JPH0496973A - Primer composition - Google Patents
Primer compositionInfo
- Publication number
- JPH0496973A JPH0496973A JP21366790A JP21366790A JPH0496973A JP H0496973 A JPH0496973 A JP H0496973A JP 21366790 A JP21366790 A JP 21366790A JP 21366790 A JP21366790 A JP 21366790A JP H0496973 A JPH0496973 A JP H0496973A
- Authority
- JP
- Japan
- Prior art keywords
- silazane
- primer composition
- minutes
- group
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 125000000547 substituted alkyl group Chemical group 0.000 claims abstract 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000002075 main ingredient Substances 0.000 claims 1
- 229920002379 silicone rubber Polymers 0.000 abstract description 27
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 abstract description 3
- 229910003814 SiH2NH Inorganic materials 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 description 32
- 239000004945 silicone rubber Substances 0.000 description 25
- 239000000853 adhesive Substances 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 229920001971 elastomer Polymers 0.000 description 15
- 239000005060 rubber Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000008096 xylene Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 229920001709 polysilazane Polymers 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 239000012925 reference material Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000007605 air drying Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- -1 methylethyl Chemical group 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 229910003828 SiH3 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 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
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000005048 methyldichlorosilane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Silicon Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、プライマー組成物、特に高温条件下での接着
性に優れ、さらには硬化速度を任意に調整できるた袷極
めて作業性のよいプライマー組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides a primer composition, particularly a primer that has excellent adhesive properties under high-temperature conditions, and furthermore, has extremely good workability as the curing speed can be arbitrarily adjusted. Regarding the composition.
シリコーンゴムと金属あるいはプラスチックなどの接着
性を改善するた於にプライマーを使用することは公知で
ある。It is known to use a primer to improve the adhesion between silicone rubber and metals, plastics, etc.
プライマーとしては、例えば、ビニルトリメトキシシラ
ン等のアルコキシシラン、テトラ−ｎ−ブチルチタネー
ト等のテトラアルキルチタネートが使用されている。し
かし、これらのプライマーは２００℃以上の高温では、
長時間その接着性を維持できず耐熱性に劣るという欠点
がある。このため、高温時における接着性の改善を目的
に、シリコーン・ポリマーにシラザン結合を導入する方
法が採用されたが、シリコーンゴムの特性を変えずに硬
化速度および接着性を調整するのが難しいという問題が
ある。As the primer, for example, alkoxysilanes such as vinyltrimethoxysilane, and tetraalkyl titanates such as tetra-n-butyl titanate are used. However, these primers cannot be used at high temperatures of 200°C or higher.
It has the disadvantage that it cannot maintain its adhesive properties for a long time and has poor heat resistance. For this reason, a method of introducing silazane bonds into silicone polymers has been adopted with the aim of improving adhesion at high temperatures, but it is difficult to adjust the curing speed and adhesion without changing the properties of silicone rubber. There's a problem.
更に、これらの問題点を解消するために、Ｓｉ２Ｎ２架
橋を有する特殊なポリシラザンをプライマーとして使用
することが提案されている。Furthermore, in order to overcome these problems, it has been proposed to use special polysilazane with Si2N2 crosslinks as a primer.
この５ｉ２Ｎ２架橋を有するラダー型のオルガノポリン
ラザンは比較的安定であり、既存のプライマーに比べ耐
熱性にも優れている。しかし、このポリマーは塩基性触
媒を使用し、かつ反応停止剤を使用して製造されるため
、５ｉ２Ｎ２架橋、ヒドロシリル基量の制御が困難であ
り一定性状のポリマーが得られない。このだ約、硬化速
度の調整が困難である、接着性が十分でないという点で
プライマーとしての特性が十分でない。そこで、本発明
は、このような問題点を解決し、高温条件下での接着性
に優れ、さらに硬化速度を調整できる作業性のよいプラ
イマー組成物を提供することを目的とする。This ladder-type organoporin lazan having 5i2N2 crosslinks is relatively stable and has superior heat resistance compared to existing primers. However, since this polymer is produced using a basic catalyst and a reaction terminator, it is difficult to control 5i2N2 crosslinking and the amount of hydrosilyl groups, and a polymer with constant properties cannot be obtained. Due to this limitation, it is difficult to adjust the curing speed, and the adhesive properties are insufficient, so the properties as a primer are insufficient. SUMMARY OF THE INVENTION An object of the present invention is to solve these problems and provide a primer composition that has excellent adhesive properties under high-temperature conditions and has good workability in which the curing speed can be adjusted.
本発明はかかる課題を解決したプライマー組成物に関す
るものであり、分子中に一３Ｉ８２ＮＨ−あるいは−５
＋ｔ（ＪＨ−及び−５ｉ［（Ｒ’Ｎｆ（Ｒ２−で示され
る骨格を有し、さらに末端に−ＳｉＨ３で示されるヒド
ロシリル基を持つポリシラザンを特徴とするものである
。The present invention relates to a primer composition that solves this problem, and contains -3I82NH- or -5 in the molecule.
It is characterized by a polysilazane having a skeleton represented by +t(JH- and -5i[(R'Nf(R2-) and a hydrosilyl group represented by -SiH3 at the end).
（ここに、Ｒ１、Ｒ２は水素原子、置換基を有してもよ
いアルキル基、アルケニル基、シクロアルキル基、アル
キルアミノ基、アリール基、アルアルキル基又はアルキ
ルシリル基を示す。但し、Ｒ１、Ｒ２の両方が水素原子
である場合を除く。）
すなわち、本発明者らは高温下で接着性が低下せず、適
度な硬化速度を有するプライマーについて鋭意検討を重
ねた結果、ベルヒドロポリシラザンとポリオルガノシラ
ザンを混合、塩基性溶媒下で共重合させることにより得
られたブロック共重合体が高温での接着性に優れ、かつ
調整された硬化速度を持つことを見出だし本発明を完成
するに至った。(Here, R1 and R2 represent a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group, a cycloalkyl group, an alkylamino group, an aryl group, an aralkyl group, or an alkylsilyl group. However, R1, (Excluding the case where both R2 are hydrogen atoms.) In other words, the present inventors have conducted intensive studies on primers that do not reduce adhesiveness at high temperatures and have an appropriate curing speed, and have found that perhydropolysilazane and polysilazane It was discovered that a block copolymer obtained by mixing organosilazane and copolymerizing it in a basic solvent has excellent adhesive properties at high temperatures and has a controlled curing speed, and has completed the present invention. Ta.
