JPH06220327A - Silicone composition for release paper - Google Patents
Silicone composition for release paperInfo
- Publication number
- JPH06220327A JPH06220327A JP3134693A JP3134693A JPH06220327A JP H06220327 A JPH06220327 A JP H06220327A JP 3134693 A JP3134693 A JP 3134693A JP 3134693 A JP3134693 A JP 3134693A JP H06220327 A JPH06220327 A JP H06220327A
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- group
- component
- platinum
- silicone composition
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は剥離紙用シリコーン組成
物、特には有機溶剤を含有させることなしで紙、ラミネ
ート紙、プラスチックフィルムなどの表面に密着塗布す
ることができ、これらの基材表面に非粘着性を与えるこ
とのできる剥離紙用シリコーン組成物に関するものであ
る。FIELD OF THE INVENTION The present invention can be applied to the surface of paper, laminated paper, plastic film and the like in close contact with a silicone composition for release paper, especially without containing an organic solvent. The present invention relates to a silicone composition for release paper, which is capable of imparting non-tackiness to.
【０００２】[0002]
【従来の技術】従来、紙、プラスチックなどの基材と粘
着物質との間の粘着ないし固着を防止するために使用さ
れる無溶剤型の離型用シリコーン組成物としては各種の
ものが知られている（特開昭49-47426号、特開昭 50-14
1591号、特公昭52-39791号、特開昭57-77395号公報参
照）。2. Description of the Related Art Conventionally, various kinds of solvent-free releasing silicone compositions have been known which are used to prevent sticking or sticking between a base material such as paper or plastic and a sticky substance. (JP-A-49-47426 and JP-A-50-14)
1591, JP-B-52-39791, JP-A-57-77395).
【０００３】しかし、これらは紙、ラミネート紙などに
対する密着性は良いけれどもプラスチックフィルム、特
にはポリエチレンテレフタレート、ポリプロピレンフィ
ルムに対してはフィルムの収縮防止のために低温で硬化
させると密着性が十分でなくなるという不利があり、特
に多湿状況下でこの硬化シリコーン皮膜を保持させた場
合には塗工一日位で指でこすったときにボロボロと剥げ
落ちるという欠点があった。However, although they have good adhesion to paper, laminated paper, etc., the adhesion to plastic films, especially polyethylene terephthalate and polypropylene films, becomes insufficient if they are cured at a low temperature to prevent film shrinkage. In particular, when the cured silicone film is held under a high humidity condition, there is a drawback that the film is rubbed off when rubbed with a finger in about one day of coating.
【０００４】[0004]
【発明が解決しようとする課題】そのため、この種のオ
ルガノシロキサン組成物についてはプラスチックフィル
ムへの密着性を良くする目的で、ある種のシラン、シロ
キサンなどを配合して自己接着性を付与することも提案
されている（特公昭 46-2187号、特公昭 52-9469号公報
参照）が、これらはいずれも縮合反応を用いて硬化させ
るもので、硬化に高温が必要とされるためにプラスチッ
クフィルム用としては不向きであり、またこのシロキサ
ンをエポキシ基をその末端または側鎖に含有するものと
し、これを付加反応で硬化させるようにした組成物も知
られている（特開昭52-24258号、特開昭 52-147657号、
特公昭 61-1471号公報参照）が、これも硬化皮膜の非粘
着性において満足できるものではなかった。なお、この
接着性向上としては被着体の表面を予めプライマーで処
理する方法もあるが、これは工程的には一工程増加とな
るし、作業時間、労力、コストの面からはマイナスの要
因となるので好ましいものではない。Therefore, for this type of organosiloxane composition, for the purpose of improving the adhesion to a plastic film, a certain amount of silane, siloxane, etc. is blended to impart self-adhesiveness. Have also been proposed (see Japanese Patent Publication No. 46-2187 and Japanese Patent Publication No. 52-9469), both of which are cured using a condensation reaction and require a high temperature for curing, so plastic films It is not suitable for use, and there is also known a composition in which this siloxane contains an epoxy group at its terminal or side chain and is cured by an addition reaction (JP-A-52-24258). , JP-A-52-147657,
Japanese Patent Publication No. 61-1471), but this was also unsatisfactory in the non-tackiness of the cured film. There is also a method of treating the surface of the adherend with a primer in advance to improve the adhesiveness, but this is one step increase in process, and it is a negative factor in terms of working time, labor, and cost. Therefore, it is not preferable.
【０００５】[0005]
【課題を解決するための手段】本発明はこのような不利
を解決した剥離紙用シリコーン組成物に関するものであ
り、これは１）平均組成式が下記の式（１）SUMMARY OF THE INVENTION The present invention relates to a silicone composition for release paper which has solved such disadvantages, and it has the following formula (1):
【化４】 （ここにＲ1 はアルケニル基、Ｒ2 、Ｒ3 、Ｒ4 は同一
または異種の１価の有機基、ｅは３≦ｅ≦100 、ｆは10
〜1,000 、ｇは１〜50の整数）で示され、25℃における
粘度が50〜10,000cpであるオルガノポリシロキサン 0.1
〜99.9重量部、２）平均組成式が下記の式（２）[Chemical 4] (Here, R 1 is an alkenyl group, R 2 , R 3 , and R 4 are the same or different monovalent organic groups, e is 3 ≦ e ≦ 100, and f is 10
~ 1,000, g is an integer of 1 to 50), and an organopolysiloxane having a viscosity at 25 ° C of 50 to 10,000 cp 0.1
~ 99.9 parts by weight, 2) The average composition formula is the following formula (2).
