JP3568148B2 - Organopolysiloxane composition - Google Patents

Description

【００２０】
この場合、cは２〜２００の整数、dは０〜１００の整数、fは０〜２００の整数、gは０〜１００の整数である。
【００２１】
これらのオルガノハイドロジェンポリシロキサンの粘度は、２５℃において数ｃｓから数十万ｃｓの広い範囲でよい。なお、この成分（２）の使用量は、本発明の組成物の使用目的や用途等によって若干異なるが、一般的には前記した成分（１）のオルガノポリシロキサン１００重量部に対して０．１〜３０重量部の範囲とすればよいが、２０重量部以下であることが好ましい。
【００２２】
本発明で使用する成分（３）は、本発明におけるもっとも重要な成分であり、成分（ａ）は、下記化５に示される基本骨格をもつアセチレンアルコールである。尚、化５中のＲ^１及びＲ^２は、水素原子；メチル基、エチル基、プロピル基、イソプロピル基、ブチル基などの直鎖状もしくは分岐状のアルキル基；フェニル基、トリル基などのアリール基である。
【化５】

【００２３】
また、Ｒ^１及びＲ^２ は、互いに結合して環を形成していても良い。Ｒ^１とＲ^２の炭素原子総数は８個以下、特に５個以下であることが好ましい。Ｒ^１とＲ^２の炭素原子の総数が８個を越えると、初期硬化性が著しく低下する。
成分（ａ）の配合量は、成分（１）、（２）及び（４）の量により左右されるが、基本的には成分（１）１００重量部に対して、０．０１〜１．０重量部の範囲であればよい。
成分（ａ）の使用量が０．０１より少ないと制御硬化性が得られなくなり、また、１．０より多くなると初期硬化性が低下する。
【００２４】
本発明で使用することのできる成分（ａ）の具体例としては、例えば、３−メチル−１−ブチン−３−オール（沸点１０４℃）、３−メチル−１−ペンチン−３−オール（沸点１２１℃）、３，５−ジメチル−１−ヘキシン−３−オール（沸点１５０℃）、１−エチニル−１−シクロヘキサノール（沸点１８０℃）等を挙げることができる。
【００２５】
また、成分（ｂ）としては下記化６で表される基本骨格を持つ、シリル化されたアセチレンアルコールを使用する。
【化６】