本発明のプライマー組成物の主剤は一３ｉＨ２ＮＨ−の
基本骨格を有し、さらに末端に一３ｉ８３基をもつ分子
量５００〜５００００のベルヒドロポリシラザン（時開
６０−１４５９０３、特告６３−１６３２５、特開平１
−１３８１０７、特開平１−１３８１０８に示す方法に
より得られる。）単独、又はこれと一５ｉＨＲ’ＮＲ’
−の基本骨格を有する分子量５００〜５０００のポリオ
ルガノシラザンを塩基性溶媒の存在下に脱水素重合反応
、あるいは反応系に更に反応剤としてアンモニア、第一
級アミン、ヒドラジンを加え脱水素重合反応させること
により得られるブロック共重合シラザン（例えば特願昭
６３−３２８４７２）である。The main component of the primer composition of the present invention has a basic skeleton of -3iH2NH-, and has a molecular weight of 500 to 50,000 and further has a -3i83 group at the terminal. 1
-138107, obtained by the method shown in JP-A-1-138108. ) Alone or with this 5iHR'NR'
A polyorganosilazane with a molecular weight of 500 to 5000 having a basic skeleton of This is a block copolymerized silazane (for example, Japanese Patent Application No. 63-328472) obtained by this method.
ここで、Ｒ１、Ｒ２は水素原子、置換基を有してもよい
アルキル基、シクロアルキル基、アルケニル基、アルキ
ルアミノ基、アリール基、アルアルキル基、を示すが、
Ｒ１，Ｒ２の両方が水素原子である場合は除かれる。こ
の場合、アルキル基としては、メチルエチル、プロビノ
ペブチノペオクチル、デシル等があげられ、アルケニル
基としては、ビニノペアリル、ブテニノペオクテニノペ
デセニル等があげられ、シクロアルキル基としては、シ
クロヘキシノペメチルシクロヘキシル等があげられ、ア
ルキルアミ７基としては、メチルアミン基、エチルアミ
ノ基等があげられ、アリール基としては、フェニル、ト
リル、キシリ）ベナフチル等があげられ、アルアルキル
基としては、ベンジル基があげられ、アルキルシリル基
としては、メチルシリル、エチルシリノベプロピルシリ
ル、ブチルシリル、オクチルシリル、デシルシリル等が
挙げられる。また、前記置換基としては、珪素原子に結
合する水素原子に反応性を示さないものであればよく、
アルキル基やアリール基、アルコキシ基、アルコキシカ
ルボニル基等が挙げられる。Here, R1 and R2 represent a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group, an alkenyl group, an alkylamino group, an aryl group, an aralkyl group,
The case where both R1 and R2 are hydrogen atoms is excluded. In this case, examples of the alkyl group include methylethyl, probinopebutinopeoctyl, decyl, etc., examples of the alkenyl group include vinylopearyl, buteninopeocteninopedecenyl, etc., and examples of the cycloalkyl group include , cyclohexynopemethylcyclohexyl, etc., examples of the alkylamino group include methylamine group, ethylamino group, etc., examples of the aryl group include phenyl, tolyl, xyly)benaphthyl, etc., and examples of the aralkyl group include phenyl, tolyl, xyly) benaphthyl, etc. Examples of the alkylsilyl group include methylsilyl, ethylsilinobepropylsilyl, butylsilyl, octylsilyl, and decylsilyl. Further, the substituent may be any substituent as long as it does not show reactivity with hydrogen atoms bonded to silicon atoms,
Examples include an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, and the like.
尚、ここでの無機ポリシラザンと有機ポリシラザンの反
応比は重量比で１００ ： ０〜１０：９０が好ましい
。有機ポリシラザンの重量が９Ｑｗｔ％を越えると無機
ポリシラザンのＳｉＨ３基による硬化の効果が充分に発
揮できない。Incidentally, the reaction ratio of the inorganic polysilazane and the organic polysilazane here is preferably 100:0 to 10:90 in terms of weight ratio. If the weight of the organic polysilazane exceeds 9 Qwt%, the curing effect of the SiH3 group of the inorganic polysilazane cannot be sufficiently exhibited.
また分子量は５００〜５００００であるが、好ましくは
５００〜１００００である。分子量が５００未満では硬
化速度が遅く、５００００超では硬化が速すぎる。この
ようにして得られたプライマー組成物は、耐熱性を有し
、接着性にも優れている。もちろん、有機、無機のポリ
シラザンとも単独でプライマーとして使用可能であるが
、特にベルヒドロポリシラザンはＳ１□Ｎ２架橋ポリマ
ーに比べ活性な一３ｉ８３基を末端に有しているため、
優れた接着性を示すが硬化速度が速く、またオルガノポ
リシラザンは比較的安定で硬化速度が遅い特徴があり、
シラザンのブロック比を任意に選択することにより、接
着強度、硬化速度を自由に制御することが可能である。Moreover, the molecular weight is 500 to 50,000, preferably 500 to 10,000. If the molecular weight is less than 500, the curing speed will be slow, and if it exceeds 50,000, the curing will be too fast. The primer composition thus obtained has heat resistance and excellent adhesiveness. Of course, both organic and inorganic polysilazane can be used alone as a primer, but in particular perhydropolysilazane has more active 13i83 groups at the end than S1□N2 crosslinked polymers.
It shows excellent adhesion but has a fast curing speed, and organopolysilazane is relatively stable and has a slow curing speed.
By arbitrarily selecting the block ratio of silazane, it is possible to freely control adhesive strength and curing speed.
