TWI651376B - Curable organopolyoxane composition and release film for use with a dielectric ceramic layer forming material using the same - Google Patents

Curable organopolyoxane composition and release film for use with a dielectric ceramic layer forming material using the same Download PDF

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TWI651376B
TWI651376B TW103139114A TW103139114A TWI651376B TW I651376 B TWI651376 B TW I651376B TW 103139114 A TW103139114 A TW 103139114A TW 103139114 A TW103139114 A TW 103139114A TW I651376 B TWI651376 B TW I651376B
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遠藤修司
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道康寧東麗股份有限公司
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    • C08J2483/00—Characterised by the use of 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; Derivatives of such polymers
    • C08J2483/14—Characterised by the use of 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; Derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms

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Abstract

本發明係關於一種可固化有機聚矽氧烷組合物，其包含：(A)具有黏度為20mPa．s或更大之液體至呈現可塑性之膠狀物中之任意形式之有機聚矽氧烷，該有機聚矽氧烷或有機聚矽氧烷混合物包含質量比為100：0至50：50之以下組分a1)及a2)：a1)包含具有4至12個碳原子之烯基之有機聚矽氧烷，該烯基具有0.5至3.0質量%之乙烯基部分含量，及a2)包含具有2至3個碳原子之烯基之有機聚矽氧烷，該烯基具有0.5至3.0質量%之乙烯基部分含量；(B)具有黏度為1,000,000mPa．s或更大之液體至呈現可塑性之膠狀物中之任意形式之有機聚矽氧烷，該有機聚矽氧烷視情況包含具有2至12個碳原子之烯基，該烯基具有小於0.100質量%之乙烯基部分含量；(C)分子內包含至少兩個矽鍵結氫原子之有機氫聚矽氧烷；(D)矽氫化觸媒；及(E)若需要，有機溶劑；組分(A)與(B)之質量比係在90：10至99：1之範圍內。 The present invention relates to a curable organic polysiloxane composition, which comprises: (A) has a viscosity of 20mPa. s or larger liquid to any form of organic polysiloxane in a plastic colloid, the organic polysiloxane or organic polysiloxane mixture containing a mass ratio of 100: 0 to 50:50 or less Components a1) and a2): a1) an organic polysiloxane containing an alkenyl group having 4 to 12 carbon atoms, the alkenyl group having a vinyl moiety content of 0.5 to 3.0% by mass, and a2) containing 2 to An organic polysiloxane of an alkenyl group of 3 carbon atoms, the alkenyl group has a vinyl content of 0.5 to 3.0% by mass; (B) has a viscosity of 1,000,000 mPa. s or larger liquid to any form of organic polysiloxane in a plastic colloid, the organic polysiloxane optionally contains an alkenyl group having 2 to 12 carbon atoms, the alkenyl group having less than 0.100 Mass% vinyl content; (C) organic hydrogen polysiloxane containing at least two silicon-bonded hydrogen atoms in the molecule; (D) hydrosilation catalyst; and (E) organic solvent if necessary; components The mass ratio of (A) to (B) is in the range of 90:10 to 99: 1.

Description

可固化有機聚矽氧烷組合物及與使用其之介電陶瓷層形成材料所共同使用的離型膜 Curable organic polysiloxane composition and release film used together with dielectric ceramic layer forming material using the same

本發明係關於一種可固化有機聚矽氧烷組合物及與使用其之介電陶瓷層形成材料所共同使用的離型膜，特別係用於形成陶瓷生胚片材之離型膜。 The invention relates to a curable organic polysiloxane composition and a release film used together with a dielectric ceramic layer forming material using the same, in particular to a release film for forming a ceramic green sheet.

習知地，當製造多層陶瓷產品(諸如多層陶瓷電容器、多層電感器及多層陶瓷電路板，尤其多層陶瓷電性組件)時，已知具有如下步驟之方法：使未燒製陶瓷材料視需要與黏合劑及溶劑或類似物混合以形成膏狀混合物，將其施加至塑膠載體膜並乾燥形成介電陶瓷層形成材料(通常為稱為「陶瓷生胚片材」之片材)，然後將具有膏狀形式之內部電極材料印刷於該陶瓷生胚片材上，以形成內部電極，複數個陶瓷生胚片材堆疊，以使得其電極圖案對齊，並將該等片材壓成單件結構，並經燒製以製造多層陶瓷產品(特別係多層陶瓷電子組件)。 Conventionally, when manufacturing multilayer ceramic products (such as multilayer ceramic capacitors, multilayer inductors and multilayer ceramic circuit boards, especially multilayer ceramic electrical components), a method with the following steps is known: making unfired ceramic materials A binder and a solvent or the like are mixed to form a paste-like mixture, which is applied to a plastic carrier film and dried to form a dielectric ceramic layer forming material (usually a sheet called "ceramic green sheet"), and then Paste-shaped internal electrode material is printed on the ceramic green sheet to form internal electrodes, a plurality of ceramic green sheets are stacked to align their electrode patterns, and the sheets are pressed into a single-piece structure, And fired to manufacture multilayer ceramic products (particularly multilayer ceramic electronic components).

陶瓷生胚片材可(例如)藉由如下方式生產：將含陶瓷材料(諸如鈦酸鋇或氧化鈦)、分散介質及類似物之陶瓷漿液施加至離型膜，然後使該漿液乾燥。在不遲於燒製陶瓷之前之後續步驟中，使藉由將陶瓷漿液施加至離型膜(亦稱為「載體膜」)，並使該漿液乾燥所獲得之 陶瓷生胚片材與該離型膜分離。典型的離型膜之實例係如下者：其中聚對苯二甲酸乙二酯或類似物之基膜之表面經聚矽氧基化合物(諸如聚矽氧烷)處理，以使得該膜可與陶瓷生胚片材分離(專利文獻1-8)。此等離型膜必須具有釋放性質，以使得離型膜上所形成之薄陶瓷生胚片材可自該離型膜移除而不致破裂。 The ceramic green sheet can be produced, for example, by applying a ceramic slurry containing a ceramic material (such as barium titanate or titanium oxide), a dispersion medium, and the like to the release film, and then drying the slurry. In a subsequent step not later than firing the ceramic, the one obtained by applying the ceramic slurry to the release film (also called "carrier film") and drying the slurry The ceramic green sheet is separated from the release film. A typical example of a release film is as follows: wherein the surface of the base film of polyethylene terephthalate or the like is treated with a polysiloxy compound (such as polysiloxane) to make the film compatible with ceramics Green embryo sheet separation (Patent Documents 1-8). The release film must have release properties so that the thin ceramic green sheet formed on the release film can be removed from the release film without cracking.

因為電子裝置在尺寸上變得較緊湊且可具有較高性能，所以多層陶瓷電容器及多層陶瓷板在尺寸上同樣變得較緊湊，且係由較多數量之層組成，同時減小陶瓷生胚片材之厚度。 Because electronic devices become more compact in size and can have higher performance, multilayer ceramic capacitors and multilayer ceramic boards also become more compact in size, and are composed of a larger number of layers, while reducing ceramic embryos The thickness of the sheet.

就可賦予基板膜可釋放性水平之適用作陶瓷生胚片材之載體膜之材料而言，本發明者已提出一種容易加工的(easy-to-handle)可固化有機聚矽氧烷組合物，該有機聚矽氧烷組合物可在基板表面上形成固化層，並賦予基板之表面相對於膠黏物質之令人滿意的可釋放性及賦予固化層平滑光滑度(slick smoothness)，該組合物包含(A)100質量份之至少一種在25℃下之黏度為20至500mPa．s且包含1.0至5.0質量%高碳數烯基(其包含4至12個碳原子)之有機聚矽氧烷，(B)0.5至15質量份之在25℃下之黏度為至少1,000,000mPa．s且包含0.005至0.100質量%烯基(其包含2至12個碳原子)之液體或膠狀有機聚矽氧烷，(C)一定量有機氫聚矽氧烷，其分子內包含至少兩個矽鍵結氫原子(Si-H)，以使得C中之SiH基團對(A)及(B)中之烯基之莫耳比為0.5至5，及(D)催化量之鉑觸媒(JP 2011-026582 A)。 With regard to the material suitable as a carrier film for ceramic green sheets that can impart a level of releasability to the substrate film, the inventors have proposed an easy-to-handle curable organic polysiloxane composition , The organopolysiloxane composition can form a cured layer on the surface of the substrate, and give the surface of the substrate a satisfactory releasability with respect to the adhesive substance and slick smoothness of the cured layer, the combination The material contains (A) 100 parts by mass of at least one having a viscosity at 25 ° C of 20 to 500 mPa. s and contains 1.0 to 5.0% by mass of high carbon number alkenyl (which contains 4 to 12 carbon atoms) of organic polysiloxane, (B) 0.5 to 15 parts by mass at 25 ℃ viscosity of at least 1,000,000mPa. s Liquid or colloidal organic polysiloxane containing 0.005 to 0.100 mass% alkenyl (which contains 2 to 12 carbon atoms), (C) a certain amount of organic hydrogen polysiloxane, which contains at least two in the molecule Silicon-bonded hydrogen atoms (Si-H) so that the molar ratio of the SiH groups in C to the alkenyl groups in (A) and (B) is 0.5 to 5, and (D) the catalytic amount of platinum catalyst (JP 2011-026582 A).

先前技術文獻Prior technical literature

1.日本未審查專利申請公開案第2002-011710號 1. Japanese Unexamined Patent Application Publication No. 2002-011710

2.日本未審查專利申請公開案第2004-182836號 2. Japanese Unexamined Patent Application Publication No. 2004-182836

3.日本未審查專利申請公開案第2004-216613號 3. Japanese Unexamined Patent Application Publication No. 2004-216613

4.日本未審查專利申請公開案第2008-254207號 4. Japanese Unexamined Patent Application Publication No. 2008-254207

5.日本未審查專利申請公開案第2009-034947號 5. Japanese Unexamined Patent Application Publication No. 2009-034947

6.日本未審查專利申請公開案第2009-215428號 6. Japanese Unexamined Patent Application Publication No. 2009-215428

7.日本未審查專利申請公開案第2009-227976號 7. Japanese Unexamined Patent Application Publication No. 2009-227976

8.日本未審查專利申請公開案第2009-227977號 8. Japanese Unexamined Patent Application Publication No. 2009-227977

9.日本未審查專利申請公開案第2011-026582號 9. Japanese Unexamined Patent Application Publication No. 2011-026582

如上所述，有必要減小由介電陶瓷層形成材料所構成之層之厚度，以減小多層陶瓷電容器或多層陶瓷板中之層之尺寸及/或增加其數量。然而，若在生產薄陶瓷生胚片材時，施加至基板膜之陶瓷漿液之乾燥後厚度為3μm或更小，則在施加陶瓷漿液並乾燥後，所施加的陶瓷漿液之邊緣可收縮，從而導致以下問題：邊緣收縮(其中所施加的片材之邊緣比內部部分厚)、形成氣孔及/或施加不均勻。其他問題包括當使陶瓷生胚片材與基板膜(亦即，離型膜)分離時，因片材較薄所致之陶瓷生胚片材之強度減小而引起片材或類似物的撕裂。 As described above, it is necessary to reduce the thickness of the layer composed of the dielectric ceramic layer forming material to reduce the size and / or increase the number of layers in the multilayer ceramic capacitor or multilayer ceramic board. However, if the thickness of the ceramic slurry applied to the substrate film after drying is 3 μm or less when producing a thin ceramic green sheet, the edge of the applied ceramic slurry may shrink after the ceramic slurry is applied and dried, thereby Causes the following problems: edge shrinkage (where the edge of the applied sheet is thicker than the inner part), formation of air holes, and / or uneven application. Other problems include when the ceramic green sheet is separated from the substrate film (that is, the release film), the strength of the ceramic green sheet is reduced due to the thinner sheet, which causes tearing of the sheet or the like crack.

此外，根據目的，使用陶瓷生胚片材所製造之電子材料及組件將使用不同類型之無機陶瓷材料、黏結劑樹脂、分散劑、有機溶劑等；因此，陶瓷漿液可與何者容易施加至離型膜係根據施加至離型膜之陶瓷漿液之類型而不同。因此，仍需要一種兼具陶瓷漿液施加之令人滿意之便捷性及令人滿意之陶瓷生胚片材可釋放性而與所使用的陶瓷漿液之類型無關之離型膜。 In addition, depending on the purpose, electronic materials and components manufactured using ceramic green sheets will use different types of inorganic ceramic materials, binder resins, dispersants, organic solvents, etc .; therefore, with which ceramic slurry can be easily applied to the release The film varies according to the type of ceramic slurry applied to the release film. Therefore, there is still a need for a release film that has both satisfactory convenience in applying ceramic slurry and satisfactory releasability of the ceramic green sheet regardless of the type of ceramic slurry used.

與此同時，如上所述，本發明者已在JP 2011-026582 A中作為用於賦予基板膜表面可釋放性之材料所揭示之可固化有機聚矽氧烷組合物係實質上無溶劑(亦即，不含溶劑)之可固化有機聚矽氧烷組合物，且可用作用於顯示螢幕保護片材或類似物之材料，但不適合(如所揭示的)用作用於陶瓷生胚片材之離型膜之材料。 Meanwhile, as described above, the present inventors have disclosed in JP 2011-026582 A that the curable organic polysiloxane composition disclosed as a material for imparting releasability to the surface of a substrate film is substantially solvent-free (also That is, it does not contain a solvent) curable organic polysiloxane composition, and can be used as a material for display screen protection sheets or the like, but is not suitable (as disclosed) for the separation of ceramic green sheet Material of type membrane.

本發明係基於上述情景而作，且其目標係提供一種用於形成陶 瓷生胚片材之離型膜(亦即，載體膜)，該膜具有將陶瓷漿液施加至其表面之優越便捷性及自於其表面上所形成之陶瓷生胚片材之優越可釋放性；及適合製造該膜之離型劑組合物。 The present invention is based on the above scenario, and its objective is to provide a A release film (ie, carrier film) of porcelain green sheets, which has superior convenience in applying ceramic slurry to its surface and superior releasability of ceramic green sheets formed on its surface ; And a release agent composition suitable for manufacturing the film.

本發明者已發現，當用作用於形成介電陶瓷層形成材料之離型膜(特別係用於形成陶瓷生胚片材之離型膜)時，如下所獲得的離型膜呈現優越性質：藉由以下文所述可固化有機聚矽氧烷組合物塗覆片狀基板(諸如基板膜)，該可固化有機聚矽氧烷組合物係作為離型劑組合物，以改質用作與介電陶瓷層形成材料共同使用之離型膜(特別係用作形成陶瓷生胚片材之離型膜)之基板之表面性質，隨後使該組合物固化；從而實現本發明。亦即，本發明可固化有機聚矽氧烷組合物包含以下組分(A)至(E)：(A)具有在25℃下之黏度為20mPa．s或更大之液體至在25℃下呈現可塑性之膠狀物中之任意形式之有機聚矽氧烷或有機聚矽氧烷混合物，該有機聚矽氧烷或有機聚矽氧烷混合物包含質量比為100：0至50：50之以下組分a1)及a2)：a1)至少一種包含具有4至12個碳原子之烯基之有機聚矽氧烷，該烯基具有0.5至3.0質量%之乙烯基(CH2=CH-)部分含量，及a2)至少一種包含具有2至3個碳原子之烯基之有機聚矽氧烷，該烯基具有0.5至3.0質量%之乙烯基(CH2=CH-)部分含量；(B)具有在25℃下之黏度為1,000,000mPa．s或更大之液體至在25℃下呈現可塑性之膠狀物中之任意形式之有機聚矽氧烷，該有機聚矽氧烷包含具有2至12個碳原子之烯基，該烯基具有至少0.005質量%且小於0.100質量%之乙烯基(CH2=CH-)部分含量；(C)分子內包含至少兩個矽鍵結氫原子(Si-H)之有機氫聚矽氧烷； (D)矽氫化觸媒；及(E)視需要之有機溶劑；組分(A)與(B)之質量比係在90：10至99：1之範圍內。在本發明之上下文中，「可塑性」係指利用塑度計根據JIS K 6249之方法測得之可塑性；具體言之，當在25℃下將1kgf負載置於4.2g球形樣本上三分鐘時所得到之數值(以mm計)。有機溶劑係該組合物之可選組分，該組合物可適宜地包含或不含有機溶劑。特定言之，本發明組合物可呈包含所需有機溶劑之所需形式，諸如溶液或懸浮液，其中以溶液特佳。 The present inventors have found that when used as a release film for forming a dielectric ceramic layer forming material (particularly a release film for forming a ceramic green sheet), the release film obtained as follows exhibits superior properties: A sheet-like substrate (such as a substrate film) is coated by a curable organic polysiloxane composition described below, which is used as a release agent composition to modify and The surface properties of the substrate of the release film (particularly used as the release film for forming the ceramic green sheet) used together with the dielectric ceramic layer forming material, and then the composition is cured; thus the present invention is achieved. That is, the curable organic polysiloxane composition of the present invention contains the following components (A) to (E): (A) has a viscosity at 25 ° C of 20mPa. s or larger liquid to any form of organic polysiloxane or organic polysiloxane mixture in a plastic that exhibits plasticity at 25 ° C. The organic polysiloxane or organic polysiloxane mixture contains mass The following components a1) and a2) with a ratio of 100: 0 to 50:50: a1) at least one organic polysiloxane containing an alkenyl group having 4 to 12 carbon atoms, the alkenyl group having 0.5 to 3.0% by mass Part of the vinyl group (CH 2 = CH-), and a2) at least one organic polysiloxane containing an alkenyl group having 2 to 3 carbon atoms, the alkenyl group having a vinyl group (CH 2 = CH-) partial content; (B) has a viscosity of 1,000,000 mPa at 25 ° C. s or larger liquid to any form of organic polysiloxane in a plastic exhibiting plasticity at 25 ° C, the organic polysiloxane containing an alkenyl group having 2 to 12 carbon atoms, the alkenyl group having At least 0.005 mass% and less than 0.100 mass% of vinyl (CH 2 = CH-) partial content; (C) an organic hydrogen polysiloxane containing at least two silicon-bonded hydrogen atoms (Si-H) in the molecule; ( D) Hydrosilation catalyst; and (E) organic solvents as needed; the mass ratio of components (A) and (B) is in the range of 90:10 to 99: 1. In the context of the present invention, "plasticity" refers to the plasticity measured using a plasticity meter according to the method of JIS K 6249; specifically, when a 1 kgf load is placed on a 4.2 g spherical sample at 25 ° C for three minutes The obtained value (in mm). The organic solvent is an optional component of the composition, and the composition may or may not suitably contain an organic solvent. In particular, the composition of the present invention may be in a desired form containing a desired organic solvent, such as a solution or suspension, with a solution being particularly preferred.

