JPH0625601A - Organopolysiloxane composition for release paper, and release paper - Google Patents
Organopolysiloxane composition for release paper, and release paperInfo
- Publication number
- JPH0625601A JPH0625601A JP4205888A JP20588892A JPH0625601A JP H0625601 A JPH0625601 A JP H0625601A JP 4205888 A JP4205888 A JP 4205888A JP 20588892 A JP20588892 A JP 20588892A JP H0625601 A JPH0625601 A JP H0625601A
- Authority
- JP
- Japan
- Prior art keywords
- release paper
- group
- organopolysiloxane
- formula
- component
- 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.)
- Granted
Links
Landscapes
- Paper (AREA)
- Adhesive Tapes (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ピンホールなどの欠陥
がない均一な皮膜を形成することができる剥離紙用オル
ガノポリシロキサン組成物及び該組成物が塗布・硬化さ
れた剥離紙に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organopolysiloxane composition for release paper which can form a uniform film free from defects such as pinholes, and a release paper coated and cured with the composition.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来よ
り、紙やプラスチックフィルム表面に離型性に優れるシ
リコーン硬化皮膜を形成した剥離紙は、粘着加工製品に
広く応用されている。2. Description of the Related Art Conventionally, a release paper having a silicone cured film having excellent releasability formed on the surface of a paper or a plastic film has been widely applied to an adhesive processed product.
【０００３】このようなシリコーン硬化皮膜を形成でき
るオルガノポリシロキサン組成物としては、ビニル基含
有オルガノポリシロキサン、オルガノハイドロジェンポ
リシロキサン及び付加反応用触媒を含有する付加反応型
のものが良く知られている（特公昭５２−４０９１８
号、特公昭６１−５３３８３号公報）。As an organopolysiloxane composition capable of forming such a cured silicone film, an addition reaction type one containing a vinyl group-containing organopolysiloxane, an organohydrogenpolysiloxane and an addition reaction catalyst is well known. There is (Japanese Patent Publication No. 52-40918)
No. 6-53383).
【０００４】しかし、この付加反応型のオルガノポリシ
ロキサン組成物は、接着ラベル、テープ、壁紙などのよ
うに剥離力の比較的小さいものには好適とされるが、工
程紙や両面テープの重面などのように大きな剥離力（重
剥離力）を必要とする分野ではその使用に著しく制約を
受け、実用性に問題があった。However, although this addition reaction type organopolysiloxane composition is suitable for adhesive labels, tapes, wallpaper and the like having a relatively small peeling force, it can be used as a heavy surface of process paper or double-sided tape. In a field requiring a large peeling force (heavy peeling force) such as, the use thereof is significantly restricted, and there is a problem in practicality.
【０００５】この問題を解決するため、剥離力を調整す
るための重剥離用調整剤としてＲ3ＳｉＯ1/2（Ｒは一価
炭化水素基）とＳｉＯ2で示される単位とからなるトル
エン可溶性共重合体を添加する方法が提案されている
（特開昭５２−８６９８５号公報）。In order to solve this problem, a toluene-soluble solvent composed of R 3 SiO 1/2 (R is a monovalent hydrocarbon group) and a unit represented by SiO 2 is used as a heavy release modifier for adjusting the peeling force. A method of adding a copolymer has been proposed (JP-A-52-86985).
【０００６】しかし、この剥離力調整剤成分を使用した
オルガノポリシロキサン組成物は、基材に塗工した場合
にハジキを生じたり、ピンホールが発生し、均一に塗工
できず、このため粘着剤を貼り合わせ後、部分的に重剥
離又は剥離不良となる問題があった。[0006] However, the organopolysiloxane composition using this peeling force modifier component cannot be applied uniformly because cissing or pinholes occur when it is applied to the substrate, and therefore the adhesiveness is reduced. After bonding the agent, there was a problem that heavy peeling or poor peeling occurred partially.
【０００７】本発明は、上記事情に鑑みなされたもの
で、基材にピンホールなどが生じずに薄く均一に塗工す
ることができる塗工性に優れた剥離紙用オルガノポリシ
ロキサン組成物及びこの組成物の硬化皮膜を形成した剥
離紙を提供することを目的とする。The present invention has been made in view of the above circumstances, and an organopolysiloxane composition for release paper, which has excellent coatability and can be applied thinly and uniformly without forming pinholes or the like on a substrate, and It is an object to provide a release paper on which a cured film of this composition is formed.
【０００８】[0008]
【課題を解決するための手段及び作用】本発明者は、上
記目的を達成するため鋭意検討を重ねた結果、（Ａ）一
分子中に珪素原子に直接結合したアルケニル基を少なく
とも２個有するアルケニル基含有ジオルガノポリシロキ
サン、（Ｂ）一分子中に珪素原子に直接結合した水素原
子を少なくとも２個含有する液状オルガノハイドロジェ
ンポリシロキサン、（Ｃ）式Ｒ3ＳｉＯ1/2（式中、Ｒは
メチル基及び／又はビニル基である）及びＳｉＯ2で示
されるシロキサン単位からなる溶剤可溶性オルガノポリ
シロキサン、（Ｄ）下記式（１）で示されるパーフロロ
アルキル基含有オルガノポリシロキサン、（Ｅ）付加反
応触媒を含有する剥離紙用オルガノポリシロキサン組成
物とすることが有効であることを知見した。Means for Solving the Problems and Actions The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, (A) an alkenyl group having at least two alkenyl groups directly bonded to a silicon atom in one molecule. Group-containing diorganopolysiloxane, (B) liquid organohydrogenpolysiloxane containing at least two hydrogen atoms directly bonded to silicon atoms in one molecule, (C) formula R 3 SiO 1/2 (wherein R is Is a methyl group and / or a vinyl group) and a solvent-soluble organopolysiloxane composed of siloxane units represented by SiO 2 , (D) a perfluoroalkyl group-containing organopolysiloxane represented by the following formula (1), (E) It has been found that it is effective to use an organopolysiloxane composition for release paper containing an addition reaction catalyst.
