JP2023026886A - Two-component room temperature quick curing organopolysiloxane composition, and article - Google Patents
Two-component room temperature quick curing organopolysiloxane composition, and article Download PDFInfo
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- JP2023026886A JP2023026886A JP2021132314A JP2021132314A JP2023026886A JP 2023026886 A JP2023026886 A JP 2023026886A JP 2021132314 A JP2021132314 A JP 2021132314A JP 2021132314 A JP2021132314 A JP 2021132314A JP 2023026886 A JP2023026886 A JP 2023026886A
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- 239000000203 mixture Substances 0.000 title claims abstract description 139
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 115
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 125
- -1 organosilane compound Chemical class 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 20
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 27
- 229910021485 fumed silica Inorganic materials 0.000 claims description 18
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
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- 229910003475 inorganic filler Inorganic materials 0.000 claims description 11
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 10
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- 230000007062 hydrolysis Effects 0.000 claims description 9
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 8
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 5
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- 206010074268 Reproductive toxicity Diseases 0.000 description 4
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- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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- Paints Or Removers (AREA)
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- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、室温（２３℃±１５℃）において大気中の湿気（水分）により加水分解・縮合反応にて架橋（硬化）する縮合硬化型の二成分型室温速硬化性オルガノポリシロキサン組成物、特には、硬化時の加水分解反応によって架橋剤（硬化剤）から脱離・発生する脱離化合物がアセト酢酸エステル、マロン酸エステル等のβ－ケトエステル化合物である架橋剤を含む、二成分型室温速硬化性オルガノポリシロキサン組成物、及び該組成物又はその硬化物（シリコーンゴム）を有する各種物品等に関するものである。 The present invention provides a condensation-curable two-component room-temperature fast-curing organopolysiloxane composition that crosslinks (cures) by hydrolysis and condensation reaction with atmospheric moisture (moisture) at room temperature (23° C.±15° C.), In particular, a two-component room temperature type containing a cross-linking agent in which the released compound that is detached and generated from the cross-linking agent (curing agent) by a hydrolysis reaction during curing is a β-ketoester compound such as acetoacetate and malonic acid ester. The present invention relates to a fast-curing organopolysiloxane composition and various articles containing the composition or its cured product (silicone rubber).
室温で硬化してシリコーンゴムとなる室温硬化性オルガノポリシロキサン組成物は従来から知られており、産業界で広く使用されてきた。室温で硬化する機構には、ヒドロシリル化付加反応によって硬化する機構、紫外線によってラジカル硬化する機構、ケイ素原子に結合する加水分解性基と水酸基との縮合反応によって硬化する機構などが知られている。中でも、縮合反応により硬化する室温硬化性オルガノポリシロキサン組成物は、室温にて容易に硬化することができ、また、ヒドロシリル化付加反応などで起こる不純物による硬化阻害を起しにくいという利点を有する。そのため、車載ガスケットやシール材、建築用シーラント、電気・電子部品などの分野で幅広く使用されている。 Room-temperature-curable organopolysiloxane compositions that cure at room temperature to give silicone rubbers have long been known and widely used in industry. Known curing mechanisms at room temperature include a mechanism of curing by hydrosilylation addition reaction, a mechanism of radical curing by ultraviolet rays, and a mechanism of curing by condensation reaction between hydrolyzable groups bonded to silicon atoms and hydroxyl groups. Among them, room-temperature-curable organopolysiloxane compositions that cure by a condensation reaction have the advantage that they can be easily cured at room temperature and are less likely to be inhibited by impurities caused by hydrosilylation addition reactions. Therefore, it is widely used in fields such as in-vehicle gaskets and sealing materials, construction sealants, and electrical and electronic parts.
縮合反応により硬化する室温硬化性オルガノポリシロキサン組成物は、硬化剤（架橋剤）として分子中に加水分解性基を有する加水分解性オルガノシラン化合物を該組成物中に含有するものであり、すでに広く利用されている硬化剤としては、硬化時に２－ブタノンオキシム等のオキシム化合物を放出する脱オキシム型の加水分解性オルガノシラン化合物や、メタノール等のアルコール化合物を放出する脱アルコール型の加水分解性オルガノシラン化合物などが知られている。これらの硬化剤を含有する組成物を硬化して得られるゴム状硬化物は、シリコーン（シロキサン構造）由来の高い耐熱性、耐薬品性、耐候性を有している。
一方で、脱オキシム型の硬化剤が硬化時に発生する２－ブタノンオキシムなどのオキシム化合物は発がん性のおそれを疑われており好ましくなく、脱アルコール型の硬化剤が硬化時に発生するメタノール等は人体に対して有毒で、劇物に指定されていることから、人体の健康の観点から好ましくない。更に、これらの組成物では、硬化触媒として、環境負荷物質として規制が強化されている錫触媒を使用するケースもあり、環境保護の観点から好ましくない。
A room temperature curable organopolysiloxane composition that cures by a condensation reaction contains a hydrolyzable organosilane compound having a hydrolyzable group in the molecule as a curing agent (crosslinking agent) in the composition. Curing agents that are widely used include deoxime-type hydrolyzable organosilane compounds that release oxime compounds such as 2-butanone oxime during curing, and dealcoholization-type hydrolyzable compounds that release alcohol compounds such as methanol. Organosilane compounds and the like are known. Rubber-like cured products obtained by curing compositions containing these curing agents have high heat resistance, chemical resistance, and weather resistance derived from silicone (siloxane structure).
On the other hand, oxime compounds such as 2-butanone oxime, which are generated when the de-oximating curing agent is cured, are suspected to be carcinogenic and are not preferable. , and is designated as a deleterious substance, it is undesirable from the viewpoint of human health. Furthermore, in these compositions, tin catalysts, which are subject to stricter regulations as environmentally hazardous substances, are used as curing catalysts in some cases, which is not preferable from the viewpoint of environmental protection.
また、従来の一成分型の縮合反応により硬化する室温硬化性オルガノポリシロキサン組成物は、大気中の湿気（水分）に触れた表面から硬化が進行するが、湿気の触れづらい深部は硬化が完了するまでに時間がかかるといった欠点がある。そのため、ベースポリマーと架橋剤、触媒等を適切に分割した二成分型の室温硬化性オルガノポリシロキサン組成物とすることで硬化性を大幅に改善する技術が知られている。 In conventional room-temperature-curing organopolysiloxane compositions that cure by a one-component condensation reaction, curing progresses from the surface exposed to moisture (moisture) in the air, but curing is completed in deeper areas where moisture is less likely to come into contact. The drawback is that it takes a long time to do so. Therefore, there is known a technique for significantly improving curability by forming a two-component room-temperature-curing organopolysiloxane composition in which the base polymer, cross-linking agent, catalyst, etc. are appropriately divided.
特許第３９１６４０３号公報（特許文献１）では、分子鎖両末端が脱離基としてオキシム構造を有する、加水分解性シリル基で封鎖されたジオルガノポリシロキサンに対し１分子中に少なくとも１個のカルボニル基（Ｃ＝Ｏ基）を有する有機化合物、及び１分子中に少なくとも１個の１級アミノ基（ＮＨ2基）を有する有機化合物を含有してなる組成物が提案されている。これはカルボニル基と１級アミノ基によるケチミン生成反応から副生する水を利用して深部硬化性、速硬化性を改良したものであるが、二成分中どちらかにカルボニル化合物を意図的に大量に添加しなければならず、カルボニル化合物を入れた組成物では分離が発生しやすいといった欠点があった。また、脱アルコール型オルガノポリシロキサン組成物では、硬化性が脱オキシム型オルガノポリシロキサン組成物に劣るため、特許文献１の手法を用いても十分な硬化速度は得られない。そのため、特開２０１１－３７９６８号公報（特許文献２）のようにシラノール基を有するオルガノポリシロキサンとケテンシリルアセタール型化合物を、窒素原子を有する有機化合物存在下で混合したのち、シラノール基が存在する組成物と混合させることで硬化性を飛躍的に改善させることを報告しているが、こちらは、深部硬化性といった点では内部より水を発生する特許文献１の技術には及ばないものである。また、これらの技術では、前記のように脱オキシム型及び脱アルコール型の室温硬化性オルガノポリシロキサン組成物が硬化時に放出する脱離基（メタノール、２－ブタノンオキシム）が有する有毒性や環境負荷を低減することはできない。 In Japanese Patent No. 3916403 (Patent Document 1), a hydrolyzable silyl group-blocked diorganopolysiloxane having an oxime structure as a leaving group at both ends of the molecular chain has at least one carbonyl in one molecule. A composition comprising an organic compound having a group (C═O group) and an organic compound having at least one primary amino group (NH 2 group) per molecule has been proposed. This was achieved by using water, which is a by-product of the ketimine formation reaction between carbonyl groups and primary amino groups, to improve deep-curing and fast-curing properties. There was a drawback that separation was likely to occur in the composition containing the carbonyl compound. In addition, the dealcoholized organopolysiloxane composition is inferior in curability to the deoximated organopolysiloxane composition, and therefore a sufficient curing speed cannot be obtained even by using the technique of Patent Document 1. Therefore, as in JP-A-2011-37968 (Patent Document 2), an organopolysiloxane having a silanol group and a ketenesilyl acetal type compound are mixed in the presence of an organic compound having a nitrogen atom, and then the silanol group is present. It is reported that the curability is dramatically improved by mixing with the composition, but this is not as good as the technology of Patent Document 1 that generates water from the inside in terms of deep part curability. . In addition, in these techniques, as described above, the leaving groups (methanol, 2-butanone oxime) released during curing of the oxime- and dealcoholization-type room-temperature-curable organopolysiloxane compositions have toxicity and environmental impact. cannot be reduced.
本発明は、上記事情に鑑みなされたもので、室温硬化性オルガノポリシロキサン組成物であって、二成分型で速硬化性、深部硬化性に優れ、硬化時に、人体に対しての発がん性や生殖毒性など健康有害性、水生生物毒性など環境有害性の報告例がなく、比較的引火点の高いアセト酢酸エステル、マロン酸エステル等のβ－ケトエステル化合物を脱離基（脱離化合物）として脱離・放出する加水分解性オルガノシラン化合物を架橋剤（硬化剤）として使用した、二成分型室温速硬化性オルガノポリシロキサン組成物、該組成物を含有する各種物品、及び該二成分型室温速硬化性オルガノポリシロキサン組成物を硬化して得られるエラストマーの成形物（シリコーンゴム硬化物）を有する各種物品等を提供することを目的とする。 The present invention has been made in view of the above circumstances, and is a room temperature curable organopolysiloxane composition, which is a two-component type, has excellent rapid curing and deep curing, and is carcinogenic to the human body when cured. There are no reported examples of health hazards such as reproductive toxicity and environmental hazards such as toxicity to aquatic organisms. A two-component room-temperature fast-curing organopolysiloxane composition using a hydrolyzable organosilane compound that releases and releases as a cross-linking agent (curing agent), various articles containing the composition, and the two-component room-temperature fast-curing composition It is an object of the present invention to provide various articles and the like having an elastomer molded product (cured silicone rubber product) obtained by curing a curable organopolysiloxane composition.
本発明者らは、上記目的を達成するために鋭意検討を重ねた結果、（Ａ）分子鎖末端にシラノール基又は加水分解性シリル基を有する特定構造のオルガノポリシロキサン、（Ｂ）下記一般式（４）で示される加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物、及び（Ｃ）硬化触媒を特定割合で含有してなる第一剤と、（Ａ’）分子鎖末端にシラノール基を有する特定構造のオルガノポリシロキサンを特定量含有してなる第二剤からなる二成分型室温速硬化性オルガノポリシロキサン組成物が、一成分型の室温硬化性オルガノポリシロキサン組成物よりも硬化性に優れ、硬化時に、脱離基（脱離化合物）としてアセト酢酸エステル、マロン酸エステル等のβ－ケトエステル化合物を脱離・放出するため、人体・環境に対する有害性や安全性の問題を解決するものであることを見出した。 As a result of intensive studies to achieve the above object, the present inventors have found (A) an organopolysiloxane having a specific structure having a silanol group or a hydrolyzable silyl group at the molecular chain end, and (B) the following general formula: (4) a hydrolyzable organosilane compound and/or a partial hydrolytic condensate thereof, and (C) a first agent containing a curing catalyst in a specific proportion, and (A') a silanol at the molecular chain end A two-component room-temperature fast-curing organopolysiloxane composition comprising a second agent containing a specific amount of an organopolysiloxane having a specific structure having groups cures faster than a one-component room-temperature-curing organopolysiloxane composition. During curing, β-ketoester compounds such as acetoacetate and malonic acid ester are eliminated and released as leaving groups (leaving compounds), which solves the problem of toxicity and safety to the human body and environment. I found that it does.
本発明の二成分型室温速硬化性オルガノポリシロキサン組成物において、ベースポリマーとして分子鎖末端が加水分解性シリル基で封鎖された特定構造のオルガノポリシロキサン、あるいは、分子鎖末端がシラノール基で封鎖されたオルガノポリシロキサンと特定の加水分解性シラン化合物を硬化触媒と共存させて生成する分子鎖末端が前記特定の加水分解性シラン化合物由来の加水分解性シリル基で封鎖されたオルガノポリシロキサンを含有する第一剤と、ベースポリマーとして分子鎖末端がシラノール基で封鎖されたオルガノポリシロキサンを含有する第二剤とを混合することにより、第一剤中のベースポリマーの末端加水分解性シリル基と第二剤中のベースポリマーの末端シラノール基が直接架橋反応することで、一成分型室温硬化性オルガノポリシロキサン組成物よりも硬化性が向上するものと推定している。 In the two-component room-temperature fast-curing organopolysiloxane composition of the present invention, the base polymer is an organopolysiloxane having a specific structure in which the molecular chain ends are blocked with hydrolyzable silyl groups, or the molecular chain ends are blocked with silanol groups. containing an organopolysiloxane whose molecular chain ends are blocked with hydrolyzable silyl groups derived from the specific hydrolyzable silane compound, produced by coexisting the obtained organopolysiloxane and a specific hydrolyzable silane compound with a curing catalyst. By mixing the first agent and the second agent containing an organopolysiloxane whose molecular chain end is blocked with a silanol group as a base polymer, the terminal hydrolyzable silyl group of the base polymer in the first agent It is presumed that the direct cross-linking reaction of the terminal silanol groups of the base polymer in the second agent improves the curability as compared with the one-component room-temperature-curable organopolysiloxane composition.
