JP5424410B2 - Epoxy resin curing fine particles - Google Patents
Epoxy resin curing fine particles Download PDFInfo
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- JP5424410B2 JP5424410B2 JP2010094316A JP2010094316A JP5424410B2 JP 5424410 B2 JP5424410 B2 JP 5424410B2 JP 2010094316 A JP2010094316 A JP 2010094316A JP 2010094316 A JP2010094316 A JP 2010094316A JP 5424410 B2 JP5424410 B2 JP 5424410B2
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- 229920000647 polyepoxide Polymers 0.000 title claims description 96
- 239000003822 epoxy resin Substances 0.000 title claims description 94
- 239000010419 fine particle Substances 0.000 title claims description 45
- 125000001424 substituent group Chemical group 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- -1 isocyanate-substituted silane Chemical class 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000000962 organic group Chemical group 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 34
- 239000003795 chemical substances by application Substances 0.000 description 28
- 239000000047 product Substances 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 229910004298 SiO 2 Inorganic materials 0.000 description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000000306 component Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000008358 core component Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000003094 microcapsule Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000013500 performance material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- XXSCONYSQQLHTH-UHFFFAOYSA-N 9h-fluoren-9-ylmethanol Chemical compound C1=CC=C2C(CO)C3=CC=CC=C3C2=C1 XXSCONYSQQLHTH-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical group CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 125000000656 azaniumyl group Chemical group [H][N+]([H])([H])[*] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Description
本発明は、エポキシ樹脂用硬化剤として用いられ、エポキシ樹脂組成物中での分散性に優れ、硬化物の線膨張係数を低下させて、硬化物の信頼性を高めることのできるエポキシ樹脂硬化用微粒子に関する。 The present invention is used as a curing agent for epoxy resins, has excellent dispersibility in an epoxy resin composition, reduces the linear expansion coefficient of cured products, and can improve the reliability of cured products. Concerning fine particles.
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。 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 the curing agent or the curing accelerator and the epoxy resin into one liquid, a latent curing agent or curing accelerator is frequently used.
例えば、特許文献１には、所定の粉末状アミン化合物（Ａ）をコアとし、上記アミン化合物（Ａ）とエポキシ樹脂（Ｂ）の反応生成物をシェルとしてなる硬化剤（Ｉ）と、所定量のエポキシ樹脂（Ｂ）とからなる一液性エポキシ樹脂配合品用マスターバッチ型硬化剤が記載されている。しかしながら、特許文献１に記載の一液性エポキシ樹脂配合品用マスターバッチ型硬化剤は、低温での硬化性に劣ることが問題である。近年、特に電子機器分野においては、回路の高密度化に対応し、接続信頼性を向上させるために、硬化剤の貯蔵安定性を損なわずに低温での硬化性を一層向上させることが強く求められている。 For example, Patent Document 1 discloses a curing agent (I) having a predetermined powdery amine compound (A) as a core and a reaction product of the amine compound (A) and the epoxy resin (B) as a shell, and a predetermined amount. A master batch type curing agent for a one-component epoxy resin blended product comprising the epoxy resin (B) is described. However, the master batch type curing agent for a one-component epoxy resin compounded product described in Patent Document 1 has a problem that it is inferior in curability at a low temperature. In recent years, especially in the field of electronic equipment, there is a strong demand to further improve curability at low temperatures without compromising the storage stability of the curing agent in order to cope with higher circuit density and improve connection reliability. It has been.
また、特許文献２には、アミンアダクト（Ａ）と低分子アミン化合物（Ｂ）を主成分とする所定のエポキシ樹脂用硬化剤（Ｃ）からなるコアの表面を合成樹脂および／または無機酸化物からなるシェルによって被覆されている構造を持つマイクロカプセル型エポキシ樹脂用硬化剤が記載されている。しかしながら、特許文献２に記載のマイクロカプセル型エポキシ樹脂用硬化剤では、特に電子機器分野において必要とされる、ばらつきの少ない小さい平均粒子径を実現することは困難である。 In Patent Document 2, the surface of the core made of a predetermined curing agent for epoxy resin (C) mainly composed of an amine adduct (A) and a low molecular amine compound (B) is formed on a synthetic resin and / or an inorganic oxide. A microcapsule type epoxy resin curing agent having a structure covered with a shell made of is described. However, with the microcapsule-type epoxy resin curing agent described in Patent Document 2, it is difficult to achieve a small average particle size with little variation, which is required particularly in the field of electronic equipment.
