TW201302919A - Release agent composition and release film for ceramic green sheet mold - Google Patents

Release agent composition and release film for ceramic green sheet mold Download PDF

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TW201302919A
TW201302919A TW101107271A TW101107271A TW201302919A TW 201302919 A TW201302919 A TW 201302919A TW 101107271 A TW101107271 A TW 101107271A TW 101107271 A TW101107271 A TW 101107271A TW 201302919 A TW201302919 A TW 201302919A
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polyorganosiloxane
release agent
group
agent composition
groups contained
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TWI519603B (en
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Shinya Ichikawa
Tomomi Fukaya
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Lintec Corp
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
    • C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6025—Tape casting, e.g. with a doctor blade
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups

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  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Ceramic Engineering (AREA)
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Abstract

A release agent composition contains: a polyorganosiloxane (A) which has at least two alkenyl groups in a molecule, and has an aryl group on each side chain of at least one silicon atom in a siloxane skeleton; and a polyorganosiloxane (B) which has an alkenyl group at only both ends in a molecule, but does not have an aryl group. The solid component ratio of the polyorganosiloxane (A) with respect to the total amount of the polyorganosiloxane (A) and the polyorganosiloxane (B) is 40 to 98 percent by mass, and the mass average molecular weight of the polyorganosiloxane (A) is 100000 to 800000. The release agent composition is excellent for ceramic slurry coatability, and is excellent for ceramic green sheet releasability.

Description

剝離劑組合物及陶瓷生片成型用剝離膜 Release agent composition and release film for ceramic green sheet molding

本發明關於剝離劑組合物以及使用該剝離劑組合物之陶瓷生片成型用的剝離膜。 The present invention relates to a release agent composition and a release film for ceramic green sheet molding using the release agent composition.

習知積層陶瓷電容器或多層陶瓷基板之積層陶瓷製品的製造，係使陶瓷生片成型，層積複數個所得陶瓷生片、燒成而進行。 In the production of a laminated ceramic product of a conventional multilayer ceramic capacitor or a multilayer ceramic substrate, a ceramic green sheet is molded, and a plurality of obtained ceramic green sheets are laminated and fired.

陶瓷生片由含有鈦酸鋇或氧化鈦等陶瓷材料的陶瓷漿料塗佈於剝離膜上而成型。剝離膜使用可於膜基材上剝離處理之聚矽氧烷等矽(silicone)系化合物者(專利文獻1~8)。此述剝離膜被要求具有成型於該剝離膜上的薄陶瓷生片可從該剝離膜剝離而沒有破裂等的剝離性。 The ceramic green sheet is formed by coating a ceramic slurry containing a ceramic material such as barium titanate or titanium oxide on a release film. As the release film, a silicone compound such as a polyoxyalkylene which can be peeled off on a film substrate is used (Patent Documents 1 to 8). The release film described above is required to have a thin ceramic green sheet formed on the release film which can be peeled off from the release film without peeling property such as cracking.

近年來，由於電子機器的小型化及高性能化，積層陶瓷電容器或多層陶瓷基板發展小型化及多層化，陶瓷生片也發展薄膜化。 In recent years, due to the miniaturization and high performance of electronic devices, laminated ceramic capacitors or multilayer ceramic substrates have been developed to be smaller and more multilayered, and ceramic green sheets have also been developed into thin films.

【先前技術文獻】 [Previous Technical Literature]

【專利文獻】 [Patent Literature]

【專利文獻1】特開2002-011710號公報 [Patent Document 1] JP-A-2002-011710

【專利文獻2】特開2004-182836號公報 [Patent Document 2] JP-A-2004-182836

【專利文獻3】特開2004-216613號公報 [Patent Document 3] JP-A-2004-216613

【專利文獻4】特開2008-254207號公報 [Patent Document 4] JP-A-2008-254207

【專利文獻5】特開2009-034947號公報 [Patent Document 5] JP-A-2009-034947

【專利文獻6】特開2009-215428號公報 [Patent Document 6] JP-A-2009-215428

【專利文獻7】特開2009-227976號公報 [Patent Document 7] JP-A-2009-227976

【專利文獻8】特開2009-227977號公報 [Patent Document 8] JP-A-2009-227977

當陶瓷生片薄膜化乾燥後的厚度成為3μm以下時，塗佈陶瓷漿料乾燥時容易發生陶瓷漿料塗佈端收縮，使該塗佈端厚度增加，即所謂的端部收縮，或者容易形成針孔或塗佈斑。又成型的陶瓷生片從剝離膜剝離時，容易發生因陶瓷生片的強度低所產生的破裂等的缺陷。 When the thickness of the ceramic green sheet after thin film drying is 3 μm or less, the coating of the ceramic slurry is likely to shrink when the coated ceramic slurry is dried, so that the thickness of the coated end is increased, that is, the so-called end shrinkage or easy formation. Pinhole or coated spot. When the formed ceramic green sheet is peeled off from the release film, defects such as cracking due to low strength of the ceramic green sheet are likely to occur.

而且，使用陶瓷生片的電子材料，根據其使用用途，無機物、黏接樹脂、分散劑、有機溶劑等的材料不同，依據此述陶瓷漿料的種類，變化陶瓷漿料對剝離膜的塗佈性。因此，剝離膜中陶瓷漿料的塗佈性能與陶瓷生片的剝離性並立有其困難。 Further, the electronic material using the ceramic green sheet differs depending on the intended use, the material of the inorganic material, the adhesive resin, the dispersant, the organic solvent, etc., and the coating of the release film by the ceramic slurry is changed according to the type of the ceramic slurry. Sex. Therefore, the coating property of the ceramic slurry in the release film and the peelability of the ceramic green sheet are both difficult.

本發明有鑑於此述實際狀況，以提供陶瓷漿料的塗佈性優良且陶瓷生片的剝離性也優良之陶瓷生片成型用之剝離膜以及適於該剝離膜之剝離劑組合物為目的。 In view of the above-described circumstances, the present invention provides a release film for ceramic green sheet molding and a release agent composition suitable for the release film, which are excellent in coating properties of a ceramic slurry and excellent in peelability of a ceramic green sheet. .

為了達到上述目的，第1，本發明提供一種剝離劑組合物，包含1分子中具有至少2個烯烴基且在矽氧烷結構中的至少1個矽原子的兩側鏈具有芳基的聚有機矽氧烷(A)，及不具有芳基且1分子中只有兩端具有烯烴基的聚有機矽氧烷(B)，其特徵在於，上述聚有機矽氧烷(A)的固形分比率，相對於上述聚有機矽氧烷(A)及上述聚有機矽氧烷 (B)的總量，為40~98質量%，上述聚有機矽氧烷(A)的質量平均分子量為100,000~800,000(發明1)。 In order to achieve the above object, the present invention provides a release agent composition comprising a polyorgano group having an aryl group having at least two olefin groups in one molecule and at least one fluorene atom in a oxoxane structure having an aryl group. a siloxane (A), and a polyorganosiloxane (B) having no aryl group and having only one end having an olefin group in one molecule, characterized by a solid content ratio of the above polyorganosiloxane (A), Relative to the above polyorganosiloxane (A) and the above polyorganooxane The total amount of (B) is 40 to 98% by mass, and the mass average molecular weight of the above polyorganosiloxane (A) is from 100,000 to 800,000 (Invention 1).

使用上述發明(發明1)所述剝離劑組合物所得的剝離膜，在陶瓷漿料的塗佈性優良，具體地說，可抑制剝離劑層表面塗佈陶瓷漿料乾燥時陶瓷漿料的塗佈端收縮而使得該塗佈端厚度增加之所謂的端部收縮的發生。又根據上述剝離膜，成型的陶瓷生片的剝離性亦優良，可以低剝離力自剝離劑層剝離陶瓷生片。 The release film obtained by using the release agent composition of the invention (Invention 1) is excellent in coating property of the ceramic slurry, and specifically, it is possible to suppress coating of the ceramic slurry when the surface of the release agent layer is coated with the ceramic slurry. The so-called end shrinkage of the cloth end shrinks to increase the thickness of the coated end. Further, according to the release film described above, the molded ceramic green sheet is also excellent in peelability, and the ceramic green sheet can be peeled off from the release agent layer with a low peeling force.

上述發明(發明1)中，較佳為該聚有機矽氧烷(B)的質量平均分子量為50,000~800,000(發明2)。 In the above invention (Invention 1), it is preferred that the polyorganosiloxane (B) has a mass average molecular weight of 50,000 to 800,000 (Invention 2).

