JPH0411624A - Epoxy resin powder containing inorganic particle and its production - Google Patents
Epoxy resin powder containing inorganic particle and its productionInfo
- Publication number
- JPH0411624A JPH0411624A JP2114432A JP11443290A JPH0411624A JP H0411624 A JPH0411624 A JP H0411624A JP 2114432 A JP2114432 A JP 2114432A JP 11443290 A JP11443290 A JP 11443290A JP H0411624 A JPH0411624 A JP H0411624A
- Authority
- JP
- Japan
- Prior art keywords
- inorganic particles
- epoxy resin
- particles
- composite
- composite granules
- 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
- 239000010954 inorganic particle Substances 0.000 title claims abstract description 82
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 43
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 43
- 239000000843 powder Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000002245 particle Substances 0.000 claims abstract description 65
- 239000012736 aqueous medium Substances 0.000 claims abstract description 13
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 10
- 239000008187 granular material Substances 0.000 claims description 63
- 239000002131 composite material Substances 0.000 claims description 55
- 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 claims description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 19
- 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 abstract description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 6
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000011246 composite particle Substances 0.000 description 6
- -1 amine compound Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000011146 organic particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000238557 Decapoda Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 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 3
- 239000006249 magnetic particle Substances 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000006247 magnetic powder Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 241000190021 Zelkova Species 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 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
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野］
本発明は、表面が親油化処理されている無機物粒子と硬
化したエポキシ樹脂とからなり、粒子サイズが広範囲に
亘って制御でき、且つ、無機物粒子の含有量が高い複合
体粒状物からなる無機物粒子含有エポキシ樹脂粒状物粉
体及びその製造法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention consists of inorganic particles whose surfaces have been treated to make them lipophilic and a hardened epoxy resin, and the particle size can be controlled over a wide range, and The present invention relates to an inorganic particle-containing epoxy resin granule powder made of a composite granule having a high content of inorganic particles, and a method for producing the same.
本発明に係る無機物粒子含有エポキシ樹脂粒状物粉体の
主な用途は、磁性キャリア、磁性トナー及び導電性磁性
粒子等の静電潜像現像剤用材料粉末、′Ｔ！ｊ、Ｍ１波
吸収材及び電磁波シールド材用材料粉末、ゴム、プラス
チック用着色材、充填材及び補強材並びにペンキ、絵具
及び接着剤用着色材、艶消材、充填材及び補強材等であ
る。The epoxy resin granule powder containing inorganic particles according to the present invention is mainly used as material powder for electrostatic latent image developers such as magnetic carriers, magnetic toners, and conductive magnetic particles, 'T! j, material powder for M1 wave absorbing materials and electromagnetic wave shielding materials, rubber, coloring materials, fillers and reinforcing materials for plastics, coloring materials for paints, pigments and adhesives, matte materials, fillers and reinforcing materials, etc.
近年、高度な性能や新規な機能を有する材料として異種
材料間における複合化がさかんに行われており、その一
つとして無機物粒子と有機高分子とからなる複合体粒状
物（以下、複合体粒状物という、）の研究、開発が種々
行われており、実用化されている。In recent years, composite granules (hereinafter referred to as composite granules) consisting of inorganic particles and organic polymers have been actively developed as materials with advanced performance and new functions. A variety of research and development activities have been carried out on (things) and have been put into practical use.
これら複合体粒状物は、無機物粒子として磁性粒子が用
いられる場合は、主として磁性キャリア、磁性トナー及
び導電性磁性粉体等の静電潜像現像剤用材料粉末として
、無機物粒子として着色顔料粒子が用いられる場合には
、主としてゴム、プラスチック用、ペンキ、絵具及び接
着剤用着色剤や艶消剤として使用されている。When magnetic particles are used as the inorganic particles, these composite granules are mainly used as material powder for electrostatic latent image developers such as magnetic carriers, magnetic toners, and conductive magnetic powders, and colored pigment particles are used as the inorganic particles. When used, it is mainly used as a coloring agent or matting agent for rubber, plastics, paints, paints, and adhesives.
上記いずれの分野においても複合体粒状物に共通して要
求される特性は、■用途に応じて、所ヱの大きさの複合
体粒状物の選択が可能となる様に粒子サイズが広範囲、
殊に、１〜１０００μｍの範囲に亘って制御できること
、■無機物粒子の緒特性及び諸機能を十分に発揮できる
欅に上記無機物粒子の含有量が可及的に高いことである
。The properties commonly required of composite granules in all of the above fields are: (1) A wide range of particle sizes so that it is possible to select a composite granule of the desired size depending on the application;
In particular, it is possible to control the particle diameter over a range of 1 to 1,000 μm, and (1) the content of the inorganic particles is as high as possible in Zelkova, which can fully exhibit the structural characteristics and various functions of the inorganic particles.
先ず、複合体粒状物の平均粒子径について言えば、従来
キャリア用材料粉末としては、特開平１２８２５６３号
公報の「・・・・キャリア粒子の粒径は、前記の現像剤
寿命と感光体キャリア付着及び画質とのバランス上から
、平均粒径２０〜４００ μｍ・・・・とするのが適当
であり・・・・」なる記載の通り、２０〜４００１１７
Ａ程度の複合体粒状物が、磁性トナー用材料粉末として
は、特開平１−１７２９７２号公報の「トナーの平均粒
径が２５μｍを超えると補給性が悪く画像がぼそついた
ものとなる。また５μｍ未満であるとクリーニング性及
び転写性が悪くなる。」なる記載の通り、５〜２５μｈ
程度の複合体粒状物が導電性磁性粉体としては、特開昭
５６−１４２５４０号公報の「導電性磁性粒子の体積平
均粒径は磁性トナー（５〜２５μ−程度）のそれの１７
５〜４１５程度であることが好ましく・・・・」なる記
載の通り、１〜２０μｍ程度の複合体粒状物が要求され
ている。First, regarding the average particle diameter of composite granules, as for conventional carrier material powder, the particle diameter of carrier particles is determined by the above-mentioned developer life and photoreceptor carrier adhesion. From the viewpoint of balance with image quality and image quality, it is appropriate to set the average particle size to 20 to 400 μm.
