JP2016175790A - Method for producing silica-based particle dispersion - Google Patents
Method for producing silica-based particle dispersion Download PDFInfo
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- JP2016175790A JP2016175790A JP2015056462A JP2015056462A JP2016175790A JP 2016175790 A JP2016175790 A JP 2016175790A JP 2015056462 A JP2015056462 A JP 2015056462A JP 2015056462 A JP2015056462 A JP 2015056462A JP 2016175790 A JP2016175790 A JP 2016175790A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000002245 particle Substances 0.000 title claims abstract description 68
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 49
- 239000006185 dispersion Substances 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000004381 surface treatment Methods 0.000 abstract description 17
- 239000011347 resin Substances 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 239000010419 fine particle Substances 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- 239000011342 resin composition Substances 0.000 description 14
- 238000002834 transmittance Methods 0.000 description 9
- 230000002209 hydrophobic effect Effects 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- -1 silane compound Chemical class 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- 241000252506 Characiformes Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、（メタ）アクリロイル基を有する化合物とアルキル基を有する化合物で表面処理したシリカ系粒子分散体の製造方法に関する。 The present invention relates to a method for producing a silica-based particle dispersion surface-treated with a compound having a (meth) acryloyl group and a compound having an alkyl group.
活性エネルギー線硬化性樹脂組成物を硬化させて得られる硬化塗膜の硬度を上げるには活性エネルギー線硬化性樹脂組成物に、シリカ微粒子を分散させる方法がある。シリカ微粒子には湿式法で製造されるコロイダルシリカや、乾式法で製造されるフュームドシリカがあり、そのシリカ微粒子の表面にはシラノール基があり、シリカ微粒子は親水性である。その為、活性エネルギー線硬化型モノマーやオリゴマー等の組成物中の主成分である有機相となじみが悪く、活性エネルギー線硬化性樹脂組成物中にシリカ微粒子を安定して分散させることは一般に困難であり、シリカ微粒子を含有する活性エネルギー線硬化性樹脂組成物は、シリカ微粒子が凝集や沈降するなど透明性に欠ける場合が多い。 In order to increase the hardness of a cured coating film obtained by curing the active energy ray-curable resin composition, there is a method of dispersing silica fine particles in the active energy ray-curable resin composition. Silica fine particles include colloidal silica produced by a wet method and fumed silica produced by a dry method. The silica fine particles have a silanol group on the surface, and the silica fine particles are hydrophilic. Therefore, it is not compatible with the organic phase which is the main component in the composition of active energy ray-curable monomers and oligomers, and it is generally difficult to stably disperse silica fine particles in the active energy ray-curable resin composition. The active energy ray-curable resin composition containing silica fine particles often lacks transparency such that the silica fine particles aggregate or settle.
一方、活性エネルギー線硬化性樹脂組成物中にシリカ微粒子を安定して分散させる方法として、例えば、シリカ微粒子を、疎水性基を有する疎水性シランカップリング剤で表面処理することでシリカ微粒子の表面を疎水性化する方法がある（例えば、特許文献１参照）。しかしながら、特許文献１に記載された方法により得られるシリカ微粒子でも活性エネルギー線硬化性樹脂組成物中での分散安定性は十分ではなく、また、その添加効果としての硬化物の硬度についても明確な記載がない。 On the other hand, as a method for stably dispersing the silica fine particles in the active energy ray-curable resin composition, for example, the surface of the silica fine particles by treating the silica fine particles with a hydrophobic silane coupling agent having a hydrophobic group. There is a method of hydrophobizing (see, for example, Patent Document 1). However, even the silica fine particles obtained by the method described in Patent Document 1 are not sufficient in dispersion stability in the active energy ray-curable resin composition, and the hardness of the cured product as an addition effect is also clear. There is no description.
シリカ粒子をシランカップリング剤で表面処理することは、極めて一般的に行われている。しかし、乾式法により得られた微細なシリカ粒子について、効果的に表面処理を行うことが困難であり、例えば、一次粒子径がナノオーダーの粒子は、一旦乾燥させてしまうと粒子同士が極めて強固な凝集を起こすので、再分散がほぼ不可能となってしまう。このような凝集した乾燥粒子にカップリング剤を用いて表面処理を行うことはできるが、元々凝集した粉末を一次粒子まで解砕することが困難な上、カップリング剤自身が重合、或いはカップリング剤により粒子同士が化学的に結合してしまうこともある。従って、乾式法により得られたナノオーダーの微細なシリカ粒子について、シランカップリング剤により効果的に表面処理を行うことは事実上不可能である。 Surface treatment of silica particles with a silane coupling agent is very common. However, it is difficult to effectively perform surface treatment on fine silica particles obtained by a dry method. For example, particles having a primary particle size of nano-order are extremely strong when they are once dried. Re-dispersion becomes almost impossible because of agglomeration. Although such agglomerated dry particles can be subjected to surface treatment using a coupling agent, it is difficult to crush the originally agglomerated powder to primary particles, and the coupling agent itself is polymerized or coupled. The particles may be chemically bonded by the agent. Therefore, it is practically impossible to effectively surface-treat nano-sized fine silica particles obtained by the dry method with a silane coupling agent.
