JPS63201041A - Glass flake - Google Patents
Glass flakeInfo
- Publication number
- JPS63201041A JPS63201041A JP3288287A JP3288287A JPS63201041A JP S63201041 A JPS63201041 A JP S63201041A JP 3288287 A JP3288287 A JP 3288287A JP 3288287 A JP3288287 A JP 3288287A JP S63201041 A JPS63201041 A JP S63201041A
- Authority
- JP
- Japan
- Prior art keywords
- glass flakes
- coupling agent
- adhesive
- glass
- glass flake
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011521 glass Substances 0.000 title claims abstract description 75
- 239000007822 coupling agent Substances 0.000 claims abstract description 33
- 239000000853 adhesive Substances 0.000 claims abstract description 27
- 230000001070 adhesive effect Effects 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- 239000012779 reinforcing material Substances 0.000 abstract description 7
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 abstract description 3
- 229920002689 polyvinyl acetate Polymers 0.000 abstract description 2
- 239000011118 polyvinyl acetate Substances 0.000 abstract description 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 26
- 239000011347 resin Substances 0.000 description 26
- 239000011159 matrix material Substances 0.000 description 11
- 239000002131 composite material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000004381 surface treatment Methods 0.000 description 7
- 239000004677 Nylon Substances 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000005368 silicate glass Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920006187 aquazol Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 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
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はガラスフレークに係り、特に熱可塑性樹脂等の
補強材として優れた効果を発揮し得るガラスフレークに
関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to glass flakes, and particularly to glass flakes that can exhibit excellent effects as reinforcing materials for thermoplastic resins and the like.
［従来の技術］
ガラスフレークはアスペクト比（粒子径／厚さ）が２〜
１０００の鱗片状ガラスで、従来より、熱硬化性樹脂や
熱可塑性樹脂の補強材、防食ライニング用充質材その他
の用途に広く利用されている。[Prior art] Glass flakes have an aspect ratio (particle size/thickness) of 2 to
1000 scale glass has been widely used as a reinforcing material for thermosetting resins and thermoplastic resins, as a filler material for anticorrosive linings, and for other purposes.
例えば、熱硬化性樹脂にガラスフレークを混合したもの
を、金属面等にコテ塗りあるいはスブレー塗装すると、
ガラスフレークは塗膜内で塗布面にほぼ平行に配向し、
樹脂に対して３０重量％のガラスフレークを混合した場
合には、塗＠１ｍｍ厚さ当り、約３５〜４０枚のガラス
フレークの層が形成される。これにより水分や酸素など
の環境剤が塗膜を透過して金属等の母材表面に達する経
路長が著しく長くなり、環境剤による腐食が防止される
ようになる。For example, if a mixture of thermosetting resin and glass flakes is applied by troweling or spray painting on a metal surface,
The glass flakes are oriented within the coating film almost parallel to the coating surface,
When 30% by weight of glass flakes are mixed with the resin, a layer of about 35 to 40 glass flakes is formed per 1 mm thickness of coating. As a result, the path length for environmental agents such as moisture and oxygen to pass through the coating film and reach the surface of the base material such as metal becomes significantly longer, and corrosion caused by environmental agents is prevented.
また、熱可塑性樹脂にガラスフレークを混合した複合材
では、ガラスフレークの２次元的な補強効果により引張
強度、曲げ強度、曲げ弾性率及び熱変形温度、寸法精度
等が改善され、またバリヤー性も付与され、優れた特性
を有する樹脂が得られるようになる。このようなフレー
クで強化された樹脂の成形品は、樹脂の流れ方向の成形
収縮率と樹脂の流れに直角な方向の成形収縮率がほぼ等
しいため、ガラス繊維補強の樹脂に比し成形品のそりが
極めて小さくなる。In addition, in composite materials made by mixing glass flakes with thermoplastic resin, the two-dimensional reinforcing effect of glass flakes improves tensile strength, bending strength, bending elastic modulus, heat distortion temperature, dimensional accuracy, etc., and also improves barrier properties. As a result, resins with excellent properties can be obtained. Molded products made of resin reinforced with such flakes have approximately the same molding shrinkage rate in the flow direction of the resin and in the direction perpendicular to the flow of the resin, so the molded products have a lower molding shrinkage rate than glass fiber-reinforced resins. Warpage becomes extremely small.