Composite particles of grade A are used as magnetic toner material powders as described in Japanese Patent Application Laid-open No. 1-172972, ``If the average particle size of the toner exceeds 25 μm, the replenishment property is poor and the image becomes blurred. If it is less than 5 μm, the cleaning performance and transfer performance will be poor.”, 5 to 25 μh
As a conductive magnetic powder, the conductive magnetic particles have a volume average particle diameter of about 17 μm compared to that of the magnetic toner (approximately 5 to 25 μ-
5 to 415 is preferable...'', composite granules with a diameter of about 1 to 20 μm are required.
また、複合体粒状物中に含まれる無機物粒子の含有量に
ついて言えば、特開昭６０−１８８４１９号公報の「エ
マルジョン重合法およびサスペンション重合法の場合の
もう一つの欠点は、粒子に無機質あるいは有機質粒子を
一般に多く配合できないことである。特に比重の重い無
機粒子を多量に配合することは困難で、このような粒子
の実現が望まれテイタ。」なる記載の通り、可及的に高
いことが要求される。Regarding the content of inorganic particles contained in composite granules, Japanese Patent Application Laid-Open No. 188419/1983 states, ``Another disadvantage of emulsion polymerization and suspension polymerization is that particles contain inorganic or organic particles. In general, it is not possible to mix large amounts of particles.In particular, it is difficult to mix large amounts of inorganic particles with heavy specific gravity, and it is desirable to realize such particles. required.
ところで、従来、有機高分子としては、大別して、ビニ
ル系、スチレン系、アクリル酸系樹脂などの熱可塑性樹
脂とフェノール系樹脂、メラミン系樹脂、エポキシ系樹
脂等の熱硬化性樹脂とが知られているが、複合体粒状物
を製造する為の樹脂としては一般に粒状化が容易な熱可
塑性樹脂が用いられており、粒状化が困難、特に、球状
粒子が得られにくい熱硬化性樹脂は用いられていなかっ
た。By the way, conventionally, organic polymers are broadly classified into thermoplastic resins such as vinyl, styrene, and acrylic resins, and thermosetting resins such as phenolic resins, melamine resins, and epoxy resins. However, thermoplastic resins, which are easy to granulate, are generally used as resins for manufacturing composite granules; thermosetting resins, which are difficult to granulate, and in particular, difficult to obtain spherical particles, are used. It wasn't.
一方、熱硬化性樹脂は、熱可塑性樹脂に比べ耐久性、耐
衝撃性、耐熱性に優れているので、これらの利点を生か
した無機物粒子と熱硬化性樹脂とからなる複合体粒状物
が強く要求されている。On the other hand, thermosetting resins have superior durability, impact resistance, and heat resistance compared to thermoplastic resins, so composite granules made of inorganic particles and thermosetting resins that take advantage of these advantages are highly durable. requested.
従来、無機物粒子と熱硬化性樹脂とからなる複合物を得
る方法としては、無機物粒子とエポキシ樹脂及び硬化剤
として作用するフェノール樹脂とからなる複合物を粉砕
する方法（特開昭５８−１２２７０５号公報）が知られ
ており、また、エポキシ樹脂を粒状化する方法としては
、乳化剤の助けにより未硬化エポキシエマルジョンを作
成し、該未硬化エポキシエマルジョンを硬化剤によって
硬化する方法（特開昭５３−７３２４９号公報）が知ら
れている。Conventionally, as a method for obtaining a composite consisting of inorganic particles and a thermosetting resin, a method of pulverizing a composite consisting of inorganic particles, an epoxy resin, and a phenol resin acting as a hardening agent (Japanese Patent Application Laid-open No. 122705/1983) has been proposed. Also, as a method of granulating an epoxy resin, a method of preparing an uncured epoxy emulsion with the help of an emulsifier and curing the uncured epoxy emulsion with a curing agent is known (Japanese Patent Application Laid-Open No. 1983-1999). 73249) is known.
更に、無機質または有機質粒子とエポキシ系樹脂とから
なる複合体粒状物を製造する方法としては、無Ｉｌ！ま
たは有機質粒子の存在下で、乳化剤の助けにより未硬化
エポキシエマルジョンを作成し、水溶性アミン系化合物
の硬化剤によって硬化する方法（特開昭６０〜１８８４
１９号公報）が知られている。Furthermore, as a method for producing a composite granular material consisting of inorganic or organic particles and an epoxy resin, there is no Il! Alternatively, a method of preparing an uncured epoxy emulsion with the help of an emulsifier in the presence of organic particles and curing it with a curing agent of a water-soluble amine compound (Japanese Patent Laid-Open No. 60-1884)
No. 19) is known.
〔発明が解決しようとする課題］
無機物粒子とエポキシ樹脂とからなり、粒子サイズが広
範囲に亘って制御でき、無機物粒子の含有量が可及的に
高い複合体粒状物は、現在量も要求されているところで
あるが、前出従来法による場合には、未だこのような複
合体粒状物は得られていない。[Problems to be Solved by the Invention] Composite granules consisting of inorganic particles and epoxy resin, whose particle size can be controlled over a wide range, and which have as high a content of inorganic particles as possible are currently in demand. However, such composite granules have not yet been obtained using the conventional method described above.
即ち、前出特開昭５８−１２２７０５号公報に記載の方
法による場合には、無機物粒子の含有蓋は高いものであ
るが、粒状化が困難である。That is, in the case of the method described in the above-mentioned Japanese Patent Application Laid-Open No. 58-122705, the content of inorganic particles is high, but granulation is difficult.
