JP6097875B1 - Silica filler, silica filler surface treatment method and epoxy resin composite - Google Patents
Silica filler, silica filler surface treatment method and epoxy resin composite Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 70
- 239000000945 filler Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims description 16
- 238000004381 surface treatment Methods 0.000 title claims description 16
- 239000003822 epoxy resin Substances 0.000 title abstract description 62
- 229920000647 polyepoxide Polymers 0.000 title abstract description 62
- 239000002131 composite material Substances 0.000 title abstract description 45
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- 239000011247 coating layer Substances 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011258 core-shell material Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical group O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 238000004581 coalescence Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 description 17
- 229920002873 Polyethylenimine Polymers 0.000 description 15
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 description 9
- 229920001690 polydopamine Polymers 0.000 description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 description 9
- 239000004642 Polyimide Substances 0.000 description 8
- 150000004985 diamines Chemical class 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 8
- 229920001721 polyimide Polymers 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- -1 alicyclic acid anhydride Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 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 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Abstract
【課題】本発明は、シリカをコアとし、重合体で構成される被覆層をシェルとするシェル−コア構造を有するシリカ充填材に関する。【解決手段】本発明のシリカ充填材は、具体的に、シリカの表面に重合体で構成される被覆層を被覆し、該被覆層によって、シリカ充填材とエポキシ樹脂の適合性及び界面結合力を向上させて、エポキシ樹脂複合材の粘度及び熱膨張係数を低下させることができる。【選択図】なしThe present invention relates to a silica filler having a shell-core structure with silica as a core and a coating layer made of a polymer as a shell. Specifically, the silica filler of the present invention covers the surface of silica with a coating layer composed of a polymer, and the compatibility of the silica filler and the epoxy resin and the interfacial bonding force by the coating layer. The viscosity and the thermal expansion coefficient of the epoxy resin composite material can be reduced. [Selection figure] None
Description
本発明は、シリカ充填材及びその表面処理方法に関し、さらに本発明は、表面処理したシリカ充填材を含むエポキシ樹脂複合材に関する。また、本発明は、材料の表面改質及び重合体複合材の分野に属する。 The present invention relates to a silica filler and a surface treatment method thereof, and the present invention further relates to an epoxy resin composite containing a surface-treated silica filler. The invention also belongs to the field of surface modification of materials and polymer composites.
エポキシ樹脂は、優れた接着性、耐薬品性、電気絶縁性、低収縮性、易加工性及び低コスト等の利点を有し、接着剤、塗料、建築、航空宇宙、電子パッケージング等の分野に幅広く適用できる。しかし、純粋なエポキシ樹脂は、硬化後の架橋密度が高いため、脆くて、内部応力が大きく、熱膨張係数が高い等の欠点があり、それにより、応用が制限される。シリカ材料は、高剛性、高弾性率及び低熱膨張係数等の長所を有するから、エポキシ樹脂の機械的特性を向上させ、硬化収縮及び熱膨張係数を低下させるため、充填材としてエポキシ樹脂に添加される。 Epoxy resins have advantages such as excellent adhesion, chemical resistance, electrical insulation, low shrinkage, easy processability and low cost, and are used in fields such as adhesives, paints, architecture, aerospace, and electronic packaging. Widely applicable to. However, a pure epoxy resin has a drawback that it is brittle, has a high internal stress, and has a high coefficient of thermal expansion because of its high cross-linking density after curing, which limits its application. Silica material has advantages such as high rigidity, high elastic modulus, and low thermal expansion coefficient, so it is added to epoxy resin as a filler to improve the mechanical properties of epoxy resin and lower the curing shrinkage and thermal expansion coefficient. The
エポキシ樹脂／シリカ複合材の特性は、充填材の寸法、寸法分布、形態、充填量、特に充填材と重合体マトリックスの界面相の性質に関わる。研究した結果、充填材の寸法がナノスケールに達すると、充填材と重合体マトリックスの界面相の性質は重合体複合材の特性を左右する重要な要素の一つとなる。従って、充填材と重合体マトリックスの界面相の性質を調整して改善することによって、エポキシ樹脂／シリカ複合材の総合的特性を更に向上させることができる。しかし、シリカの比表面積が高く、表面に大量のヒドロキシ基を有することによって、エポキシ樹脂マトリックスとの適合性が悪く、粒子同士が凝集しやすくて、エポキシ樹脂の粘度が急激に増大し、エポキシ樹脂のワーカビリティー及び取扱い性の低下を招いてしまう。 The properties of the epoxy resin / silica composite are related to the size, size distribution, morphology, and loading of the filler, especially the nature of the interfacial phase between the filler and the polymer matrix. As a result of research, when the size of the filler reaches nanoscale, the nature of the interfacial phase between the filler and the polymer matrix becomes one of the important factors affecting the properties of the polymer composite. Accordingly, the overall properties of the epoxy resin / silica composite can be further improved by adjusting and improving the nature of the interfacial phase between the filler and the polymer matrix. However, since silica has a high specific surface area and has a large amount of hydroxy groups on the surface, compatibility with the epoxy resin matrix is poor, particles tend to aggregate, and the viscosity of the epoxy resin increases rapidly. The workability and handling of the machine will be reduced.