また、上述した硬化性の問題に対して、本発明の（Ｂ）成分である人体に対しての発がん性や生殖毒性など健康有害性、水生生物毒性など環境有害性の報告例がなく、比較的引火点の高いアセト酢酸エステル、マロン酸エステル等のβ－ケトエステル化合物を脱離基（脱離化合物）とする加水分解性オルガノシラン化合物（架橋剤）と、（Ｄ）成分である１分子中に少なくとも１個の１級アミノ基（ＮＨ2基）を有する有機化合物を併用して使用することによって、特許文献１のようにケトン化合物の添加を必要とせずとも、ケチミン反応によって内部より水分を生成し、オルガノポリシロキサン組成物の分離を抑制しながらも、速硬化性に優れた組成物が得られることを見出し、本発明をなすに至った。 In addition, regarding the above-mentioned curability problem, there are no reports of health hazards such as carcinogenicity and reproductive toxicity to the human body, which is the component (B) of the present invention, and environmental hazards such as aquatic organism toxicity. A hydrolyzable organosilane compound (crosslinking agent) having a leaving group (leaving compound) of a β-ketoester compound such as acetoacetate and malonic ester, which has a high flash point, and component (D) in one molecule By using an organic compound having at least one primary amino group (NH 2 group) in combination, even without the addition of a ketone compound as in Patent Document 1, moisture is removed from the inside by the ketimine reaction. The inventors have found that a composition excellent in rapid curing property can be obtained while suppressing the separation of the organopolysiloxane composition, and have completed the present invention.
即ち、本発明は、下記の二成分型室温速硬化性オルガノポリシロキサン組成物、及び該組成物又はその硬化物を有する各種物品（自動車用部品、自動車用オイルシール、電気・電子用部品、建築用構造物、土木工事用構造物、接着剤、シーリング剤、ポッティング剤、コーティング剤など）等を提供するものである。
［１］
（Ａ）下記一般式（１）、（２）又は（３）で示されるオルガノポリシロキサン：１０～９０質量部（ただし、（Ａ）成分及び（Ａ’）成分の合計は１００質量部である）、
（Ｂ）下記一般式（４）で示される加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物：（Ａ）成分及び（Ａ’）成分の合計１００質量部に対して０．１～３０質量部、
及び、
（Ｃ）硬化触媒：（Ａ）成分及び（Ａ’）成分の合計１００質量部に対して０．００１～１０質量部
を含有してなる第一剤と、
（Ａ’）下記一般式（１）又は（２）で示されるオルガノポリシロキサン：１０～９０質量部（ただし、（Ａ）成分及び（Ａ’）成分の合計は１００質量部である）
を含有してなる第二剤からなるものである二成分型室温速硬化性オルガノポリシロキサン組成物。
［２］
更に、（Ｄ）硬化促進剤として一級アミノ基を有するアミン化合物を、（Ａ）成分及び（Ａ’）成分の合計１００質量部に対して第一剤及び第二剤中にそれぞれ０～２０質量部含有する（ただし、少なくとも第一剤、第二剤のいずれか一方に０．１質量部以上含有する）ものである［１］に記載の二成分型室温速硬化性オルガノポリシロキサン組成物。
［３］
（Ｂ）成分の加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物が、加水分解によってβ－ケトエステル化合物を脱離するものである［１］又は［２］に記載の二成分型室温速硬化性オルガノポリシロキサン組成物。
［４］
脱離するβ－ケトエステル化合物が、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸プロピル、アセト酢酸アリル、アセト酢酸フェニル、アセト酢酸ベンジル、マロン酸ジメチル、マロン酸ジエチル、マロン酸ジプロピル、マロン酸ジペンチル、マロン酸ジアリル、マロン酸ジフェニル又はマロン酸ジベンジルである［３］に記載の二成分型室温速硬化性オルガノポリシロキサン組成物。
［５］
更に、（Ｅ）無機質充填剤を、（Ａ）成分及び（Ａ’）成分の合計１００質量部に対して、第一剤及び第二剤中にそれぞれ０～１，０００質量部含有する（ただし、少なくとも第一剤、第二剤のいずれか一方に０．１質量部以上含有する）ものである［１］～［４］のいずれかに記載の二成分型室温速硬化性オルガノポリシロキサン組成物。
［６］
（Ｅ）成分が、炭酸カルシウム、煙霧質シリカ、沈降性シリカ、カーボンブラック及び酸化アルミニウムから選ばれる１種又は２種以上の無機質充填剤である［５］に記載の二成分型室温速硬化性オルガノポリシロキサン組成物。
［７］
更に、（Ｆ）接着促進剤を、（Ａ）成分及び（Ａ’）成分の合計１００質量部に対して、第一剤及び第二剤中にそれぞれ０～１０質量部含有する（ただし、少なくとも第一剤、第二剤のいずれか一方に０．００１質量部以上含有する）ものである［１］～［６］のいずれかに記載の二成分型室温速硬化性オルガノポリシロキサン組成物。
［８］
第一剤と第二剤との配合割合が質量比で１：１～１０：１である［１］～［７］のいずれかに記載の二成分型室温速硬化性オルガノポリシロキサン組成物。
［９］
［１］～［８］のいずれかに記載の二成分型室温速硬化性オルガノポリシロキサン組成物の硬化物を有する自動車用部品。
［１０］
［１］～［８］のいずれかに記載の二成分型室温速硬化性オルガノポリシロキサン組成物の硬化物を有する自動車用オイルシール。
［１１］
［１］～［８］のいずれかに記載の二成分型室温速硬化性オルガノポリシロキサン組成物の硬化物を有する電気・電子用部品。
［１２］
［１］～［８］のいずれかに記載の二成分型室温速硬化性オルガノポリシロキサン組成物の硬化物を有する建築用構造物。
［１３］
［１］～［８］のいずれかに記載の二成分型室温速硬化性オルガノポリシロキサン組成物の硬化物を有する土木工事用構造物。
［１４］
［１］～［８］のいずれかに記載の二成分型室温速硬化性オルガノポリシロキサン組成物を含有する接着剤。
［１５］
［１］～［８］のいずれかに記載の二成分型室温速硬化性オルガノポリシロキサン組成物を含有するシーリング剤。
［１６］
［１］～［８］のいずれかに記載の二成分型室温速硬化性オルガノポリシロキサン組成物を含有するポッティング剤。
［１７］
［１］～［８］のいずれかに記載の二成分型室温速硬化性オルガノポリシロキサン組成物を含有するコーティング剤。
That is, the present invention provides the following two-component room-temperature fast-curing organopolysiloxane composition, and various articles (automobile parts, automotive oil seals, electrical and electronic parts, building structures for construction, structures for civil engineering work, adhesives, sealing agents, potting agents, coating agents, etc.).
[1]
(A) Organopolysiloxane represented by the following general formula (1), (2) or (3): 10 to 90 parts by mass (where the total of components (A) and (A') is 100 parts by mass) ),
(B) a hydrolyzable organosilane compound represented by the following general formula (4) and/or a partial hydrolytic condensate thereof: 0.1 to 0.1 parts per 100 parts by mass of components (A) and (A') 30 parts by mass,
as well as,
(C) curing catalyst: a first agent containing 0.001 to 10 parts by mass with respect to a total of 100 parts by mass of components (A) and (A');
(A') organopolysiloxane represented by the following general formula (1) or (2): 10 to 90 parts by mass (where the total of components (A) and (A') is 100 parts by mass)
A two-component room-temperature fast-curing organopolysiloxane composition comprising a second agent containing
[2]
Furthermore, 0 to 20 masses of an amine compound having a primary amino group as a curing accelerator (D) is added to each of the first agent and the second agent with respect to a total of 100 parts by mass of the components (A) and (A'). The two-component room-temperature fast-curing organopolysiloxane composition according to [1], containing at least 0.1 part by mass of the first and second agents.
[3]
The two-component room temperature type according to [1] or [2], wherein the hydrolyzable organosilane compound and/or its partial hydrolytic condensate of component (B) eliminates the β-ketoester compound by hydrolysis. A fast-curing organopolysiloxane composition.
[4]
The β-ketoester compound to be eliminated is methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, allyl acetoacetate, phenyl acetoacetate, benzyl acetoacetate, dimethyl malonate, diethyl malonate, dipropyl malonate, dipentyl malonate, malon The two-component room-temperature fast-curing organopolysiloxane composition according to [3], which is diallyl acid, diphenyl malonate or dibenzyl malonate.
[5]
Furthermore, 0 to 1,000 parts by mass of an inorganic filler (E) is contained in each of the first and second parts with respect to a total of 100 parts by mass of components (A) and (A') (however, , 0.1 parts by mass or more in at least one of the first agent and the second agent) The two-component room temperature fast-curing organopolysiloxane composition according to any one of [1] to [4] thing.
[6]
Two-component room-temperature fast-curing according to [5], wherein component (E) is one or more inorganic fillers selected from calcium carbonate, fumed silica, precipitated silica, carbon black and aluminum oxide. Organopolysiloxane composition.
[7]
Furthermore, 0 to 10 parts by mass of (F) an adhesion promoter is contained in each of the first agent and the second agent with respect to a total of 100 parts by mass of the components (A) and (A') (however, at least The two-component room-temperature fast-curing organopolysiloxane composition according to any one of [1] to [6], which contains 0.001 parts by mass or more in either the first agent or the second agent.
[8]
The two-component room-temperature fast-curing organopolysiloxane composition according to any one of [1] to [7], wherein the mass ratio of the first component and the second component is 1:1 to 10:1.
[9]
An automotive part comprising a cured product of the two-component room-temperature fast-curing organopolysiloxane composition according to any one of [1] to [8].
[10]
An automotive oil seal comprising a cured product of the two-component room-temperature fast-curing organopolysiloxane composition according to any one of [1] to [8].
[11]
An electric/electronic part comprising a cured product of the two-component room-temperature fast-curing organopolysiloxane composition according to any one of [1] to [8].
[12]
An architectural structure comprising a cured product of the two-component room-temperature fast-curing organopolysiloxane composition according to any one of [1] to [8].
[13]
A structure for civil engineering work comprising a cured product of the two-component room-temperature fast-curing organopolysiloxane composition according to any one of [1] to [8].
[14]
An adhesive containing the two-component room-temperature fast-curing organopolysiloxane composition according to any one of [1] to [8].
[15]
A sealant containing the two-component room-temperature fast-curing organopolysiloxane composition according to any one of [1] to [8].
[16]
A potting agent containing the two-component room-temperature fast-curing organopolysiloxane composition according to any one of [1] to [8].
[17]
A coating agent containing the two-component room-temperature fast-curing organopolysiloxane composition according to any one of [1] to [8].
本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、第一剤と第二剤の二成分型からなる。これにより、第一剤と第二剤を混合した際に、速硬化性、深部硬化性に優れる。 The two-component room-temperature fast-curing organopolysiloxane composition of the present invention consists of a two-component type consisting of a first component and a second component. As a result, when the first part and the second part are mixed, they are excellent in rapid curability and deep part curability.
本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、特に、室温における空気中での速硬化性に優れ、作業性も良好である。更に保存安定性を備える。そのため本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、長期間、例えば６か月間の貯蔵後でも、第一剤と第二剤とを混合し、空気中に曝すと速やかに硬化して、優れた物性を示す。更に、本発明に用いる架橋剤は、硬化時に人体に対しての発がん性や生殖毒性など健康有害性、水生生物毒性など環境有害性の報告例がなく、比較的引火点の高い、アセト酢酸エステル、マロン酸エステル等のβ－ケトエステル化合物を脱離基（脱離物質）として放出するため、人体の健康や安全、環境保護（負荷軽減）に配慮した、各種接着剤、シーリング剤、ポッティング剤、コーティング剤等として好適に使用できる。 The two-component room-temperature fast-curing organopolysiloxane composition of the present invention is particularly excellent in fast-curing properties in air at room temperature, and has good workability. Furthermore, it has storage stability. Therefore, the two-component room-temperature fast-curing organopolysiloxane composition of the present invention can be rapidly cured by mixing the first part and the second part and exposing it to the air even after storage for a long period of time, for example, six months. and exhibit excellent physical properties. Furthermore, the cross-linking agent used in the present invention has no reports of health hazards such as carcinogenicity and reproductive toxicity to the human body when cured, and environmental hazards such as toxicity to aquatic organisms, and has a relatively high flash point. , β-keto ester compounds such as malonic acid esters are released as leaving groups (leaving substances), so various adhesives, sealants, potting agents, It can be suitably used as a coating agent or the like.
以下、本発明を更に詳細に説明する。
＜二成分型室温速硬化性オルガノポリシロキサン組成物＞
本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、後述する（Ａ）成分、（Ｂ）成分及び（Ｃ）成分の特定量を含有してなる第一剤と、（Ａ’）成分を含有してなる第二剤とからなるものである。なお、第二剤には（Ｂ）成分、（Ｃ）成分を含まないものである。
以下に、各成分について詳述する。なお、本発明において、粘度は、２３℃において、ＪＩＳ Ｚ－８８０３に規定する方法に順じた回転粘度計による測定値である。特に記述がない限り、「室温」とは温度２３℃±１５℃、湿度５０％ＲＨ±５％ＲＨの状態をいう。
The present invention will now be described in more detail.
