JPH0569863B2 - - Google Patents
Info
- Publication number
- JPH0569863B2 JPH0569863B2 JP8655088A JP8655088A JPH0569863B2 JP H0569863 B2 JPH0569863 B2 JP H0569863B2 JP 8655088 A JP8655088 A JP 8655088A JP 8655088 A JP8655088 A JP 8655088A JP H0569863 B2 JPH0569863 B2 JP H0569863B2
- Authority
- JP
- Japan
- Prior art keywords
- organopolysiloxane
- group
- molecule
- component
- bonded
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001296 polysiloxane Polymers 0.000 claims description 38
- 125000001931 aliphatic group Chemical group 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 125000000962 organic group Chemical group 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- -1 mercaptopropyl group Chemical group 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 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
- 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 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
産業上の利用分野
本発明は、長時間太陽光等に曝しても硬化物が
劣化することがない耐光性に優れた紫外線反応型
オルガノポリシロキサン組成物に関する。
従来の技術及び発明が解決しようとする課題
従来より、紫外線反応型オルガノポリシロキサ
ン組成物としては、分子中にケイ素原子に結合し
た脂肪族不飽和基を有するオルガノポリシロキサ
ンと、ケイ素原子に結合したメルカプト基含有有
機基を有するオルガノポリシロキサンとを主成分
とし、紫外線を照射することにより、上記不飽和
基とメルカプト基との付加反応により硬化するオ
ルガノポリシロキサン組成物が知られている。
このオルガノポリシロキサン組成物は、硬化が
速い上、一液型で触媒を混合する必要がなく、ま
た可使時間が長いなど作業性は優れているが、例
えばケイ素に結合した脂肪族不飽和基がビニル基
であるオルガノポリシロキサンと、ケイ素に結合
したメルカプト基含有有機基がメルカプトプロピ
ル基であるオルガノポリシロキサンとを使用した
場合、紫外線照射により硬化した組成物を太陽光
や紫外線に長時間曝しておくと、シロキサンの分
解が進んで遂には硬化物が原形を留めなくなると
いう欠点を有する。このことは、メルカプト−ビ
ニル基反応型のオルガノポリシロキサン組成物に
とつて本質的な欠点であり、特に上記オルガノポ
リシロキサン組成物を硬化後に太陽光や紫外線に
曝される状態に使用する場合、例えば光フアイバ
用被覆剤、ガラスレンズの接着剤、ガラススリー
ブのコーテイング剤等として用いる場合は重大な
問題となる。
従つて耐候性の高い硬化物を与える紫外線反応
型オルガノポリシロキサン組成物の開発が望まれ
る。
本発明は上記事情に鑑みなされたもので、硬化
後に太陽光や紫外線に長時間曝しても硬化物が劣
化せず、その硬化物が硬化時のままの状態で保持
される耐候性に優れた紫外線反応型オルガノポリ
シロキサン組成物を提供することを目的とする。
課題を解決するための手段及び作用
本発明者らは上記目的を達成するため鋭意検討
を重ねた結果、メルカプト基−脂肪族不飽和基反
応型オルガノポリシロキサン組成物において、下
記式(1)
INDUSTRIAL APPLICATION FIELD The present invention relates to an ultraviolet-reactive organopolysiloxane composition which has excellent light resistance and whose cured product does not deteriorate even when exposed to sunlight or the like for a long period of time. Conventional techniques and problems to be solved by the invention Conventionally, ultraviolet-reactive organopolysiloxane compositions include organopolysiloxanes having aliphatic unsaturated groups bonded to silicon atoms in the molecule, and organopolysiloxanes having aliphatic unsaturated groups bonded to silicon atoms in the molecule. Organopolysiloxane compositions are known that contain an organopolysiloxane having a mercapto group-containing organic group as a main component and are cured by an addition reaction between the unsaturated group and the mercapto group when irradiated with ultraviolet rays. This organopolysiloxane composition