本発明は、シリカの表面に重合体シェルが被覆されることによって、シリカとエポキシ樹脂マトリックスの適合性及び界面結合力を向上させるとともに、エポキシ樹脂複合材の粘度及び熱膨張係数を効果的に低下させるシリカ充填材を提供することを第一目的とする。 In the present invention, the silica shell is coated with a polymer shell to improve the compatibility between silica and the epoxy resin matrix and the interfacial bonding force, and to effectively reduce the viscosity and thermal expansion coefficient of the epoxy resin composite. It is a first object to provide a silica filler to be made.
本発明は、シリカの表面に重合体シェルを被覆することによって、シリカとエポキシ樹脂マトリックスの適合性及び界面結合力を向上させるとともに、エポキシ樹脂複合材の粘度及び熱膨張係数を効果的に低下させるシリカ充填材の表面処理方法を提供することを第二目的とする。 The present invention improves the compatibility and interfacial bond strength between silica and epoxy resin matrix by coating a polymer shell on the surface of silica and effectively reduces the viscosity and thermal expansion coefficient of the epoxy resin composite. A second object is to provide a surface treatment method for a silica filler.
本発明は、表面処理したシリカ充填材を含むエポキシ樹脂複合材を提供することを第三目的とし、シリカの表面に重合体シェルが被覆されるため、エポキシ樹脂とシリカは優れた適合性及び界面結合力を有するとともに、エポキシ樹脂複合材の粘度と熱膨張係数が効果的に低下する。 The third object of the present invention is to provide an epoxy resin composite containing a surface-treated silica filler. Since the polymer shell is coated on the surface of the silica, the epoxy resin and silica have excellent compatibility and interface. In addition to having bonding strength, the viscosity and thermal expansion coefficient of the epoxy resin composite are effectively reduced.
本発明に係る前記シリカ充填材は、シリカをコア、重合体で構成される被覆層をシェルとするコア−シェル構造を有する。 The silica filler according to the present invention has a core-shell structure in which silica is a core and a coating layer made of a polymer is a shell.
好ましくは、前記重合体は線状重合体であり、
好ましくは、前記線状重合体の相対分子質量は５０００〜７００００、好ましくは１００００〜６００００、より好ましくは２００００〜４５０００、更に好ましくは３００００〜４００００であり、
線状重合体の相対分子質量は５５００、８０００、１００００、１２０００、１８０００、２００００、２３０００、２７０００、３００００、３６０００、４３０００、４８０００、５３０００、５６０００、６００００、６２０００、６５０００又は６７０００であってもよい。
Preferably, the polymer is a linear polymer,
Preferably, the relative molecular mass of the linear polymer is 5000 to 70000, preferably 10000 to 60000, more preferably 20000 to 45000, still more preferably 30000 to 40000,
The relative molecular mass of the linear polymer may be 5500, 8000, 10000, 12000, 18000, 20000, 23000, 27000, 30000, 36000, 43000, 48000, 53000, 56000, 60000, 62000, 65000 or 67000.
