JPH0715093B2 - Adhesive composition - Google Patents
Adhesive compositionInfo
- Publication number
- JPH0715093B2 JPH0715093B2 JP27922985A JP27922985A JPH0715093B2 JP H0715093 B2 JPH0715093 B2 JP H0715093B2 JP 27922985 A JP27922985 A JP 27922985A JP 27922985 A JP27922985 A JP 27922985A JP H0715093 B2 JPH0715093 B2 JP H0715093B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- adhesive composition
- polymetallocarbosilane
- bonding
- polymer
- 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 - Lifetime
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Description
【発明の詳細な説明】 本発明は、ポリメタロカルボシランを含有する新規な接
着剤組成物に関する。さらに詳しくは、ポリメタロカル
ボシラン及びシリコン樹脂を含有する新規な接着剤組成
物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel adhesive composition containing a polymetallocarbosilane. More specifically, it relates to a novel adhesive composition containing polymetallocarbosilane and a silicone resin.
（従来技術） 耐熱性あるいは化学的耐久性の要求される接合用途に
は、従来はボルト・リベツトなどの機械的接合が採用さ
れてきたが、最近の技術革新に伴ない多種多様な分野に
おいて接着剤による接合が実施され始め、これに応じて
各種の接着剤が上市されている。(Prior art) Mechanical joining such as bolts and rivets has been conventionally used for joining applications requiring heat resistance or chemical durability, but bonding in a wide variety of fields due to recent technological innovation. Adhesives have started to be bonded, and various adhesives have been put on the market accordingly.
このうち、有機系の接着剤であるポリイミド系やポリベ
ンツイミダゾール系の耐熱温度は200〜400℃であり、こ
れより高温になると接着強度が低下し、耐久性も劣る。Of these, the heat resistance temperature of organic adhesives such as polyimide and polybenzimidazole is 200 to 400 ° C., and if the temperature is higher than this, the adhesive strength is lowered and the durability is also poor.
一方、無機化合物を結合剤とする無機系接着剤には数多
くの種類が知られている。On the other hand, many types of inorganic adhesives using an inorganic compound as a binder are known.
このうち、水和物の生成により硬化するタイプとして、
ポルトランドセメント、石こう等がある。しかし、これ
らの硬化物は再加熱により結晶水を失ない、結合力を失
うなど耐熱性が不十分であり、しかも耐水性、耐酸性に
劣る。Among these, as a type that hardens due to the formation of hydrates,
There are Portland cement, gypsum, etc. However, these cured products have insufficient heat resistance such as loss of water of crystallization and loss of binding force by reheating, and are inferior in water resistance and acid resistance.
また水分の蒸発により硬化するタイプとして、水ガラス
などの水溶性ケイ酸塩を成分とするものは接着耐水性が
低く、アルカリステインが生成するなどの欠点を有す
る。Further, as a type that is cured by evaporation of water, a type that contains a water-soluble silicate, such as water glass, has low adhesive water resistance, and has the drawback that alkali stain is generated.
もう一つのタイプとして溶融接着させる低融点ガラス、
ハンダがある。これらは当然の事ながら融点以上の温度
での接着性はなく、高耐熱温度を満足させるには高融点
組成物を用いねばならない。Another type is a low melting glass that is melt-bonded,
I have solder. As a matter of course, these do not have adhesiveness at a temperature equal to or higher than the melting point, and a high melting point composition must be used to satisfy the high heat resistant temperature.
（発明が解決しようとする問題点） 本発明は、空気中においても比較的低温下での接合がで
き、高温度雰囲気下における接着強度の低下が極めて少
なく、耐久性を有し、さらには耐水性に優れた接着剤組
成物の提供により、苛酷な雰囲気下での実用に耐えうる
金属部材及び非金属部材の接合を可能ならしめようとす
るものである。(Problems to be Solved by the Invention) The present invention is capable of performing bonding at a relatively low temperature even in air, has very little decrease in adhesive strength in a high temperature atmosphere, has durability, and further has water resistance. By providing an adhesive composition having excellent properties, it is possible to bond a metal member and a non-metal member that can withstand practical use in a harsh atmosphere.