化６中のＲ^３及びＲ^４は、水素原子；メチル基、エチル基、プロピル基、イソプロピル基、ブチル基などの直鎖状もしくは分岐状のアルキル基；フェニル基、トリル基などのアリール基であり、Ｒ^３及びＲ^４ は、互いに結合して環を形成していても良い。
【００２６】
Ｒ^３及びＲ^４の炭素原子の総数は８個以下であり、特に炭素原子の総数が５個以下であることが好ましい。Ｒ^３、Ｒ^４の炭素原子の総数が８個を越えると初期硬化性が低下する。また、Ｒ^５は、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基などの直鎖状もしくは分岐状のアルキル基；フェニル基、トリル基などのアリール基等から選択される。
【００２７】
本発明で使用することのできる成分（ｂ）の具体例としては、例えばトリメチル（３-メチル-１−ブチン−３−オキシ）シラン(沸点１１５℃）などを挙げることができる。
【００２８】
これら成分（３）の配合量は、成分（１）、（２）及び（４）の量により左右されるが、基本的には組成物中の成分（１）１００重量部に対して０．１〜６．０重量部となる量の範囲であればよい。成分（３）の使用量が０．１重量部より小さいと十分なポットライフが得られなくなり、６．０重量部より多くなると処理浴経時後の硬化性が低下する。さらに、（ａ）と（ｂ）の使用比率は５＜（ｂ）／（ａ）≦１００の範囲であることが必要である。この比率が５より小さいと、（ａ）と（ｂ）の使用総量が多い場合は初期の硬化性が低下し易く、（ａ）と（ｂ）の使用総量が少ない場合には十分なポットライフが得られ難い。また、この比率が１００より大きいと、処理浴経時で硬化性の低下が見られる。（ａ）と（ｂ）とは共に沸点が１３０℃から１７０℃の範囲にあることが好ましく、また、（ａ）と（ｂ）のいずれか一方の沸点が１３０℃以下の場合には、もう一方の沸点が１７０℃以上であることが好ましい。
【００２９】
この二種類の化合物を併用する本発明における制御系の作用機構は次のように考えられる。先ず少量の、成分（ａ）であるアセチレンアルコールが、処理浴調整後に触媒に強く配位して触媒活性を低下させる。一方、わずかながら進行する付加反応の基質として過剰に存在する、成分（ｂ）であるシリル化されたアセチレンアルコールが働き、シリル化されていないアセチレンアルコールの減少を抑制する。
【００３０】
つまり、シリル化されたアセチレンアルコールは付加反応の基質として働くため、アセチレンアルコールの消費（付加反応）を抑える。一方、系中でアセチレンアルコールの消費が抑えられるため、触媒活性の低い状態が長く続き、ＳｉＨの消費が抑えられる。以上の作用機構により初期硬化性を低下させるほどのアセチレンアルコールを使用しなくても、十分ポットライフの長い組成物を得ることができる。
【００３１】
本発明においては、付加硬化反応を有効に進行させるために、従来この種の付加触媒として公知の白金族系触媒を成分（４）として使用する。このような白金族系触媒としては、例えば、白金系、パラジウム系、ロジウム系等の触媒があるが、特に白金系触媒が好ましく、具体的には塩化白金酸、塩化白金酸のアルコール溶液やアルデヒド溶液、塩化白金酸と各種オレフィン、ビニルシロキサンとの錯体などが挙げられる。白金系触媒の添加量は触媒量とすればよいが、良好な硬化皮膜を得ると共に経済的な見地から、成分（１）及び（２）に対する白金族金属量として、１〜１，０００ｐｐｍの範囲とすることが好ましい。
【００３２】
本発明のシリコーン組成物には、上記成分以外に、任意成分をさらに添加することができる。例えば、剥離力を調整する目的で、ビニル基やケイ素原子に結合する水素原子を有しないオルガノポリシロキサン等を必要に応じて添加することができる。なお、任意成分の添加量は、本発明の効果を妨げない範囲で適宜決定することができる。
【００３３】
本発明のシリコーン組成物は、上記した成分（１）〜（４）及び任意成分の所定量を配合することにより得ることができるが、この場合、成分（４）をのぞく各成分をあらかじめ均一に混合した後成分（４）を添加することが好ましい。また、必要に応じてトルエン、キシレン、ｎ−ヘキサン等の有機溶剤に溶解して使用しても良い。
上記のごとく調製されたシリコーン組成物は、例えば紙、プラスチックフィルム等の基材に塗布された後、常法によって加熱硬化される。この様にして、本発明の組成物の硬化被膜が形成された基材は、剥離紙として使用に供される。
【００３４】
【発明の効果】
本発明のシリコーン組成物は、触媒に強く配位して触媒活性を低下させるアセチレンアルコール系付加制御剤の少量と、わずかながら進行する付加反応の基質として働くシリル化されたアセチレンアルコールの過剰量を同時に含有しているので、ポットライフが長く、処理浴が経時しても剥離特性や硬化性能に変化を生じないという利点がある。
【００３５】
【実施例】
次に本発明を、実施例及び比較例によって更に説明するが、本発明はこれらによって限定されるものではない。尚、例中の部は重量部を表し、例中における物性値は下記の試験法による測定値を意味する。
処理浴粘度
本発明のオルガノポリシロキサン組成物の、調製直後における３０℃での粘度を初期粘度として、この組成物を３０℃で２４時間保存した後の粘度を経時粘度とした。
【００３６】
硬化性
初期の硬化性は、本発明のオルガノポリシロキサン組成物調製直後にポリエチレンラミネート紙に０．６ｇ／ｍ^２となるように塗布し、１００℃の熱風式乾燥機中で所定時間加熱して形成される硬化皮膜を指で数回こすったときの、くもり及び脱落の有無を目視により評価し、硬化に要した時間を用いて硬化性を示した。また、経時での硬化性については、本発明のオルガノポリシロキサン組成物を３０℃で２４時間保存した後、上記と同様にして硬化性を測定した。
【００３７】
剥離力
初期の剥離力は、本発明のオルガノポリシロキサン組成物を調製した直後に、硬化性の測定の場合と同様にして１００℃で３０秒間硬化させ、その硬化皮膜表面にＴｅｓａ−７４７５テープ（ＢＤＦ社製）を張りつけ、７０℃で２時間加熱処理し、引っ張り試験機を用いて、１８０°の角度で剥離速度０．３ｍ／分でテープを引っ張り、剥離するのに要する力（ｇ／２．５ｃｍ）を測定し、この値を初期剥離力とした。
また、経時の剥離力は、本発明のオルガノポリシロキサン組成物を３０℃で２４時間保存した後、上記と同様にして剥離力を測定し、この値を経時剥離力とした。
【００３８】
残留接着率
初期の残留接着率は、剥離力の場合と同様にしてオルガノポリシロキサン組成物の硬化皮膜を形成させ、その表面にポリエステルテープ・ニットー３１Ｂ（日東電工（株）製商品名）を貼り合わせ、２０ｇ／ｃｍ^２の荷重をのせ、７０℃で２０時間加熱処理してからテープをはがし、ステンレンス板に張り付けた。次に、この処理テープを剥がし、ステンレス板から剥離するのに要した力（ｇ／２．５ｃｍ）を測定し、未処理の標準テープを剥離するのに要した力に対する百分率を初期残留接着率とした。
【００３９】
尚、未処理の標準テープとは、テフロンシートにポリエステルテープ・ニット−３１Ｂ（日東電工（株）製商品名）を貼り合わせ、２０ｇ／ｃｍ^２の荷重をのせ、７０℃で２０時間加熱処理してからテープをはがし、次いでステンレス板に貼り付けた物をいう。上記の如くテープをステンレス版から剥離するのに要した力（ｇ／２．５ｃｍ）を測定し、これを未処理の標準テープを剥離するのに要した力とした。
また、経時後での残留接着率は、本発明のオルガノポリシロキサン組成物を３０℃で２４時間保存した後、上記と同様にして測定し、この値を経時残留接着率とした。
【００４０】
実施例１．
成分（１）として、ビニル化が０．００７５モル／１００ｇであり、トルエンで３０重量％に希釈したときの粘度が１０，０００ｃｐである、下記化７の平均組成式で表されるビニル基含有オルガノポリシロキサン３０部をトルエン５７０部に溶解した。
【化７】

