WO2024116437A1 - Release film for producing ceramic green sheet - Google Patents
Release film for producing ceramic green sheet Download PDFInfo
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- WO2024116437A1 WO2024116437A1 PCT/JP2023/020428 JP2023020428W WO2024116437A1 WO 2024116437 A1 WO2024116437 A1 WO 2024116437A1 JP 2023020428 W JP2023020428 W JP 2023020428W WO 2024116437 A1 WO2024116437 A1 WO 2024116437A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ceramic green
- producing
- green sheet
- substrate
- agent layer
- Prior art date
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Images
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
Definitions
- the present invention relates to a release film for producing ceramic green sheets, and more specifically, to a release film for producing ceramic green sheets that allows easy peeling of the green sheets, effectively prevents contamination of the green sheets, and is particularly suitable for use in the manufacture of ceramic products that require high positional accuracy in the manufacture of laminated ceramic capacitors, multilayer ceramic substrates, and the like.
- a release film for producing a ceramic green sheet has been used.
- a ceramic green sheet is formed on a release film for producing a ceramic green sheet, and a plurality of the obtained ceramic green sheets are stacked and fired.
- the miniaturization and multilayering of multilayer ceramic capacitors and multilayer ceramic substrates are progressing.
- the ceramic green sheet is required to be thin, and from the viewpoint of preventing defects such as pinholes and uneven thickness in the thinned ceramic green sheet and effectively suppressing breakage when the thinned ceramic green sheet is peeled off from the release film, a release film for producing ceramic green sheets has been proposed, which has a substrate and a release agent layer of a specific component, and the arithmetic mean roughness (Ra) and maximum protrusion height (Rp) on the surface opposite to the substrate of the release agent layer are each equal to or less than a predetermined value, and the arithmetic mean roughness (Ra) and maximum protrusion height (Rp) on the surface opposite to the substrate of the release agent layer are each within a predetermined numerical range (see, for example, Patent Document 1).
- the present invention aims to provide a release film for producing ceramic green sheets, which has a base material and a release agent layer, and which allows easy peeling of the green sheet while effectively suppressing contamination of the green sheet.
- the present invention provides: [1] A release film for producing a ceramic green sheet, comprising a substrate and a release agent layer provided on at least one side of the substrate,
- the present invention relates to the release film for producing a ceramic green sheet, wherein the polar component ( ⁇ sp ) of the surface free energy of the release agent layer on the side opposite to the substrate is 0.3 (mN/m) or more.
- [2] to [12] are each a preferred aspect or embodiment of the present invention.
- the curable composition further contains a film-forming compound (a3) having two or more (meth)acryloyl groups in one molecule.
- [10] a) applying a ceramic slurry onto the release film for producing a ceramic green sheet according to any one of [1] to [8]; b) forming a ceramic green sheet from the ceramic slurry applied in the step a); and c) peeling the ceramic green sheet formed in the step b) from the release film for producing a ceramic green sheet.
- the method for producing a ceramic green sheet comprising the steps of: [11] A method for producing a ceramic product, comprising the step of producing a ceramic green sheet by the method for producing a ceramic green sheet according to [10]. [12] The method for producing a ceramic product according to [11], wherein the ceramic product is a multilayer ceramic capacitor or a multilayer ceramic substrate.
- the release film for producing ceramic green sheets of the present invention allows easy release of the ceramic green sheets formed thereon, while also effectively suppressing contamination of the ceramic green sheets, simultaneously achieving a high level of technical effects with high practical value that surpass the limits of conventional technology, and can be suitably used in the production of various ceramic products.
- it is particularly suitable for use in the production of ceramic products such as multilayer ceramic capacitors and multilayer ceramic substrates, which are made up of thin ceramic layers and require high positional precision during production.
- FIG. 1 is a schematic diagram showing one embodiment of a release film for producing a ceramic green sheet.
- the present invention provides a release film for producing a ceramic green sheet, comprising a substrate and a release agent layer provided on at least one side of the substrate,
- the polar component ( ⁇ sp ) of the surface free energy of the release agent layer on the side opposite to the substrate is 0.3 (mN/m) or more. That is, the release film for producing a ceramic green sheet of the present invention has a substrate and a release agent layer.