上述發明(發明1、2)中，較佳更含有鉑系金屬化合物作為觸媒(發明3)。 In the above inventions (Inventions 1 and 2), it is preferred to further contain a platinum-based metal compound as a catalyst (Invention 3).

上述發明(發明1~3)中，較佳更包含交聯劑(C)(發明4)。 In the above invention (Inventions 1 to 3), it is preferred to further contain a crosslinking agent (C) (Invention 4).

上述發明(發明1~4)中，較佳為上述聚有機矽氧烷(A)所含的烯烴基數，相對於上述聚有機矽氧烷(A)所含的烷基數，為莫耳比0.005~0.1者(發明5)。 In the above invention (Inventions 1 to 4), it is preferred that the number of the olefin groups contained in the polyorganosiloxane (A) is a molar ratio of 0.005 based on the number of alkyl groups contained in the polyorganosiloxane (A). ~0.1 (Invention 5).

上述發明(發明1~5)中，較佳為上述聚有機矽氧烷(A)所含的芳基數，相對於上述聚有機矽氧烷(A)所含的烷基數，為莫耳比0.01~0.5者(發明6)。 In the above invention (Inventions 1 to 5), it is preferred that the number of aryl groups contained in the polyorganosiloxane (A) is Mohs ratio 0.01 with respect to the number of alkyl groups contained in the polyorganosiloxane (A). ~0.5 (invention 6).

上述發明(發明1~6)中，較佳為上述聚有機矽氧烷(B)所含的烯烴基數，相對於上述聚有機矽氧烷(B)所含的烷基數，為莫耳比0.0005~0.01者(發明7)。 In the above invention (Inventions 1 to 6), it is preferred that the number of olefin groups contained in the polyorganosiloxane (B) is Mobi ratio 0.0005 based on the number of alkyl groups contained in the polyorganosiloxane (B). ~0.01 (Invention 7).

上述發明(發明4~7)中，較佳為上述剝離劑組合物中交聯劑(C)的含量為，相對於上述聚有機矽氧烷(A)及上述聚有機矽氧烷(B)所含的烯烴基數，交聯劑(C)所含的氫矽烷基(hydrosilyl)數成為莫耳比1.0~5.0的含量(發明8)。 In the above invention (Inventions 4 to 7), it is preferred that the content of the crosslinking agent (C) in the release agent composition is relative to the polyorganosiloxane (A) and the polyorganosiloxane (B). The number of olefin groups contained, and the number of hydrosilyl groups contained in the crosslinking agent (C) are as a molar ratio of 1.0 to 5.0 (Invention 8).

第2，本發明提供一種陶瓷生片成型用的剝離膜，具有基材及形成於該基材的至少一表面上的剝離劑層，為陶瓷生片成型用的剝離膜，其特徵為，上述剝離劑層使用上述剝離劑組合物(發明1~8)所形成者(發明9)。 Secondly, the present invention provides a release film for ceramic green sheet molding, comprising a substrate and a release agent layer formed on at least one surface of the substrate, and is a release film for ceramic green sheet molding, characterized in that The release agent layer was formed by using the above release agent composition (Inventions 1 to 8) (Invention 9).

使用本發明所述之剝離劑組合物所得到的剝離膜或本發明所述之陶瓷生片成型用的剝離膜，在陶瓷漿料的塗佈性優良，具體地說，可抑制於剝離劑層表面塗佈陶瓷漿料乾燥時陶瓷漿料的塗佈端收縮而使得該塗佈端厚度增加之所謂的端部收縮的發生。又使用本發明所述之剝離劑組合物所得到的剝離膜或本發明所述之陶瓷生片成型用的剝離膜，成型的陶瓷生片的剝離性亦優良，可以低剝離力自剝離劑層剝離陶瓷生片。 The release film obtained by using the release agent composition of the present invention or the release film for molding a ceramic green sheet according to the present invention is excellent in coating property to a ceramic slurry, and specifically, can be suppressed in a release agent layer. When the surface-coated ceramic slurry is dried, the coated end of the ceramic slurry shrinks to cause the so-called end shrinkage of the thickness of the coated end to increase. Further, the release film obtained by using the release agent composition of the present invention or the release film for molding a ceramic green sheet according to the present invention has excellent peelability of the formed ceramic green sheet, and can be easily peeled off from the release agent layer. Peel the ceramic green sheets.

以下說明本發明之實施型態。 The embodiment of the present invention will be described below.

[剝離劑組合物] [Peeling agent composition]

本實施型態所述之剝離劑組合物包含：1分子中具有至少2個烯烴基且在矽氧烷結構中的至少1個矽原子的兩側鏈具有芳基的聚有機矽氧烷(A)，及不具有芳基且1分子中只有兩端具有烯烴基的聚有機 矽氧烷(B)，以及較佳更含有交聯劑(C)及/或觸媒(D)。 The release agent composition of the present embodiment comprises: a polyorganosiloxane having an aryl group having at least two olefin groups in one molecule and at least one fluorene atom in a oxoxane structure having an aryl group (A) ), and polyorganisms which do not have an aryl group and have only one end having an olefin group in one molecule The oxoxane (B), and preferably further contains a crosslinking agent (C) and/or a catalyst (D).

聚有機矽氧烷(A)為下式(a)所示之含矽化合物之聚合物。 The polyorganosiloxane (A) is a polymer of a ruthenium-containing compound represented by the following formula (a).

式(a)中，1為1以上的整數。R1及R2為碳數1~12的烷基，例如甲基、乙基、丙基、丁基、戊基、己基、辛基等。R1及R2可為相同或相異。R1及R2較佳為甲基。 In the formula (a), 1 is an integer of 1 or more. R 1 and R 2 are an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group or the like. R 1 and R 2 may be the same or different. R 1 and R 2 are preferably a methyl group.

式(a)中，m為1以上的整數。R3及R4為芳基，R3及R4可為相同也可不同，但較佳為相同者。因此，聚有機矽氧烷(A)成為在矽氧烷結構中的矽原子的兩側鏈具有芳基。根據此構造，當塗佈剝離劑組合物於基材時，所得的剝離劑層中，聚有機矽氧烷(A)，相對於聚有機矽氧烷(B)，偏在於剝離劑層的基材側，判斷因此可得到後述的效果。 In the formula (a), m is an integer of 1 or more. R 3 and R 4 are an aryl group, and R 3 and R 4 may be the same or different, but are preferably the same. Therefore, the polyorganosiloxane (A) has an aryl group on both sides of the ruthenium atom in the siloxane structure. According to this configuration, when the release agent composition is applied to the substrate, the polyorganosiloxane (A) in the resulting release agent layer is biased to the base of the release agent layer with respect to the polyorganosiloxane (B). On the material side, it is judged that the effect described later can be obtained.

芳基可列舉苯基、苯甲基、甲苯基、鄰二甲苯等，其中以苯基為佳。 The aryl group may, for example, be a phenyl group, a benzyl group, a tolyl group or an o-xylene group, and among them, a phenyl group is preferred.

式(a)中，n為1以上或2以上的整數。R5~R8至少2個為烯烴基，亦即，1個分子中有至少2個烯烴基。例如R7及R8兩個可為烯烴基(n為1以上)，或者R7及R8一個為烯烴基，R5及R6的一個或兩個可為烯烴基(n為1以上)，或者R7及R8為烯烴基以外的官能基時，R5及R6兩個可為烯烴基(n為1以上)或R5及R6的一個可為烯烴基(n為2以上)。也 可為R5及R6兩個為烯烴基者，與R5及R6的一個為烯烴基者混合。各R5可各自相同也可不同。各R6可各自相同也可不同。 In the formula (a), n is an integer of 1 or more or 2 or more. At least two of R 5 to R 8 are an olefin group, that is, at least two olefin groups in one molecule. For example, two of R 7 and R 8 may be an olefin group (n is 1 or more), or one of R 7 and R 8 may be an olefin group, and one or both of R 5 and R 6 may be an olefin group (n is 1 or more). When R 7 and R 8 are a functional group other than the olefin group, two of R 5 and R 6 may be an olefin group (n is 1 or more) or one of R 5 and R 6 may be an olefin group (n is 2 or more) ). It is also possible that both of R 5 and R 6 are an alkene group, and one of R 5 and R 6 is an alkene group. Each of R 5 may be the same or different. Each of R 6 may be the same or different.