（問題点を解決するための手段） 本発明は、ポリメタロカルボシラン及びシリコン樹脂を
混合させてなる接着剤組成物である。(Means for Solving Problems) The present invention is an adhesive composition obtained by mixing polymetallocarbosilane and a silicone resin.
なお、ここでシリコン樹脂とは、ポリオルガノシロキサ
ン、シリコンオイル、シリコンワニス及びシリコンゴム
からなる群から選ばれた少なくとも１種の重合体を意味
する。Here, the silicone resin means at least one polymer selected from the group consisting of polyorganosiloxane, silicone oil, silicone varnish and silicone rubber.
本発明で用いるポリメタロカルボシランは、下記（Ａ）
カルボシラン結合単位及び少なくとも１種の下記（Ｂ）
メタロキサン結合単位からなり、 （但し、R1及びR2は同一又は異なつてもよく相互に独立
に低級アルキル基、フエニール基又は水素原子を表わ
す） （Ｂ）：Ｍ−Ｏ （但し、ＭはTi、Zr、Mo及びCrからなる群から選ばれた
少なくとも１種の元素を示し、場合によつては前記各元
素の少なくとも１部分が側鎖基として低級アルコキシ基
又はフエノキシ基を少なくとも１個有する） 前記（Ａ）及び（Ｂ）各結合単位が主鎖骨格中でランダ
ムに結合した重合体、及び／又は前記（Ａ）の結合単位
のケイ素原子の少なくとも１部が前記（Ｂ）の結合単位
の前記各元素と酸素原子を介して結合し、これらによつ
て前記（Ａ）の結合単位の連鎖によりえられるポリカル
ボシラン部分が前記（Ｂ）の結合単位によつて架橋され
た重合体であり、 前記（Ａ）の結合単位の全数対前記（Ｂ）の結合単位の
全数の比率が1:1から10:1の範囲にあり数平均分子量が4
00〜50,000であることからなる有機金属重合体である。The polymetallocarbosilane used in the present invention has the following (A)
Carbosilane bond unit and at least one of the following (B)
Consisting of a metalloxane bond unit, (However, R 1 and R 2 may be the same or different and independently represent a lower alkyl group, a phenyl group or a hydrogen atom) (B): MO (where M is Ti, Zr, Mo and Cr) (A) represents at least one element selected from the group consisting of, and in some cases, at least one part of each element has at least one lower alkoxy group or phenoxy group as a side chain group) (A) and ( B) A polymer in which each bonding unit is randomly bonded in the main chain skeleton, and / or at least a part of the silicon atom of the bonding unit of (A) is an oxygen atom with each element of the bonding unit of (B). A polycarbosilane moiety obtained by the chain of the bonding units of the above (A) is crosslinked by the bonding units of the above (B), Total number of bond units vs. bond of (B) above The ratio of the position of the total number of 1: 1 to 10: Number is in the first range average molecular weight of 4
It is an organometallic polymer consisting of 00 to 50,000.
このポリメタロカルボシランとシリコン樹脂とからなる
接着剤組成物を金属あるいは非金属被着体表面に塗布
し、被着体同士を貼り合せた後、酸化性あるいは非酸化
性雰囲気中で200〜2000℃の温度範囲で加熱を行うと、
金属、非金属の被着体は強固に接着され、しかも耐久性
に優れていることを見出し、本発明に到達した。An adhesive composition consisting of this polymetallocarbosilane and a silicone resin is applied to the surface of a metal or non-metal adherend, and the adherends are attached to each other, and then 200 to 2000 in an oxidizing or non-oxidizing atmosphere. When heating in the temperature range of ℃,
The present invention has been completed by finding that metal and non-metal adherends are strongly bonded and have excellent durability.
本発明で用いるポリメタロカルボシランは、空気雰囲気
下で1000℃で10時間以上熱処理しても加熱減量は僅かに
10〜15重量％に過ぎないため、焼付塗膜の重量減少によ
る収縮、ヒビ割れが起りにくい。したがつて形成された
接着層の加熱による寸法変化は少なく接着剤層は緻密で
ある。The polymetallocarbosilane used in the present invention has a slight heating loss even when heat-treated at 1000 ° C. for 10 hours or more in an air atmosphere.
