JP4775565B2 - Cooking sheet - Google Patents
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Description
本発明は、薄膜塗工性、硬化性及び加熱調理後の食材との離型性に優れる硬化皮膜を与える、付加反応型のシリコーン組成物の硬化皮膜が形成された調理用シートに関する。 The present invention relates to a cooking sheet on which a cured film of an addition reaction type silicone composition is provided , which provides a cured film excellent in thin film coating properties, curability and releasability from foods after cooking.
従来、肉や魚などを電子レンジ、オーブン、ホットプレート、フライパンなどの調理器具を用いて加熱調理する場合の調理シートとして、吸液層とこれに積層される非透過液層とを含んでなるフライパン用焼き魚シート（特開２００１−１９０４１６号公報）や板紙にシリコーン樹脂が被覆された高密度耐油紙を接着したシートを用いた再加熱用の包み箱（特開平１１−１０５９４３号公報）などが知られている。 Conventionally, as a cooking sheet when cooking meat and fish using cooking utensils such as a microwave oven, oven, hot plate, frying pan, etc., it comprises a liquid absorbing layer and a non-permeable liquid layer laminated thereon A frying pan grilled fish sheet (Japanese Patent Laid-Open No. 2001-190416), a reheating wrapping box (Japanese Patent Laid-Open No. 11-105943) using a sheet of paperboard and a high-density oil-resistant paper coated with a silicone resin. Are known.
さらに、食用油の主成分であるオレイン酸との接触角を離型性の指標として、特開２００５−８７５２６号公報には、耐熱性素材シートにシリコーン樹脂又はフッ素樹脂を塗布したオレイン酸の接触角が６５°以上のフライパン用調理シートが知られている。 Furthermore, using a contact angle with oleic acid, which is a main component of edible oil, as an index of releasability, JP 2005-87526 A discloses contact of oleic acid in which a silicone resin or a fluororesin is applied to a heat-resistant material sheet A frying pan cooking sheet having an angle of 65 ° or more is known.
離型剤としてのシリコーン樹脂は、加熱硬化皮膜形成後に残留トルエンの心配が全くなく、食品包装用に適した付加反応型の無溶剤タイプが求められている。また、生産性の面より高速でのシリコーン塗工が求められており、レベリング性，ミスト発生防止の観点より、より低粘度の無溶剤タイプのシリコーンが要求されている。 The silicone resin as a mold release agent has no concern about residual toluene after the heat-cured film is formed, and an addition reaction type solventless type suitable for food packaging is required. Further, high-speed silicone coating is required from the viewpoint of productivity, and a solvent-free type silicone having a lower viscosity is required from the viewpoint of leveling properties and prevention of mist generation.
本発明は上記事情に鑑みなされたもので、高速での塗工において優れた薄膜塗工性、硬化性を有し、食材が調理器具にこびり付くことがなく後片付けが簡単であり、しかも調理後の食材との離型性が良好なため、出来映えが良く調理できる調理用シート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, has excellent thin film coating properties and curability in high-speed coating, food is not stuck to cooking utensils, and easy to clean up, and cooking because after food and releasability is good in, and an object thereof is to provide a cooking sheet that workmanship can cook well.
本発明者は上記目的を達成するため主成分となるアルケニル基含有オルガノポリシロキサンとヒドロシリル化反応するオルガノハイドロジェンポリシロキサンに加え、分子鎖両末端にケイ原子に結合する水酸基を有するジオルガノポリシロキサンを用いることにより、食用油とシリコーン硬化皮膜との接触角を６５°以上にでき、料理用シートと特に卵料理や魚などのこびり付きやすい食材との付着防止を格段に向上できるため、調理品の見栄えがよく出来ることを見出した。 In order to achieve the above object, the present inventor, in addition to an organohydrogenpolysiloxane that undergoes a hydrosilylation reaction with an alkenyl group-containing organopolysiloxane that is a main component, a diorganopolysiloxane having hydroxyl groups that are bonded to silicon atoms at both ends of the molecular chain by using, because you to the contact angle between the edible oil and the silicone cured film can more than 65 °, significantly improved the adhesion prevention with sticking easily ingredients, especially eggs, fish and cooking sheet, the cooking I found that the product looks good.
また、付加反応遅延剤、白金族金属系触媒、さらに場合によっては、ジメチルポリシロキサンを含むシリコーン組成物の２５℃における粘度を５０〜１，０００ｍＰａ．ｓの範囲内とすることにより、高速塗工時における塗工ロール間から生じるシリコーンミストの発生を防止でき、均一なシリコーン塗工皮膜が形成可能な調理用シートが得られる知見を得た。 Moreover, the viscosity at 25 ° C. of the silicone composition containing an addition reaction retarder, a platinum group metal catalyst, and, in some cases, dimethylpolysiloxane is 50 to 1,000 mPa.s. With the range of s, it is possible to avoid the occurrence of silicone mist generated from between the coating roll during high speed coating, uniform silicone coating film is formable cooking sheet was obtained a finding obtained.