好ましくは、前記線状重合体はポリオレフィンアルコール及び／又はアミノ基を含有する重合体であり、
好ましくは、前記線状重合体はポリビニルアルコール、ポリドーパミン、ポリエチレンイミン、ポリイミド、ポリアミド酸のうちの１種又は２種以上であり、前記組合せの代表例として、ポリビニルアルコールとポリドーパミンの組合せ、ポリビニルアルコールとポリエチレンイミンの組合せ、ポリビニルアルコールとポリアミド酸の組合せ、ポリビニルアルコール、ポリドーパミン及びポリエチレンイミンの組合せ、ポリドーパミン、ポリエチレンイミン及びポリイミドの組合せ、ポリエチレンイミン、ポリイミド及びポリアミド酸の組合せ等が挙げられるが、これらに制限されない。
Preferably, the linear polymer is a polymer containing a polyolefin alcohol and / or an amino group,
Preferably, the linear polymer is one or more of polyvinyl alcohol, polydopamine, polyethyleneimine, polyimide, and polyamic acid. As a representative example of the combination, a combination of polyvinyl alcohol and polydopamine, polyvinyl Examples include combinations of alcohol and polyethyleneimine, combinations of polyvinyl alcohol and polyamic acid, combinations of polyvinyl alcohol, polydopamine and polyethyleneimine, combinations of polydopamine, polyethyleneimine and polyimide, and combinations of polyethyleneimine, polyimide and polyamic acid. Not limited to these.
好ましくは、前記被覆層の厚さは５〜１００ｎｍ、好ましくは５〜８５ｎｍ、より好ましくは１０〜６０ｎｍ、更に好ましくは１０〜３０ｎｍである。 Preferably, the coating layer has a thickness of 5 to 100 nm, preferably 5 to 85 nm, more preferably 10 to 60 nm, and still more preferably 10 to 30 nm.
被覆層の厚さは１０ｎｍ、１５ｎｍ、２０ｎｍ、２５ｎｍ、３０ｎｍ、３５ｎｍ、４０ｎｍ、４５ｎｍ、５０ｎｍ、５５ｎｍ、６０ｎｍ、６５ｎｍ、７０ｎｍ、７５ｎｍ、８０ｎｍ、８５ｎｍ、９０ｎｍ、９３ｎｍ、９５ｎｍ又は９８ｎｍであってもよい。 The thickness of the coating layer may be 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 93 nm, 95 nm or 98 nm. .
本発明の前記シリカ充填材の表面処理方法は、
（１）シリカを溶剤に溶解して、シリカ分散液を調製するステップと、
（２）前記シリカ分散液と重合体水溶液又は重合体のアルコール溶液を混合して、２０〜６０℃で２〜２４ｈ超音波分離して、洗浄し、コア−シェル構造を有するシリカ充填材を得るステップとを含む。
The surface treatment method of the silica filler of the present invention,
(1) dissolving silica in a solvent to prepare a silica dispersion;
(2) The silica dispersion and polymer aqueous solution or polymer alcohol solution are mixed, subjected to ultrasonic separation at 20 to 60 ° C. for 2 to 24 hours, washed, and a silica filler having a core-shell structure is obtained. Steps.
好ましくは、ステップ（１）では、前記溶剤は水又は無水エタノールである。 Preferably, in step (1), the solvent is water or absolute ethanol.
好ましくは、前記シリカ分散液において、シリカ濃度は１〜４００ｇ／Ｌ、好ましくは５〜３５０ｇ／Ｌ、より好ましくは５０〜３００ｇ／Ｌ、更に好ましくは１００〜２００ｇ／Ｌである。 Preferably, in the silica dispersion, the silica concentration is 1 to 400 g / L, preferably 5 to 350 g / L, more preferably 50 to 300 g / L, and still more preferably 100 to 200 g / L.
前記シリカ分散液において、シリカ濃度は５ｇ／Ｌ、５０ｇ／Ｌ、１００ｇ／Ｌ、１３０ｇ／Ｌ、１５０ｇ／Ｌ、１８０ｇ／Ｌ、２００ｇ／Ｌ、２２０ｇ／Ｌ、２５０ｇ／Ｌ、２７０ｇ／Ｌ、３００ｇ／Ｌ、３２０ｇ／Ｌ、３５０ｇ／Ｌ又は３７０ｇ／Ｌであってもよい。 In the silica dispersion, the silica concentration is 5 g / L, 50 g / L, 100 g / L, 130 g / L, 150 g / L, 180 g / L, 200 g / L, 220 g / L, 250 g / L, 270 g / L, 300 g. / L, 320 g / L, 350 g / L, or 370 g / L.
好ましくは、前記重合体水溶液又は重合体のアルコール溶液の濃度は０．２〜５０ｇ／Ｌ、好ましくは５〜４５ｇ／Ｌ、より好ましくは１０〜４０ｇ／Ｌ、更に好ましくは１５〜３０ｇ／Ｌである。 Preferably, the concentration of the polymer aqueous solution or polymer alcohol solution is 0.2 to 50 g / L, preferably 5 to 45 g / L, more preferably 10 to 40 g / L, and still more preferably 15 to 30 g / L. is there.