【化５】 （ここにＲ5 はアルケニル基、Ｒ6 は同一または異種の
１価の有機基、ａは１〜３の正数、ｐ≧０、ｑ≧１）で
示され、25℃における粘度が50〜10,000cpであるオルガ
ノポリシロキサン99.9〜0.1 重量部、３）オルガノハイ
ドロジェンポリシロキサン 1.0〜100 重量部、４）触媒
量の白金または白金系化合物とからなることを特徴とす
るものである。[Chemical 5] (Wherein R 5 is an alkenyl group, R 6 is the same or different monovalent organic group, a is a positive number of 1 to 3, p ≧ 0, q ≧ 1), and the viscosity at 25 ° C. is 50 to 50 ° C. It is characterized by comprising 99.9 to 0.1 parts by weight of organopolysiloxane having a weight of 10,000 cp, 3) 1.0 to 100 parts by weight of organohydrogenpolysiloxane, and 4) a catalytic amount of platinum or a platinum-based compound.
【０００６】すなわち、本発明者らは紙、プラスチック
フィルムなどにすぐれた離型性を与える無溶剤型の離型
用シリコーン組成物について種々検討した結果、この主
剤となるアルケニル基を含有するオルガノポリシロキサ
ンを上記した式（１）、（２）で示されるものとし、こ
れにオルガノハイドロジェンポリシロキサンと白金系触
媒を配合した組成物とすると、このシリコーン組成物は
70〜 200℃の温度での１〜30秒間の加熱処理によって容
易に被処理物表面に硬化皮膜を形成し、このようにして
得られた硬化皮膜は基材特にプラスチックフィルムに対
する密着性がよく、離型性にすぐれていて、高温高湿の
条件下でも密着性が低下しないということを見出すと共
に、この組成物は有機溶剤で希釈しなくても無溶剤のま
まで基材に対する塗布が可能であり、その硬化が低温、
短時間で行なうことができるので、これを処理したフィ
ルムは収縮したりすることがなく、また粘着物質と長時
間接触しても粘着物質に悪影響を与えることがないし、
さらに剥離性に優れるということを確認して本発明を完
成させた。That is, the inventors of the present invention have made various studies on a solvent-free silicone composition for mold release which gives excellent mold release property to papers, plastic films and the like. When the siloxane is represented by the above formulas (1) and (2) and the composition is a mixture of the organohydrogenpolysiloxane and the platinum-based catalyst, the silicone composition is
A cured film is easily formed on the surface of the object to be treated by heat treatment at a temperature of 70 to 200 ° C for 1 to 30 seconds, and the cured film thus obtained has good adhesion to a substrate, particularly a plastic film, It was found that the composition has excellent releasability and that the adhesiveness does not decrease even under the conditions of high temperature and high humidity, and that this composition can be applied to a substrate without being diluted with an organic solvent. Yes, its curing is low temperature,
Since it can be carried out in a short time, the film treated with this does not shrink, and even if it is in contact with the adhesive substance for a long time, it does not adversely affect the adhesive substance,
The present invention was completed by confirming that the peelability was excellent.
【０００７】[0007]
【作用】本発明の剥離紙用シリコーン組成物は１）前記
した式（１）で示されるオルガノポリシロキサン 0.1〜
99.9重量部と２）前記した式（２）で示されるオルガノ
ポリシロキサン99.9〜0.1 重量部とからなるオルガノポ
リシロキサン組成物に、３）オルガノハイドロジェンポ
リシロキサン 1.0〜100 重量部および４）触媒量の白金
または白金化合物とからなることを特徴とする付加反応
型のオルガノシロキサン組成物であるが、このものは有
機溶剤を含有させないでも紙、ラミネート紙、プラスチ
ックフィルムなどの表面に密着塗布させることができ、
これらの基材表面に非粘着性を与えることができるとい
う有利性をもつものである。The silicone composition for release paper of the present invention comprises 1) 0.1 to 0.1 parts of the organopolysiloxane represented by the above formula (1).
39.9 parts by weight of organopolysiloxane composition consisting of 99.9 parts by weight and 2) 99.9-0.1 parts by weight of the organopolysiloxane represented by the formula (2) and 3) organohydrogenpolysiloxane in an amount of 10-100 parts by weight and 4) amount of catalyst. Which is an addition reaction type organosiloxane composition characterized by comprising platinum or a platinum compound, which can be applied in close contact with the surface of paper, laminated paper, plastic film or the like without containing an organic solvent. You can
It has the advantage that non-tackiness can be imparted to the surface of these substrates.