- the release film for producing a ceramic green sheet of the present invention only needs to have a substrate and a release agent layer, and may or may not have other layers. Therefore, the release film for producing a ceramic green sheet of the present invention may be composed of only a substrate and a release agent layer, or may have other layers such as an antistatic layer in addition to the substrate and the release agent layer.
- Substrate there is no particular restriction on the substrate constituting the release film for producing ceramic green sheets of the present invention, and any substrate can be appropriately selected from those conventionally known as substrates in the technical field.
- substrates include films made of plastics such as polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polypropylene and polymethylpentene, polycarbonate, and ethylene-vinyl acetate copolymers, and may be single-layered or multi-layered of two or more layers of the same or different kinds.
- polyester films are preferred, and polyethylene terephthalate films are particularly preferred, and biaxially stretched polyethylene terephthalate films are even more preferred.
- Polyethylene terephthalate films are less likely to generate dust during processing, use, etc., and therefore, for example, ceramic slurry coating defects due to dust, etc. can be effectively prevented.
- this substrate may be subjected to a surface treatment such as an oxidation method or a primer treatment in order to improve adhesion to a release agent layer provided on at least one surface of the substrate.
- a surface treatment such as an oxidation method or a primer treatment
- the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone treatment, and ultraviolet irradiation treatment.
- the thickness of the substrate there is no particular restriction on the thickness of the substrate, and the thickness may be appropriately set based on the mechanical strength and ease of handling during production and use, but it is usually 10 to 300 ⁇ m, preferably 12 to 200 ⁇ m, and particularly preferably 15 to 125 ⁇ m.
- the arithmetic mean roughness (Ra) of the surface of the substrate on the release agent layer side is preferably from 0.1 to 70 nm, and more preferably from 1 to 60 nm.
- the arithmetic mean roughness (Ra) of the surface on the release agent layer side of the substrate is preferably 0.1 to 70 nm in terms of handling of the substrate, suppression of poor electrical continuity, etc.
- substrates having a surface arithmetic mean roughness (Ra) of 1 to 70 nm are relatively easy and inexpensive to obtain, and are therefore also preferable in terms of availability and production costs of the release film for producing the ceramic green sheet of the present invention.
- the arithmetic mean roughness (Ra) of the surface of the substrate opposite to the release agent layer side is preferably from 5 to 70 nm, and particularly preferably from 10 to 60 nm.
- the arithmetic mean roughness (Ra) of the surface of the substrate opposite the release agent layer side is not less than the above-mentioned lower limit, blocking during winding of the release film for producing a ceramic green sheet of the present invention can be effectively suppressed, while when it is not more than the above-mentioned upper limit, it becomes easy to smooth the surface of the release agent layer.
- the release agent layer constituting the release film for producing a ceramic green sheet of the present invention
- any material can be used as long as it satisfies the condition that the polar component ( ⁇ sp ) of the surface free energy on the side opposite the substrate is 0.3 (mN/m) or more.
- the curable composition preferably used for forming the release agent layer in the present invention preferably contains at least one reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group.
- at least one reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group By using a curable composition containing at least one reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, the release agent layer of the release film for producing the ceramic green sheet of this embodiment can be easily formed with good controllability of the surface free energy, etc.
- the curable composition may contain only one type of reactive compound (a) having at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups, or may contain two or more types of reactive compounds (a) having at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups.
- reactive compound (a) having at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups.
- it is preferable to use two or more types of reactive compounds (a) in combination and it is particularly preferable to use a combination of the reactive silicone (a1) and the crosslinkable compound (a2) described below, and it is further preferable to combine a film-forming compound (a3).
- the curable composition may be composed only of a reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, or may contain other components such as a solvent, a radical initiator, a cationic initiator, a leveling agent, an antistatic agent, a dye, and a pigment.
- the amount of reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group used is preferably 50 mass% or more, and particularly preferably 60 to 96 mass%, of the mass of the release agent layer.
- the reactive compound (a) preferably used for forming the release agent layer in the present invention has at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group.
- a reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group it is possible to impart photocurability and/or thermosetting property to the curable composition.
- the reactive compound (a) may have one or more reactive functional groups, but from the viewpoint of photocurability and/or thermosetting property, it preferably has two or more reactive functional groups, more preferably has 2 to 15 reactive functional groups, and particularly preferably has 2 to 10 reactive functional groups.
