JP5845044B2 - Curing agent and / or curing accelerator encapsulating capsule, and thermosetting resin composition - Google Patents
Curing agent and / or curing accelerator encapsulating capsule, and thermosetting resin composition Download PDFInfo
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- JP5845044B2 JP5845044B2 JP2011219490A JP2011219490A JP5845044B2 JP 5845044 B2 JP5845044 B2 JP 5845044B2 JP 2011219490 A JP2011219490 A JP 2011219490A JP 2011219490 A JP2011219490 A JP 2011219490A JP 5845044 B2 JP5845044 B2 JP 5845044B2
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- Prior art keywords
- curing
- curing accelerator
- curing agent
- agent
- accelerator
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- 239000003795 chemical substances by application Substances 0.000 title claims description 121
- 239000002775 capsule Substances 0.000 title claims description 76
- 239000011342 resin composition Substances 0.000 title claims description 25
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 10
- 239000000178 monomer Substances 0.000 claims description 44
- -1 imidazole compound Chemical class 0.000 claims description 32
- 229920001169 thermoplastic Polymers 0.000 claims description 29
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 15
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 26
- 239000002904 solvent Substances 0.000 description 26
- 239000011259 mixed solution Substances 0.000 description 23
- 239000012736 aqueous medium Substances 0.000 description 20
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- 239000000203 mixture Substances 0.000 description 15
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- 238000010438 heat treatment Methods 0.000 description 10
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- 125000001165 hydrophobic group Chemical group 0.000 description 9
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- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 6
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- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 1
- 229960003868 paraldehyde Drugs 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003203 poly(dimethylsilylene-co-phenylmethyl- silylene) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920003257 polycarbosilane Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001709 polysilazane Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000002053 thietanyl group Chemical group 0.000 description 1
- 150000003553 thiiranes Chemical group 0.000 description 1
- 125000001730 thiiranyl group Chemical group 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Epoxy Resins (AREA)
Description
本発明は、硬化剤及び／又は硬化促進剤の放出性に優れ、硬化性樹脂組成物に配合された場合に優れた貯蔵安定性、熱安定性及び速硬化性を発揮することができる硬化剤及び／又は硬促進剤内包カプセルに関する。また、本発明は、該硬化剤及び／又は硬化促進剤内包カプセルを含有する熱硬化性樹脂組成物に関する。 The present invention is excellent in the release of a curing agent and / or curing accelerator, and can exhibit excellent storage stability, thermal stability, and rapid curing when blended in a curable resin composition. And / or a hard accelerator-encapsulating capsule. Moreover, this invention relates to the thermosetting resin composition containing this hardening | curing agent and / or hardening accelerator inclusion capsule.
エポキシ樹脂は、接着剤、シール剤、コーティング剤等の様々な用途に用いられている。一般に、エポキシ樹脂には、硬化反応を進行させるための成分として硬化剤が、また、硬化性を向上させるための成分として硬化促進剤が添加される。特に、硬化剤又は硬化促進剤とエポキシ樹脂とを安定な一液にするために、潜在性をもたせた硬化剤又は硬化促進剤が多用されている。このような潜在性硬化剤又は硬化促進剤には、配合されたエポキシ樹脂組成物の安定性を低下させることなく、硬化時には速やかに硬化を進行させることが求められている。 Epoxy resins are used in various applications such as adhesives, sealants, and coating agents. Generally, a curing agent is added to the epoxy resin as a component for causing the curing reaction to proceed, and a curing accelerator is added as a component for improving the curability. In particular, in order to make a curing agent or a curing accelerator and an epoxy resin into a stable liquid, a latent curing agent or a curing accelerator is frequently used. Such latent curing agents or curing accelerators are required to rapidly cure during curing without reducing the stability of the blended epoxy resin composition.
潜在性硬化剤又は硬化促進剤としては、シェルに硬化剤又は硬化促進剤を内包したマイクロカプセル型硬化剤が知られている（例えば、特許文献１及び２）。しかしながら、これらの硬化剤では、エポキシ樹脂組成物の安定性及び速硬化性を充分に両立することは難しかった。 As a latent curing agent or curing accelerator, a microcapsule type curing agent in which a curing agent or a curing accelerator is encapsulated in a shell is known (for example, Patent Documents 1 and 2). However, with these curing agents, it has been difficult to sufficiently achieve both the stability and rapid curability of the epoxy resin composition.
また、特許文献３には、アミン化合物と、有機溶媒中に所定のポリマーからなる膜物質が溶解された疎水性溶液とを、混合して溶解し、これを乳化剤を溶解した水性媒体中に乳化分散させた後、加熱して上記有機溶媒を除去することにより、上記アミン化合物と膜物質とを相分離させて膜物質によってアミン化合物を被覆保護するマイクロカプセルの製法が記載されている。しかしながら、このような方法では、アミン化合物と膜物質との相分離を利用してマイクロカプセル構造を形成することから、使用するアミン化合物及び膜物質の選択の幅が狭く、使用するアミン化合物及び膜物質の極性によっては、マイクロカプセル構造が形成されないこともある。 Patent Document 3 discloses that an amine compound and a hydrophobic solution in which a film substance made of a predetermined polymer is dissolved in an organic solvent are mixed and dissolved, and this is emulsified in an aqueous medium in which an emulsifier is dissolved. A method for producing a microcapsule is described in which after the dispersion, the organic solvent is removed by heating to phase-separate the amine compound and the membrane material, and the amine compound is coated and protected by the membrane material. However, in such a method, since the microcapsule structure is formed by utilizing phase separation between the amine compound and the membrane material, the selection range of the amine compound and the membrane material to be used is narrow, and the amine compound and the membrane to be used are used. Depending on the polarity of the substance, the microcapsule structure may not be formed.
更に、特許文献４には、アミン類を主成分とする固体状の芯物質、および重合性二重結合を有する有機酸を含むラジカル重合性単量体の重合体を被覆層とするエポキシ樹脂マイクロカプセルが記載されている。しかしながら、このようなラジカル重合性モノマーの重合体をシェルとする硬化剤であっても、依然としてエポキシ樹脂組成物の安定性及び速硬化性を充分に両立するには至っていない。 Further, Patent Document 4 discloses an epoxy resin micro comprising a coating of a solid core substance mainly composed of amines and a polymer of a radical polymerizable monomer containing an organic acid having a polymerizable double bond. Capsules are described. However, even with a curing agent having such a polymer of a radical polymerizable monomer as a shell, the stability and rapid curability of the epoxy resin composition have not been sufficiently achieved.
本発明は、硬化剤及び／又は硬化促進剤の放出性に優れ、硬化性樹脂組成物に配合された場合に優れた貯蔵安定性、熱安定性及び速硬化性を発揮することができる硬化剤及び／又は硬化促進剤内包カプセルを提供することを目的とする。また、本発明は、該硬化剤及び／又は硬化促進剤内包カプセルを含有する熱硬化性樹脂組成物を提供することを目的とする。 The present invention is excellent in the release of a curing agent and / or curing accelerator, and can exhibit excellent storage stability, thermal stability, and rapid curing when blended in a curable resin composition. And / or it aims at providing a hardening accelerator inclusion capsule. Moreover, an object of this invention is to provide the thermosetting resin composition containing this hardening | curing agent and / or hardening accelerator inclusion capsule.
本発明は、シェルに、コア剤として硬化剤及び／又は硬化促進剤を内包する硬化剤及び／又は硬化促進剤内包カプセルであって、前記シェルは、少なくとも、ラジカル重合性モノマーの重合体を含有する最内層と、熱可塑性ポリマーを含有する最外層とを有し、前記最内層には、前記硬化剤及び／又は硬化促進剤との反応性基が存在しない硬化剤及び／又は硬化促進剤内包カプセルである。
以下、本発明を詳述する。
The present invention is a curing agent and / or a curing accelerator-encapsulating capsule containing a curing agent and / or a curing accelerator as a core agent in a shell, wherein the shell contains at least a polymer of a radical polymerizable monomer. An innermost layer and an outermost layer containing a thermoplastic polymer, and the innermost layer contains a curing agent and / or a curing accelerator containing no reactive group with the curing agent and / or the curing accelerator. It is a capsule.
The present invention is described in detail below.
本発明者は、ラジカル重合性モノマーの重合体をシェルとする硬化剤及び／又は硬化促進剤内包カプセルについて、硬化性樹脂組成物に配合された場合の安定性及び速硬化を両立することを検討した。その結果、本発明者は、ラジカル重合性モノマーの重合体をシェルとする硬化剤及び／又は硬化促進剤内包カプセルは、保管時にシェルの隙間から硬化剤及び／又は硬化促進剤が漏れ出ることがあり、貯蔵安定性及び熱安定性の低下の原因となっていることを見出した。
このような問題に対し、本発明者は、シェルを、少なくとも、ラジカル重合性モノマーの重合体を含有する最内層と、熱可塑性ポリマーを含有する最外層とを有する構造とすることにより、硬化剤及び／又は硬化促進剤内包カプセルの強度及び耐熱性を高め、硬化性樹脂組成物に配合された場合の貯蔵安定性及び熱安定性を改善できることを見出した。更に、本発明者は、最内層に硬化剤及び／又は硬化促進剤との反応性基を存在させないことにより、硬化剤及び／又は硬化促進剤を失活させることなくカプセルに内包し、硬化性樹脂組成物に配合された場合の速硬化性をも改善できることを見出し、本発明を完成させるに至った。
The present inventor has considered that both a curing agent and / or a curing accelerator-encapsulated capsule having a polymer of a radical polymerizable monomer as a shell can achieve both stability and rapid curing when blended in a curable resin composition. did. As a result, the inventor has found that the curing agent and / or curing accelerator-encapsulating capsule containing the polymer of the radical polymerizable monomer as a shell leaks from the gap between the shells during storage. It has been found that it causes a decrease in storage stability and thermal stability.
