JP2000345043A - Curable-methylpolysiloxane resin composition - Google Patents
Curable-methylpolysiloxane resin compositionInfo
- Publication number
- JP2000345043A JP2000345043A JP11201109A JP20110999A JP2000345043A JP 2000345043 A JP2000345043 A JP 2000345043A JP 11201109 A JP11201109 A JP 11201109A JP 20110999 A JP20110999 A JP 20110999A JP 2000345043 A JP2000345043 A JP 2000345043A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- formula
- sio
- parts
- resin composition
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は硬化性メチルポリシロキ
サンレジン組成物に関し、詳しくは、保存安定性、皮膜
形成性に優れ、硬化後は、撥水性、耐熱性、離型性に優
れた硬化皮膜を形成し得る硬化性メチルポリシロキサン
レジン組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable methylpolysiloxane resin composition, and more particularly to a curable resin having excellent storage stability and film forming properties, and having excellent water repellency, heat resistance and release properties after curing. The present invention relates to a curable methylpolysiloxane resin composition capable of forming a film.
【０００２】[0002]
【従来の技術】従来、メチルポリシロキサンレジンと両
末端水酸基封鎖ジメチルポリシロキサンとメチルトリス
（メチルエチルケトキシム）シラン等の加水分解性基含
有オルガノシランを主成分として、縮合反応触媒の存在
下で硬化する硬化性メチルポリシロキサンレジン組成物
は知られており、このものは、水、油、粘着剤等の付着
を防止するためのコーティング剤として有用とされてい
る（特開昭５５−４８２４５号公報参照）。しかし、こ
の組成物の硬化皮膜は、耐熱性、離型性の持続性等が今
一つ不十分であり、用途によっては必ずしも満足できる
ものではなかった。また、メチルフェニルポリシロキサ
ンレジンを主剤とする組成物であり、加熱により硬化す
る組成物も知られているが、この組成物は高温度条件下
で使用する際に、硬化皮膜が劣化して揮発物が発生する
ことがある等の不都合があり、用途によっては必ずしも
満足できるものではなかった。2. Description of the Related Art Conventionally, a curing method in which a main component is a methylpolysiloxane resin, a dimethylpolysiloxane having hydroxyl groups capped at both terminals and an organosilane having a hydrolyzable group such as methyltris (methylethylketoxime) silane, and is cured in the presence of a condensation reaction catalyst. A water-soluble methylpolysiloxane resin composition is known, which is useful as a coating agent for preventing adhesion of water, oil, pressure-sensitive adhesive and the like (see JP-A-55-48245). . However, the cured film of this composition has insufficient heat resistance, releasability, etc., and is not always satisfactory depending on the use. In addition, a composition comprising methylphenylpolysiloxane resin as a main component and a composition that cures by heating is also known, but when this composition is used under high temperature conditions, the cured film deteriorates and volatilizes. There are inconveniences, such as the generation of substances, and this is not always satisfactory depending on the use.
【０００３】[0003]
【発明が解決しようとする課題】本発明者らは上記問題
点を解消するために鋭意研究した結果、本発明に到達し
た。即ち、本発明の目的は保存安定性、皮膜形成性に優
れ、硬化後は、撥水性、耐熱性、離型性に優れた硬化皮
膜を形成し得る硬化性メチルポリシロキサンレジン組成
物を提供することにある。DISCLOSURE OF THE INVENTION The present inventors have made intensive studies to solve the above problems, and as a result, have reached the present invention. That is, an object of the present invention is to provide a curable methylpolysiloxane resin composition which is excellent in storage stability and film-forming properties and, after curing, can form a cured film having excellent water repellency, heat resistance and releasability. It is in.
【０００４】[0004]
【課題を解決するための手段】本発明は、 Ａ)平均単位式：ＭｅaＳｉＯ(4-a-b-c)/2(ＯＨ)b(ＯＲ1)c （式中、Ｍｅはメチル基であり、Ｒ1は炭素原子数１〜４のアルキル基である。 ａは１≦ａ≦２の範囲で表わされる数値であり、ｂは本化合物中におけるケイ素 原子に結合した水酸基の含有量が１〜５重量％となる値であり、ｃは本化合物中 におけるケイ素原子に結合したＯＲ1基の含有量が０.１〜４重量％となる値であ り、かつ、水酸基とＯＲ1基の含有量の合計は２．１〜５．１重量％である。） で示されるメチルポリシロキサンレジン １００重量部、 (Ｂ)一般式： Ｒ2Ｏ(Ｍｅ2ＳｉＯ)dＭｅ2ＳｉＯＲ2 （式中、Ｍｅはメチル基であり、Ｒ2はアルキル基または水素原子であり、ｄは 自然数である。） で示されるジメチルポリシロキサン １〜２０重量部、 (Ｃ）一般式： Ｒ3Ｒ4Ｒ5ＳｉＯ(Ｍｅ2ＳｉＯ)eＳｉＲ3Ｒ4Ｒ5 （式中、Ｍｅはメチル基であり、Ｒ3、Ｒ4、Ｒ5はアルキル基または水素原子で あり、eは０または２０以下の整数である。） で示されるジメチルポリシロキサン、または一般式： (Ｍｅ2ＳｉＯ)f （式中、Ｍｅはメチル基であり、ｆは、４〜２０の整数である。） で示されるポリジメチルシクロシロキサン １０重量部〜１,０００重量部 および (Ｄ)硬化促進触媒（本発明組成物を硬化させるのに十分な量） からなることを特徴とする、硬化性メチルポリシロキサンレジン組成物に関する 。The present invention provides: A) an average unit formula: MeaSiO(4-abc) / 2(OH)b(OR1)c (Wherein Me is a methyl group;1Is an alkyl group having 1 to 4 carbon atoms. a is a numerical value represented by the range of 1 ≦ a ≦ 2, b is a value at which the content of a hydroxyl group bonded to a silicon atom in the present compound is 1 to 5% by weight, and c is a silicon compound in the present compound. OR bonded to an atom1The content of the group is 0.1 to 4% by weight.1The sum of the group contents is 2.1-5.1% by weight. 100 parts by weight of a methylpolysiloxane resin represented by the following formula (B):TwoO (MeTwoSiO)dMeTwoSiORTwo (Wherein Me is a methyl group;TwoIs an alkyl group or a hydrogen atom, and d is a natural number. 1) to 20 parts by weight of a dimethylpolysiloxane represented by the following formula (C):ThreeRFourRFiveSiO (MeTwoSiO)eSiRThreeRFourRFive (Wherein Me is a methyl group;Three, RFour, RFiveIs an alkyl group or a hydrogen atom, and e is 0 or an integer of 20 or less. Or a dimethylpolysiloxane represented by the general formula: (MeTwoSiO)f (In the formula, Me is a methyl group, f is an integer of 4 to 20.) 10 parts by weight to 1,000 parts by weight of polydimethylcyclosiloxane represented by the following formula: A curable methylpolysiloxane resin composition comprising: an amount sufficient to cure the product.
