JPH0536458B2 - - Google Patents
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- JPH0536458B2 JPH0536458B2 JP1126025A JP12602589A JPH0536458B2 JP H0536458 B2 JPH0536458 B2 JP H0536458B2 JP 1126025 A JP1126025 A JP 1126025A JP 12602589 A JP12602589 A JP 12602589A JP H0536458 B2 JPH0536458 B2 JP H0536458B2
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- 229920001296 polysiloxane Polymers 0.000 claims description 29
- -1 polysiloxane Polymers 0.000 claims description 24
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002736 nonionic surfactant Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 230000000740 bleeding effect Effects 0.000 description 4
- 239000002978 dental impression material Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002683 reaction inhibitor Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000011505 plaster Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013005 condensation curing Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 150000003058 platinum compounds Chemical group 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Landscapes
- Dental Preparations (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
〔産業上の利用分野〕
本発明は、硬化性シリコーン組成物に関し、特
に硬化物の親水性に優れる硬化性シリコーン組成
物に関する。
〔従来の技術〕
硬化性シリコーン組成物は、硬化物の特性に優
れ、平版印刷版、離型剤、接着剤、塗料、シーラ
ント、反射シート、歯科用印象材等の種々の用途
に使用されている。例えば、近年、縮合硬化型及
び付加硬化型の硬化性シリコーン組成物がともに
印象材料として広く使用されるようになつた。こ
れらは無味無臭である、硬化物の強度が優れてい
るなどの優れた諸特性を有している。
しかし、硬化性シリコーン組成物は、疎水性で
あるため、例えば、歯科用印象材として使用して
湿潤な口腔内の型を取つても寸法が不正確な印象
しか得られず、また得られた印象に石膏泥を注型
して模型を作製するときには石膏泥の濡れに問題
があり、正確な模型を得ることができないことが
あつた。そこで、親水性を有する硬化性シリコー
ン組成物として、親水性基を含有する非イオン系
界面活性剤を配合した硬化性シリコーン組成物が
提案されている。（公表昭63−501368号）
〔発明が解決しようとする課題〕
しかし、上記の親水性基を含有する非イオン系
界面活性剤を配合した硬化性シリコーン組成物
は、硬化物の表面に界面活性剤がブリードしてし
まう、硬化後の寸法安定性が悪い、また硬化物の
親水性が長期間にわたつて持続しないなどの欠点
がある。
そこで本発明の目的は、硬化物が優れた親水性
及び寸法安定性を有し、しかもその親水性が半氷
久的に持続する硬化性シリコーン組成物を提供す
ることにある。
〔課題を解決するための手段〕
本発明者らは、前記課題を解決するため、鋭意
研究の結果、ケイ素原子に結合した水素原子ある
いは脂肪族不飽和炭化水素基を有する非イオン系
界面活性剤を必須の成分として配合したシリコー
ン組成物の硬化物が優れた親水性、例えば、硬化
物の表面と水との接触角が65゜以下であり、しか
もその親水性の長期間にわたり持続することを見
出し、本発明に到達した。
すなわち、本発明は、
(A) １分子中にケイ素原子に結合した脂肪族不飽
和炭化水素基を少なくとも２個有するオルガノ
ポリシロキサン、
(B) １分子中にケイ素原子に結合した水素原子を
少なくとも３個有するオルガノハイドロジエン
ポリシロキサン、当該成分中のケイ素原子に結
合した水素原子が前記(A)成分中の脂肪族不飽和
炭化水素基１個に対して0.5〜10個の割合とな
る量、
(C) 下記一般式（）：
〔式中、Ｒは、同一でも異なつていてもよ
く、
一価の炭化水素基であり、
Reは、下記式（）：
−R1O（C2H4O）aR2 （）
（ここでR1は二価の炭化水素基であり、
ａは１以上の整数である）で表される基であ
り、
ｘは、０以上の整数、
ｙは、１以上の整数、
ｚは、１以上の整数である、〕
または下記一般式（）：
〔式中、Ｒ，Re．ｘ，ｙ及びｚは、前記の
通りである、〕
で表されるシロキサン化合物から成る非イオン
系界面活性剤、前記(A)成分100重量部当り、0.5
〜15重量部、及び、
(D) 白金族金属系触媒、前記(A)成分に対して白金
族金属換算で１〜300ppm、
を含有してなる硬化性シリコーン組成物を提供
するものである。
本発明の組成物の(A)成分であるオルガノポリシ
ロキサンは、１分子中にケイ素原子に結合した脂
肪族不飽和炭化水素基を少なくとも２個含有する
ものであり、直鎖状、分岐状あるいは二次元又は
三次元の網状構造のいずれの形態のものでもよ
く、またこれらの混合物であつてもよい。脂肪族
不飽和炭化水素基としては、例えば、ビニル基、
アリル基、ブテニル基、ペンテニル基、ヘキセニ
ル基等が挙げられ、好ましくはビニル基である。
脂肪族不飽和炭化水素基以外のケイ素原子に結合
する有機基としては、例えば、メチル基、エチル
基、プロピル基等のアルキル基；フエニル基、ト
リル基等の芳香族炭化水素基；シクロヘキシル