- the reactive compound (a) may have two or more of the same type of reactive functional groups, or may have a combination of two or more different types of reactive functional groups in total.
- the reactive compound (a) when active energy rays are used, preferably has a (meth)acryloyl group, and when heat curing is also used, a material containing a hydroxyl group or an epoxy group can be appropriately selected.
- the reactive compound (a) include a reactive silicone (a1) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, and a siloxane skeleton; a reactive compound (a2) having the same reactive functional group as the reactive silicone (a1) and having a reactive functional group equivalent of 1000 g/mol or less; and a film-forming compound (a3) having two or more (meth)acryloyl groups in one molecule.
- a reactive silicone (a1) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, and a siloxane skeleton
- a reactive compound (a2) having the same reactive functional group as the reactive silicone (a1) and having a reactive functional group equivalent of 1000 g/mol or less
- a film-forming compound (a3) having two or more (meth)acryloyl groups in one molecule.
- the curable composition preferably contains, as the reactive compound (a), at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, and a reactive silicone (a1) having a siloxane skeleton.
- the reactive silicone (a1) is not limited as long as it has at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, and has a siloxane skeleton.
- the reactive functional group reacts by irradiation with active energy rays or by a separate reaction step (for example, a heating step), and the siloxane skeleton is incorporated into a crosslinked structure and fixed, which makes it possible to more effectively prevent the reactive silicone (a1) from contaminating the ceramic green sheet formed on the release agent layer.
- a separate reaction step for example, a heating step
- the reactive functional group an epoxy group is particularly preferred.
- the reactive functional group may be introduced into one end of the siloxane skeleton, may be introduced into both ends, or may be introduced into a side chain.It is preferable that at least one reactive functional group selected from the group consisting of (meth)acryloyl group, hydroxyl group, and epoxy group is introduced into one molecule of the reactive silicone (a1) in an amount of two or more.When having two or more reactive functional groups, it may have two or more of the same type of reactive functional groups, or may have a combination of two or more different reactive functional groups in total.
- the compound may further have a vinyl group, a maleimide group, a carboxyl group, an isocyanate group, or the like.
- the molecular weight of the reactive silicone (a1) is preferably 5,000 to 100,000, and particularly preferably 10,000 to 70,000.
- the reactive silicone (a1) may be used alone or in combination of two or more kinds.
- the content of the reactive silicone (a1) in the curable composition is not particularly limited, but is preferably from 0.1 to 20 mass %, and particularly preferably from 0.2 to 15 mass %, based on the total mass of the release agent layer.
- the curable composition preferably contains, as the reactive compound (a), a reactive compound (a2) having the same reactive functional group as the reactive silicone (a1) and having a reactive functional group equivalent of 1000 g/mol or less. It is particularly preferable to use the reactive compound (a2) in combination with the reactive silicone (a1).
- the reactive compound (a2) functions as a crosslinking agent for the reactive silicone (a1) and the like, promotes the effect of the curable composition, and can incorporate and fix the reactive silicone (a1) and the like into a crosslinked structure. This makes it possible to more effectively suppress contamination of the ceramic green sheet.
- the reactive compound (a2) is also referred to as a "crosslinkable compound (a2)" in this specification.
- the reactive functional group equivalent of the reactive compound (a2) is 1000 g/mol or less, preferably 500 g/mol or less, particularly preferably 300 g/mol or less.
- the polymer has a sufficient number of (meth)acryloyl groups, hydroxyl groups, and/or epoxy groups to achieve suitable crosslinking performance.
- the reactive compound (a2) preferably has a total of 1 or more reactive functional groups ((meth)acryloyl group, hydroxyl group, and/or epoxy group), preferably has 2 to 15 reactive functional groups, and particularly preferably has 2 to 6 reactive functional groups. When the number of reactive functional groups is within the above range, more appropriate crosslinking performance can be achieved.
- the molecular weight of the crosslinkable compound (a2) is not particularly limited, but from the viewpoint of crosslinking performance, etc., it is preferably from 150 to 3,500, and particularly preferably from 150 to 1,500.
- the crosslinkable compound (a2) may have a siloxane skeleton. In this case, by introducing a sufficient amount of siloxane skeleton into the release agent layer together with the siloxane skeleton of the reactive silicone (a1), more preferable release performance can be achieved.
- the crosslinkable compound (a2) may be used alone or in combination of two or more kinds.
