JP4048644B2 - Cationic polymerizable UV curable silicone composition for peeling - Google Patents
Cationic polymerizable UV curable silicone composition for peeling Download PDFInfo
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- JP4048644B2 JP4048644B2 JP09171599A JP9171599A JP4048644B2 JP 4048644 B2 JP4048644 B2 JP 4048644B2 JP 09171599 A JP09171599 A JP 09171599A JP 9171599 A JP9171599 A JP 9171599A JP 4048644 B2 JP4048644 B2 JP 4048644B2
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- silicone composition
- peeling
- silicon dioxide
- curable silicone
- polyorganosiloxane
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- 239000000203 mixture Substances 0.000 title claims description 48
- 229920001296 polysiloxane Polymers 0.000 title claims description 43
- 125000002091 cationic group Chemical group 0.000 title description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 49
- 235000012239 silicon dioxide Nutrition 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- 239000004593 Epoxy Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000000123 paper Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001723 curing Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 4
- 238000010538 cationic polymerization reaction Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011086 glassine Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- -1 γ-glycidyloxypropyl group Chemical group 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- 229920006268 silicone film Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は剥離用カチオン重合性紫外線硬化型シリコーン組成物に関する。
【０００２】
【従来の技術】
ポリオルガノシロキサンを主剤とするシリコーン組成物は、粘着性物質に対する剥離性を有することから、紙、合成フィルム等の各種剥離基材の表面処理剤（塗工液）として用いられている。このようなシリコーン組成物としては、熱硬化型と紫外線硬化型が知られている。紫外線硬化型は、紫外線の照射により速やかに硬化してシリコーン皮膜を形成するため、熱硬化型に比較して、設備投資が安価なこと、省エネルギーであること、設置スペースが狭くても対応可能なこと、さらには環境に優しい硬化システムであること等の特徴から関心も高く、今後多方面への使用が期待されている。
【０００３】
さらに、紫外線硬化型シリコーン組成物は、硬化メカニズムによってラジカル付加反応型、ヒドロシリル化反応型、ラジカル重合型、カチオン重合型の４つに分類される。なかでもカチオン重合型は、ラジカル重合型のように酸素による硬化阻害がないため硬化時に窒素雰囲気下にする必要がないこと、硬化後の体積収縮が少なく基材との密着性が良好であること、粘着性物質に対する剥離性能も重剥離から軽剥離までの制御が可能であること等の特徴があり、カチオン重合型は紫外線硬化型シリコーン組成物の中でも非常に注目を浴びている硬化メカニズムである。
【０００４】
