JPS6260412B2 - - Google Patents
Info
- Publication number
- JPS6260412B2 JPS6260412B2 JP58218205A JP21820583A JPS6260412B2 JP S6260412 B2 JPS6260412 B2 JP S6260412B2 JP 58218205 A JP58218205 A JP 58218205A JP 21820583 A JP21820583 A JP 21820583A JP S6260412 B2 JPS6260412 B2 JP S6260412B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- general formula
- reaction
- white powder
- polysiloxane
- 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
- 229920001296 polysiloxane Polymers 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- -1 polysiloxane Polymers 0.000 description 22
- 239000000843 powder Substances 0.000 description 19
- 230000009102 absorption Effects 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 238000002329 infrared spectrum Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- MASNVFNHVJIXLL-UHFFFAOYSA-N ethenyl(ethoxy)silicon Chemical compound CCO[Si]C=C MASNVFNHVJIXLL-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- BYOIQYHAYWYSCZ-UHFFFAOYSA-N prop-2-enoxysilane Chemical compound [SiH3]OCC=C BYOIQYHAYWYSCZ-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002635 aromatic organic solvent Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical class OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- FFFLABUGDFDEBD-UHFFFAOYSA-N pent-4-enoxysilane Chemical compound [SiH3]OCCCC=C FFFLABUGDFDEBD-UHFFFAOYSA-N 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Silicon Polymers (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は新規なシリコーン化合物の製法に関す
る。DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD OF THE INVENTION The present invention relates to a novel process for producing silicone compounds.
従来から光重合性化合物が多く開発され、半導
体製造などの分野でレジストなどとして使用され
ているが耐熱性に劣つている。
Many photopolymerizable compounds have been developed and used as resists in fields such as semiconductor manufacturing, but they have poor heat resistance.
本発明は耐熱性レジストなどに使用されうる光
重合性を有する耐熱性シリコーン化合物の製法に
関するもので、一般式(1)：
（式中、ｎは２〜100の整数、R1はフエニル基
またはメチル基、エチル基、プロピル基などの低
級アルキル基を表わす）で示されるオルガノラダ
ー型ポリシロキサンと一般式(2)：
（式中、Ｘは水素原子、メチル基、エチル基ま
たはフエニル基、ｍは０〜４の整数、R2，R3は
メチル基、エチル基、プロピル基などの低級アル
キル基、ｌは１〜３の整数である）で示される不
飽和化合物とを反応させる光重合性を有する耐熱
性シリコーン化合物の製法に関する。
The present invention relates to a method for producing a heat-resistant silicone compound having photopolymerizability that can be used in heat-resistant resists, etc., and has the general formula (1): (In the formula, n is an integer from 2 to 100, and R 1 represents a phenyl group or a lower alkyl group such as a methyl group, an ethyl group, or a propyl group) and the general formula (2): (In the formula , The present invention relates to a method for producing a heat-resistant silicone compound having photopolymerizability, which involves reacting with an unsaturated compound represented by the integer 3).
本発明に用いるオルガノラダー型ポリシロキサ
ンは、前記一般式(1)で示される末端ヒドロキシラ
ダー型オルガノポリシロキサンであり、重合度は
２〜100、好ましくは５〜20である。該ラダー構
造を有するオルガノラダーポリシロキサンはきわ
めて耐熱性が優れているが、該重合度が２未満に
なるとオルガノラダー型ポリシロキサンとはなら
ず、耐熱性が劣り、100をこえると該オルガノラ
ダー型ポリシロキサンを用いて製造したシリコー
ン化合物の架橋点が少なくなり、重合性が劣る。
該重合度が５〜20のばあいには、耐熱性に優れ、
かつ光重合性に優れたシリコーン化合物がえられ
る。
The organo ladder type polysiloxane used in the present invention is a terminal hydroxy ladder type organopolysiloxane represented by the general formula (1), and has a degree of polymerization of 2 to 100, preferably 5 to 20. The organo-ladder polysiloxane having the ladder structure has extremely excellent heat resistance, but if the degree of polymerization is less than 2, it will not become an organo-ladder type polysiloxane and the heat resistance will be poor, and if it exceeds 100, it will not become an organo-ladder type polysiloxane. Silicone compounds produced using polysiloxane have fewer crosslinking points, resulting in poor polymerizability.