更に、特許文献１及び２に記載のエポキシ樹脂用硬化剤は、アミン系硬化剤とエポキシ樹脂とを途中段階まで反応させて得られた粉体であり、アミン系硬化剤とエポキシ樹脂との接触界面が硬化しているにすぎない。そのため、このようなエポキシ樹脂用硬化剤は時間の経過とともに硬化反応が進行しやすく、充分な貯蔵安定性を得ることは困難である。 Furthermore, the curing agent for epoxy resins described in Patent Documents 1 and 2 is a powder obtained by reacting an amine curing agent and an epoxy resin to an intermediate stage, and contact between the amine curing agent and the epoxy resin. The interface is only cured. For this reason, such a curing agent for an epoxy resin is likely to undergo a curing reaction with time, and it is difficult to obtain sufficient storage stability.
そこで、硬化反応を途中段階まで進行させることによって得られるエポキシ樹脂用硬化剤ではなく、アミン系硬化剤からなるコア成分を、ラジカル重合性単量体を重合させて得られる重合体からなるシェル成分に内包したエポキシ樹脂用硬化剤が検討されている。例えば、特許文献３には、芯成分が水に対する溶解度が１０重量パーセント以下であるアミン系硬化剤を含み、殻壁成分がラジカル重合性単量体を主重合成分にしてラジカル重合法により反応させて形成された重合体であるアミン系硬化剤のマイクロカプセルが記載さている。
しかしながら、特許文献３に記載のマイクロカプセルにおいては、コア成分としてイミダゾール化合物を用いた場合、イミダゾール化合物がラジカルを補足するため、ラジカル重合が途中で停止してしまうことがあった。このように不完全な状態でラジカル重合が停止すると、未反応のラジカル重合性単量体が残留し、例えば、エポキシ樹脂組成物の硬化物の信頼性が低下する等の不具合を生じることが問題であった。
Therefore, a shell component composed of a polymer obtained by polymerizing a radical polymerizable monomer with a core component composed of an amine-based curing agent, not a curing agent for an epoxy resin obtained by proceeding the curing reaction to an intermediate stage. A curing agent for epoxy resin encapsulated in is being studied. For example, in Patent Document 3, the core component contains an amine-based curing agent having a solubility in water of 10 weight percent or less, and the shell wall component is reacted by a radical polymerization method using a radical polymerizable monomer as a main polymerization component. A microcapsule of an amine-based curing agent, which is a polymer formed in this manner, is described.
However, in the microcapsules described in Patent Document 3, when an imidazole compound is used as a core component, the imidazole compound supplements radicals, and radical polymerization sometimes stops in the middle. When radical polymerization is stopped in such an incomplete state, unreacted radically polymerizable monomer remains, resulting in problems such as reduced reliability of the cured product of the epoxy resin composition. Met.
本発明は、エポキシ樹脂用硬化剤として用いられ、エポキシ樹脂組成物中での分散性に優れ、硬化物の線膨張係数を低下させて、硬化物の信頼性を高めることのできるエポキシ樹脂硬化用微粒子を提供することを目的とする。 The present invention is used as a curing agent for epoxy resins, has excellent dispersibility in an epoxy resin composition, reduces the linear expansion coefficient of cured products, and can improve the reliability of cured products. An object is to provide fine particles.
本発明は、無機微粒子の表面に熱によって塩基が生成する基を有するエポキシ樹脂硬化用微粒子であって、前記熱により塩基が生成する基は、下記一般式（１）で表される構造を有するエポキシ樹脂硬化用微粒子である。 The present invention is an epoxy resin curing fine particle having a group that generates a base by heat on the surface of inorganic fine particles, and the group that generates a base by heat has a structure represented by the following general formula (1). Fine particles for curing epoxy resin.
一般式（１）中、Ｙは二価の有機基を表し、Ｒ１及びＲ２は水素原子、メチル基又は芳香族基を表し、Ｒ３及びＲ４は、Ｒ３とＲ４とのハメット置換基定数σの総和が０〜０．８５となる置換基を表す。
以下、本発明を詳述する。
In General Formula (1), Y represents a divalent organic group, R 1 and R 2 represent a hydrogen atom, a methyl group, or an aromatic group, and R 3 and R 4 represent Hammett of R 3 and R 4. This represents a substituent having a total sum of substituent constants σ of 0 to 0.85.
The present invention is described in detail below.
本発明者らは、無機微粒子の表面に、熱によって塩基が生成する所定の構造の基を有するエポキシ樹脂硬化用微粒子は、エポキシ樹脂用硬化剤として好適に用いられることを見出した。本発明者らは、該エポキシ樹脂硬化用微粒子は、エポキシ樹脂組成物中で均一に分散し、硬化物の線膨張係数を低下させて、硬化物の信頼性を高めることができることを見出し、本発明を完成させるに至った。 The inventors of the present invention have found that fine particles for curing an epoxy resin having a group having a predetermined structure in which a base is generated by heat on the surface of the inorganic fine particles are suitably used as a curing agent for an epoxy resin. The present inventors have found that the epoxy resin curing fine particles can be uniformly dispersed in the epoxy resin composition, reduce the linear expansion coefficient of the cured product, and increase the reliability of the cured product. The invention has been completed.
