JP5427364B2 - Fine particle-containing composition, fine particle-containing resin composition, and production method thereof - Google Patents
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- 239000010419 fine particle Substances 0.000 title claims description 90
- 239000000203 mixture Substances 0.000 title claims description 58
- 239000011342 resin composition Substances 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 71
- 239000011347 resin Substances 0.000 claims description 49
- 229920005989 resin Polymers 0.000 claims description 49
- 239000002612 dispersion medium Substances 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 39
- 239000011859 microparticle Substances 0.000 claims description 30
- 125000000524 functional group Chemical group 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 8
- 229910010272 inorganic material Inorganic materials 0.000 claims description 8
- 239000011147 inorganic material Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000000101 thioether group Chemical group 0.000 claims description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000000113 methacrylic resin Substances 0.000 claims description 3
- 229920006122 polyamide resin Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 229920002050 silicone resin Polymers 0.000 claims description 3
- 229920005575 poly(amic acid) Polymers 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 77
- 239000000377 silicon dioxide Substances 0.000 description 37
- 238000000034 method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 8
- 230000009257 reactivity Effects 0.000 description 7
- 238000009826 distribution Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- -1 glycidoxy group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 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
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
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Description
本発明は、常温で液体状の樹脂材料中に無機材料から形成される微小粒子を分散した微小粒子含有樹脂組成物及びその微小粒子含有樹脂組成物の原料となる微小粒子含有組成物並びにそれらの製造方法に関する。 The present invention relates to a microparticle-containing resin composition in which microparticles formed from an inorganic material are dispersed in a resin material that is liquid at room temperature, a microparticle-containing composition that is a raw material for the microparticle-containing resin composition, and their It relates to a manufacturing method.
シリカなどの無機材料は樹脂材料と比較して熱安定性などに優れる材料が多く、シリカなどの無機材料から形成された微小粒子を樹脂材料中に分散させた微小粒子含有樹脂組成物が種々の用途に用いられている。 Many inorganic materials such as silica are superior in thermal stability compared to resin materials, and there are various fine particle-containing resin compositions in which fine particles formed from inorganic materials such as silica are dispersed in a resin material. Used for applications.
樹脂材料中に微小粒子を分散させる方法としては、微小粒子の表面に樹脂材料に対して反応性を有する反応性基を持つシランカップリング剤を接触・反応させる方法がある（特許文献１）。樹脂に反応性をもつ反応性基を微小粒子の表面に導入することで安定性の高い微小粒子含有樹脂組成物を得ることが出来る。シランカップリング剤は無機材料の表面に結合可能な化合物であり、微小粒子の表面に反応性基を導入することが可能である。
ところで、微小粒子の粒径が小さく比表面積が大きい場合に、樹脂材料の種類によっては、反応性シランカップリング剤を反応させることで、樹脂材料との反応性が予想外に向上して、反応の制御が充分に出来ない場合があった。例えば、反応の進行が進みすぎてゲル化する場合などがあった。また、反応性基を持つシランカップリング剤の間にて反応が進行してゲル化する場合もあった。 By the way, depending on the type of resin material when the particle size of the fine particles is small and the specific surface area is large, the reactivity with the resin material is unexpectedly improved by reacting with the reactive silane coupling agent. In some cases, it was not possible to sufficiently control. For example, there was a case where the reaction progressed too much and gelled. In some cases, the reaction progresses between silane coupling agents having reactive groups to cause gelation.
本発明は上記実情に鑑み完成したものであり、微小粒子の粒径にかかわらず、組み合わせられる樹脂材料及びシランカップリング剤の種類の制限を少なくすることが出来る微小粒子含有組成物及びその製造方法を提供することを解決すべき課題とする。また、そのような微小粒子含有組成物と樹脂材料との混合物である微小粒子含有樹脂組成物及びその製造方法を提供することを解決すべき課題とする。 The present invention has been completed in view of the above circumstances, regardless of the particle size of the fine particles, fine particle-containing composition in combination is a resin material及beauty Shi can be reduced type of restriction of silane coupling agent and Providing a manufacturing method is a problem to be solved. Another object of the present invention is to provide a fine particle-containing resin composition that is a mixture of such a fine particle-containing composition and a resin material, and a method for producing the same.