When the degree of polymerization is 5 to 20, it has excellent heat resistance,
A silicone compound with excellent photopolymerizability can also be obtained.
一般式(1)で示される化合物は、たとえばフエニ
ル基またはアルキル基を有するトリクロロシラン
を公知の方法によつて加水分解し、さらに水酸化
カリウム、カルボジイミド類、クロロギ酸エステ
ル類などの縮合触媒を必要に応じて用い、任意の
分子量を有するものが合成される。 The compound represented by the general formula (1) can be obtained by hydrolyzing trichlorosilane having a phenyl group or an alkyl group by a known method, and further requires a condensation catalyst such as potassium hydroxide, carbodiimides, or chloroformates. It can be used to synthesize compounds with arbitrary molecular weights.
本発明に用いる一般式(2)で示される不飽和化合
物は、化合物中に一般式(3)：
（式中、Ｘ，ｍは前記と同じ）で示される感光
基と、一般式(4)： −Si（OR2）l（R3）3-l (4)
（式中、R2，R3、ｌは前記と同じ）で示され
るアルコキシシラノ基を有する化合物である。 The unsaturated compound represented by the general formula (2) used in the present invention has the general formula (3): (In the formula, X and m are the same as above) and the general formula (4): -Si( OR2 ) l ( R3 ) 3-l ( 4 ) 3 , l is the same as above).
一般式(3)で示される感光基におけるＸとして
は、水素原子、メチル基、エチル基またはフエニ
ル基などが合成されたシリコーン化合物の光重合
性の点から好ましく、ｍとしては０〜４であるこ
とが耐熱性の点から好ましい。 As X in the photosensitive group represented by general formula (3), a hydrogen atom, methyl group, ethyl group, or phenyl group is preferable from the viewpoint of photopolymerizability of the synthesized silicone compound, and m is 0 to 4. This is preferable from the viewpoint of heat resistance.
一方、一般式(4)で示されるアルコキシシラノ基
におけるR2としてはメチル基、エチル基、プロ
ピル基などの低級アルキル基であることが、脱ア
ルコール反応性などの点から好ましく、ｌとして
は該アルコキシシラノ基が一般式(3)で示される感
光基と結合し、アルコキシシラノ基であるために
１〜３であることが好ましい。 On the other hand, R 2 in the alkoxysilano group represented by general formula (4) is preferably a lower alkyl group such as a methyl group, ethyl group, or propyl group from the viewpoint of dealcoholization reactivity, and l is preferably a lower alkyl group such as a methyl group, ethyl group, or propyl group. Since the alkoxysilano group is bonded to the photosensitive group represented by the general formula (3) and is an alkoxysilano group, the number is preferably 1 to 3.
一般式(2)で示される不飽和化合物としては、た
とえばビニルメトキシシラン、ビニルエトキシシ
ラン、ビニルプロポキシシラン、ビニルメチルジ
メトキシシラン、ビニルメチルジエトキシシラ
ン、アリルメトキシシラン、アリルエトキシシラ
ンなどがあげられるが、これらに限定されるもの
ではない。 Examples of the unsaturated compound represented by the general formula (2) include vinylmethoxysilane, vinylethoxysilane, vinylpropoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, allylmethoxysilane, and allylethoxysilane. , but not limited to these.
本発明において、一般式(1)で示されるオルガノ
ラダー型ポリシロキサンと一般式(2)で示される不
飽和化合物との反応により、光重合性ラダーポリ
シロキサンが製造される。すなわち、たとえばオ
ルガノラダー型ポリシロキサンの水酸基１個に対
し、不飽和化合物のアルコキシ基１〜３個の割合
でオルガノラダーポリシロキサンと不飽和化合物
とを混合し、反応を促進させるための触媒などを
添加し、50〜130℃程度の温度で５〜20時間加熱
撹拌して水酸基とアルコキシシラノ基との間で脱
アルコール反応させ、光重合性を有する耐熱性シ
リコーン化合物が製造される。 In the present invention, a photopolymerizable ladder polysiloxane is produced by reacting an organoladder polysiloxane represented by general formula (1) with an unsaturated compound represented by general formula (2). That is, for example, an organoladder polysiloxane and an unsaturated compound are mixed in a ratio of 1 to 3 alkoxy groups of the unsaturated compound to one hydroxyl group of the organoladder polysiloxane, and a catalyst or the like is added to promote the reaction. A heat-resistant silicone compound having photopolymerizability is produced by heating and stirring at a temperature of about 50 to 130°C for 5 to 20 hours to cause a dealcoholization reaction between the hydroxyl group and the alkoxysilano group.