本発明により得られるプライマー組成物は、分子内に適
度なシラザン結合及び活性なヒドロシリル基（５ＩＨ３
）を有するため、金属、及びＯＨ結合を持つプラスチッ
ク類との接着力が強い。また、５ｉＨＲ’ＮＲ’−の量
により硬化速度が任意に制御出来る。The primer composition obtained by the present invention has a moderate silazane bond and an active hydrosilyl group (5IH3) in the molecule.
), it has strong adhesive strength with metals and plastics with OH bonds. Further, the curing speed can be arbitrarily controlled by the amount of 5iHR'NR'-.
本発明によって得られるプライマー組成物は、調整され
た硬化速度をもつため、極めて作業性に優れており、ま
た、優れた接着強度を有すると同時に耐熱性が高いため
、高温条件下でも接着力が維持される。耐熱性の要求さ
れる各種シリコーンゴム用のプライマーとして有用であ
る。The primer composition obtained by the present invention has a controlled curing speed, so it has excellent workability, and also has excellent adhesive strength and high heat resistance, so it has strong adhesive strength even under high temperature conditions. maintained. It is useful as a primer for various silicone rubbers that require heat resistance.
参考例１
内容積１βの四つロフラスコにガス吹きこみ管、メカニ
カルスターラー、ジュワーコンデンサーを装置した。反
応器内部を脱酸素した乾燥窒素で置換した後、四つロフ
ラスコに脱気した乾燥ピリジン４９０ｍｊ２を入れ、こ
れを氷冷した。次にジクロロシラン５１．６ ｇを加え
ると白色固体状のアダクト（ＳｉＨ２Ｃｌ２・２Ｃｓ）
ＩｓＮ）が生成した。反応混合物を氷冷し、攪拌しなが
ら、水酸化ナトリウム管及び活性炭管を通して精製した
アンモニア５１．０ ｇを吹き込んだ。Reference Example 1 A four-loop flask with an internal volume of 1β was equipped with a gas blowing pipe, a mechanical stirrer, and a dewar condenser. After purging the inside of the reactor with deoxygenated dry nitrogen, 490 mj2 of degassed dry pyridine was placed in a four-bottle flask and cooled on ice. Next, when 51.6 g of dichlorosilane was added, a white solid adduct (SiH2Cl2.2Cs) was formed.
IsN) was generated. The reaction mixture was ice-cooled, and while stirring, 51.0 g of purified ammonia was blown into the reaction mixture through a sodium hydroxide tube and an activated carbon tube.
反応終了後、反応混合物を遠心分離し、乾燥ピリジンを
用いて洗浄した後、更に窒素雰囲気下で濾過し、濾液８
５０ｍ１を得た。濾液５ｍｌから溶媒を減圧留去すると
樹脂固体ベルヒドロポリシラザン０、１０２ ｇが得ら
れた。After completion of the reaction, the reaction mixture was centrifuged, washed with dry pyridine, and further filtered under nitrogen atmosphere to obtain filtrate 8.
50ml was obtained. The solvent was distilled off from 5 ml of the filtrate under reduced pressure to obtain 0.102 g of solid resin perhydropolysilazane.
得られたポリマーの数平均分子量はＧＰＣにより測定し
たところ、９８０であった。また、このポリマーのＩＲ
（赤外吸収）スペクトル（溶液：乾燥ｏ−キシレン；ベ
ルヒドロポリシラザンの濃度：１０、２ ｇ ／ １２
）を検討すると、波数（ａｍ ’） ３３５０（見か
けの吸光係数ε＝ ０．５５７Ａ ｇ ’ａｍ ’）及
び１１７５のＮＨに基づく吸収、２１７０ （ε＝３．
１４）のＳｉＨに基づく吸収； １０２０〜８２０のＳ
ｉＨ及び５ｉＮＳｉに基づく吸収を示すことが確認され
た。またこのポリマーの’ＨＮＭＲ（プロトン核磁気共
鳴）スペクトル（６０ＭＨｚ、溶媒ＣＤＣｊ！３／基準
物質ＴＭＳ）測定結果、δ４．４ ｐｐｍ（ｂｒＳｉＨ
３） 、δ４．８ｐｐｍ（ＳｉＨ，５ｉＨ２） ：δ
Ｌ ４ ｐｐｍ （ｂｒＮＨ）の吸収が確認された。The number average molecular weight of the obtained polymer was 980 as measured by GPC. Also, the IR of this polymer
(Infrared absorption) spectrum (solution: dry o-xylene; concentration of perhydropolysilazane: 10, 2 g/12
), the wave number (am') is 3350 (apparent extinction coefficient ε=0.557A g'am') and the absorption based on NH of 1175, 2170 (ε=3.
14) SiH-based absorption; 1020-820 S
It was confirmed that absorption based on iH and 5iNSi was exhibited. In addition, as a result of measuring the 'HNMR (proton nuclear magnetic resonance) spectrum (60 MHz, solvent CDCj!3/reference material TMS) of this polymer, δ4.4 ppm (brSiH
3) , δ4.8ppm (SiH, 5iH2): δ
Absorption of L 4 ppm (brNH) was confirmed.
参考例２
内容積１βの四つロフラスコにガス吹き込み管、メカニ
カルスターラー、ジュワーコンデンサーを装置した。反
応器内部を脱酸素した乾燥窒素で置換した後、四つロフ
ラスコに乾燥ジクロロメタン３００ｍ７！及びメチルジ
クロロシラン２４．３ｇ （０，２１１ｍｏｌ）を入れ
、氷冷した。攪拌しながら水酸化ナトリウム管及び活性
炭管を通して精製したアンモニア１８．１ ｇ （１，
０６ｍｏｌ）を吹き込んだ。Reference Example 2 A four-loop flask with an internal volume of 1β was equipped with a gas blowing pipe, a mechanical stirrer, and a dewar condenser. After purging the inside of the reactor with deoxygenated dry nitrogen, 300 m7 of dry dichloromethane was placed in a four-bottle flask. and 24.3 g (0,211 mol) of methyldichlorosilane were added and cooled on ice. 18.1 g (1,
06 mol) was injected.
