WO2012132682A1 - Composition d'agent de démoulage et film de démoulage pour moule à feuille de céramique crue - Google Patents

Composition d'agent de démoulage et film de démoulage pour moule à feuille de céramique crue Download PDF

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Publication number
WO2012132682A1
WO2012132682A1 PCT/JP2012/054536 JP2012054536W WO2012132682A1 WO 2012132682 A1 WO2012132682 A1 WO 2012132682A1 JP 2012054536 W JP2012054536 W JP 2012054536W WO 2012132682 A1 WO2012132682 A1 WO 2012132682A1
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Prior art keywords
polyorganosiloxane
release agent
agent composition
group
groups contained
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PCT/JP2012/054536
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English (en)
Japanese (ja)
Inventor
慎也 市川
知巳 深谷
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リンテック株式会社
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Priority to KR1020137026700A priority Critical patent/KR101908391B1/ko
Priority to CN201280015624.XA priority patent/CN103476896B/zh
Publication of WO2012132682A1 publication Critical patent/WO2012132682A1/fr

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Classifications

    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • 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
    • 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

Definitions

  • the present invention relates to a release agent composition and a release film for molding a ceramic green sheet using the release agent composition.
  • 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 applying a ceramic slurry containing a ceramic material such as barium titanate or titanium oxide on a release film.
  • a ceramic slurry containing a ceramic material such as barium titanate or titanium oxide
  • a release film a film substrate in which a silicone-based compound such as polysiloxane is released is used (Patent Documents 1 to 8).
  • the peelable film is required to have a peelability capable of peeling a thin ceramic green sheet molded on the peelable film without breaking the peelable film.
  • the thickness of the ceramic green sheet is reduced to 3 ⁇ m or less after drying, when the ceramic slurry is applied and dried, the coating end portion of the ceramic slurry contracts, and the thickness of the coating end portion is reduced. So-called end shrinkage, pinholes, or uneven coating easily occur. Further, when the molded ceramic green sheet is peeled from the release film, problems such as breakage due to a decrease in strength of the ceramic green sheet are likely to occur.
  • ceramic green sheets differ in materials such as inorganic substances, binder resins, dispersants, organic solvents, etc., depending on the intended use, and the coating properties of the ceramic slurry on the release film depend on the type of ceramic slurry. Change. Therefore, it has been difficult for the release film to achieve both the coating performance of the ceramic slurry and the release performance of the ceramic green sheet.
  • the present invention has been made in view of such a situation, and it is excellent in the coating property of the ceramic slurry and the release film for forming a ceramic green sheet which is also excellent in the peelability of the ceramic green sheet, and the release film.
  • An object is to provide a suitable release agent composition.
  • the present invention provides a polyorganosiloxane having at least two alkenyl groups in one molecule and aryl groups on both side chains of at least one silicon atom in the siloxane skeleton.
  • A polyorganosiloxane
  • B polyorganosiloxane
  • C branched organosiloxane oligomer
  • the organosiloxane (A) has a solid component ratio of 40 to 98% by mass
  • the polyorganosiloxane (A) A release agent composition, wherein a solid component ratio of the polyorganosiloxane (B) to the total amount of the polyorganosiloxane (B) and the branched organosiloxane oligomer (C) is 2 to 60% by mass.
  • a solid component ratio of the polyorganosiloxane (B) to the total amount of the polyorganosiloxane (B) and the branched organosiloxane oligomer (C) is 2 to 60% by mass.
  • the ceramic slurry is excellent in coating properties. Specifically, the ceramic slurry is applied to the surface of the release agent layer. When dried, the coating end portion of the ceramic slurry contracts and the thickness of the coating end portion increases, so-called end portion contraction is suppressed. Moreover, according to the said peeling film, it is excellent also in the peelability of the shape
  • the polyorganosiloxane (A) preferably has a mass average molecular weight of 100,000 to 800,000 (Invention 2).
  • the polyorganosiloxane (B) preferably has a mass average molecular weight of 50,000 to 800,000 (Invention 3).
  • the branched organosiloxane oligomer (C) preferably has a mass average molecular weight of 1,000 to 50,000 (Invention 4).