本発明の目的は、微細な粒径を有していながら、高い疎水性を示し、透明樹脂に対しても分散性が著しく高められた、表面処理したシリカ系粒子分散体の製造方法を提供することにある。 An object of the present invention is to provide a method for producing a surface-treated silica-based particle dispersion that has a fine particle size, exhibits high hydrophobicity, and has significantly improved dispersibility even with a transparent resin. There is.
本発明のシリカ系粒子分散体の製造方法は、一般式（１）（Ｍ）Ａ−（ＣＨ２）ｎ−Ｓｉ（ＯＲ１）３ （式中、（Ｍ）Ａは、（メタ）アクリロイル基であり、Ｒ１は、炭素数１〜４のアルキル基であり、ｎは、１〜４の整数である）で表される（メタ）アクリロイル基を有するトリアルコキシシラン化合物と一般式（２）Ｒ２−Ｓｉ（ＯＲ３）３ （式中、Ｒ２は、炭素数１０以下のアルキル基であり、Ｒ３は、炭素数１〜４のアルキル基である）で表されるアルキル基を有するトリアルコキシシラン化合物とからなるシランカップリング剤と、湿式法により得られるシリカ粒子が分散した分散液とを混合してシリカ系粒子を表面処理する工程を含むことを特徴とする。
また、前記シリカ粒子は平均粒子径が１〜５０ｎｍであり、前記シリカ粒子を親水性有機溶媒に分散させる工程を含むことを特徴とする。
Method for producing a silica-based particle dispersion of the present invention have the general formula (1) (M) A- ( CH 2) n-Si (OR 1) 3 ( wherein, (M) A is (meth) acryloyl groups And R 1 is an alkyl group having 1 to 4 carbon atoms and n is an integer of 1 to 4) and a trialkoxysilane compound having a (meth) acryloyl group represented by the general formula (2) R 2 —Si (OR 3 ) 3 (wherein R 2 is an alkyl group having 10 or less carbon atoms, and R 3 is an alkyl group having 1 to 4 carbon atoms). It includes a step of surface-treating silica-based particles by mixing a silane coupling agent comprising a trialkoxysilane compound and a dispersion in which silica particles obtained by a wet method are dispersed.
The silica particles have an average particle diameter of 1 to 50 nm and include a step of dispersing the silica particles in a hydrophilic organic solvent.
本発明によれば、分散安定性に優れ、高硬度を有する膜を調製する際に好ましく用いることのできるシリカ系粒子分散体の提供が可能となる。 According to the present invention, it is possible to provide a silica-based particle dispersion that can be preferably used when preparing a film having excellent dispersion stability and high hardness.
表面処理したシリカ系粒子分散体の製造について以下に示す。
本発明の実施形態にかかわる表面処理したシリカ系粒子分散体は、湿式法により得られたシリカ粒子が親水性有機溶媒に分散した分散液を使用し、この分散液に、一般式（１）（Ｍ）Ａ−（ＣＨ２）ｎ−Ｓｉ（ＯＲ１）３ （式中、（Ｍ）Ａは、（メタ）アクリロイル基であり、Ｒ１は、炭素数１〜４のアルキル基であり、ｎは、１〜４の整数である）で表される（メタ）アクリロイル基を有する化合物と、一般式（２）Ｒ２−Ｓｉ（ＯＲ３）３ （式中、Ｒ２は、炭素数１０以下のアルキル基であり、Ｒ３は、炭素数１〜４のアルキル基である）で表されるアルキル基を有するトリアルコキシシラン化合物とからなるシランカップリング剤を添加して表面処理を行うことにより、製造される。
The production of the surface-treated silica-based particle dispersion will be described below.
As the surface-treated silica-based particle dispersion according to the embodiment of the present invention, a dispersion in which silica particles obtained by a wet method are dispersed in a hydrophilic organic solvent is used, and the general formula (1) ( M) A- (CH 2 ) n -Si (OR 1 ) 3 (wherein (M) A is a (meth) acryloyl group, R 1 is an alkyl group having 1 to 4 carbon atoms, n Is a compound having a (meth) acryloyl group represented by formula (2) R 2 —Si (OR 3 ) 3 (wherein R 2 has 10 or less carbon atoms). A surface treatment by adding a silane coupling agent comprising a trialkoxysilane compound having an alkyl group represented by: R 3 is an alkyl group having 1 to 4 carbon atoms) Manufactured.
シリカ粒子について以下に示す。
表面処理に供するシリカ粒子は、所定のナノサイズの平均粒子径、具体的には１〜５０ｎｍ、好適には１〜３５ｎｍ、最も好ましくは５〜２５ｎｍの平均粒子径を有するものであり、湿式法により得られたものであればよい。
The silica particles are shown below.