重合体水溶液又は重合体のアルコール溶液の濃度は０．３ｇ／Ｌ、０．５ｇ／Ｌ、０．８ｇ／Ｌ、１ｇ／Ｌ、５ｇ／Ｌ、８ｇ／Ｌ、１０ｇ／Ｌ、１２ｇ／Ｌ、１５ｇ／Ｌ、１８ｇ／Ｌ、２０ｇ／Ｌ、２３ｇ／Ｌ、２５ｇ／Ｌ、２７ｇ／Ｌ、３０ｇ／Ｌ、３３ｇ／Ｌ、３５ｇ／Ｌ、３９ｇ／Ｌ、４０ｇ／Ｌ、４２ｇ／Ｌ、４５ｇ／Ｌ又は４８ｇ／Ｌであってもよい。 The concentration of the polymer aqueous solution or polymer alcohol solution is 0.3 g / L, 0.5 g / L, 0.8 g / L, 1 g / L, 5 g / L, 8 g / L, 10 g / L, 12 g / L, 15 g / L, 18 g / L, 20 g / L, 23 g / L, 25 g / L, 27 g / L, 30 g / L, 33 g / L, 35 g / L, 39 g / L, 40 g / L, 42 g / L, 45 g / It may be L or 48 g / L.
好ましくは、ステップ（２）において、超音波処理温度は室温であり、好ましくは、超音波処理時間は５〜２０ｈ、好ましくは８〜１５ｈ、更に好ましくは１０〜１５ｈである。超音波処理時間は６ｈ、７ｈ、８ｈ、９ｈ、１０ｈ、１１ｈ、１２ｈ、１３ｈ、１４ｈ、１５ｈ、１６ｈ、１７ｈ、１８ｈ、１９ｈであってもよい。 Preferably, in step (2), the sonication temperature is room temperature, preferably the sonication time is 5 to 20 h, preferably 8 to 15 h, more preferably 10 to 15 h. The ultrasonic treatment time may be 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h.
本発明の前記エポキシ樹脂複合材は、エポキシ樹脂と充填材を含み、前記充填材は上記シリカ充填材である。 The epoxy resin composite material of the present invention includes an epoxy resin and a filler, and the filler is the silica filler.
好ましくは、前記エポキシ樹脂はビスフェノールＡエポキシ樹脂、ビスフェノールＦエポキシ樹脂、脂環族エポキシ樹脂のうちの１種又は２種以上であり、
好ましくは、前記エポキシ樹脂複合材は硬化剤を更に含み、
好ましくは、前記硬化剤は脂環族酸無水物系硬化剤又はアミン系硬化剤であり、
好ましくは、前記エポキシ樹脂複合材は更に触媒を含み、
好ましくは、前記触媒はイミダゾール又はイミダゾール誘導体である。
Preferably, the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, and alicyclic epoxy resin,
Preferably, the epoxy resin composite further includes a curing agent,
Preferably, the curing agent is an alicyclic acid anhydride curing agent or an amine curing agent,
Preferably, the epoxy resin composite further includes a catalyst,
Preferably, the catalyst is imidazole or an imidazole derivative.
本発明の前記エポキシ樹脂複合材中のエポキシ樹脂、硬化剤、触媒はすべて本分野においてよく使用される物質を使用し、本願では、各成分について特に限定がなく、さらに、本発明の前記エポキシ樹脂複合材では、エポキシ樹脂、充填材、硬化剤、触媒の含有量は本分野の従来技術と同様であり、本願では各成分の含有量について限定がない。 The epoxy resin, the curing agent, and the catalyst in the epoxy resin composite material of the present invention are all materials commonly used in this field. In the present application, each component is not particularly limited, and further, the epoxy resin of the present invention. In the composite material, the contents of the epoxy resin, the filler, the curing agent, and the catalyst are the same as in the prior art in this field, and the content of each component is not limited in the present application.