  • the number of alkenyl groups contained in the polyorganosiloxane (A) is 0.005 to 0 in molar ratio to the number of alkyl groups contained in the polyorganosiloxane (A). 1 is preferable (Invention 7).
  • the number of the aryl groups which the said polyorganosiloxane (A) contains is 0.01 by molar ratio with respect to the number of the alkyl groups which the said polyorganosiloxane (A) contains. It is preferably 0.5 to 0.5 (Invention 8).
  • the number of alkenyl groups contained in the polyorganosiloxane (B) is 0.0005 in molar ratio to the number of alkyl groups contained in the polyorganosiloxane (B). Is preferably 0.01 (Invention 9).
  • the number of alkenyl groups contained in the branched organosiloxane oligomer (C) is a molar ratio with respect to the number of alkyl groups contained in the branched organosiloxane oligomer (C). It is preferably 0.05 to 0.35 (Invention 10).
  • the content of the crosslinking agent (D) in the release agent composition is such that the polyorganosiloxane (A), the polyorganosiloxane (B), and the branched organosiloxane oligomer (C It is preferable that the number of hydrosilyl groups contained in the crosslinking agent (D) is 1.0 to 5.0 in molar ratio with respect to the number of alkenyl groups contained in (Invention 11).
  • the present invention is a release film for molding a ceramic green sheet, comprising a base material and a release agent layer formed on at least one surface of the base material, wherein the release agent layer is A release film for molding a ceramic green sheet, characterized by being formed using a release agent composition (Invention 1 to 11) (Invention 12).
  • the coating property of the ceramic slurry is excellent.
  • the coating end portion of the ceramic slurry contracts and the thickness of the coating end portion increases, so-called end contraction is suppressed.
  • the formed ceramic green sheet is also excellent in releasability and has a very low release. The ceramic green sheet can be peeled from the release agent layer by force.
  • the release agent composition is A polyorganosiloxane (A) having at least two alkenyl groups in one molecule and having aryl groups on both side chains of at least one silicon atom in the siloxane skeleton; A polyorganosiloxane (B) having no aryl group and having an alkenyl group only at both ends in one molecule; A branched organosiloxane oligomer (C) having no aryl group, having a branched chain containing an organosiloxane skeleton, and having at least two alkenyl groups in one molecule; Preferably, it further contains a crosslinking agent (D) and / or a catalyst (E).
  • a crosslinking agent D
  • E a catalyst
  • the polyorganosiloxane (A) is a polymer of a silicon-containing compound represented by the following general formula (a).
  • R 1 and R 2 are alkyl groups having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an octyl group.
  • R 1 and R 2 may be the same or different.
  • R 1 and R 2 are preferably methyl groups.
  • m is an integer of 1 or more.
  • R 3 and R 4 are aryl groups, and R 3 and R 4 may be the same or different, but are preferably the same.
  • polyorganosiloxane (A) will have an aryl group in the both side chain of the silicon atom in a siloxane skeleton.
  • the release agent composition is applied to the substrate, the polyorganosiloxane (A) is unevenly distributed on the substrate side of the release agent layer with respect to the polyorganosiloxane (B) in the resulting release agent layer.
  • the effects described later can be obtained.
  • aryl group examples include a phenyl group, a benzyl group, a tolyl group, and an o-xylyl group, and among them, a phenyl group is preferable.
  • n is an integer of 1 or more or 2 or more.
  • At least two of R 5 to R 8 are alkenyl groups, that is, at least two in one molecule are alkenyl groups.
  • both R 7 and R 8 may be an alkenyl group (n is 1 or more), one of R 7 and R 8 is an alkenyl group, and one or both of R 5 and R 6 are alkenyl groups (N is 1 or more), R 7 and R 8 are functional groups other than alkenyl groups, and both R 5 and R 6 are alkenyl groups (n is 1 or more), or R One of 5 and R 6 may be an alkenyl group (n is 2 or more). Note that both R 5 and R 6 may be alkenyl groups and one of R 5 and R 6 may be alkenyl groups.
  • Each R 5 may be the same or different. Also, each R 6 may be the same or different.
  • alkenyl group examples include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group, and among them, a vinyl group is particularly preferable.
  • the functional group other than the alkenyl group in R 5 and R 6 is an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an octyl group. Preferably, it is a methyl group.
