JPH02174929A - Silica-antimony oxide sol, its preparation and flame retardant derived therefrom - Google Patents
Silica-antimony oxide sol, its preparation and flame retardant derived therefromInfo
- Publication number
- JPH02174929A JPH02174929A JP33236388A JP33236388A JPH02174929A JP H02174929 A JPH02174929 A JP H02174929A JP 33236388 A JP33236388 A JP 33236388A JP 33236388 A JP33236388 A JP 33236388A JP H02174929 A JPH02174929 A JP H02174929A
- Authority
- JP
- Japan
- Prior art keywords
- sol
- silica
- antimony oxide
- antimony
- oxide composite
- 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
- 229910000410 antimony oxide Inorganic materials 0.000 title claims abstract description 54
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 7
- 239000003063 flame retardant Substances 0.000 title claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 33
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000000725 suspension Substances 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000002612 dispersion medium Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052787 antimony Inorganic materials 0.000 abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 9
- 238000001879 gelation Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002270 dispersing agent Substances 0.000 abstract 3
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 239000000084 colloidal system Substances 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 20
- -1 methacryloxy group Chemical group 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 11
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000000499 gel Substances 0.000 description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001462 antimony Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 239000003729 cation exchange resin Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/146—After-treatment of sols
- C01B33/149—Coating
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Colloid Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はシリカ酸化アンチモン複合ゾル、その製造方法
およびそれよりなる難燃化剤に係るものであり、さらに
詳しくは、酸化アンチモンゾルのオルガノゾル化に際し
優れた安定性および優れた難燃効果を示すシリカ酸化ア
ンチモン複合ゾルおよびその製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silica antimony oxide composite sol, a method for producing the same, and a flame retardant made of the same, and more specifically relates to organosolization of antimony oxide sol. The present invention relates to a silica antimony oxide composite sol that exhibits excellent stability and excellent flame retardant effect in the production of sol, and a method for producing the same.
酸化アンチモンゾルは、プラスチック、織物。 Antimony oxide sol is used for plastics and textiles.
繊維などの難燃助剤、プラスチック、ガラスのコーティ
ング剤などとして使用されており１種々の酸化アンチモ
ンゾルの製造方法が知られている。Antimony oxide sol is used as a flame retardant aid for fibers and as a coating agent for plastics and glass, and various methods for producing antimony oxide sol are known.
特公昭５７−１．１８４８には、ｓｂ、ｏ、をＫＯＨ及
び１１．０□と約１：２．ｌ：２モルの割合で反応させ
てアンチモン酸カリウムを形成させた後、脱イオンを行
うことにより２〜１００ｍμの粒子径を有する５ｂ２０
、のコロイドゾルを製造する方法が開示されており、ま
た、特開昭５９−２３２９２１には、三酸化アンチモン
と過酸化水素を反応させて酸化アンチモンのコロイドゾ
ルを形成する際に、反応系にＬｉ、 Ｋ、 Ｎａ、 Ｍ
ｇ、 Ｃａ、 Ｂａ、リン酸ナトリウムなどの無機系ア
ルカリ物質を５ｂ２ｏ、に対して１．５〜３０モル％添
加すると、５ｂ２ｏ、とＨ２Ｏ２の反応速度が加速され
、微細粒子径のコロイド状アンチモンが得られることが
開示されている。さらに、特開昭６０−１３７８２８に
は、ｓｂ、ｏ、と８２０□を反応させて酸化アンチモン
のコロイドゾルを形成させる際に、ｓｂ、ｏ３とＨ２Ｏ
２のモル比を１ ： １．２５〜１．８とし、且つ反応
系に無機アルカリ物質を添加することにより、微細な粒
子径で化学的に安定なコロイド状酸化アンチモンの製造
方法が記載されている。Tokuko Sho 57-1.1848 has sb, o, KOH and 11.0□ approximately 1:2. 5b20 having a particle size of 2 to 100 mμ by reacting at a ratio of l:2 mol to form potassium antimonate and then deionizing it.
A method for producing a colloidal sol of K, Na, M
When 1.5 to 30 mol% of inorganic alkaline substances such as g, Ca, Ba, and sodium phosphate are added to 5b2o, the reaction rate between 5b2o and H2O2 is accelerated, and colloidal antimony with a fine particle size is It is disclosed that it can be obtained. Furthermore, in JP-A-60-137828, when sb, o, and 820□ are reacted to form a colloidal sol of antimony oxide, sb, o3 and H2O
A method for producing chemically stable colloidal antimony oxide with a fine particle size is described by setting the molar ratio of 2 to 1:1.25 to 1.8 and adding an inorganic alkaline substance to the reaction system. There is.