従来技術に比べて、本発明の利点は以下のとおりである：
本発明の前記シリカ充填材はシリカの表面に重合体で構成される被覆層を被覆し、被覆層中の重合体がシリカの表面におけるヒドロキシ基を置換又は被覆できるため、シリカの高表面エネルギー及び反応活性を低下させることが可能であり、更に、該被覆層は、シリカ充填材とエポキシ樹脂との適合性及び界面結合力を向上させ、それにより、エポキシ樹脂複合材の粘度と熱膨張係数を低下させ、また、被覆層中の重合体の官能基とエポキシ樹脂又は硬化剤の相互作用によって、エポキシ樹脂複合材の室温での粘度安定性を向上させる。
Compared to the prior art, the advantages of the present invention are as follows:
The silica filler of the present invention coats a coating layer composed of a polymer on the surface of silica, and the polymer in the coating layer can replace or coat hydroxy groups on the surface of the silica. It is possible to reduce the reaction activity, and further, the coating layer improves the compatibility and interfacial bond strength between the silica filler and the epoxy resin, thereby reducing the viscosity and thermal expansion coefficient of the epoxy resin composite. Further, the viscosity stability at room temperature of the epoxy resin composite is improved by the interaction between the functional group of the polymer in the coating layer and the epoxy resin or the curing agent.
テストした結果、エポキシ樹脂複合材に本発明の前記シリカ充填材を添加すると、エポキシ樹脂の粘度は９０％程度低下し、熱膨張係数は１０％程度低下し、２４ｈ放置後の粘度は９９．９％程度低下する。 As a result of the test, when the silica filler of the present invention is added to the epoxy resin composite, the viscosity of the epoxy resin is reduced by about 90%, the thermal expansion coefficient is reduced by about 10%, and the viscosity after being left for 24 hours is 99.9. % Decrease.
また、本発明のシリカ充填材の表面処理方法はプロセスがシンプルで、操作しやすく、更に環境に優しい。 The silica filler surface treatment method of the present invention is simple in process, easy to operate, and environmentally friendly.
以下、実施例を利用して本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail using examples.
実施例１
本実施例のシリカ充填材の表面処理方法は、
（１）シリカ粒子２ｇを超音波で４００ｍｌの水溶液に分散させて、シリカ分散液を調製するステップと、
（２）相対分子質量１００００のポリビニルアルコール０．２ｇを水１００ｍｌに溶解して、質量濃度２ｇ／Ｌのポリビニルアルコール水溶液を調製するステップと、
（３）上記シリカ分散液とポリビニルアルコール水溶液を混合して、得た混合液を室温で５時間超音波反応させて、分離して洗浄し、シリカ充填材を得るステップとを含む。
Example 1
The surface treatment method of the silica filler of this example is
(1) Dispersing 2 g of silica particles in a 400 ml aqueous solution with ultrasonic waves to prepare a silica dispersion;
(2) Dissolving 0.2 g of polyvinyl alcohol having a relative molecular mass of 10,000 in 100 ml of water to prepare a polyvinyl alcohol aqueous solution having a mass concentration of 2 g / L;
(3) mixing the silica dispersion and the aqueous polyvinyl alcohol solution, subjecting the obtained mixture to an ultrasonic reaction at room temperature for 5 hours, separating and washing to obtain a silica filler.
本実施例で製造されたシリカ充填材はシリカ粒子をコア、ポリビニルアルコールで構成された厚さ５ｎｍの被覆層をシェルとするコア−シェル構造を有する。 The silica filler produced in this example has a core-shell structure in which the silica particles are the core and the coating layer made of polyvinyl alcohol and having a thickness of 5 nm is the shell.
本実施例で製造されたポリビニルアルコールで被覆されたシリカナノ粒子を充填材としてビスフェノールＦエポキシ樹脂、酸無水物硬化剤及びイミダゾール触媒の系に添加して、エポキシ樹脂複合材を得た。本実施例のエポキシ樹脂複合材において、各成分の質量百分率は、ビスフェノールＦエポキシ樹脂３２％、シリカ充填材４０％、酸無水物硬化剤２７％、イミダゾール触媒１％であった。 Silica nanoparticles coated with polyvinyl alcohol produced in this example were added as fillers to a system of bisphenol F epoxy resin, acid anhydride curing agent and imidazole catalyst to obtain an epoxy resin composite. In the epoxy resin composite of this example, the mass percentage of each component was 32% bisphenol F epoxy resin, 40% silica filler, 27% acid anhydride curing agent, and 1% imidazole catalyst.