また、前出特開昭６０−１８８４１９号公報に記載の方
法による場合には、複合体粒状物の粒子サイズは０．５
〜１００μｍ程度であり、１００μｍを越える複合体粒
状物を得ることは困難であり、また、無機質又は有機質
粒子の含有量は高々７５重量％であり、含有量に限界が
あった。In addition, in the case of the method described in the above-mentioned Japanese Patent Application Laid-Open No. 60-188419, the particle size of the composite granules is 0.5
~100 μm, and it is difficult to obtain composite particles with a diameter exceeding 100 μm. Furthermore, the content of inorganic or organic particles is at most 75% by weight, which is a limit to the content.
更に、硬化したエポキシ系樹脂粒子は、樹脂に対して５
重量％、好ましくは、１０重量％以上の乳化剤の存在下
で製造される為、乳化剤が含まれている可能性が非常に
高く、その結果、複合体粒状物の帯電量が変動しやすく
なり、製品の品質面における問題が生起する。Furthermore, the cured epoxy resin particles have a ratio of 5% to the resin.
Since it is manufactured in the presence of an emulsifier of 10% by weight or more, it is very likely that the emulsifier is included, and as a result, the amount of charge of the composite granules tends to fluctuate. Problems arise in terms of product quality.
そこで、本発明は、無機物粒子とエポキシ樹脂とからな
り、粒子サイズが広範囲に亘って制御でき、且つ、無機
物粒子の含有量が可及的に高い複合体粒状物を乳化剤等
を使用することなく得ることを技術的課題とする。Therefore, the present invention aims to produce a composite granular material consisting of inorganic particles and an epoxy resin, whose particle size can be controlled over a wide range, and which has as high a content of inorganic particles as possible without using an emulsifier or the like. The technical challenge is to obtain
前記技術的課題は、次の通りの本発明によって達成でき
る。The above technical problem can be achieved by the present invention as follows.
即ち、本発明は、表面が親油化処理されている無機物粒
子と硬化したエポキシ樹脂とからなり、平均粒子径が１
〜１０００μ霧であって、前記無機物粒子の含有量が８
０〜９９重量％である複合体粒状物からなる無機物粒子
含有エポキシ樹脂粒状物粉体及び無機物粒子の存在下で
、ビスフェノール類とエピハロヒドリンとをアルカリ性
水性媒体中で反応硬化させるか、又は、未硬化エポキシ
樹脂を水性媒体中で硬化させて、無機物粒子と硬化した
エポキシ樹脂とからなる複合体粒状物を生産させるにあ
たり、前記無機物粒子として表面が親油化処理されてい
る無機物粒子を用いることよりなる表面が親油化処理さ
れている無機物粒子と硬化したエポキシ樹脂とからなり
、平均粒子径が１〜１０００μ論であって、前記無機物
粒子の含有量が８０〜９９重量％である複合体粒状物か
らなる無機物粒子含有エポキシ樹脂粒状物粉体の製造法
である。That is, the present invention consists of inorganic particles whose surfaces have been treated to make them lipophilic and a hardened epoxy resin, and whose average particle diameter is 1.
~1000 μm fog, and the content of the inorganic particles is 8
Bisphenols and epihalohydrin are reacted and cured in an alkaline aqueous medium in the presence of inorganic particle-containing epoxy resin granule powder and inorganic particles consisting of 0 to 99% by weight of composite granules, or uncured. In curing the epoxy resin in an aqueous medium to produce a composite granular material consisting of inorganic particles and the cured epoxy resin, inorganic particles whose surfaces have been treated to make them lipophilic are used as the inorganic particles. Composite granules consisting of inorganic particles whose surfaces have been subjected to lipophilic treatment and a hardened epoxy resin, having an average particle diameter of 1 to 1000 μm, and a content of the inorganic particles of 80 to 99% by weight. This is a method for producing epoxy resin granule powder containing inorganic particles.
先ず、本発明において最も重要な点は、無機物粒子の存
在下で、ビスフェノール類とエピハロヒドリンとをアル
カリ性水性媒体中で反応硬化させるか、又は、未硬化エ
ポキシ樹脂を水性媒体中で硬化させて、無機物粒子と硬
化したエポキシ樹脂とからなる複合体粒状物を生成させ
るにあたり、前記無機物粒子として表面が親油化処理さ
れている無機物粒子を用いた場合には、表面が親油化処
理されている無機物粒子と硬化したエポキシ樹脂とから
なり、平均粒子径が１〜１０００μＭであって、前記無
機物粒子の含有量が８０〜９９重量％である複合体粒状
物が得られるという事実である。First, the most important point in the present invention is to react and cure bisphenols and epihalohydrin in an alkaline aqueous medium in the presence of inorganic particles, or to cure an uncured epoxy resin in an aqueous medium to form an inorganic substance. In producing a composite granular material consisting of particles and a hardened epoxy resin, when inorganic particles whose surfaces have been treated to make them lipophilic are used as the inorganic particles, the inorganic particles whose surfaces have been treated to make them lipophilic are used. The fact is that composite granules are obtained which are composed of particles and a cured epoxy resin, have an average particle diameter of 1 to 1000 μM, and have an inorganic particle content of 80 to 99% by weight.
本発明における粒子サイズは、複合体粒状物の生成にあ
たって仕込まれる原料中の固形物濃度、無機物粒子に対
するエポキシ樹脂成分の割合並びに無機物粒子表面の親
油化の程度等により制御することができ、これらの値が
大きくなる程生成する複合体粒状物の粒子サイズは大き
くなる傾向にある。The particle size in the present invention can be controlled by the concentration of solids in the raw materials charged in the production of composite granules, the ratio of the epoxy resin component to the inorganic particles, the degree of lipophilization of the surface of the inorganic particles, etc. The larger the value of , the larger the particle size of the generated composite particles tends to be.