特開昭６０−４１５３６には、アンチモン酸アルカリを
化学量論比で０．７〜５倍量の一価または二価の無機酸
と反応させて五酸化アンチモンゲルを生成し、次いでこ
のゲルを分離、水洗後、アミンなどの有機塩基で解膠す
ると高濃度で低粘度の安定な五酸化アンチモンゾルが得
られることが開示されている。JP-A No. 60-41536 discloses that an antimony pentoxide gel is produced by reacting an alkali antimonate with a 0.7 to 5 times stoichiometric amount of a monovalent or divalent inorganic acid, and then this gel is It is disclosed that a stable antimony pentoxide sol with high concentration and low viscosity can be obtained by peptizing it with an organic base such as an amine after separation and washing with water.
特開昭６１−２２７９１８には、アンチモン酸アルカリ
と一価又は二価の無機酸と反応させて得られる五酸化ア
ンチモンゲルを解膠して五酸化アンチモンゾルを製造す
る方法において２反応時、及び／又は解膠時に燐酸をＰ
、 ＯＳ／５ｂ２０．重量％が０゜２〜５．０％になる
よう添加すると、有機溶媒で溶媒置換してオルガノゾル
化する際に安定性に優れた五酸化アンチモンゾルが得ら
れることが開示されている。JP-A No. 61-227918 discloses a method for producing antimony pentoxide sol by peptizing an antimony pentoxide gel obtained by reacting an alkali antimonate with a monovalent or divalent inorganic acid. /or P phosphoric acid during peptization
, OS/5b20. It is disclosed that when added at a weight percentage of 0.2 to 5.0%, an antimony pentoxide sol with excellent stability can be obtained when the solvent is replaced with an organic solvent to form an organosol.
特開昭６０−２５１１２９には、コロイド分散液中の酸
化アンチモンに対して０．５〜２５重量％の割合のＲ工
／
一般式 ＲＳＩ Ｒ２（但し、ＲはＣ□〜、でかつ＼
Ｒ３
アミノ基、メルカプト基、メタクリロキシ基又はハロゲ
ン原子を含まない置換基、Ｒ工及びＲ２は、０８〜４の
置換基、Ｒ１はＣ１〜４のアルキル基、アルコキシ置換
アルキル基又はアセチル基を示す、）で示される有機珪
素化合物で処理し１次いでコロイド分散液のｐＨを２．
５〜１２の範囲内に調整することにより、とりわけ化学
的安定性に優れた、有機溶媒の混和に対しても安定なコ
ロイド状酸化アンチモンが得られることが開示されてい
る。JP-A No. 60-251129 discloses R engineering/general formula RSI R2 (wherein R is C□~, and ＼ R3 amino group, mercapto group, methacryloxy group or a substituent not containing a halogen atom, R and R2 are 08-4 substituents, R1 is a C1-4 alkyl group, an alkoxy-substituted alkyl group or an acetyl group) After treatment with the indicated organosilicon compound, the pH of the colloidal dispersion was adjusted to 2.
It is disclosed that by adjusting the molecular weight within the range of 5 to 12, colloidal antimony oxide which has especially excellent chemical stability and is stable even when mixed with an organic solvent is obtained.
特開昭６１−２２７９１９には、五酸化アンチモンゾル
と、３価及び／又は４価の金属の塩基性塩の少なくとも
１種の水溶液とを所定の割合で混合することにより、有
機溶媒を加えても凝集しない特性を有するコロイド粒子
の表面が３価および／または４価の金属で覆われた五酸
化アンチモンゾルの製造方法が開示されている。JP-A-61-227919 discloses that antimony pentoxide sol and an aqueous solution of at least one basic salt of a trivalent and/or tetravalent metal are mixed in a predetermined ratio, and then an organic solvent is added. A method for producing an antimony pentoxide sol in which the surface of colloidal particles is coated with trivalent and/or tetravalent metal is disclosed.
しかし、従来の酸化アンチモンゾルには、無機珪酸化合
物を含有するシリカ酸化アンチモン複合ゾルに関しては
何んら開示されていない。However, in the conventional antimony oxide sols, nothing is disclosed regarding a silica antimony oxide composite sol containing an inorganic silicate compound.