【０００８】本発明の剥離性シリコーン組成物を構成す
る第１成分としてのオルガノポリシロキサンは平均組成
式が下記の式（１）The organopolysiloxane as the first component constituting the peelable silicone composition of the present invention has an average composition formula represented by the following formula (1):
【化６】 で示され、このＲ1 はビニル基、アリル基、ヘキセニル
基などのアルケニル基、Ｒ2 、Ｒ3 、Ｒ4 はそれぞれメ
チル基、エチル基、プロピル基、ブチル基などのアルキ
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あるいはこれらの炭素原子に結合
した水素原子の一部または全部をハロゲン原子、シアノ
基などで置換したクロロメチル基、トリフルオロプロピ
ル基、シアノエチル基などのような非置換または置換１
価炭化水素基、さらにはメトキシ基、エトキシ基、プロ
ポキシ基、メトキシエトキシ基などのアルコキシ基、水
酸基、エポキシ基などから選択される原子または基、ｅ
は３≦ｅ≦100 、ｆは10〜1,000 、ｇは１〜50の整数で
あるオルガノシロキサンとされるが、この全有機基はそ
の少なくとも80％がメチル基のものとすることが好まし
い。[Chemical 6] R 1 is a vinyl group, an allyl group, an alkenyl group such as a hexenyl group, R 2 , R 3 and R 4 are each a methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group, a cyclohexyl group, etc. Cycloalkyl group, alkenyl group such as vinyl group and allyl group, aryl group such as phenyl group and tolyl group, or chloro group in which some or all of the hydrogen atoms bonded to these carbon atoms are substituted with halogen atoms, cyano groups, etc. Unsubstituted or substituted 1 such as methyl, trifluoropropyl, cyanoethyl, etc.
A valent hydrocarbon group, further an atom or a group selected from an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a methoxyethoxy group, a hydroxyl group, an epoxy group, e
Is 3 ≦ e ≦ 100, f is 10 to 1,000, and g is an organosiloxane having an integer of 1 to 50. It is preferable that at least 80% of all the organic groups are methyl groups.
【０００９】このオルガノポリシロキサンにおけるＳｉ
に結合するアルケニル基の量はそれが 0.1モル％未満で
は硬化性が悪く、20モル％より大きい値とするとこの組
成物から得られる硬化被膜が剥離抵抗の大きいものとな
って実用上において粘着剤との離型が不安定なものとな
るので、 0.1〜20モル％の範囲とすることが望ましい。Si in this organopolysiloxane
If the amount of alkenyl groups bonded to is less than 0.1 mol%, the curability is poor, and if it is more than 20 mol%, the cured film obtained from this composition has a large peel resistance and is practically used as an adhesive. Since the mold release from and becomes unstable, it is desirable to set it in the range of 0.1 to 20 mol%.
【００１０】また、本発明の離型性シリコーン組成物を
構成する第２成分としてのオルガノポリシロキサンは平
均組成式が下記の式（２）The organopolysiloxane as the second component constituting the mold-releasing silicone composition of the present invention has an average composition formula represented by the following formula (2).
【化７】 で示され、Ｒ5 はビニル基、アリル基、ヘキセニル基な
どのアルケニル基、好ましくはビニル基、Ｒ6 はメチル
基、エチル基、プロピル基、ブチ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、フェニ
ル基、トリル基などのアリール基、さらにはこれらの基
の炭素原子に結合している水素原子の一部または全部を
ハロゲン原子、シアノ基などで置換したクロロメチル
基、トリフルオロプロピル基、シアノエチル基などから
選択される非置換または置換の１価炭化水素基で、剥離
性から全有機基の80％以上がメチル基であることが望ま
しいものであり、このｐはｐ≧０、好ましくはｐ＝０
で、ｑはｑ≧１とされるものであるが、これはこのもの
が25℃の粘度が50〜10,000cpの範囲に入る数値であれば
よい。粘度については塗工性などから 100〜400cp が好
ましい。[Chemical 7] R 5 is an alkenyl group such as a vinyl group, an allyl group or a hexenyl group, preferably a vinyl group, R 6 is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, or a cycloalkyl group such as a cyclohexyl group. Groups, phenyl groups, aryl groups such as tolyl groups, and chloromethyl groups and trifluoropropyl groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are replaced with halogen atoms, cyano groups, etc. It is an unsubstituted or substituted monovalent hydrocarbon group selected from the group consisting of cyanoethyl groups and the like, and it is desirable that 80% or more of all organic groups are methyl groups in view of releasability, and p is p ≧ 0, preferably Is p = 0
In the above, q is q ≧ 1, but this may be any value as long as the viscosity at 25 ° C. falls within the range of 50 to 10,000 cp. The viscosity is preferably 100 to 400 cp in view of coatability.
【００１１】このオルガノポリシロキサンはその分子鎖
末端にアルケニル基を有することによってすぐれた硬化
性を示すのであるが、この効果は分子中におけるアルケ
ニル基の含有量が少ないほど大きいが、分子鎖末端にお
けるアルケニル基の数は１個よりも複数個のほうが硬化
速度の面ですぐれている。なお、上記した第１成分とし
てのオルガノシロキサンとこの第２成分としてのオルガ
ノポリシロキサンはいずれも通常、被処理面に厚さ５μ
ｍ以下の薄膜で塗工されるのであるが、これは25℃にお
ける粘度が50cp未満あるいは10,000cpより大きくなると
薄膜塗工性が劣るようになるために、この粘度は50〜1
0,000cpの範囲、好ましくは 100〜3,000cp の範囲のも
のが好ましく、さらには 100〜300cpのものが好まし
い。This organopolysiloxane exhibits excellent curability by having an alkenyl group at the end of its molecular chain. This effect is greater as the content of the alkenyl group in the molecule is smaller, but at the end of the molecular chain. A plurality of alkenyl groups are more excellent than one in terms of curing speed. Both the organosiloxane as the first component and the organopolysiloxane as the second component described above usually have a thickness of 5 μm on the surface to be treated.
It is applied with a thin film of m or less, but if the viscosity at 25 ° C is less than 50 cp or greater than 10,000 cp, the thin film coating property will be poor, so this viscosity is 50 to 1
It is preferably in the range of 0,000 cp, preferably in the range of 100 to 3,000 cp, and more preferably in the range of 100 to 300 cp.