- the content of the crosslinkable compound (a2) in the curable composition is not particularly limited, but is preferably 0.08 to 99 mass%, particularly preferably 0.4 to 50 mass%, based on the total mass of the release agent layer.
- the amount of reactive silicone (a1) used it is preferably 81 to 9900 mass parts, particularly preferably 85 to 1000 mass parts, based on 100 mass parts of reactive silicone (a1).
- the curable composition preferably contains, as the reactive compound (a), a film-forming compound (a3) having two or more (meth)acryloyl groups in one molecule.
- the curable composition can be cured by irradiation with active energy rays.
- the film-forming compound (a3) may be any of a monomer, an oligomer, or a polymer, or may be a mixture thereof.
- the film-forming compound (a3) is preferably a (meth)acrylic acid ester.
- the (meth)acrylic acid ester means both an acrylic acid ester and a methacrylic acid ester. The same applies to other similar terms.
- the (meth)acrylic acid ester is preferably at least one selected from polyfunctional (meth)acrylate monomers and (meth)acrylate oligomers, particularly at least one selected from difunctional or higher functional (meth)acrylate monomers and (meth)acrylate oligomers, and more preferably a trifunctional or higher functional (meth)acrylate monomer.
- difunctional or higher, more preferably trifunctional or higher results in excellent curability of the curable composition, and also in excellent release properties of the surface of the resulting release agent layer.
- polyfunctional (meth)acrylate monomers examples include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, and isocyanurate di(meth)acrylate.
- acrylate trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, tris((meth)acryloxyethyl)isocyanurate, propionic acid modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, and the like. These may be used alone or in combination of two or more.
- polyfunctional (meth)acrylate oligomers examples include polyester acrylate oligomers, epoxy acrylate oligomers, urethane acrylate oligomers, polyether acrylate oligomers, polybutadiene acrylate oligomers, silicone acrylate oligomers, etc.
- Polyester acrylate oligomers can be obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends, obtained by condensation of a polycarboxylic acid with a polyhydric alcohol, with (meth)acrylic acid, or by esterifying the terminal hydroxyl groups of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid, with (meth)acrylic acid.
- Epoxy acrylate oligomers can be obtained, for example, by reacting (meth)acrylic acid with the oxirane ring of a relatively low molecular weight bisphenol epoxy resin or novolac epoxy resin to esterify it. It is also possible to use a carboxyl-modified epoxy acrylate oligomer in which an epoxy acrylate oligomer is partially modified with a dibasic carboxylic acid anhydride.
- Urethane acrylate oligomers can be obtained, for example, by esterifying polyurethane oligomers obtained by reacting polyether polyol or polyester polyol with polyisocyanate with (meth)acrylic acid.
- Polyether acrylate oligomers can be obtained by esterifying the hydroxyl groups of polyether polyol with (meth)acrylic acid.
- the film-forming compound (a3) may be used alone or in combination of two or more kinds.
- the content of the film-forming compound (a3) in the curable composition is not particularly limited, but is preferably from 50 to 90 mass %, and particularly preferably from 60 to 85 mass %, based on the total mass of the release agent layer.
- the release agent layer can be formed by applying a raw material for the release agent layer, preferably the above-mentioned curable composition, to at least one surface of the substrate, followed by drying as necessary and curing by irradiation with active energy rays such as light. If the reactive functional group of the reactive compound (a) is one that reacts with heat, the drying at this time causes a reaction, and the reactive compound (a), preferably having a siloxane skeleton, can be incorporated into a crosslinked structure.
- the method for applying the curable composition and for example, gravure coating, bar coating, spray coating, spin coating, knife coating, roll coating, die coating, etc. can be used.
- the active energy ray ultraviolet rays, electron beams, etc. are usually used.
- the irradiation amount of the active energy ray varies depending on the type of energy ray, but for example, in the case of ultraviolet rays, the light amount is preferably 10 to 1000 mJ/ cm2 , and more preferably 20 to 500 mJ/ cm2 . In the case of electron beams, the amount is preferably about 0.1 to 50 kGy.
- the polar component ( ⁇ sp ) of the surface free energy of the surface opposite to the substrate of the release agent layer constituting the release film for producing a ceramic green sheet of the present invention is 0.3 (mN/m) or more.
