TWI525153B - A release agent composition, and a release film for forming a ceramic green sheet - Google Patents

Description

Release agent composition and release film for ceramic green sheet molding

The present invention relates to a release agent composition and a release film for ceramic green sheet molding using the release agent composition.

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.

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.

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.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2002-011710

[Patent Document 2] JP-A-2004-182836

[Patent Document 3] JP-A-2004-216613

[Patent Document 4] JP-A-2008-254207

[Patent Document 5] JP-A-2008-150515

[Patent Document 6] JP-A-2009-034947

[Patent Document 7] JP-A-2009-215428

[Patent Document 8] JP-A-2009-227976

[Patent Document 9] JP-A-2009-227977

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.

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.

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. .

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, and a group having no aryl group and having a structure containing an organic oxime a branched organooxane oligomer (C) having at least two olefin groups in one molecule and having a solid content ratio of the above polyorganosiloxane (A) relative to the above polyorganoindole The total amount of the oxane (A) and the branched organooxane oligomer (C) is 40 to 98% by mass, and the solid content ratio of the polyorganosiloxane (B) is relative to the above polyorganoindene The total amount of the oxyalkylene (A), the polyorganosiloxane (B), and the branched organooxane oligomer (C) is 2 to 60% by mass (Invention 1).

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.

In the above invention (Invention 1), it is preferred that the polyorganosiloxane (A) has a mass average molecular weight of from 100,000 to 800,000 (Invention 2).

In the above inventions (Inventions 1 and 2), it is preferred that the polyorganosiloxane (B) has a mass average molecular weight of 50,000 to 800,000 (Invention 3).

In the above invention (Inventions 1 to 3), it is preferred that the branched organosiloxane oligomer (C) has a mass average molecular weight of 1,000 to 50,000 (Invention 4).

In the above invention (Inventions 1 to 4), it is preferable to further contain a platinum-based metal compound as a catalyst (Invention 5).

In the above invention (Inventions 1 to 5), it is preferred to further contain a crosslinking agent (D) (Invention 6).

In the above invention (Invention 6), the polyorganosiloxane (A) is preferably used. The number of olefin groups contained is from 0.005 to 0.1 with respect to the number of alkyl groups contained in the polyorganosiloxane (A) (Invention 7).

In the above invention (Invention 6, 7), 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 8).

In the above invention (Inventions 6 to 8), 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 9).

In the above invention (Inventions 6 to 9), it is preferred that the number of olefin groups contained in the branched organooxane oligomer (C) is relative to the branched organooxane oligomer (C). The number of alkyl groups is from 0.05 to 0.35 molar ratio (Invention 10).

In the above invention (Inventions 6 to 10), it is preferred that the content of the crosslinking agent (D) in the release agent composition is relative to the polyorganosiloxane (A) and the polyorganosiloxane (B). And the number of olefin groups contained in the branched organooxane oligomer (C), and the number of hydrosilyl groups contained in the crosslinking agent (D) is an amount of from 1.0 to 5.0 in terms of a molar ratio (Invention 11).

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 11) (Invention 12).

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 coated on a ceramic slurry. It is excellent in the properties, and specifically, it is possible to suppress the occurrence of so-called end shrinkage in which the coating end of the ceramic slurry shrinks when the ceramic slurry is dried on the surface of the release agent layer to increase the thickness of the coated end. 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.

The embodiment of the present invention will be described below.

[Peeling agent composition]

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 a polyorganosiloxane (B) having no aryl group and having only one end having an olefin group in one molecule, and a branch chain having no aryl group and having a structure containing an organic oxirane and having at least 2 in one molecule The olefin-based branched organooxane oligomer (C) preferably further contains a crosslinking agent (D) and/or a catalyst (E).

The polyorganosiloxane (A) is a polymer of a ruthenium-containing compound represented by the following formula (a).

In the formula (a), l 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.

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.

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.