本発明のエポキシ樹脂硬化用微粒子は、無機微粒子の表面に熱によって塩基が生成する基を有する。
上記無機微粒子が用いられることで、本発明のエポキシ樹脂硬化用微粒子は、通常エポキシ樹脂組成物に添加される無機フィラーと同様に硬化物の線膨張係数を低下させることができ、硬化物の信頼性を高めることができる。
また、一般に、無機フィラーはエポキシ樹脂との間で界面剥離が生じやすく、このような界面剥離は、エポキシ樹脂組成物の硬化物の信頼性を低下させている。これに対し、本発明のエポキシ樹脂硬化用微粒子は、後述するように、上記無機微粒子の表面に熱によって塩基が生成する基を有し、エポキシ樹脂用硬化剤として働くことで、エポキシ樹脂との間の界面剥離を抑制して、硬化物の信頼性を高めることができる。
The fine particle for epoxy resin curing of the present invention has a group that generates a base by heat on the surface of the inorganic fine particle.
By using the above-mentioned inorganic fine particles, the epoxy resin curing fine particles of the present invention can reduce the linear expansion coefficient of the cured product in the same manner as the inorganic filler usually added to the epoxy resin composition, and the reliability of the cured product can be reduced. Can increase the sex.
In general, the inorganic filler is likely to undergo interfacial delamination with the epoxy resin, and such interfacial delamination reduces the reliability of the cured product of the epoxy resin composition. On the other hand, the epoxy resin curing fine particles of the present invention have a group that generates a base by heat on the surface of the inorganic fine particles, as described later, and acts as a curing agent for the epoxy resin. Interfacial peeling between them can be suppressed, and the reliability of the cured product can be improved.
また、一般に、無機フィラーはエポキシ樹脂組成物中での分散性に劣るのに対し、本発明のエポキシ樹脂硬化用微粒子は、上記無機微粒子の表面に上記熱によって塩基が生成する基を有することで、エポキシ樹脂との親和性が高く、エポキシ樹脂組成物中で均一に分散して、硬化物の信頼性を高めることができる。 In general, the inorganic filler is inferior in dispersibility in the epoxy resin composition, whereas the epoxy resin curing fine particles of the present invention have a group that generates a base by the heat on the surface of the inorganic fine particles. It has a high affinity with the epoxy resin and can be uniformly dispersed in the epoxy resin composition to increase the reliability of the cured product.
上記無機微粒子を構成する材料は特に限定されず、例えば、周期表３、４及び５周期の２族〜１４族のうちの少なくとも１種からなる酸化物及びそれらの複合酸化物が挙げられ、具体的には、例えば、Ａｌ２Ｏ３、ＳｉＯ２、ＴｉＯ２、ＺｒＯ２、Ｆｅ２Ｏ３、ＺｎＯ、ＭｇＯ、ＣａＯ、ＣｕＯ、ＳｉＯ２−Ａｌ２Ｏ３、ＴｉＯ２−Ａｌ２Ｏ３、ＳｎＯ２−Ｓｂ２Ｏ３、ＴｉＯ２−ＺｒＯ２、ＳｉＯ２−ＴｉＯ２、ＳｉＯ２−Ａｌ２Ｏ３−ＭｇＯ、ＳｉＯ２−Ａｌ２Ｏ３−Ａｇ２Ｏ、ＳｉＯ２−ＴｉＯ２−Ｆｅ２Ｏ３、ＳｉＯ２−Ａｌ２Ｏ３−ＣａＯ、ＳｉＯ２−ＴｉＯ２−Ａｌ２Ｏ３、ＳｉＯ２−Ａｌ２Ｏ３−ＺｎＯ、ＩＴＯ等が挙げられる。なかでも、安価かつ安定性及び透明性に優れることから、上記無機微粒子は、ＳｉＯ２（シリカ）又はＴｉＯ２からなることが好ましい。
更に、上記ＳｉＯ２（シリカ）又はＴｉＯ２からなる無機微粒子は、表面に水酸基を有することが好ましい。
The material constituting the inorganic fine particles is not particularly limited, and examples thereof include oxides composed of at least one of groups 2 to 14 of periodic tables 3, 4 and 5 and complex oxides thereof. in, for example, Al 2 O 3, SiO 2 , TiO 2, ZrO 2, Fe 2 O 3, ZnO, MgO, CaO, CuO, SiO 2 -Al 2 O 3, TiO 2 -Al 2 O 3, SnO 2- Sb 2 O 3 , TiO 2 —ZrO 2 , SiO 2 —TiO 2 , SiO 2 —Al 2 O 3 —MgO, SiO 2 —Al 2 O 3 —Ag 2 O, SiO 2 —TiO 2 —Fe 2 O 3 , SiO 2 —Al 2 O 3 —CaO, SiO 2 —TiO 2 —Al 2 O 3 , SiO 2 —Al 2 O 3 —ZnO, ITO, and the like. Among these, because of excellent low cost and stability and transparency, the inorganic fine particles is preferably made of SiO 2 (silica), or TiO 2.
