JPH01129032A - Ladderlike polytitanoxane and its production - Google Patents
Ladderlike polytitanoxane and its productionInfo
- Publication number
- JPH01129032A JPH01129032A JP28588287A JP28588287A JPH01129032A JP H01129032 A JPH01129032 A JP H01129032A JP 28588287 A JP28588287 A JP 28588287A JP 28588287 A JP28588287 A JP 28588287A JP H01129032 A JPH01129032 A JP H01129032A
- Authority
- JP
- Japan
- Prior art keywords
- polytitanoxane
- ladder
- sample
- reaction
- molecular weight
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000009835 boiling Methods 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 57
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Chemical group 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 22
- 239000003960 organic solvent Substances 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 12
- 238000003980 solgel method Methods 0.000 abstract description 7
- 125000001424 substituent group Chemical group 0.000 abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical group 0.000 abstract 2
- 239000002245 particle Substances 0.000 abstract 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 35
- 239000007787 solid Substances 0.000 description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 16
- 239000010409 thin film Substances 0.000 description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 12
- 238000007710 freezing Methods 0.000 description 10
- 230000008014 freezing Effects 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- -1 2-ethylhexyl group Chemical group 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004380 ashing Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000013365 molecular weight analysis method Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 4
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229960005235 piperonyl butoxide Drugs 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- KFVUXNKQQOUCAH-UHFFFAOYSA-N butan-1-ol;propan-2-ol Chemical compound CC(C)O.CCCCO KFVUXNKQQOUCAH-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- RASBDVLERRNNLJ-UHFFFAOYSA-N CCCCO[Ti] Chemical compound CCCCO[Ti] RASBDVLERRNNLJ-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000010792 warming Methods 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、ポリチタノキサンに係り、さらに詳しくは、
ラダー状構造を有する新規ポリチタノキサンおよびその
選択的な製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to polytitanoxane, and more specifically,
The present invention relates to a novel polytitanoxane having a ladder-like structure and a selective manufacturing method thereof.
本発明のポリチタノキサンは、有機溶剤溶解性であるこ
とから、その溶液をゾル−ゲル法による酸化チタン薄膜
、高純度酸化チタン微粒子、各種チタン酸塩等の製造原
料として利用することができる。Since the polytitanoxane of the present invention is soluble in organic solvents, its solution can be used as a raw material for producing titanium oxide thin films, high-purity titanium oxide fine particles, various titanates, etc. by the sol-gel method.
また、ヒドロキシ基およびアルコキシ基以外の置換基を
有するラダー状ポリチタノキサン誘導体の製造原料とし
て、極めて有用である。In addition, it is extremely useful as a raw material for producing ladder-like polytitanoxane derivatives having substituents other than hydroxy groups and alkoxy groups.
テトラアルコキシチタンを加水分解して得られるポリチ
タノキサンの構造として、鎖状構造や環状構造を推定す
る報告が種々なされているが（ソビエト科学アカデミー
速報、化学部門、 ｐ１０４５． （１９６Ｂ） 、工
業化学雑誌、第５８巻、第１号、ｐ３６〜（１９５５）
、ジャーナル・オプ・アメリカンケミカルソサイエティ
ー、ム、 １７２０〜（１９６５）、ネイチャー、 Ｖ
ｏｌ、１８８．３１３〜（１９６０）等参照）、ラダー
状構造を有するポリチタノキサンおよびそれを選択的に
製造する方法を記載した文献は知られていない。There have been various reports estimating a chain structure or a cyclic structure as the structure of polytitanoxane obtained by hydrolyzing tetraalkoxytitanium (Bulletin of the Soviet Academy of Sciences, Department of Chemistry, p1045. (196B), Journal of Industrial Chemistry, Volume 58, No. 1, p36~ (1955)
, Journal of the American Chemical Society, Mu, 1720-(1965), Nature, V
No literature is known that describes polytitanoxane having a ladder structure and a method for selectively producing it.
テトラアルコキシチチクを加水分解、縮重合して得られ
る有機溶剤可溶性のポリチタノキサンは、通常、下記一
般式
％式％）
（ここに、Ｒｏは、１僅の炭化水素基を表し、ｌは、１
〜２０の正数である。）
で表される鎖状ポリチタノキサンであり、ゾル−ゲル法
用の薬剤として広く使用されている。しかしながら、こ
の鎖状ポリチタノキサンは、式中のｌが大きくなるとゲ
ル化し、有機溶剤に不溶となる。また、この鎖状ポリチ
タノキサンの溶液を用いゾル−ゲル法により酸化チタン
薄膜を製造すると、テトラアルコキシチタン溶液を用い
た場合よりは緻密な薄膜が得られるものの、その緻密度
は電気・電子グレードや光学グレードとしては不十分で
ある。Organic solvent-soluble polytitanoxane obtained by hydrolyzing and polycondensing tetraalkoxylic acid is usually prepared using the following general formula (% formula %) (where Ro represents one small hydrocarbon group, and l is 1
It is a positive number of ~20. ) It is a chain polytitanoxane represented by the following formula, and is widely used as a drug for the sol-gel method. However, when l in the formula becomes large, this chain polytitanoxane gels and becomes insoluble in organic solvents. In addition, when a titanium oxide thin film is manufactured by the sol-gel method using a solution of this linear polytitanoxane, a thin film that is denser than that obtained using a tetraalkoxytitanium solution can be obtained; The grade is insufficient.
ゾル−ゲル法による酸化チタン薄膜の緻密度は、有機溶
剤溶解性のさらに高分子量のポリチタノキ度の高いポリ
チタノキサンを用いることにより、向上可能と推定され
る。It is presumed that the density of the titanium oxide thin film produced by the sol-gel method can be improved by using polytitanoxane, which has a higher molecular weight and a higher degree of polytitanolyte, and is soluble in an organic solvent.
合密度の高いラダー状構造を有する新規ポリチクツキサ
ンおよびその選択的な製造方法を提供することを、その
目的とする。The object of the present invention is to provide a novel polythicutuxane having a ladder-like structure with high integration density and a selective manufacturing method thereof.
本発明者等は、前記目的を達成すべく鋭意研究した結果
、通常の方法でテトラアルコキシチタンを加水分解した
後、低沸物を留去して得られたポリチタノキサンが、分
子量が２０．０００にも達するにも拘らず有機溶剤に可
溶性であること、およびこのポリチタノキサンがラダー
状構造を有する新規ポリチタノキサンであることを見出
し、本発明を完成した。As a result of intensive research to achieve the above object, the present inventors have found that polytitanoxane obtained by hydrolyzing tetraalkoxytitanium in a conventional manner and then distilling off low-boiling substances has a molecular weight of 20.000. The present invention was completed based on the discovery that the polytitanoxane is soluble in organic solvents even though the polytitanoxane has a ladder-like structure.
本発明は、下記構造式（１１または（２）で表されるラ
ダー状ポリチタノキサンである。The present invention is a ladder-like polytitanoxane represented by the following structural formula (11 or (2)).
本発明のラダー状ポリチタノキサンにおいて、前記構造
式（１１および（２）中のＲは、水素原子および炭素数
１〜１８の１価の炭化水素基よりなる群から選ばれた１
種または２種以上（ただし、水素原子は、全Ｒの１５％
を越えない、）であり、ｎおよびｍが１〜８０の正数で
ある。In the ladder polytitanoxane of the present invention, R in the structural formulas (11 and (2)) is 1 selected from the group consisting of a hydrogen atom and a monovalent hydrocarbon group having 1 to 18 carbon atoms.
species or two or more species (however, hydrogen atoms account for 15% of the total R)
), and n and m are positive numbers from 1 to 80.