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) ). May also be R ⁵ and R ⁶ are two olefin groups, mixed with a R ⁵ and R ⁶ is a group by olefin. Each of R ⁵ may be the same or different. Each of R ⁶ may be the same or different.

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 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.

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.

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 to which the effects described later can be formed can be formed.

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 the present specification is a value in terms of polystyrene measured by a colloidal permeation chromatography (GPC) method.

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.

On the other hand, the polyorganosiloxane (B) is a polymer containing a ruthenium compound represented by the following formula (b).

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 substrate (surface of the release agent layer) of the release agent layer, and it is judged that the effect described later can be obtained.

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.

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.

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).

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.

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.

The branched organooxane oligomer (C) is an organooxyalkylene oligomer having a branched chain having a mercaptooxyl structure, as shown in the following formula (c).

In the formula (c), q, r, s and t are integers of 1 or more. R is not an aryl group, and at least two of R are an olefin group. 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 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 R may be the same or different.

As described above, since the branched organooxane oligomer (C) does not have an aryl group, when the release agent composition is applied to the substrate, the polyorganosiloxane (A) is biased in the resulting release agent layer. On the substrate side of the release agent layer, the polyorganosiloxane (B) is biased on the side opposite to the substrate (surface of the release agent layer) of the release agent layer, and it is judged that the effect described later can be obtained.

As described above, the branched organooxane oligomer (C) has at least two olefin groups in one molecule, but the site in which the olefin group is present may be a main chain, a branched chain, or both. .

The number of olefin groups contained in the branched organooxane oligomer (C) is preferably from 0.05 to 0.35 based on the number of alkyl groups contained in the branched organooxane oligomer (C), particularly 0.1~0.2 is better. When the number of olefin groups is two or more in one molecule and is within the above range, a crosslinked structure having a crosslinking density can be formed by the effect described later.

The mass average molecular weight of the branched organooxane oligomer (C) is preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, still more preferably from 3,000 to 10,000.

When the mass average molecular weight of the branched organooxane oligomer (C) is less than 1,000, the viscosity of the coating liquid of the release agent composition may be lowered, and in this case, shrinkage cavities may occur when the release agent composition is applied. It may be difficult to obtain a uniform coated surface. When the mass average molecular weight of the branched organooxane oligomer (C) exceeds 50,000, it may be difficult to form a crosslinked structure having a low crosslinking density which is imparted by the effect described later.

The solid content ratio of the polyorganosiloxane (A) is from 40 to 98% by mass, preferably 45, based on the total amount of the polyorganosiloxane (A) and the branched organooxane oligomer (C). ~95% by mass, more preferably 50 to 90% by mass. The solid content ratio of the polyorganosiloxane (B) is 2 with respect to the total amount of the polyorganosiloxane (A), the polyorganosiloxane (B), and the branched organooxane oligomer (C). ~60% by mass, preferably 2 to 55% by mass, more preferably 5 to 50% by mass. The solid content ratio of polyorganosiloxane (A) to polyorganosiloxane (B) is outside this range, Tao The coatability of the porcelain slurry or the peelability of the ceramic green sheets is remarkably lowered.

The crosslinking agent (D) is not particularly limited as long as it can crosslink the polyorganosiloxane (A), the polyorganosiloxane (B) or the branched organooxane oligomer (C), but is preferably. a polyorgano group having at least two hydrogen atoms bonded to a ruthenium atom in one molecule other than the polyorganosiloxane (A), the polyorganosiloxane (B), and the branched organooxane oligomer (C) Oxane. The polyorganosiloxane such as the dimethylhydroquinoneoxy terminal block dimethyl methoxy oxane-methyl hydride hydride copolymer, trimethyl decyloxy terminal block dimethyl methoxy oxane - Polyorganotinium hydride such as methylhydroperoxane copolymer, trimethyl decyloxy terminal block methyl hydrogenated polyoxyalkylene or poly(hydrogen silsesquioxane) .