本発明において、無機物粒子の含有量が高い複合体粒状
物が得られる理由について、本発明者は、後出する比較
例に示す通り、無機物粒子の粒子表面が親油化処理され
ていない場合には、無機物粒子の含有量が制限されるこ
とから、無機物粒子の粒子表面が親油化処理されている
ことによるものと考えている。In the present invention, the reason why composite granules with a high content of inorganic particles can be obtained is that when the particle surface of the inorganic particles is not subjected to lipophilic treatment, as shown in the comparative example shown later, Since the content of inorganic particles is limited, it is believed that this is due to the fact that the particle surface of the inorganic particles has been subjected to a lipophilic treatment.
本発明において、乳化剤を用いなくてもよい理由につい
て、本発明者は、無機物粒子の表面が親油化されること
によって、反応初期生成物である未硬化エポキシ樹脂と
無機物粒子とからなる複合物の性状が非常にエマルジョ
ン化し易いものになっているためであろうと考えている
。In the present invention, the reason why it is not necessary to use an emulsifier is that the surface of the inorganic particles is made lipophilic, so that a composite consisting of an uncured epoxy resin, which is an initial product of the reaction, and inorganic particles. We believe that this is because the properties of the compound make it very easy to form an emulsion.
次に、本発明実施にあたっての諸条件について述べる。Next, various conditions for implementing the present invention will be described.
本発明における無機物粒子としては、水に溶解せず、ま
たは、水によって変質、変性しないものであればよく、
たとえば、マグネタイト粒子（ＦｅＯ・□Ｘ
・Ｆｅ２Ｏ３（０＜ｘ≦１））、マグヘマイト粒子、こ
れらにコバルトを被着させ又は含有させた粒子、ヘマタ
イト粒子、含水酸化第二鉄粒子、バリウム又はストロン
チウムを含むフェライト粒子並びにマンガン、ニッケル
亜鉛等から選ばれた金属のＩ種又は２種以上を含むスピ
ネル型フヱライト粒子等の鉄酸化物粒子や酸化チタン粒
子、シリカ粒子、タルク粒子、アルミナ粒子、硫酸バリ
ウム粒子、炭酸バリウム粒子、カドミウムイエロー粒子
、炭酸カルシウム粒子、亜鉛華粒子等が使用できる。The inorganic particles in the present invention may be any inorganic particles as long as they do not dissolve in water or are not altered or denatured by water.
For example, magnetite particles (FeO □ Iron oxide particles, titanium oxide particles, silica particles, talc particles, alumina particles, barium sulfate particles, such as spinel-type ferrite particles containing type I or two or more of metals selected from manganese, nickel-zinc, etc. , barium carbonate particles, cadmium yellow particles, calcium carbonate particles, zinc white particles, etc. can be used.
これら無機物粒子の粒子形態は、立方体状、多面体状、
球状、針状、板状等のいずれの形態の粒子をも使用する
ことができ、平均粒子径は、目的とする複合体粒状物の
平均粒子径よりも小さいものであれば使用できるが、０
．０１〜５．０μｍ、殊に、０．１〜２．０μ剛の範囲
のものが好ましい。The particle morphology of these inorganic particles is cubic, polyhedral,
Particles in any form, such as spherical, acicular, or plate-like, can be used as long as the average particle diameter is smaller than the average particle diameter of the desired composite granule.
．． A stiffness in the range of 0.01 to 5.0 μm, particularly 0.1 to 2.0 μm is preferred.
本発明における表面が親油化処理されている無機物粒子
は、無機物粒子と親油化処理剤とを単に混合する方法、
又は、無機物粒子と親油化処理剤とを水性溶媒体中で混
合して粒子表面に親油化処理剤を吸着させる方法等いず
れの方法によっても得ることができる。In the present invention, the inorganic particles whose surfaces have been subjected to a lipophilic treatment can be obtained by simply mixing the inorganic particles and a lipophilic treatment agent;
Alternatively, it can be obtained by any method such as a method in which inorganic particles and a lipophilic treatment agent are mixed in an aqueous medium and the lipophilic treatment agent is adsorbed onto the particle surface.
親油化処理剤としては、親油基を有するチタネート系、
シラン系等のカンプリング剤、シリル化剤、並びにシリ
コーンオイル等を使用することができ、殊に、エポキシ
樹脂と反応しうる官能基、０＼
（−ＮＨ，＋−Ｃ−ｃ等）を持つものは、複合体粒状物
自体の強度を高める等の効果を有する為好ましいもので
ある。As a lipophilic treatment agent, a titanate type having a lipophilic group,
Camping agents such as silanes, silylation agents, silicone oils, etc. can be used, especially those with functional groups that can react with epoxy resins, such as 0\ (-NH, +-C-c, etc.) This is preferable because it has the effect of increasing the strength of the composite granules themselves.
親油基を有するチタネート系カップリング剤としては、
イソプロピルトリイソステアロイルチタネート、イソプ
ロビルトリドデシルヘジインスルホニルチタ不一ト、イ
ソプロピルトリス（ジオクチルピロホスフェート）チタ
ネート、ビス（ジオクチルピロホスフェート）オキシア
セテートチタネート、ビス（ジオクチルピロホスフェー
ト）エチレンチタネート等が、親油基を有するシラン系
カンプリング剤としては、Ｎ−β （アミノエチル）Ｔ
−アミノプロルトリメトキシシラン、Ｎ−β（アミノエ
チル）Ｔ−アミノプロピルメチルジメトキシシラン、Ｔ
−アミノプロピルトリエトキシシラン、Ｎ−フェニル−
γ−アミノプロピルトリメトキシシラン、Ｔ−グリシド
キシプロピルメチルジェトキシシラン、β−（３，４エ
ポキシシクロヘキシル）エチルトリメトキシシラン（以
上は、エポキシ樹脂と反応しろる官能基を有するシラン
系カップリング剤である。）、ビニルトリクロロシラン
、ビニルトリエトキシシラン、ビニルトリス （βメト
キシエトキシ）シラン等が、シリル化剤としては、ヘキ
サメチルジシラザン、トリアルキルアルコキシシラン、
トリメチルエトキシシラン等が、シリコーンオイルとし
ては、ジメチルシリコーンオイル、メチル水素シリコー
ンオイル等が挙げられる。As a titanate coupling agent having a lipophilic group,
Isopropyl triisostearoyl titanate, isopropyl tridodecylhediyne sulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, bis(dioctyl pyrophosphate) ethylene titanate, etc. are lipophilic. As a silane camping agent having a group, N-β (aminoethyl)T
-aminoproltrimethoxysilane, N-β(aminoethyl)T-aminopropylmethyldimethoxysilane, T
-aminopropyltriethoxysilane, N-phenyl-
γ-aminopropyltrimethoxysilane, T-glycidoxypropylmethyljethoxysilane, β-(3,4epoxycyclohexyl)ethyltrimethoxysilane (the above are silane-based couplings having a functional group that reacts with an epoxy resin) ), vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, etc., and silylating agents include hexamethyldisilazane, trialkylalkoxysilane,
Examples of the silicone oil include trimethylethoxysilane and the like, and examples of the silicone oil include dimethyl silicone oil and methyl hydrogen silicone oil.