炭素数１〜１８の１価の炭化水素基として、直鎖または
分岐を有する飽和または不飽和の脂肪族炭化水素基、ア
ルキル基またはアルコキシ基で置換されていてもよい環
状脂肪族炭化水素基、芳香族炭化水素基、アリル基など
が挙げられ、さらに具体的には、メチル基、エチル基、
プロピル基、イソプロピル基、ブチル基、ｔ−ブチル基
、ペンチル基、ヘキシル基、シクロヘキシル基、オクチ
ル基、２−エチルヘキシル基、デシル基、ドデシル基、
ステアリル基等の脂肪族炭化水素基、フェニル基、メチ
ルフェニル基、エトキシフェニル基、ベンジル基等の芳
香族炭化水素基が例示できる。As a monovalent hydrocarbon group having 1 to 18 carbon atoms, a cyclic aliphatic hydrocarbon group optionally substituted with a linear or branched saturated or unsaturated aliphatic hydrocarbon group, an alkyl group or an alkoxy group, Examples include aromatic hydrocarbon groups, allyl groups, and more specifically, methyl groups, ethyl groups,
Propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group,
Examples include aliphatic hydrocarbon groups such as stearyl group, and aromatic hydrocarbon groups such as phenyl group, methylphenyl group, ethoxyphenyl group, and benzyl group.
これらは、１種の単独でもよく、また、２種以上であっ
てもよい。These may be used alone or in combination of two or more.
また、Ｒとして水素原子を含有する場合には、水素原子
は、全Ｒの１５％を越えることはない。Further, when hydrogen atoms are contained as R, the hydrogen atoms do not exceed 15% of the total R.
Ｒ中の水素原子が過大となると、ポリチタノキサン中の
水素原子と炭化水素基とが反応してより複雑なポリマー
構造をとるため、極めて不安定であり、かつ、有機溶媒
に不溶性となる。If the hydrogen atoms in R are too large, the hydrogen atoms and hydrocarbon groups in polytitanoxane react to form a more complex polymer structure, making it extremely unstable and insoluble in organic solvents.
前記構造式（１）中のｎおよび構造式（２）中のｍは、
ラダー状ポリチタノキサンの縮合度を表し、縮合度が１
〜８０の範囲では、有機溶剤に可溶である。n in the structural formula (1) and m in the structural formula (2) are,
It represents the degree of condensation of ladder-like polytitanoxane, and the degree of condensation is 1.
-80, it is soluble in organic solvents.
本発明のラダー状ポリチタノキサンは、置換基Ｒの種類
、縮合度等により異なるが、白色固体物質または粘稠な
液体物質であり、各種の有機溶剤に可溶性である。The ladder-like polytitanoxane of the present invention is a white solid substance or a viscous liquid substance, and is soluble in various organic solvents, although it varies depending on the type of substituent R, degree of condensation, etc.
本発明のラダー状ポリチタノキサンは、下記−般式（３
）
％式％
（ここに、Ｒｏは、炭素数１〜１８の１価の炭化水素基
の少なくとも１種を表す、）
で表されるテトラアルコキシチタンを、１．０倍モル以
上１．７倍モル以下の水を用いて２０〜９０℃の温度下
において加水分解し、ついで低沸物を留去することによ
り製造することができる。The ladder-like polytitanoxane of the present invention has the following general formula (3
) % Formula % (Here, Ro represents at least one type of monovalent hydrocarbon group having 1 to 18 carbon atoms.) Tetraalkoxytitanium represented by It can be produced by hydrolyzing at a temperature of 20 to 90° C. using less than a molar amount of water, and then distilling off low-boiling substances.
一般式（３）中のＲｏとして、前記構造式（２）および
（３）中のＲとして例示した炭素数１〜１８の炭化水素
基が挙げられる。Examples of Ro in the general formula (3) include the hydrocarbon groups having 1 to 18 carbon atoms as exemplified as R in the structural formulas (2) and (3).
ラダー状ポリチタノキサン合成の容易さを考慮すると、
原料テトラアルコキシチタンとして、−般式（３）中の
Ｒｏが炭素数１〜６の低級アルキル基であるテトラアル
コキシチタンを使用するのが好ましく、さらに好ましく
は入手の容易なテトライソプロポキシチタンまたはテト
ラブトキシチタンを使用する Ｒｌ として、さらに大
きな炭素数の炭化水素基を導入する場合には、Ｒｏが低
級アルキル基であるテトラアルコキシチタンを用いて加
水分解を行った後、常法によりエステル変換を行うこと
により、目的とする置換基を有するラダー状ポリチタノ
キサンを得ることができる。Considering the ease of synthesizing ladder-like polytitanoxane,
As the raw material tetraalkoxytitanium, it is preferable to use tetraalkoxytitanium in which Ro in the general formula (3) is a lower alkyl group having 1 to 6 carbon atoms, more preferably tetraisopropoxytitanium or tetraisopropoxytitanium, which is easily available. When introducing a hydrocarbon group with a larger number of carbon atoms as Rl using butoxytitanium, perform hydrolysis using tetraalkoxytitanium in which Ro is a lower alkyl group, and then perform ester conversion using a conventional method. By doing so, it is possible to obtain a ladder-like polytitanoxane having the desired substituent.
本発明において、前記テトラアルコキシチタンを常法に
より加水分解した後、要すればエステル変換を行い、つ
いで、溶剤、副生アルコール、未反応テトラアルコキシ
チタンなどの低沸物を、減圧下に留去する。加水分解反
応は、加水分解により副生ずるアルコールと同一のアル
コールを反応溶剤とし、さらに同一のアルコールに原料
テトラアルコキシチタン１モルに対して水１．０〜１．
７モルを溶解した溶液を徐々に添加し、さらに加熱還流
下に攪拌保持して熟成する。エステル変換反応は、ポリ
チタノキサン１モルに対してエステル変換を希望するモ
ル数の目的とする１価の炭化水素基を有するアルコール
を添加し、加熱還流下に攪拌保持することにより行う。In the present invention, after the tetraalkoxytitanium is hydrolyzed by a conventional method, ester conversion is performed if necessary, and then low-boiling substances such as the solvent, by-product alcohol, and unreacted tetraalkoxytitanium are distilled off under reduced pressure. do. In the hydrolysis reaction, the same alcohol as the alcohol by-produced by the hydrolysis is used as a reaction solvent, and 1.0-1.
A solution containing 7 mol of the solution was gradually added, and the mixture was heated and kept stirring under reflux for ripening. The ester conversion reaction is carried out by adding the desired number of moles of alcohol having a monovalent hydrocarbon group to 1 mole of polytitanoxane, and stirring and maintaining the mixture under heating and reflux.
本発明は、前記構造式＋１＋または（２）で表されるラ
ダー状構造を有することを特徴とする新規ポリチタノキ
サンである。The present invention is a novel polytitanoxane characterized by having a ladder-like structure represented by the structural formula +1+ or (2).
本発明のラダー状ポリチタノキサンは、前記したように
分子量が、２０．０００にも達するに拘らず各種有機溶
剤に可溶性である。この有機溶剤可溶性は、そのラダー
状構造に起因するものと推定される。したがって、本発
明のラダー状ポリチタノキサンは、有機溶剤に可溶性で
あり、かつ、分子中の−Ｔｉ −０−Ｔｉ−結合密度が
、鎖状ポリチタノキサンに比較して大きいため、ゾル−
ゲル法用のチタン原料として好適である。As described above, the ladder-shaped polytitanoxane of the present invention is soluble in various organic solvents even though its molecular weight reaches 20,000. This solubility in organic solvents is presumed to be due to its ladder-like structure. Therefore, the ladder-like polytitanoxane of the present invention is soluble in organic solvents and has a larger -Ti-0-Ti- bond density in the molecule than that of the chain polytitanoxane.