Since it is only 10 to 15% by weight, shrinkage and cracking due to the reduction in the weight of the baked coating are unlikely to occur. Therefore, the dimensional change of the adhesive layer formed by heating is small and the adhesive layer is dense.
また、ポリメタロカルボシランは金属を含有するため、
これを特に金属基材表面に塗布し加熱すると超微粒子の
金属化物あるいは金属酸化物が接着剤層と金属基材との
間に強固な結合を形成する。このため空気中で1000℃以
上に加熱しても接着強度の低下が少ない接着剤層が形成
される。おなじようにセラミツク、ガラス表面上におい
ても前記超微粒子がバインダーとして機能するから、被
着体と強固に結合した接着剤層を形成する。さらに、こ
のポリメタロカルボシランとシリコン樹脂とから成る接
着剤組成物は、ポリメタロカルボシラン単独から成る接
着剤よりも強固に被着材に密着し、さらに耐熱性を向上
させると共に可撓性が優れているという驚くべき効果を
有することを見出した。即ち、ポリメタロカルボシラン
単独から成る接着剤層は可撓性に欠け、Ｔ型ピールのよ
うに曲げを伴う剥離力には良好な接着性を示さない。ま
たポリメタロカルボシランは高温熱処理による加熱減量
が少ないとはいえ存在するため、体積収縮を生ずる。そ
こで、このポリメタロカルボシランの有する欠点を補
い、更に優れた接着剤組成物を得るため鋭意研究に努め
た結果、ポリメタロカルボシランにシリコン樹脂を併用
すると、可撓性、成膜性及び耐熱性に優れた接着剤組成
物が得られることを見出し、本発明な到達したものであ
る。Further, since polymetallocarbosilane contains a metal,
When this is applied to the surface of a metal substrate in particular and heated, the metal compound or metal oxide of ultrafine particles forms a strong bond between the adhesive layer and the metal substrate. For this reason, an adhesive layer is formed in which the decrease in adhesive strength is small even when heated to 1000 ° C. or higher in air. As in the same manner, since the ultrafine particles function as a binder even on the surface of ceramics or glass, an adhesive layer firmly bonded to the adherend is formed. Further, the adhesive composition composed of this polymetallocarbosilane and the silicone resin is more closely adhered to the adherend than the adhesive composed of polymetallocarbosilane alone, and further has improved heat resistance and flexibility. It has been found to have the surprising effect of being excellent. That is, the adhesive layer consisting of polymetallocarbosilane alone lacks flexibility, and does not show good adhesiveness with respect to peeling force accompanied by bending like T-peel. Further, polymetallocarbosilane is present even though the loss on heating due to the high temperature heat treatment is small, so that volume shrinkage occurs. Therefore, as a result of intensive research to compensate for the drawbacks of this polymetallocarbosilane and to obtain a more excellent adhesive composition, the use of silicone resin in combination with polymetallocarbosilane results in flexibility, film-forming property and heat resistance. The present invention has been achieved by finding that an adhesive composition having excellent properties can be obtained.
シリコン樹脂をポリメタロカルボシラン100重量部に対
し、10〜900重量部好ましくは50〜200重量部添加する。Silicon resin is added in an amount of 10 to 900 parts by weight, preferably 50 to 200 parts by weight, based on 100 parts by weight of polymetallocarbosilane.
シリコン樹脂の添加量が10部以下であると、得られる接
着剤層の可撓性が乏しくなり、一方、900部をこえると
ポリメタロカルボシランの優れた耐久性が発揮できず高
温加熱後の接着性が極端に低下する。If the addition amount of the silicone resin is 10 parts or less, the flexibility of the adhesive layer obtained becomes poor, while if it exceeds 900 parts, the excellent durability of polymetallocarbosilane cannot be exhibited and after heating at high temperature. The adhesiveness is extremely reduced.