しかしながら、カチオン重合性紫外線硬化型シリコーン組成物は、粘度が非常に低いために、塗工方法によっては、操業性を必ずしも満足できるものではなかった。たとえば、オフセット印刷においては、ロール間でのシリコーン組成物の移行性が悪く、均一できれいな硬化皮膜が得られない。それゆえ、基材への塗工量の調節も困難であった。また、塗工方法として高速塗工法などを採用した場合には、塗工液が霧状粒子となって飛散するミスチング現象が起こり、著しく作業環境を悪化させるなどの問題があった。これらの塗工時における操業性の問題は、本来、シリコーン組成物が有している粘着性物質に対する剥離性能にも影響を及ぼす大きな問題になっている。
【０００５】
【発明が解決しようとする課題】
本発明は、剥離用カチオン重合性紫外線硬化型シリコーン組成物が本来有する硬化性や粘着性物質に対する剥離性能を有し、しかも当該シリコーン組成物の粘度を、塗工方法に応じて、容易に高粘度に調節しうるものを提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明者らは前記目的を達成すべく鋭意検討を重ねた結果、剥離用カチオン重合性紫外線硬化型シリコーン組成物中に、以下に示す特定の微粉末二酸化珪素を添加することにより、前記課題を解決できることを見出し、本発明を解決するに至った。
【０００７】
すなわち、本発明は、（ａ）１分子中に少なくとも２個のエポキシ官能基を有するポリオルガノシロキサン、（ｂ）４重量％水分散液中のｐＨが５．５以上の微粉末二酸化珪素および（ｃ）オニウム塩系光開始剤を含有してなる剥離用カチオン重合性紫外線硬化型シリコーン組成物、に関する。
【０００８】
【発明の実施の形態】
本発明の（ａ）ポリオルガノシロキサンは、１分子中に少なくとも２個のエポキシ官能基を有するものを使用できる。また、（ａ）ポリオルガノシロキサンは、直鎖状、分岐鎖状のいずれでもよく、これらの混合物であってもよい。かかる（ａ）ポリオルガノシロキサンとしては、たとえば、一般式（１）：
【０００９】
【化１】
で表される化合物があげられる。一般式（１）中のＲは炭素数１〜１０のアルキル基を表し、Ｘはエポキシ官能基を表す。Ｒとしては、特に限定されるものではないがメチル基が好ましい。エポキシ官能基（Ｘ）は、オニウム塩系光開始剤によって開環カチオン重合が進行するものであれば特に制限されないが、たとえば、γ−グリシジルオキシプロピル基、β−（３，４−エポキシシクロヘキシル）エチル基、β−（４−メチル−３，４エポキシシクロヘキシル）プロピル基などを例示できる。
【００１１】
また、一般式（１）中の繰り返し単位数を表すｍ、ｎは整数であり、（ａ）ポリオルガノシロキサンは、少なくとも２個のエポキシ官能基を有することからｎは２以上である。また、ｎ／（ｍ＋ｎ）＝０．０１〜０．５であることが望ましい。ｍ＋ｎは通常３０〜１０００程度である。なお、一般式（１）中の繰り返し単位ｍとｎは、便宜上ブロック共重合体として記載しているが、繰り返し単位ｍとｎはブロック共重合体である必要はない。通常、一般式（１）中、繰り返し単位ｍとｎは不規則に組み込まれている。
【００１２】
本発明は、前記（ｂ）微粉末二酸化珪素を、前記（ａ）ポリオルガノシロキサンを主成分とするシリコーン組成物中に含有させることにより、当該シリコーン組成物の粘度を、所望の高粘度に調節したものである。ただし、本発明で用いる（ｂ）微粉末二酸化珪素は、その４重量％水分散液中のｐＨが５．５以上の弱酸性から中性ものを用いる。ｐＨが５．５未満の強酸を示すものは、シリコーン組成物の反応の制御が難しく、当該組成物の安定性が著しく低下するため、当該組成物は、調製後、通常、数分間でゲル化する。一方、ｐＨの上限は特に制限されないが、強アルカリ性を示す場合は、シリコーン組成物の硬化反応に影響を及ぼし剥離性能が安定しなくなるおそれがあるため、ｐＨは９以下とするのが好ましく、さらには７．５以下とするのがより好ましい。
【００１３】
また、本発明の（ｂ）微粉末二酸化珪素は、平均粒度分布径が０．０５〜１００μｍ程度のものである。平均粒度分布径が小さくなると、（ａ）ポリオルガノシロキサンとの混合が悪くなる傾向があることから、（ｂ）微粉末二酸化珪素の平均粒度分布径は１μｍ以上とするのが好ましい。一方、平均粒度分布径が大きくなると、シリコーン組成物の剥離性能に影響を及ぼす他、シリコーン組成物の保存安定性も悪くなる傾向があることから、（ｂ）微粉末二酸化珪素の平均粒度分布径は３０μｍ以下とするのが好ましい。
【００１４】
なお、本発明の（ｂ）微粉末二酸化珪素は、前記条件を満足するものであれば、乾式法、湿式法のいずれの方法によっても製造しうるが、乾式法により製造する場合には塩酸が副生して、微粉末二酸化珪素のｐＨが低くなる傾向があるため、ｐＨを弱酸性から中性付近に調整し易い湿式法によるのが好ましい。
【００１５】
（ｂ）微粉末二酸化珪素の使用量は、特に制限されず、本発明のシリコーン組成物を所望の高粘度になるように任意の量を適宜に調整して使用できるが、（ｂ）微粉末二酸化珪素の添加量が多くなると、シリコーン組成物の剥離性能に悪影響を及ぼすため、（ｂ）微粉末二酸化珪素の添加量は、（ａ）ポリオルガノシロキサン１００重量部に対して５０重量部以下となるようにするのが好ましい。