（１）本発明者らは上記課題を解決する目的で鋭意検討を行った結果、採用する樹脂材料などに対応した反応性基をもつ第２シランカップリング剤を反応させる前に、第１シランカップリング剤にて表面処理を行うことで、前述したような不都合が生じなくなることを見出した。本発明の微小粒子含有組成物は上記知見に基づき完成したものであり、常温で液体である分散媒と、 (1) As a result of intensive studies aimed at solving the above-mentioned problems, the inventors of the present invention have made the first silane before reacting with the second silane coupling agent having a reactive group corresponding to the resin material to be employed. It has been found that the above-described inconvenience does not occur by performing the surface treatment with a coupling agent. The fine particle-containing composition of the present invention has been completed based on the above findings, a dispersion medium that is liquid at room temperature,
体積平均粒径が３００ｎｍ超であり、前記分散媒中に分散された無機物からなる微小粒子材料と、を有する微粒子含有組成物であって、
前記微小粒子材料の表面には、第１シランカップリング剤、第２シランカップリング剤の順で反応がなされており、
A fine particle-containing composition having a volume average particle diameter of more than 300 nm and a fine particle material made of an inorganic material dispersed in the dispersion medium,
The surface of the fine particle material is reacted in the order of the first silane coupling agent and the second silane coupling agent ,
前記無機物は表面にＯＨ基を有しており、 The inorganic substance has an OH group on the surface,
前記第１シランカップリング剤は一般式（２）：Ｓｉ（Ｒ The first silane coupling agent has the general formula (2): Si (R
3Three
）)
YY
（ＯＲ(OR
4Four
）)
4-Y4-Y
：（式（２）中、Ｙは１、２又は３；Ｒ: (In formula (2), Y is 1, 2 or 3; R
3Three
はそれぞれ独立して選択される炭化水素基、ＯＲAre independently selected hydrocarbon groups, OR
4Four
は加水分解可能な官能基）で表される化合物であり、Is a compound represented by a hydrolyzable functional group),
前記第２シランカップリング剤は一般式（１）：Ｓｉ（Ｒ1）X（ＯＲ2）4-X：（式（１）中、Ｘは１又は２；Ｒ1は、アミノ基、水酸基、カルボキシル基、チオール基、イソシアネート基、シアネート基、ウレタン基、ウレア基、チオエーテル基及びグリシドキシ基から選択される基で水素が置換されたプロピル基であり、それぞれ独立して選択される；Ｒ2は加水分解可能な官能基）で表される化合物であることを特徴とする。 The second silane coupling agent has the general formula (1): Si (R 1 ) X (OR 2 ) 4-X : (wherein X is 1 or 2; R 1 is an amino group, a hydroxyl group, carboxyl group, thiol group, isocyanate group, cyanate group, a urethane group, a urea group, a thioether group and a glycidoxy propyl hydrogen is substituted with a group selected from the group, each independently selected; R 2 is It is a compound represented by a hydrolyzable functional group).
更に、前記分散媒は５質量％〜１００質量％の水と０質量％〜９５質量％の有機溶媒との混合物であることが望ましい。
（２）また、上記課題を解決する本発明の微小粒子含有樹脂組成物は上述の微小粒子含有組成物と、熱硬化性樹脂及び／又は光硬化性樹脂からなる群から選択される硬化性樹脂材料とを混合物であることを特徴とする。
Further, the dispersion medium is preferably a mixture of 5% by mass to 100% by mass of water and 0% by mass to 95% by mass of an organic solvent.
(2) Further, the fine particle-containing resin composition of the present invention that solves the above problems is a curable resin selected from the group consisting of the above-mentioned fine particle-containing composition, a thermosetting resin, and / or a photocurable resin. The material is a mixture.
その硬化性樹脂材料としては、エポキシ樹脂、アクリル樹脂、メタクリル樹脂、ポリオール樹脂、ポリアミック酸樹脂、ポリアミド樹脂、シリコーン樹脂及びシアネート樹脂からなる群から選択されることが望ましい。そして、前記分散媒を除去したものであることが望ましい。
（３）また、上記課題を解決する本発明の微小粒子含有組成物の製造方法は、全体の質量を基準として５％以上含む水と、その水と混和可能な有機溶媒とを含む混合物である分散媒と、体積平均粒径が３００ｎｍ超であり、前記分散媒中に分散された無機物からなる微小粒子材料と、を有する組成物に対して、第１シランカップリング剤を添加してその表面に反応させる前処理工程と、
第２シランカップリング剤を添加してその表面に反応させる表面処理工程と、を有し、
前記無機物は表面にＯＨ基を有しており、
The curable resin material is preferably selected from the group consisting of epoxy resin, acrylic resin, methacrylic resin, polyol resin, polyamic acid resin, polyamide resin, silicone resin and cyanate resin. It is desirable that the dispersion medium is removed.
(3) Moreover, the manufacturing method of the microparticle containing composition of this invention which solves the said subject is a mixture containing the water which contains 5% or more on the basis of the whole mass, and the organic solvent miscible with the water. A first silane coupling agent is added to the surface of the composition having a dispersion medium and a fine particle material made of an inorganic material having a volume average particle diameter of more than 300 nm and dispersed in the dispersion medium. a pretreatment step of Ru reacted,
A surface treatment step of Ru reacted on the surface by adding a second silane coupling agent, was closed,
The inorganic substance has an OH group on the surface,
前記第１シランカップリング剤は一般式（２）：Ｓｉ（Ｒ The first silane coupling agent has the general formula (2): Si (R 3Three ）) YY （ＯＲ(OR 4Four ）) 4-Y4-Y ：（式（２）中、Ｙは１、２又は３；Ｒ: (In formula (2), Y is 1, 2 or 3; R 3Three はそれぞれ独立して選択される炭化水素基、ＯＲAre independently selected hydrocarbon groups, OR 4Four は加水分解可能な官能基）で表される化合物であり、Is a compound represented by a hydrolyzable functional group),
前記第２シランカップリング剤は一般式（１）：Ｓｉ（Ｒ1）X（ＯＲ2）4-X：（式（１）中、Ｘは１又は２；Ｒ1は、アミノ基、水酸基、カルボキシル基、チオール基、イソシアネート基、シアネート基、ウレタン基、ウレア基、チオエーテル基及びグリシドキシ基から選択される基で水素が置換されたプロピル基であり、それぞれ独立して選択される；Ｒ2は加水分解可能な官能基）で表される化合物であることを特徴とする。 The second silane coupling agent has the general formula (1): Si (R 1 ) X (OR 2 ) 4-X : (wherein X is 1 or 2; R 1 is an amino group, a hydroxyl group, carboxyl group, thiol group, isocyanate group, cyanate group, a urethane group, a urea group, a thioether group and a glycidoxy propyl hydrogen is substituted with a group selected from the group, each independently selected; R 2 is It is a compound represented by a hydrolyzable functional group).