<Two-Component Room-Temperature Fast Curing Organopolysiloxane Composition>
The two-component room-temperature fast-curing organopolysiloxane composition of the present invention comprises a first component containing specific amounts of components (A), (B), and (C), which will be described later, and (A') and a second agent containing the ingredients. The second agent does not contain component (B) and component (C).
Each component will be described in detail below. In the present invention, viscosity is measured at 23° C. using a rotational viscometer according to the method specified in JIS Z-8803. Unless otherwise specified, "room temperature" refers to a temperature of 23° C.±15° C. and a humidity of 50% RH±5% RH.
［（Ａ）成分、（Ａ’）成分：オルガノポリシロキサン］
（Ａ）成分は、後述する一般式（１）、（２）もしくは（３）で示されるオルガノポリシロキサンで、第一剤に配合するものであり、（Ａ’）成分は、後述する一般式（１）もしくは（２）で示されるオルガノポリシロキサンで、第二剤に配合するものであり、これら（Ａ）成分及び（Ａ’）成分は、本発明の二成分型室温速硬化性オルガノポリシロキサン組成物において主剤（ベースポリマー）として作用するものである。
[(A) component, (A') component: organopolysiloxane]
Component (A) is an organopolysiloxane represented by the general formula (1), (2) or (3) described later and is to be blended in the first agent, and component (A') is represented by the general formula described later. The organopolysiloxane represented by (1) or (2) is compounded in the second agent, and these components (A) and (A') are the two-component room-temperature fast-curing organopolysiloxane of the present invention. It acts as the main agent (base polymer) in the siloxane composition.
本発明の二成分型室温速硬化性オルガノポリシロキサン組成物に用いられる（Ａ）成分は、下記一般式（１）、（２）もしくは（３）で示される、好ましくは２３℃における粘度が２０～１，０００，０００ｍＰａ・ｓのオルガノポリシロキサンであり、（Ａ’）成分は、下記一般式（１）もしくは（２）で示される、好ましくは２３℃における粘度が２０～１，０００，０００ｍＰａ・ｓのオルガノポリシロキサンである。
一般式（１）、（２）、（３）中、Ｒは炭素数１～１０の非置換又はハロゲン原子置換の一価炭化水素基であり、例えば、メチル基、エチル基、プロピル基などのアルキル基；シクロヘキシル基などのシクロアルキル基；ビニル基、アリル基などのアルケニル基；フェニル基、トリル基などのアリール基；及びこれらの基の炭素原子に結合している水素原子が部分的にハロゲン原子で置換された基、例えば３，３，３－トリフルオロプロピル基等が挙げられる。これらの中でも、メチル基、ビニル基、フェニル基、３，３，３－トリフルオロプロピル基が好ましく、メチル基が特に好ましい。一般式（１）、（２）、（３）中の複数のＲは同一の基であっても異種の基であってもよい。 In general formulas (1), (2) and (3), R is an unsubstituted or halogen atom-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, etc. Alkyl groups; cycloalkyl groups such as cyclohexyl groups; alkenyl groups such as vinyl groups and allyl groups; aryl groups such as phenyl groups and tolyl groups; Atom-substituted groups such as a 3,3,3-trifluoropropyl group and the like can be mentioned. Among these, a methyl group, a vinyl group, a phenyl group and a 3,3,3-trifluoropropyl group are preferred, and a methyl group is particularly preferred. Plural R's in general formulas (1), (2) and (3) may be the same group or different groups.
また、ｎは５以上の整数、ｎ１は３以上の整数、ｎ２は１以上の整数であり、特にこれらのジオルガノポリシロキサンの２３℃における粘度が２０～１，０００，０００ｍＰａ・ｓの範囲、好ましくは１００～３００，０００ｍＰａ・ｓの範囲となる整数である。このような粘度を与えるｎの値、あるいはｎ１＋ｍ＋（ｍ×ｎ２）の値としては、具体的には、通常、５～２，０００、好ましくは２０～１，５００、より好ましくは５０～１，０００程度の整数であればよい。本発明において、重合度（又は分子量）は、通常、トルエン等を展開溶媒としてゲルパーミエーションクロマトグラフィ（ＧＰＣ）分析におけるポリスチレン換算での数平均重合度（数平均分子量）等として求めることができる。 In addition, n is an integer of 5 or more, n1 is an integer of 3 or more, and n2 is an integer of 1 or more. It is preferably an integer in the range of 100 to 300,000 mPa·s. Specifically, the value of n that gives such a viscosity, or the value of n1+m+(m×n2), is generally 5 to 2,000, preferably 20 to 1,500, more preferably 50 to 1,500. An integer of about 000 may be used. In the present invention, the degree of polymerization (or molecular weight) can usually be determined as the number average degree of polymerization (number average molecular weight) in terms of polystyrene in gel permeation chromatography (GPC) analysis using toluene or the like as a developing solvent.
また、一般式（２）中、ｍは分岐鎖の数（分子中の分岐点の数）を示し、１～１０の整数、好ましくは１～５の整数、より好ましくは１～３の整数である。なお、式（２）において、各繰り返し単位はランダムに結合されていてよい。 Further, in the general formula (2), m represents the number of branched chains (the number of branch points in the molecule), an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3 be. In formula (2), each repeating unit may be randomly bonded.
また、一般式（３）中、Ｘは酸素原子又は炭素数２～５のアルキレン基であり、炭素数２～５のアルキレン基としては、例えば、エチレン基、プロピレン基、ブチレン基等が例示される。Ｘとしては、これらの中でも、酸素原子、エチレン基が好ましい。
ｋは結合するケイ素原子毎に独立に０又は１である。
Further, in general formula (3), X is an oxygen atom or an alkylene group having 2 to 5 carbon atoms, and examples of the alkylene group having 2 to 5 carbon atoms include an ethylene group, a propylene group, and a butylene group. be. Among these, X is preferably an oxygen atom or an ethylene group.
k is independently 0 or 1 for each bonding silicon atom.
（Ａ）成分及び（Ａ’）成分のオルガノポリシロキサンは、２３℃における粘度が２０～１，０００，０００ｍＰａ・ｓであり、好ましくは１００～３００，０００ｍＰａ・ｓであり、更に好ましくは１，０００～２００，０００ｍＰａ・ｓであり、特に好ましくは１０，０００～１００，０００ｍＰａ・ｓである。オルガノポリシロキサンの粘度が上記下限値（２０ｍＰａ・ｓ）未満であると、後述する（Ｂ）成分が多量に必要となるため、経済的に不利となる。また、オルガノポリシロキサンの粘度が上記上限値（１，０００，０００ｍＰａ・ｓ）超では、作業性が低下するので、好ましくない。 The organopolysiloxane of components (A) and (A') has a viscosity at 23° C. of 20 to 1,000,000 mPa·s, preferably 100 to 300,000 mPa·s, more preferably 1, 000 to 200,000 mPa·s, particularly preferably 10,000 to 100,000 mPa·s. If the viscosity of the organopolysiloxane is less than the above lower limit (20 mPa·s), a large amount of component (B), which will be described later, is required, which is economically disadvantageous. Moreover, if the viscosity of the organopolysiloxane exceeds the above upper limit (1,000,000 mPa·s), the workability is lowered, which is not preferable.
（Ａ）成分及び（Ａ’）成分のオルガノポリシロキサンは、それぞれ１種単独で用いてもよく、２種以上を併用してもよい。また、（Ａ）成分及び（Ａ’）成分のオルガノポリシロキサンは、同じものを用いても異なったものを用いてもよい。 The organopolysiloxanes (A) and (A') may be used singly or in combination of two or more. The same or different organopolysiloxanes may be used as the components (A) and (A').
［（Ｂ）成分 加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物］
本発明の室温硬化性オルガノポリシロキサン組成物に用いられる（Ｂ）成分は、下記一般式（４）で示される加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物で、架橋剤（硬化剤）として用いられるものであり、加水分解によってアセト酢酸エステル、マロン酸エステル等のβ－ケトエステル化合物を脱離基（脱離物質）として放出するものであることを特徴とする。
なお、本発明において「部分加水分解縮合物」とは、該加水分解性オルガノシラン化合物を部分的に加水分解・縮合して生成する、分子中に残存加水分解性基を３個以上、好ましくは４個以上有するオルガノシロキサンオリゴマーを意味する。
The component (B) used in the room-temperature-curable organopolysiloxane composition of the present invention is a hydrolyzable organosilane compound represented by the following general formula (4) and/or a partial hydrolytic condensate thereof, a crosslinking agent (curing It is characterized by releasing a β-ketoester compound such as acetoacetate and malonic acid ester as a leaving group (leaving substance) by hydrolysis.
In the present invention, the term "partially hydrolyzed condensate" means that the hydrolyzable organosilane compound is partially hydrolyzed and condensed and has 3 or more residual hydrolyzable groups in the molecule, preferably It means an organosiloxane oligomer having 4 or more.
ここで、上記一般式（４）において、Ｒ1は炭素数１～１０の一価炭化水素基であり、特に炭素数１～１０、好ましくは炭素数１～６の一価脂肪族炭化水素基、炭素数６～１０のアリール基又は炭素数７～１０のアラルキル基であり、このＲ1としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、オクチル基、２－エチルヘキシル基、ノニル基、デシル基等のアルキル基、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、ヘキセニル基等のアルケニル基、フェニル基、トリル基等のアリール基、ベンジル基、フェニルエチル基等のアラルキル基などを例示することができる。これらの中でも、メチル基、エチル基、ビニル基、フェニル基が好ましく、メチル基、ビニル基が特に好ましい。 Here, in the general formula (4), R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. , an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and R 1 includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, Alkyl groups such as tert-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, nonyl group and decyl group, alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group and hexenyl group aryl groups such as phenyl group and tolyl group; and aralkyl groups such as benzyl group and phenylethyl group. Among these, a methyl group, an ethyl group, a vinyl group and a phenyl group are preferred, and a methyl group and a vinyl group are particularly preferred.
上記一般式（４）において、Ｒ2はエーテル結合酸素原子を有していてもよい炭素数１～１０、好ましくは炭素数１～６の一価脂肪族炭化水素基、エーテル結合酸素原子を有していてもよい炭素数６～１０のアリール基又はエーテル結合酸素原子を有していてもよい炭素数７～１０のアラルキル基であり、このＲ2としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、オクチル基、２－エチルヘキシル基、ノニル基、デシル基等のアルキル基、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、ヘキセニル基等のアルケニル基、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、ｓｅｃ－ブトキシ基、ｔｅｒｔ－ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基等のアルコキシ基、ビニルオキシ基、アリルオキシ基、プロペノキシ基、イソプロペノキシ基等のアルケニルオキシ基、フェニル基、トリル基等のアリール基、ベンジル基、フェニルエチル基等のアラルキル基、フェノキシ基等のアリールオキシ基、ベンジルオキシ基、フェニルエチルオキシ基等のアラルキルオキシ基などを例示することができる。これらの中でも、メチル基、エチル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基、アリルオキシ基、フェノキシ基、ベンジルオキシ基が好ましく、メチル基、エトキシ基が特に好ましい。 In the above general formula (4), R 2 is a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, which may have an ether-bonded oxygen atom; an aryl group having 6 to 10 carbon atoms which may be substituted or an aralkyl group having 7 to 10 carbon atoms which may have an ether-bonded oxygen atom, and R 2 is a methyl group, an ethyl group or a propyl group. , isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, nonyl group, alkyl group such as decyl group, vinyl group, allyl group, alkenyl groups such as propenyl group, isopropenyl group, butenyl group and hexenyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, Alkoxy groups such as hexyloxy group, alkenyloxy groups such as vinyloxy group, allyloxy group, propenoxy group and isopropenoxy group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and phenylethyl group; Aralkyloxy groups such as an aryloxy group, a benzyloxy group, and a phenylethyloxy group can be exemplified. Among these, methyl group, ethyl group, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, allyloxy group, phenoxy group and benzyloxy group are preferred, and methyl group and ethoxy group are particularly preferred.
上記一般式（４）において、Ｒ3は炭素数１～１０の一価炭化水素基であり、特に炭素数１～１０、好ましくは炭素数１～６の一価脂肪族炭化水素基、炭素数６～１０のアリール基又は炭素数７～１０のアラルキル基であり、このＲ3としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、オクチル基、２－エチルヘキシル基、ノニル基、デシル基等のアルキル基、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、ヘキセニル基等のアルケニル基、フェニル基、トリル基等のアリール基、ベンジル基、フェニルエチル基等のアラルキル基などを例示することができる。これらの中でも、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、アリル基、フェニル基、ベンジル基が好ましく、メチル基、エチル基が特に好ましい。 In the above general formula (4), R 3 is a monovalent hydrocarbon group with 1 to 10 carbon atoms, particularly a monovalent aliphatic hydrocarbon group with 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and R 3 is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group; pentyl group, hexyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group and other alkyl groups; vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group and other alkenyl groups; groups, aryl groups such as tolyl group, aralkyl groups such as benzyl group and phenylethyl group, and the like. Among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an allyl group, a phenyl group and a benzyl group are preferred, and a methyl group and an ethyl group are particularly preferred.
また、上述したとおり、ａは３又は４である。この数が３未満である場合（即ち、ａが０、１又は２である場合）は架橋反応によるゴム硬化が起こらず、室温硬化性オルガノポリシロキサン組成物の架橋剤として不適である。 Also, a is 3 or 4 as described above. When this number is less than 3 (that is, when a is 0, 1 or 2), the rubber does not harden due to the cross-linking reaction and is unsuitable as a cross-linking agent for room temperature curable organopolysiloxane compositions.