Furthermore, the inorganic fine particles made of SiO 2 (silica) or TiO 2 preferably have a hydroxyl group on the surface.
上記無機微粒子の平均粒子径は特に限定されないが、好ましい下限は０．０５μｍ、好ましい上限は１．０μｍである。上記無機微粒子の平均粒子径が０．０５μｍ未満であると、得られるエポキシ樹脂硬化用微粒子を添加したエポキシ樹脂組成物の粘度が上昇し、流動性が低下して、取扱性が低下することがある。上記無機微粒子の平均粒子径が１．０μｍを超えると、得られるエポキシ樹脂硬化用微粒子を添加したエポキシ樹脂組成物の透明性が低下することがある。上記無機微粒子の平均粒子径のより好ましい下限は０．０７μｍ、より好ましい上限は０．５μｍである。 The average particle diameter of the inorganic fine particles is not particularly limited, but a preferable lower limit is 0.05 μm and a preferable upper limit is 1.0 μm. When the average particle size of the inorganic fine particles is less than 0.05 μm, the viscosity of the epoxy resin composition to which the obtained fine particles for curing the epoxy resin are added increases, the fluidity decreases, and the handleability decreases. is there. When the average particle diameter of the inorganic fine particles exceeds 1.0 μm, the transparency of the epoxy resin composition to which the fine particles for curing an epoxy resin obtained are added may be lowered. The more preferable lower limit of the average particle diameter of the inorganic fine particles is 0.07 μm, and the more preferable upper limit is 0.5 μm.
上記熱によって塩基が生成する基は、下記一般式（１）で表される構造を有する。 The group from which the base is generated by the heat has a structure represented by the following general formula (1).
一般式（１）中、Ｙは二価の有機基を表し、Ｒ１及びＲ２は水素原子、メチル基又は芳香族基を表し、Ｒ３及びＲ４は、Ｒ３とＲ４とのハメット置換基定数σの総和が０〜０．８５となる置換基を表す。
なお、Ｒ３とＲ４とのハメット置換基定数σの総和が上記範囲を外れると、上記熱によって塩基が生成する基の自己触媒反応が起こらなくなり、得られるエポキシ樹脂硬化用微粒子をエポキシ樹脂用硬化剤として用いることが困難となる。
In General Formula (1), Y represents a divalent organic group, R 1 and R 2 represent a hydrogen atom, a methyl group, or an aromatic group, and R 3 and R 4 represent Hammett of R 3 and R 4. This represents a substituent having a total sum of substituent constants σ of 0 to 0.85.
If the sum of Hammett substituent constants σ of R 3 and R 4 is out of the above range, the autocatalytic reaction of the group generated by the base by the heat does not occur, and the resulting epoxy resin curing fine particles are used for epoxy resin. It becomes difficult to use as a curing agent.
上記Ｒ１及びＲ２が芳香族基である場合、該芳香族基は特に限定されず、例えば、フェニル基等が挙げられる。 When R 1 and R 2 are aromatic groups, the aromatic group is not particularly limited, and examples thereof include a phenyl group.
上記Ｒ３及びＲ４は、Ｒ３とＲ４とのハメット置換基定数σの総和が上記範囲内であれば特に限定されないが、電子吸引性であることが好ましく、オレフィン性二重結合と共役しうる置換基であることが好ましい。
上記Ｒ３及びＲ４として、具体的には、例えば、チエニル基、ピリジル基、フリル基、ピリミジル基、チアゾリル基等の芳香族性複素環残基、ビニル基、クロチル基、フェニル基、置換フェニル基、シアノ基、ホルミル基、ケトン性カルボニル基、エステル性カルボニル基、アミド性カルボニル基、アンモニオ基、ニトロ基、アセトアミド基、トリフルオロメトキシ基、フェノキシ基、アルコキシ基、アセトキシ基、アルキルスルホニル基、アリールスルホニル基、アリールチオ基、アルキルチオ基、イミド基等が挙げられる。
The R 3 and R 4 is the sum of the Hammett substituent constant σ of R 3 and R 4 are not particularly limited as long as it is within the above range is preferably an electron-withdrawing, olefinic double bond and conjugated It is preferably a substituent that can be used.