従来、ガラスフレークは、複合材への使用にあたり、マ
トリックス樹脂との接着力の増大及び均一分散化のため
に、シラン系カップリング剤、チタン系カップリング剤
、ジルコニア系カップリング剤などのカップリング剤で
表面処理されることがあった。また、特公昭５４−４０
１０１号のごとく、無機酸で処理されたり、無機酸で処
理した後にシランカップリング剤で表面処理されること
もあった。Conventionally, when glass flakes are used in composite materials, coupling agents such as silane coupling agents, titanium coupling agents, zirconia coupling agents, etc. are used to increase adhesive strength with matrix resins and uniformly disperse them. The surface was sometimes treated with chemicals. In addition, special public service
As in No. 101, the surface was sometimes treated with an inorganic acid, or the surface was treated with a silane coupling agent after being treated with an inorganic acid.
即ち、従来において、ガラスフレークは主に塗料や反応
性インジェクションモールディング（ＲＩ Ｍ）成形用
補強材として用いられており、これらの用途においては
ガラスフレークの均一分散性を確保するために、カップ
リング剤による表面処理が行なわれていた。That is, conventionally, glass flakes have been mainly used as reinforcing materials for paints and reactive injection molding (RIM), and in these applications, coupling agents have been used to ensure uniform dispersion of glass flakes. surface treatment was carried out.
［発明が解決しようとする問題点］
このようなカップリング剤等による表面処理により、特
にシラン系カップリング剤による表面処理により、複合
材におけるガラスフレークとマトリックス樹脂との密着
性ないし接着性は無処理のものに比しある程度改善され
る。しかしながら、カップリング剤のみによる表面処理
では、ガラスフレークと樹脂との界面が脆性的で、両者
の親和性が十分でないため、ガラスフレークと樹脂との
接着力、密着力が不足し、得られる複合材の物性が十分
満足し得るものとはいえず、なお改良の余地が残されて
いるのが現状であった。[Problems to be Solved by the Invention] Due to surface treatment using such a coupling agent, especially a silane coupling agent, there is no adhesion or adhesion between glass flakes and matrix resin in a composite material. It is improved to some extent compared to the processed one. However, with surface treatment using only a coupling agent, the interface between the glass flakes and the resin is brittle and the affinity between the two is insufficient, resulting in insufficient adhesion and adhesion between the glass flakes and the resin, and the resulting composite At present, the physical properties of the material cannot be said to be fully satisfactory, and there is still room for improvement.
［問題点を解決するための手段］
本発明のガラスフレークは、接着剤及びカップリング剤
を含む処理剤で表面処理したことを特徴とするものであ
る。[Means for Solving the Problems] The glass flakes of the present invention are characterized in that they are surface-treated with a treatment agent containing an adhesive and a coupling agent.
本発明においてこの表面処理に用いられる接着剤として
は、ポリ酢酸ビニル系、ポリアクリレート系、ポリウレ
タン系、エポキシ樹脂系及びこれらの共重合体又は変性
物が挙げられる。これらのうちポリウレタン系としては
、芳香族及び脂肪族インシアネートタイプでポリエステ
ル型、ポリエーテル型のいずれでもよい。又、エポキシ
系としては、ビスフェノールＡタイプ、ノボラックエポ
キシタイプが好適である。In the present invention, adhesives used for this surface treatment include polyvinyl acetate, polyacrylate, polyurethane, epoxy resin, and copolymers or modified products thereof. Among these, the polyurethane type may be either an aromatic or aliphatic incyanate type, a polyester type, or a polyether type. Furthermore, as the epoxy type, bisphenol A type and novolac epoxy type are suitable.