【０００５】これを説明するに、本発明に使用される
(Ａ)成分のメチルポリシロキサンレジンは、本発明の組
成物の主成分であり、平均単位式： ＭｅaＳｉＯ(4-a-b-c)/2(ＯＨ)b(ＯＲ1)cで示される。
式中、Ｍｅはメチル基であり、Ｒ1は、メチル基、エチ
ル基、プロピル基、ブチル基で例示される炭素原子数１
〜４のアルキル基である。ａは１≦ａ≦２の範囲で表わ
される数値であり、ｂは本化合物中におけるケイ素原子
に結合した水酸基の含有量が１〜５重量％となる値であ
り、ｃは本化合物中におけるケイ素原子に結合したＯＲ
1基の含有量が０.１〜４重量％となる値であり、好まし
くは２.５〜４．８重量％となる値である。かつ、水酸
基とＯＲ1基の含有量の合計は２．１〜５．１重量％で
あり、好ましくは２.５〜４．８重量％となる値であ
る。水酸基とＯＲ1基の含有量の合計が２．１重量％未
満であると、硬化皮膜の持続性が十分でなく、５．１重
量％を超えると溶液中の保存安定性が低下する。かかる
メチルポリシロキサンレジンの製造方法は知られてお
り、例えば、メチルトリクロロシラン、ジメチルジクロ
ロシラン、トリメチルクロロシラン、テトラクロロシラ
ン、メチルトリアルコキシシラン、ジメチルジアルコキ
シシラン、トリメチルアルコキシシラン、テトラアルコ
キシシラン等から選択される加水分解性シラン化合物を
出発原料として、これらの１種または２種以上の混合物
を有機溶媒存在下で加水分解した後、縮合反応させるこ
とによって容易に製造することができる。[0005] To explain this, it is used in the present invention.
The methylpolysiloxane resin of the component (A) is a main component of the composition of the present invention, and is represented by an average unit formula: Me a SiO (4-abc) / 2 (OH) b (OR 1 ) c .
In the formula, Me is a methyl group, and R 1 is a group having 1 carbon atom exemplified by a methyl group, an ethyl group, a propyl group, and a butyl group.
To 4 alkyl groups. a is a numerical value represented by the range of 1 ≦ a ≦ 2; b is a value at which the content of a hydroxyl group bonded to a silicon atom in the present compound is 1 to 5% by weight; OR bonded to an atom
The value is such that the content of one group is 0.1 to 4% by weight, and preferably 2.5 to 4.8% by weight. The total content of the hydroxyl group and the OR 1 group is 2.1 to 5.1% by weight, and preferably 2.5 to 4.8% by weight. If the total content of hydroxyl group and OR 1 group is less than 2.1 wt%, durability of the cured film is not sufficient storage stability in the solution exceeds 5.1% by weight is reduced. Methods for producing such a methylpolysiloxane resin are known and include, for example, selected from methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, tetrachlorosilane, methyltrialkoxysilane, dimethyldialkoxysilane, trimethylalkoxysilane, tetraalkoxysilane, and the like. Using the hydrolyzable silane compound to be used as a starting material, the compound can be easily produced by hydrolyzing one or a mixture of two or more of these compounds in the presence of an organic solvent, followed by a condensation reaction.
【０００６】(Ｂ)成分のジメチルポリシロキサンは、本
発明の組成物から得られる硬化皮膜の離型性を増加させ
る働きをする成分である。かかる（Ｂ）成分は、一般
式： Ｒ2Ｏ(Ｍｅ2ＳｉＯ)dＭｅ2ＳｉＯＲ2 で示される。ここで、式中、Ｍｅはメチル基であり、Ｒ
2はメチル基、エチル基、プロピル基、ブチル基等のア
ルキル基または水素原子であり、特にメチル基または水
素原子が好ましい。dは自然数であるが、より良好な離
型性を発現させるためには、１０以上の整数であること
が好ましい。本成分の配合量は、(Ａ)成分１００重量部
に対して１〜２０重量部の範囲であり、好ましくは１〜
１０重量部の範囲である。[0006] The dimethylpolysiloxane of the component (B) is
Increases the releasability of the cured film obtained from the composition of the invention
It is a component that works. The component (B) is generally
Formula: RTwoO (MeTwoSiO)dMeTwoSiORTwo Indicated by Here, in the formula, Me is a methyl group, and R
TwoAre methyl, ethyl, propyl, butyl, etc.
Alkyl or hydrogen, especially methyl or water
Elementary atoms are preferred. d is a natural number, but better separation
Must be an integer of 10 or more to express the pattern
Is preferred. The amount of this component is 100 parts by weight of component (A).
In the range of 1 to 20 parts by weight, preferably 1 to
The range is 10 parts by weight.
【０００７】（Ｃ）成分は、本発明組成物を各種基材表
面上に塗布するに際して、表面張力を低下させ、皮膜の
ヨリやハジキを改善し、均一な皮膜を形成させる働きを
する。かかる(Ｃ)成分のひとつは、一般式： Ｒ3Ｒ4Ｒ5ＳｉＯ(Ｍｅ2ＳｉＯ)eＳｉＲ3Ｒ4Ｒ5 で示されるジメチルポリシロキサンである。ここで、式
中、Ｍｅは、メチル基であり、Ｒ3、Ｒ4、Ｒ5はメチル
基、エチル基、プロピル基、ブチル基等のアルキル基ま
たは水素原子であり、これらの中でもメチル基が好まし
い。eは０〜２０の整数であり、好ましくは、０〜１０
の整数であり、さらに好ましくは０〜３の整数である。
従って、本成分は揮発性のジメチルポリシロキサンであ
ることが好ましい。かかるジメチルポリシロキサンの具
体例としては、ヘキサメチルジシロキサン、オクタメチ
ルトリシロキサン、デカメチルテトラシロキサンがあ
る。[0007] The component (C) has a function of lowering the surface tension when coating the composition of the present invention on the surface of various substrates, improving twisting and repelling of the film, and forming a uniform film. One such component (C) is a dimethylpolysiloxane represented by the general formula: R 3 R 4 R 5 SiO (Me 2 SiO) e SiR 3 R 4 R 5 . Here, in the formula, Me is a methyl group, and R 3 , R 4 , and R 5 are an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or a hydrogen atom. preferable. e is an integer of 0 to 20, preferably 0 to 10
And more preferably an integer of 0 to 3.
Accordingly, this component is preferably a volatile dimethylpolysiloxane. Specific examples of such dimethylpolysiloxane include hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane.
【０００８】(Ｃ)成分のもうひとつの成分は、一般式： (Ｍｅ2ＳｉＯ)f で示されるポリジメチルシクロシロキサンである。式
中、Ｍｅはメチル基であり、ｆは、４〜２０の整数であ
り、好ましくは４〜１０の整数である。本成分の配合量
は、(Ａ)成分１００重量部に対して１０〜１０００重量
部の範囲であり、好ましくは１０〜１００重量部の範囲
である。Another component of the component (C) has the general formula: (MeTwoSiO)f Is a polydimethylcyclosiloxane represented by formula
Wherein Me is a methyl group and f is an integer of 4 to 20
And preferably an integer of 4 to 10. Amount of this component
Is 10 to 1000 parts by weight based on 100 parts by weight of the component (A).
Parts by weight, preferably in the range of 10 to 100 parts by weight.
It is.