前記反応において使用される触媒としては硫
酸、リン酸、酸化アルミニウム、オルソチタン酸
イソプロピルエステルなどを使用することができ
る。該触媒の使用量は、オルガノラダー型ポリシ
ロキサン100部（重量部、以下同様）に対し0.01
〜５部であることが好ましい。 As the catalyst used in the reaction, sulfuric acid, phosphoric acid, aluminum oxide, orthotitanate isopropyl ester, etc. can be used. The amount of the catalyst used is 0.01 parts per 100 parts (parts by weight, hereinafter the same) of organo ladder type polysiloxane.
It is preferable that it is 5 parts.
本発明に用いるオルガノラダー型ポリシロキサ
ンは通常固体状であるため、前記脱アルコール反
応には溶剤を使用することが好ましい。そのよう
な溶剤としては、メチルエチルケトン、メチルイ
ソブチルケトンなどのケトン系溶剤、ベンゼン、
トルエン、キシレンなどの芳香族炭化水素系溶剤
またはＮ−メチルピロリドンなどがあげられる
が、これらに限定されるものではない。 Since the organoladder polysiloxane used in the present invention is usually solid, it is preferable to use a solvent in the dealcoholization reaction. Such solvents include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, benzene,
Examples include, but are not limited to, aromatic hydrocarbon solvents such as toluene and xylene, and N-methylpyrrolidone.
前記脱アルコール反応は、反応生成物のIRス
ペクトル分析により、原料の末端ヒドロキシラダ
ー型ポリシロキサンに由来する水酸基の3200〜
3600cm-1の吸収減少と、XHC＝CH−にもとづく
1270cm-1付近の吸収の観察によつて確認しうる。 The above-mentioned dealcoholization reaction revealed that the hydroxyl groups originating from the terminal hydroxy ladder type polysiloxane of the raw material were determined by IR spectrum analysis of the reaction product.
Based on the absorption decrease of 3600 cm -1 and XHC=CH-
This can be confirmed by observing absorption near 1270 cm -1 .
つぎに本発明の方法を実施例にもとづき説明す
るが、本発明はこれらに限定されるものではな
い。 Next, the method of the present invention will be explained based on Examples, but the present invention is not limited thereto.
製造例 １
（末端ヒドロキシラダー型オルガノポリシロキ
サンの合成）
フエニルトリクロロシラン（C6H5SiCl3）105.8
ｇ（0.5モル）をメチルイソブチルケトン 200ml
に溶解した溶液を、撹拌器および温度計を取付
け、氷浴で冷却中の２の４つ口フラスコに入れ
た１のイオン交換水に、撹拌下、徐々に滴下
し、加水分解を行なつた。該滴下中、反応温度を
10℃以下に保持し、滴下終了までに４時間要し
た。そののち室温にもどし、さらに30分間撹拌
し、加水分解反応を完結させた。Production example 1 (Synthesis of terminal hydroxy ladder type organopolysiloxane) Phenyltrichlorosilane (C 6 H 5 SiCl 3 ) 105.8
g (0.5 mol) of methyl isobutyl ketone 200ml
The solution was gradually added dropwise under stirring to the ion-exchanged water in Step 1, which was placed in a four-neck flask equipped with a stirrer and a thermometer and cooled in an ice bath, to perform hydrolysis. . During the dropping, the reaction temperature was
The temperature was maintained below 10°C, and it took 4 hours to complete the dropwise addition. Thereafter, the mixture was returned to room temperature and stirred for an additional 30 minutes to complete the hydrolysis reaction.
撹拌停止後、２層に分離した反応液からケトン
層を分取したのち、イオン交換水で中性になるま
で数回水洗した。該溶液から溶剤を除去し、減圧
乾燥器中で150℃×１時間乾燥させ、白色粉末
（）55ｇをえた。 After the stirring was stopped, the ketone layer was separated from the reaction solution separated into two layers, and then washed with ion-exchanged water several times until it became neutral. The solvent was removed from the solution, and it was dried in a vacuum dryer at 150° C. for 1 hour to obtain 55 g of a white powder.
えられた白色粉末（）をIRスペクトル分析
したところ、3400cm-1にOHの吸収、さらにジヤ
ーナル・オブ・ポリマー・サイエンス（J.polym.