これらの接着剤と併用するカップリング剤としては、γ
−アミノプロピルトリメトキシシラン、γ−アミノプロ
ピルトリエトキシシラン、Ｎ−β−アミノエチル−γ−
アミノプロピルトリメトキシシラン、γ−グリシドオキ
シプロビルトリメトキシシラン、ビニルトリエトキシシ
ラン、γ−メタクリルオキシプロピルトリメトキシシラ
ンなどのシラン系カップリング剤、チタン系カップリン
グ剤、ジルコニア系カップリング剤などのカップリング
剤が挙げられる。Coupling agents used in combination with these adhesives include γ
-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-
Silane coupling agents such as aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, titanium coupling agents, zirconia coupling agents, etc. Coupling agents include:
本発明において、接着剤及びカップリング剤を含む処理
剤は、ガラスフレークとマトリックスとの接着性、密着
性向上に有効なものであれば良く、上記のものに何ら限
定されるものではない。In the present invention, the processing agent including the adhesive and the coupling agent may be any agent that is effective in improving the adhesion and adhesion between the glass flakes and the matrix, and is not limited to the above-mentioned ones.
例えば、処理剤として、更に各種の帯電防止剤、潤滑剤
、フィルム形成物質等を併用することもできる。For example, as a processing agent, various antistatic agents, lubricants, film-forming substances, etc. can also be used in combination.
処理剤中の接着剤とカップリング剤との混合割合は特に
制限はなく、接着剤とカップリング剤との重量比で１：
１〜５０：１の割合となるようにするのが好ましい。The mixing ratio of the adhesive and the coupling agent in the treatment agent is not particularly limited, and the weight ratio of the adhesive and the coupling agent is 1:
Preferably, the ratio is 1 to 50:1.
ガラスフレークを、接着剤及びカップリング剤を含有す
る処理剤で表面処理するには、例えば、所定割合で混合
した接着剤及びカップリング剤を、必要に応じて水、有
機溶剤で更に２〜１００倍程度に希釈した処理液を調製
し、回転真空加熱装置等を用い、ガラスフレークに装置
を回転しつつ処理液を噴露し、その後乾燥する。In order to surface-treat glass flakes with a treatment agent containing an adhesive and a coupling agent, for example, the adhesive and coupling agent mixed in a predetermined ratio are further mixed with water and an organic solvent as needed for 2 to 100% A processing solution diluted to approximately twice the original temperature is prepared, and using a rotary vacuum heating device or the like, the processing solution is sprayed onto the glass flakes while rotating the device, and then dried.
本発明において、ガラスフレークは、ガラスフレーク１
００重量部に対し、接着剤０．１〜３．０重量部、カッ
プリング剤０．０１〜０．５重量部で表面処理されてい
ることが好ましい。In the present invention, the glass flakes are glass flakes 1
It is preferable that the surface be treated with 0.1 to 3.0 parts by weight of an adhesive and 0.01 to 0.5 parts by weight of a coupling agent based on 0.00 parts by weight.
なお、本発明のガラスフレークとしては、通常提供され
ているガラスフレークを適用することができ、例えば平
均厚さ０．５〜７．０μｍ１平均粒径５〜１０００μｍ
、アスペクト比２〜１０００程度のものが好適である。In addition, as the glass flakes of the present invention, commonly provided glass flakes can be applied, for example, average thickness 0.5 to 7.0 μm, average particle size 5 to 1000 μm.
, an aspect ratio of about 2 to 1000 is suitable.
また、ガラスフレークの組成としては、Ｅガラスのよう
な所謂無アルカリ珪酸塩ガラスやＣガラスのような含ア
ルカリ珪酸塩ガラスを用いることができる。後者の例と
しては、例えば、重量比で６０〜７５％の５ｉ０２、及
び８〜２０％のＲ２０（Ｎａ２０、Ｋ２Ｏなどのアルカ
リ金属酸化物）を主として含有し、（ただしＳｉＯ２＋
Ｒ２０は７５〜９０％）、その他に、例えばＣａｂ、Ｍ
ｇＯ，Ｂ２０３ 、Ａｕ２０３、ＺｎＯ，Ｆｅ２ｅ３な
どの１種又は２種以上を含む、含アルカリ珪酸塩ガラス
が挙げられる。Further, as the composition of the glass flakes, so-called alkali-free silicate glass such as E glass or alkali-containing silicate glass such as C glass can be used. An example of the latter is, for example, mainly containing 60 to 75% 5i02 and 8 to 20% R20 (alkali metal oxides such as Na20 and K2O) by weight (however, SiO2+
R20 is 75-90%), in addition, for example, Cab, M
Examples include alkali-containing silicate glasses containing one or more of gO, B203, Au203, ZnO, Fe2e3, and the like.