此外，在上述可固化有機聚矽氧烷組合物中，組分(A)較佳係具有在25℃下黏度為1,000,000mPa．s或更大之液體至在25℃下呈現可塑性之膠狀物中之任意形式之有機聚矽氧烷或有機聚矽氧烷混合物。 In addition, in the above curable organic polysiloxane composition, component (A) preferably has a viscosity of 1,000,000 mPa at 25 ° C. s or larger liquid to any form of organic polysiloxane or organic polysiloxane mixture in a plastic that exhibits plasticity at 25 ° C.

因此，本發明之較佳組分(A)係「高聚合物」有機聚矽氧烷或有機聚矽氧烷混合物，其物理性質隨著聚合度的增加而從高黏度液體區連續跨度至塑性膠狀物區。亦即，若該有機聚矽氧烷之聚合度增加至25℃下之黏度超過15,000,000mPa．s之程度，則黏度通常變得難以測定，且有機聚矽氧烷自高黏度區(亦即，液體)過渡為其中其物理性質依據可塑性來定義之區域(亦即，膠狀物)。換言之，本發明之組分(A)涵蓋自以下範圍變化之有機聚矽氧烷及有機聚矽氧烷混合物：彼等具有使得該有機聚矽氧烷或有機聚矽氧烷混合物係黏度為1,000,000mPa．s或更大(可在25℃下測量)之液體之聚合度者跨度至彼等具有使得該有機聚矽氧烷或有機聚矽氧烷混合物係黏度無法輕易在25℃下測量且其物理性質較佳依據可塑性來定義之膠狀物之較高聚合度者。特定言之，組分(A)較佳係具有25℃下之黏度為1,000,000mPa．s或更大之液體至25℃下呈現3.0mm或更小之可塑性之膠狀物中之任意形式之有機聚矽氧烷或有機聚矽氧烷混合物。最佳地，組分(A)係25℃下之可塑性為0.5至3.0mm之有機聚矽氧烷或有機聚矽氧烷混合物。 Therefore, the preferred component (A) of the present invention is a "high polymer" organopolysiloxane or a mixture of organopolysiloxanes whose physical properties continuously span from a high-viscosity liquid region to plasticity as the degree of polymerization increases Gum area. That is, if the degree of polymerization of the organic polysiloxane increases to 25 ° C viscosity exceeds 15,000,000mPa. To the extent of s, the viscosity usually becomes difficult to measure, and the organic polysiloxane transitions from a high-viscosity region (ie, liquid) to a region where its physical properties are defined in terms of plasticity (ie, jelly). In other words, the component (A) of the present invention covers organic polysiloxanes and organic polysiloxane mixtures varying from the following ranges: they have such that the viscosity of the organic polysiloxane or organic polysiloxane mixture is 1,000,000 mPa. s or greater (can be measured at 25 ° C) the degree of polymerization of the liquids spans to them so that the viscosity of the organopolysiloxane or organopolysiloxane mixture cannot be easily measured at 25 ° C and its physical properties It is better to define a higher degree of polymerization of the jelly based on plasticity. In particular, component (A) preferably has a viscosity of 1,000,000 mPa at 25 ° C. s or a larger liquid exhibits any form of organic polysiloxane or organic polysiloxane mixture in a plastic gum of 3.0 mm or less at 25 ° C. Most preferably, component (A) is an organic polysiloxane or an organic polysiloxane mixture having a plasticity at 25 ° C of 0.5 to 3.0 mm.

此外，在組分(A)中，較佳地：組分a1)為a1-1)一種包含己烯基作為具有4至12個碳原子之烯基之有機聚矽氧烷，該己烯基具有0.5至3.0質量%之乙烯基(CH2=CH-)部分含量；且組分a2)為a2-1)一種包含乙烯基作為具有2至3個碳原子之烯基之有機聚矽氧烷，該乙烯基含量係在0.5至3.0質量%之範圍內。 In addition, in component (A), preferably: component a1) is a1-1) an organic polysiloxane containing hexenyl as an alkenyl group having 4 to 12 carbon atoms, the hexenyl Having a partial content of vinyl groups (CH 2 = CH-) of 0.5 to 3.0% by mass; and component a2) is a2-1) an organic polysiloxane containing a vinyl group as an alkenyl group having 2 to 3 carbon atoms The vinyl content is in the range of 0.5 to 3.0% by mass.

特佳地，組分a1-1)之烯基為己烯基，且組分a2-1)之烯基為乙烯基。 Particularly preferably, the alkenyl group of component a1-1) is hexenyl, and the alkenyl group of component a2-1) is vinyl group.

亦較佳地，本發明可固化有機聚矽氧烷組合物之組分(B)係兩端經二甲基乙烯基矽氧基封端之二甲基聚矽氧烷。如組分(A)之情形一般，組分(B)之物理性質自25℃下顯示高黏度之液體範圍連續跨度至呈現可塑性之膠狀物範圍，此端視聚合度而定。具體言之，本發明之較佳組分(B)可係具有高黏度液體形式之二甲基聚矽氧烷或具有可塑性膠狀物形式之二甲基聚矽氧烷。特佳地，組分(B)係兩端經二甲基乙烯基矽氧基封端之二甲基聚矽氧烷，其具有25℃下之黏度為1,000,000mPa．s或更大之液體至可塑性為3.0mm或更小之膠狀物中之任意形式。最佳地，組分(B)係兩端經二甲基乙烯基矽氧基封端之二甲基聚矽氧烷，其具有25℃下之可塑性為0.5至3.0mm之膠狀物之形式。 Also preferably, component (B) of the curable organic polysiloxane composition of the present invention is dimethylpolysiloxane terminated at both ends with dimethylvinylsiloxy groups. As in the case of component (A), the physical properties of component (B) range from a continuous range of liquids showing high viscosity at 25 ° C to a range of plastics exhibiting plasticity, depending on the degree of polymerization. Specifically, the preferred component (B) of the present invention may be dimethyl polysiloxane having a high-viscosity liquid form or dimethyl polysiloxane having a plastic colloidal form. Particularly preferably, component (B) is a dimethylpolysiloxane end capped with dimethylvinylsiloxy at both ends, which has a viscosity of 1,000,000 mPa at 25 ° C. Any form of liquid from s or more to plastics with a plasticity of 3.0 mm or less. Most preferably, component (B) is a dimethylpolysiloxane end capped with dimethylvinylsiloxy at both ends, which has the form of a colloid having a plasticity of 0.5 to 3.0 mm at 25 ° C .

本發明可固化有機聚矽氧烷組合物亦可包含(G)光聚合引發劑，其不僅容許進行熱固化，而且容許使用能量輻射(亦稱為化學活性輻射)(諸如UV輻射或電子束)進行固化。 The curable organic polysiloxane composition of the present invention may also contain (G) a photopolymerization initiator, which not only allows thermal curing, but also allows the use of energy radiation (also called chemically active radiation) (such as UV radiation or electron beam) Carry out curing.

亦較佳地，本發明可固化有機聚矽氧烷組合物之總體組合物黏度為100至50,000mPa．s。本發明亦提供片狀物件，其包含藉由使上述含溶劑的可固化有機聚矽氧烷組合物固化所形成之固化層及片狀基板。 It is also preferred that the total composition viscosity of the curable organic polysiloxane composition of the present invention is 100 to 50,000 mPa. s. The present invention also provides a sheet-shaped article, which includes a cured layer formed by curing the above-mentioned solvent-containing curable organic polysiloxane composition and a sheet-shaped substrate.

片狀物件之固化層可藉由如下步驟得到：將上述任何含溶劑的可固化有機聚矽氧烷組合物以0.01至0.5g/m2施加至片狀基板，然後利用加熱或加熱及能量輻射之組合使該所施加的組合物固化。 The cured layer of the sheet-like article can be obtained by the following steps: applying any of the above-mentioned solvent-containing curable organic polysiloxane composition to the sheet-like substrate at 0.01 to 0.5 g / m 2 , and then using heating or heating and energy radiation The combination cures the applied composition.

該片狀基板較佳係塑膠膜。 The sheet substrate is preferably a plastic film.

本發明亦提供與介電陶瓷層形成材料共同使用之離型膜，特別係用於形成由片狀物件所構成之陶瓷生胚片材之離型膜。 The present invention also provides a release film used together with a dielectric ceramic layer forming material, especially for forming a release film of a ceramic green sheet composed of sheet-like objects.

本發明亦提供一種製造介電陶瓷層形成材料，特別係陶瓷生胚片材之方法，該方法包括使用與介電陶瓷層形成材料共同使用之離型膜或用於形成陶瓷生胚片材之離型膜作為載體膜，將陶瓷漿液施加至該膜上之固化有機聚矽氧烷層上，並使所施加的漿液乾燥之步驟。 The invention also provides a method for manufacturing a dielectric ceramic layer forming material, in particular a ceramic green sheet, the method includes using a release film used together with the dielectric ceramic layer forming material or for forming a ceramic green sheet The release film serves as a carrier film, a step of applying a ceramic slurry to the cured organic polysiloxane layer on the film, and drying the applied slurry.

利用由本發明可固化聚有機矽氧烷組合物構成之離型劑組合物獲得之本發明之離型片材或與介電陶瓷層形成材料共同使用之離型膜或用於形成陶瓷生胚片材之離型膜容許優越便捷地將陶瓷漿液施加至該膜上。具體言之，將陶瓷漿液施加至藉由使由本發明可固化聚有機矽氧烷組合物構成之離型劑組合物固化所得到之固化層表面，隨後使該漿液固化，容許使邊緣收縮最小化，其中所施加的陶瓷漿液邊緣收縮，會導致邊緣比內部部分更厚。此外，利用本發明離型劑組合物獲得之本發明之離型膜或與介電陶瓷層形成材料共同使用之離型膜或用於形成陶瓷生胚片材之離型膜呈現自於其上所形成之陶瓷生胚片材之優越可釋放性，從而容許以極小剝離力使該陶瓷生胚片材自該膜(亦即載體膜)之離型劑層移除。 The release sheet of the present invention obtained by using the release agent composition composed of the curable polyorganosiloxane composition of the present invention or the release film used together with the dielectric ceramic layer forming material or for forming a ceramic green sheet The release film of the material allows superior and convenient application of ceramic slurry onto the film. Specifically, the ceramic slurry is applied to the surface of the cured layer obtained by curing the release agent composition composed of the curable polyorganosiloxane composition of the present invention, and then the slurry is cured, allowing the edge shrinkage to be minimized , Where the edge of the applied ceramic slurry shrinks, causing the edge to be thicker than the inner part. In addition, the release film of the present invention obtained by using the release agent composition of the present invention or the release film used together with the dielectric ceramic layer forming material or the release film used to form the ceramic green sheet appear on it The superior releasability of the formed ceramic green sheet allows the ceramic green sheet to be removed from the release agent layer of the film (ie, carrier film) with minimal peeling force.

如上所述，本發明提供一種用於形成陶瓷生胚片材之離型片 材，其容許優越便捷地自離型膜釋放介電陶瓷層形成材料，特別係陶瓷生胚片材，及優越便捷地將陶瓷漿液施加至該膜；及適用於製造該離型片材之可固化有機聚矽氧烷組合物。本發明可固化有機聚矽氧烷組合物之特徵在於包含上文所列組分(A)至(D)，及視需要可選的組分(E)。特佳實施例包含組分(E)。現將詳細描述可固化有機聚矽氧烷組合物之各種組分、使用本發明組合物製造之片狀物件及用於形成陶瓷生胚片材之離型片材。 As described above, the present invention provides a release sheet for forming ceramic green sheet Material, which allows superior and convenient release of the dielectric ceramic layer forming material from the release film, especially ceramic green sheet, and superior and convenient application of ceramic slurry to the film; and suitable for manufacturing the release sheet Curing organic polysiloxane composition. The curable organic polysiloxane composition of the present invention is characterized by comprising the components (A) to (D) listed above, and optionally the component (E) if necessary. A particularly preferred embodiment contains component (E). The various components of the curable organopolysiloxane composition, the sheet-shaped article manufactured using the composition of the present invention, and the release sheet used to form the ceramic green sheet will now be described in detail.

在本發明之上下文中，該有機聚矽氧烷在25℃下之黏度係使用旋轉黏度計所測得之數值。「可塑性」係指利用塑度計根據JIS K 6249之方法測得之可塑性；具體言之，當在25℃下將1kgf負載置於4.2g球形樣本上三分鐘時所得到之數值(以mm計)。 In the context of the present invention, the viscosity of the organopolysiloxane at 25 ° C is the value measured using a rotary viscometer. "Plasticity" refers to the plasticity measured using a plasticity meter according to the method of JIS K 6249; specifically, the value (in mm) obtained when a load of 1 kgf is placed on a 4.2 g spherical sample at 25 ° C for three minutes ).

組分AComponent A

本發明可固化有機聚矽氧烷組合物之組分(A)係具有25℃下之黏度為20mPa．s或更大之液體至25℃下呈現可塑性之膠狀物中之任意形式且包含質量比為100：0至50：50之以下組分a1)及a2)之有機聚矽氧烷或有機聚矽氧烷混合物。 The component (A) of the curable organic polysiloxane composition of the present invention has a viscosity of 20 mPa at 25 ° C. Organic polysiloxane or organic polymer of s or larger liquid that exhibits any form in plastic jelly at 25 ° C and contains the following components a1) and a2) with a mass ratio of 100: 0 to 50:50 Siloxane mixture.

a1)至少一種包含具有4至12個碳原子之烯基之有機聚矽氧烷，該烯基具有0.5至3.0質量%之乙烯基(CH2=CH-)部分含量。 a1) At least one organic polysiloxane containing an alkenyl group having 4 to 12 carbon atoms, the alkenyl group having a vinyl (CH 2 = CH—) partial content of 0.5 to 3.0% by mass.

a2)至少一種包含具有2至3個碳原子之烯基之有機聚矽氧烷，該烯基具有0.5至3.0質量%之乙烯基(CH2=CH-)部分含量。 a2) At least one organic polysiloxane containing an alkenyl group having 2 to 3 carbon atoms, the alkenyl group having a vinyl (CH 2 = CH—) partial content of 0.5 to 3.0% by mass.

因此，組分(A)係僅由組分a1)構成或係組分a1)及a2)之混合物，且因此係由一或多種有機聚矽氧烷構成。 Therefore, component (A) is composed only of component a1) or is a mixture of components a1) and a2), and thus is composed of one or more organic polysiloxanes.

組分a1Component a1

形成組分(A)之一部分之組分a1)可選自直鏈有機聚矽氧烷、分支鏈有機聚矽氧烷及具有部分環結構之直鏈及分支鏈；從工業角度上看，以由以下化學式(1)表示之直鏈有機聚矽氧烷較佳。 Component a1) forming part of component (A) can be selected from linear organic polysiloxanes, branched organic polysiloxanes, and linear and branched chains with partial ring structures; from an industrial point of view, to The linear organic polysiloxane represented by the following chemical formula (1) is preferable.

在該式中，各R11獨立地表示未經取代或經鹵素取代之具有1至20個碳原子之烷基(諸如甲基)、具有6至22個碳原子之芳基(諸如苯基)、具有2或3個碳原子之烯基(乙烯基或烯丙基)或羥基。Ra係具有4至12個碳原子之烯基。R係以R11或Ra表示之基團。m為等於0或更大之數字，且n為等於1或更大之數字。m、n及R之數值係使得以上文式1表示之有機聚矽氧烷分子中之具有4至12個碳原子之烯基之乙烯基(CH2=CH-)部分含量為0.5至3.0質量%。 In this formula, each R 11 independently represents an unsubstituted or halogen-substituted alkyl group having 1 to 20 carbon atoms (such as methyl), and aryl group having 6 to 22 carbon atoms (such as phenyl) , Alkenyl (vinyl or allyl) or hydroxyl with 2 or 3 carbon atoms. Ra is an alkenyl group having 4 to 12 carbon atoms. R is a group represented by R 11 or Ra. m is a number equal to 0 or greater, and n is a number equal to 1 or greater. The numerical values of m, n, and R are such that the vinyl (CH 2 = CH-) portion of the alkenyl group having 4 to 12 carbon atoms in the organopolysiloxane molecule represented by Formula 1 above has a content of 0.5 to 3.0 mass %.

例如，若式(1)兩端之R均係烯基(Ra)，則此等烯基之乙烯基(CH2=CH-)部分含量係以以下公式表示：{(Ra中之乙烯基部分之分子量：約27)×(m+2)}/總分子量×100(質量%)，且在式(1)中，組分a1)係其中具有4至12個碳原子之烯基之乙烯基(CH2=CH-)部分含量係在0.5至3.0質量%，更佳1.0至2.0質量%之範圍內之有機聚矽氧烷。亦較佳地，在組分a1)中，式(1)中之m+n之總和係在使得以式(1)表示之有機聚矽氧烷在25℃下之黏度為20mPa．s或更大之範圍內之數字，特別係使得該有機聚矽氧烷具有25℃下之黏度為1,000,000mPa．s或更大之液體至25℃下之可塑性為0.5至3.0mm之膠狀物中之任意形式之數字。 For example, if R at both ends of formula (1) is alkenyl (Ra), the content of vinyl (CH 2 = CH-) part of these alkenyl groups is expressed by the following formula: {(the vinyl part in Ra Molecular weight: about 27) × (m + 2)} / total molecular weight × 100 (mass%), and in formula (1), component a1) is a vinyl group having an alkenyl group having 4 to 12 carbon atoms (CH 2 = CH-) part of the organic polysiloxane in the range of 0.5 to 3.0% by mass, more preferably 1.0 to 2.0% by mass. Also preferably, in component a1), the sum of m + n in formula (1) is such that the viscosity of the organic polysiloxane represented by formula (1) at 25 ° C is 20 mPa. The number in the range of s or greater, in particular, makes the organic polysiloxane have a viscosity of 1,000,000 mPa at 25 ° C. s or larger liquid to 25 ° C with a plasticity of 0.5 to 3.0 mm in any form of number.