【０００９】[0009]
【化２】 〔但し、式中Ｒ1は炭素数１〜１８の一価炭化水素基、
Ｒ2 はＣ2Ｈ4ＣnＦ2n+1（ｎは１〜８の整数）で示される
パーフロロアルキル基、ｋは１以上の整数、ｍは０又は
１以上の整数である。〕[Chemical 2][However, in the formula R1Is a monovalent hydrocarbon group having 1 to 18 carbon atoms,
R2 Is C2HFourCnF2n + 1(N is an integer of 1 to 8)
Perfluoroalkyl group, k is an integer of 1 or more, m is 0 or
It is an integer of 1 or more. ]
【００１０】即ち、上記（Ａ）、（Ｂ）及び（Ｅ）成分
からなる付加反応型オルガノポリシロキサン組成物に
（Ｃ）成分の剥離力調整剤を配合したものは、上述した
ように、基材に塗工した場合、ピンホールなどの不良が
発生して均一に塗工できないという問題があったが、本
発明者はこの原因について検討を行った結果、（Ｃ）成
分の剥離調整剤を配合すると、そのオルガノポリシロキ
サン組成物が発泡し易くなり、かつその泡が消滅しにく
く、その状態で紙、プラスチックフィルム基材に塗工し
た場合、泡が核となり、このためはじきを生じたり、ピ
ンホールが発生することを知見した。そこで、（Ｃ）成
分を配合した場合に生じる問題を解決するため更に検討
を重ねた結果、上記（Ｄ）成分のパーフロロアルキル基
含有オルガノポリシロキサンを配合した場合、かかる発
泡を有効に抑制し、ハジキやピンホールなどの不良がな
く、均一な塗工を可能とすること、また、この（Ｄ）成
分の配合により（Ｃ）成分の剥離力調整剤配合の問題点
が解消され、剥離力調整剤の効果が有効に発揮され、粘
着剤の粘着力を低下させることがなく剥離力が調整でき
ること、このように均一な硬化皮膜が形成された剥離紙
は、ピンホールなどがないため、部分的に重剥離となっ
たり、剥離不良などが生じることがなく、良好な剥離特
性を有することを見い出し、本発明をなすに至ったもの
である。That is, the addition reaction type organopolysiloxane composition comprising the above-mentioned components (A), (B) and (E) and the peeling force adjusting agent as the component (C) is blended as described above. When coated on a material, there was a problem that defects such as pinholes occurred and the coating could not be performed uniformly. However, as a result of studying the cause, the present inventor found that a release control agent of component (C) was used. When blended, the organopolysiloxane composition easily foams, and the bubbles are hard to disappear, and when applied to paper or a plastic film substrate in that state, the bubbles become nuclei, which may cause repelling, We have found that pinholes occur. Therefore, as a result of further studies to solve the problem that occurs when the component (C) is blended, when the perfluoroalkyl group-containing organopolysiloxane of the component (D) is blended, such foaming is effectively suppressed. It enables uniform coating without defects such as cissing and pinholes, and that the blending of this (D) component eliminates the problems of blending the peeling force modifier of the (C) component, and the peeling force The effect of the adjusting agent is effectively exhibited, the peeling force can be adjusted without lowering the adhesive force of the adhesive, and the release paper on which a uniform cured film is formed does not have pinholes, etc. The present invention has been accomplished by finding that it has good peeling characteristics without causing heavy peeling or peeling failure.
【００１１】従って、本発明は、上記（Ａ）〜（Ｅ）成
分を含有することを特徴とする剥離紙用オルガノポリシ
ロキサン組成物、及び該組成物を塗工・硬化してなる剥
離紙を提供する。Therefore, the present invention provides an organopolysiloxane composition for release paper, which comprises the above-mentioned components (A) to (E), and a release paper obtained by coating and curing the composition. provide.
【００１２】以下、本発明について更に詳しく説明する
と、上述したように、本発明の剥離紙用オルガノポリシ
ロキサン組成物は上記（Ａ）〜（Ｅ）成分を必須成分と
するものである。The present invention will be described in more detail below. As described above, the organopolysiloxane composition for release paper of the present invention contains the above-mentioned components (A) to (E) as essential components.