更に、前記分散媒中に含まれる有機溶媒は水よりも沸点が高く、前記前処理工程後に、前記分散媒中に含まれる水を除去する工程をもつことが望ましい。分散媒を蒸発により除去する際に、沸点が低い水から蒸発させることが可能になって分散媒の主成分を有機溶媒にすることができる。
（４）そして、上記課題を解決する本発明の微小粒子含有樹脂組成物の製造方法は、上述の微小粒子含有組成物の製造方法と、熱硬化性樹脂及び／又は光硬化性樹脂からなる群から選択される硬化性樹脂材料を混合する混合工程と、前記分散媒を除去する分散媒除去工程と、を有することを特徴とする。
Furthermore, it is desirable that the organic solvent contained in the dispersion medium has a boiling point higher than that of water and has a step of removing water contained in the dispersion medium after the pretreatment step. When the dispersion medium is removed by evaporation, the dispersion medium can be evaporated from water having a low boiling point, and the main component of the dispersion medium can be an organic solvent.
(4) And the manufacturing method of the fine particle containing resin composition of this invention which solves the said subject is the group which consists of the manufacturing method of the above-mentioned fine particle containing composition, and a thermosetting resin and / or a photocurable resin. A mixing step of mixing a curable resin material selected from the above, and a dispersion medium removing step of removing the dispersion medium.
本発明の微小粒子含有組成物は上記構成を有することで、第２シランカップリング剤の作用の程度を簡単に制御することが可能になり、粒径が小さい微小粒子を採用しても、第２シランカップリング剤と樹脂材料との組み合わせの選択の幅が広くなる。 Since the composition containing fine particles of the present invention has the above-described configuration, it is possible to easily control the degree of action of the second silane coupling agent . The range of selection of combinations of 2- silane coupling agent and resin material is widened.
樹脂材料と組み合わせた本発明の微小粒子含有組成物、そして本発明の微小粒子含有樹脂組成物は、コーティング剤や塗料、半導体封止材、アンダーフィル材、接着剤、ダイアタッチペーストなどに添加して用いたり、適正な材料と混合した状態で固化・成形して、電子基板に用いられるワニス、プリプレグ、絶縁用のフィルム、ダイアタッチフィルムなどに用いることができる。以下、実施形態に基づき詳細に説明を行う。 The fine particle-containing composition of the present invention combined with a resin material, and the fine particle-containing resin composition of the present invention are added to coating agents, paints, semiconductor encapsulants, underfill materials, adhesives, die attach pastes, etc. It can be used as a varnish, prepreg, insulating film, die attach film, etc. used for electronic substrates. Hereinafter, a detailed description will be given based on the embodiment.
（微小粒子含有組成物及びその製造方法）
本実施形態の微小粒子含有組成物は、分散媒と微小粒子とを含有する。本微小粒子含有組成物は特に樹脂材料に混合して樹脂組成物として用いられる用途がある。分散媒と微小粒子との含有割合は特に限定されず、必要に応じて適宜設定される。混合可能な樹脂材料については熱及び／又は光により硬化する熱及び／又は光硬化性の樹脂材料であり、その添加量も必要に応じて適宜設定される。樹脂材料としては、例えば、エポキシ樹脂、アクリル樹脂、メタクリル樹脂、ポリオール樹脂、ポリアミド樹脂、シリコーン樹脂及びシアネート樹脂からなる群から選択される。
(Microparticle-containing composition and method for producing the same)
The fine particle-containing composition of the present embodiment contains a dispersion medium and fine particles. The fine particle-containing composition has a use that is mixed with a resin material and used as a resin composition. The content ratio of the dispersion medium and the fine particles is not particularly limited, and is appropriately set as necessary. The resin material that can be mixed is a heat and / or photo-curing resin material that is cured by heat and / or light, and the addition amount thereof is appropriately set as necessary. The resin material is selected from the group consisting of epoxy resin, acrylic resin, methacrylic resin, polyol resin, polyamide resin, silicone resin and cyanate resin, for example.
分散媒は常温で液体であること以外は特に限定されず、採用する樹脂材料との関係で適宜選択される。分散媒としては、例えば、樹脂材料を分散乃至溶解可能な溶媒が採用できる。分散媒は単独の化合物（溶媒）であっても良いし、２以上の化合物の混合物であっても良い。分散媒としてはアルコール類、エステル類、エーテル類、環状エーテル類、水などを採用することが出来る。水を添加する場合には分散媒の質量を基準として５質量％以上含有させることができる。 The dispersion medium is not particularly limited except that it is liquid at normal temperature, and is appropriately selected in relation to the resin material to be employed. As the dispersion medium, for example, a solvent capable of dispersing or dissolving the resin material can be employed. The dispersion medium may be a single compound (solvent) or a mixture of two or more compounds. As the dispersion medium, alcohols, esters, ethers, cyclic ethers, water and the like can be used. When water is added, it can be contained in an amount of 5% by mass or more based on the mass of the dispersion medium.