- the polar component ( ⁇ sp ) of the surface free energy of the release agent layer on the side opposite the substrate is 0.3 (mN/m) or more, which, in combination with other technical features of the present invention, enables the release film for producing ceramic green sheets of the present invention to achieve excellent technical effects of great practical value, such as a high level of compatibility between ease of peeling of the ceramic green sheet formed thereon and inhibition of contamination of the ceramic green sheet.
- the mechanism by which the ease of peeling the ceramic green sheet and the prevention of contamination of the ceramic green sheet can be achieved simultaneously by setting the polar component ( ⁇ sp ) of the surface free energy of the release agent layer opposite the substrate to 0.3 (mN/m) or more is not necessarily clear; however, since the surface free energy of the release agent layer may be closely related to the releasability and the contamination of the ceramic green sheet and other adherends, it is presumed that there is an optimal value of the surface free energy that can achieve both releasability and contamination resistance.
- the polar component ( ⁇ sp ) of the surface free energy of the surface of the release agent layer opposite to the substrate can be measured by a method conventionally known in the art, for example, a contact angle method, and the polar component ( ⁇ sp ) can be calculated by, for example, analyzing contact angles measured for multiple types of liquids by applying them to the Kitazaki-Hata and extended Foulkes equations (Kitazaki-Hata equations), etc. More specifically, it can be measured by the method described in the examples of the present specification.
- the polar component ( ⁇ sp ) of the surface free energy of the release agent layer on the side opposite to the substrate is preferably 0.3 to 1.0 (mN/m), and particularly preferably 0.3 to 0.8 (mN/m).
- the polar component ( ⁇ sp ) of the surface free energy of the surface of the release agent layer opposite to the substrate can be appropriately adjusted by adjusting the type and amount of the material constituting the release agent layer or the coating amount of the release agent layer.
- the release film for producing a ceramic green sheet of the present invention is not particularly limited as long as the polar component ( ⁇ sp ) of the surface free energy of the release agent layer on the side opposite the substrate satisfies the above-mentioned conditions, but it is preferable that the dispersive component ( ⁇ sd ) of the surface free energy of the release agent layer on the side opposite the substrate be 22 (mN/m) or more.
- the dispersion component ( ⁇ sd ) of the surface free energy of the release agent layer on the side opposite the substrate is 22 (mN/m) or more, which, in combination with other technical features of the present invention, enables the release film for producing ceramic green sheets of this embodiment to achieve excellent technical effects of even greater practical value, such as achieving a higher level of ease in peeling the ceramic green sheet formed thereon while suppressing contamination of the ceramic green sheet.
- a dispersion component ( ⁇ sd ) of the surface free energy of the release agent layer on the side opposite the substrate is 22 (mN/m) or more can achieve a higher level of both ease of peeling of the ceramic green sheet and suppression of contamination of the ceramic green sheet is not necessarily clear; however, since the surface free energy of the release agent layer may be closely related to releasability and contamination of the ceramic green sheet and other adherends, it is presumed that there is an optimal value of surface free energy that can achieve both releasability and contamination resistance.
- the dispersion component ( ⁇ sd ) of the surface free energy of the surface of the release agent layer opposite to the substrate can be measured by a method conventionally known in the art, for example, a contact angle method, and the dispersion component ( ⁇ sd ) can be calculated, for example, by analyzing contact angles measured for multiple types of liquids by applying them to the Kitazaki-Hata and extended Foulkes equations (Kitazaki-Hata equations), etc. More specifically, it can be measured by the method described in the examples of the present specification.
- the dispersion component ( ⁇ sd ) of the surface free energy of the release agent layer on the side opposite to the substrate is preferably 22 (mN/m) to 30 (mN/m), particularly preferably 22 to 28 (mN/m).
- the dispersion component ( ⁇ sd ) of the surface free energy of the surface of the release agent layer opposite to the substrate can be appropriately adjusted by adjusting the type and amount of the material constituting the release agent layer or the coating amount of the release agent layer.
- the thickness of the release agent layer is preferably 0.05 to 2 ⁇ m, and particularly preferably 0.2 to 1.5 ⁇ m.
- a thickness of 0.05 ⁇ m or more is preferable from the viewpoint of smoothness of the release agent layer surface and suppression of pinholes and uneven thickness of the ceramic green sheet.