【００１３】本発明の組成物を構成する（Ａ）成分のア
ルケニル基含有ジオルガノポリシロキサンは、一分子中
に珪素原子に直結したアルケニル基を少なくとも２個含
有することが必要であり、好ましくはジオルガノポリシ
ロキサン１００ｇ中に０．００２〜０．１５モルのアル
ケニル基を含有するものが好適である。このオルガノポ
リシロキサンは、直鎖状でも分枝状であっても差し支え
なく、これらの混合物であっても良い。アルケニル基以
外の珪素原子に直結した有機基としては、例えばメチル
基、プロピル基、ブチル基、へキシル基などのアルキル
基；フェニル基、トリル基などのアリール基；β−フェ
ニルエチル基、β−フェニルプロピル基などのアラルキ
ル基；クロロメチル基などのハロゲン置換炭化水素基等
の置換又は非置換の一価炭化水素基が挙げられるが、こ
れらの中でも合成の容易性、粘着物質に対して剥離性に
優れる硬化皮膜が得られる点からメチル基が好ましい。
（Ａ）成分のオルガノポリシロキサンの粘度は特に制限
されないが、硬化性の面から６０ｃｓ以上とすることが
好ましい。なお、５００００ｃｓ以上の高粘度のものを
使用することもできるが、このような高粘度のものを使
用する場合は、数μｍ以下の塗膜を形成するため、有機
溶剤に溶解して使用することが良い。The alkenyl group-containing diorganopolysiloxane of the component (A) constituting the composition of the present invention must contain at least two alkenyl groups directly bonded to a silicon atom in one molecule, preferably. The thing containing 0.002-0.15 mol of alkenyl groups in 100 g of diorganopolysiloxane is suitable. This organopolysiloxane may be linear or branched, and may be a mixture thereof. Examples of the organic group directly bonded to a silicon atom other than the alkenyl group include alkyl groups such as methyl group, propyl group, butyl group and hexyl group; aryl groups such as phenyl group and tolyl group; β-phenylethyl group, β- Examples include aralkyl groups such as phenylpropyl groups; substituted or unsubstituted monovalent hydrocarbon groups such as halogen-substituted hydrocarbon groups such as chloromethyl groups. Of these, ease of synthesis and releasability from adhesive substances A methyl group is preferable from the viewpoint that a cured film having excellent properties can be obtained.
Although the viscosity of the organopolysiloxane as the component (A) is not particularly limited, it is preferably 60 cs or more from the viewpoint of curability. It is also possible to use a highly viscous product having a viscosity of 50,000 cs or more. However, when using such a highly viscous product, it is necessary to dissolve it in an organic solvent to form a coating film of several μm or less. Is good.
【００１４】また、（Ｂ）成分のオルガノハイドロジェ
ンポリシロキサンは、一分子中に珪素原子に直結した水
素原子（≡ＳｉＨ）を少なくとも２個有するものを使用
する。このオルガノハイドロジェンポリシロキサンは、
直鎖状、分枝状、環状のいずれであっても差し支えない
が、室温で液状である必要があり、具体的には２５℃の
粘度が１０〜３００ｃｓの範囲が好ましい。また、珪素
原子に直結した水素原子以外の有機基としては、上述し
た（Ａ）成分のオルガノポリシロキサンで例示した有機
基を同様に例示することができる。The organohydrogenpolysiloxane as the component (B) has at least two hydrogen atoms (≡SiH) directly bonded to a silicon atom in one molecule. This organohydrogenpolysiloxane is
It may be linear, branched or cyclic, but it needs to be liquid at room temperature, and specifically, the viscosity at 25 ° C. is preferably in the range of 10 to 300 cs. Further, as the organic group other than the hydrogen atom directly bonded to the silicon atom, the organic groups exemplified in the above-mentioned organopolysiloxane (A) can be similarly exemplified.
【００１５】このようなオルガノハイドロジェンポリシ
ロキサンとしては、例えばα，ω−ビス（ジメチルハイ
ドロジェンシリル）ポリジメチルシロキサン、α，ω−
ビス（トリメチルシリル）ポリメチルハイドロジェンシ
ロキサン、α，ω−ビス（トリメチルシリル）ポリ（メ
チルハイドロジェン）（ジメチル）シロキサン共重合体
などが挙げられる。As such an organohydrogenpolysiloxane, for example, α, ω-bis (dimethylhydrogensilyl) polydimethylsiloxane, α, ω-
Examples thereof include bis (trimethylsilyl) polymethylhydrogensiloxane, α, ω-bis (trimethylsilyl) poly (methylhydrogen) (dimethyl) siloxane copolymer, and the like.
【００１６】（Ｂ）成分の配合量は、上記（Ａ）成分の
アルケニル基含有オルガノポリシロキサン１００部（重
量部、以下同様）に対して０．１〜２０部、特に２〜１
５部の範囲が好ましい。０．１部より配合量が少ない
と、得られる剥離紙用組成物の硬化性が悪くなる場合が
あり、２０部より多く配合すると、この剥離紙用組成物
から得られた硬化皮膜の粘着物質との剥離性が不安定と
なる場合がある。また、（Ａ）成分と（Ｃ）成分中のア
ルケニル基に対する（Ｂ）成分中の≡ＳｉＨ基のモル比
としては、アルケニル基／≡ＳｉＨ基を０．５〜１０の
範囲とすることが良い。The blending amount of the component (B) is 0.1 to 20 parts, especially 2-1 to 100 parts by weight of the alkenyl group-containing organopolysiloxane of the above component (A).
A range of 5 parts is preferred. If the amount is less than 0.1 part, the curability of the resulting release paper composition may deteriorate, and if it is more than 20 parts, the adhesive substance of the cured film obtained from this release paper composition. The releasability from and may become unstable. The molar ratio of ≡SiH groups in the component (B) to alkenyl groups in the components (A) and (C) is preferably in the range of 0.5 to 10 alkenyl groups / ≡SiH groups. .