Specific examples of R 3 and R 4 include aromatic heterocyclic residues such as thienyl group, pyridyl group, furyl group, pyrimidyl group, and thiazolyl group, vinyl group, crotyl group, phenyl group, and substituted phenyl. Group, cyano group, formyl group, ketone carbonyl group, ester carbonyl group, amido carbonyl group, ammonio group, nitro group, acetamide group, trifluoromethoxy group, phenoxy group, alkoxy group, acetoxy group, alkylsulfonyl group, An arylsulfonyl group, an arylthio group, an alkylthio group, an imide group and the like can be mentioned.
また、上記Ｒ３及びＲ４は、結合して環状構造を形成してもよい。このような環状構造として、例えば、フルオレニル基、インダニル基等の環状基が挙げられる。 R 3 and R 4 may combine to form a cyclic structure. Examples of such a cyclic structure include cyclic groups such as a fluorenyl group and an indanyl group.
上記熱によって塩基が生成する基は、加熱されると分解し、塩基が生成する。生成した塩基は硬化剤となってエポキシ樹脂と反応し、硬化物を形成することから、上記熱によって塩基が生成する基を有することで、本発明のエポキシ樹脂硬化用微粒子はエポキシ樹脂用硬化剤として好適に用いられる。また、上記熱によって塩基が生成する基は加熱されてはじめて分解することから、本発明のエポキシ樹脂硬化用微粒子は、エポキシ樹脂組成物に添加されてもエポキシ樹脂組成物の貯蔵安定性を低下させることはない。
なお、上記熱によって塩基が生成する基は、例えば、１００℃等の温度に加熱された場合に分解し、塩基を生成することが好ましい。
The group that generates a base by the heat decomposes when heated to generate a base. Since the generated base becomes a curing agent and reacts with the epoxy resin to form a cured product, the fine particles for curing the epoxy resin of the present invention have the group that the base is generated by the heat. Is preferably used. In addition, since the group generating a base by the heat is decomposed only when heated, the epoxy resin curing fine particles of the present invention reduce the storage stability of the epoxy resin composition even when added to the epoxy resin composition. There is nothing.
In addition, it is preferable that the group which produces | generates a base with the said heat decomposes | disassembles, for example, when heated to temperature, such as 100 degreeC, and produces | generates a base.
また、本発明のエポキシ樹脂硬化用微粒子は、上記熱によって塩基が生成する基を表面に有することで、エポキシ樹脂との親和性が高く、エポキシ樹脂組成物中で均一に分散して、硬化物の信頼性を高めることができる。 In addition, the epoxy resin curing fine particles of the present invention have a group on the surface which generates a base by the above heat, and thus has high affinity with the epoxy resin, and is uniformly dispersed in the epoxy resin composition to obtain a cured product. Can improve the reliability.
上記熱によって塩基が生成する基は、上記一般式（１）で表される構造を有していれば特に限定されないが、下記一般式（２）で表される構造を有するイソシアネート置換されたシランカップリング剤と、下記一般式（３）で表される構造を有するアルコールとを反応させることによって得られることが好ましい。 Although the group which a base produces | generates by the said heat is not specifically limited if it has the structure represented by the said General formula (1), The isocyanate substituted silane which has a structure represented by the following General formula (2) It is preferably obtained by reacting a coupling agent with an alcohol having a structure represented by the following general formula (3).
一般式（２）中、Ｙは二価の有機基を表し、Ｒ５はメチル基又はエチル基を表し、Ｒ６はメチル基、メトキシ基又はエトキシ基を表す。 In general formula (2), Y represents a divalent organic group, R 5 represents a methyl group or an ethyl group, and R 6 represents a methyl group, a methoxy group, or an ethoxy group.
一般式（３）中、Ｒ１及びＲ２は水素原子、メチル基又は芳香族基を表し、Ｒ３及びＲ４は、Ｒ３とＲ４とのハメット置換基定数σの総和が０〜０．８５となる置換基を表す。 In General Formula (3), R 1 and R 2 represent a hydrogen atom, a methyl group or an aromatic group, and R 3 and R 4 have a sum of Hammett substituent constants σ of R 3 and R 4 of 0 to 0 The substituent which becomes .85 is represented.
上記一般式（２）で表される構造を有するイソシアネート置換されたシランカップリング剤は特に限定されず、例えば、３−イソシアネートプロピルトリエトキシシラン（上記一般式（２）中、Ｙはプロピレン基であり、Ｒ５はエチル基であり、Ｒ６はエトキシ基である）、３−イソシアネートプロピルトリメトキシシラン（上記一般式（２）中、Ｙはプロピレン基であり、Ｒ５はメチル基であり、Ｒ６はメトキシ基である）等が挙げられる。 The isocyanate-substituted silane coupling agent having the structure represented by the general formula (2) is not particularly limited. For example, 3-isocyanatopropyltriethoxysilane (in the general formula (2), Y is a propylene group). R 5 is an ethyl group, R 6 is an ethoxy group), 3-isocyanatopropyltrimethoxysilane (in the general formula (2), Y is a propylene group, R 5 is a methyl group, R 6 is a methoxy group).