The polyorganosiloxane having the crosslinking agent (D) preferably has a mass average molecular weight of 500 to 5,000, particularly preferably 500 to 2,000.

The content of the crosslinking agent (D) in the stripper composition of the present embodiment is oligomeric with respect to polyorganosiloxane (A), polyorganosiloxane (B) and branched organooxane The number of the olefin groups contained in the compound (C) is such that the number of crosslinkable functional groups such as a hydrogenated alkylene group contained in the crosslinking agent (D) is from 1.0 to 5.0, particularly preferably from 1.5 to 3.0. More preferably, it forms an amount of 1.8 to 2.0.

The crosslinking agent (D) crosslinks the polyorganosiloxane (A), the polyorganosiloxane (B) or the branched organooxane oligomer (C) to impart stable peelability to the resulting release agent layer. .

The catalyst (E) is such that the stripper composition of the present embodiment can be cured. There is a particular limitation, but among them, a platinum group 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 (E), the curing reaction of the release agent composition can be carried out more efficiently.

The content of the catalyst (E) in the release agent composition of the present embodiment is preferably about 1 to 1000 pm with respect to the total amount of components other than the catalyst (E).

The release agent composition of the present embodiment may contain a reaction inhibitor, a adhesion promoter, and the like in addition to the above components (A) to (E).

The release agent composition described above contains a polyorganosiloxane (A), a polyorganosiloxane (B), and a branched organooxane oligomer (C) in a specific ratio to form a coating of a ceramic slurry. A release agent layer excellent in peelability and excellent in ceramic green sheets. 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 has a low ceramic forming green sheet film, defects such as cracks and cracks do not occur, and the ceramic green sheets can be peeled off from the release agent layer using a very 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. Moreover, since the branched organooxane oligomer (C) is contained, the crosslinking density in the release agent layer is increased, and as a result, When the ceramic green sheet is thinned, the ceramic green sheet is not broken and can be peeled off.

[Release film for ceramic green sheet molding]

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.

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 the above, a polyester film, particularly a polyethylene terephthalate film is preferred, and a biaxially stretched polyethylene terephthalate film is more preferred. 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.

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 effect and operability of the general corona discharge treatment method At the level, it is better to use.

The thickness of the substrate may be usually 10 to 300 μm, preferably 15 to 200 μm, more preferably 20 to 125 μm.

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.

The above organic solvent is not particularly limited, and various types can be used. For example, a hydrocarbon compound starting from toluene, hexane, heptane or the like is used, and acetone, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like are used.

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.

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-like manner, and a defect at the time of extraction occurs.

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 be suppressed The shrinkage of the coated end of the ceramic slurry causes the thickness of the coated end to increase, 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 very low peeling force can be obtained, specifically, a peeling force of less than 10 mN/100 mm. The ceramic green sheet is 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.

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.

For example, another layer such as an antistatic layer may be provided between the opposite surface of the release agent layer in the substrate 1 or between the substrate 1 and the release agent layer.

[Examples]

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.

[Example 1]

a polyorganooxy oxane (A) 90.25 mass portion composed of a copolymer having two or more vinyl groups and no vinyl group in one molecule, and a dimethyl oxoxane-diphenyl fluorene copolymer, and a mass fraction of a polyorganosiloxane (B) having an aryl group and having only a vinyl group at both ends and a methyl group at the other, and a branch chain having a structure containing a sulfonate having no aryl group And a branched organosiloxane oligo (C) having 2 or more vinyl groups and other functional groups in a molecule of 4.75 parts by mass, added by trimethyl group After the crosslinking agent (D) composed of a decane-terminated block methyl hydrogenated polyoxyalkylene was diluted with an organic solvent containing toluene as a main component, a coating liquid of a release agent composition having a solid content of 1.5% by mass was prepared. The solid content ratio (% by mass) of the polyorganosiloxane (A) relative to the total amount of the polyorganosiloxane (A) and the branched organooxane oligomer (C), and relative to the polyorganoindene The total amount of oxyalkylene (A), polyorganosiloxane (B) and branched organooxane oligomer (C), and the solid content ratio (% by mass) of polyorganosiloxane (B), as shown in Table 1 is shown.