また、上記一般式（４）の加水分解性オルガノシラン化合物の加水分解によって生じる脱離基（脱離化合物）は、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸プロピル、アセト酢酸アリル、アセト酢酸フェニル、アセト酢酸ベンジル等のアセト酢酸エステル、マロン酸ジメチル、マロン酸ジエチル、マロン酸ジプロピル、マロン酸ジペンチル、マロン酸ジアリル、マロン酸ジフェニル、マロン酸ジベンジル等のマロン酸エステルなどのβ－ケトエステル化合物であり、好ましくはアセト酢酸エチル、マロン酸ジエチルである。これらの化合物は、食品添加物や香料として使用されており、安全性の高い化合物である。 Further, the leaving group (leaving compound) generated by hydrolysis of the hydrolyzable organosilane compound of the general formula (4) includes methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, allyl acetoacetate, phenyl acetoacetate, β-keto ester compounds such as acetoacetate esters such as benzyl acetoacetate, dimethyl malonate, diethyl malonate, dipropyl malonate, dipentyl malonate, diallyl malonate, diphenyl malonate, dibenzyl malonate and the like, Ethyl acetoacetate and diethyl malonate are preferred. These compounds are used as food additives and flavors, and are highly safe compounds.
（Ｂ）成分の加水分解性オルガノシラン化合物は、例えば、クロロシランとアセト酢酸エステルもしくはマロン酸エステル等のβ－ケトエステル化合物を塩基性物質の存在下に反応（例えば脱塩酸反応）させることで製造できる。この反応式は、例えば下記式［１］で表される。 The hydrolyzable organosilane compound (B) can be produced, for example, by reacting chlorosilane with a β-ketoester compound such as acetoacetate or malonic acid ester in the presence of a basic substance (for example, dehydrochlorination reaction). . This reaction formula is represented, for example, by the following formula [1].
ここで、クロロシランとしては、下記に示すものが例示できる。
また、β－ケトエステル化合物としては、下記に示すアセト酢酸エステル、マロン酸エステル等が例示できる。
クロロシランと反応させるアセト酢酸エステル、マロン酸エステル等のβ－ケトエステル化合物の添加量は、クロロシラン中の塩素原子数１モルに対して、０．９５～２．０モルが好ましく、０．９９～１．５モルがより好ましく、１．０～１．２モルが更に好ましい。β－ケトエステル化合物の添加量が少ないと反応が終結しないおそれがあり、β－ケトエステル化合物の添加量が多すぎると精製に時間がかかり、製造時間が増加してしまう。 The amount of the β-ketoester compound such as acetoacetate and malonic acid ester to be reacted with chlorosilane is preferably 0.95 to 2.0 mol, preferably 0.99 to 1 mol, per 1 mol of chlorine atoms in the chlorosilane. 0.5 mol is more preferred, and 1.0 to 1.2 mol is even more preferred. If the amount of the β-ketoester compound added is too small, the reaction may not be completed.
反応に使用する塩基性物質としては、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、尿素、ジアザビシクロウンデセン、ジアザビシクロノネンなどの求核性の低い塩基性物質が使用できる。この中でもトリメチルアミン、トリエチルアミン、トリブチルアミンが好ましく、特にトリエチルアミンが好ましい。
塩基性物質の添加量としては、クロロシラン中の塩素原子数１モルに対して０．９５～２．０モルが好ましく、０．９９～１．５モルがより好ましく、１．０～１．２モルが更に好ましい。塩基性物質の添加量が少ないと反応が終結しないおそれがあり、塩基性物質の添加量が多すぎると経済的に不利である。
Basic substances used in the reaction include low nucleophilic basic substances such as trimethylamine, triethylamine, tripropylamine, tributylamine, urea, diazabicycloundecene, and diazabicyclononene. Among these, trimethylamine, triethylamine and tributylamine are preferred, and triethylamine is particularly preferred.
The amount of the basic substance to be added is preferably 0.95 to 2.0 mol, more preferably 0.99 to 1.5 mol, more preferably 1.0 to 1.2 mol, per 1 mol of chlorine atoms in the chlorosilane. Molar is more preferred. If the amount of the basic substance added is too small, the reaction may not be completed, and if the amount of the basic substance added is too large, it is economically disadvantageous.
（Ｂ）成分の加水分解性オルガノシラン化合物の製造には、一般に使用される溶剤を使用してもよく、例えば、トルエン、キシレン、ベンゼン等の芳香族炭化水素類、ペンタン、ヘキサン、ヘプタン、ノナン、オクタン、デカンなどの脂肪族炭化水素類、ジメチルエーテル、メチルエチルエーテル、テトラヒドロフラン、ジオキサンなどのエーテル類、パークロロエタン、パークロロエチレン、トリクロロエタン、クロロホルム、四塩化炭素などのハロゲン化炭化水素、ジメチルホルムアミドなどのアミド類、酢酸エチル、酢酸メチル、酢酸ブチルなどのエステル類などの有機溶剤が挙げられる。
溶剤の使用量としては特に限定されないが、通常、使用するβ－ケトエステル化合物１００質量部に対して、１０～５００質量部、好ましくは３０～３００質量部、より好ましくは５０～２００質量部の範囲で使用される。
In the production of the component (B) hydrolyzable organosilane compound, commonly used solvents may be used, for example, toluene, xylene, aromatic hydrocarbons such as benzene, pentane, hexane, heptane, nonane , octane, decane and other aliphatic hydrocarbons, dimethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane and other ethers, perchloroethane, perchlorethylene, trichloroethane, chloroform, carbon tetrachloride and other halogenated hydrocarbons, dimethylformamide, etc. amides, esters such as ethyl acetate, methyl acetate and butyl acetate.
The amount of the solvent to be used is not particularly limited, but is usually in the range of 10 to 500 parts by mass, preferably 30 to 300 parts by mass, more preferably 50 to 200 parts by mass with respect to 100 parts by mass of the β-ketoester compound used. used in
クロロシランとβ－ケトエステル化合物との反応条件としては、通常、０～８０℃、好ましくは０～６０℃でクロロシランにβ－ケトエステル化合物を滴下し、３０～８０℃、好ましくは４０～６０℃で１～４８時間、好ましくは３～３０時間程度反応させることが好ましい。反応時の温度が低すぎると反応が完結しない場合があり、温度が高すぎると生成物の着色が大きくなる場合がある。また、反応時間が短すぎると反応が完結しない場合があり、反応時間が長すぎると生産性に不利に働く。また、反応終了後の精製は減圧環境下で加熱することで、未反応物及び溶剤を留去することが可能であり、この減圧度は好ましくは０～３，０００Ｐａ、より好ましくは０～２，０００Ｐａであり、温度は好ましくは５０～１５０℃、より好ましくは７０～１２０℃である。減圧度が高すぎると未反応物、溶剤の留去が困難となる場合がある。また、精製時の温度が低すぎると、未反応物、溶剤の留去が困難となる場合があり、高すぎると反応物の着色や分解を招くおそれがある。 As for the reaction conditions between the chlorosilane and the β-ketoester compound, the β-ketoester compound is usually added dropwise to the chlorosilane at 0 to 80°C, preferably 0 to 60°C, and the mixture is stirred at 30 to 80°C, preferably 40 to 60°C. It is preferable to react for about 48 hours, preferably about 3 to 30 hours. If the temperature during the reaction is too low, the reaction may not be completed, and if the temperature is too high, the product may become highly colored. On the other hand, if the reaction time is too short, the reaction may not be completed, and if the reaction time is too long, the productivity is adversely affected. In addition, purification after completion of the reaction can be carried out by heating in a reduced pressure environment to distill off unreacted substances and solvents. ,000 Pa, and the temperature is preferably 50 to 150°C, more preferably 70 to 120°C. If the degree of pressure reduction is too high, it may become difficult to distill off unreacted substances and solvents. On the other hand, if the temperature during purification is too low, it may become difficult to distill off the unreacted substances and solvent, and if it is too high, the reactants may be colored or decomposed.
（Ｂ）成分の加水分解性オルガノシラン化合物の具体例としては、例えば、下記式で表されるものが挙げられる。
（Ｂ）成分の加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物は、１種単独で使用しても、２種以上を併用してもよい。
（Ｂ）成分は第一剤に配合するものであり、その配合量は、（Ａ）成分及び（Ａ’）成分の合計１００質量部に対して０．１～３０質量部であり、好ましくは０．５～２５質量部である。（Ｂ）成分の配合量が少なすぎると組成物を硬化させる際に十分な架橋が得られず、多すぎると得られる硬化物（シリコーンゴム）の機械特性（ゴム物性）が低下し、経済的に不利となるという問題が発生する場合がある。
The (B) component hydrolyzable organosilane compound and/or its partial hydrolysis condensate may be used singly or in combination of two or more.
Component (B) is to be blended in the first agent, and its blending amount is 0.1 to 30 parts by mass with respect to a total of 100 parts by mass of components (A) and (A'), preferably 0.5 to 25 parts by mass. If the amount of component (B) is too small, sufficient cross-linking cannot be obtained when the composition is cured. There may be a problem that it is disadvantageous to
［（Ｃ）成分：硬化触媒］
（Ｃ）成分の硬化触媒は、加水分解縮合反応を促進させるために使用され、一般的に硬化触媒と呼ばれるものである。これは湿分の存在下で硬化する室温硬化性シリコーン樹脂組成物に通常使用されている公知のものを使用することができる。
[(C) component: curing catalyst]
The (C) component curing catalyst is used to accelerate the hydrolytic condensation reaction and is generally called a curing catalyst. Any known material commonly used in room-temperature-curable silicone resin compositions that cure in the presence of moisture can be used.
（Ｃ）成分の硬化触媒のうち、非金属系有機触媒は特に制限されないが、縮合硬化型オルガノポリシロキサン組成物の硬化促進剤として公知のものを使用することができる。例えば、Ｎ，Ｎ，Ｎ’，Ｎ’，Ｎ''，Ｎ''－ヘキサメチル－Ｎ'''－（トリメチルシリルメチル）－ホスホリミディックトリアミド等のホスファゼン含有化合物；ベンジルトリエチルアンモニウムアセテート等の第４級アンモニウム塩；ジメチルヒドロキシルアミン、ジエチルヒドロキシルアミン等のジアルキルヒドロキシルアミン；γ－（Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルグアニジル）プロピルトリメトキシシラン、γ－（Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルグアニジル）プロピルメチルジメトキシシラン、γ－（Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルグアニジル）プロピルトリス（トリメチルシロキシ）シラン等のグアニジル基を含有するシラン及びシロキサン等が挙げられる。また、非金属系有機触媒は１種単独で使用してもよく、２種以上混合して使用してもよい。 Among the curing catalysts of component (C), the non-metallic organic catalysts are not particularly limited, but those known as curing accelerators for condensation-curable organopolysiloxane compositions can be used. For example, phosphazene-containing compounds such as N,N,N',N',N'',N''-hexamethyl-N'''-(trimethylsilylmethyl)-phosphorimidic triamide; quaternary ammonium salts; dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; γ-(N,N,N',N'-tetramethylguanidyl)propyltrimethoxysilane, γ-(N,N,N Silanes containing a guanidyl group such as ',N'-tetramethylguanidyl)propylmethyldimethoxysilane and γ-(N,N,N',N'-tetramethylguanidyl)propyltris(trimethylsiloxy)silane and siloxane. Also, the non-metallic organic catalysts may be used singly or in combination of two or more.
（Ｃ）成分の硬化触媒のうち、金属系触媒は特に制限されないが、縮合硬化型オルガノポリシロキサンの硬化触媒として公知のものを使用することができる。例えば、ジブチルスズジアセテート、ジブチルスズジラウレート、ジブチルスズジオクトエート、ジメチルスズジネオデカノエート、ジオクチルスズジネオデカノエート、ジ－ｎ－ブチル－ジメトキシスズ等のアルキルスズエステル化合物；テトライソプロポキシチタン、テトラ－ｎ－ブトキシチタン、テトラキス（２－エチルヘキソキシ）チタン、ジプロポキシビス（アセチルアセトナト）チタン、チタニウムイソプロポキシオクチレングリコール等のチタン酸エステル又はチタンキレート化合物；ナフテン酸亜鉛、ステアリン酸亜鉛、亜鉛－２－エチルオクトエート；アルミニウムイソプロピレート、アルミニウムセカンダリーブチレートなどのアルコレートアルミニウム化合物；アルミニウムアルキルアセテート・ジイソプロピレート、アルミニウムビスエチルアセトアセテート・モノアセチルアセトネート等のアルミニウムキレート化合物；ネオデカン酸ビスマス（ＩＩＩ）、２－エチルヘキサン酸ビスマス（ＩＩＩ）、クエン酸ビスマス（ＩＩＩ）、オクチル酸ビスマス、鉄－２－エチルヘキソエート、コバルト－２－エチルヘキソエート、マンガン－２－エチルヘキソエート、ナフテン酸コバルト等の有機金属化合物；酢酸カリウム、酢酸ナトリウム、シュウ酸リチウム等のアルカリ金属の低級脂肪酸塩が挙げられる。金属系触媒はこれらに限定されない。金属系触媒は、１種単独で使用してもよく、２種以上混合して使用してもよい。 Among the curing catalysts for component (C), the metal-based catalyst is not particularly limited, but those known as curing catalysts for condensation-curable organopolysiloxane can be used. For example, alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctate, dimethyltin dineodecanoate, dioctyltin dineodecanoate, di-n-butyl-dimethoxytin; tetraisopropoxytitanium, Titanate esters or titanium chelate compounds such as tetra-n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetonato)titanium, titanium isopropoxyoctylene glycol; zinc naphthenate, zinc stearate, zinc -2-ethyl octoate; alcoholate aluminum compounds such as aluminum isopropylate and aluminum secondary butyrate; aluminum alkylacetate/diisopropylate, aluminum chelate compounds such as aluminum bisethylacetoacetate/monoacetylacetonate; bismuth neodecanoate ( III), bismuth (III) 2-ethylhexanoate, bismuth (III) citrate, bismuth octylate, iron-2-ethylhexoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate , organic metal compounds such as cobalt naphthenate; alkali metal lower fatty acid salts such as potassium acetate, sodium acetate and lithium oxalate. Metal-based catalysts are not limited to these. The metal-based catalysts may be used singly or in combination of two or more.