微小粒子は無機物から形成される。無機物としてはその表面にＯＨ基が存在するものである。例えばシリカ、アルミナ、チタニア、ジルコニアなどが挙げられる。これらの無機物においてはその表面に存在するＯＨ基の酸素に対してシランカップリング剤が反応する。微小粒子は体積平均粒径が３００ｎｍ超である。微小粒子は真球状（例えば真球度が０．９以上）であることが望ましい。微小粒子は対応する無機物が含有する金属元素のアルコキシドを加水分解する方法（いわゆるゾルゲル法）、ＶＭＣ法、火炎溶融法などの公知の方法にて製造することができ、特にゾルゲル法にて製造されたものが望ましい。 Microparticles are formed from inorganic materials. An inorganic substance has an OH group on its surface. Such as silica, alumina, titania, etc. zirconia A and the like. In these inorganic substances, the silane coupling agent reacts with oxygen of OH groups present on the surface. The fine particles have a volume average particle size of more than 300 nm. The fine particles are preferably spherical (for example, the sphericity is 0.9 or more). The fine particles can be produced by a known method such as a method of hydrolyzing an alkoxide of a metal element contained in a corresponding inorganic substance (so-called sol-gel method), a VMC method, a flame melting method, and the like. Is desirable.
微小粒子の表面は第１シランカップリング剤、第２シランカップリング剤の順で処理され、微小粒子の表面に反応している。第１シランカップリング剤にて先に表面処理を行うことで第２シランカップリング剤の量を相対的に減少できるので、第１シランカップリング剤の処理量を制御することで第２シランカップリング剤由来の反応性基の導入量、反応性を制御できる。 The surface of the microparticles is treated in the order of the first silane coupling agent and the second silane coupling agent, and reacts with the surface of the microparticles . Since the amount of the second silane coupling agent by the surface treatment earlier in the first silane coupling agent can be relatively reduced, the second silane coupling by controlling the process amount of the first silane coupling agent The introduction amount and reactivity of the reactive group derived from the ring agent can be controlled.
ここで、第１シランカップリング剤及び第２シランカップリング剤の組み合わせ並びに組み合わせる量は、組み合わされる樹脂材料によって変化できる。 Here, the combination and the amount of the first silane coupling agent and the second silane coupling agent can be changed depending on the resin material to be combined .
第２シランカップリング剤としては一般式（１）：Ｓｉ（Ｒ1）X（ＯＲ2）4-X：（式（１）中、Ｘは１又は２；Ｒ1は、アミノ基、水酸基、カルボキシル基、チオール基、イソシアネート基、シアネート基、ウレタン基、ウレア基、チオエーテル基及びグリシドキシ基から選択される基で水素が置換されたプロピル基であり、それぞれ独立して選択される；Ｒ2は加水分解可能な官能基であることが望ましい。）である。ここで、本明細書中における加水分解可能な官能基（−ＯＲ2）とは加水分解により水酸基が生成するアルコキシ基であり炭素数が１〜５程度の官能基を採用することが望ましい。 As the second silane coupling agent, general formula (1): Si (R 1 ) X (OR 2 ) 4-X : (in formula (1), X is 1 or 2; R 1 is an amino group, a hydroxyl group, carboxyl group, thiol group, isocyanate group, cyanate group, a urethane group, a urea group, a thioether group and a glycidoxy propyl hydrogen is substituted with a group selected from the group, each independently selected; R 2 is It is preferably a hydrolyzable functional group. Here, the hydrolyzable functional group (—OR 2 ) in the present specification is an alkoxy group in which a hydroxyl group is generated by hydrolysis, and it is desirable to employ a functional group having about 1 to 5 carbon atoms.
第１シランカップリング剤としては一般式（２）：Ｓｉ（Ｒ3）Y（ＯＲ4）4-Y：（式（２）中、Ｙは１、２又は３；Ｒ3はそれぞれ独立して選択される炭化水素基、ＯＲ4は加水分解可能な官能基）で表される化合物である。なお、Ｒ3は炭素数１〜５程度であることが望ましい。 As the first silane coupling agent, general formula (2): Si (R 3 ) Y (OR 4 ) 4-Y : (in formula (2), Y is 1, 2 or 3; R 3 is independently hydrocarbon group selected, OR 4 is Ru compound der represented by hydrolysable functional group). R 3 is preferably about 1 to 5 carbon atoms.
（微小粒子含有樹脂組成物及びその製造方法）
本実施形態の微小粒子含有樹脂組成物は本実施形態の微小粒子含有組成物に樹脂材料を含有させたものである。樹脂材料としては前述の樹脂材料がそのまま採用できる。樹脂材料を含有させる方法としては特に限定しないが、微小粒子を分散媒中に分散させて第１シランカップリング剤にて処理して微小粒子含有組成物を製造した後に第２シランカップリング剤と共に樹脂材料を添加する方法がある。樹脂材料を含有させた後には必要に応じて分散媒を除去することも出来る。分散媒の除去は分散媒のすべてを除去する場合の方法ほか、分散媒の一部を除去したり、分散媒として複数種類の溶媒を組み合わせている場合にその一部の溶媒のみを除去することもできる。例えば、水と水に混和可能な有機溶媒との混合物を分散媒に採用し、その分散媒に樹脂材料を添加した後に、水のみを除去することで水に親和性が高い材料を有機溶媒に分散させることが出来る。
(Microparticle-containing resin composition and method for producing the same)
The fine particle-containing resin composition of the present embodiment is obtained by adding a resin material to the fine particle-containing composition of the present embodiment. As the resin material, the above-described resin materials can be used as they are. Although it does not specifically limit as a method of containing a resin material, After dispersing a microparticle in a dispersion medium and processing with a 1st silane coupling agent and manufacturing a microparticle containing composition, with a 2nd silane coupling agent There is a method of adding a resin material. After the resin material is contained, the dispersion medium can be removed as necessary. In addition to the method of removing all of the dispersion medium, the removal of the dispersion medium is to remove a part of the dispersion medium, or to remove only part of the solvent when combining multiple types of solvents as the dispersion medium. You can also. For example, a mixture of water and an organic solvent miscible with water is adopted as the dispersion medium, and after adding a resin material to the dispersion medium, a material having a high affinity for water is used as the organic solvent by removing only water. Can be dispersed.