基、シクロヘプチル基等の脂環式炭化水素基；又
はこれらの炭化水素基の炭素原子に結合している
水素原子の一部もしくは全部がハロゲン原子等で
置換された基、例えば、クロロメチル基、３，
３，３−トリフルオロプロピル基などが挙げられ
る。これらのうちで好ましいものとしては、メチ
ル基、フエニル基、３，３，３−トリフルオロプ
ロピル基である。特に、この(A)のオルガノポリシ
ロキサンの好ましいものとしては、脂肪族不飽和
炭化水素基以外の置換基の全てがメチル基である
もの、もしくはメチル基とフエニル基からなるも
のがある。
この(A)成分のオルガノポリシロキサンの25℃に
おける粘度は、通常、50cSt以上、好ましくは100
〜5000000cStである。
本発明の組成物の(B)成分であるオルガノハイド
ロジエンポリシロキサンは、１分子中にケイ素原
子に結合した水素原子を少なくとも３個有するも
のであり、直鎖状、分岐状、環状のいずれの構造
のものでもよい。好ましくは直鎖状のものであ
る。このオルガノハイドロジエンポリシロキサン
において、ケイ素原子に結合した水素原子以外の
有機基としては、前記(A)のオルガノポリシロキサ
ンにおいて脂肪族不飽和炭化水素基以外の置換基
として例示したものと同じものを挙げることがで
きる。
(B)成分のオルガノハイドロジエンポリシロキサ
ンの25℃における粘度は、通常、0.5〜10000cSt、
好ましくは１〜1000cStである。
本発明の(B)成分の配合量は、当該成分中のケイ
素原子に結合した水素原子が前記(A)成分中の脂肪
族不飽和炭化水素基１個に対して0.5〜10個、好
ましくは0.75〜10個の割合となる量である。(B)成
分の配合量が多すぎると得られる組成物の硬化物
が脆くなつたり、過剰のヒドロシリル基（Si−
Ｈ）が残存して諸物性の経時変化の原因となつた
り、少なすぎると組成物の硬化が不充分となり易
い。
本発明の組成物の(C)成分の非イオン系界面活性
剤は、前記一般式（）または（）で表される
シロキサン化合物である。
前記一般式（）において、複数のＲは同一で
も異なつていてもよく、一価の炭化水素基であ
り、例えばメチル基、エチル基、プロピル基、ブ
チル基等のアルキル基；シクロヘキシル基、シク
ロブチル基等のシクロアルキル基；フエニル基、
トリル基、キシリル基等の芳香族炭化水素基；あ
るいはこれらの基の炭素原子に結合している水素
原子の一部又は全部がフツ素、塩素などのハロゲ
ン原子等で置換されている基、例えばクロロメチ
ル基、３，３，３−トルフルオロプロピル基等を
挙げることができ、これらの中でも好ましい基は
メチル基である。また基Reは、前記式（）で
表される基であつて、該式中、R1は二価の炭化
水素基、例えばメチレン基、エチレン基、プロピ
レン基、テトラメチレン基、ペンタメチレン基、
ヘキサメチレン基等であり、好ましくはプロピレ
ン基である。また（）式中、R2は水素原子ま
たは一価の炭化水素基であり、例えばメチル基、
エチル基、プロピル基、ブチル基等であり、好ま
しくはメチル基である。更に（）式中、ａは１
以上の整数であつて、得られる組成物の硬化物が
十分に低い水接触角を発現する点で、３〜20の整
数であることが好ましい。また一般式（）にお
いて、ｘは０以上の整数、好ましくは０であり、
ｙは１以上の整数、好ましくは３〜150の整数、
さらに好ましくは３〜10の整数であり、ｚは１以
上の整数であり、特に界面活性剤としての機能が
十分に発揮されることから、１〜15の整数、さら
には２〜10の整数であることが好適である。
また一般式（）のシロキサン化合物におい
て、R.Re．ｘ，ｙ及びｚは、前記の通りである
が、Ｒ及びReを表す式（）中のR2は、メチル
基が好ましく、またｘ＋ｙ＋ｚが３〜10の整数、
特に４であることが好ましい。
上述した一般式（）及び（）で表されるシ
ロキサン化合物からなる非イオン系界面活性剤は
１種単独でも２種以上の組み合わせでも使用する
ことができる。
これらの非イオン系界面活性剤において、最も
重要なことは、そのシロキサン化合物が、炭素原
子に結合した水素原子を有していることである。
即ち、この水素原子の存在により、本発明の組成
物を硬化した時、成分(B)または成分(A)と該非イオ
ン系界面活性剤であるシロキサン化合物が反応し
て硬化物中に組み込まれ、非イオン系界面活性剤
が硬化物中に安定に保持され、ブリードアウト等
の不都合が有効に回避され、また後述する実施例
からも明らかな通り、親水性が安定に保持され、
さらに硬化物の寸法安定性も良好なものとなる。
この(C)成分の配合量は、通常、(A)成分100重量
部に対して、0.5〜15重量部の割合であり、組成
物中のケイ素原子に結合した水素原子／ケイ素原
子に結合した脂肪族不飽和炭化水素基のモル比が
0.5〜10、好ましくは0.75〜５となるように、(A)
成分と(B)成分の配合量に応じて適宜調節される。
(C)成分の配合量が多すぎると硬化遅れを生ずる
場合があり、少なすぎると本発明の組成物及びそ
の硬化物において親水性が低くなる場合がある。
本発明の組成物の(D)成分である白金族金属系触
媒は特に限定されないが、好ましくは白金化合物
であり、例えば、塩化白金酸、アルコール変性塩
化白金酸、白金−ビニルシロキサン錯体、白金
黒、塩化白金酸とオレフインもしくはアルデヒド
との錯体等を挙げることができる。この(D)成分の
配合量は、所望の硬化速度が得られるように適宜
調節できるが、通常、(A)成分に対して白金量（重
量）で１〜300ppmである。
本発明の組成物は、前記(A)〜(D)成分の他に、硬
化性シリコーン組成物に通常配合される成分、例
えば、充填剤、顔料、補強剤、可塑剤、反応抑制
剤等を適宜配合してもよい。
本発明の組成物は、通常、(A)成分及び(B)成分の
それぞれを含む甲、乙２剤からなる２成分型とし
て調製されるのが一般的である。この場合、(C)成
分はそれがケイ素原子に結合した水素原子あるい
は脂肪族不飽和炭化水素基のいずれを有するかに
応じて、いずれか一方の剤に配合される。すなわ
ち、(C)成分がケイ素原子に結合した水素原子を有
する場合は、(B)成分を含む乙剤に、(C)成分がケイ
素原子に結合した脂肪族不飽和炭化水素基を有す
る場合は、(A)成分を含む甲剤に配合される。しか
し、反応抑制剤を配合して(A)、(B)、(C)及び(D)成分
を同時に含む、一成分型として調製することもで
きる。用いられる反応抑制剤としては、例えば、
特公昭44−31476号に記載されているアセチレン
アルコール類；特公昭48−10947号に記載されて
