JPH0668084B2 - Manufacturing method of surface hydrophobic metal material - Google Patents
Manufacturing method of surface hydrophobic metal materialInfo
- Publication number
- JPH0668084B2 JPH0668084B2 JP61205466A JP20546686A JPH0668084B2 JP H0668084 B2 JPH0668084 B2 JP H0668084B2 JP 61205466 A JP61205466 A JP 61205466A JP 20546686 A JP20546686 A JP 20546686A JP H0668084 B2 JPH0668084 B2 JP H0668084B2
- Authority
- JP
- Japan
- Prior art keywords
- metal material
- group
- hydrophobic
- resin
- treated
- 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.)
- Expired - Lifetime
Links
- 239000007769 metal material Substances 0.000 title claims description 32
- 230000002209 hydrophobic effect Effects 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 21
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical compound [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 claims description 16
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000005372 silanol group Chemical group 0.000 claims description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000007822 coupling agent Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 3
- -1 etc. Substances 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- AIXYPMUYMUOTOM-UHFFFAOYSA-N isocyanato(methyl)silane Chemical compound C[SiH2]N=C=O AIXYPMUYMUOTOM-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は、金属粉等の金属材料の表面を疎水化するため
の表面処理方法に関し、特に高度に疎水化された金属材
料の製造法に関する。Description: TECHNICAL FIELD The present invention relates to a surface treatment method for hydrophobizing the surface of a metal material such as metal powder, and particularly to a method for producing a highly hydrophobized metal material. .
＜従来技術とその問題点＞ 金属粉、カーボンブラック、セラミック粉等の無機材料
は、塗料、インキなどに使用される顔料プラスチック、
磁気テープ、導電塗料、ゴム、プラスチックマグネッ
ト、半導体封止樹脂、等の有機材に混入して、機械的強
度の強化、導電性の付与、磁気シールドなどの機能性付
与材料として、工業的に幅広く利用される。<Prior art and its problems> Inorganic materials such as metal powder, carbon black, and ceramic powder are pigment plastics used for paints, inks, and the like.
Widely used industrially as a functional material such as magnetic tape, conductive paint, rubber, plastic magnet, semiconductor encapsulating resin, and other organic materials to enhance mechanical strength, impart conductivity, and magnetic shield. Used.
ところが、無機物質の表面は本質的に親水性であり、こ
れを有機素材と結合させて使用する場合、有機素材との
界面親和性、無機物質の分散性等が最終的な材料の物性
機能性に大きな影響を及ぼす。このため従来より無機物
質の表面を有機化し疎水性にするために、シラン系カッ
プリング剤、アルミニウム系カップリング剤、リン酸系
カップリング剤等のカップリング剤で処理することが工
業的に行われ、ある程度の効果が得られている。However, the surface of an inorganic substance is essentially hydrophilic, and when it is used in combination with an organic material, the interfacial affinity with the organic material, dispersibility of the inorganic substance, etc. are the physical properties of the final material. Have a great effect on. Therefore, it has been industrially practiced to treat the surface of inorganic substances with a coupling agent such as a silane coupling agent, an aluminum coupling agent, or a phosphoric acid coupling agent in order to make the surface of the inorganic substance hydrophobic. Well, some effect has been obtained.
しかしながら、これらのカップリング剤による表面処理
法では複合材料の高機能が十分引き出されているとは言
い難い。この原因としては無機物表面と上記カップリン
グ剤との親和力が小さいことがあげられる。However, it cannot be said that the high-performance composite materials are sufficiently brought out by the surface treatment method using these coupling agents. The reason for this is that the affinity between the surface of the inorganic material and the coupling agent is small.
シラン系カップリング剤では金属およびカーボンブラッ
クには効果が少ないし、他のカップリング剤は加水分解
により無機表面からはなれやすい。Silane-based coupling agents have little effect on metals and carbon black, and other coupling agents tend to be released from the inorganic surface by hydrolysis.