烯烴基例如乙烯基、烯丙基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基等，其中以乙烯基特別為佳。 The olefin group is, for example, a vinyl group, an allyl group, a propylene group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group or the like, and among them, a vinyl group is particularly preferred.

R5及R6中烯烴基以外的官能基為碳數1~12的烷基，例如甲基、乙基、丙基、丁基、戊基、己基、辛基等，較佳為甲基。R7及R8中烯烴基以外的官能基可列舉與R5及R6相同的烷基、矽烷醇基(silanol)、氫化矽烷基(hydrosilyl)等。 The functional group other than the olefin group in R 5 and R 6 is an alkyl group having 1 to 12 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or an octyl group, and a methyl group is preferable. Examples of the functional group other than the olefin group in R 7 and R 8 include the same alkyl group as R 5 and R 6 , a silanol group, a hydrosilyl group, and the like.

聚有機矽氧烷(A)所含的芳基數，相對於聚有機矽氧烷(A)所含的烷基數，較佳為莫耳比0.01~0.5，特別是0.05~0.3為佳。芳基數在此範圍者，當塗佈剝離劑組合物於基材時，所得的剝離劑層中的聚有機矽氧烷(A)，相對於聚有機矽氧烷(B)，偏在於剝離劑層的基材側，判斷因此可得到後述的效果。 The number of aryl groups contained in the polyorganosiloxane (A) is preferably from 0.01 to 0.5, particularly preferably from 0.05 to 0.3, based on the number of alkyl groups contained in the polyorganosiloxane (A). When the number of aryl groups is in this range, when the release agent composition is applied to the substrate, the polyorganosiloxane (A) in the obtained release agent layer is biased to the release agent relative to the polyorganosiloxane (B). On the substrate side of the layer, it is judged that the effect described later can be obtained.

聚有機矽氧烷(A)所含的烯烴基數，相對於聚有機矽氧烷(A)所含的烷基數，較佳為莫耳比0.005~0.1，特別是0.01~0.05為佳。烯烴基的數目為1分子中有2個以上且為上述範圍者，可形成寄予後述效果之交聯密度高的交聯構造。 The number of olefin groups contained in the polyorganosiloxane (A) is preferably from 0.005 to 0.1, particularly preferably from 0.01 to 0.05, based on the number of alkyl groups contained in the polyorganosiloxane (A). When the number of the olefin groups is two or more in one molecule and is in the above range, a crosslinked structure having a high crosslinking density which imparts the effect described later can be formed.

聚有機矽氧烷(A)的質量平均分子量必須為100,000~800,000，較佳為150,000~600,000，更佳為200,000~380,000。本說明書中的質量平均分子量為以膠體 滲透層析(GPC)法所測定的聚苯乙烯換算的值。 The polyorganosiloxane (A) must have a mass average molecular weight of from 100,000 to 800,000, preferably from 150,000 to 600,000, more preferably from 200,000 to 380,000. The mass average molecular weight in this specification is colloid The value in terms of polystyrene measured by a permeation chromatography (GPC) method.

聚有機矽氧烷(A)的質量平均分子量未滿100,000時，當剝離劑組合物塗佈於基材時發生縮孔等，塗佈性差，難以得到均勻的平面狀態。又聚有機矽氧烷(A)的質量平均分子量超過800,000時，剝離劑組合物的黏度增加，對稀釋溶劑的溶解變得困難。 When the mass average molecular weight of the polyorganosiloxane (A) is less than 100,000, when the release agent composition is applied to the substrate, shrinkage cavities or the like occur, and the coatability is poor, and it is difficult to obtain a uniform planar state. When the mass average molecular weight of the polyorganosiloxane (A) exceeds 800,000, the viscosity of the release agent composition increases, and dissolution of the diluent solvent becomes difficult.

另一方面，聚有機矽氧烷(B)為下式(b)所示含矽化合物之聚合物。 On the other hand, the polyorganosiloxane (B) is a polymer containing a ruthenium compound represented by the following formula (b).

式(b)中，p為1以上的整數。R9及R10為碳數1~12的烷基，例如甲基、乙基、丙基、丁基、戊基、己基、辛基等，不為芳基或烯烴基。R9及R10可為相同也可為不同。R9及R10較佳為甲基。聚有機矽氧烷(B)不含芳基，因此當塗佈剝離劑組合物於基材時，所得的剝離劑層中，聚有機矽氧烷(B)，相對於聚有機矽氧烷(A)，偏在於剝離劑層的與基材的相反面(剝離劑層的表面)側，判斷因此可得到後述的效果。 In the formula (b), p is an integer of 1 or more. R 9 and R 10 are an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group or the like, and are not an aryl group or an olefin group. R 9 and R 10 may be the same or different. R 9 and R 10 are preferably a methyl group. The polyorganosiloxane (B) does not contain an aryl group, so when the release agent composition is applied to the substrate, the resulting release agent layer, the polyorganosiloxane (B), relative to the polyorganosiloxane ( A) is biased on the side opposite to the base material (surface of the release agent layer) of the release agent layer, and it is judged that the effect described later can be obtained.

式(b)中，R11至少1個為烯烴基，或R12至少1個為烯烴基。亦即，聚有機矽氧烷(B)的兩端具有烯烴基。烯烴基例如乙烯基、烯丙基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基等，其中以乙烯基特別為佳。R12中烯烴基以外的官能基為碳數1~12的烷基，例如甲基、乙基、丙基、 丁基、戊基、己基、辛基等，較佳為甲基。各R11可各自相同也可為不同。各R12可各自相同也可為不同。 In the formula (b), at least one of R 11 is an olefin group, or at least one of R 12 is an olefin group. That is, the polyorganosiloxane (B) has an olefin group at both ends. The olefin group is, for example, a vinyl group, an allyl group, a propylene group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group or the like, and among them, a vinyl group is particularly preferred. The functional group other than the olefin group in R 12 is an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or an octyl group, and a methyl group is preferable. Each of R 11 may be the same or different. Each of R 12 may be the same or different.

聚有機矽氧烷(B)為1分子中僅有兩端具有烯烴基，可形成後述效果所寄予的交聯密度低的交聯構造。 The polyorganosiloxane (B) has an olefin group at only two ends in one molecule, and can form a crosslinked structure having a low crosslinking density depending on the effect described later.

聚有機矽氧烷(B)所含的烯烴基數，相對於聚有機矽氧烷(B)所含的烷基數，較佳為莫耳比0.0005~0.01，特別是0.001~0.005為佳。 The number of olefin groups contained in the polyorganosiloxane (B) is preferably from 0.0005 to 0.01, particularly preferably from 0.001 to 0.005, based on the number of alkyl groups contained in the polyorganosiloxane (B).

聚有機矽氧烷(B)的質量平均分子量較佳為50,000~800,000，特別較佳為100,000~700,000，更佳為300,000~500,000。 The polyorganosiloxane (B) preferably has a mass average molecular weight of 50,000 to 800,000, particularly preferably 100,000 to 700,000, more preferably 300,000 to 500,000.

聚有機矽氧烷(B)的質量平均分子量未滿50,000時，恐怕難以形成後述效果所寄予的交聯密度低之交聯構造。又聚有機矽氧烷(B)的質量平均分子量超過800,000時，則剝離劑組合物的黏度增加，對稀釋溶劑的溶解恐有困難。又剝離劑組合物的硬化性變差，陶瓷生片的矽(silicone)轉移量恐怕也會增加。 When the mass average molecular weight of the polyorganosiloxane (B) is less than 50,000, it may be difficult to form a crosslinked structure having a low crosslinking density depending on the effect described later. When the mass average molecular weight of the polyorganosiloxane (B) exceeds 800,000, the viscosity of the release agent composition increases, and it may be difficult to dissolve the diluent solvent. Further, the hardenability of the release agent composition is deteriorated, and the amount of silicone transfer of the ceramic green sheet may increase.

相對於聚有機矽氧烷(A)及聚有機矽氧烷(B)的總量，聚有機矽氧烷(A)的固形分比率為40~98質量%，較佳為50~95質量%。聚有機矽氧烷(A)的固形分比率在此範圍以外者，雖陶瓷漿料的塗佈性良好，但陶瓷生片的剝離性則顯著地低。 The solid content ratio of the polyorganosiloxane (A) is from 40 to 98% by mass, preferably from 50 to 95% by mass, based on the total amount of the polyorganosiloxane (A) and the polyorganosiloxane (B). . When the solid content ratio of the polyorganosiloxane (A) is outside this range, the coating property of the ceramic slurry is good, but the peelability of the ceramic green sheet is remarkably low.