has excellent workability, such as quick curing, no need to mix a catalyst as it is a one-component type, and a long pot life. When using an organopolysiloxane in which the is a vinyl group and an organopolysiloxane in which the mercapto group-containing organic group bonded to silicon is a mercaptopropyl group, the composition cured by ultraviolet irradiation may be exposed to sunlight or ultraviolet light for a long time. If left untreated, the decomposition of the siloxane progresses and the cured product eventually loses its original shape. This is an essential drawback for mercapto-vinyl group-reactive organopolysiloxane compositions, especially when the organopolysiloxane compositions are used in conditions where they are exposed to sunlight or ultraviolet rays after curing. For example, when used as a coating agent for optical fibers, an adhesive for glass lenses, a coating agent for glass sleeves, etc., a serious problem arises. Therefore, it is desired to develop an ultraviolet-reactive organopolysiloxane composition that provides a cured product with high weather resistance. The present invention was developed in view of the above circumstances, and has excellent weather resistance such that the cured product does not deteriorate even if exposed to sunlight or ultraviolet rays for a long time after curing, and the cured product remains in the same state as when cured. An object of the present invention is to provide an ultraviolet-reactive organopolysiloxane composition. Means and Effects for Solving the Problems In order to achieve the above object, the present inventors have made intensive studies and found that in a mercapto group-aliphatically unsaturated group reactive organopolysiloxane composition, the following formula (1) is used.
【式】
（但し、式中Ｒは一価の脂肪族炭化水素基であ
る。）
で示される化合物を後述する配合量で配合した場
合、その硬化物が太陽光や紫外線等に長時間曝さ
れた際にシロキサンが分解するのを可及的に抑制
し得、経時による硬化物の劣化がほとんどない、
耐候性に優れた硬化物を与える紫外線反応型オル
ガノポリシロキサン組成物が得られることを知見
し、本発明をなすに至つた。
従つて、本発明は、
(A) 下記に示す(イ)成分中の脂肪族不飽和基一個に
対して(ロ)成分中のメルカプト基が0.5〜５個と
なるような(イ)成分と(ロ)成分との混合物又は分子
中に脂肪族不飽和基一個に対してメルカプト基
を0.5〜５個の割合で有する(ハ)成分のオルガノ
ポリシロキサン成分、
(イ) １分子中に少なくとも１個のケイ素原子に
結合した脂肪族不飽和基を有するオルガノポ
リシロキサン、
(ロ) １分子中に少なくとも１個のケイ素原子に
結合したメルカプト基含有有機基を有するオ
ルガノポリシロキサン、
(ハ) １分子中に少なくとも１個のケイ素原子に
結合した脂肪族不飽和基と少なくとも１個の
ケイ素原子に結合したメルカプト基含有有機
基とを有するオルガノポリシロキサン、及
び、
(B) 光重合開始剤を(A)成分の総量に対して20重量
％以下
を配合してなる紫外線反応型オルガノポリシロキ
サン組成物において、
(C) 下記一般式(1)[Formula] (However, in the formula, R is a monovalent aliphatic hydrocarbon group.) If the compound represented by the following formula is blended in the amount described below, the cured product will not be exposed to sunlight or ultraviolet rays for a long time. It can suppress the decomposition of siloxane as much as possible when it is cured, and there is almost no deterioration of the cured product over time.