従来、酸化アンチモンゾルは織物、繊維、プラスチック
等の兼燃助剤として使用される外、プラスチック、ガラ
スなどの透明基材の表面に塗布して屈折率の調整、紫外
線遮蔽などを行うためのコーティング剤として使用され
ている。Conventionally, antimony oxide sol has been used not only as a combustion aid for textiles, fibers, and plastics, but also as a coating for adjusting the refractive index and blocking ultraviolet rays by applying it to the surface of transparent substrates such as plastics and glass. used as an agent.
酸化アンチモンゾルは、コーティング剤などの用途によ
っては１分散媒が有機溶媒であるオルガノ酸化アンチモ
ンゾルにして使用される。The antimony oxide sol is used as an organo antimony oxide sol in which one dispersion medium is an organic solvent depending on the application such as a coating agent.
通常、オルガノゾルの製造方法としては、水ゾルの分散
媒である水を有機溶媒で置換してオルガノゾルにする方
法が用いられている。Usually, as a method for producing an organosol, a method is used in which water, which is a dispersion medium of an aqueous sol, is replaced with an organic solvent to form an organosol.
水を分散媒とする酸化アンチモンゾルは、有機溶媒で置
換する際に、凝集、ゲル化を生じオルガノゾル化ができ
ないという問題があった。Antimony oxide sol using water as a dispersion medium has a problem in that when it is replaced with an organic solvent, it aggregates and gels, making it impossible to form an organosol.
そこで、従来は先に述べた様に酸化アンチモンゾルのオ
ルガノゾル化に際し、燐酸、有機安定化剤、３価及び／
又は４価の金属の塩基性塩の水溶液などを添加して安定
化する方法が行なわれていた。Therefore, as mentioned above, when converting antimony oxide sol into organosol, phosphoric acid, organic stabilizer, trivalent and/or
Alternatively, a method of stabilizing by adding an aqueous solution of a basic salt of a tetravalent metal has been used.
本発明は、オルガノゾル化に際し、ゲル化することなく
安定してゾル状態を維持することができる水を分散媒と
するシリカ酸化アンチモン複合ゾル及びその製造方法を
提供する。さらに本発明は、有機溶媒を分散媒とするシ
リカ酸化アンチモン複合ゾルを提供する。The present invention provides a silica antimony oxide composite sol using water as a dispersion medium, which can stably maintain a sol state without gelation during organosolization, and a method for producing the same. Furthermore, the present invention provides a silica antimony oxide composite sol using an organic solvent as a dispersion medium.
本発明は、分散媒中にＳｉｎ、として０．１〜５０ｗｔ
％の無機珪酸化合物を含有する酸化アンチモンコロイド
粒子を分散せしめたシリカ酸化アンチモン複合ゾルに関
する。In the present invention, 0.1 to 50 wt of Sin is contained in the dispersion medium.
The present invention relates to a silica antimony oxide composite sol in which antimony oxide colloidal particles containing % of an inorganic silicate compound are dispersed.
前記分散媒として水を用いた本発明のシリカ酸化アンチ
モン複合ゾルは、有機溶媒に対して非常に安定である。The silica antimony oxide composite sol of the present invention using water as the dispersion medium is very stable against organic solvents.
したがって、分散媒の水を種々の有機溶媒で容易に置換
してオルガノシリカ酸化アンチモン複合ゾルを得ること
ができる４本発明で分散媒として使用できる有機溶媒と
しては、メタノール、エタノール、ブタノール、イソプ
ロパツールなどのアルコール類、エーテル類、エステル
類などが挙げられる。Therefore, an organosilica antimony oxide composite sol can be obtained by easily replacing water as a dispersion medium with various organic solvents.4 Examples of organic solvents that can be used as a dispersion medium in the present invention include methanol, ethanol, butanol, and isopropanol. Examples include alcohols, ethers, esters, etc., such as tools.
本発明の有機溶媒を分散媒とするシリカ酸化アンチモン
複合ゾルは、各種樹脂と混合することができ、織物、繊
維、プラスチック等の薙燃止剤として優れた効果を示す
。又、本発明のシリカ酸化アンチモン複合ゾルの製造方
法は、三酸化アンチモンの懸濁水に過酸化水素を反応さ
せるにさいし、Ｓ ｊ、０ 、として計算して０．１〜
５０ＩＩＩｔ％の無機珪酸化合物の存在下に反応を行う
ことを特徴とするものである。通常、三酸化アンチモン
を水に分散させ、次いで過酸化水素を添加し、所定量の
無機珪酸化合物を加えて加熱すれば安定なシリカ酸化ア
ンチモン複合ゾルを得ることができる。The silica antimony oxide composite sol of the present invention using an organic solvent as a dispersion medium can be mixed with various resins and exhibits excellent effects as a flame retardant for fabrics, fibers, plastics, etc. In addition, in the method for producing a silica antimony oxide composite sol of the present invention, when hydrogen peroxide is reacted with a suspension of antimony trioxide, S j,0 is calculated as 0.1 to 0.