好ましいガラス組成の例を第１表に示す。Examples of preferred glass compositions are shown in Table 1.
第 １ 表
※１：Ｃガラス
※２：Ｅガラス
このような本発明のガラスフレークは、ナイロン、飽和
ポリエステル、ポリカーボネート、ポリアセタール、ポ
リフェニレンオキサイド、ポリフェニレンサルファイド
、ポリ塩化ビニル、ポリスチレン、ポリプロピレン、ポ
リエチレンなどの熱可塑性樹脂、フェノール樹脂、不飽
和ポリエステル樹脂、エポキシ樹脂などの熱硬化性樹脂
等の補強材として極めて有効である。これらのうちでも
、特に本発明のガラスフレークは熱可塑性樹脂の補強材
として好適である。本発明のガラスフレークを含有する
熱可塑性樹脂を押出成形、インジェクション成形した場
合、フレークは樹脂マトリックス中に極めて均一に分散
される。Table 1 *1: C glass *2: E glass Such glass flakes of the present invention include heat-resistant materials such as nylon, saturated polyester, polycarbonate, polyacetal, polyphenylene oxide, polyphenylene sulfide, polyvinyl chloride, polystyrene, polypropylene, and polyethylene. It is extremely effective as a reinforcing material for thermosetting resins such as plastic resins, phenolic resins, unsaturated polyester resins, and epoxy resins. Among these, the glass flakes of the present invention are particularly suitable as reinforcing materials for thermoplastic resins. When a thermoplastic resin containing the glass flakes of the present invention is extruded or injection molded, the flakes are extremely uniformly dispersed in the resin matrix.
［作用］
本発明のガラスフレークは接着剤及びカップリング剤を
含む処理剤で表面処理されているため、補強材として樹
脂等と混合使用した場合、マトリックス樹脂との密着性
及び接着性が高く得られる複合材の物性が大幅に向上さ
れる。[Function] Since the glass flakes of the present invention are surface-treated with a treatment agent containing an adhesive and a coupling agent, when mixed with a resin etc. as a reinforcing material, they have high adhesion and adhesion with the matrix resin. The physical properties of the composite material are significantly improved.
接着剤及びカップリング剤を含む処理剤で表面処理する
ことにより、このような物性の大幅な改善がみられるの
は次のような理由によるものと考えられる。The reason why the physical properties are significantly improved by surface treatment with a treatment agent containing an adhesive and a coupling agent is considered to be as follows.
■ 接着剤がカップリング剤等の処理剤により有機化さ
れたガラスフレーク表面に強固に接着し、更にマトリッ
クス樹脂と強固に接着する。■ The adhesive firmly adheres to the surface of glass flakes that have been made organic by a treatment agent such as a coupling agent, and also firmly adheres to the matrix resin.
即ち、ガラスフレークとマトリックス樹脂との界面に、
親和性を高める多層構造が形成されるため、ガラスフレ
ークとマトリックス樹脂との接着力及び密着力は著しく
向上される。That is, at the interface between the glass flakes and the matrix resin,
Since a multilayer structure is formed that increases the affinity, the adhesive strength and adhesion between the glass flakes and the matrix resin are significantly improved.
■ 接着剤及びカップリング剤等の処理剤が、ガラスフ
レーク表面を高い被覆率で覆い、この接着剤と処理剤に
よる被覆層によりマトリックス樹脂とガラスフレークと
が強固に連結される。(2) A treatment agent such as an adhesive and a coupling agent covers the glass flake surface with a high coverage rate, and the matrix resin and the glass flake are firmly connected by the coating layer of the adhesive and treatment agent.