Here, the mass average molecular weight of the polyorganosiloxane (A) is 360,000, and the number of phenyl groups contained in the polyorganosiloxane (A) is relative to the number of methyl groups contained in the polyorganosiloxane (A). The molar ratio of the polyorganosiloxane (A) in the molar ratio of 0.125 is a molar ratio of 0.025 to the number of methyl groups contained in the polyorganosiloxane (A).

The polyorganosiloxane (B) has a mass average molecular weight of 440,000, and the polyorganosiloxane (B) has a vinyl group content, which is a molar ratio with respect to the number of methyl groups contained in the polyorganosiloxane (B). 0.0024.

The branched organooxane oligomer (C) has a mass average molecular weight of 6000, and the number of vinyl groups contained in the branched organooxane oligomer (C) relative to the branched organooxane oligomer (C) The number of methyl groups contained is 0 to 3 molar ratio.

On the other hand, the crosslinking agent (D) has a mass average molecular weight of 1,000, and the content of the crosslinking agent (D) in the release agent composition is relative to the polyorganosiloxane (A) and polyorganosiloxane ( B) and the number of vinyl groups contained in the branched organooxane oligomer (C), and the number of hydroquinone groups contained in the crosslinking agent (D) is an amount of the molar ratio of 1.91.

A platinum-based catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) having a solid content of 10 parts by mass, and a 2-axis stretched polyester film as a substrate (DIAFOIL, manufactured by Mitsubishi Plastics Co., Ltd., DIAFOIL) 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 circulating dryer to cure the silicone resin release agent to form a release agent layer on the substrate. Thereafter, the film was stored under dry conditions at 70 ° C for 24 hours due to the influence of the remaining functional groups of the polyorganohydrogen hydride of the crosslinking agent of the release agent to obtain a release film.

[Embodiment 2]

47.5 parts by mass of polyorganosiloxane (A) and 50 parts by mass of polyorganosiloxane (B) used in Example 1 were mixed with 2.5 parts by mass of branched organooxane oligomer (C). (D) is contained in the crosslinking agent (D) with respect to the number of vinyl groups contained in the polyorganosiloxane (A), the polyorganosiloxane (B), and the branched organooxane oligomer (C) A coating liquid was prepared in the same manner as in Example 1 except that the number of hydroquinone groups was changed to a molar ratio of 1.91, and a release film was produced.

[Example 3]

85.5 parts by mass of polyorganosiloxane (A) and 5 parts by mass of polyorganosiloxane (B) used in Example 1 were mixed with 9.5 mass parts of branched organooxane oligomer (C), and a crosslinking agent was used. (D) is contained in the crosslinking agent (D) with respect to the number of vinyl groups contained in the polyorganosiloxane (A), the polyorganosiloxane (B), and the branched organooxane oligomer (C) A coating liquid was prepared in the same manner as in Example 1 except that the number of hydroquinone groups was changed to a molar ratio of 1.91, and a release film was produced.

[Example 4]

The polyorganosiloxane (A) 63 mass fraction used in Example 1 and the polyorganosiloxane (B) 30 mass fraction were mixed with the branched organooxane oligomer (C) 7 mass fraction, and the crosslinking agent was mixed. (D) is contained in the crosslinking agent (D) with respect to the number of vinyl groups contained in the polyorganosiloxane (A), the polyorganosiloxane (B), and the branched organooxane oligomer (C) A coating liquid was prepared in the same manner as in Example 1 except that the number of hydroquinone groups was changed to a molar ratio of 1.93, and a release film was produced.