Suitable as a titanium raw material for gel method.
また、本発明のラダー状ポリチタノキサンの製造方法に
おいて、ポリチタノキサンのラダー化は、テトラアルコ
キシチタンの加水分解反応後の低沸物の留去操作により
進行するものと推定される。In addition, in the method for producing ladder-shaped polytitanoxane of the present invention, it is presumed that the formation of polytitanoxane into a ladder proceeds by the operation of distilling off low-boiling substances after the hydrolysis reaction of tetraalkoxytitanium.
本発明を、実施例および参考例によりさらに詳細に説明
する。The present invention will be explained in more detail by Examples and Reference Examples.
ただし、本発明の範囲は、以下の実施例により同等限定
されるものではない。However, the scope of the present invention is not limited to the same extent by the following examples.
なお、以下の例中において、「部」および「％」は、断
りのない限り重量基準である。In addition, in the following examples, "parts" and "%" are based on weight unless otherwise specified.
（１） ラダー状ポリチタノキサンの合成（ａ）
試料（Ｔ−１）
ポリチタノキサンイソプロポキシド
攪拌装置、温度計、加熱冷却装置および還流冷却機を備
えた反応フラスコに、テトライソプロポキシチタン２８
４ｇ （１モル）を仕込み、良く混合しながら８０℃に
加温保持した。この中に、水１８ｇ（１モル）とイソプ
ロパツール２７０ｇとの混合溶液を徐々に添加した後、
８５℃に昇温し還流下に１時間攪拌保持して反応を熟成
した。(1) Synthesis of ladder-like polytitanoxane (a)
Sample (T-1) Polytitanoxane isopropoxide In a reaction flask equipped with a stirrer, a thermometer, a heating and cooling device, and a reflux condenser, tetraisopropoxytitanium 28
4 g (1 mol) was charged and kept heated at 80° C. with thorough mixing. After gradually adding a mixed solution of 18 g (1 mol) of water and 270 g of isopropanol into this,
The temperature was raised to 85° C. and the reaction was aged by stirring and maintaining under reflux for 1 hour.
反応液を冷却後、ロータリーエバポレーターを用いて５
０℃Ｘ ２０ Ｔｏｒｒの条件で溶剤のイソプロパツー
ルを留去し、さらに真空蒸留装置を用いて１２０℃Ｘ
０． Ｉ Ｔｏｒｒの条件で低沸物を留去し、白色固体
物質（Ａ−１）１３１ｇを得た。After cooling the reaction solution, use a rotary evaporator for 5
The solvent, isopropanol, was distilled off under conditions of 0°C and 20 Torr, and further heated to 120°C and 20 Torr using a vacuum distillation apparatus.
0. Low-boiling substances were distilled off under I Torr conditions to obtain 131 g of a white solid substance (A-1).
得られた白色固体物質の凝固点降下法で測定した分子量
および元素分析値は、下記の遺りであった。The molecular weight and elemental analysis values of the obtained white solid substance measured by the freezing point depression method were as follows.
分子量 Ｔｉ１ｔ −０ＣＩＩ（Ｃ）Ｉｓ）
ｚ分析値 １．２００ ５０．７％ ５６．６％理
論値 １，２５２ ５１．１％ ５６．６％（Ｔｉ
Ｏｚは、灰化法による測定値）
また、この白色固体物質を熱重量分析した結果、添付第
１図（ａ）に示すように、３５０℃と３８０℃付近の２
個所に発熱ピークが認められ、３５０℃付近の１個所に
発熱ピークが認められる従来法で合成したポリチタノキ
サン（第１図（ｂｌ参照）と異なるパターンを示した。Molecular weight Ti1t-0CII(C)Is)
Z analysis value 1.200 50.7% 56.6% theoretical value 1,252 51.1% 56.6% (Ti
(Oz is the value measured by the ashing method) In addition, as a result of thermogravimetric analysis of this white solid substance, as shown in attached Figure 1 (a),
An exothermic peak was observed at one location near 350° C., showing a different pattern from polytitanoxane synthesized by the conventional method (see FIG. 1 (see BL)).
以上の結果より、得られた白色固体物質は、下記構造式
（４）で示すラダー状ポリチタノキサンと推定した。From the above results, it was estimated that the obtained white solid substance was a ladder-like polytitanoxane represented by the following structural formula (4).
Ｒ麿−ＣＨ（ＣＨい鵞
（ｂｌ 試料（Ａ−２）
ポリチタノキサンブトキシド
攪拌装置、温度計、加熱冷却装置および還流冷却機を備
えた反応フラスコに、テトラブトキシチタン３４０ｇ
（１モル）を仕込み、良（混合しながら７０℃に加温保
持した。この中に、水１８ｇ（１モル）とｎ−ブタノー
ル２７０ｇとの混合溶液を徐々に添加した後、８５℃に
昇温し還流下に１時間攪拌保持して反応を熟成した。R Maro-CH (CH Iro (bl Sample (A-2)) Polytitanoxane butoxide 340 g of tetrabutoxy titanium was placed in a reaction flask equipped with a stirrer, a thermometer, a heating and cooling device, and a reflux condenser.
(1 mol) was heated and maintained at 70°C while mixing. After gradually adding a mixed solution of 18 g (1 mol) of water and 270 g of n-butanol, the temperature was raised to 85°C. The reaction was aged by warming and maintaining stirring under reflux for 1 hour.
反応液を冷却後、ロータリーエバポレーターを用いて８
０℃×２〜３ Ｔｏｒｒの条件で溶剤のｎ−ブタノール
を留去し、さらに真空蒸留装置を用いて１９０〜２００
℃ｘ ０． Ｉ Ｔｏｒｒの条件で低沸物を留去し、白
色固体物質（Ａ−２）１６５ｇを得た。After cooling the reaction solution, use a rotary evaporator to
The solvent n-butanol was distilled off under the conditions of 0°C x 2-3 Torr, and then the temperature was reduced to 190-200°C using a vacuum distillation apparatus.
°C x 0. Low-boiling substances were distilled off under I Torr conditions to obtain 165 g of a white solid substance (A-2).
得られた白色固体物質の凝固点降下法で測定した分子量
および元素分析値は、下記構造式（５）で示すラダー状
ポリチタノキサンの分子量および理論値と良く一致した
。The molecular weight and elemental analysis value of the obtained white solid substance measured by the freezing point depression method were in good agreement with the molecular weight and theoretical value of ladder-like polytitanoxane represented by the following structural formula (5).
分子量 Ｔｉ（ｈ −０（ＣＩ（ｇ）＋ＣＨｓ
分析値 １，１００ ４５．３％ ６２．７％理論
値 １．０？４ ４５．８％ ６２．８％（Ｔｉ（
ｈは、灰化法による測定値）
Ｒ−−Ｈｘｌおよび−（ＣＨｚ）ｓＣＨｓ Ｘ ９（Ｃ
１試料（Ａ−３）
ポリチタノキサン２−エチルヘキソキシド攪拌装置、温
度計、加熱冷却装置および還流冷却機を備えた反応フラ
スコに、テトラ２−゛エチルヘキソキシチク２５６５ｇ
（１モル）を仕込み、良く混合しながら８０℃に加温
保持した。この中に、水１８ｇ（１モル）と２−エチル
ヘキサノール２７０ｇとの混合溶液を徐々に添加した後
、８５℃に昇温し還流下に１時間攪拌保持して反応を熟
成した。Molecular weight Ti(h −0(CI(g)+CHs
Analytical value 1,100 45.3% 62.7% Theoretical value 1.0?4 45.8% 62.8% (Ti(
h is a value measured by the ashing method) R--Hxl and -(CHz)sCHs
1 sample (A-3) Polytitanoxane 2-ethylhexoxide 2565 g of tetra-2-ethylhexoxide was placed in a reaction flask equipped with a stirrer, a thermometer, a heating and cooling device, and a reflux condenser.