本発明においては、このような接着剤とカップリング剤
を含む処理剤とによる相乗的な作用効果により、ガラス
フレークによる物性改善効果が向上し、従って、得られ
る複合材の物性は大幅に向上する。In the present invention, the synergistic effect of the adhesive and the treatment agent containing the coupling agent improves the physical property improvement effect of the glass flakes, and therefore the physical properties of the resulting composite material are significantly improved. .
［実施例］ 以下実施例について説明する。[Example] Examples will be described below.
実施例１
回転真空加熱装置（容量５００℃）にガラスフレーク（
日本硝子繊維■製ＣＥＦ−１５０）を１００ｋｇ入れ、
装置を回転させつつ、下記配合の処理剤１０ｋｇを噴露
し、その後乾燥して、ガラスフレークの表面処理を行な
った。ガラスフレーク重量に対する表面処理剤量は、固
形分で表わしてシランカップリング剤０．１重量％、接
着剤０．７重量％とじた。Example 1 Glass flakes (
Put 100 kg of CEF-150 manufactured by Nippon Glass Fiber ■,
While rotating the apparatus, 10 kg of a treatment agent of the following composition was sprayed, and then dried to perform surface treatment on the glass flakes. The amount of the surface treatment agent based on the weight of the glass flakes was 0.1% by weight of the silane coupling agent and 0.7% by weight of the adhesive, expressed as solid content.
処理剤配合 （重量％）
アミノシラン １．５
ウレタンエマルジョン １０．０
水 ８８．５７０重量部のナ
イロン６．６に対し、上記の処理を行なったガラスフレ
ークを３０重量部加え、スクリュー径５０ｍｍφのベン
ト付押出機にて、シリンダ一温度２９０℃で押出成形し
、ガラスフレーク強化ナイロンベレットを得た。得られ
たベレットを乾燥後、射出成形機によって試験片を作成
し、機械的特性を調べた。Treatment agent formulation (wt%) Aminosilane 1.5 Urethane emulsion 10.0 Water 88.30 parts by weight of the glass flakes treated above were added to 570 parts by weight of nylon 6.6, and a vent with a screw diameter of 50 mm was added. Extrusion molding was performed using an extruder at a cylinder temperature of 290° C. to obtain a glass flake reinforced nylon pellet. After drying the obtained pellet, a test piece was prepared using an injection molding machine and its mechanical properties were examined.
結果を第２表に示す。The results are shown in Table 2.
実施例２〜４
マトリックス樹脂として第２表に示すものを用い、実施
例１と同様にして試験片を作製し、その機械的特性を調
べた。Examples 2 to 4 Test pieces were prepared in the same manner as in Example 1 using matrix resins shown in Table 2, and their mechanical properties were investigated.
タタシ、ＰＢＴ樹脂に対しては、ガラスフレークの表面
処理用接着剤としてＰＢＴ用エポキシエマルジョンを用
いた。また、ＡＳ樹脂に対しては、ガラスフレークの処
理剤として、下記配合の処理剤を用いた。For PBT resin, an epoxy emulsion for PBT was used as an adhesive for surface treatment of glass flakes. Furthermore, for the AS resin, a treatment agent with the following formulation was used as a treatment agent for glass flakes.
ＡＳ樹脂用処理剤 （重量％）アミノシラン
１．５
ポリエチルオキサゾリン １０，０
第４級アンモニウム塩 ０． ２
（ｆ電防止剤）
水 ８８．３結果を第２表に
示す。Treatment agent for AS resin (weight%) Aminosilane
1.5 Polyethyloxazoline 10.0 Quaternary ammonium salt 0. 2 (antistatic agent) Water 88.3 The results are shown in Table 2.
比較例１〜４
アミノシランのみで表面処理したガラスフレークを用い
たこと以外は、各々、実施例１〜４と同様にして試験片
を作製し、その機械的特性を調べた。結果を第２表に示
す。Comparative Examples 1 to 4 Test pieces were prepared in the same manner as in Examples 1 to 4, except that glass flakes surface-treated only with aminosilane were used, and their mechanical properties were examined. The results are shown in Table 2.