This method is characterized in that the reaction is carried out in the presence of 50IIIt% of an inorganic silicic acid compound. Usually, a stable antimony silica oxide composite sol can be obtained by dispersing antimony trioxide in water, then adding hydrogen peroxide, adding a predetermined amount of an inorganic silicate compound, and heating.
本発明で使用される三酸化アンチモンとしては、水への
分散性、過酸化水素との反応性等の観点から粒子径の小
さいものが望ましく、特に１０μｍ以下の粒子径のもの
が好ましい。The antimony trioxide used in the present invention is preferably one with a small particle size from the viewpoint of dispersibility in water, reactivity with hydrogen peroxide, etc., and particularly preferably one with a particle size of 10 μm or less.
三酸化アンチモンの懸濁水に使用される水の量は、製造
されるシリカ酸化アンチモン複合ゾルの濃度どの関係で
調整されるが、一般に５ｂ２０□として５〜４（ｈｔ％
となるように調整するのが好ましい。また、過酸化水素
は５ｂ２０．１モルに対し約１．５〜２゜５モル使用さ
れる。The amount of water used for suspension of antimony trioxide is adjusted depending on the concentration of the silica antimony oxide composite sol to be produced, but it is generally 5 to 4 (ht%) as 5b20□.
It is preferable to adjust so that Further, hydrogen peroxide is used in an amount of about 1.5 to 2.5 moles per 20.1 moles of 5b.
本発明において無機珪酸化合物とは、珪酸（無水珪酸を
含む）及び珪酸塩を意味する。本発明に使用される無機
珪酸化合物は溶液又はゾルの形で使用され、例えば、珪
酸ソーダ溶液、希釈珪酸ソーダ溶液を陽イオン交換樹脂
が充填されたカラムに通して得られる珪酸液、シリカゾ
ルなどが使用可能である。特に珪酸液、シリカゾルの使
用は、生成されるシリカ酸化アンチモン複合ゾル中に原
料にもとづく不純物の混入がなく、製造工程が簡単にな
るので好ましい。In the present invention, the inorganic silicic acid compound means silicic acid (including silicic anhydride) and silicate. The inorganic silicic acid compound used in the present invention is used in the form of a solution or sol, such as a sodium silicate solution, a silicic acid solution obtained by passing a diluted sodium silicate solution through a column packed with a cation exchange resin, and a silica sol. Available for use. In particular, the use of silicic acid liquid or silica sol is preferable because the produced silica-antimony oxide composite sol is free from contamination with impurities based on the raw materials and the manufacturing process is simplified.
上記無機珪酸化合物の量は、酸化物基準で５ｉ０２とし
て０．１〜５０ｗｔ％の範囲、夕ｒましくは１〜２０ｗ
ｔ％の範囲である。無機珪酸化合物の量が０．１ｗｔ％
より少ない場合はオルガノゾル化に際し、安定なシリカ
酸化アンチモン複合ゾルが得られず、また５０ｗｔ％よ
りも多い場合は、酸化アンチモンゾルとしての特性が失
なわれるので望ましくない。The amount of the inorganic silicate compound is in the range of 0.1 to 50 wt%, preferably 1 to 20 wt% as 5i02 based on the oxide.
It is in the range of t%. The amount of inorganic silicate compound is 0.1wt%
If the amount is less, a stable silica antimony oxide composite sol cannot be obtained during organosolization, and if it is more than 50 wt %, the characteristics as an antimony oxide sol will be lost, which is not desirable.
本発明の方法におけるＭｉＪ記無機珪酸化合物の添加時
期は加熱前、加熱中あるいは加熱後のいずれであっても
よい。加熱温度としては５０℃以上、好ましくは８０〜
１３０℃の範囲ひ、５分〜５時間攪拌処理するのが望ま
しい。In the method of the present invention, the inorganic silicic acid compound MiJ may be added before, during, or after heating. The heating temperature is 50°C or higher, preferably 80°C or higher.