交聯劑(C)為可使聚有機矽氧烷(A)及/或聚有機矽氧烷(B)交聯者，沒有特別限定，但較佳為聚有機矽氧烷(A)及聚有機矽氧烷(B)以外的1分子中具有至少2個結合於矽 原子的氫原子之聚有機矽氧烷。此述的聚有機矽氧烷例如二甲基氫化矽氧基末端嵌段二甲基矽氧烷-甲基氫化矽氧烷共聚物、三甲基矽氧基末端嵌段二甲基矽氧烷-甲基氫化矽氧烷共聚物、三甲基矽氧基末端嵌段甲基氫化聚矽氧烷、聚(氫化乙基矽倍半環丙烷)(poly(hydrogensilsesquioxane))等。 The crosslinking agent (C) is not particularly limited as long as it can crosslink the polyorganosiloxane (A) and/or the polyorganosiloxane (B), but is preferably a polyorganosiloxane (A) and a poly At least 2 of one molecule other than the organic siloxane (B) is bound to ruthenium A polyorganosiloxane which is a hydrogen atom of an atom. The polyorganosiloxane such as the dimethylhydroquinoneoxy terminal block dimethyl methoxy oxane-methyl hydride hydride copolymer, trimethyl decyloxy terminal block dimethyl methoxy oxane a methylhydroperoxide copolymer, a trimethyldecyloxy terminal block methyl hydrogenated polyoxyalkylene, a poly(hydrogensilsesquioxane) or the like.

作為交聯劑(C)的聚有機矽氧烷的質量平均分子量較佳為100~5000，特別以500~2000為佳。 The polyorganosiloxane having the crosslinking agent (C) preferably has a mass average molecular weight of from 100 to 5,000, particularly preferably from 500 to 2,000.

本實施型態所述之剝離劑組合物中的交聯劑(C)的含量，相對於聚有機矽氧烷(A)及聚有機矽氧烷(B)所含有的烯烴基數，為交聯劑(C)所含的氫化矽烷基等的交聯性官能基數成為莫耳比1.0~5.0的量，特別是形成1.5~3.0的量為佳。 The content of the crosslinking agent (C) in the release agent composition of the present embodiment is crosslinked with respect to the number of olefin groups contained in the polyorganosiloxane (A) and the polyorganosiloxane (B). The number of crosslinkable functional groups such as a hydrogenated alkylene group contained in the agent (C) is an amount of from 1.0 to 5.0 in terms of a molar ratio, and particularly preferably an amount of from 1.5 to 3.0.

交聯劑(C)為使聚有機矽氧烷(A)與聚有機矽氧烷(B)交聯者，可賦予所得剝離劑層安定的剝離性。 The crosslinking agent (C) is a crosslinker which imparts stability to the obtained release agent layer by crosslinking the polyorganosiloxane (A) and the polyorganosiloxane (B).

觸媒(D)為可使本實施型態之剝離劑組合物硬化者，沒有特別限定，然而其中以鉑系金屬化合物為佳。鉑系金屬化合物例如微粒子狀鉑、吸附於碳粉載體上的微粒子狀鉑、氯鉑酸、醇改質氯鉑酸、氯鉑酸的烴錯合物、鈀、銠等。剝離劑組合物含有此述觸媒(D)者，可更有效率地進行該剝離劑組合物的硬化反應。 The catalyst (D) is not particularly limited as long as the release agent composition of the present embodiment can be cured. However, a platinum-based metal compound is preferred. A platinum-based metal compound such as fine-grained platinum, fine-particle platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, a hydrocarbon complex of chloroplatinic acid, palladium, rhodium, and the like. When the release agent composition contains the catalyst (D), the curing reaction of the release agent composition can be carried out more efficiently.

本實施型態之剝離劑組合物中觸媒(D)的含量，相對於觸媒(D)以外的成分的總量，較佳為約1~1000ppm。 The content of the catalyst (D) in the release agent composition of the present embodiment is preferably about 1 to 1000 ppm based on the total amount of components other than the catalyst (D).

本實施型態之剝離劑組合物除上述成分(A)~(D)以 外，也可含有反應抑制劑、密接促進劑等。 The stripper composition of the present embodiment is in addition to the above components (A) to (D). In addition, a reaction inhibitor, a adhesion promoter, or the like may be contained.

上述說明之剝離劑組合物以特定比例含有聚有機矽氧烷(A)及聚有機矽氧烷(B)，可形成陶瓷漿料的塗佈性優良且陶瓷生片的剝離性亦優良之剝離劑層。因此，根據本實施態樣之剝離劑組合物所形成之剝離劑層，可抑制剝離劑層表面塗佈陶瓷漿料乾燥時陶瓷漿料的塗佈端收縮而使得該塗佈端的厚度增加即端部收縮，以及抑制針孔、塗佈斑等的發生。又即使在該剝離劑層成型強度低的薄膜陶瓷生片時，也不會發生龜裂、破裂等的缺陷，可使用低的剝離力將陶瓷生片自剝離劑層剝離。雖然不必清楚知道理由，但推測如上述聚有機矽氧烷(A)具有芳基，聚有機矽氧烷(B)只有兩端具有烯烴基，聚有機矽氧烷(A)偏在剝離劑層的基材側，聚有機矽氧烷(B)偏在剝離劑層的表面層，判斷因此得到抑制端部收縮、針孔、塗佈斑等的抑制效果。 The release agent composition described above contains a polyorganosiloxane (A) and a polyorganosiloxane (B) in a specific ratio, and can form a ceramic slurry which is excellent in coatability and excellent in peelability of a ceramic green sheet. Agent layer. Therefore, according to the release agent layer formed by the release agent composition of the present embodiment, it is possible to suppress shrinkage of the coated end of the ceramic slurry when the surface of the release agent layer is coated with the ceramic slurry, so that the thickness of the coated end is increased, that is, the end Shrinkage of the part, and suppression of the occurrence of pinholes, coating spots, and the like. Further, even when the release film layer is formed into a thin film ceramic green sheet having low strength, defects such as cracks and cracks do not occur, and the ceramic green sheet can be peeled off from the release agent layer with a low peeling force. Although it is not necessary to clearly understand the reason, it is presumed that the polyorganosiloxane (A) has an aryl group, and the polyorganosiloxane (B) has an olefin group only at both ends, and the polyorganosiloxane (A) is biased to the release agent layer. On the substrate side, the polyorganosiloxane (B) was biased to the surface layer of the release agent layer, and it was judged that the effect of suppressing shrinkage of the end portion, pinholes, coating spots, and the like was obtained.

[陶瓷生片成型用的剝離膜] [Release film for ceramic green sheet molding]

本實施型態所述之陶瓷生片成型用的剝離膜(以下簡稱「剝離膜」)由具有基材及形成於基材的一表面之剝離劑層所構成。 The release film for ceramic green sheet molding (hereinafter referred to as "release film") according to the present embodiment is composed of a base material and a release agent layer formed on one surface of the base material.

基材，沒有特別限制，可適當選擇公知的種類中任意一種來使用。此述基材例如聚對苯二甲二乙酯或聚萘二甲二乙酯等的聚酯、聚丙烯或聚甲基戊烯等的聚烯烴、聚碳酸酯、聚乙酸乙烯酯等的塑膠所構成的膜，可為單層，也可為同種類或不同種類的2層以上的多層。此述之中，較佳為聚酯膜，特別是聚對苯二甲二乙酯膜為佳，更佳為二 軸延伸的聚對苯二甲二乙酯膜。聚對苯二甲二乙酯膜在加工、使用等之時，因為不易發生塵埃等，因此可有效地防止例如因塵埃等所造成的陶瓷漿料塗佈不良等。再者，聚對苯二甲二乙酯膜進行防靜電處理可提高防止塗佈不良等的效果。 The substrate is not particularly limited, and any one of known types can be appropriately selected and used. The base material is, for example, a polyester such as polyethylene terephthalate or polyethylene naphthalate, a polyolefin such as polypropylene or polymethylpentene, a plastic such as polycarbonate or polyvinyl acetate. The film to be formed may be a single layer or a multilayer of two or more layers of the same type or different types. Among these, a polyester film, particularly a polyethylene terephthalate film is preferred, and more preferably two. Axial extended polyethylene terephthalate film. When the polyethylene terephthalate film is processed, used, or the like, since dust or the like is less likely to occur, it is possible to effectively prevent, for example, coating failure of the ceramic slurry due to dust or the like. Further, the antistatic treatment of the polyethylene terephthalate film can improve the effect of preventing coating failure and the like.