[Example 5]

45 parts by mass of polyorganosiloxane (A) used in Example 1, 50 parts by mass of polyorganosiloxane (B), and 5 parts by mass of branched organooxane oligomer (C), crosslinking agent (D) is contained in the crosslinking agent (D) with respect to the number of vinyl groups contained in the polyorganosiloxane (A), the polyorganosiloxane (B), and the branched organooxane oligomer (C) A coating liquid was prepared in the same manner as in Example 1 except that the number of hydroquinone groups was changed to a molar ratio of 1.98, and a release film was produced.

[Embodiment 6]

47.5 parts by mass of polyorganosiloxane (A) and 5 parts by mass of polyorganosiloxane (B) used in Example 1 and 47.5 parts by mass of branched organooxane oligomer (C), crosslinking agent (D) is contained in the crosslinking agent (D) with respect to the number of vinyl groups contained in the polyorganosiloxane (A), the polyorganosiloxane (B), and the branched organooxane oligomer (C) A coating liquid was prepared in the same manner as in Example 1 except that the number of hydroquinone groups was changed to a molar ratio of 1.90, and a release film was produced.

[Embodiment 7]

35 parts by mass of polyorganosiloxane (A) used in Example 1, 30 parts by mass of polyorganosiloxane (B), and branched organooxane oligomer (C) 35 The mass fraction is mixed, and the crosslinking agent (D) is given in terms of the number of vinyl groups contained in the polyorganosiloxane (A), the polyorganosiloxane (B), and the branched organooxane oligomer (C). 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 (D) was changed to a molar ratio of 1.92, and a release film was prepared.

[Embodiment 8]

25 parts by mass of the polyorganosiloxane (A) used in Example 1, 50 parts by mass of polyorganosiloxane (B), and 25 parts by mass of branched organooxane oligomer (C), crosslinking agent (D) is contained in the crosslinking agent (D) with respect to the number of vinyl groups contained in the polyorganosiloxane (A), the polyorganosiloxane (B), and the branched organooxane oligomer (C) A coating liquid was prepared in the same manner as in Example 1 except that the number of hydroquinone groups was changed to a molar ratio of 1.94, and a release film was prepared.

[Embodiment 9]

The polyorganosiloxane (A) 42.75 mass portion, the polyorganosiloxane (B) 5 mass portion used in Example 1 and the branched organooxane oligomer (C) 52.25 mass portions were mixed, and the crosslinking agent was used. (D) is contained in the crosslinking agent (D) with respect to the number of vinyl groups contained in the polyorganosiloxane (A), the polyorganosiloxane (B), and the branched organooxane oligomer (C) A coating liquid was prepared in the same manner as in Example 1 except that the number of hydroquinone groups was changed to a molar ratio of 1.90, and a release film was produced.

[Embodiment 10]

22.5 parts by mass of the polyorganosiloxane (A) used in Example 1, 50 parts by mass of polyorganosiloxane (B), and 27.5 parts by mass of branched organooxane oligomer (C), crosslinking agent (D) is contained in the crosslinking agent (D) with respect to the number of vinyl groups contained in the polyorganosiloxane (A), the polyorganosiloxane (B), and the branched organooxane oligomer (C) The number of hydroquinones becomes Mohiel 1.94 The coating liquid was prepared in the same manner as in Example 1 except that the amount was added to prepare a release film.

[Comparative Example 1]

The mass portion of polyorganosiloxane (A) 27 used in Example 1 and 70 parts by mass of polyorganosiloxane (B) were mixed with 3 mass portions of branched organooxane oligomer (C), and the crosslinking agent was mixed. (D) is contained in the crosslinking agent (D) with respect to the number of vinyl groups contained in the polyorganosiloxane (A), the polyorganosiloxane (B), and the branched organooxane oligomer (C) A coating liquid was prepared in the same manner as in Example 1 except that the number of hydroquinone groups was changed to a molar ratio of 2.06 to prepare a release film.