親油化処理剤による処理蓋は、無機物粒子に対し０．１
〜５．０重量％である。The lid treated with a lipophilic treatment agent has a 0.1
~5.0% by weight.
０．１重量％未満の場合には、親油化処理が不十分なた
めに、本発明の目的とする無機物粒子の含有量が高い複
合体粒状物を得ることができない。If it is less than 0.1% by weight, the lipophilization treatment will be insufficient, making it impossible to obtain composite granules with a high content of inorganic particles, which is the object of the present invention.
５．０重量％を越える場合には、親油化の度合が大きす
ぎるために、生成した複合体粒状物同志の粘着力が増加
して複合体粒状物の凝集が生し、大きな１個の塊となる
ので、複合体粒状物の粒子サイズの制御が困難となる。If it exceeds 5.0% by weight, the degree of lipophilization is too large, and the adhesion between the formed composite particles increases, resulting in agglomeration of the composite particles, resulting in the formation of one large piece. This makes it difficult to control the particle size of the composite granules.
本発明におけるビスフェノール類としては、ビスフェノ
ールＡ１ビフエノールＦ１ビスフエノールＳ、レゾルシ
ン等フェノール性水素基を２個以上有する化合物を使用
することができる。経済性の面からビスフェノールＡが
好ましい。As the bisphenols in the present invention, compounds having two or more phenolic hydrogen groups, such as bisphenol A, biphenol F, bisphenol S, and resorcinol, can be used. Bisphenol A is preferred from the economic point of view.
ビスフェノール類の使用量は無機物粒子に対し０．５〜
２５重量％である。The amount of bisphenols used is 0.5 to inorganic particles.
It is 25% by weight.
０．５重量％未満の場合には、生成するエポキシ樹脂の
量が無機物粒子に対して不十分となる為に、複合体粒状
物を得ることが困難となる。If it is less than 0.5% by weight, the amount of epoxy resin produced will be insufficient relative to the inorganic particles, making it difficult to obtain composite granules.
２５重量％を越える場合には、生成するエポキシ樹脂の
量が無機物粒子に対して過剰となり、本発明の目的とす
る無機物粒子の含有量が高い複合体粒状物を得ることが
出来ない。また、複合体粒状物同志の凝集が起こりやす
くなり、複合体粒状物の粒子サイズの制御が困難となる
。If it exceeds 25% by weight, the amount of epoxy resin produced will be excessive relative to the inorganic particles, making it impossible to obtain composite granules with a high content of inorganic particles, which is the object of the present invention. In addition, agglomeration of the composite granules tends to occur, making it difficult to control the particle size of the composite granules.
本発明におけるエビハロヒドリンとしては、エピクロル
ヒドリン、エビブロムヒドリン、エビヨードヒドリン等
を使用することができ、エピクロルヒドリンが好ましい
。As the shrimp halohydrin in the present invention, epichlorohydrin, shrimp bromohydrin, shrimp iodohydrin, etc. can be used, and epichlorohydrin is preferable.
エピハロヒドリンの使用量は、無機物粒子に対し０，３
〜２０重量％である。The amount of epihalohydrin used is 0.3 to inorganic particles.
~20% by weight.
０，３重量％未満の場合には、生成するエポキシ樹脂の
量が無機物粒子に対して不十分となる為、複合体粒状物
を得ることが困難となる。If it is less than 0.3% by weight, the amount of epoxy resin produced will be insufficient relative to the inorganic particles, making it difficult to obtain composite granules.
２０！１％を越える場合には、生成するエポキシ樹脂の
量が無機物粒子に対して過剰となり、本発明の目的とす
る無機物粒子の含有量が高い複合体粒状物を得ることが
出来ない。また、複合体粒状物同志の凝集が起こりやす
くなり、複合体粒状物の粒子サイズの制御が困難となる
。If it exceeds 20!1%, the amount of epoxy resin produced will be excessive relative to the inorganic particles, making it impossible to obtain composite granules with a high content of inorganic particles, which is the object of the present invention. In addition, agglomeration of the composite granules tends to occur, making it difficult to control the particle size of the composite granules.
本発明におけるビスフェノール類とエピハロヒドリンと
の使用割合は、モル比で０．５〜１．０ ：１．０であ
る。The molar ratio of bisphenols and epihalohydrin in the present invention is 0.5 to 1.0:1.0.
０．５ 未満の場合には、余剰のエピハロヒドリンに起
因する反応副生物等の影響により粒状化が困難となる。If it is less than 0.5, granulation becomes difficult due to the influence of reaction by-products caused by excess epihalohydrin.
１．０を越える場合には、硬化速度が早くなり、複合体
粒状物が得られ難く、得られたとしても粒度分布の拡が
りが大きくなる。If it exceeds 1.0, the curing speed will be too fast, making it difficult to obtain composite particles, and even if they are obtained, the particle size distribution will be widened.