(1 mol) was added and heated and maintained at 80° C. while thoroughly mixing. After gradually adding a mixed solution of 18 g (1 mole) of water and 270 g of 2-ethylhexanol to this mixture, the temperature was raised to 85° C. and stirred and maintained under reflux for 1 hour to ripen the reaction.
反応液を冷却後、ロータリーエバポレーターを用いて８
０℃Ｘ Ｉ Ｔｏｒｒの条件で溶剤の２−エチルヘキサ
ノールを留去し、さらに真空蒸留装置を用いて１５０
Ｘ ０． Ｉ Ｔｏｒｒの条件で低沸物を留去し、白色
固体物質（Ａ−３）２３３ｇを得た。After cooling the reaction solution, use a rotary evaporator to
The solvent, 2-ethylhexanol, was distilled off under the conditions of 0°C x I Torr, and then heated to 150°C using a vacuum distillation apparatus.
X 0. Low-boiling substances were distilled off under I Torr conditions to obtain 233 g of a white solid substance (A-3).
得られた白色固体物質の凝固点降下法で測定した分子量
および元素分析値は、下記構造式（６）で示すラダー状
ポリチタノキサンの分子量および理論値と良く一致した
。The molecular weight and elemental analysis value of the obtained white solid substance measured by freezing point depression method were in good agreement with the molecular weight and theoretical value of ladder-like polytitanoxane represented by the following structural formula (6).
分子量 ＴｉＯ□ −０ＣＨｚＣＩＩ（ＣＨｔ）
５ＣＨｓＣ，Ｈ。Molecular weight TiO□ -0CHzCII(CHt)
5CHsC,H.
分析値 １．７１０ ２７．６％ ６２．７％理論
値 １，６９０ ２７．４％ ６２．８％（ＴｉＯ
ｇは、灰化法による測定値）
ＲＯＯＲＯＲ
Ｒ−−ｃｏ＊ｃｏ（ｃｚｕｓ）（Ｃｕｔ） ｓｃＨ。Analytical value 1.710 27.6% 62.7% Theoretical value 1,690 27.4% 62.8% (TiO
g is a value measured by the ashing method) ROOROR R--co*co(czus)(Cut) scH.
（ｄ） 試料（Ａ−４）
ポリチタノキサンイソプロポキシド
試料（Ａ−１）の合成において、水およびイソプロパツ
ールの使用量を、水２３．４ｇ （１，３モル）および
イソプロパツール３５１ｇに代えた以外には、試料（Ａ
−１）の合成と条件と同一の条件で反応および後処理を
行い白色固体物質（Ａ−４）１５１ｇを得た。(d) Sample (A-4) In the synthesis of polytitanoxane isopropoxide sample (A-1), the amounts of water and isopropanol used were changed to 23.4 g (1.3 mol) of water and isopropanol. Except for replacing it with 351g, the sample (A
The reaction and post-treatment were carried out under the same conditions as the synthesis and conditions of -1) to obtain 151 g of a white solid substance (A-4).
得られた白色固体物質Φ凝固点降下法で測定した分子量
および元素分析値は、下記構造式（７）で示すラダー状
ポリチタノキサンの分子量および理論値と良く一致した
。The molecular weight and elemental analysis values of the obtained white solid substance measured by the Φ freezing point depression method were in good agreement with the molecular weight and theoretical value of the ladder-like polytitanoxane represented by the following structural formula (7).
分子量 ＴｉＯｘ −０ＣＲ（ＣＨ３） ｚ分
析値 １，２９０ ５１．２％ ５６．８％理論値
１．２５２ ５１．１％ ５６．６％（ＴｉＯｉ
は、灰化法による測定値）
ＲＯＯＲＯＲＯＲ
Ｒ０−Ｔｉ−０−Ｔｉ−０−Ｔｉ ０−Ｔｉ ＯＲ
Ｒ＝ Ｃ０（ＣＬ）ｔ
（ｅ） 試料（Ａ−５）
ポリチタノキサンブトキシド
試料（Ａ−２）の合成において、水およびブタノールの
使用量を、水３０．６ｇ（１，７モル）およびブタノー
ル４５９ｇに代えた以外には、試料（Ａ−２）の合成と
条件と同一の条件で反応および後処理を行い白色固体物
質（Ａ−５）、 １１９ｇを得た。Molecular weight TiOx -0CR(CH3) z analysis value 1,290 51.2% 56.8% theoretical value 1.252 51.1% 56.6% (TiOi
is the value measured by the ashing method) ROOROROR R0-Ti-0-Ti-0-Ti 0-Ti OR
R= C0(CL)t (e) Sample (A-5) In the synthesis of polytitanoxane butoxide sample (A-2), the amount of water and butanol used was changed to 30.6 g (1.7 mol) of water and The reaction and post-treatment were carried out under the same conditions as the synthesis and conditions of sample (A-2), except that 459 g of butanol was used instead, and 119 g of a white solid substance (A-5) was obtained.
得られた白色固体物質の凝固点降下法で測定した分子量
および元素分析値は、下記構造式（８）で示すラダー状
ポリチタノキサンの分子量および理論値と良く一致した
。The molecular weight and elemental analysis values of the obtained white solid substance measured by the freezing point depression method were in good agreement with the molecular weight and theoretical value of ladder-like polytitanoxane represented by the following structural formula (8).
分子量 ７ｉ０１ −０（ＣＨｔ）ｉｃＨｓ分析
値 ２０．０００ ５７．３％ ４６．６％理論値
２０．０２０ ５？、５％ ４６．７％（Ｔｉ（ｈは
、灰化法による測定値）
Ｒ−−（ＣＬ） ｓｃＨコ
（ｆ） 試料（Ａ−６）
ポリチタノキサンイソプロポキシドー
ジ（２−エチルヘキソキシド）
試料（Ａ−１＞のポリチタノキサンイソプロポキシド１
，２００ｇ（１モル）を脱水イソプロパツール１２００
ｇに溶解して試料（Ａ−１）の合成に用いた反応装置に
仕込み、攪拌下に２−エチルヘキサノール２６０ｇ（２
モル）を徐々に添加した。添加終了後、８０℃に昇温し
２時間反応を継続した。ついで、ロータリーエバポレー
ターを用い５０℃Ｘ ２０Ｔｏｒｒの条件でイソプロパ
ツールおよび低沸物を留去し、白色固体物質（Ａ−６）
を得た。Molecular weight 7i01 -0(CHt)icHs Analysis value 20.000 57.3% 46.6% Theoretical value
20.020 5? , 5% 46.7% (Ti (h is the value measured by the ashing method) R--(CL) scH co(f) Sample (A-6) Polytitanoxane isopropoxide d) Sample (A-1> polytitanoxane isopropoxide 1
, 200g (1 mol) of isopropanol 1200
g of 2-ethylhexanol and charged into the reaction apparatus used for the synthesis of sample (A-1), and 260 g of 2-ethylhexanol (2
mol) was added gradually. After the addition was completed, the temperature was raised to 80°C and the reaction was continued for 2 hours. Then, isopropanol and low-boiling substances were distilled off using a rotary evaporator at 50°C and 20 Torr to obtain a white solid substance (A-6).
I got it.
得られた白色固体物質の凝固点降下法により測定した分
子量は、１，３４０であり、また、回収したイソプロパ
ツールは、１，３２０．５ｇであった。The molecular weight of the obtained white solid substance measured by freezing point depression method was 1,340, and the amount of recovered isopropanol was 1,320.5 g.