In order to solve such a problem, the present inventor has made the shell a structure having at least an innermost layer containing a polymer of a radical polymerizable monomer and an outermost layer containing a thermoplastic polymer. It was also found that the strength and heat resistance of the capsules containing the curing accelerator can be increased, and the storage stability and thermal stability can be improved when blended in the curable resin composition. Furthermore, the present inventor encapsulates the curable agent and / or the curing accelerator without deactivation by making the innermost layer free of a reactive group with the curable agent and / or the accelerating agent, and is curable. The present inventors have found that the quick curability when blended in the resin composition can be improved, and have completed the present invention.
本発明の硬化剤及び／又は硬化促進剤内包カプセルは、シェルに、コア剤として硬化剤及び／又は硬化促進剤を内包する。
上記シェルは、少なくとも、ラジカル重合性モノマーの重合体を含有する最内層と、熱可塑性ポリマーを含有する最外層とを有する。シェルをこのような構造とすることにより、硬化剤及び／又は硬化促進剤内包カプセルの強度及び耐熱性を高め、硬化性樹脂組成物に配合された場合の貯蔵安定性及び熱安定性を向上させることができる。なお、最内層とは、コア剤としての硬化剤及び／又は硬化促進剤を被覆する最も内側の層を意味し、最外層とは、硬化剤及び／又は硬化促進剤内包カプセルの表面となる最も外側の層を意味する。
The capsule containing the curing agent and / or curing accelerator of the present invention encapsulates the curing agent and / or curing accelerator as a core agent in the shell.
The shell has at least an innermost layer containing a polymer of a radical polymerizable monomer and an outermost layer containing a thermoplastic polymer. By making the shell into such a structure, the strength and heat resistance of the capsule containing the curing agent and / or curing accelerator are increased, and the storage stability and thermal stability when blended in the curable resin composition are improved. be able to. The innermost layer means the innermost layer that coats the curing agent and / or the curing accelerator as the core agent, and the outermost layer is the surface of the capsule containing the curing agent and / or the curing accelerator. Refers to the outer layer.
上記シェルは、少なくとも最内層と最外層とを有していれば、最内層と最外層との間に更に別の層を有していてもよい。 The shell may have another layer between the innermost layer and the outermost layer as long as it has at least the innermost layer and the outermost layer.
上記最内層は、ラジカル重合性モノマーの重合体を含有し、上記最内層には、上記硬化剤及び／又は硬化促進剤との反応性基が存在しない。最内層に硬化剤及び／又は硬化促進剤との反応性基を形成させないことにより、硬化剤及び／又は硬化促進剤を失活させることなくカプセルに内包することができる。これにより、本発明の硬化剤及び／又は硬化促進剤内包カプセルは、硬化性樹脂組成物に配合された場合に優れた速硬化性を発揮することができる。 The innermost layer contains a polymer of a radical polymerizable monomer, and the innermost layer has no reactive group with the curing agent and / or curing accelerator. By not forming a reactive group with the curing agent and / or curing accelerator in the innermost layer, it can be encapsulated in the capsule without deactivating the curing agent and / or curing accelerator. Thereby, the hardening | curing agent and / or hardening accelerator inclusion | inner_cover capsule of this invention can exhibit the quick-curing property which was excellent when it mix | blended with the curable resin composition.
このような最内層を形成する方法として、硬化剤及び／又は硬化促進剤と、硬化剤及び／又は硬化促進剤との反応性基をもたないラジカル重合性モノマーとを油性溶媒に溶解した混合溶液（１）を、水性媒体に分散させて乳化液（１）とし、次いで、ラジカル重合性モノマーを重合させて最内層を形成する方法が好ましい。
また、硬化剤及び／又は硬化促進剤との反応性基をもたないラジカル重合性モノマーを油性溶媒に溶解した混合溶液（２）を、水性媒体に分散させて乳化液（２）とし、次いで、混合溶液（２）の液滴に硬化剤及び／又は硬化促進剤を含浸させた後、ラジカル重合性モノマーを重合させて最内層を形成する方法も好ましい。
As a method for forming such an innermost layer, mixing a curing agent and / or a curing accelerator and a radical polymerizable monomer having no reactive group of the curing agent and / or the curing accelerator in an oily solvent. A method in which the solution (1) is dispersed in an aqueous medium to form an emulsion (1) and then a radical polymerizable monomer is polymerized to form an innermost layer.
Further, a mixed solution (2) obtained by dissolving a radical polymerizable monomer having no reactive group with a curing agent and / or a curing accelerator in an oily solvent is dispersed in an aqueous medium to obtain an emulsion (2). Also preferred is a method in which a droplet of the mixed solution (2) is impregnated with a curing agent and / or a curing accelerator and then a radical polymerizable monomer is polymerized to form an innermost layer.
上記硬化剤及び／又は硬化促進剤との反応性基をもたないラジカル重合性モノマーは、使用する硬化剤及び／又は硬化促進剤に応じて選択される。例えば、上記硬化剤及び／又は硬化促進剤がアミン化合物を含有する場合、アミン化合物との反応性基として、例えば、エポキシ基、グリシジル基、オキセタン基、エピスルフィド基、チイラン基、チエタン基等が挙げられる。 The radical polymerizable monomer having no reactive group with the curing agent and / or curing accelerator is selected according to the curing agent and / or curing accelerator to be used. For example, when the curing agent and / or curing accelerator contains an amine compound, examples of the reactive group with the amine compound include an epoxy group, a glycidyl group, an oxetane group, an episulfide group, a thiirane group, and a thietane group. It is done.
アミン化合物との反応性基をもたないラジカル重合性モノマーは、単官能性モノマーであっても、多官能性モノマーであってもよい。上記単官能性モノマーとして、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、クミル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ミリスチル（メタ）アクリレート、パルミチル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート等のアルキル（メタ）アクリレート、（メタ）アクリロニトリル、（メタ）アクリルアミド、（メタ）アクリル酸、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレート等の（メタ）アクリル系モノマー、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ｐ−クロロスチレン等の芳香族ビニルモノマー、酢酸ビニル、プロピオン酸ビニル等のビニルエステル、塩化ビニル、塩化ビニリデン等のハロゲン含有モノマー、ビニルピリジン、２−アクリロイルオキシエチルフタル酸、イタコン酸、フマル酸、エチレン、プロピレン等が挙げられる。また、上記多官能性モノマーとして、例えば、ジビニルベンゼン等の芳香族ジビニルモノマー、エチレングリコールジ（メタ）アクリート、プロピレングリコールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート等のアルキレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリート、トリエチレングリコールジ（メタ）アクリート、ポリエチレングリコールジ（メタ）アクリート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート等のポリアルキレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート等のポリオールポリ（メタ）アクリレート、アリル（メタ）アクリレート、アリルマレート、ジアリルフマレート、ジアリルイタコネート、トリアリルイソシアヌレート等のアリル化合物等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。 The radically polymerizable monomer having no reactive group with the amine compound may be a monofunctional monomer or a polyfunctional monomer. Examples of the monofunctional monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cumyl (meth) acrylate, cyclohexyl (meth) acrylate, and myristyl (meth) acrylate. , Alkyl (meth) acrylates such as palmityl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, (meth) acrylic acid, 2-hydroxyethyl methacrylate, 2- (Meth) acrylic monomers such as hydroxypropyl methacrylate, aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, vinyl acetate, propion Vinyl esters of vinyl such as vinyl chloride, halogen-containing monomers vinylidene chloride, vinyl pyridine, 2-acryloyloxyethyl phthalic acid, itaconic acid, fumaric acid, ethylene, propylene, and the like. Examples of the polyfunctional monomer include aromatic divinyl monomers such as divinylbenzene, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate alkylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) Polyalkylene glycol di (meth) acrylates such as acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and trimethylolpropane di (meth) acrylate Polyol (poly) acrylates such as relate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, allyl (meth) acrylate, allyl maleate And allyl compounds such as diallyl fumarate, diallyl itaconate and triallyl isocyanurate. These may be used alone or in combination of two or more.
上記最内層は、多孔質であることが好ましい。最内層を多孔質とすることにより、硬化剤及び／又は硬化促進剤の放出性を更に向上させ、硬化性樹脂組成物に配合された場合の硬化剤及び／又は硬化促進剤内包カプセルの速硬化性を更に高めることができる。なお、最内層が多孔質であるとは、最内層が、ラジカル重合性モノマーの重合体からなる粒子が互いに繋がって微細な隙間のある層を形成した構造を有することを意味する。最内層が多孔質であることは、硬化剤及び／又は硬化促進剤内包カプセルの断面を電子顕微鏡で観察することで確認することができる。
上述のように、硬化剤及び／又は硬化促進剤と、硬化剤及び／又は硬化促進剤との反応性基をもたないラジカル重合性モノマーとを油性溶媒に溶解した混合溶液（１）を、水性媒体に分散させて乳化液（１）とし、次いで、ラジカル重合性モノマーを重合させたり、また、硬化剤及び／又は硬化促進剤との反応性基をもたないラジカル重合性モノマーを油性溶媒に溶解した混合溶液（２）を、水性媒体に分散させて乳化液（２）とし、次いで、混合溶液（２）の液滴に硬化剤及び／又は硬化促進剤を含浸させた後、ラジカル重合性モノマーを重合させたりすることにより、上記最内層を多孔質とすることができる。
The innermost layer is preferably porous. By making the innermost layer porous, the release property of the curing agent and / or curing accelerator is further improved, and the curing agent and / or curing accelerator-encapsulating capsule is rapidly cured when blended in the curable resin composition. The sex can be further enhanced. Note that the innermost layer being porous means that the innermost layer has a structure in which particles made of a polymer of a radical polymerizable monomer are connected to each other to form a layer having a fine gap. Whether the innermost layer is porous can be confirmed by observing the cross section of the capsule containing the curing agent and / or the curing accelerator with an electron microscope.
As described above, a mixed solution (1) in which a curing agent and / or a curing accelerator and a radical polymerizable monomer having no reactive group of the curing agent and / or the curing accelerator are dissolved in an oily solvent, Disperse in an aqueous medium to make an emulsion (1), then polymerize the radical polymerizable monomer, or convert the radical polymerizable monomer having no reactive group with the curing agent and / or curing accelerator into an oily solvent. The mixed solution (2) dissolved in the aqueous solution is dispersed in an aqueous medium to obtain an emulsion (2). Next, the droplets of the mixed solution (2) are impregnated with a curing agent and / or a curing accelerator, and then radical polymerization is performed. The innermost layer can be made porous by polymerizing a polymerizable monomer.
