JPH0314853B2 - - Google Patents
Info
- Publication number
- JPH0314853B2 JPH0314853B2 JP20087686A JP20087686A JPH0314853B2 JP H0314853 B2 JPH0314853 B2 JP H0314853B2 JP 20087686 A JP20087686 A JP 20087686A JP 20087686 A JP20087686 A JP 20087686A JP H0314853 B2 JPH0314853 B2 JP H0314853B2
- Authority
- JP
- Japan
- Prior art keywords
- methanol
- acetylacetonate
- bis
- polymer
- titanosiloxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920000642 polymer Polymers 0.000 claims description 21
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 15
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- KVIKMJYUMZPZFU-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O KVIKMJYUMZPZFU-UHFFFAOYSA-N 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 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 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 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 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Description
（産業上の利用分野）
本発明は、新規のチタノシロキサン重合体の製
造法に関する。本発明のチタノシロキサン重合体
は、常温でメタノール可溶性の固体であつて急激
なメタノール不溶性化を起さない安定性を有す
る。この重合体は、更に加水分解及び縮合反応さ
せることにより、或いは加熱下縮合反応させるこ
とにより、チタン原子、珪素原子及び酸素原子か
らなる無機質の酸化物硬化体に変る性質を有し、
無機繊維、無機コーテイング剤、無機接着剤、無
機結合剤等の原料又はその成分として用いられ
る。
（従来の技術）
ポリチタノシロキサンに関しては、ポリチタノ
メチルシロキサン等耐熱性のポリチタノオルガノ
シロキサンが既に、ジヤーナル・オブ・ポリマ
ー・サイエンス（Journal of Polymer Science）
第52巻第257〜276頁（1961年）に記載されてお
り、また窯業協会誌第84巻第614〜618頁（1976
年）にも、シリコンテトラエトキシドとチタンテ
トライソプロポキシドとの共加水分解によつて生
成することが示されている。
（発明が解決しようとする問題点）
ポリチタノオルガノシロキサンは、高価な有機
珪素化合物を原料とし、また、その生成反応及び
製造方法が複雑である。更にこのポリマーには、
炭素−珪素の直接結合が存するために、低温では
このポリマーを完全に無機化することができな
い。
一方、シリコンテトラエトキシドとチタンテト
ライソプロポキシドの共加水分解によつて生成す
るポリチタノシロキサンは、極めて不安定であつ
て、縮合反応の進行による溶媒不溶化を起し易
い。例えば、有用性が高い曳糸性を示す状態にあ
る期間は約１時間以内であるから、これを工業製
品として提供することは困難である。従つて、こ
れを用いることによつては、品質一定の無機繊
維、塗料、接着剤等は得られない。
本発明の目的は、常温での安定性は高いが、容
易に完全無機化せしめ得るメタノール可溶性チタ
ノシロキサン重合体の製造法を提供することにあ
る。
（問題点を解決するための手段）
本発明の安定性が高いメタノール可溶性のチタ
ノシロキサン重合体は、珪酸とビス（アセチルア
セトネート）チタンジイソプロポキシドを、
SiO2／TiO2モル比0.25〜４の比率に反応させる
ことによつて得られる。
本発明に用いられる珪酸は、従来から知られて
いる方法によつて容易に得られ、例えば、水ガラ
ス、メタ珪酸ソーダ、珪酸アンモニウム等の可溶
性珪酸塩の水溶液によつて中和処理することによ
り、或いは陽イオン交換樹脂で処理することによ
り水溶液として得られる。
本発明のチタノシロキサン重合体の生成反応に
は、上記例示の如き処理で得られた水溶液を、テ
トラヒドロフランで抽出処理することにより得ら
れる珪酸のテトラヒドロフラン溶液が用いられ
る。
本発明のチタノシロキサン重合体は、上記珪酸