- a thickness of 2 ⁇ m or less is preferable from the viewpoint of suppressing curling due to cure shrinkage of the release agent layer. It is also preferable from the viewpoint of suppressing blocking and static electricity.
- the release film for producing a ceramic green sheet of the present invention may have layers other than the above-mentioned substrate and release agent layer, such as a protective layer, an adhesive layer, an antistatic layer, etc.
- the substrate and the release agent layer may be laminated directly to each other, or may be laminated via another layer such as an adhesive layer.
- the release film for producing ceramic green sheets of the present invention allows easy release of the ceramic green sheets formed thereon and can effectively suppress contamination of the ceramic green sheets, and therefore can be suitably used in the production of ceramic green sheets for use in various ceramic products, such as multilayer ceramic capacitors or multilayer ceramic substrates.
- the release film for producing a ceramic green sheet of the present invention can be preferably used in a production method having the following steps. a) applying a ceramic slurry onto the release film for producing a ceramic green sheet of the present invention; b) forming a ceramic green sheet from the ceramic slurry applied in the a) step; and c) peeling the ceramic green sheet formed in the b) step from the release film for producing a ceramic green sheet.
- a step of printing internal electrodes on the green sheet is provided between the above steps b) and c), followed by step c) (peeling), lamination and pressure bonding, cutting and separation, firing, and external electrode formation steps to manufacture the multilayer ceramic capacitor.
- Kitazaki-Hata and extended Foulkes equation (Kitazaki-Hata equation) was used, and the contact angle ( ⁇ ) with the solid (sample) measured for the above three types of liquid and the known surface free energy of each liquid were inserted into the following equation, and the resulting three-dimensional linear equation was solved to obtain the surface free energy of the solid (sample). obtained.
- Example 1 Polyfunctional acrylate 1, epoxy modified silicone 1, epoxy modified silicone 2, cationic initiator 1, and radical initiator 1 were mixed in the mass ratio shown in Table 1 to prepare a curable composition for the release agent layer.
- the curable composition prepared above was applied to one side of the substrate, dried at 100°C for 15 seconds, and then cured by irradiating with ultraviolet light using a high-pressure mercury lamp (accumulated light amount: approximately 40 mJ/ cm2 ) to form a release agent layer, thereby producing a release film having a substrate and a release agent layer provided on one side of the substrate.
- the release films produced above were evaluated for surface free energy, backside contamination, and tape peel strength by the methods described above. The results are shown in Table 1.
- Examples 2 to 4 and Comparative Examples 1 to 2 A release film was produced and evaluated in the same manner as in Example 1, except that the formulation of the curing agent composition for the release agent layer was changed to that shown in Table 1. The results are shown in Table 1.
- the release film for producing ceramic green sheets of the present invention allows easy release of the ceramic green sheets formed thereon, while also effectively suppressing contamination of the ceramic green sheets, simultaneously achieving a high level of technical effects with high practical value that surpass the limits of conventional technology, and can be suitably used in the manufacture of various ceramic products, making it highly applicable in various industrial fields including the electrical and electronics industry, electronic parts industry, machinery industry, and automotive industry.
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Abstract
Provided is a release film that is for producing a ceramic green sheet and that comprises: a substrate; and a release agent layer. The film facilitates release of the green sheet and effectively inhibits contamination of the green sheet. This release film is for producing a ceramic green sheet and comprises: a substrate; and a release agent layer provided on at least one side of the substrate. The polar component (γsp) of the surface free energy in the surface on the side of the release agent layer opposite to said substrate is at least 0.3 (mN/m).
Description
本発明は、セラミックグリーンシート製造用剥離フィルムに関し、より具体的には、グリーンシートの剥離が容易であるとともに、グリーンシートの汚染が効果的に抑制され、積層セラミックコンデンサや多層セラミック基板等の製造にあたり高い位置精度を要するセラミック製品の製造に特に好適に用いられる、セラミックグリーンシート製造用剥離フィルムに関する。
The present invention relates to a release film for producing ceramic green sheets, and more specifically, to a release film for producing ceramic green sheets that allows easy peeling of the green sheets, effectively prevents contamination of the green sheets, and is particularly suitable for use in the manufacture of ceramic products that require high positional accuracy in the manufacture of laminated ceramic capacitors, multilayer ceramic substrates, and the like.
