JPH07179655A - One-pack oxygen-curing resin composition - Google Patents
One-pack oxygen-curing resin compositionInfo
- Publication number
- JPH07179655A JPH07179655A JP5324354A JP32435493A JPH07179655A JP H07179655 A JPH07179655 A JP H07179655A JP 5324354 A JP5324354 A JP 5324354A JP 32435493 A JP32435493 A JP 32435493A JP H07179655 A JPH07179655 A JP H07179655A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- resin composition
- oxygen
- activated alumina
- composition
- 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.)
- Withdrawn
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ＳＨ基を含有するポリ
マーをベースとし、接着剤、シーリング材、コーティン
グ剤等として使用しうる一液型酸素硬化性樹脂組成物に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-pack type oxygen-curable resin composition which is based on a polymer having an SH group and can be used as an adhesive, a sealing material, a coating agent and the like.
【０００２】[0002]
【従来の技術】ＳＨ基を含有するポリマーは、そのＳＨ
の反応性を利用して、種々の硬化方法が考えられてき
た。その形態として、ポリマーを有する基剤と硬化剤を
使用直前に混合して硬化させる二液型と、ポリマーと硬
化触媒とを予め混合し、密閉された容器に入れて貯蔵
し、使用時に容器から外に出して周囲の雰囲気により硬
化させる一液型の２種類がある。二液型は、ポリマーの
ＳＨ基に対して酸化剤として働く二酸化鉛、有機過酸化
物等が硬化剤として使用されている。しかし、使用直前
の混合が不十分であったり、気泡が入ってしまう等し
て、硬化不良、硬化物の物性の低下等、様々な問題を生
じることがある。これに対して一液型は、予めＳＨ基含
有ポリマーと硬化触媒が混合されているため、二液型の
ような問題を生じることがなく、次第に二液型から一液
型へと移りつつある。BACKGROUND OF THE INVENTION Polymers containing SH groups are
Various curing methods have been considered by making use of the reactivity of. As its form, a two-pack type in which a base having a polymer and a curing agent are mixed and cured immediately before use, and a polymer and a curing catalyst are mixed in advance, stored in a closed container and stored, and from the container at the time of use. There are two types, one-pack type that is put out and cured by the surrounding atmosphere. The two-pack type uses lead dioxide, an organic peroxide, or the like, which acts as an oxidizing agent for the SH group of the polymer, as a curing agent. However, various problems may occur, such as insufficient curing immediately before use and the inclusion of bubbles, which may result in poor curing, deterioration of the physical properties of the cured product, and the like. On the other hand, in the one-pack type, since the SH group-containing polymer and the curing catalyst are mixed in advance, the problem of the two-pack type does not occur, and the two-pack type is gradually shifting to the one-pack type. .
【０００３】一液型樹脂を硬化させる周囲の雰囲気とし
て、空気中の湿気、酸素等があるが、地理的にまたは季
節によって変動する条件下では、硬化性、硬化物性等が
大きく変動するという問題があった。すなわち、湿気硬
化の場合は乾燥した地域や冬場のような低湿時には、硬
化が著しく遅れて硬化不良を起こす。これら一液型の欠
点を改良するべく、濃度のほぼ一定な空気中の酸素を用
いる硬化法が研究されてきており、例えば、特公昭５８
−１７５４９号公報には、亜鉛のジチオカルバミン酸キ
レート化合物とマンガンのβ−ジケトン化合物を硬化触
媒とする組成物が、また特公平４−１５２６１号公報に
は、ジメチルジチオカルバミン酸銅とジメチルジチオカ
ルバミン酸第二鉄とを硬化触媒とする組成物が開示され
ている。しかしながら、これらの酸素硬化性組成物は、
その貯蔵中に次第に含有する硬化触媒の活性が失われた
り、また硬化速度が非常に遅い等の欠点があった。これ
に対して、例えば特開昭５７−３８８５２号公報には、
湿気で活性化される過酸化金属を同時に含ませた組成物
が、また特開平５−１４０５３４号公報には、湿気硬化
性のシリコーンあるいは変性シリコーンのシーラントを
同時に配合した組成物の開示がある。これらは、酸素と
湿気の両硬化システムを合わせ持たせることで硬化速度
を上げようとするものであるが、結局湿気に依存する部
分が大きく、前述したような湿気硬化の問題を含むこと
になり、満足のいく解決法になっていない。The ambient atmosphere for curing the one-pack type resin is humidity, oxygen, etc. in the air, but under the condition that it varies geographically or depending on the season, the curability, the cured physical properties, etc. greatly change. was there. That is, in the case of moisture curing, curing is significantly delayed and curing failure occurs in low humidity such as a dry area or winter. In order to improve these one-pack type defects, a curing method using oxygen in the air having a substantially constant concentration has been studied, for example, Japanese Patent Publication No.