【００１２】つぎに本発明の剥離性シリコーン組成物を
構成する第３成分としてのオルガノハイドロジェンポリ
シロキサンはこの種の付加反応型シリコーン組成物に使
用される公知のもでよく、これは１分子中に少なくとも
２個、好ましくは３個以上のけい素原子に結合した水素
原子を有するものであればよいが、この他の有機基はそ
の80モル％以上がメチル基のものとすることがよい。Next, the organohydrogenpolysiloxane as the third component constituting the peelable silicone composition of the present invention may be a known one used in this type of addition reaction type silicone composition, and one molecule thereof is used. Any organic group having at least two, preferably three or more, hydrogen atoms bonded to a silicon atom may be contained therein, and 80 mol% or more of the other organic groups are preferably methyl groups. .
【００１３】この種のポリシロキサンとしては(CH3)HSi
O 単位、HSiO1.5 単位、(CH3)2SiO単位、CH3SiO1.5 単
位、(CH3)2HSiO0.5 単位あるいは(CH3)3SiO0.5単位から
なるホモポリマーまたはコポリマーが例示されるが、こ
れは直鎖状、分枝状、環状のいずれであってもよく、25
℃での粘度が10〜10,000cpの範囲のものが好ましい。This type of polysiloxane includes (CH 3 ) HSi
O units, HSiO 1.5 units, (CH 3 ) 2 SiO units, CH 3 SiO 1.5 units, (CH 3 ) 2 HSiO 0.5 units or homopolymers or copolymers composed of (CH 3 ) 3 SiO 0.5 units are exemplified, It may be linear, branched or cyclic, 25
It preferably has a viscosity in the range of 10 to 10,000 cp at ° C.
【００１４】なお、このポリシロキサンの配合量は前記
した第１成分、第２成分およびこの第３成分中に含有さ
れているアルケニル基量に応じたものとすればよく、こ
れはSiH/C=C のモル比が１〜10となる量とすればよい
が、通常は硬化皮膜形成および剥離性能からみて第１成
分と第２成分との配合物 100重量部に対し 1.0〜 100重
量部の範囲とすればよい。The amount of the polysiloxane blended may be determined according to the amount of alkenyl groups contained in the above-mentioned first component, second component and third component, which is SiH / C = The molar ratio of C may be 1 to 10, but usually in the range of 1.0 to 100 parts by weight based on 100 parts by weight of the mixture of the first component and the second component in view of cured film forming and peeling performance. And it is sufficient.
【００１５】また、本発明の剥離性シリコーン組成物に
おける第４成分は上記した第１〜第３成分を付加反応さ
せるための触媒とされるものであるが、これはこの種の
反応触媒として公知のものでよく、これには塩化白金
酸、塩化白金酸のアルコール溶液、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塩
などが例示されるが、これは白金黒、各種担体に白金を
担持させたものでもよい。なお、この添加量は触媒量と
すればよく、良好な硬化膜を得るため、また経済的な見
地からは第１成分、第２成分、第３成分の配合物 100重
量部に対し白金量として１〜1,000ppmの範囲とすればよ
い。The fourth component in the peelable silicone composition of the present invention is a catalyst for addition reaction of the above-mentioned first to third components, which is known as a reaction catalyst of this kind. Examples thereof include chloroplatinic acid, alcohol solutions of chloroplatinic acid, aldehyde solutions, and complex salts of chloroplatinic acid with various olefins and vinyl siloxane. These are platinum black, platinum with various carriers. May be carried. It should be noted that this addition amount may be a catalytic amount, in order to obtain a good cured film, and from an economical point of view, the platinum amount relative to 100 parts by weight of the first component, the second component and the third component is added. It should be in the range of 1 to 1,000 ppm.
【００１６】本発明の剥離性シリコーン組成物は上記し
た第１〜第４成分の所定量を配合することによって得ら
れるが、これは第１〜第３成分を予め均一に混合したの
ち第４成分を添加することが好ましく、これにはまた第
４成分としての白金触媒の活性を抑制する目的で各種有
機窒素化合物、有機りん化合物、アセチレン系化合物、
オキシム化合物、有機クロロ化合物などの活性抑制剤を
必要に応じて添加してもよい。The peelable silicone composition of the present invention can be obtained by blending the above-mentioned predetermined amounts of the first to fourth components, which are prepared by uniformly mixing the first to third components and then the fourth component. It is preferable to add various organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, for the purpose of suppressing the activity of the platinum catalyst as the fourth component.
An activity inhibitor such as an oxime compound or an organic chloro compound may be added if necessary.
【００１７】本発明の組成物を被処理物に塗工するに当
ってはこれをそのまま塗工すればよく、これは必要に応
じて溶剤に希釈して用いてもよいが、これには必要に応
じて基材に対する密着性向上助剤としてのｒ−グリシド
キシプロピルトリメトキシシラン、ｒ−メタクリロキシ
プロピルトリメトキシシランまたはこれらの共加水分解
物を添加してもよいし、さらにはヒュームドシリカなど
の乾式法シリカ、湿式法シリカ、酸化チタン、酸化カリ
ウム、カーボンブラック、マイカなどの無機質充填剤、
顔料などを添加してもよい。When the composition of the present invention is applied to an object to be treated, it may be applied as it is, and it may be diluted with a solvent if necessary, but it is necessary for this. In accordance with the above, r-glycidoxypropyltrimethoxysilane, r-methacryloxypropyltrimethoxysilane or a cohydrolyzate of these may be added as an adhesion-improving aid for the base material, and further fumed. Inorganic fillers such as dry process silica such as silica, wet process silica, titanium oxide, potassium oxide, carbon black, mica, etc.