此述基材中，以提升與其表面所設置的剝離劑層的密接性為目的，可視需要在一表面或兩表面施以氧化法或凹凹化法等的表面處理或者施以電漿處理。上述氧化法例如電暈放電處理、電漿放電處理、鉻酸化處理(濕式)、火焰處理、熱風處理、臭氧、紫外線照射處理等，凹凹化法例如噴沙法、溶射處理法等。此述的表面處理法可視基材膜的種類適當選擇，但一般電暈放電處理法從效果及操作性層面來看，為較佳使用。 In the above-mentioned substrate, for the purpose of improving the adhesion between the release agent layer provided on the surface thereof, a surface treatment such as an oxidation method or a concave concave method or a plasma treatment may be applied to one surface or both surfaces as needed. The oxidation method is, for example, a corona discharge treatment, a plasma discharge treatment, a chromic acid treatment (wet), a flame treatment, a hot air treatment, an ozone, an ultraviolet irradiation treatment, or the like, and a concave-concave method such as a sandblasting method or a spray treatment method. The surface treatment method described above can be appropriately selected depending on the type of the base film, but the general corona discharge treatment method is preferably used from the viewpoint of effect and workability.

基材的厚度通常可為10~300μm，較佳為15~200μm，更佳為20~125μm。 The thickness of the substrate may be usually 10 to 300 μm, preferably 15 to 200 μm, more preferably 20 to 125 μm.

本實施型態中的剝離劑層由前述之剝離劑組合物所形成。具體地說，剝離劑層由含有剝離劑組合物及視需要的有機溶劑之塗佈液塗佈於基材的一表面後、乾燥、硬化所形成。塗佈方法可使用例如凹版塗佈法、棒塗佈法、噴霧塗佈法、旋轉塗佈法、刀塗佈法、輥塗佈法、模具塗佈法等。 The release agent layer in this embodiment is formed of the aforementioned release agent composition. Specifically, the release agent layer is formed by applying a coating liquid containing a release agent composition and an optional organic solvent to one surface of the substrate, followed by drying and curing. As the coating method, for example, a gravure coating method, a bar coating method, a spray coating method, a spin coating method, a knife coating method, a roll coating method, a die coating method, or the like can be used.

上述有機溶劑沒有特別限定，各種皆可使用。例如以甲苯、己烷、庚烷等的烴化合物開始，使用丙酮、乙酸乙酯、甲基乙基酮、甲基異丁基酮及這些混合物等。 The above organic solvent is not particularly limited, and various types can be used. For example, starting with a hydrocarbon compound such as toluene, hexane or heptane, acetone, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like are used.

上述已塗佈的剝離劑組合物較佳使其熱硬化。此情形的加熱溫度較佳為90~140℃，加熱時間較佳為約10~120秒。 The above coated release agent composition is preferably thermally hardened. The heating temperature in this case is preferably from 90 to 140 ° C, and the heating time is preferably from about 10 to 120 seconds.

剝離劑層的厚度沒有特別限制，但較佳為0.01~3μm，更佳為0.03~1μm。剝離劑層的厚度未滿0.01μm時，根據構成剝離劑層的材料等，會有剝離劑層的功能無法充分發揮的情形。另一方面，當剝離劑層的厚度超過3μm時，將剝離膜輥狀捲取時會有阻斷發生而產生抽出時缺陷的情形。 The thickness of the release agent layer is not particularly limited, but is preferably 0.01 to 3 μm, more preferably 0.03 to 1 μm. When the thickness of the release agent layer is less than 0.01 μm, the function of the release agent layer may not be sufficiently exhibited depending on the material constituting the release agent layer or the like. On the other hand, when the thickness of the release agent layer exceeds 3 μm, there is a case where the release film is wound up in a roll shape, and a defect at the time of extraction occurs.

使用以上說明的剝離膜，可經由使用狹縫模具塗佈方式或刮刀塗佈方式等，在剝離劑層的表面塗佈陶瓷漿料、乾燥，成型陶瓷生片。此時，本實施型態之剝離膜可抑制陶瓷漿料塗佈端收縮而使得塗佈端厚度增加亦即所謂的端部收縮，也可抑制針孔或塗佈斑的發生。另一方面，即使在剝離劑層成型強度低的薄膜陶瓷生片的情形時，也不會發生龜裂、破裂等的缺陷，可以低的剝離力，具體為低於13mN/100mm的剝離力，自剝離劑層剝離陶瓷生片。因此，本實施型態之剝離膜在陶瓷漿料的塗佈性優良且陶瓷生片的剝離性也優良。 Using the release film described above, a ceramic slurry can be applied to the surface of the release agent layer by using a slit die coating method or a blade coating method, and dried to form a ceramic green sheet. At this time, the release film of this embodiment can suppress the shrinkage of the coated end of the ceramic slurry so that the thickness of the coated end is increased, that is, the so-called end shrinkage, and the occurrence of pinholes or coated spots can also be suppressed. On the other hand, even in the case of a thin film ceramic green sheet having a low release strength of the release agent layer, defects such as cracks and cracks do not occur, and a low peeling force can be obtained, specifically, a peeling force of less than 13 mN/100 mm. The ceramic green sheets were peeled off from the release agent layer. Therefore, the release film of this embodiment is excellent in the coating property of a ceramic slurry, and the peeling property of a ceramic green sheet is also excellent.

上述說明之實施型態係為了容易理解本發明所記載，並非用於限定本發明所記載。因此，上述實施型態所揭示之各要素也包含本發明技術範圍所屬之所有設計變更或均等物之旨趣。 The embodiments described above are intended to facilitate the understanding of the present invention and are not intended to limit the invention. Therefore, the elements disclosed in the above embodiments are intended to encompass all design changes or equivalents of the technical scope of the invention.

例如，基材1中的剝離劑層的相反面或基材1與剝離 劑層之間，也可設置防靜電層等其他層。 For example, the opposite side of the release agent layer in the substrate 1 or the substrate 1 and the peeling Other layers such as an antistatic layer may be provided between the agent layers.

[實施例] [Examples]

以下依實施例等更具體說明本發明，但是本發明之範圍不限於此述實施例等之限定。 Hereinafter, the present invention will be specifically described by way of Examples and the like, but the scope of the present invention is not limited to the examples and the like.

[實施例1] [Example 1]

將由1分子中具有2個以上乙烯基、不具有乙烯基之部分為二甲基矽氧烷-二苯基矽氧烷共聚物所構成之聚有機矽氧烷(A)95質量部，與不具有芳基且1分子中僅有兩端具有乙烯基、其他官能基為甲基之聚有機矽氧烷(B)5質量部混合，添加三甲基矽氧烷末端嵌段甲基氫化聚矽氧烷所構成之交聯劑(C)後，以甲苯為主成分之有機溶劑稀釋，調製成固形分濃度1.5質量%之剝離劑組合物之塗佈液。相對於聚有機矽氧烷(A)與聚有機矽氧烷(B)的總量，聚有機矽氧烷(A)的固形分比例(質量%)如表1所示。 95 mass parts of polyorganosiloxane (A) composed of a copolymer having two or more vinyl groups and no vinyl group in one molecule, which is a dimethyl methoxy alkane-diphenyl decane copolymer, and 5 parts of polyorganooxy oxane (B) having an aryl group and having only a vinyl group at both ends and a methyl group having another functional group, and a trimethyl decane-terminated terminal methyl hydrogenated polyoxy siloxane After the cross-linking agent (C) was formed, it was diluted with an organic solvent containing toluene as a main component to prepare a coating liquid of a release agent composition having a solid content of 1.5% by mass. The solid content ratio (% by mass) of the polyorganosiloxane (A) is shown in Table 1 with respect to the total amount of the polyorganosiloxane (A) and the polyorganosiloxane (B).

此處，聚有機矽氧烷(A)的質量平均分子量為360,000，聚有機矽氧烷(A)所含的苯基數(相對於聚有機矽氧烷(A)所含的甲基數)為莫耳比0.125，聚有機矽氧烷(A)所含的乙烯基數(相對於聚有機矽氧烷(A)所含的甲基數)為莫耳比0.025。 Here, the mass average molecular weight of the polyorganosiloxane (A) is 360,000, and the number of phenyl groups contained in the polyorganosiloxane (A) (relative to the number of methyl groups contained in the polyorganosiloxane (A)) is The molar ratio of the vinyl group contained in the polyorganosiloxane (A) (relative to the number of methyl groups contained in the polyorganosiloxane (A)) was Mohr ratio of 0.125.