  • Examples of the functional group other than the alkenyl group in R 7 and R 8 include the same alkyl group, silanol group, hydrosilyl group, and the like as R 5 and R 6 .
  • the number of aryl groups contained in the polyorganosiloxane (A) is preferably 0.01 to 0.5 in terms of molar ratio with respect to the number of alkyl groups contained in the polyorganosiloxane (A), particularly 0. .05 to 0.3 is preferable.
  • the number of aryl groups is within this range, when the release agent composition is applied to the substrate, the polyorganosiloxane (A) is released from the polyorganosiloxane (B) in the resulting release agent layer. It is considered that it is unevenly distributed on the base material side of the agent layer, thereby obtaining the effects described later.
  • the number of alkenyl groups contained in the polyorganosiloxane (A) is preferably 0.005 to 0.1 in terms of molar ratio with respect to the number of alkyl groups contained in the polyorganosiloxane (A). In particular, it is preferably 0.01 to 0.05.
  • the number of alkenyl groups is 2 or more in one molecule, and further within the above range, a crosslinked structure having a high crosslinking density that contributes to the effects described later can be formed.
  • the mass average molecular weight of the polyorganosiloxane (A) needs to be 100,000 to 800,000, preferably 150,000 to 600,000, particularly preferably 200,000 to 380000.
  • the mass mean molecular weight in this specification is the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method.
  • the polyorganosiloxane (A) has a mass average molecular weight of less than 100,000, when the release agent composition is applied to a substrate, repelling occurs and the coatability is inferior, and it is difficult to obtain a uniform surface state. Become. Moreover, when the mass average molecular weight of polyorganosiloxane (A) exceeds 800000, the viscosity of a release agent composition will rise and the solubility to a dilution solvent will become difficult.
  • the polyorganosiloxane (B) is a polymer of a silicon-containing compound represented by the following general formula (b).
  • R 9 and R 10 are each 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, and an octyl group, and is an aryl group or an alkenyl group. must not.
  • R 9 and R 10 may be the same or different.
  • R 9 and R 10 are preferably methyl groups.
  • this polyorganosiloxane (B) does not have an aryl group, when the release agent composition is applied to a substrate, the polyorganosiloxane (B) in the resulting release agent layer is polyorganosiloxane (A). ) Is unevenly distributed on the side opposite to the base material of the release agent layer (the surface side of the release agent layer), and it is considered that the effect described later is obtained.
  • At least one of R 11 is an alkenyl group
  • at least one of R 12 is an alkenyl group. That is, the polyorganosiloxane (B) has alkenyl groups at both ends.
  • the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group.
  • a vinyl group is particularly preferable.
  • the functional group other than the alkenyl group in R 12 is an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an octyl group. Is a methyl group.
  • Each R 11 may be the same or different.
  • each R 12 may be the same or different.
  • the polyorganosiloxane (B) Since the polyorganosiloxane (B) has an alkenyl group only at both ends in one molecule, a crosslinked structure having a low crosslinking density that contributes to the effects described later can be formed.
  • the number of alkenyl groups contained in the polyorganosiloxane (B) is preferably 0.0005 to 0.01 in terms of molar ratio with respect to the number of alkyl groups contained in the polyorganosiloxane (B). It is preferably 0.001 to 0.005.
  • the mass average molecular weight of the polyorganosiloxane (B) is preferably 50,000 to 800,000, particularly preferably 100,000 to 700,000, and more preferably 300,000 to 500,000.
  • the mass average molecular weight of the polyorganosiloxane (B) is less than 50000, it may be difficult to form a crosslinked structure having a low crosslinking density that contributes to the effects described below.
  • the mass average molecular weight of polyorganosiloxane (B) exceeds 800000, there exists a possibility that the viscosity of a releasing agent composition may rise and it may become difficult to melt
  • the branched organosiloxane oligomer (C) is an organosiloxane oligomer having a branched chain containing an organosiloxane skeleton, and is represented by the following general formula (c).
  • R is not an aryl group, and at least two of R are alkenyl groups.
  • alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group.
  • a vinyl group is particularly preferable.
  • the functional group other than the alkenyl group in R is an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an octyl group. It is a methyl group.
  • Each R may be the same or different.