The silica particles subjected to the surface treatment have a predetermined nano-sized average particle diameter, specifically 1 to 50 nm, preferably 1 to 35 nm, and most preferably 5 to 25 nm. What is necessary is just to be obtained.
尚、粒径が上記範囲よりも小さいものは、製造が困難な上、シランカップリング剤による表面処理も難しく、また、上記範囲よりも大きな粒子は、可視光の散乱が大きくなるため、例えば、透明樹脂に配合したときに透明性を低下させてしまう。 In addition, those having a particle size smaller than the above range are difficult to produce and surface treatment with a silane coupling agent is difficult, and particles larger than the above range have a large scattering of visible light. When blended with a transparent resin, the transparency is lowered.
湿式法には、加水分解法、中和法、イオン交換法、沈殿法など多くの方法が提案、実施されているが、溶媒中に分散した微細な粒子を容易に、しかも比較的粒径の揃った形態で得ることができるという観点から、シラン化合物を加水分解、縮合させるゾルゲル法を用いることが最も好適である。 Many methods such as a hydrolysis method, a neutralization method, an ion exchange method, and a precipitation method have been proposed and implemented as a wet method, but fine particles dispersed in a solvent are easily and relatively small in particle size. From the viewpoint that it can be obtained in a uniform form, it is most preferable to use a sol-gel method in which a silane compound is hydrolyzed and condensed.
シランカップリング剤について以下に示す。
上述した分散液中のシリカ粒子の表面処理剤として、（メタ）アクリロイル基を有するトリアルコキシシラン化合物とアルキル基を有するトリアルコキシシラン化合物が使用される。前者のシランカップリング剤は、活性エネルギー線硬化性樹脂組成物との相溶性を直接的に向上させるという点で、樹脂を構成するモノマーとの共重合性を有する官能基である（メタ）アクリロイル基とシリカ粒子表面のシラノール基と反応し得る基を生成する加水分解性の官能基とを有する化合物である。後者は本質的に疎水性の官能基であるアルキル基と前者と同様なシリカ粒子表面のシラノール基と反応し得る基を生成する加水分解性の官能基とを有する化合物である。したがって、シリカ粒子表面との反応性及び活性エネルギー線硬化性樹脂組成物との相溶性と疎水性の観点から、１分子中に（メタ）アクリロイル基及びアルキル基を１個有し、且つ加水分解性の官能基を３個有するシラン化合物が好適に使用される。
The silane coupling agent is shown below.
As the surface treatment agent for the silica particles in the dispersion described above, a trialkoxysilane compound having a (meth) acryloyl group and a trialkoxysilane compound having an alkyl group are used. The former silane coupling agent is a (meth) acryloyl functional group having a copolymerizability with the monomer constituting the resin in that the compatibility with the active energy ray-curable resin composition is directly improved. And a hydrolyzable functional group that generates a group capable of reacting with a silanol group on the surface of silica particles. The latter is a compound having an alkyl group that is essentially a hydrophobic functional group and a hydrolyzable functional group that generates a group that can react with a silanol group on the surface of the silica particles similar to the former. Therefore, from the viewpoint of reactivity with the silica particle surface and compatibility with the active energy ray-curable resin composition and hydrophobicity, each molecule has one (meth) acryloyl group and alkyl group, and hydrolysis. A silane compound having three functional groups is preferably used.
一般式（１）（Ｍ）Ａ−（ＣＨ２）ｎ−Ｓｉ（ＯＲ１）３ （式中、（Ｍ）Ａは、（メタ）アクリロイル基であり、Ｒ１は、炭素数１〜４のアルキル基であり、ｎは、１〜４の整数である）で表される（メタ）アクリロイル基を有する化合物として、３−アクリロキシプロピルトリメトキシシランや３−メタクリロキシプロピルトリメトキシシランが好適に用いられる。 Formula (1) (M) A- ( CH 2) n-Si (OR 1) 3 ( wherein, (M) A is a (meth) acryloyl group, R 1 is 1 to 4 carbon atoms 3-acryloxypropyltrimethoxysilane or 3-methacryloxypropyltrimethoxysilane is preferably used as the compound having a (meth) acryloyl group represented by the following formula: n is an alkyl group, and n is an integer of 1 to 4. Used.
また、一般式（２）Ｒ２−Ｓｉ（ＯＲ３）３ （式中、Ｒ２は、炭素数１０以下のアルキル基であり、Ｒ３は、炭素数１〜４のアルキル基である）で表されるアルキル基を有するトリアルコキシシラン化合物としては、メチルトリメトキシシラン、ｎ−プロピルトリメトキシシラン、ｎ−ブチルトリメトキシシラン、ｎ−ヘキシルトリメトキシシラン、ｎ−オクチルトリメトキシシラン、イソオクチルトリメトキシシラン、ｎ−デシルトリメトキシシラン、等を挙げることができ、これらは１種単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 In general formula (2) R 2 -Si (OR 3) 3 ( wherein, R 2 is an alkyl group having 10 or less carbon atoms, R 3 is an alkyl group having 1 to 4 carbon atoms) in Examples of the trialkoxysilane compound having an alkyl group include methyltrimethoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, and isooctyltri A methoxysilane, n-decyltrimethoxysilane, etc. can be mentioned, These can also be used individually by 1 type and can also be used in combination of 2 or more type.