更に無機充填剤をポリメタロカルボシラン100重量部に
対して10〜500重量部加えてもよい。無機充填剤を添加
すると、接着剤層の高温時における軟化性を向上せしめ
る点で望ましいが、加え過ぎると機械的強度を減少せし
めるので好ましくない。Further, an inorganic filler may be added in an amount of 10 to 500 parts by weight based on 100 parts by weight of polymetallocarbosilane. Addition of an inorganic filler is desirable from the viewpoint of improving the softening property of the adhesive layer at high temperatures, but it is not preferable because addition of an inorganic filler will reduce the mechanical strength.
本発明で用いる無機充填剤は公知添加剤、ホウ素、マグ
ネシウム、アルミニウム、ケイ素、カルシウム、チタ
ン、バナジウム、クロム、マンガン、亜鉛、ジルコニウ
ム、モリブデン、カドミウム、スズ、アンチモン、バリ
ウム、タングステン、鉛、ビスマスの酸化物、それらの
炭化物、それらの窒化物、リチウム、ナトリウム、カリ
ウム、マグネシウム、カルシウム、亜鉛のホウ酸塩、リ
ン酸塩、ケイ酸塩などである。Inorganic fillers used in the present invention are known additives such as boron, magnesium, aluminum, silicon, calcium, titanium, vanadium, chromium, manganese, zinc, zirconium, molybdenum, cadmium, tin, antimony, barium, tungsten, lead and bismuth. Oxides, their carbides, their nitrides, borates, phosphates, silicates of lithium, sodium, potassium, magnesium, calcium, zinc.
これらは単独で使用しても良く、又混合して使用しても
良い。These may be used alone or in combination.
ポリメタロカルボシラン、シリコン樹脂及び無機充填材
を混合、粉砕して粉末状の接着剤組成物を得る。あるい
はベンセン、トルエン、キシレン等の適当な溶剤に溶解
又は分散させて液体状の接着剤組成物を得ても良い。A polymetallocarbosilane, a silicone resin and an inorganic filler are mixed and pulverized to obtain a powdery adhesive composition. Alternatively, a liquid adhesive composition may be obtained by dissolving or dispersing in a suitable solvent such as benzene, toluene, xylene.
この接着剤組成物を予め清浄化した金属被着体あるいは
ガラス、セラミツク、耐火レンガ等の非金属被着体の片
面あるいは両面に、粉末状接着剤の場合は均一にふりか
け、液体状接着剤の場合はハケ、スプレイ、ローラ、浸
清等の方法で塗布し、被着面同士を貼り合わせ、必要に
応じて外側から圧力をかけながら加熱を行なう。This adhesive composition is preliminarily cleaned on a metal adherend or glass, ceramic, on one or both sides of a non-metal adherend such as refractory brick, in the case of a powdery adhesive, it is evenly sprinkled to give a liquid adhesive. In this case, coating is carried out by a method such as brushing, spraying, roller, sterilization, the adherends are adhered to each other, and heating is carried out while applying pressure from the outside if necessary.
加熱温度は、200℃以上が好ましいが、塗装後非塗装物
が200℃以上の使用環境に置かれる場合には特に加熱工
程を設けなくとも良い。加熱温度が200℃以下では接着
剤層の乾燥、硬化が不十分であり十分な接着強度が得ら
れない。The heating temperature is preferably 200 ° C. or higher, but when the unpainted object after coating is placed in a use environment of 200 ° C. or higher, a heating step may not be particularly provided. When the heating temperature is 200 ° C or lower, the adhesive layer is insufficiently dried and cured, and sufficient adhesive strength cannot be obtained.
この加熱により接着剤層は完全に硬化して被着体に強固
に密着する。接着剤層の乾燥、硬化後の厚さは、一般に
0.1〜100μ、最も好ましくは１〜10μであればよく、必
要に応じ適宜選択できる。By this heating, the adhesive layer is completely cured and firmly adheres to the adherend. The thickness of the adhesive layer after drying and curing is generally
It may be 0.1 to 100 μ, and most preferably 1 to 10 μ, and can be appropriately selected as necessary.
以下、実施例により、更に具体的に説明する。なお、実
施例において、％及び部は特に断わりのない限り重量％
及び重量部を示す。Hereinafter, the present invention will be described more specifically by way of examples. In the examples,% and parts are by weight unless otherwise specified.
