JPH03269020A - Production of silsesqueoxane globular fine powder containing acryloxy group and mercapto group - Google Patents
Production of silsesqueoxane globular fine powder containing acryloxy group and mercapto groupInfo
- Publication number
- JPH03269020A JPH03269020A JP6906190A JP6906190A JPH03269020A JP H03269020 A JPH03269020 A JP H03269020A JP 6906190 A JP6906190 A JP 6906190A JP 6906190 A JP6906190 A JP 6906190A JP H03269020 A JPH03269020 A JP H03269020A
- Authority
- JP
- Japan
- Prior art keywords
- group
- fine powder
- mercapto
- silsesquioxane
- formula
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 34
- -1 acryloxy group Chemical group 0.000 title claims abstract description 31
- 125000003396 thiol group Chemical group [H]S* 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- MOVRCMBPGBESLI-UHFFFAOYSA-N prop-2-enoyloxysilicon Chemical compound [Si]OC(=O)C=C MOVRCMBPGBESLI-UHFFFAOYSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 16
- 239000007864 aqueous solution Substances 0.000 abstract description 11
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 239000004033 plastic Substances 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract description 6
- 150000004756 silanes Chemical class 0.000 abstract description 4
- 230000001050 lubricating effect Effects 0.000 abstract description 2
- 239000007859 condensation product Substances 0.000 abstract 2
- QWHHBVWZZLQUIH-UHFFFAOYSA-N 2-octylbenzenesulfonic acid Chemical compound CCCCCCCCC1=CC=CC=C1S(O)(=O)=O QWHHBVWZZLQUIH-UHFFFAOYSA-N 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 22
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000010419 fine particle Substances 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 9
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 4
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 4
- 229940043264 dodecyl sulfate Drugs 0.000 description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XYPTZZQGMHILPQ-UHFFFAOYSA-N 2-methyl-6-trimethoxysilylhex-1-en-3-one Chemical compound CO[Si](OC)(OC)CCCC(=O)C(C)=C XYPTZZQGMHILPQ-UHFFFAOYSA-N 0.000 description 1
- JNQGZKQFQNENTC-UHFFFAOYSA-N 2-methyl-7-trimethoxysilylhept-1-en-3-one Chemical compound CO[Si](OC)(OC)CCCCC(=O)C(C)=C JNQGZKQFQNENTC-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
- LMAFAQBMCIYHQS-UHFFFAOYSA-N 4-trimethoxysilylbutane-1-thiol Chemical compound CO[Si](OC)(OC)CCCCS LMAFAQBMCIYHQS-UHFFFAOYSA-N 0.000 description 1
- HDSQGILQHJLCFA-UHFFFAOYSA-N 5-trimethoxysilylpentane-1-thiol Chemical compound CO[Si](OC)(OC)CCCCCS HDSQGILQHJLCFA-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WXZRYJJFFLDKBW-UHFFFAOYSA-N C(C)(=O)O.IBr Chemical compound C(C)(=O)O.IBr WXZRYJJFFLDKBW-UHFFFAOYSA-N 0.000 description 1
- QJJITLHOOAHJLQ-UHFFFAOYSA-N OS(=O)(=O)c1ccccc1[SiH3] Chemical compound OS(=O)(=O)c1ccccc1[SiH3] QJJITLHOOAHJLQ-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZUBJEHHGZYTRPH-KTKRTIGZSA-N [(z)-octadec-9-enyl] hydrogen sulfate Chemical compound CCCCCCCC\C=C/CCCCCCCCOS(O)(=O)=O ZUBJEHHGZYTRPH-KTKRTIGZSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229940080284 cetyl sulfate Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 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
- LPTIRUACFKQDHZ-UHFFFAOYSA-N hexadecyl sulfate;hydron Chemical compound CCCCCCCCCCCCCCCCOS(O)(=O)=O LPTIRUACFKQDHZ-UHFFFAOYSA-N 0.000 description 1
- IDUWTCGPAPTSFB-UHFFFAOYSA-N hexyl hydrogen sulfate Chemical compound CCCCCCOS(O)(=O)=O IDUWTCGPAPTSFB-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- NIQQIJXGUZVEBB-UHFFFAOYSA-N methanol;propan-2-one Chemical compound OC.CC(C)=O NIQQIJXGUZVEBB-UHFFFAOYSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- VXNSQGRKHCZUSU-UHFFFAOYSA-N octylbenzene Chemical compound [CH2]CCCCCCCC1=CC=CC=C1 VXNSQGRKHCZUSU-UHFFFAOYSA-N 0.000 description 1
- FURYAADUZGZUGQ-UHFFFAOYSA-N phenoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 FURYAADUZGZUGQ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はアクリロキシ基、メルカプト基含有シルセスキ
オキサン球状微粉末の製造方法、特には自由流動性がす
ぐれており、これを配合したプラスチック、ゴムなどの
特性が損なわれることがないことから、潤滑性、撥水性
、離型性、応力緩和性などの付与剤として有用であり、
これらの特性の耐久性が期待されるアクリロキシ基、メ
ルカプト基含有シルセスキオキサン球状微粉末の製造方
法に関するものである。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for producing a spherical fine powder of silsesquioxane containing acryloxy groups and mercapto groups, and particularly a method for producing a spherical fine powder of silsesquioxane containing an acryloxy group and a mercapto group. Since it does not impair the properties of rubber, it is useful as an agent that imparts lubricity, water repellency, mold release properties, stress relaxation properties, etc.
The present invention relates to a method for producing a spherical fine powder of silsesquioxane containing an acryloxy group and a mercapto group, which is expected to have the durability of these properties.
（従来の技術）
ポリメチルシルセスキオキサン微粉末は自由流動性がす
ぐれていることからプラスチック、ゴム、塗料、インク
、化粧品などの分野における潤滑性、撥水性、防汚性、
離型性付与剤として、また応力緩和向上剤として広く使
用されている。(Prior art) Polymethylsilsesquioxane fine powder has excellent free-flowing properties, so it is used for lubricity, water repellency, stain resistance, and water repellency in fields such as plastics, rubber, paints, inks, and cosmetics.
It is widely used as a release property imparting agent and as a stress relaxation improver.
また、このポリメチルシルセスキオキサン粉末は形状が
球状であることから、合成樹脂の充填剤または添加剤と
して、例えば合成樹脂フィルム、紙などのすべり性付与
や離型性付与剤として用いられており、特に粒径分布が
極めて狭いことから塗料などのように薄膜の厚さが厳し
く管理されるよな用途に適するものとされている。In addition, since this polymethylsilsesquioxane powder has a spherical shape, it is used as a filler or additive for synthetic resins, for example, as an agent for imparting slipperiness and release properties to synthetic resin films, paper, etc. In particular, because the particle size distribution is extremely narrow, it is said to be suitable for applications where the thickness of a thin film is strictly controlled, such as in paints.