上記最外層は、熱可塑性ポリマーを含有する。最外層に熱可塑性ポリマーを用い、加熱によって容易に溶解又は軟化する層とすることにより、硬化剤及び／又は硬化促進剤の放出性を損なうことなく、硬化剤及び／又は硬化促進剤内包カプセルの強度及び耐熱性を高め、硬化性樹脂組成物に配合された場合の貯蔵安定性及び熱安定性を向上させることができる。 The outermost layer contains a thermoplastic polymer. By using a thermoplastic polymer for the outermost layer and making it a layer that is easily dissolved or softened by heating, the release of the curing agent and / or curing accelerator is not impaired, and the capsule containing the curing agent and / or curing accelerator is Strength and heat resistance can be increased, and storage stability and thermal stability when blended in a curable resin composition can be improved.
このような最外層を形成する方法として、最内層を形成した後、得られた粒子（プレカプセル）と、熱可塑性ポリマーを油性溶媒に溶解した混合溶液（３）とを、水性媒体に分散させ、次いで、加熱等により油性溶媒を除去して熱可塑性ポリマーを析出させ、最内層の表面に最外層を形成する方法が好ましい。 As a method for forming such an outermost layer, after forming the innermost layer, the obtained particles (precapsules) and a mixed solution (3) in which a thermoplastic polymer is dissolved in an oily solvent are dispersed in an aqueous medium. Then, a method of removing the oily solvent by heating or the like to precipitate a thermoplastic polymer and forming the outermost layer on the surface of the innermost layer is preferable.
上記熱可塑性ポリマーは、親水性基と疎水性基とを有する熱可塑性ポリマー、水酸基を有するポリビニルアセタール樹脂、又は、アクリロニトリルに由来するセグメントを有する共重合体を含有することが好ましい。
上記親水性基と疎水性基とを有する熱可塑性ポリマーにおける親水性基として、例えば、グリシジル基、水酸基、カルボキシル基、スルホン基等が挙げられる。なかでも、グリシジル基が好ましい。上記親水性基と疎水性基とを有する熱可塑性ポリマーにおける疎水性基として、例えば、フェニル基、メチル基、エチル基、プロピル基、メタクリル基等が挙げられる。なかでも、フェニル基が好ましい。
The thermoplastic polymer preferably contains a thermoplastic polymer having a hydrophilic group and a hydrophobic group, a polyvinyl acetal resin having a hydroxyl group, or a copolymer having a segment derived from acrylonitrile.
Examples of the hydrophilic group in the thermoplastic polymer having the hydrophilic group and the hydrophobic group include a glycidyl group, a hydroxyl group, a carboxyl group, and a sulfone group. Of these, a glycidyl group is preferable. Examples of the hydrophobic group in the thermoplastic polymer having the hydrophilic group and the hydrophobic group include a phenyl group, a methyl group, an ethyl group, a propyl group, and a methacryl group. Of these, a phenyl group is preferred.
上記親水性基と疎水性基とを有する熱可塑性ポリマーとして、具体的には例えば、ポリスチレン誘導体、ポリメタクリル酸誘導体等が挙げられる。なかでも、ポリスチレン誘導体が好ましい。
上記ポリスチレン誘導体は、上記親水性基と上記疎水性基とを有していればよく、例えば、上記親水性基としてグリシジル基を有し、上記疎水性基としてポリスチレン骨格に由来するフェニル基を有するポリスチレン誘導体が好ましい。
Specific examples of the thermoplastic polymer having the hydrophilic group and the hydrophobic group include polystyrene derivatives and polymethacrylic acid derivatives. Of these, polystyrene derivatives are preferred.
The polystyrene derivative only needs to have the hydrophilic group and the hydrophobic group. For example, the polystyrene derivative has a glycidyl group as the hydrophilic group and a phenyl group derived from a polystyrene skeleton as the hydrophobic group. Polystyrene derivatives are preferred.
上記親水性基と疎水性基とを有する熱可塑性ポリマーの重量平均分子量は、好ましい下限が５０００、好ましい上限が１０万である。重量平均分子量が５０００未満であると、硬化剤及び／又は硬化促進剤内包カプセルの強度、耐熱性又は耐溶剤性が低下し、硬化性樹脂組成物に配合された場合の貯蔵安定性又は熱安定性が低下することがある。重量平均分子量が１０万を超えると、加熱しても最外層が溶融又は軟化せず、硬化剤及び／又は硬化促進剤の放出性が低下し、硬化反応に長時間を要することがある。 As for the weight average molecular weight of the thermoplastic polymer which has the said hydrophilic group and hydrophobic group, a preferable minimum is 5000 and a preferable upper limit is 100,000. When the weight average molecular weight is less than 5000, the strength, heat resistance or solvent resistance of the capsule containing the curing agent and / or curing accelerator decreases, and storage stability or thermal stability when blended in the curable resin composition May decrease. When the weight average molecular weight exceeds 100,000, the outermost layer does not melt or soften even when heated, and the release of the curing agent and / or the curing accelerator is lowered, and the curing reaction may take a long time.
上記水酸基を有するポリビニルアセタール樹脂は、通常、ポリ酢酸ビニルのけん化反応により得られたポリビニルアルコールを、アルデヒドでアセタール化することにより得られる。上記アセタール化に使用するアルデヒドとして、例えば、ホルムアルデヒド、アセトアルデヒド、パラアセトアルデヒド、ブチルアルデヒド等が挙げられる。なかでも、ブチルアルデヒドが好ましい。
上記水酸基を有するポリビニルアセタール樹脂の水酸基の含有量、アセタール化度、原料であるポリ酢酸ビニルのアセチル基に由来するアセチル基の含有量、重量平均分子量等を調整することにより、目的に合わせて最外層の物性を調整することができる。
The polyvinyl acetal resin having a hydroxyl group is usually obtained by acetalizing polyvinyl alcohol obtained by a saponification reaction of polyvinyl acetate with an aldehyde. Examples of the aldehyde used for the acetalization include formaldehyde, acetaldehyde, paraacetaldehyde, butyraldehyde and the like. Of these, butyraldehyde is preferred.
By adjusting the hydroxyl content, the degree of acetalization, the content of acetyl groups derived from the acetyl group of polyvinyl acetate as the raw material, the weight average molecular weight, etc. of the polyvinyl acetal resin having a hydroxyl group, the most suitable for the purpose. The physical properties of the outer layer can be adjusted.
上記水酸基を有するポリビニルアセタール樹脂の重量平均分子量は、好ましい下限が５０００、好ましい上限が５０万である。重量平均分子量が５０００未満であると、硬化剤及び／又は硬化促進剤内包カプセルの強度、耐熱性又は耐溶剤性が低下し、硬化性樹脂組成物に配合された場合の貯蔵安定性又は熱安定性が低下することがある。重量平均分子量が５０万を超えると、加熱しても最外層が溶融又は軟化せず、硬化剤及び／又は硬化促進剤の放出性が低下し、硬化反応に長時間を要することがある。重量平均分子量のより好ましい下限は３万、より好ましい上限は３０万である。 As for the weight average molecular weight of the said polyvinyl acetal resin which has a hydroxyl group, a preferable minimum is 5000 and a preferable upper limit is 500,000. When the weight average molecular weight is less than 5000, the strength, heat resistance or solvent resistance of the capsule containing the curing agent and / or curing accelerator decreases, and storage stability or thermal stability when blended in the curable resin composition May decrease. When the weight average molecular weight exceeds 500,000, even when heated, the outermost layer does not melt or soften, the release property of the curing agent and / or the curing accelerator decreases, and the curing reaction may take a long time. The more preferable lower limit of the weight average molecular weight is 30,000, and the more preferable upper limit is 300,000.
上記水酸基を有するポリビニルアセタール樹脂の市販品として、例えば、ＢＬ−１０（積水化学工業社製）、ＢＬ−２Ｈ（積水化学工業社製）、ＢＭ−Ｓ（積水化学工業社製）、ＢＨ−３（積水化学工業社製）、♯−３０００Ｋ（電気化学工業社製）、ＭＯＷＩＴＡＬ Ｂ６０Ｔ（クラレ社製）等が挙げられる。 As a commercial item of the polyvinyl acetal resin which has the said hydroxyl group, for example, BL-10 (made by Sekisui Chemical Co., Ltd.), BL-2H (made by Sekisui Chemical Co., Ltd.), BM-S (made by Sekisui Chemical Co., Ltd.), BH-3 (Manufactured by Sekisui Chemical Co., Ltd.), # -3000K (manufactured by Denki Kagaku Kogyo Co., Ltd.), MOWITAL B60T (manufactured by Kuraray Co., Ltd.) and the like.
熱可塑性ポリマーにアクリロニトリルに由来するセグメントを有する共重合体を用いることにより、最外層のガスバリア性及び耐溶剤性を向上させることができる。
上記アクリロニトリルに由来するセグメントを有する共重合体において、上記アクリロニトリルに由来するセグメント以外の他のモノマーに由来するセグメントは特に限定されない。上記他のモノマーとして、例えば、ビニル基を有する化合物等のラジカル重合性モノマーが挙げられる。上記ビニル基を有する化合物は特に限定されず、例えば、グリシジルメタクリレート（ＧＭＡ）、メチルメタクリレート（ＭＭＡ）等のメタクリル酸エステル、アクリル酸エステル、スチレン、ジビニルベンゼン、塩化ビニリデン、ビニルアルコール、ビニルピロリドン、エチレングリコールジメタクリレート、ブタジエン等が挙げられる。なかでも、スチレン、グリシジルメタクリレート（ＧＭＡ）、メチルメタクリレート（ＭＭＡ）が好ましい。
By using a copolymer having a segment derived from acrylonitrile as the thermoplastic polymer, the gas barrier property and solvent resistance of the outermost layer can be improved.