即ち、本発明は、
（Ａ）下記一般式（１）で示され、１分子中にケイ素原子に結合したアルケニル基を少なくとも２個有し、２５℃における粘度が６０〜８００ｍＰａ．ｓであるオルガノポリシロキサン １００質量部、
（Ｂ）下記一般式（２）で示され、分子鎖両末端にケイ素原子に結合した水酸基を有し、２５℃における粘度が５，０００ｍＰａ．ｓ以上であるジオルガノポリシロキサン １．０〜２０質量部、
（Ｃ）１分子中にケイ素原子に結合した水素原子を少なくとも２個有し、２５℃の粘度が５〜１０，０００ｍＰａ・ｓであるオルガノハイドロジェンポリシロキサン １．０〜３０質量部、
（Ｄ）付加反応遅延剤 ０．０２〜５質量部、
（Ｅ）触媒量の白金族金属系触媒、及び
（Ｆ）２５℃における粘度が５０〜５００，０００ｍＰａ・ｓの範囲内である分子鎖両末端がトリメチルシロキシ基で封鎖されたジメチルポリシロキサン １．０〜２０質量部
を含み、２５℃における粘度が５０〜１，０００ｍＰａ．ｓの範囲内である硬化性シリコーン離型剤組成物の硬化皮膜が耐熱性素材からなる基材の少なくとも片面に形成されてなる調理用シートを提供する。
That is, the present invention
(A) It is represented by the following general formula (1), and has at least two alkenyl groups bonded to silicon atoms in one molecule, and has a viscosity at 25 ° C. of 60 to 800 mPa.s. 100 parts by mass of organopolysiloxane which is s
(B) It is represented by the following general formula (2), has hydroxyl groups bonded to silicon atoms at both ends of the molecular chain, and has a viscosity at 25 ° C. of 5,000 mPa.s. 1.0 to 20 parts by mass of a diorganopolysiloxane that is s or more,
(C) the hydrogen atoms bonded to silicon atoms and at least two chromatic in one molecule, 1.0 to 30 parts by weight a viscosity of 25 ℃ 5~10,000mPa · s der Ru organohydrogenpolysiloxane,
(D) 0.02 to 5 parts by mass of an addition reaction retarder ,
(E) a catalytic amount of a platinum group metal catalyst , and
(F) 1.0 to 20 parts by mass of dimethylpolysiloxane having a viscosity at 25 ° C. within a range of 50 to 500,000 mPa · s and having both ends of a molecular chain blocked with a trimethylsiloxy group , 25 The viscosity at 50 ° C. is 50 to 1,000 mPa.s. Provided is a cooking sheet in which a cured film of a curable silicone release agent composition in the range of s is formed on at least one surface of a base material made of a heat-resistant material .
本発明の無溶剤型シリコーン組成物は薄膜塗工性、硬化性、密着性に優れるものであり、これを用いた調理用シートはシリコーン移行を大幅に増加させることなく、こびり付きやすい調理食材との離型性が良好にできる。調理品としては見栄えがよくでき、しかも調理器具の後片付け時間を短縮することができる。 The solvent-free silicone composition of the present invention is excellent in thin film coating properties, curability, and adhesion, and a cooking sheet using the same can be used as a cooking food that is easily stuck without greatly increasing silicone migration. Good releasability. It can look good as a cooked product, and the time for cleaning up the cooking utensils can be shortened.
以下、本発明を更に詳しく説明すると、（Ａ）成分のオルガノポリシロキサンはケイ素原子に結合したアルケニル基を１分子中に少なくとも２個有するものであり直鎖状であっても分岐状であっても構わない。 Hereinafter, the present invention will be described in more detail. The organopolysiloxane of component (A) has at least two alkenyl groups bonded to silicon atoms in one molecule, and even if it is linear, it is branched. It doesn't matter.
このようなアルケニル基含有オルガノポリシロキサンとしては、下記一般式（１）で示されるものである。 Examples of such an alkenyl group containing O Ruga Bruno polysiloxane is represented by the following general formula (1).
Ｒ１のアルケニル基としてはビニル基，アリル基，プロペニル基，ヘキセニル基，オクテニル基，デセニル基，等が例示される。 Examples of the alkenyl group for R 1 include a vinyl group, an allyl group, a propenyl group, a hexenyl group, an octenyl group, and a decenyl group.
Ｒとしては、炭素原子数１〜１２、好ましくは炭素原子数１〜６の脂肪族不飽和結合を含有しない同種又は異種の一価の炭化水素基であり、具体的にはメチル基、エチル基、プロピル基等のアルキル基、フェニル基、トリル基等のアリール基などが挙げられるが、硬化性，剥離性の向上の点から８０モル％以上がメチル基であることが好ましい。 R is the same or different monovalent hydrocarbon group containing 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms and not containing an aliphatic unsaturated bond, specifically a methyl group or an ethyl group. , An alkyl group such as a propyl group, and an aryl group such as a phenyl group and a tolyl group, but 80 mol% or more is preferably a methyl group from the viewpoint of improving curability and peelability.
更に、２５℃における粘度は５０ｍＰａ・ｓより低いと基材への染み込みが多くなるという不具が生じ、１，０００ｍＰａ・ｓより高い場合は塗工性が低下し高速塗工におけるミスト発生の問題剥離が生じるため、２５℃における粘度が５０〜１，０００ｍＰａ・ｓ、好ましくは６０〜８００ｍＰａ・ｓである。そのためには、重合度（ｍ＋ｎ）は８から２５０の範囲とされ、好ましくは、１０から２００である。 Further, when the viscosity at 25 ° C. is lower than 50 mPa · s, there is a disadvantage that the penetration into the base material increases. When the viscosity is higher than 1,000 mPa · s, the coating property is lowered and the problem of mist generation in high-speed coating is removed. Therefore, the viscosity at 25 ° C. is 50 to 1,000 mPa · s, preferably 60 to 800 mPa · s. For this purpose, the degree of polymerization (m + n) is in the range of 8 to 250, preferably 10 to 200.