A pigment or the like may be added.
【００１８】本発明の組成物は例えばポリエチレンラミ
ネート紙、各種プラスチックフィルムなどにロールコー
ター、グラビヤコーター、エアーコーター、カーテンフ
ローコーター、オフセット転写ロールコーターなどの公
知の技術で塗工すればよい。The composition of the present invention may be applied to polyethylene laminated paper, various plastic films and the like by a known technique such as a roll coater, a gravure coater, an air coater, a curtain flow coater and an offset transfer roll coater.
【００１９】本発明の組成物で処理した基材はこれを70
〜 200℃の温度で１〜30秒間加熱することによってその
表面に硬化皮膜を形成させればよいが、この組成物は有
機溶剤で希釈しなくてもそのまま基材に薄膜塗工するこ
とができるので省エネルギー、安全性、無公害である
し、この硬化が上記のように低温、短時間でよいのでプ
ラスチックフィルムなどに収縮させることなく適用する
ことができ、このようにして得られた硬化被膜は基材特
にプラスチックフィルムなどにもよく密着し、すぐれた
離型性、耐摩耗性を示すので、このものはプラスチック
フィルムに対する離型処理用として特に有用とされる。Substrates treated with the composition of the present invention have 70%
A cured film may be formed on the surface by heating at a temperature of ~ 200 ° C for 1 to 30 seconds, but this composition can be applied as a thin film to a substrate as it is without being diluted with an organic solvent. Therefore, it is energy-saving, safe, and pollution-free, and since this curing can be performed at low temperature and for a short time as described above, it can be applied to plastic films without shrinking, and the cured coating thus obtained is Since it adheres well to a base material, especially a plastic film, and has excellent mold releasability and abrasion resistance, it is particularly useful as a mold release treatment for a plastic film.
【００２０】[0020]
【実施例】つぎに本発明の実施例で使用される第１成分
の合成例、実施例、比較例をあげるが、例中の部は重量
部、また粘度は25℃での測定値を示したものである。な
お、以下に実施例における各物性の測定法をあげる。[Examples] Next, synthesis examples, examples and comparative examples of the first component used in the examples of the present invention will be given. Parts in the examples are parts by weight, and viscosities are measured values at 25 ° C. It is a thing. In addition, the measuring method of each physical property in an Example is given below.
【００２１】［硬化性］組成物の所定量を薄膜状フィル
ムまたはシート状の基材の表面に塗布したのち、所定温
度の熱風循環式乾燥炉中で所定時間加熱して塗膜が完全
に硬化するまでの時間を測定する。ただし、この硬化の
判定は塗工面を指でこすっても塗工面が脱落せず、かつ
曇らない時点とした。 ［密着性］上記の方法で硬化皮膜を形成した薄膜状フィ
ルムを40℃×95％ＲＨの恒温恒湿槽に所定日数保存した
のち、その硬化皮膜を指で強く10回こすり、白化、脱落
までの時間（日数）で密着性の程度を表わす。[Curing] A predetermined amount of the composition is applied to the surface of a thin film or sheet substrate and then heated in a hot air circulation drying oven at a predetermined temperature for a predetermined time to completely cure the coating film. Measure the time to do. However, this determination of curing was made at the time when the coated surface did not fall off even if the coated surface was rubbed with a finger, and the coating surface did not become cloudy. [Adhesiveness] The thin film on which a cured film has been formed by the above method is stored in a thermo-hygrostat at 40 ° C x 95% RH for a specified number of days, and then the cured film is rubbed with the finger 10 times, whitening and falling off. The time (number of days) indicates the degree of adhesion.
【００２２】［剥離力］シリコーン組成物をＯＰＰフィ
ルム（40μｍ）にその塗布量が 0.5g/m2となるように塗
工し、熱風循環式乾燥炉中で 120℃×30秒間加熱処理し
て塗膜を硬化させた後、この基材を25℃で１日静置し、
ついでこの面にゴム系溶剤型粘着剤ＢＰＳ−3942［東洋
インキ製造（株）製商品名］を固形分が25g/m2となるよ
うに塗布し、 100℃で３分間乾燥させた後ＯＰＰフィル
ム（40μｍ）に貼り合わせ、２kgのゴムロールで１往復
圧着後、25℃で１日静置し剥離力測定用試験片（幅５c
m）を作りオートグラフを用いて剥離角度 180°、剥離
速度 0.3m/分で剥離力を測定した。また同様にして剥離
速度30m/分で剥離した時の剥離音を評価した。 ［残留接着率］上記で得たシリコーン処理フィルムにル
ミラー31Ｂテープ［日東電工（株）製商品名］を貼り合
わせて70℃で20g/cm2 の荷重をかけて20時間圧着処理す
ると共に基準となる接着力を測定するためにテフロン板
に同様のルミラー31Ｂを貼り合わせ同様の圧着処理を行
い、これらのテープを剥しステンレス板に貼りつけ２kg
のゴムローラーを１往復させた後、接着力を測定し、基
準としたルミラー31Ｂの接着力を 100として各サンプル
の残留接着率を百分率で表した。[Peeling power] A silicone composition was coated on an OPP film (40 μm) so that the coating amount was 0.5 g / m 2 and heat-treated at 120 ° C. for 30 seconds in a hot air circulation type drying furnace. After curing the coating, leave this substrate at 25 ° C for 1 day,
Then, a rubber solvent type adhesive BPS-3942 [trade name of Toyo Ink Mfg. Co., Ltd.] was applied to this surface so that the solid content was 25 g / m 2, and dried at 100 ° C. for 3 minutes, and then the OPP film The test piece for peeling force measurement (width: 5c)
m) was prepared and the peeling force was measured using an autograph at a peeling angle of 180 ° and a peeling speed of 0.3 m / min. Similarly, the peeling noise when peeling at a peeling speed of 30 m / min was evaluated. [Residual Adhesion Rate] Lumirror 31B tape (trade name of Nitto Denko Corporation) was attached to the silicone-treated film obtained above, and a pressure of 20 g / cm 2 was applied at 70 ° C. for 20 hours for pressure bonding and the standard. In order to measure the adhesive strength, the same Lumirror 31B is attached to the Teflon plate and the same pressure treatment is performed, and these tapes are peeled off and attached to the stainless steel plate 2 kg.