No. 17549 discloses a composition having a zinc dithiocarbamate chelate compound and a manganese β-diketone compound as a curing catalyst, and Japanese Patent Publication No. 15261/1992 discloses a composition containing copper dimethyldithiocarbamate and dimethyldithiocarbamate secondary. A composition using iron as a curing catalyst is disclosed. However, these oxygen curable compositions
There were drawbacks such that the activity of the curing catalyst gradually contained during storage was lost, and the curing rate was very slow. On the other hand, for example, Japanese Patent Laid-Open No. 57-38852 discloses that
A composition containing a moisture-activated metal peroxide at the same time, and JP-A-5-140534 discloses a composition containing a moisture-curable silicone or a modified silicone sealant at the same time. These try to increase the curing speed by combining both oxygen and moisture curing systems, but in the end, they depend largely on moisture and include the moisture curing problem described above. , Not a satisfactory solution.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、従来の一液
型硬化性組成物の欠点である使用時の周囲の湿気等、条
件の変化による硬化性等の諸特性によるばらつきを減少
させうる一液型酸素硬化性樹脂組成物を提供するもので
ある。DISCLOSURE OF THE INVENTION The present invention can reduce variations due to various properties such as curability due to changes in conditions such as ambient humidity during use, which is a drawback of conventional one-pack type curable compositions. A one-pack type oxygen-curable resin composition is provided.
【０００５】[0005]
【課題を解決するための手段】本願の発明者等は、かか
る現状に鑑み、一液型硬化性樹脂組成物の有するこれら
の問題点を改良すべく鋭意検討を重ねた結果、ＳＨ基を
含有するポリマーに活性アルミナを加えると室温下で酸
素硬化することを知見し、本発明を完成するに至った。
すなわち、ＳＨ基を含有するポリマーと、該ポリマー１
００重量部当たり、活性アルミナ５〜１００重量部とか
ら成る一液型酸素硬化性樹脂組成物を提供する。SUMMARY OF THE INVENTION In view of the above situation, the inventors of the present application have made diligent studies to improve these problems of the one-pack type curable resin composition, and as a result, the SH group was contained. It was found that the addition of activated alumina to the polymer causes oxygen curing at room temperature, and has completed the present invention.
That is, a polymer containing an SH group and the polymer 1
A one-pack type oxygen-curable resin composition comprising 5 to 100 parts by weight of activated alumina per 00 parts by weight.
【０００６】以下に、本発明をさらに詳細に説明する。
本発明に用いるＳＨ基を含有するポリマーは、分子内に
ＳＨ基を平均して１個を越える量を含有するものであれ
ばいかなるポリマーでもよく、具体例としては、東レチ
オコール（株）のポリサルファイドポリマーチオコール
ＬＰ、例えばＬＰ３２等、日本触媒（株）の変性ポリサ
ルファイドポリマーパーマポールＰ２、Ｐ７８５、信越
化学工業（株）のＸ−２２−１６７Ｂ等が挙げられ、ま
た、米国特許第２４６６９６３号に記載されているよう
に、多硫化アルカリと有機ポリハロゲン化合物とを反応
させて固体のポリサルファイドの−Ｓ−Ｓ−結合の一部
を還元することにより得られる。更に具体例を挙げれ
ば、米国特許第３９２３７４８号及び特公昭６０−１８
６８７号に記載のポリオキシアルキレンポリサルファイ
ドポリマー、米国特許第３７１１４５２号に記載のメル
カプタン末端ポリアクリレート、米国特許第３８６２９
７５号に記載のメルカプタン末端ポリ（ブタジエン−ア
クリロニトリル）等のＳＨ基を含有するポリマーがあ
る。また、たとえば米国特許第３８１７９３６号に記載
のポリ（オキシアルキレン）−ポリエステル−ポリ（モ
ノスルフィド）−ポリチオールまたは米国特許第３２５
８４９５に記載のポリオキシアルキレンポリメルカプタ
ンまたは一般式The present invention will be described in more detail below.