本発明における（Ｂ）成分のジオルガノポリシロキサンは、分子鎖両末端にケイ素原子に結合した水酸基をそれぞれ１個有するジオルガノポリシロキサンであり、この成分により、シリコーン硬化皮膜と食用油の接触角を大きくすることができ、食材とのこびり付き防止効果が持続できるようになる。 The diorganopolysiloxane of component (B) in the present invention is a diorganopolysiloxane having one hydroxyl group bonded to a silicon atom at both ends of the molecular chain. By this component, the contact angle between the cured silicone film and the edible oil is determined. And the effect of preventing sticking to ingredients can be sustained.
このようなジオルガノポリシロキサンとしては、下記一般式（２）で示されるものである。 Such a diorganopolysiloxane is represented by the following general formula (2).
（ここで、Ｒは脂肪族不飽和結合を含有しない同種又は異種の一価炭化水素基であり、４５０≦ｏ≦１０，０００ ）
(Here, R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, and 450 ≦ o ≦ 10,000)
ここで、Ｒで示される基としては、上記と同様の炭素原子数１〜１２、好ましくは炭素原子数１〜６の脂肪族不飽和結合を含有しない同種又は異種の一価の炭化水素基であり、具体的にはメチル基，エチル基，プロピル基等のアルキル基、フェニル基，トリル基等のアリール基などが挙げられるが、離型性，（Ａ）成分との相溶性の点から８０モル％以上がメチル基であることが好ましい。 Here, the group represented by R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, as described above. Specific examples include alkyl groups such as methyl group, ethyl group, and propyl group, and aryl groups such as phenyl group and tolyl group. From the viewpoint of releasability and compatibility with component (A), 80 It is preferable that mol% or more is a methyl group.
また、２５℃における粘度は５，０００ｍＰａ．ｓ以上とされるが、５，０００ｍＰａ．ｓより低いと効果がないためであり、好ましくは１０，０００ｍＰａ．ｓ以上とされる。高粘度ほど食用油との接触角が改善できるため粘度の上限は特に制限はないが、組成物としての仕上がり粘度の観点より５，０００，０００ｍＰａ．ｓ以下が好ましい。 The viscosity at 25 ° C. is 5,000 mPa.s. s or more, but 5,000 mPa.s. If it is lower than s, there is no effect, and preferably 10,000 mPa.s. s or more. The upper limit of the viscosity is not particularly limited because the higher the viscosity, the better the contact angle with the edible oil, but from the viewpoint of the finished viscosity as a composition, 5,000,000 mPa.s. S or less is preferable.
また、（Ｂ）成分の配合量は（Ａ）成分１００質量部に対して０．５〜２５質量部とされ０．５質量部より少ないと食用油との接触角が改善できず、２５質量部をこえると組成物としての仕上がり粘度が上昇するためで、好ましくは１．０〜２０質量部の範囲内とすればよい。 Moreover, the compounding quantity of (B) component shall be 0.5-25 mass parts with respect to 100 mass parts of (A) component, and when less than 0.5 mass part , a contact angle with edible oil cannot be improved, and 25 masses. When the amount exceeds 100 parts , the finished viscosity of the composition increases, and the content is preferably in the range of 1.0 to 20 parts by mass .
（Ｃ）成分のオルガノハイドロジェンポリシロキサンは、１分中にケイ素原子に結合した水素原子を２個以上有し、このＳｉＨ基と（Ａ）成分中のビニル基とが付加反応して硬化皮膜が形成されるものであり、直鎖状、分岐状、環状の何れであってもよく、２５℃における粘度が５〜１０，０００ｍＰａ．ｓのものとすればよい。 The organohydrogenpolysiloxane of component (C) has two or more hydrogen atoms bonded to silicon atoms in 1 minute, and this SiH group and the vinyl group in component (A) undergo an addition reaction to form a cured film. Which may be linear, branched or cyclic, and has a viscosity at 25 ° C. of 5 to 10,000 mPa.s. s.
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、下記一般式（３）で示されるものである。 Such an organohydrogenpolysiloxane is represented by the following general formula (3).
Ｒとしては上記したと同様の炭素原子数１〜１２、好ましくは炭素原子数１〜６の脂肪族不飽和結合を含有しない同種又は異種の一価炭化水素基があげられ、メチル基、エチル基、プロピル基等のアルキル基、フェニル基，トリル基等のアリール基などが挙げられるが、付加反応速度の向上の点からメチル基であることが好ましい。 Number same carbon atom and the above-mentioned 1 to 12 as R, preferably is from monovalent hydrocarbon groups free of aliphatic unsaturation having 1 to 6 carbon atoms Agerare, a methyl group, an ethyl group And an alkyl group such as a propyl group, and an aryl group such as a phenyl group and a tolyl group, and a methyl group is preferable from the viewpoint of improving the addition reaction rate.
また、（Ｃ）成分の配合量は（Ａ）成分１００重量部に対して１．０〜３０．０部とされるが、アルケニル基量とＳｉＨ基量によって調整されるものでありモル比で０．８〜５．０の範囲とされる。モル比で０．８より小さいと良好な硬化皮膜が形成できず、モル比で５．０より大きくなると、離型性及び塗工液としての安定性が低下するので好ましくないためである。 The amount of the component (C) is 1.0 to 30.0 parts with respect to 100 parts by weight of the component (A), and is adjusted by the amount of alkenyl group and the amount of SiH group. The range is 0.8 to 5.0. When the molar ratio is less than 0.8, a good cured film cannot be formed, and when the molar ratio is more than 5.0, the release property and the stability as a coating liquid are lowered, which is not preferable.