After reciprocating the rubber roller of No. 1 once, the adhesive force was measured, and the residual adhesive ratio of each sample was expressed as a percentage, with the adhesive force of the Lumirror 31B as a reference being 100.
【００２３】合成例 メチルトリメトキシシラン68部とオクタメチルシクロテ
トラシロキサン 444部とをアルカリ触媒の存在下で５時
間重合させたのち、未反応物を減圧留去したところ粘度
20cpの重合体が 300部得られたので、この重合体 300部
にテトラメチルジビニルジシロキサン 140部を添加し、
これらを塩酸水中で加水分解縮合させ、減圧下、低沸点
分を留去したところ、式Synthetic Example 68 parts of methyltrimethoxysilane and 444 parts of octamethylcyclotetrasiloxane were polymerized in the presence of an alkali catalyst for 5 hours, and unreacted substances were distilled off under reduced pressure to obtain a viscosity.
Since 300 parts of a 20 cp polymer was obtained, 140 parts of tetramethyldivinyldisiloxane was added to 300 parts of this polymer,
These were hydrolyzed and condensed in hydrochloric acid water, and the low boiling point component was distilled off under reduced pressure.
【化８】 で示される粘度70cpのポリビニルシロキサン（以下これ
を成分Ａと略記する） 320部が得られた。[Chemical 8] As a result, 320 parts of a polyvinyl siloxane having a viscosity of 70 cp (hereinafter abbreviated as component A) were obtained.
【００２４】実施例１ 上記の合成例で得た成分Ａ50部、分子鎖両末端がトリビ
ニルシリル基で封鎖された、重合度が 150、粘度が 600
cpのジメチルポリシロキサン（以下成分Ｂと略記する）
50部、分子鎖末端がトリメチルシリル基で封鎖されてお
り、CH3HSiO 単位が90モル％で粘度が100cpsであるメチ
ルハイドロジェンポリシロキサン（以下成分Ｃと略記す
る）20部、３−メチル−１−ブチン（以下成分Ｄと略記
する）１部を均一に混合撹拌したものに、塩化白金酸と
ビニルシロキサンとの錯体（白金換算 80ppm）（以下成
分Ｅと略記する）３部を加えてシリコーン組成物（Ｉ）
を作った。Example 1 50 parts of the component A obtained in the above synthesis example, both ends of the molecular chain were blocked with trivinylsilyl groups, the degree of polymerization was 150, and the viscosity was 600.
cp dimethyl polysiloxane (hereinafter abbreviated as component B)
50 parts, 20 parts of methylhydrogenpolysiloxane (hereinafter abbreviated as component C) having 90 mol% CH 3 HSiO units and a viscosity of 100 cps, the ends of which are blocked with trimethylsilyl groups, 3-methyl-1 -Butine (hereinafter abbreviated as Component D) 1 part was uniformly mixed and stirred, and 3 parts of a complex of chloroplatinic acid and vinylsiloxane (80 ppm in platinum) (hereinafter abbreviated as Component E) was added to the silicone composition. Thing (I)
made.
【００２５】ついで、この組成物を厚さ40μｍのポリプ
ロピレンフィルムにオフセット転写機を用いて 0.5g/m2
となるように塗工し、 100℃に加熱処理して硬化させた
のち、この塗膜の硬化性、得られた硬化被膜の密着性、
剥離力、残留接着率を調べたところ、後記する表１に示
したとおりの結果が得られた。Then, this composition was applied to a polypropylene film having a thickness of 40 μm using an offset transfer machine at 0.5 g / m 2
And then heat treated to 100 ° C to cure, then the curability of this coating, the adhesion of the resulting cured coating,
When the peeling force and the residual adhesion rate were examined, the results shown in Table 1 below were obtained.
【００２６】実施例２ 成分Ａ50部、分子鎖両末端がビニルジメチルシリル基で
封鎖された、粘度が5,000cpsのポリビニルメチルシロキ
サン（以下成分Ｆと略記する）50部、成分Ｃ20部、成分
Ｄ１部を均一に混合撹拌したのち、成分Ｅを３部加えて
シリコーン組成物（II）を作り、これを実施例１と同様
にポリプロピレンフィルムに処理して硬化させ、この硬
化被膜の物性を調べたところ、後記する表１に示したと
おりの結果が得られた。Example 2 50 parts of component A, 50 parts of polyvinyl methyl siloxane having a viscosity of 5,000 cps (hereinafter abbreviated as component F) blocked at both molecular chain ends with vinyldimethylsilyl groups, 20 parts of component C, 1 part of component D After uniformly mixing and stirring, 3 parts of component E was added to prepare a silicone composition (II), which was treated into a polypropylene film and cured in the same manner as in Example 1, and the physical properties of this cured film were examined. The results shown in Table 1 below were obtained.