【００４１】
次に、成分（２）として、粘度が２５０ｃｐでＳｉＨ価が１．０ｍｌ／１００ｇである、下記化８の平均組成式で表されるメチルハイドロジェンポリシロキサン０．６５部、
【化８】

成分（３）の、成分（ａ）として３，５−ジメチル−１−ヘキシン−３−オール（沸点１５０℃）０．１部、及び成分（ｂ）として１，１−ジメチルプロピニロキシトリメチルシラン（沸点１１５℃）０．８部を加え、よく混合した。
【００４２】
この混合物に、成分（４）として白金とビニルシロキサンとの錯体を、上記ポリシロキサンに対し、白金換算で２００ｐｐｍ添加して攪拌し、シリコーン組成物１を得た。得られた組成物についてポットライフ、硬化性、剥離力、及び残留接着率を測定した結果を、使用した制御剤の種類、触媒量、及び組成物の粘度と共に表１に示した。
【００４３】
【表１】

【００４４】
実施例２．
実施例１において、成分（３）の成分（ｂ）として使用した１，１−ジメチルプロピニロキシトリメチルシランの添加量を１．２部としたこと以外は、実施例１と全く同様にしてシリコーン組成物２を得た。得られた組成物２の特性を調べた結果は表１に示した通りである。
【００４５】
実施例３．
実施例１において成分（３）の成分（ａ）として使用した３，５−ジメチル−ヘキシン−３−オールの添加量を０．０５部としたこと以外は、実施例１と全く同様にしてシリコーン組成物３を得た。得られた組成物３の特性を調べた結果は表１に示した通りである。
【００４６】
実施例４．
実施例１において使用した成分（３）の成分（ａ）の代りに３−メチル−１−ブチン−３−オール（沸点１０４℃）を０．０７部添加したこと以外は、実施例１と全く同様にしてシリコーン組成物４を得、その特性を調べた結果を表１に示した。
【００４７】
実施例５．
実施例１において使用した成分（３）の成分（ａ）の代りに１−エチニル−１−シクロヘキサノール（沸点１９２℃）を０．１部添加したこと以外は、実施例１と全く同様にしてシリコーン組成物５を得、その特性を調べた結果を表１に示した。
【００４８】
実施例６．
実施例１で使用した成分（４）の添加量を白金換算で４００ｐｐｍとしたこと以外は、実施例１と全く同様にしてシリコーン組成物６を得、その特性を調べた結果を、使用した制御剤の種類、触媒量、及び組成物の粘度と共に表２に示した。
【００４９】
【表２】