The polymer containing SH groups used in the present invention may be any polymer as long as it contains more than one SH group on average in the molecule. Specific examples thereof include polysulfide of Toray Thiokol Co., Ltd. Polymer Thiocol LP, such as LP32, modified polysulfide polymers Permapol P2 and P785 of Nippon Shokubai Co., Ltd., X-22-167B of Shin-Etsu Chemical Co., Ltd., and the like, and also described in US Pat. No. 2,466,963. As described above, it is obtained by reacting an alkali polysulfide with an organic polyhalogen compound to reduce a part of the —S—S— bond of solid polysulfide. More specific examples include U.S. Pat. No. 3,923,748 and Japanese Patent Publication No. 60-18.
687, polyoxyalkylene polysulfide polymers, mercaptan terminated polyacrylates, US Pat. No. 3,711,452, US Pat. No. 38,629.
There are polymers containing SH groups such as the mercaptan-terminated poly (butadiene-acrylonitrile) described in No. 75. Also, for example, poly (oxyalkylene) -polyester-poly (monosulfide) -polythiol described in U.S. Pat. No. 3,817,936 or U.S. Pat. No. 325.
Polyoxyalkylene polymer captan described in 8495 or the general formula
【０００７】[0007]
【化１】 [Chemical 1]
【０００８】を有するメルカプト基末端のポリ（オキシ
アルキレングリコール） （式中、Ｒ’はＣ1 〜Ｃ18のアルキル基、ｎ’は２また
は３）などがある。And mercapto group-terminated poly (oxyalkylene glycol) (in the formula, R ′ is a C 1 to C 18 alkyl group, n ′ is 2 or 3) and the like.
【０００９】活性アルミナとは、ガンマー結晶タイプの
吸着力を有する活性の強いアルミナのことで、具体的に
は、西尾工業（株）や住友化学工業（株）製のＮＫＨ−
Ｄ，ＮＫＨ−Ｏ，ＮＫＨ−３，ＫＨＤ−２４，ＫＨＤ−
４６，ＫＨＯ−２４，ＫＨＯ−４６，ＫＨＡ−２４，Ｋ
ＨＡ−４６，ＫＨＳ−２４，ＫＨＳ−４６、Ａ−１１、
ＡＣ−１１、Ｘ５等が挙げられる。[0009] Activated alumina is a highly active alumina having a gamma crystal type adsorption power, and specifically, NKH- manufactured by Nishio Industry Co., Ltd. and Sumitomo Chemical Co., Ltd.
D, NKH-O, NKH-3, KHD-24, KHD-
46, KHO-24, KHO-46, KHA-24, K
HA-46, KHS-24, KHS-46, A-11,
AC-11, X5, etc. are mentioned.
【００１０】活性アルミナの配合量は、ＳＨ基を有する
ポリマー１００重量部に対して、５〜１００重量部、特
に、１０〜７０重量部であるのが好ましい。５重量部未
満では、十分な酸素硬化性が得られない。また、配合量
が１００重量部を越えると、貯蔵安定性が悪く、また硬
化物性の低下を招きやすくなる。The compounding amount of activated alumina is preferably 5 to 100 parts by weight, particularly 10 to 70 parts by weight, based on 100 parts by weight of the polymer having SH groups. If it is less than 5 parts by weight, sufficient oxygen curability cannot be obtained. On the other hand, if the blending amount exceeds 100 parts by weight, the storage stability will be poor and the cured product properties will tend to deteriorate.
【００１１】本発明の一液型酸素硬化性樹脂組成物は、
ＳＨ基含有ポリマーと、活性アルミナとの必須成分の他
に、該組成物の用途分野に応じて、例えば炭酸カルシウ
ム等の充填剤、可塑剤、酸化防止剤、紫外線吸収剤、粘
度調節剤、接着付与剤、顔料、溶剤等の添加剤を添加す
ることができる。また、促進剤として、Ｆｅ，Ｃｕ，Ｚ
ｎ等のジチオカルバミン酸金属やフッ化カリウム等のよ
うなハロゲン化金属、ジアザビシクロウンデセンやジア
ザビシクロオクタンなどのアミン化合物等を加えてもよ
い。The one-pack type oxygen-curable resin composition of the present invention is
In addition to the essential components of SH group-containing polymer and activated alumina, for example, fillers such as calcium carbonate, plasticizers, antioxidants, ultraviolet absorbers, viscosity modifiers, and adhesives, depending on the field of use of the composition. Additives such as an imparting agent, a pigment and a solvent can be added. Further, as a promoter, Fe, Cu, Z
A metal dithiocarbamate such as n, a metal halide such as potassium fluoride, an amine compound such as diazabicycloundecene or diazabicyclooctane may be added.