反応終了後、反応混合物を遠心分離し、乾燥ジクロロメ
タンを用いて洗浄後、窒素雰囲気下で濾過した。濾液か
ら溶媒を減圧留去すると、無色透明の液体を８．８１
ｇ得た。この生成物の数平均分子量はＧＰＣにより測定
したところ、５６０であった。After the reaction was completed, the reaction mixture was centrifuged, washed with dry dichloromethane, and filtered under a nitrogen atmosphere. When the solvent was distilled off from the filtrate under reduced pressure, a colorless and transparent liquid was obtained with a concentration of 8.81
I got g. The number average molecular weight of this product was 560 as measured by GPC.
またこのポリマーの’ＨＮＭＲ（プロトン核磁気共鳴）
スペクトル（６０Ｍｌ（ｚ、溶媒ＣＤＣβ３／基準物質
ＴＭＳ）測定結果δ４．７ｐｐｍ（ｂｒＳｉＨ） ：δ
ｌ、 ４ ｐｐｍ （ｂｒＮＨ） ：δＱ、 ３ｐｐ
ｍ（Ｓｔ Ｃ）＋３）の吸収が確認サレタ。In addition, 'HNMR (proton nuclear magnetic resonance) of this polymer
Spectrum (60Ml (z, solvent CDCβ3/reference material TMS) measurement result δ4.7ppm (brSiH): δ
l, 4 ppm (brNH): δQ, 3 ppm
Absorption of m(St C) + 3) was confirmed.
実施例１
参考例１で得られたベルヒドロポリシラザンのピリジン
溶液７０ｃｃ （ベルヒドロポリシラザン純分４．０ｇ
ｒ）に参考例２で得られたメチルボリシラザン０．４４
ｇｒを加え、内容積３００ｍの耐圧容器に入れ精製した
無水アンモニア９ ｇｒ （０，５３ｍｏｌ）を加えて
密閉系で１２０℃、３時間攪拌しながら反応を行った。Example 1 70 cc of pyridine solution of perhydropolysilazane obtained in Reference Example 1 (4.0 g of pure perhydropolysilazane)
r) 0.44 methylborisilazane obtained in Reference Example 2
9 gr (0.53 mol) of purified anhydrous ammonia was added in a pressure-resistant container with an internal volume of 300 m, and the reaction was carried out in a closed system at 120° C. with stirring for 3 hours.
室温に冷却後、乾ｎｏ−キシレン２００ｍ１を加え圧力
３〜５ｍｍＨｇ、温度５０℃で溶媒を除いたところ４．
、Ｏｇｒの白色粉末が得られた。After cooling to room temperature, 200 ml of dry no-xylene was added and the solvent was removed at a pressure of 3 to 5 mmHg and a temperature of 50°C. 4.
, Ogr white powder was obtained.
この粉末はトルエン、テトラヒドロフラン、クロロホル
ム及びその他の有機溶媒に可溶であった。This powder was soluble in toluene, tetrahydrofuran, chloroform and other organic solvents.
この共重合体の数平均分子量は、ＧＰＣ測定したところ
１８５０であった。また’ＨＮＭＲ（核磁気共鳴）スヘ
クトル（６０Ｍ七、溶媒ＣＤＣｊ’＋／基準物質ＴＭＳ
）測定結果δ４．８ ｐｐｍ （ｂｒＳ ｉ Ｈ）、δ
４．４ Ｐｐｍ（ｂｒｋＳｉＬ） ：δ１．４ ｐｐｍ
（ｂｒＮＨ）、δＯ１３ｐｐｍ（ｂｒＳｉＣＨ３）が
確認された。The number average molecular weight of this copolymer was 1850 when measured by GPC. In addition, 'HNMR (nuclear magnetic resonance) spectrum (60M7, solvent CDCj' +/reference material TMS
) Measurement result δ4.8 ppm (brS i H), δ
4.4 Ppm (brkSiL): δ1.4 ppm
(brNH) and δO of 13 ppm (brSiCH3) were confirmed.
この共重合シラザンを０−キシレンに溶解して１９ｗｔ
％溶液とし、鉄板に塗布した室温で１０分間風乾後、こ
の塗膜上にシリコーンゴム組成物を厚さ２ ｍｍになる
ように１５０℃、７０ｋｇ ｆ ／ｃｍ２．１０分間の
条件で成形した。This copolymerized silazane was dissolved in 0-xylene to give a weight of 19wt.
After air-drying at room temperature for 10 minutes, the silicone rubber composition was molded onto the coating film to a thickness of 2 mm at 150° C. and 70 kg f /cm for 10 minutes.
このシリコーンゴムの鉄板への接着性を調べたところ、
１７ｋｇ ｆ ／２５＋ｎｍでゴム破壊したが接着面で
の剥離は認釣られなかった。When we investigated the adhesion of this silicone rubber to an iron plate, we found that
The rubber broke at 17 kg f /25+nm, but no peeling was observed on the adhesive surface.
尚、この接着界を２００℃のシリコーンオイル中に２０
０時間時間後にその接着性を調べたところ、１６ｋｇ
ｆ ／２５ｍでゴム破壊をしたが接着面での剥離は認め
られなかった。In addition, this adhesive field was soaked in silicone oil at 200℃ for 20 minutes.
When we checked its adhesive properties after 0 hours, we found that it weighed 16 kg.
Although the rubber broke at f/25m, no peeling was observed on the adhesive surface.
また、アルミニウム板に塗布し、室温で１ｏ分間放置風
乾後、塗膜上にシリコーンゴム組成物を厚さ２ｍｍにな
るように１５０℃、７０ｋｇ ｆ ／ｃｍ２．１０分間
の条件で成形した。Further, it was coated on an aluminum plate, left to air dry for 10 minutes at room temperature, and then a silicone rubber composition was molded on the coated film to a thickness of 2 mm at 150° C. and 70 kg f /cm for 10 minutes.