【００５０】
実施例７．
実施例２で使用した成分（４）の添加量を４００ｐｐｍとしたこと以外は、実施例２と全く同様にしてシリコーン組成物７を得、その特性を調べた結果を表２に示した。
【００５１】
実施例８．
実施例３で使用した成分（４）の添加量を４００ｐｐｍとしたこと以外は、実施例３と全く同様にしてシリコーン組成物８を得、その特性を調べた結果を表２に示した。
【００５２】
実施例９．
実施例４で使用した成分（４）の添加量を４００ｐｐｍとしたこと以外は、実施例４と全く同様にしてシリコーン組成物９を得、その特性を調べた結果を表２に示した。
【００５３】
実施例１０．
実施例５で使用した成分（４）の添加量を４００ｐｐｍとしたこと以外は、実施例５と全く同様にしてシリコーン組成物１０を得、その特性を調べた結果を表２に示した。
【００５４】
比較例１．
実施例１で使用した成分（３）の代わりに、３，５−ジメチル−１−ヘキシン−３−オール０．１部を単独で使用したこと以外は、実施例１と全く同様にしてシリコーン組成物１１を得た。得られた組成物についてポットライフ、硬化性、剥離力、及び残留接着率を測定した結果を表１に示した。
【００５５】
比較例２．
比較例１で使用した制御剤の添加量を０．２部としたこと以外は、比較例１と全く同様にしてシリコーン組成物１２を得た。得られた組成物についてポットライフ、硬化性、剥離力、及び残留接着率を測定した結果を表１に示した。
【００５６】
比較例３．
比較例１で使用した制御剤及びその添加量を、１，１−ジメチルプロピニロキシトリメチルシラン０．８部としたこと以外は、比較例１と全く同様にしてシリコーン組成物１２を得た。得られた組成物についてポットライフ、硬化性、剥離力、及び残留接着率を測定した結果を表１に示した。
【００５７】
比較例４．
比較例１で使用した成分（４）の添加量を白金換算で４００ｐｐｍとしたこと以外は、比較例１と全く同様にしてシリコーン組成物１４を得た。得られた組成物についてポットライフ、硬化性、剥離力、及び残留接着率を測定した結果を表２に示した。
【００５８】
比較例５．
比較例２における成分（４）の添加量を４００ｐｐｍとしたこと以外は、比較例２と全く同様にしてシリコーン組成物１５を得た。得られた組成物についてポットライフ、硬化性、剥離力、及び残留接着率を測定し、結果を表２に示した。
【００５９】
比較例６．
比較例３における成分（４）の添加量を４００ｐｐｍとしたこと以外は、比較例３と全く同様にしてシリコーン組成物１６を得た。得られた組成物についてポットライフ、硬化性、剥離力、及び残留接着率を測定した結果を表２に示した。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an organopolysiloxane composition, and more particularly to an organopolysiloxane composition excellent in stability suitable for forming a release cured film.
[0002]
[Prior art]
Conventionally, release agents using organopolysiloxanes are classified according to the type of curing reaction at the time of curing. Among them, in particular, alkenyl group-containing organopolysiloxanes, organohydrogenpolysiloxanes, and platinum-based catalysts, so-called release agents. Addition reaction type organopolysiloxane compositions are widely used, and these are used as release agents for adhesive labels and adhesive tapes.
[0003]
In this case, in order to utilize the addition reaction for release paper silicone, a control agent that suppresses the reaction of the platinum catalyst at room temperature and rapidly progresses the addition reaction of the alkenyl group-containing siloxane and the hydrogen siloxane at a high temperature is required. Required. Various such control agents have already been proposed, and it is disclosed that acetylene alcohols are particularly useful (JP-B-44-31476, JP-A-6-329917, and JP-A-6-329917). JP-A-9-143371).
[0004]
On the other hand, in recent years, there has been a demand for high-speed and low-temperature curing of silicone from the viewpoint of improving productivity, and therefore, the amount of catalyst used is often increased as a countermeasure. However, when the amount of the catalyst is increased, the initial curability is improved, but there is a disadvantage that the gelation proceeds with the aging of the treatment bath. Even if the amount of the catalyst is not particularly increased, if the silicone treatment bath after the addition of the platinum catalyst is exposed to a high temperature for a long time, the same gelling phenomenon as in the case of increasing the amount of the catalyst occurs.
[0005]
Therefore, when the amount of the addition reaction controlling agent is increased to prevent the gelation, the pot life is prolonged, but there is a disadvantage that the initial curability is reduced. Further, when long-chain α-acetylene alcohols as described in JP-A-6-329917 are used as an addition reaction controlling agent, the pot life is prolonged even with a small amount thereof, but the initial curability is lowered. I do.
[0006]
On the other hand, as a control agent that does not decrease the curability of the silicone composition even if the amount of the control agent used is increased in order to obtain a sufficient control action, a control agent in which a hydroxyl group of acetylene alcohol is silylated is known ( JP-A-61-261). However, when this control agent is used in a large amount, although the initial curability does not change, there is a disadvantage that the curability may decrease with the aging of the treatment bath.
[0007]
Furthermore, Japanese Patent Application Laid-Open No. 9-143371 discloses that by using two types of control agents having different boiling points together, the time until gelation in a thin film can be extended. It has been difficult to maintain a sufficient pot life without deteriorating the curability under severe conditions such as when the amount of catalyst is increased or the treatment bath is left at a high temperature.
Therefore, even when the amount of the catalyst is increased or the temperature of the treatment bath is high, a control agent that can achieve both pot life and curability has been strongly desired.
[0008]
The present inventors have further studied the control action of conventional acetylene alcohols and silylated products thereof, and as a result, it has been found that these compounds behave as follows in a silicone treatment bath.
First, when acetylene alcohols are used as a control agent, immediately after preparation of the treatment bath, the acetylene alcohols strongly coordinate with the platinum group catalyst to lower the activity of the catalyst in the treatment bath. As a result, the activity of the catalyst to which the acetylenic alcohol is coordinated decreases with respect to the addition reaction, but the addition reaction cannot be completely stopped, and the catalyst tends to advance the catalytic cycle of the addition reaction.
[0009]