上記一般式（２）で表される構造を有するイソシアネート置換されたシランカップリング剤の市販品として、例えば、ＫＢＥ−９００７（信越化学工業社製）、Ａ−１３１０（モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）、Ｙ−５１８７（モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）等が挙げられる。 As a commercial item of the isocyanate substituted silane coupling agent having the structure represented by the above general formula (2), for example, KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.), A-1310 (Momentive Performance Materials) Japan), Y-5187 (made by Momentive Performance Materials Japan), and the like.
上記一般式（３）で表される構造を有するアルコールは特に限定されず、例えば、下記式（ａ）〜（ｒ）で表される構造を有するアルコール等が挙げられる。 The alcohol having the structure represented by the general formula (3) is not particularly limited, and examples thereof include alcohols having structures represented by the following formulas (a) to (r).
本発明のエポキシ樹脂硬化用微粒子を製造する方法は特に限定されないが、溶剤中で、上記無機微粒子に対して、上記一般式（２）で表される構造を有するイソシアネート置換されたシランカップリング剤と、上記一般式（３）で表される構造を有するアルコールとを反応させることにより、上記無機微粒子の表面に上記熱によって塩基が生成する基を結合させる方法が好ましい。
上記溶剤は特に限定されず、例えば、水、メタノール、エタノール、プロパノール、イソプロパノール、ｔ−ブタノール等が挙げられる。これらの溶剤は単独で用いてもよく、他の溶剤と併用してもよい。
The method for producing the epoxy resin curing fine particles of the present invention is not particularly limited, but an isocyanate-substituted silane coupling agent having a structure represented by the general formula (2) with respect to the inorganic fine particles in a solvent. And a method in which a group that generates a base by the heat is bonded to the surface of the inorganic fine particles by reacting with an alcohol having a structure represented by the general formula (3).
The said solvent is not specifically limited, For example, water, methanol, ethanol, a propanol, isopropanol, t-butanol etc. are mentioned. These solvents may be used alone or in combination with other solvents.
本発明によれば、エポキシ樹脂用硬化剤として用いられ、エポキシ樹脂組成物中での分散性に優れ、硬化物の線膨張係数を低下させて、硬化物の信頼性を高めることのできるエポキシ樹脂硬化用微粒子を提供することができる。 According to the present invention, an epoxy resin that is used as a curing agent for an epoxy resin, has excellent dispersibility in the epoxy resin composition, can reduce the linear expansion coefficient of the cured product, and can improve the reliability of the cured product. Fine particles for curing 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.
（表面に水酸基を有するシリカ粒子の製造）
エタノール１１０ｍＬ中に、オルトケイ酸エチル５．７ｇを添加して撹拌し、次いで、２５％アンモニア水溶液９．３ｇとイオン交換水２７．０ｇとを添加して、５０℃で５時間撹拌することにより、平均粒子径０．４μｍの表面に水酸基を有するシリカ粒子を得た。得られたシリカ粒子をイオン交換水で洗浄した後、２４時間真空乾燥を行った。
(Production of silica particles having hydroxyl groups on the surface)
In 110 mL of ethanol, 5.7 g of ethyl orthosilicate was added and stirred, and then 9.3 g of 25% aqueous ammonia solution and 27.0 g of ion-exchanged water were added and stirred at 50 ° C. for 5 hours. Silica particles having a hydroxyl group on the surface having an average particle diameter of 0.4 μm were obtained. The obtained silica particles were washed with ion-exchanged water and then vacuum-dried for 24 hours.
（実施例１）
３−イソシアネートプロピルトリエトキシシラン０．０２５ｇと、９−フルオレニルメタノール０．０２０ｇとをエタノール１００ｇ中に添加して攪拌した。次いで、上記で得られた表面に水酸基を有するシリカ粒子４．５ｇ、酢酸１ｇ、イオン交換水５ｇを反応液に添加して、５時間室温にて攪拌後、５０℃に加熱して５時間反応を行うことにより、シリカ粒子の表面に一般式（１）で表される構造を有する熱によって塩基を生成する基（一般式（１）中、Ｙはプロピレン基であり、Ｒ１及びＲ２は水素原子であり、Ｒ３及びＲ４は一緒になってフルオレニル基である）を有するエポキシ樹脂硬化用微粒子を得た。
Example 1
0.025 g of 3-isocyanatopropyltriethoxysilane and 0.020 g of 9-fluorenylmethanol were added to 100 g of ethanol and stirred. Next, 4.5 g of silica particles having a hydroxyl group on the surface obtained above, 1 g of acetic acid and 5 g of ion-exchanged water were added to the reaction solution, stirred for 5 hours at room temperature, and then heated to 50 ° C. for 5 hours. To generate a base by heat having a structure represented by the general formula (1) on the surface of the silica particles (in the general formula (1), Y is a propylene group, R 1 and R 2 are It was a hydrogen atom, and R 3 and R 4 together were a fluorenyl group) to obtain fine particles for curing an epoxy resin.