【０００９】(Ｄ)成分は本発明組成物の硬化を促進する
ための触媒であり、シラノール基の脱水縮合反応に用い
られる縮合反応促進触媒が使用され、高温度条件下でも
硬化皮膜に悪影響を与えることの少ない触媒が好まし
い。かかる触媒としては、例えば、」チタン化合物、亜
鉛化合物、鉄化合物、アルミニウム化合物、ジルコニウ
ム化合物があり、具体的には、テトラアルキルチタネー
ト，ジアルキルチタネートの錯塩，オルガノシロキシチ
タネートなどのチタネート類、亜鉛オクトエート、鉄オ
クトエート、ジルコニウムオクトエートなどのカルボン
酸金属塩、アルミニウムキレートが挙げられる。本成分
の添加量は本発明組成物を硬化させるのに十分な量であ
り、通常、(Ａ)成分１００重量部に対して０.０００１
〜４０重量部の範囲である。The component (D) is a catalyst for accelerating the curing of the composition of the present invention, and a condensation reaction accelerating catalyst used for a dehydration condensation reaction of a silanol group is used. Catalysts that give less are preferred. Such catalysts include, for example, titanium compounds, zinc compounds, iron compounds, aluminum compounds, zirconium compounds, and specifically, tetraalkyl titanates, complex salts of dialkyl titanates, titanates such as organosiloxy titanates, zinc octoate, Examples thereof include metal carboxylate such as iron octoate and zirconium octoate, and aluminum chelates. The amount of this component is sufficient to cure the composition of the present invention, and is usually 0.0001 per 100 parts by weight of component (A).
It is in the range of ４０40 parts by weight.
【００１０】本発明組成物は上記のような（Ａ）成分〜
（Ｄ）成分からなるものであるが、本発明組成物の各種
基材への塗布性を向上させるためには、これらの成分に
加えて（Ｅ）成分として有機溶剤を配合することが好ま
しい。かかる有機溶剤としてはヘキサン、ヘプタン、オ
クタンなどの脂肪族飽和炭化水素類;ヘキセン、ヘプテ
ン、オクテンなどの脂肪族不飽和炭化水素類；シクロヘ
キサンなどの環状飽和炭化水素類;シクロヘキセンなど
の環状不飽和炭化水素類；ベンゼン、トルエン、キシレ
ンなどの芳香族飽和炭化水素類；ジエチルエーテル、エ
チルブチルエーテル、ジブチルエーテル、テトラヒドロ
フランなどのエーテル類;アセトン、メチルエチルケト
ン、メチルイソブチルケトン、ジエチルケトン、エチル
イソブチルケトンなどのケトン類;酢酸エチル、酢酸プ
ロピル、酢酸ブチル、酢酸イソアミル、乳酸メチル、乳
酸エチル、乳酸ブチルなどのカルボン酸エステル類が例
示される．本成分の配合量は、(Ａ)成分１００重量部に
対して１０〜１,０００重量部の範囲であり、好ましく
は１００〜１,０００重量部の範囲である。[0010] The composition of the present invention comprises the components (A) and
Although it is composed of the component (D), in order to improve the applicability of the composition of the present invention to various substrates, it is preferable to add an organic solvent as the component (E) in addition to these components. Such organic solvents include aliphatic saturated hydrocarbons such as hexane, heptane and octane; aliphatic unsaturated hydrocarbons such as hexene, heptene and octene; cyclic saturated hydrocarbons such as cyclohexane; cyclic unsaturated hydrocarbons such as cyclohexene. Hydrogens; aromatic saturated hydrocarbons such as benzene, toluene and xylene; ethers such as diethyl ether, ethyl butyl ether, dibutyl ether and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone and ethyl isobutyl ketone Carboxylic acid esters such as ethyl acetate, propyl acetate, butyl acetate, isoamyl acetate, methyl lactate, ethyl lactate and butyl lactate; The compounding amount of this component is in the range of 10 to 1,000 parts by weight, preferably 100 to 1,000 parts by weight, per 100 parts by weight of component (A).
【００１１】本発明組成物には食品部材等各種基材に対
する密着性を向上させる目的で、各種接着促進剤を添加
配合することは本発明の目的を損なわない限り差し支え
ない。かかる接着促進剤としては、メチルトリメトキシ
シラン；メチルトリアセトキシシラン；ビニルトリメト
キシシラン、ビニルトリエトキシシラン等のビニル基含
有オルガノアルコキシシラン：γ−メタクリロキシプロ
ピルトリメトキシラン、γ−アクリロキシプロピルトリ
メトキシシラン等のアクリロキシ基含有オルガノアルコ
キシシラン；γ−アミノプロピルトリメトキシラン等の
アミノ基含有オルガノアルコキシシラン；γ-グリシド
キシプロピルトリメトキシシラン等のエポキシ基含有オ
ルガノアルコキシシランが例示される。本成分の添加量
は（Ａ）成分１００重量部に対して０.０１〜１０重量
％の範囲内で使用される。The addition of various adhesion promoters to the composition of the present invention for the purpose of improving the adhesion to various base materials such as food members may be carried out as long as the object of the present invention is not impaired. Examples of such adhesion promoters include methyltrimethoxysilane; methyltriacetoxysilane; vinyl-containing organoalkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane: γ-methacryloxypropyltrimethoxylan, γ-acryloxypropyltrisilane. Examples thereof include organoalkoxysilanes containing an acryloxy group such as methoxysilane; organoalkoxysilanes containing an amino group such as γ-aminopropyltrimethoxysilane; and organoalkoxysilanes containing an epoxy group such as γ-glycidoxypropyltrimethoxysilane. The component is used in an amount of 0.01 to 10% by weight based on 100 parts by weight of the component (A).
【００１２】以上のような本発明組成物は湿気非存在下
では保存安定性に優れ、長期間貯蔵可能であり、湿気存
在下では室温で硬化して皮膜を形成する。また、加熱に
よって硬化皮膜を形成する。このときの加熱条件は１０
０℃〜３５０℃の温度範囲で５分〜５時間が好ましい。The above composition of the present invention has excellent storage stability in the absence of moisture and can be stored for a long period of time, and cures at room temperature in the presence of moisture to form a film. Further, a cured film is formed by heating. The heating condition at this time is 10
A temperature range of 0 ° C to 350 ° C for 5 minutes to 5 hours is preferred.
【００１３】以上のような本発明の硬化性メチルポリシ
ロキサンレジン組成物は、保存安定性、皮膜形成性に優
れ、硬化後は、撥水性、耐熱性、離型性等に優れた硬化
皮膜を形成する。そして、この硬化皮膜は、高温度条件
下で使用された場合でも離型性の持続性が良く、かつ、
食品と接触しても人体に悪影響を与えることのないとい
う特性を有するので、これらの特性を生かして、特に
は、食品加工部材、例えば、パン焼き用鉄板、ケーキ焼
き用鉄板、フライパン、焼き肉用鉄板の離型性コーティ
ング剤として有用である。[0013] The curable methylpolysiloxane resin composition of the present invention as described above is excellent in storage stability and film forming property, and after curing, forms a cured film excellent in water repellency, heat resistance, release property and the like. Form. And, this cured film has good releasability even when used under high temperature conditions, and
Since it has the property that it does not adversely affect the human body even when it comes into contact with food, taking advantage of these properties, in particular, food processing components, such as baking iron plate, cake baking iron plate, frying pan, grilled iron plate It is useful as a releasable coating agent.
【００１４】[0014]
【実施例】以下、本発明を実施例にて詳細に説明する。
尚、実施例中、部とあるのは重量部をのことであり、Ｍ
ｅはメチル基示す。また水に対する接触角の測定は、自
動接触角測定装置（協和界面化学株式会社製 ＣＡ−Ｒ
１）を使用した。The present invention will be described below in detail with reference to examples.
In the examples, "parts" means "parts by weight".
e represents a methyl group. In addition, the measurement of the contact angle with water is performed by using an automatic contact angle measuring device (CA-R manufactured by Kyowa Interface Chemical Co., Ltd.