さらに、上記で例示した化合物中のメトキシ基をエトキシ基に置換した化合物（例えば３−メタクリロキシプロピルトリエトキシシランやメチルトリエトキシシランなど）も、疎水性のシランカップリング剤として、上記と同様に好適に使用できる。 Further, a compound in which the methoxy group in the compound exemplified above is substituted with an ethoxy group (for example, 3-methacryloxypropyltriethoxysilane, methyltriethoxysilane, etc.) is also used as a hydrophobic silane coupling agent in the same manner as described above. It can be used suitably.
表面処理について以下に示す。
シランカップリング剤と、前述した微細なシリカ粒子が分散した分散液とを混合することにより、該粒子の表面処理が行われる。上記混合は、一般に、シリカ粒子が分散した分散液にシランカップリング剤を滴下して行なう方法が推奨される。
The surface treatment is shown below.
By mixing the silane coupling agent and the dispersion liquid in which the fine silica particles are dispersed, the surface treatment of the particles is performed. In general, it is recommended that the mixing be performed by dropping a silane coupling agent into a dispersion in which silica particles are dispersed.
尚、表面処理に際して用いるシランカップリング剤の量は、この微細なシリカ粒子をシランカップリング剤により均一に被覆するための理論使用量（ｇ）を上限とし、下記式（３）
［カップリング剤の理論使用量］＝Ａ×Ｂ／Ｃ ・・・（３）
（式中、Ａは、表面処理すべきシリカ系ナノ粒子の重量（ｇ）であり、Ｂは、上記ナノ粒子の比表面積（ｍ２／ｇ）であり、Ｃは、カップリング剤の最小被覆面積（ｍ２／ｇ）である。）によって求めることができる。
Incidentally, the amount of the silane coupling agent used for the surface treatment is limited to the theoretical amount (g) for uniformly coating the fine silica particles with the silane coupling agent, and the following formula (3)
[Theoretical use amount of coupling agent] = A × B / C (3)
(In the formula, A is the weight (g) of the silica-based nanoparticles to be surface-treated, B is the specific surface area (m 2 / g) of the nanoparticles, and C is the minimum coating of the coupling agent. Area (m 2 / g)).
また、上記のカップリング剤の最小被覆面積Ｃ（ｍ２／ｇ）は下記式（４）
最小被覆面積Ｃ＝（６．０２×１０２３×１３×１０−２０）／（シランカップリング剤の分子量）
・・・（４）
によって求められる。
The minimum coating area C (m 2 / g) of the above coupling agent is expressed by the following formula (4)
Minimum covering area C = (6.02 × 10 23 × 13 × 10 −20 ) / (Molecular weight of silane coupling agent)
... (4)
Sought by.
表面処理したシリカ系粒子について以下に示す。
本実施形態の表面処理したシリカ系粒子は、前述したシリカ粒子と同様、極めて微細なナノオーダーの粒径を有しており、電子顕微鏡で測定して平均粒子径が１〜５０ｎｍ、好ましくは１〜３５ｎｍの範囲、最も好ましくは５〜２５ｎｍの範囲にあり、凝集しておらず、前述したシランカップリング剤によって個々の粒子が被覆されている。
The surface-treated silica-based particles are shown below.
The surface-treated silica-based particles of the present embodiment have a very fine nano-order particle size, similar to the silica particles described above, and have an average particle size of 1 to 50 nm, preferably 1 as measured with an electron microscope. It is in the range of -35 nm, most preferably in the range of 5-25 nm, is not agglomerated, and the individual particles are coated with the silane coupling agent described above.
また、高い疎水性を示し、しかもナノオーダーの微細な粒径を有しており、凝集していないことから、重量比が１：１のトルエンとｎ−ヘキサンの混合溶媒に該粒子を２質量％含む分散液では、その可視光透過率が８０％以上、特に８５％以上、最も好ましくは９０％以上となっており、該分散液は高い透明性を有している。 Further, since it exhibits high hydrophobicity and has a nano-order fine particle size and is not agglomerated, 2 mass of the particles are mixed in a mixed solvent of toluene and n-hexane having a weight ratio of 1: 1. %, The visible light transmittance is 80% or more, particularly 85% or more, most preferably 90% or more, and the dispersion has high transparency.