[Comparative Example 2]

15 parts by mass of polyorganosiloxane (A) used in Example 1, 70 parts by mass of polyorganosiloxane (B), and 15 parts by mass of branched organosiloxane oligomer (C), crosslinking agent (D) is contained in the crosslinking agent (D) with respect to the number of vinyl groups contained in the polyorganosiloxane (A), the polyorganosiloxane (B), and the branched organooxane oligomer (C) A coating liquid was prepared in the same manner as in Example 1 except that the number of hydroquinone groups was changed to a molar ratio of 1.98, and a release film was produced.

[Comparative Example 3]

The polyorganosiloxane (B) used in Example 1 was used, and 90 parts by mass of the polyorganosiloxane (A) was mixed with 10 parts by mass of the branched organomethoxyalkane oligomer (C), and the crosslinking agent was used. (D) The number of hydroquinones contained in the crosslinking agent (D) relative to the number of vinyl groups contained in the polyorganosiloxane (A) and the branched organooxane oligomer (C) becomes a molar ratio of 1.90. The coating liquid was prepared in the same manner as in Example 1 except that the amount was added to prepare a release film.

[Comparative Example 4]

Without using the polyorganosiloxane (A) used in Example 1, the polyorganic 10 parts by mass of the oxoxane (B) is mixed with 90 parts by mass of the branched organooxane oligomer (C), and the crosslinking agent (D) is relative to the polyorganosiloxane (B) and the branched organic argon The coating liquid was prepared in the same manner as in Example 1 except that the number of vinyl groups contained in the alkene oligomer (C) and the number of hydroquinone groups contained in the crosslinking agent (D) were changed to a molar ratio of 1.86, and a release film was prepared.

[Comparative Example 5]

The branched organooxosiloxane oligomer (C) used in Example 1 was used, and the polyorganosiloxane (A) 95 mass portion was mixed with the polyorganosiloxane (B) 5 mass portion, and the crosslinking agent was used. (D) The amount of the hydroquinone contained in the crosslinking agent (D) is not more than the amount of the vinyl group contained in the polyorganosiloxane (A) and the polyorganosiloxane (B). The coating liquid was prepared in the same manner as in Example 1 to prepare a release film.

[Comparative Example 6]

The branched organooxosiloxane oligomer (C) used in Example 1 was used, and 50 parts by mass of the polyorganosiloxane (A) and 50 parts by mass of the polyorganosiloxane (B) were mixed, and the crosslinking agent was used. (D) The amount of the hydroquinone contained in the crosslinking agent (D) is not more than the amount of the vinyl group contained in the polyorganosiloxane (A) and the polyorganosiloxane (B). The coating liquid was prepared in the same manner as in Example 1 to prepare a release film.

[Comparative Example 7]

The polyorganosiloxane (B) and the branched organooxane oligomer (C) used in Example 1 were not used, and only 100 parts by mass of the polyorganosiloxane (A) and the crosslinking agent (D) were used. The number of hydroquinones contained in the crosslinking agent (D) is increased by a molar ratio of 1.90 relative to the number of vinyl groups contained in the polyorganosiloxane (A). Except for the addition, the coating liquid was prepared in the same manner as in Example 1 to prepare a release film.

[Comparative Example 8]

The polyorganosiloxane (A) and the branched organooxane oligomer (C) used in Example 1 were not used, and only 100 parts by mass of the polyorganosiloxane (B) and the crosslinking agent (D) were used. The coating liquid was prepared in the same manner as in Example 1 except that the number of vinyl groups contained in the polyorganosiloxane (B) and the number of alkylhydrazine groups contained in the crosslinking agent (D) were changed to a molar ratio of 3.00. Release the film.

[Test Example 1] (Evaluation of coating properties of ceramic slurry)

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.

From the surface of the release agent layer of the release film (width: 300 nm) which was produced at room temperature for 48 hours, which was produced in the examples and the comparative examples, the ceramic slurry was dried to a thickness of 3 μm 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.