And parts by weight are shown.
（参考例１） ５の三口フラスコに無水キシレン2.5とナトリウム4
00gとを入れ、窒素ガス気流下でキシレンの沸点まで加
熱し、ジメチルジクロロシラン１を１時間で滴下し
た。滴下終了後、10時間加熱還流し沈殿物を生成させ
た。この沈殿を過し、まずメタノールで洗浄した後、
水で洗浄して、白色粉末のポリジメチルシラン420gを得
た。Reference Example 1 Anhydrous xylene 2.5 and sodium 4 in a three-necked flask of No. 5
00g was added, the mixture was heated to the boiling point of xylene under a nitrogen gas stream, and dimethyldichlorosilane 1 was added dropwise over 1 hour. After completion of the dropping, the mixture was heated under reflux for 10 hours to generate a precipitate. After passing this precipitate, first washing with methanol,
After washing with water, 420 g of white powdery polydimethylsilane was obtained.
上記のポリジメチルシラン400gを、ガス導入管、撹拌
機、冷却器および留出管を備えた３の三つのフラスコ
に仕込み、撹拌しながら窒素気流下（50ml/min）で420
℃で加熱処理することによつて留出容器に350gの無色透
明な少し粘性のある液体を得た。この液体の数平均分子
量は蒸気圧浸透法（VPO法）により測定したところ470で
あつた。400 g of the above polydimethylsilane was charged into three flasks of 3 equipped with a gas introduction tube, a stirrer, a cooler and a distilling tube, and stirred under a nitrogen gas stream (50 ml / min) to produce 420
By heat-treating at ℃, 350 g of colorless transparent and slightly viscous liquid was obtained in the distillation vessel. The number average molecular weight of this liquid was 470 as measured by the vapor pressure permeation method (VPO method).
またこの物質の遠赤外吸収の測定により主としてSi−
CH2結合単位およびSi−Si結合単位からなり、ケ
イ素の側鎖に水素原子及びメチル基を有する有機ケイ素
ポリマーであることを確認した。In addition, the far infrared absorption of this substance was mainly measured by measuring the Si-
It was confirmed that the organosilicon polymer was composed of a CH 2 bond unit and a Si-Si bond unit and had a hydrogen atom and a methyl group in the side chain of silicon.
（参考例２） 次にこの有機ケイ素ポリマー40gとチタンテトライソプ
ロポキシド20gとを秤取し、この混合物にキシレン400ml
を加えて均一相からなる混合溶液とし、窒素ガス雰囲気
下で、130℃で１時間撹拌しながら還流反応を行なつ
た。還流反応終了後、さらに温度を上昇させて溶媒のキ
シレンを留出させたのち、300℃で10時間重合を行ない
シリコンとチタンを含有する有機金属架橋重合体を得
た。この重合体の数平均分子量はVPO法により測定した
ところ1165であつた。ゲルバーミエーシヨンクロマトグ
ラフ、赤外吸収スペクトルからここで得られたポリマー
は、有機ケイ素ポリマー中のSi−Ｈ結合が一部消失し、
この部分のケイ素原子が、チタンテトライソプロポキシ
ドのチタン原子と酸素原子を介して結合し、これによつ
て一部は有機ケイ素ポリマーの側鎖に−Ｏ−Ti（OC
3H7）３基を有し、また一部は有機ケイ素ポリマーがT
i−Ｏ結合で架橋したポリチタノカルボシランであ
り、このポリマー中のSi−Ｈ結合部分での反応率および
／又は架橋率は、44.5％である。このポリマーの有機ケ
イ素ポリマー部分のSi−CH2結合単位Si−Si結
合単位の全数対−Ｏ−Ti（OC4H9）３および−Ti−Ｏ−
結合単位の全数の比率は約6:1であることを確認した。Reference Example 2 Next, 40 g of this organosilicon polymer and 20 g of titanium tetraisopropoxide were weighed out, and 400 ml of xylene was added to this mixture.