【００１７】次に、本発明の組成物を構成する（Ｃ）成
分の溶剤可溶性のオルガノポリシロキサンは、本剥離紙
用組成物の重剥離性を調整するための成分であり、式Ｒ
3ＳｉＯ1/2（式中、Ｒはメチル基及び／又はビニル基で
ある）及びＳｉＯ2で示されるシロキサン単位からな
る。この場合、Ｒ3ＳｉＯ1/2単位とＳｉＯ2単位とのモ
ル比は、Ｒ3ＳｉＯ1/2単位／ＳｉＯ2単位＝０．６〜
１．３の範囲が好ましく、また、ビニル基の含有量は、
０〜０．２モル／１００ｇの範囲が好ましい。（Ｃ）成
分のオルガノポリシロキサンは溶剤可溶性である必要が
あり、このような溶剤としては、例えばトルエン、キシ
レン、ｎ−ヘキサンなどが挙げられる。Next, the solvent-soluble organopolysiloxane of the component (C) constituting the composition of the present invention is a component for adjusting the heavy release property of the present release paper composition, and has the formula R
3 SiO 1/2 (wherein R is a methyl group and / or a vinyl group) and a siloxane unit represented by SiO 2 . In this case, the molar ratio of the R 3 SiO 1/2 unit and the SiO 2 unit is R 3 SiO 1/2 unit / SiO 2 unit = 0.6 to
The range of 1.3 is preferable, and the vinyl group content is
The range of 0 to 0.2 mol / 100 g is preferable. The organopolysiloxane as the component (C) needs to be soluble in a solvent, and examples of such a solvent include toluene, xylene, and n-hexane.
【００１８】この（Ｃ）成分の配合量は、（Ａ）成分の
アルケニル基含有オルガノポリシロキサン１００部に対
し、５〜１００部、特に１０〜５０部の範囲が好まし
い。５部より少ない配合量では、目的とする剥離力の制
御ができなくなる場合があり、一方１００部より多く配
合すると本剥離紙用組成物の硬化性が悪くなる場合があ
る。The amount of the component (C) blended is preferably 5 to 100 parts, more preferably 10 to 50 parts, per 100 parts of the alkenyl group-containing organopolysiloxane of the component (A). If the blending amount is less than 5 parts, the desired peeling force may not be controlled, whereas if the blending amount is more than 100 parts, the curability of the present release paper composition may be deteriorated.
【００１９】本発明の組成物を構成する（Ｄ）成分のパ
ーフロロアルキル基含有オルガノポリシロキサンは、基
材へ薄膜、例えば１μｍ前後の薄膜を形成する際の処理
液の発泡性を制御し、かつレベリング性を向上させて基
材上への未塗工部が発生することを防止するための成分
で、下記式（１）で示されるものである。The perfluoroalkyl group-containing organopolysiloxane of the component (D) constituting the composition of the present invention controls the foamability of the treatment liquid when forming a thin film, for example, a thin film of about 1 μm on the substrate, In addition, it is a component for improving the leveling property and preventing the uncoated portion from being formed on the substrate, which is represented by the following formula (1).
【００２０】[0020]
【化３】 [Chemical 3]
【００２１】式（１）中、Ｒ1は炭素数１〜１８の置換
又は非置換の一価炭化水素基であり、例えばメチル基、
エチル基、プロピル基、ブチル基、へキシル基などのア
ルキル基；フェニル基、トリル基などのアリール基；ベ
ンジル基などのアラルキル基などが挙げられるが、これ
らの中でも合成の容易性からメチル基が望ましい。ま
た、Ｒ2はＣ2Ｈ4ＣnＦ2n+1（ｎは１〜８の整数）で示さ
れるパーフロロアルキル基であり、例えば−Ｃ2Ｈ4ＣＦ
3、−Ｃ2Ｈ4Ｃ4Ｆ9、−Ｃ2Ｈ4Ｃ8Ｆ17などが挙げられ
る。ｋは１以上の整数、ｍは０又は１以上の整数であ
り、特に制限されないが、有機溶剤可溶性、消泡性、レ
ベリング性から５０≦ｋ＋ｍ≦１０００、２０≦ｋ／
（ｋ＋ｍ）≦６０を満たす数であることが好ましい。In the formula (1), R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms, such as a methyl group,
Examples thereof include alkyl groups such as ethyl group, propyl group, butyl group, and hexyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group. Of these, methyl group is preferred because of its ease of synthesis. desirable. R 2 is a perfluoroalkyl group represented by C 2 H 4 C n F 2n + 1 (n is an integer of 1 to 8), for example, -C 2 H 4 CF.
3, -C 2 H 4 C 4 F 9, and the like -C 2 H 4 C 8 F 17 . k is an integer of 1 or more, m is 0 or an integer of 1 or more, and is not particularly limited, but 50 ≦ k + m ≦ 1000, 20 ≦ k / in terms of organic solvent solubility, defoaming property, and leveling property.
It is preferable that the number satisfies (k + m) ≦ 60.
【００２２】この（Ｄ）成分の配合量は、上記（Ａ）成
分１００部に対して０．００１〜１０部、特に０．０１
〜５部の範囲が好ましい。０．００１部より配合量が少
ないと、本組成物を基材に塗工する際に泡立ちが大き
く、かつレベリング性も不足する場合があり、一方１０
部より多く配合すると、基材に塗工して硬化させた硬化
皮膜が粘着剤の粘着性を低下させる場合がある。The amount of the component (D) blended is 0.001 to 10 parts, especially 0.01 to 100 parts of the component (A).
A range of up to 5 parts is preferred. If the blending amount is less than 0.001 part, foaming may be large when the present composition is applied to a substrate, and the leveling property may be insufficient.