本発明におけるアルカリ性水性媒体は、水酸化ナトリウ
ム、水酸化カリウム等のアルカリを水に添加することに
よって得られる。The alkaline aqueous medium in the present invention is obtained by adding an alkali such as sodium hydroxide or potassium hydroxide to water.
本発明における反応は、無機物粒子とビスフェノール類
及びエピハロヒドリンとを含むアルカリ性水性媒体を硬
化剤の存在下で攪拌しながら６０〜９０°Ｃの範囲の温
度まで昇温し、約１〜５時間重合反応を進行させるか、
又は、無機物粒子と未硬化エポキシ樹脂とを含む水性媒
体中で硬化剤の存在下で攪拌しながら、６０〜９０°Ｃ
の範囲の温度まで昇温し、約１〜８時間硬化反応を進行
させることによって行われる。The reaction in the present invention involves heating an alkaline aqueous medium containing inorganic particles, bisphenols, and epihalohydrin to a temperature in the range of 60 to 90°C while stirring in the presence of a curing agent, and polymerizing for about 1 to 5 hours. or proceed with
Alternatively, at 60 to 90°C while stirring in the presence of a curing agent in an aqueous medium containing inorganic particles and uncured epoxy resin.
The curing reaction is carried out by raising the temperature to a temperature in the range of 1 to 8 hours.
硬化剤としては、一般にエポキシ樹脂の硬化剤として広
く知られている、例えば、酸無水物、アミン類を使用す
ることができる。As the curing agent, for example, acid anhydrides and amines, which are generally widely known as curing agents for epoxy resins, can be used.
未硬化エポキシ樹脂としては、ビスフェノールへの両末
端グリシジルエーテル、ポリエチレングリコールの両末
端グリシジルエーテル等の分子内に２個以上のエポキシ
基を有するエポキシ系化合物が使用出来る。As the uncured epoxy resin, epoxy compounds having two or more epoxy groups in the molecule can be used, such as glycidyl ether at both ends of bisphenol and glycidyl ether at both ends of polyethylene glycol.
本発明において、アルカリ性水性媒体中又は水性媒体中
に生成した複合粒状物は、濾過、遠心分離等の通常の方
法によって固液分離し、次いで、水洗後加熱乾燥すれば
よい。In the present invention, the composite granules produced in or in an alkaline aqueous medium may be subjected to solid-liquid separation by a conventional method such as filtration or centrifugation, and then washed with water and then heated and dried.
（実施例〕 次に、実施例並びに比較例により、本発明を説明する。(Example〕 Next, the present invention will be explained with reference to Examples and Comparative Examples.
尚、以下の実施例並びに比較例における数平均粒子径は
、レーザ回折式粒度分布計（板場製作所■製）により計
測した値で示し、また、複合体粒状物の粒子形態は、走
査型電子顕微鏡Ｓ−８００（■日立製作断裂）で観察し
たものである。The number average particle diameters in the following Examples and Comparative Examples are shown as values measured using a laser diffraction particle size distribution analyzer (manufactured by Itaba Seisakusho ■). Observation was made using a microscope S-800 (*Tear made by Hitachi).
飽和磁化は、振動試料型磁力計ＶＳＭ−３５−１５（東
英工業■製）を用いて、外部磁場１０ＫＯｅのもとで測
定した値で示した。The saturation magnetization was expressed as a value measured under an external magnetic field of 10 KOe using a vibrating sample magnetometer VSM-35-15 (manufactured by Toei Kogyo ■).
複合体粒状物における無機物粒子の含有量は、複合体粒
状物の真比重をマルチボリウム密度計（マイクロメティ
クス社製）を用いて測定し、この比重の大きさから計算
によって算出した値で示した。The content of inorganic particles in the composite granules is determined by measuring the true specific gravity of the composite granules using a multivolume densitometer (manufactured by Micrometics), and is calculated from the magnitude of this specific gravity. Ta.
実施例１
５００ ｄの４つロフラスコに、水５０ｄ、水酸化ナト
リウム５．５０ｇ 、ビスフェノールＡ ２０ｇ、エピ
クロルヒドリン１０ｇ、無水フタル酸２．０ｇ及び粒子
表面が０．５重量％のシランカップリング剤ＫＢＭ ６
０２（信越化学■製）で被覆されているマグネタイト粒
子（平均粒子径０．２４μ＋ｗ ）２００ｇを投入し、
攪拌した。Example 1 In a 500 d four Lough flask, 50 d of water, 5.50 g of sodium hydroxide, 20 g of bisphenol A, 10 g of epichlorohydrin, 2.0 g of phthalic anhydride, and a silane coupling agent KBM 6 with a particle surface of 0.5% by weight were added.
200 g of magnetite particles (average particle size 0.24μ + w) coated with 02 (manufactured by Shin-Etsu Chemical) were added,
Stirred.
１．０〜１．５°Ｃ／分の速度で８０°Ｃまで昇温した
後、同温度で１．５時間撹拌を続けて複合体粒状物の生
成を行った。After raising the temperature to 80°C at a rate of 1.0 to 1.5°C/min, stirring was continued at the same temperature for 1.5 hours to produce composite granules.
次に、フラスコ内の内容物を炉別した後、水洗、乾燥し
て複合体粒状物を得た。Next, the contents in the flask were separated in a furnace, washed with water, and dried to obtain composite granules.
得られた複合体粒状物は、数平均粒子径が３６．６μＭ
であり、図１に示す走査型電子顕微鏡写真（ｘ １５０
０）に示す通り、真珠に近い形状を呈していた。The obtained composite granules had a number average particle diameter of 36.6 μM.
The scanning electron micrograph shown in Figure 1 (x 150
As shown in 0), it had a shape similar to a pearl.