また、（ｂ）微粉末二酸化珪素の添加量が少なくなると、微粉末二酸化珪素を添加する大きな効果が見られないため、（ｂ）微粉末二酸化珪素の添加量は、（ａ）ポリオルガノシロキサン１００重量部に対して０．０１重量部以上であることが好ましい。
【００１６】
なお、（ｂ）微粉末二酸化珪素は、（ａ）ポリオルガノシロキサンに直接添加混合してもよいし、（ｂ）微粉末二酸化珪素をトルエン等の有機溶剤等で湿らせてから（ａ）ポリオルガノシロキサンに添加混合してもよい。
【００１７】
本発明の（ｃ）オニウム塩系光開始剤としては、公知のものを使用できる。その具体例としては、（Ｒ１）２Ｉ＋Ｘ−、ＡｒＮ２ ＋Ｘ−、（Ｒ１）３Ｓ＋Ｘ−で表される化合物があげられる。但し、Ｒ１はアルキル基またはアリール基を、Ａｒはアリール基を示す。Ｘ−としては[Ｂ（Ｃ６Ｈ５）４]−、[Ｂ（Ｃ６Ｆ５）４]−、[Ｂ（Ｃ６Ｈ４ＣＦ３）４]−、[（Ｃ６Ｆ５）２ＢＦ２]−、[Ｃ６Ｆ５ＢＦ３]−、[Ｂ（Ｃ６Ｈ３Ｆ２）４]−、ＢＦ４ −、ＰＦ６ −、ＡｓＦ６ −、ＳｂＦ６ −、ＳｂＣｌ６ −、ＨＳＯ４ −、またはＣｌＯ４ −などが挙げられる。
【００１８】
（ｃ）オニウム塩系光開始剤の使用量は、特に制限されるものではなく、適宜に使用量を調整できる。ただし、経済性や生産操業性の観点からすると、（ａ）ポリオルガノシロキサン１００重量部に対して、１〜２０重量部程度とするのが望ましい。
【００１９】
【発明の効果】
本発明の剥離用カチオン重合性紫外線硬化シリコーン組成物は、その粘度を、塗工方法に応じて、所望の高粘度に容易に調整できるため、操業性が非常によい。しかも、本発明の剥離用カチオン重合性紫外線硬化シリコーン組成物は、カチオン重合性紫外線硬化型シリコーン組成物が本来有する硬化性や粘着性物質に対する剥離性能を有する。そのため、オフセット印刷においても、ロール間でのシリコーン組成物の移行性が良く、均一できれいな硬化皮膜が得られる。それゆえ、基材への塗工量の調節も容易である。また、塗工方法として高速塗工法などを採用した場合にも、塗工液が霧状粒子となって飛散するミスチング現象がない。
【００２０】
【実施例】
以下、実施例および比較例をあげて本発明を具体的に説明する。なお、各例中の部および％は特記がない限り重量基準である。
【００２１】
実施例１
ポリオルガノシロキサン（ローディア社製、商品名「シリコリースＰＯＬＹ２００」）１００重量部に、微粉末二酸化珪素（シオノギ株式会社製、商品名「カープレックス ＃８０」、４重量％水分散液中のｐＨ値は６．３、平均粒度分布径６．８μｍ）を５重量部添加してよく攪拌混合した。その混合物に、オニウム塩系光開始剤（ローディア社製、商品名「シリコリースＣＡＴＡ２１１」）５重量部を添加混合し、剥離用カチオン重合性紫外線硬化型シリコーン組成物を得た。
【００２２】
実施例２
実施例１において、微粉末二酸化珪素の添加量を０．１重量部に変えた以外は実施例１と同様にしてシリコーン組成物を得た。
【００２３】
実施例３
実施例１において、微粉末二酸化珪素の添加量を２０重量部に変えた以外は実施例１と同様にしてシリコーン組成物を得た。
【００２４】
実施例４
実施例１において、微粉末二酸化珪素の種類を商品名「カープレックス ＣＳ−７０１」（シオノギ株式会社製、４重量％水分散液中のｐＨ値は７．０、平均粒度分布径３．１μｍ）に変えた以外は実施例１と同様にしてシリコーン組成物を得た。
【００２５】
比較例１
実施例１において、微粉末二酸化珪素を添加しないこと以外は実施例１と同様にしてシリコーン組成物を得た。
【００２６】
比較例２
実施例１において、微粉末二酸化珪素の種類を商品名「アエロジルＲ９７２Ｄ」（日本アエロジル株式会社製、４重量％水分散液中のｐＨ値は４．５、１次粒子の平均径１６ｎｍ）に変更した以外は実施例１と同様にしてシリコーン組成物を得た。
【００２７】
実施例１〜４および比較例１〜２で得られたシリコーン組成物について以下の試験を行なった。その結果を表１に示す。
【００２８】
（シリコーン組成物の粘度測定）
シリコーン組成物の２５℃における粘度を、ＢＬ形粘度計にて測定した。
【００２９】
（剥離力の測定）
シリコーン組成物をＲＩテスターにて、グラシン紙に塗工量を約１．０ｇ／ｍ2で塗布した後、紫外線の照射により硬化させ剥離紙を作成した。作製した剥離紙の硬化皮膜表面に、アクリル系エマルション型粘着剤（東洋インキ製造株式会社製、商品名「オリバインＢＰＷ−５５２６」）を２０ｇ／ｍ２で塗布し１１０℃で６０秒乾燥処理した。ついで、この処理表面に上質紙を貼り合わせ、２５℃で２０ｇ／ｃｍ２の荷重下に１５時間保存した。これを５０ｍｍ幅に切り、引張試験機を用いて１８０℃の角度で剥離速度０．３ｍ／ｍｉｎ．、および５０ｍ／ｍｉｎ．で貼り合わせた上質紙を引っ張り、剥離するのに要する力（ｇ／５０ｍｍ）を測定した。結果を表１に示す。
【００３０】
（残留接着率）