【００２７】比較例１ 成分Ａ 100部、成分Ｃ20部、成分Ｄ１部を均一に混合撹
拌し、これに成分Ｅ３部を加えてシリコーン組成物(II
I) を作り、これを実施例１と同様にポリプロピレンフ
ィルムに処理し、硬化してその硬化被膜の物性を調べた
ところ、後記する表１に示したとおりの結果が得られ
た。Comparative Example 1 100 parts of the component A, 20 parts of the component C and 1 part of the component D were uniformly mixed and stirred, and 3 parts of the component E was added thereto to obtain a silicone composition (II
I) was prepared, and treated in the same manner as in Example 1 to prepare a polypropylene film and cured, and the physical properties of the cured film were examined. The results shown in Table 1 below were obtained.
【００２８】比較例２ 成分Ｂ 100部、成分Ｃ20部、成分Ｄ１部を均一に混合撹
拌したのち、これに成分Ｅ３部を加えてシリコーン組成
物（IV）を作り、これを実施例１と同様にポリプロピレ
ンフィルムに処理し、硬化してその硬化被膜の物性を調
べたところ、後記する表１に示したとおりの結果が得ら
れた。Comparative Example 2 100 parts of the component B, 20 parts of the component C and 1 part of the component D were uniformly mixed and stirred, and then 3 parts of the component E was added thereto to prepare a silicone composition (IV), which was prepared in the same manner as in Example 1. When a polypropylene film was treated and cured, and the cured film was examined for physical properties, the results shown in Table 1 below were obtained.
【００２９】比較例３ 成分Ｆ 100部、成分Ｃ20部、成分Ｄ１部を均一に混合撹
拌したのち、これに成分Ｅ３部を加えてシリコーン組成
物（Ｖ）を作り、これを実施例１と同様にポリプロピレ
ンフィルムに処理し、硬化してその硬化被膜の物性を調
べたところ、つぎの表１に示したとおりの結果が得られ
た。Comparative Example 3 100 parts of the component F, 20 parts of the component C and 1 part of the component D were uniformly mixed and stirred, and then 3 parts of the component E was added thereto to prepare a silicone composition (V), which was prepared in the same manner as in Example 1. When the polypropylene film was treated and cured, and the cured coating was examined for physical properties, the results shown in Table 1 below were obtained.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【発明の効果】本発明は剥離性シリコーン組成物に関す
るものであり、これは前記したように１）式（１）で示
されるオルガノポリシロキサン 0.1〜99.9重量部、２）
式（２）で示されるオルガノポリシロキサン99.9〜0.1
重量部、３）オルガノハイドロジェンポリシロキサン
1.0〜100 重量部、４）触媒量の白金または白金系化合
物とからなることを特徴とするものであるが、このもの
は特に有機溶剤を含有させなくても紙、ラミネート紙、
プラスチックフィルムなどの表面に密着塗布させること
ができ、これらの基材表面に非粘着性を与えることがで
きるという有利性をもつものである。The present invention relates to a releasable silicone composition, which is, as mentioned above, 1) 0.1 to 99.9 parts by weight of organopolysiloxane represented by the formula (1), 2).
Organopolysiloxane represented by the formula (2) 99.9 to 0.1
Parts by weight, 3) organohydrogenpolysiloxane
It is characterized by comprising 1.0 to 100 parts by weight, and 4) a catalytic amount of platinum or a platinum-based compound.
It has the advantage that it can be applied in close contact with the surface of a plastic film or the like, and non-tackiness can be imparted to the surface of these substrates.
Claims (2)
または異種の１価有機基、ｅは３≦ｅ≦100 、ｆは10〜
1,000 、ｇは１〜50の整数）で示され、25℃における粘
度が50〜10,000cpであるオルガノポリシロキサン 0.1〜
99.9重量部、 ２）平均組成式が 【化２】 （ここにＲ5 はアルケニル基、Ｒ6 は同一または異種の１価の有機基、ａは１〜 ３の正数、ｐ≧０、ｑ≧１）で示され、25℃における粘度が50〜10,000cpである オルガノポリシロキサン 99.9〜0.1 重量部、 ３）オルガノハイドロジェンポリシロキサン 1.0〜100 重量部、 ４）触媒量の白金または白金系化合物 とからなることを特徴とする剥離紙用シリコーン組成
物。1. The average composition formula is: (Here, R 1 is an alkenyl group, R 2 , R 3 , and R 4 are the same or different monovalent organic groups, e is 3 ≦ e ≦ 100, and f is 10 to 10
Organopolysiloxane having a viscosity of 50 to 10,000 cp at 25 ° C.
99.9 parts by weight, 2) The average composition formula is (Wherein R 5 is an alkenyl group, R 6 is the same or different monovalent organic group, a is a positive number from 1 to 3, p ≧ 0, q ≧ 1), and the viscosity at 25 ° C. is 50 to 50 ° C. 10,000 cp organopolysiloxane 99.9 to 0.1 parts by weight, 3) organohydrogenpolysiloxane 1.0 to 100 parts by weight, 4) a catalytic amount of platinum or a platinum-based compound, and a silicone composition for release paper .