Sci.），Ｃ−１巻、83頁（1963）に記載されてい
るようなSi−Ｏ−Siの逆対称伸縮振動に帰属され
る吸収が1135cm-1および1045cm-1に観測された。
これらの結果からえられた白色粉末（）が一般
式(1)に示す末端ヒドロキシラダー型ポリシロキサ
ンであることを確認した。また該粉末は溶融温度
90℃、分子量約1500（ｎ＝６）であつた。 An IR spectrum analysis of the white powder obtained () revealed an OH absorption at 3400 cm -1 , which was also found in the Journal of Polymer Science (J.polym.
Sci.), Vol. C-1, p. 83 (1963), absorptions attributed to antisymmetric stretching vibrations of Si-O-Si were observed at 1135 cm -1 and 1045 cm -1 .
From these results, it was confirmed that the white powder () obtained was a terminal hydroxy ladder type polysiloxane represented by the general formula (1). The powder also has a melting temperature of
The temperature was 90°C and the molecular weight was about 1500 (n=6).
製造例 ２
（末端ヒドロキシラダー型オルガノポリシロキ
サンの合成）
還流冷却管、撹拌器および温度計を取付けた３
つ口フラスコに製造例１でえられた白色粉末10ｇ
およびキシレン30mlの入れ、溶解して均一にした
のち縮合触媒としてクロロギ酸エチル0.4ｇを加
え溶解し、130℃×５時間反応させた。反応終了
後、反応混合物を放冷し、10倍量（容量）のメタ
ノール中にそそいでポリマーを析出させ、分取後
減圧乾燥した（収量９ｇ）。Production example 2 (Synthesis of terminal hydroxy ladder type organopolysiloxane) 3 equipped with a reflux condenser, stirrer and thermometer
10g of white powder obtained in Production Example 1 in a neck flask
After adding 30 ml of xylene and dissolving the mixture to make it homogeneous, 0.4 g of ethyl chloroformate as a condensation catalyst was added and dissolved, and the mixture was reacted at 130°C for 5 hours. After the reaction was completed, the reaction mixture was allowed to cool and poured into 10 times the amount (volume) of methanol to precipitate the polymer, which was separated and dried under reduced pressure (yield: 9 g).
えられたポリマーをIRスペクトル分析したと
ころ、3400cm-1にOHの吸収が、さらに1135cm-1
と1045cm-1とにSi−Ｏ−Siの逆対称伸縮振動に帰
属される吸収が観測された。これらの結果からえ
られたポリマーは末端ヒドロキシラダー型ポリシ
ロキサンであることを確認した。またえられたポ
リマーの分子量は約3000（ｎ＝12）であつた。 IR spectrum analysis of the obtained polymer revealed that OH absorption was observed at 3400 cm -1 and further at 1135 cm -1
Absorption attributed to the antisymmetric stretching vibration of Si-O-Si was observed at and 1045 cm -1 . From these results, it was confirmed that the obtained polymer was a terminal hydroxy ladder type polysiloxane. The molecular weight of the obtained polymer was about 3000 (n=12).
実施例 １
製造例１でえられた末端ヒドロキシフエニルラ
ダー型ポリシロキサン（重合度約６、水酸基４
個）30ｇ、ビニルエトキシシラン15.2ｇおよびト
ルエン50ｇを３つ口フラスコに入れ、撹拌器、温
度計、冷却器を取付け、約110℃で10時間撹拌
し、反応させた。反応終了後、トルエンを減圧蒸
留により除去し、白色粉末（）をえた。収率は
95％であつた。Example 1 Terminated hydroxyphenyl ladder type polysiloxane obtained in Production Example 1 (polymerization degree of about 6, hydroxyl group 4
30 g of vinyl ethoxysilane, 15.2 g of vinyl ethoxysilane, and 50 g of toluene were placed in a three-necked flask, equipped with a stirrer, a thermometer, and a condenser, and stirred at about 110° C. for 10 hours to react. After the reaction was completed, toluene was removed by vacuum distillation to obtain a white powder. The yield is
It was 95%.
えられた白色粉末（）のIRスペクトル分析
を行なつたところ、原料の末端ヒドロキシフエニ
ルラダー型ポリシロキサンと比較して3400cm-1の
OHによる吸収は減少し、あらたにビニル基によ
る1270cm-1の吸収が認められた。 IR spectrum analysis of the obtained white powder () revealed that it had a 3400 cm -1
The absorption due to OH decreased, and a new absorption at 1270 cm -1 due to vinyl groups was observed.