シリコーン塗工液をＲＩテスターにて、グラシン紙に塗工量を約１．０ｇ／ｍ2で塗布した後、紫外線を照射より硬化させ剥離紙を作成した。作製した剥離紙の硬化皮膜表面に、ポリエステル粘着テープ（日東電工株式会社製、商品名「Ｎｏ．３１Ｂ」）を貼り合わせ、７０℃で２５ｇ／ｃｍ２荷重下に１５時間保存した。保存後、粘着テープを剥がしてステンレス板（ＪＩＳ Ｃ２１０７）に２ｋｇのゴムローラーで貼り付けた。ついで、この粘着テープをＳＵＳ板から１８０°の角度で剥離速度０．３ｍ／ｍｉｎ．にて引っ張り、剥離するのに要する力（ｇ／２５ｍｍ）を測定した。ブランクとして、直接、粘着テープをＳＵＳ板に張り合わせ同様の条件で剥がした時の剥離力を測定し、前者の剥離力の後者の剥離力に対する割合（％）を残留接着率として求めた。シリコーン未硬化の部分が多いと、粘着剤にシリコーンが移行するために粘着テープの粘着力が低下し、この値は小さくなる。結果を表１に示す。
【００３１】
【表１】
表１の結果より、本発明のシリコーン組成物は、比較例１のシリコーン組成物に比べて、高粘度に調整されていることが認められる。そのため、本発明のシリコーン組成物は、これを塗工液として用いた場合の操業性が非常によかった。しかも、本発明のシリコーン組成物の剥離性能は比較例１と殆ど同等である。なお、比較例２は、シリコーン組成物の安定性が悪く通常の使用条件下でもゲル化（硬化）したため、剥離性能の評価はできなかった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cationically polymerizable UV-curable silicone composition for peeling.
[0002]
[Prior art]
Silicone compositions containing polyorganosiloxane as the main agent have releasability from adhesive substances, and are therefore used as surface treating agents (coating solutions) for various release substrates such as paper and synthetic films. As such a silicone composition, a thermosetting type and an ultraviolet curable type are known. The UV-curing type cures quickly by UV irradiation to form a silicone film, so it is less expensive to invest in equipment, saves energy, and can be used even when the installation space is narrow compared to the thermosetting type. In addition, it is highly interested because of its characteristics such as an environmentally friendly curing system, and is expected to be used in many fields in the future.
[0003]
Furthermore, ultraviolet curable silicone compositions are classified into four types, radical addition reaction type, hydrosilylation reaction type, radical polymerization type, and cationic polymerization type, depending on the curing mechanism. Among them, the cationic polymerization type does not need to be in a nitrogen atmosphere at the time of curing because it is not inhibited by oxygen unlike the radical polymerization type, and there is little volume shrinkage after curing and good adhesion to the substrate. Also, the release performance for adhesive substances is characterized by the ability to control from heavy release to light release, and the cationic polymerization type is a curing mechanism that has received much attention among ultraviolet curable silicone compositions. .