（実施例１）
１００質量部のシリカ微小粒子（アドマファインＳＯ−Ｃ２、アドマテックス製：体積平均粒径０．５μｍ：ＶＭＣ法にて製造）に４２質量部のメチルイソブチルケトン（分散媒に相当）とシリカ微小粒子の表面積に応じた量（シリカ微小粒子の質量を基準として１．０質量％：シリカ微小粒子の表面をすべて反応できる量）のシランカップリング剤（ＫＢＭ−１００３：第１シランカップリング剤に相当：官能基としてビニル基をもつ）とを混合し、４０℃で７２時間保持することでシリカ微小粒子の表面を第１シランカップリング剤にて処理した。
Example 1
100 parts by mass of silica fine particles (Admafine SO-C2, manufactured by Admatechs: volume average particle size 0.5 μm: produced by the VMC method) and 42 parts by mass of methyl isobutyl ketone (corresponding to a dispersion medium) and silica fine particles Of silane coupling agent (KBM-1003: equivalent to the first silane coupling agent) in an amount according to the surface area (1.0% by mass based on the mass of the silica microparticles: an amount capable of reacting all the surfaces of the silica microparticles) : Having a vinyl group as a functional group), and the surface of the silica fine particles was treated with the first silane coupling agent by holding at 40 ° C. for 72 hours.
その後、シリカ微小粒子の表面積に応じた量（シリカ微小粒子の質量を基準として１．０質量％：シリカ微小粒子の表面をすべて反応できる量）のシランカップリング剤（ＫＢＭ９０３：３−アミノプロピルトリメトキシシラン：第２シランカップリング剤に相当：反応性基としてのアミノ基をもつ）とを混合・分散した結果、シリカ微粒子が均一に分散し、３ヶ月以上、分散安定であり、シリカハードケーキが発生しない微小粒子含有組成物が得られた。 Thereafter, a silane coupling agent (KBM903: 3-aminopropyltrimethyl) in an amount corresponding to the surface area of the silica microparticles (1.0 mass% based on the mass of the silica microparticles: an amount capable of reacting all the surfaces of the silica microparticles). As a result of mixing and dispersing methoxysilane (corresponding to the second silane coupling agent: having an amino group as a reactive group), the silica fine particles are uniformly dispersed, and the dispersion is stable for more than 3 months. A fine particle-containing composition in which no generation occurs was obtained.
（実施例２）
第２シランカップリング剤として、ＫＢＥ−９００７（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：反応性基としてのイソシアネート基をもつ）を用いた以外は実施例１と同様にしてそれぞれの微小粒子含有組成物を調製した。シリカ微粒子が均一に分散した無色透明の微小粒子含有組成物が得られた。
(Example 2)
Each fine particle was the same as in Example 1 except that KBE-9007 (Example 2: 3-isocyanatopropyltriethoxysilane: having an isocyanate group as a reactive group) was used as the second silane coupling agent. A containing composition was prepared. A colorless and transparent fine particle-containing composition in which silica fine particles were uniformly dispersed was obtained.
（比較例１及び２）
第１シランカップリング剤を用いないこと以外は実施例１及び２のそれぞれと同様の操作を行い、比較例１及び２の微小粒子含有組成物を得た。得られた微小粒子含有組成物はどれも凝集乃至ゲル化していた。
(Comparative Examples 1 and 2)
Except not using a 1st silane coupling agent, operation similar to each of Example 1 and 2 was performed, and the microparticle containing composition of the comparative examples 1 and 2 was obtained. All of the obtained fine particle-containing compositions were aggregated or gelled.
以上の結果から、第２シランカップリング剤にて処理する前に、予め第１シランカップリング剤にて微小粒子を処理することで、第２シランカップリング剤の反応性を制御することが可能になって、微小粒子を均一に混合・分散することが出来ることが分かった。なお、第２シランカップリング剤により表面に導入された官能基の存在は後述するＩＲスペクトルにより確認した。また、その官能基と反応する樹脂組成物を混合すると、極めて均一に分散することが確認され、表面に必要量の官能基が導入されていることが確認できた。このことは以下の実施例のシリカ微粒子含有組成物についても同じである。 These results, before processing in the second silane coupling agent, to treat the fine particles in advance first silane coupling agent, it can control the reactivity of the second silane coupling agent As a result, it was found that the fine particles can be uniformly mixed and dispersed. The presence of a functional group introduced to the surface by the second silane coupling agent was confirmed by an IR spectrum described later. Moreover, when the resin composition which reacts with the functional group was mixed, it was confirmed that the resin composition was dispersed extremely uniformly, and it was confirmed that a necessary amount of the functional group was introduced on the surface. This also applies to the silica fine particle-containing compositions of the following examples.