第２表より、本発明のガラスフレークを配合した複合材
は、従来のガラスフレークを配合したものに比し、機械
的特性が著しく向上していることが明らかである。From Table 2, it is clear that the composite material containing the glass flakes of the present invention has significantly improved mechanical properties as compared to the composite material containing the conventional glass flakes.
実施例５
下記配合の処理剤を用い、実施例１と同様の方法でガラ
スフレークを表面処理した。Example 5 Glass flakes were surface-treated in the same manner as in Example 1 using a treatment agent with the following composition.
処理剤 （重量％）
アミノシラン ２
エポキシエマルジョン １０
水 ８８
７０重量部のナイロン６．６に上記表面処理ガラスフレ
ーク３０重量部を加え、実施例１と同様にして押出し成
形し、ガラスフレーク強化ナイロンベレットを得た。次
に、このベレットを同じく５０ｍｍφの押出し機にて熔
融後、Ｔダイにて厚さ０．５ｍｍのシートを成形し、得
られたシートの物性を調へた。Treatment agent (wt%) Aminosilane 2 Epoxy emulsion 10 Water 88 30 parts by weight of the above surface-treated glass flakes were added to 70 parts by weight of nylon 6.6, and extrusion molded in the same manner as in Example 1 to obtain glass flake-reinforced nylon pellets. Obtained. Next, this pellet was melted using an extruder having a diameter of 50 mm, and then a sheet having a thickness of 0.5 mm was formed using a T-die, and the physical properties of the obtained sheet were examined.
結果を第３表に示す。The results are shown in Table 3.
比較例５
アミノシランのみで表面処理したガラスフレークを用い
たこと以外は実施例５と同様にしてシートを成形し、得
られたシートの物性を調べ、結果を第３表に示した。Comparative Example 5 A sheet was molded in the same manner as in Example 5 except that glass flakes surface-treated with only aminosilane were used, and the physical properties of the obtained sheet were examined. The results are shown in Table 3.
第３表
第３表より、本発明のガラスフレークを配合した複合材
は、シールド効果が極めて高いことが明らかである。From Table 3, it is clear that the composite material containing the glass flakes of the present invention has an extremely high shielding effect.
［発明の効果コ
以上詳述した通り、本発明のガラスフレークは、接着剤
及びカップリング剤を含む！Ａ埋剤で表面処理されたも
のであって、樹脂マトリックスとの密着力、接着力が極
めて高い。このため、本発明のガラスフレークを用いる
ことにより引張強度、曲げ強度、曲げ弾性率、熱変形温
度、寸法精度、シールド性、成形性等の諸特性が大幅に
改善されたガラスフレーク強化複合材が提供される。[Effects of the Invention As detailed above, the glass flakes of the present invention contain an adhesive and a coupling agent! It is surface-treated with filler A, and has extremely high adhesion and adhesion to the resin matrix. Therefore, by using the glass flakes of the present invention, a glass flake-reinforced composite material with significantly improved properties such as tensile strength, bending strength, bending modulus, heat distortion temperature, dimensional accuracy, shielding properties, and formability has been created. provided.