[0004]
However, the cationic polymerizable ultraviolet curable silicone composition has a very low viscosity, so that the operability is not always satisfactory depending on the coating method. For example, in offset printing, the transferability of the silicone composition between rolls is poor, and a uniform and clean cured film cannot be obtained. Therefore, it is difficult to adjust the coating amount on the substrate. Further, when a high-speed coating method or the like is adopted as a coating method, there is a problem that a misting phenomenon occurs in which the coating liquid is scattered as mist particles and the working environment is remarkably deteriorated. The problem of operability at the time of coating has become a major problem that has an influence on the peelability of the adhesive composition inherent to the silicone composition.
[0005]
[Problems to be solved by the invention]
The present invention has a peeling performance for the curable and tacky substances inherent to the cationically polymerizable UV-curable silicone composition for peeling, and the viscosity of the silicone composition can be easily increased depending on the coating method. It aims at providing what can be adjusted to a viscosity.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have added the specific fine powdered silicon dioxide shown below to the cationically polymerizable ultraviolet curable silicone composition for peeling. The present inventors have found that the problem can be solved and solved the present invention.
[0007]
That is, the present invention comprises (a) a polyorganosiloxane having at least two epoxy functional groups in one molecule, (b) a finely divided silicon dioxide having a pH of 5.5 or more in a 4% by weight aqueous dispersion and ( c) It relates to a cationically polymerizable UV-curable silicone composition for peeling comprising an onium salt photoinitiator.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
As the (a) polyorganosiloxane of the present invention, one having at least two epoxy functional groups in one molecule can be used. Further, (a) the polyorganosiloxane may be linear or branched, or a mixture thereof. As such (a) polyorganosiloxane, for example, the general formula (1):
[0009]
[Chemical 1]
The compound represented by these is mention | raise | lifted. R in the general formula (1) represents an alkyl group having 1 to 10 carbon atoms, and X represents an epoxy functional group. R is not particularly limited, but is preferably a methyl group. The epoxy functional group (X) is not particularly limited as long as ring-opening cationic polymerization proceeds by an onium salt photoinitiator. For example, γ-glycidyloxypropyl group, β- (3,4-epoxycyclohexyl) Examples thereof include an ethyl group and a β- (4-methyl-3,4 epoxy cyclohexyl) propyl group.
[0011]
In addition, m and n representing the number of repeating units in the general formula (1) are integers. (A) Since the polyorganosiloxane has at least two epoxy functional groups, n is 2 or more. Moreover, it is desirable that n / (m + n) = 0.01 to 0.5. m + n is usually about 30 to 1000. In addition, although the repeating units m and n in General formula (1) are described as a block copolymer for convenience, the repeating units m and n do not need to be a block copolymer. Usually, in the general formula (1), the repeating units m and n are incorporated irregularly.
[0012]
The present invention adjusts the viscosity of the silicone composition to a desired high viscosity by incorporating the fine powder silicon dioxide (b) in the silicone composition mainly comprising the polyorganosiloxane (a). It is a thing. However, (b) finely powdered silicon dioxide used in the present invention is a weakly acidic to neutral one having a pH of 5.5 or more in its 4 wt% aqueous dispersion. Those having a strong acid with a pH of less than 5.5 are difficult to control the reaction of the silicone composition, and the stability of the composition is significantly reduced. Therefore, the composition usually gels within a few minutes after preparation. To do. On the other hand, the upper limit of the pH is not particularly limited, but if it exhibits strong alkalinity, it may affect the curing reaction of the silicone composition and the peeling performance may become unstable, so the pH is preferably 9 or less. Is more preferably 7.5 or less.
[0013]
The fine powder silicon dioxide (b) of the present invention has an average particle size distribution diameter of about 0.05 to 100 μm. When the average particle size distribution diameter is small, (a) the mixture with the polyorganosiloxane tends to be poor. Therefore, it is preferable that the average particle size distribution diameter of (b) finely divided silicon dioxide is 1 μm or more. On the other hand, when the average particle size distribution diameter is increased, it affects the peeling performance of the silicone composition and also tends to deteriorate the storage stability of the silicone composition. Is preferably 30 μm or less.
[0014]
The finely powdered silicon dioxide (b) of the present invention can be produced by either a dry method or a wet method as long as the above conditions are satisfied. As a by-product, the pH of finely powdered silicon dioxide tends to be low. Therefore, it is preferable to use a wet method that can easily adjust the pH from weakly acidic to near neutral.