（Ｄ）成分の付加反応遅延剤は、常温での（Ｅ）成分である白金族金属系触媒の触媒活性を抑制させて、該組成物の可使時間を長くする所謂ポットライフ延長剤であり、例えば、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公知のものを使用でき、特にアセチレンアルコール類及びアセチレンアルコールのシリル化物などが好適である。 (D) an addition reaction retarder of the component, by inhibiting the catalytic activity of platinum group metal-based catalyst which is the component (E) at room temperature, so-called pot life extending agent to extend the pot life of the composition There, for example, various organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, oxime compounds, can be used known ones such as an organic chloro compounds, are preferred, particularly acetylenic alcohols and silylated acetylenic alcohols.
なお、（Ｄ）成分の配合量は、硬化性および、ポットライフのバランスを考慮すると（Ａ）成分１００質量部に対して、０．０１〜１０質量部、好ましくは０．０２〜５．０質量部の範囲とすればよい。 In addition, the compounding quantity of (D) component considers sclerosis | hardenability and the balance of a pot life, 0.01-10 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.02-5.0. What is necessary is just to set it as the range of a mass part.
（Ｅ）成分の白金族金属系触媒は、（Ａ）成分と（Ｃ）成分との付加反応を促進するための触媒であり、付加反応触媒として公知のものが使用できる。このような白金族金属系触媒としては、例えば白金系、パラジウム系、ロジウム系などの触媒が挙げられ、これらの中で特に白金系触媒が好ましい。このような白金系触媒としては、例えば塩化白金酸、塩化白金酸のアルコール溶液やアルデヒド溶液、塩化白金酸の各種オレフィン又はビニルシロキサンとの錯体などが挙げられる。 The (E) component platinum group metal-based catalyst is a catalyst for promoting the addition reaction between the (A) component and the (C) component, and known addition reaction catalysts can be used. Examples of such platinum group metal catalysts include platinum-based, palladium-based, and rhodium-based catalysts, and among these, platinum-based catalysts are particularly preferable. Examples of such platinum-based catalysts include chloroplatinic acid, chloroplatinic acid alcohol solutions and aldehyde solutions, chloroplatinic acid complexes with various olefins or vinyl siloxanes, and the like.
これら白金族金属系触媒の添加量は触媒量であるが、良好な硬化皮膜を得ると共に経済的な見地から、（Ａ）成分１００部に対して白金族金属量として１〜１，０００ｐｐｍ、好ましくは５〜５００ｐｐｍの範囲とすることが好ましい。 The amount of the platinum group metal catalyst added is a catalyst amount. From the economical viewpoint, an excellent cured film is obtained, and the platinum group metal amount is preferably 1 to 1,000 ppm, preferably 100 parts of component (A). Is preferably in the range of 5 to 500 ppm.
本発明の組成物には、上記（Ａ）〜（Ｅ）成分の所定量を配合することによって得られるが、以上の各成分の外に、食材とのこびり付き防止を更に向上させるために（Ｆ）成分として２５℃における粘度が１０〜１，０００，０００ｍＰａ．ｓ、好ましくは５０〜５００，０００ｍＰａ・ｓであるジメチルポリシロキサンを（Ａ）成分１００質量部に対して、０．５〜２５質量部、好ましくは１．０〜２０質量部含むことができる。 The composition of the present invention can be obtained by blending predetermined amounts of the above components (A) to (E). In addition to the above components, in order to further improve the prevention of sticking to foods (F ) As a component, the viscosity at 25 ° C. is 10 to 1,000,000 mPa.s. s, preferably 50 to 500,000 mPa · s of dimethylpolysiloxane can be contained in an amount of 0.5 to 25 parts by mass, preferably 1.0 to 20 parts by mass with respect to 100 parts by mass of component (A).
ここで、粘度が１０ｍＰａ．ｓ未満では効果がなく、１，０００，０００ｍＰａ．ｓを超えると組成物全体の粘度が上昇するため好ましくない。また、配合量が０．５質量部未満では効果がなく、２５質量部を超えると、シリコーン転移量（Ｓｉ移行量）が増えて好ましくないためである。
また、他の任意成分、例えばケイ素原子に結合したアルケニル基を有する高分子のジオルガノポリシロキサンなどを、必要に応じて添加することができる。なお、任意成分の添加量は、本発明の効果を妨げない範囲で通常量とすることができる。
Here, the viscosity is 10 mPa.s. Less than s, there is no effect and 1,000,000 mPa.s. Exceeding s is not preferable because the viscosity of the entire composition increases. Further, if the blending amount is less than 0.5 parts by mass, there is no effect, and if it exceeds 25 parts by mass, the silicone transfer amount (Si transfer amount) increases, which is not preferable.
Further, other optional components such as a high molecular diorganopolysiloxane having an alkenyl group bonded to a silicon atom can be added as necessary. In addition, the addition amount of an arbitrary component can be made into a normal amount in the range which does not inhibit the effect of this invention.
本発明のシリコーン組成物の調製に際しては、（Ａ）〜（Ｄ）及び（Ｆ）更には任意成分を均一混合後、最後に（Ｅ）成分を添加することが好ましく、各成分は単一で使用しても２種以上を併用してもよい。ただし、組成物全体としての２５℃における粘度は５０〜１，０００ｍＰａ．ｓの範囲内とされ、１，０００ｍＰａ．ｓを越えると塗工時における塗工ロール間から発生するミストのため高速塗工出来ず生産性が低下するため実用上の使用困難となる。 In preparing the silicone composition of the present invention, it is preferable to add (A) to (D) and (F), and further add optional components, and then add component (E) at the end. Two or more kinds may be used in combination. However, the viscosity at 25 ° C. of the entire composition is 50 to 1,000 mPa.s. s, and is 1,000 mPa.s. If it exceeds s, high-speed coating cannot be performed due to mist generated between coating rolls at the time of coating, and productivity is lowered, so that practical use becomes difficult.