1) was used.
【００１５】[0015]
【実施例１】式：(ＣＨ3)ＳｉＯ3/2で示されるシロキサ
ン単位８６モル％と式：(ＣＨ3)2ＳｉＯ2/2で示される
シロキサン単位１４モル％からなるメチルポリシロキサ
ンレジン（ケイ素原子に結合した水酸基の含有量は３．
４重量％であり、エトキシ基の含有量は０．６重量％で
ある。）１００部をトルエン１００部に溶解した後、
式： ＨＯ(Ｍｅ2ＳｉＯ)130Ｍｅ2ＳｉＯＨで示される両末端
水酸基封鎖ジメチルポリシロキサンオイル６部、式：Ｍ
ｅ3ＳｉＯＳｉＭｅ3で示されるで示されるヘキサメチル
ジシロキサン３０部、ヘプタン４０部およびジルコニウ
ムオクトエート１部を加えて均一に混合して、本発明の
硬化性メチルポリシロキサンレジン組成物を調製した。
この組成物２ｇをアルミ皿に採り１５０℃の加熱オーブ
ン中に３０分間入れて不揮分を測定した結果、その値は
３３重量％であった。また、この組成物をガラス瓶に封
入して、密封状態で、室温下、３か月間放置したとこ
ろ、この組成物の粘度や外観の変化はなかった。次い
で、この硬化性メチルポリシロキサンレジン組成物を平
滑な鉄板上に塗布し、２００℃で３０分間加熱して厚さ
５μｍの硬化皮膜を形成させた。得られた硬化皮膜の水
に対する接触角を測定したところ、その値は１０５度で
あった。また、鉛筆硬度を測定したところ、その値は５
Ｈと非常に硬い皮膜であった。この硬化皮膜を形成させ
た鉄板を２２０℃に加熱し、その上に小麦粉１００ｇと
水４０ｇとの混合物を置き、２２０℃の温度条件下で加
熱して、焼き上げてケーキを得た。次いで、このケーキ
を木製のへらを使って鉄板から剥がし取った。この操作
を毎日１０回７日間続けて行い、７日間後に鉄板の硬化
皮膜を調べたところ鉄板上に形成された硬化皮膜に異常
は認められなかった。EXAMPLE 1 A methylpolysiloxane resin comprising 86 mol% of a siloxane unit represented by the formula: (CH 3 ) SiO 3/2 and 14 mol% of a siloxane unit represented by the formula: (CH 3 ) 2 SiO 2/2 ( The content of the hydroxyl group bonded to the silicon atom is 3.
4% by weight and the content of ethoxy groups is 0.6% by weight. After dissolving 100 parts in 100 parts of toluene,
Formula: HO (Me 2 SiO) 130 Me 2 SiOH, 6 parts of dimethylpolysiloxane oil having both hydroxyl groups blocked at both ends, Formula: M
30 parts of hexamethyldisiloxane represented by e 3 SiOSiMe 3 , 40 parts of heptane and 1 part of zirconium octoate were added and uniformly mixed to prepare a curable methylpolysiloxane resin composition of the present invention.
2 g of this composition was placed in an aluminum dish, placed in a heating oven at 150 ° C. for 30 minutes, and the non-volatile content was measured. As a result, the value was 33% by weight. Further, when this composition was sealed in a glass bottle and left in a sealed state at room temperature for 3 months, there was no change in the viscosity or appearance of the composition. Next, the curable methylpolysiloxane resin composition was applied on a smooth iron plate and heated at 200 ° C. for 30 minutes to form a cured film having a thickness of 5 μm. When the contact angle of the obtained cured film to water was measured, the value was 105 degrees. When the pencil hardness was measured, the value was 5
H and a very hard film. The iron plate on which the cured film was formed was heated to 220 ° C., a mixture of 100 g of flour and 40 g of water was placed thereon, and heated at 220 ° C. to obtain a cake. The cake was then peeled off the iron plate using a wooden spatula. This operation was repeated 10 times a day for 7 days, and after 7 days, the cured film formed on the iron plate was examined. No abnormality was found in the cured film formed on the iron plate.
【００１６】[0016]
【実施例２】式：(ＣＨ3)ＳｉＯ3/2で示されるシロキサ
ン単位８８モル％と式：(ＣＨ3)2ＳｉＯ2/2で示される
シロキサン単位１２モル％からなるメチルポリシロキサ
ンレジン（ケイ素原子に結合した水酸基の含有量は２．
０重量％であり、イソプロポキシ基の含有量は０．３重
量％である。）１００部をトルエン１００部に溶解した
後、式： ＨＯ（Ｍｅ2ＳｉＯ)130Ｍｅ2ＳｉＯＨで示される両末端
シラノール封鎖ジメチルポリシロキサンオイル６部、
式：Ｍｅ3ＳｉＯＳｉＭｅ3で示されるで示されるヘキサ
メチルジシロキサン３０部、ヘプタン４０部およびジル
コニウムオクトエート１部を加えて均一に混合して、本
発明の硬化性メチルポリシロキサンレジン組成物を調製
した。この組成物２ｇをアルミ皿に採り１５０℃の加熱
オーブン中に３０分間入れて不揮発分を測定した結果、
その値は３３重量％であった。また、この組成物をガラ
ス瓶に封入して、密封状態で、室温下、３か月放置した
ところ、この組成物の粘度や外観の変化はなかった。次
いで、この硬化性メチルポリシロキサンレジン組成物を
平滑な鉄板上に塗布し、２００℃で３０分間加熱して厚
さ５μｍの硬化皮膜を形成させた。得られた硬化皮膜の
水に対する接触角を測定したところ、その値は１０６度
であった。また、鉛筆硬度を測定したところ、その値は
３Ｈと硬い皮膜であった。この硬化皮膜を形成させた鉄
板を２２０℃に加熱し、その上に小麦粉１００ｇと水４
０ｇとの混合物を置き、２２０℃の温度条件下で加熱し
て、焼き上げてケーキを得た。次いで、このケーキを木
製のへらを使って鉄板から剥がし取った。この操作を毎
日１０回７日間続けて行い、７日間後に鉄板の硬化皮膜
を調べたところ鉄板上に形成された硬化皮膜に異常は認
められなかった。EXAMPLE 2 A methylpolysiloxane resin comprising 88 mol% of a siloxane unit represented by the formula: (CH 3 ) SiO 3/2 and 12 mol% of a siloxane unit represented by the formula: (CH 3 ) 2 SiO 2/2 ( The content of the hydroxyl group bonded to the silicon atom is 2.
0% by weight and the content of isopropoxy groups is 0.3% by weight. ) After dissolving 100 parts in 100 parts of toluene, 6 parts of a silanol-capped dimethylpolysiloxane oil represented by the formula: HO (Me 2 SiO) 130 Me 2 SiOH,
A curable methylpolysiloxane resin composition of the present invention is prepared by adding 30 parts of hexamethyldisiloxane represented by the formula: Me 3 SiOSiMe 3 , 40 parts of heptane and 1 part of zirconium octoate and uniformly mixing. did. As a result of taking 2 g of this composition in an aluminum dish and placing it in a heating oven at 150 ° C. for 30 minutes to measure the nonvolatile content,
Its value was 33% by weight. Further, when this composition was sealed in a glass bottle and left in a sealed state at room temperature for 3 months, there was no change in the viscosity or appearance of the composition. Next, the curable methylpolysiloxane resin composition was applied on a smooth iron plate and heated at 200 ° C. for 30 minutes to form a cured film having a thickness of 5 μm. When the contact angle of the obtained cured film with water was measured, the value was 106 degrees. When the pencil hardness was measured, the value was 3H, which was a hard film. The iron plate on which the cured film was formed was heated to 220 ° C., and 100 g of flour and 4
The mixture with 0 g was placed, heated under a temperature condition of 220 ° C., and baked to obtain a cake. The cake was then peeled off the iron plate using a wooden spatula. This operation was repeated 10 times a day for 7 days, and after 7 days, the cured film formed on the iron plate was examined. No abnormality was found in the cured film formed on the iron plate.