また別の原因としては、これらのカップリング剤に結合
している有機基が、複合しようとする有機樹脂と十分に
一体化しているとは考えられないことがあげられる。従
って従来法においては、無機物表面を高度に疎水化する
ことは不可能である。Another cause is that the organic groups bonded to these coupling agents are not considered to be sufficiently integrated with the organic resin to be composited. Therefore, in the conventional method, it is impossible to make the surface of the inorganic material highly hydrophobic.
＜発明の目的＞ 本発明の目的は、金属材料表面を高度に疎水化し、高機
能複合材料として広く利用できる表面疎水性金属材料の
製造法を提供するものである。<Object of the Invention> An object of the present invention is to provide a method for producing a surface-hydrophobic metal material which is highly hydrophobic on the surface of the metal material and can be widely used as a high-performance composite material.
＜発明の構成＞ 本発明はシリルイソシアネートが金属材料表面の水酸基
及び／又は吸着水と極めて強い親和性あるいは反応性を
有することを応用し、金属表面に強く結合したシリルイ
ソシアネートにさらに優れた疎水性を有し、かつNCOと
反応する基を有する疎水性化合物を結合させ、これによ
って金属材料の表面を高度に疎水化するものである。<Structure of the Invention> The present invention applies the fact that silyl isocyanate has a very strong affinity or reactivity with the hydroxyl groups and / or adsorbed water on the surface of the metal material, and further improves the hydrophobicity of the silyl isocyanate strongly bonded to the metal surface. And a hydrophobic compound having a group that reacts with NCO is bound, thereby making the surface of the metal material highly hydrophobic.
本発明は、金属材料の表面をSi−NCO結合を有するシリ
ルイソシアネートで処理し、次いで得られたシリルイソ
シアネート処理金属材料を、分子中にシラノール基、水
酸基、メルカプト基、アミノ基、エポキシ基、カルボキ
シル基からなる群から選ばれた少なくとも１個の基をも
つ疎水性化合物で処理することを特徴とする表面疎水性
金属材料の製造法を提供する。The present invention, the surface of the metal material is treated with silyl isocyanate having a Si-NCO bond, then the resulting silyl isocyanate-treated metal material, silanol group, hydroxyl group, mercapto group, amino group, epoxy group, carboxyl in the molecule. Provided is a method for producing a surface-hydrophobic metallic material, which comprises treating with a hydrophobic compound having at least one group selected from the group consisting of groups.
以下本発明を詳細に説明する。The present invention will be described in detail below.
本発明で使用される金属材料としては、通常、顔料や充
填剤として使用されるもののほか、導電性顔料、導電性
フィラー等として使用されるもの、さらには磁気記録材
料素材として使用される磁性粉等があり、例えば、Al、
As、Bi、Ca、Cd、Co、Cr、Cu、Fe、Mg、Ni、Pb、Sb、S
i、Ti、Zn等の金属等主として元素単体からなるもの、
鋼、ステンレス等の金属と他の元素の混合物、およびこ
れらの合金等をあげることができ、その形状についても
粉末状、鱗片状、繊維状、板状、針状等如何なる形状の
ものであっても良い。As the metal material used in the present invention, in addition to those usually used as pigments and fillers, those used as conductive pigments, conductive fillers, etc., and magnetic powder used as a magnetic recording material material. , Such as Al,
As, Bi, Ca, Cd, Co, Cr, Cu, Fe, Mg, Ni, Pb, Sb, S
i, Ti, Zn, and other metals, etc., which are mainly composed of elemental elements,
Examples thereof include a mixture of a metal such as steel and stainless steel, and other elements, and alloys thereof. The shape thereof is powder, scale, fiber, plate, needle, or any other shape. Is also good.
上記金属材料の表面処をまず始めに処理するSi−NCO結
合を有するシリルイソシアネートとしては、RnSi（NC
O）4-nで表わされ、ｎは0,1,2,3で、Ｒは炭素数１以上
のアルキル基、アルコキシ基、アリール基、ビニル基な
どである。As the silyl isocyanate having a Si-NCO bond, which is the first to treat the surface treatment of the metal material, RnSi (NC
O) 4- n, n is 0, 1, 2, 3 and R is an alkyl group having 1 or more carbon atoms, an alkoxy group, an aryl group, a vinyl group or the like.