組分a1)尤佳係在兩端及一側鏈上包含己烯基之有機聚矽氧烷，其係由以下化學式(2)表示。 Component a1) is particularly preferably an organic polysiloxane containing hexenyl groups at both ends and one side chain, which is represented by the following chemical formula (2).

式2Formula 2

(在式(2)中，m1為等於0或更大之數字，且n1為正整數，m1係使得以式(2)顯示之分子中之己烯基(-(CH2)4CH=CH2)之乙烯基(CH2=CH-)部分含量係於0.5至3.0質量%範圍內，更佳於1.0至2.0質量%範圍內之數字。m1+n1之總和係於使得以式(2)表示之有機聚矽氧烷在25℃下之黏度為20mPa．s或更大，更佳地黏度為1,000,000mPa．s或更大至25℃下可塑性為0.5至3.0mm之膠狀物中之任意形式之範圍內之數字。) (In formula (2), m1 is a number equal to 0 or greater, and n1 is a positive integer, and m1 is such that the hexenyl group in the molecule shown in formula (2) (-(CH 2 ) 4 CH = CH 2 ) The content of vinyl (CH 2 = CH-) is in the range of 0.5 to 3.0% by mass, more preferably in the range of 1.0 to 2.0% by mass. The sum of m1 + n1 is based on the formula (2) Said organic polysiloxane has a viscosity at 25 ° C of 20 mPa · s or greater, more preferably a viscosity of 1,000,000 mPa · s or greater to any of the gums having a plasticity of 0.5 to 3.0 mm at 25 ° C Numbers within the scope of the form.)

組分a1)在25℃下之黏度為20mPa．s或更大。若黏度低於此，則可能難以使具有4至12個碳原子之烯基之含量達到上文所列範圍內。另一方面，若黏度超過20mPa．s，則組分a1)在25℃下可為液體或膠狀物(通常地，黏度為10,000,000mPa．s或更大之高度聚合的半固體可塑性聚矽氧聚合物)。如上所述，本發明之較佳組分(A)係「高聚合物」有機聚矽氧烷或有機聚矽氧烷混合物，其物理性質隨著聚合度的增加而從高黏度液體區連續跨度至塑性膠狀物區。亦即，若有機聚矽氧烷之聚合度增加至25℃下之黏度超過15,000,000mPa．s之程度，則黏度通常變得難以測定，且有機聚矽氧烷自高黏度區(亦即，液體)過渡為其中其物理性質係依據可塑性來定義之區域(亦即，膠狀物)。 Component a1) The viscosity at 25 ℃ is 20mPa. s or greater. If the viscosity is lower than this, it may be difficult to bring the content of alkenyl groups having 4 to 12 carbon atoms into the range listed above. On the other hand, if the viscosity exceeds 20mPa. s, then component a1) can be liquid or gum at 25 ° C (typically, highly polymerized semi-solid plastic silicone polymer with a viscosity of 10,000,000 mPa · s or more). As mentioned above, the preferred component (A) of the present invention is a "high polymer" organopolysiloxane or a mixture of organopolysiloxanes whose physical properties continue to span from the high viscosity liquid region as the degree of polymerization increases To the plastic jelly zone. That is, if the degree of polymerization of the organic polysiloxane increases to 25 ° C, the viscosity exceeds 15,000,000 mPa. To the extent of s, the viscosity usually becomes difficult to measure, and the organic polysiloxane transitions from a high-viscosity region (ie, liquid) to a region where its physical properties are defined in terms of plasticity (ie, jelly).

為獲得將本發明可固化有機聚矽氧烷組合物施加至片狀基板之令人滿意的便捷性，組分a1)在25℃下之黏度較佳為10,000,000mPa．s或更大。組分a1)在25℃下之黏度並無上限，但是，為確保加工之便捷性，以25℃下黏度為1,000,000mPa．s或更大之液體至25℃下可塑性為3.0mm或更小之膠狀物中之任意形式較佳。 In order to obtain satisfactory convenience of applying the curable organic polysiloxane composition of the present invention to a sheet substrate, the viscosity of component a1) at 25 ° C is preferably 10,000,000 mPa. s or greater. There is no upper limit for the viscosity of component a1) at 25 ° C. However, to ensure the convenience of processing, the viscosity at 25 ° C is 1,000,000 mPa. Liquids of s or greater are preferably in any form of gums having a plasticity of 3.0 mm or less at 25 ° C.

組分a1)可係兩種或更多種具有不同黏度之組分a1)之混合物。若 與低黏度液體有機聚矽氧烷混合在一起，則可有利地使用形式為可塑性超過3.0mm之膠狀物之有機聚矽氧烷，且本發明涵蓋此形式。 Component a1) can be a mixture of two or more components a1) with different viscosities. If When mixed with a low-viscosity liquid organic polysiloxane, an organic polysiloxane in the form of a colloid with a plasticity exceeding 3.0 mm can be advantageously used, and the present invention covers this form.

組分a2Component a2

形成組分(A)之一部分之組分a2)可選自直鏈有機聚矽氧烷、分支鏈有機聚矽氧烷及具有部分環結構之直鏈或分支鏈有機聚矽氧烷；從工業角度上看，以由以下化學式(1)表示之直鏈有機聚矽氧烷較佳。 Component a2) forming part of component (A) can be selected from linear organic polysiloxanes, branched organic polysiloxanes, and linear or branched organic polysiloxanes with partial ring structures; from industry From a viewpoint, a linear organic polysiloxane represented by the following chemical formula (1) is preferable.

在該式中，各R11獨立地表示未經取代或經鹵素取代之具有1至20個碳原子之烷基(諸如甲基)、具有6至22個碳原子之芳基(諸如苯基)、具有2或3個碳原子之烯基(乙烯基或烯丙基)或羥基。Ra' 係具有2或3個碳原子之烯基(乙烯基或烯丙基)。R係以R11或Ra' 表示之基團。m為等於0或更大之數字，且n為等於1或更大之數字。m、n及R之數值係使得以上文式1表示之有機聚矽氧烷分子中之具有2或3個碳原子之烯基之乙烯基(CH2=CH-)部分含量為0.5至3.0質量%，更佳1.0至2.0質量%。 In this formula, each R 11 independently represents an unsubstituted or halogen-substituted alkyl group having 1 to 20 carbon atoms (such as methyl), and aryl group having 6 to 22 carbon atoms (such as phenyl) , Alkenyl (vinyl or allyl) or hydroxyl with 2 or 3 carbon atoms. Ra ' is an alkenyl group (vinyl or allyl) having 2 or 3 carbon atoms. R is a group represented by R 11 or Ra ' . m is a number equal to 0 or greater, and n is a number equal to 1 or greater. The values of m, n and R are such that the vinyl (CH 2 = CH-) portion of the alkenyl group having 2 or 3 carbon atoms in the organopolysiloxane molecule represented by Formula 1 above has a content of 0.5 to 3.0 mass %, More preferably 1.0 to 2.0% by mass.

例如，若兩端之R均係具有2或3個碳原子之烯基(Ra)，則該烯基的含量係以以下公式表示：(存在於該分子中之具有2或3個碳原子之烯基中之乙烯基(CH2=CH-)部分之總分子量)/總分子量×100(質量%)，且在式(1)中，組分a2)係其中具有2或3個碳原子之烯基之乙烯基(CH2=CH-)部分含量為0.5至3.0質量%，更佳1.0至2.0質量%之有機聚矽氧烷。亦較佳地，在組分a2)中，式(1)中之m+n之總和係在使得以式(1)表示之有機聚矽氧烷在25℃下之黏度為20mPa．s或更大之範圍內 之數字，較佳係使得黏度為1,000,000mPa．s或更大之數字，特佳係得到25℃下之黏度為1,000,000mPa．s或更大之液體至25℃下之可塑性為3.0mm或更小之膠狀物中之任意形式之數字。為獲得將可固化有機聚矽氧烷組合物施加至片狀基板之令人滿意的便捷性，組分a2)較佳具有在25℃下之10,000,000mPa．s或更大之黏度至在25℃下具有可塑性為3.0mm或更小之膠狀形式中之任意形式。 For example, if R at both ends is an alkenyl group (Ra) having 2 or 3 carbon atoms, the content of the alkenyl group is expressed by the following formula: (the ones having 2 or 3 carbon atoms present in the molecule The total molecular weight of the vinyl group in the alkenyl group (CH 2 = CH-)) / total molecular weight × 100 (mass%), and in formula (1), component a2) is one of which has 2 or 3 carbon atoms The content of the vinyl group (CH 2 = CH-) of the alkenyl group is 0.5 to 3.0% by mass, more preferably 1.0 to 2.0% by mass of organic polysiloxane. Also preferably, in component a2), the sum of m + n in formula (1) is such that the viscosity of the organic polysiloxane represented by formula (1) at 25 ° C is 20 mPa. The number in the range of s or greater is preferably such that the viscosity is 1,000,000 mPa. For s or greater, Tejia obtained a viscosity of 1,000,000 mPa at 25 ° C. The plasticity of a liquid of s or greater to 25 ° C is 3.0 mm or less in any form of gel. In order to obtain satisfactory convenience of applying the curable organic polysiloxane composition to the sheet substrate, component a2) preferably has 10,000,000 mPa at 25 ° C. Any of s or greater viscosity to a colloidal form with a plasticity of 3.0 mm or less at 25 ° C.

組分a2)可係兩種或更多種具有不同黏度之組分a2)之混合物。若與低黏度液體有機聚矽氧烷混合，則可有利地使用具有可塑性超過3.0mm之膠狀物之形式，且本發明涵蓋此情形。 Component a2) can be a mixture of two or more components a2) with different viscosities. If mixed with a low-viscosity liquid organic polysiloxane, a form of colloid having a plasticity exceeding 3.0 mm can be advantageously used, and the present invention covers this case.

組分(A)包含質量比為100：0至50：50，較佳100：0至70：30，更佳100：0至90：10之組分a1)及a2)。換言之，組分(A)僅係由組分a1)構成，或係組分a1)及a2)之組合。若組分(A)係組分a1)及a2)之混合物，其較佳係高度聚合的塑膠半固體(膠狀)有機聚矽氧烷或有機聚矽氧烷混合物；其中組分a1)及a2)中一者呈現可塑性之有機聚矽氧烷之組合及其中兩種組分均呈現可塑性之有機聚矽氧烷之組合兩種組合均可。以其中有機聚矽氧烷或有機聚矽氧烷混合物在25℃下之可塑性為0.5至10.0mm之膠狀形式特佳。 Component (A) contains components a1) and a2) in a mass ratio of 100: 0 to 50:50, preferably 100: 0 to 70:30, more preferably 100: 0 to 90:10. In other words, component (A) consists only of component a1) or a combination of components a1) and a2). If component (A) is a mixture of components a1) and a2), it is preferably a highly polymerized plastic semi-solid (colloidal) organic polysiloxane or organic polysiloxane mixture; wherein component a1) and a2) One of the combinations of plastic polyorganosiloxane and the combination of two components of plastic polyorganosiloxane is acceptable. The colloidal form in which the plasticity of the organic polysiloxane or organic polysiloxane mixture at 25 ° C is 0.5 to 10.0 mm is particularly preferred.

組分a1)及a2)可使用上述有機聚矽氧烷之所期望組合。特佳組合包含a1-1)至少一種包含己烯基作為具有4至12個碳原子之烯基之有機聚矽氧烷作為組分a1)，該己烯基具有0.5至3.0質量%，較佳1.0至2.0質量%之乙烯基(CH2=CH-)部分含量，及a2-1)至少一種包含乙烯基作為具有2或3個碳原子之烯基之有機聚矽氧烷作為組分a2)，該乙烯基的含量為0.5至3.0質量%，較佳1.0至2.0質量%。特佳地，組分a1-1之具有4至12個碳原子之烯基全部為己烯基。特佳地，組分a2-1)之具有2或3個碳原子之烯基全部為乙烯基。 Components a1) and a2) can use the desired combination of the aforementioned organic polysiloxanes. The particularly preferred combination contains a1-1) at least one organic polysiloxane containing hexenyl as an alkenyl group having 4 to 12 carbon atoms as component a1), the hexenyl group having 0.5 to 3.0% by mass, preferably 1.0 to 2.0% by mass of vinyl (CH 2 = CH-) partial content, and a2-1) at least one organic polysiloxane containing vinyl as an alkenyl group having 2 or 3 carbon atoms as component a2) The content of the vinyl group is 0.5 to 3.0% by mass, preferably 1.0 to 2.0% by mass. Particularly preferably, the alkenyl groups of component a1-1 having 4 to 12 carbon atoms are all hexenyl groups. Particularly preferably, the alkenyl groups of component a2-1) having 2 or 3 carbon atoms are all vinyl groups.

若組分(A)係兩種或更多種有機聚矽氧烷之混合物，則該混合物 總體具有膠狀形式，可塑性(亦即，如利用塑度計，根據JIS K 6249所指定之方法測量之可塑性：藉由在25℃下將1kgf負載置於4.2g球形樣本上3分鐘所獲得之數值)較佳係在0.5至10.0mm之範圍內，特佳係在0.9至3.0mm之範圍內。 If component (A) is a mixture of two or more organic polysiloxanes, the mixture Overall has a colloidal form, plasticity (ie, plasticity as measured using a plasticometer according to the method specified in JIS K 6249: obtained by placing a 1 kgf load on a 4.2 g spherical sample at 25 ° C for 3 minutes (Value) is preferably in the range of 0.5 to 10.0 mm, and particularly good is in the range of 0.9 to 3.0 mm.

組分BComponent B

組分(B)係用於對離型膜賦予陶瓷漿液施加之優越便捷性之添加劑；使用組分(B)容許對所得離型膜賦予陶瓷漿液施加之令人滿意的便捷性。更具體言之，據推測，可經由改變離型膜之表面性質來對離型膜賦予陶瓷漿液施加之令人滿意的便捷性，改變表面性質係藉由在使用組分(A)所獲得之高交聯密度的固化有機聚矽氧烷層之表面上有效溢出組分(B)來實現。 The component (B) is an additive for imparting superior convenience to the ceramic slurry application to the release film; using the component (B) allows to impart satisfactory convenience to the ceramic slurry application to the resulting release film. More specifically, it is speculated that the release film can be given a satisfactory convenience of ceramic slurry application by changing the surface properties of the release film, which is obtained by using component (A) The high crosslinking density of the cured organic polysiloxane layer effectively overflows the component (B) on the surface.

組分(B)係視情況包含烯基之有機聚矽氧烷，且其中該等具有2至12個碳原子之烯基具有小於0.100質量%，較佳至少0.005質量%，較佳0.010至0.050質量%之乙烯基(CH2=CH-)部分含量。連接至有機聚矽氧烷之矽原子之非烯基基團之實例包括烷基，諸如甲基、乙基及丙基；芳基，諸如苯基；鹵烷基，諸如3,3,3-三氟丙基及九氟己基；及矽烷醇基。非烯基基團係選自此等基團。組分(B)之具有2至12個碳原子之烯基並無特別限制；實例包括乙烯基、烯丙基、丁烯基、戊烯基、己烯基、辛烯基、癸烯基及十二烯基，其中以乙烯基、烯丙基或己烯基較佳，以乙烯基及/或己烯基更佳，且以乙烯基特佳。 Component (B) is optionally an organic polysiloxane containing alkenyl groups, and wherein the alkenyl groups having 2 to 12 carbon atoms have less than 0.100% by mass, preferably at least 0.005% by mass, preferably 0.010 to 0.050 Partial content of vinyl by mass (CH 2 = CH-). Examples of non-alkenyl groups attached to the silicon atom of the organopolysiloxane include alkyl groups such as methyl, ethyl and propyl; aryl groups such as phenyl; haloalkyl groups such as 3,3,3- Trifluoropropyl and nonafluorohexyl; and silanol groups. The non-alkenyl group is selected from these groups. The alkenyl group of component (B) having 2 to 12 carbon atoms is not particularly limited; examples include vinyl, allyl, butenyl, pentenyl, hexenyl, octenyl, decenyl and Dodecenyl, among which vinyl, allyl or hexenyl is preferred, vinyl and / or hexenyl is more preferred, and vinyl is particularly preferred.

為實現本發明之目標，組分(B)較佳係低反應性有機聚矽氧烷，其中具有2至12個碳原子之烯基之乙烯基(CH2=CH-)部分含量係小於0.100質量%，較佳0.005至0.100或較佳0.010至0.050質量%，及90%或更大，較佳地所有連接至矽原子之非烯基基團較佳均為非反應性烷基或芳基。非反應性烷基及芳基係未經取代之烷基或芳基，實例包括上文所列之烷基及芳基，其中特佳基團係選自甲基及苯基。 In order to achieve the object of the present invention, component (B) is preferably a low-reactivity organic polysiloxane, in which the vinyl (CH 2 = CH-) portion of the alkenyl group having 2 to 12 carbon atoms is less than 0.100 % By mass, preferably 0.005 to 0.100 or preferably 0.010 to 0.050% by mass, and 90% or more, preferably all non-alkenyl groups attached to the silicon atom are preferably non-reactive alkyl or aryl groups . Non-reactive alkyl and aryl groups are unsubstituted alkyl or aryl groups. Examples include the alkyl and aryl groups listed above, with particularly preferred groups selected from methyl and phenyl.