（実施例３）
１００質量部のシリカ微小粒子（アドマファインＳＯ−Ｃ２、アドマテックス製：体積平均粒径０．５μｍ）に、４１質量部のプロロピレングリコールモノメチルエーテルアセテート（分散媒に相当）と、シリカ微小粒子の表面積に応じた量（シリカ微小粒子の表面をすべて反応できる量）のシランカップリング剤（ＫＢＭ−１００３：第１シランカップリング剤に相当：官能基としてビニル基をもつ）とを混合し、４０℃で７２時間保持することでシリカ微小粒子の表面を第１シランカップリング剤にて処理した。
(Example 3)
100 parts by mass of silica fine particles (Admafine SO-C2, manufactured by Admatechs: volume average particle size 0.5 μm), 41 parts by mass of propylene glycol monomethyl ether acetate (corresponding to a dispersion medium), and silica fine particles A silane coupling agent (KBM-1003: equivalent to the first silane coupling agent: having a vinyl group as a functional group) in an amount corresponding to the surface area (amount capable of reacting all the surfaces of the silica fine particles) is mixed. The surface of the silica fine particles was treated with the first silane coupling agent by maintaining at 72 ° C. for 72 hours.
その後、シリカ微小粒子の表面積に応じた量（シリカ微小粒子の表面をすべて反応できる量）のシランカップリング剤（ＫＢＭ４０３：３−グリシドキシプロピルトリエトキシシラン：第２シランカップリング剤に相当：反応性基としてのグリシドキシ基をもつ）とを混合・分散した結果、シリカ微粒子が均一に分散し、３ヶ月以上、分散安定であり、シリカハードケーキが発生しない微小粒子含有組成物が得られた。 Thereafter, an amount of silane coupling agent (KBM403: 3-glycidoxypropyltriethoxysilane: equivalent to the second silane coupling agent) in an amount corresponding to the surface area of the silica microparticles (amount capable of reacting all the surfaces of the silica microparticles): As a result of mixing and dispersing (having a glycidoxy group as a reactive group), a fine particle-containing composition was obtained in which the silica fine particles were uniformly dispersed and the dispersion was stable for 3 months or more and no silica hard cake was generated. .
（実施例４）
シリカ微粒子として体積平均粒径が１０μｍの熔融シリカ（アドマテックス製、熔融法にて製造）を用いたこと以外は実施例３と同様の操作を行い、実施例４の微小粒子含有組成物を得た。得られた微小粒子含有組成物はシリカ微粒子が均一に分散した微小粒子含有組成物が得られた。
Example 4
The same procedure as in Example 3 was performed except that fused silica (manufactured by Admatechs, manufactured by the melting method) having a volume average particle size of 10 μm was used as the silica fine particles, and the fine particle-containing composition of Example 4 was obtained. It was. The obtained fine particle-containing composition was a fine particle-containing composition in which silica fine particles were uniformly dispersed.
（比較例３及び４）
第１シランカップリング剤を用いないこと以外は実施例３及び４と同様の操作を行い、比較例３及び４の微小粒子含有組成物を得た。得られた微小粒子含有組成物はシリカ微粒子が均一に分散した無色透明の微小粒子含有組成物が得られた。
(Comparative Examples 3 and 4)
Except not using a 1st silane coupling agent, operation similar to Example 3 and 4 was performed, and the fine particle containing composition of the comparative examples 3 and 4 was obtained. The obtained fine particle-containing composition was a colorless and transparent fine particle-containing composition in which silica fine particles were uniformly dispersed.
（実施例３、４及び比較例３、４の微小粒子含有組成物の比較）
実施例３、４及び比較例３、４の微小粒子含有組成物について、常温で２週間放置した後の性状を目視で観察した。実施例３及び４の微小粒子含有組成物は試料調製直後と同様に均一に分散されていることが分かった。比較例３及び４の微小粒子含有組成物は含有させているシリカ微粒子の沈殿が観測され、更にその沈殿物はゲル化していた。以上のことから、実施例３の微小粒子含有組成物は２週間経過後でも安定した分散状態を保持できたのに対し、比較例３の微小粒子含有組成物は分離、ゲル化することが分かった。これは第１シランカップリング剤にて予め処理することにより、その後、反応させた第２シランカップリング剤の過剰な反応性を抑制することができるものと考えられる。
(Comparison of compositions containing fine particles of Examples 3 and 4 and Comparative Examples 3 and 4)
About the fine particle containing composition of Example 3, 4 and Comparative Example 3, 4, the property after leaving to stand at normal temperature for 2 weeks was observed visually. It was found that the fine particle-containing compositions of Examples 3 and 4 were uniformly dispersed in the same manner as immediately after sample preparation. In the fine particle-containing compositions of Comparative Examples 3 and 4, precipitation of silica fine particles contained was observed, and the precipitate was gelled. From the above, it was found that the fine particle-containing composition of Example 3 could maintain a stable dispersion state even after 2 weeks, whereas the fine particle-containing composition of Comparative Example 3 separated and gelled. It was. This by pre-processed by the first silane coupling agent, then it is considered that it is possible to suppress the excessive reactivity of the second silane coupling agent reacted.