シート状のセラミック部材の製造においては、従来よりセラミックグリーンシート製造用剥離フィルムが用いられている。例えば、積層セラミックコンデンサや多層セラミック基板といった積層セラミック製品を製造するには、セラミックグリーンシート製造用剥離フィルム上にセラミックグリーンシートを成形し、得られたセラミックグリーンシートを複数枚積層して焼成することが行われている。
近年、電子機器の小型化および高性能化に伴い、積層セラミックコンデンサや多層セラミック基板の小型化および多層化が進んでいる。多層化実現のためセラミックグリーンシートは薄膜化が求められ、薄膜化したセラミックグリーンシートにおけるピンホールや厚みむら等の欠陥の発生を防止し、薄膜化したセラミックグリーンシートを剥離フィルムから剥離するときの破断を効果的に抑制する等の観点から、基材と特定の成分の剥離剤層とを有するセラミックグリーンシート製造用剥離フィルムであって、剥離剤層の基材とは反対側の面における算術平均粗さ（Ｒａ）、及び最大突起高さ（Ｒｐ）がそれぞれ所定値以下であり、かつ、基材の剥離剤層とは反対側の面における算術平均粗さ（Ｒａ）、及び最大突起高さ（Ｒｐ）がそれぞれ所定の数値範囲内である、セラミックグリーンシート製造用剥離フィルムが提案されている（例えば、特許文献１参照）。 In the manufacture of sheet-like ceramic members, a release film for producing a ceramic green sheet has been used. For example, in order to manufacture a multilayer ceramic product such as a multilayer ceramic capacitor or a multilayer ceramic substrate, a ceramic green sheet is formed on a release film for producing a ceramic green sheet, and a plurality of the obtained ceramic green sheets are stacked and fired.
In recent years, with the miniaturization and high performance of electronic devices, the miniaturization and multilayering of multilayer ceramic capacitors and multilayer ceramic substrates are progressing. To realize multilayering, the ceramic green sheet is required to be thin, and from the viewpoint of preventing defects such as pinholes and uneven thickness in the thinned ceramic green sheet and effectively suppressing breakage when the thinned ceramic green sheet is peeled off from the release film, a release film for producing ceramic green sheets has been proposed, which has a substrate and a release agent layer of a specific component, and the arithmetic mean roughness (Ra) and maximum protrusion height (Rp) on the surface opposite to the substrate of the release agent layer are each equal to or less than a predetermined value, and the arithmetic mean roughness (Ra) and maximum protrusion height (Rp) on the surface opposite to the substrate of the release agent layer are each within a predetermined numerical range (see, for example, Patent Document 1).
近年、電子機器の小型化および高性能化に伴い、積層セラミックコンデンサや多層セラミック基板の小型化および多層化が進んでいる。多層化実現のためセラミックグリーンシートは薄膜化が求められ、薄膜化したセラミックグリーンシートにおけるピンホールや厚みむら等の欠陥の発生を防止し、薄膜化したセラミックグリーンシートを剥離フィルムから剥離するときの破断を効果的に抑制する等の観点から、基材と特定の成分の剥離剤層とを有するセラミックグリーンシート製造用剥離フィルムであって、剥離剤層の基材とは反対側の面における算術平均粗さ（Ｒａ）、及び最大突起高さ（Ｒｐ）がそれぞれ所定値以下であり、かつ、基材の剥離剤層とは反対側の面における算術平均粗さ（Ｒａ）、及び最大突起高さ（Ｒｐ）がそれぞれ所定の数値範囲内である、セラミックグリーンシート製造用剥離フィルムが提案されている（例えば、特許文献１参照）。 In the manufacture of sheet-like ceramic members, a release film for producing a ceramic green sheet has been used. For example, in order to manufacture a multilayer ceramic product such as a multilayer ceramic capacitor or a multilayer ceramic substrate, a ceramic green sheet is formed on a release film for producing a ceramic green sheet, and a plurality of the obtained ceramic green sheets are stacked and fired.