若組分(B)之烯基含量係小於上文所列最小值，則將大大降低固化反應性，從而增加遷至陶瓷片材之聚矽氧聚合物之量。使用此陶瓷片材來製造多層陶瓷電容器可導致所得電容器性能降低之溫度。另一方面，若烯基含量超過上文所列最大值，則組分(B)將經由加成反應併入固化聚有機矽氧烷(亦即，聚矽氧)層中，潛在地導致本發明之以下效果表現不足：對離型膜表面賦予陶瓷漿液施加之令人滿意的便捷性，此由於組分(B)自固化聚矽氧層溢出至該離型膜表面所致。另一方面，雖然烯基係組分(B)中之可選官能團，但若烯基含量超過上文所列最小值，則將提升固化反應性，同時大大減少遷至陶瓷片材之聚矽氧聚合物之量。與使用分子中無烯基之組分(B)相比，藉由使用乙烯基(CH2=CH-)部分含量為0.010至0.050質量%之組分(B)，可進一步改良所得用於製造多層陶瓷電容器之陶瓷片材之性能。 If the alkenyl content of component (B) is less than the minimum value listed above, the curing reactivity will be greatly reduced, thereby increasing the amount of polysiloxane polymer migrated to the ceramic sheet. The use of this ceramic sheet to manufacture multilayer ceramic capacitors can lead to a temperature at which the performance of the resulting capacitor is degraded. On the other hand, if the alkenyl content exceeds the maximum value listed above, component (B) will be incorporated into the cured polyorganosiloxane (ie, polysiloxane) layer via an addition reaction, potentially causing The following effects of the invention are insufficiently presented: the surface of the release film is provided with satisfactory convenience in applying the ceramic slurry, which is caused by the overflow of the component (B) from the cured polysiloxane layer to the surface of the release film. On the other hand, although the optional functional group in the alkenyl component (B), if the alkenyl content exceeds the minimum value listed above, it will increase the curing reactivity and at the same time greatly reduce the polysilicon migrated to the ceramic sheet The amount of oxygen polymer. Compared with the use of the component (B) having no alkenyl group in the molecule, by using the component (B) having a vinyl content (CH 2 = CH-) part content of 0.010 to 0.050% by mass, the resulting product can be further improved for manufacturing The performance of ceramic sheets of multilayer ceramic capacitors.

組分(B)較佳在25℃下具有液體至可塑性膠狀物中之任意形式，若為液體，25℃下之黏度較佳為1,000,000mPa．s或更大，更佳10,000,000mPa．s或更大。對最大黏度並無特定限制，但是，為令人滿意地易化可固化有機聚矽氧烷組合物之施加及易化添加該組合物時之加工起見，組分(B)較佳係呈25℃下之可塑性為10.0mm或更小之可塑性膠狀物形式。若組分(B)係呈膠狀物形式，則可塑性(亦即，如利用塑度計，根據JIS K6249所指定之方法測量之可塑性：藉由在25℃下將1kgf負載置於4.2g球形樣本上3分鐘所獲得之數值)較佳係在0.5至10.0mm之範圍內，特佳係在0.9至3.0mm之範圍內。 Component (B) preferably has any form of liquid to plastic colloid at 25 ° C. If it is liquid, the viscosity at 25 ° C is preferably 1,000,000 mPa. s or greater, better 10,000,000mPa. s or greater. There is no specific limit to the maximum viscosity, but for satisfactory ease of application of the curable organic polysiloxane composition and ease of processing when the composition is added, component (B) is preferably in the form of The plasticity at 25 ° C is in the form of a plastic jelly of 10.0 mm or less. If the component (B) is in the form of a jelly, the plasticity (that is, the plasticity measured according to the method specified in JIS K6249, as using a plasticity meter: by placing a 1 kgf load at 4.2 g in a spherical shape at 25 ° C The value obtained on the sample for 3 minutes) is preferably in the range of 0.5 to 10.0 mm, and particularly preferably in the range of 0.9 to 3.0 mm.

組分(B)之具體實例包括由聚二甲基矽氧烷、二甲基矽氧烷/苯基甲基矽氧烷共聚物或二甲基矽氧烷/二苯基矽氧烷共聚物構成且具有上文所列烯基含量之有機聚矽氧烷，在此等情形之任一情形下，該分子之末端經相同或不同基團封端，該等基團係選自由連接至矽原子之烷基、烯基、芳基、鹵烷基或矽烷醇基組成之群。特佳地組分(B)係 視情況具有上文所列烯基含量之直鏈或分支鏈二甲基聚矽氧烷，該分子之末端經相同或不同基團封端，該等基團係選自由三甲基矽氧基、矽烷醇基及乙烯基組成之群。組分(B)亦可係兩種或更多種有機聚矽氧烷之混合物，諸如具有不同聚合度之聚二甲基矽氧烷之混合物。 Specific examples of component (B) include polydimethyl siloxane, dimethyl siloxane / phenylmethyl siloxane copolymer or dimethyl siloxane / diphenyl siloxane copolymer An organic polysiloxane composed of alkenyl groups listed above, in any of these cases, the end of the molecule is terminated by the same or different groups selected from the group connected to the silicon Group of atoms consisting of alkyl, alkenyl, aryl, haloalkyl or silanol groups. Tejiadi component (B) Straight-chain or branched-chain dimethylpolysiloxanes with alkenyl content as listed above, the end of the molecule is terminated with the same or different groups, these groups are selected from trimethylsiloxy , Silanol group and vinyl group. Component (B) may also be a mixture of two or more organic polysiloxanes, such as a mixture of polydimethylsiloxanes with different degrees of polymerization.

最佳地，組分(B)係分子兩端經二甲基乙烯基矽氧基封端之聚二甲基矽氧烷，其中以呈膠狀物形式之聚二甲基矽氧烷特佳。 Most preferably, component (B) is polydimethylsiloxane terminated with dimethylvinylsiloxy groups at both ends of the molecule, of which polydimethylsiloxane in the form of colloid is particularly preferred .

組分(A)及組分(B)之比例The ratio of component (A) and component (B)

本發明可固化有機聚矽氧烷組合物中之組分(A)及組分(B)之莫耳比係在90：10至99：1之範圍內，更佳97：3至94：6，又更佳95.5：4.5至94.5：5.5及特佳95：5。組分(A)及組分(B)之莫耳比在上文所列範圍內容許對離型膜賦予陶瓷漿液施加之令人滿意的便捷性。若組分(B)之比例超過上文所列範圍之最大值，則可減小所得可固化有機聚矽氧烷組合物之可固化性，從而潛在地降低形成於離型膜上之陶瓷生胚片材自該離型膜之可釋放性。 The molar ratio of component (A) and component (B) in the curable organic polysiloxane composition of the present invention is in the range of 90:10 to 99: 1, more preferably 97: 3 to 94: 6 , And even better 95.5: 4.5 to 94.5: 5.5 and especially good 95: 5. The molar ratio of component (A) and component (B) within the ranges listed above allows satisfactory ease of application of ceramic slurry to the release film. If the ratio of component (B) exceeds the maximum value in the above-listed range, the curability of the resulting curable organic polysiloxane composition can be reduced, thereby potentially reducing the ceramic greens formed on the release film The releasability of the embryonic sheet from the release film.

組分(C)Component (C)

組分(C)係分子中包含至少兩個矽鍵結氫原子(Si-H)之有機氫聚矽氧烷，且係組分(A)之交聯劑。組分(C)較佳在其分子中包含至少三個矽原子鍵結氫原子，該等氫原子在該分子中之鍵結位置並無特別限制。矽原子鍵結氫原子含量較佳係等於該可固化有機聚矽氧烷組合物之總質量之0.1至2.0質量%，更佳0.5至1.8質量%之量。除氫原子以外連接至組分(C)之矽原子之有機基團之實例包括烷基，諸如甲基、乙基、丙基、丁基及辛基，其中以甲基較佳。組分(C)之有機氫聚矽氧烷之分子結構之實例包括直鏈、分支鏈、分支環(branch-ringed)及以上一或多者之組合。該分子中之矽鍵結氫原子之數量係整個分子之平均值。 Component (C) is an organic hydrogen polysiloxane containing at least two silicon-bonded hydrogen atoms (Si-H) in the molecule, and is a crosslinking agent of component (A). Component (C) preferably contains at least three silicon atoms bonded to hydrogen atoms in its molecule, and the bonding positions of these hydrogen atoms in the molecule are not particularly limited. The content of silicon atom-bonded hydrogen atoms is preferably equal to 0.1 to 2.0% by mass, more preferably 0.5 to 1.8% by mass of the total mass of the curable organic polysiloxane composition. Examples of the organic group connected to the silicon atom of the component (C) other than the hydrogen atom include alkyl groups such as methyl, ethyl, propyl, butyl, and octyl, with methyl being preferred. Examples of the molecular structure of the organohydrogenpolysiloxane of component (C) include straight chain, branched chain, branch-ringed, and combinations of one or more of the above. The number of silicon-bonded hydrogen atoms in the molecule is the average of the entire molecule.

組分(C)在25℃下之黏度為1至1,000mPa．s，較佳5至500mPa．s。 若組分(C)在25℃下之黏度小於1mPa．s，則作為可固化有機聚矽氧烷組合物一部分之組分(C)將較容易自其蒸發；且若黏度超過1,000mPa．s，則該含組分(C)之可固化有機聚矽氧烷組合物之固化時間將增加。對組分(C)並無特別限制；實例包括兩端經三甲基矽氧基封端之二甲基矽氧烷/甲基氫矽氧烷共聚物、兩端經二甲基氫矽氧基封端之二甲基矽氧烷/甲基氫矽氧烷共聚物、兩端經二甲基氫矽氧基封端之二甲基聚矽氧烷、兩端經三甲基矽氧基封端之甲基氫聚矽氧烷、環狀甲基氫聚矽氧烷及環狀甲基氫矽氧烷/二甲基矽氧烷共聚物。組分(C)可同時使用兩種或更多種有機氫聚矽氧烷。 The viscosity of component (C) at 25 ° C is 1 to 1,000 mPa. s, preferably 5 to 500 mPa. s. If the viscosity of component (C) at 25 ℃ is less than 1mPa. s, the component (C) that is part of the curable organic polysiloxane composition will easily evaporate from it; and if the viscosity exceeds 1,000 mPa. s, the curing time of the curable organic polysiloxane composition containing component (C) will increase. There is no particular restriction on the component (C); examples include dimethylsiloxane / methylhydrogensiloxane copolymers terminated with trimethylsiloxy groups on both ends, and dimethylhydrogensiloxane on both ends. Base-terminated dimethylsiloxane / methylhydrosiloxane copolymer, dimethylpolysiloxane terminated at both ends by dimethylhydrosiloxy, trimethylsiloxy at both ends End-capped methylhydrogenpolysiloxane, cyclic methylhydrogenpolysiloxane and cyclic methylhydrogensiloxane / dimethylsiloxane copolymer. Component (C) may use two or more organic hydrogen polysiloxanes simultaneously.

更佳地，組分(C)係一種由以下通式(2)表示之有機氫聚矽氧烷或兩種或更多種由以下通式(2)表示之有機氫聚矽氧烷之混合物，且可透過與組分(A)及(B)中所含矽原子鍵結烯基之加成反應(氫矽化)形成固化有機聚矽氧烷層。 More preferably, the component (C) is an organic hydrogen polysiloxane represented by the following general formula (2) or a mixture of two or more organic hydrogen polysiloxanes represented by the following general formula (2) And, through the addition reaction (hydrosilylation) with the silicon atom-bonded alkenyl group contained in the components (A) and (B), a cured organic polysiloxane layer can be formed.

在式(2)中，R12係經取代或未經取代的烷基或芳基，較佳具有1至10個碳原子之烷基、具有1至10個碳原子之鹵化烷基或苯基。RH係以R12表示之基團或鍵結至矽原子之氫原子(H)；若q=0，則RH係鍵結至矽原子之氫原子(H)。p及q係大於或等於0且滿足關係式10≦(p+q)≦200之數字。若(p+q)小於上文所列最小值，則組分(C)可自該可固化有機聚矽氧烷組合物蒸發，端視固化條件而定，從而潛在地導致該組合物固化不充分。若(p+q)超過上文所列最大極限，則可在施加至該膜前形成凝膠。將r定義為組分(C)中鍵結至矽原子之氫原子(H)之數量，p及q較佳滿足關係式0.01≦r/(p+q)≦1，更佳滿足關係 式0.2≦r/(p+q)≦1，特佳滿足關係式0.4≦r/(p+q)≦1。若r/(p+q)小於上文所列最小值，則本發明可固化有機聚矽氧烷組合物無法充分固化。r係q與鍵結至矽原子之氫原子(H)之數量RH之總和，若兩端之RH均為鍵結至矽原子之氫原子(H)，則r為(例如)q+2。 In formula (2), R 12 is a substituted or unsubstituted alkyl or aryl group, preferably an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group or phenyl group having 1 to 10 carbon atoms . RH is a group represented by R 12 or a hydrogen atom (H) bonded to a silicon atom; if q = 0, RH is a hydrogen atom (H) bonded to a silicon atom. p and q are numbers greater than or equal to 0 and satisfying the relationship 10 ≦ (p + q) ≦ 200. If (p + q) is less than the minimum value listed above, component (C) can evaporate from the curable organic polysiloxane composition, depending on the curing conditions, potentially causing the composition to cure without full. If (p + q) exceeds the maximum limits listed above, a gel can form before being applied to the membrane. Define r as the number of hydrogen atoms (H) in the component (C) bonded to silicon atoms, p and q preferably satisfy the relationship 0.01 ≦ r / (p + q) ≦ 1, more preferably satisfy the relationship 0.2 ≦ r / (p + q) ≦ 1, Tejia satisfies the relationship 0.4 ≦ r / (p + q) ≦ 1. If r / (p + q) is less than the minimum value listed above, the curable organic polysiloxane composition of the present invention cannot be fully cured. r is the sum of q and the number RH of hydrogen atoms (H) bonded to silicon atoms. If RH at both ends is hydrogen atoms (H) bonded to silicon atoms, then r is (for example) q + 2.

本發明可固化有機聚矽氧烷組合物中組分(C)之量係使得組分(C)中SiH基團對組分(A)及組分(B)中烯基之總莫耳數之莫耳比為0.5至5，較佳1至3。若莫耳比小於上文所列最小值，則所得可固化組合物之可固化性將降低，且若其超過上文所列最大值，則介電陶瓷層形成材料(特別係陶瓷生胚片材)自離型片材剝離之阻力將增加，從而潛在地防止得到實務水平之可釋放性。 The amount of component (C) in the curable organic polysiloxane composition of the present invention is such that the number of moles of SiH groups in component (C) to the total number of alkenyl groups in component (A) and component (B) The molar ratio is 0.5 to 5, preferably 1 to 3. If the molar ratio is less than the minimum values listed above, the curability of the resulting curable composition will decrease, and if it exceeds the maximum values listed above, the dielectric ceramic layer forming material (particularly ceramic green sheets Material) The resistance to peeling from the release sheet will increase, thereby potentially preventing a practical level of releasability.

組分(D)Component (D)

組分(D)係促進可固化有機聚矽氧烷組合物中存在之矽原子鍵結烯基與矽原子鍵結氫原子間之加成反應(矽氫化)之矽氫化觸媒。較佳的矽氫化觸媒係含鉑基金屬之矽氫化觸媒，具體實例包括氯鉑酸、經醇改質之氯鉑酸、氯鉑酸之烯烴錯合物、氯鉑酸-酮錯合物、氯鉑酸-乙烯基矽氧烷錯合物、氯化鉑(IV)、細鉑粉、氧化鋁或二氧化矽載體上載固體鉑(solid platinum carried on a carrier of alumina or silica)、鉑黑、鉑-烯烴錯合物、鉑-烯基矽氧烷錯合物、鉑-羰基錯合物、含此等鉑基觸媒之甲基丙烯酸甲酯樹脂或粉末狀熱塑性有機樹脂(諸如聚碳酸酯樹脂、聚苯乙烯樹脂或聚矽氧樹脂)。以鉑烯基矽氧烷錯合物(諸如氯鉑酸-二乙烯基四甲基二矽氧烷錯合物、氯鉑酸-四甲基四乙烯基環四矽氧烷錯合物、鉑二乙烯基四甲基二矽氧烷錯合物或鉑四甲基四乙烯基環四矽氧烷錯合物)特佳。 Component (D) is a hydrosilation catalyst that promotes the addition reaction (hydrogenation of silicon) between the silicon atom-bonded alkenyl group and the silicon atom-bonded hydrogen atom present in the curable organic polysiloxane composition. The preferred hydrosilation catalyst is a platinum-containing metal hydrosilation catalyst. Specific examples include chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid olefin complex, chloroplatinic acid-ketone complex Substance, chloroplatinic acid-vinylsiloxane complex, platinum (IV) chloride, fine platinum powder, alumina or silica carrier solid platinum (solid platinum carried on a carrier of alumina or silica), platinum Black, platinum-olefin complexes, platinum-alkenylsiloxane complexes, platinum-carbonyl complexes, methyl methacrylate resins containing these platinum-based catalysts or powdered thermoplastic organic resins (such as poly Carbonate resin, polystyrene resin or polysiloxane resin). Platinum alkenyl siloxane complex (such as chloroplatinic acid-divinyltetramethyldisilaxane complex, chloroplatinic acid-tetramethyltetravinylcyclotetrasiloxane complex, platinum (Divinyltetramethyldisilazane complex or platinum tetramethyltetravinylcyclotetrasiloxane complex) is particularly preferred.

將催化量之組分(D)添加至可固化有機聚矽氧烷組合物係足夠；通常，以使得組分(D)中之鉑基金屬之量相對於本發明可固化有機聚矽氧烷組合物之總質量係1至1,000ppm，更佳5至500ppm之量較佳。 It is sufficient to add a catalytic amount of component (D) to the curable organopolysiloxane composition; usually, such that the amount of platinum-based metal in component (D) is relative to the curable organopolysiloxane of the present invention The total mass of the composition is 1 to 1,000 ppm, more preferably 5 to 500 ppm.