It is preferable to carry out the stirring treatment at 130° C. for 5 minutes to 5 hours.
本発明の方法により得られたシリカ酸化アンチモン複合
ゾルは、必要に応じて陽イオン交換樹脂に通して陽イオ
ンを除去し、濃縮して適当な濃度のゾルとすることがで
きる。The silica antimony oxide composite sol obtained by the method of the present invention can be passed through a cation exchange resin to remove cations, if necessary, and concentrated to obtain a sol of an appropriate concentration.
実施例−１
純度９８％の三酸化アンチモン４６４ｇを水５３９３ｇ
に分散させ、この分散液の中に、濃度３１％の過酸化水
素水溶液１１５２ｇとＳｉＯ□として３％に希釈した３
号珪酸ソーダ１．５００ｇを添加し、次いで１２０℃で
１０分間オートクレーブ中で加熱処理してシリカ酸化ア
ンチモン複合ゾルを調製した。このアンチモンゾルを陽
イオン交換樹脂に通してナトリウムイオンを除去した後
、限外濾過膜を通して濃縮し、 ５ｉ０２−３ｂ２０．
としてｌＯ冒ｔ％のシリカ酸化アンチモン複合ゾルを得
た。このシリカ酸化アンチモン複合ゾルは５ｉｎ２を８
ｗｔ％含んでおり、安定で室温放置して沈澱、ゲル化を
生じることなくゾル状態を維持した。このシリカ酸化ア
ンチモン複合ゾルをＡとする。Example-1 464g of antimony trioxide with a purity of 98% and 5393g of water
In this dispersion, 1152 g of hydrogen peroxide aqueous solution with a concentration of 31% and 3 diluted to 3% as SiO□ were added.
1.500 g of sodium silicate was added thereto, followed by heat treatment in an autoclave at 120° C. for 10 minutes to prepare a silica antimony oxide composite sol. This antimony sol is passed through a cation exchange resin to remove sodium ions, and then concentrated through an ultrafiltration membrane to obtain 5i02-3b20.
A silica antimony oxide composite sol with 1O % was obtained. This silica antimony oxide composite sol has 5in2 to 8
wt%, and was stable and maintained a sol state without precipitation or gelation when left at room temperature. This silica antimony oxide composite sol is designated as A.
実施例−２
純度９８％の三酸化アンチモン４６４ｇを水５３９３ｇ
に分散させ、次いで濃度３１％の過酸化水素水溶液１１
５２ｇを添加し、更に希釈した珪酸ソーダ溶液を陽イオ
ン交換樹脂に通して得られたＳｉｎ、として濃度５％の
珪酸液３８９７ ｇを添加し、混合溶液を調製した。Example-2 464g of antimony trioxide with a purity of 98% and 5393g of water
and then a hydrogen peroxide aqueous solution 11 with a concentration of 31%.
A mixed solution was prepared by adding 3897 g of a silicic acid solution with a concentration of 5% as Sin, which was obtained by passing a diluted sodium silicate solution through a cation exchange resin.
この混合溶液を還流器の付いたセパラブルフラスコに入
れ、８０℃で１時間加熱処理してシリカ酸化アンチモン
複合ゾルを調製し、次いでこのシリカ酸化アンチモン複
合ゾルを限外濾過膜を通して濃縮し、Ｓｉｎ、−３ｂ２
０ｓとして１０ｖｔ％のアンチモンゾルを得た。このシ
リカ酸化アンチモン複合ゾルはＳｉＯ□を２８ｗｔ％含
んでおり、安定で室温放置して沈澱、ゲル化を生じるこ
となくゾル状態を維持した。このシリカ酸化アンチモン
複合ゾルをＢとする。This mixed solution was placed in a separable flask equipped with a reflux device and heat-treated at 80°C for 1 hour to prepare a silica antimony oxide composite sol.Then, this silica antimony oxide composite sol was concentrated through an ultrafiltration membrane and , -3b2
An antimony sol of 10 vt% was obtained as 0s. This silica antimony oxide composite sol contained 28 wt % of SiO□, and was stable and maintained a sol state without precipitation or gelation when left at room temperature. This silica antimony oxide composite sol is designated as B.
実施例−３
純度９８％の三酸化アンチモン４６４ｇを水５３９３ｇ
に分散し、次いで濃度３１％の過酸化水素水溶液１１５
２ｇを添加し、更にＳｉｎ、として２０％のシリカゾル
９５０ｇを添加して反応混合物を調製した。Example-3 464g of antimony trioxide with a purity of 98% and 5393g of water
and then aqueous hydrogen peroxide solution 115 with a concentration of 31%.