【００１２】本発明の一液型酸素硬化性樹脂組成物の製
造方法は、ＳＨ基を含有するポリマー、活性アルミナ、
およびその他の添加剤を、室温下で、窒素雰囲気の条件
下で十分に混練して行われる。上述のようにして得られ
た本発明の一液型酸素硬化性樹脂組成物は、室温下で硬
化可能であり取扱が容易である点でも優れている。そし
て、この組成物は、密閉容器で保存し、使用時に空気中
の酸素に触れることにより硬化する。このため、接着
剤、シーリング材、コーティング剤として有用である。The method for producing a one-pack type oxygen-curable resin composition of the present invention comprises a SH group-containing polymer, activated alumina,
And other additives are sufficiently kneaded at room temperature under a nitrogen atmosphere. The one-pack type oxygen-curable resin composition of the present invention obtained as described above is excellent in that it can be cured at room temperature and is easy to handle. Then, this composition is stored in a closed container and cured by being exposed to oxygen in the air during use. Therefore, it is useful as an adhesive, a sealing material, and a coating agent.
【００１３】[0013]
【実施例】以下に、実施例を用いて、具体的に説明する
が、これによって本発明の範囲は、限定されるものでは
ない。 （実施例１〜８）下記表１に示す成分組成を室温、窒素
雰囲気の条件下で混練し、一液型酸素硬化性樹脂組成物
を得た。さらに、得られた各組成物について、ＪＩＳＡ
５７５８に準拠してタックフリータイムを測定した。EXAMPLES The present invention will be specifically described below with reference to examples, but the scope of the present invention is not limited thereby. (Examples 1 to 8) The component compositions shown in Table 1 below were kneaded at room temperature under a nitrogen atmosphere to obtain a one-pack type oxygen-curable resin composition. Furthermore, regarding each composition obtained, JISA
The tack free time was measured according to 5758.
【００１４】 注）* ：ポリサルファイドポリマー（東レチオコール
（株）製）** ：変性ポリサルファイドポリマー（日本触媒（株）
製）*** ：住友化学工業（株）製のＮＫＨＤ[0014] Note) * : Polysulfide polymer (Toray Thiokol Co., Ltd.) ** : Modified polysulfide polymer (Nippon Shokubai Co., Ltd.)
Etsu Chemical Co., Ltd.) ***: Sumitomo Chemical Co., Ltd. of NKHD
【００１５】 注）* ：ポリサルファイドポリマー（東レチオコール
（株）製）** ：変性ポリサルファイドポリマー（日本触媒（株）
製）*** ：住友化学工業（株）製のＮＫＨＤ[0015] Note) * : Polysulfide polymer (Toray Thiokol Co., Ltd.) ** : Modified polysulfide polymer (Nippon Shokubai Co., Ltd.)
Etsu Chemical Co., Ltd.) ***: Sumitomo Chemical Co., Ltd. of NKHD
【００１６】[0016]
【発明の効果】本発明の酸素硬化性樹脂組成物は、室温
にて空気中の酸素により良好に硬化する。したがって、
本発明の酸素硬化性樹脂組成物は、接着剤、シーリング
材、コーティング剤等、各種用途に有効に使用できるも
のである。The oxygen-curable resin composition of the present invention is well cured by oxygen in the air at room temperature. Therefore,
INDUSTRIAL APPLICABILITY The oxygen-curable resin composition of the present invention can be effectively used for various applications such as adhesives, sealing materials, coating agents and the like.
Claims (1)
１００重量部当たり、活性アルミナ５〜１００重量部と
から成ることを特徴とする一液型酸素硬化性樹脂組成
物。1. A one-pack type oxygen-curable resin composition comprising an SH group-containing polymer and 5 to 100 parts by weight of activated alumina per 100 parts by weight of the polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5324354A JPH07179655A (en) | 1993-12-22 | 1993-12-22 | One-pack oxygen-curing resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5324354A JPH07179655A (en) | 1993-12-22 | 1993-12-22 | One-pack oxygen-curing resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07179655A true JPH07179655A (en) | 1995-07-18 |
Family
ID=18164850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5324354A Withdrawn JPH07179655A (en) | 1993-12-22 | 1993-12-22 | One-pack oxygen-curing resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07179655A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012225393A (en) * | 2011-04-18 | 2012-11-15 | Yokohama Rubber Co Ltd:The | Method of rust-proofing laminate rubber bearing |
-
1993
- 1993-12-22 JP JP5324354A patent/JPH07179655A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012225393A (en) * | 2011-04-18 | 2012-11-15 | Yokohama Rubber Co Ltd:The | Method of rust-proofing laminate rubber bearing |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20010306 |