のテトラヒドロフラン溶液にビス（アセチルアセ
トネート）チタンジイソプロポキシドを上記モル
比に加えて室温〜溶媒の還流温度で反応させるこ
とにより容易に生成する。この反応はメタノー
ル、エタノール、イソプロパノール等の溶媒中で
行わせることもできる。反応時間としては、0.5
〜12時間程度でよい。
メタノール中で反応させると、この反応の後に
溶媒を留去させることにより重合体の濃縮液が得
られる。この濃縮液にガラス棒を接触させた後引
き上げると、液は曳糸性を示し、本発明のメタノ
ール可溶性のチタノシロキサン重合体の繊維が得
られる。また、テトラヒドロフラン中での反応で
は、本発明のチタノシロキサン重合体は沈澱物と
して生成するが、これを取り出しメタノール又は
エタノールに加えると溶解する。この溶液をヘキ
サン等非溶媒中に投入すると再び沈澱物が生じ、
これを回収すると粉状物が得られる。
（作 用）
本発明により、珪酸とビス（アセチルアセトネ
ート）チタンジイソプロポキシドを反応させる
と、ビス（アセチルアセトネート）チタノシロキ
サン結合（Ti−Ｏ−Si）による重合体が生成す
る。このチタノシロキサン結合は、上記粉状物の
赤外線吸収スペクトルに930cm-1の吸収ピークが
表われることにより確認された。また、1520〜
1580cm-1にもカルボニル基に基ずく吸収が観測さ
れた。
しかし、本発明のメタノール可溶性のビス（ア
セチルアセトネート）チタノシロキサン重合体
は、珪酸とビス（アセチルアセトネート）チタン
ジイソプロポキシドの反応モル比がSiO2／TiO2
として４を越えると得られない。このモル比４以
上ではメタノール不溶性物質が生成する。このモ
ル比が0.25〜４であるとメタノール、エタノール
等の溶媒に溶ける生成物となり、曳糸性を示す。
本発明のチタノシロキサン重合体は、上記原料成
分の珪酸とビス（アセチルアセトネート）チタン
ジイソプロポキシドをテトラヒドロフラン又はメ
タノール中で反応させることにより円滑に収率よ
く生成せしめ得る。
（実施例）
実施例 １
SiO2として0.85モル／の珪酸のテトラヒドロ
フラン溶液(A)11.8mlと、SiO2／TiO2モル比が１
となるようにビス（アセチルアセトネート）チタ
ンジイソプロポキシド(B)3.6ｇをメタノール20ml
に加え、溶媒の還流下0.5時間反応させることに
より粘稠な反応混合物を得た。この溶液から溶媒
を留去すると濃縮液が得られ、これにガラス棒を
接触させた後引き上げると曳糸性を示した。別
途、上記濃縮液をエタノールに加えると溶液が得
られ、これを多量のヘキサン中に投入したとこ
ろ、沈澱が生じた。この沈澱を回収し、乾燥する
ことにより2.5ｇの粉末を得た。
上記粉末を赤外線吸収スペクトル分析したとこ
ろ、930cm-1にチタノシロキサン結合に基ずつ吸
収と、1520〜1580cm-1にカルボニル基に基づく吸
収が観測された。
実施例 ２
実施例１に用いられたものと同じ原料(A)と(B)と
を、第１表に記載の量用いた他は、実施例１と同
様にして実験No.１〜４の反応混合液を得た。曳糸
性として繊維長を測定すると共に、この混合液の
性状及び回収されたチタノシロキサン重合体の収
量を第１表に示す。
(Industrial Application Field) The present invention relates to a method for producing a novel titanosiloxane polymer. The titanosiloxane polymer of the present invention is a methanol-soluble solid at room temperature and has stability that does not cause rapid methanol insolubility. This polymer has the property of converting into an inorganic oxide cured product consisting of titanium atoms, silicon atoms, and oxygen atoms by further hydrolysis and condensation reaction, or by condensation reaction under heating,
It is used as a raw material or component of inorganic fibers, inorganic coating agents, inorganic adhesives, inorganic binders, etc. (Prior art) Regarding polytitanosiloxanes, heat-resistant polytitanoorganosiloxanes such as polytitanomethylsiloxane have already been published in the Journal of Polymer Science.