即ち、本実施形態の表面処理したシリカ系粒子分散体中のシリカ系粒子は、疎水性が高いために、もはや水には分散しないが、イソプロパノールなどの低分子量のアルコールに良く分散し透明な状態を維持する一方、ｎ−ヘキサンのような疎水性の著しく高い飽和炭化水素類に対しては、完全に相溶できず、その分散液が白濁する場合がある。粒度分布計のデータなどから、表面処理したシリカ系粒子の疎水性の度合いが不十分な場合に起こる上記白濁の原因は、粒子同士が凝集し、粒径が大きくなったためであるが、本発明では、上記のように疎水性有機溶媒であるトルエンとｎ−ヘキサンとの１：１（重量比）混合溶媒中で高い可視光透過率を示していることから、該ナノ粒子は高い疎水性を示すと同時に粒子同士の凝集が効果的に抑制され、所謂単分散の状態で存在しているものと言える。 That is, the silica-based particles in the surface-treated silica-based particle dispersion of the present embodiment are no longer dispersed in water because of their high hydrophobicity, but are well dispersed and transparent in low molecular weight alcohols such as isopropanol. On the other hand, saturated hydrocarbons with extremely high hydrophobicity such as n-hexane cannot be completely compatible with each other, and the dispersion liquid may become cloudy. From the data of the particle size distribution meter and the like, the cause of the white turbidity that occurs when the hydrophobicity of the surface-treated silica-based particles is insufficient is that the particles are aggregated and the particle size is increased. Then, since the high visible light transmittance is shown in the 1: 1 (weight ratio) mixed solvent of toluene and n-hexane which is a hydrophobic organic solvent as described above, the nanoparticles have high hydrophobicity. At the same time, it can be said that the aggregation of the particles is effectively suppressed and exists in a so-called monodispersed state.
樹脂コンポジットについて以下に示す。
上述した本実施形態の表面処理したシリカ系粒子分散体は、その粒子径が著しく微細であり、しかも凝集による濁りをほとんど生じておらず、単分散性と同時に、疎水性を示すため、各種樹脂に均一分散させることができ、これにより、樹脂の耐熱性（熱膨張係数）や表面硬度、強度などの機械的特性の調整を行うことができ、さらに、透明樹脂の場合には、この粒子が凝集せずに均一に分散されるため、その優れた透明性が維持されることとなる。
The resin composite is shown below.
The surface-treated silica-based particle dispersion of the present embodiment described above has a remarkably fine particle diameter, hardly generates turbidity due to aggregation, and exhibits a hydrophobic property as well as a monodispersity. This makes it possible to adjust the heat resistance (thermal expansion coefficient), surface hardness, strength, and other mechanical properties of the resin. Since it is uniformly dispersed without agglomeration, its excellent transparency is maintained.
例えば、本実施形態の表面処理したシリカ系粒子分散体（Ａ）を含む活性エネルギー線硬化性樹脂組成物を得るには、（メタ）アクリロイル基等の重合性基を有する化合物との分散体を調製すればよい。また、該硬化物を得るには、上記樹脂組成物に活性エネルギー線硬化剤（光重合開始剤）を添加し、活性エネルギー線を照射することにより硬化物とすることができる。 For example, in order to obtain the active energy ray-curable resin composition containing the surface-treated silica-based particle dispersion (A) of the present embodiment, a dispersion with a compound having a polymerizable group such as a (meth) acryloyl group is used. What is necessary is just to prepare. Moreover, in order to obtain this hardened | cured material, it can be set as hardened | cured material by adding an active energy ray hardening | curing agent (photoinitiator) to the said resin composition, and irradiating an active energy ray.
実施例
以下、本実施形態の実施例を挙げて具体的に説明するが、本実施形態はこれらの実施例によって何ら制限されるものではない。
尚、以下の例において、各種の測定は以下の方法により行った。
平均粒子径は、走査型電子顕微鏡または透過型電子顕微鏡の撮影像を用いて１００個以上の粒子のデータを解析することにより求めた。
Examples Hereinafter, the present embodiment will be specifically described with reference to examples. However, the present embodiment is not limited to these examples.
In the following examples, various measurements were performed by the following methods.
The average particle diameter was obtained by analyzing data of 100 or more particles using a scanning image of a scanning electron microscope or a transmission electron microscope.
表面処理したシリカ系粒子を、質量比１：１のトルエンとｎ−ヘキサンの混合溶媒にＳｉＯ２としての濃度が２質量％になるように分散した。該分散液を光路長１ｃｍの石英セルに入れて分光光度計にセットし、波長５９３ｎｍの透過率を測定して、可視光透過率とした。なお、光路長１ｃｍの空の石英セルを参照セルとして用いた。 The surface-treated silica-based particles were dispersed in a mixed solvent of toluene and n-hexane having a mass ratio of 1: 1 so that the concentration as SiO 2 was 2% by mass. The dispersion was placed in a quartz cell having an optical path length of 1 cm and set in a spectrophotometer, and the transmittance at a wavelength of 593 nm was measured to obtain the visible light transmittance. An empty quartz cell having an optical path length of 1 cm was used as a reference cell.