  • the resulting release agent layer contains polyorganosiloxane (A). It is unevenly distributed on the base material side of the release agent layer, and does not prevent the polyorganosiloxane (B) from being unevenly distributed on the side opposite to the base material of the release agent layer (the surface side of the release agent layer). can get.
  • the branched organosiloxane oligomer (C) has at least two alkenyl groups in one molecule, but the site where the alkenyl group exists may be a main chain or a branched chain. There may be both of them.
  • the number of alkenyl groups contained in the branched organosiloxane oligomer (C) is 0.05 to 0.35 in molar ratio with respect to the number of alkyl groups contained in the branched organosiloxane oligomer (C). Particularly preferred is 0.1 to 0.2.
  • the number of alkenyl groups is 2 or more in one molecule, and further within the above range, a crosslinked structure having a crosslinking density that contributes to the effects described later can be formed.
  • the mass average molecular weight of the branched organosiloxane oligomer (C) is preferably 1000 to 50000, particularly preferably 2000 to 30000, and further preferably 3000 to 10000.
  • the weight average molecular weight of the branched organosiloxane oligomer (C) is less than 1000, the viscosity of the coating solution of the release agent composition may be reduced. In that case, when the release agent composition is applied, There is a possibility that repelling or the like occurs and it becomes difficult to obtain a uniform coated surface. Moreover, when the mass average molecular weight of the branched organosiloxane oligomer (C) exceeds 50000, it may be difficult to form a crosslinked structure having a crosslinking density that contributes to the effects described below.
  • the solid component ratio of the polyorganosiloxane (A) to the total amount of the polyorganosiloxane (A) and the branched organosiloxane oligomer (C) is 40 to 98% by mass, preferably 45 to 95% by mass, more Preferably, it is 50 to 90% by mass.
  • the solid component ratio of the polyorganosiloxane (B) to the total amount of the polyorganosiloxane (A), polyorganosiloxane (B) and branched organosiloxane oligomer (C) is 2 to 60% by mass, preferably It is 2 to 55% by mass, and more preferably 5 to 50% by mass.
  • the crosslinking agent (D) is not particularly limited as long as it can crosslink the polyorganosiloxane (A), polyorganosiloxane (B), or branched organosiloxane oligomer (C), but the polyorganosiloxane (A) ), Polyorganosiloxane (B) and branched organosiloxane oligomer (C) other than polyorganosiloxane having hydrogen atoms bonded to at least two silicon atoms in one molecule are preferable.
  • polyorganosiloxane examples include dimethylhydrogensiloxy group end-capped dimethylsiloxane-methylhydrogensiloxane copolymer, trimethylsiloxy group end-capped dimethylsiloxane-methylhydrogensiloxane copolymer, and trimethylsiloxy group end-capped methylhydrol.
  • polyorganohydrogensiloxanes such as genpolysiloxane and poly (hydrogensilsesquioxane).
  • the mass average molecular weight of the polyorganosiloxane as the crosslinking agent (D) is preferably 500 to 5,000, particularly preferably 500 to 2,000.
  • the content of the crosslinking agent (D) in the release agent composition according to this embodiment is the number of alkenyl groups contained in the polyorganosiloxane (A), the polyorganosiloxane (B), and the branched organosiloxane oligomer (C).
  • the number of crosslinkable functional groups such as hydrosilyl groups contained in the crosslinking agent (D) is preferably 1.0 to 5.0 in terms of molar ratio, particularly 1.5 to 3.
  • the amount is preferably 0, more preferably 1.8 to 2.0.
  • the crosslinking agent (D) can impart stable release properties to the resulting release agent layer by crosslinking the polyorganosiloxane (A), polyorganosiloxane (B) or branched organosiloxane oligomer (C). it can.
  • the catalyst (E) is not particularly limited as long as it can cure the release agent composition according to this embodiment, but among them, a platinum group metal compound is preferable.
  • the platinum group metal compounds include fine platinum, fine platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, palladium, rhodium and the like. .
  • the release agent composition contains such a catalyst (E)
  • the curing reaction of the release agent composition can proceed more efficiently.
  • the content of the catalyst (E) in the release agent composition according to this embodiment is preferably about 1 to 1000 ppm with respect to the total amount of components other than the catalyst (E).