このシリコーンゴムのアルミニウム板への接着性を調べ
たところ１０ｋｇ ｆ ／２５＋ｎｍで破壊したが、接
着面でのゴムの剥離は全く見られなかった。When the adhesion of this silicone rubber to an aluminum plate was examined, it broke at 10 kg f /25+nm, but no peeling of the rubber at the adhesive surface was observed.
実施例２
参考例１で得られたベルヒドロポリシラザンのピリジン
溶液５０ｃｃ （ベルヒドロポリシラザン純分３ｇｒ）
に参考例２で得られたメチルポリシラザン２、Ｏｇｒを
加え、内容積３００ｍ１！の耐圧容器に入れ精製した無
水アンモニア９ｇｒ（０，５３ｍｏｌ）を加えて密閉系
で１２０℃、３時間攪拌しながら反応を行った。Example 2 50 cc of pyridine solution of perhydropolysilazane obtained in Reference Example 1 (purity of perhydropolysilazane 3 gr)
Methylpolysilazane 2 obtained in Reference Example 2 and Ogr were added to the solution, and the internal volume was 300 m1! 9 grams (0.53 mol) of purified anhydrous ammonia was added to a pressure-resistant container, and the reaction was carried out in a closed system at 120° C. with stirring for 3 hours.
室温に冷却後、乾Ｃ４ｏ−キシレン２００ｒｎ１．を加
工圧力３〜５ｍｍＨｇ、温度５０℃で溶媒を除いたとこ
ろ４．５ｇｒの白色粉末が得られた。After cooling to room temperature, dry C4o-xylene 200rn1. When the solvent was removed at a processing pressure of 3 to 5 mmHg and a temperature of 50°C, 4.5 gr of white powder was obtained.
この粉末はトルエン、テトラヒドロフラン、クロロホル
ム及びその他の有機溶媒に可溶であった。This powder was soluble in toluene, tetrahydrofuran, chloroform and other organic solvents.
この共重合体の数平均分子量は、ＧＰＣ測定したところ
１６５０であった。また’）ＩＮＭＲ（核磁気共鳴）ス
ヘ’） ） ／ｌ／（６０ＭＨ２，溶媒ＣＤＣｊ７３／
基準物質ＴＭＳ）測定結果、δ４．８ｐＩ］Ｉ７＋（ｂ
ｒＳｉＨ）、６４．４ｐｐｍ（ｂｒｋＳｉＨ３） ；δ
１゜４ ｐｐｍ （ｂｒＮＨ） ；δ０．３ｆ］ｐｍ
（ｂｒｓｉｃＬ）が確＋ｆｆ＋Ｄされた。The number average molecular weight of this copolymer was 1650 when measured by GPC. Also ') INMR (nuclear magnetic resonance) ') /l/(60MH2, solvent CDCj73/
Reference material TMS) measurement result, δ4.8pI]I7+(b
rSiH), 64.4ppm (brkSiH3); δ
1゜4 ppm (brNH); δ0.3f]pm
(brsicL) was confirmed +ff+D.
この共重合シラザンを０−キシレンに溶解して１９ｗｔ
％溶液とし、鉄板に塗布した室温で１５分間風乾後、こ
の塗膜上にシリコーンゴム組成物を厚さ２ｍｍになるよ
うに１５０℃、７Ｑｋｇ ｆ ／ｃｍ２．１３分間の条
件で成形した。This copolymerized silazane was dissolved in 0-xylene to give a weight of 19wt.
After air drying at room temperature for 15 minutes, the silicone rubber composition was molded onto the coating film to a thickness of 2 mm at 150° C. and 7 Q kg f /cm for 2.13 minutes.
このシリコーンゴムの鉄板への接着性を調べたところ、
１６ｋｇ ｆ ／２５ｍｍでゴム破壊したが接着面での
剥離は認められなかった。When we investigated the adhesion of this silicone rubber to an iron plate, we found that
The rubber broke at 16 kg f /25 mm, but no peeling was observed on the adhesive surface.
尚、この接着界を２００℃のシリコーンオイル中に２０
０時間時間後にその接着性を調べたところ、１６ ｋｇ
ｆ ／ ２５ ＋ｎ＋ｎでゴム破壊をしたが接着面で
の剥離は認められなかった。In addition, this adhesive field was soaked in silicone oil at 200℃ for 20 minutes.
When the adhesiveness was examined after 0 hours, the weight was 16 kg.
Although the rubber was destroyed at f/25+n+n, no peeling was observed on the adhesive surface.
また、アルミニウム板に塗布し、室温で１５分間放置風
乾後、塗膜上にシリコーンゴム組成物を厚さ２ＩｌｌＩ
ｌｌになるように１５０℃、７ｏｋｇｆ／ｃｍ２．１ｏ
分間の条件で成形した。In addition, the silicone rubber composition was applied to an aluminum plate, left to air dry for 15 minutes at room temperature, and then a silicone rubber composition was applied on the coating film to a thickness of 2IllI.
150℃, 7okf/cm2.1o so that
It was molded under conditions of 1 minute.
このシリコーンゴムのアルミニウム板への接着性を調べ
たところ１０ｋｇ ｆ ／２５ｍｍで破壊したが、接着
面でのゴムの剥離は全く見られなかった。When the adhesion of this silicone rubber to an aluminum plate was examined, it broke at 10 kg f /25 mm, but no peeling of the rubber at the adhesive surface was observed.
実施例３
参考例１で得られたベルヒドロポリシラザンのピリジン
溶液５０ｃｃ （ペノ吐ドロポリシラザン純分２．５ｇ
ｒ）に参考例２で得られたメチルポリシラザン３．７５
ｇｒを加え、内容積３００−の耐圧容器に入れ精製した
無水アンモニア９ ｇｒ （０，５３ｍｏｌ＞ ヲ加え
て密閉系で１２０℃、３時間攪拌しながら反応を行った
。室温に冷却後、乾燥。−キシレン２００ｍ１を加え圧
力３〜５ｍｍＨｇ、温度５０℃で溶媒を除いたところ５
．８ｇｒの白色粉末が得られた。Example 3 50 cc of pyridine solution of perhydropolysilazane obtained in Reference Example 1 (2.5 g of pure perhydropolysilazane)
r) methylpolysilazane obtained in Reference Example 2 3.75
9 gr of purified anhydrous ammonia (0.53 mol>) was added to a pressure-resistant container with an internal volume of 300 mm, and the mixture was reacted in a closed system at 120° C. with stirring for 3 hours. After cooling to room temperature, it was dried. - After adding 200 ml of xylene and removing the solvent at a pressure of 3 to 5 mmHg and a temperature of 50°C, 5
．． 8 gr of white powder was obtained.