いる高ビニル含有オルガノポリシロキサン；特公
昭55−41626号に記載されているトリアリルイソ
シアヌレート；特公昭63−56563号に記載されて
いるテトラメチルテトラビニルシクロテトラシロ
キサンなどが挙げられる。
〔実施例〕
つぎに、本発明の方法を実施例及び比較例によ
り詳細に説明する。なお、以下の例において、
「部」及び「％」は、それぞれ「重量部」及び
「重量％」を示す。
実施例１〜２、比較例１
各例において、両末端がジメチルビニルシロキ
シ基で封鎖され、主鎖がジメチルシロキサン単位
からなり、粘度が5000cSt（25℃）であるメチルビ
ニルポリシロキサン100部、平均組成式：
で表されるメチルハイドロジエンポリシロキサン
２部、塩化白金酸の１％イソプロピルアルコール
溶液をメチルビニルポリシロキサンの配合量に対
し白金分として40ppmとなる量、及び表１に示す
界面活性剤をそれぞれ１部配合してなる３種の組
成物を調製した。
得られた組成物を平滑なガラス板上に塗布して
室温で10分間硬化させた。この硬化物の表面に慎
重に蒸留水を１滴落とし３分後の水滴と硬化物の
表面との接触角（以下、単に「水接触角」とい
う）を測定した。結果を表１に示す。
[Industrial Field of Application] The present invention relates to a curable silicone composition, and particularly to a curable silicone composition whose cured product has excellent hydrophilicity. [Prior Art] Curable silicone compositions have excellent properties as cured products and are used in various applications such as lithographic printing plates, release agents, adhesives, paints, sealants, reflective sheets, and dental impression materials. There is. For example, in recent years, both condensation-curing and addition-curing curable silicone compositions have become widely used as impression materials. These have excellent properties such as being tasteless and odorless and having excellent strength as a cured product. However, since curable silicone compositions are hydrophobic, for example, when used as a dental impression material to take a mold of a moist oral cavity, only impressions with inaccurate dimensions can be obtained; When creating a model by casting plaster mud on an impression, there was a problem with the wetness of the plaster mud, making it impossible to obtain an accurate model. Therefore, as a curable silicone composition having hydrophilic properties, a curable silicone composition containing a nonionic surfactant containing a hydrophilic group has been proposed. (Publication No. 63-501368) [Problems to be Solved by the Invention] However, the curable silicone composition containing the above-mentioned nonionic surfactant containing a hydrophilic group has surface-active properties on the surface of the cured product. There are disadvantages such as bleeding of the agent, poor dimensional stability after curing, and the hydrophilicity of the cured product does not last for a long period of time. SUMMARY OF THE INVENTION An object of the present invention is to provide a curable silicone composition whose cured product has excellent hydrophilicity and dimensional stability, and whose hydrophilicity lasts for an indefinite period of time. [Means for Solving the Problems] In order to solve the above problems, the present inventors, as a result of intensive research, developed a nonionic surfactant having a hydrogen atom or an aliphatic unsaturated hydrocarbon group bonded to a silicon atom. The cured product of the silicone composition containing as an essential