れるものである請求項１に記載した剥離紙用シリコーン
組成物。2. The second component has an average composition formula: (Wherein R 5 , R 6 , a, p, and q are the same as above), the silicone composition for release paper according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5031346A JP2965231B2 (en) | 1993-01-27 | 1993-01-27 | Silicone composition for release paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5031346A JP2965231B2 (en) | 1993-01-27 | 1993-01-27 | Silicone composition for release paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06220327A true JPH06220327A (en) | 1994-08-09 |
| JP2965231B2 JP2965231B2 (en) | 1999-10-18 |
Family
ID=12328673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5031346A Expired - Fee Related JP2965231B2 (en) | 1993-01-27 | 1993-01-27 | Silicone composition for release paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2965231B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6432268B1 (en) | 2000-09-29 | 2002-08-13 | Kimberly-Clark Worldwide, Inc. | Increased hydrophobic stability of a softening compound |
| JP2005060554A (en) * | 2003-08-14 | 2005-03-10 | Shin Etsu Chem Co Ltd | Release agent composition for silicone adhesive and release sheet using the same |
| JP2006152265A (en) * | 2004-10-29 | 2006-06-15 | Shin Etsu Chem Co Ltd | Hardening silicone release agent composition and release paper using it |
| JP2007284685A (en) * | 2007-06-01 | 2007-11-01 | Shin Etsu Chem Co Ltd | Silicone releasing agent composition and release coated paper |
| JP2012056316A (en) * | 2011-10-03 | 2012-03-22 | Dow Corning Toray Co Ltd | Base material whose surface is formed with peelable cured film |
| WO2018012296A1 (en) | 2016-07-11 | 2018-01-18 | 信越化学工業株式会社 | Silicone composition, release paper and release film |
| WO2018139269A1 (en) | 2017-01-25 | 2018-08-02 | 信越化学工業株式会社 | Silicone composition, release paper, and release film |
| WO2020009007A1 (en) | 2018-07-03 | 2020-01-09 | 信越化学工業株式会社 | Silicone composition, peelable sheet, peelable film, and method for manufacturing peelable sheet and peelable film |
| CN115975428A (en) * | 2021-10-15 | 2023-04-18 | 山东东岳高分子材料有限公司 | Anchoring agent for fluorine-silicon release agent and application thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6485262B2 (en) | 2015-07-16 | 2019-03-20 | 信越化学工業株式会社 | Release paper or silicone composition for release film, release paper and release film |
| KR20220157399A (en) | 2020-03-25 | 2022-11-29 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Silicone composition for release sheet and release sheet |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6432268B1 (en) | 2000-09-29 | 2002-08-13 | Kimberly-Clark Worldwide, Inc. | Increased hydrophobic stability of a softening compound |
| JP2005060554A (en) * | 2003-08-14 | 2005-03-10 | Shin Etsu Chem Co Ltd | Release agent composition for silicone adhesive and release sheet using the same |
| KR101022611B1 (en) * | 2003-08-14 | 2011-03-16 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Mold Releasing Agent Composition for Silicone Adhesive and Mold Releasing Sheet Using the Same |
| JP2006152265A (en) * | 2004-10-29 | 2006-06-15 | Shin Etsu Chem Co Ltd | Hardening silicone release agent composition and release paper using it |
| JP2007284685A (en) * | 2007-06-01 | 2007-11-01 | Shin Etsu Chem Co Ltd | Silicone releasing agent composition and release coated paper |
| JP2012056316A (en) * | 2011-10-03 | 2012-03-22 | Dow Corning Toray Co Ltd | Base material whose surface is formed with peelable cured film |
| KR20190029580A (en) | 2016-07-11 | 2019-03-20 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Silicone composition, release paper and release film |
| WO2018012296A1 (en) | 2016-07-11 | 2018-01-18 | 信越化学工業株式会社 | Silicone composition, release paper and release film |
| WO2018139269A1 (en) | 2017-01-25 | 2018-08-02 | 信越化学工業株式会社 | Silicone composition, release paper, and release film |
| KR20190105599A (en) | 2017-01-25 | 2019-09-17 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Silicone composition, release paper and release film |
| US11104812B2 (en) | 2017-01-25 | 2021-08-31 | Shin-Etsu Chemical Co., Ltd. | Silicone composition, release paper, and release film |
| WO2020009007A1 (en) | 2018-07-03 | 2020-01-09 | 信越化学工業株式会社 | Silicone composition, peelable sheet, peelable film, and method for manufacturing peelable sheet and peelable film |
| KR20210027275A (en) | 2018-07-03 | 2021-03-10 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Silicone composition, release sheet, release film, and release sheet and method for producing release film |
| CN115975428A (en) * | 2021-10-15 | 2023-04-18 | 山东东岳高分子材料有限公司 | Anchoring agent for fluorine-silicon release agent and application thereof |
| CN115975503A (en) * | 2021-10-15 | 2023-04-18 | 山东东岳高分子材料有限公司 | Anchoring agent for fluorine-silicon release agent and application thereof |
| CN115975428B (en) * | 2021-10-15 | 2023-07-18 | 山东东岳高分子材料有限公司 | Anchoring agent for fluorine-silicon release agent and application thereof |
| CN115975503B (en) * | 2021-10-15 | 2023-09-15 | 山东东岳高分子材料有限公司 | Anchoring agent for fluorine-silicon release agent and application thereof |
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|---|---|
| JP2965231B2 (en) | 1999-10-18 |
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