このシリルイソシアネートの使用量は、金属材料の表面
積、シリルイソシアネートの種類によって異なるが通常
金属材料に対し0.1〜10重量％程度である。The amount of the silyl isocyanate used depends on the surface area of the metal material and the type of the silyl isocyanate, but is usually about 0.1 to 10% by weight based on the metal material.
次に、金属材料を処理する疎水性化合物としては、以下
の基を有する疎水性化合物がある。Next, as the hydrophobic compound for treating the metal material, there are hydrophobic compounds having the following groups.
（１）シラノール基 一般式RnSi（OH）4-n、Ｒはアルキル基等、またはなく
てもよい。ｎ＝3,2,1,0を持つ疎水性化合物であればい
かなるものであってもよいが、α（１）−ジハイドロキ
シジメチルポリシロキサン等を代表的に挙げることがで
きる。(1) Silanol group RnSi (OH) 4- n, R may be an alkyl group or the like, or may not be present. Any hydrophobic compound having n = 3,2,1,0 may be used, and α (1) -dihydroxydimethylpolysiloxane and the like can be typically mentioned.
（２）水酸基 −OHを持つ疎水性化合物は、上記シラノール基以外の水
酸基を有する化合物であればいかなるものでもよいが、
フェノール樹脂等が好ましい。(2) The hydrophobic compound having a hydroxyl group —OH may be any compound as long as it has a hydroxyl group other than the silanol group.
Phenolic resin and the like are preferable.
（３）メルカプト基 −SHを持つ疎水性化合物は、γ−メルカプトプロピルト
リエトキシシラン等を代表的に挙げることができる。(3) Typical examples of the hydrophobic compound having a mercapto group —SH include γ-mercaptopropyltriethoxysilane.
（４）アミノ基 −NH2を持つ疎水性化合物は、ユリア樹脂、メラミン樹
脂、グアナミン樹脂等のアミノ樹脂等が好ましい。(4) The hydrophobic compound having an amino group —NH 2 is preferably an amino resin such as urea resin, melamine resin or guanamine resin.
（５）エポキシ基 （ｎは０以上の整数） を持つ疎水性化合物は、エポキシ樹脂に称される、ビス
フェノール類とエピクロロヒドリンの重縮合体、および
それをハロゲン化した樹脂、多価アルコール、ダイマー
酸、トリマー酸およびノボラックなどにエピクロロヒド
リンを反応させてエポキシ基を導入した樹脂、ポリオレ
フィンに過酸化水素でエポキシ樹脂を導入した樹脂、脂
環式エポキシ樹脂等を代表的に挙げることができる。(5) Epoxy group Hydrophobic compounds having (n is an integer of 0 or more) are referred to as epoxy resins, polycondensates of bisphenols and epichlorohydrin, and halogenated resins, polyhydric alcohols, dimer acids, trimers. Typical examples thereof include a resin obtained by reacting an acid and novolac with epichlorohydrin to introduce an epoxy group, a resin obtained by introducing an epoxy resin into a polyolefin with hydrogen peroxide, and an alicyclic epoxy resin.
（６）カルボキシル基 −COOHを持つ疎水性化合物は、ステアリン酸等が好まし
い。(6) The hydrophobic compound having a carboxyl group —COOH is preferably stearic acid.
以上の疎水性化合物は単独で用いてもよいし、複合して
用いてもよい。またこれらの化合物の共重合体でもよ
い。シラノール基、水酸基、メルカプト基、エポキシ
基、カルボキシル基を単独で有する疎水性化合物でもよ
いし、多種のこれらの基を有してもよいし、これらの基
を多数有してもよい。The above hydrophobic compounds may be used alone or in combination. It may also be a copolymer of these compounds. It may be a hydrophobic compound having a silanol group, a hydroxyl group, a mercapto group, an epoxy group, or a carboxyl group alone, may have various kinds of these groups, or may have a large number of these groups.
金属材料の表面をシリルイソシアネートで処理し、その
後疎水性化合物で処理する方法は以下の方法がある。There are the following methods for treating the surface of a metal material with silyl isocyanate and then treating with a hydrophobic compound.