実施例２
本実施例のシリカ充填材の表面処理方法は、
（１）シリカ粒子５ｇを超音波で水溶液４５０ｍｌに分散させて、シリカ分散液を調製するステップと、
（２）分子量７００００のポリエチレンイミン０．０２５ｇを水溶液５０ｍｌに溶解して、濃度０．５ｇ／Ｌのポリエチレンイミン水溶液を調製するステップと、
（３）上記シリカ水溶液とポリエチレンイミン水溶液を混合して、得た混合液を室温で２時間超音波反応させて、分離して洗浄し、シリカ充填材を得るステップとを含む。
Example 2
The surface treatment method of the silica filler of this example is
(1) A step of preparing a silica dispersion by dispersing 5 g of silica particles in 450 ml of an aqueous solution with ultrasonic waves;
(2) dissolving 0.025 g of polyethyleneimine having a molecular weight of 70,000 in 50 ml of an aqueous solution to prepare a polyethyleneimine aqueous solution having a concentration of 0.5 g / L;
(3) mixing the silica aqueous solution and the polyethyleneimine aqueous solution, subjecting the obtained mixture to ultrasonic reaction at room temperature for 2 hours, separating and washing to obtain a silica filler.
本実施例で製造されたシリカ充填材は、シリカ粒子をコア、ポリエチレンイミンで構成される厚さ約１０ｎｍの被覆層をシェルとするコア−シェル構造を有する。 The silica filler produced in the present example has a core-shell structure in which silica particles are used as a core and a coating layer made of polyethyleneimine and having a thickness of about 10 nm is used as a shell.
本実施例で製造されたポリエチレンイミンで被覆されたシリカ粒子を充填材としてビスフェノールＦエポキシ樹脂とジアミン硬化剤系に添加して、エポキシ樹脂複合材を製造した。本実施例のエポキシ樹脂複合材において、各成分の質量百分率は、ビスフェノールＦエポキシ樹脂５５％、シリカ充填材３０％、ジアミン硬化剤１５％であった。 An epoxy resin composite was produced by adding the silica particles coated with polyethyleneimine produced in this example as a filler to a bisphenol F epoxy resin and a diamine curing agent system. In the epoxy resin composite of this example, the mass percentage of each component was 55% bisphenol F epoxy resin, 30% silica filler, and 15% diamine curing agent.
実施例３
本実施例のシリカ充填材の表面処理方法は、
（１）シリカ粒子５ｇを超音波で水溶液４５０ｍｌに分散させて、シリカ分散液を調製するステップと、
（２）分子量７００００のポリエチレンイミン０．０５ｇを水溶液５０ｍｌに溶解して、濃度１ｇ／Ｌのポリエチレンイミン水溶液を調製するステップと、
（３）上記シリカ分散液とポリエチレンイミン水溶液を混合して、得た混合液を室温で２時間超音波反応させ、分離して洗浄し、シリカ充填材を製造するステップとを含む。
Example 3
The surface treatment method of the silica filler of this example is
(1) A step of preparing a silica dispersion by dispersing 5 g of silica particles in 450 ml of an aqueous solution with ultrasonic waves;
(2) dissolving 0.05 g of polyethyleneimine having a molecular weight of 70,000 in 50 ml of an aqueous solution to prepare a polyethyleneimine aqueous solution having a concentration of 1 g / L;
(3) mixing the silica dispersion and the polyethyleneimine aqueous solution, subjecting the obtained mixture to ultrasonic reaction at room temperature for 2 hours, separating and washing, and producing a silica filler.
本実施例で製造されたシリカ充填材は、シリカ粒子をコア、ポリエチレンイミンで構成される厚さ約２０ｎｍの被覆層をシェルとするコア−シェル構造を有する。 The silica filler produced in this example has a core-shell structure in which the silica particles are the core and the coating layer having a thickness of about 20 nm made of polyethyleneimine is the shell.
本実施例で製造されたポリエチレンイミンで被覆されたシリカ粒子を充填材としてビスフェノールＦエポキシ樹脂とジアミン硬化剤系に添加して、エポキシ樹脂複合材を製造した。本実施例のエポキシ樹脂複合材において、各成分の質量百分率は、ビスフェノールＦエポキシ樹脂５５％、シリカ充填材３０％、ジアミン硬化剤１５％であった。 An epoxy resin composite was produced by adding the silica particles coated with polyethyleneimine produced in this example as a filler to a bisphenol F epoxy resin and a diamine curing agent system. In the epoxy resin composite of this example, the mass percentage of each component was 55% bisphenol F epoxy resin, 30% silica filler, and 15% diamine curing agent.