  • the release agent composition according to this embodiment may contain a reaction inhibitor, an adhesion improver, and the like in addition to the components (A) to (E).
  • the release agent composition described above contains the polyorganosiloxane (A), polyorganosiloxane (B), and branched organosiloxane oligomer (C) in a predetermined blending ratio, thereby improving the coating properties of the ceramic slurry.
  • A polyorganosiloxane
  • B polyorganosiloxane
  • C branched organosiloxane oligomer
  • the ceramic green sheet can be released from the release agent layer with a very low release force without causing defects such as cracks and breakage. Can do.
  • the polyorganosiloxane (A) has an aryl group as described above and the polyorganosiloxane (B) has an alkenyl group only at both ends, the polyorganosiloxane (A) It is expected that the polyorganosiloxane (B) is unevenly distributed on the base material side of the release agent layer, and the polyorganosiloxane (B) is unevenly distributed on the surface layer side of the release agent layer, and as a result, an effect of suppressing edge shrinkage, pinholes, coating unevenness, etc. is obtained. Conceivable.
  • the crosslink density in the release agent layer is increased.
  • the ceramic green sheet is thinned, the ceramic green sheet is peeled off without breaking. It becomes possible.
  • a release film for molding a ceramic green sheet according to the present embodiment (hereinafter sometimes simply referred to as “release film”) includes a base material and a release agent layer formed on one surface of the base material.
  • the base material is not particularly limited, and any one of conventionally known materials can be appropriately selected and used.
  • a substrate include films made of polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polypropylene and polymethylpentene, polycarbonates, and plastics such as polyvinyl acetate. It may be a multilayer of two or more of the same or different types. Among these, a polyester film is preferable, a polyethylene terephthalate film is particularly preferable, and a biaxially stretched polyethylene terephthalate film is more preferable.
  • the polyethylene terephthalate film hardly generates dust or the like during processing or use, for example, it is possible to effectively prevent a ceramic slurry coating failure due to dust or the like. Furthermore, the effect which prevents a coating defect etc. can be heightened by performing an antistatic process to a polyethylene terephthalate film.
  • a surface treatment by an oxidation method or a concavo-convex method or a primer treatment is performed on one side or both sides as desired.
  • the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, and the like.
  • Examples include a thermal spraying method.
  • the thickness of the substrate is usually 10 to 300 ⁇ m, preferably 15 to 200 ⁇ m, and particularly preferably 20 to 125 ⁇ m.
  • the release agent layer in this embodiment is formed by the release agent composition described above. Specifically, the release agent layer is formed by applying a release agent composition and a coating solution containing an organic solvent, if desired, on one surface of the base material, followed by drying and curing.
  • a coating method for example, gravure coating method, bar coating method, spray coating method, spin coating method, knife coating method, roll coating method, die coating method and the like can be used.
  • the organic solvent is not particularly limited, and various types can be used.
  • hydrocarbon compounds such as toluene, hexane, heptane, acetone, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof are used.
  • the release agent composition coated as described above is preferably thermoset.
  • the heating temperature is preferably 90 to 140 ° C.
  • the heating time is preferably about 10 to 120 seconds.
  • the thickness of the release agent layer is not particularly limited, but is preferably 0.01 to 3 ⁇ m, and more preferably 0.03 to 1 ⁇ m.
  • the thickness of the release agent layer is less than 0.01 ⁇ m, the function as the release agent layer may not be sufficiently exhibited depending on the material constituting the release agent layer.
  • the thickness of the release agent layer exceeds 3 ⁇ m, blocking may occur when the release film is wound up in a roll shape, resulting in problems in feeding.
  • a ceramic green sheet is formed by applying a ceramic slurry to the surface of the release agent layer and drying using a slot die coating method, a doctor blade method, or the like.
  • the coating end of the ceramic slurry contracts, the thickness of the coating end increases, so-called end contraction is suppressed, and a pinhole is also generated. And the occurrence of coating unevenness are also suppressed.
  • even when a thin ceramic green sheet with low strength is molded into a release agent layer it does not cause defects such as cracks and breakage, and has a very low peel force, specifically a peel force of less than 10 mN / 100 mm.
  • the ceramic green sheet can be peeled from the release agent layer.