可固化有機聚矽氧烷組合物Curable organic polysiloxane composition

若需要，本發明可固化有機聚矽氧烷組合物可包含(E)有機溶劑。特定言之，由於本發明可固化有機聚矽氧烷組合物中含有大量組分(B)，故為令人滿意地易化加工及施加起見，較佳將含組分(A)至(D)之組合物分散或溶解於已知(E)有機溶劑中。然而，在不妨礙本發明目標之程度下，亦可將組分(A)至(D)分散或溶解於低黏度液體有機聚矽氧烷(諸如在25℃下具有約0.5至10mPa．s之低黏度之鏈狀或環狀有機聚矽氧烷)而非所需有機溶劑中。有機溶劑之實例包括：芳族烴溶劑，諸如甲苯及二甲苯；脂族烴溶劑，諸如己烷、辛烷及異鏈烷烴；酮溶劑，諸如丙酮、甲基乙基酮及甲基異丁基酮；酯溶劑，諸如乙酸乙酯及乙酸異丁酯；醚溶劑，諸如二異丙基醚及1,4-噁烷；聚合度(polymerization level)為3至6之環狀聚矽氧烷，諸如六甲基環三矽氧烷、八甲基環四矽氧烷及十甲基環五矽氧烷；及鹵化烴，諸如三氯乙烯、全氟乙烯、三氟甲基苯、1,3-雙(三氟甲基)苯、甲基五氟苯。若將本發明可固化有機聚矽氧烷組合物之薄層施加至具有低耐熱性之聚烯烴或類似物之片狀基板，則以芳族烴溶劑(諸如甲苯或二甲苯)較佳，因為此等對該組合物之可固化性具有極少影響。 If necessary, the curable organic polysiloxane composition of the present invention may contain (E) an organic solvent. In particular, since the curable organopolysiloxane composition of the present invention contains a large amount of component (B), in order to satisfactorily facilitate processing and application, it is preferable to include components (A) to ( The composition of D) is dispersed or dissolved in the known (E) organic solvent. However, the components (A) to (D) can also be dispersed or dissolved in a low-viscosity liquid organic polysiloxane (such as having a value of about 0.5 to 10 mPa · s at 25 ° C without disturbing the object of the present invention) Low-viscosity chain or cyclic organic polysiloxane) instead of the required organic solvent. Examples of organic solvents include: aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, octane and isoparaffin; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl Ketones; ester solvents such as ethyl acetate and isobutyl acetate; ether solvents such as diisopropyl ether and 1,4-oxane; cyclic polysiloxanes with a polymerization level of 3 to 6, Such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane; and halogenated hydrocarbons such as trichloroethylene, perfluoroethylene, trifluoromethylbenzene, 1,3 -Bis (trifluoromethyl) benzene, methylpentafluorobenzene. If a thin layer of the curable organic polysiloxane composition of the present invention is applied to a sheet substrate of polyolefin or the like having low heat resistance, an aromatic hydrocarbon solvent such as toluene or xylene is preferred because These have little influence on the curability of the composition.

除組分(A)至(D)及可選的組分(E)以外，本發明可固化有機聚矽氧烷組合物較佳亦包含(F)矽氫化抑制劑，其使常溫下之膠化及固化最小化，從而提高儲存穩定性，並在加熱時賦予可固化性。矽氫化抑制劑之實例包括乙炔化合物、烯炔化合物、有機氮化合物、有機磷化合物及肟化合物。具體化合物之實例包括：炔醇，諸如2-甲基-3-丁炔-2-醇、3,5-二甲基-1-己炔-3-醇、3-甲基-1-戊炔-3-醇、2-苯基-3-丁炔-2-醇及1-乙炔基-1-環己醇(ETCH)；烯炔化合物，諸如3-甲基-3-三甲基矽氧基-1-丁炔、3-甲基-3-三甲基矽氧基-1-戊炔、3,5-二甲基-3-三甲基矽氧基-1-己炔、3-甲基-3-戊烯-1-烯及3,5-二甲基-3-己烯-1-烯； 及烯基矽氧烷，諸如1-乙炔基-1-三甲基矽氧基環己烷、雙(2,2-二甲基-3-丁炔氧基)二甲基矽烷、1,3,5,7-四甲基-1,3,5,7-四乙烯基環四矽氧烷及1,3,5,7-四甲基-1,3,5,7-四己烯基環四矽氧烷。添加至可固化有機聚矽氧烷組合物之(F)矽氫化抑制劑之量通常將在0.001至5質量份組分(F)/100質量份組分(A)之範圍內；所添加的組分(F)之較佳量可容易地根據以下因素確定：組分(F)之類型、所使用的矽氫化觸媒之物理性質及用量、組分(A)之C4至C12烯基含量、組分(C)中矽原子鍵結氫原子之量及可固化組合物之所需使用時長及使用環境。 In addition to components (A) to (D) and optional component (E), the curable organic polysiloxane composition of the present invention preferably also contains (F) a hydrosilation inhibitor, which makes the glue at room temperature Minimization and curing, thereby improving storage stability and imparting curability when heated. Examples of hydrosilation inhibitors include acetylene compounds, enyne compounds, organic nitrogen compounds, organic phosphorus compounds, and oxime compounds. Examples of specific compounds include: alkynols, such as 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyne -3-ol, 2-phenyl-3-butyn-2-ol and 1-ethynyl-1-cyclohexanol (ETCH); enyne compounds such as 3-methyl-3-trimethylsiloxy 1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 3- Methyl-3-pentene-1-ene and 3,5-dimethyl-3-hexene-1-ene; And alkenylsiloxanes, such as 1-ethynyl-1-trimethylsiloxycyclohexane, bis (2,2-dimethyl-3-butynyloxy) dimethylsilane, 1,3 , 5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenyl Cyclotetrasiloxane. The amount of (F) hydrosilation inhibitor added to the curable organic polysiloxane composition will generally be in the range of 0.001 to 5 parts by mass of component (F) / 100 parts by mass of component (A); the added The preferred amount of component (F) can be easily determined based on the following factors: the type of component (F), the physical properties and amount of the hydrosilation catalyst used, and the C4 to C12 alkenyl content of component (A) 1. The amount of silicon atom-bonded hydrogen atoms in component (C) and the required duration and use environment of the curable composition.

本發明可固化有機聚矽氧烷組合物包含上述組分(A)、(B)、(C)及(D)，及可選組分(E)(若需要)、可選組分(F)。本發明可固化組合物適合用作含溶劑之溶液型可固化有機聚矽氧烷組合物。特定言之，本發明可固化有機聚矽氧烷組合物在25℃下之總體黏度較佳係在100至100,000mPa．s，更佳100至50,000mPa．s之範圍內，以便該組合物呈現令人滿意的片狀基板塗覆性質。 The curable organic polysiloxane composition of the present invention comprises the above components (A), (B), (C) and (D), and optional component (E) (if required) and optional component (F ). The curable composition of the present invention is suitable for use as a solvent-containing solution-type curable organic polysiloxane composition. In particular, the curable organic polysiloxane composition of the present invention has an overall viscosity at 25 ° C of preferably 100 to 100,000 mPa. s, better 100 to 50,000mPa. within the range of s so that the composition exhibits satisfactory coating properties of the sheet substrate.

除彼等上文所述者以外，可向本發明可固化有機聚矽氧烷組合物添加其他可選組分。其他可選組分之實例包括：由烷氧基矽烷化合物(諸如3-縮水甘油氧基丙基三甲氧基矽烷及3-甲基丙烯醯氧基丙基三甲氧基矽烷)構成之黏著促進劑；酚-、醌-、胺-、磷-、亞磷酸酯-、硫-及硫醚基抗氧化劑；***-及二苯甲酮基光穩定劑；磷酸酯基、鹵素基、磷基及銻基阻燃劑；一或多種選自陽離子表面活性劑、陰離子表面活性劑及非離子表面活性劑之表面活性劑；及已知添加劑，諸如抗靜電劑、耐熱劑、染料及顏料。可向本發明可固化有機聚矽氧烷組合物添加此等組分中之一者或者其中二者或更多者之組合。 In addition to those described above, other optional components may be added to the curable organic polysiloxane composition of the present invention. Examples of other optional components include: adhesion promoters composed of alkoxysilane compounds (such as 3-glycidoxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane) ; Phenol-, quinone-, amine-, phosphorus-, phosphite-, sulfur- and thioether-based antioxidants; triazole- and benzophenone-based light stabilizers; phosphate-based, halogen-based, phosphorus-based and Antimony-based flame retardant; one or more surfactants selected from cationic surfactants, anionic surfactants and nonionic surfactants; and known additives such as antistatic agents, heat resistant agents, dyes and pigments. One or a combination of two or more of these components may be added to the curable organic polysiloxane composition of the present invention.

本發明可固化有機聚矽氧烷組合物包含上述組分(A)至(D)、可選組分(E)(若需要)及可選組分(F)(若需要)，且可透過在室溫下或在50至200℃之溫度下，在鉑基觸媒(組分(D))存在下進行之加成反應形成具 有優越釋放性質之固化塗層。此外，因為所得固化塗層之優越物理性質及可釋放性，本發明可固化有機聚矽氧烷組合物較佳係利用能量輻射(亦稱為化學活性輻射)諸如UV輻射或電子束，特別係UV輻射進行固化。在此等情形下，UV固化可單獨進行或與熱固化組合進行。該可固化組合物之固化時間可適當地根據所使用的固化條件進行調整。為賦予本發明可固化有機聚矽氧烷組合物令人滿意的UV可固化性，該組合物中較佳另外包含(G)光聚合引發劑。下文將詳細描述組分(G)。 The curable organic polysiloxane composition of the present invention comprises the above components (A) to (D), optional component (E) (if required) and optional component (F) (if required), and is permeable The addition reaction formed at room temperature or at a temperature of 50 to 200 ° C in the presence of a platinum-based catalyst (component (D)) forms a A cured coating with superior release properties. In addition, because of the superior physical properties and releasability of the resulting cured coating, the curable organic polysiloxane composition of the present invention preferably utilizes energy radiation (also called chemically active radiation) such as UV radiation or electron beam, especially UV radiation for curing. In these cases, UV curing can be performed alone or in combination with thermal curing. The curing time of the curable composition can be appropriately adjusted according to the curing conditions used. In order to impart satisfactory UV curability to the curable organopolysiloxane composition of the present invention, it is preferred that the composition further contains (G) a photopolymerization initiator. The component (G) will be described in detail below.

(G)光聚合引發劑賦予本發明可固化有機聚矽氧烷組合物UV可固化性；加成反應誘導型熱固化及UV固化之組合使用可減少對低耐熱性塑膠膜基板之熱損傷，從而有利地提高本發明固化產物與塑膠膜之間之結合強度。有利之處亦在於，可防止聚矽氧組分自由本發明可固化組合物所形成之固化塗層表面遷至陶瓷片材，從而進一步減少聚矽氧遷移，因為該遷移會造成聚矽氧組分污染該陶瓷片材(所謂的「聚矽氧遷移」)。可適當地選擇在UV輻射下產生自由基之已知化合物(諸如有機過氧化物、羰基化合物、有機硫化合物或偶氮化合物)用作組分(G)。具體化合物包括苯乙酮、苯丙酮、二苯甲酮、咕吨酮(xantol)、芴精(fluorein)、苯甲醛、蒽醌、三苯胺、4-甲基苯乙酮、3-戊基苯乙酮、4-甲氧基苯乙酮、3-溴苯乙酮、4-烯丙基苯乙酮、對二乙醯基苯、3-甲氧基二苯甲酮、4-甲基二苯甲酮、4-氯二苯甲酮、4,4-二甲氧基二苯甲酮、4-氯-4-苄基二苯甲酮、3-氯呫噸酮、3,9-二氯呫噸酮、3-氯-8-壬基呫噸酮、安息香、安息香甲醚、安息香丁醚、雙(4-二甲基胺基苯基)酮、苄基甲氧基縮酮、2-氯呫噸酮、二乙基苯乙酮、1-羥基環己基苯基酮、2-甲基〔4-(甲基硫基)苯基〕2-嗎啉基-1-丙酮、2,2-二甲氧基-2-苯基苯乙酮及二乙氧基苯乙酮。若本發明組合物係使用UV輻射固化，則組分(G)較佳係二苯甲酮、4-甲氧基苯乙 酮、4-甲基二苯甲酮、二乙氧基苯乙酮或1-羥基環己基苯基酮。特佳的組分(G)係二乙氧基苯乙酮及1-羥基環己基苯基酮。 (G) The photopolymerization initiator imparts UV curability to the curable organic polysiloxane composition of the present invention; the combined use of addition reaction-induced thermal curing and UV curing can reduce thermal damage to the plastic film substrate with low heat resistance, Therefore, the bonding strength between the cured product of the present invention and the plastic film is advantageously improved. The advantage is also that the polysiloxane component can be prevented from migrating from the surface of the cured coating formed by the curable composition of the present invention to the ceramic sheet, thereby further reducing the migration of polysiloxane, because the migration will cause Contaminate the ceramic sheet (so-called "polysilicon migration"). Known compounds that generate free radicals under UV radiation (such as organic peroxides, carbonyl compounds, organic sulfur compounds, or azo compounds) can be appropriately selected as the component (G). Specific compounds include acetophenone, phenylacetone, benzophenone, xantol, fluorein, benzaldehyde, anthraquinone, triphenylamine, 4-methylacetophenone, 3-pentylbenzene Acetone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diethylacetophenone, 3-methoxybenzophenone, 4-methyldiacetone Benzophenone, 4-chlorobenzophenone, 4,4-dimethoxybenzophenone, 4-chloro-4-benzylbenzophenone, 3-chloroxanthone, 3,9-di Chloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzyl methoxy ketal, 2 -Chloroxanthone, diethylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl [4- (methylthio) phenyl] 2-morpholinyl-1-acetone, 2, 2-Dimethoxy-2-phenylacetophenone and diethoxyacetophenone. If the composition of the present invention is cured using UV radiation, then component (G) is preferably benzophenone, 4-methoxystyrene Ketone, 4-methylbenzophenone, diethoxyacetophenone or 1-hydroxycyclohexyl phenyl ketone. Particularly preferred components (G) are diethoxyacetophenone and 1-hydroxycyclohexyl phenyl ketone.

可使用一種(G)光聚合引發劑或兩種或更多種(G)光聚合引發劑之組合。對其用量並無特別限制，但該用量將在0.01至10質量份，較佳0.01至2.5質量份/100質量份組分(A)之範圍內。若組分(G)之用量在上文所列範圍內，則藉由使本發明組合物固化所獲得之可釋放固化塗層之聚矽氧遷移方面將有所改良，且將具有優越強度及其他物理性質。 One (G) photopolymerization initiator or a combination of two or more (G) photopolymerization initiators may be used. The amount of use is not particularly limited, but the amount of use will be in the range of 0.01 to 10 parts by mass, preferably 0.01 to 2.5 parts by mass per 100 parts by mass of component (A). If the amount of component (G) is within the range listed above, the silicone migration of the releasable cured coating obtained by curing the composition of the present invention will be improved and will have superior strength and Other physical properties.

本發明組合物可藉由均勻地混合上述組分(A)至(D)、可選組分(E)、可選組分(F)(若需要)及任何其他可選組分產生。各種組分之添加次序並無特別限制，但若所得組合物將不會在混合後立即使用，較佳分開儲存組分(D)與組分(A)、(B)及(C)之混合物，並在緊接著使用前將兩者混合在一起。在組合物包含組分(A)至(D)、可選組分(E)及組分(F)之情形下，組分(F)之用量較佳經調整，以得到在常溫下不形成交聯物但確實在加熱時形成交聯物並固化之組合物。 The composition of the present invention can be produced by uniformly mixing the above components (A) to (D), optional component (E), optional component (F) (if necessary), and any other optional components. The order of addition of various components is not particularly limited, but if the resulting composition will not be used immediately after mixing, it is better to store the mixture of component (D) and components (A), (B) and (C) separately , And mix the two together immediately before use. In the case where the composition contains components (A) to (D), optional component (E) and component (F), the amount of component (F) is preferably adjusted so as not to form at normal temperature A composition that crosslinks but does form a crosslink and cure when heated.

當將上述本發明可固化有機聚矽氧烷組合物均勻地施加至片狀基板，並加熱、以能量(諸如UV輻射或電子束)照射，或在適合誘導組分(A)及組分(B)之矽氫化及形成交聯物之條件下經歷兩者之組合時，在該片狀基板表面上得到包含聚矽氧塗層(亦即，固化有機聚矽氧烷塗層)之片狀物件。本發明片狀物件之特徵在於提供將陶瓷漿液施加至固化聚矽氧塗層之令人滿意的便捷性，及使該漿液乾燥後所得之介電陶瓷層形成材料，特別係陶瓷生胚片材易於自基板移除。換言之，由此所得之本發明片狀物件可用作與介電陶瓷層形成材料共同使用之離型膜，特別係用於形成陶瓷生胚片材之離型膜。此外，藉由使本發明可固化組合物固化所得之固化層具有優越可撓性，因此當將該層施加至非平坦物體時具有令人滿意的基板順應性(conformation)及極少包絡(envelopment)氣穴之優勢。結果，該物件可極為有利地用於需要 固化層的可釋放性及固化層緊密地結合至待保護之物體之應用，如用於光學顯示器及玻璃表面之保護膜之情形一般。 When the above curable organic polysiloxane composition of the present invention is uniformly applied to a sheet-like substrate and heated, irradiated with energy (such as UV radiation or electron beam), or suitable for inducing component (A) and component ( B) When undergoing a combination of the two under the conditions of hydrosilation and cross-linking formation, a sheet containing a polysiloxane coating (that is, a cured organic polysiloxane coating) is obtained on the surface of the sheet substrate object. The sheet-like article of the present invention is characterized by providing satisfactory convenience for applying a ceramic slurry to a cured polysiloxane coating, and a dielectric ceramic layer forming material obtained after drying the slurry, especially a ceramic green sheet Easy to remove from the substrate. In other words, the sheet-like article of the present invention thus obtained can be used as a release film used together with a dielectric ceramic layer forming material, particularly for forming a release film of a ceramic green sheet. In addition, the cured layer obtained by curing the curable composition of the present invention has excellent flexibility, and therefore has satisfactory substrate conformation and little envelope when applying the layer to non-flat objects The advantage of cavitation. As a result, the object can be used very advantageously The releasability of the cured layer and the application in which the cured layer is tightly coupled to the object to be protected, such as the case of protective films for optical displays and glass surfaces.