（実施例２）
３−イソシアネートプロピルトリエトキシシラン０．０２５ｇと、エチレンシアノヒドリン０．０７０ｇとをエタノール１００ｇ中に添加して攪拌した。次いで、上記で得られた表面に水酸基を有するシリカ粒子４．５ｇ、酢酸１ｇ、イオン交換水５ｇを反応液に添加して、５時間室温にて攪拌後、５０℃に加熱して５時間反応を行うことにより、シリカ粒子の表面に一般式（１）で表される構造を有する熱によって塩基を生成する基（一般式（１）中、Ｙはプロピレン基であり、Ｒ１、Ｒ２及びＲ３は水素原子であり、Ｒ４はニトリル基である）を有するエポキシ樹脂硬化用微粒子を得た。
(Example 2)
0.025 g of 3-isocyanatopropyltriethoxysilane and 0.070 g of ethylene cyanohydrin were added to 100 g of ethanol and stirred. Next, 4.5 g of silica particles having a hydroxyl group on the surface obtained above, 1 g of acetic acid and 5 g of ion-exchanged water were added to the reaction solution, stirred for 5 hours at room temperature, and then heated to 50 ° C. for 5 hours. To generate a base by heat having a structure represented by the general formula (1) on the surface of the silica particles (in general formula (1), Y is a propylene group, R 1 , R 2 and R 3 is a hydrogen atom, and R 4 is a nitrile group.
（比較例１）
未処理のシリカ粒子４．５ｇ、硬化剤として酸無水物（ＹＨ３０６、ジャパンエポキシレジン社製）１．０ｇ、硬化促進剤として２−ウンデシルイミダゾール０．５ｇ、エポキシ樹脂（ＹＬ９８０、ジャパンエポキシレジン社製）１５ｇを用いて、エポキシ樹脂組成物を調製した。
(Comparative Example 1)
4.5 g of untreated silica particles, 1.0 g of acid anhydride (YH306, manufactured by Japan Epoxy Resin) as a curing agent, 0.5 g of 2-undecylimidazole as a curing accelerator, epoxy resin (YL980, Japan Epoxy Resin) An epoxy resin composition was prepared using 15 g.
（評価）
実施例で得られたエポキシ樹脂硬化用微粒子、及び、比較例で得られたエポキシ樹脂組成物について、以下の評価を行った。結果を表１に示す。
(Evaluation)
The following evaluation was performed about the epoxy resin hardening microparticles | fine-particles obtained by the Example, and the epoxy resin composition obtained by the comparative example. The results are shown in Table 1.
（１）エポキシ樹脂組成物中での分散性
実施例で得られたエポキシ樹脂硬化用微粒子１０ｇ、エポキシ樹脂（ＹＬ９８０、ジャパンエポキシレジン社製）１５ｇを、ホモディスパーを用いて攪拌混合し、エポキシ樹脂組成物を調製した。得られたエポキシ樹脂組成物と、比較例で得られたエポキシ樹脂組成物とを用いて、以下の評価を行った。
エポキシ樹脂組成物を厚さ５００μｍに塗布し、１００℃１２０分加熱した。加熱後のエポキシ樹脂組成物の断面を、走査型電子顕微鏡を用いて５０００倍で１０視野観察することにより、エポキシ樹脂組成物中でのエポキシ樹脂硬化用微粒子又は未処理のシリカ粒子の分散性を評価した。１０視野観察において粒子の凝集がなかった場合を○、１０視野観察において粒子の凝集があった場合を×とした。
(1) Dispersibility in epoxy resin composition 10 g of epoxy resin curing fine particles obtained in the examples and 15 g of epoxy resin (YL980, manufactured by Japan Epoxy Resin Co., Ltd.) are stirred and mixed using a homodisper, and epoxy resin is obtained. A composition was prepared. The following evaluation was performed using the obtained epoxy resin composition and the epoxy resin composition obtained by the comparative example.
The epoxy resin composition was applied to a thickness of 500 μm and heated at 100 ° C. for 120 minutes. By observing the cross section of the epoxy resin composition after heating with 10 fields of view at 5000 times using a scanning electron microscope, the dispersibility of the epoxy resin curing fine particles or untreated silica particles in the epoxy resin composition is improved. evaluated. The case where there was no aggregation of particles in 10 field observations was marked as ◯, and the case where there was particle aggregation in 10 field observations was marked as x.