（発明が解決しようとする課Ｉ！り
しかし、このポリメチルシルセスキオキサンも上記した
ような諸特性を付与する目的でプラスチック、ゴムなど
に配合すると、ポリメチルシルセスキオキサンとプラス
チック、ゴムとの間に親和性がないためにプラスチック
、ゴムなどの特性が損なわれることがあり、またこれら
に付与される諸特性も十分な耐久性をもつものにならな
いという不利がある。(The problem that the invention aims to solve!) However, when this polymethylsilsesquioxane is blended into plastics, rubber, etc. for the purpose of imparting the above-mentioned properties, polymethylsilsesquioxane and plastics, rubber, etc. There is a disadvantage that the properties of plastics, rubbers, etc. may be impaired due to the lack of affinity between them, and the properties imparted to them may not have sufficient durability.
そのため、ポリメチルシルセスキオキサン微粉末にベー
ス材となるプラスチック、ゴムなどとの親和性の良好な
官能基、例えばエポキシ基、ビニル基などを導入するも
提案されており（特願平１−３１９４８号、特願平１−
９８４２２号明細書参照）、このような官能基含有ポリ
メチルシルセスキオキサンは一般に目的とする組成に対
応するアルコキシシラン類を塩基性触媒の存在下で加水
分解するという方法で製造されているが、アクリロキシ
基またはメルカプト基の導入についての例は報告されて
いない。Therefore, it has been proposed to introduce functional groups, such as epoxy groups and vinyl groups, which have good affinity with plastics, rubbers, etc. that serve as base materials into the polymethylsilsesquioxane fine powder (Japanese Patent Application No. No. 31948, patent application No. 1-
98422), such functional group-containing polymethylsilsesquioxanes are generally produced by a method in which alkoxysilanes corresponding to the desired composition are hydrolyzed in the presence of a basic catalyst. , no examples have been reported regarding the introduction of acryloxy groups or mercapto groups.
また、オレフィン系樹脂、アクリル樹脂などのようなラ
ジカル反応性樹脂や５ＢＲＳＮＢＲなどのようなイオウ
を用いて加硫されるゴム製品などに、アクリロキシ基や
メルカプト基などを含有するポリメチルシルセスキオキ
サン粉末を添加して、その特性を向上させることも期待
されているが、これについてはこれらの官能基を有する
ポリメチルシルセスキオキサンをこれに対応するシラン
またはその混合物のアルカリ触媒を用いる加水分解によ
って製造しようとしても、これらの官能基がアルカリ触
媒の作用によって変賀してしまうために所定量の官能基
を有する粉末を得ることができず、アルカリ触媒の代わ
りに酸性触媒を用いる場合には粗大なゲルが大量に発生
するために樹脂の特性向上に有用とされる均質な球状粉
末を得ることができず、したがってこれについては未だ
に充分な検討が行なわれていない。In addition, polymethylsilsesquioxane containing acryloxy groups and mercapto groups is used in radically reactive resins such as olefin resins and acrylic resins, and rubber products that are vulcanized using sulfur such as 5BRSNBR. It is also expected that the properties of polymethylsilsesquioxanes containing these functional groups can be improved by adding powders, which can be achieved by hydrolyzing polymethylsilsesquioxanes containing these functional groups using alkaline catalysts of the corresponding silanes or their mixtures. However, if an acidic catalyst is used instead of an alkaline catalyst, it is not possible to obtain a powder with a predetermined amount of functional groups because these functional groups are changed by the action of an alkali catalyst. Since a large amount of coarse gel is generated, it is not possible to obtain a homogeneous spherical powder that is useful for improving the properties of resins, and therefore, sufficient studies have not yet been conducted on this issue.
（課題を解決するための手段）
本発明はこのような不利を解決したアクリロキシ基、メ
ルカプト基を含有するシルセスキオキサン球状微粉末の
製造方法に関するものであり、これは平均式ＣＨｓＳｆ
（ＯＲ’） ｓ （ここにＲ１は炭素数１〜４のア
ルキル基）で示されるメチルアルコキシシランまたはそ
の部分加水分解縮合物と、平均式Ｒ’Ｓｉ （ＯＲ’）
ｓ （ここにＲ２はアクリロキシ基、メルカプト基か
ら選択される基）で示されるオルガノアルコキシシラン
またはその混合物あるいはその部分加水分解縮合物とを
、アニオン界面活性剤水溶液中で加水分解し、中和、乾
燥することを特徴とするものである。(Means for Solving the Problems) The present invention relates to a method for producing silsesquioxane spherical fine powder containing an acryloxy group and a mercapto group, which solves the above-mentioned disadvantages, and which has an average formula of CHsSf.
(OR') s (herein, R1 is an alkyl group having 1 to 4 carbon atoms) methylalkoxysilane or its partially hydrolyzed condensate, and the average formula R'Si (OR')
s (wherein R2 is a group selected from an acryloxy group and a mercapto group) or a mixture thereof or a partially hydrolyzed condensate thereof, is hydrolyzed in an anionic surfactant aqueous solution, neutralized, It is characterized by drying.
すなわち、本発明者らはアクリロキシ基、メルカプト基
を含有するシルセスキオキサン球状微粉末の製造方法に
ついて種々検討した結果、これについてはメチルアルコ
キシシランとアクリロキシ基またはメルカプト基を含有
するトリアルコキシシランンをアニオン界面活性剤水溶
液中で加水分解させると、アクリロキシ基、メルカプト
基という官能基が破壊されずに加水分解されるので、こ
れらの官能基を仕込み量で設定した量で含有するシルセ
スキオキサン球状微粉末が得られることを見出すと共に
、このようにして得られるシルセスキオキサンはメチル
シルセスキオキサンとアクリロキシ基、メルカプト基含
有シルセスキオキサンとの混合物となるのですぐれた潤
滑性、撥水性、離型性を示すものになるということ、ま
たこのものは０．１〜２０μ■という粒径にコントロー
ルすることができ、このものは粉体の取り出しが容易で
簡単な解砕で凝集のない一次粒子として取得することが
できることを確認して本発明を完成させた。That is, as a result of various studies by the present inventors regarding the production method of silsesquioxane spherical fine powder containing an acryloxy group or a mercapto group, it was found that methylalkoxysilane and a trialkoxysilane containing an acryloxy group or a mercapto group were used. When hydrolyzed in an anionic surfactant aqueous solution, the functional groups such as acryloxy groups and mercapto groups are hydrolyzed without being destroyed. It was discovered that a fine spherical powder can be obtained, and since the silsesquioxane thus obtained is a mixture of methyl silsesquioxane and silsesquioxane containing acryloxy groups and mercapto groups, it has excellent lubricity and repellency. It is water-based and exhibits mold releasability, and the particle size can be controlled to 0.1 to 20μ■, making it easy to take out the powder and prevent agglomeration by simple crushing. The present invention was completed by confirming that the particles can be obtained as primary particles.