In the copolymer having a segment derived from acrylonitrile, a segment derived from another monomer other than the segment derived from acrylonitrile is not particularly limited. As said other monomer, radical polymerizable monomers, such as a compound which has a vinyl group, are mentioned, for example. The compound having a vinyl group is not particularly limited, and examples thereof include methacrylic acid esters such as glycidyl methacrylate (GMA) and methyl methacrylate (MMA), acrylic acid esters, styrene, divinylbenzene, vinylidene chloride, vinyl alcohol, vinyl pyrrolidone, and ethylene. Examples include glycol dimethacrylate and butadiene. Of these, styrene, glycidyl methacrylate (GMA), and methyl methacrylate (MMA) are preferable.
上記アクリロニトリルに由来するセグメントを有する共重合体の重量平均分子量は、好ましい下限が５０００、好ましい上限が１０万である。重量平均分子量が５０００未満であると、硬化剤及び／又は硬化促進剤内包カプセルの強度、耐熱性又は耐溶剤性が低下し、硬化性樹脂組成物に配合された場合の貯蔵安定性又は熱安定性が低下することがある。重量平均分子量が１０万を超えると、加熱しても最外層が溶融又は軟化せず、硬化剤及び／又は硬化促進剤の放出性が低下し、硬化反応に長時間を要することがある。重量平均分子量のより好ましい下限は８０００、より好ましい上限は５万であり、更に好ましい下限は１万、更に好ましい上限は３万である。 As for the weight average molecular weight of the copolymer having a segment derived from acrylonitrile, a preferable lower limit is 5000 and a preferable upper limit is 100,000. When the weight average molecular weight is less than 5000, the strength, heat resistance or solvent resistance of the capsule containing the curing agent and / or curing accelerator decreases, and storage stability or thermal stability when blended in the curable resin composition May decrease. When the weight average molecular weight exceeds 100,000, the outermost layer does not melt or soften even when heated, and the release of the curing agent and / or the curing accelerator is lowered, and the curing reaction may take a long time. The more preferred lower limit of the weight average molecular weight is 8000, the more preferred upper limit is 50,000, the still more preferred lower limit is 10,000, and the more preferred upper limit is 30,000.
なお、上記熱可塑性ポリマーは、グリシジル基を有することが好ましい。上記熱可塑性ポリマーがグリシジル基を有する場合として、例えば、上記親水性基と疎水性基とを有する熱可塑性ポリマーにおける親水性基がグリシジル基である場合、上記アクリロニトリルに由来するセグメントを有する共重合体において他のモノマーとしてグリシジルメタクリレート（ＧＭＡ）等のグリシジル基含有モノマーを用いる場合等が挙げられる。上記アクリロニトリルに由来するセグメントを有する共重合体にグリシジル基含有モノマーを用いることにより、アクリロニトリルに由来するセグメントの凝集を適度に緩和することで、硬化剤及び／又は硬化促進剤の放出温度をコントロールすることができる。 In addition, it is preferable that the said thermoplastic polymer has a glycidyl group. When the thermoplastic polymer has a glycidyl group, for example, when the hydrophilic group in the thermoplastic polymer having the hydrophilic group and the hydrophobic group is a glycidyl group, the copolymer has a segment derived from the acrylonitrile. In the case of using a glycidyl group-containing monomer such as glycidyl methacrylate (GMA) as another monomer. By using a glycidyl group-containing monomer in the copolymer having a segment derived from acrylonitrile, the aggregation temperature of the segment derived from acrylonitrile is moderately moderated to control the release temperature of the curing agent and / or curing accelerator. be able to.
上記最外層は、更に、無機ポリマーを含有してもよい。最外層に無機ポリマーを用いることにより、硬化剤及び／又は硬化促進剤内包カプセルの強度、耐熱性及び耐溶剤性が向上し、例えば溶剤と混合する場合であっても好適に用いられる。 The outermost layer may further contain an inorganic polymer. By using an inorganic polymer for the outermost layer, the strength, heat resistance and solvent resistance of the capsule containing the curing agent and / or curing accelerator are improved. For example, the capsule is preferably used even when mixed with a solvent.
上記無機ポリマーとして、分子中に２個以上の炭素数１〜６のアルコキシ基を有し、かつ、Ｓｉ、Ａｌ、Ｚｒ及びＴｉからなる群より選択される少なくとも１種の金属元素を含有する有機金属化合物の重合体が好ましい。このような有機金属化合物の重合体として、例えば、シリコーン樹脂、ポリボロシロキサン樹脂、ポリカルボシラン樹脂、ポリシラスチレン樹脂、ポリシラザン樹脂、ポリチタノカルボシラン樹脂等が挙げられる。なかでも、シリコーン樹脂が好ましく、グリシジル基を有するシリコーン樹脂がより好ましい。 Organic having at least one metal element selected from the group consisting of Si, Al, Zr, and Ti as the inorganic polymer, having 2 or more C1-C6 alkoxy groups in the molecule Polymers of metal compounds are preferred. Examples of such a polymer of an organometallic compound include silicone resins, polyborosiloxane resins, polycarbosilane resins, polysilastyrene resins, polysilazane resins, and polytitanocarbosilane resins. Among these, a silicone resin is preferable, and a silicone resin having a glycidyl group is more preferable.
上記硬化剤及び／又は硬化促進剤は、融点が１００℃未満であることが好ましく、例えば、三級アミン化合物、イミダゾール化合物等のアミン化合物、又は、リン系触媒等が挙げられる。なかでも、硬化性に優れることから、イミダゾール化合物が好ましい。
上記イミダゾール化合物は特に限定されず、例えば、１，２−ジメチルイミダゾール、２−エチル−４−メチルイミダゾール、１−ベンジル−２−メチルイミダゾール、１−ベンジル−２−フェニルイミダゾール、１−シアノエチル−２−メチルイミダゾール、１−シアノエチル−２−ウンデシルイミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾール、１−ドデシル−２−メチル−３−ベンジルイミダゾリウムクロライド、及び、これらの付加体等が挙げられる。
The curing agent and / or curing accelerator preferably has a melting point of less than 100 ° C., and examples thereof include amine compounds such as tertiary amine compounds and imidazole compounds, or phosphorus-based catalysts. Especially, since it is excellent in sclerosis | hardenability, an imidazole compound is preferable.
The imidazole compound is not particularly limited. For example, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2 -Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, and adducts thereof Can be mentioned.
また、上記イミダゾール化合物として、疎水性イミダゾール化合物を用いることが好ましい。なお、疎水性イミダゾール化合物とは、水に最大限溶解させたときの濃度が５重量％未満であるイミダゾール化合物を意味する。
上記疎水性イミダゾール化合物は、炭素数１１以上の炭化水素基を有するイミダゾール化合物が好ましい。上記炭素数１１以上の炭化水素基を有するイミダゾール化合物として、例えば、２−ウンデシルイミダゾール、２−ヘプタデシルイミダゾール、１−シアノエチルイミダゾール等が挙げられる。なかでも、２−ウンデシルイミダゾールが好ましい。
Moreover, it is preferable to use a hydrophobic imidazole compound as the imidazole compound. The hydrophobic imidazole compound means an imidazole compound having a concentration of less than 5% by weight when dissolved in water to the maximum.
The hydrophobic imidazole compound is preferably an imidazole compound having a hydrocarbon group having 11 or more carbon atoms. Examples of the imidazole compound having a hydrocarbon group having 11 or more carbon atoms include 2-undecylimidazole, 2-heptadecylimidazole, 1-cyanoethylimidazole, and the like. Of these, 2-undecylimidazole is preferable.
本発明の硬化剤及び／又は硬化促進剤内包カプセルのシェル厚みは、好ましい下限が０．０５μｍ、好ましい上限が０．８μｍである。シェル厚みが０．０５μｍ未満であると、硬化剤及び／又は硬化促進剤内包カプセルの強度、耐熱性又は耐溶剤性が低下し、硬化性樹脂組成物に配合された場合の貯蔵安定性又は熱安定性が低下することがある。シェル厚みが０．８μｍを超えると、硬化剤及び／又は硬化促進剤の放出性が低下し、硬化反応に長時間を要することがある。シェル厚みのより好ましい下限は０．０８μｍ、より好ましい上限は０．５μｍである。
なお、シェル厚みとは、最内層、最外層及び必要に応じて別の層を含むシェル全体の厚みを意味する。また、硬化剤及び／又は硬化促進剤内包カプセルのシェル厚みとは、下記式（１）により算出される、カプセルの体積と内包体積比率から算出したシェルの体積を、カプセルの表面積で割ることで求められる値を意味する。
シェル厚み＝｛カプセルの体積−（カプセルの体積×内包体積比率）｝／カプセルの表面積 （１）
The preferable lower limit of the shell thickness of the capsule containing the curing agent and / or curing accelerator of the present invention is 0.05 μm, and the preferable upper limit is 0.8 μm. When the shell thickness is less than 0.05 μm, the strength, heat resistance or solvent resistance of the capsule containing the curing agent and / or curing accelerator decreases, and storage stability or heat when blended in the curable resin composition Stability may be reduced. When the shell thickness exceeds 0.8 μm, the release property of the curing agent and / or curing accelerator is lowered, and the curing reaction may take a long time. A more preferable lower limit of the shell thickness is 0.08 μm, and a more preferable upper limit is 0.5 μm.
In addition, shell thickness means the thickness of the whole shell containing an innermost layer, an outermost layer, and another layer as needed. Further, the shell thickness of the encapsulating capsule with the curing agent and / or curing accelerator is obtained by dividing the volume of the shell calculated from the volume of the capsule and the encapsulating volume ratio calculated by the following formula (1) by the surface area of the capsule. Means the desired value.