Claims (1)
理したことを特徴とするガラスフレーク。 （２）接着剤とカップリング剤との固形成分配合割合が
重量比で１：１〜５０：１である特許請求の範囲第１項
に記載のガラスフレーク。 （３）カップリング剤がシラン系カップリング剤、チタ
ン系カップリング剤、ジルコニア系カップリング剤のい
ずれかである特許請求の範囲第１項又は第２項に記載の
ガラスフレーク。 （４）ガラスフレーク１００重量部に対し ０．１〜３．０重量部の接着剤で表面処理した特許請求
の範囲第１項ないし第３項のいずれか１項に記載のガラ
スフレーク。 （５）ガラスフレーク１００重量部に対し ０．０５〜１．０重量部のカップリング剤で表面処理し
た特許請求の範囲第１項ないし第４項のいずれか１項に
記載のガラスフレーク。 （６）ガラスフレークは、平均厚さ０．５〜７．０μｍ
、平均粒径５〜１０００μｍ、アスペクト比２〜１００
０である特許請求の範囲第１項ないし第５項のいずれか
１項に記載のガラスフレーク。[Scope of Claims] (1) Glass flakes characterized by being surface-treated with a treatment agent containing an adhesive and a coupling agent. (2) The glass flakes according to claim 1, wherein the solid component mixing ratio of the adhesive and the coupling agent is 1:1 to 50:1 by weight. (3) The glass flakes according to claim 1 or 2, wherein the coupling agent is any one of a silane coupling agent, a titanium coupling agent, and a zirconia coupling agent. (4) The glass flakes according to any one of claims 1 to 3, which are surface-treated with an adhesive in an amount of 0.1 to 3.0 parts by weight per 100 parts by weight of the glass flakes. (5) The glass flakes according to any one of claims 1 to 4, which are surface-treated with 0.05 to 1.0 parts by weight of a coupling agent per 100 parts by weight of the glass flakes. (6) Glass flakes have an average thickness of 0.5 to 7.0 μm
, average particle size 5-1000 μm, aspect ratio 2-100
The glass flake according to any one of claims 1 to 5, wherein the glass flake is 0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62032882A JPH0776113B2 (en) | 1987-02-16 | 1987-02-16 | Reinforcing material for molding thermoplastic resin or thermosetting resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62032882A JPH0776113B2 (en) | 1987-02-16 | 1987-02-16 | Reinforcing material for molding thermoplastic resin or thermosetting resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63201041A true JPS63201041A (en) | 1988-08-19 |
| JPH0776113B2 JPH0776113B2 (en) | 1995-08-16 |
Family
ID=12371245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62032882A Expired - Lifetime JPH0776113B2 (en) | 1987-02-16 | 1987-02-16 | Reinforcing material for molding thermoplastic resin or thermosetting resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0776113B2 (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5075354A (en) * | 1989-08-30 | 1991-12-24 | Polyplastics Co., Ltd. | Polyester resin composition and process for the preparation thereof |
| JPH0848535A (en) * | 1994-08-08 | 1996-02-20 | Nippon Glass Fiber Co Ltd | Granular flaky glass for corrosion resistant lining |
| JP2006152198A (en) * | 2004-12-01 | 2006-06-15 | Nippon Sheet Glass Co Ltd | Flaky glass aggregate |
| US7285508B2 (en) | 2003-08-29 | 2007-10-23 | Nippon Sheet Glass Company, Limited | Glass flake |
| US7641730B2 (en) | 2003-02-27 | 2010-01-05 | Nippon Sheet Glass Company, Limited | Glass flake and method of manufacrturing the same |
| WO2012026127A1 (en) * | 2010-08-26 | 2012-03-01 | 日本板硝子株式会社 | Resin composition and granular flaky glass |
| WO2012096182A1 (en) | 2011-01-14 | 2012-07-19 | 日本板硝子株式会社 | Glass flake and cosmetics comprising same |
| US8383532B2 (en) | 2006-06-23 | 2013-02-26 | Nippon Sheet Glass Company, Limited | Glass flake |
| JP6054587B1 (en) * | 2015-07-31 | 2016-12-27 | 日本板硝子株式会社 | Flaked glass and resin composition |
| JP2017538852A (en) * | 2014-11-24 | 2017-12-28 | エヌジーエフ ヨーロッパ リミテッドＮｇｆ Ｅｕｒｏｐｅ Ｌｉｍｉｔｅｄ | Printed goods and feedstock |
| WO2018079335A1 (en) | 2016-10-27 | 2018-05-03 | 日本板硝子株式会社 | Flaky glass and resin composition |
| WO2018088488A1 (en) | 2016-11-10 | 2018-05-17 | 日本板硝子株式会社 | Glass filler and method for manufacturing same |