以上の結果から、第２シランカップリング剤にて処理する前に、予め第１シランカップリング剤にて微小粒子を処理することで、第２シランカップリング剤の反応性を制御することが可能になって、微小粒子を均一に混合・分散することが出来ることが分かった。また、シリカ微粒子としては粒径が１０μｍと大きなものでも効果が発揮できることが分かった。また、ＶＭＣ法以外にも熔融法にて製造したシリカ微粒子であっても効果が発揮されることが分かった。
・表面状態の評価
（参考例１〜３）
第１シランカップリング剤（ＫＢＭ１００３）のみを用いたこと以外はそれぞれ実施例１及び３と同様の操作を行い、参考例１及び２の微小粒子含有組成物を得た。また第２シランカップリング剤（ＫＢＭ４０３）のみを用いたこと以外は実施例３と同様の操作を行い、参考例３の微小粒子含有組成物を得た。得られた微小粒子含有組成物はシリカ微粒子が均一に分散した無色透明の微小粒子含有組成物が得られた。
These results, before processing in the second silane coupling agent, to treat the fine particles in advance first silane coupling agent, it can control the reactivity of the second silane coupling agent As a result, it was found that the fine particles can be uniformly mixed and dispersed. It was also found that the silica fine particles can be effective even when the particle size is as large as 10 μm. It was also found that the silica fine particles produced by the melting method other than the VMC method can exert the effect.
・ Evaluation of surface condition (Reference Examples 1 to 3)
Except having used only the 1st silane coupling agent (KBM1003), operation similar to Example 1 and 3 was performed, respectively, and the fine particle containing composition of the reference examples 1 and 2 was obtained. Moreover, the same operation as Example 3 was performed except having used only the 2nd silane coupling agent (KBM403), and the microparticle containing composition of the reference example 3 was obtained. The obtained fine particle-containing composition was a colorless and transparent fine particle-containing composition in which silica fine particles were uniformly dispersed.
実施例１、実施例３、参考例１〜３のそれぞれについて、分散媒を揮散除去した後にＦＴ−ＩＲにてＩＲスペクトルを測定した。結果を図１（実施例１及び参考例１）及び図２（実施例３及び参考例２、３）に示す。 For each of Example 1, Example 3, and Reference Examples 1 to 3, the dispersion medium was volatilized and removed, and then the IR spectrum was measured by FT-IR. The results are shown in FIG. 1 (Example 1 and Reference Example 1) and FIG. 2 (Example 3 and Reference Examples 2 and 3).
実施例１のシリカ微小粒子はＫＢＭ１００３による処理に加えてＫＢＭ９０３（反応基としてアミノ基を有する）にて表面処理を行っており、 実施例３のシリカ微小粒子はＫＢＭ１００３による処理に加えてＫＢＭ４０３（反応基としてグリシドキシ基を有する）にて表面処理を行っている。参考例１及び２のシリカ微粒子はＫＢＭ１００３による処理のみのものである。 The silica fine particles of Example 1 are subjected to surface treatment with KBM903 (having an amino group as a reactive group) in addition to the treatment with KBM1003. The silica fine particles of Example 3 are subjected to KBM403 (reaction) in addition to the treatment with KBM1003. Surface treatment is performed with a glycidoxy group as a group. The silica fine particles of Reference Examples 1 and 2 are only treated with KBM1003.
図１及び２より明らかなように、実施例１及び３、参考例１及び２のそれぞれはＫＢＭ１００３由来のピークが２８００〜３１００ｃｍ-1に確認できた。参考例３はＫＢＭ４０３由来のピークが２８００〜３０００ｃｍ-1に確認できた。更に、実施例１及び３についてはそれぞれＫＢＭ９０３（２９００〜３０００ｃｍ-1：実施例１）とＫＢＭ４０３（２８００〜３０００ｃｍ-1：実施例３）とに由来するピークが重畳したピークが観測された。すなわち、ＫＢＭ１００３に加え、それぞれの第２シランカップリング剤についてもシリカ微小粒子の表面に付着乃至反応していることが明らかになった。
・粒径分布の評価
実施例１の微小粒子含有組成物について粒度分布をレーザー回折式粒度分布計（ＬＡ５００、堀場製作所製）にて測定した。結果を図３に示す。図３より明らかなように、その粒度分布は鋭く、その中央値も０．５２μｍと原料のシリカ微粒子の０．５μｍから殆ど変化していないことが分かった。つまり、第１シランカップリング剤により予め処理した後に第２シランカップリング剤によって処理することで、その反応性を抑制することができることが分かった。
As is clear from FIGS. 1 and 2, in Examples 1 and 3 and Reference Examples 1 and 2, a peak derived from KBM1003 could be confirmed at 2800 to 3100 cm −1 . In Reference Example 3, a peak derived from KBM403 was confirmed at 2800 to 3000 cm −1 . Further, in Examples 1 and 3, peaks in which peaks derived from KBM903 (2900 to 3000 cm −1 : Example 1) and KBM403 (2800 to 3000 cm −1 : Example 3) were superimposed were observed. That is, it was revealed that in addition to KBM1003, each second silane coupling agent also adhered to or reacted with the surface of the silica microparticles.
-Evaluation of particle size distribution The particle size distribution of the fine particle-containing composition of Example 1 was measured with a laser diffraction particle size distribution meter (LA500, manufactured by Horiba, Ltd.). The results are shown in FIG. As apparent from FIG. 3, the particle size distribution is sharp, and the median is 0.52 μm, which is almost unchanged from 0.5 μm of the raw silica fine particles. That is, it turned out that the reactivity can be suppressed by processing with the 2nd silane coupling agent after processing beforehand with the 1st silane coupling agent.