得られた白色固体物質の分子量は、試料（Ａ−１）のイ
ソプロポキシ基の２個が、２−エチルヘキソキシ基で置
換したポリチタノキサンイソプロポキシドージ（２−エ
チルヘキソキシド）の理論分子量１，３４０と良（一致
した。The molecular weight of the obtained white solid substance is the theoretical molecular weight of polytitanoxane isopropoxide (2-ethylhexoxide) in which two of the isopropoxy groups of sample (A-1) are substituted with 2-ethylhexoxy groups. 1,340 and good (matched).
（酌 試料（Ａ−７）
ポリチタノキサンステアロキシド
試料（Ａ−１）のポリチタノキサンイソプロポキシド１
，２００ｇ（１モル）を脱水イソプロパツール１２００
ｇに溶解して試料（Ａ−１）の合成に用いた反応装置に
仕込み、攪拌下にステアリルアルコール３，２４０ｇ（
１２モル）を徐々に添加した。添加終了後、８０℃に昇
温し２時間反応を継続した。ついで、ロータリーエバポ
レーターを用い５０℃Ｘ ２０Ｔｏｒｒの条件でイソプ
ロパツールおよび低沸物を留去し、粘稠な白色液体物質
（Ａ−７）を得た。(Sample (A-7) Polytitanoxane isopropoxide 1 of polytitanoxane stearoxide sample (A-1)
, 200g (1 mol) of isopropanol 1200
g and charged into the reaction apparatus used for the synthesis of sample (A-1), and 3,240 g of stearyl alcohol (
12 mol) was added gradually. After the addition was completed, the temperature was raised to 80°C and the reaction was continued for 2 hours. Then, isopropanol and low-boiling substances were distilled off using a rotary evaporator at 50° C. and 20 Torr to obtain a viscous white liquid substance (A-7).
得られた白色液体物質の凝固点降下法により測定した分
子量は、３．７００であり、また、回収したイソプロパ
ツールは、１，９２０ｇであった。The molecular weight of the obtained white liquid substance measured by freezing point depression method was 3.700, and the amount of recovered isopropanol was 1,920 g.
得られた白色固体物質は、その分子量が、試料（Ａ−１
）のイソプロポキシ基の全部が、ステアロキ、シ基で置
換したポリチタノキサンステアロキシドの理論分子量３
．７２０と良く一致した。The obtained white solid substance has a molecular weight similar to that of the sample (A-1).
) Theoretical molecular weight of polytitanoxane stearoxide in which all of the isopropoxy groups are substituted with stearoxy and cy groups is 3.
．． It was in good agreement with 720.
（ｈｌ 試料（Ａ−８）
ポリチタノキサンイソプロポキシドブトキシド試料（Ａ
−１）合成に用いた反応装置に、テトライソプロポキシ
チタン２８４ｇ （１モル）およびテトラブトキシチタ
ン３４０ｇ （１モル）を仕込み、攪拌、混合しながら
７０℃に加熱保持した。(hl Sample (A-8) Polytitanoxane isopropoxide butoxide sample (A-8)
-1) 284 g (1 mol) of tetraisopropoxytitanium and 340 g (1 mol) of tetrabutoxytitanium were charged into the reaction apparatus used for the synthesis, and heated and maintained at 70° C. while stirring and mixing.
この中に、水３６ｇ１イソプロパツール２７０ｇおよび
ｎ−ブタノール２７０ｇの混合溶液を徐々に添加し、添
加終了後８５℃に昇温し還流下に１時間攪拌保持して反
応を熟成した。A mixed solution of 36 g of water, 270 g of isopropanol and 270 g of n-butanol was gradually added to the mixture, and after the addition was completed, the temperature was raised to 85° C. and stirred and maintained under reflux for 1 hour to ripen the reaction.
反応液を冷却後、ロータリーエバポレーターを用いて８
０℃×２〜３ Ｔｏｒｒの条件で低沸物を留去し、さら
に真空蒸留装置を用いて１９０〜２００’ｃ ｘ ｏ、
ｓ〜１．０ Ｔｏｒｒの条件で蒸留を行い、缶残とし
て白色固体物質（Ａ−８）２９６ｇを得た。After cooling the reaction solution, use a rotary evaporator to
The low-boiling substances were distilled off under the conditions of 0°C x 2-3 Torr, and then 190-200'c x o, using a vacuum distillation apparatus.
Distillation was performed under the conditions of s~1.0 Torr to obtain 296 g of a white solid substance (A-8) as a residue.
得られた白色固体物質の凝固点降下法で測定した分子量
は、２．３００であった。また、得られた白色固体物質
をイソプロパツールに溶解し、希アンモニア水を加えて
５０℃に加熱し、分解生成したイソプロパツールおよび
ｎ−ブタノールをガスクロマトグラフにより分析した結
果、イソプロパツール／ｎ−ブタノール（モル比）＝５
２／４８であった。The molecular weight of the obtained white solid substance measured by freezing point depression method was 2.300. In addition, the obtained white solid substance was dissolved in isopropanol, diluted aqueous ammonia was added and heated to 50°C, and the decomposed isopropanol and n-butanol were analyzed by gas chromatography. n-butanol (molar ratio) = 5
It was 2/48.
以上から、この白色固体物質（Ａ−８）は、ラダー状ポ
リチタノキサンイソプロポキシドブトキシドと推定した
。From the above, it was estimated that this white solid substance (A-8) was ladder-like polytitanoxane isopropoxide butoxide.
（１）試料（Ａ−９）
ポリチタノキサンイソプロポキシド
試料（Ａ−１）合成に用いた反応装置に、テトライソプ
ロポキシチタン２８４ｇ（１モル）を仕込み、攪拌、混
合しながら７０℃に加熱保持した。(1) Sample (A-9) Polytitanoxane isopropoxide sample (A-1) 284 g (1 mol) of tetraisopropoxytitanium was charged into the reaction apparatus used for synthesis, and heated to 70°C while stirring and mixing. It was kept heated.
この中に、水２１．６ｇ（１，２モル）、イソプロパツ
ール２７０ｇとの混合溶液を徐々に添加した後、８５℃
に昇温し還流下に１時間攪拌を保持して反応を熟成した
。A mixed solution of 21.6 g (1.2 moles) of water and 270 g of isopropanol was gradually added to this, and the mixture was heated to 85°C.
The reaction was aged by raising the temperature to 100 mL and maintaining stirring under reflux for 1 hour.
反応液を冷却後、ロータリーエバポレーターを用いて５
０℃Ｘ ２０Ｔｏｒｒの条件で溶媒のイソプロパツール
を留去し、さらに真空蒸留装置を用いて、１２０Ｘ０．
ＩＴｏｒｒの条件で低沸物を留去し、白色固体物質（Ａ
−９）１５９ｇを得た。After cooling the reaction solution, use a rotary evaporator for 5
The solvent, isopropanol, was distilled off under conditions of 0° C. and 20 Torr, and further, using a vacuum distillation apparatus, 120×0.
Low-boiling substances were distilled off under ITorr conditions, and a white solid substance (A
-9) 159g was obtained.
得られた白色固体物質の凝固点降下法で測定した分子量
は、および元素分析値は、下記構造式（９）で示すラダ
ー状ポリチタノキサンの分子量および理論値と良く一致
した。The molecular weight measured by the freezing point depression method and the elemental analysis value of the obtained white solid substance were in good agreement with the molecular weight and theoretical value of ladder-like polytitanoxane shown by the following structural formula (9).