[0015]
(B) The amount of finely powdered silicon dioxide used is not particularly limited, and the silicone composition of the present invention can be used by appropriately adjusting an arbitrary amount so as to obtain a desired high viscosity. When the amount of silicon dioxide added is increased, the release performance of the silicone composition is adversely affected. Therefore, the amount of (b) finely powdered silicon dioxide added is 50 parts by weight or less based on 100 parts by weight of the polyorganosiloxane. It is preferable to do so.
Further, when (b) the addition amount of fine powder silicon dioxide is reduced, a large effect of adding fine powder silicon dioxide is not seen. Therefore, the addition amount of (b) fine powder silicon dioxide is (a) polyorganosiloxane 100. It is preferable that it is 0.01 weight part or more with respect to a weight part.
[0016]
In addition, (b) fine powder silicon dioxide may be directly added to and mixed with (a) polyorganosiloxane, or (b) fine powder silicon dioxide is moistened with an organic solvent such as toluene, and then (a) poly You may add and mix with organosiloxane.
[0017]
As the (c) onium salt photoinitiator of the present invention, known ones can be used. Specific examples thereof include compounds represented by (R 1 ) 2 I + X − , ArN 2 + X − , (R 1 ) 3 S + X − . R 1 represents an alkyl group or an aryl group, and Ar represents an aryl group. X − includes [B (C 6 H 5 ) 4 ] − , [B (C 6 F 5 ) 4 ] − , [B (C 6 H 4 CF 3 ) 4 ] − , [(C 6 F 5 ) 2 BF 2 ] − , [C 6 F 5 BF 3 ] − , [B (C 6 H 3 F 2 ) 4 ] − , BF 4 − , PF 6 − , AsF 6 − , SbF 6 − , SbCl 6 − , HSO 4 - or ClO 4 - and the like.
[0018]
(C) The amount of onium salt photoinitiator used is not particularly limited, and the amount used can be appropriately adjusted. However, from the viewpoint of economic efficiency and production operability, it is desirable that the amount be about 1 to 20 parts by weight per 100 parts by weight of (a) polyorganosiloxane.
[0019]
【The invention's effect】
Since the viscosity of the cationic polymerizable UV-curable silicone composition for peeling according to the present invention can be easily adjusted to a desired high viscosity according to the coating method, the operability is very good. In addition, the cationically polymerizable UV-curable silicone composition for peeling according to the present invention has a peeling property for the curability and adhesive substances inherent to the cationically polymerizable UV-curable silicone composition. Therefore, even in offset printing, the transferability of the silicone composition between rolls is good, and a uniform and clean cured film can be obtained. Therefore, it is easy to adjust the coating amount on the substrate. Further, even when a high-speed coating method or the like is employed as a coating method, there is no misting phenomenon in which the coating liquid is scattered as mist particles.
[0020]
【Example】
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Parts and% in each example are based on weight unless otherwise specified.
[0021]
Example 1
To 100 parts by weight of polyorganosiloxane (made by Rhodia, trade name “Silicolys POLY200”), fine powder silicon dioxide (made by Shionogi Co., Ltd., trade name “Carplex # 80”, pH value in 4 wt% aqueous dispersion is (6.3, average particle size distribution diameter 6.8 μm) was added in an amount of 5 parts by weight, followed by stirring and mixing. To the mixture, 5 parts by weight of an onium salt photoinitiator (trade name “Silicolys CATA211”, manufactured by Rhodia Co., Ltd.) was added and mixed to obtain a release cationically polymerizable UV-curable silicone composition.
[0022]
Example 2
In Example 1, a silicone composition was obtained in the same manner as in Example 1 except that the amount of finely powdered silicon dioxide added was changed to 0.1 parts by weight.
[0023]
Example 3
In Example 1, a silicone composition was obtained in the same manner as in Example 1 except that the amount of finely divided silicon dioxide added was changed to 20 parts by weight.
[0024]
Example 4
In Example 1, the type of finely divided silicon dioxide is trade name “Carplex CS-701” (manufactured by Shionogi Co., Ltd., pH value in 4 wt% aqueous dispersion is 7.0, average particle size distribution diameter is 3.1 μm). A silicone composition was obtained in the same manner as in Example 1 except that
[0025]
Comparative Example 1
A silicone composition was obtained in the same manner as in Example 1 except that fine powder silicon dioxide was not added.
[0026]
Comparative Example 2
In Example 1, the type of finely divided silicon dioxide was changed to the trade name “Aerosil R972D” (manufactured by Nippon Aerosil Co., Ltd., pH value in 4 wt% aqueous dispersion was 4.5, average diameter of primary particles 16 nm). A silicone composition was obtained in the same manner as in Example 1 except that.