（Ｃ）成分は第一剤に配合するものであり、その配合量は、（Ａ）成分及び（Ａ’）成分の合計１００質量部に対して０．００１～１０質量部であり、０．００５～８質量部が好ましく、０．０１～５質量部が更に好ましい。０．００１質量部未満であると良好な硬化性を得ることができないため、硬化速度が遅れる不具合を生じる。逆に、１０質量部を超える量になると、組成物の硬化性が速すぎるため、組成物塗布後の作業時間の許容範囲が短くなったり、得られる硬化物（シリコーンゴム）の機械特性（ゴム物性）が低下したりする。 Component (C) is compounded in the first agent, and its compounding amount is 0.001 to 10 parts by mass with respect to a total of 100 parts by mass of components (A) and (A'). 005 to 8 parts by mass, more preferably 0.01 to 5 parts by mass. If the amount is less than 0.001 parts by mass, good curability cannot be obtained, resulting in a problem of slow curing speed. Conversely, if the amount exceeds 10 parts by mass, the curing of the composition is too rapid, and the allowable range of working time after application of the composition is shortened. physical properties) are degraded.
［（Ｄ）成分：硬化促進剤］
（Ｄ）成分は１級アミノ基（即ち、－ＮＨ2構造を有するアミノ基、ただし、グアニジル基を除く）を有するアミン化合物であり、（Ｂ）成分が加水分解して生成するβ－ケトエステル化合物と反応して水を生成し、組成物の深部硬化性を著しく向上させるものである。（Ｄ）成分としては、１級アミノ基を有するものであれば特に制限されないが、具体的にはメチルアミン、エチルアミン、ブチルアミン、ペンチルアミン、ヘキシルアミン、ヘプチルアミン、オクチルアミン、ノニルアミン、ドデシルアミン等の脂肪族アミン；エチレンジアミン、トリエチレンテトラミン等の脂肪族ポリアミン；アニリン等の芳香族アミン；シクロペンチルアミン、シクロヘキシルアミン、２－エチルシクロヘキシルアミン等の環状脂肪族アミン類；γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、３－２－（アミノエチルアミノ）プロピルトリメトキシシラン［別名：Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン］等のアミノシランなどの１級アミノ基含有シランカップリング剤（１級アミノ官能性基含有１価炭化水素基を有する加水分解性オルガノシラン化合物）；及び１級アミノ基含有ポリシロキサン等の１級アミノ基含有有機ケイ素化合物等が例示される。これらは１種単独で用いても２種以上併用してもよい。
[(D) component: curing accelerator]
Component (D) is an amine compound having a primary amino group (that is, an amino group having a —NH 2 structure, excluding a guanidyl group), and a β-keto ester compound produced by hydrolysis of component (B). It reacts with to generate water and significantly improves the deep-part curability of the composition. Component (D) is not particularly limited as long as it has a primary amino group. Specific examples include methylamine, ethylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, and dodecylamine. aliphatic amines such as ethylenediamine and triethylenetetramine; aromatic amines such as aniline; cyclic aliphatic amines such as cyclopentylamine, cyclohexylamine and 2-ethylcyclohexylamine; γ-aminopropyltrimethoxysilane, Primary amino groups such as aminosilanes such as γ-aminopropyltriethoxysilane, 3-2-(aminoethylamino)propyltrimethoxysilane [alias: N-2-(aminoethyl)-3-aminopropyltrimethoxysilane] containing silane coupling agent (hydrolyzable organosilane compound having a monovalent hydrocarbon group containing a primary amino functional group); and primary amino group-containing organosilicon compounds such as primary amino group-containing polysiloxane, etc. be. These may be used singly or in combination of two or more.
（Ｄ）成分を配合する場合、第一剤に配合しても、第二剤に配合しても、両方に配合してもよく、その配合量は、（Ａ）成分及び（Ａ’）成分の合計１００質量部に対して、第一剤及び第二剤中にそれぞれ０～２０質量部とする（ただし、少なくとも第一剤、第二剤のいずれか一方に０．１質量部以上含有する）ことが好ましく、０～１０質量部とする（ただし、少なくとも第一剤、第二剤のいずれか一方に０．１質量部以上含有する）ことがより好ましい。即ち、（Ｄ）成分を配合する場合の組成物中における総配合量は、（Ａ）成分及び（Ａ’）成分の合計１００質量部に対して０．１～２０質量部、特に０．５～１０質量部であることが好ましい。（Ｄ）成分の添加量が０．１質量部未満の場合、（Ｂ）成分の加水分解によって生じるβ－ケトエステル化合物と反応して生成する水の量が少なく、十分な深部硬化性が発現せず、２０質量部を超えると得られる硬化物の特性や保存性の面から不利となる。 When component (D) is blended, it may be blended in the first agent, the second agent, or both. 0 to 20 parts by mass in each of the first and second agents for a total of 100 parts by mass (however, at least one of the first and second agents contains 0.1 parts by mass or more ), more preferably 0 to 10 parts by mass (provided that at least one of the first agent and the second agent contains 0.1 part by mass or more). That is, when the component (D) is blended, the total blending amount in the composition is 0.1 to 20 parts by mass, particularly 0.5 parts per 100 parts by mass of the total of the components (A) and (A'). It is preferably to 10 parts by mass. When the amount of component (D) added is less than 0.1 parts by mass, the amount of water produced by reaction with the β-ketoester compound produced by hydrolysis of component (B) is small, and sufficient deep-section curability cannot be exhibited. However, if it exceeds 20 parts by mass, it is disadvantageous in terms of the properties and storage stability of the resulting cured product.
［（Ｅ）成分：無機質充填剤］
本発明の二成分型室温速硬化性オルガノポリシロキサン組成物には、必要に応じて（Ｅ）成分の無機質充填剤を任意成分として配合することができる。（Ｅ）成分の無機質充填剤は、本発明の二成分型室温速硬化性オルガノポリシロキサン組成物にゴム物性を付与するための補強性、非補強性充填剤である。（Ｅ）成分の無機質充填剤としては、表面疎水化処理又は無処理の、焼成シリカ、溶融シリカ、破砕シリカ、煙霧質シリカ（ヒュームドシリカ）等の乾式シリカ、沈降性シリカ、ゾル－ゲル法シリカ等の湿式シリカ、結晶性シリカ（微粉末石英）などのシリカ系充填剤、珪藻土、カーボンブラック、タルク、ベントナイト、表面処理又は無処理の炭酸カルシウム、炭酸亜鉛、炭酸マグネシウム、表面処理又は無処理の酸化カルシウム、酸化亜鉛、酸化マグネシウム、酸化アルミニウム、水酸化アルミニウム等が例示され、その中でも炭酸カルシウム、煙霧質シリカ、沈降性シリカ、カーボンブラック、酸化アルミニウムが好ましく、より好ましくは表面が疎水化処理された、炭酸カルシウム、煙霧質シリカ、沈降性シリカ、カーボンブラック、酸化アルミニウムである。この場合、これら無機質充填剤は、水分量が少ないことが好ましい。
なお、該表面処理剤（疎水化処理剤）の種類、量や処理方法等については特に制限はないが、代表的には、クロロシラン、アルコキシシラン、オルガノシラザン等の有機ケイ素化合物や、脂肪酸、パラフィン、シランカップリング剤、チタンカップリング剤等の処理剤が適用できる。
（Ｅ）成分の無機質充填剤は、１種単独で用いてもよく、２種以上を併用してもよい。
[(E) component: inorganic filler]
The two-component room-temperature fast-curing organopolysiloxane composition of the present invention may optionally contain an inorganic filler (E) as an optional component. The (E) component inorganic filler is a reinforcing or non-reinforcing filler for imparting rubber physical properties to the two-component room temperature fast-curing organopolysiloxane composition of the present invention. Inorganic fillers of component (E) include dry silica such as pyrogenic silica, fused silica, crushed silica, fumed silica, precipitated silica, sol-gel method, with or without surface hydrophobizing treatment. Wet silica such as silica, silica-based filler such as crystalline silica (fine powder quartz), diatomaceous earth, carbon black, talc, bentonite, surface-treated or untreated calcium carbonate, zinc carbonate, magnesium carbonate, surface-treated or untreated Examples include calcium oxide, zinc oxide, magnesium oxide, aluminum oxide, and aluminum hydroxide, among which calcium carbonate, fumed silica, precipitated silica, carbon black, and aluminum oxide are preferred, and the surface is more preferably hydrophobized. Calcium carbonate, fumed silica, precipitated silica, carbon black, aluminum oxide. In this case, these inorganic fillers preferably have a low water content.
The type, amount, treatment method, etc. of the surface treatment agent (hydrophobic treatment agent) are not particularly limited. , a silane coupling agent, a titanium coupling agent, and the like can be applied.
The (E) component inorganic filler may be used singly or in combination of two or more.
（Ｅ）成分を配合する場合、第一剤に配合しても、第二剤に配合しても、両方に配合してもよく、その配合量は、（Ａ）成分及び（Ａ’）成分の合計１００質量部に対して、第一剤及び第二剤中にそれぞれ０～１，０００質量部とする（ただし、少なくとも第一剤、第二剤のいずれか一方に０．１質量部以上含有する）ことが好ましく、０～５００質量部とする（ただし、少なくとも第一剤、第二剤のいずれか一方に０．１質量部以上含有する）ことがより好ましい。１，０００質量部よりも多量に使用すると、組成物の粘度が増大して作業性が悪くなるばかりでなく、硬化後のゴム強度が低下してゴム弾性が得難くなる。即ち、（Ｅ）成分を配合する場合の組成物中における総配合量は、（Ａ）成分及び（Ａ’）成分の合計１００質量部に対して０．１～１，０００質量部、特に１～５００質量部であることが好ましい。 When the component (E) is blended, it may be blended in the first agent, the second agent, or both, and its blending amount is the (A) component and (A') component. 0 to 1,000 parts by mass in each of the first agent and the second agent for a total of 100 parts by mass of the more preferably 0 to 500 parts by mass (at least one of the first agent and the second agent contains 0.1 part by mass or more). If the amount is more than 1,000 parts by mass, the viscosity of the composition increases and workability deteriorates, and the rubber strength after curing decreases, making it difficult to obtain rubber elasticity. That is, when component (E) is blended, the total amount in the composition is 0.1 to 1,000 parts by mass, particularly 1 part by mass, per 100 parts by mass of components (A) and (A'). It is preferably up to 500 parts by mass.
［（Ｆ）成分：接着促進剤］
（Ｆ）成分は接着促進剤であり、必要に応じて配合できる任意成分であり、本発明の二成分型室温速硬化性オルガノポリシロキサン組成物から形成される硬化物に十分な接着性を与えるために使用される。接着促進剤としては公知のものが好適に使用され、官能性基含有加水分解性シラン等のシランカップリング剤（ただし、前記（Ｂ）成分、及び硬化促進剤（Ｄ）に記載の一級アミノ基を有するアミノシラン類を除く）、具体的には、ビニルシランカップリング剤、（メタ）アクリルシランカップリング剤、エポキシシランカップリング剤、メルカプトシランカップリング剤、イソシアネートシランカップリング剤などが例示され、具体的には、ビニルトリス（β－メトキシエトキシ）シラン、γ－アクリロキシプロピルトリメトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、γ－メルカプトプロピルトリメトキシシラン、３－イソシアネートプロピルトリエトキシシラン等が例示される。
これらの中でも、特にγ－メタクリロキシプロピルトリメトキシシラン、γ－アクリロキシプロピルトリメトキシシラン等の（メタ）アクリルシラン類、γ－グリシドキシプロピルトリメトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシシラン類、３－イソシアネートプロピルトリエトキシシラン等のイソシアネートシラン類が好ましい。
[(F) component: adhesion promoter]
Component (F) is an adhesion promoter, which is an optional component that can be blended as necessary, and which imparts sufficient adhesion to the cured product formed from the two-component room-temperature fast-curing organopolysiloxane composition of the present invention. used for As the adhesion promoter, a known one is preferably used, and a silane coupling agent such as a functional group-containing hydrolyzable silane (however, the primary amino group described in the component (B) and the curing accelerator (D) (excluding aminosilanes having Specifically, vinyltris(β-methoxyethoxy)silane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycides Examples include xypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and the like.
Among these, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane and other (meth)acrylsilanes, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl ) Epoxysilanes such as ethyltrimethoxysilane and isocyanatesilanes such as 3-isocyanatopropyltriethoxysilane are preferred.
（Ｆ）成分を配合する場合、第一剤に配合しても、第二剤に配合しても、両方に配合してもよく、その配合量は、（Ａ）成分及び（Ａ’）成分の合計１００質量部に対して、第一剤及び第二剤中にそれぞれ０～１０質量部とする（ただし、少なくとも第一剤、第二剤のいずれか一方に０．００１質量部以上含有する）ことが好ましく、特に０．１～１０質量部とすることが好ましい。無機質充填剤及び被着体により接着促進剤を使用しなくても接着するときは、これを使用しなくてもよい。 When the component (F) is blended, it may be blended in the first agent, the second agent, or both. 0 to 10 parts by mass in each of the first agent and the second agent for a total of 100 parts by mass (however, at least one of the first agent and the second agent contains 0.001 parts by mass or more ) is preferable, and 0.1 to 10 parts by mass is particularly preferable. When the inorganic filler and the adherend are adhered without the use of an adhesion promoter, this may not be used.