A reaction mixture was prepared by adding 2 g of silica sol and 950 g of 20% silica sol as Sin.
この反応混合物をオートクレーブで１２０℃１０分間加
熱してシリカ酸化アンチモン複合ゾルを調製した。この
シリカ酸化アンチモン複合ゾルをロータリーエバポレー
ターで加熱濃縮して、５ｉｎ２−Ｓｂ２０．として１５
ｉ＋ｔ％の安定なアンチモンゾル得た。このシリカ酸化
アンチモン複合ゾルはＳｉｎ、を２７ｗｔ％含んでいた
。このゾルをＣとする。This reaction mixture was heated in an autoclave at 120° C. for 10 minutes to prepare a silica antimony oxide composite sol. This silica antimony oxide composite sol was heated and concentrated using a rotary evaporator to form a 5in2-Sb20. as 15
A stable antimony sol of i+t% was obtained. This silica antimony oxide composite sol contained 27 wt% of Sin. This sol is designated as C.
比較例−１
純度９８％の三酸化アンチモン４６４ｇを水５３９３ｇ
に分散させ、次いで濃度３１％の過酸化水素水溶液１１
５２ ｇを添加して反応混合物を調製した。この反応混
合物を１２０℃で２０分間オートクレーブで加熱攪拌処
理し、次いで限外濾過膜を通して濃縮し、５ｂ２ｏ、と
して１０１１ｔ％のアンチモンゾルを調製した。このア
ンチモンゾルをＤとする。Comparative Example-1 464g of antimony trioxide with a purity of 98% and 5393g of water
and then a hydrogen peroxide aqueous solution 11 with a concentration of 31%.
A reaction mixture was prepared by adding 52 g. This reaction mixture was heated and stirred in an autoclave at 120° C. for 20 minutes, and then concentrated through an ultrafiltration membrane to prepare a 1011 t% antimony sol as 5b2o. This antimony sol is designated as D.
比較例−２
純度９８％の三酸化アンチモン２９１ｇを水２５９９ｇ
に分散させ１次いで１０ｗｔ％の水酸化ナトリウム水溶
液２０ｇを添加した。Comparative Example-2 291g of antimony trioxide with a purity of 98% and 2599g of water
Then, 20 g of a 10 wt % aqueous sodium hydroxide solution was added.
この混合溶液を還流器付きのセパラブルフラスコに入れ
、８０℃に加熱し、次いで濃度３１％の過酸化水素水溶
液１４１ｇを添加し１時間加熱して。This mixed solution was placed in a separable flask equipped with a reflux device and heated to 80°C, then 141 g of a 31% hydrogen peroxide aqueous solution was added and heated for 1 hour.
ｓｂ、 ｏ、として１０ｗｔ％のアンチモンゾルを得た
。A 10 wt% antimony sol was obtained as sb, o.
このアンチモンゾルをＥとする。This antimony sol is designated as E.
比較例−３
純度９８％の三酸化アンチモン１３３ｇを水８００ｇに
分散し、濃度３％の水酸化ナトリウム３４ｇを添加して
十分に攪拌し、８０℃に加熱した。次いで濃度３１％の
過酸化水素水溶液２２３ｇを添加し。Comparative Example-3 133 g of antimony trioxide with a purity of 98% was dispersed in 800 g of water, 34 g of sodium hydroxide with a concentration of 3% was added, and the mixture was thoroughly stirred and heated to 80°C. Next, 223 g of hydrogen peroxide aqueous solution with a concentration of 31% was added.
更に１時間加熱した。さらにこのアンチモンゾルにモノ
メチルトリメトキシシラン５．５ｇを添加して８５℃で
１時間加熱した後、トリエタノールアミンを７ｇ加えて
ゾルのＰＨを７に調整した。The mixture was further heated for 1 hour. Further, 5.5 g of monomethyltrimethoxysilane was added to this antimony sol and heated at 85° C. for 1 hour, and then 7 g of triethanolamine was added to adjust the pH of the sol to 7.
このアンチモンゾルは５ｂ２ｏ、として１０ｗｔ％であ
った。このゾルをＦとする。This antimony sol was 10 wt% as 5b2o. Let this sol be F.