分子量 ＴｉＯ□ −ＯＣＨ（ＣＨｓ）ｇ分析値
１４３５ ５０．６％ ５８．６％理論値 １４
２９ ５０．４％ ５７．８％（ＴｉＯ□は、灰化
法による測定値）
Ｒ＝ −ＣＨ（ＣＨｓ）ｘ
０１ 比較試料（Ｃ−１）
試料（Ａ−１）の合成において、水の添加量を１８ｇ（
１モル）から、３２．４ｇ（１，８モル）に代えた以外
には、試料（Ａ−１）と同一の条件で反応を行った結果
、熟成過程でゲル化し、それ以上の反応を継続できなう
がた。Molecular weight TiO□ -OCH(CHs)g Analysis value 1435 50.6% 58.6% Theoretical value 14
29 50.4% 57.8% (TiO□ is the value measured by the ashing method) R= -CH(CHs)x 01 Comparative sample (C-1) In the synthesis of sample (A-1), addition of water Change the amount to 18g (
The reaction was carried out under the same conditions as sample (A-1) except that 32.4 g (1.8 mol) was changed from 1 mol) to 32.4 g (1.8 mol), and as a result, it gelled during the aging process and continued the reaction further. I can't do it.
得られたゲル状物質は、イソプロパツール等のアルコー
ル系溶剤、トルエン等の芳香族系溶剤の何れにも溶解し
なかった。The obtained gel-like substance did not dissolve in either alcoholic solvents such as isopropanol or aromatic solvents such as toluene.
（ト）） 比較試料（Ｃ−２）
試料（Ａ−１）の合成において、水の添加量を１８ｇ（
１モル）から、１０ｇ（０，５５モル）に代えた以外に
は、試料（Ａ−１）と同一の条件で反応および後処理を
行い、粘稠な液状物質を（Ｃ−２）を得た。(g)) Comparative sample (C-2) In the synthesis of sample (A-1), the amount of water added was 18 g (
The reaction and post-treatment were carried out under the same conditions as for sample (A-1), except that 10 g (0.55 mol) was changed from 1 mol) to 10 g (0.55 mol), and a viscous liquid substance (C-2) was obtained. Ta.
得られた液状物質の分子量は７２９であり、鎖状ポリチ
タノキサンイソプロポキシドの理論分子量７２８と良く
一致した。The molecular weight of the obtained liquid substance was 729, which was in good agreement with the theoretical molecular weight of chain polytitanoxane isopropoxide, 728.
（２）熱重量分析
前記第（１）項で合成したラダー状チタノキサン（Ａ−
１）〜（Ａ−９）および比較試料（Ｃ−１）ならびに（
Ｃ−２）の各１４ｍｇを秤取し、示差熱走査熱量計（Ｒ
ＴＧ−ＤＴＡ、理学電機■製）を用い、Ｎ８気流中にお
いて昇温速度２０℃／分の条件で熱重量分析を行った。(2) Thermogravimetric analysis Ladder titanoxane (A-
1) to (A-9) and comparative samples (C-1) and (
14 mg of each of C-2) was weighed out and placed in a differential scanning calorimeter (R
Thermogravimetric analysis was carried out using a TG-DTA (manufactured by Rigaku Denki ■) under conditions of a heating rate of 20°C/min in an N8 stream.
各試料の吸熱および発熱ピーク温度を第１表中に示す。The endothermic and exothermic peak temperatures of each sample are shown in Table 1.
また、試料（Ａ−１）、比較試料（Ｃ−２）および原料
テトライソプロポキシチタンの熱重量分析曲線を、添付
第１図に示す。Further, the thermogravimetric analysis curves of the sample (A-1), the comparative sample (C-2), and the raw material tetraisopropoxy titanium are shown in the attached FIG. 1.
（３） 有機溶媒に対する溶解性
前記第（１１項で合成したラダー状チタノキサン（Ａ−
１）〜（Ａ−９）および比較試料（Ｃ−１）ならびに（
Ｃ−２）の各０．５ｇを秤取し、２０℃のトルエンおよ
び酢酸エチル１００ｇに添加して撹拌し、溶剤溶解性を
調べた。(3) Solubility in organic solvents Ladder titanoxane (A-
1) to (A-9) and comparative samples (C-1) and (
0.5 g of each of C-2) was weighed out, added to 20° C. toluene and 100 g of ethyl acetate, and stirred to examine solvent solubility.
各試料および比較試料の有機溶剤溶解性を、第１表中に
示す。The organic solvent solubility of each sample and comparative sample is shown in Table 1.
（４）加水分解水量と分子量（縮合度）前記第＋１１項
（ｄｌ試料（Ａ−４）ポリチタノキサンブトキシドの合
成において、テトラブトキシチタン１モルに対する加水
分解水量を０．５〜１．７モルの範囲で変化させ、それ
以外は試料（Ａ−４）と同一の条件で反応および後処理
を行い白色油状物質または白色固体物質を得た。(4) Amount of hydrolyzed water and molecular weight (degree of condensation) In the +11 above (dl sample (A-4) synthesis of polytitanoxane butoxide, the amount of hydrolyzed water per mole of tetrabutoxytitanium is 0.5 to 1.7 The reaction and post-treatment were carried out under the same conditions as Sample (A-4) except that the amount was varied within a molar range to obtain a white oily substance or a white solid substance.
得られた各物質の分子量を凝固点降下法で測定し、分子
量と加水分解水量の閑係を求めた。The molecular weight of each substance obtained was measured by the freezing point depression method, and the relationship between the molecular weight and the amount of hydrolyzed water was determined.
得られたポリチタノキサンブトキシドの分子量と使用し
た加水分解水量の関係を、添付第２図に示す。The relationship between the molecular weight of the obtained polytitanoxane butoxide and the amount of hydrolysis water used is shown in the attached FIG. 2.
（５）酸化チタン薄膜の製造（応用例１）＋ａ） 酸
化チタン薄膜形成用組成物の調製前記第＋１１項で合成
したラダー状ポリチタノキサン：試料（Ａ−１）〜（Ａ
’−９）のそれぞれを、イソプロパツール５０％、酢酸
エチル４０％およびアセチルアセトン１０％の混合溶液
に溶解し、ＴｉＯ□に換算した濃度が５％の酸化チタン
薄膜形成用組成物： （Ｂ−１）〜（Ｂ−９）を調製
した。(5) Production of titanium oxide thin film (Application example 1)+a) Preparation of composition for forming titanium oxide thin film Ladder-shaped polytitanoxane synthesized in the above item +11: Samples (A-1) to (A
'-9) in a mixed solution of 50% isopropanol, 40% ethyl acetate, and 10% acetylacetone to form a composition for forming a titanium oxide thin film with a concentration of 5% in terms of TiO 1) to (B-9) were prepared.
また、テトライソプロポキシチタン５６．８ｇ。Also, 56.8 g of tetraisopropoxy titanium.
エタノール２．８７ ｇおよび７０％乳酸５１．４ ｇ
を試料（Ａ−１）の合成に用いた反応容器に仕込み、室
温で均一に混合した後、７０℃に昇温し２時間攪拌保持
してテトライソプロポキシチタンと乳酸との反応生成物
を得た。この溶液に２８％アンモニア水を添加してｐ
Ｈ７，０に調整し、Ｔｉｅ、換算濃度５％の比較用の酸
化チタン薄膜形成用組成物＝（Ｃ−３）を調製した。2.87 g ethanol and 51.4 g 70% lactic acid
were charged into the reaction vessel used for the synthesis of sample (A-1), mixed uniformly at room temperature, heated to 70°C and kept stirring for 2 hours to obtain a reaction product of tetraisopropoxytitanium and lactic acid. Ta. Add 28% ammonia water to this solution and p
A titanium oxide thin film forming composition (C-3) was prepared by adjusting the titanium oxide thin film to H7.0 and having a Tie equivalent concentration of 5%.