However, in the treatment bath, since the triple bond of acetylene alcohol causes the addition reaction earlier than the alkenyl group in the siloxane causes the addition reaction, the amount of acetylene alcohol decreases with time and the control action becomes insufficient. The treatment bath gels. Further, it was found that when the amount of acetylene alcohol used was increased, the time until gelation could be extended, but the control action was too strong and the initial curability was reduced.
[0010]
On the other hand, when a silylated product of acetylene alcohols is used as a control agent, they are coordinated with the platinum group metal-based catalyst to reduce the activity of the catalyst as in the case of acetylene alcohols, but the coordination force is reduced. Since it is weaker than acetylene alcohol and has a small ability to suppress the addition reaction, the triple bond of the silylated product causes the addition reaction in the treatment bath. For this reason, even if a large amount of the silylated compound is used, the initial curability does not change much. However, since the triple bond of the silylated compound is present in a large amount in the system, SiH is consumed over time of the treatment bath, and Curability after bath aging decreases.
[0011]
Therefore, the present inventors presume that if these two control agents are used in combination, it will be possible to achieve both pot life and curability, and as a result of various studies, it was found that a small amount of acetylene alcohol and a large amount of silylated product were obtained. By combining these, it is found that a composition having a good initial curability, a curability that does not decrease even with the passage of time in a treatment bath with an increased amount of catalyst, and a small change in peeling properties can be obtained. did.
[0012]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide an addition-curable silicone composition which cures and exhibits peelability, and the peeling properties and curability over time can be increased even when the amount of catalyst is increased or when the treatment bath is at a high temperature. Another object of the present invention is to provide a silicone composition which is hard to change and has excellent stability.
[0013]
The object of the present invention is to provide (1) 100 parts by weight of an organopolysiloxane having at least two unsaturated groups in one molecule, and (2) silicon represented by the following general formula 1 or 2, 0.1 to 30 parts by weight of one kind of liquid organohydrogenpolysiloxane having at least two hydrogen atoms (≡SiH bonds) directly bonded to atoms, (3) as an addition reaction controlling agent, acetylenic alcohol having the structure of, and, (b) having a specific structure, the mixture 0.1 to 6.0 parts by weight of acetylene alcohol is silylated, and, (4) a catalytic amount of a platinum group metal catalyst And the ratio (b) / (a) of the components (a) and (b) in the component (3) is more than 5 and not more than 100 by weight. Achieved by It was.
[0014]
As the organopolysiloxane having at least two alkenyl groups in one molecule of the component (1) constituting the silicone composition of the present invention, R ⁶ _a R ⁷ _b SiO _{(4-ab) / 2} ( In the formula, R ⁶ is the same or different, substituted or unsubstituted hydrocarbon group; R ⁷ is an alkenyl group represented by —C _n H _2n CH ＝ CH ₂ (n is 0 to 6); -3 and b are 3 or less and positive numbers other than 0, and a + b is 1-3.).
[0015]
In this organopolysiloxane, the ratio of the alkenyl group R ⁷ directly bonded to the silicon atom in one molecule to the total substituent R ⁶ + R ^{7 is} 0.05 to 50 mol%, particularly 0.2 to 10 mol%. It is preferred to contain. If the amount of the alkenyl group is less than 0.05% by mole, a substantial curing rate may not be obtained, and if it exceeds 50% by mole, the peeling property is deteriorated.
[0016]
Examples of R ⁶ other than the alkenyl group bonded to the silicon atom include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, An alkyl group such as an octadecyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group, a naphthyl group and a tolyl group; or a part or all of the hydrogen atoms bonded to carbon atoms of these groups are halogen atoms Unsubstituted with 1 to 30 carbon atoms of the same or different kind, such as chloromethyl group, 3,3,3-trifluoropropyl group, cyanopropyl group, phenol group, hindered phenol group and the like, substituted by cyano group, hydroxyl group, etc. Or a substituted monovalent hydrocarbon group. In the present invention, a methyl group, a phenyl group and an alkyl group having 2 to 8 carbon atoms are particularly preferable. Particularly, it is preferable that at least 50 mol% of all the substituents other than the alkenyl group bonded to the silicon atom is a methyl group.
[0017]
This organopolysiloxane may be either linear or branched, and its terminal may be, for example, any organic group such as a methyl group, a hydroxyl group, an alkenyl group, a phenyl group, and an acryloxyalkyl group. It is preferably an alkenyl group. The viscosity of the organopolysiloxane may be 50 cs or more at 25 ° C.
[0018]
The organohydrogenpolysiloxane of the component (2) constituting the organopolysiloxane composition of the present invention is particularly preferably one in which 90 mol% or more of the organic groups are methyl groups. These organohydrogenpolysiloxanes are shown in the following chemical formula 3.
[0019]
Embedded image