  • the peeling film which concerns on this embodiment, while being excellent in the coating property of a ceramic slurry, it is very excellent also in the peeling property of a ceramic green sheet.
  • another layer such as an antistatic layer may be provided between the surface of the substrate 1 opposite to the release agent layer and between the substrate 1 and the release agent layer.
  • Example 1 The portion having two or more vinyl groups in one molecule and having no vinyl group has 90.25 parts by mass of polyorganosiloxane (A) made of a dimethylsiloxane-diphenylsiloxane copolymer, and has an aryl group.
  • A polyorganosiloxane
  • polyorganosiloxane (B) having vinyl groups only at both ends in one molecule and other functional groups being methyl groups, and having no aryl group and containing an organosiloxane skeleton
  • the trimethylsiloxy is mixed with 4.75 parts by mass of a branched organosiloxane oligomer (C) having a branched chain and having two or more vinyl groups in one molecule and the other functional groups being methyl groups.
  • the solid component ratio (mass%) of polyorganosiloxane (A) with respect to the total amount of polyorganosiloxane (A) and branched organosiloxane oligomer (C), and polyorganosiloxane (A) and polyorganosiloxane (B) Table 1 shows the solid component ratio (% by mass) of the polyorganosiloxane (B) with respect to the total amount of the branched organosiloxane oligomer (C).
  • the mass average molecular weight of the polyorganosiloxane (A) is 360,000, and the number of phenyl groups contained in the polyorganosiloxane (A) is based on the number of methyl groups contained in the polyorganosiloxane (A).
  • the molar ratio was 0.125, and the number of vinyl groups contained in the polyorganosiloxane (A) was 0.025 in molar ratio with respect to the number of methyl groups contained in the polyorganosiloxane (A). .
  • the mass average molecular weight of the polyorganosiloxane (B) is 440000, and the number of vinyl groups contained in the polyorganosiloxane (B) is in molar ratio to the number of methyl groups contained in the polyorganosiloxane (B). 0.0024.
  • the weight average molecular weight of the branched organosiloxane oligomer (C) is 6000, and the number of vinyl groups contained in the branched organosiloxane oligomer (C) is equal to the number of methyl groups contained in the branched organosiloxane oligomer (C). On the other hand, the molar ratio was 0.13.
  • the weight average molecular weight of the crosslinking agent (D) is 1000, and the content of the crosslinking agent (D) in the release agent composition is polyorganosiloxane (A), polyorganosiloxane (B), and branched organosiloxane.
  • the number of hydrosilyl groups contained in the crosslinking agent (D) was 1.91 in a molar ratio with respect to the number of vinyl groups contained in the oligomer (C).
  • Example 2 47.5 parts by mass of the polyorganosiloxane (A) used in Example 1, 50 parts by mass of the polyorganosiloxane (B), and 2.5 parts by mass of the branched organosiloxane oligomer (C) were mixed, and a crosslinking agent.
  • the coating liquid was prepared like Example 1 and the peeling film was produced.
  • Example 3 85.5 parts by mass of the polyorganosiloxane (A) used in Example 1, 5 parts by mass of the polyorganosiloxane (B), and 9.5 parts by mass of the branched organosiloxane oligomer (C) were mixed, and a crosslinking agent.
  • the coating liquid was prepared like Example 1 and the peeling film was produced.
  • Example 4 63 parts by mass of the polyorganosiloxane (A) used in Example 1, 30 parts by mass of the polyorganosiloxane (B), and 7 parts by mass of the branched organosiloxane oligomer (C) were mixed, and the crosslinking agent (D) was added.
  • the number of hydrosilyl groups contained in the crosslinking agent (D) with respect to the number of vinyl groups contained in the polyorganosiloxane (A), polyorganosiloxane (B) and branched organosiloxane oligomer (C) is a molar ratio.
  • a coating solution was prepared in the same manner as in Example 1 except that it was added to 1.93 to prepare a release film.
  • Example 5 45 parts by mass of the polyorganosiloxane (A) used in Example 1, 50 parts by mass of the polyorganosiloxane (B), and 5 parts by mass of the branched organosiloxane oligomer (C) are mixed, and the crosslinking agent (D) is added.