component has excellent hydrophilic properties, for example, the contact angle between the surface of the cured product and water is 65° or less, and this hydrophilicity persists for a long period of time. Heading, we arrived at the present invention. That is, the present invention provides (A) an organopolysiloxane having at least two silicon-bonded aliphatic unsaturated hydrocarbon groups in one molecule; (B) an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule; an organohydrodiene polysiloxane having 3 hydrogen atoms in an amount such that the hydrogen atoms bonded to silicon atoms in the component are 0.5 to 10 per one aliphatic unsaturated hydrocarbon group in the component (A); (C) The following general formula (): [In the formula, R may be the same or different and is a monovalent hydrocarbon group, and R e is the following formula (): -R 1 O (C 2 H 4 O) a R 2 () (where R 1 is a divalent hydrocarbon group, a is an integer of 1 or more), x is an integer of 0 or more, y is an integer of 1 or more, z is , is an integer of 1 or more,] or the following general formula (): [In the formula, R, R e . x, y, and z are as described above.] A nonionic surfactant consisting of a siloxane compound represented by: 0.5 per 100 parts by weight of component (A)
-15 parts by weight, and (D) a platinum group metal catalyst, 1 to 300 ppm in terms of platinum group metal based on component (A). The organopolysiloxane which is component (A) of the composition of the present invention contains at least two aliphatic unsaturated hydrocarbon groups bonded to a silicon atom in one molecule, and may be linear, branched or It may be in the form of a two-dimensional or three-dimensional network structure, or a mixture thereof. Examples of aliphatic unsaturated hydrocarbon groups include vinyl groups,
Examples thereof include an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a vinyl group is preferable.
Examples of organic groups bonded to silicon atoms other than aliphatic unsaturated hydrocarbon groups include alkyl groups such as methyl, ethyl and propyl groups; aromatic hydrocarbon groups such as phenyl and tolyl groups; cyclohexyl groups; Alicyclic hydrocarbon groups such as cycloheptyl groups; or groups in which some or all of the hydrogen atoms bonded to carbon atoms of these hydrocarbon groups are substituted with halogen atoms, etc., such as chloromethyl groups, 3 ，
Examples include 3,3-trifluoropropyl group. Among these, preferred are a methyl group, a phenyl group, and a 3,3,3-trifluoropropyl group. Particularly preferred organopolysiloxanes (A) include those in which all substituents other than aliphatic unsaturated hydrocarbon groups are methyl groups, or those consisting of methyl groups and phenyl groups. The viscosity of the organopolysiloxane of component (A) at 25°C is usually 50 cSt or more, preferably 100 cSt or more.