以下にこれをさらに詳述する。This will be explained in further detail below.
（作用）
本発明はアクリロキシ基、メルカプト基を含有するシル
セスキオキサン球状微粒子の製造方法に関するものであ
る。(Function) The present invention relates to a method for producing silsesquioxane spherical fine particles containing an acryloxy group and a mercapto group.
本発明において始発材とされるアルコキシシランは平均
式
％式％（１）
で示され、Ｒ１はメチル基、エチル基、プロビル基、ブ
チル基などのような炭素数１〜４のアルキル基であるメ
チルトリアルコキシシラン、例えばメチルトリメトキシ
シラン、メチルトリエトキシシラン、メチルトリプロポ
キシシラン、メチルトリブトキシシランまたはその部分
加水分解縮合物と、平均式
％式％（２）
で示され、Ｒ１が前記と同じ炭素数１〜４のアルキル基
、Ｒ２がアクリロキシ基、メルカプト基から選択される
基であるトルアルコキシシラン、例えばアクリロキシ基
含有シランの例としてはメタクリルプロピルトリメトキ
シシラン、メタクリルブチルトリメトキシシラン、メル
カプトペンチルトリメトキシシラン、メタクリルプロピ
ルトリエトキシシラン、メタクリルブチルトリエトキシ
シランなど、メルカプト基含有シランの例としてはメル
カプトプロピルトリメトキシシラン、メルカプトブチル
トリメトキシシラン、メルカプトペンチルトリメトキシ
シラン、メルカプトプロピルトリエトキシシランなど、
またはこれらの混合物、さらにはこれらの部分加水分解
縮合物などとの混合物とされる。The alkoxysilane used as the starting material in the present invention is represented by the average formula % (1), where R1 is an alkyl group having 1 to 4 carbon atoms such as a methyl group, ethyl group, probyl group, butyl group, etc. Methyltrialkoxysilane, such as methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane or a partially hydrolyzed condensate thereof, and the average formula % is represented by the formula % (2), and R1 is as above. Tolualkoxysilane in which the same alkyl group having 1 to 4 carbon atoms, R2 is a group selected from an acryloxy group and a mercapto group, for example, examples of silanes containing an acryloxy group include methacrylpropyltrimethoxysilane, methacrylbutyltrimethoxysilane, and mercapto. Examples of mercapto group-containing silanes include mercaptopropyltrimethoxysilane, mercaptobutyltrimethoxysilane, mercaptopentyltrimethoxysilane, mercaptopropyltriethoxysilane, etc. ,
Or a mixture thereof, or a mixture with a partially hydrolyzed condensate thereof.
なお、この部分加水分解縮合物は上記した式（１）、（
２）で示されるトリアルコキシシランを部分加水分解し
、縮合させたものであるが、これは式（１）、（２）で
示されるトリアルコキシシラン１モルに対してギ酸、酢
酸のような有機カルボン酸を溶解した水２モル以上と反
応させて、例えば式％式％（）
たは３でａ＋ｂ−３である数）で示されるようにしてシ
ラノール基を含む化合物としたものとすればよいが、こ
のものは安定に存在するものであるし、シラノール基を
含有しているので親木性となり、後記するアニオン界面
活性剤水溶液中に滴下されたときにより均一に分散され
る。In addition, this partial hydrolysis condensate has the above-mentioned formula (1), (
The trialkoxysilane represented by formula (2) is partially hydrolyzed and condensed. A compound containing a silanol group may be obtained by reacting carboxylic acid with 2 moles or more of water in which it is dissolved, for example, as shown by the formula % () or a number where 3 is a+b-3. However, this product exists stably, and since it contains a silanol group, it becomes wood-philic, and when it is dropped into an anionic surfactant aqueous solution described later, it is more uniformly dispersed.
本発明では上記したトルアルコキシシランまたはその加
水分解締金物の混合物をアニオン系界面活性剤水溶液中
で加水分解するのであるが、このアニオン系界面活性剤
は酸性を示すものであるから加水分解、縮合のための触
媒として作動すると共に、この加水分解で生成したシル
セスキオキサン球状微粉末の分散剤としての役目を果す
ものである。In the present invention, the above-mentioned tolualkoxysilane or a mixture of its hydrolyzed fasteners is hydrolyzed in an aqueous solution of anionic surfactant, but since this anionic surfactant is acidic, hydrolysis and condensation may occur. In addition to acting as a catalyst for this, it also serves as a dispersant for the spherical fine powder of silsesquioxane produced by this hydrolysis.
このアニオン系界面活性剤としては一般式％式％
Ｒ６は炭素数６〜１８の脂肪族−偏度化水素基で、ｐ、
ｑはそれぞれ正の整数である脂肪族ベンゼンスルホン酸
または脂肪族サルフェート、ポリオキシエチレン脂肪族
フェニルエーテルサルフェートおよびポリオキシエチレ
ン脂肪族エーテルサルフェートから選ばれるものとする
ことがよく、したがってこれについてはオクチルベンゼ
ンスルホン酸、ドデシルベンゼンスルホン酸、シリルベ
ンゼンスルホン酸、ヘキシルサルフェート、ラウリルサ
ルフェート、セチルサルフェート、オレイルサルフェー
ト、ポリオキシエチレンノニルフェニルエーテルサルフ
ェート、ポリオキシエチレンラウリルエーテルサルフェ
ートなどが例示される。This anionic surfactant has the general formula %, where R6 is an aliphatic hydrogen group having 6 to 18 carbon atoms, p,
Preferably, q shall be selected from aliphatic benzene sulfonic acid or aliphatic sulfate, polyoxyethylene aliphatic phenyl ether sulfate and polyoxyethylene aliphatic ether sulfate, each of which is a positive integer; therefore, octylbenzene Examples include sulfonic acid, dodecylbenzenesulfonic acid, silylbenzenesulfonic acid, hexyl sulfate, lauryl sulfate, cetyl sulfate, oleyl sulfate, polyoxyethylene nonylphenyl ether sulfate, and polyoxyethylene lauryl ether sulfate.