Was added to prepare a mixed solution consisting of a homogeneous phase, and a reflux reaction was performed in a nitrogen gas atmosphere while stirring at 130 ° C. for 1 hour. After the completion of the reflux reaction, the temperature was further raised to distill off the solvent xylene, and then polymerization was carried out at 300 ° C. for 10 hours to obtain an organometallic crosslinked polymer containing silicon and titanium. The number average molecular weight of this polymer was 1165 as measured by the VPO method. In the polymer obtained here from the gel vermi-ion chromatography and infrared absorption spectrum, the Si-H bond in the organosilicon polymer partially disappears,
The silicon atom of this portion is bonded to the titanium atom of titanium tetraisopropoxide through the oxygen atom, whereby a part of the silicon atom is attached to the side chain of the organosilicon polymer by —O—Ti (OC
3 H 7 ) 3 groups, and some of the organosilicon polymers are T
It is a polytitanocarbosilane crosslinked with an i-O bond, and the reaction rate and / or the crosslinking rate at the Si-H bond portion in this polymer is 44.5%. The total number pairs Si-CH 2 bond units Si-Si bond units of the organosilicon polymer portion of the polymer -O-Ti (OC 4 H 9 ) 3 and -Ti-O-
It was confirmed that the ratio of the total number of binding units was about 6: 1.
（参考例３） 参考例２における出発物質の１つであるチタンテトライ
ソプロボキシドの代わりに、ジルコニウムテトライソプ
ロポキシドを用いてポリジルコノカルボシランを得た。
反応条件、操作法は参考例２と実質的に同一である。Reference Example 3 Polyzirconocarbosilane was obtained by using zirconium tetraisopropoxide instead of titanium tetraisopropoxide, which is one of the starting materials in Reference Example 2.
The reaction conditions and operating method are substantially the same as in Reference Example 2.
〔実施例１〕 参考例２で得たポリチタノカルボシラン100部及びメチ
ルフエニルシリコンワニスの50％キシレン溶液（東芝シ
リコン社勢TSR−116）200部を混合してスラリー状組成
物を得た。この組成物をサンドブラスト処理後アセトン
脱脂した50×50（mm）SUS304鋼板に約５ミクロン厚みで
塗布し、同一処理したもう一枚の鋼板を重ねて固定した
まま、200℃空気オーブン中に１時間放置して乾燥、硬
化させた。Example 1 100 parts of the polytitanocarbosilane obtained in Reference Example 2 and 200 parts of a 50% xylene solution of methylphenyl silicon varnish (TSR-116 from Toshiba Silicon Co., Ltd.) were mixed to obtain a slurry composition. It was This composition was applied to a 50 × 50 (mm) SUS304 steel plate degreased with acetone and then degreased with acetone to a thickness of about 5 μm, and another steel plate treated in the same manner was overlaid and fixed for 1 hour in a 200 ° C. air oven. It was left to dry and cure.
次いで接着サンプルを下表に示す各条件で空気オーブン
中で加熱し、炉内放冷後、接着強度を引張張剪断応力に
よつて評価した。測定は室温で引張速度5mm1分の条件下
で行つた。測定結果を表−１に示す。Next, the adhesive sample was heated in an air oven under the conditions shown in the table below, allowed to cool in the furnace, and the adhesive strength was evaluated by tensile shear stress. The measurement was performed at room temperature under the condition of a pulling speed of 5 mm for 1 minute. The measurement results are shown in Table-1.
ここで、例えば（Ｂ）は（Ａ）の加熱条件終了後、200
℃から350℃まで10℃／分で更に加熱処理を施したこと
を示す。以下（Ｃ）から（Ｆ）はこれに準ずる。 Here, for example, (B) is 200 after the heating conditions of (A) are completed.
It shows that a further heat treatment was performed at 10 ° C / min from ℃ to 350 ° C. The following (C) to (F) are based on this.