~5000000cSt. The organohydrodiene polysiloxane which is the component (B) of the composition of the present invention has at least three silicon-bonded hydrogen atoms in one molecule, and may be linear, branched, or cyclic. It may be of a structure. Preferably it is linear. In this organohydrodiene polysiloxane, organic groups other than hydrogen atoms bonded to silicon atoms are the same as those exemplified as substituents other than aliphatic unsaturated hydrocarbon groups in the organopolysiloxane (A) above. can be mentioned. The viscosity of component (B) organohydrodiene polysiloxane at 25°C is usually 0.5 to 10,000 cSt,
Preferably it is 1 to 1000 cSt. The blending amount of component (B) of the present invention is such that the number of silicon-bonded hydrogen atoms in the component is 0.5 to 10, preferably 0.5 to 10 per aliphatic unsaturated hydrocarbon group in component (A). The amount is a ratio of 0.75 to 10 pieces. If the amount of component (B) is too large, the cured product of the resulting composition may become brittle or there may be an excess of hydrosilyl groups (Si-
If H) remains, it may cause changes in physical properties over time, and if it is too small, the composition tends to be insufficiently cured. The nonionic surfactant as component (C) of the composition of the present invention is a siloxane compound represented by the above general formula () or (). In the general formula (), a plurality of R's may be the same or different and are monovalent hydrocarbon groups, such as alkyl groups such as methyl group, ethyl group, propyl group, butyl group; cyclohexyl group, cyclobutyl group. Cycloalkyl groups such as groups; phenyl groups,
Aromatic hydrocarbon groups such as tolyl and xylyl groups; or groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms such as fluorine and chlorine, e.g. Examples include chloromethyl group, 3,3,3-trifluoropropyl group, and among these, methyl group is preferred. Furthermore, the group R e is a group represented by the above formula (), in which R 1 is a divalent hydrocarbon group, such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, a pentamethylene group. ,
It is a hexamethylene group, etc., and preferably a propylene group. In the formula (), R 2 is a hydrogen atom or a monovalent hydrocarbon group, such as a methyl group,
Examples include ethyl group, propyl group, butyl group, and preferably methyl group. Furthermore, in the formula (), a is 1
Among the above integers, an integer of 3 to 20 is preferable in that the resulting cured product of the composition exhibits a sufficiently low water contact angle. Furthermore, in the general formula (), x is an integer greater than or equal to 0, preferably 0,
y is an integer of 1 or more, preferably an integer of 3 to 150,
More preferably, it is an integer of 3 to 10, and z is an integer of 1 or more, especially an integer of 1 to 15, more preferably an integer of 2 to 10, since the function as a surfactant is sufficiently exhibited. It is preferable that there be. Further, in the siloxane compound of general formula (), RR e . x, y and z are as described above, but R 2 in the formula () representing R and Re is preferably a methyl group, and x + y + z is an integer of 3 to 10,
In particular, it is preferably 4. The nonionic surfactants made of the siloxane compounds represented by the above-mentioned general formulas () and () can be used alone or in combination of two or more. The most important thing about these nonionic surfactants is that the siloxane compound has a hydrogen atom bonded to a carbon atom.
That is, due to the presence of this hydrogen atom, when the composition of the present invention is cured, component (B) or component (A) and the nonionic surfactant siloxane compound react and are incorporated into the cured product. The nonionic surfactant is stably retained in the cured product, problems such as bleed-out are effectively avoided, and as is clear from the examples described later, hydrophilicity is stably retained,
Furthermore, the dimensional stability of the cured product is also good. The amount of component (C) is usually 0.5 to 15 parts by weight per 100 parts by weight of component (A). The molar ratio of aliphatic unsaturated hydrocarbon groups is
(A) so that it is 0.5-10, preferably 0.75-5.