このアニオン系界面活性剤は２種あるいは２種以上を組
合せて使用してもよいが、このものは水溶液中における
アニオン系界面活性剤の濃度がｏ、ｏｏｓ重量％未満で
は分散力が弱いために粒子同志の融合が起ってゲル化し
易くなり、５重量％より濃いと懸濁液からのシルセスキ
オキサンの分離、取り出しが困難となるので、水溶液中
におけるアニオン系界面活性剤の濃度はｏ、ｏｏｓ〜５
重量％のものとして使用することがよい。These anionic surfactants may be used in combination of two or more types, but if the concentration of the anionic surfactant in the aqueous solution is less than o, oos weight percent, the dispersing power is weak. The concentration of the anionic surfactant in the aqueous solution should be set at o. ,oos~5
It is preferable to use it as a percentage by weight.
前記した始発剤としてのトリアルコキシシランの加水分
解はこのトリアルコキシシランを前記した濃度に調整し
たアニオン系界面活性剤水溶液中に攪拌しつつ滴下する
ことによって行なえばよいが、このアニオン系界面活性
剤が種類によフては触媒活性の低いものであることがあ
るので、このようなときには硫酸などのような酸あるい
は触媒活性の高いアニオン系界面活性剤を添加すればよ
く、この添加量は触媒濃度として０．０００１〜０．１
モル％とすればよい。Hydrolysis of the above-mentioned trialkoxysilane as an initiator can be carried out by dropping this trialkoxysilane into an aqueous solution of anionic surfactant adjusted to the above-mentioned concentration while stirring. Depending on the type, the catalytic activity may be low, so in such cases, it is sufficient to add an acid such as sulfuric acid or an anionic surfactant with high catalytic activity. 0.0001 to 0.1 as concentration
It may be expressed as mol%.
この加水分解系に添加されるトリアルコキシシランの量
は水に対して１００重量％以上とするとゲル化を起すお
それがあり、水に対して５重量％未満とすると生成する
シルセスキオキサン微粉末の粒径が０．１μ厘以下とな
って分離、取り出しが困難となり、乾燥後解砕しても一
次粒子として得ることが難しくなるので、水に対して５
〜１００重量％の範囲となるようにすることがよく、こ
れは全量を一度に添加しても何回かに分けてしてもよい
が、何回かに分けて添加するときに最初に添加する量が
少ないとき、例えば全体の５重量％以下であるときには
得られるシルセスキオキサン微粒子が粒径０，１μｍの
ものとなって分離、取り出しが困難となり、乾燥解砕後
に一次粒子として得ることが難しくなるのでこれは５重
量％以上とすることがよい。また、このアルコキシシラ
ンは前記したように式（１）で示されるメチルトリアル
コキシシランと式（２）で示されるアクリロキシ基、メ
ルカプト基含有トリアルコキシシランとの混合物とされ
るが、何回かに分けて添加する場合、ある回に、式（２
）で示されるトリアルコキシシランが含まれていれば他
の回では式（１）で示されるトリアルコキシシランだけ
としてもよい。If the amount of trialkoxysilane added to this hydrolysis system is more than 100% by weight based on water, gelation may occur, and if it is less than 5% by weight based on water, fine silsesquioxane powder will be produced. The particle size of the particles becomes less than 0.1μ, making it difficult to separate and take out, and it becomes difficult to obtain primary particles even if crushed after drying.
The amount is often in the range of ~100% by weight, and this can be done by adding the whole amount at once or dividing it into several times, but when adding it in several times, it is better to add it at the beginning. When the amount of silsesquioxane is small, for example, 5% by weight or less of the total, the resulting silsesquioxane fine particles have a particle size of 0.1 μm and are difficult to separate and take out, making it difficult to obtain them as primary particles after drying and crushing. Therefore, it is preferable to set this amount to 5% by weight or more. Furthermore, as mentioned above, this alkoxysilane is a mixture of methyltrialkoxysilane represented by formula (1) and trialkoxysilane containing an acryloxy group or mercapto group represented by formula (2). When adding in parts, at a certain time, the formula (2
) If the trialkoxysilane represented by formula (1) is included, only the trialkoxysilane represented by formula (1) may be used in other times.
また、この加水分解、縮合反応を行なわせる温度は特に
限定されるものではないが、０℃未満では氷結するおそ
れがあり、６０℃より高い温度とすると加水分解速度が
速すぎてゲル化を起すおそれがあるので、これは０〜６
０℃の範囲、好ましくは５〜４０℃とすることがよく、
この攪拌も特に限定されるものではないが、ホモジナイ
ザーのように剪断力の大きな攪拌とすると粒子同志の衝
突によって不定形なゲル体が生成し、好ましくないので
、これは攪拌羽根による５〜１．ＯＯＯｒｐｍ、好まし
くは２０〜３００ｒｐ層程度のものとすればよい。また
、懸濁液の形成にも攪拌は必要とされるが、１．ＯＯＯ
ｒｐｍ以上の攪拌は粒子同志の衝突によって不定形のゲ
ル体が生成するので、この攪拌もゆるやかなものとすれ
ばよい。In addition, the temperature at which this hydrolysis and condensation reaction is carried out is not particularly limited, but if it is below 0°C, freezing may occur, and if the temperature is higher than 60°C, the hydrolysis rate is too fast and gelation may occur. Because there is a risk, this is 0 to 6.
The temperature is preferably in the range of 0°C, preferably 5 to 40°C,
This stirring is not particularly limited either, but stirring with a large shearing force, such as with a homogenizer, will result in the formation of an amorphous gel body due to collisions between particles, which is undesirable. OOO rpm, preferably about 20 to 300 rpm layer may be used. Stirring is also required to form a suspension, but 1. OOO
Since stirring at a speed higher than rpm will produce an amorphous gel body due to collisions between particles, this stirring should also be gentle.
上記のようにして始発剤としてのトルアルコキシシラン
の滴下を終了した加水分解反応系は、ついで０〜９０℃
の温度においてさらに３０分以上攪拌を継続して行なう
ことによフてその加水分解、縮合が完結させられるが、
これによって作られたシルセスキオキサンを含有する懸
濁液は系中に残存する酸触媒を必要に応じ中和する。こ
の中和はアルカリ性物賞であればいかなるものであって
もよく、これには水酸化ナトリウム、炭酸ナトリウム、
アンモニア水などが例示される。The hydrolysis reaction system in which tolualkoxysilane as an initiator has been added dropwise as described above is then heated to a temperature of 0 to 90°C.