＜Q2＞、＜Q3＞ 〔実施例２〕 参考例３で得たポリジルコノカルボシラン80％、キシレ
ン溶液60部及びジメチルシリコンオイル（東芝シリコン
社製TSF431）20部を混合してペースト状接着剤とした。
２枚の市販炭化ケイ素板（密度3.0g/cm3）のそれぞれ片
面に上記ペーストを塗布後重ね合せた。200℃の空気オ
ーブン中に１時間放置して乾燥、硬化させた結果、引張
剪断強度200kg/cm2の接着が達成された。この接着片を8
00℃空気オーブン中に１時間放置後、炉内放冷した。冷
却後の引張剪断強度は50kg/cm2であり、上記ペースト状
接着剤は耐熱性に優れていることが判明した。<Q2>, <Q3> [Example 2] 80% of the polyzirconocarbosilane obtained in Reference Example 3, 60 parts of xylene solution and 20 parts of dimethyl silicone oil (TSF431 manufactured by Toshiba Silicon Co.) are mixed to form a paste. I used it as an agent.
The above paste was applied to one surface of each of two commercially available silicon carbide plates (density 3.0 g / cm 3 ) and then laminated. After being left in an air oven at 200 ° C. for 1 hour to be dried and cured, adhesion having a tensile shear strength of 200 kg / cm 2 was achieved. 8 this adhesive piece
After left in an air oven at 00 ° C. for 1 hour, it was left to cool in the furnace. The tensile shear strength after cooling was 50 kg / cm 2 , and it was found that the above paste-like adhesive had excellent heat resistance.
〔比較例１〕 ポリチタノカルボシラン80％キシレン溶液を実施例１と
同一の方法で200℃で乾燥硬化させたものの引張剪断強
度は10kg/cm2であり、この低接着性は接着剤層の可撓性
の乏しさにあると思われた。[Comparative Example 1] Polytitanocarbosilane 80% xylene solution was dried and cured at 200 ° C in the same manner as in Example 1 to have a tensile shear strength of 10 kg / cm 2 , and this low adhesiveness is an adhesive layer. Seemed to have poor flexibility.
上記の説明から明らかなように、本発明の接着剤組成物
は、比較的低温下において接合ができ、高温度雰囲気下
における強度低下が少なく、苛酷な雰囲気下における金
属部材及び非金属部材の接合を可能ならしめるものであ
る。さらに本発明の接着剤組成物は絶縁性の大きい金属
酸化物を無機充填剤として使用したときには、耐熱絶縁
接着剤として優れている等、それぞれの用途に適した無
機充填剤を選択することにより各種の特性を有する接着
剤の提供を可能ならしめるものである。As is clear from the above description, the adhesive composition of the present invention can be bonded at a relatively low temperature, has a small strength decrease in a high temperature atmosphere, and can bond a metal member and a non-metal member in a harsh atmosphere. Is what makes it possible. Furthermore, the adhesive composition of the present invention is excellent as a heat-resistant insulating adhesive when a metal oxide having a large insulating property is used as an inorganic filler, and thus various inorganic fillers can be selected by selecting an appropriate inorganic filler. It is possible to provide an adhesive having the characteristics of
Claims (3)
シロキサン、シリコンオイル、シリコンワニス及びシリ
コンゴムからなる群から選ばれた少なくとも１種の重合
体とを混合させてなる接着剤組成物にして、 該ポリメタロカルボシランが下記（Ａ）カルボシラン結
合単位及び少なくとも１種の下記（Ｂ）メタロキサン結
合単位からなり、 （但し、R1及びR2は同一又は異なってもよく相互に独立
に低級アルキル基、フエニール基又は水素原子を表わ
す） （Ｂ）：−（Ｍ−Ｏ （但し、ＭはTi、Zr、Mo及びCrからなる群から選ばれた
少なくとも１種の元素を示し、場合によっては前記各元
素の少なくとも１部分が側鎖基として低級アルコキシ基
又はフエノキシ基を少なくとも１個有する） 前記（Ａ）及び（Ｂ）各結合単位が主鎖骨格中でランダ
ムに結合した重合体、及び／又は前記（Ａ）の結合単位
のケイ素原子の少なくとも１部が前記（Ｂ）の結合単位
の前記各元素と酸素原子を介して結合し、これによって
前記（Ａ）の結合単位の連鎖によりえられるポリカルボ
シラン部分が前記（Ｂ）の結合単位によって架橋された
重合体であり、 前記（Ａ）の結合単位の全数対前記（Ｂ）の結合単位の
全数の比率が1:1から10:1の範囲にあり数平均分子量が4