Shell thickness = {Capsule volume− (Capsule volume × Internal volume ratio)} / Capsule surface area (1)
また、上記最内層の厚みと上記最外層の厚みとの比率は、１５：１〜２：１であることが好ましい。上記範囲よりも最内層の厚みの比率が大きくなると、硬化剤及び／又は硬化促進剤内包カプセルの強度、耐熱性又は耐溶剤性が低下し、硬化性樹脂組成物に配合された場合の貯蔵安定性又は熱安定性が低下することがある。上記範囲よりも最外層の厚みの比率が大きくなると、硬化剤及び／又は硬化促進剤の放出性が低下し、硬化反応に長時間を要することがある。上記最内層の厚みと上記最外層の厚みとの比率は、８：１〜３：１であることがより好ましい。 The ratio of the innermost layer thickness to the outermost layer thickness is preferably 15: 1 to 2: 1. When the ratio of the thickness of the innermost layer is larger than the above range, the strength, heat resistance or solvent resistance of the capsule containing the curing agent and / or curing accelerator decreases, and storage stability when blended in the curable resin composition Or thermal stability may be reduced. When the ratio of the thickness of the outermost layer is larger than the above range, the release property of the curing agent and / or the curing accelerator is lowered, and the curing reaction may take a long time. The ratio between the thickness of the innermost layer and the thickness of the outermost layer is more preferably 8: 1 to 3: 1.
本発明の硬化剤及び／又は硬化促進剤内包カプセルの内包体積比率は、好ましい下限が１５体積％、好ましい上限が７０体積％である。内包体積比率が１５体積％未満であると、硬化剤及び／又は硬化促進剤の放出性が低下し、硬化反応に長時間を要したり硬化剤及び／又は硬化促進剤内包カプセルを多量に配合する必要が生じたりすることがある。内包体積比率が７０体積％を超えると、硬化剤及び／又は硬化促進剤内包カプセルのシェルが薄くなりすぎて強度、耐熱性又は耐溶剤性が低下し、貯蔵安定性又は熱安定性が低下することがある。内包体積比率のより好ましい下限は２５体積％、より好ましい上限は５０体積％である。
なお、硬化剤及び／又は硬化促進剤内包カプセルの内包体積比率は、平均粒子径を用いて算出したカプセルの体積とガスクロマトグラフィーを用いて測定したコア剤の含有量から、下記式（２）により算出される値を意味する。
内包体積比率（％）＝（コア剤の含有量（重量％）×コア剤の比重（ｇ／ｃｍ３））／カプセルの体積（ｃｍ３） （２）
The preferable lower limit of the encapsulating volume ratio of the curing agent and / or curing accelerator-encapsulating capsule of the present invention is 15% by volume, and the preferable upper limit is 70% by volume. When the encapsulated volume ratio is less than 15% by volume, the release property of the curing agent and / or curing accelerator is lowered, and it takes a long time for the curing reaction or contains a large amount of the encapsulating capsule containing the curing agent and / or curing accelerator. May need to be done. When the encapsulated volume ratio exceeds 70% by volume, the shell of the encapsulating agent and / or curing accelerator encapsulating capsule becomes too thin and the strength, heat resistance or solvent resistance is lowered, and the storage stability or thermal stability is lowered. Sometimes. A more preferable lower limit of the inclusion volume ratio is 25% by volume, and a more preferable upper limit is 50% by volume.
The encapsulated volume ratio of the capsulating agent and / or the accelerating agent-encapsulating capsule is expressed by the following formula (2) from the capsule volume calculated using the average particle diameter and the content of the core agent measured using gas chromatography. Means the value calculated by.
Encapsulated volume ratio (%) = (content of core agent (% by weight) × specific gravity of core agent (g / cm 3 )) / volume of capsule (cm 3 ) (2)
本発明の硬化剤及び／又は硬化促進剤内包カプセルの平均粒子径は、好ましい下限が０．５μｍ、好ましい上限が１０μｍである。平均粒子径が０．５μｍ未満であると、所望の範囲の内包率を維持しようとすると、硬化剤及び／又は硬化促進剤内包カプセルの強度、耐熱性又は耐溶剤性が低下し、硬化性樹脂組成物に配合された場合の貯蔵安定性又は熱安定性が低下することがある。平均粒子径が１０μｍを超えると、硬化剤及び／又は硬化促進剤内包カプセルを硬化性樹脂組成物に配合した場合に、加熱により硬化剤及び／又は硬化促進剤が放出された後、大きなボイドが生じて硬化物の信頼性が低下することがある。平均粒子径のより好ましい上限は３．０μｍである。
なお、硬化剤及び／又は硬化促進剤内包カプセルの平均粒子径とは、走査型電子顕微鏡を用いて１視野に約１００個のカプセルが観察できる倍率で観察し、任意に選択した５０個のカプセルの最長径をノギスで測定した平均値を意味する。
The preferable lower limit of the average particle size of the curing agent and / or curing accelerator-encapsulating capsule of the present invention is 0.5 μm, and the preferable upper limit is 10 μm. If the average particle size is less than 0.5 μm, the strength, heat resistance or solvent resistance of the capsules containing the curing agent and / or curing accelerator will be reduced when maintaining the encapsulation rate within the desired range. Storage stability or thermal stability may decrease when blended in the composition. When the average particle size exceeds 10 μm, when the curing agent and / or curing accelerator-encapsulating capsule is blended with the curable resin composition, a large void is generated after the curing agent and / or the curing accelerator is released by heating. It may occur and the reliability of the cured product may be reduced. A more preferable upper limit of the average particle diameter is 3.0 μm.
The average particle size of the capsules containing the curing agent and / or curing accelerator is 50 capsules arbitrarily selected by observing at a magnification at which about 100 capsules can be observed in one visual field using a scanning electron microscope. Means the average value of the longest diameter measured with calipers.
本発明の硬化剤及び／又は硬化促進剤内包カプセルを製造する方法は、コア剤として硬化剤及び／又は硬化促進剤を内包する最内層を形成した後、最内層の表面に最外層を形成する方法が好ましい。
上記最内層を形成する方法は、上述したように、硬化剤及び／又は硬化促進剤と、硬化剤及び／又は硬化促進剤との反応性基をもたないラジカル重合性モノマーとを油性溶媒に溶解した混合溶液（１）を、水性媒体に分散させて乳化液（１）とし、次いで、ラジカル重合性モノマーを重合させる方法が好ましい。また、硬化剤及び／又は硬化促進剤との反応性基をもたないラジカル重合性モノマーを油性溶媒に溶解した混合溶液（２）を、水性媒体に分散させて乳化液（２）とし、次いで、混合溶液（２）の液滴に上記硬化剤及び／又は硬化促進剤を含浸させた後、ラジカル重合性モノマーを重合させる方法も好ましい。
In the method for producing a capsule containing a curing agent and / or a curing accelerator according to the present invention, an outermost layer is formed on the surface of the innermost layer after forming an innermost layer enclosing the curing agent and / or the curing accelerator as a core agent. The method is preferred.
As described above, the innermost layer is formed by using a curing agent and / or a curing accelerator and a radical polymerizable monomer having no reactive group of the curing agent and / or the curing accelerator in an oily solvent. A method of dispersing the dissolved mixed solution (1) in an aqueous medium to obtain an emulsion (1) and then polymerizing a radical polymerizable monomer is preferred. Further, a mixed solution (2) obtained by dissolving a radical polymerizable monomer having no reactive group with a curing agent and / or a curing accelerator in an oily solvent is dispersed in an aqueous medium to obtain an emulsion (2). Also preferred is a method in which the radical polymerizable monomer is polymerized after impregnating the above-mentioned curing agent and / or curing accelerator into the droplets of the mixed solution (2).
上記油性溶媒は特に限定されず、例えば、ベンゼン、イソプレン、ヘキサン、ヘプタン、シクロヘキサン、ギ酸イソブチル、酢酸メチル、酢酸エチル、ジプロピルエーテル、ジブチルエーテル、エタノール、アリルアルコール、１−プロパノール、２−プロパノール、ｔ−ブチルアルコール、アセトン、エチルメチルケトン、Ｎ，Ｎ−ジメチルホルムアミド、アセトニトリル等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。 The oily solvent is not particularly limited. For example, benzene, isoprene, hexane, heptane, cyclohexane, isobutyl formate, methyl acetate, ethyl acetate, dipropyl ether, dibutyl ether, ethanol, allyl alcohol, 1-propanol, 2-propanol, Examples thereof include t-butyl alcohol, acetone, ethyl methyl ketone, N, N-dimethylformamide, acetonitrile and the like. These may be used alone or in combination of two or more.
上記水性媒体は特に限定されず、例えば、水に、乳化剤、分散安定剤等を添加した水性媒体が用いられる。上記乳化剤は特に限定されず、例えば、アルキル硫酸スルホン酸塩、アルキルベンゼンスルホン酸塩、アルキル硫酸トリエタノールアミン、ポリオキシエチレンアルキルエーテル等が挙げられる。上記分散安定剤は特に限定されず、例えば、ポリビニルアルコール、ポリビニルピロリドン、ポリエチレングリコール等が挙げられる。 The aqueous medium is not particularly limited, and for example, an aqueous medium in which an emulsifier, a dispersion stabilizer and the like are added to water is used. The emulsifier is not particularly limited, and examples thereof include alkyl sulfate sulfonate, alkyl benzene sulfonate, alkyl sulfate triethanolamine, and polyoxyethylene alkyl ether. The dispersion stabilizer is not particularly limited, and examples thereof include polyvinyl alcohol, polyvinyl pyrrolidone, and polyethylene glycol.
上記乳化液（１）又は（２）を調製する際には、混合溶液（１）又は（２）に水性媒体を添加してもよく、水性媒体に混合溶液（１）又は（２）を添加してもよい。乳化方法として、例えば、ホモジナイザーを用いて攪拌する方法、超音波照射により乳化する方法、マイクロチャネル又はＳＰＧ膜を通過させて乳化する方法、スプレーで噴霧する方法、転相乳化法等が挙げられる。 When preparing the emulsion (1) or (2), an aqueous medium may be added to the mixed solution (1) or (2), and the mixed solution (1) or (2) is added to the aqueous medium. May be. Examples of the emulsification method include a method of stirring using a homogenizer, a method of emulsifying by ultrasonic irradiation, a method of emulsifying by passing through a microchannel or an SPG film, a method of spraying with a spray, and a phase inversion emulsification method.