The hydrolysis and condensation can be completed by continuing stirring for 30 minutes or more at a temperature of
The suspension containing silsesquioxane thus produced neutralizes the acid catalyst remaining in the system as necessary. This neutralization can be done with any alkaline substance, including sodium hydroxide, sodium carbonate,
Examples include ammonia water.
この中和後の懸濁液は遠心分離法あるいはろ過分離性に
より脱水し、得られたペースト状物を２０〜１５０℃で
加熱乾燥するか、または懸濁液を直接スプレードライヤ
ーなどで乾燥すればよい、なお、この遠心分離、ろ過分
離するときにはシルセスキオキサン微粒子の分離を容易
にするために、これに塩化ナトリウム、硫酸ナトリウム
などの無機塩類や、アルキルトリメチルアンモニウムク
ロライド、アルキルベンジルアンモニウムクロライドな
どのカチオン系界面活性剤を添加して、分散しているシ
ルセスキオキサン微粒子を凝集させてもよく、さらに必
要に応じて水およびメタノール、エタノール、イソプロ
パツールなどの水溶性アルコールで洗浄して反応の際使
用したアニオン系界面活性剤、酸触媒、中和剤、凝集剤
などを取り除いておくこともよい。The neutralized suspension is dehydrated by centrifugation or filtration, and the resulting paste is dried by heating at 20 to 150°C, or the suspension is directly dried with a spray dryer. In order to facilitate the separation of silsesquioxane fine particles during centrifugation and filtration, inorganic salts such as sodium chloride and sodium sulfate, alkyltrimethylammonium chloride, alkylbenzylammonium chloride, etc. A cationic surfactant may be added to aggregate the dispersed silsesquioxane fine particles, and if necessary, the reaction may be performed by washing with water and a water-soluble alcohol such as methanol, ethanol, or isopropanol. It is also a good idea to remove the anionic surfactant, acid catalyst, neutralizing agent, flocculant, etc. used during this process.
このように得られた乾燥品はこれをジェットミル粉砕機
などを用いて解砕することによりシルセスキオキサン微
粉末とされるが、このものは一般式（ＣＬＳｌｏｓｚｚ
）、（Ｒ２ｓｉ０３７２）ｙｌで示されるアクリロキシ
基、メルカプト基含有シルセスキオキサン微粉末である
が、このものはｎ／＋＋ｎが０．００１〜４．０のもの
で、真球状あるいは略々真球状で粒子径が０．１〜２０
μＩの微粉状のものとなる。The dried product thus obtained is crushed using a jet mill or the like to obtain a fine silsesquioxane powder, which has the general formula (CLSloszz
), (R2si0372)yl is an acryloxy group- and mercapto group-containing silsesquioxane fine powder, which has an n/++n of 0.001 to 4.0 and a true spherical or almost true spherical shape. and the particle size is 0.1-20
It becomes a fine powder of μI.
上記した本発明により得られたアクリロキシ基、メルカ
プト基含有シルセスキオキサン球状微粒子は各種合成樹
脂の充填剤および添加剤として、例えば合成樹脂フィル
ム、紙などに対するすべり性、離型性付与剤、補強剤と
して用いられるし、またシリコーンフェスをビヒクルと
する耐熱塗料の体買顔料として従来のタルクやマイカ粉
の代わりに使用することができ、さらには半導体封止材
料としてのエポキシ樹脂の応力緩和剤、磁気記録媒体の
テープ滑性改良剤、カーワックスなどのつや出し剤に配
合する光沢を保持したままつやを出すためのつや出し剤
の研磨性、作業性向上剤として使用することができる。The acryloxy group- and mercapto group-containing silsesquioxane spherical fine particles obtained according to the present invention can be used as fillers and additives for various synthetic resins, for example, as lubricating and releasable agents and reinforcing agents for synthetic resin films, paper, etc. It can also be used in place of conventional talc or mica powder as a body pigment in heat-resistant paints using silicone as a vehicle, and as a stress reliever for epoxy resins as semiconductor encapsulation materials. It can be used as a tape lubricity improver for magnetic recording media, and as an abrasive and workability improver for polishing agents, such as car wax, to provide gloss while maintaining gloss.
（実施例）
つぎに本発明の実施例、比較例をあげるが、例中におけ
るアクリル価、メルカプト価はつぎの方法による測定値
を示したものである。(Example) Next, Examples and Comparative Examples of the present invention will be given, and the acrylic value and mercapto value in the examples are the values measured by the following method.
［アクリル価コ
試料約１０ｇを四塩化炭素１００＋＋Ｊ２に懸濁させ、
これに０．２Ｎの臭化ヨウ素−酢酸溶液２０ｍｊＺを加
えて２５℃で２時間恒温の暗所に置いてアクリル基を反
応させ、２０重量％のヨウ化カリウム水溶液１５ｍｊｌ
を加えて遊離するヨウ素を０．１Ｎチオ硫酸ナトリウム
水溶液にてデンプン終点まで滴定し、消費されたヨウ素
量からアクリル価を再出する。[Approximately 10 g of acrylic value sample was suspended in carbon tetrachloride 100++ J2,
To this, 20 mjZ of 0.2N iodine bromide-acetic acid solution was added and kept in a dark place at a constant temperature for 2 hours at 25°C to react the acrylic groups.
is added and the liberated iodine is titrated with a 0.1N aqueous sodium thiosulfate solution to the end point of starch, and the acrylic value is recalculated from the amount of consumed iodine.
［メルカプト価］
試料約１０ｇをアセトン−メタノール（１：４）１０ｈ
Ｊ２に懸濁させ、０．０２Ｎの硝酸銀水溶液で電位差滴
定を行ない、メルカプト価を算出する。[Mercapto value] Approximately 10 g of sample was mixed with acetone-methanol (1:4) for 10 hours.
J2 and subjected to potentiometric titration with a 0.02N silver nitrate aqueous solution to calculate the mercapto value.
実施例１
プロペラ型攪拌器、加熱および冷却用ジャケットを設け
た２互のガラス容器に水４２５ｇとドデシルベンゼンス
ルホン酸１．２５ｇを入れて２０℃に加温した。Example 1 425 g of water and 1.25 g of dodecylbenzenesulfonic acid were placed in two glass containers equipped with a propeller-type stirrer and heating and cooling jackets, and the mixture was heated to 20°C.