| CN108697078A (en) * | 2015-11-23 | 2018-10-23 | 美可帮产品公司 | Surface disinfection agent with remaining biocidal properties |
| US10842147B2 (en) | 2014-11-26 | 2020-11-24 | Microban Products Company | Surface disinfectant with residual biocidal property |
| US10925281B2 (en) | 2014-11-26 | 2021-02-23 | Microban Products Company | Surface disinfectant with residual biocidal property |
| US11026418B2 (en) | 2014-11-26 | 2021-06-08 | Microban Products Company | Surface disinfectant with residual biocidal property |
| US11033023B2 (en) | 2014-11-26 | 2021-06-15 | Microban Products Company | Surface disinfectant with residual biocidal property |
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| JP6966438B2 (en) * | 2015-11-23 | 2021-11-17 | マイクロバン プロダクツ カンパニー | Surface bactericidal agent with residual bactericidal properties |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5048012A (en) * | 1973-08-27 | 1975-04-28 |
-
1987
- 1987-02-16 JP JP62032882A patent/JPH0776113B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5048012A (en) * | 1973-08-27 | 1975-04-28 |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0415739B1 (en) * | 1989-08-30 | 1996-05-22 | Polyplastics Co. Ltd. | Polyester resin composition and process for the preparation thereof |
| US5075354A (en) * | 1989-08-30 | 1991-12-24 | Polyplastics Co., Ltd. | Polyester resin composition and process for the preparation thereof |
| JPH0848535A (en) * | 1994-08-08 | 1996-02-20 | Nippon Glass Fiber Co Ltd | Granular flaky glass for corrosion resistant lining |
| US7641730B2 (en) | 2003-02-27 | 2010-01-05 | Nippon Sheet Glass Company, Limited | Glass flake and method of manufacrturing the same |
| US7285508B2 (en) | 2003-08-29 | 2007-10-23 | Nippon Sheet Glass Company, Limited | Glass flake |
| JP2006152198A (en) * | 2004-12-01 | 2006-06-15 | Nippon Sheet Glass Co Ltd | Flaky glass aggregate |
| US8383532B2 (en) | 2006-06-23 | 2013-02-26 | Nippon Sheet Glass Company, Limited | Glass flake |
| WO2012026127A1 (en) * | 2010-08-26 | 2012-03-01 | 日本板硝子株式会社 | Resin composition and granular flaky glass |
| JP5858916B2 (en) * | 2010-08-26 | 2016-02-10 | 日本板硝子株式会社 | Resin composition |
| WO2012096182A1 (en) | 2011-01-14 | 2012-07-19 | 日本板硝子株式会社 | Glass flake and cosmetics comprising same |
| JP2017538852A (en) * | 2014-11-24 | 2017-12-28 | エヌジーエフ ヨーロッパ リミテッドＮｇｆ Ｅｕｒｏｐｅ Ｌｉｍｉｔｅｄ | Printed goods and feedstock |
| US10842147B2 (en) | 2014-11-26 | 2020-11-24 | Microban Products Company | Surface disinfectant with residual biocidal property |
| US10925281B2 (en) | 2014-11-26 | 2021-02-23 | Microban Products Company | Surface disinfectant with residual biocidal property |
| US11026418B2 (en) | 2014-11-26 | 2021-06-08 | Microban Products Company | Surface disinfectant with residual biocidal property |
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| US11134678B2 (en) | 2014-11-26 | 2021-10-05 | Microban Products Company | Surface disinfectant with residual biocidal property |
| JP6054587B1 (en) * | 2015-07-31 | 2016-12-27 | 日本板硝子株式会社 | Flaked glass and resin composition |
| CN108697078A (en) * | 2015-11-23 | 2018-10-23 | 美可帮产品公司 | Surface disinfection agent with remaining biocidal properties |
| WO2018079335A1 (en) | 2016-10-27 | 2018-05-03 | 日本板硝子株式会社 | Flaky glass and resin composition |
| WO2018088488A1 (en) | 2016-11-10 | 2018-05-17 | 日本板硝子株式会社 | Glass filler and method for manufacturing same |
| US11440832B2 (en) | 2016-11-10 | 2022-09-13 | Nippon Sheet Glass Company, Limited | Glass filler and method for producing the same |
| WO2022168964A1 (en) | 2021-02-05 | 2022-08-11 | 日本板硝子株式会社 | Glass composition, and glass filler and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0776113B2 (en) | 1995-08-16 |
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