このようにして調製されたシリコーン組成物は、例えばグラシン紙、パーチメント紙、硫酸紙、アラミド紙などの耐熱紙に塗布した後、常法によって加熱硬化される。特にシリコーン組成物の塗工のしやすさの観点より、硬化皮膜を形成する基材としてはグラシン紙、パーチメント紙の使用が好適である。 The silicone composition thus prepared is applied to heat-resistant paper such as glassine paper, parchment paper, sulfuric acid paper, aramid paper, and the like, and then heat-cured by a conventional method. In particular, from the viewpoint of ease of application of the silicone composition, glassine paper or parchment paper is preferably used as the substrate for forming the cured film.
上記基材に本発明の組成物を塗布するには、グラビア・オフセット３本ロール方式または５本、６本などの多段ロール方式などの公知の方法を用いることができる。塗布量としては０．１〜５．０ｇ／ｍ２、特に、０．２〜３．０ｇ／ｍ２の範囲内が好適であり、基材の全面または離型性の必要な箇所に部分的に塗布する。基材に塗布した後、７０〜２５０℃で、１〜６０秒の加熱によって硬化させて、本発明の調理用シートを得る。 In order to apply the composition of the present invention to the substrate, a known method such as a gravure / offset three roll method or a multi-stage roll method such as five or six can be used. 0.1 to 5.0 g / m 2 as a coating amount, in particular, is suitable in the range of 0.2 to 3.0 g / m 2, partially where required over the entire surface or release properties of the substrate Apply to. After apply | coating to a base material, it is made to harden | cure by heating for 1 to 60 second at 70-250 degreeC, and the sheet | seat for cooking of this invention is obtained.
以下、実施例と比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、各例中の部はいずれも質量部であり、粘度は２５℃における値である。
また、シリコーン組成物の硬化性、接触角、Ｓｉ移行量、目玉焼き離型性、は下記の方法により測定した。
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, all the parts in each example are mass parts, and a viscosity is a value in 25 degreeC.
Further, the curability, contact angle, Si transfer amount, and fried egg releasability of the silicone composition were measured by the following methods.
硬化性
シリコーン組成物をシート状の基材表面に所定量塗布し、所定温度の熱風式乾燥機中で加熱して形成される硬化皮膜を指で数回こすり、くもり及び脱落のない状態になるまでの時間を測定した。
A predetermined amount of the curable silicone composition is applied to the surface of the sheet-like base material, and the cured film formed by heating in a hot-air dryer at a predetermined temperature is rubbed several times with a finger so that there is no cloudiness or dropping off. The time until was measured.
接触角
シリコーン組成物をシート状の基材表面に所定量塗布し、所定温度の熱風式乾燥機中で加熱して硬化皮膜を成形した後、２５℃で１日セパレ−タ−エ−ジング後、この硬化皮膜表面に商品名：日清サラダ油（日清オイリオグループ株式会社製）を４μＬ垂らし、３分後及び５分後の接触角を、自動接触角計ＣＡ−Ｚ型（協和界面科学株式会社製）を用いて測定した。
A predetermined amount of the contact angle silicone composition is applied to the surface of the sheet-like substrate, heated in a hot-air dryer at a predetermined temperature to form a cured film, and then separated at 25 ° C. for 1 day. 4 μL of Nissin Salad Oil (manufactured by Nisshin Oillio Group Co., Ltd.) is dropped on the surface of the cured film, and the contact angle after 3 and 5 minutes is measured using an automatic contact angle meter CA-Z (Kyowa Interface Science Co., Ltd.) (Manufactured by company).
Ｓｉ移行量
シリコーン組成物をシート状の基材表面に所定量塗布し、所定温度の熱風式乾燥機中で加熱して硬化皮膜を成形した直後、形成されたシリコーン組成物の硬化皮膜の表面に３６μｍのＰＥＴフィルムを重ね室温で０．９８ＭＰａで２０時間圧着した後、シリコーン塗工面に接した側のＰＥＴフィルムのＳｉカウント数（ｃｐｓ）を蛍光Ｘ線分析装置（株式会社リガク製Ｓｙｓｔｅｍ３０３０）により測定した。未処理のＰＥＴフィルムのＳｉカウウント数を差し引きしてＳｉ移行量とした。
Immediately after a predetermined amount of Si transfer amount silicone composition is applied to the surface of a sheet-like substrate and heated in a hot-air dryer at a predetermined temperature to form a cured film, the surface of the cured film of the formed silicone composition is applied. 36 μm PET film was stacked and pressure-bonded at 0.98 MPa for 20 hours at room temperature, and then the Si count number (cps) of the PET film in contact with the silicone coated surface was measured with a fluorescent X-ray analyzer (System 3030 manufactured by Rigaku Corporation). did. The number of Si counts of the untreated PET film was subtracted to obtain the Si transfer amount.
目玉焼き離型性
シリコーン組成物をシート状の基材表面に所定量塗布し、所定温度の熱風式乾燥機中で加熱して硬化皮膜を成形した後、２５℃で１日セパレ−タ−エ−ジング後、１５０ｍｍ×１５０ｍｍの大きさに切断して、フライパンにシリコーン塗布面を上になるように調理シートを敷いた。この調理シートの上に卵を割って載せ、さらにフタをして弱火で約３分間加熱して半熟の目玉焼きを調理した。
調理シートと目玉焼きのはがれ具合を下記のように評価した。
◎：シートに目玉焼きのこびり付きが全くない。
○：シートに目玉焼きのこびり付きが殆どない。（使用可能な程度）
△：シートに目玉焼が一部こびり付く。
×：シートに目玉焼きがこびり付く。
A predetermined amount of the fried egg releasable silicone composition is applied to the surface of the sheet-like substrate, heated in a hot air dryer at a predetermined temperature to form a cured film, and then separated at 25 ° C. for 1 day. After the ding, it was cut into a size of 150 mm × 150 mm, and a cooking sheet was laid on the frying pan so that the silicone-coated surface was up. Eggs were cracked and placed on the cooking sheet, and the lid was further capped and heated on low heat for about 3 minutes to prepare a half-boiled fried egg.