對本發明可固化有機聚矽氧烷組合物所施加之片狀基板並無特別限制；可適當地選擇使用所期望的已知材料。此等基板材料之實例包括以下物質之膜；聚酯，諸如聚對苯二甲酸乙二酯及聚萘二甲酸乙二酯；聚烯烴，諸如聚丙烯及聚甲基戊烯；聚碳酸酯；及塑膠，諸如聚乙酸乙烯酯。可使用單層膜或可使用兩層或更多層類型相同或不同的塑膠。塑膠膜，特別係聚酯膜及特定言之聚對苯二甲酸乙二酯膜較佳作為片狀基板，特別係本發明之與介電陶瓷層形成材料共同使用之離型膜，特定言之用於形成陶瓷生胚片材之離型膜。特定言之，雙軸定向聚對苯二甲酸乙二酯膜較佳用作片狀基板。聚對苯二甲酸乙二酯膜在機器加工或使用時將不容易產生粉塵。此容許有效防止在將陶瓷漿液施加至片狀基板時由於存在粉塵或類似物而引起之缺陷。使用已接受抗靜電處理之聚對苯二甲酸乙二酯膜作為片狀基板亦有效防止在將陶瓷漿液施加至片狀基板中之缺陷。 The sheet substrate to which the curable organic polysiloxane composition of the present invention is applied is not particularly limited; the desired known materials can be appropriately selected and used. Examples of such substrate materials include films of polyesters such as polyethylene terephthalate and polyethylene naphthalate; polyolefins such as polypropylene and polymethylpentene; polycarbonate; And plastics, such as polyvinyl acetate. A single layer of film can be used or two or more layers of the same or different types of plastic can be used. Plastic films, especially polyester films and specific polyethylene terephthalate films are preferred as sheet substrates, especially the release films of the present invention used together with dielectric ceramic layer forming materials, specific words It is used to form the release film of ceramic green sheet. In particular, the biaxially oriented polyethylene terephthalate film is preferably used as a sheet substrate. Polyethylene terephthalate film will not easily generate dust when machined or used. This allows to effectively prevent defects caused by the presence of dust or the like when applying the ceramic slurry to the sheet substrate. The use of polyethylene terephthalate film that has undergone antistatic treatment as the sheet substrate also effectively prevents defects in the application of ceramic slurry to the sheet substrate.

若需要，亦可經由氧化或粗糙化或以底漆處理片狀基板之一側或兩側之表面，以在將本發明可固化有機聚矽氧烷施加至片狀基板表面並乾燥後，改良該片狀基板表面與本發明可固化有機聚矽氧烷之間之結合。氧化方法包括電暈放電處理、電漿放電處理、鉻酸處理(濕法)、火焰處理、熱空氣處理、臭氧處理及UV照射處理。粗糙化方法包括噴砂法及熱噴霧法。此等不同表面處理方法可適當地根據所使用的片狀基板之類型來選擇；然而，電暈放電處理係較佳，因為該法將產生表面處理片狀基板所期望之高水平效果，且易於實施。 If necessary, the surface of one or both sides of the sheet substrate may also be treated by oxidation or roughening or primer to improve after applying the curable organic polysiloxane of the present invention to the surface of the sheet substrate and drying The combination between the surface of the sheet substrate and the curable organic polysiloxane of the present invention. Oxidation methods include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet method), flame treatment, hot air treatment, ozone treatment and UV irradiation treatment. Roughening methods include sand blasting and thermal spraying. These different surface treatment methods can be appropriately selected according to the type of sheet substrate used; however, corona discharge treatment is preferred because this method will produce the high level of effect desired for surface treatment of the sheet substrate and is easy Implementation.

該片狀基板之厚度通常將為10至300μm，較佳15至200μm，特佳20至125μm。 The thickness of the sheet substrate will generally be 10 to 300 μm, preferably 15 to 200 μm, and particularly preferably 20 to 125 μm.

可使用所期望的已知方法來將本發明可固化有機聚矽氧烷組合 物施加至片狀基板；實例包括凹版塗佈、棒式塗佈、噴塗、旋塗、刀塗、輥塗及模具式塗佈。 The desired known methods can be used to combine the curable organopolysiloxane of the present invention The substrate is applied to the sheet substrate; examples include gravure coating, bar coating, spray coating, spin coating, knife coating, roll coating, and die coating.

當將本發明可固化有機聚矽氧烷組合物施加至片狀基板並使該組合物固化時，對固化有機聚矽氧烷組合物層之厚度並無特別限制，但以0.01至3μm之厚度較佳，且以0.03至1μm更佳。若片狀基板上之固化有機聚矽氧烷組合物層之厚度小於0.01μm，則當用作用於形成陶瓷生胚片材之離型片材時，該層可能不足以充當離型層。另一方面，若片狀基板上之固化有機聚矽氧烷組合物層之厚度超過3μm，則當將所得片狀物件包成卷狀物時可出現阻滯。上述抗靜電層及其他所需層可設置於片狀基板之與其上形成固化有機聚矽氧烷組合物層之一側相反之表面上，或設置於片狀基板與有機聚矽氧烷組合物層之間。 When the curable organopolysiloxane composition of the present invention is applied to a sheet substrate and the composition is cured, the thickness of the cured organopolysiloxane composition layer is not particularly limited, but the thickness is 0.01 to 3 μm Preferably, it is more preferably 0.03 to 1 μm. If the thickness of the cured organic polysiloxane composition layer on the sheet substrate is less than 0.01 μm, when used as a release sheet for forming a ceramic green sheet, the layer may not be sufficient as a release layer. On the other hand, if the thickness of the cured organopolysiloxane composition layer on the sheet-like substrate exceeds 3 μm, retardation may occur when the resulting sheet-like article is wrapped into a roll. The above antistatic layer and other required layers may be provided on the surface of the sheet substrate opposite to the side on which the cured organic polysiloxane composition layer is formed, or on the sheet substrate and the organic polysiloxane composition Between layers.

包含片狀基板及藉由將本發明可固化有機聚矽氧烷組合物施加至該基板上並使該組合物固化所得之固化層之片狀物件適合用作與介電陶瓷層形成材料共同使用之離型膜，特別係用作用於形成陶瓷生胚片材之離型膜。陶瓷生胚片材可利用包含以下步驟之方法生產：將陶瓷漿液施加至本發明之用於形成陶瓷生胚片材之離型膜(亦即，施加至其上存在固化有機聚矽氧烷組合物之表面)，並使該漿液乾燥。更具體言之，利用所需施加方法(諸如，經由狹縫模具式塗佈或使用刮刀片)將陶瓷漿液施加至形成於本發明之用於形成陶瓷生胚片材之離型膜上之固化有機聚矽氧烷組合物層之表面，然後乾燥形成陶瓷生胚片材。該製程使用與介電陶瓷層形成材料共同使用之離型膜，特別係用於形成陶瓷生胚片材之離型膜(其上已利用本發明可固化有機聚矽氧烷組合物形成離型層)可使邊緣收縮現象最少化(在邊緣收縮現象中，所施加陶瓷漿液之邊緣收縮，從而導致邊緣比陶瓷漿液之內部部分更厚)，並使所施加陶瓷漿液表面中之氣孔之形成及陶瓷漿液之施加之不一致性最少化。若使用本發明之用於形成陶瓷生胚片材之離型 膜，則藉由固化有機聚矽氧烷組合物所形成之表面所呈現之令人滿意的可釋放性容許以極小剝離力使陶瓷生胚片材與其下部之固化有機聚矽氧烷層分離，而不致陶瓷生胚片材開裂或撕裂，即使該膜上形成低強度之薄陶瓷生胚片材亦然。以此方式，本發明之用於形成陶瓷生胚片材之離型膜提供陶瓷漿液施加之優越便捷性及後續形成的陶瓷生胚片材之優越可釋放性。 A sheet-like article comprising a sheet-shaped substrate and a cured layer obtained by applying the curable organic polysiloxane composition of the present invention to the substrate and curing the composition is suitable for use in conjunction with a dielectric ceramic layer forming material The release film is especially used as a release film for forming ceramic green sheets. The ceramic green sheet can be produced by a method including the following steps: applying the ceramic slurry to the release film of the present invention for forming the ceramic green sheet (ie, applying the cured organic polysiloxane combination thereon The surface of the product) and allow the slurry to dry. More specifically, the ceramic slurry is applied to the cured film formed on the release film for forming a ceramic green sheet according to the present invention using a desired application method (such as coating through a slit die or using a doctor blade) The surface of the organic polysiloxane composition layer is then dried to form a ceramic green sheet. This process uses a release film that is used together with the dielectric ceramic layer forming material, especially a release film used to form a ceramic green sheet (on which the curable organic polysiloxane composition of the present invention has been used to form a release film Layer) can minimize the edge shrinkage phenomenon (in the edge shrinkage phenomenon, the edge of the applied ceramic slurry shrinks, causing the edge to be thicker than the inner part of the ceramic slurry), and the formation of pores in the surface of the applied ceramic slurry and Inconsistencies in the application of ceramic slurries are minimized. If using the release of the invention for forming a ceramic green embryo sheet Film, the satisfactory releasability of the surface formed by curing the organopolysiloxane composition allows separation of the ceramic green sheet and the cured organopolysiloxane layer underneath with minimal peeling force, There is no cracking or tearing of the ceramic green sheet, even if a low-strength thin ceramic green sheet is formed on the film. In this way, the release film for forming a ceramic green embryo sheet of the present invention provides the superior convenience of ceramic slurry application and the superior releasability of the ceramic green embryo sheet subsequently formed.

如上所述，本發明可固化有機聚矽氧烷組合物適用於與介電陶瓷形成材料共同使用之離型膜，特別係用於形成陶瓷生胚片材之離型膜共同使用，但不限於此等用途且可用於處理各種膜及片材之表面。特定言之，包含由本發明組合物構成之固化層之片狀物件可用作保護光學組件(諸如LCD面板、電漿顯示器、偏光板及相差板)及電性及電子組件(諸如印刷電路板積體電路、電晶體及電容器)之表面之表面保護膜；在此等情形下，較佳將抗靜電劑添加至本發明組合物中。 As described above, the curable organic polysiloxane composition of the present invention is suitable for the release film used together with the dielectric ceramic forming material, especially for the release film used to form the ceramic green sheet, but is not limited to These applications can be used to treat the surface of various films and sheets. In particular, a sheet-like article including a cured layer composed of the composition of the present invention can be used as a protective optical component (such as LCD panel, plasma display, polarizing plate, and phase difference plate) and electrical and electronic components (such as printed circuit board Surface protection film on the surface of bulk circuits, transistors and capacitors; in such cases, it is preferred to add an antistatic agent to the composition of the present invention.

已知的離子或非離子抗靜電劑可無特定限制地使用；方法之實例包括添加主要組分包含親水性基團之聚矽氧油(日本未審查專利申請公開案S52-103499)、添加磺酸鹽(日本經審查專利申請案H03-059096)、添加含氟聚矽氧油(日本未審查專利申請公開案H01-083085、H01-083086、H01-121390)、添加含表面活性劑之聚矽氧油(日本未審查專利申請公開案H01-294099)及添加導電粉末(日本未審查專利申請公開案H02-069763、H03-292180、H04-086765)。特定言之，為與本發明可固化有機聚矽氧烷組合物相容起見，較佳使用由鋰鹽或經聚醚改質之聚矽氧烷構成之抗靜電劑。(例如)日本未審查專利公開案2009-030028、2012-157978及2011-178828中所揭示之離子抗靜電劑及經聚醚改質之聚矽氧烷可無特定限制地使用。為防止靜電起見，亦可利用表面活性劑、聚矽氧、有機硼、導電聚合物、金屬氧化物、氣相沉積金屬或其他類型之抗靜電劑而非僅添加上述抗靜電劑中 之一者作為添加劑來進行處理。 Known ionic or non-ionic antistatic agents can be used without particular limitations; examples of methods include adding polysiloxane oil whose main component contains a hydrophilic group (Japanese Unexamined Patent Application Publication S52-103499), adding sulfone Acid salt (Japanese Examined Patent Application H03-059096), added fluorine-containing polysiloxane oil (Japanese Unexamined Patent Application Publication H01-083085, H01-083086, H01-121390), added polysilicon containing surfactant Oxygen oil (Japanese Unexamined Patent Application Publication H01-294099) and added conductive powder (Japanese Unexamined Patent Application Publication H02-069763, H03-292180, H04-086765). In particular, for compatibility with the curable organic polysiloxane composition of the present invention, it is preferable to use an antistatic agent composed of lithium salt or polyether-modified polysiloxane. For example, the ionic antistatic agents and polyether-modified polysiloxanes disclosed in Japanese Unexamined Patent Publications 2009-030028, 2012-157978, and 2011-178828 can be used without specific restrictions. In order to prevent static electricity, surfactants, polysiloxane, organoboron, conductive polymers, metal oxides, vapor-deposited metals or other types of antistatic agents can also be used instead of just adding the above antistatic agents One of them is treated as an additive.

工作實例Working example

現將藉助工作實例及比較實例更詳細地描述本發明，但本發明並不限於下文所述工作實例。在以下實例中，當用於指量時，「份」意指質量份，「Hex」指己烯基，「Vi」指乙烯基，且「Me」指甲基。「乙烯基(CH2=CH-)部分」係指矽原子鍵結烯基之由乙烯基(CH2=CH-)構成之部分，且係依據相對於總分子量之質量%乙烯基含量指示；若烯基係乙烯基，則將使用「乙烯基含量」。黏度及可塑性值係在25℃下測量。可塑性係如上文所述測量，且黏度係使用Shibaura Systems之Vismetron VDA2數位顯示B型旋轉黏度計測量。由可固化有機聚矽氧烷組合物形成之固化層之抗剝離值(剝離力)係根據以下方法測量。 The present invention will now be described in more detail with the help of working examples and comparative examples, but the present invention is not limited to the working examples described below. In the following examples, when used for reference, "parts" means parts by mass, "Hex" means hexenyl, "Vi" means vinyl, and "Me" means methyl. "Vinyl (CH 2 = CH-) moiety" refers to the portion of silicon atom-bonded alkenyl composed of vinyl (CH 2 = CH-), and is indicated based on the mass% vinyl content relative to the total molecular weight; If the vinyl group is alkenyl, the "vinyl content" will be used. Viscosity and plasticity values are measured at 25 ° C. The plasticity is measured as described above, and the viscosity is measured using a Vismetron VDA2 digital display B-type rotary viscometer from Shibaura Systems. The peeling resistance value (peeling force) of the cured layer formed from the curable organic polysiloxane composition was measured according to the following method.

形成固化層之方法Method for forming cured layer

利用Mayer棒將可固化有機聚矽氧烷組合物以等於0.15g/m2無溶劑固體重量的量施加至雙軸定向聚酯膜(38μm厚；Mitsubishi Plastics)之表面。施加後，將施加該組合物之基板在130℃熱空氣循環烘箱中熱處理30秒，以在該聚酯膜基板表面上形成有機聚矽氧烷固化層。 The curable organopolysiloxane composition was applied to the surface of the biaxially oriented polyester film (38 μm thick; Mitsubishi Plastics) in an amount equal to 0.15 g / m 2 of the weight of solvent-free solid using a Mayer bar. After the application, the substrate to which the composition was applied was heat-treated in a 130 ° C. hot air circulation oven for 30 seconds to form an organic polysiloxane cured layer on the surface of the polyester film substrate.

評估陶瓷黏結劑樹脂施加之便捷性Evaluate the ease of application of ceramic binder resin

將55質量份甲苯添加至3質量份聚乙烯縮丁醛(S-LEC B,K,BM-1；Sekisui Chemical)中，並混合至均勻一致，此後，向該混合物添加33質量份甲醇及9質量份正丁醇，並整體攪拌至均勻一致，以製得陶瓷黏結劑樹脂溶液。 55 parts by mass of toluene was added to 3 parts by mass of polyvinyl butyral (S-LEC B, K, BM-1; Sekisui Chemical), and mixed until uniform, after which, 33 parts by mass of methanol and 9 were added to the mixture Mass parts of n-butanol, and the whole is stirred to be uniform to prepare a ceramic binder resin solution.

在生產工作實例及比較實例之固化層後，利用Mayer棒將上述陶瓷黏結劑樹脂溶液均勻地施加至固化層表面，此係在後者已在25℃及60%濕度下儲存24小時，以使得乾燥後厚度為2μm後，並根據針對工 作實例及比較實例所列方法進行固化。以此方式，製得包含陶瓷黏結劑樹脂之離型膜片材。 After producing the cured layer of the working example and the comparative example, the above ceramic binder resin solution was evenly applied to the surface of the cured layer using a Mayer bar, which was stored in the latter at 25 ° C and 60% humidity for 24 hours to make it dry After the thickness is 2μm, and according to the target The methods listed as examples and comparative examples are used for curing. In this way, a release film sheet containing ceramic binder resin is produced.

施加便捷性測試Convenience test

肉眼觀察所得包含陶瓷黏結劑樹脂之離型膜片材，以確認存在或不存在邊緣收縮(在邊緣收縮之情形下，所施加陶瓷黏結劑樹脂之邊緣比內部部分更厚)。將其中未出現邊緣收縮之情形評為￮，將其中出現輕微邊緣收縮之情形評為△，並將其中出現顯著邊緣收縮之情形評為×。 Visual inspection of the release film sheet containing the ceramic binder resin to confirm the presence or absence of edge shrinkage (in the case of edge shrinkage, the edge of the applied ceramic binder resin is thicker than the inner part). The case in which no edge shrinkage occurred was rated as ￮, the case in which slight edge shrinkage occurred was rated as △, and the case in which significant edge shrinkage occurred was rated as ×.