It is adjusted as appropriate depending on the amount of the component and component (B). If the amount of component (C) is too large, curing may be delayed, and if it is too small, the composition of the present invention and its cured product may have low hydrophilicity. The platinum group metal catalyst that is component (D) of the composition of the present invention is not particularly limited, but is preferably a platinum compound, such as chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum-vinylsiloxane complex, platinum black , a complex of chloroplatinic acid and an olefin or an aldehyde, and the like. The amount of component (D) to be blended can be adjusted as appropriate to obtain a desired curing speed, but is usually 1 to 300 ppm of platinum (by weight) relative to component (A). In addition to the above-mentioned components (A) to (D), the composition of the present invention also contains components that are usually added to curable silicone compositions, such as fillers, pigments, reinforcing agents, plasticizers, and reaction inhibitors. They may be blended as appropriate. The composition of the present invention is generally prepared as a two-component type consisting of two agents, A and B, each containing component (A) and component (B). In this case, component (C) is blended into one of the agents depending on whether it has a hydrogen atom bonded to a silicon atom or an aliphatic unsaturated hydrocarbon group. In other words, if component (C) has a hydrogen atom bonded to a silicon atom, the agent containing component (B) may contain an aliphatic unsaturated hydrocarbon group bonded to a silicon atom. , is added to Agent A containing component (A). However, it can also be prepared as a one-component type containing components (A), (B), (C) and (D) at the same time by adding a reaction inhibitor. Examples of reaction inhibitors used include:
Acetylene alcohols described in Japanese Patent Publication No. 44-31476; high vinyl-containing organopolysiloxanes described in Japanese Patent Publication No. 48-10947; triallylisocyanurate described in Japanese Patent Publication No. 55-41626; Examples include tetramethyltetravinylcyclotetrasiloxane described in Publication No. 63-56563. [Example] Next, the method of the present invention will be explained in detail with reference to Examples and Comparative Examples. In addition, in the following example,
"Parts" and "%" indicate "parts by weight" and "% by weight," respectively. Examples 1 to 2, Comparative Example 1 In each example, 100 parts of methylvinylpolysiloxane whose both ends are blocked with dimethylvinylsiloxy groups, whose main chain consists of dimethylsiloxane units, and whose viscosity is 5000 cSt (25°C), average Composition formula: 2 parts of methylhydrodiene polysiloxane represented by , 1% isopropyl alcohol solution of chloroplatinic acid in an amount that gives a platinum content of 40 ppm based on the amount of methyl vinyl polysiloxane, and 1 part each of the surfactants shown in Table 1. Three types of compositions were prepared. The resulting composition was applied onto a smooth glass plate and cured at room temperature for 10 minutes. One drop of distilled water was carefully dropped on the surface of this cured product, and after 3 minutes, the contact angle between the water drop and the surface of the cured product (hereinafter simply referred to as "water contact angle") was measured. The results are shown in Table 1.
【表】
比較例 ２〜４
各例において、界面活性剤として表２に示す化
合物を用いた以外は実施例１と同様にして組成物
を調製し、実施例１と同様にして水接触角を測定
した。結果を表２に示す。[Table] Comparative Examples 2 to 4 In each example, a composition was prepared in the same manner as in Example 1 except that the compound shown in Table 2 was used as a surfactant, and the water contact angle was determined in the same manner as in Example 1. It was measured. The results are shown in Table 2.
【表】【table】
【表】
比較例２及び３は、用いた界面活性剤がケイ素
原子に結合した水素原子及び脂肪族不飽和炭化水
素基を含有しない例であり、それぞれの組成物は
硬化後24時間、48時間後には硬化物の表面に界面
活性剤がブリードしていることが目視で確認され
た。また比較例４はシロキサン単位を含有しない
界面活性剤を使用した例であり、組成物の硬化速
度が遅く、しかも硬化後に表面に界面活性剤のブ
リードが認められた。
実施例３〜４、比較例５〜８
各例において、実施例１及び２並びに比較例１
〜４で得られた硬化物をそれぞれ２つに切断し、
一方の片を10日間室温下に放置し、他方の片を２
日間流水で洗つて２種の試験片を得た。得られた
２種の試験片のそれぞれについて実施例１と同様
にして水接触角を測定した。結果を表３に示す。[Table] Comparative Examples 2 and 3 are examples in which the surfactants used do not contain hydrogen atoms bonded to silicon atoms or aliphatic unsaturated hydrocarbon groups, and the respective compositions were cured for 24 hours and 48 hours after curing. Afterward, it was visually confirmed that the surfactant was bleeding onto the surface of the cured product. Comparative Example 4 is an example in which a surfactant containing no siloxane units was used, and the curing speed of the composition was slow, and bleeding of the surfactant was observed on the surface after curing. Examples 3-4, Comparative Examples 5-8 In each example, Examples 1 and 2 and Comparative Example 1
Cut each of the cured products obtained in ~4 into two pieces,
Leave one piece at room temperature for 10 days and leave the other piece for 2 days.