また、マグネタイト粒子の含有量は、８６．６重量％で
あって、飽和磁化は７３．６ｅｍｕ／ｇであった。Further, the content of magnetite particles was 86.6% by weight, and the saturation magnetization was 73.6 emu/g.
実施例２〜１７、比較例１〜２
無機物粒子の種類、ビスフェノールの量、エピクロルヒ
ドリンの量、水酸化ナトリウムの量、硬化剤の種類及び
量並びに水の量を種々変化させた以外は、実施例１と同
様にして複合体粒状物の生成を行った。実施例２乃至１
７の各実施例により、複合体粒状物Ｂ乃至Ｑを得た。Examples 2 to 17, Comparative Examples 1 to 2 Examples except that the type of inorganic particles, the amount of bisphenol, the amount of epichlorohydrin, the amount of sodium hydroxide, the type and amount of curing agent, and the amount of water were varied. Composite granules were produced in the same manner as in Example 1. Examples 2 to 1
Composite granules B to Q were obtained according to each of Examples No. 7.
実施例２、実施例３、実施例５及び実施例ｉｏで得られ
た複合体粒状物は、それぞれ、図２乃至図４及び図６の
走査型電子顕微鏡写真（Ｘ １５００）に示す通り、球
状を呈していた。また、実施例６で得られた複合体粒状
物は、図５の走査型電子顕微鏡写真（ｘ ３００００）
に示す通り、球状を呈していた。The composite granules obtained in Example 2, Example 3, Example 5, and Example io were spherical, as shown in the scanning electron micrographs (X 1500) of FIGS. 2 to 4 and 6, respectively. It was exhibiting. In addition, the composite granules obtained in Example 6 are shown in the scanning electron micrograph (x 30000) in FIG.
As shown, it had a spherical shape.
この時の主要製造条件を表１に、複合体粒状物の緒特性
を表２に示す。The main manufacturing conditions at this time are shown in Table 1, and the properties of the composite granules are shown in Table 2.
比較例１及び２で得られた生成物は、電子顕微鏡観察の
結果、無機物粒子と樹脂とが分離した混合物であった。As a result of electron microscopic observation, the products obtained in Comparative Examples 1 and 2 were mixtures in which inorganic particles and resin were separated.
尚、親油化剤として用いたｒ）［ＢＥ ４０３ Ｊ及び
ｒＫＢＥ ９０３ Ｊは、いずれも信越化学■製のシラ
ンカップリング剤であり、また、［プレンアクトＴＴＳ
」は味の素■製のチタネート系カップリング剤である。Note that r)[BE 403 J and rKBE 903 J used as lipophilic agents are both silane coupling agents manufactured by Shin-Etsu Chemical ■, and [Plenact TTS
” is a titanate coupling agent manufactured by Ajinomoto ■.
実施例１８
５００ ｄの４つロフラスコに、水８０蛙、未硬化エポ
キシ樹脂 ＥＰＩＣＬＯ）Ｉ ８５０ （大日本イン
キ化学工業■製） ３２ｇ 、ピペリジン３．Ｏｇ及び
粒子表面が１゜０重量％のシランカップリング剤 ＫＢ
Ｅ９０３（信越化学■製）で被覆されているマグネタイ
ト粒子（平均粒径０，２３μｍ ） ２５０ｇを投入し
、攪拌した。Example 18 Into four 500 d flasks, 80 g of water, 32 g of uncured epoxy resin EPICLO) I 850 (manufactured by Dainippon Ink & Chemicals), and 3.0 g of piperidine. Silane coupling agent with Og and particle surface of 1゜0% by weight KB
250 g of magnetite particles (average particle size: 0.23 μm) coated with E903 (manufactured by Shin-Etsu Chemical Co., Ltd.) were added and stirred.
１．５°Ｃ／分の速度で８０まで昇温した後、同温度で
３．０時間攪拌を続けて複合体粒状物の作成を行い、実
施例１と同様にして複合体粒状物を得た。After raising the temperature to 80 °C at a rate of 1.5 ° C / min, stirring was continued at the same temperature for 3.0 hours to create a composite granule, and the composite granule was obtained in the same manner as in Example 1. Ta.
得られた粒状物は数平均粒子径が２６，５μ翔であり、
走査型電子顕微鏡観察の結果、球状を呈しており、マグ
ネタイトの含有率は８７゜２重量％であった。また、飽
和磁化は７４．Ｏｅｍｕ／ｇであった。The obtained granules had a number average particle diameter of 26.5μ,
As a result of observation using a scanning electron microscope, it was found to have a spherical shape, and the magnetite content was 87.2% by weight. Also, the saturation magnetization is 74. It was Oemu/g.
ＬＸ１５００ノ
〔発明の効果〕
本発明に係る無機物粒子含有エポキシ樹脂粒状物粉体は
、表面が親油化処理されている無機物粒子とエポキシ樹
脂とからなり、粒子サイズが広範囲に亘って制御でき、
無機物粒子の含有量が高いものである。LX1500 [Effects of the Invention] The inorganic particle-containing epoxy resin granule powder according to the present invention is composed of inorganic particles whose surfaces have been treated to make them lipophilic and an epoxy resin, and the particle size can be controlled over a wide range.
It has a high content of inorganic particles.
また、本発明に係る無機物粒子含有エポキシ樹脂粒状物
粉体は、乳化剤を含まないので、帯電量の変動がないた
め、製品の品質面の問題が生起することがなく、また、
耐久性、耐衝撃性、耐熱性においても優れている。Furthermore, since the inorganic particle-containing epoxy resin granule powder according to the present invention does not contain an emulsifier, there is no change in the amount of charge, so there is no problem in product quality.
It also has excellent durability, impact resistance, and heat resistance.