実施例４
本実施例のシリカ充填材の表面処理方法は、
（１）シリカ粒子１０ｇを超音波で水溶液８００ｍｌに分散させ、シリカ分散液を調製するステップと、
（２）分子量４００００のポリドーパミン０．０５ｇを水溶液２００ｍｌに溶解して、濃度０．２５ｇ／Ｌのポリドーパミン水溶液を調製するステップと、
（３）上記シリカ分散液とポリドーパミン水溶液を混合し、得た混合液を室温で１２時間超音波反応させ、分離して洗浄し、シリカ充填材を得るステップとを含む。
Example 4
The surface treatment method of the silica filler of this example is
(1) Dispersing 10 g of silica particles in 800 ml of an aqueous solution with ultrasonic waves to prepare a silica dispersion;
(2) dissolving 0.05 g of polydopamine having a molecular weight of 40000 in 200 ml of an aqueous solution to prepare a polydopamine aqueous solution having a concentration of 0.25 g / L;
(3) mixing the silica dispersion and the polydopamine aqueous solution, subjecting the obtained mixture to ultrasonic reaction at room temperature for 12 hours, separating and washing to obtain a silica filler.
本実施例で製造されたシリカ充填材は、シリカ粒子をコア、ポリドーパミンで構成される厚さ約２０ｎｍの被覆層をシェルとするコア−シェル構造を有する。 The silica filler produced in this example has a core-shell structure in which the silica particles are the core and the coating layer made of polydopamine and having a thickness of about 20 nm is the shell.
本実施例で製造されたポリドーパミンで被覆されたシリカ粒子を充填材としてビスフェノールＦエポキシ樹脂とジアミン硬化剤系に添加して、エポキシ樹脂複合材を製造した。本実施例のエポキシ樹脂複合材において、各成分の質量百分率は、ビスフェノールＦエポキシ樹脂５５％、シリカ充填材３０％、ジアミン硬化剤１５％であった。 Silica particles coated with polydopamine produced in this example were added as fillers to a bisphenol F epoxy resin and a diamine curing agent system to produce an epoxy resin composite. In the epoxy resin composite of this example, the mass percentage of each component was 55% bisphenol F epoxy resin, 30% silica filler, and 15% diamine curing agent.
実施例５
本実施例のシリカ充填材の表面処理方法は、
（１）シリカ粒子２０ｇを超音波で水溶液１０００ｍｌに分散させ、シリカ分散液を調製するステップと、
（２）分子量１００００のポリイミド０．１ｇを水溶液２００ｍｌに溶解して、濃度０．５ｇ／Ｌのポリイミド水溶液を調製するステップと、
（３）上記シリカ分散液とポリイミド水溶液を混合し、得た混合液を室温で２４時間超音波反応させ、分離して洗浄し、シリカ充填材を得るステップとを含む。
Example 5
The surface treatment method of the silica filler of this example is
(1) Dispersing 20 g of silica particles in 1000 ml of an aqueous solution with ultrasonic waves to prepare a silica dispersion;
(2) dissolving 0.1 g of polyimide having a molecular weight of 10,000 in 200 ml of an aqueous solution to prepare a polyimide aqueous solution having a concentration of 0.5 g / L;
(3) The above silica dispersion and polyimide aqueous solution are mixed, and the obtained mixture is subjected to ultrasonic reaction at room temperature for 24 hours, separated and washed to obtain a silica filler.
本実施例で製造されたシリカ充填材は、シリカ粒子をコア、ポリイミドで構成される厚さ約１５ｎｍの被覆層をシェルとするコア−シェル構造を有する。 The silica filler produced in this example has a core-shell structure in which silica particles are used as a core and a coating layer made of polyimide and having a thickness of about 15 nm is used as a shell.
本実施例で製造されたポリイミドで被覆されるシリカ粒子を充填材としてビスフェノールＦエポキシ樹脂とジアミン硬化剤系に添加して、エポキシ樹脂複合材を製造した。本実施例のエポキシ樹脂複合材において、各成分の質量百分率は、ビスフェノールＦエポキシ樹脂５５％、シリカ充填材３０％、ジアミン硬化剤１５％であった。 An epoxy resin composite was produced by adding silica particles coated with polyimide produced in this example as a filler to a bisphenol F epoxy resin and a diamine curing agent system. In the epoxy resin composite of this example, the mass percentage of each component was 55% bisphenol F epoxy resin, 30% silica filler, and 15% diamine curing agent.