If the amount is larger than the amount, the cured film applied to the base material and cured may reduce the tackiness of the pressure-sensitive adhesive.
【００２３】本発明の（Ｅ）成分を構成する付加反応触
媒は、アルケニル基とヒドロシリル基（≡ＳｉＨ）とを
反応させるための触媒で、このような反応に用いられて
いる公知の触媒を採用することができ、例えば白金黒、
塩化白金酸、塩化白金酸−オレフィン錯体、ロジウム−
オレフィン錯体、塩化白金酸−ビニルシロキサン錯体な
どの貴金属系の触媒を好適に使用することができる。こ
の（Ｅ）成分の配合量は触媒量であり、上記（Ａ）〜
（Ｄ）成分の合計量に対し、金属として通常５〜１００
０ｐｐｍの範囲で使用することができるが、これら
（Ａ）〜（Ｄ）成分の反応性、経済性、あるいは所望の
反応速度に応じて適宜調節することができる。The addition reaction catalyst constituting the component (E) of the present invention is a catalyst for reacting an alkenyl group with a hydrosilyl group (≡SiH), and a known catalyst used in such a reaction is adopted. Can be, for example, platinum black,
Chloroplatinic acid, chloroplatinic acid-olefin complex, rhodium-
A noble metal-based catalyst such as an olefin complex or a chloroplatinic acid-vinyl siloxane complex can be preferably used. The blending amount of the component (E) is a catalytic amount, and
Generally 5 to 100 as a metal based on the total amount of the component (D).
Although it can be used in the range of 0 ppm, it can be appropriately adjusted according to the reactivity, economy, or desired reaction rate of these components (A) to (D).
【００２４】本発明の剥離紙用オルガノポリシロキサン
組成物は、上述した（Ａ）〜（Ｅ）成分を所定量均一に
混合することによって得ることができるが、必要に応じ
て反応抑制剤、シリカなどの無機質充填剤、顔料などを
配合することができる。The organopolysiloxane composition for release paper of the present invention can be obtained by uniformly mixing the above-mentioned components (A) to (E) in a predetermined amount, and if necessary, a reaction inhibitor and silica. Inorganic fillers such as, pigments and the like can be blended.
【００２５】このようにして得られた本発明の剥離紙用
オルガノポリシロキサン組成物は、そのまま無溶剤で、
あるいはトルエン、キシレン、ｎ−ヘキサンなどのよう
な適宜な溶剤で希釈し、ロールコート、リバースコー
ト、グラビヤコートなどの塗布方法を用いて、紙、プラ
スチックフィルムなどに塗工し、加熱して硬化させるこ
とにより剥離紙を製造することができる。この場合、塗
工量は０．０５〜５０ｇ／ｍ2の範囲、加熱条件は、温
度８０〜１８０℃で４〜６０秒間の範囲が一般的であ
る。The organopolysiloxane composition for release paper of the present invention thus obtained is solvent-free as it is,
Alternatively, it is diluted with an appropriate solvent such as toluene, xylene, n-hexane, etc., and is applied to paper, plastic film, etc. using a coating method such as roll coating, reverse coating, gravure coating, etc. and cured by heating. By doing so, a release paper can be manufactured. In this case, the coating amount is generally in the range of 0.05 to 50 g / m 2 , and the heating condition is generally in the range of 80 to 180 ° C. for 4 to 60 seconds.
【００２６】[0026]
【実施例】以下、実施例と比較例を示し、本発明を具体
的に示すが、本発明は下記の実施例に制限されるもので
はない。なお、以下の例において、部は重量部、粘度は
２５℃での測定値である。EXAMPLES Hereinafter, the present invention will be specifically shown by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, parts are parts by weight and viscosity is a measured value at 25 ° C.
【００２７】［実施例１］（Ａ）成分として、分枝鎖両
末端がジメチルビニルシリル基で封鎖された、ビニル基
量が０．０１５モル／１００ｇで重合度約８０００であ
るビニル基含有ジメチルジフェニルポリシロキサン（フ
ェニル基含量５モル％）１００部、（Ｂ）成分として分
枝鎖両末端がトリメチルシリル基で封鎖された≡ＳｉＨ
基量が１．６モル／１００ｇで粘度が２０ｃｓであるメ
チルハイドロジェンポリシロキサン５部、（Ｃ）成分と
して、式（ＣＨ3）2ＳｉＯ0.5及び式（ＣＨ3）（ＣＨ2
＝ＣＨ）ＳｉＯ0.5と式ＳｉＯ2で示されるシロキサン単
位（モル比１．０：０．０５：１．０）からなるキシレ
ン可溶性オルガノポリシロキサンレジンを固形分で２５
部加え、更にアセチレンアルコール２部を添加し、全重
量が２５００部となるようにトルエンで希釈溶解したも
のを組成物Ａとした。[Example 1] As the component (A), vinyl group-containing dimethyl having a branched chain both ends blocked with dimethylvinylsilyl groups and having a vinyl group content of 0.015 mol / 100 g and a degree of polymerization of about 8000. 100 parts of diphenylpolysiloxane (phenyl group content 5 mol%), as a component (B), both ends of the branched chain are blocked with trimethylsilyl groups ≡SiH
5 parts of methylhydrogenpolysiloxane having a base amount of 1.6 mol / 100 g and a viscosity of 20 cs, as the component (C), the formula (CH 3 ) 2 SiO 0.5 and the formula (CH 3 ) (CH 2
= CH) SiO 0.5 and a siloxane unit represented by the formula SiO 2 (molar ratio 1.0: 0.05: 1.0) of a xylene-soluble organopolysiloxane resin with a solid content of 25
In addition, 2 parts of acetylene alcohol was added, and the mixture was diluted and dissolved in toluene so that the total weight became 2500 parts, to obtain a composition A.