えられた白色粉末（）（シリコーン化合物）
をトルエンに溶解し（濃度15重量％）スピンナー
を用いてガラス基板上に塗布したところ、0.8μ
ｍの薄膜がえられた。 The resulting white powder () (silicone compound)
When dissolved in toluene (concentration 15% by weight) and applied on a glass substrate using a spinner, it was found that 0.8μ
A thin film of m was obtained.
実施例 ２
実施例１で用いた原料に酸化アルミニウム粉末
１ｇを加え、酸化アルミニウムが分散した状態
で、約110℃×５時間反応させた以外は実施例１
と同様にして反応を行なつた。反応終了後酸化ア
ルミニウムを過し、トルエンを減圧蒸留により
除去し、白色粉末（）をえた。収率は95％であ
つた。Example 2 Example 1 except that 1 g of aluminum oxide powder was added to the raw material used in Example 1, and the reaction was carried out at approximately 110°C for 5 hours in a state where aluminum oxide was dispersed.
The reaction was carried out in the same manner. After the reaction was completed, aluminum oxide was filtered and toluene was removed by distillation under reduced pressure to obtain a white powder. The yield was 95%.
えられた白色粉末（）のIRスペクトル分析
を行なつたところ、原料の末端ヒドロキシフエニ
ルラダー型ポリシロキサンと比較して3400cm-1の
OHによる吸収は減少し、あらたにビニル基によ
る1270cm-1の吸収がみとめられた。 IR spectrum analysis of the obtained white powder () revealed that it had a 3400 cm -1
The absorption due to OH decreased, and a new absorption at 1270 cm -1 due to vinyl groups was observed.
えられた白色粉末（）（シリコーン化合物）
をトルエンに溶解し（濃度15重量％）、スピンナ
ーを用いてガラス基板上に回転塗布したところ、
0.8μｍの薄膜がえられた。 The resulting white powder () (silicone compound)
was dissolved in toluene (concentration 15% by weight) and spin-coated onto a glass substrate using a spinner.
A thin film of 0.8 μm was obtained.
実施例 ３
製造例１でえられた末端ヒドロキシフエニルラ
ダー型ポリシロキサン30ｇ、ビニルメトキシシラ
ン11.9ｇ、オルソチタン酸イソプロピルエステル
１ｇおよびキシレン50ｇを実施例１と同様の装置
を用いて120℃×５時間反応させた。反応終了後
減圧蒸留によりキシレンを除去し、白色粉末
（）をえた。収率は95％であつた。Example 3 30 g of the terminal hydroxyphenyl ladder type polysiloxane obtained in Production Example 1, 11.9 g of vinylmethoxysilane, 1 g of isopropyl orthotitanate and 50 g of xylene were heated at 120°C x 5 using the same apparatus as in Example 1. Allowed time to react. After the reaction was completed, xylene was removed by distillation under reduced pressure to obtain a white powder. The yield was 95%.
えられた白色粉末（）のIRスペクトル分析
を行なつたところ、原料の末端ヒドロキシラダー
型ポリシロキサンと比較して3400cm-1のOHによ
る吸収は減少し、あらたにビニル基による1270cm
-1の吸収がみとめられた。 An IR spectrum analysis of the obtained white powder () revealed that the absorption due to OH at 3400 cm -1 decreased compared to the raw material terminal hydroxy ladder type polysiloxane, and the absorption due to OH at 3400 cm -1 was newly observed at 1270 cm due to the vinyl group.
-1 absorption was observed.
えられた白色粉末（）（シリコーン化合物）
をトルエンに溶解し（濃度15重量％）、スピンナ
ーを用いてガラス基板上に回転塗布したところ、
0.8μｍの薄膜がえられた。 The resulting white powder () (silicone compound)
was dissolved in toluene (concentration 15% by weight) and spin-coated onto a glass substrate using a spinner.
A thin film of 0.8 μm was obtained.