上記混合溶液（２）の液滴に上記硬化剤及び／又は硬化促進剤を含浸させる方法として、例えば、乳化液（２）に固体状の硬化剤及び／又は硬化促進剤を添加し、固体状の硬化剤及び／又は硬化促進剤の融点以上に乳化液（２）を加熱して、固体状の硬化剤及び／又は硬化促進剤を液体状とする方法が挙げられる。なかでも、固体状の硬化剤及び／又は硬化促進剤の融点以上かつ１００℃未満に乳化液（２）を加熱して、水性媒体を蒸発させることなく硬化剤及び／又は硬化促進剤を含浸させることが好ましい。
また、例えば、乳化液（２）に液体状の硬化剤及び／又は硬化促進剤を添加し、乳化液（２）を攪拌する方法も挙げられる。
As a method of impregnating the above-mentioned curing agent and / or curing accelerator into the droplets of the mixed solution (2), for example, a solid curing agent and / or a curing accelerator is added to the emulsion (2) to obtain a solid state. And a method of heating the emulsion (2) to a temperature equal to or higher than the melting point of the curing agent and / or curing accelerator to make the solid curing agent and / or curing accelerator liquid. Among them, the emulsified liquid (2) is heated above the melting point of the solid curing agent and / or curing accelerator and below 100 ° C. to impregnate the curing agent and / or curing accelerator without evaporating the aqueous medium. It is preferable.
Moreover, for example, a method of adding a liquid curing agent and / or a curing accelerator to the emulsion (2) and stirring the emulsion (2) can also be mentioned.
上記ラジカル重合性モノマーを重合させる方法は特に限定されず、使用する重合開始剤の種類等に従って、光を照射したり加熱したりすることにより重合を開始させることができる。重合開始剤は特に限定されないが、水に難溶性（２３℃における水への溶解度が２０重量％以下）であることが好ましく、具体的には例えば、ベンゾイルパーオキサイド等の過酸化物、アゾビスイソブチロニトリル等のアゾ化合物等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。 The method for polymerizing the radical polymerizable monomer is not particularly limited, and the polymerization can be initiated by irradiating light or heating according to the kind of the polymerization initiator used. The polymerization initiator is not particularly limited, but is preferably hardly soluble in water (the solubility in water at 23 ° C. is 20% by weight or less). Specifically, for example, peroxides such as benzoyl peroxide, azobis Examples include azo compounds such as isobutyronitrile. These may be used alone or in combination of two or more.
上記重合開始剤の配合量は特に限定されず、上記ラジカル重合性モノマー１００重量部に対する好ましい下限が０．０１重量部、好ましい上限が２０重量部である。配合量が０．０１重量部未満であると、硬化剤及び／又は硬化促進剤内包カプセルが形成されないことがある。２０重量部を超えて配合してもほとんど反応には寄与せず、ブリードアウト等の原因となることがある。上記ラジカル重合性モノマー１００重量部に対する配合量のより好ましい下限は０．１重量部、より好ましい上限は１０重量部である。 The blending amount of the polymerization initiator is not particularly limited, and a preferable lower limit with respect to 100 parts by weight of the radical polymerizable monomer is 0.01 part by weight, and a preferable upper limit is 20 parts by weight. If the blending amount is less than 0.01 parts by weight, the capsule containing the curing agent and / or curing accelerator may not be formed. Even if it exceeds 20 parts by weight, it hardly contributes to the reaction and may cause bleeding out. A more preferable lower limit of the blending amount with respect to 100 parts by weight of the radical polymerizable monomer is 0.1 part by weight, and a more preferable upper limit is 10 parts by weight.
なお、乳化液（２）に固体状の硬化剤及び／又は硬化促進剤を添加する場合には、乳化液（２）に、固体状の硬化剤及び／又は硬化促進剤の融点以下の温度領域に１０時間半減期温度を有する重合開始剤を添加してもよいし、予め混合溶液（２）に固体状の硬化剤及び／又は硬化促進剤の融点以上の温度領域に１０時間半減期温度を有する重合開始剤を添加しておいてもよい。 In addition, when adding a solid hardening | curing agent and / or a hardening accelerator to an emulsion (2), it is the temperature range below the melting point of a solid hardening | curing agent and / or a hardening accelerator to an emulsion (2). A polymerization initiator having a 10-hour half-life temperature may be added to the mixture solution, and a 10-hour half-life temperature is previously added to the mixed solution (2) in a temperature region above the melting point of the solid curing agent and / or curing accelerator. You may add the polymerization initiator which has.
上記最外層を形成する方法は、上述したように、最内層を形成した後、得られた粒子（プレカプセル）と、熱可塑性ポリマーを油性溶媒に溶解した混合溶液（３）とを、水性媒体に分散させ、次いで、加熱等により油性溶媒を除去して熱可塑性ポリマーを析出させ、最内層の表面に最外層を形成する方法が好ましい。 The method for forming the outermost layer is, as described above, after forming the innermost layer, the obtained particles (precapsules) and a mixed solution (3) in which a thermoplastic polymer is dissolved in an oily solvent are mixed with an aqueous medium. Then, the method is preferably used in which the oily solvent is removed by heating or the like to precipitate the thermoplastic polymer, and the outermost layer is formed on the surface of the innermost layer.
上記最外層を形成する方法において使用される油性溶媒及び水性媒体は、熱可塑性ポリマーの種類に応じて選択されるが、上記最内層を形成する方法において使用される油性溶媒及び水性媒体と同様のものが挙げられる。
プレカプセルと混合溶液（３）とを水性媒体に分散させる方法は特に限定されないが、プレカプセルを水性媒体に分散させた後、得られた水性媒体を混合溶液（３）に添加する方法が好ましい。
The oily solvent and the aqueous medium used in the method for forming the outermost layer are selected according to the kind of the thermoplastic polymer, but are the same as the oily solvent and the aqueous medium used in the method for forming the innermost layer. Things.
A method of dispersing the precapsule and the mixed solution (3) in the aqueous medium is not particularly limited, but a method of adding the obtained aqueous medium to the mixed solution (3) after dispersing the precapsule in the aqueous medium is preferable. .
油性溶媒を除去して熱可塑性ポリマーを析出させる方法として、３０〜７０℃に加熱する方法が好ましく、加熱に加えて、０．０９５〜０．０８０ＭＰａの圧力となるよう設定して減圧を行う方法がより好ましい。 As a method for precipitating the thermoplastic polymer by removing the oily solvent, a method of heating to 30 to 70 ° C. is preferable. In addition to heating, a method of reducing the pressure by setting to a pressure of 0.095 to 0.080 MPa Is more preferable.
得られた硬化剤及び／又は硬化促進剤内包カプセルは、純水を用いて繰り返して洗浄された後、真空乾燥等により乾燥されてもよい。 The obtained curing agent and / or curing accelerator-encapsulating capsule may be repeatedly washed with pure water and then dried by vacuum drying or the like.
本発明の硬化剤及び／又は硬化促進剤内包カプセルは、硬化剤及び／又は硬化促進剤の放出性に優れ、硬化性樹脂組成物に配合された場合に優れた貯蔵安定性、熱安定性及び速硬化性を発揮することができることから、エポキシ樹脂等の熱硬化性樹脂用の潜在性硬化剤又は硬化促進剤として好適に用いられる。
本発明の硬化剤及び／又は硬化促進剤内包カプセルと、熱硬化性化合物とを含有する熱硬化性樹脂組成物もまた、本発明の１つである。
The curing agent and / or curing accelerator-encapsulating capsule of the present invention has excellent release properties of the curing agent and / or curing accelerator, and excellent storage stability, thermal stability, and the like when blended in a curable resin composition. Since it can exhibit fast curability, it is suitably used as a latent curing agent or curing accelerator for thermosetting resins such as epoxy resins.
A thermosetting resin composition containing the capsule containing the curing agent and / or curing accelerator of the present invention and a thermosetting compound is also one aspect of the present invention.
本発明によれば、硬化剤及び／又は硬化促進剤の放出性に優れ、硬化性樹脂組成物に配合された場合に優れた貯蔵安定性、熱安定性及び速硬化性を発揮することができる硬化剤及び／又は硬化促進剤内包カプセルを提供することができる。また、本発明によれば、該硬化剤及び／又は硬化促進剤内包カプセルを含有する熱硬化性樹脂組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, it is excellent in the discharge | release property of a hardening | curing agent and / or a hardening accelerator, and when it is mix | blended with a curable resin composition, it can exhibit the outstanding storage stability, heat stability, and quick-hardening property. A capsule containing a curing agent and / or a curing accelerator can be provided. Moreover, according to this invention, the thermosetting resin composition containing this hardening | curing agent and / or hardening accelerator inclusion capsule can be provided.
以下に実施例を掲げて本発明の態様を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Examples of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
（プレカプセルＰ−１の製造）
重合反応容器に、水１５１０重量部と、分散安定剤として５重量％のポリビニルアルコール水溶液（ＫＨ−２０、日本合成化学社製）３８０重量部とを投入し、水性媒体を調製した。次いで、ジビニルベンゼン１１．５重量部と、トリメチロールプロパントリアクリレート２７重量部と、３−メタクリロキシプロピルトリメトキシシラン（サイラエースＳ７１０、チッソ製）１１．５重量部とからなる混合溶液を、水性媒体に添加し、乳化液を調製した。得られた乳化液をホモジナイザーを用いて１００００ｒｐｍで攪拌混合し、重合器内へ投入した。乳化液を８０℃に加熱後、２−ウンデシルイミダゾール（Ｃ１１Ｚ、四国化成工業社製、融点６９〜７４℃）４０重量部を添加し２時間攪拌し、その後、ジメチル−２，２’−アゾビス（２−メチルプロピオネート）（Ｖ−６０１、和光純薬工業社製、１０時間半減期温度６６℃）０．４４重量部を添加し９時間反応させることにより、反応生成物を得た。得られた反応生成物を遠心分離後、乾燥することにより、プレカプセルＰ−１を得た。
なお、ジビニルベンゼン、トリメチロールプロパントリアクリレート、及び、３−メタクリロキシプロピルトリメトキシシランは、２−ウンデシルイミダゾールとの反応性基をもたないラジカル重合性モノマーである。
(Preparation of precapsule P-1)
A polymerization reaction vessel was charged with 1510 parts by weight of water and 380 parts by weight of a 5% by weight polyvinyl alcohol aqueous solution (KH-20, manufactured by Nippon Synthetic Chemical Co., Ltd.) as a dispersion stabilizer to prepare an aqueous medium. Subsequently, a mixed solution composed of 11.5 parts by weight of divinylbenzene, 27 parts by weight of trimethylolpropane triacrylate, and 11.5 parts by weight of 3-methacryloxypropyltrimethoxysilane (Syraace S710, manufactured by Chisso) To prepare an emulsion. The obtained emulsion was stirred and mixed at 10,000 rpm using a homogenizer, and charged into the polymerization vessel. After heating the emulsion to 80 ° C., 40 parts by weight of 2-undecylimidazole (C11Z, manufactured by Shikoku Kasei Kogyo Co., Ltd., melting point 69-74 ° C.) is added and stirred for 2 hours, and then dimethyl-2,2′-azobis. (2-Methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd., 10 hour half-life temperature 66 ° C.) 0.44 parts by weight was added and reacted for 9 hours to obtain a reaction product. The obtained reaction product was centrifuged and then dried to obtain a precapsule P-1.