実施例１
ゾルゲル法により製造されたシリカ粒子（Ｂ）として、市販のシリカ分散液（ＳｉＯ２濃度３０質量％、平均粒径１２ｎｍ、粒子密度２．０ｇ／ｃｍ３、最大含水量３質量％、イソプロパノール溶媒）を用いた。そのシリカ粒子分散液４０ｇ（ＳｉＯ２として１２ｇ）をトリアルコキシシリル系のシランカップリング剤により均一に被覆するための理論使用量は、０．０３８３ｍｏｌと計算される。
Example 1
As silica particles (B) produced by the sol-gel method, a commercially available silica dispersion (SiO 2 concentration 30 mass%, average particle diameter 12 nm, particle density 2.0 g / cm 3 , maximum water content 3 mass%, isopropanol solvent) Was used. The theoretical amount used to uniformly coat 40 g of the silica particle dispersion (12 g as SiO 2 ) with a trialkoxysilyl-based silane coupling agent is calculated to be 0.0383 mol.
上記シリカ分散液４０ｇにイソプロパノール８０ｇとトルエン４０ｇを添加し、撹拌下、３−メタクリロキシプロピルトリメトキシシラン２．８５ｇ（０．０１１５ ｍｏｌ）とメチルトリメトキシシラン３．６５ｇ（０．０２６８ ｍｏｌ）を加え、２４時間以上加熱還流させた。トリアルコキシシリル系シランカップリング剤の合計添加量は０．０３８３ｍｏｌであり、前者と後者の割合は３：７（モル比）である。その後、エバポレーターで溶媒を除去、濃縮し、トルエン分散液４０ｇを得た（ＳｉＯ２として３０質量％）。 80 g of isopropanol and 40 g of toluene are added to 40 g of the silica dispersion, and 2.85 g (0.0115 mol) of 3-methacryloxypropyltrimethoxysilane and 3.65 g (0.0268 mol) of methyltrimethoxysilane are added with stirring. In addition, the mixture was heated to reflux for 24 hours or more. The total amount of trialkoxysilyl silane coupling agent added is 0.0383 mol, and the ratio of the former and the latter is 3: 7 (molar ratio). Then, the solvent was removed and concentrated with an evaporator to obtain 40 g of a toluene dispersion (30% by mass as SiO 2 ).
次に、得られたトルエン分散液、トルエン、ｎ−ヘキサンを用いてトルエンとｎ−ヘキサンの質量比が１：１、且つ、ＳｉＯ２濃度が２％になるようにして、３つの溶液を混合した。その結果、トルエンとｎ−ヘキサンとの１：１（質量比）混合溶媒に２質量％の濃度で表面処理したシリカ系粒子が分散された分散液が準備できた。 Next, using the obtained toluene dispersion, toluene, and n-hexane, the three solutions were mixed so that the mass ratio of toluene and n-hexane was 1: 1 and the SiO 2 concentration was 2%. . As a result, a dispersion in which silica-based particles surface-treated at a concentration of 2% by mass in a 1: 1 (mass ratio) mixed solvent of toluene and n-hexane was prepared.
上記分散液の可視光透過率を測定したところ、９６％であった。また、透過型電子顕微鏡で分散液中の粒子を観察したところ、粗粒は観察されず、粒子形状は球状で、平均粒径は１２ｎｍ、粒径の変動係数は１０％であった。特に、平均粒径に関し、表面処理前のシリカ粒子と同等であった。 The visible light transmittance of the dispersion was measured and found to be 96%. When the particles in the dispersion were observed with a transmission electron microscope, no coarse particles were observed, the particle shape was spherical, the average particle size was 12 nm, and the variation coefficient of the particle size was 10%. In particular, the average particle size was equivalent to the silica particles before the surface treatment.
実施例２
実施例１のメチルトリメトキシシランの代わりに、分子内にアルコキシ基を３個有するトリアルコキシシランの一種であるｎ−プロピルトリメトキシシラン４．４０ｇ（０．０２６８ ｍｏｌ）を用い、実施例１と同様にして表面処理を行った。
その結果、可視光透過率は９３％であった。
Example 2
Instead of methyltrimethoxysilane in Example 1, 4.40 g (0.0268 mol) of n-propyltrimethoxysilane, which is a kind of trialkoxysilane having three alkoxy groups in the molecule, was used. The surface treatment was performed in the same manner.
As a result, the visible light transmittance was 93%.
実施例３
実施例１のメチルトリメトキシシランの代わりに、分子内にアルコキシ基を３個有するトリアルコキシシランの一種であるデシルトリメトキシシラン７．０４ｇ（０．０２６８ ｍｏｌ）を用い、実施例１と同様にして表面処理を行った。
その結果、可視光透過率は９０％であった。
Example 3
Instead of methyltrimethoxysilane in Example 1, 7.04 g (0.0268 mol) of decyltrimethoxysilane, which is a kind of trialkoxysilane having three alkoxy groups in the molecule, was used in the same manner as in Example 1. The surface treatment was performed.
As a result, the visible light transmittance was 90%.