Two types of test pieces were obtained by washing with running water for several days. The water contact angle was measured in the same manner as in Example 1 for each of the two types of test pieces obtained. The results are shown in Table 3.
【表】
実施例１及び２で得られた硬化物は10日間室温
下に放置してもその表面に界面活性剤のブリード
は認められなかつた。
実施例５〜６、比較例９
実施例１、２及び比較例１で得られた３種の組
成物を、それぞれ深さ１mm×縦20mm×横20mmの内
寸法の金型を上下に２個重ね合わせてなる深さ２
mmの割型の中に注型して硬化させた。組成物の硬
化後、割型の上半分を取外し、硬化物の上半分を
切取り、切断面の水接触角を実施例１と同様にし
て測定した。その結果、実施例１、２及び比較例
１の硬化物の切断面の水接触角は、それぞれ63゜、
60゜及び94゜であつた。
実施例７〜８、比較例10〜12
実施例１及び２、並びに比較例２、３及び４で
得られた組成物を、それぞれ金型に注型して長さ
50mm×幅20mm×厚さ４mmの長方体状で長さ方向に
40mmの間隔で２つの目盛りを有する成形体を複数
体製した。得られた各成形体を、２群に分け、一
方を室温で相対湿度20％の雰囲気中に放置し、他
方を流水中で24時間洗浄した後、各成形体の目盛
りの間隔を測定し、寸法変化率を式：
〔40−（放置後の目盛りの間隔）〕／40
で求めた。結果を表４で示す。[Table] Even when the cured products obtained in Examples 1 and 2 were left at room temperature for 10 days, no surfactant bleeding was observed on their surfaces. Examples 5 to 6, Comparative Example 9 The three types of compositions obtained in Examples 1 and 2 and Comparative Example 1 were placed in two upper and lower molds each having internal dimensions of 1 mm deep x 20 mm long x 20 mm wide. Depth 2 of overlapping
It was poured into a split mold of mm and allowed to harden. After curing the composition, the upper half of the split mold was removed, the upper half of the cured product was cut off, and the water contact angle of the cut surface was measured in the same manner as in Example 1. As a result, the water contact angles of the cut surfaces of the cured products of Examples 1 and 2 and Comparative Example 1 were 63° and 63°, respectively.
The angles were 60° and 94°. Examples 7 to 8, Comparative Examples 10 to 12 The compositions obtained in Examples 1 and 2 and Comparative Examples 2, 3, and 4 were cast into molds, and the length was measured.
50mm x width 20mm x thickness 4mm rectangular shape in length direction
A plurality of molded bodies having two scales at an interval of 40 mm were manufactured. The obtained molded bodies were divided into two groups, one group was left in an atmosphere with a relative humidity of 20% at room temperature, and the other was washed in running water for 24 hours, and then the interval between the scales of each molded body was measured, The rate of dimensional change was determined using the formula: [40 - (interval between scales after standing)]/40. The results are shown in Table 4.
本発明の硬化性シリコーン組成物は、その硬化
物が優れた親水性及び寸法安定性を有し、しかも
その親水性が長期間にわたつて持続する。そのた
め、例えば、歯科用印象材、平版印刷版、離型
剤、反射シート、接着剤、塗料、シーラントとし
て好適である。さらに、本発明の組成物は、例え
ば、コンタクトレンズ、シリコーン移植片、傷の
包帯等の用途にも好適である。特に、歯科用印象
材として好適である。
The cured product of the curable silicone composition of the present invention has excellent hydrophilicity and dimensional stability, and its hydrophilicity persists for a long period of time. Therefore, it is suitable for use as, for example, dental impression materials, lithographic printing plates, mold release agents, reflective sheets, adhesives, paints, and sealants. Additionally, the compositions of the invention are suitable for use in, for example, contact lenses, silicone implants, wound dressings, and the like. It is particularly suitable as a dental impression material.