【００２８】この組成物Ａをそれぞれ３０部づつ５つの
１００ｍｌの蓋付き瓶に入れた。これらに（Ｄ）成分と
して下記式（１−ａ）で示されるパーフロロアルキル基
含有オルガノポリシロキサンを組成物Ａ中の（Ａ）成分
のビニル基含有オルガノポリシロキサンに対し２０、１
００、１０００、１００００ｐｐｍとなるように添加し
たものを試料１〜４とし、更に比較用として未添加のも
のを試料５とした。Each 30 parts of this composition A was placed in 5 100 ml bottles with a lid. As the component (D), a perfluoroalkyl group-containing organopolysiloxane represented by the following formula (1-a) is added to the vinyl group-containing organopolysiloxane of the component (A) in the composition A in an amount of 20: 1.
Samples 1 to 4 were added so as to have a concentration of 00, 1000, and 10000 ppm, and a sample 5 was added for comparison and was not added.
【００２９】[0029]
【化４】 [Chemical 4]
【００３０】これらの試料１〜５それぞれに（Ｅ）成分
として塩化白金酸−テトラメチルジビニルジシロキサン
錯体を白金として５０ｐｐｍ加えて剥離紙用組成物を調
整した。50 ppm of chloroplatinic acid-tetramethyldivinyldisiloxane complex was added as a component (E) to each of these samples 1 to 5 to prepare a release paper composition.
【００３１】次いで、得られた剥離紙用組成物の発泡性
を下記方法によって評価すると共に、これら組成物をポ
リエチレンラミネート紙の表面にワイヤーバーを用いて
塗工量が約０．５ｇ／ｍ2になるように塗工し、１４０
℃の熱風循環式乾燥機中で３０秒間熱処理し、剥離紙を
得た。Next, the foamability of the obtained release paper composition was evaluated by the following method, and the composition was coated on the surface of polyethylene laminated paper with a wire bar to give a coating amount of about 0.5 g / m 2. So that it becomes 140
The release paper was obtained by heat treatment for 30 seconds in a hot air circulation dryer at ℃.
【００３２】この剥離紙の硬化皮膜に対し、下記方法に
従い、剥離力、残留接着率を測定すると共に、目視にて
硬化皮膜面のピンホールを観察した。以上の結果を表１
に示す。発泡性 直径４ｃｍの透明蓋付き１００ｍｌのガラス瓶に上記試
料１〜５をそれぞれ３０ｇとり、振盪機で３０分振盪し
た後、２分間静置し、液面の高さを測定し、下記式に従
い振盪前の液面の高さとの比率で発泡性を評価した。 発泡性＝Ｈ／Ｈ0×１００（％） （Ｈ：振盪後の液面までの高さ、Ｈ0：振盪前の液面の
高さ）剥離力 グラシン紙片の硬化皮膜の表面にアクリル系溶剤型粘着
剤（東洋インキ社製、商品名オリバインＢＰＳ−５１２
７）又はアクリル系エマルジョン型粘着剤（東洋インキ
社製、商品名オリバインＢＰＷ−３１１０Ｈ）を塗布
後、１００℃で３分間加熱処理して硬化皮膜の上に粘着
剤層を有する紙片を作成した。次に、この紙片の粘着剤
層に坪量６４ｇ／ｍ3の貼り合わせ紙を貼り合わせ、室
温で２０時間エイジングした。エイジング後、紙片を幅
５ｃｍ×長さ１０ｃｍに切断して試験片を作成し、引張
試験機にかけて１８０°の角度で剥離速度３００ｍｍ／
分で引張り、硬化皮膜が粘着剤層から剥離するのに要す
る力（ｇ／５ｃｍ幅）を測定した。残留接着率 剥離紙の硬化皮膜の表面にポリエステル粘着テープ（商
品名ルミラー３１Ｂ、日東電工（株）製）を貼り合わ
せ、２０ｇ／ｃｍ2の加重をかけながら、７０℃で２０
時間加熱処理した。加熱処理後、ポリエステル粘着テー
プを硬化皮膜から剥がし、ステンレススチール板の表面
に貼りつけた。With respect to the cured film of this release paper, the peeling force and the residual adhesion rate were measured by the following methods, and the pinholes on the surface of the cured film were visually observed. The above results are shown in Table 1.
Shown in. Take the sample 1-5 respectively 30g glass bottle transparent lid 100ml effervescent diameter 4 cm, was shaken 30 minutes with a shaker, and allowed to stand for 2 minutes, to measure the height of the liquid surface, shaking according to the following formula The foamability was evaluated by the ratio with the height of the previous liquid surface. Foaming property = H / H 0 × 100 (%) (H: height to liquid surface after shaking, H 0 : height of liquid surface before shaking) Peeling power Acrylic solvent on the surface of cured film of glassine paper piece Type Adhesive (manufactured by Toyo Ink Co., Ltd., trade name Olivine BPS-512
7) or an acrylic emulsion type pressure-sensitive adhesive (manufactured by Toyo Ink Co., Ltd., trade name Olivine BPW-3110H) was applied and then heat-treated at 100 ° C. for 3 minutes to prepare a paper piece having a pressure-sensitive adhesive layer on the cured film. Next, a bonding paper having a basis weight of 64 g / m 3 was bonded to the pressure-sensitive adhesive layer of this piece of paper and aged at room temperature for 20 hours. After aging, a piece of paper is cut into a piece having a width of 5 cm and a length of 10 cm to prepare a test piece, which is subjected to a tensile tester at an angle of 180 ° and a peeling speed of 300 mm /
It was pulled in minutes, and the force (g / 5 cm width) required for the cured film to peel from the pressure-sensitive adhesive layer was measured. Residual Adhesion Rate Polyester adhesive tape (trade name Lumirror 31B, Nitto Denko Co., Ltd.) was attached to the surface of the cured film of the release paper, and a load of 20 g / cm 2 was applied to the polyester adhesive tape at 70 ° C.