【００１７】[0017]
【実施例３】式：(ＣＨ3)ＳｉＯ3/2で示されるシロキサ
ン単位８６モル％と式：(ＣＨ3)2ＳｉＯ2/2で示される
シロキサン単位１４モル％からなるメチルポリシロキサ
ンレジン（ケイ素原子に結合した水酸基の含有量は３．
４重量％であり、エトキシ基の含有量は０．６重量％で
ある。）１００部をトルエン１００部に溶解した後、
式： ＨＯ（Ｍｅ2ＳｉＯ)50Ｍｅ2ＳｉＯＨで示される両末端
シラノール封鎖ジメチルポリシロキサンオイル１５部、
式：Ｍｅ3ＳｉＯＳｉＭｅ3で示されるで示されるヘキサ
メチルジシロキサン３０部、ヘプタン４０部およびジル
コニウムオクトエート１部を加えて均一に混合して、本
発明の硬化性メチルポリシロキサンレジン組成物を調製
した。この組成物２ｇをアルミ皿に採り１５０℃の加熱
オーブン中に３０分間入れて不揮発分を測定した結果、
その値は３６重量％であった。また、この組成物をガラ
ス瓶に封入して、密封状態で室温下、３か月放置したと
ころ、この組成物の粘度や外観の変化はなかった。次い
で、この硬化性メチルポリシロキサンレジン組成物を平
滑な鉄板上に塗布し、２００℃で３０分間加熱して厚さ
５μｍの硬化皮膜を形成させた。得られた硬化皮膜の水
に対する接触角を測定したところ、その値は１０８度で
あった。また、鉛筆硬度を測定したところ、その値は３
Ｈと硬い皮膜であった。この硬化皮膜を形成させた鉄板
を２２０℃に加熱し、その上に小麦粉１００ｇと水４０
ｇとの混合物を置き、２２０℃の温度条件下で加熱し
て、焼き上げてケーキを得た。次いで、このケーキを木
製のへらを使って鉄板から剥がし取った。この操作を毎
日１０回７日間続けて行い、７日間後に鉄板の硬化皮膜
を調べたところ鉄板上に形成された硬化皮膜に異常は認
められなかった。EXAMPLE 3 A methylpolysiloxane resin comprising 86 mol% of a siloxane unit represented by the formula: (CH 3 ) SiO 3/2 and 14 mol% of a siloxane unit represented by the formula: (CH 3 ) 2 SiO 2/2 ( The content of the hydroxyl group bonded to the silicon atom is 3.
4% by weight and the content of ethoxy groups is 0.6% by weight. After dissolving 100 parts in 100 parts of toluene,
Formula: HO (Me 2 SiO) 50 Me 2 SiOH 15 parts silanol-blocked dimethylpolysiloxane oil at both ends,
A curable methylpolysiloxane resin composition of the present invention is prepared by adding 30 parts of hexamethyldisiloxane represented by the formula: Me 3 SiOSiMe 3 , 40 parts of heptane and 1 part of zirconium octoate and uniformly mixing. did. As a result of taking 2 g of this composition in an aluminum dish and placing it in a heating oven at 150 ° C. for 30 minutes to measure the nonvolatile content,
Its value was 36% by weight. When this composition was sealed in a glass bottle and left in a sealed state at room temperature for 3 months, there was no change in the viscosity or appearance of the composition. Next, the curable methylpolysiloxane resin composition was applied on a smooth iron plate and heated at 200 ° C. for 30 minutes to form a cured film having a thickness of 5 μm. When the contact angle of the obtained cured film with water was measured, the value was 108 degrees. When the pencil hardness was measured, the value was 3
It was a hard film with H. The iron plate on which the cured film was formed was heated to 220 ° C., and 100 g of flour and 40
g and heated under a temperature condition of 220 ° C. and baked to obtain a cake. The cake was then peeled off the iron plate using a wooden spatula. This operation was repeated 10 times a day for 7 days, and after 7 days, the cured film formed on the iron plate was examined. No abnormality was found in the cured film formed on the iron plate.
【００１８】[0018]
【実施例４】式：(ＣＨ3)ＳｉＯ3/2で示されるシロキサ
ン単位８６モル％と式：(ＣＨ3)2ＳｉＯ2/2で示される
シロキサン単位１４モル％からなるメチルポリシロキサ
ンレジン（ケイ素原子に結合した水酸基の含有量は３．
４重量％であり、エトキシ基の含有量は０．６重量％で
ある。）１００部をトルエン１００部に溶解した後、
式： ＨＯ（Ｍｅ2ＳｉＯ)130Ｍｅ2ＳｉＯＨで示される両末端
シラノール封鎖ジメチルポリシロキサンオイル６部、
式：(Ｍｅ2ＳｉＯ)4で示されるオクタメチルシクロテト
ラシロキサン３０部、ヘプタン４０部およびジルコニウ
ムオクトエート１部を加えて均一に混合して、本発明の
硬化性メチルポリシロキサンレジン組成物を調製した。
この組成物２ｇをアルミ皿に採り１５０℃の加熱オーブ
ン中に３０分間入れて不揮発分を測定した結果、その値
は３３重量％であった。また、この組成物をガラス瓶に
封入して、密封状態で室温下、３か月放置したところ、
この組成物の粘度や外観の変化はなかった。次いで、こ
の硬化性メチルポリシロキサンレジン組成物を平滑な鉄
板上に塗布し、２００℃で３０分間加熱して厚さ５μｍ
の硬化皮膜を形成させた。得られた硬化皮膜の水に対す
る接触角を測定したところ、その値は１０５度であっ
た。また、鉛筆硬度を測定したところ、その値は５Ｈと
非常に硬い皮膜であった。この硬化皮膜を形成させた鉄
板を２２０℃に加熱し、その上に小麦粉１００ｇと水４
０ｇとの混合物を置き、２２０℃の温度条件下で加熱し
て、焼き上げてケーキを得た。次いで、このケーキを木
製のへらを使って鉄板から剥がし取った。この操作を毎
日１０回７日間続けて行い、７日間後に鉄板の硬化皮膜
を調べたところ鉄板上に形成された硬化皮膜に異常は認
められなかった。EXAMPLE 4 A methylpolysiloxane resin comprising 86 mol% of a siloxane unit represented by the formula: (CH 3 ) SiO 3/2 and 14 mol% of a siloxane unit represented by the formula: (CH 3 ) 2 SiO 2/2 ( The content of the hydroxyl group bonded to the silicon atom is 3.
4% by weight and the content of ethoxy groups is 0.6% by weight. After dissolving 100 parts in 100 parts of toluene,
Formula: HO (Me 2 SiO) 130 6 parts of silanol-blocked dimethylpolysiloxane oil having silanol at both ends represented by Me 2 SiOH,
30 parts of octamethylcyclotetrasiloxane represented by the formula: (Me 2 SiO) 4 , 40 parts of heptane and 1 part of zirconium octoate are added and uniformly mixed to prepare a curable methylpolysiloxane resin composition of the present invention. did.