Divinylbenzene, trimethylolpropane triacrylate, and 3-methacryloxypropyltrimethoxysilane are radically polymerizable monomers that do not have a reactive group with 2-undecylimidazole.
（プレカプセルＰ−２の製造）
ジビニルベンゼン１１．５重量部と、トリメチロールプロパントリアクリレート２７重量部と、３−メタクリロキシプロピルトリメトキシシラン（サイラエースＳ７１０、チッソ製）１１．５重量部とからなる混合溶液の代わりに、グリシジルメタクリレート１１．５重量部と、トリメチロールプロパントリアクリレート２７重量部と、３−メタクリロキシプロピルトリメトキシシラン（サイラエースＳ７１０、チッソ社製）１１．５重量部とからなる混合溶液を用いたこと以外はプレカプセルＰ−１の製造と同様にして、プレカプセルＰ−２を得た。
なお、グリシジルメタクリレートは、２−ウンデシルイミダゾールとの反応性基を有するラジカル重合性モノマーである。
(Preparation of precapsule P-2)
Instead of a mixed solution consisting of 11.5 parts by weight of divinylbenzene, 27 parts by weight of trimethylolpropane triacrylate, and 11.5 parts by weight of 3-methacryloxypropyltrimethoxysilane (Syra Ace S710, manufactured by Chisso), glycidyl methacrylate Except for using a mixed solution consisting of 11.5 parts by weight, 27 parts by weight of trimethylolpropane triacrylate, and 11.5 parts by weight of 3-methacryloxypropyltrimethoxysilane (Syra Ace S710, manufactured by Chisso Corporation). Precapsule P-2 was obtained in the same manner as in the production of capsule P-1.
Glycidyl methacrylate is a radically polymerizable monomer having a reactive group with 2-undecylimidazole.
（実施例１）
熱可塑性ポリマーとしてマープルーフ（Ｇ−０１３０Ｓ、ポリスチレン一部エポキシ置換、日油社製）４．５重量部と、無機ポリマーとしてシリコーン樹脂（Ｘ−４１−１０５３、アルコキシオリゴマー一部エポキシ置換、信越化学工業社製）１．５重量部とを、酢酸エチルと２−プロパノールとの混合溶媒（酢酸エチル：２−プロパノール＝３：２）１７０重量部に溶解させて、混合溶液を得た。この混合溶液に、乳化剤としてポリオキシエチレンラウリルエーテル２重量％を含有する水１０００重量部にプレカプセルＰ−１を９重量部分散させた溶液を滴下した。その後、得られた分散液を減圧装置付反応器で５０℃に加熱しながら０．０９５〜０．０９０ＭＰａとなるように減圧して、溶媒を除去することにより、反応生成物を得た。得られた生成物を、純水を用いて繰り返して洗浄した後、真空乾燥することにより、硬化促進剤内包カプセルＭ−１を得た。
(Example 1)
Marpproof (G-0130S, polystyrene partially epoxy-substituted, NOF Corporation) 4.5 parts by weight as thermoplastic polymer, silicone resin (X-41-1053, alkoxy oligomer partially epoxy-substituted, Shin-Etsu Chemical) as inorganic polymer 1.5 parts by weight of Kogyo Co., Ltd. was dissolved in 170 parts by weight of a mixed solvent of ethyl acetate and 2-propanol (ethyl acetate: 2-propanol = 3: 2) to obtain a mixed solution. To this mixed solution, a solution in which 9 parts by weight of precapsule P-1 was dispersed in 1000 parts by weight of water containing 2% by weight of polyoxyethylene lauryl ether as an emulsifier was dropped. Thereafter, the resulting dispersion was decompressed to 0.095 to 0.090 MPa while being heated to 50 ° C. in a reactor equipped with a decompression device, and the reaction product was obtained by removing the solvent. The obtained product was repeatedly washed with pure water and then vacuum-dried to obtain a curing accelerator-encapsulating capsule M-1.
（実施例２）
熱可塑性ポリマーとしてマープルーフ（Ｇ−０１３０Ｓ、ポリスチレン一部エポキシ置換、日油社製）４．５重量部と、無機ポリマーとしてシリコーン樹脂（Ｘ−４１−１０５３、アルコキシオリゴマー一部エポキシ置換、信越化学工業社製）１．５重量部との代わりに、熱可塑性ポリマーとしてマープルーフ（Ｇ−０１３０Ｓ、ポリスチレン一部エポキシ置換、日油社製）６重量部を用いたこと以外は実施例１と同様にして、硬化促進剤内包カプセルＭ−２を得た。
(Example 2)
Marpproof (G-0130S, polystyrene partially epoxy-substituted, NOF Corporation) 4.5 parts by weight as thermoplastic polymer, silicone resin (X-41-1053, alkoxy oligomer partially epoxy-substituted, Shin-Etsu Chemical) as inorganic polymer The same as in Example 1 except that 6 parts by weight of Marproof (G-0130S, polystyrene partially epoxy-substituted, manufactured by NOF Corporation) was used as the thermoplastic polymer instead of 1.5 parts by weight. Thus, a curing accelerator-encapsulating capsule M-2 was obtained.
（比較例１）
プレカプセルＰ−１の代わりに、プレカプセルＰ−２を用いたこと以外は実施例１と同様にして、硬化促進剤内包カプセルＣ−１を得た。
(Comparative Example 1)
A curing accelerator-encapsulating capsule C-1 was obtained in the same manner as in Example 1 except that the precapsule P-2 was used instead of the precapsule P-1.
（比較例２）
プレカプセルＰ−１の代わりに、プレカプセルＰ−２を用い、熱可塑性ポリマーとしてマープルーフ（Ｇ−０１３０Ｓ、ポリスチレン一部エポキシ置換、日油社製）４．５重量部と、無機ポリマーとしてシリコーン樹脂（Ｘ−４１−１０５３、アルコキシオリゴマー一部エポキシ置換、信越化学工業社製）１．５重量部との代わりに、熱可塑性ポリマーとしてポリメタクリル酸メチル６重量部を用いたこと以外は実施例１と同様にして、硬化促進剤内包カプセルＣ−２を得た。
(Comparative Example 2)
Precapsule P-2 is used instead of precapsule P-1, 4.5 parts by weight of proof (G-0130S, polystyrene partially epoxy-substituted, manufactured by NOF Corporation) as the thermoplastic polymer, and silicone as the inorganic polymer Example except that 6 parts by weight of polymethyl methacrylate was used as a thermoplastic polymer instead of 1.5 parts by weight of resin (X-41-1053, alkoxy oligomer partially epoxy-substituted, manufactured by Shin-Etsu Chemical Co., Ltd.) In the same manner as in No. 1, a curing accelerator-encapsulating capsule C-2 was obtained.
（比較例３）
熱可塑性ポリマーとしてマープルーフ（Ｇ−０１３０Ｓ、ポリスチレン一部エポキシ置換、日油社製）３重量部と、疎水性イミダゾール化合物として２−ウンデシルイミダゾール３．２重量部と、無機ポリマーとしてシリコーン樹脂（Ｘ−４１−１０５３、アルコキシオリゴマー一部エポキシ置換、信越化学工業社製）３重量部とを、酢酸エチルと２−プロパノールとの混合溶媒（酢酸エチル：２−プロパノール＝３：２）２５０重量部に溶解させて、混合溶液を得た。この混合溶液に、乳化剤としてポリオキシエチレンラウリルエーテル３重量％を含有する水１０００重量部を滴下して、ホモジナイザーを用いて３０００ｒｐｍで攪拌して乳化分散させた。その後、得られた分散液を減圧装置付反応器で加熱しながら減圧して、溶媒を除去することにより、反応生成物を得た。得られた生成物を、純水を用いて繰り返して洗浄した後、真空乾燥することにより、硬化促進剤内包カプセルＣ−３を得た。
(Comparative Example 3)
3 parts by weight of proof (G-0130S, polystyrene partially epoxy-substituted, manufactured by NOF Corporation) as a thermoplastic polymer, 3.2 parts by weight of 2-undecylimidazole as a hydrophobic imidazole compound, and a silicone resin (inorganic polymer) 3 parts by weight of X-41-1053, alkoxy oligomer partially epoxy-substituted, manufactured by Shin-Etsu Chemical Co., Ltd.), 250 parts by weight of a mixed solvent of ethyl acetate and 2-propanol (ethyl acetate: 2-propanol = 3: 2) To obtain a mixed solution. To this mixed solution, 1000 parts by weight of water containing 3% by weight of polyoxyethylene lauryl ether as an emulsifier was dropped, and the mixture was emulsified and dispersed by stirring at 3000 rpm using a homogenizer. Thereafter, the obtained dispersion was decompressed while being heated in a reactor equipped with a decompression device, and the solvent was removed to obtain a reaction product. The obtained product was repeatedly washed with pure water and then vacuum-dried to obtain a curing accelerator-encapsulating capsule C-3.