実施例４
実施例１のシランカップリング剤として、３−メタクリロキシプロピルトリメトキシシラン１．４３ｇ（０．００５７５ ｍｏｌ）とメチルトリメトキシシラン４．４３ｇ（０．０３２６ ｍｏｌ）を用い、実施例１と同様にして表面処理を行った。
その結果、可視光透過率は９６％であった。
Example 4
As the silane coupling agent of Example 1, 1.43 g (0.00575 mol) of 3-methacryloxypropyltrimethoxysilane and 4.43 g (0.0326 mol) of methyltrimethoxysilane were used in the same manner as in Example 1. The surface treatment was performed.
As a result, the visible light transmittance was 96%.
実施例５
実施例１で得られた表面処理したシリカ系粒子分散液を用いて、ナノコンポジットの実験を行った。
ペンタエリスリトールテトラアクリレート２０ｇと光重合開始剤０．２ｇとを混合して紫外線硬化性樹脂を用意した。
Example 5
Using the surface-treated silica-based particle dispersion obtained in Example 1, a nanocomposite experiment was conducted.
An ultraviolet curable resin was prepared by mixing 20 g of pentaerythritol tetraacrylate and 0.2 g of a photopolymerization initiator.
実施例１で得られた表面処理したシリカ系粒子のトルエン分散液を用いて、前記紫外線硬化性樹脂に対して、重量比でシリカ粒子の含有量が１０％になるように添加し、十分に撹拌し、表面処理したシリカ系粒子を含有した紫外線硬化性樹脂組成物を得た。該樹脂組成物は透明であった。 Using the toluene dispersion of the surface-treated silica-based particles obtained in Example 1, it was added to the ultraviolet curable resin so that the content of silica particles was 10% by weight, and sufficiently An ultraviolet curable resin composition containing silica-based particles that were stirred and surface-treated was obtained. The resin composition was transparent.
次に、ピラニア洗浄液で洗浄し、風乾したガラス板にバーコーターを用いて上記紫外線硬化性樹脂組成物を塗布し、８０Ｗの高圧水銀ランプを窒素雰囲気中３０秒間照射して樹脂を硬化させ、コーティング膜を得た。上記膜は透明で、鉛筆硬度は２Ｈであった。 Next, the UV curable resin composition is applied to a glass plate that has been washed with piranha cleaning liquid and dried in air using a bar coater, and the resin is cured by irradiation with a 80 W high-pressure mercury lamp in a nitrogen atmosphere for 30 seconds. A membrane was obtained. The film was transparent and the pencil hardness was 2H.
実施例６
実施例５の表面処理したシリカ系粒子分散液の添加量を３０％にした以外は、実施例５と同様にナノコンポジットの実験を行った。その結果、得られた膜は透明で、その鉛筆硬度は３Ｈであった。
Example 6
A nanocomposite experiment was conducted in the same manner as in Example 5 except that the amount of the surface-treated silica-based particle dispersion in Example 5 was changed to 30%. As a result, the obtained film was transparent and the pencil hardness was 3H.
実施例７
実施例５の表面処理したシリカ系粒子分散液の添加量を６０％にした以外は、実施例５と同様にナノコンポジットの実験を行った。その結果、得られた膜は透明で、その鉛筆硬度は４Ｈであった。
Example 7
A nanocomposite experiment was conducted in the same manner as in Example 5 except that the amount of the surface-treated silica-based particle dispersion in Example 5 was changed to 60%. As a result, the obtained film was transparent and the pencil hardness was 4H.
比較例１
シリカ粒子として、表面処理を施していないシリカ粒子（Ｂ）分散液を使用した以外は、実施例５と同様にナノコンポジットの実験を行った。
その結果、上記の紫外線硬化性樹脂組成物は、顕著な白濁が見られ、シリカ粒子が凝集していることが確認された。硬化した膜も透明でなく、濁りが観察された。
Comparative Example 1
A nanocomposite experiment was conducted in the same manner as in Example 5 except that the silica particle (B) dispersion without surface treatment was used as the silica particles.
As a result, the above-mentioned ultraviolet curable resin composition was markedly clouded, and it was confirmed that the silica particles were aggregated. The cured film was not transparent and turbidity was observed.