The degree of peeling between the cooking sheet and the fried egg was evaluated as follows.
A: There is no sticking of fried egg on the sheet.
○: There is almost no sticking of fried egg to the sheet. (Available)
Δ: Some fried eggs stick to the sheet.
X: Fried egg sticks to the sheet.
［参考例１］
（Ａ）成分として（１）式において、Ｒをメチル基（以下Ｍｅと記す。）、Ｒ1をビニル基（以下Ｖｉと記す。）、ｍ＝０、ｎ＝６８とした粘度が９５ｍＰａ・ｓである分子鎖両末端がジメチルビニルシロキシ基で封鎖されたポリジメチルシロキサン（Ａ−１）５０部、及びＲをメチル基、Ｒ1をビニル基，ｍ＝０、ｎ＝１４６とした粘度が３９０ｍＰａ・ｓである分子鎖両末端がジメチルビニルシロキシ基で封鎖されたポリジメチルシロキサン（Ａ−２）５０部の混合物に（Ｂ）成分として（２）式において、Ｒをメチル基、ｏ＝１，３００、とした粘度が１００，０００ｍＰａ．ｓである分子鎖両末端がジメチルハイドロキシシロキシ基で封鎖されたジメチルポリシロキサン（Ｂ−１）３．８部、及びＲをメチル基、ｏ＝３，０００、とした粘度が１，０００，０００ｍＰａ．ｓである分子鎖両末端がジメチルハイドロキシシロキシ基で封鎖されたジメチルポリシロキサン（Ｂ−２）３．６部の混合物を加え、（Ｂ）成分が（Ａ）成分中に均一溶解するまで充分に撹拌した。これにさらに（Ｃ）成分として、（３）式において、Ｒ及びＲ2をメチル基、ｐ＝５０、ｑ＝０とした粘度が２０ｍＰａ・ｓであるメチルハイドロジェンポリシロキサン（Ｃ−１）２．５部（ＳｉＨ／ＳｉＶｉ＝１．３）及び更に（Ｄ）成分として１−エチニル−１−シクロヘキサノ−ル（Ｄ−１）０．２部及び１，１−ジメチル−２−プロペニルオキシトリメチルシラン（Ｄ−２）０．３部を加え、均一になるまで攪拌した後、（Ｅ）成分として白金とビニルシロキサンとの錯体を上記（Ａ）成分に対して白金換算で５０ｐｐｍになるように添加し、粘度が４１０ｍＰａ・ｓであるシリコーン組成物を調製した。
[ Reference Example 1]
In the formula (1) as component (A), R is a methyl group (hereinafter referred to as Me), R 1 is a vinyl group (hereinafter referred to as Vi), m = 0, n = 68, and a viscosity of 95 mPa · s. 50 parts of polydimethylsiloxane (A-1) blocked at both ends of the molecular chain with dimethylvinylsiloxy groups, and R is a methyl group, R 1 is a vinyl group, m = 0, n = 146, and a viscosity of 390 mPa A mixture of 50 parts of polydimethylsiloxane (A-2) in which both ends of the molecular chain as s are blocked with dimethylvinylsiloxy groups, as component (B), in formula (2), R is a methyl group, o = 1, 300, the viscosity is 100,000 mPa.s. s is 3.8 parts of dimethylpolysiloxane (B-1) blocked at both ends with a dimethylhydroxysiloxy group, and R is a methyl group, o = 3,000, and a viscosity of 1,000,000 mPa . Add a mixture of 3.6 parts of dimethylpolysiloxane (B-2) having both ends of the molecular chain blocked with dimethylhydroxysiloxy groups, and s enough until component (B) is uniformly dissolved in component (A) Stir. Further, as component (C), methyl hydrogen polysiloxane (C-1) 2 having a viscosity of 20 mPa · s with R and R 2 being methyl groups, p = 50, q = 0 in the formula (3) 0.5 part (SiH / SiVi = 1.3) and 0.2 part of 1-ethynyl-1-cyclohexanol (D-1) and 1,1-dimethyl-2-propenyloxytrimethyl as component (D) After adding 0.3 part of silane (D-2) and stirring until uniform, the complex of platinum and vinylsiloxane as component (E) is 50 ppm in terms of platinum with respect to component (A). This was added to prepare a silicone composition having a viscosity of 410 mPa · s.
ポリジメチルシロキサン（Ａ−１） Polydimethylsiloxane (A-1)
ポリジメチルシロキサン（Ａ−２） Polydimethylsiloxane (A-2)
ポリジメチルシロキサン（Ｂ−１） Polydimethylsiloxane (B-1)
ポリジメチルシロキサン（Ｂ−２） Polydimethylsiloxane (B-2)
メチルハイドロジェンポリシロキサン（Ｃ−１） Methyl hydrogen polysiloxane (C-1)
次に、得られたシリコーン組成物をグラシン紙（坪量４０ｇ／ｍ２）に０．６〜０．７ｇ／ｍ２塗布し、キュアー性試験用としては１２０℃で硬化するまでの秒数をもとめた。また接触角、Ｓｉ移行量、目玉焼き離型性評価用サンプルとしては１４０℃で３０秒間加熱処理して硬化皮膜を形成させた。これらの評価結果を表１に示す。 Then, the resulting silicone composition 0.6~0.7g / m 2 was applied to glassine paper (basis weight 40 g / m 2), the number of seconds before curing at 120 ° C. As for cured test I asked. Moreover, as a sample for contact angle, Si transfer amount, and fried egg releasability evaluation, heat treatment was performed at 140 ° C. for 30 seconds to form a cured film. These evaluation results are shown in Table 1.