まず始めに、金属材料をシリルイソシアネートで処理す
る。その方法としては、例えば、Ｖブレンダー、ヘンシ
ェルミキサー等で金属材料を強制的に攪拌しながら溶剤
の存在下、若しくは存在させることなく表面処理する。
具体的には、スプレー等によりシリルイソシアネート単
独若しくは活性水素を含有しない溶剤、たとえばエステ
ル、ケトン、エーテル、炭化水素に溶解したシリルイソ
シアネートを噴霧して処理する乾式法、金属材料を活性
水素を含有しない溶剤に分散させ、スラリー状にし、こ
れにシリルイソシアネートを添加する湿式法等、通常良
く用いられる方法を採用することができる。First, the metallic material is treated with silyl isocyanate. As the method, for example, the surface treatment is carried out in the presence or absence of a solvent while forcibly stirring the metal material with a V blender, a Henschel mixer or the like.
Specifically, a dry method in which silyl isocyanate alone or a solvent not containing active hydrogen, such as ester, ketone, ether, or silyl isocyanate dissolved in hydrocarbon is sprayed for treatment by spraying or the like, a metal material does not contain active hydrogen. A commonly used method such as a wet method of dispersing in a solvent to form a slurry and adding silyl isocyanate thereto can be employed.
次に、シリルイソシアネートで処理して得られた金属材
料と疎水性化合物とを反応させる方法としては、両者を
均一に混合することが必要であるが、上述したシリルイ
ソシアネートで処理する方法と同様の方法で均一に混合
した後、必要に応じて加熱する方法を採用することがで
きる。例えば、疎水性化合物の官能基がエポキシ基であ
る場合には、両者の混合物を乾燥器もしくは反応器で加
熱することにより容易に行うことができる。Next, as a method of reacting the metal material and the hydrophobic compound obtained by treating with silyl isocyanate, it is necessary to uniformly mix the two, but the same method as the above-mentioned method of treating with silyl isocyanate is used. After uniformly mixing by the method, a method of heating if necessary can be adopted. For example, when the functional group of the hydrophobic compound is an epoxy group, it can be easily carried out by heating a mixture of the two in a dryer or a reactor.
上記手法により処理された金属材料の疎水性の判定は、
簡単には水とこれに不溶性の有機溶剤の二相系溶液に該
金属材料を入れ、激しく攪拌したあと金属材料の分散相
を観察する一般的な方法で行うことができる。例えば、
20mlのｎ−ヘプタンと80mlの水からなる二相系溶液を容
積140mlの密封付沈降管に入れ、これに疎水性を判定す
べき金属材料1.0gを添加し、激しく振りまぜたのち、静
置して金属材料の分散状態を観察する。完全に疎水化し
た金属材料はｎ−ヘプタン相に安定に分散する、疎水化
が不完全な金属材料は水層に移りやすい。Determination of the hydrophobicity of the metal material treated by the above method,
Briefly, it can be carried out by a general method in which the metal material is put in a two-phase system solution of water and an insoluble organic solvent, stirred vigorously, and then the dispersed phase of the metal material is observed. For example,
A two-phase solution consisting of 20 ml of n-heptane and 80 ml of water was placed in a sealed settling tube with a volume of 140 ml, 1.0 g of a metal material whose hydrophobicity was to be determined was added, and the mixture was shaken vigorously and allowed to stand. Then, the dispersed state of the metal material is observed. The completely hydrophobized metal material is stably dispersed in the n-heptane phase, and the incompletely hydrophobized metal material easily moves to the water layer.
＜実施例＞ 以下、実施例に基づいて本発明法を具体的に説明する。<Example> Hereinafter, the method of the present invention will be specifically described based on Examples.