実施例 ４
製造例２でえられた末端ヒドロキシフエニルラ
ダー型ポリシロキサン（重合度約12、水酸基４
個）30ｇ、ビニルメトキシシラン6.0ｇ、オルソ
チタン酸イソプロピルエステル１ｇおよびキシレ
ン50ｇを実施例１と同様の装置を用いて120℃×
５時間反応させた。そののち10倍量のメタノール
に注ぎ、白色沈殿をえた。収率は92％であつた。Example 4 Terminated hydroxyphenyl ladder type polysiloxane obtained in Production Example 2 (polymerization degree of about 12, hydroxyl group 4
), 6.0 g of vinylmethoxysilane, 1 g of isopropyl orthotitanate, and 50 g of xylene were heated at 120°C using the same equipment as in Example 1.
The reaction was allowed to proceed for 5 hours. Thereafter, the mixture was poured into 10 times the amount of methanol to obtain a white precipitate. The yield was 92%.
えられた白色沈殿（シリコーン化合物）のIR
スペクトル分析を行なつたところ、原料の末端ヒ
ドロキシフエニルラダー型ポリシロキサンと比較
して3400cm-1のOHによる吸収は減少し、あらた
にビニル基による1270cm-1の吸収がみとめられ
た。 IR of the white precipitate (silicone compound) obtained
When spectral analysis was performed, it was found that the absorption due to OH at 3400 cm -1 decreased compared to the raw material terminal hydroxyphenyl ladder type polysiloxane, and the absorption at 1270 cm -1 due to vinyl groups was newly observed.
えられた白色沈殿（シリコーン化合物）を芳香
族系有機溶剤に溶解し（濃度15重量％）、スピン
ナーを用いて、ガラス基板上に回転塗布したとこ
ろ、0.9μｍの薄膜がえられた。 The resulting white precipitate (silicone compound) was dissolved in an aromatic organic solvent (concentration 15% by weight) and spin-coated onto a glass substrate using a spinner, resulting in a 0.9 μm thin film.
実施例 ５
製造例１でえられた白色粉末（）30ｇ、アリ
ルエトキシシラン16.3ｇおよびトルエン50ｇを実
施例１と同様にして約110℃×10時間反応させ、
白色粉末（）をえた。収率は95％であつた。Example 5 30 g of the white powder obtained in Production Example 1, 16.3 g of allyl ethoxysilane, and 50 g of toluene were reacted in the same manner as in Example 1 at about 110°C for 10 hours.
A white powder () was obtained. The yield was 95%.
えられた白色粉末（）（シリコーン化合物）
のIRスペクトル分析を行なつたところ、原料の
末端ヒドロキシフエニルラダー型ポリシロキサン
と比較して3400cm-1のOHによる吸収は減少し、
あらたにアリル基による1620cm-1の吸収がみとめ
られた。 The resulting white powder () (silicone compound)
An IR spectrum analysis of the material revealed that the absorption due to OH at 3400 cm -1 decreased compared to the raw material terminal hydroxyphenyl ladder type polysiloxane.
A new absorption of 1620 cm -1 due to the allyl group was observed.
えられた白色粉末（）をトルエンに溶解し
（濃度15重量％）、スピンナーを用いて回転塗布し
たところ、0.8μｍの薄膜がえられた。 The obtained white powder (2) was dissolved in toluene (concentration 15% by weight) and spin coated using a spinner to obtain a 0.8 μm thin film.
本発明の方法によると耐熱性が良好であり、光
重合性を有するシリコーン化合物が容易に製造し
うる。
According to the method of the present invention, a silicone compound having good heat resistance and photopolymerizability can be easily produced.