聚有機矽氧烷(B)的質量平均分子量為440,000，聚有機矽氧烷(B)所含的乙烯基數(相對於聚有機矽氧烷(B)所含的甲基數)為莫耳比0.0024。 The polyorganosiloxane (B) has a mass average molecular weight of 440,000, and the polyorganosiloxane (B) contains a vinyl group (relative to the number of methyl groups contained in the polyorganosiloxane (B)) as a molar ratio. 0.0024.

另一方面，交聯劑(C)的質量平均分子量為1000，剝離劑組合物中的交聯劑(C)的含量為，相對於聚有機矽氧烷 (A)及聚有機矽氧烷(B)所含的乙烯基數，交聯劑(C)所含的氫矽烷基數成為莫耳比1.91的量。 On the other hand, the crosslinking agent (C) has a mass average molecular weight of 1,000, and the content of the crosslinking agent (C) in the release agent composition is relative to the polyorganosiloxane. The number of vinyl groups contained in (A) and the polyorganosiloxane (B), and the number of hydroquinone groups contained in the crosslinking agent (C) is an amount of the molar ratio of 1.91.

於上述塗佈液100質量部添加固形分比7質量部的鉑系觸媒(信越化學工業公司製，PL-50T)，在作為基材的2軸延伸聚酯膜(三菱樹脂公司製，DIAFOIL T-100，厚度：38μm)上以麥勒棒塗佈法(Mayer bar coating)，將所得的塗佈液以形成乾燥後膜厚為0.1μm的量均勻塗佈。之後，以熱風循環式乾燥機135℃加熱處理60秒，使矽(silicone)樹脂剝離劑硬化，得到基材上層積剝離劑層之剝離膜。 A platinum-based catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) having a solid content of 7 parts by mass is added to the mass portion of the coating liquid, and a 2-axis stretch polyester film as a substrate (DIAFOIL, manufactured by Mitsubishi Plastics Co., Ltd.) T-100, thickness: 38 μm) was applied by Mayer bar coating, and the obtained coating liquid was uniformly coated in an amount of 0.1 μm after drying. Thereafter, the film was heat-treated at 135 ° C for 60 seconds in a hot air circulation dryer to cure the silicone resin release agent to obtain a release film in which the release agent layer was laminated on the substrate.

[實施例2] [Embodiment 2]

將聚有機矽氧烷(A)90質量部與聚有機矽氧烷(B)10質量部混合，交聯劑(C)以相對於聚有機矽氧烷(A)及聚有機矽氧烷(B)所含的乙烯基數，交聯劑(C)所含的氫矽烷基數成為莫耳比1.91的量添加以外，其餘同實施例1調製塗佈液，製作剝離膜。 90 parts by mass of polyorganosiloxane (A) and 10 parts by mass of polyorganosiloxane (B), the crosslinking agent (C) is relative to polyorganosiloxane (A) and polyorganosiloxane ( B) The number of vinyl groups contained was changed, and the number of hydroquinone groups contained in the crosslinking agent (C) was changed to a molar ratio of 1.91. The coating liquid was prepared in the same manner as in Example 1 to prepare a release film.

[實施例3] [Example 3]

將聚有機矽氧烷(A)70質量部與聚有機矽氧烷(B)30質量部混合，交聯劑(C)以相對於聚有機矽氧烷(A)及聚有機矽氧烷(B)所含的乙烯基數，交聯劑(C)所含的氫矽烷基數成為莫耳比1.95的量添加以外，其餘同實施例1調製塗佈液，製作剝離膜。 70 parts by mass of polyorganosiloxane (A) and 30 parts by mass of polyorganosiloxane (B), the crosslinking agent (C) is relative to polyorganosiloxane (A) and polyorganosiloxane ( B) The number of vinyl groups contained was changed, and the number of hydroquinone groups contained in the crosslinking agent (C) was changed to a molar ratio of 1.95. The coating liquid was prepared in the same manner as in Example 1 to prepare a release film.

[實施例4] [Example 4]

將聚有機矽氧烷(A)50質量部與聚有機矽氧烷(B)50 質量部混合，交聯劑(C)以相對於聚有機矽氧烷(A)及聚有機矽氧烷(B)所含的乙烯基數，交聯劑(C)所含的氫矽烷基數成為莫耳比2.00的量添加以外，其餘同實施例1調製塗佈液，製作剝離膜。 50 parts of polyorganosiloxane (A) and polyorganosiloxane (B) 50 The mass portion is mixed, and the crosslinking agent (C) is compared with the number of vinyl groups contained in the polyorganosiloxane (A) and the polyorganosiloxane (B), and the number of hydroquinone groups contained in the crosslinking agent (C) becomes Mo. A coating liquid was prepared in the same manner as in Example 1 except that the amount of the ear was added in an amount of 2.00 to prepare a release film.

[比較例1] [Comparative Example 1]

不使用聚有機矽氧烷(B)，只使用聚有機矽氧烷(A)100質量部，交聯劑(C)以相對於聚有機矽氧烷(A)所含的乙烯基數，交聯劑(C)所含的氫矽烷基數成為莫耳比1.90的量添加以外，其餘同實施例1調製塗佈液，製作剝離膜。 Without using polyorganosiloxane (B), only 100 parts by mass of polyorganosiloxane (A) is used, and crosslinking agent (C) is crosslinked with respect to the number of vinyl groups contained in polyorganosiloxane (A). The coating liquid was prepared in the same manner as in Example 1 except that the number of hydroquinone groups contained in the agent (C) was changed to a molar ratio of 1.90, and a release film was prepared.

[比較例2] [Comparative Example 2]

將聚有機矽氧烷(A)99質量部與聚有機矽氧烷(B)1質量部混合，交聯劑(C)以相對於聚有機矽氧烷(A)及聚有機矽氧烷(B)所含的乙烯基數，交聯劑(C)所含的氫矽烷基數成為莫耳比1.90的量添加以外，其餘同實施例1調製塗佈液，製作剝離膜。 The mass fraction of the polyorganosiloxane (A) 99 is mixed with the mass portion of the polyorganosiloxane (B), and the crosslinking agent (C) is relative to the polyorganosiloxane (A) and the polyorganosiloxane ( B) The number of vinyl groups contained was changed, and the number of hydroquinone groups contained in the crosslinking agent (C) was changed to a molar ratio of 1.90. The coating liquid was prepared in the same manner as in Example 1 to prepare a release film.

[比較例3] [Comparative Example 3]

將聚有機矽氧烷(A)30質量部與聚有機矽氧烷(B)70質量部混合，交聯劑(C)以相對於聚有機矽氧烷(A)及聚有機矽氧烷(B)所含的乙烯基數，交聯劑(C)所含的氫矽烷基數成為莫耳比2.11的量添加以外，其餘同實施例1調製塗佈液，製作剝離膜。 30 parts by mass of polyorganosiloxane (A) and 70 parts by mass of polyorganosiloxane (B), the crosslinking agent (C) is relative to polyorganosiloxane (A) and polyorganosiloxane ( B) The number of vinyl groups contained was changed, and the number of hydroquinone groups contained in the crosslinking agent (C) was changed to a molar ratio of 2.11. The coating liquid was prepared in the same manner as in Example 1 to prepare a release film.

[比較例4] [Comparative Example 4]

將聚有機矽氧烷(A)10質量部與聚有機矽氧烷(B)90質量部混合，交聯劑(C)以相對於聚有機矽氧烷(A)及聚有 機矽氧烷(B)所含的乙烯基數，交聯劑(C)所含的氫矽烷基數成為莫耳比2.42的量添加以外，其餘同實施例1調製塗佈液，製作剝離膜。 10 parts by mass of polyorganosiloxane (A) and 90 parts by mass of polyorganosiloxane (B), the crosslinking agent (C) is combined with polyorganosiloxane (A) and The coating liquid was prepared in the same manner as in Example 1 except that the number of vinyl groups contained in the oxime (B) and the number of hydroquinone groups contained in the crosslinking agent (C) were changed to a molar ratio of 2.42, and a release film was prepared.