陶瓷黏結劑樹脂的剝離力評估Evaluation of peel force of ceramic binder resin

將50質量份甲苯添加至8質量份聚乙烯縮丁醛(S-LEC B,K,BH-3；Sekisui Chemical)中，並混合至均勻一致，此後，向其添加33質量份甲醇及9質量份正丁醇，並整體攪拌至均勻一致，以製得陶瓷黏結劑樹脂溶液。 50 parts by mass of toluene was added to 8 parts by mass of polyvinyl butyral (S-LEC B, K, BH-3; Sekisui Chemical) and mixed until uniform, after which 33 parts by mass of methanol and 9 parts by mass were added to it A portion of n-butanol, and stir the whole until it is uniform, to prepare a ceramic binder resin solution.

在生產工作實例及比較實例之固化層後，利用施料器將上述陶瓷黏結劑樹脂溶液施加至離型層表面，此係在後者在25℃及60%濕度下儲存24小時，以使得乾燥後厚度為10μm後，並在100℃熱空氣循環烘箱中乾燥一分鐘。將由此得到之包含陶瓷黏結劑樹脂之離型膜片材切成5cm寬，以產生測試條，向其施加20g/cm2負載，並整體在25℃及60%濕度下靜置24小時。用A&D通用Tensilon拉伸試驗機以90°角及0.3m/min之剝離速率拉長陶瓷黏結劑樹脂層，並測量所需剝離力(mN/50mm)。若如根據此方法所測得的剝離力為20mN/50mm或更小，則將釋放性質評定為令人滿意，且若剝離力為20mN/50mm或更大，則評定為不令人滿意。 After producing the cured layers of the working examples and comparative examples, the above-mentioned ceramic binder resin solution was applied to the surface of the release layer using an applicator, which was stored in the latter at 25 ° C and 60% humidity for 24 hours, so that after drying After the thickness is 10 μm, it is dried in a hot air circulating oven at 100 ° C. for one minute. The thus-obtained release film sheet containing the ceramic binder resin was cut into a width of 5 cm to produce a test strip, a load of 20 g / cm 2 was applied thereto, and the whole was allowed to stand at 25 ° C. and 60% humidity for 24 hours. Use an A & D universal Tensilon tensile tester to stretch the ceramic adhesive resin layer at a 90 ° angle and a peel rate of 0.3m / min, and measure the required peel force (mN / 50mm). If the peel force as measured according to this method is 20 mN / 50 mm or less, the release property is evaluated as satisfactory, and if the peel force is 20 mN / 50 mm or more, it is evaluated as unsatisfactory.

工作實例1-組合物1Working Example 1-Composition 1

將(A)30.0份兩端及一側鏈具有己烯基之聚二甲基矽氧烷(可塑性：1.15；己烯基的乙烯基(CH2=CH-)部分含量：0.80質量%)、(B)1.5 份分子末端經乙烯基封端之二甲基矽氧烷(可塑性：1.20；乙烯基含量：0.02質量%)、(C)1.3份25mPa．s黏度之二甲基甲基氫聚矽氧烷(以使得組合物整體之SiH/Vi比為1.5)、(E)66.2份甲苯及(F)1.0份3-甲基-1-丁炔-3-醇混合至均勻一致，以得到含溶劑之可固化有機聚矽氧烷組合物(組合物1)。接著，以(E)50：50質量%之甲苯及己烷混合物稀釋所得有機聚矽氧烷組合物，以將固體濃度調整為3.0質量%，並添加(D)氯鉑酸/1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物(金屬鉑含量：0.6質量%)，其添加量使得組合物整體之金屬鉑含量為120ppm，並將該組合物以等於0.15g/m2的量施加至雙軸定向聚酯膜(厚度：38μm；Mitsubishi Plastics)之表面，並在120℃下固化30秒，以得到固化層。測量將陶瓷黏結劑樹脂施加至由此所得之固化層之便捷性及自該固化層剝離該陶瓷黏結劑樹脂所需之剝離力。結果顯示於表1中。 (A) 30.0 parts of polydimethylsiloxane having hexenyl at both ends and one side chain (plasticity: 1.15; vinyl vinyl (CH 2 = CH-) part content of hexenyl: 0.80% by mass), (B) 1.5 parts of dimethylsiloxane (moldability: 1.20; vinyl content: 0.02% by mass) vinyl terminated with molecular ends, (C) 1.3 parts 25mPa. s viscosity of dimethylmethylhydrogenpolysiloxane (so that the overall SiH / Vi ratio of the composition is 1.5), (E) 66.2 parts toluene and (F) 1.0 part 3-methyl-1-butyne- The 3-alcohol is mixed to be uniform to obtain a solvent-containing curable organic polysiloxane composition (Composition 1). Next, the obtained organic polysiloxane composition was diluted with (E) 50: 50% by mass of toluene and hexane mixture to adjust the solid concentration to 3.0% by mass, and (D) chloroplatinic acid / 1,3- was added Divinyl-1,1,3,3-tetramethyldisilazane complex (metal platinum content: 0.6% by mass), the amount of which is added so that the metal platinum content of the entire composition is 120 ppm, and the combination The substance was applied to the surface of a biaxially oriented polyester film (thickness: 38 μm; Mitsubishi Plastics) in an amount equal to 0.15 g / m 2 and cured at 120 ° C. for 30 seconds to obtain a cured layer. The convenience of applying the ceramic binder resin to the cured layer thus obtained and the peeling force required to peel the ceramic binder resin from the cured layer were measured. The results are shown in Table 1.

工作實例2-組合物2Working Example 2-Composition 2

以類似於工作實例1之方式得到組合物2，但將工作實例1中組分(B)之用量變成0.4份。使用該組合物，測量將陶瓷黏結劑樹脂施加至固化層之便捷性及自該固化層剝離該陶瓷黏結劑樹脂所需之剝離力。結果顯示於表1中。 Composition 2 was obtained in a manner similar to Working Example 1, but the amount of component (B) in Working Example 1 was changed to 0.4 parts. Using the composition, the convenience of applying the ceramic binder resin to the cured layer and the peeling force required to peel the ceramic binder resin from the cured layer were measured. The results are shown in Table 1.

工作實例3-組合物3Working Example 3-Composition 3

以類似於工作實例1之方式得到組合物3，但將工作實例1中組分(B)之用量變成3.0份。使用該組合物，測量將陶瓷黏結劑樹脂施加至固化層之便捷性及自該固化層剝離該陶瓷黏結劑樹脂所需之剝離力。結果顯示於表1中。 Composition 3 was obtained in a manner similar to Working Example 1, but the amount of component (B) in Working Example 1 was changed to 3.0 parts. Using the composition, the convenience of applying the ceramic binder resin to the cured layer and the peeling force required to peel the ceramic binder resin from the cured layer were measured. The results are shown in Table 1.

工作實例4-組合物4Working Example 4-Composition 4

將(A)a1)15.0份分子兩端及一側鏈具有己烯基之聚二甲基矽氧烷(可塑性：1.15；己烯基的乙烯基(CH2=CH-)部分含量：0.80質量%)、a2)15.0份分子末端經矽烷醇基封端且一側鏈具有乙烯基之聚二甲基矽 氧烷(可塑性：1.20；乙烯基含量：0.90質量%)、(B)1.5份分子末端經乙烯基封端之二甲基矽氧烷(可塑性：1.20；乙烯基含量：0.02質量%)、(C)1.5份25mPa．s黏度之分子兩端經三甲基矽氧基封端之二甲基甲基氫聚矽氧烷(以使得組合物整體之SiH/Vi比為1.5)、(E)66.1份甲苯及(F)1.0份3-甲基-1-丁炔-3-醇混合至均勻一致，以得到含溶劑之可固化有機聚矽氧烷組合物(組合物4)。然後，以(E)50：50質量%之甲苯及己烷混合物將所得有機聚矽氧烷組合物稀釋至固體濃度為3.0質量%，並向該組合物添加氯鉑酸/1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物(金屬鉑含量：0.6質量%)，其添加量使得金屬鉑含量為120ppm，此後，根據上述方法將該組合物以等於0.15g/m2的量施加至雙軸定向聚酯膜(厚度：38μm；Mitsubishi Plastics)之表面，然後在120℃下固化30秒，以得到固化層，此後，測量將陶瓷黏結劑樹脂施加至固化層之便捷性及自該固化層移除該陶瓷黏結劑樹脂所需之剝離力。結果顯示於表1中。 (A) a1) 15.0 parts of polydimethylsiloxane with hexenyl groups on both ends and one side of the molecule (plasticity: 1.15; vinyl (CH 2 = CH-) part of hexenyl group content: 0.80 mass %), A2) 15.0 parts of polydimethylsiloxane (moldability: 1.20; vinyl content: 0.90% by mass) of polydimethylsiloxane end-capped with silanol groups and vinyl groups on one side of the molecule, (B) 1.5 parts The end is vinyl-terminated dimethylsiloxane (plasticity: 1.20; vinyl content: 0.02% by mass), (C) 1.5 parts 25mPa. s Viscosity of the molecule is terminated with trimethylsiloxy-terminated dimethyl methyl hydrogen polysiloxane (so that the overall composition of SiH / Vi ratio is 1.5), (E) 66.1 parts toluene and (F ) 1.0 part of 3-methyl-1-butyn-3-ol is mixed to be uniform to obtain a solvent-containing curable organic polysiloxane composition (Composition 4). Then, the obtained organic polysiloxane composition was diluted to a solid concentration of 3.0% by mass with (E) 50: 50% by mass of toluene and hexane mixture, and chloroplatinic acid / 1,3-dichloromethane was added to the composition Vinyl-1,1,3,3-tetramethyldisilaxane complex (metal platinum content: 0.6% by mass), the amount of which is added so that the metal platinum content is 120 ppm, and thereafter, the composition is applied according to the above method Applied to the surface of a biaxially oriented polyester film (thickness: 38 μm; Mitsubishi Plastics) in an amount equal to 0.15 g / m 2 and then cured at 120 ° C. for 30 seconds to obtain a cured layer, after which, the ceramic binder resin was measured The ease of application to the cured layer and the peel force required to remove the ceramic binder resin from the cured layer. The results are shown in Table 1.

工作實例5-組合物5Working Example 5-Composition 5

另外將0.04份二乙氧基苯乙酮添加至工作實例1之組合物1作為組分(G)，以得到含溶劑之可固化有機聚矽氧烷組合物(組合物5)。接著，以(E)50：50質量%之甲苯及己烷混合物稀釋所得有機聚矽氧烷組合物，以將固體濃度調整至3.0質量%，並混合(D)氯鉑酸/1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物(金屬鉑含量：0.6質量%)，其用量使得組合物整體之金屬鉑含量為120ppm，並根據上述方法將該組合物以等於0.15g/m2的量施加至雙軸定向聚酯膜(厚度：38μm；Mitsubishi Plastics)之表面。施加可固化有機聚矽氧烷組合物後，利用熱空氣循環烘箱在130℃下熱處理基板30秒，然後利用Eye Graphics Eye Grandage固化裝置(總照射能量：110mJ/cm2)進行UV照射，以在聚酯膜表面上形成有機聚矽氧烷固化層。測量將陶瓷黏結劑樹脂施加 至該有機聚矽氧烷固化層之便捷性及自該固化層分離該陶瓷黏結劑樹脂所需之剝離力。結果顯示於表1中。 In addition, 0.04 parts of diethoxyacetophenone was added to composition 1 of working example 1 as component (G) to obtain a solvent-containing curable organic polysiloxane composition (composition 5). Next, the obtained organic polysiloxane composition was diluted with a (E) 50: 50% by mass toluene and hexane mixture to adjust the solid concentration to 3.0% by mass, and (D) chloroplatinic acid / 1,3- was mixed Divinyl-1,1,3,3-tetramethyldisilaxane complex (metallic platinum content: 0.6% by mass), the amount of which is such that the overall metallic platinum content of the composition is 120 ppm, and according to the above method The composition was applied to the surface of a biaxially oriented polyester film (thickness: 38 μm; Mitsubishi Plastics) in an amount equal to 0.15 g / m 2 . After applying the curable organic polysiloxane composition, the substrate was heat-treated at 130 ° C for 30 seconds using a hot air circulation oven, and then UV irradiation was performed using an Eye Graphics Eye Grandage curing device (total irradiation energy: 110 mJ / cm 2 ) to A cured layer of organic polysiloxane is formed on the surface of the polyester film. The convenience of applying the ceramic binder resin to the cured layer of organic polysiloxane and the peel force required to separate the ceramic binder resin from the cured layer were measured. The results are shown in Table 1.

工作實例6-組合物6Working Example 6-Composition 6

將0.04份二乙氧基苯乙酮添加至工作實例4之組合物4作為組分(G)，以得到含溶劑之可固化有機聚矽氧烷組合物(組合物6)。接著，以(E)50：50質量%之甲苯及己烷混合物稀釋所得有機聚矽氧烷組合物，以將固體濃度調整至3.0質量%，並混合(D)氯鉑酸/1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物(金屬鉑含量：0.6質量%)，其用量使得組合物整體之金屬鉑含量為120ppm，並根據上述方法將該組合物以等於0.15g/m2的量施加至雙軸定向聚酯膜(厚度：38μm；Mitsubishi Plastics)之表面。施加可固化有機聚矽氧烷組合物後，利用熱空氣循環烘箱在130℃下熱處理聚酯膜30秒，然後利用Eye Graphics Eye Grandage固化裝置(總照射能量：110mJ/cm2)進行UV照射，以在聚酯膜表面上形成有機聚矽氧烷固化層。測量將陶瓷黏結劑樹脂施加至該有機聚矽氧烷固化層之便捷性及自該固化層分離該陶瓷黏結劑樹脂所需之剝離力。結果顯示於表1中。 0.04 parts of diethoxyacetophenone was added to composition 4 of working example 4 as component (G) to obtain a solvent-containing curable organic polysiloxane composition (composition 6). Next, the obtained organic polysiloxane composition was diluted with a (E) 50: 50% by mass toluene and hexane mixture to adjust the solid concentration to 3.0% by mass, and (D) chloroplatinic acid / 1,3- was mixed Divinyl-1,1,3,3-tetramethyldisilaxane complex (metallic platinum content: 0.6% by mass), the amount of which is such that the overall metallic platinum content of the composition is 120 ppm, and according to the above method The composition was applied to the surface of a biaxially oriented polyester film (thickness: 38 μm; Mitsubishi Plastics) in an amount equal to 0.15 g / m 2 . After applying the curable organic polysiloxane composition, the polyester film was heat-treated at 130 ° C for 30 seconds using a hot air circulation oven, and then UV irradiation was performed using an Eye Graphics Eye Grandage curing device (total irradiation energy: 110 mJ / cm 2 ). In order to form an organic polysiloxane cured layer on the surface of the polyester film. The convenience of applying the ceramic binder resin to the cured layer of organic polysiloxane and the peel force required to separate the ceramic binder resin from the cured layer were measured. The results are shown in Table 1.

工作實例7-組合物7Working Example 7-Composition 7

以類似於工作實例3之方式得到組合物7，但將工作實例3中所使用之組分(B)之類型變成分子末端經矽烷醇基封端之二甲基矽氧烷(可塑性：1.43)。使用該組合物，測量將陶瓷黏結劑樹脂施加至固化層之便捷性及自該固化層剝離該陶瓷黏結劑樹脂所需之剝離力。結果顯示於表1中。剝離測試後，膜上觀察到少量聚矽氧遷移。 Composition 7 was obtained in a similar manner to Working Example 3, but the type of component (B) used in Working Example 3 was changed to dimethylsiloxane (moldability: 1.43) whose molecular ends were terminated with silanol groups . Using the composition, the convenience of applying the ceramic binder resin to the cured layer and the peeling force required to peel the ceramic binder resin from the cured layer were measured. The results are shown in Table 1. After the peel test, a small amount of polysiloxane migration was observed on the film.

工作實例8-組合物8Working Example 8-Composition 8

以類似於工作實例3之方式得到組合物8，但將工作實例3中所使用之組分(B)之類型變成分子末端經三甲基矽烷基封端之二甲基矽氧烷(可塑性：1.29)。使用該組合物，測量將陶瓷黏結劑樹脂施加至固 化層之便捷性及自該固化層剝離該陶瓷黏結劑樹脂所需之剝離力。結果顯示於表1中。剝離測試後，膜上觀察到少量聚矽氧遷移。 Composition 8 was obtained in a manner similar to Working Example 3, but the type of component (B) used in Working Example 3 was changed to dimethylsiloxane with molecular ends capped with trimethylsilyl groups (plasticity: 1.29). Using this composition, the measurement of the application of the ceramic binder resin to the solid The convenience of the chemical layer and the peel force required to peel the ceramic binder resin from the cured layer. The results are shown in Table 1. After the peel test, a small amount of polysiloxane migration was observed on the film.

比較實例1-比較組合物1Comparative Example 1-Comparative Composition 1

以類似於工作實例1之方式得到比較組合物1，但略去工作實例1之組分(B)。使用該組合物，測量將陶瓷黏結劑樹脂施加至有機聚矽氧烷固化層之便捷性及自該固化層剝離該陶瓷黏結劑樹脂所需之剝離力。結果顯示於表1中。 Comparative composition 1 was obtained in a similar manner to working example 1, but the component (B) of working example 1 was omitted. Using the composition, the convenience of applying the ceramic binder resin to the cured layer of the organic polysiloxane and the peeling force required to peel the ceramic binder resin from the cured layer were measured. The results are shown in Table 1.

比較實例2-比較組合物2Comparative Example 2-Comparative Composition 2

以類似於工作實例1之方式得到比較組合物2，但將工作實例1中組分(B)之用量變成5.0份。使用該組合物，測量將陶瓷黏結劑樹脂施加至有機聚矽氧烷固化層之便捷性及自該固化層剝離該陶瓷黏結劑樹脂所需之剝離力。結果顯示於表1中。 Comparative composition 2 was obtained in a similar manner to working example 1, but the amount of component (B) in working example 1 was changed to 5.0 parts. Using the composition, the convenience of applying the ceramic binder resin to the cured layer of the organic polysiloxane and the peeling force required to peel the ceramic binder resin from the cured layer were measured. The results are shown in Table 1.