比較例−４
純度９８％のアンチモン酸ソーダ１４６９ ｇを水４５
０ｇに分散し、攪拌しながら濃度３５％塩酸４９０ｇを
徐々に添加した。Comparative Example-4 1469 g of sodium antimonate with a purity of 98% was added to 45 g of water.
0 g, and 490 g of 35% hydrochloric acid was gradually added while stirring.
次いで６５℃に加温し、４時間反応させて五酸化アンチ
モンゲルスラリーを得た。この五酸化アンチモンゲルス
ラリーを吸引濾過し、次いで純水で洗浄を行った。この
洗浄された五酸化アンチモンゲルケーキ１５００ｇに水
７６０ｇを添加し攪拌しなからジェタノールアミン３６
ｇを添加した。次いでこのものを９５℃で６時間保持し
て、ｓｂ、ｏ、として４０ｗｔ％のアンチモンゾルを得
た。Next, the mixture was heated to 65°C and reacted for 4 hours to obtain an antimony pentoxide gel slurry. This antimony pentoxide gel slurry was suction filtered and then washed with pure water. Add 760 g of water to 1500 g of this washed antimony pentoxide gel cake, stir, and add 36 g of jetanolamine.
g was added. This product was then held at 95° C. for 6 hours to obtain an antimony sol containing 40 wt % as sb,o.
このアンチモンゾルをＧとする。This antimony sol is designated as G.
実施例−４
実施例及び比較例で得たアンチモンゾルＡ〜Ｇの各々に
ついて、イソプロピルアルコールで溶媒置換してオルガ
ノゾル化を行った。Example 4 Each of antimony sols A to G obtained in Examples and Comparative Examples was converted into an organosol by replacing the solvent with isopropyl alcohol.
夫々のアンチモンゾル５００ｇをロータリーエバポレー
ターに入れ、イソプロピルアルコールを徐々に添加しな
がら加熱して水分を蒸発させ、水分含有量が３ｗｔ％以
下にして、オルガノゾル化した。500 g of each antimony sol was placed in a rotary evaporator and heated while gradually adding isopropyl alcohol to evaporate water to reduce the water content to 3 wt % or less to form an organosol.
表−１に夫々のオルガノアンチモンゾルの性状を示す。Table 1 shows the properties of each organoantimony sol.
表−１
ぞれのゾルに浸漬した後、１３０℃で２４時間乾燥した
。次いでブンゼンバーナーの酸化炎中に２秒間保持し、
燃え残りの重量を測定して難燃性を次式により表わした
。Table 1 After being immersed in each sol, it was dried at 130°C for 24 hours. Then held in the oxidizing flame of a Bunsen burner for 2 seconds,
The weight of the unburnt residue was measured and the flame retardancy was expressed by the following formula.
本発明によるアンチモンゾルはオルガノゾル化するに際
し、ゲル化することなく、また、得られたオルガノゾル
も長期間放置しても沈澱を生じることなく安定であった
。The antimony sol according to the present invention did not gel during organosolization, and the obtained organosol was stable without forming a precipitate even after being left for a long period of time.
実施例−５
実施例３のシリカ酸化アンチモン複合ゾルＣ及び比較例
１の酸化アンチモンゾルＤを用いて難燃性のテストを行
った。定量用濾紙片をそれこの尺度で表わした難燃性の
値はシリカ酸化アンチモン複合ゾルＣは４２％で酸化ア
ンチモンゾルＤは３８％であった。Example 5 A flame retardancy test was conducted using the silica antimony oxide composite sol C of Example 3 and the antimony oxide sol D of Comparative Example 1. The flame retardance values of quantitative filter paper pieces expressed on a scale were 42% for silica antimony oxide composite sol C and 38% for antimony oxide sol D.
本発明のシリカ酸化アンチモン複合ゾルは、長期間の放
置に対しても安定であり、またオルガノゾル化に際し、
ゲル化することなく安定してゾルの状態を維持する特徴
を有する。The silica antimony oxide composite sol of the present invention is stable even when left for a long period of time, and when converted into an organosol,
It has the characteristic of stably maintaining a sol state without gelation.
また本発明のゾルは、温度変化、ｐＨ変化に対しても安
定であり、高分子ラテックス、高分子溶液への添加にも
安定であり、織物、ａｔ維、プラスチック等の難燃化剤
として広く利用されるほか、コーティング剤としても有
用である。Furthermore, the sol of the present invention is stable against temperature changes and pH changes, and is also stable when added to polymer latex and polymer solutions, and is widely used as a flame retardant for textiles, AT fibers, plastics, etc. In addition to being used as a coating agent, it is also useful.