[0020]
In this case, c is an integer of 2 to 200, d is an integer of 0 to 100, f is an integer of 0 to 200, and g is an integer of 0 to 100.
[0021]
The viscosity of these organohydrogenpolysiloxanes may range from several cs to several hundred thousand cs at 25 ° C. The amount of the component (2) varies slightly depending on the purpose and use of the composition of the present invention, but is generally 0.1 to 100 parts by weight of the organopolysiloxane of the component (1). The amount may be in the range of 1 to 30 parts by weight, but is preferably 20 parts by weight or less.
[0022]
The component (3) used in the present invention is the most important component in the present invention, and the component (a) is an acetylene alcohol having a basic skeleton represented by the following formula (5). In addition, R ¹ and R ² in Chemical Formula 5 are hydrogen atoms; linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, and butyl group; aryl groups such as phenyl group and tolyl group. Group.
Embedded image

[0023]
Further, R ¹ and R ² may be bonded to each other to form a ring . The total number of carbon atoms of R ¹ and R ² is preferably 8 or less, particularly preferably 5 or less. When the total number of carbon atoms of R ¹ and R ² exceeds 8, the initial curability is significantly reduced.
The amount of the component (a) depends on the amounts of the components (1), (2) and (4), but is basically from 0.01 to 1.10 parts by weight based on 100 parts by weight of the component (1). It may be in the range of 0 parts by weight.
If the amount of the component (a) is less than 0.01, controlled curability cannot be obtained, and if it is more than 1.0, the initial curability decreases.
[0024]
Specific examples of the component (a) that can be used in the present invention include, for example, 3-methyl-1-butyn-3-ol (boiling point: 104 ° C.), 3-methyl-1-pentyn-3-ol (boiling point: 121 ° C.), 3,5-dimethyl-1-hexyn-3-ol (boiling point 150 ° C.), 1-ethynyl-1-cyclohexanol (boiling point 180 ° C.), and the like.
[0025]
Further, as the component (b), a silylated acetylene alcohol having a basic skeleton represented by the following formula 6 is used.
Embedded image

R ³ and R ^{4 in} Chemical Formula 6 are hydrogen atoms; linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, and butyl group; and aryl groups such as phenyl group and tolyl group. There, R ³ and R ⁴ may be bonded to each other to form a ring.
[0026]
The total number of carbon atoms of R ³ and R ⁴ is 8 or less, and particularly preferably the total number of carbon atoms is 5 or less. When the total number of carbon atoms of R ³ and R ⁴ exceeds 8, the initial curability decreases. R ⁵ is selected from a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group; and an aryl group such as a phenyl group and a tolyl group.
[0027]
Specific examples of the component (b) that can be used in the present invention include, for example, trimethyl (3-methyl-1-butyne-3-oxy) silane (boiling point 115 ° C.).
[0028]
The amount of the component (3) depends on the amounts of the components (1), (2) and (4), but is basically 0.1% based on 100 parts by weight of the component (1) in the composition. The amount may be in the range of 1 to 6.0 parts by weight. If the amount of the component (3) is less than 0.1 part by weight, a sufficient pot life cannot be obtained, and if it is more than 6.0 parts by weight, the curability after treatment bath aging decreases. Further, the usage ratio of (a) and (b) needs to be in the range of 5 <(b) / (a) ≦ 100. If this ratio is less than 5, the initial curability tends to decrease when the total amount of (a) and (b) is large, and sufficient pot life is obtained when the total amount of (a) and (b) is small. Is difficult to obtain. Further, when this ratio is larger than 100, the curability is reduced over time in the treatment bath. Both (a) and (b) preferably have a boiling point in the range of 130 ° C. to 170 ° C., and when one of (a) and (b) has a boiling point of 130 ° C. or less, Preferably, one of the boiling points is 170 ° C. or higher.
[0029]
The mechanism of action of the control system of the present invention using these two compounds in combination is considered as follows. First, a small amount of acetylene alcohol, which is the component (a), strongly coordinates with the catalyst after the treatment bath is adjusted to lower the catalytic activity. On the other hand, the silylated acetylene alcohol which is a component (b), which is excessively present as a substrate for the addition reaction which proceeds slightly, acts to suppress the reduction of the non-silylated acetylene alcohol.
[0030]
That is, since the silylated acetylene alcohol acts as a substrate for the addition reaction, consumption of the acetylene alcohol (addition reaction) is suppressed. On the other hand, since the consumption of acetylene alcohol is suppressed in the system, the state of low catalytic activity continues for a long time, and the consumption of SiH is suppressed. By the above action mechanism, a composition having a sufficiently long pot life can be obtained without using acetylene alcohol that reduces the initial curability.
[0031]
In the present invention, in order to effectively advance the addition curing reaction, a platinum group catalyst conventionally known as this kind of addition catalyst is used as the component (4). Examples of such platinum group catalysts include, for example, platinum-based, palladium-based, and rhodium-based catalysts. Platinum-based catalysts are particularly preferred.Specifically, chloroplatinic acid, alcohol solutions of chloroplatinic acid and aldehydes Solutions, complexes of chloroplatinic acid with various olefins, vinyl siloxane, and the like. The amount of the platinum-based catalyst may be the same as the amount of the catalyst, but from the viewpoint of obtaining a good cured film and being economical, the amount of the platinum group metal relative to the components (1) and (2) is in the range of 1 to 1,000 ppm. It is preferable that