＜評価＞
実施例及び比較例で得られたプレカプセル及び硬化促進剤内包カプセルについて以下の評価を行った。結果を表１に示した。
<Evaluation>
The following evaluation was performed about the precapsule and hardening accelerator inclusion capsule which were obtained in the Example and the comparative example. The results are shown in Table 1.
（１）貯蔵安定性（ゲル分率の測定）
エポキシ樹脂（ＹＬ９８０、ｊＥＲ社製）０．５８重量部及び酸無水物硬化剤（ＹＨ３０９、ｊＥＲ社製）０．２９重量部中に、プレカプセル又は硬化促進剤内包カプセルを０．１３重量部添加して、公転自転撹拌機で撹拌した後、得られたエポキシ樹脂組成物を５０μｍの厚さに塗布して樹脂フィルムを得た。得られた樹脂フィルムを４０℃で３日間放置した後、酢酸エチル中で２４時間以上浸漬、振とうさせた。浸漬後の樹脂フィルムを取り出し、酢酸エチル浸漬前後の樹脂フィルムの重量を測定することで、ゲル分率測定を行った。
なお、本明細書中、ゲル分率とは、酢酸エチル浸漬後に乾燥させた樹脂フィルム重量を酢酸エチル浸漬前の樹脂フィルム重量で割ることにより得られる値を意味する。
(1) Storage stability (measurement of gel fraction)
0.13 parts by weight of a precapsule or a curing accelerator-encapsulating capsule is added to 0.58 parts by weight of an epoxy resin (YL980, manufactured by jER) and 0.29 parts by weight of an acid anhydride curing agent (YH309, manufactured by jER). Then, after stirring with a revolutionary rotating agitator, the obtained epoxy resin composition was applied to a thickness of 50 μm to obtain a resin film. The obtained resin film was allowed to stand at 40 ° C. for 3 days, and then immersed and shaken in ethyl acetate for 24 hours or more. The resin film after immersion was taken out, and the gel fraction was measured by measuring the weight of the resin film before and after immersion in ethyl acetate.
In the present specification, the gel fraction means a value obtained by dividing the weight of the resin film dried after immersion in ethyl acetate by the weight of the resin film before immersion in ethyl acetate.
（２）熱安定性
エポキシ樹脂（ＹＬ９８０、ｊＥＲ社製）０．５８重量部及び酸無水物硬化剤（ＹＨ３０９、ｊＥＲ社製）０．２９重量部中に、プレカプセル又は硬化促進剤内包カプセルを０．１３量部添加して、公転自転撹拌機で撹拌した後、得られたエポキシ樹脂組成物をオーブンで１２０℃に加熱し、エポキシ樹脂組成物の粘度が初期粘度から２倍になるまでの時間を測定した。
なお、エポキシ樹脂組成物の粘度は、Ｅ型粘度計（ＶＩＳＣＯＭＥＴＥＲ ＴＶ−２２、東海産業社製、φ１５ｍｍローターを使用）を用いて、２５℃、１０ｒｐｍの条件で測定した。
(2) A pre-capsule or a curing accelerator-containing capsule is contained in 0.58 parts by weight of a heat-stable epoxy resin (YL980, manufactured by jER) and 0.29 parts by weight of an acid anhydride curing agent (YH309, manufactured by jER). After adding 0.13 parts by weight and stirring with a revolutionary rotating agitator, the resulting epoxy resin composition was heated to 120 ° C. in an oven until the viscosity of the epoxy resin composition doubled from the initial viscosity. Time was measured.
The viscosity of the epoxy resin composition was measured using an E-type viscometer (VISCOMETER TV-22, manufactured by Tokai Sangyo Co., Ltd., using a φ15 mm rotor) at 25 ° C. and 10 rpm.
（３）速硬化性（硬化速度の測定）
エポキシ樹脂（ＹＬ９８０、ｊＥＲ社製）０．５８重量部及び酸無水物硬化剤（ＹＨ３０９、ｊＥＲ社製）０．２９重量部中に、プレカプセル又は硬化促進剤内包カプセルを０．１３量部添加して、公転自転撹拌機で撹拌した後、得られたエポキシ樹脂組成物を２１０℃に熱したホットプレート上に置いたスライドガラスの上に滴下して、エポキシ樹脂組成物が硬化するまでの時間を測定した。
（４）カプセル強度
製造時、乾燥してプレカプセル又は硬化促進剤内包カプセルを得た後、目開き１５０μｍの篩を用いてプレカプセル又は硬化促進剤内包カプセルを解砕した。解砕したプレカプセル又は硬化促進剤内包カプセルを走査型電子顕微鏡で倍率１０００倍、３視野観察した。このとき、破壊されたカプセルをカウントした。
(3) Fast curability (Measurement of cure speed)
0.13 part by weight of precapsule or curing accelerator-encapsulated capsule is added to 0.58 parts by weight of epoxy resin (YL980, manufactured by jER) and 0.29 parts by weight of acid anhydride curing agent (YH309, manufactured by jER). Then, after stirring with a revolutionary rotating stirrer, the obtained epoxy resin composition was dropped on a slide glass placed on a hot plate heated to 210 ° C., and the time until the epoxy resin composition was cured Was measured.
(4) At the time of capsule strength production, after drying to obtain a precapsule or a curing accelerator-encapsulating capsule, the precapsule or the curing accelerator-encapsulating capsule was crushed using a sieve having an opening of 150 μm. The crushed precapsule or the curing accelerator-encapsulating capsule was observed with a scanning electron microscope at a magnification of 1000 times and three fields of view. At this time, broken capsules were counted.
本発明によれば、硬化剤及び／又は硬化促進剤の放出性に優れ、硬化性樹脂組成物に配合された場合に優れた貯蔵安定性、熱安定性及び速硬化性を発揮することができる硬化剤及び／又は硬化促進剤内包カプセルを提供することができる。また、本発明によれば、該硬化剤及び／又は硬化促進剤内包カプセルを含有する熱硬化性樹脂組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, it is excellent in the discharge | release property of a hardening | curing agent and / or a hardening accelerator, and when it is mix | blended with a curable resin composition, it can exhibit the outstanding storage stability, heat stability, and quick-hardening property. A capsule containing a curing agent and / or a curing accelerator can be provided. Moreover, according to this invention, the thermosetting resin composition containing this hardening | curing agent and / or hardening accelerator inclusion capsule can be provided.
Claims (4)
前記シェルは、少なくとも、ラジカル重合性モノマーの重合体を含有する多孔質の最内層と、
グリシジル基を有する熱可塑性ポリマーを含有する最外層とを有し、
前記最内層は、前記硬化剤及び／又は硬化促進剤との反応性基が存在せず、
前記最内層の厚みと前記最外層の厚みとの比率は、１５：１〜２：１である
ことを特徴とする硬化剤及び／又は硬化促進剤内包カプセル。 A shell and / or a curing accelerator-encapsulating capsule containing a curing agent and / or a curing accelerator as a core agent in the shell,
The shell includes at least a porous innermost layer containing a polymer of a radical polymerizable monomer,
An outermost layer containing a thermoplastic polymer having a glycidyl group ,
The innermost layer has no reactive group with the curing agent and / or curing accelerator,
The ratio of the thickness of the outermost layer and the innermost layer has a thickness of 15: 1 to 2: 1 is hardening agent you wherein the <br/> and / or curing accelerator containing capsules.
前記シェルは、少なくとも、ラジカル重合性モノマーの重合体を含有する多孔質の最内層と、
熱可塑性ポリマーを含有する最外層とを有し、
前記最内層は、前記硬化剤及び／又は硬化促進剤との反応性基が存在せず、
前記最内層の厚みと前記最外層の厚みとの比率は、１５：１〜２：１であり、
最外層は、更に、分子中に２個以上の炭素数１〜６のアルコキシ基を有し、かつ、Ｓｉ、Ａｌ、Ｚｒ、及びＴｉからなる群より選択される少なくとも１種の金属元素を含有する有機金属化合物の重合体を含有する
ことを特徴とする硬化剤及び／又は硬化促進剤内包カプセル。 A shell and / or a curing accelerator-encapsulating capsule containing a curing agent and / or a curing accelerator as a core agent in the shell,
The shell includes at least a porous innermost layer containing a polymer of a radical polymerizable monomer,
An outermost layer containing a thermoplastic polymer,
The innermost layer has no reactive group with the curing agent and / or curing accelerator,
The ratio of the thickness of the innermost layer to the thickness of the outermost layer is 15: 1 to 2: 1,
The outermost layer further contains at least one metal element selected from the group consisting of Si, Al, Zr, and Ti, having two or more C 1-6 alkoxy groups in the molecule. wherein the hardening agent and / or curing accelerator containing capsules you that it contains a polymer of an organic metal compound.
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| KR101809935B1 (en) | 2016-09-21 | 2017-12-19 | 충북대학교 산학협력단 | Imidazole agent with synthesized copolymers for latent curing of epoxy resin and method of producing the same |
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| JP5933977B2 (en) * | 2012-01-10 | 2016-06-15 | 積水化学工業株式会社 | Curing agent and / or curing accelerator encapsulating capsule, and thermosetting resin composition |
| JP2015232119A (en) * | 2014-05-13 | 2015-12-24 | 積水化学工業株式会社 | Water soluble curing agent- and/or curing accelerator-including capsule, manufacturing method of water soluble curing agent and/or curing accelerator-including capsule and thermosetting resin composition |
| JP2016035056A (en) * | 2014-07-31 | 2016-03-17 | 積水化学工業株式会社 | Microcapsule for curing epoxy resin, and epoxy resin composition |
| CN107108913A (en) * | 2014-12-23 | 2017-08-29 | 3M创新有限公司 | Curable and cured epoxy resin compositions |
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| JPH04215840A (en) * | 1990-06-14 | 1992-08-06 | Hitachi Kasei Mold Kk | Microcapsule including curing catalyst for resol type phenol resin |
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