Claims (1)
の無機珪酸化合物を含有する酸化アンチモンコロイド粒
子を分散せしめたシリカ酸化アンチモン複合ゾル。 ２、請求項１記載のシリカ酸化アンチモン複合ゾルより
なる難燃化剤。 ３、三酸化アンチモンの懸濁水に過酸化水素を反応させ
るにさいし、ＳｉＯ＿２として０．１〜５０ｗｔ％の無
機珪酸化合物の存在下に反応を行うことを特徴とするシ
リカ酸化アンチモン複合ゾルの製造方法。[Claims] 1. 0.1 to 50 wt% as SiO_2 in the dispersion medium
A silica antimony oxide composite sol in which antimony oxide colloidal particles containing an inorganic silicate compound are dispersed. 2. A flame retardant comprising the silica antimony oxide composite sol according to claim 1. 3. A method for producing a silica antimony oxide composite sol, characterized in that the reaction is carried out in the presence of 0.1 to 50 wt% of an inorganic silicate compound as SiO_2 when reacting hydrogen peroxide to a suspension of antimony trioxide. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63332363A JPH0725549B2 (en) | 1988-12-28 | 1988-12-28 | Silica antimony oxide composite sol, method for producing the same and flame retardant comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63332363A JPH0725549B2 (en) | 1988-12-28 | 1988-12-28 | Silica antimony oxide composite sol, method for producing the same and flame retardant comprising the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02174929A true JPH02174929A (en) | 1990-07-06 |
| JPH0725549B2 JPH0725549B2 (en) | 1995-03-22 |
Family
ID=18254119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63332363A Expired - Lifetime JPH0725549B2 (en) | 1988-12-28 | 1988-12-28 | Silica antimony oxide composite sol, method for producing the same and flame retardant comprising the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0725549B2 (en) |
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| CN104045854A (en) * | 2014-06-09 | 2014-09-17 | 无棣润泽化工有限公司 | Nano Sb2O3-SiO2 composite aerogel inorganic flame retardant and preparation method thereof |
| CN109056341A (en) * | 2018-08-03 | 2018-12-21 | 安徽农业大学 | A kind of fire-retardant, vapor-permeable type automotive interior material preparation method |
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| JP4561955B2 (en) * | 2002-12-03 | 2010-10-13 | 日産化学工業株式会社 | Modified stannic oxide sol, stannic oxide-zirconium oxide composite sol and method for producing the same |
| US7556682B2 (en) | 2005-08-09 | 2009-07-07 | Nissan Chemical Industries, Ltd. | Zirconium oxide-tin oxide composite sol, coating composition and optical member |
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- 1988-12-28 JP JP63332363A patent/JPH0725549B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52140490A (en) * | 1976-05-19 | 1977-11-24 | Nitto Chem Ind Co Ltd | Production of fluid catalyst containing antimony oxide |
| JPS5425949A (en) * | 1977-07-29 | 1979-02-27 | Iwata Air Compressor Mfg | Electroststic coating gun |
| JPS59108064A (en) * | 1982-11-26 | 1984-06-22 | ダウ・コ−ニング・コ−ポレ−シヨン | Aqueous composition for coating |
| JPS60166039A (en) * | 1984-02-07 | 1985-08-29 | Nitto Chem Ind Co Ltd | Manufacture of oxide catalyst containing antimony |
| JPS62273270A (en) * | 1986-05-21 | 1987-11-27 | Nissan Chem Ind Ltd | Electrically conductive inorganic coating agent and its production |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045854A (en) * | 2014-06-09 | 2014-09-17 | 无棣润泽化工有限公司 | Nano Sb2O3-SiO2 composite aerogel inorganic flame retardant and preparation method thereof |
| CN104045854B (en) * | 2014-06-09 | 2016-11-02 | 无棣润泽化工有限公司 | A kind of nanometer Sb2o3-SiO2composite aerogel inorganic combustion inhibitor and preparation method |
| CN109056341A (en) * | 2018-08-03 | 2018-12-21 | 安徽农业大学 | A kind of fire-retardant, vapor-permeable type automotive interior material preparation method |
| CN109056341B (en) * | 2018-08-03 | 2021-07-23 | 安徽农业大学 | Preparation method of flame-retardant and breathable automobile interior material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0725549B2 (en) | 1995-03-22 |
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