図１乃至図６は、それぞれ、実施例１、実施例２、実施
例３、実施例５、実施例６並びに実施例１０で得られた
複合体粒状物の粒子構造を示す走査型電子顕微鏡写真で
ある。
特許出馴人
戸田工業株式会社
一ハ
ＣＸ／！；ＤＯ）
ＧＯ３Ｇ1 to 6 are scanning electron micrographs showing the particle structure of the composite granules obtained in Example 1, Example 2, Example 3, Example 5, Example 6, and Example 10, respectively. It is. Patent expert Toda Kogyo Co., Ltd. Ichiha CX/! ;DO) GO3G
Claims (2)
たエポキシ樹脂とからなり、数平均粒子径が１〜１００
０μｍであって、前記無機物粒子の含有量が８０〜９９
重量％である複合体粒状物からなる無機物粒子含有エポ
キシ樹脂粒状物粉体。(1) Consists of inorganic particles whose surface has been treated to make them lipophilic and a hardened epoxy resin, and has a number average particle diameter of 1 to 100.
0 μm, and the content of the inorganic particles is 80 to 99
% by weight of an epoxy resin granule powder containing inorganic particles consisting of a composite granule.
ハロヒドリンとをアルカリ性水性媒体中で反応硬化させ
るか、又は、未硬化エポキシ樹脂を水性媒体中で硬化さ
せて、無機物粒子と硬化したエポキシ樹脂とからなる複
合体粒状物を生成させるにあたり、前記無機物粒子とし
て表面が親油化処理されている無機物粒子を用いること
を特徴とする請求項１記載の無機物粒子含有エポキシ樹
脂粒状物粉体の製造法。(2) In the presence of inorganic particles, bisphenols and epihalohydrin are reacted and cured in an alkaline aqueous medium, or uncured epoxy resin is cured in an aqueous medium, and the inorganic particles and the cured epoxy resin are combined. The method for producing an epoxy resin granule powder containing inorganic particles according to claim 1, characterized in that in producing the composite granular material, inorganic particles whose surfaces have been subjected to lipophilic treatment are used as the inorganic particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2114432A JP2814007B2 (en) | 1990-04-27 | 1990-04-27 | Epoxy resin granular material powder containing inorganic particles and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2114432A JP2814007B2 (en) | 1990-04-27 | 1990-04-27 | Epoxy resin granular material powder containing inorganic particles and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0411624A true JPH0411624A (en) | 1992-01-16 |
| JP2814007B2 JP2814007B2 (en) | 1998-10-22 |
Family
ID=14637572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2114432A Expired - Fee Related JP2814007B2 (en) | 1990-04-27 | 1990-04-27 | Epoxy resin granular material powder containing inorganic particles and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08283604A (en) * | 1995-04-10 | 1996-10-29 | Merck Japan Kk | Surface treating agent, surface-treated flaky pigment and its production |
| WO1998014962A1 (en) * | 1996-09-30 | 1998-04-09 | Tokin Corporation | Compound magnetic material and electromagnetic interference suppressor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08283604A (en) * | 1995-04-10 | 1996-10-29 | Merck Japan Kk | Surface treating agent, surface-treated flaky pigment and its production |
| WO1998014962A1 (en) * | 1996-09-30 | 1998-04-09 | Tokin Corporation | Compound magnetic material and electromagnetic interference suppressor |
| US6051156A (en) * | 1996-09-30 | 2000-04-18 | Tokin Corporation | Compound magnetic material and electromagnetic interference suppressor |
| US6156172A (en) * | 1997-06-02 | 2000-12-05 | Sadao Kadkura | Facing target type sputtering apparatus |
| US6794278B2 (en) | 2001-05-14 | 2004-09-21 | Junji Kido | Method for producing organic thin-film device by use of facing-targets-type sputtering apparatus |
| JP2003073558A (en) * | 2001-09-04 | 2003-03-12 | Mitsui Chemicals Inc | Composition comprising metal oxide ultramicroparticle and polymer |
| JP4499962B2 (en) * | 2001-09-04 | 2010-07-14 | 三井化学株式会社 | Composition of metal oxide ultrafine particles and polymer |
| JP2009209367A (en) * | 2008-03-03 | 2009-09-17 | Xerox Corp | Pigment particle, developer, and method for producing pigment particle |
| WO2013024740A1 (en) | 2011-08-12 | 2013-02-21 | 堺化学工業株式会社 | Coated magnesium oxide particles, method for producing same, heat-dissipating filler, and resin composition |
| JP2013056816A (en) * | 2011-08-12 | 2013-03-28 | Sakai Chem Ind Co Ltd | Coated magnesium oxide particles, method for producing the same, heat-dissipating filler, and resin composition |
| CN103648982A (en) * | 2011-08-12 | 2014-03-19 | 堺化学工业株式会社 | Coated magnesium oxide particles, method for producing same, heat-dissipating filler, and resin composition |
| EP2743233A4 (en) * | 2011-08-12 | 2015-04-01 | Sakai Chemical Industry Co | Coated magnesium oxide particles, method for producing same, heat-dissipating filler, and resin composition |
| US9340661B2 (en) | 2011-08-12 | 2016-05-17 | Sakai Chemical Industry Co., Ltd. | Coated magnesium oxide particles, method for the production thereof, heat-releasing filler, and resin composition |
| GB2531668B (en) * | 2013-07-18 | 2020-05-13 | Somar Corp | Magnetic powder, magnetic-powder composition, magnetic powder composition molded product, and methods of producing same |
| US11004582B2 (en) | 2013-07-18 | 2021-05-11 | Somar Corporation | Molded product of magnetic powder composition comprising magnetic powder of surface-treated magnetite particles, and methods of producing thereof |
| CN109880171A (en) * | 2019-03-07 | 2019-06-14 | 武汉理工大学 | Have effects that toughening and reduces the double epoxy resin additive of solidification temperature and its preparation, application method |
| CN109880171B (en) * | 2019-03-07 | 2021-03-23 | 武汉理工大学 | Epoxy resin additive with double effects of toughening and curing temperature reduction and preparation and use methods thereof |
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|---|---|
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