[0032]
Optional components other than the above components can be further added to the silicone composition of the present invention. For example, for the purpose of adjusting the peeling force, an organopolysiloxane having no hydrogen atom bonded to a vinyl group or a silicon atom or the like can be added as needed. In addition, the addition amount of the optional component can be appropriately determined as long as the effect of the present invention is not hindered.
[0033]
The silicone composition of the present invention can be obtained by blending the above components (1) to (4) and a predetermined amount of an optional component. In this case, each component except the component (4) is uniformly mixed in advance. It is preferable to add the component (4) after mixing. Further, if necessary, it may be used by dissolving it in an organic solvent such as toluene, xylene, n-hexane or the like.
The silicone composition prepared as described above is applied to a substrate such as paper or plastic film and then heat-cured by an ordinary method. Thus, the substrate on which the cured film of the composition of the present invention is formed is used as a release paper.
[0034]
【The invention's effect】
The silicone composition of the present invention comprises a small amount of an acetylene alcohol-based addition control agent that strongly coordinates with a catalyst to reduce catalytic activity, and an excess amount of a silylated acetylene alcohol that acts as a substrate for a slightly progressing addition reaction. Since they are simultaneously contained, there is an advantage that the pot life is long and the peeling characteristics and the curing performance do not change even if the treatment bath is aged.
[0035]
【Example】
Next, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the part in an example represents a weight part, and the physical property value in an example means the value measured by the following test methods.
Treatment bath viscosity The viscosity at 30 ° C immediately after preparation of the organopolysiloxane composition of the present invention was defined as the initial viscosity, and the viscosity after storing this composition at 30 ° C for 24 hours was defined as the viscosity over time.
[0036]
Curable <br/> initial curability after organopolysiloxane composition prepared was applied to a 0.6 g / m ² polyethylene laminated paper of the present invention, given in a 100 ° C. hot air dryer When the cured film formed by heating for a few hours was rubbed with a finger several times, the presence or absence of cloudiness and falling off was visually evaluated, and the curability was shown using the time required for curing. Regarding the curability over time, the curability was measured in the same manner as described above after storing the organopolysiloxane composition of the present invention at 30 ° C. for 24 hours.
[0037]
Peeling force The initial peeling force was determined immediately after preparing the organopolysiloxane composition of the present invention at 100 ° C. for 30 seconds in the same manner as in the measurement of curability, and the surface of the cured film was Tesa. Attach -7475 tape (manufactured by BDF), heat-treat at 70 ° C for 2 hours, pull the tape at 180 ° angle at a peeling speed of 0.3 m / min using a tensile tester, and force to peel. (G / 2.5 cm), and this value was used as the initial peel force.
The peeling force over time was determined by storing the organopolysiloxane composition of the present invention at 30 ° C. for 24 hours and then measuring the peeling force in the same manner as described above.
[0038]
Residual adhesion rate The initial residual adhesion rate is determined by forming a cured film of the organopolysiloxane composition in the same manner as in the case of the peeling force, and forming a polyester tape Nitto 31B (a product manufactured by Nitto Denko Corporation) on the surface. ) Was applied thereto, a load of 20 g / cm ² was applied thereto, and heat treatment was performed at 70 ° C. for 20 hours. Then, the tape was peeled off and attached to a stainless steel plate. Next, the force (g / 2.5 cm) required for peeling the treated tape and peeling from the stainless steel plate was measured, and the percentage of the force required for peeling the untreated standard tape was expressed as the initial residual adhesive ratio. And
[0039]
The untreated standard tape was obtained by laminating a polyester tape knit-31B (trade name, manufactured by Nitto Denko Corporation) on a Teflon sheet, applying a load of 20 g / cm ² and heating at 70 ° C. for 20 hours. The tape is peeled off and then attached to a stainless steel plate. As described above, the force (g / 2.5 cm) required to peel the tape from the stainless steel plate was measured, and this was defined as the force required to peel the untreated standard tape.
The residual adhesion rate after aging was measured in the same manner as described above after storing the organopolysiloxane composition of the present invention at 30 ° C. for 24 hours, and this value was defined as the aging residual adhesion rate.
[0040]
Embodiment 1 FIG.
Component (1) having a vinyl group content of 0.0075 mol / 100 g and a viscosity of 10,000 cp when diluted to 30% by weight with toluene. 30 parts of the organopolysiloxane was dissolved in 570 parts of toluene.
Embedded image