比較實例3-比較組合物3Comparative Example 3-Comparative Composition 3

將0.04份二乙氧基苯乙酮添加至比較實例1之比較組合物1中作為組分(G)，以得到含溶劑之可固化有機聚矽氧烷組合物(比較組合物3)。接著，以(E)50：50質量%之甲苯及己烷混合物稀釋所得有機聚矽氧烷組合物，以將固體濃度調整至3.0質量%，並混合(D)氯鉑酸/1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物(金屬鉑含量：0.6質量%)，其用量使得組合物整體之金屬鉑含量為120ppm，並根據上述方法將該組合物以等於0.15g/m2的量施加至雙軸定向聚酯膜(厚度：38μm；Mitsubishi Plastics)之表面。施加可固化有機聚矽氧烷組合物後，利用熱空氣循環烘箱在130℃下熱處理聚酯膜30秒，然後利用Eye Graphics Eye Grandage固化裝置(總照射能量：110mJ/cm2)進行UV照射，以在聚酯膜基板表面上形成有機聚矽氧烷固化層。測量將陶瓷黏結劑樹脂施加至該有機聚矽氧烷固化層之便捷性及自該固化層分離該陶瓷黏結劑樹脂所需之剝離力。結果顯示於表1中。 0.04 parts of diethoxyacetophenone was added to Comparative Composition 1 of Comparative Example 1 as component (G) to obtain a solvent-containing curable organic polysiloxane composition (Comparative Composition 3). Next, the obtained organic polysiloxane composition was diluted with a (E) 50: 50% by mass toluene and hexane mixture to adjust the solid concentration to 3.0% by mass, and (D) chloroplatinic acid / 1,3- was mixed Divinyl-1,1,3,3-tetramethyldisilaxane complex (metallic platinum content: 0.6% by mass), the amount of which is such that the overall metallic platinum content of the composition is 120 ppm, and according to the above method The composition was applied to the surface of a biaxially oriented polyester film (thickness: 38 μm; Mitsubishi Plastics) in an amount equal to 0.15 g / m 2 . After applying the curable organic polysiloxane composition, the polyester film was heat-treated at 130 ° C for 30 seconds using a hot air circulation oven, and then UV irradiation was performed using an Eye Graphics Eye Grandage curing device (total irradiation energy: 110 mJ / cm 2 ). In order to form an organic polysiloxane cured layer on the surface of the polyester film substrate. The convenience of applying the ceramic binder resin to the cured layer of organic polysiloxane and the peel force required to separate the ceramic binder resin from the cured layer were measured. The results are shown in Table 1.

比較實例4-比較組合物4Comparative Example 4-Comparative Composition 4

將0.04份二乙氧基苯乙酮添加至比較實例2之比較組合物2中作為組分(G)，以得到含溶劑之可固化有機聚矽氧烷組合物(比較組合物4)。接著，以(E)50：50重量%之甲苯及己烷混合物稀釋所得有機聚矽氧烷組合物，以將固體濃度調整至3.0質量%，另外混合(D)氯鉑酸/1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物(金屬鉑含量：0.6質量%)，其用量使得組合物整體之金屬鉑含量為120ppm，並根據上述方法將該組合物以等於0.15g/m2的量施加至雙軸定向聚酯膜(厚度：38μm；Mitsubishi Plastics)之表面。施加可固化有機聚矽氧烷組合物後，利用熱空氣循環烘箱在130℃下熱處理聚酯膜30秒，然後利用Eye Graphics Eye Grandage固化裝置(總照射能量：110mJ/cm2)進行UV照射，以在聚酯膜基板表面上形成有機聚矽氧烷固化層。測量將陶瓷黏結劑樹脂施加至該有機聚矽氧烷固化層之便捷性及自該固化層分離該陶瓷黏結劑樹脂所需之剝離力。結果顯示於表1中。 0.04 parts of diethoxyacetophenone was added to Comparative Composition 2 of Comparative Example 2 as component (G) to obtain a solvent-containing curable organic polysiloxane composition (Comparative Composition 4). Next, the obtained organic polysiloxane composition was diluted with (E) 50: 50% by weight of a mixture of toluene and hexane to adjust the solid concentration to 3.0% by mass, and (D) chloroplatinic acid / 1,3- was additionally mixed Divinyl-1,1,3,3-tetramethyldisilaxane complex (metallic platinum content: 0.6% by mass), the amount of which is such that the overall metallic platinum content of the composition is 120 ppm, and according to the above method The composition was applied to the surface of a biaxially oriented polyester film (thickness: 38 μm; Mitsubishi Plastics) in an amount equal to 0.15 g / m 2 . After applying the curable organic polysiloxane composition, the polyester film was heat-treated at 130 ° C for 30 seconds using a hot air circulation oven, and then UV irradiation was performed using an Eye Graphics Eye Grandage curing device (total irradiation energy: 110 mJ / cm 2 ). In order to form an organic polysiloxane cured layer on the surface of the polyester film substrate. The convenience of applying the ceramic binder resin to the cured layer of organic polysiloxane and the peel force required to separate the ceramic binder resin from the cured layer were measured. The results are shown in Table 1.

比較實例5-組合物5Comparative Example 5-Composition 5

將(A)a1)12.0份分子兩端及一側鏈具有己烯基之聚二甲基矽氧烷(可塑性：1.15；己烯基的乙烯基(CH2=CH-)部分含量：0.80質量%)、a2)18.0份分子兩端經矽烷醇基封端且一側鏈具有乙烯基之聚二甲基矽氧烷(可塑性：1.20；乙烯基含量：0.90質量%)、(B)1.5份1.20可塑性之分子末端經乙烯基封端之二甲基矽氧烷(乙烯基含量：0.02質量%)、(C)1.4份25mPa．s黏度之分子兩端經三甲基矽氧基封端之二甲基甲基氫聚矽氧烷(結果，組合物整體之SiH/Vi比為1.5)、(E)66.1份甲苯及(F)1.0份3-甲基-1-丁炔-3-醇混合至均勻一致，以得到含溶劑之可固化有機聚矽氧烷組合物(組合物4)。然後，以(E)50：50重量%之甲苯及己烷混合物將所得有機聚矽氧烷組合物稀釋至固體濃度為3.0質量%，並向該組合物添加氯鉑酸/1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合 物(金屬鉑含量：0.6質量%)，其添加量使得金屬鉑含量為120ppm，以得到可固化組合物。根據上述方法將該組合物以等於015g/m2的量施加至雙軸定向聚酯膜(厚度：38μm；Mitsubishi Plastics)之表面，然後在120℃下固化30秒，以得到固化層，此後，測量將陶瓷黏結劑樹脂施加至固化層之便捷性及自該固化層移除該陶瓷黏結劑樹脂所需之剝離力。結果顯示於表1中。 (A) a1) 12.0 parts of polydimethylsiloxane with hexenyl groups at both ends and one side of the molecule (plasticity: 1.15; vinyl (CH 2 = CH-) part of hexenyl content: 0.80 mass %), A2) 18.0 parts of polydimethylsiloxane (moldability: 1.20; vinyl content: 0.90% by mass) of polydimethylsiloxane end capped with silanol groups at both ends of the molecule and having vinyl groups on one side, (B) 1.5 parts 1.20 Plasticized molecular ends are vinyl terminated dimethylsiloxane (vinyl content: 0.02% by mass), (C) 1.4 parts 25mPa. s Viscosity of the molecule is terminated with trimethylsiloxy-terminated dimethylmethylhydrogen polysiloxane (result, the overall composition of SiH / Vi ratio is 1.5), (E) 66.1 parts toluene and (F ) 1.0 part of 3-methyl-1-butyn-3-ol is mixed to be uniform to obtain a solvent-containing curable organic polysiloxane composition (Composition 4). Then, the obtained organic polysiloxane composition was diluted to a solid concentration of 3.0% by mass with (E) 50: 50% by weight of a mixture of toluene and hexane, and chloroplatinic acid / 1,3-dichloromethane was added to the composition Vinyl-1,1,3,3-tetramethyldisilazane complex (metal platinum content: 0.6% by mass), the amount of which is added so that the metal platinum content is 120 ppm, to obtain a curable composition. The composition was applied to the surface of a biaxially oriented polyester film (thickness: 38 μm; Mitsubishi Plastics) in an amount equal to 015 g / m 2 according to the method described above, and then cured at 120 ° C. for 30 seconds to obtain a cured layer, after which, The convenience of applying the ceramic binder resin to the cured layer and the peel force required to remove the ceramic binder resin from the cured layer were measured. The results are shown in Table 1.

自表1中所示結果可明瞭，離型膜之在工作實例1至8聚有機矽氧烷中所得之聚有機矽氧烷固化層顯示陶瓷黏結劑樹脂施加之便捷性， 且陶瓷黏結劑樹脂可藉助極小剝離力與該固化聚有機矽氧烷分離，此表明具有優越的陶瓷黏結劑樹脂可釋放性。與此同時，利用比較實例1至5所得之聚有機矽氧烷固化層在陶瓷黏結劑樹脂施加之便捷性或可釋放性方面係不令人滿意的。 From the results shown in Table 1, it is clear that the polyorganosiloxane cured layer of the release film obtained in the working examples 1 to 8 polyorganosiloxane shows the ease of application of the ceramic binder resin, Moreover, the ceramic binder resin can be separated from the cured polyorganosiloxane with a very small peeling force, which shows that it has excellent releasability of the ceramic binder resin. At the same time, the polyorganosiloxane cured layers obtained using Comparative Examples 1 to 5 are unsatisfactory in terms of the ease of application or releasability of the ceramic binder resin.

Claims (19)

一種可固化有機聚矽氧烷組合物，其包含：(A)具有在25℃下呈現0.5至3.0mm之可塑性之膠狀物之形式之有機聚矽氧烷或有機聚矽氧烷混合物，該有機聚矽氧烷或有機聚矽氧烷混合物包含質量比為100：0至50：50之以下組分a1)及a2)：a1)至少一種包含具有4至12個碳原子之烯基之有機聚矽氧烷，該烯基具有0.5至3.0質量%之乙烯基(CH2=CH-)部分含量，及a2)至少一種包含具有2至3個碳原子之烯基之有機聚矽氧烷，該烯基具有0.5至3.0質量%之乙烯基(CH2=CH-)部分含量；(B)具有在25℃下之黏度為1,000,000mPa．s或更大之液體至在25℃下呈現可塑性之膠狀物中之任意形式之有機聚矽氧烷，該有機聚矽氧烷視情況包含具有2至12個碳原子之烯基，該烯基具有小於0.100質量%之乙烯基(CH2=CH-)部分含量；(C)分子內包含至少兩個矽鍵結氫原子(Si-H)之有機氫聚矽氧烷；(D)矽氫化觸媒；及(E)若需要，任何所選有機溶劑；組分(A)與(B)之質量比係在90：10至99：1之範圍內。A curable organopolysiloxane composition comprising: (A) an organopolysiloxane or an organopolysiloxane mixture in the form of a plastic colloid exhibiting 0.5 to 3.0 mm at 25 ° C, the Organic polysiloxane or organic polysiloxane mixture containing the following components a1) and a2): a1) at least one organic group containing alkenyl groups having 4 to 12 carbon atoms in a mass ratio of 100: 0 to 50:50 Polysiloxane, the alkenyl group has a vinyl (CH 2 = CH-) partial content of 0.5 to 3.0% by mass, and a2) at least one organic polysiloxane containing an alkenyl group having 2 to 3 carbon atoms, The alkenyl group has a vinyl (CH 2 = CH-) content of 0.5 to 3.0% by mass; (B) has a viscosity of 1,000,000 mPa at 25 ° C. s or larger liquid to any form of organic polysiloxane in a plastic exhibiting plasticity at 25 ° C. The organic polysiloxane optionally contains an alkenyl group having 2 to 12 carbon atoms. The base has a vinyl content (CH 2 = CH-) fraction of less than 0.100% by mass; (C) an organic hydrogen polysiloxane containing at least two silicon-bonded hydrogen atoms (Si-H) in the molecule; (D) silicon Hydrogenation catalyst; and (E) if necessary, any selected organic solvent; the mass ratio of components (A) to (B) is in the range of 90:10 to 99: 1. 如請求項1之可固化有機聚矽氧烷組合物，其另外包含有機溶劑。The curable organic polysiloxane composition according to claim 1, which additionally contains an organic solvent. 如請求項1或2之可固化有機聚矽氧烷組合物，其中該矽氫化觸媒係鉑基觸媒。The curable organic polysiloxane composition according to claim 1 or 2, wherein the hydrosilation catalyst is a platinum-based catalyst. 如請求項1或2之可固化有機聚矽氧烷組合物，其中組分(A)係具有25℃下黏度為1,000,000mPa．s或更大之液體至25℃下呈現可塑性之膠狀物中之任意形式之有機聚矽氧烷或有機聚矽氧烷混合物。The curable organic polysiloxane composition as in claim 1 or 2, wherein component (A) has a viscosity of 1,000,000 mPa at 25 ° C. s or larger liquid to any form of organic polysiloxane or organic polysiloxane mixture in a plastic gel at 25 ° C. 如請求項1或2之可固化有機聚矽氧烷組合物，其中組分a1)係a1-1)包含己烯基作為具有4至12個碳原子之烯基之有機聚矽氧烷。The curable organic polysiloxane composition as claimed in claim 1 or 2, wherein component a1) is a1-1) an organic polysiloxane containing hexenyl as an alkenyl group having 4 to 12 carbon atoms. 如請求項1或2之可固化有機聚矽氧烷組合物，其中組分a2)係a2-1)包含乙烯基作為具有2至3個碳原子之烯基之有機聚矽氧烷。The curable organopolysiloxane composition as claimed in claim 1 or 2, wherein component a2) is a2-1) an organopolysiloxane containing a vinyl group as an alkenyl group having 2 to 3 carbon atoms. 如請求項1或2之可固化有機聚矽氧烷組合物，其中組分(B)係包含具有2至12個碳原子之烯基之二甲基聚矽氧烷，該烯基具有至少0.005質量%且小於0.100質量%之乙烯基(CH2=CH-)部分含量。The curable organic polysiloxane composition as claimed in claim 1 or 2, wherein component (B) comprises a dimethyl polysiloxane having an alkenyl group having 2 to 12 carbon atoms, the alkenyl group having at least 0.005 The content of vinyl (CH 2 = CH-) in mass% and less than 0.100 mass%. 如請求項1或2之可固化有機聚矽氧烷組合物，其中組分(B)係兩端經二甲基乙烯基矽氧基封端之二甲基聚矽氧烷。The curable organic polysiloxane composition as claimed in claim 1 or 2, wherein component (B) is dimethyl polysiloxane terminated at both ends with dimethyl vinyl siloxy groups. 如請求項1或2之含溶劑之可固化有機聚矽氧烷組合物，其另外包含(G)光聚合引發劑。The solvent-containing curable organic polysiloxane composition according to claim 1 or 2, which additionally contains (G) a photopolymerization initiator. 如請求項1或2之可固化有機聚矽氧烷組合物，其中該組合物在25℃下之總體黏度為100至50,000mPa．s。As claimed in claim 1 or 2, the curable organic polysiloxane composition, wherein the overall viscosity of the composition at 25 ℃ is 100 to 50,000mPa. s. 一種片狀物件，其包含藉由使如請求項1至10中任一項之可固化有機聚矽氧烷組合物固化所形成之固化層及片狀基板。A sheet-like article comprising a cured layer formed by curing the curable organic polysiloxane composition according to any one of claims 1 to 10 and a sheet-shaped substrate. 如請求項11之片狀物件，其係藉由將如請求項1至11中任一項之可固化有機聚矽氧烷組合物施加至該片狀基板，隨後使該施加的組合物固化得到。The sheet-like article according to claim 11, which is obtained by applying the curable organic polysiloxane composition according to any one of claims 1 to 11 to the sheet-like substrate, and then curing the applied composition . 如請求項11或12之片狀物件，其中該固化層係藉由將如請求項1至10中任一項之可固化有機聚矽氧烷組合物以0.01至0.5g/m2施加至該片狀基板，隨後使該施加的組合物固化得到。The sheet-like article according to claim 11 or 12, wherein the cured layer is applied to the curable organic polysiloxane composition according to any one of claims 1 to 10 at 0.01 to 0.5 g / m 2 A sheet-shaped substrate is then cured by applying the applied composition. 如請求項11或12之片狀物件，其中固化係使用加熱、能量輻射或加熱及能量輻射之組合進行。The sheet-like article according to claim 11 or 12, wherein the curing is performed using heating, energy radiation, or a combination of heating and energy radiation. 如請求項11或12之片狀物件，其中該片狀基板係塑膠膜。The sheet-like article according to claim 11 or 12, wherein the sheet-like substrate is a plastic film. 一種與介電陶瓷層形成材料共同使用之離型膜，該膜係由如請求項11至15中任一項之片狀物件構成。A release film used together with a dielectric ceramic layer forming material, the film being composed of a sheet-like article according to any one of claims 11 to 15. 一種用於形成陶瓷生胚片材之離型膜，該膜係由如請求項11至15中任一項之片狀物件構成。A release film for forming a ceramic green embryo sheet, the film being composed of the sheet-like article according to any one of claims 11 to 15. 一種製造介電陶瓷層形成材料或陶瓷生胚片材之方法，該方法包括使用如請求項16之與介電陶瓷層形成材料共同使用之離型膜或如請求項17之用於形成陶瓷生胚片材之離型膜，將陶瓷漿液施加至該膜上之固化有機聚矽氧烷層上，並使該所施加的陶瓷漿液乾燥之步驟。A method for manufacturing a dielectric ceramic layer forming material or a ceramic green embryo sheet, the method comprising using a release film used together with the dielectric ceramic layer forming material as in claim 16 or for forming ceramic green as in claim 17 A step of applying a ceramic slurry to the cured organic polysiloxane layer on the film of the release film of the embryonic sheet, and drying the applied ceramic slurry. 如請求項18之製造方法，該方法係一種製造陶瓷生胚片材之方法。As in the manufacturing method of claim 18, the method is a method for manufacturing ceramic green sheet.
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