2 g of this composition was placed in an aluminum dish and placed in a heating oven at 150 ° C. for 30 minutes to measure the nonvolatile content. As a result, the value was 33% by weight. Further, when the composition was sealed in a glass bottle and left at room temperature in a sealed state for 3 months,
There was no change in the viscosity or appearance of this composition. Next, this curable methylpolysiloxane resin composition is applied on a smooth iron plate and heated at 200 ° C. for 30 minutes to form a 5 μm thick
To form a cured film. When the contact angle of the obtained cured film to water was measured, the value was 105 degrees. When the pencil hardness was measured, the value was 5H, which was a very hard film. The iron plate on which the cured film was formed was heated to 220 ° C., and 100 g of flour and 4
The mixture with 0 g was placed, heated under a temperature condition of 220 ° C., and baked to obtain a cake. The cake was then peeled off the iron plate using a wooden spatula. This operation was repeated 10 times a day for 7 days, and after 7 days, the cured film formed on the iron plate was examined. No abnormality was found in the cured film formed on the iron plate.
【００１９】[0019]
【実施例５】式：(ＣＨ3)ＳｉＯ3/2で示されるシロキサ
ン単位８６モル％と式：(ＣＨ3)2ＳｉＯ2/2で示される
シロキサン単位１４モル％からなるメチルポリシロキサ
ンレジン（ケイ素原子に結合した水酸基の含有量は３．
４重量％であり、エトキシ基の含有量は０．６重量％で
ある。）１００部をトルエン１００部に溶解した後、
式： ＨＯ（Ｍｅ2ＳｉＯ)130Ｍｅ2ＳｉＯＨで示される両末端
シラノール封鎖ジメチルポリシロキサンオイル６部、
式：Ｍｅ3ＳｉＯＳｉＭｅ3で示されるで示されるヘキサ
メチルジシロキサン８０部、Ｍｅ3ＳｉＯ（Ｍｅ2Ｓｉ
Ｏ）ＳｉＭｅ3で示されるオクタメチルトリシロキサン
２０部およびジルコニウムオクトエート１部を加えて均
一に混合して、硬化性メチルポリシロキサンレジン組成
物を調製した。この組成物２ｇをアルミ皿に採り１５０
℃の加熱オーブン中に３０分間入れて不揮発分を測定し
た結果、その値は３０重量％であった。また、この組成
物をガラス瓶に封入して、密封状態で室温下、３か月放
置したところ、この組成物の粘度や外観の変化はなかっ
た。次いで、この硬化性メチルポリシロキサンレジン組
成物を平滑な鉄板上に塗布し、２００℃で３０分間加熱
して厚さ３μｍの硬化皮膜を形成させた。得られた硬化
皮膜の水に対する接触角を測定したところ、その値は１
０５度であった。また、鉛筆硬度を測定したところ、そ
の値は５Ｈと非常に硬い皮膜であった。この硬化皮膜を
形成させた鉄板を２２０℃に加熱し、その上に小麦粉１
００ｇと水４０ｇとの混合物を置き、２２０℃の温度条
件下で加熱して、焼き上げてケーキを得た。次いで、こ
のケーキを木製のへらを使って鉄板から剥がし取った。
この操作を毎日１０回７日間続けて行い、７日間後に鉄
板の硬化皮膜を調べたところ鉄板上に形成された硬化皮
膜に異常は認められなかった。EXAMPLE 5 A methylpolysiloxane resin comprising 86 mol% of a siloxane unit represented by the formula: (CH 3 ) SiO 3/2 and 14 mol% of a siloxane unit represented by the formula: (CH 3 ) 2 SiO 2/2 ( The content of the hydroxyl group bonded to the silicon atom is 3.
4% by weight and the content of ethoxy groups is 0.6% by weight. After dissolving 100 parts in 100 parts of toluene,
Formula: HO (Me 2 SiO) 130 6 parts of silanol-blocked dimethylpolysiloxane oil having silanol at both ends represented by Me 2 SiOH,
80 parts of hexamethyldisiloxane represented by the formula: Me 3 SiOSiMe 3 , Me 3 SiO (Me 2 Si
O) 20 parts of octamethyltrisiloxane represented by SiMe 3 and 1 part of zirconium octoate were added and uniformly mixed to prepare a curable methylpolysiloxane resin composition. 2 g of this composition is placed in an aluminum dish and placed in an aluminum dish.
As a result of placing the sample in a heating oven at 30 ° C. for 30 minutes and measuring the nonvolatile content, the value was 30% by weight. When this composition was sealed in a glass bottle and left in a sealed state at room temperature for 3 months, there was no change in the viscosity or appearance of the composition. Next, this curable methylpolysiloxane resin composition was applied on a smooth iron plate, and heated at 200 ° C. for 30 minutes to form a cured film having a thickness of 3 μm. When the contact angle of the obtained cured film to water was measured, the value was 1
It was 05 degrees. When the pencil hardness was measured, the value was 5H, which was a very hard film. The iron plate on which the cured film was formed was heated to 220 ° C. and flour 1
A mixture of 00 g and 40 g of water was placed, heated under a temperature condition of 220 ° C., and baked to obtain a cake. The cake was then peeled off the iron plate using a wooden spatula.
This operation was repeated 10 times a day for 7 days, and after 7 days, the cured film formed on the iron plate was examined. No abnormality was found in the cured film formed on the iron plate.
【００２０】[0020]
【実施例６】式：(ＣＨ3)ＳｉＯ3/2で示されるシロキサ
ン単位８６モル％と式：(ＣＨ3)2ＳｉＯ2/2で示される
シロキサン単位１４モル％からなるメチルポリシロキサ
ンレジン（ケイ素原子に結合した水酸基の含有量は３．
４重量％であり、エトキシ基の含有量は０．６重量％で
ある。）１００部をトルエン１００部に溶解した後、
式： ＨＯ（Ｍｅ2ＳｉＯ)130Ｍｅ2ＳｉＯＨで示される両末端
シラノール封鎖ジメチルポリシロキサンオイル６部、
式：Ｍｅ3ＳｉＯＳｉＭｅ3で示されるで示されるヘキサ
メチルジシロキサン３０部、Ｎ−ヘプタン４０部および
亜鉛オクトエート１部を加えて均一に混合して、硬化性
メチルポリシロキサンレジン組成物を調製した。この組
成物２ｇをアルミ皿に採り１５０℃の加熱オーブン中に
３０分間入れて不揮発分を測定した結果、その値は３３
重量％であった。また、この組成物をガラス瓶に封入し
て、密封状態で、室温下、３か月放置したところ、この
組成物の粘度や外観の変化はなかった。次いで、この硬
化性メチルポリシロキサンレジン組成物を平滑な鉄板上
に塗布し、２００℃で３０分間加熱して厚さ５μｍの硬
化皮膜を形成させた。得られた硬化皮膜の水に対する接
触角を測定したところ、その値は１０５度であった。ま
た、鉛筆硬度を測定したところ、その値は５Ｈと非常に
硬い皮膜であった。この硬化皮膜を形成させた鉄板を２
２０℃に加熱し、その上に小麦粉１００ｇと水４０ｇと
の混合物を置き、２２０℃の温度条件下で加熱して、焼
き上げてケーキを得た。次いで、このケーキを木製のへ
らを使って鉄板から剥がし取った。この操作を毎日１０
回７日間続けて行い、７日間後に鉄板の硬化皮膜を調べ
たところ鉄板上に形成された硬化皮膜に異常は認められ
なかった。EXAMPLE 6 A methylpolysiloxane resin comprising 86 mol% of a siloxane unit represented by the formula: (CH 3 ) SiO 3/2 and 14 mol% of a siloxane unit represented by the formula: (CH 3 ) 2 SiO 2/2 ( The content of the hydroxyl group bonded to the silicon atom is 3.