実施例1. 厚さ0.3μ・平均直径20μのステンレスフレーク100重量
部をキシレン100重量部に分散させ、これにオルガチッ
クスSI310（松本製薬工業（株）製メチルシリルイソシ
アネートCH3Si（NCO）３）1.7重量部、を加え、90℃で3
0分反応させた。その後ブレンマーCP30（日本油脂
（株）製のグリシジルメタアクリレートとアクリル酸エ
ステルのラジカル共重合体で、エポキシ当量529）5.3重
量部（メチルシリルイソシアネート１モルに対し、１当
量）を添加し、更に90℃で30分攪拌し反応させた。その
後ステンレスフレークをロ別し、乾燥することにより表
面疎水性ステンレスフレークを得た。得られたステンレ
スフレークはｎ−ヘプタン／水系二層溶液中でｎ−ヘプ
タン中に分散した。Example 1 100 parts by weight of stainless flakes having a thickness of 0.3 μm and an average diameter of 20 μm were dispersed in 100 parts by weight of xylene, and added to Organix SI310 (Methylsilylisocyanate CH 3 Si (NCO) 3 manufactured by Matsumoto Pharmaceutical Co., Ltd.). ) 1.7 parts by weight, and add 3 at 90 ℃
The reaction was allowed for 0 minutes. After that, 5.3 parts by weight of Blemmer CP30 (a radical copolymer of glycidyl methacrylate and acrylic acid ester manufactured by NOF CORPORATION, an epoxy equivalent of 529) (1 equivalent to 1 mol of methylsilyl isocyanate) was added, and further 90 The mixture was stirred at 30 ° C for 30 minutes for reaction. Then, the stainless flakes were separated by filtration and dried to obtain surface-hydrophobic stainless steel flakes. The obtained stainless flakes were dispersed in n-heptane in an n-heptane / water bilayer solution.
このステンレスフレークをABS樹脂中に30％添加し、コ
ンパウンドを得た。このコンパウンドの破断面の走査型
電子顕微鏡観察では、樹脂とステンレスフレークの破断
面が巨視的な剥離試験における“接着が良好な場合”に
相当する界面破壊様式と凝集破壊様式が混在したような
状態であり、ステンレスフレークと樹脂が強固に結合し
たことを示していた。30% of this stainless steel flake was added to ABS resin to obtain a compound. Scanning electron microscope observation of the fracture surface of this compound showed that the fracture surface of resin and stainless flakes had a mixture of interfacial fracture mode and cohesive fracture mode corresponding to "when adhesion is good" in macroscopic peel test. It was shown that the stainless flakes and the resin were firmly bonded.
一方、ABS樹脂へ５％〜30％の範囲で段階的に添加量を
変えたコンパウンドを作り、射出成形により試片を作り
テストした結果、引張り強度、曲げ強度は添加量に比例
して増加し、本発明法による表面疎水性ステンレスフレ
ークと樹脂が強固に結合する事を示した。On the other hand, as a result of making a compound into ABS resin by gradually changing the addition amount in the range of 5% to 30% and making a test piece by injection molding and testing it, the tensile strength and bending strength increase in proportion to the addition amount. It was shown that the surface-hydrophobic stainless steel flakes and the resin were firmly bonded by the method of the present invention.
比較例1. 上記実施例２と同様のステンレスフレークをブレンマー
CP30を使用することなく、オルガチックスSI310のみで
表面処理した。得られたステンレスフレークはｎ−ヘプ
タン／水系二層溶剤中でｎ−ヘプタン側に分散した。し
かし、ABS樹脂中に10％添加し、実施例１と同様に顕微
鏡観察を行ったところ、界面破壊様式であり、表面処理
ステンレスとABS樹脂の結合が不十分であった。Comparative Example 1. The same stainless flakes as in Example 2 above were blended with a blemmer.
Surface treatment was performed only with Organix SI310 without using CP30. The obtained stainless flakes were dispersed on the n-heptane side in an n-heptane / water-based two-layer solvent. However, when 10% was added to the ABS resin and observed under a microscope in the same manner as in Example 1, it was an interfacial fracture mode, and the bonding between the surface-treated stainless steel and the ABS resin was insufficient.
＜発明の効果＞ 本発明法によれば、金属材料の表面疎水化を非常に高度
に達成することができる。<Effects of the Invention> According to the method of the present invention, it is possible to achieve extremely high degree of surface hydrophobization of a metal material.