この粉末はトルエン、テトラヒドロフラン、クロロホル
ム及びその他の有機溶媒に可溶であった。This powder was soluble in toluene, tetrahydrofuran, chloroform and other organic solvents.
この共重合体の数平均分子量は、ＧＰＣ測定したところ
１５００であった。また’ＨＮＭＲ（核磁気共鳴）スペ
クトル（６０ＭＨｚ、溶媒ＣＤ（：ｊ！＊／基準物質Ｔ
ＭＳ）測定結果、６４．８ｐｐｍ（ｂｒｓｉＨ）、δ４
．４ ｐｐｍ（ｂｒｋＳｉＬ） ：δ１．４１］ｐｍ（
ｂｒＮＨ） ；δ０．３ ｐｐｍ（ｂｒＳｉＣＬ）が
確δ忍された。The number average molecular weight of this copolymer was 1500 when measured by GPC. In addition, 'HNMR (nuclear magnetic resonance) spectrum (60 MHz, solvent CD (:j!*/reference material T
MS) measurement results, 64.8 ppm (brsiH), δ4
．． 4 ppm(brkSiL): δ1.41]pm(
brNH); δ0.3 ppm (brSiCL) was confirmed.
この共重合シラザンを○−キシレンに溶解してｌＱｗｔ
％溶液とし、鉄板に塗布した室温で２０分間風乾後、こ
の塗膜上にシリコーンゴム組成物を厚さ２丁になるよう
に１５０℃、７０ｋｇ ｆ ／Ｃｍ２．１０分間の条件
で成形した。This copolymerized silazane was dissolved in ○-xylene and lQwt
After air-drying at room temperature for 20 minutes, the silicone rubber composition was molded onto the coating film to a thickness of 2 at 150° C. and 70 kg f /Cm for 10 minutes.
このシリコーンゴムの鉄板への接着性を調べたところ、
１６ｋｇ ｆ ／２５ｍｍでゴム破壊したが接着面での
剥離は認められなかった。When we investigated the adhesion of this silicone rubber to an iron plate, we found that
The rubber broke at 16 kg f /25 mm, but no peeling was observed on the adhesive surface.
尚、この接着品を２００℃のシリコーンオイル中に２０
０時間時間後にその接着性を調べたところ、１６ｋｇ
ｆ ／ ２５ｍｍでゴム破壊をしたが接着面での剥離は
認められなかった。In addition, this adhesive product was placed in silicone oil at 200℃ for 20 minutes.
When we checked its adhesive properties after 0 hours, we found that it weighed 16 kg.
Although the rubber broke at f/25 mm, no peeling was observed on the adhesive surface.
また、アルミニウム板に塗布し、室温で２０分間放置風
乾後、塗膜上にシリコーンゴム組成物を厚さ２ｍｍにな
るように１５０℃、７Ｑｋｇ ｆ ／ａｍ２．１０分間
の条件で成形した。Further, it was coated on an aluminum plate, left to air dry for 20 minutes at room temperature, and then a silicone rubber composition was molded on the coated film to a thickness of 2 mm at 150° C. and 7 Q kg f /am 2.10 minutes.
このシリコーンゴムのアルミニウム板への接着性を調べ
たところ１０ｋｇ ｆ ／２５ｍｍで破壊したが、接着
面でのゴムの剥離は全く見られなかった。When the adhesion of this silicone rubber to an aluminum plate was examined, it broke at 10 kg f /25 mm, but no peeling of the rubber at the adhesive surface was observed.
実施例４
参考例１で得られたベルヒドロポリシラザンのピリジン
溶液５３ｃｃ （ベルヒドロポリシラザン純分０．５ｐ
ｐ）に参考例２で得られたメチルポリシラザン４．５ｐ
ｐを加え、内容積３００−の耐圧容器に入れ精製した無
水アンモニア９ ｇｒ （０，５３ｍｏｌ）を加えて密
閉系で１２０℃、３時間攪拌しながら反応を行った。室
温に冷却後、乾燥０−キシレン２００ｍ１を加え圧力３
〜５ｍｍＨｇ、温度５０℃で溶媒を除いたところ４．５
ｐｐの白色粉末が得られた。Example 4 53 cc of pyridine solution of perhydropolysilazane obtained in Reference Example 1 (0.5 p of perhydropolysilazane purity)
p) 4.5p of methylpolysilazane obtained in Reference Example 2
9 gr (0.53 mol) of purified anhydrous ammonia was added in a pressure-resistant container with an internal volume of 300 mm, and the reaction was carried out in a closed system at 120° C. with stirring for 3 hours. After cooling to room temperature, add 200 ml of dry 0-xylene and reduce the pressure to 3.
When the solvent was removed at ~5 mmHg and a temperature of 50°C, the result was 4.5
A pp white powder was obtained.
この粉末はトルエン、テトラヒドロフラン、クロロホル
ム及びその他の有機溶媒に可溶であった。This powder was soluble in toluene, tetrahydrofuran, chloroform and other organic solvents.
この共重合体の数平均分子量は、ＧＰＣ測定したところ
１２５０であった。また’ＨＮＭＲ（核磁気共鳴）スペ
クトル（６０Ｍ七、溶媒ＣＤＣｆ３／基準物質ＴＭＳ）
測定結果、６４．３ ｐｐｍ（ｂｒｓｉｌ（）、δ４．
４ ｐｐｍ（ｂｒｋｓｉＨ３） ：δ１．４ ｐｐｍ
（ｂｒＮＨ） ；δＱ、 ３ ｐｐｍ（ｂｒＳｉＣＬ
）が確言忍された。The number average molecular weight of this copolymer was 1250 when measured by GPC. Also 'HNMR (nuclear magnetic resonance) spectrum (60M7, solvent CDCf3/reference material TMS)
Measurement result: 64.3 ppm (brsil(), δ4.