山） 粘度測定
前記＋８１項で調製した酸化チタン薄膜形成用組成物：
（Ｂ−１）〜（Ｂ−９）および（Ｃ−３）の粘度を
、ＢＬ型粘度計（東京計器■製）を用いて測定した。Viscosity measurement Composition for forming a titanium oxide thin film prepared in Section +81 above:
The viscosities of (B-1) to (B-9) and (C-3) were measured using a BL type viscometer (manufactured by Tokyo Keiki ■).
各試料の粘度を、第２表に示す。The viscosity of each sample is shown in Table 2.
第２表
番号１０は、比較応用例
ＴＣＩ 酸化チタン薄膜の形成
良（洗浄した５０ｍｍｘｌＯＱｍｍＸ１．１ｍｍのソー
ダライムガラス基板を、前記調製した酸化チタン薄膜形
成用組成物： （Ｂ−１）〜（Ｂ−９）および（Ｃ−
３）のそれぞれに浸漬し、２０〜５Ｑｃｍ／分の一定速
度で引き上げて塗布した後、１５０℃の温度に１０分間
保持して乾燥し、ラダー状ポリチタノキサンまたはテト
ライソプロポキシチタンと乳酸との反応生成物の皮膜を
、ガラス基板上に形成した。Table 2 No. 10 shows Comparative Application Example TCI Good Formation of Titanium Oxide Thin Film (Cleaned 50mm x lOQmm x 1.1mm soda lime glass substrate was coated with the titanium oxide thin film forming composition prepared above: (B-1) to (B- 9) and (C-
3) and then pulled up at a constant speed of 20 to 5 Qcm/min to coat, and then kept at a temperature of 150°C for 10 minutes to dry to form a reaction between ladder-like polytitanoxane or tetraisopropoxytitanium and lactic acid. A film of the product was formed on a glass substrate.
ついで、これらのガラス基板を、５００℃の温度に保持
した電気炉内に３０分間保持して焼成しガラス基板上に
Ｔｉ０１薄膜を形成した。These glass substrates were then fired by holding them in an electric furnace maintained at a temperature of 500° C. for 30 minutes to form a Ti01 thin film on the glass substrates.
＋ｄ） 屈折率の測定゛
前記製造したＴｉ０ｔＮ膜付きガラス基板の可視光域の
屈折率を、自記分光光度計（日立製作断裂・３４０型）
を用いて測定した。+d) Measurement of refractive index: The refractive index in the visible light range of the glass substrate with the Ti0tN film manufactured above was measured using a self-recording spectrophotometer (Hitachi manufactured rupture type 340).
Measured using
Ｔｉ０１薄膜の厚さおよび５００ｎｍにおける屈折率を
第２表中に示す。The thickness of the Ti01 thin film and the refractive index at 500 nm are shown in Table 2.
（６） ラダー状ポリチタノキサン誘導体の合成（応
用例２）
（ａｌ ポリチタノキサンイソプロポキシドジイソス
テアレート
ラダー状ポリチタノキサン：試料（Ａ−１）１゜２００
ｇ（１モル）を、脱水イソプロパツール１゜２００ｇに
溶解し、試料（Ａ−１）の合成に用いた反応装置に仕込
み、攪拌下にイソステアリン酸５６８ｇ（２モル）を徐
々に添加した０発熱が起こり約６０℃に昇温しで発熱が
納まった。さらに、反応液を８０℃に加熱保持して２時
間反応を継続した後、イソプロパツールおよび低沸物を
５０℃Ｘ ２０Ｔｏｒｒの条件で留去し、反応生成物を
得た。(6) Synthesis of ladder-shaped polytitanoxane derivative (Application example 2) (al Polytitanoxane isopropoxide diisostearate Ladder-shaped polytitanoxane: Sample (A-1) 1°200
g (1 mol) was dissolved in 1.200 g of dehydrated isopropanol, charged into the reaction apparatus used for the synthesis of sample (A-1), and 568 g (2 mol) of isostearic acid was gradually added with stirring. Heat generation occurred, and the temperature rose to approximately 60°C, which subsided. Further, the reaction solution was heated and maintained at 80° C. to continue the reaction for 2 hours, and then isopropanol and low-boiling substances were distilled off at 50° C. and 20 Torr to obtain a reaction product.
得られた反応生成物を、赤外線吸収スペクトル分析（Ｉ
Ｒ分析）した結果、原料のイソステアリン酸のカルボキ
シルに基づ＜１．７８０ｃｍ”の吸収が消失し、アシル
オキシ基に基づ＜１．６８０Ｃｍ−’の吸収が認められ
た。The obtained reaction product was subjected to infrared absorption spectroscopy (I
As a result of the R analysis), the absorption at <1.780 cm'' based on the carboxyl of isostearic acid as a raw material disappeared, and the absorption at <1.680 Cm-' based on the acyloxy group was observed.
以上のＩＲ分析の結果から、得られた反応生成物は、ラ
ダー状ポリチタノキサン：試料（Ａ−１）のイソプロポ
キシ基の２個が、イソステアロイルオキシ基と置換した
ラダー状ポリチタノキサン誘導体・ポリチタノキサンイ
ソプロポキシドジイソステアレートと推定した。From the results of the above IR analysis, the obtained reaction product is a ladder-like polytitanoxane: a ladder-like polytitanoxane derivative in which two of the isopropoxy groups of sample (A-1) are substituted with isostearoyloxy groups. It was assumed to be xane isopropoxide diisostearate.
この誘導体は、高分子物質−無機物質系の複合材料の無
機物質の表面処理剤として有用である。This derivative is useful as a surface treatment agent for an inorganic substance in a polymeric substance-inorganic substance composite material.
伽） ポリチタノキサン−ｎ−ブトキシドジプチルフォ
スフェート
ラダー状ポリチタノキサン：試料（Ａ−２）１゜１００
ｇ（１モル）を、脱水ｎ−ブタノール１，１００ｇに溶
解し、試料（Ａ−１）の合成に用いた反応装置に仕込み
、攪拌下にジプチルリン酸２１０ｇ（１モル）を徐々に
添加した０発熱が起こり約６０℃に昇温しで発熱が納ま
った。さらに、反応液を８０℃に加熱保持して２時間反
応を継続した後、イソプロパツールおよび低沸物を５０
℃×２０Ｔｏｒｒの条件で留去し、反応生成物を得た。) Polytitanoxane-n-butoxide diptyl phosphate ladder-like polytitanoxane: Sample (A-2) 1°100
g (1 mol) was dissolved in 1,100 g of dehydrated n-butanol, charged into the reaction apparatus used for the synthesis of sample (A-1), and 210 g (1 mol) of diptyl phosphoric acid was gradually added with stirring. Heat generation occurred, and the temperature rose to approximately 60°C, which subsided. Furthermore, after heating and maintaining the reaction solution at 80°C and continuing the reaction for 2 hours, isopropanol and low-boiling substances were added at 50°C.
Distillation was carried out under conditions of ℃×20 Torr to obtain a reaction product.
得られた反応生成物は、ＩＲ分析の結果から、ラダー状
ポリチタノキサン誘導体・ポリチタノキサン−ｎ−ブト
キシドジプチルフォスフェートと推定した。The obtained reaction product was estimated to be a ladder-like polytitanoxane derivative/polytitanoxane-n-butoxide diptyl phosphate based on the results of IR analysis.
この誘導体も、高分子物質−無機物質系の複合材料の無
機物質の表面処理剤として有用である。This derivative is also useful as a surface treatment agent for inorganic substances in composite materials of polymeric substances and inorganic substances.