以上述べたように、本実施形態にかかわるシリカ系粒子分散体の製造方法は、一般式（１）（Ｍ）Ａ−（ＣＨ２）ｎ−Ｓｉ（ＯＲ１）３ （式中、（Ｍ）Ａは、（メタ）アクリロイル基であり、Ｒ１は、炭素数１〜４のアルキル基であり、ｎは、１〜４の整数である）で表される（メタ）アクリロイル基を有するトリアルコキシシラン化合物と、一般式（２）Ｒ２−Ｓｉ（ＯＲ３）３ （式中、Ｒ２は、炭素数１０以下のアルキル基であり、Ｒ３は、炭素数１〜４のアルキル基である）で表されるアルキル基を有するトリアルコキシシラン化合物とからなるシランカップリング剤と、湿式法により得られるシリカ粒子が分散した分散液とを混合してシリカ系粒子を表面処理する工程を含む。
また、本実施形態にかかわるシリカ系粒子分散体の製造方法は、シリカ粒子は平均粒子径が１〜５０ｎｍであり、シリカ粒子を親水性有機溶媒に分散させる工程を含む。
As described above, the method for producing a silica-based particle dispersion according to this embodiment has the general formula (1) (M) A— (CH 2 ) n—Si (OR 1 ) 3 (wherein (M) A is a (meth) acryloyl group, R 1 is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 4), and a trialkoxy having a (meth) acryloyl group represented by Silane compound and general formula (2) R 2 —Si (OR 3 ) 3 (wherein R 2 is an alkyl group having 10 or less carbon atoms, and R 3 is an alkyl group having 1 to 4 carbon atoms. And a surface treatment of the silica-based particles by mixing a silane coupling agent composed of a trialkoxysilane compound having an alkyl group represented by (II) and a dispersion in which silica particles obtained by a wet method are dispersed.
In addition, the method for producing a silica-based particle dispersion according to the present embodiment includes a step in which the silica particles have an average particle diameter of 1 to 50 nm and the silica particles are dispersed in a hydrophilic organic solvent.
本実施形態にかかわる表面処理したシリカ系粒子分散体は、平均粒径が１〜５０ｎｍと著しく微細であり、親油性有機溶媒のトルエンとｎ−ヘキサンとの１：１（重量比）混合溶媒に分散させたときに、８０％以上の高い可視光透過率を示すという点に顕著な特徴を有している。即ち、このような疎水性の高い混合溶媒に分散させた時にも高い透明性が確保されることは、この表面処理したシリカ系粒子は、著しく微細な粒径であるにもかかわらず、粒子同士が結合しての凝集をほとんど生じていないことを示している。 The surface-treated silica-based particle dispersion according to the present embodiment has an extremely fine average particle diameter of 1 to 50 nm, and is a 1: 1 (weight ratio) mixed solvent of toluene and n-hexane, which is a lipophilic organic solvent. It has a remarkable feature in that it exhibits a high visible light transmittance of 80% or more when dispersed. That is, high transparency is ensured even when dispersed in such a highly hydrophobic mixed solvent. This is because the surface-treated silica-based particles have extremely fine particle sizes. Shows almost no aggregation due to binding.
上記のような特性を有する表面処理したシリカ系粒子は、湿式法により得られたシリカ粒子を原料とし、所定のナノオーダーの粒径を有する微細なシリカ粒子が親水性有機溶媒に分散した分散液を使用し、この分散液に、疎水性シランカップリング剤を添加して反応させることにより製造される。 Surface-treated silica-based particles having the above characteristics are dispersions in which fine silica particles having a predetermined nano-order particle size are dispersed in a hydrophilic organic solvent using silica particles obtained by a wet method as a raw material And a hydrophobic silane coupling agent is added to the dispersion and reacted.
湿式法により得られるシリカ粒子では、一次粒子径が５０ｎｍ以下と微細であったとしても、液中に存在していれば、凝集せずに、一次粒子の形態が保持されるため、その状態でシランカップリング剤による処理が良好に実施できれば、被覆率の高い、効率の良い表面処理が実現できる可能性がある。
In the silica particles obtained by the wet method, even if the primary particle diameter is as fine as 50 nm or less, if present in the liquid, the form of the primary particles is maintained without agglomeration. If the treatment with the silane coupling agent can be carried out satisfactorily, an efficient surface treatment with a high coverage may be realized.
Claims (2)
湿式法により得られるシリカ粒子が分散した分散液と、を混合してシリカ系粒子を表面処理する工程を含むことを特徴とするシリカ系粒子分散体の製造方法。 Formula (1) (M) A- ( CH 2) n-Si (OR 1) 3 ( wherein, (M) A is a (meth) acryloyl group, R 1 is 1 to 4 carbon atoms A trialkoxysilane compound having a (meth) acryloyl group represented by formula (2) R 2 —Si (OR 3 ) 3 (wherein n is an integer of 1 to 4). , R 2 is an alkyl group having 10 or less carbon atoms, and R 3 is an alkyl group having 1 to 4 carbon atoms), and a silane coupling agent comprising a trialkoxysilane compound having an alkyl group represented by: ,
A method for producing a silica-based particle dispersion, comprising a step of mixing a dispersion in which silica particles obtained by a wet method are dispersed to surface-treat the silica-based particles.
The method for producing a silica-based particle dispersion according to claim 1, wherein the silica particles have an average particle diameter of 1 to 50 nm and include a step of dispersing the silica particles in a hydrophilic organic solvent.
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| US20220213296A1 (en) * | 2019-09-27 | 2022-07-07 | Fujifilm Corporation | Dispersion liquid, composition, cured film, color filter, solid-state imaging element, and image display device |
| JP2024123721A (en) * | 2023-03-01 | 2024-09-12 | 株式会社トラディショナルインテリジェンス | Siliceous mixture for forming a siliceous coating layer |
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