[0041]
Next, as a component (2), 0.65 part of methyl hydrogen polysiloxane represented by the following average composition formula having a viscosity of 250 cp and a SiH value of 1.0 ml / 100 g,
Embedded image

1 component of (3), as 3, 5-dimethyl-1-hexyne-3-ol (boiling point 0.99 ° C.) 0.1 part components (a), and as component (b), 1 - dimethyl propylene Niro trimethyl silane 0.8 parts (boiling point 115 ° C.) were added and mixed well.
[0042]
To this mixture, a complex of platinum and vinyl siloxane was added as component (4) to the above polysiloxane in an amount of 200 ppm in terms of platinum, followed by stirring to obtain a silicone composition 1. Table 1 shows the results of measuring the pot life, curability, peeling force, and residual adhesiveness of the obtained composition, together with the type of control agent used, the amount of the catalyst, and the viscosity of the composition.
[0043]
[Table 1]

[0044]
Embodiment 2. FIG.
In Example 1, 1, 1 was used as a component of component (3) (b) - except that the amount of dimethyl propylene Niro trimethyl silane was 1.2 parts, in the same manner as in Example 1 Silicone Composition 2 was obtained. The results of examining the properties of the obtained composition 2 are as shown in Table 1.
[0045]
Embodiment 3 FIG.
Silicone was prepared in the same manner as in Example 1 except that the amount of 3,5-dimethyl-hexyn-3-ol used as component (a) of component (3) was changed to 0.05 part in Example 1. Composition 3 was obtained. The results of examining the properties of the obtained composition 3 are as shown in Table 1.
[0046]
Embodiment 4. FIG.
Except that 0.07 part of 3-methyl-1-butyn-3-ol (boiling point 104 ° C.) was added instead of the component (a) of the component (3) used in the example 1, In the same manner, a silicone composition 4 was obtained, and the characteristics were examined. The results are shown in Table 1.
[0047]
Embodiment 5 FIG.
Exactly the same as Example 1 except that 0.1 part of 1-ethynyl-1-cyclohexanol (boiling point 192 ° C.) was added instead of component (a) of component (3) used in Example 1. Table 1 shows the results of examining the properties of the obtained silicone composition 5.
[0048]
Embodiment 6 FIG.
A silicone composition 6 was obtained in exactly the same manner as in Example 1 except that the addition amount of the component (4) used in Example 1 was 400 ppm in terms of platinum, and the characteristics were examined. Table 2 shows the type of the agent, the amount of the catalyst, and the viscosity of the composition.
[0049]
[Table 2]

[0050]
Embodiment 7 FIG.
A silicone composition 7 was obtained in exactly the same manner as in Example 2 except that the addition amount of the component (4) used in Example 2 was 400 ppm, and the characteristics were examined. Table 2 shows the results.
[0051]
Embodiment 8 FIG.
A silicone composition 8 was obtained in exactly the same manner as in Example 3 except that the addition amount of the component (4) used in Example 3 was 400 ppm, and the characteristics were examined. The results are shown in Table 2.
[0052]
Embodiment 9 FIG.
A silicone composition 9 was obtained in exactly the same manner as in Example 4 except that the addition amount of the component (4) used in Example 4 was 400 ppm, and the characteristics were examined.
[0053]
Embodiment 10 FIG.
A silicone composition 10 was obtained in exactly the same manner as in Example 5 except that the addition amount of the component (4) used in Example 5 was 400 ppm, and the characteristics were examined. Table 2 shows the results.
[0054]
Comparative Example 1
Instead of the components used in Example 1 (3), 3, 5-dimethyl-1-hexyne-3 except for using alone 0.1 parts ol silicone composition in the same manner as in Example 1 The product 11 was obtained. Table 1 shows the results of measuring the pot life, curability, peeling force, and residual adhesiveness of the obtained composition.
[0055]
Comparative Example 2.
A silicone composition 12 was obtained in exactly the same manner as in Comparative Example 1, except that the amount of the control agent used in Comparative Example 1 was changed to 0.2 part. Table 1 shows the results of measuring the pot life, curability, peeling force, and residual adhesiveness of the obtained composition.
[0056]
Comparative Example 3
The control agent and its amount used in Comparative Example 1, 1, 1 - except that the dimethylpropylidene Niro trimethyl silane 0.8 parts to obtain a silicone composition 12 in the same manner as in Comparative Example 1. Table 1 shows the results of measuring the pot life, curability, peeling force, and residual adhesiveness of the obtained composition.
[0057]
Comparative Example 4.
A silicone composition 14 was obtained in exactly the same manner as in Comparative Example 1, except that the amount of the component (4) used in Comparative Example 1 was 400 ppm in terms of platinum. Table 2 shows the results of measuring the pot life, curability, peeling force, and residual adhesiveness of the obtained composition.
[0058]
Comparative Example 5
A silicone composition 15 was obtained in exactly the same manner as in Comparative Example 2, except that the addition amount of the component (4) in Comparative Example 2 was changed to 400 ppm. The obtained composition was measured for pot life, curability, peeling force, and residual adhesiveness. The results are shown in Table 2.
[0059]
Comparative Example 6
A silicone composition 16 was obtained in exactly the same manner as in Comparative Example 3, except that the addition amount of the component (4) in Comparative Example 3 was changed to 400 ppm. Table 2 shows the results of measuring the pot life, curability, peeling force, and residual adhesiveness of the obtained composition.

Claims (1)

(1) 100 parts by weight of an organopolysiloxane having at least two unsaturated groups in one molecule, (2) a hydrogen atom directly bonded to a silicon atom in one molecule represented by the following general formula 1 or 2 ( (SiH bond) 0.1 to 30 parts by weight of one kind of liquid organohydrogenpolysiloxane having at least two

(However, c is an integer of 2 to 200, d is an integer of 0 to 100, f is an integer of 0 to 200, and g is an integer of 0 to 100.)
(3) As an addition reaction controlling agent, (a) acetylene alcohol having the structure of the following formula 1

(However, R ¹ and R ² in Chemical formula ¹ are a hydrogen atom or a group selected from an alkyl group and an aryl group, and R ¹ and R ² may be bonded to each other to form a ring. ) And (b) a silylated acetylene alcohol having the structure

(However, R ³ and R ⁴ in Chemical Formula 2 are a hydrogen atom or a group selected from an alkyl group and an aryl group, and R ³ and R ⁴ may be bonded to each other to form a ring. R ⁵ is a group selected from an alkyl group and an aryl group.)
And (4) a catalytic amount of a platinum group metal-based catalyst, and a ratio (b) / (b) of (a) and (b) in the component (3). An organopolysiloxane composition wherein a) is greater than 5 and less than 100 by weight.