Vol. 52, pp. 257-276 (1961), and Journal of the Ceramic Industry Association, Vol. 84, pp. 614-618 (1976).
(2013) also showed that it is produced by cohydrolysis of silicon tetraethoxide and titanium tetraisopropoxide. (Problems to be Solved by the Invention) Polytitanoorganosiloxane uses an expensive organic silicon compound as a raw material, and its production reaction and manufacturing method are complicated. Furthermore, this polymer has
Due to the presence of direct carbon-silicon bonds, this polymer cannot be completely mineralized at low temperatures. On the other hand, polytitanosiloxane produced by cohydrolysis of silicone tetraethoxide and titanium tetraisopropoxide is extremely unstable and tends to become insolubilized in solvents due to the progress of the condensation reaction. For example, it is difficult to provide this as an industrial product because the period in which it is in a state where it exhibits highly useful stringiness is about one hour or less. Therefore, by using this, inorganic fibers, paints, adhesives, etc. of constant quality cannot be obtained. An object of the present invention is to provide a method for producing a methanol-soluble titanosiloxane polymer that is highly stable at room temperature but can be easily completely mineralized. (Means for Solving the Problems) The highly stable methanol-soluble titanosiloxane polymer of the present invention combines silicic acid and bis(acetylacetonate)titanium diisopropoxide.
It is obtained by reacting with a SiO 2 /TiO 2 molar ratio of 0.25 to 4. The silicic acid used in the present invention can be easily obtained by a conventionally known method, for example, by neutralization with an aqueous solution of a soluble silicate such as water glass, sodium metasilicate, or ammonium silicate. Alternatively, it can be obtained as an aqueous solution by treatment with a cation exchange resin. In the production reaction of the titanosiloxane polymer of the present invention, a tetrahydrofuran solution of silicic acid obtained by extracting an aqueous solution obtained by the treatment as exemplified above with tetrahydrofuran is used. The titanosiloxane polymer of the present invention is easily produced by adding bis(acetylacetonate)titanium diisopropoxide to the above-mentioned tetrahydrofuran solution of silicic acid at the above-mentioned molar ratio and reacting the mixture at room temperature to the reflux temperature of the solvent. This reaction can also be carried out in a solvent such as methanol, ethanol, isopropanol or the like. The reaction time is 0.5
~12 hours is sufficient. When the reaction is carried out in methanol, a concentrated solution of the polymer can be obtained by distilling off the solvent after the reaction. When a glass rod is brought into contact with this concentrated liquid and then pulled up, the liquid exhibits stringiness and the fibers of the methanol-soluble titanosiloxane polymer of the present invention are obtained. Further, in the reaction in tetrahydrofuran, the titanosiloxane polymer of the present invention is produced as a precipitate, but when this is taken out and added to methanol or ethanol, it dissolves. When this solution is poured into a non-solvent such as hexane, a precipitate is formed again.
When this is collected, a powder is obtained. (Function) According to the present invention, when silicic acid and bis(acetylacetonate) titanium diisopropoxide are reacted, a polymer with bis(acetylacetonate) titanosiloxane bonds (Ti-O-Si) is generated. This titanosiloxane bond was confirmed by the appearance of an absorption peak at 930 cm -1 in the infrared absorption spectrum of the powder. Also, from 1520
Absorption based on carbonyl groups was also observed at 1580 cm -1 . However, in the methanol-soluble bis(acetylacetonate) titanosiloxane polymer of the present invention, the reaction molar ratio of silicic acid and bis(acetylacetonate) titanium diisopropoxide is SiO 2 /TiO 2
If it exceeds 4, it cannot be obtained. At this molar ratio of 4 or more, methanol-insoluble substances are produced. When this molar ratio is 0.25 to 4, the product becomes soluble in solvents such as methanol and ethanol, and exhibits stringiness.
The titanosiloxane polymer of the present invention can be produced smoothly and in good yield by reacting the above raw material components silicic acid and bis(acetylacetonate)titanium diisopropoxide in tetrahydrofuran or methanol. (Example) Example 1 11.8 ml of a tetrahydrofuran solution (A) of silicic acid containing 0.85 mol/SiO 2 and a SiO 2 /TiO 2 molar ratio of 1.