[比較例5] [Comparative Example 5]

不使用聚有機矽氧烷(A)，只使用聚有機矽氧烷(B)100質量部混合，交聯劑(C)以相對於聚有機矽氧烷(B)所含的乙烯基數，交聯劑(C)所含的氫矽烷基數成為莫耳比3.00的量添加以外，其餘同實施例1調製塗佈液，製作剝離膜。 Without using polyorganosiloxane (A), only 100 parts by mass of polyorganosiloxane (B) is used, and the crosslinking agent (C) is used in comparison with the number of vinyl groups contained in the polyorganosiloxane (B). The coating liquid was prepared in the same manner as in Example 1 except that the number of hydroquinone groups contained in the crosslinking agent (C) was changed to a molar ratio of 3.00 to prepare a release film.

[比較例6] [Comparative Example 6]

將由1分子中具有2個以上乙烯基、不具有乙烯基之部分為二甲基矽氧烷-甲基苯基矽氧烷共聚物(矽氧烷構造的一側鏈有芳基)所構成之聚有機矽氧烷(A’)95質量部，與實施例1所使用之聚有機矽氧烷(B)5質量部混合，添加三甲基矽氧烷末端嵌段甲基氫化聚矽氧烷所構成之交聯劑(C)後，以甲苯為主成分之有機溶劑稀釋，調製成固形分濃度1.5質量%之剝離劑組合物之塗佈液。相對於聚有機矽氧烷(A’)與聚有機矽氧烷(B)的總量，聚有機矽氧烷(A’)的固形分比例(質量%)如表1所示。 A copolymer having two or more vinyl groups in one molecule and having no vinyl group is a dimethyl methoxy oxo-methylphenyl decane copolymer (a side chain having an aryl group in the structure of a siloxane) 95 mass parts of polyorganosiloxane (A'), mixed with 5 mass parts of polyorganosiloxane (B) used in Example 1, and added with trimethylsulfoxane terminal block methyl hydrogenated polyoxyalkylene After the crosslinking agent (C), it was diluted with an organic solvent containing toluene as a main component to prepare a coating liquid of a release agent composition having a solid content of 1.5% by mass. The solid content ratio (% by mass) of the polyorganosiloxane (A') is shown in Table 1 with respect to the total amount of the polyorganosiloxane (A') and the polyorganosiloxane (B).

此處，聚有機矽氧烷(A’)的質量平均分子量為390,000，聚有機矽氧烷(A’)所含的苯基數(相對於聚有機矽氧烷(A’)所含的甲基數)為莫耳比0.012，聚有機矽氧烷(A’)所含的乙烯基數(相對於聚有機矽氧烷(A’)所含的甲基數)為莫耳比0.019。 Here, the polyorganosiloxane (A') has a mass average molecular weight of 390,000, and the polyorganosiloxane (A') contains a number of phenyl groups (relative to the methyl group contained in the polyorganosiloxane (A'). The number is a molar ratio of 0.012, and the number of vinyl groups contained in the polyorganosiloxane (A') (relative to the number of methyl groups contained in the polyorganosiloxane (A')) is a molar ratio of 0.019.

剝離劑組合物中的交聯劑(C)的含量為，相對於聚有機 矽氧烷(A’)及聚有機矽氧烷(B)所含的乙烯基數，交聯劑(C)所含的氫矽烷基數成為莫耳比2.53的量。 The content of the crosslinking agent (C) in the stripper composition is relative to the polyorganic The number of vinyl groups contained in the oxane (A') and the polyorganosiloxane (B) and the number of hydroquinone groups contained in the crosslinking agent (C) were such an amount of molar ratio of 2.53.

除使用上述塗佈液以外，其餘同實施例1調製塗佈液，製作剝離膜。 A coating liquid was prepared in the same manner as in Example 1 except that the above coating liquid was used to prepare a release film.

[比較例7] [Comparative Example 7]

將聚有機矽氧烷(A’)50質量部與聚有機矽氧烷(B)50質量部混合，交聯劑(C)以相對於聚有機矽氧烷(A’)及聚有機矽氧烷(B)所含的乙烯基數，交聯劑(C)所含的氫矽烷基數成為莫耳比2.57的量添加以外，其餘同比較例6調製塗佈液，製作剝離膜。 50 parts of polyorganosiloxane (A') is mixed with 50 parts by mass of polyorganosiloxane (B), and crosslinker (C) is relative to polyorganosiloxane (A') and polyorganosiloxane The coating liquid was prepared in the same manner as in Comparative Example 6 except that the number of vinyl groups contained in the alkane (B) and the number of hydroquinone groups contained in the crosslinking agent (C) were changed to a molar ratio of 2.57, and a release film was prepared.

[比較例8] [Comparative Example 8]

不使用聚有機矽氧烷(B)，只使用聚有機矽氧烷(A’)100質量部，交聯劑(C)以相對於聚有機矽氧烷(A’)所含的乙烯基數，交聯劑(C)所含的氫矽烷基數成為莫耳比2.53的量添加以外，其餘同比較例6調製塗佈液，製作剝離膜。 Without using polyorganosiloxane (B), only 100 parts by mass of polyorganosiloxane (A') and crosslinker (C) with respect to the number of vinyl groups contained in polyorganosiloxane (A') are used. The coating liquid was prepared in the same manner as in Comparative Example 6 except that the number of hydroquinone groups contained in the crosslinking agent (C) was changed to a molar ratio of 2.53 to prepare a release film.

[比較例9] [Comparative Example 9]

將聚有機矽氧烷(A’)10質量部與聚有機矽氧烷(B)90質量部混合，交聯劑(C)以相對於聚有機矽氧烷(A’)及聚有機矽氧烷(B)所含的乙烯基數，交聯劑(C)所含的氫矽烷基數成為莫耳比2.76的量添加以外，其餘同比較例6調製塗佈液，製作剝離膜。 Mixing 10 mass parts of polyorganosiloxane (A') with 90 mass parts of polyorganosiloxane (B), cross-linking agent (C) with respect to polyorganosiloxane (A') and polyorganosiloxane The number of vinyl groups contained in the alkane (B) and the number of hydroquinone groups contained in the crosslinking agent (C) were changed to a molar ratio of 2.76, and the coating liquid was prepared in the same manner as in Comparative Example 6, to prepare a release film.

[試驗例1](陶瓷漿料塗佈性的評估) [Test Example 1] (Evaluation of coating properties of ceramic slurry)

於鈦酸鋇(BaTiO3；堺化學工業公司製，BT-03)100質 量部、聚乙烯醇丁縮醛(積水化學工業公司製，S-LEC BK BM-2)10質量部、及鄰苯二甲酸二辛酯(關東化學公司製，鄰苯二甲酸二辛酯，鹿1級)5質量部中加入甲苯及乙醇混合液(質量比6：4)115質量部，於粉碎機中混合分散，調製陶瓷漿料。 100 parts by mass of barium titanate (BaTiO 3 ; BT-03), 10 parts by mass of polyvinyl butyral (S-LEC BK BM-2, manufactured by Sekisui Chemical Co., Ltd.), and o-benzene Dioctyl dicarboxylate (manufactured by Kanto Chemical Co., Ltd., dioctyl phthalate, deer 1) was added to a mass fraction of 115 parts by mass of toluene and ethanol (mass ratio 6:4), and mixed and dispersed in a pulverizer. , modulating ceramic slurry.

從實施例與比較例所製造於常溫保存48小時之剝離膜(寬：300mm)之剝離劑層表面，使用模具塗佈機(寬250mm)將上述陶瓷漿料以形成乾燥後的膜厚成為3μm的量，均勻塗佈，之後以乾燥機在80℃下乾燥1分鐘。如此製造具有陶瓷生片的剝離膜的捲膜300m。 From the surface of the release agent layer of the release film (width: 300 mm) which was produced at room temperature for 48 hours, which was produced in the examples and the comparative examples, the film thickness of the ceramic slurry was 3 μm after drying using a die coater (width: 250 mm). The amount was uniformly coated and then dried in a dryer at 80 ° C for 1 minute. The roll film 300m having the release film of the ceramic green sheet was produced in this manner.

所得的具有陶瓷生片的剝離膜的捲膜300m中，以目視確認寬方向端部是否發生端部收縮。其結果，端部收縮未發生者以○表示，端部收縮發生者以×表示。再者，以目視確認是否發生可目視確認的陶瓷漿料的微少縮孔即針孔，或是是否發生因陶瓷漿料塗佈厚度不均所導致的塗佈斑。未發生可目視的針孔及塗佈斑者以○表示，發生可目視的針孔及塗佈斑者以×表示。結果如表1所示。 In the roll film 300m of the obtained release film having a ceramic green sheet, it was visually confirmed whether or not end portion shrinkage occurred in the end portion in the width direction. As a result, the case where the end contraction did not occur was indicated by ○, and the end contraction occurred by ×. Further, it was visually confirmed whether or not pinholes, which are microscopically small pores of the ceramic slurry which were visually confirmed, or whether coating unevenness due to uneven thickness of the ceramic slurry coating occurred. The visible pinholes and the coated spots are not indicated by ○, and the visible pinholes and coated spots are indicated by ×. The results are shown in Table 1.