この液を２００ｒｐｍで攪拌しながら、これにメチルト
リメトキシシラン９３ｇとメタクリロキシプロピルトリ
メトキシラン７ｇとの混合液を滴下し、２０℃に保ちな
がら２時間攪拌し、さらに８０℃に加熱して３時間攪拌
したのち室温まで冷却し、炭酸ナトリウム０．２５ｇを
添加して中和した。While stirring this solution at 200 rpm, a mixed solution of 93 g of methyltrimethoxysilane and 7 g of methacryloxypropyltrimethoxylane was added dropwise to the solution, stirred for 2 hours while maintaining the temperature at 20°C, and then heated to 80°C for 3 hours. After stirring for an hour, the mixture was cooled to room temperature and neutralized by adding 0.25 g of sodium carbonate.
生成した懸濁液にアルキルトリメチルアンモニウムクロ
ライド１．２０ｇを添加して分散物を凝集させ、ろ過分
間してケーキ状物を得、これを乾燥器を用いて含水率が
２０％以下になるまで１１０℃で乾燥し、生成した粉末
をジェットミルで解砕してポリメチル（メタクリロキシ
プロピル）シルセスキオキサンの白色粉末を作り、これ
を電子顕微鏡で観察したところ、このものは各粒子が夫
々独立した１〜６μ臘の球状の微粉末であり、このもの
の平均粒径をコールタ−Ｎ４型装置（コールタ−・エレ
クトリック社製商品名）で測定したところ、これは４μ
−であり、このアクリル価は０．０３３モル／１００ｇ
であフた。1.20 g of alkyltrimethylammonium chloride was added to the resulting suspension to coagulate the dispersion, which was filtered for several minutes to obtain a cake-like product. After drying at ℃, the resulting powder was crushed with a jet mill to produce a white powder of polymethyl(methacryloxypropyl)silsesquioxane, and when observed under an electron microscope, it was found that each particle was independent of the other. It is a spherical fine powder of 1 to 6 microns, and the average particle size of this material was measured using a Coulter N4 type device (trade name, manufactured by Coulter Electric Co., Ltd.), and it was 4 microns.
-, and this acrylic value is 0.033 mol/100g
It was dead.
実施例２
実施例１におけるメチルトリメトキシシラン９３ｇとメ
タクリロキシプロピルトリメトキシシラン７ｇを、メチ
ルトリメトキシシラン９３ｇとメルカプトプロピルトリ
メトキシシラン７ｇとしたほかは実施例１と同様に処理
したところ、ポリメチル（メルカプトプロピル）シルセ
スキオキサンの白色粉末が得られ、このものは球形で平
均粒径が３μ■であり、メルカプト価は０．０４２をモ
ル／１００ｇであった。Example 2 The same process as in Example 1 was performed except that 93 g of methyltrimethoxysilane and 7 g of methacryloxypropyltrimethoxysilane in Example 1 were changed to 93 g of methyltrimethoxysilane and 7 g of mercaptopropyltrimethoxysilane. A white powder of silsesquioxane (mercaptopropyl) was obtained, which was spherical and had an average particle size of 3 μι and a mercapto number of 0.042 mol/100 g.
実施例３
実施例１で使用したガラス容器に水４２５ｇとラウリル
サルフェート２．５ｇを入れて２０℃に加温した。Example 3 425 g of water and 2.5 g of lauryl sulfate were placed in the glass container used in Example 1 and heated to 20°C.
この液を２００ｒｐ■で攪拌しながら、これにメチルト
リメトキシシランの部分加水分解縮合物５０ｇを添加し
、２０℃に保ちながら２時間攪拌し、ついでメチルトリ
メトキシシラン６．５ｇとメタクリロキシプロピルトリ
メトキシシラン１．５ｇとの混合物を添加し、２０℃に
保ちながら２時間攪拌した後、８０℃に加熱して３時間
攪拌し、室温で冷却してから炭酸ナトリウム０．５ｇを
添加して中和した。While stirring this solution at 200 rpm, 50 g of a partially hydrolyzed condensate of methyltrimethoxysilane was added thereto, and the mixture was stirred for 2 hours while maintaining the temperature at 20°C. A mixture with 1.5 g of methoxysilane was added, stirred for 2 hours while maintaining the temperature at 20°C, heated to 80°C and stirred for 3 hours, cooled to room temperature, and then added with 0.5 g of sodium carbonate. It was peaceful.
つぎにここに生成した懸濁液を遠心分離器で処理してシ
ルセスキオキサンをケーキ状に分離し、乾燥器を用いて
１１０℃で含水率が２０％以下になるまで乾燥してから
、この粉末をジェットミルで解砕したところ、ポリメチ
ル（メタクリロキシプロピル）シルセスキオキサンの白
色粉末が得られたが、このものは球形で平均粒径が０，
５μｍのものであり、このアクリル価は０．０１２モル
／１００ｇであった。Next, the suspension produced here is treated with a centrifugal separator to separate the silsesquioxane into a cake, which is dried using a dryer at 110°C until the water content becomes 20% or less. When this powder was crushed with a jet mill, a white powder of polymethyl(methacryloxypropyl)silsesquioxane was obtained, which was spherical and had an average particle size of 0.
The acrylic value was 0.012 mol/100 g.
実施例４
実施例３におけるメチルトリメトキシシラン６．５ｇと
メタクリロキシプロピルトリメトキシシラン１，５ｇと
の混合物をメチルトリメトキシシラン６．５ｇとメルカ
プトプロピルトリメトキシシラン１．５ｇとの混合物と
したほかは実施例３と同様に処理したところ、ポリメチ
ル（メルカプトプロピル）シルセスキオキサンの白色粉
末が得られ、このものは球形で平均粒径が０．５ｇ厘で
あり、このメルカプト価は０．０１５モルフ１００ｇで
あった。Example 4 The mixture of 6.5 g of methyltrimethoxysilane and 1.5 g of methacryloxypropyltrimethoxysilane in Example 3 was changed to a mixture of 6.5 g of methyltrimethoxysilane and 1.5 g of mercaptopropyltrimethoxysilane. was treated in the same manner as in Example 3 to obtain a white powder of polymethyl(mercaptopropyl)silsesquioxane, which was spherical and had an average particle size of 0.5 g, and its mercapto value was 0.015. The amount of morph was 100g.