Add 3.6 g of bis(acetylacetonate) titanium diisopropoxide (B) to 20 ml of methanol so that
In addition, a viscous reaction mixture was obtained by reacting for 0.5 hour under reflux of the solvent. When the solvent was distilled off from this solution, a concentrated solution was obtained, and when a glass rod was brought into contact with this and then pulled up, it exhibited stringability. Separately, when the above concentrate was added to ethanol, a solution was obtained, and when this was poured into a large amount of hexane, precipitation occurred. This precipitate was collected and dried to obtain 2.5 g of powder. When the above powder was subjected to infrared absorption spectrum analysis, absorption based on titanosiloxane bonds was observed at 930 cm -1 and absorption based on carbonyl groups was observed at 1520 to 1580 cm -1 . Example 2 Experiments Nos. 1 to 4 were carried out in the same manner as in Example 1, except that the same raw materials (A) and (B) as used in Example 1 were used in the amounts listed in Table 1. A reaction mixture was obtained. Table 1 shows the properties of the mixture and the yield of the titanosiloxane polymer recovered, as well as measuring the fiber length as a measure of spinnability.
【表】
実施例 ３
上記と同じ(A)液及び(B)液を用い、第１表記載の
如くSiO2／TiO2モル比別に反応時間を変えた他
は実施例１と同様にして実験No.１〜13の反応混合
液を得、曳糸性を測定した。結果を第２表に示
す。[Table] Example 3 Using the same liquids (A) and (B) as above, the experiment was carried out in the same manner as in Example 1, except that the reaction time was changed depending on the SiO 2 /TiO 2 molar ratio as shown in Table 1. Reaction mixtures Nos. 1 to 13 were obtained and their stringability was measured. The results are shown in Table 2.
【表】
実施例 ４
メタノール溶媒を用いない他は、実施例１と同
様にして、SiO2／TiO2モル比１となるように原
料(A)に(B)を加えて反応させたところ、沈澱が生じ
た。直ちに、この沈澱物を回収し、メタノールに
加えたところ溶解した。この溶液をヘキサン中に
投入したところ、再び沈澱が生じた。
別途、SiO2／TiO2モル比を0.25、0.5、2.0及び
4.0に変えて上記と同様に反応させたが、やはり
沈澱が生じ、この沈澱物はメタノールに溶解し
た。これらメタノール溶液をヘキサン中に投入す
ると、再び沈澱が生じた。
上記ヘキサン中の沈澱物を回収し、赤外線吸収
スペクトル分析を行つたところ、930cm-1にTi−
Ｏ−Si結合の吸収を、また、1520〜1580cm-1には
Ｃ＝Ｏ結合の吸収を観測した。別途上記回収沈
澱物について灰分量を測定したところ、55〜63重
量％であつた。
（発明の効果）
本発明によると、珪酸とビス（アセチルアセト
ネート）チタンジイソプロポキシドをSiO2／
TiO2モル比４以下で溶媒中で反応させるのみで、
容易にメタノール可溶性のビス（アセチルアセト
ネート）チタノシロキサン重合体が得られる。こ
の重合体は急激なメタノール不溶性化が起らない
ので、安定な工業製品としての生産が可能であ
る。[Table] Example 4 In the same manner as in Example 1 except that the methanol solvent was not used, (B) was added to the raw material (A) so that the molar ratio of SiO 2 /TiO 2 was 1, and the reaction was carried out. A precipitate formed. This precipitate was immediately collected and dissolved in methanol. When this solution was poured into hexane, precipitation occurred again. Separately, the SiO 2 /TiO 2 molar ratio was set to 0.25, 0.5, 2.0 and
4.0 and the reaction was carried out in the same manner as above, but a precipitate still formed, and this precipitate was dissolved in methanol. When these methanol solutions were poured into hexane, precipitation occurred again. When the precipitate in hexane was collected and subjected to infrared absorption spectrum analysis, Ti-
Absorption of O--Si bonds and absorption of C=O bonds at 1520 to 1580 cm -1 were observed. The ash content of the recovered precipitate was separately measured and found to be 55 to 63% by weight. (Effects of the Invention) According to the present invention, silicic acid and bis(acetylacetonate) titanium diisopropoxide are combined into SiO 2 /
By simply reacting in a solvent with a TiO 2 molar ratio of 4 or less,
A methanol-soluble bis(acetylacetonate) titanosiloxane polymer is easily obtained. Since this polymer does not undergo rapid methanol insolubility, it can be produced as a stable industrial product.