（２）硬化物の線膨張係数
実施例で得られたエポキシ樹脂硬化用微粒子１０ｇ、エポキシ樹脂（ＹＬ９８０、ジャパンエポキシレジン社製）１５ｇを、ホモディスパーを用いて攪拌混合し、エポキシ樹脂組成物を調製した。得られたエポキシ樹脂組成物と、比較例で得られたエポキシ樹脂組成物とを用いて、以下の評価を行った。
エポキシ樹脂組成物について、１１０℃４０分、更に、１７０℃３０分で硬化させた厚さ５００μｍの硬化物を作製した。この硬化物について、熱応力歪測定装置（型式「ＥＸＴＥＡＲ ＴＭＡ／ＳＳ ６１００」、エスアイアイ・ナノテクノロジー社製）を用い、荷重２Ｎ、昇温速度５℃／分、サンプル長１ｃｍで３００℃まで昇温し、このとき得られたＳＳカーブの傾きから線膨張係数を求めた。なお、α１はエポキシ樹脂組成物のガラス転移温度以下での線膨張係数であり、α２はエポキシ樹脂組成物のガラス転移温度以上での線膨張係数である。
(2) Coefficient of linear expansion of cured product 10 g of epoxy resin curing fine particles obtained in the examples and 15 g of epoxy resin (YL980, manufactured by Japan Epoxy Resin Co., Ltd.) were stirred and mixed using a homodisper to obtain an epoxy resin composition. Prepared. The following evaluation was performed using the obtained epoxy resin composition and the epoxy resin composition obtained by the comparative example.
About the epoxy resin composition, a cured product having a thickness of 500 μm cured at 110 ° C. for 40 minutes and further at 170 ° C. for 30 minutes was produced. About this cured | curing material, using a thermal stress strain measuring device (model “EXTEAR TMA / SS 6100”, manufactured by SII Nanotechnology), the temperature was increased to 300 ° C. with a load of 2 N, a temperature rising rate of 5 ° C./min, and a sample length of 1 cm. The linear expansion coefficient was determined from the slope of the SS curve obtained at this time. Α1 is a linear expansion coefficient below the glass transition temperature of the epoxy resin composition, and α2 is a linear expansion coefficient above the glass transition temperature of the epoxy resin composition.
（３）硬化物の信頼性（鉛筆硬度試験）
実施例で得られたエポキシ樹脂硬化用微粒子の４０重量％分散液０．６ｇ、エポキシ樹脂（ＹＬ９８０、ナガセケムテックス社製）０．１ｇを攪拌混合し、エポキシ樹脂組成物を調製した。得られたエポキシ樹脂組成物と、比較例で得られたエポキシ樹脂組成物とを用いて、以下の評価を行った。
エポキシ樹脂組成物をガラス基板上にバーコーティングして塗膜を作製し、この塗膜を１４０℃で３０分加熱して得られた硬化膜の硬度を、鉛筆硬度試験により評価した。鉛筆硬度試験では、硬化膜を鉛筆で引っかいて３ｍｍ以上のキズが入った状態を不具合とし、キズが生じなかった最も硬い鉛筆硬度を評価した。鉛筆硬度が硬いほど、硬化物の信頼性が高いことを意味する。
(3) Reliability of cured product (pencil hardness test)
An epoxy resin composition was prepared by stirring and mixing 0.6 g of a 40 wt% dispersion of epoxy resin curing fine particles obtained in Examples and 0.1 g of an epoxy resin (YL980, manufactured by Nagase ChemteX Corporation). The following evaluation was performed using the obtained epoxy resin composition and the epoxy resin composition obtained by the comparative example.
The epoxy resin composition was bar coated on a glass substrate to prepare a coating film, and the hardness of the cured film obtained by heating the coating film at 140 ° C. for 30 minutes was evaluated by a pencil hardness test. In the pencil hardness test, the cured film was scratched with a pencil, and a state in which scratches of 3 mm or more were included was regarded as a defect, and the hardest pencil hardness without scratches was evaluated. The higher the pencil hardness, the higher the reliability of the cured product.
本発明によれば、エポキシ樹脂用硬化剤として用いられ、エポキシ樹脂組成物中での分散性に優れ、硬化物の線膨張係数を低下させて、硬化物の信頼性を高めることのできるエポキシ樹脂硬化用微粒子を提供することができる。 According to the present invention, an epoxy resin that is used as a curing agent for an epoxy resin, has excellent dispersibility in the epoxy resin composition, can reduce the linear expansion coefficient of the cured product, and can improve the reliability of the cured product. Fine particles for curing can be provided.
Claims (2)
前記熱により塩基が生成する基は、下記一般式（１）で表される構造を有する
ことを特徴とするエポキシ樹脂硬化用微粒子。
The group for generating a base by heat has a structure represented by the following general formula (1).
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