[試驗例2](陶瓷生片剝離性的評估) [Test Example 2] (Evaluation of peelability of ceramic green sheets)

同試驗例1，將所得具有陶瓷生片的剝離膜於室溫23度、濕度50%的雰圍氣下靜置24小時後，裁切為100mm×100mm體積，其一邊從陶瓷生片表面側黏貼長100mm的丙烯酸黏著帶(日東電工公司製，31B Tape)。將此樣品以剝離膜的表面側與平板相接的狀態固定於該平板，將黏貼丙烯酸黏著帶的一端邊側向下傾斜45°，設置於剝離試 驗機(島津製作所公司製，AG-IS 500N)。之後將黏貼丙烯酸黏著帶的端邊的剝離膜自陶瓷生片剝除，將丙烯酸黏著帶側放入剝離試驗機的夾具上。以此狀態，將丙烯酸黏著帶以剝離速度200mm/min垂直向上拉伸，測定自剝離膜剝除陶瓷生片時的剝離力(mN/100mm)。結果如表1所示。 In the same manner as in Test Example 1, the obtained release film having a ceramic green sheet was allowed to stand under an atmosphere of a room temperature of 23 degrees and a humidity of 50% for 24 hours, and then cut into a volume of 100 mm × 100 mm, which was pasted from the surface side of the ceramic green sheet. 100mm long acrylic adhesive tape (made by Nitto Denko Corporation, 31B Tape). The sample was fixed to the flat plate in a state where the surface side of the release film was in contact with the flat plate, and the one end side of the adhesive acrylic adhesive tape was inclined downward by 45°, and was set on the peeling test. Inspection machine (made by Shimadzu Corporation, AG-IS 500N). Thereafter, the release film adhered to the edge of the acrylic adhesive tape was peeled off from the ceramic green sheet, and the acrylic adhesive tape side was placed on the jig of the peeling tester. In this state, the acrylic pressure-sensitive adhesive tape was stretched vertically upward at a peeling speed of 200 mm/min, and the peeling force (mN/100 mm) at the time of peeling off the ceramic green sheets from the release film was measured. The results are shown in Table 1.

因為作為陶瓷生片成型用之剝離膜的較佳剝離力為低於13mN/100mm，所以測定的剝離力低於13mN/100mm者評價為○，13mN/100mm以上者評價為×。結果如表1所示。 Since the peeling film for the ceramic green sheet molding has a preferable peeling force of less than 13 mN/100 mm, the peeling force measured is less than 13 mN/100 mm, and it is evaluated as ○, and 13 mN/100 mm or more is evaluated as ×. The results are shown in Table 1.

從表1所示之結果可清楚知道，實施例1~4所得到的剝離膜在陶瓷漿料的塗佈性優良且可以低剝離力剝離陶瓷生片，在陶瓷生片的剝離性上也優良。另一方面，比較例1~9所得的剝離膜在陶瓷漿料的塗佈性上雖優良，但是即使高剝離力也無法剝離陶瓷生片，陶瓷生片的剝離性差。 As is clear from the results shown in Table 1, the release films obtained in Examples 1 to 4 are excellent in coating properties of ceramic slurry, and can peel ceramic green sheets with low peeling force, and are excellent in peelability of ceramic green sheets. . On the other hand, the release film obtained in Comparative Examples 1 to 9 was excellent in the coatability of the ceramic slurry, but the ceramic green sheet could not be peeled off even with a high peeling force, and the peelability of the ceramic green sheet was inferior.

【產業可利用性】 [Industrial Availability]

本發明之剝離劑組合物適合形成陶瓷生片成型用剝離膜的剝離劑層。又本發明之陶瓷生片成型用之剝離膜有效作為陶瓷漿料塗佈性優良且陶瓷生片剝離性也優良的剝離膜。 The release agent composition of the present invention is suitable for forming a release agent layer of a release film for ceramic green sheet molding. Further, the release film for molding a ceramic green sheet of the present invention is effective as a release film having excellent ceramic slurry coating properties and excellent ceramic green sheet peelability.

Claims (9)

一種剝離劑組合物，包含：(A)1分子中具有至少2個烯烴基且在矽氧烷結構中的至少1個矽原子的兩側鏈具有芳基的聚有機矽氧烷，及(B)不具有芳基且1分子中只有兩端具有烯烴基的聚有機矽氧烷，其特徵在於，上述聚有機矽氧烷(A)的固形分比率，相對於上述聚有機矽氧烷(A)及上述聚有機矽氧烷(B)的總量，為40~98質量%，上述聚有機矽氧烷(A)的質量平均分子量為100,000~800,000。 A stripper composition comprising: (A) a polyorganosiloxane having at least two olefin groups in one molecule and having an aryl group on both sides of at least one ruthenium atom in a siloxane structure, and (B) a polyorganosiloxane having no aryl group and having only one end having an olefin group in one molecule, characterized in that the solid content ratio of the above polyorganosiloxane (A) is relative to the above polyorganosiloxane (A) And the total amount of the polyorganosiloxane (B) is 40 to 98% by mass, and the polyorganosiloxane (A) has a mass average molecular weight of 100,000 to 800,000. 如申請專利範圍第1項所述之剝離劑組合物，其中，上述聚有機矽氧烷(B)的質量平均分子量為50,000~800,000。 The release agent composition according to claim 1, wherein the polyorganosiloxane (B) has a mass average molecular weight of 50,000 to 800,000. 如申請專利範圍第1項所述之剝離劑組合物，更包含鉑系金屬化合物作為觸媒。 The release agent composition according to claim 1, further comprising a platinum group metal compound as a catalyst. 如申請專利範圍第1項所述之剝離劑組合物，更包含交聯劑(C)。 The release agent composition according to claim 1, further comprising a crosslinking agent (C). 如申請專利範圍第1項所述之剝離劑組合物，其中，上述聚有機矽氧烷(A)所含的烯烴基數，相對於上述聚有機矽氧烷(A)所含的烷基數，為莫耳比0.005~0.1。 The release agent composition according to claim 1, wherein the polyorganosiloxane (A) has an olefin group content of the number of alkyl groups contained in the polyorganosiloxane (A). Moerby is 0.005~0.1. 如申請專利範圍第1項所述之剝離劑組合物，其中，上述聚有機矽氧烷(A)所含的芳基數，相對於上述聚有機矽氧烷(A)所含的烷基數，為莫耳比0.01~0.5。 The release agent composition according to claim 1, wherein the number of the aryl groups contained in the polyorganosiloxane (A) is based on the number of alkyl groups contained in the polyorganosiloxane (A). The molar ratio is 0.01~0.5. 如申請專利範圍第1項所述之剝離劑組合物，其中，上述聚有機矽氧烷(B)所含的烯烴基數，相對於上述聚有機矽氧烷(B)所含的烷基數，為莫耳比0.0005~0.01。 The release agent composition according to claim 1, wherein the polyorganosiloxane (B) has an olefin group content of the number of alkyl groups contained in the polyorganosiloxane (B). Moerby is 0.0005~0.01. 如申請專利範圍第4項所述之剝離劑組合物，其中，上述剝離劑組合物中交聯劑(C)的含量為，相對於上述聚有機矽氧烷(A)及上述聚有機矽氧烷(B)所含的烯烴基數，交聯劑(C)所含的氫矽烷基(hydrosilyl)數成為莫耳比1.0~5.0的含量。 The release agent composition according to claim 4, wherein the content of the crosslinking agent (C) in the release agent composition is relative to the polyorganosiloxane (A) and the polyorganosiloxane The number of olefin groups contained in the alkane (B) and the number of hydrosilyl groups contained in the crosslinking agent (C) are as a molar ratio of 1.0 to 5.0. 一種陶瓷生片成型用的剝離膜，具有基材及形成於該基材的至少一表面上的剝離劑層，其中該剝離劑層係使用如申請專利範圍第1至8項任一項所述之剝離劑組合物所形成者。 A release film for forming a ceramic green sheet, comprising: a substrate; and a release agent layer formed on at least one surface of the substrate, wherein the release agent layer is used according to any one of claims 1 to 8 The composition of the stripper composition.
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