Claims (1)
またはメチル基、エチル基、プロピル基などの低
級アルキル基を表わす）で示されるオルガノラダ
ー型ポリシロキサンと一般式(2)： （式中、Ｘは水素原子、メチル基、エチル基ま
たはフエニル基、ｍは０〜４の整数、R2，R3は
メチル基、エチル基、プロピル基などの低級アル
キル基、ｌは１〜３の整数である）で示される不
飽和化合物とを反応させることを特徴とする光重
合性を有する耐熱性シリコーン化合物の製法。[Claims] 1 General formula (1): (In the formula, n is an integer from 2 to 100, and R 1 represents a phenyl group or a lower alkyl group such as a methyl group, an ethyl group, or a propyl group) and the general formula (2): (In the formula , A method for producing a heat-resistant silicone compound having photopolymerizability, the method comprising reacting a heat-resistant silicone compound with an unsaturated compound represented by (an integer of 3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58218205A JPS60110726A (en) | 1983-11-18 | 1983-11-18 | Production of silicone compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58218205A JPS60110726A (en) | 1983-11-18 | 1983-11-18 | Production of silicone compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60110726A JPS60110726A (en) | 1985-06-17 |
| JPS6260412B2 true JPS6260412B2 (en) | 1987-12-16 |
Family
ID=16716264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58218205A Granted JPS60110726A (en) | 1983-11-18 | 1983-11-18 | Production of silicone compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60110726A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4118973B2 (en) | 1997-03-14 | 2008-07-16 | 新日鐵化学株式会社 | Silicone compound and method for producing the same |
| CN1206019A (en) * | 1997-07-17 | 1999-01-27 | 中国科学院化学研究所 | Tubular organosilicon polymer and its preparation and application |
| CN1206021A (en) * | 1997-07-17 | 1999-01-27 | 中国科学院化学研究所 | Tubular organosilicon polymer compound and its preparation |
| JP5350571B2 (en) * | 2000-08-21 | 2013-11-27 | ダウ グローバル テクノロジーズ エルエルシー | Organic silicate resin as hard mask for organic polymer insulating film used in microelectronic device manufacturing |
| JP5855552B2 (en) * | 2012-10-15 | 2016-02-09 | 信越化学工業株式会社 | Method for producing polyorganosiloxane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3294737A (en) * | 1963-12-23 | 1966-12-27 | Gen Electric | Organopolysiloxanes |
| JPS5712057A (en) * | 1980-06-26 | 1982-01-21 | Hitachi Chem Co Ltd | Preparation of silicone compound |
| JPS5859222A (en) * | 1981-10-03 | 1983-04-08 | Japan Synthetic Rubber Co Ltd | Organopolysilsesquioxane and its production |
-
1983
- 1983-11-18 JP JP58218205A patent/JPS60110726A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3294737A (en) * | 1963-12-23 | 1966-12-27 | Gen Electric | Organopolysiloxanes |
| JPS5712057A (en) * | 1980-06-26 | 1982-01-21 | Hitachi Chem Co Ltd | Preparation of silicone compound |
| JPS5859222A (en) * | 1981-10-03 | 1983-04-08 | Japan Synthetic Rubber Co Ltd | Organopolysilsesquioxane and its production |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60110726A (en) | 1985-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4381396A (en) | Silynorbornane anhydrides and method for making | |
| JPS58171416A (en) | Heat-resistant polymer | |
| JP3224830B2 (en) | Organosilicon compound and method for producing the same | |
| JP2843620B2 (en) | One-terminal branched aminoalkyl group-blocked organopolysiloxane and method for producing the same | |
| JP2631739B2 (en) | Phenol group-containing siloxane compound | |
| JP3112686B2 (en) | Curable polymethylsilsesquioxane, curing method thereof, and cured product thereof | |
| JPS6260412B2 (en) | ||
| JPS60108841A (en) | Photosensitive heat resistant material | |
| JPS6155524B2 (en) | ||
| JPS6322822A (en) | Silicone-modified epoxy resin and production thereof | |
| JP2705432B2 (en) | Methacrylic group-containing bis (4'-phthalic anhydride) siloxane derivative and method for producing the same | |
| JP2007023163A (en) | Composition for forming film, insulating film and their production method | |
| JPS6313446B2 (en) | ||
| US3548025A (en) | Novel silicon - substituted glycol monoesters and process for their preparation | |
| JP2716346B2 (en) | Alpha, omega-phenylethynylsiloxane monomers, oligomers and polymers thereof | |
| JPH07258416A (en) | Both end-functional diphenylsiloxane oligomer and method for producing the same | |
| JPH0586071A (en) | Process for producing dianhydride-terminated polydiorganosiloxane | |
| JP2541060B2 (en) | Method for producing organosilicon compound | |
| JPH0215864B2 (en) | ||
| JPS61278532A (en) | Production of hydroxyphenyl-terminated ladder polysiloxane | |
| JPH08325381A (en) | Organosilicon compound and its production | |
| JPH0442414B2 (en) | ||
| SU1073248A1 (en) | Carbazole- and anthracene-containing polysiloxanes as substrate to electrophotographic layers and method of producing them | |
| JP4276805B2 (en) | Novel silazane compound and method for producing the same, and novel silazane compound polymer and method for producing the same | |
| JPH0215863B2 (en) |