実施例５
実施例３におけるメチルトリメトキシシランの部分加水
分解縮合物５０ｇの代わりにメチルトリメトキシシラン
６８ｇ、水１８ｇおよび酢酸０．７ｇを均一に溶解した
メチルトリメトキシシランの酸性水溶液８６．７ｇとし
、さらにメチルトリメトキシシラン６．５ｇとメタクリ
ロキシプロピルトリメトキシシラン１．５ｇとの混合物
をメチルトリメトキシシラン１３ｇとメルカプトプロピ
ルトリメトキシシラン３ｇの混合物としたほかは実施例
３と同様に処理したところ、ポリメチル（メルカプトプ
ロピル）シルセスキオキサンの白色粉末が得られたが、
このものは球形で平均粒径が０．９μＩであり、メルカ
プト価は０．０２０モルフ１００ｇであった。Example 5 Instead of 50 g of the partially hydrolyzed condensate of methyltrimethoxysilane in Example 3, 86.7 g of an acidic aqueous solution of methyltrimethoxysilane was prepared by uniformly dissolving 68 g of methyltrimethoxysilane, 18 g of water, and 0.7 g of acetic acid. The same process as in Example 3 was carried out, except that the mixture of 6.5 g of methyltrimethoxysilane and 1.5 g of methacryloxypropyltrimethoxysilane was replaced with a mixture of 13 g of methyltrimethoxysilane and 3 g of mercaptopropyltrimethoxysilane. , a white powder of polymethyl(mercaptopropyl)silsesquioxane was obtained,
This product was spherical, had an average particle size of 0.9 μI, and had a mercapto value of 0.020 morph (100 g).
実施例６
プロペラ型攪拌器、加熱および冷却用ジャケットを設け
た６１のガラス容器に水３２０ｇとラウリルサルフェー
ト２．０ｇを入れ、２０℃に加温した。Example 6 320 g of water and 2.0 g of lauryl sulfate were placed in a 61 glass container equipped with a propeller-type stirrer and a heating and cooling jacket, and heated to 20°C.
ついでこれを２００ｒｐ腸で攪拌しながら、これにメチ
ルトリメトキシシランの部分加水分解縮合物１４０ｇを
６０ｇ 、 ４０ｇ、４０ｇに分けて２時間おきに添加
し、全量添加終了さらに２時間攪拌してから、ここにメ
チルトリメトキシシラン５，２ｇとメタクリロキシプロ
ピルトリメトキシシラン１．２ｇとの混合物を添加し、
２０℃で２時間攪拌をし、その後８０℃に昇温して３時
間攪拌してから室温まで冷却し、炭酸ナトリウム０．４
ｇを添加して中和した。Next, while stirring this at 200 rpm, 140 g of a partially hydrolyzed condensate of methyltrimethoxysilane was added in 60 g, 40 g, and 40 g portions every 2 hours, and after the addition of the entire amount was completed, the mixture was stirred for another 2 hours. A mixture of 5.2 g of methyltrimethoxysilane and 1.2 g of methacryloxypropyltrimethoxysilane was added thereto,
Stir at 20°C for 2 hours, then raise the temperature to 80°C, stir for 3 hours, cool to room temperature, and add 0.4 ml of sodium carbonate.
g was added to neutralize.
つぎにこのよにして生成した懸濁液を遠心分離器で脱水
したのちイソプロピルアルコールで洗浄してケーキ状物
を取り、これを１１０℃に保持した乾燥器で乾燥して含
水率２０％以下のものとし、生成した粉末をジェットミ
ルで解砕したところ、ポリメチル（メタクリロキシプロ
ピル）シルセスキオキサンの白色粉末が得られ、このも
のは球形で平均粒径が１．０ｇ層であり、アクリル価は
０．００３モル／１００ｇのものであった。Next, the suspension thus produced is dehydrated using a centrifugal separator, washed with isopropyl alcohol to obtain a cake-like material, and dried in a dryer maintained at 110°C to a water content of 20% or less. When the resulting powder was crushed with a jet mill, a white powder of polymethyl (methacryloxypropyl)silsesquioxane was obtained, which was spherical in shape, had an average particle size of 1.0 g, and had an acrylic value. was 0.003 mol/100g.
比較例１
実施Ｍ１で使用した２にＬのガラス容器に水４２５ｇと
ドデシルベンゼンスルホン酸５．４ｇを入れ６０℃に加
熱した。Comparative Example 1 425 g of water and 5.4 g of dodecylbenzenesulfonic acid were placed in a 2-L glass container used in Example M1 and heated to 60°C.
ついでこれを２００ｒｐｍで攪拌しながら、これにメチ
ルトリメトキシシラン１００ｇを６０ｇ／時の速度で連
続的に徐々に添加し、シランの添加完了後も６０℃に保
つって２４時間攪拌を続けたのち室温まで冷却し、炭酸
ナトリウム１．０ｇを添加して中和した。Next, while stirring at 200 rpm, 100 g of methyltrimethoxysilane was gradually added continuously at a rate of 60 g/hour, and even after the addition of silane was completed, the temperature was kept at 60°C and stirring was continued for 24 hours. The mixture was cooled to room temperature and neutralized by adding 1.0 g of sodium carbonate.
つぎに生成した懸濁液中に分散しているシルセスキオキ
サン微粒子を分離したところ、このものは形状が不定形
であり、分離の際の脱水率がわるく、得られた粉末も各
々が独立しておらず、凝集した状態であった。Next, when we separated the silsesquioxane fine particles dispersed in the resulting suspension, we found that the particles had an amorphous shape, the dehydration rate during separation was poor, and the resulting powders were also independent. It was in a coagulated state.
比較例２
比較例１におけるドデシルベンゼンスルホン酸５．４ｇ
の代わりにラウリルサルフェート８ｇ、メチルトリメト
キシシラン１００ｇの代わりにメチルトリメトキシシラ
ン５０ｇとメチルトリメトキシシランの部分加水分解縮
合物５０ｇとの混合物１００ｇとし、この混合物１００
ｇを連続的に４時間かけて滴下するということのほかは
比較例１と同様に処理したところ、懸濁液中に分散して
いるシルセスキオキサン微粒子は分離の際の脱水率がわ
るく、得られた粒子は形状が不定形で平均粒径も０．０
５μｍで、これらは各々独立しておらず、凝集した状態
であった。Comparative Example 2 5.4 g of dodecylbenzenesulfonic acid in Comparative Example 1
In place of 8 g of lauryl sulfate, and in place of 100 g of methyltrimethoxysilane, use 100 g of a mixture of 50 g of methyltrimethoxysilane and 50 g of a partially hydrolyzed condensate of methyltrimethoxysilane, and 100 g of this mixture.
When treated in the same manner as in Comparative Example 1 except that g was continuously added dropwise over 4 hours, the silsesquioxane fine particles dispersed in the suspension had a poor dehydration rate during separation; The obtained particles have an irregular shape and an average particle size of 0.0.