Claims (8)
体積平均粒径が３００ｎｍ超であり、前記分散媒中に分散された無機物からなる微小粒子材料と、を有する微粒子含有組成物であって、
前記微小粒子材料の表面には、第１シランカップリング剤、第２シランカップリング剤の順で反応がなされており、
前記無機物は表面にＯＨ基を有しており、
前記第１シランカップリング剤は一般式（２）：Ｓｉ（Ｒ3）Y（ＯＲ4）4-Y：（式（２）中、Ｙは１、２又は３；Ｒ3はそれぞれ独立して選択される炭化水素基、ＯＲ4は加水分解可能な官能基）で表される化合物であり、
前記第２シランカップリング剤は一般式（１）：Ｓｉ（Ｒ1）X（ＯＲ2）4-X：（式（１）中、Ｘは１又は２；Ｒ1は、アミノ基、水酸基、カルボキシル基、チオール基、イソシアネート基、シアネート基、ウレタン基、ウレア基、チオエーテル基及びグリシドキシ基から選択される基で水素が置換されたプロピル基であり、それぞれ独立して選択される；Ｒ2は加水分解可能な官能基）で表される化合物であることを特徴とする微小粒子含有組成物。 A dispersion medium that is liquid at room temperature;
A fine particle-containing composition having a volume average particle diameter of more than 300 nm and a fine particle material made of an inorganic material dispersed in the dispersion medium,
The surface of the fine particle material is reacted in the order of the first silane coupling agent and the second silane coupling agent,
The inorganic substance has an OH group on the surface,
The first silane coupling agent has the general formula (2): Si (R 3 ) Y (OR 4 ) 4-Y : (wherein Y is 1, 2 or 3; R 3 is independently A selected hydrocarbon group, OR 4 is a hydrolyzable functional group),
The second silane coupling agent has the general formula (1): Si (R 1 ) X (OR 2 ) 4-X : (wherein X is 1 or 2; R 1 is an amino group, a hydroxyl group, carboxyl group, thiol group, isocyanate group, cyanate group, a urethane group, a urea group, a thioether group and a glycidoxy propyl hydrogen is substituted with a group selected from the group, each independently selected; R 2 is A fine particle-containing composition, which is a compound represented by a hydrolyzable functional group).
熱硬化性樹脂及び／又は光硬化性樹脂からなる群から選択される硬化性樹脂材料との混合物であることを特徴とする微小粒子含有樹脂組成物。 The fine particle-containing composition according to claim 1 or 2,
A fine particle-containing resin composition, which is a mixture with a curable resin material selected from the group consisting of a thermosetting resin and / or a photocurable resin.
第２シランカップリング剤を添加してその表面に反応させる表面処理工程と、を有し、 前記無機物は表面にＯＨ基を有しており、
前記第１シランカップリング剤は一般式（２）：Ｓｉ（Ｒ3）Y（ＯＲ4）4-Y：（式（２）中、Ｙは１、２又は３；Ｒ3はそれぞれ独立して選択される炭化水素基、ＯＲ4は加水分解可能な官能基）で表される化合物であり、
前記第２シランカップリング剤は一般式（１）：Ｓｉ（Ｒ1）X（ＯＲ2）4-X：（式（１）中、Ｘは１又は２；Ｒ1は、アミノ基、水酸基、カルボキシル基、チオール基、イソシアネート基、シアネート基、ウレタン基、ウレア基、チオエーテル基及びグリシドキシ基から選択される基で水素が置換されたプロピル基であり、それぞれ独立して選択される；Ｒ2は加水分解可能な官能基）で表される化合物であることを特徴とする微小粒子含有組成物の製造方法。 A dispersion medium that is a mixture containing water containing 5% or more based on the total mass of the organic solvent and an organic solvent miscible with the water, and an inorganic substance having a volume average particle size of more than 300 nm and dispersed in the dispersion medium A pretreatment step of adding a first silane coupling agent to react with the surface of the composition having a fine particle material comprising:
A surface treatment step of adding a second silane coupling agent to react with the surface thereof, wherein the inorganic substance has an OH group on the surface,
The first silane coupling agent has the general formula (2): Si (R 3 ) Y (OR 4 ) 4-Y : (wherein Y is 1, 2 or 3; R 3 is independently A selected hydrocarbon group, OR 4 is a hydrolyzable functional group),
The second silane coupling agent has the general formula (1): Si (R 1 ) X (OR 2 ) 4-X : (wherein X is 1 or 2; R 1 is an amino group, a hydroxyl group, carboxyl group, thiol group, isocyanate group, cyanate group, a urethane group, a urea group, a thioether group and a glycidoxy propyl hydrogen is substituted with a group selected from the group, each independently selected; R 2 is A method for producing a composition containing fine particles, which is a compound represented by a hydrolyzable functional group).
前記前処理工程後に、前記分散媒中に含まれる水を除去する工程をもつ請求項６に記載の微小粒子含有組成物の製造方法。 The organic solvent contained in the dispersion medium has a boiling point higher than that of water,
The method for producing a fine particle-containing composition according to claim 6, further comprising a step of removing water contained in the dispersion medium after the pretreatment step.
熱硬化性樹脂及び／又は光硬化性樹脂からなる群から選択される硬化性樹脂材料を混合する混合工程と、
前記分散媒を除去する分散媒除去工程と、を有することを特徴とする微小粒子含有樹脂組成物の製造方法。 A method for producing the microparticle-containing composition according to claim 6 or 7,
A mixing step of mixing a curable resin material selected from the group consisting of a thermosetting resin and / or a photocurable resin;
And a dispersion medium removing step of removing the dispersion medium.
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