Claims (1)
不飽和炭化水素基を少なくとも２個有するオル
ガノポリシロキサン、 (B) １分子中にケイ素原子に結合した水素原子を
少なくとも３個有するオルガノハイドロジエン
ポリシロキサン、当該成分中のケイ素原子に結
合した水素原子が前記(A)成分中の脂肪族不飽和
炭化水素基１個に対して0.5〜10個の割合とな
る量、 (C) 下記一般式（）： 〔式中、Ｒは、同一でも異なつていてもよ
く、 一価の炭化水素基であり、 Reは、下記式（）： −R1O（C2H4O）aR2 （） （ここでR1は二価の炭化水素基であり、 ａは１以上の整数である）で表される基であ
り、 ｘは、０以上の整数、 ｙは、１以上の整数、 ｚは、１以上の整数である、〕 または下記一般式（）： 〔式中、Ｒ，Re．ｘ，ｙ及びｚは、前記の
通りである、〕 で表されるシロキサン化合物から成る非イオン
系界面活性剤、前記(A)成分100重量部当り、0.5
〜15重量部、及び、 (D) 白金族金属系触媒、前記(A)成分に対して白金
族金属換算で１〜300ppm、 を含有して成る硬化性シリコーン組成物。[Scope of Claims] 1 (A) an organopolysiloxane having at least two aliphatic unsaturated hydrocarbon groups bonded to a silicon atom in one molecule; (B) an organopolysiloxane having a hydrogen atom bonded to a silicon atom in one molecule; An organohydrodiene polysiloxane having at least 3 hydrogen atoms in an amount such that the number of silicon-bonded hydrogen atoms in the component is 0.5 to 10 per one aliphatic unsaturated hydrocarbon group in the component (A). , (C) The following general formula (): [In the formula, R may be the same or different and is a monovalent hydrocarbon group, and R e is the following formula (): -R 1 O (C 2 H 4 O) a R 2 () (where R 1 is a divalent hydrocarbon group, a is an integer of 1 or more), x is an integer of 0 or more, y is an integer of 1 or more, z is , is an integer of 1 or more,] or the following general formula (): [In the formula, R, R e . x, y, and z are as described above.] A nonionic surfactant consisting of a siloxane compound represented by: 0.5 per 100 parts by weight of component (A)
-15 parts by weight, and (D) a platinum group metal catalyst, 1 to 300 ppm in terms of platinum group metal based on component (A).
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1126025A JPH02305857A (en) | 1989-05-19 | 1989-05-19 | Curable silicone composition |
| US07/525,047 US5064891A (en) | 1989-05-19 | 1990-05-18 | Curable silicone compositions |
| DE69028346T DE69028346T2 (en) | 1989-05-19 | 1990-05-18 | Curable silicone materials |
| EP90305414A EP0398745B1 (en) | 1989-05-19 | 1990-05-18 | Curable silicone compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1126025A JPH02305857A (en) | 1989-05-19 | 1989-05-19 | Curable silicone composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02305857A JPH02305857A (en) | 1990-12-19 |
| JPH0536458B2 true JPH0536458B2 (en) | 1993-05-31 |
Family
ID=14924840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1126025A Granted JPH02305857A (en) | 1989-05-19 | 1989-05-19 | Curable silicone composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02305857A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4129613A1 (en) * | 1991-09-06 | 1993-03-11 | Wacker Chemie Gmbh | STORAGE-RESISTANT, PERMANENTLY WET-WETTABLE VULCANISATE-RESULTING POLYSILOXANE |
| JP4528419B2 (en) * | 2000-05-30 | 2010-08-18 | 東レ・ダウコーニング株式会社 | Fabric softener composition |
| JP4626759B2 (en) * | 2005-08-01 | 2011-02-09 | 信越化学工業株式会社 | Injection molding method of two-part silicone resin composition |
| ATE525057T1 (en) * | 2007-12-18 | 2011-10-15 | 3M Innovative Properties Co | DENTAL COMPOSITION WITH A SURFACTANT AND A COMPOUND CONTAINING F, METHOD OF PRODUCTION AND USE THEREOF |
| JP7403281B2 (en) * | 2019-11-01 | 2023-12-22 | ダウ・東レ株式会社 | Curable silicone composition and cured product thereof for forming microchannel, microchannel device and manufacturing method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6356561A (en) * | 1986-08-26 | 1988-03-11 | Shin Etsu Chem Co Ltd | Silicone composition for release film |
-
1989
- 1989-05-19 JP JP1126025A patent/JPH02305857A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6356561A (en) * | 1986-08-26 | 1988-03-11 | Shin Etsu Chem Co Ltd | Silicone composition for release film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02305857A (en) | 1990-12-19 |
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