Heat treated for hours. After the heat treatment, the polyester adhesive tape was peeled off from the cured film and attached to the surface of the stainless steel plate.
【００３３】次に、加熱処理したポリエステル粘着テー
プをステンレススチール板から１８０°の方向に剥離速
度３００ｍｍ／分で剥がし、剥離するのに要する力Ｗ
（ｇ／２．５ｃｍ幅）を測定した。一方、上記加熱処理
をしないポリエステル粘着テープをステンレススチール
板に貼りつけ、これを上記と同様の条件でステンレスス
チール板から剥離するのに要する力Ｗ0（ｇ／２．５ｃ
ｍ幅）を測定し、このＷ0に対するＷの比（Ｗ／Ｗ0）
（百分率）を求めて残留接着率とした。Next, the heat-treated polyester adhesive tape was peeled from the stainless steel plate in the direction of 180 ° at a peeling speed of 300 mm / min, and the force W required for peeling was peeled off.
(G / 2.5 cm width) was measured. On the other hand, the force W 0 (g / 2.5c) required to attach the polyester adhesive tape not subjected to the heat treatment to a stainless steel plate and peel it from the stainless steel plate under the same conditions as above.
m width) was measured, the ratio of W to the W 0 (W / W 0)
The (percentage) was calculated as the residual adhesion rate.
【００３４】[0034]
【表１】 [Table 1]
【００３５】［実施例２、比較例］（Ａ）成分として、
分子鎖両末端がジメチルビニルシリル基で封鎖された重
合度６０のジメチルポリシロキサン６０部に対し、
（Ｃ）成分として、トルエン溶解性の式（ＣＨ3）2Ｓｉ
Ｏ0.5と式ＳｉＯ2で示されるシロキサン単位（モル比
０．８：１．０）からなるオルガノポリシロキサンレジ
ンを固形分で４０部加えた後、溶剤を留去し、（Ｂ）成
分として分子鎖両末端がトリメチルシリル基で封鎖され
た≡ＳｉＨ基量が１．６モル／１００ｇで粘度が２０ｃ
ｓであるメチルハイドロジェンポリシロキサン３部とア
セチレンアルコール１部とを添加し、剥離紙用の無溶剤
型組成物Ｂを調製した。[Example 2, Comparative Example] As the component (A),
For 60 parts of dimethylpolysiloxane having a degree of polymerization of 60 and having both ends of the molecular chain blocked with dimethylvinylsilyl groups,
As the component (C), a toluene-soluble formula (CH 3 ) 2 Si is used.
After adding 40 parts by mass of an organopolysiloxane resin composed of O 0.5 and a siloxane unit represented by the formula SiO 2 (molar ratio 0.8: 1.0) in a solid content, the solvent was distilled off to prepare a molecule as the component (B). The both ends of the chain are blocked with trimethylsilyl groups, and the amount of ≡SiH groups is 1.6 mol / 100 g and the viscosity is 20 c.
3 parts of methyl hydrogen polysiloxane which is s and 1 part of acetylene alcohol were added to prepare a solventless composition B for release paper.
【００３６】この組成物Ｂ１０部に対し、（Ｄ）成分と
して上記実施例で使用した式（１−ａ）で示されるパー
フロロアルキル基含有オルガノポリシロキサンをそれぞ
れ１００、１０００、１００００ｐｐｍ添加した試料
６、７、８を調製すると共に、比較として該オルガノポ
リシロキサン未添加の試料９を得た。Sample 6 was prepared by adding 100 parts, 1000 parts, and 10000 ppm of the perfluoroalkyl group-containing organopolysiloxane represented by the formula (1-a) used in the above-mentioned examples as the component (D) to 10 parts of this composition B. , 7 and 8 were prepared and, as a comparison, a sample 9 to which the organopolysiloxane was not added was obtained.
【００３７】これらの試料６〜９それぞれに（Ｅ）成分
として塩化白金酸−テトラメチルビニルジシロキサン錯
体を５０ｐｐｍ加えて十分混合したものの発泡性を上記
と同様に評価した。また、これら組成物を、ポリエチレ
ンラミネート紙の表面に印刷適性試験機を用いてシリコ
ーン塗工量約０．５ｇ／ｍ2になるように塗工した。こ
の際、試料６〜８を塗工する場合、試料９を塗工する場
合に比べて塗工面のレベリングが良いことが認められ
た。次いで、１５０℃の熱風循環式乾燥機中で２０秒間
熱処理し、得られた皮膜に対し、実施例１と同様に剥離
力、残留接着力を測定した。これらの結果を表２に示し
た。なお、剥離力は、日東電工（株）製Ｎｏ５０２テー
プを貼り合わせた後、７０℃・圧力２０ｇ／ｃｍ2で１
日圧着後、測定した。To each of these samples 6 to 9, 50 ppm of chloroplatinic acid-tetramethylvinyldisiloxane complex was added as a component (E) and mixed sufficiently, and the foamability was evaluated in the same manner as above. Further, these compositions were coated on the surface of polyethylene laminated paper using a printability tester so that the silicone coating amount was about 0.5 g / m 2 . At this time, it was confirmed that the leveling of the coated surface was better when the samples 6 to 8 were applied than when the sample 9 was applied. Then, heat treatment was performed for 20 seconds in a hot air circulation dryer at 150 ° C., and the peeling force and the residual adhesive force of the obtained film were measured in the same manner as in Example 1. The results are shown in Table 2. The peeling force is 1 at 70 ° C. and a pressure of 20 g / cm 2 after sticking No502 tape manufactured by Nitto Denko Corporation.