At 5 μm, these particles were not independent but were in an aggregated state.
（発明の効果）
本発明はアクリロキシ基、メルカプト基含有シルセスキ
オキサン球状微粒子の製造方法に関するものであり、こ
れは前記したようにメチルトリアルコキシシランとアク
リロキシ基、メルカプト基含有オルガノトリアルコキシ
シランとをアニオン系界面活性剤水溶液中に加水分解し
、中和、乾燥するものであるが、これによればアクリロ
キシ基、メルカプト基を破壊せずにこれらを加水分解す
ることができるので、これらの官能基を仕込み量で設定
した量で含有するシルセスキオキサン球状微粒子を得る
ことができ、このものは０．１〜２．０μＩという粒径
で、しかも凝集のない−次粒子として得ることができる
ので、すぐれた潤滑性、撥水性、離型性を示すアクリロ
キシ基、メルカプト基含有シルセスキオキサン球状微粒
子を容易に得ることができるという有利性が与えられる
。(Effects of the Invention) The present invention relates to a method for producing spherical fine particles of silsesquioxane containing an acryloxy group or a mercapto group, and as described above, this method involves combining methyltrialkoxysilane with an organotrialkoxysilane containing an acryloxy group or a mercapto group. is hydrolyzed in an aqueous anionic surfactant solution, neutralized, and dried. This method allows hydrolysis of acryloxy groups and mercapto groups without destroying them, so these functional groups can be It is possible to obtain silsesquioxane spherical fine particles containing the group in an amount set by the amount of charge, and these particles have a particle size of 0.1 to 2.0 μI and can be obtained as secondary particles without agglomeration. Therefore, it is advantageous in that spherical fine particles of silsesquioxane containing acryloxy groups and mercapto groups that exhibit excellent lubricity, water repellency, and mold release properties can be easily obtained.
Claims (1)
１は炭素数１〜４のアルキル基）で示されるメチルトリ
アルコキシシランまたはその部分加水分解縮合物と、平
均式Ｒ＾２Ｓｉ（ＯＲ＾１）＿３（ここにＲ＾２はアク
リロキシ基、メルカプト基から選択される基）で示され
るオルガノアルコキシシランまたはその混合物あるいは
その部分加水分解縮合物とを、アニオン系界面活性剤水
溶液中で加水分解し、中和、乾燥してなることを特徴と
するアクリロキシ基、メルカプト基含有シルセスキオキ
サン球状微粉末の製造方法。1. Average formula CH_3Si(OR^1)_3 (here R^
1 is an alkyl group having 1 to 4 carbon atoms) or a partially hydrolyzed condensate thereof, and the average formula R^2Si(OR^1)_3 (where R^2 is an acryloxy group or a mercapto group) Acryloxysilane, which is obtained by hydrolyzing an organoalkoxysilane represented by (a group selected from ), a mixture thereof, or a partially hydrolyzed condensate thereof in an aqueous anionic surfactant solution, neutralizing it, and drying it. A method for producing a spherical fine powder of silsesquioxane containing mercapto and mercapto groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6906190A JPH0623254B2 (en) | 1990-03-19 | 1990-03-19 | Method for producing spherical silsesquioxane fine powder containing acryloxy group and mercapto group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6906190A JPH0623254B2 (en) | 1990-03-19 | 1990-03-19 | Method for producing spherical silsesquioxane fine powder containing acryloxy group and mercapto group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03269020A true JPH03269020A (en) | 1991-11-29 |
| JPH0623254B2 JPH0623254B2 (en) | 1994-03-30 |
Family
ID=13391680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6906190A Expired - Lifetime JPH0623254B2 (en) | 1990-03-19 | 1990-03-19 | Method for producing spherical silsesquioxane fine powder containing acryloxy group and mercapto group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0623254B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003113243A (en) * | 2001-07-06 | 2003-04-18 | Degussa Ag | Oligomeric organosilane, process for producing the same, its use, rubber mixture containing the same, and molded product including the mixture |
| JP2004099630A (en) * | 2002-09-04 | 2004-04-02 | Nitto Denko Corp | Method for producing polysilsesquioxane fine particle and polysilsesquioxane fine particle obtained by the producing method |
| WO2007142316A1 (en) * | 2006-06-08 | 2007-12-13 | The University Of Tokushima | Method for production of novel nano silica particle and use of the nano silica particle |
| JP2008038117A (en) * | 2006-08-10 | 2008-02-21 | Denki Kagaku Kogyo Kk | Resin composition and photocurable casting method |
| JP2009068019A (en) * | 2008-11-26 | 2009-04-02 | Takemoto Oil & Fat Co Ltd | Spherical silsesquioxane fine particle and surface modifier for polymer material |
| JP2021533219A (en) * | 2018-07-27 | 2021-12-02 | 浙江三時紀新材科技有限公司Zhejiang Third Age Material Technology Co., Ltd | Method for preparing spherical or angular powder filler, spherical or angular powder filler obtained from the same, and its use. |
-
1990
- 1990-03-19 JP JP6906190A patent/JPH0623254B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003113243A (en) * | 2001-07-06 | 2003-04-18 | Degussa Ag | Oligomeric organosilane, process for producing the same, its use, rubber mixture containing the same, and molded product including the mixture |
| JP2004099630A (en) * | 2002-09-04 | 2004-04-02 | Nitto Denko Corp | Method for producing polysilsesquioxane fine particle and polysilsesquioxane fine particle obtained by the producing method |
| WO2007142316A1 (en) * | 2006-06-08 | 2007-12-13 | The University Of Tokushima | Method for production of novel nano silica particle and use of the nano silica particle |
| US8455255B2 (en) | 2006-06-08 | 2013-06-04 | The University Of Tokushima | Method for production of novel nano silica particle and use of the nano silica particle |
| JP5311340B2 (en) * | 2006-06-08 | 2013-10-09 | 国立大学法人徳島大学 | Production method and use of novel nanosilica particles |
| JP2008038117A (en) * | 2006-08-10 | 2008-02-21 | Denki Kagaku Kogyo Kk | Resin composition and photocurable casting method |
| JP2009068019A (en) * | 2008-11-26 | 2009-04-02 | Takemoto Oil & Fat Co Ltd | Spherical silsesquioxane fine particle and surface modifier for polymer material |
| JP2021533219A (en) * | 2018-07-27 | 2021-12-02 | 浙江三時紀新材科技有限公司Zhejiang Third Age Material Technology Co., Ltd | Method for preparing spherical or angular powder filler, spherical or angular powder filler obtained from the same, and its use. |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0623254B2 (en) | 1994-03-30 |
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