［その他の成分］
また、本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、（Ａ）、（Ａ’）、（Ｂ）、（Ｃ）成分を必須成分とし、更に、（Ｄ）、（Ｅ）及び（Ｆ）成分を配合することが好ましい。その他、添加剤として、顔料、染料、老化防止剤、酸化防止剤、帯電防止剤、酸化アンチモン、塩化パラフィン等の難燃剤など公知の添加剤を配合することができる。更に、チクソ性向上剤としてのポリエーテル、防かび剤、抗菌剤を配合することもできる。
[Other ingredients]
The two-component room-temperature fast-curing organopolysiloxane composition of the present invention comprises components (A), (A'), (B) and (C) as essential components, and further comprises (D) and (E). and (F) component are preferably blended. In addition, known additives such as pigments, dyes, antioxidants, antioxidants, antistatic agents, flame retardants such as antimony oxide and chlorinated paraffin can be blended. Furthermore, a polyether as a thixotropic agent, an antifungal agent, and an antibacterial agent can be blended.
また、本発明の二成分型室温速硬化性オルガノポリシロキサン組成物には、必要に応じて有機溶剤を用いてもよい。有機溶剤としては、ｎ－ヘキサン、ｎ－ヘプタン、イソオクタン、イソドデカンなどの脂肪族炭化水素系化合物；トルエン、キシレンなどの芳香族炭化水素系化合物；ヘキサメチルジシロキサン、オクタメチルトリシロキサン、デカメチルテトラシロキサン、ドデカメチルペンタシロキサン、２－（トリメチルシロキシ）－１，１，１，２，３，３，３－ヘプタメチルトリシロキサンなどの鎖状シロキサン；オクタメチルシクロペンタシロキサン、デカメチルシクロペンタシロキサンなどの環状シロキサンなどが挙げられる。有機溶剤の量は本発明の効果を妨げない範囲で適宜調製すればよい。 In addition, an organic solvent may be used in the two-component room-temperature fast-curing organopolysiloxane composition of the present invention, if necessary. Examples of organic solvents include aliphatic hydrocarbon compounds such as n-hexane, n-heptane, isooctane and isododecane; aromatic hydrocarbon compounds such as toluene and xylene; hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetra chain siloxanes such as siloxane, dodecamethylpentasiloxane, 2-(trimethylsiloxy)-1,1,1,2,3,3,3-heptamethyltrisiloxane; octamethylcyclopentasiloxane, decamethylcyclopentasiloxane, etc. and the like. The amount of the organic solvent may be appropriately adjusted within a range that does not impair the effects of the present invention.
［二成分型室温速硬化性オルガノポリシロキサン組成物の調製］
本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分を含有してなる第一剤と、（Ａ’）成分を含有してなり、（Ｂ）成分、（Ｃ）成分を含有しない第二剤とからなるものである。上記第一剤と第二剤とからなる二成分型の組成物とすることにより、速硬化性、深部硬化性に優れる。これは第一剤と第二剤を混合した際に、第一剤中のベースポリマーである（Ａ）成分の分子鎖末端が加水分解性シリル基で封鎖された特定構造のオルガノポリシロキサン、あるいは、（Ａ）成分の分子鎖末端がシラノール基で封鎖されたオルガノポリシロキサンと（Ｂ）成分の特定の加水分解性シラン化合物を（Ｃ）成分の硬化触媒と共存させて生成する分子鎖末端が前記（Ｂ）成分の特定の加水分解性シラン化合物由来の加水分解性シリル基で封鎖されたオルガノポリシロキサンにおける加水分解性シリル基と、第二剤中のベースポリマーである（Ａ’）成分の分子鎖末端がシラノール基で封鎖されたオルガノポリシロキサンにおけるシラノール基が直接加水分解・縮合反応（架橋反応）することによるものと推定される。
[Preparation of two-component room-temperature fast-curing organopolysiloxane composition]
The two-component room-temperature fast-curing organopolysiloxane composition of the present invention comprises a first component comprising components (A), (B) and (C), and a component (A'). It consists of a second agent that does not contain the (B) component and the (C) component. A two-component composition consisting of the first agent and the second agent provides excellent rapid curability and deep curability. This is an organopolysiloxane having a specific structure in which the molecular chain ends of component (A), which is the base polymer in the first agent, are blocked with hydrolyzable silyl groups, or , Component (A), an organopolysiloxane whose molecular chain ends are blocked with silanol groups, and component (B), a specific hydrolyzable silane compound, together with component (C), a curing catalyst, to form molecular chain ends of Hydrolyzable silyl groups in the organopolysiloxane blocked with hydrolyzable silyl groups derived from the specific hydrolyzable silane compound of component (B) and component (A'), which is the base polymer in the second agent. It is presumed that this is due to direct hydrolysis and condensation reaction (crosslinking reaction) of the silanol groups in the organopolysiloxane whose molecular chain ends are blocked with silanol groups.
第一剤は、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分の全部と、必要により（Ｄ）、（Ｅ）、（Ｆ）成分及びその他の成分の一部又は全部とを常法に従い混合することによって調製できる。また、第二剤は、（Ａ’）成分の全部と、必要により（Ｄ）、（Ｅ）、（Ｆ）成分及びその他の成分の残部又は全部とを常法に従い混合することによって調製できる。 The first agent consists of all of the components (A), (B) and (C), and if necessary some or all of the components (D), (E), (F) and other components It can be prepared by mixing according to In addition, the second agent can be prepared by mixing all of the component (A') and, if necessary, the rest or all of the components (D), (E), (F) and other components in a conventional manner.
なお、ベースポリマーである（Ａ）成分及び（Ａ’）成分において、（Ａ）成分は第一剤に、（Ａ’）成分は第二剤に配合するが、第一剤には（Ａ）成分を１０～９０質量部、特に３０～７０質量部、第二剤には（Ａ’）成分を１０～９０質量部、特に３０～７０質量部（ただし、（Ａ）成分及び（Ａ’）成分の合計は１００質量部）配合するものである。この割合としては、第一剤と第二剤を質量比で１００：１０～１００：１００、特に１００：２５～１００：１００となるように配合することが、作業性や第一剤と第二剤を混合する際の組成物の均一性（混ざり易さ）の点から好ましい。また、任意成分である（Ｄ）、（Ｅ）、（Ｆ）成分及びその他の成分は、第一剤と第二剤のどちらに配合してもよく、どちらか一方に配合しても両方に配合してもよいが、特には、第一剤に（Ｄ）、（Ｅ）、（Ｆ）成分を配合し、第二剤に（Ｄ）、（Ｅ）成分を配合することが好ましい。
ここで、（Ｄ）成分を第一剤と第二剤に配合する場合、この割合としては、第一剤と第二剤に質量比で１：９９～９９：１、特に３０：７０～７０：３０となるように配合することが、組成物の保存安定性の点から好ましい。
また、（Ｅ）成分を第一剤と第二剤に配合する場合、この割合としては、第一剤と第二剤に質量比で８０：２０～２０：８０、特に６０：４０～４０：６０となるように配合することが、混合する際の組成物の均一性（混ざり易さ）の点から好ましい。
In the components (A) and (A'), which are base polymers, component (A) is blended in the first agent and component (A') is blended in the second agent. 10 to 90 parts by mass, particularly 30 to 70 parts by mass of component, and 10 to 90 parts by mass, particularly 30 to 70 parts by mass of component (A') for the second agent (wherein component (A) and component (A') The total amount of components is 100 parts by mass). As this ratio, the mass ratio of the first agent and the second agent is 100:10 to 100:100, especially 100:25 to 100:100. This is preferable from the point of uniformity (ease of mixing) of the composition when the agents are mixed. In addition, the optional components (D), (E), (F) and other components may be blended in either the first agent or the second agent, or may be blended in either one or both. Although they may be blended, it is particularly preferable to blend components (D), (E) and (F) in the first agent and blend components (D) and (E) in the second agent.
Here, when the component (D) is blended in the first agent and the second agent, the ratio is 1:99 to 99:1, especially 30:70 to 70, in terms of mass ratio between the first agent and the second agent. :30 is preferable from the viewpoint of storage stability of the composition.
In addition, when the component (E) is blended in the first agent and the second agent, the ratio is 80:20 to 20:80, particularly 60:40 to 40, in terms of mass ratio between the first agent and the second agent. Blending so as to achieve 60 is preferable from the point of uniformity (ease of mixing) of the composition when mixed.
本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、上記各成分、更にはこれに上記各種添加剤の所定量を、乾燥雰囲気中において均一に混合することにより得ることができる。
また、本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、保存安定性を備えるため、上記のようにして製造された第一剤及び第二剤を、湿分を避けた雰囲気下で保存することができる。
The two-component room-temperature fast-curing organopolysiloxane composition of the present invention can be obtained by uniformly mixing the above-described components and the above-described various additives in predetermined amounts in a dry atmosphere.
In addition, since the two-component room-temperature fast-curing organopolysiloxane composition of the present invention has storage stability, the first agent and the second agent produced as described above are placed in a moisture-free atmosphere. can be saved in .
［二成分型室温速硬化性オルガノポリシロキサン組成物の硬化方法］
本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、これらを適する比率、具体的には第一剤と第二剤との割合が質量比で１：１～１０：１、特には１：１～４：１で混合することにより、通常、室温にて１０分～５日で硬化する。
本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、速硬化性を有するものであって、２３℃、５０％ＲＨで厚み２ｍｍのシート状に成型する条件の場合、通常は３日～５日で硬化するものが、１０分～３日と短時間で硬化するものである。
また、本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、深部硬化性を有するものであって、２３℃、５０％ＲＨで内径が１０ｍｍ、深さが２０ｍｍのガラスシャーレで硬化させる条件の場合、通常は２時間で深部（測定可能な厚さ）まで硬化するものが、３０分と短時間で深部まで硬化するものである。
[Method for Curing Two-Component Room-Temperature Fast Curing Organopolysiloxane Composition]
The two-component room-temperature fast-curing organopolysiloxane composition of the present invention has a ratio suitable for these, specifically, the ratio of the first component and the second component in a mass ratio of 1:1 to 10:1, particularly A 1:1 to 4:1 mix generally cures at room temperature in 10 minutes to 5 days.
The two-component room-temperature fast-curing organopolysiloxane composition of the present invention has fast-curing properties, and when molded into a sheet having a thickness of 2 mm at 23° C. and 50% RH, it usually takes 3 days. Those that cure in up to 5 days will cure in as short a time as 10 minutes to 3 days.
The two-component room-temperature fast-curing organopolysiloxane composition of the present invention has deep-part curability and is cured at 23° C. and 50% RH in a glass petri dish having an inner diameter of 10 mm and a depth of 20 mm. In the case of conditions, the hardening to the deep part (measurable thickness) is usually performed in 2 hours, but the hardening to the deep part is as short as 30 minutes.
本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、室温で放置することにより硬化するが、その成形方法、硬化条件などは、電子部品用や車載用、建築用途など、種々の用途や使用目的に応じた公知の方法、条件を採用することができる。 The two-component room-temperature fast-curing organopolysiloxane composition of the present invention cures when left at room temperature. It is possible to adopt known methods and conditions according to the purpose of use.
本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、硬化時の加水分解反応によって架橋剤から発生する化合物が安全性の高いアセト酢酸エチルやマロン酸ジエチル等のβ－ケトエステル化合物であり、人体、環境に配慮されているものである。更に、シクロペンタノンでは、引火点が３５℃と、組成物の硬化時にメタノール等のアルコール化合物を放出する脱アルコール型のものよりも引火点が高く、安全性の高いものである。このような本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、既存の様々な触媒を使用することで良好な硬化性を示し、その硬化物（シリコーンゴム）は接着性にも優れる。 In the two-component room-temperature fast-curing organopolysiloxane composition of the present invention, the compound generated from the cross-linking agent by the hydrolysis reaction during curing is a highly safe β-ketoester compound such as ethyl acetoacetate and diethyl malonate. , the human body and the environment. Furthermore, cyclopentanone has a flash point of 35° C., which is higher than that of a dealcoholized type that releases an alcohol compound such as methanol when the composition is cured, and is highly safe. The two-component room-temperature fast-curing organopolysiloxane composition of the present invention exhibits good curability when used with various existing catalysts, and its cured product (silicone rubber) exhibits excellent adhesiveness. .
そのため、本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、接着剤、シーリング剤、ポッティング剤、又はコーティング剤等として有用である。本発明の二成分型室温速硬化性オルガノポリシロキサン組成物を接着剤、シーリング剤、ポッティング剤、又はコーティング剤として使用する方法は、従来公知の方法に従えばよい。 Therefore, the two-component room-temperature fast-curing organopolysiloxane composition of the present invention is useful as an adhesive, sealing agent, potting agent, coating agent, or the like. The method of using the two-component room-temperature fast-curing organopolysiloxane composition of the present invention as an adhesive, sealing agent, potting agent, or coating agent may follow conventionally known methods.
対象となる物品としては、例えば、自動車用部品、自動車用オイルシール、電気・電子用部品、建築用構造物、土木工事用構造物等が挙げられる。 Examples of target articles include automobile parts, automobile oil seals, electric/electronic parts, architectural structures, civil engineering structures, and the like.
以下、本発明を具体的に説明する合成例、実施例及び比較例を示すが、本発明は下記実施例に制限されるものではない。なお、下記の例において、粘度はＪＩＳ Ｚ ８８０３に規定する方法に準じた２３℃における回転粘度計による測定値である。 Synthesis examples, examples and comparative examples for specifically describing the present invention are shown below, but the present invention is not limited to the following examples. In the examples below, the viscosity is measured by a rotational viscometer at 23° C. according to the method specified in JIS Z 8803.