It was discovered that an ultraviolet-reactive organopolysiloxane composition that gives a cured product with excellent weather resistance can be obtained, and the present invention was completed. Therefore, the present invention provides (A) component (A) in which the number of mercapto groups in component (B) is 0.5 to 5 for each aliphatic unsaturated group in component (A) shown below. (b) An organopolysiloxane component of component (c) having a ratio of 0.5 to 5 mercapto groups per aliphatic unsaturated group in the mixture or molecule with component (b) At least one mercapto group in one molecule. an organopolysiloxane having an aliphatic unsaturated group bonded to at least one silicon atom; (b) an organopolysiloxane having an organic group containing a mercapto group bonded to at least one silicon atom in one molecule; (B) an organopolysiloxane having at least one aliphatic unsaturated group bonded to a silicon atom and at least one mercapto group-containing organic group bonded to a silicon atom; ) In an ultraviolet-reactive organopolysiloxane composition containing 20% by weight or less based on the total amount of components, (C) the following general formula (1)
【式】
（但し、式中Ｒは一価の脂肪族炭化水素基であ
る。）で示される化合物を(A)成分の総量に対し
0.05〜10重量％配合してなることを特徴とする紫
外線反応型オルガノポリシロキサン組成物を提供
する。
以下、本発明につき更に詳述する。
本発明においては、(イ)１分子中に少なくとも１
個のケイ素原子に結合した脂肪族不飽和基を有す
るオルガノポリシロキサンと(ロ)１分子中に少なく
とも１個のケイ素原子に結合したメルカプト基含
有有機基を有するオルガノポリシロキサンとの混
合物、又は、(ハ)１分子中に少なくとも１個のケイ
素原子に結合した脂肪族不飽和基と少なくとも１
個のケイ素原子に結合したメルカプト基含有有機
基とを有するオルガノポリシロキサンを使用す
る。
ここで、(イ)成分の１分子中に少なくとも１個の
ケイ素原子に結合した脂肪族不飽和基を有するオ
ルガノポリシロキサンとしては、１分子中に少な
くとも１個のシロキサン結合（≡Si−Ｏ−Si≡）
とケイ素に直結した少なくとも１個の脂肪族不飽
和基とを有するオルガノポリシロキサンであれば
別に制限はなく、種々のオルガノポリシロキサン
を用いることができる。
この場合、分子中の脂肪族不飽和基としては、
例えばビニル基、アリル基等が挙げられ、更にこ
の脂肪族不飽和以外の残余の有機基としては、例
えばメチル基、エチル基、プロピル基などのアル
キル基、フエニル基、トリル基などのアリール
基、シクロヘキシル基、シクロブチル基などのシ
クロアルキル基、これらの炭化水素基の炭素原子
に結合した水素基を部分的にハロゲン原子、シア
ノ基、メルカプト基等で置換した基などが例示さ
れ、これらは同種または異種の組み合わせとする
ことができる。
また、上記オルガノポリシロキサンは、直鎖
状、分子鎖状、網状、環状等、種々のものを使用
し得る。
上述のような分子中に少なくとも１個のケイ素
に結合した脂肪族不飽和基を有するオルガノポリ
シロキサンとして具体的には下記式(2)〜(9)[Formula] (However, R in the formula is a monovalent aliphatic hydrocarbon group) is added to the total amount of component (A).
Provided is an ultraviolet-reactive organopolysiloxane composition characterized by containing 0.05 to 10% by weight. The present invention will be explained in more detail below. In the present invention, (a) at least one in one molecule
a mixture of an organopolysiloxane having an aliphatic unsaturated group bonded to at least one silicon atom and (b) an organopolysiloxane having at least one mercapto group-containing organic group bonded to a silicon atom in one molecule, or (c) At least one aliphatic unsaturated group bonded to at least one silicon atom in one molecule and at least one
An organopolysiloxane having mercapto group-containing organic groups bonded to six silicon atoms is used. Here, as the organopolysiloxane having at least one aliphatic unsaturated group bonded to a silicon atom in one molecule of component (a), at least one siloxane bond (≡Si-O- Si≡)
There is no particular restriction on the organopolysiloxane as long as it has at least one aliphatic unsaturated group directly bonded to silicon, and various organopolysiloxanes can be used. In this case, the aliphatic unsaturated group in the molecule is
For example, vinyl groups, allyl groups, etc. are mentioned, and the remaining organic groups other than the aliphatic unsaturation include, for example, alkyl groups such as methyl, ethyl, and propyl groups; aryl groups such as phenyl and tolyl groups; Examples include cycloalkyl groups such as cyclohexyl and cyclobutyl groups, and groups in which the hydrogen group bonded to the carbon atom of these hydrocarbon groups is partially substituted with a halogen atom, cyano group, mercapto group, etc. It can be a combination of different types. Furthermore, various organopolysiloxanes such as linear, molecular chain, network, and cyclic organopolysiloxanes can be used. Specifically, the organopolysiloxanes having at least one silicon-bonded aliphatic unsaturated group in the molecule as described above include the following formulas (2) to (9).