Claims (1)
ジイソプロポキシドとを反応させることを特徴と
するビス（アセチルアセトネート）チタノシロキ
サン結合を含有するメタノール可溶性のビス（ア
セチルアセトネート）チタノシロキサン重合体の
製造法。 ２ 反応させる珪酸とビス（アセチルアセトネー
ト）チタンジイソプロポキシドの比率を、
SiO2／TiO2モル比として0.25〜４とする特許請
求の範囲第１項に記載のビス（アセチルアセトネ
ート）チタノシロキサン重合体の製造法。[Scope of Claims] 1. A methanol-soluble bis(acetylacetonate) titanium diisopropoxide containing a bis(acetylacetonate) titanium diisopropoxide bond, which is characterized by reacting silicic acid and bis(acetylacetonate) titanium diisopropoxide. ) Method for producing titanosiloxane polymer. 2 The ratio of silicic acid and bis(acetylacetonate) titanium diisopropoxide to be reacted is
The method for producing a bis(acetylacetonate) titanosiloxane polymer according to claim 1, wherein the SiO 2 /TiO 2 molar ratio is 0.25 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20087686A JPS6356529A (en) | 1986-08-27 | 1986-08-27 | Novel titanosiloxane polymer and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20087686A JPS6356529A (en) | 1986-08-27 | 1986-08-27 | Novel titanosiloxane polymer and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6356529A JPS6356529A (en) | 1988-03-11 |
| JPH0314853B2 true JPH0314853B2 (en) | 1991-02-27 |
Family
ID=16431706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20087686A Granted JPS6356529A (en) | 1986-08-27 | 1986-08-27 | Novel titanosiloxane polymer and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6356529A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4985460B2 (en) * | 2007-07-27 | 2012-07-25 | Ｄｉｃ株式会社 | Organic-inorganic hybrid resin aqueous dispersions, paints and painted products |
| JP5889568B2 (en) | 2011-08-11 | 2016-03-22 | メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ | Composition for forming tungsten oxide film and method for producing tungsten oxide film using the same |
| US9315636B2 (en) | 2012-12-07 | 2016-04-19 | Az Electronic Materials (Luxembourg) S.A.R.L. | Stable metal compounds, their compositions and methods |
| US9201305B2 (en) | 2013-06-28 | 2015-12-01 | Az Electronic Materials (Luxembourg) S.A.R.L. | Spin-on compositions of soluble metal oxide carboxylates and methods of their use |
| US9296922B2 (en) | 2013-08-30 | 2016-03-29 | Az Electronic Materials (Luxembourg) S.A.R.L. | Stable metal compounds as hardmasks and filling materials, their compositions and methods of use |
| US9409793B2 (en) | 2014-01-14 | 2016-08-09 | Az Electronic Materials (Luxembourg) S.A.R.L. | Spin coatable metallic hard mask compositions and processes thereof |
| US9499698B2 (en) | 2015-02-11 | 2016-11-22 | Az Electronic Materials (Luxembourg)S.A.R.L. | Metal hardmask composition and processes for forming fine patterns on semiconductor substrates |
| TWI755564B (en) | 2017-09-06 | 2022-02-21 | 德商馬克專利公司 | Spin-on inorganic oxide containing composition, method of manufacturing an electronic device and process of coating a hard mask composition on silicon substrates |
-
1986
- 1986-08-27 JP JP20087686A patent/JPS6356529A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6356529A (en) | 1988-03-11 |
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