[0027]
The following test was done about the silicone composition obtained in Examples 1-4 and Comparative Examples 1-2. The results are shown in Table 1.
[0028]
(Viscosity measurement of silicone composition)
The viscosity of the silicone composition at 25 ° C. was measured with a BL type viscometer.
[0029]
(Measurement of peel force)
The silicone composition was applied to glassine paper with an RI tester at a coating amount of about 1.0 g / m 2 , and then cured by irradiation with ultraviolet rays to prepare a release paper. An acrylic emulsion-type pressure-sensitive adhesive (manufactured by Toyo Ink Manufacturing Co., Ltd., trade name “Olivein BPW-5526”) was applied at 20 g / m 2 on the surface of the cured film of the produced release paper and dried at 110 ° C. for 60 seconds. Then, a high quality paper was bonded to the treated surface and stored at 25 ° C. under a load of 20 g / cm 2 for 15 hours. This was cut into a width of 50 mm, and a peeling speed of 0.3 m / min. , And 50 m / min. The quality paper (g / 50 mm) required for pulling and peeling off the high-quality paper bonded together in step 1 was measured. The results are shown in Table 1.
[0030]
(Residual adhesion rate)
The silicone coating solution was applied to glassine paper with an RI tester at a coating amount of about 1.0 g / m 2 , and then cured by irradiation with ultraviolet rays to prepare a release paper. A polyester pressure-sensitive adhesive tape (manufactured by Nitto Denko Corporation, trade name “No. 31B”) was bonded to the cured film surface of the produced release paper, and stored at 70 ° C. under a load of 25 g / cm 2 for 15 hours. After storage, the adhesive tape was peeled off and attached to a stainless steel plate (JIS C2107) with a 2 kg rubber roller. Next, the adhesive tape was peeled from the SUS plate at an angle of 180 ° and a peeling speed of 0.3 m / min. The force (g / 25 mm) required for pulling and peeling was measured. As a blank, the peel force when the adhesive tape was directly pasted on a SUS plate and peeled off under the same conditions was measured, and the ratio (%) of the former peel force to the latter peel force was determined as the residual adhesion rate. If there are many uncured portions of silicone, the silicone is transferred to the pressure-sensitive adhesive, so that the adhesive strength of the pressure-sensitive adhesive tape is reduced, and this value becomes small. The results are shown in Table 1.
[0031]
[Table 1]
From the results of Table 1, it can be seen that the silicone composition of the present invention is adjusted to have a higher viscosity than the silicone composition of Comparative Example 1. Therefore, the operability when the silicone composition of the present invention is used as a coating liquid is very good. Moreover, the peeling performance of the silicone composition of the present invention is almost equivalent to that of Comparative Example 1. In Comparative Example 2, the silicone composition was poor in stability and gelled (cured) even under normal use conditions, and therefore, the peeling performance could not be evaluated.
Claims (1)
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| JP09171599A JP4048644B2 (en) | 1999-03-31 | 1999-03-31 | Cationic polymerizable UV curable silicone composition for peeling |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR2818169B1 (en) * | 2000-12-20 | 2003-03-07 | Rhodia Chimie Sa | METHOD FOR CONTROLLING THE APPEARANCE OF FOG DURING THE COATING OF FLEXIBLE SUPPORTS WITH A CROSSLINKABLE LIQUID SILICONE COMPOSITION IN A CYLINDER DEVICE |
| JP4626055B2 (en) * | 2000-12-25 | 2011-02-02 | 東洋紡績株式会社 | Release film |
| JP4986423B2 (en) | 2005-08-03 | 2012-07-25 | 日東電工株式会社 | Peeling treatment substrate and method for producing the same |
| JP5101919B2 (en) | 2007-04-09 | 2012-12-19 | 日東電工株式会社 | Double-sided adhesive tape or sheet for printed circuit board and printed circuit board with double-sided adhesive tape |
| JP5528286B2 (en) | 2010-10-01 | 2014-06-25 | 日東電工株式会社 | Adhesive sheet |
| JP5528285B2 (en) | 2010-10-01 | 2014-06-25 | 日東電工株式会社 | Adhesive sheet |
| JP5528284B2 (en) | 2010-10-01 | 2014-06-25 | 日東電工株式会社 | Adhesive sheet |
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1999
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