4% by weight and the content of ethoxy groups is 0.6% by weight. After dissolving 100 parts in 100 parts of toluene,
Formula: HO (Me 2 SiO) 130 6 parts of silanol-blocked dimethylpolysiloxane oil having silanol at both ends represented by Me 2 SiOH,
A curable methylpolysiloxane resin composition was prepared by adding 30 parts of hexamethyldisiloxane represented by the formula: Me 3 SiOSiMe 3 , 40 parts of N-heptane and 1 part of zinc octoate and uniformly mixing. 2 g of this composition was placed in an aluminum dish and placed in a heating oven at 150 ° C. for 30 minutes to measure the nonvolatile content.
% By weight. Further, when this composition was sealed in a glass bottle and left in a sealed state at room temperature for 3 months, there was no change in the viscosity or appearance of the composition. Next, the curable methylpolysiloxane resin composition was applied on a smooth iron plate and heated at 200 ° C. for 30 minutes to form a cured film having a thickness of 5 μm. When the contact angle of the obtained cured film with water was measured, the value was 105 degrees. When the pencil hardness was measured, the value was 5H, which was a very hard film. The iron plate on which this cured film was formed
The mixture was heated to 20 ° C., and a mixture of 100 g of flour and 40 g of water was placed thereon, heated at 220 ° C. and baked to obtain a cake. The cake was then peeled off the iron plate using a wooden spatula. Perform this operation 10 times a day.
The test was performed continuously for 7 days, and after 7 days, the cured film formed on the iron plate was examined. No abnormality was found in the cured film formed on the iron plate.
【００２１】[0021]
【比較例１】実施例１において、式： Ｍｅ3ＳｉＯＳｉＭｅ3 で示されるヘキサメチルジシロキサン３０部の代わり
に、トルエン３０部を使用した以外は実施例１と同様に
して硬化性メチルポリシロキサンレジン組成物を調製し
た。この組成物２ｇをアルミ皿に採り、１５０℃の加熱
オーブン中で３０分間加熱して不揮発分を測定したとこ
ろ、その値は３３重量％であった。また、この組成物を
ガラス瓶に封入して密封状態で室温下で３か月保存した
ところ、粘度や外観の変化はなかった。しかし、実施例
１と同様に、メチルポリシロキサンレジン組成物を平滑
な鉄板上に塗布し、２００℃で３０分間加熱して硬化皮
膜を形成させたところ、硬化皮膜にヨリが発生して均一
な硬化皮膜が得られなかった。Comparative Example 1 In Example 1, the formula: MeThreeSiOSiMeThree Instead of 30 parts of hexamethyldisiloxane
In the same manner as in Example 1 except that 30 parts of toluene was used.
To prepare a curable methylpolysiloxane resin composition
Was. 2 g of this composition is placed in an aluminum dish and heated at 150 ° C.
Heating in an oven for 30 minutes and measuring the nonvolatile content
The value was 33% by weight. Also, this composition
Stored in a glass bottle in a sealed state at room temperature for 3 months
However, there was no change in viscosity or appearance. But the example
Smooth the methylpolysiloxane resin composition as in 1.
Coated on a flat iron plate and heated at 200 ° C for 30 minutes to cure the skin
When a film is formed, the cured film is twisted and uniform
No cured film was obtained.
【００２２】[0022]
【比較例２】実施例１において、式：(ＣＨ3)ＳｉＯ3/2
で示されるシロキサン単位８６モル％と式：(ＣＨ3)2Ｓ
ｉＯ2/2で示されるシロキサン単位１４モル％からなる
メチルポリシロキサンレジン１００部の代わりに、式：
(ＣＨ3)ＳｉＯ3/2で示されるシロキサン単位からなるメ
チルポリシロキサンレジン（ケイ素原子に結合した水酸
基の含有量は４重量％であり、ケイ素原子に結合したエ
トキシ基の含有量は１．２重量％であった。）１００部
を用いた以外は実施例１と同様にして硬化性メチルポリ
シロキサンレジン組成物を調製した。この組成物２ｇを
アルミ皿に採り１５０℃の加熱オーブンに３０分間入れ
て不揮発分を測定したところ、その値は３２重量％であ
った。この硬化性メチルポリシロキサンレジン組成物を
平滑な鉄板上に塗布し、２００℃で３０分間加熱して厚
さ５μｍの硬化皮膜を形成させた。得られた硬化皮膜の
水に対する接触角を測定したところ、その値は１０４度
であった。また、鉛筆硬度を測定したところ、その値は
４Ｈと硬い皮膜であった。しかし、この組成物をガラス
瓶に入れ、密封状態で室温下で３か月保存したところ、
内容物に白濁したものが生じており、この組成物は保存
安定性に劣るものであることが分かった。Comparative Example 2 In Example 1, the formula: (CH 3 ) SiO 3/2
86 mol% of a siloxane unit represented by the formula: (CH 3 ) 2 S
Instead of 100 parts of a methylpolysiloxane resin consisting of 14 mol% of siloxane units represented by iO 2/2 , the formula:
A methylpolysiloxane resin comprising a siloxane unit represented by (CH 3 ) SiO 3/2 (the content of hydroxyl groups bonded to silicon atoms is 4% by weight, and the content of ethoxy groups bonded to silicon atoms is 1.2% by weight. A curable methylpolysiloxane resin composition was prepared in the same manner as in Example 1 except that 100 parts was used. When 2 g of this composition was placed in an aluminum dish and placed in a heating oven at 150 ° C. for 30 minutes, and the nonvolatile content was measured, the value was 32% by weight. The curable methylpolysiloxane resin composition was applied on a smooth iron plate and heated at 200 ° C. for 30 minutes to form a cured film having a thickness of 5 μm. When the contact angle of the obtained cured film to water was measured, the value was 104 degrees. When the pencil hardness was measured, the value was 4H, which was a hard film. However, when this composition was placed in a glass bottle and stored in a sealed state at room temperature for 3 months,
The content was cloudy, indicating that the composition had poor storage stability.