【表】
｜
CH−CH＝CH２
[Table] ｜
CH−CH= CH2
【表】
｜ ｜
CH＝CH２ CH３
（但し、上記式中ｐ，ｑ，ｒ，ｓ，ｔ，ｕ，ｖ
はいずれも正の整数である。）
で示されるオルガノポリシロキサンや、
CH3SiO1 [Table] ｜ ｜
CH=CH 2 CH 3
(However, in the above formula, p, q, r, s, t, u, v
are all positive integers. ) and organopolysiloxanes represented by CH 3 SiO 1
Claims (1)
又は上記(ハ)成分のオルガノポリシロキサン成
分、 (イ) １分子中に少なくとも１個のケイ素原子に
結合した脂肪族不飽和基を有するオルガノポ
リシロキサン、 (ロ) １分子中に少なくとも１個のケイ素原子に
結合したメルカプト基含有有機基を有するオ
ルガノポリシロキサン、 (ハ) １分子中に少なくとも１個のケイ素原子に
結合した脂肪族不飽和基と少なくとも１個の
ケイ素原子に結合したメルカプト基含有有機
基とを有するオルガノポリシロキサン、及
び、 (B) 光重合開始剤を(A)成分の総量に対して20重量
％以下 を配合してなる紫外線反応型オルガノポリシロ
キサン組成物において、 (C) 下記一般式(1) 【式】 （但し、式中Ｒは一価の脂肪族炭化水素基であ
る。）で示される化合物を(A)成分の総量に対し
0.05〜10重量％配合してなることを特徴とする紫
外線反応型オルガノポリシロキサン組成物。[Scope of Claims] 1(A) A mixture of the above components (a) and (b) as shown below, or an organopolysiloxane component of the above (c) component, (b) at least one silicon in one molecule an organopolysiloxane having an aliphatic unsaturated group bonded to an atom; (b) an organopolysiloxane having at least one mercapto group-containing organic group bonded to a silicon atom in one molecule; (c) an organopolysiloxane having at least one mercapto group-containing organic group in one molecule an organopolysiloxane having an aliphatic unsaturated group bonded to one silicon atom and an organic group containing a mercapto group bonded to at least one silicon atom; In a UV-reactive organopolysiloxane composition containing 20% by weight or less based on the total amount, (C) the following general formula (1) [Formula] (wherein R is a monovalent aliphatic hydrocarbon group) ) relative to the total amount of component (A).
An ultraviolet-reactive organopolysiloxane composition characterized by containing 0.05 to 10% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8655088A JPH01259065A (en) | 1988-04-08 | 1988-04-08 | UV-reactive organopolysiloxane composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8655088A JPH01259065A (en) | 1988-04-08 | 1988-04-08 | UV-reactive organopolysiloxane composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01259065A JPH01259065A (en) | 1989-10-16 |
| JPH0569863B2 true JPH0569863B2 (en) | 1993-10-01 |
Family
ID=13890114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8655088A Granted JPH01259065A (en) | 1988-04-08 | 1988-04-08 | UV-reactive organopolysiloxane composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01259065A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7694933B2 (en) * | 2020-02-28 | 2025-06-18 | デュポン・東レ・スペシャルティ・マテリアル株式会社 | Ultraviolet-curable silicone composition and sealing material or sheet film made using the same |
| JP2023082381A (en) * | 2021-12-02 | 2023-06-14 | ローム・アンド・ハース・エレクトロニック・マテリアルズ・コリア・リミテッド | Curable silicone composition and its cured product |
-
1988
- 1988-04-08 JP JP8655088A patent/JPH01259065A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01259065A (en) | 1989-10-16 |
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