本発明のラダー状ポリチタノキサンは、前記実施例に示
したように、高分子量であるにかかわらず各種の有機溶
剤に可溶性のポリチタノキサンである。したがりて、応
用例に示したように、酸化チタン薄膜形成用組成物の主
成分として、また、高分子物質−無機物質系の複合材料
の無機物質の表面処理剤として有用な誘導体の製造原料
として有用な新規なポリチタノキサンである。As shown in the above examples, the ladder-shaped polytitanoxane of the present invention is a polytitanoxane that is soluble in various organic solvents despite its high molecular weight. Therefore, as shown in the application example, raw materials for producing derivatives useful as the main component of compositions for forming titanium oxide thin films and as surface treatment agents for inorganic substances in composite materials of polymeric substances and inorganic substances. This is a novel polytitanoxane useful as a polytitanoxane.
本発明は、ゾル−ゲル法による酸化チタン薄膜形成用と
して、また、誘導体に製造原料として有用な新規な構造
を有するラダー状ポリチタノキサンおよびその製造方法
を提供するものであり、その産業的意義は、極めて大き
い。The present invention provides a ladder-like polytitanoxane having a novel structure useful for forming titanium oxide thin films by the sol-gel method and as a raw material for producing derivatives, and a method for producing the same.The industrial significance thereof is as follows: Extremely large.
（１） 第１図 熱重量分析曲線
ｌａｌ 実施例筒（１１項（ａｌで合成した試料（Ａ
−１）Ｑｌｌ）実施例筒（１）項（Ｊ）で合成した比較
試料（Ｃ−２）
（Ｃ１原料テトライソプロポキシチタン（２） 第
２図 実施例筒（４）項で得られた加水分解水量と分子
量との関係曲線(1) Figure 1 Thermogravimetric analysis curve lal Example cylinder (item 11 (sample synthesized with al) (A
-1) Qll) Comparative sample (C-2) synthesized in Example tube (1) section (J) (C1 raw material tetraisopropoxy titanium (2) Figure 2 Hydrogenated sample synthesized in Example tube (4) section Relationship curve between amount of decomposed water and molecular weight
Claims (2)
の１価の炭化水素基よりなる群から選ばれた１種または
２種以上（ただし、水素原子は、全Ｒの１５％を越えな
い。）であり、ｎおよびｍが、１〜８０の正数であるこ
とを特徴とするラダー状ポリチタノキサン(1) Structural formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Represented by the following formula, where R is a hydrogen atom and a carbon number of 1 to 18
is one or more selected from the group consisting of monovalent hydrocarbon groups (however, hydrogen atoms do not exceed 15% of the total R), and n and m are positive from 1 to 80. Ladder-shaped polytitanoxane characterized by a number of
の少なくとも１種を表す。） で表されるテトラアルコキシチタンを、１．０倍モル以
上１．７倍モル以下の水を用いて２０〜９０℃の温度下
において加水分解し、ついで低沸物を留去することを特
徴とするラダー状ポリチタノキサンの製造方法(2) Tetraalkoxytitanium represented by the general formula Ti(OR')_4 (herein, R' represents at least one type of monovalent hydrocarbon group having 1 to 18 carbon atoms), 1. A method for producing ladder-shaped polytitanoxane, which comprises hydrolyzing it at a temperature of 20 to 90°C using 0 to 1.7 moles of water, and then distilling off low-boiling substances.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28588287A JPH01129032A (en) | 1987-11-12 | 1987-11-12 | Ladderlike polytitanoxane and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28588287A JPH01129032A (en) | 1987-11-12 | 1987-11-12 | Ladderlike polytitanoxane and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01129032A true JPH01129032A (en) | 1989-05-22 |
Family
ID=17697247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28588287A Pending JPH01129032A (en) | 1987-11-12 | 1987-11-12 | Ladderlike polytitanoxane and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01129032A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02258841A (en) * | 1989-03-31 | 1990-10-19 | Fuji Xerox Co Ltd | Production of inorganic and organic composite material |
| JPH02258842A (en) * | 1989-03-31 | 1990-10-19 | Fuji Xerox Co Ltd | Production of semiconductive inorganic and organic composite material |
| US5681974A (en) * | 1995-05-22 | 1997-10-28 | Kaken Co., Ltd. | Mo adsorbent for 99 Mo-99m Tc generators and manufacturing thereof |
| JPWO2005012215A1 (en) * | 2003-06-02 | 2006-09-14 | 日本曹達株式会社 | Metal compounds having a new skeleton |
| JP2006299049A (en) * | 2005-04-19 | 2006-11-02 | Nippon Soda Co Ltd | Organic-inorganic compounded material and silylated derivative |
| JP2008156280A (en) * | 2006-12-23 | 2008-07-10 | Matsumoto Fine Chemical Co Ltd | Organic titanium oligomer and method for producing the same |
| US7909929B2 (en) | 2002-11-13 | 2011-03-22 | Nippon Soda Co., Ltd. | Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film |
| KR20180086202A (en) | 2015-11-26 | 2018-07-30 | 도레이 카부시키가이샤 | Polymetaloxic acid, a method for producing the same, a composition thereof, a cured film, a method for producing the same, and a member and an electronic component |
| WO2019188835A1 (en) | 2018-03-29 | 2019-10-03 | 東レ株式会社 | Polymetalloxane, composition, cured film, member, electronic component, fiber, binder for ceramic molding, cured film production method, and fiber production method |
-
1987
- 1987-11-12 JP JP28588287A patent/JPH01129032A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02258841A (en) * | 1989-03-31 | 1990-10-19 | Fuji Xerox Co Ltd | Production of inorganic and organic composite material |
| JPH02258842A (en) * | 1989-03-31 | 1990-10-19 | Fuji Xerox Co Ltd | Production of semiconductive inorganic and organic composite material |
| US5681974A (en) * | 1995-05-22 | 1997-10-28 | Kaken Co., Ltd. | Mo adsorbent for 99 Mo-99m Tc generators and manufacturing thereof |
| US7909929B2 (en) | 2002-11-13 | 2011-03-22 | Nippon Soda Co., Ltd. | Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film |
| JPWO2005012215A1 (en) * | 2003-06-02 | 2006-09-14 | 日本曹達株式会社 | Metal compounds having a new skeleton |
| JP4633628B2 (en) * | 2003-06-02 | 2011-02-16 | 日本曹達株式会社 | Metal compounds having a new skeleton |
| JP2006299049A (en) * | 2005-04-19 | 2006-11-02 | Nippon Soda Co Ltd | Organic-inorganic compounded material and silylated derivative |
| JP2008156280A (en) * | 2006-12-23 | 2008-07-10 | Matsumoto Fine Chemical Co Ltd | Organic titanium oligomer and method for producing the same |
| KR20180086202A (en) | 2015-11-26 | 2018-07-30 | 도레이 카부시키가이샤 | Polymetaloxic acid, a method for producing the same, a composition thereof, a cured film, a method for producing the same, and a member and an electronic component |
| US11795064B2 (en) | 2015-11-26 | 2023-10-24 | Toray Industries, Inc. | Polymetalloxane, method for producing same, composition thereof, cured film and method for producing same, and members and electronic components provided with same |
| WO2019188835A1 (en) | 2018-03-29 | 2019-10-03 | 東レ株式会社 | Polymetalloxane, composition, cured film, member, electronic component, fiber, binder for ceramic molding, cured film production method, and fiber production method |
| KR20200138205A (en) | 2018-03-29 | 2020-12-09 | 도레이 카부시키가이샤 | Polymetalloxane, composition, cured film, member, electronic component, fiber, binder for molding ceramics, method for producing cured film, and method for producing fiber |
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