4 ppm (brksiH3): δ1.4 ppm
(brNH) ; δQ, 3 ppm (brSiCL
) was confirmed.
この共重合シラザンを０−キシレンに溶解して１０ｗｔ
％溶液とし、鉄板に塗布した室温で２５分間風乾後、こ
の塗膜上にシリコーンゴム組成物を厚さ２配になるよう
に１５０℃、７０ｋｇ ｆ ／ｃｍ２．１０分間の条件
で成形した。This copolymerized silazane was dissolved in 0-xylene and 10wt.
After air-drying at room temperature for 25 minutes, the silicone rubber composition was molded on the coating film to a thickness of 2 layers at 150° C. and 70 kg f /cm for 10 minutes.
このシリコーンゴムの鉄板への接着性を調べたところ、
１６ｋｇ ｆ ／２５ｍｍでゴム破壊したが接着面での
剥離は認められなかった。When we investigated the adhesion of this silicone rubber to an iron plate, we found that
The rubber broke at 16 kg f /25 mm, but no peeling was observed on the adhesive surface.
尚、この接着品を２００℃のシリコーンオイル中に２０
０時間時間後にその接着性を調べたところ、１５ ｋｇ
ｆ ／ ２５ ｍｍでゴム破壊をしたが接着面での剥
離はδ忍められなかった。In addition, this adhesive product was placed in silicone oil at 200℃ for 20 minutes.
When the adhesiveness was examined after 0 hours, the weight was 15 kg.
The rubber broke at f/25 mm, but peeling on the adhesive surface could not be tolerated by δ.
また、アルミニウム板に塗布し、室温で２５分間放置風
乾後、塗膜上にシリコーンゴム組成物を厚さ２ｍｍにな
るように１５０℃、７０ｋｇ ｆ ／ｃｍ’ 、１０分
間の条件で成形した。Further, it was coated on an aluminum plate, left to air dry for 25 minutes at room temperature, and then a silicone rubber composition was molded onto the coated film to a thickness of 2 mm at 150° C. and 70 kg f/cm′ for 10 minutes.
このシリコーンゴムのアルミニウム板への接着性を調べ
たところ、９ ｋｇ ｆ ／２５ｍｍで破壊したが、接
着面でのゴムの剥離は全く見られなかった。When the adhesion of this silicone rubber to an aluminum plate was examined, it broke at 9 kg f /25 mm, but no peeling of the rubber at the adhesive surface was observed.
実施例５
参考例１で得られたベルヒドロポリシラザンのピリジン
溶液７Ｑｃｃ （ベルヒドロポリシラザン純分４．００
ｇｒ）を内容積３００ｍ１ｌ！の耐圧容器に入れ、精製
した無水アンモニア４．０ ｇｒ （０，２３５ｍｏｌ
）を加えて密閉系で１２０℃、３時間攪拌しながら反応
を行った。Example 5 Pyridine solution of perhydropolysilazane obtained in Reference Example 1 7Qcc (purity of perhydropolysilazane 4.00
gr) with an internal volume of 300ml! 4.0 gr (0,235 mol) of purified anhydrous ammonia in a pressure-resistant container.
) was added, and the reaction was carried out in a closed system at 120°C with stirring for 3 hours.
室温に冷却後、乾燥０−キシレン２０〇−加え圧力３〜
５ｍｍＨｇ、温度５０℃で溶媒を除いたところ３．８ｐ
ｐの白色粉末が得られた。After cooling to room temperature, add 200% of dry 0-xylene under a pressure of 3~
When the solvent was removed at 5mmHg and 50℃, the result was 3.8p.
A white powder of p was obtained.
この粉末はトルエン、テトラヒドロフラン、クロロホル
ム及びその他の有機溶媒に可溶であった。This powder was soluble in toluene, tetrahydrofuran, chloroform and other organic solvents.
この共重合体の数平均分子量は、１８５０であった。The number average molecular weight of this copolymer was 1,850.
また’ＨＮＭＲ（核磁気共鳴）スペクトル（６０ＭＨｚ
、溶媒ＣＤＣｊ！３／基準物質ＴＭＳ）測定結果、δ４
．８ｐｐｍ（ｂｒｓｉＨ） 、６４．４ｐｐｍ（ｂｒｋ
ｓｉＨ３） ；δ１．４ ｐｐｍ （ｂｒＮＨ）が確認
された。Also 'HNMR (nuclear magnetic resonance) spectrum (60MHz
, solvent CDCj! 3/Reference material TMS) measurement results, δ4
．． 8ppm (brsiH), 64.4ppm (brk
siH3) ; δ1.4 ppm (brNH) was confirmed.
このアンモニア架橋したベルヒドロポリシラザンを○−
キシレンに溶解して１３ｗｔ％とし鉄板に塗布した。室
温で５分間風乾後、この塗膜上にシリコーンゴム組成物
を厚さ２加になるように１５０℃、７０ｋｇ ｆ ／ａ
ｍ２．１０分間の条件で成形した。This ammonia-crosslinked perhydropolysilazane is
It was dissolved in xylene to a concentration of 13 wt% and applied to an iron plate. After air-drying at room temperature for 5 minutes, a silicone rubber composition was applied to the coating film to a thickness of 2 mm at 150° C. at 70 kg f/a.
Molding was performed under conditions of m2.10 minutes.
このシリコーンゴムの鉄板への接着性を調べたところ、
１７ｋｇ ｆ ／２５ｍｍでゴム破壊したが、接着面で
の剥離は認められなかった。When we investigated the adhesion of this silicone rubber to an iron plate, we found that
The rubber broke at 17 kg f /25 mm, but no peeling was observed on the adhesive surface.