［実施例１］
（Ａ）成分として参考例１で使用したと同じポリジメチルシロキサン（Ａ−１）１００部に、（Ｂ）成分として参考例１で使用したと同じポリジメチルシロキサン（Ｂ−１）６．７部、（Ｃ）成分として参考例１で使用したと同じメチルハイドロジェンポリシロキサン（Ｃ−１）３．６部（ＳｉＨ／ＳｉＶｉ＝１．４）、（Ｄ）成分として１−エチニル−１−シクロヘキサノ−ル（Ｄ−１）０．３部及び更に追加成分（Ｆ）として分子鎖両末端がトリメチルシロキシ基で封鎖された粘度が１，０００ｍＰａ．ｓであるジメチルポリシロキサン（Ｆ−１）１２．２部を加え、均一になるまで攪拌した後、（Ｅ）成分として白金とビニルシロキサンとの錯体を上記（Ａ）成分に対して白金換算で５０ｐｐｍになるように添加し、粘度が２００ｍＰａ・ｓであるシリコーン組成物を調製し、参考例１と同様の物性試験を行った。結果を表１に併記する。
[Example 1 ]
The same polydimethylsiloxane and was used in Reference Example 1 as the component (A) (A-1) to 100 parts, (B) the same polydimethylsiloxane and was used in Reference Example 1 as the component (B-1) 6.7 parts In addition, 3.6 parts (SiH / SiVi = 1.4) of the same methyl hydrogen polysiloxane (C-1) used in Reference Example 1 as the (C) component and 1-ethynyl-1-cyclohexene as the (D) component As the additional component (F), 0.3 part of sanol (D-1) and a viscosity at which both ends of the molecular chain were blocked with trimethylsiloxy groups were 1,000 mPa.s. After adding 12.2 parts of dimethylpolysiloxane (F-1) which is s and stirring until uniform, a complex of platinum and vinylsiloxane as a component (E) in terms of platinum with respect to the component (A) A silicone composition having a viscosity of 200 mPa · s was prepared by adding 50 ppm, and the same physical property test as in Reference Example 1 was performed. The results are also shown in Table 1.
ジメチルポリシロキサン（Ｆ−１） Dimethylpolysiloxane (F-1)
［比較例１］
参考例１中で（Ｂ）成分は使用しないこととした以外は参考例１と同様にして粘度が１８０ｍＰａ・ｓであるシリコーン組成物を調製し、参考例１と同様の物性試験を行った。結果を表１に併記する。
[Comparative Example 1]
A silicone composition having a viscosity of 180 mPa · s was prepared in the same manner as in Reference Example 1 except that the component (B) was not used in Reference Example 1, and the same physical property test as in Reference Example 1 was performed. The results are also shown in Table 1.
［比較例２］
実施例１中で（Ｂ）成分は使用せず、ジメチルポリシロキサン（Ｆ−１）の量を１８．９部とした以外は実施例１と同様にして粘度が１４０ｍＰａ・ｓであるシリコーン組成物を調製し、参考例１と同様の物性試験を行った。結果を表１に併記する。
[Comparative Example 2]
Example 1 in component (B) is not used, dimethylpolysiloxane (F-1) The amount of the silicone composition viscosity in the same manner as in Example 1 except for using 18.9 parts of a 140 mPa · s of The same physical property test as in Reference Example 1 was performed. The results are also shown in Table 1.
［比較例３］
実施例１中で（Ｆ）成分は使用せず、（Ｂ）成分として（２）式において、Ｒをメチル基、ｏ＝２３０、とした粘度が１，０００ｍＰａ．ｓである分子鎖両末端がジメチルハイドロキシシロキシ基で封鎖されたジメチルポリシロキサン（Ｂ−３）を７．４部とした以外は実施例１と同様にして粘度が１２０ｍＰａ・ｓであるシリコーン組成物を調製し、参考例１と同様の物性試験を行った。結果を表１に併記する。
[Comparative Example 3]
In Example 1 , the component (F) was not used, and as the component (B), in the formula (2), the viscosity was 1,000 mPa.s where R was a methyl group and o = 230. silicone composition having a viscosity of 120 mPa · s in the same manner as in Example 1 except that 7.4 parts of dimethylpolysiloxane (B-3) having both molecular chain ends s blocked with dimethylhydroxysiloxy groups is used. The same physical property test as in Reference Example 1 was performed. The results are also shown in Table 1.
ポリジメチルシロキサン（Ｂ−３） Polydimethylsiloxane (B-3)
［比較例４］
参考例１中で（Ｂ）成分として（Ｂ−１）は使用せず、（Ｂ−２）の量を０．３部とした以外は参考例１と同様にして粘度が１９０ｍＰａ・ｓであるシリコーン組成物を調製し、参考例１と同様の物性試験を行った。結果を表１に併記する。
[Comparative Example 4]
In Reference Example 1, (B-1) is not used as the component (B), and the viscosity is 190 mPa · s as in Reference Example 1 except that the amount of (B-2) is 0.3 part. A silicone composition was prepared and subjected to the same physical property test as in Reference Example 1. The results are also shown in Table 1.