00〜50,000であることを特徴とする接着剤組成物。1. An adhesive composition comprising a mixture of polymetallocarbosilane and at least one polymer selected from the group consisting of polyorganosiloxane, silicone oil, silicone varnish and silicone rubber. The polymetallocarbosilane comprises the following (A) carbosilane bond unit and at least one of the following (B) metalloxane bond unit, (However, R 1 and R 2 may be the same or different and independently represent a lower alkyl group, a phenyl group or a hydrogen atom.) (B) :-( MO (where M is Ti, Zr or Mo. And at least one element selected from the group consisting of Cr, and in some cases, at least one portion of each element has at least one lower alkoxy group or phenoxy group as a side chain group) (A) and ( B) A polymer in which each bonding unit is randomly bonded in the main chain skeleton, and / or at least a part of the silicon atom of the bonding unit of (A) is an oxygen atom with each element of the bonding unit of (B). Is a polymer in which the polycarbosilane moiety obtained by the chain of the bonding units of the above (A) is crosslinked by the bonding units of the above (B), and the total number of the bonding units of the above (A) is To the above (B) The ratio of the total number of units from 1: 1 to 10: Number is in the first range average molecular weight of 4
An adhesive composition characterized in that it is from 00 to 50,000.
対して前記ポリオルガノシロキサン、シリコンオイル、
シリコンワニス及びシリコンゴムからなる群から選ばれ
た少なくとも１種の重合体が10〜900重量部であること
を特徴とする特許請求の範囲第１項記載の接着剤組成
物。2. The polyorganosiloxane, silicone oil, and 100 parts by weight of the polymetallocarbosilane.
The adhesive composition according to claim 1, wherein the amount of at least one polymer selected from the group consisting of silicon varnish and silicone rubber is 10 to 900 parts by weight.
溶解もしくは分散させてなる液体状である特許請求の範
囲第１項記載の接着剤組成物。3. The adhesive composition according to claim 1, which is in the form of powder or liquid which is dissolved or dispersed in a solvent.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27922985A JPH0715093B2 (en) | 1985-12-13 | 1985-12-13 | Adhesive composition |
| US06/939,058 US4808659A (en) | 1985-12-13 | 1986-12-08 | Adhesive composition comprising organometallic polymer |
| DE8686309676T DE3680998D1 (en) | 1985-12-13 | 1986-12-11 | COMPOSED WITH AN ADHESIVE COMPOSITION CONTAINING ORGANOMETALLIC POLYMER. |
| EP86309676A EP0226460B1 (en) | 1985-12-13 | 1986-12-11 | Binding structures with an adhesive composition comprising organometallic polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27922985A JPH0715093B2 (en) | 1985-12-13 | 1985-12-13 | Adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62138574A JPS62138574A (en) | 1987-06-22 |
| JPH0715093B2 true JPH0715093B2 (en) | 1995-02-22 |
Family
ID=17608229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27922985A Expired - Lifetime JPH0715093B2 (en) | 1985-12-13 | 1985-12-13 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0715093B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06241913A (en) * | 1993-02-16 | 1994-09-02 | Chubu Sukegawa Kogyo Kk | Thermocouple temperature sensor |
| EP1659162B1 (en) | 2003-08-28 | 2012-04-11 | Yushi-Seihin Co., Ltd. | Heat-resistant label applicable at high temperature |
| WO2005023953A1 (en) * | 2003-08-28 | 2005-03-17 | Yushi-Seihin Co., Ltd. | Heat-resistant label applicable at high temperature |
| CN100393840C (en) * | 2003-08-28 | 2008-06-11 | 油脂制品株式会社 | Heat-resistant label applicable at high temperature |
| JP5118495B2 (en) * | 2005-12-21 | 2013-01-16 | 日本碍子株式会社 | Marking composition and information display method |
| WO2021009827A1 (en) * | 2019-07-16 | 2021-01-21 | 川崎重工業株式会社 | Flue gas desulfurization device |
-
1985
- 1985-12-13 JP JP27922985A patent/JPH0715093B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62138574A (en) | 1987-06-22 |
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