【００２３】[0023]
【比較例３】実施例１において、式：(ＣＨ3)ＳｉＯ3/2
で示されるシロキサン単位８６モル％と式：(ＣＨ3)2Ｓ
ｉＯ2/2で示されるシロキサン単位１４モル％からなる
メチルポリシロキサンレジン１００部の代わりに、式：
(ＣＨ3)ＳｉＯ3/2で示されるシロキサン単位８８モル％
と式：(ＣＨ3)2ＳｉＯ2/2で示されるシロキサン単位１
２モル％からなるメチルポリシロキサンレジン（ケイ素
原子に結合した水酸基の含有量は１．２重量％であり、
ケイ素原子に結合したイソプロポキシ基の含有量は０．
３重量％であった。）１００部を用いた以外は実施例１
と同様にして硬化性メチルポリシロキサンレジン組成物
を調製した。この組成物２ｇをアルミ皿に採り１５０℃
の加熱オーブンに３０分間入れて不揮発分を測定したと
ころ、その値は３８重量％であった。また、密封状態で
室温で３か月保存したところ、粘度や外観の変化はなか
った。次いで、この硬化性メチルポリシロキサンレジン
組成物を平滑な鉄板上に塗布し、２００℃で３０分間加
熱して厚さ５μｍの硬化皮膜を形成させた。得られた硬
化皮膜の水に対する接触角を測定したところ、その値は
１０５度であった。また、鉛筆硬度を測定したところ、
その値は２Ｈであった。この硬化皮膜を形成させた鉄板
を２２０℃に加熱し、その上に小麦粉１００ｇと水４０
ｇの混合物を置き、２２０℃の温度条件下で加熱して、
焼き上げてケーキを得た。次いで、このケーキを木製の
へらを使って鉄板から剥がし取った。この操作を毎日１
０回７日間続けて行い、７日間後に鉄板の硬化皮膜を調
べたところこの硬化皮膜に汚れとキズが認められた。Comparative Example 3 In Example 1, the formula: (CH 3 ) SiO 3/2
86 mol% of a siloxane unit represented by the formula: (CH 3 ) 2 S
Instead of 100 parts of a methylpolysiloxane resin consisting of 14 mol% of siloxane units represented by iO 2/2 , the formula:
88 mol% of a siloxane unit represented by (CH 3 ) SiO 3/2
And a siloxane unit 1 represented by the formula: (CH 3 ) 2 SiO 2/2
Methylpolysiloxane resin consisting of 2 mol% (the content of hydroxyl groups bonded to silicon atoms is 1.2% by weight,
The content of the isopropoxy group bonded to the silicon atom is 0.1.
It was 3% by weight. Example 1 except that 100 parts were used.
In the same manner as in the above, a curable methylpolysiloxane resin composition was prepared. 2 g of this composition is placed in an aluminum dish and placed at 150 ° C.
Was placed in a heating oven for 30 minutes and the nonvolatile content was measured. The value was 38% by weight. When stored in a sealed state at room temperature for 3 months, there was no change in viscosity or appearance. Next, the curable methylpolysiloxane resin composition was applied on a smooth iron plate and heated at 200 ° C. for 30 minutes to form a cured film having a thickness of 5 μm. When the contact angle of the obtained cured film to water was measured, the value was 105 degrees. Also, when the pencil hardness was measured,
Its value was 2H. The iron plate on which the cured film was formed was heated to 220 ° C., and 100 g of flour and 40
g of the mixture, and heated under a temperature condition of 220 ° C.,
I baked it and got a cake. The cake was then peeled off the iron plate using a wooden spatula. Perform this operation daily
The test was repeated 0 times for 7 days, and after 7 days, when the cured film on the iron plate was examined, dirt and scratches were found on the cured film.
【００２４】[0024]
【発明の効果】本発明の硬化性メチルポリシロキサンレ
ジン組成物は、上記(Ａ)成分〜(Ｄ)成分からなるので、
保存安定性、皮膜形成性に優れ、硬化後は、撥水性、耐
熱性、離型性に優れた硬化皮膜を形成するいう特徴を有
する。The curable methylpolysiloxane resin composition of the present invention comprises the above components (A) to (D).
It has the characteristics of being excellent in storage stability and film forming properties, and of forming a cured film having excellent water repellency, heat resistance and release properties after curing.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4J002 CP03X CP033 CP04X CP06W CP063 EC077 EG047 EX036 EZ007 FD157 GH00 HA05 4J035 BA04 BA14 CA022 CA052 CA062 GA01 GB01 GB09 LB01 4J038 DL031 DL032 DL051 JA43 JC38 KA04 NA07 NA10 NA14 PB02 PC02 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 CP03X CP033 CP04X CP06W CP063 EC077 EG047 EX036 EZ007 FD157 GH00 HA05 4J035 BA04 BA14 CA022 CA052 CA062 GA01 GB01 GB09 LB01 4J038 DL031 DL032 DL051 JA43 J073802 NA43
Claims (4)
であり、Ｒ3、Ｒ4およびＲ5の内、少なくとも２つがメ
チル基である請求項１に記載の硬化性メチルポリシロキ
サンレジン組成物。2. Component (C) wherein e is 0, 1, 2, or 3
The curable methylpolysiloxane resin composition according to claim 1, wherein at least two of R 3 , R 4 and R 5 are a methyl group.
物、鉄化合物、アルミニウム化合物およびジルコニウム
化合物からなる群から選択された金属化合物である、請
求項１または請求項２に記載の硬化性メチルポリシロキ
サンレジン組成物。3. The curable methyl poly according to claim 1, wherein the component (D) is a metal compound selected from the group consisting of a titanium compound, a zinc compound, an iron compound, an aluminum compound and a zirconium compound. A siloxane resin composition.
ある請求項１〜請求項３のいずれか１項記載の硬化性メ
チルポリシロキサンレジン組成物4. The curable methylpolysiloxane resin composition according to claim 1, which is a release coating agent for a food processing member.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20110999A JP3475128B2 (en) | 1999-03-30 | 1999-07-15 | Curable methyl polysiloxane resin composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11-88784 | 1999-03-30 | ||
| JP8878499 | 1999-03-30 | ||
| JP20110999A JP3475128B2 (en) | 1999-03-30 | 1999-07-15 | Curable methyl polysiloxane resin composition |
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| Publication Number | Publication Date |
|---|---|
| JP2000345043A true JP2000345043A (en) | 2000-12-12 |
| JP3475128B2 JP3475128B2 (en) | 2003-12-08 |
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ID=26430126
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20110999A Expired - Fee Related JP3475128B2 (en) | 1999-03-30 | 1999-07-15 | Curable methyl polysiloxane resin composition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002322418A (en) * | 2001-04-26 | 2002-11-08 | Sumitomo Light Metal Ind Ltd | Water-repellent coated layer forming composition |
| WO2019148341A1 (en) * | 2018-01-31 | 2019-08-08 | Dow Global Technologies Llc | Polysiloxane resin composition |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3679100B1 (en) | 2017-09-07 | 2022-05-11 | Dow Global Technologies LLC | Thermally conductive ice-phobic coatings |
| JP6953339B2 (en) * | 2018-03-22 | 2021-10-27 | 信越化学工業株式会社 | Water repellent composition |
-
1999
- 1999-07-15 JP JP20110999A patent/JP3475128B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002322418A (en) * | 2001-04-26 | 2002-11-08 | Sumitomo Light Metal Ind Ltd | Water-repellent coated layer forming composition |
| WO2019148341A1 (en) * | 2018-01-31 | 2019-08-08 | Dow Global Technologies Llc | Polysiloxane resin composition |
| CN111655793A (en) * | 2018-01-31 | 2020-09-11 | 陶氏环球技术有限责任公司 | Silicone resin composition |
| US20210115295A1 (en) * | 2018-01-31 | 2021-04-22 | Dow Global Technologies Llc | Polysiloxane resin composition |
| EP3746511A4 (en) * | 2018-01-31 | 2021-12-22 | Dow Global Technologies, LLC | Polysiloxane resin composition |
| CN111655793B (en) * | 2018-01-31 | 2022-05-03 | 陶氏环球技术有限责任公司 | Silicone resin composition |
| TWI793256B (en) * | 2018-01-31 | 2023-02-21 | 美商陶氏全球科技公司 | Polysiloxane resin composition |
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| Publication number | Publication date |
|---|---|
| JP3475128B2 (en) | 2003-12-08 |
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