尚、この接着品を２００℃のシリコーンオイル中に２０
０時間時間後にその接着性を調べたところ、１７ｋｇ
ｆ ７２５市でゴム破壊をしたが接着面での剥離は認め
られなかった。In addition, this adhesive product was placed in silicone oil at 200℃ for 20 minutes.
When we checked its adhesive properties after 0 hours, we found that it weighed 17 kg.
f 725 city, the rubber was destroyed, but no peeling was observed on the adhesive surface.
また、アルミニウム板に塗布し、室温で５分間放置風乾
後、塗膜上にシリコーンゴム組成物を厚さ２關になるよ
うに１５０℃、７０ｋｇ ｆ ／ｃｍ２．１０分間の条
件で成形した。Further, it was coated on an aluminum plate, left to air dry at room temperature for 5 minutes, and then a silicone rubber composition was molded on the coated film to a thickness of 2 cm at 150° C. and 70 kg f /cm for 10 minutes.
このシリコーンゴムのアルミニウム板への接着性を調べ
たところ１２ｋｇ ｆ ／２５ｍｍで破壊したが、接着
面でのゴムの剥離は全く見られなかった。When the adhesion of this silicone rubber to an aluminum plate was examined, it broke at 12 kg f /25 mm, but no peeling of the rubber at the adhesive surface was observed.
比較例
鉄板、アルミニウム板にシリコーンゴム組成物を厚さ２
ｍｍになるように１５０℃、７０ｋｇｆ／ｃｍ２１０
分間の条件で成形した。Comparative Example A silicone rubber composition was applied to an iron plate and an aluminum plate to a thickness of 2
150℃, 70kgf/cm210 so that it is mm
It was molded under conditions of 1 minute.
このシリコーンゴムのそれぞれの基板上への接着性を調
べたところ、鉄板では３ ｋｇ ｆ ／２５ｍｍで剥離
しアルミニウムでは全く接着しなかった。When the adhesion of this silicone rubber to each substrate was examined, it peeled off at 3 kgf/25 mm on an iron plate and did not adhere at all on aluminum.
Claims (1)
端に−ＳｉＨ＿３基を持つ分子量５００〜５００００の
無機シラザンを主剤としてなることを特徴とするプライ
マー組成物。 ２、分子中に−ＳｉＨ＿２ＮＨ−と−ＳｉＨＲ＾１ＮＲ
＾２−（式中、Ｒ＾１、Ｒ＾２は水素原子、置換アルキ
ル基、アルケニル基、シクロアルキル基、アルキルアミ
ノ基、アリール基、アルアルキル基、アルキルシリル基
、又はこれらの置換基を示すが、Ｒ＾１、Ｒ＾２のうち
少なくとも１方は水素でない。）の基本骨格を有し、末
端に−ＳｉＨ＿３基を持つ分子量５００〜５００００の
ブロック共重合シラザンを主剤としてなることを特徴と
するプライマー組成物。[Scope of Claims] 1. A primer composition comprising as a main ingredient an inorganic silazane having a basic skeleton of -SiH_2NH- in the molecule and having a -SiH_3 group at the end and a molecular weight of 500 to 50,000. 2. -SiH_2NH- and -SiHR^1NR in the molecule
^2-(In the formula, R^1 and R^2 are hydrogen atoms, substituted alkyl groups, alkenyl groups, cycloalkyl groups, alkylamino groups, aryl groups, aralkyl groups, alkylsilyl groups, or these substituents. However, at least one of R^1 and R^2 is not hydrogen. A primer composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2213667A JP2980352B2 (en) | 1990-08-14 | 1990-08-14 | Primer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2213667A JP2980352B2 (en) | 1990-08-14 | 1990-08-14 | Primer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0496973A true JPH0496973A (en) | 1992-03-30 |
| JP2980352B2 JP2980352B2 (en) | 1999-11-22 |
Family
ID=16642968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2213667A Expired - Fee Related JP2980352B2 (en) | 1990-08-14 | 1990-08-14 | Primer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2980352B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002105676A (en) * | 2000-07-27 | 2002-04-10 | Contamination Control Service:Kk | Coating film, member coated with the same and method for producing the coating film |
| JP2005226048A (en) * | 2004-02-16 | 2005-08-25 | Hitachi Chem Co Ltd | Adhesive composition, film-formed adhesive and circuit-joining material by using the same, and joining structure of circuit member and method for producing the same |
| JP2006083399A (en) * | 1995-02-03 | 2006-03-30 | Osi Specialties Inc | Polysiloxane composition |
| JP2012144652A (en) * | 2011-01-13 | 2012-08-02 | Shin-Etsu Chemical Co Ltd | Primer composition and photosemiconductor device using the same |
| JP2017193688A (en) * | 2016-04-22 | 2017-10-26 | パンサーフェス株式会社 | Hydrophilicity adding agent, hydrophilic coated film forming method, hydrophilic coated film and sunlight panel |
-
1990
- 1990-08-14 JP JP2213667A patent/JP2980352B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006083399A (en) * | 1995-02-03 | 2006-03-30 | Osi Specialties Inc | Polysiloxane composition |
| JP2002105676A (en) * | 2000-07-27 | 2002-04-10 | Contamination Control Service:Kk | Coating film, member coated with the same and method for producing the coating film |
| JP2005226048A (en) * | 2004-02-16 | 2005-08-25 | Hitachi Chem Co Ltd | Adhesive composition, film-formed adhesive and circuit-joining material by using the same, and joining structure of circuit member and method for producing the same |
| JP4655487B2 (en) * | 2004-02-16 | 2011-03-23 | 日立化成工業株式会社 | Adhesive composition, film-like adhesive and circuit connecting material using the same, circuit member connecting structure, and manufacturing method thereof |
| JP2012144652A (en) * | 2011-01-13 | 2012-08-02 | Shin-Etsu Chemical Co Ltd | Primer composition and photosemiconductor device using the same |
| JP2017193688A (en) * | 2016-04-22 | 2017-10-26 | パンサーフェス株式会社 | Hydrophilicity adding agent, hydrophilic coated film forming method, hydrophilic coated film and sunlight panel |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2980352B2 (en) | 1999-11-22 |
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