［合成例１］加水分解性オルガノシラン化合物１の合成
機械攪拌機、温度計及び滴下ロートを備えた２，０００ｍＬの四つ口セパラブルフラスコに、アセト酢酸エチル３９０ｇ（３．０ｍｏｌ）、トリエチルアミン３０４ｇ（３．０ｍｏｌ）、ヘキサン８００ｍｌを仕込み、氷浴下でビニルトリクロロシラン１６０．６ｇ（０．９９５ｍｏｌ）を約２時間かけて滴下した。その後、４０℃で４時間撹拌後、生成したトリエチルアミン塩酸塩を濾過して取り除き、ろ液を９０℃、３００Ｐａの条件でヘキサンと過剰のトリエチルアミン、アセト酢酸エチルを留去することで、加水分解性オルガノシラン化合物１を得た（収量３４８ｇ、収率７８％）。この反応式は、下記式［２］で表される。
［合成例２］加水分解性オルガノシラン化合物２の合成
機械攪拌機、温度計及び滴下ロートを備えた２，０００ｍＬの四つ口セパラブルフラスコに、マロン酸ジエチル４８０ｇ（３．０ｍｏｌ）、トリエチルアミン３０４ｇ（３．０ｍｏｌ）、ヘキサン８００ｍｌを仕込み、氷浴下でメチルトリクロロシラン１４８．７ｇ（０．９９５ｍｏｌ）を約２時間かけて滴下した。その後、４０℃で４時間撹拌後、生成したトリエチルアミン塩酸塩を濾過して取り除き、ろ液を１２０℃、３００Ｐａの条件でヘキサンと過剰のトリエチルアミン、マロン酸ジエチルを留去することで、加水分解性オルガノシラン化合物２を得た（収量２８０ｇ、収率５４％）。この反応式は、下記式［３］で表される。
［実施例１］
第一剤ａの調製
（（Ａ）成分）２３℃における粘度が２０，０００ｍＰａ・ｓの分子鎖両末端がシラノール基（ケイ素原子に結合した水酸基）で封鎖されたジメチルポリシロキサン（前記一般式（１）において、Ｒ＝メチル基、ａ＝約６２０に該当するジメチルポリシロキサン）５０質量部と、（（Ｅ）成分）ＢＥＴ比表面積が１３０ｍ2／ｇの表面ジメチルジクロロシラン処理ヒュームドシリカ（煙霧質シリカ）５質量部と、（（Ｂ）成分）合成例１で得られた加水分解性オルガノシラン化合物１を３．５質量部と、（（Ｃ）成分）γ－（Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルグアニジル）プロピルトリメトキシシラン０．４質量部と、（（Ｄ）成分）γ－アミノプロピルトリメトキシシラン０．５質量部を減圧下にて均一に混合して第一剤ａを調製した。
[Example 1]
Preparation of first agent a (Component (A)) A dimethylpolysiloxane having a viscosity of 20,000 mPa s at 23°C and having both molecular chain ends blocked with silanol groups (hydroxyl groups bonded to silicon atoms) (the above general formula ( In 1), 50 parts by mass of dimethylpolysiloxane corresponding to R = methyl group and a = about 620) and (component (E)) surface dimethyldichlorosilane-treated fumed silica having a BET specific surface area of 130 m 2 /g (fumed Silica) 5 parts by mass, (Component (B)) 3.5 parts by mass of the hydrolyzable organosilane compound 1 obtained in Synthesis Example 1, (Component (C)) γ-(N, N, N 0.4 parts by mass of ',N'-tetramethylguanidyl)propyltrimethoxysilane and 0.5 parts by mass of γ-aminopropyltrimethoxysilane (component (D)) were uniformly mixed under reduced pressure. A first agent a was prepared.
第二剤ａの調製
（（Ａ’）成分）２３℃における粘度が２０，０００ｍＰａ・ｓの分子鎖両末端がシラノール基（ケイ素原子に結合した水酸基）で封鎖されたジメチルポリシロキサン（前記一般式（１）において、Ｒ＝メチル基、ａ＝約６２０に該当するジメチルポリシロキサン）５０質量部と、（（Ｅ）成分）ＢＥＴ比表面積が１３０ｍ2／ｇの表面ジメチルジクロロシラン処理ヒュームドシリカ（煙霧質シリカ）５質量部を減圧下にて均一に混合して第二剤ａを調製した。
Preparation of second agent a (Component (A')) Dimethylpolysiloxane (the general formula In (1), 50 parts by mass of dimethylpolysiloxane corresponding to R=methyl group and a=about 620) and (E) component (E) surface dimethyldichlorosilane-treated fumed silica having a BET specific surface area of 130 m 2 /g ( Fumed silica) (5 parts by mass) was uniformly mixed under reduced pressure to prepare the second agent a.
上記第一剤ａと第二剤ａを混合比（質量比）１：１で均一に混合して組成物１を製造した。また、該組成物１を２３℃，５０％ＲＨ条件下で、１日間及び３日間それぞれ静置して硬化させたものを、硬化物１－１、１－２とした。 A composition 1 was produced by uniformly mixing the first agent a and the second agent a at a mixing ratio (mass ratio) of 1:1. Cured products 1-1 and 1-2 were obtained by curing the composition 1 under conditions of 23° C. and 50% RH for 1 day and 3 days, respectively.
［実施例２］
第二剤ｂの調製
（（Ａ’）成分）２３℃における粘度が２０，０００ｍＰａ・ｓの分子鎖両末端がシラノール基（ケイ素原子に結合した水酸基）で封鎖されたジメチルポリシロキサン（前記一般式（１）において、Ｒ＝メチル基、ａ＝約６２０に該当するジメチルポリシロキサン）５０質量部と、（（Ｅ）成分）ＢＥＴ比表面積が１３０ｍ2／ｇの表面ジメチルジクロロシラン処理ヒュームドシリカ（煙霧質シリカ）５質量部と、（（Ｄ）成分）オクチルアミン２質量を減圧下にて均一に混合して第二剤ｂを調製した。
[Example 2]
Preparation of second agent b (Component (A')) A dimethylpolysiloxane having a viscosity of 20,000 mPa s at 23°C and having both ends of the molecular chain blocked with silanol groups (hydroxyl groups bonded to silicon atoms) (the general formula In (1), 50 parts by mass of dimethylpolysiloxane corresponding to R=methyl group and a=about 620) and (E) component (E) surface dimethyldichlorosilane-treated fumed silica having a BET specific surface area of 130 m 2 /g ( 5 parts by mass of fumed silica) and 2 parts by mass of octylamine (component (D)) were uniformly mixed under reduced pressure to prepare second agent b.
実施例１で調製した第一剤ａと上記第二剤ｂを混合比（質量比）１：１で均一に混合して組成物２を製造した。また、該組成物２を２３℃，５０％ＲＨ条件下で、１日間及び３日間それぞれ静置して硬化させたものを、硬化物２－１、２－２とした。 A composition 2 was produced by uniformly mixing the first agent a prepared in Example 1 and the second agent b at a mixing ratio (mass ratio) of 1:1. Cured products 2-1 and 2-2 were obtained by curing the composition 2 under conditions of 23° C. and 50% RH for 1 day and 3 days, respectively.
［実施例３］
第一剤ｂの調製
（（Ａ）成分）２３℃における粘度が２０，０００ｍＰａ・ｓの分子鎖両末端がシラノール基（ケイ素原子に結合した水酸基）で封鎖されたジメチルポリシロキサン（前記一般式（１）において、Ｒ＝メチル基、ａ＝約６２０に該当するジメチルポリシロキサン）５０質量部と、（（Ｅ）成分）ＢＥＴ比表面積が１３０ｍ2／ｇの表面ジメチルジクロロシラン処理ヒュームドシリカ（煙霧質シリカ）５質量部と、（（Ｂ）成分）合成例１で得られた加水分解性オルガノシラン化合物１を３．５質量部と、（（Ｃ）成分）γ－（Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルグアニジル）プロピルトリメトキシシラン０．４質量部と、（（Ｄ）成分）γ－アミノプロピルトリメトキシシラン０．５質量部と、（（Ｆ）成分）γ－グリシドキシプロピルトリメトキシシラン０．５質量部を減圧下にて均一に混合して第一剤ｂを調製した。
[Example 3]
Preparation of first agent b (Component (A)) A dimethylpolysiloxane having a viscosity of 20,000 mPa s at 23°C and having both molecular chain ends blocked with silanol groups (hydroxyl groups bonded to silicon atoms) (the above general formula ( In 1), 50 parts by mass of dimethylpolysiloxane corresponding to R = methyl group and a = about 620) and (component (E)) surface dimethyldichlorosilane-treated fumed silica having a BET specific surface area of 130 m 2 /g (fumed Silica) 5 parts by mass, (Component (B)) 3.5 parts by mass of the hydrolyzable organosilane compound 1 obtained in Synthesis Example 1, (Component (C)) γ-(N, N, N 0.4 parts by mass of ',N'-tetramethylguanidyl)propyltrimethoxysilane, (component (D)) 0.5 parts by mass of γ-aminopropyltrimethoxysilane, and (component (F)) γ- First agent b was prepared by uniformly mixing 0.5 parts by mass of glycidoxypropyltrimethoxysilane under reduced pressure.
上記第一剤ｂと実施例２で調製した第二剤ｂを混合比（質量比）１：１で均一に混合して組成物３を製造した。また、該組成物３を２３℃，５０％ＲＨ条件下で、１日間及び３日間それぞれ静置して硬化させたものを、硬化物３－１、３－２とした。 Composition 3 was produced by uniformly mixing the first agent b and the second agent b prepared in Example 2 at a mixing ratio (mass ratio) of 1:1. Cured products 3-1 and 3-2 were obtained by curing the composition 3 under conditions of 23° C. and 50% RH for 1 day and 3 days, respectively.
［実施例４］
第一剤ｃの調製
（（Ａ）成分）２３℃における粘度が２０，０００ｍＰａ・ｓの分子鎖両末端がシラノール基（ケイ素原子に結合した水酸基）で封鎖されたジメチルポリシロキサン（前記一般式（１）において、Ｒ＝メチル基、ａ＝約６２０に該当するジメチルポリシロキサン）５０質量部と、（（Ｅ）成分）ＢＥＴ比表面積が１３０ｍ2／ｇの表面ジメチルジクロロシラン処理ヒュームドシリカ（煙霧質シリカ）５質量部と、（（Ｂ）成分）合成例２で得られた加水分解性オルガノシラン化合物２を３．５質量部と、（（Ｃ）成分）γ－（Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルグアニジル）プロピルトリメトキシシラン０．４質量部と、（（Ｄ）成分）γ－アミノプロピルトリメトキシシラン０．５質量部と、（（Ｆ）成分）γ－グリシドキシプロピルトリメトキシシラン０．５質量部を減圧下にて均一に混合して第一剤ｃを調製した。
[Example 4]
Preparation of first agent c (Component (A)) A dimethylpolysiloxane having a viscosity of 20,000 mPa s at 23°C and having both molecular chain ends blocked with silanol groups (hydroxyl groups bonded to silicon atoms) (the above general formula ( In 1), 50 parts by mass of dimethylpolysiloxane corresponding to R = methyl group and a = about 620) and (component (E)) surface dimethyldichlorosilane-treated fumed silica having a BET specific surface area of 130 m 2 /g (fumed Silica) 5 parts by mass, (Component (B)) 3.5 parts by mass of the hydrolyzable organosilane compound 2 obtained in Synthesis Example 2, (Component (C)) γ-(N, N, N 0.4 parts by mass of ',N'-tetramethylguanidyl)propyltrimethoxysilane, (component (D)) 0.5 parts by mass of γ-aminopropyltrimethoxysilane, and (component (F)) γ- First agent c was prepared by uniformly mixing 0.5 parts by mass of glycidoxypropyltrimethoxysilane under reduced pressure.
上記第一剤ｃと実施例２で調製した第二剤ｂを混合比（質量比）１：１で均一に混合して組成物４を製造した。また、該組成物４を２３℃，５０％ＲＨ条件下で、１日間及び３日間それぞれ静置して硬化させたものを、硬化物４－１、４－２とした。 A composition 4 was produced by uniformly mixing the first agent c and the second agent b prepared in Example 2 at a mixing ratio (mass ratio) of 1:1. Cured products 4-1 and 4-2 were obtained by curing the composition 4 under conditions of 23° C. and 50% RH for 1 day and 3 days, respectively.
［比較例１］
第一剤ｄの調製
（（Ａ）成分）２３℃における粘度が２０，０００ｍＰａ・ｓの分子鎖両末端がシラノール基（ケイ素原子に結合した水酸基）で封鎖されたジメチルポリシロキサン（前記一般式（１）において、Ｒ＝メチル基、ａ＝約６２０に該当するジメチルポリシロキサン）５０質量部と、（（Ｅ）成分）ＢＥＴ比表面積が１３０ｍ2／ｇの表面ジメチルジクロロシラン処理ヒュームドシリカ（煙霧質シリカ）５質量部と、ビニルトリメトキシシラン２．５質量部と、（（Ｃ）成分）ジオクチル錫ジラウレート０．０５質量部と、（（Ｄ）成分）γ－アミノプロピルトリメトキシシラン０．５質量部と、（（Ｆ）成分）γ－グリシドキシプロピルトリメトキシシラン０．５質量部を減圧下にて均一に混合して第一剤ｄを調製した。
[Comparative Example 1]
Preparation of first agent d (Component (A)) A dimethylpolysiloxane having a viscosity of 20,000 mPa s at 23°C and having both molecular chain ends blocked with silanol groups (hydroxyl groups bonded to silicon atoms) (the above general formula ( In 1), 50 parts by mass of dimethylpolysiloxane corresponding to R = methyl group and a = about 620) and (component (E)) surface dimethyldichlorosilane-treated fumed silica having a BET specific surface area of 130 m 2 /g (fumed quality silica) 5 parts by mass, 2.5 parts by mass of vinyltrimethoxysilane, (component (C)) dioctyltin dilaurate 0.05 parts by mass, and (component (D)) γ-aminopropyltrimethoxysilane 0.05 part by mass. 5 parts by mass and (component (F)) 0.5 parts by mass of γ-glycidoxypropyltrimethoxysilane were uniformly mixed under reduced pressure to prepare the first agent d.
上記第一剤ｄと実施例２で調製した第二剤ｂを混合比（質量比）１：１で均一に混合して組成物５を製造した。また、該組成物５を２３℃，５０％ＲＨ条件下で、１日間及び３日間それぞれ静置して硬化させたものを、硬化物５－１、５－２とした。 Composition 5 was produced by uniformly mixing the first agent d and the second agent b prepared in Example 2 at a mixing ratio (mass ratio) of 1:1. Cured products 5-1 and 5-2 were obtained by curing the composition 5 under the conditions of 23° C. and 50% RH for 1 day and 3 days, respectively.