比較例１
エポキシ樹脂複合材中の充填材であるシリカを表面処理しない以外、本実施例のエポキシ樹脂複合材は実施例１と同様である。エポキシ樹脂複合材中の各成分及びその添加量は実施例１と同様である。
Comparative Example 1
The epoxy resin composite of this example is the same as that of Example 1 except that the silica that is the filler in the epoxy resin composite is not surface-treated. Each component in the epoxy resin composite and the amount added are the same as in Example 1.
比較例２
エポキシ樹脂複合材中の充填材であるシリカを表面処理しない以外、本実施例のエポキシ樹脂複合材は実施例２と同様である。エポキシ樹脂複合材中の各成分及びその添加量は実施例２と同様である。
Comparative Example 2
The epoxy resin composite material of this example is the same as that of Example 2 except that the silica that is the filler in the epoxy resin composite material is not surface-treated. Each component in the epoxy resin composite and the amount added are the same as in Example 2.
比較例３
エポキシ樹脂複合材中の充填材であるシリカを表面処理しない以外、本実施例のエポキシ樹脂複合材は実施例３と同様である。エポキシ樹脂複合材中の各成分及びその添加量は実施例３と同様である。
Comparative Example 3
The epoxy resin composite material of this example is the same as that of Example 3 except that the silica that is the filler in the epoxy resin composite material is not surface-treated. Each component in the epoxy resin composite and the amount added are the same as in Example 3.
比較例４
エポキシ樹脂複合材中の充填材であるシリカを表面処理しない以外、本実施例のエポキシ樹脂複合材は実施例４と同様である。エポキシ樹脂複合材中の各成分及びその添加量は実施例４と同様である。
Comparative Example 4
The epoxy resin composite material of this example is the same as that of Example 4 except that the silica that is the filler in the epoxy resin composite material is not surface-treated. Each component in the epoxy resin composite and the amount added are the same as in Example 4.
比較例５
エポキシ樹脂複合材中の充填材であるシリカを表面処理しない以外、本実施例のエポキシ樹脂複合材は実施例５と同様である。エポキシ樹脂複合材中の各成分及びその添加量は実施例５と同様である。
Comparative Example 5
The epoxy resin composite material of this example is the same as that of Example 5 except that the silica that is the filler in the epoxy resin composite material is not surface-treated. Each component in the epoxy resin composite and the amount added are the same as in Example 5.
テストした結果、各実施例のエポキシ樹脂複合材の特性は表１に示される。 As a result of the test, the properties of the epoxy resin composite material of each example are shown in Table 1.
表１から明らかなように、シリカを表面処理することで、シリカの表面に重合体被覆層を被覆することによって、エポキシ樹脂の粘度と熱膨張係数を著しく低下させることができる。 As is apparent from Table 1, by subjecting the silica to surface treatment, the viscosity and thermal expansion coefficient of the epoxy resin can be remarkably reduced by coating the surface of the silica with the polymer coating layer.
以上は本発明の好適な実施例に過ぎず、当業者であれば、本発明の趣旨に基づき、具体的な実施形態及び適用範囲を変更することができ、本明細書は本発明を制限するものではない。 The above is only a preferred embodiment of the present invention, and those skilled in the art can change specific embodiments and application scope based on the spirit of the present invention, and the present specification limits the present invention. It is not a thing.
Claims (5)
（１）シリカを溶剤に分散して、シリカ分散液を調製するステップと、
（２）前記シリカ分散液と重合体水溶液又は重合体のアルコール溶液を混合して、２０〜６０℃で超音波処理を２〜２４ｈ行って、分離して、洗浄し、シリカをコアとし、重合体で構成される被覆層をシェルとするコア−シェル構造を有するシリカ充填材を得るステップとを、含むことを特徴とする表面処理方法。 A surface treatment method for silica filler,
(1) Dispersing silica in a solvent to prepare a silica dispersion;
(2) The silica dispersion and the polymer aqueous solution or polymer alcohol solution are mixed, subjected to ultrasonic treatment at 20 to 60 ° C. for 2 to 24 hours, separated, washed, silica as the core, heavy And a step of obtaining a silica filler having a core-shell structure with a coating layer composed of coalescence as a shell .
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Also Published As
| Publication number | Publication date |
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| JP2017122209A (en) | 2017-07-13 |
| CN105440311A (en) | 2016-03-30 |
| WO2017117878A1 (en) | 2017-07-13 |
| CN105440311B (en) | 2018-02-27 |
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