  • the number of hydrosilyl groups contained in the crosslinking agent (D) with respect to the number of vinyl groups contained in the polyorganosiloxane (A), polyorganosiloxane (B) and branched organosiloxane oligomer (C) is a molar ratio.
  • a coating solution was prepared in the same manner as in Example 1 except that it was added to 1.98 to prepare a release film.
  • Example 6 47.5 parts by mass of the polyorganosiloxane (A) used in Example 1, 5 parts by mass of the polyorganosiloxane (B), and 47.5 parts by mass of the branched organosiloxane oligomer (C) were mixed, and a crosslinking agent.
  • the coating liquid was prepared like Example 1 and the peeling film was produced.
  • Example 7 35 parts by mass of the polyorganosiloxane (A) used in Example 1, 30 parts by mass of the polyorganosiloxane (B), and 35 parts by mass of the branched organosiloxane oligomer (C) are mixed, and the crosslinking agent (D) is added.
  • the number of hydrosilyl groups contained in the crosslinking agent (D) with respect to the number of vinyl groups contained in the polyorganosiloxane (A), polyorganosiloxane (B) and branched organosiloxane oligomer (C) is a molar ratio.
  • a coating solution was prepared in the same manner as in Example 1 except that it was added to 1.92 to prepare a release film.
  • Example 8 25 parts by mass of the polyorganosiloxane (A) used in Example 1, 50 parts by mass of the polyorganosiloxane (B), and 25 parts by mass of the branched organosiloxane oligomer (C) are mixed, and the crosslinking agent (D) is added.
  • the number of hydrosilyl groups contained in the crosslinking agent (D) with respect to the number of vinyl groups contained in the polyorganosiloxane (A), polyorganosiloxane (B) and branched organosiloxane oligomer (C) is a molar ratio.
  • a coating solution was prepared in the same manner as in Example 1 except that it was added to 1.94 to prepare a release film.
  • Example 9 42.75 parts by mass of the polyorganosiloxane (A) used in Example 1, 5 parts by mass of the polyorganosiloxane (B), and 52.25 parts by mass of the branched organosiloxane oligomer (C) are mixed, and a crosslinking agent.
  • the coating liquid was prepared like Example 1 and the peeling film was produced.
  • Example 10 22.5 parts by mass of the polyorganosiloxane (A) used in Example 1, 50 parts by mass of the polyorganosiloxane (B), and 27.5 parts by mass of the branched organosiloxane oligomer (C) were mixed, and a crosslinking agent.
  • the coating liquid was prepared like Example 1 and the peeling film was produced.
  • a die coater (width) is formed on the surface of the release agent layer of a release film (width: 300 mm) that has been manufactured in Examples and Comparative Examples and stored at room temperature for 48 hours so that the film thickness after drying the ceramic slurry becomes 3 ⁇ m. 250 mm), and then dried at 80 ° C. for 1 minute in a dryer. In this way, a 300 m release film roll with ceramic green was produced.
  • Test Example 2 Evaluation of green sheet peelability
  • the ceramic slurry prepared in the same manner as in Test Example 1 is applied to the surface of the release agent layer of the release film obtained in the same manner as in Test Example 1 using a 25 ⁇ m applicator so that the film thickness after drying is 3 ⁇ m. Worked. Then, it was made to dry at 80 degreeC with a dryer for 1 minute, and the peeling film with a ceramic green was obtained.
  • the obtained release film with ceramic green was allowed to stand in an atmosphere of room temperature 23 degrees and humidity 50% for 24 hours, and then cut into a size of 100 mm ⁇ 100 mm.
  • a 100 mm acrylic adhesive tape (manufactured by Nitto Denko, 31B tape) was attached. This sample was fixed to the flat plate so that the peelable film surface side was in contact with the flat plate, and the peel side was tilted to 45 ° with the end side to which the acrylic adhesive tape was applied facing down, and a peel tester (manufactured by Shimadzu Corporation, AG-IS). 500N). And the peeling film of the edge which stuck the acrylic adhesive tape was peeled from the ceramic green sheet, and the acrylic adhesive tape side was attached to the jig
  • the release films obtained in Examples 1 to 10 are excellent in the coating properties of the ceramic slurry and can peel the ceramic green sheet with a very low peeling force.