［比較例２］
第一剤ｅの調製
（（Ａ）成分）２３℃における粘度が２０，０００ｍＰａ・ｓの分子鎖両末端がシラノール基（ケイ素原子に結合した水酸基）で封鎖されたジメチルポリシロキサン（前記一般式（１）において、Ｒ＝メチル基、ａ＝約６２０に該当するジメチルポリシロキサン）５０質量部と、（（Ｅ）成分）ＢＥＴ比表面積が１３０ｍ2／ｇの表面ジメチルジクロロシラン処理ヒュームドシリカ（煙霧質シリカ）５質量部と、ビニルトリス（メチルエチルケトオキシム）シラン３．５質量部と、（（Ｃ）成分）ジオクチル錫ジラウレート０．０５質量部と、（（Ｄ）成分）γ－アミノプロピルトリメトキシシラン０．５質量部と、（（Ｆ）成分）γ－グリシドキシプロピルトリメトキシシラン０．５質量部を減圧下にて均一に混合して第一剤ｅを調製した。
[Comparative Example 2]
Preparation of first agent e (Component (A)) A dimethylpolysiloxane having a viscosity of 20,000 mPa s at 23°C and having both molecular chain ends blocked with silanol groups (hydroxyl groups bonded to silicon atoms) (the above general formula ( In 1), 50 parts by mass of dimethylpolysiloxane corresponding to R = methyl group and a = about 620) and (component (E)) surface dimethyldichlorosilane-treated fumed silica having a BET specific surface area of 130 m 2 /g (fumed quality silica) 5 parts by mass, vinyltris(methylethylketoxime)silane 3.5 parts by mass, (component (C)) dioctyltin dilaurate 0.05 parts by mass, and (component (D)) γ-aminopropyltrimethoxysilane 0.5 part by mass and 0.5 part by mass of γ-glycidoxypropyltrimethoxysilane (component (F)) were uniformly mixed under reduced pressure to prepare the first agent e.
上記第一剤ｅと実施例２で調製した第二剤ｂを混合比（質量比）１：１で均一に混合して組成物６を製造した。また、該組成物６を２３℃，５０％ＲＨ条件下で、１日間及び３日間それぞれ静置して硬化させたものを、硬化物６－１、６－２とした。 A composition 6 was produced by uniformly mixing the first agent e and the second agent b prepared in Example 2 at a mixing ratio (mass ratio) of 1:1. Cured products 6-1 and 6-2 were obtained by curing the composition 6 under conditions of 23° C. and 50% RH for 1 day and 3 days, respectively.
［試験方法］
上記実施例１～４及び比較例１、２で調製した各組成物を用いて、下記に示す方法により、硬化性、ゴム物性、接着性を評価した。
[Test method]
Using the compositions prepared in Examples 1 to 4 and Comparative Examples 1 and 2, curability, rubber physical properties, and adhesiveness were evaluated by the methods described below.
［硬化性］
タックフリータイム：
実施例１～４及び比較例１、２で調製した各組成物を用いて、ＪＩＳ Ａ－５７５８に規定する方法に準じてタックフリータイム（指触乾燥時間）を測定した。
[Curability]
Tack free time:
Using each composition prepared in Examples 1 to 4 and Comparative Examples 1 and 2, the tack-free time (dry time to the touch) was measured according to the method specified in JIS A-5758.
深部硬化性：
内径が１０ｍｍ、深さが２０ｍｍのガラスシャーレに実施例１～４及び比較例１、２で調製した各組成物を充填し、２３℃，５０％ＲＨで２０分後に空気に触れた表面部分から硬化した部分までの厚さを測定し、深部硬化性を評価した。
Deep Curability:
A glass petri dish having an inner diameter of 10 mm and a depth of 20 mm was filled with each composition prepared in Examples 1 to 4 and Comparative Examples 1 and 2, and after 20 minutes at 23 ° C. and 50% RH, from the surface exposed to air The thickness up to the cured portion was measured to evaluate the deep-part curability.
初期シール性：
硬化性を比較するため、初期シール性を測定した。初期シール性の試験方法は、試験装置としてＪＩＳ Ｋ－６８２０に規定されている耐圧試験用フランジ圧力容器に類似する圧力容器を用い、耐圧試験を行った。該圧力容器は、内径５８ｍｍ、外径８０ｍｍ、厚さ１０ｍｍの上側フランジを有する上側容器と、上側フランジと同寸法の下側フランジを有する下側容器からなり、下側フランジのシール面のインナー側縁部には、幅３ｍｍ、深さ３ｍｍの環状の切り欠きが円周に沿って設けられている。この下側のフランジのシール面をトルエンにより洗浄した。その後、上記組成物をシール面が十分に満たされるだけの塗布量で、下側のシール面中央部にビード状に塗布した。塗布後直ちに、上側容器を、上側フランジと下側フランジのシール面とが当接するように、下側容器に載せ、上下フランジのシール面間の距離を規定するための（上記フランジの厚さ方向の）高さ２１ｍｍの鉄製スペーサーを設置して４本の締め付けボルトを組み付けた。当該スペーサーによりシール面間は１ｍｍの間隔が生じているが、これはシール材に対する耐圧試験をより過酷にする、いわゆる促進試験とするためである。その後、２３℃、５０％ＲＨで３０分間硬化させた後、上側の加圧口から気体を挿入し、上記組成物の硬化物であるシール材が耐えうる気体圧を測定し、４００ｋＰａ以上のものを合格と判定した。
Initial sealability:
In order to compare curability, initial sealability was measured. As a test method for the initial sealability, a pressure vessel similar to the flange pressure vessel for pressure resistance test specified in JIS K-6820 was used as a test apparatus, and a pressure resistance test was performed. The pressure vessel consists of an upper vessel having an upper flange with an inner diameter of 58 mm, an outer diameter of 80 mm, and a thickness of 10 mm, and a lower vessel having a lower flange having the same dimensions as the upper flange. The edge is provided with an annular notch 3 mm wide and 3 mm deep along the circumference. The sealing surface of this lower flange was cleaned with toluene. Thereafter, the above composition was applied in a bead shape to the central portion of the lower sealing surface in an amount sufficient to sufficiently fill the sealing surface. Immediately after application, the upper container is placed on the lower container so that the seal surfaces of the upper flange and the lower flange are in contact, and the distance between the seal surfaces of the upper and lower flanges is defined (thickness direction of the flange ), a steel spacer with a height of 21 mm was installed and four tightening bolts were assembled. The spacer creates a gap of 1 mm between the sealing surfaces, but this is to make the pressure resistance test for the sealing material more severe, that is, to conduct a so-called accelerated test. Then, after curing for 30 minutes at 23 ° C. and 50% RH, gas is introduced from the upper pressurization port, and the gas pressure that the sealing material, which is a cured product of the above composition, can withstand is measured. was judged to pass.
［ゴム物性］
実施例１～４及び比較例１、２で調製した調製直後の各組成物を厚さ２ｍｍのシート状に押し出し、２３℃，５０％ＲＨの空気に曝し、次いで、該シートを同じ雰囲気下に１日間又は３日間放置して得た硬化物のゴム物性（硬さ、切断時伸び、引張強さ）を、ＪＩＳ Ｋ－６２４９に準拠して測定した。なお、硬さは、ＪＩＳ Ｋ－６２４９のデュロメーターＡ硬度計を用いて測定した。
[Rubber physical properties]
Each composition immediately after preparation prepared in Examples 1 to 4 and Comparative Examples 1 and 2 was extruded into a sheet with a thickness of 2 mm, exposed to air at 23 ° C. and 50% RH, and then the sheet was placed under the same atmosphere. The rubber physical properties (hardness, elongation at break, tensile strength) of the cured product obtained by standing for 1 day or 3 days were measured according to JIS K-6249. The hardness was measured using a JIS K-6249 durometer A hardness tester.
［接着性］
実施例１～４及び比較例１，２で調製した組成物より、幅２５ｍｍ、長さ１００ｍｍのアルミニウム又はガラスを被着体として、それぞれ同材の被着体同士を、上記組成物を用いて、各試験片の接着面積２．５ｍｍ2、接着厚さ１ｍｍで接着したせん断（シア）接着試験体を作製し、２３℃，５０％ＲＨで１日間又は３日間養生した後、これらの試験体を用いてアルミニウム又はガラスに対するせん断接着力をＪＩＳ Ｋ－６２４９に規定する方法に準じて測定した。
[Adhesiveness]
From the compositions prepared in Examples 1 to 4 and Comparative Examples 1 and 2, aluminum or glass having a width of 25 mm and a length of 100 mm was used as an adherend, and adherends of the same material were used. , Shear adhesion test specimens were prepared by bonding each test piece with an adhesion area of 2.5 mm 2 and an adhesion thickness of 1 mm, and after curing at 23 ° C. and 50% RH for 1 day or 3 days, these specimens was used to measure the shear adhesive strength to aluminum or glass according to the method specified in JIS K-6249.
実施例１～４の試験結果を表１に、比較例１、２の試験結果を表２に示す。また、硬化時に硬化剤から脱離する化合物、及び該化合物の健康有害性、環境有害性の有無について表１、２に併記する。 Table 1 shows the test results of Examples 1 to 4, and Table 2 shows the test results of Comparative Examples 1 and 2. Tables 1 and 2 also show the compounds released from the curing agent during curing, and the presence or absence of health hazards and environmental hazards of these compounds.
上記の結果より、本発明の二成分型室温速硬化性オルガノポリシロキサン組成物（実施例１～４の組成物）は、深部硬化性、初期シール性が高い値を示し、１日硬化と３日硬化でゴム物性、接着強度の差が小さいことから、従来の脱アルコール（比較例１の組成物）、脱オキシム（比較例２の組成物）の硬化形態と比較して、高い硬化性を有することが分かる。
また、実施例の組成物が硬化中に放出する化合物は、アセト酢酸エチルもしくはマロン酸ジエチルであり、人体に対しての発がん性や生殖毒性など健康有害性、水生生物毒性など環境有害性の報告例がなく安全性の高い化合物である。一方で、比較例の組成物が硬化中に放出する化合物はいずれもＳＤＳ（安全データシート）等で健康有害性が表示されており、劇物に指定され、人体に強い有害性を有しているメタノール、発がん性のおそれ、水生生物への毒性を有する２－ブタノンオキシムである。また、メタノールは、β－ケトエステル化合物と比較して引火点や沸点が低いことからも、本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、人体の健康、環境保護の観点からより優れていることが分かる。
From the above results, the two-component room-temperature fast-curing organopolysiloxane compositions of the present invention (compositions of Examples 1 to 4) exhibit high values of deep-section curability and initial sealability. Since the difference in rubber physical properties and adhesive strength is small in day curing, compared to conventional dealcoholization (composition of Comparative Example 1) and deoximation (composition of Comparative Example 2), high curability is obtained. I know you have.
In addition, the compound released during curing of the compositions of the examples is ethyl acetoacetate or diethyl malonate, and reports of health hazards such as carcinogenicity and reproductive toxicity to the human body, and environmental hazards such as toxicity to aquatic organisms. It is an unprecedented and highly safe compound. On the other hand, the compounds released by the compositions of the comparative examples during curing all display health hazards in SDS (Safety Data Sheets), etc., are designated as deleterious substances, and are highly harmful to the human body. Methanol is 2-butanone oxime, a potentially carcinogenic and toxic to aquatic organisms. In addition, since methanol has a lower flash point and boiling point than β-ketoester compounds, the two-component room-temperature fast-curing organopolysiloxane composition of the present invention is more suitable for human health and environmental protection. It turns out to be excellent.
Claims (17)
（Ｂ）下記一般式（４）で示される加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物：（Ａ）成分及び（Ａ’）成分の合計１００質量部に対して０．１～３０質量部、
及び、
（Ｃ）硬化触媒：（Ａ）成分及び（Ａ’）成分の合計１００質量部に対して０．００１～１０質量部
を含有してなる第一剤と、
（Ａ’）下記一般式（１）又は（２）で示されるオルガノポリシロキサン：１０～９０質量部（ただし、（Ａ）成分及び（Ａ’）成分の合計は１００質量部である）
を含有してなる第二剤からなるものである二成分型室温速硬化性オルガノポリシロキサン組成物。 (A) Organopolysiloxane represented by the following general formula (1), (2) or (3): 10 to 90 parts by mass (where the total of components (A) and (A') is 100 parts by mass) ),
(B) a hydrolyzable organosilane compound represented by the following general formula (4) and/or a partial hydrolytic condensate thereof: 0.1 to 0.1 parts per 100 parts by mass of components (A) and (A') 30 parts by mass,
as well as,
(C) curing catalyst: a first agent containing 0.001 to 10 parts by mass with respect to a total of 100 parts by mass of components (A) and (A');
(A') organopolysiloxane represented by the following general formula (1) or (2): 10 to 90 parts by mass (where the total of components (A) and (A') is 100 parts by mass)
A two-component room-temperature fast-curing organopolysiloxane composition comprising a second agent containing
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| JP5062430B2 (en) | 2007-04-12 | 2012-10-31 | 信越化学工業株式会社 | Room temperature fast-curing organopolysiloxane composition and curing method thereof |
| JP6031008B2 (en) | 2013-07-16 | 2016-11-24 | 信越化学工業株式会社 | Method for producing room temperature curable organopolysiloxane composition, and automobile oil seal, architectural sealant and method for producing electrical and electronic parts using cured product of said composition |
| WO2018037682A1 (en) | 2016-08-26 | 2018-03-01 | 信越化学工業株式会社 | Dealcoholization room-temperature curable organopolysiloxane composition, and article sealed by cured product of same |
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