このため本発明法で製造された表面疎水性金属材料は、
有機樹脂との混練性が強固で、有機樹脂の機械的強度の
強化、導電性の付与、磁気シールドなどの機能性付与材
料として広範囲に利用できる。Therefore, the surface hydrophobic metal material produced by the method of the present invention,
It has a strong kneadability with an organic resin and can be widely used as a material that enhances the mechanical strength of an organic resin, imparts conductivity, and imparts functionality such as a magnetic shield.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 遠藤 清司 千葉県市川市南八幡５丁目13番２号 松本 製薬工業株式会社内 (56)参考文献 特開 昭60−123561（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Kiyoji Endo 5-13-2 Minamihachiman, Ichikawa-shi, Chiba Matsumoto Pharmaceutical Industry Co., Ltd. (56) References JP-A-60-123561 (JP, A)
Claims (1)
リルイソシアネートで処理し、次いで得られたシリルイ
ソシアネート処理金属材料を、分子中にシラノール基、
水酸基、メルカプト基、アミノ基、エポキシ基、カルボ
キシル基からなる群から選ばれた少なくとも１個の基を
もつ疎水性化合物で処理することを特徴とする表面疎水
性金属材料の製造法。1. A surface of a metal material is treated with a silylisocyanate having a Si—NCO bond, and the obtained silylisocyanate-treated metal material is treated with a silanol group in the molecule.
A method for producing a surface-hydrophobic metallic material, which comprises treating with a hydrophobic compound having at least one group selected from the group consisting of a hydroxyl group, a mercapto group, an amino group, an epoxy group and a carboxyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61205466A JPH0668084B2 (en) | 1986-09-01 | 1986-09-01 | Manufacturing method of surface hydrophobic metal material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61205466A JPH0668084B2 (en) | 1986-09-01 | 1986-09-01 | Manufacturing method of surface hydrophobic metal material |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6042281A Division JP2561435B2 (en) | 1994-03-14 | 1994-03-14 | Manufacturing method of surface hydrophobic metal material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6361057A JPS6361057A (en) | 1988-03-17 |
| JPH0668084B2 true JPH0668084B2 (en) | 1994-08-31 |
Family
ID=16507329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61205466A Expired - Lifetime JPH0668084B2 (en) | 1986-09-01 | 1986-09-01 | Manufacturing method of surface hydrophobic metal material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0668084B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2705118B2 (en) * | 1988-06-28 | 1998-01-26 | 大日本インキ化学工業株式会社 | High brightness gravure ink |
| JPH02258855A (en) * | 1989-03-31 | 1990-10-19 | Idemitsu Kosan Co Ltd | Surface-treated inorganic filler and styrene resin composition |
| JP2530025B2 (en) * | 1989-05-12 | 1996-09-04 | 日本碍子株式会社 | Generation method of ruthenium tetroxide |
| JPH085992B2 (en) * | 1989-06-29 | 1996-01-24 | 積水ファインケミカル株式会社 | Colored fine particles and method for producing the same |
| EP0513690B1 (en) * | 1991-05-17 | 1997-02-26 | Asahi Glass Company Ltd. | Surface-treated substrate |
| JP3210045B2 (en) * | 1991-11-20 | 2001-09-17 | 旭硝子株式会社 | Surface treated substrate |
| JP2800558B2 (en) * | 1992-04-22 | 1998-09-21 | 富士ゼロックス株式会社 | Microcapsule toner for electrostatic image development and method of forming microcapsules |
| US5482768A (en) * | 1993-05-14 | 1996-01-09 | Asahi Glass Company Ltd. | Surface-treated substrate and process for its production |
| EP1661628A1 (en) * | 2004-11-25 | 2006-05-31 | Total Petrochemicals Research Feluy | Process for dispersing functional molecules on the surface of a support and support made by this process |
| US7998649B2 (en) * | 2008-03-03 | 2011-08-16 | Xerox Corporation | Grafting functionalized pearlescent or metallic pigment onto polyester polymers for special effect images |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60123561A (en) * | 1983-12-07 | 1985-07-02 | Kao Corp | Ceramic powder having modified surface |
-
1986
- 1986-09-01 JP JP61205466A patent/JPH0668084B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6361057A (en) | 1988-03-17 |
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