  • the ceramic green sheet was excellent in releasability.
  • the release films obtained in Comparative Examples 1, 2, 5 to 8 were excellent in the coating properties of the ceramic slurry, but could release the ceramic green sheet only with a relatively high release force. It was inferior to the peelability of the ceramic green sheet.
  • the peeling film obtained by Comparative Examples 3 and 4 was excellent in the peelability of a ceramic green sheet, it was inferior to the coating property of a ceramic slurry.
  • the release agent composition of the present invention is suitable for forming a release agent layer of a release film for forming a ceramic green sheet.
  • the release film for molding a ceramic green sheet of the present invention is useful as a release film that is excellent in the coating property of the ceramic slurry and very excellent in the peelability of the ceramic green sheet.

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  • Medicinal Chemistry (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

L'invention concerne une composition d'agent de démoulage contenant un organopolysiloxane (A) présentant au moins deux groupes alcényle dans une molécule et un groupe aryle sur chaque chaîne latérale d'au moins un atome de silicium dans un squelette de siloxane; un organopolysiloxane (B) ayant un groupe alcényle uniquement aux deux extrémités dans une molécule et n'ayant pas de groupe aryle; et un oligomère organosiloxane ramifié (C) n'ayant pas de groupe aryle mais une chaîne ramifiée contenant un squelette d'organosiloxane et au moins deux groupes alcényle dans une molécule. Le rapport de constituants solides d'organopolysiloxane (A) par rapport à la quantité totale d'organopolysiloxane (A) et d'oligomère organosiloxane ramifié (C) est de 40 à 98 % en masse; et le rapport de constituants solides d'organopolysiloxane (B) par rapport à la quantité totale d'organopolysiloxane (A), d'organopolysiloxane (B) et d'oligomère organosiloxane ramifié (C) est de 2 à 60 % en masse.
PCT/JP2012/054536 2011-03-29 2012-02-24 Composition d'agent de démoulage et film de démoulage pour moule à feuille de céramique crue WO2012132682A1 (fr)

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WO2015030262A1 (fr) * 2013-08-28 2015-03-05 Dow Corning Toray Co., Ltd. Composition durcissable de silicone, son produit durci, et dispositif semi-conducteur optique

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TWI599490B (zh) * 2013-01-18 2017-09-21 財團法人工業技術研究院 離形層、應用其之可撓式裝置及可撓式基板的製造方法
JP6091287B2 (ja) * 2013-03-28 2017-03-08 リンテック株式会社 グリーンシート製造用剥離フィルム
TWI651376B (zh) * 2013-11-11 2019-02-21 道康寧東麗股份有限公司 可固化有機聚矽氧烷組合物及與使用其之介電陶瓷層形成材料所共同使用的離型膜
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CN106103635A (zh) * 2014-03-19 2016-11-09 琳得科株式会社 剥离剂组合物、剥离薄膜、剥离薄膜的卷绕体及该卷绕体的制造方法
JP6285778B2 (ja) * 2014-03-31 2018-02-28 リンテック株式会社 剥離シート及び剥離シートの製造方法
JP6519267B2 (ja) * 2015-03-27 2019-05-29 東レフィルム加工株式会社 離型フィルム
WO2018012296A1 (fr) * 2016-07-11 2018-01-18 信越化学工業株式会社 Composition de silicone, papier antiadhésif et film antiadhésif
KR102572480B1 (ko) 2017-03-01 2023-08-30 도요보 가부시키가이샤 세라믹 그린 시트 제조용 이형 필름 및 그의 제조 방법
CN110382186A (zh) * 2017-03-09 2019-10-25 琳得科株式会社 生片形成用剥离膜
JP6477989B1 (ja) * 2017-08-24 2019-03-06 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
JP6813124B2 (ja) 2018-09-03 2021-01-13 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
JP7176990B2 (ja) * 2019-03-27 2022-11-22 リンテック株式会社 剥離剤組成物の塗布液およびセラミックグリーンシート製造工程用剥離フィルムの製造方法

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WO2015030262A1 (fr) * 2013-08-28 2015-03-05 Dow Corning Toray Co., Ltd. Composition durcissable de silicone, son produit durci, et dispositif semi-conducteur optique
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