After the day pressure bonding, it was measured.
【００３８】[0038]
【表２】 [Table 2]
【００３９】[0039]
【発明の効果】本発明の剥離紙用オルガノポリシロキサ
ン組成物は、基材に均一な剥離皮膜を形成できるもので
あり、本組成物を塗工・硬化してなる剥離紙は、ピンホ
ールなどがない良好な皮膜が形成されたもので、良好な
剥離特性を有するものである。The organopolysiloxane composition for release paper of the present invention can form a uniform release film on a substrate. The release paper obtained by coating and curing the composition is a pinhole or the like. A good film having no cracks was formed and had good peeling properties.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｊ 7/04 ＪＫＶ 6770−4Ｊ Ｄ２１Ｈ 19/32 27/00 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C09J 7/04 JKV 6770-4J D21H 19/32 27/00
Claims (2)
たアルケニル基を少なくとも２個有するアルケニル基含
有ジオルガノポリシロキサン、（Ｂ）一分子中に珪素原
子に直接結合した水素原子を少なくとも２個含有する液
状オルガノハイドロジェンポリシロキサン、（Ｃ）式Ｒ
3ＳｉＯ1/2（式中、Ｒはメチル基及び／又はビニル基で
ある）及びＳｉＯ2で示されるシロキサン単位からなる
溶剤可溶性オルガノポリシロキサン、（Ｄ）下記式
（１）で示されるパーフロロアルキル基含有オルガノポ
リシロキサン、 【化１】 〔但し、式中Ｒ1は炭素数１〜１８の一価炭化水素基、
Ｒ2 はＣ2Ｈ4ＣnＦ2n+1（ｎは１〜８の整数）で示される
パーフロロアルキル基、ｋは１以上の整数、ｍは０又は
１以上の整数である。〕（Ｅ）付加反応触媒を含有する
ことを特徴とする剥離紙用オルガノポリシロキサン組成
物。1. (A) A direct bond to a silicon atom in one molecule
Containing an alkenyl group having at least two alkenyl groups
Diorganopolysiloxane, (B) Silicon source in one molecule
Liquid containing at least two hydrogen atoms directly bound to a child
Organohydrogenpolysiloxane, (C) formula R
3SiO1/2(In the formula, R is a methyl group and / or a vinyl group.
Yes) and SiO2Consisting of siloxane units
Solvent-soluble organopolysiloxane, (D) the following formula
Organopo containing a perfluoroalkyl group represented by (1)
Lisiloxane, embedded image[However, in the formula R1Is a monovalent hydrocarbon group having 1 to 18 carbon atoms,
R2 Is C2HFourCnF2n + 1(N is an integer of 1 to 8)
Perfluoroalkyl group, k is an integer of 1 or more, m is 0 or
It is an integer of 1 or more. ] (E) Contains an addition reaction catalyst
Organopolysiloxane composition for release paper characterized in that
object.
ロキサン組成物を基材に塗布・硬化してなる剥離紙。2. A release paper obtained by applying and curing the organopolysiloxane composition for release paper according to claim 1 on a substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4205888A JP2630179B2 (en) | 1992-07-09 | 1992-07-09 | Organopolysiloxane composition for release paper and release paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4205888A JP2630179B2 (en) | 1992-07-09 | 1992-07-09 | Organopolysiloxane composition for release paper and release paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0625601A true JPH0625601A (en) | 1994-02-01 |
| JP2630179B2 JP2630179B2 (en) | 1997-07-16 |
Family
ID=16514396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4205888A Expired - Fee Related JP2630179B2 (en) | 1992-07-09 | 1992-07-09 | Organopolysiloxane composition for release paper and release paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2630179B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102479168B1 (en) * | 2022-01-28 | 2022-12-20 | 김규동 | Silicone adhesive composition and silicone adhesive tape comprising the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55110155A (en) * | 1979-02-16 | 1980-08-25 | Toray Silicone Co Ltd | Organopolysiloxane composition forming releasable film |
| JPH032270A (en) * | 1989-05-31 | 1991-01-08 | Toray Dow Corning Silicone Co Ltd | Organopolysiloxane composition for forming releasable curing coating film |
-
1992
- 1992-07-09 JP JP4205888A patent/JP2630179B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55110155A (en) * | 1979-02-16 | 1980-08-25 | Toray Silicone Co Ltd | Organopolysiloxane composition forming releasable film |
| JPH032270A (en) * | 1989-05-31 | 1991-01-08 | Toray Dow Corning Silicone Co Ltd | Organopolysiloxane composition for forming releasable curing coating film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2630179B2 (en) | 1997-07-16 |
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