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.

[Test Example 2] (Evaluation of peelability of ceramic green sheets)

The ceramic slurry prepared in the same manner as in Test Example 1 was applied to the surface of the release agent layer of the release film obtained in Test Example 1 by a 25 μm applicator in an amount of 3 μm after drying. Thereafter, it was dried at 80 ° C for 1 minute in a dryer to obtain a release film having a ceramic green sheet.

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, and adhered to the acrylic adhesive having a length of 100 mm from the surface side of the ceramic green sheet. Belt (made by Nitto Denko Co., Ltd., 31B Tape). The sample was fixed to the flat plate in a state in which the surface 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 placed on a peeling tester (AG-IS 500N, manufactured by Shimadzu Corporation). ). 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 measurement was performed 3 times, and the average value thereof was the peeling force of the evaluation object. The results are shown in Table 1.

Since the peeling film for the ceramic green sheet molding has a preferable peeling force of less than 10 mN/100 mm, the peeling force measured is less than 10 mN/100 mm, and it is evaluated as ○, and 10 mN/100 mm or more is evaluated as ×. The results are shown in Table 1.

As is clear from the results shown in Table 1, the release films obtained in Examples 1 to 10 were excellent in coatability of the ceramic slurry, and the ceramic green sheets were peeled off at a very low peeling force, and the peelability of the ceramic green sheets was also improved. excellent. On the other hand, the release film obtained in Comparative Examples 1, 2, and 5 to 8 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. The release film obtained in Comparative Examples 3 and 4 had good peelability of the ceramic green sheet, but the coating property of the ceramic slurry was poor.

[Industrial Availability]

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 forming a ceramic green sheet of the present invention is effective A release film which is excellent in coating property of a ceramic slurry and also excellent in ceramic green sheet peelability.

Claims (12)

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, (B) a polyorganosiloxane having no aryl group and having only an olefin group at both ends, and (C) having no aryl group, having a branched chain having a sulfonium-oxygen structure and having at least 2 olefin groups in one molecule a branched organooxane oligomer, characterized in that the solid content ratio of the polyorganosiloxane (A) is oligomeric with respect to the polyorganosiloxane (A) and the branched organooxane The total amount of the substance (C) is 40 to 98% by mass, and the solid content ratio of the above polyorganosiloxane (B) is relative to the above polyorganosiloxane (A) and the above polyorganosiloxane (B). The total amount of the branched organooxane oligomer (C) is 2 to 60% by mass. The release agent composition according to claim 1, wherein the polyorganosiloxane (A) has a mass average molecular weight of 200,000 to 380,000. The release agent composition according to claim 1 or 2, wherein the polyorganosiloxane (B) has a mass average molecular weight of 300,000 to 500,000. The release agent composition according to claim 1 or 2, wherein the branched organosiloxane oxide oligomer (C) has a mass average molecular weight of 3,000 to 10,000. A release agent composition as described in claim 1 or 2, Further, a platinum group metal compound is contained as a catalyst. The release agent composition according to claim 1 or 2, further comprising a crosslinking agent (D). The release agent composition according to claim 6, 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. The release agent composition according to claim 6, wherein the number of aryl groups contained in the polyorganosiloxane (A) is based on the number of alkyl groups contained in the polyorganosiloxane (A). Mohr ratio is 0.05~0.3. The release agent composition according to claim 6, 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. The release agent composition according to claim 6, wherein the branched organooxane oligomer (C) has an olefin group content relative to the branched organooxane oligomer (C) The number of alkyl groups contained is from 0 to 0.2. The release agent composition according to claim 6, wherein the content of the crosslinking agent (D) 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 branched organooxane oligomer (C) and the number of hydrosilyl groups contained in the crosslinking agent (D) are in an amount of from 1.0 to 5.0. A release film for molding 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 a release agent as described in claim 1 or 2 Composition Adult.