［比較例５］
参考例１中で（Ｂ）成分として（Ｂ−２）は使用せず、（Ｂ−１）の量を３０．０部とした以外は参考例１と同様にして粘度が１，３００ｍＰａ・ｓであるシリコーン組成物を調製したが、塗工においてミストが発生したため、物性試験は断念した。
[Comparative Example 5]
In Reference Example 1, (B-2) was not used as the component (B), and the viscosity was 1,300 mPa · s as in Reference Example 1 except that the amount of (B-1) was 30.0 parts. However, since mist was generated during coating, the physical property test was abandoned.
Claims (4)
（Ｂ）下記一般式（２）で示され、分子鎖両末端にケイ素原子に結合した水酸基を有し、２５℃における粘度が５，０００ｍＰａ．ｓ以上であるジオルガノポリシロキサン
１．０〜２０質量部、
（Ｃ）１分子中にケイ素原子に結合した水素原子を少なくとも２個有し、２５℃の粘度が５〜１０，０００ｍＰａ・ｓであるオルガノハイドロジェンポリシロキサン
１．０〜３０質量部、
（Ｄ）付加反応遅延剤 ０．０２〜５質量部、
（Ｅ）触媒量の白金族金属系触媒、及び
（Ｆ）２５℃における粘度が５０〜５００，０００ｍＰａ・ｓの範囲内である分子鎖両末端がトリメチルシロキシ基で封鎖されたジメチルポリシロキサン
１．０〜２０質量部
を含み、２５℃における粘度が５０〜１，０００ｍＰａ．ｓの範囲内である硬化性シリコーン離型剤組成物の硬化皮膜が耐熱性素材からなる基材の少なくとも片面に形成されてなる調理用シート。 (A) It is represented by the following general formula (1), and has at least two alkenyl groups bonded to silicon atoms in one molecule, and has a viscosity at 25 ° C. of 60 to 800 mPa.s. 100 parts by mass of organopolysiloxane which is s
(B) It is represented by the following general formula (2), has hydroxyl groups bonded to silicon atoms at both ends of the molecular chain, and has a viscosity at 25 ° C. of 5,000 mPa.s. diorganopolysiloxanes greater than or equal to s
1.0 to 20 parts by mass,
(C) 1 a hydrogen atom bonded to a silicon atom and at least two chromatic in the molecule, the viscosity of 25 ° C. Ru 5~10,000mPa · s der organohydrogenpolysiloxane
1.0-30 parts by mass,
(D) 0.02 to 5 parts by mass of an addition reaction retarder ,
(E) a catalytic amount of a platinum group metal catalyst , and
(F) Dimethylpolysiloxane having a viscosity at 25 ° C. in the range of 50 to 500,000 mPa · s and having both ends blocked with trimethylsiloxy groups
1.0 to 20 parts by mass and a viscosity at 25C of 50 to 1,000 mPa.s. A cooking sheet in which a cured film of a curable silicone release agent composition within the range of s is formed on at least one side of a substrate made of a heat-resistant material .
請求項１記載の調理用シート。 The organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule of the component (C) is represented by the following general formula (3).
According to claim 1 Symbol placement cooking sheet.
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| JP4936013B2 (en) * | 2008-04-25 | 2012-05-23 | 信越化学工業株式会社 | Solvent-free curable silicone release agent composition for plastic film and peelable plastic film |
| KR101989905B1 (en) * | 2014-09-29 | 2019-06-18 | 주식회사 엘지화학 | Silicon based coating composition and silicon based release film |
| CN108883615B (en) * | 2016-05-20 | 2020-11-10 | 三菱化学株式会社 | Mold release film |
| JP7153308B2 (en) * | 2018-05-30 | 2022-10-14 | 積水ポリマテック株式会社 | Curable silicone composition for dispenser |
| KR102512223B1 (en) * | 2020-12-17 | 2023-03-21 | 주식회사 에이치알에스 | Composition for silicone release coating and release film comprising same |
| KR102714863B1 (en) * | 2021-11-18 | 2024-10-08 | 주식회사 에이치알에스 | Composition for silicone release coating and release film comprising same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS59126475A (en) * | 1983-01-07 | 1984-07-21 | Toray Silicone Co Ltd | Composition for forming releasable film |
| JPS61264052A (en) * | 1985-05-17 | 1986-11-21 | Shin Etsu Chem Co Ltd | Silicone composition for release paper |
| JP2640486B2 (en) * | 1987-11-26 | 1997-08-13 | 東レ・ダウコーニング・シリコーン株式会社 | Release agent composition |
| JPH0791471B2 (en) * | 1988-11-25 | 1995-10-04 | 東レ・ダウコーニング・シリコーン株式会社 | Organopolysiloxane composition for peelable film formation |
| JPH0660287B2 (en) * | 1989-09-05 | 1994-08-10 | 信越化学工業株式会社 | Silicone composition for release paper and release paper |
| JP2946963B2 (en) * | 1992-09-09 | 1999-09-13 | 信越化学工業株式会社 | Silicone composition for forming release film and release film |
| JP2971357B2 (en) * | 1995-02-13 | 1999-11-02 | ジーイー東芝シリコーン株式会社 | Peeling composition |
| JP3813467B2 (en) * | 2001-05-31 | 2006-08-23 | 信越化学工業株式会社 | Curable silicone release agent composition |
| GB0227066D0 (en) * | 2002-11-20 | 2002-12-24 | Dow Corning | Silicone release coatings |
| WO2006070947A1 (en) * | 2004-12-28 | 2006-07-06 | Dow Corning Toray Co., Ltd. | Solvent-free organopolysiloxane composition for forming releasable cured coating film |
| JP2006125831A (en) * | 2005-10-07 | 2006-05-18 | Dow Corning Toray Co Ltd | Kitchen protective sheet |
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