity and storage stability.
  • a curable resin composition is a curable resin composition having both storage stability and reactivity. Therefore, it is useful in a wide range of fields, such as mounting underfill agents used in the manufacture of semiconductor devices, heat-dissipating resin compositions, and conductive resin compositions.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une microcapsule d'un composé aminé liquide, qui peut être produite de manière simple, tout en présentant une qualité stable. La microcapsule d'un composé aminé liquide présente une stabilité au stockage et une maniabilité lorsqu'elle est mélangée avec une résine durcissable et utilisée en tant qu'agent de durcissement ou accélérateur de durcissement. La microcapsule est composée des composants (A) à (C) décrits ci-dessous. Le composant (B) sert de support de capsule sur lequel le composant (A) est adsorbé. Un film de revêtement est formé par réaction du composant (C) avec le composant (A) présent à la surface du composant (B). Composant (A) : un composé aminé liquide présentant une constante de dissociation acide (pKa) supérieure ou égale à 8,0 ou un de ses sels d'acide organique Composant (B) : de fines particules poreuses capables d'adsorber le composant (A) Composant (C) : un anhydride d'acide
PCT/JP2009/054110 2008-02-29 2009-02-26 Microcapsule et composition de résine durcissable contenant des microcapsules WO2009107861A1 (fr)

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JP2008051249A JP5304984B2 (ja) 2008-02-29 2008-02-29 マイクロカプセルおよびマイクロカプセル含有硬化性樹脂組成物
JP2008-051249 2008-02-29

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CN105435723A (zh) * 2015-11-26 2016-03-30 江苏大学 含有石榴多酚微胶囊的香皂及石榴多酚微胶囊的制备方法
JP2017082219A (ja) * 2015-10-29 2017-05-18 株式会社Ｔ＆Ｋ Ｔｏｋａ 液状潜在性硬化剤組成物及びそれを用いた一液性の硬化性エポキシド組成物
JP2018503711A (ja) * 2014-12-04 2018-02-08 ピーアールシー−デソト インターナショナル，インコーポレイティド 作用時間が長いポリチオエーテルシーラント
CN108697595A (zh) * 2016-02-29 2018-10-23 积水化成品工业株式会社 内含二氧化硅的微胶囊树脂颗粒、其生产方法及其用途
WO2023090026A1 (fr) * 2021-11-17 2023-05-25 株式会社スリーボンド Composition de résine durcissable de type microcapsule

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JP2011012168A (ja) * 2009-07-01 2011-01-20 Enex Co Ltd 多孔質微粒子状潜在性硬化剤及び、これを用いた潜在硬化性エポキシ組成物と潜在硬化性ウレタン組成物
JP5941318B2 (ja) * 2012-03-29 2016-06-29 積水化学工業株式会社 硬化剤及び／又は硬化促進剤内包カプセル、及び、熱硬化性樹脂組成物
JP2015086249A (ja) 2013-10-28 2015-05-07 スリーボンドファインケミカル株式会社 マイクロカプセル型硬化性樹脂組成物
JP6417536B2 (ja) * 2014-05-16 2018-11-07 協立化学産業株式会社 低温硬化性樹脂組成物及びその使用
EP3424486B1 (fr) * 2016-02-29 2021-12-29 Sekisui Plastics Co., Ltd. Particules de résine en microcapsule contenant de la silice, procédé de production de celles-ci, et application de celles-ci
JP6711534B2 (ja) * 2016-06-13 2020-06-17 株式会社ブリヂストン ゴム組成物

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JP2018503711A (ja) * 2014-12-04 2018-02-08 ピーアールシー−デソト インターナショナル，インコーポレイティド 作用時間が長いポリチオエーテルシーラント
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CN105435723A (zh) * 2015-11-26 2016-03-30 江苏大学 含有石榴多酚微胶囊的香皂及石榴多酚微胶囊的制备方法
CN108697595A (zh) * 2016-02-29 2018-10-23 积水化成品工业株式会社 内含二氧化硅的微胶囊树脂颗粒、其生产方法及其用途
CN108697595B (zh) * 2016-02-29 2022-01-14 积水化成品工业株式会社 内含二氧化硅的微胶囊树脂颗粒、其生产方法及其用途
WO2023090026A1 (fr) * 2021-11-17 2023-05-25 株式会社スリーボンド Composition de résine durcissable de type microcapsule

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