In recent years, with the miniaturization and high performance of electronic devices, the miniaturization and multilayering of multilayer ceramic capacitors and multilayer ceramic substrates are progressing. To realize multilayering, the ceramic green sheet is required to be thin, and from the viewpoint of preventing defects such as pinholes and uneven thickness in the thinned ceramic green sheet and effectively suppressing breakage when the thinned ceramic green sheet is peeled off from the release film, a release film for producing ceramic green sheets has been proposed, which has a substrate and a release agent layer of a specific component, and the arithmetic mean roughness (Ra) and maximum protrusion height (Rp) on the surface opposite to the substrate of the release agent layer are each equal to or less than a predetermined value, and the arithmetic mean roughness (Ra) and maximum protrusion height (Rp) on the surface opposite to the substrate of the release agent layer are each within a predetermined numerical range (see, for example, Patent Document 1).
積層セラミックコンデンサや多層セラミック基板の小型化および多層化にあたっては、積層の際に非常に高い位置精度も求められるが、セラミックグリーンシート製造用剥離フィルムの剥離剤層からの汚染物質により位置ずれが発生し位置精度を低下させる場合があり、その解決が求められている。この様な汚染物質は、剥離剤層中に残存する未反応のシリコーン成分等であると推定されるが、単に剥離剤層の製造におけるシリコーン成分の使用量を低減すると、グリーンシートの剥離性が低下するため、グリーンシートへの汚染物質の移行の低減とグリーンシートの易剥離性とを両立することは困難であった。
In order to miniaturize and multilayer multilayer ceramic capacitors and multilayer ceramic substrates, extremely high positional accuracy is required during lamination, but contaminants from the release agent layer of the release film used to manufacture ceramic green sheets can cause misalignment and reduce positional accuracy, and a solution is needed. Such contaminants are presumed to be unreacted silicone components remaining in the release agent layer, but simply reducing the amount of silicone components used in manufacturing the release agent layer reduces the releasability of the green sheet, making it difficult to simultaneously reduce the migration of contaminants to the green sheet and ensure easy releasability of the green sheet.
上記技術背景に鑑み、本発明は、基材と剥離剤層とを有するセラミックグリーンシート製造用剥離フィルムであって、グリーンシートの剥離が容易であるとともに、グリーンシートの汚染が効果的に抑制された、セラミックグリーンシート製造用剥離フィルムを提供すること課題とする。
In view of the above technical background, the present invention aims to provide a release film for producing ceramic green sheets, which has a base material and a release agent layer, and which allows easy peeling of the green sheet while effectively suppressing contamination of the green sheet.
本発明者らは、鋭意検討の結果、基材と、前記基材の少なくとも一方に設けられた剥離剤層とを有するセラミックグリーンシート製造用剥離フィルムにおいて、前記剥離剤層の前記基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）を所定値以上とすることで、従来技術の限界を超えた高い水準で、グリーンシートへの汚染物質の移行の低減とグリーンシートの易剥離性とをバランスさせることができることを見出し、本発明を完成するに至った。
すなわち本発明は、
［１］
基材と、前記基材の少なくとも一方に設けられた剥離剤層とを有するセラミックグリーンシート製造用剥離フィルムであって、
前記剥離剤層の前記基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が０．３（ｍＮ／ｍ）以上である、上記セラミックグリーンシート製造用剥離フィルム、に関する。 As a result of intensive research, the inventors have found that in a release film for producing a ceramic green sheet having a substrate and a release agent layer provided on at least one side of the substrate, by setting the polar component (γ sp ) of the surface free energy of the release agent layer on the side opposite the substrate to a predetermined value or more, it is possible to achieve a balance between the reduction in migration of contaminants to the green sheet and the easy peelability of the green sheet at a high level that exceeds the limits of conventional technology, and have completed the present invention.
That is, the present invention provides:
[1]
A release film for producing a ceramic green sheet, comprising a substrate and a release agent layer provided on at least one side of the substrate,
The present invention relates to the release film for producing a ceramic green sheet, wherein the polar component (γ sp ) of the surface free energy of the release agent layer on the side opposite to the substrate is 0.3 (mN/m) or more.
すなわち本発明は、
［１］
基材と、前記基材の少なくとも一方に設けられた剥離剤層とを有するセラミックグリーンシート製造用剥離フィルムであって、
前記剥離剤層の前記基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が０．３（ｍＮ／ｍ）以上である、上記セラミックグリーンシート製造用剥離フィルム、に関する。 As a result of intensive research, the inventors have found that in a release film for producing a ceramic green sheet having a substrate and a release agent layer provided on at least one side of the substrate, by setting the polar component (γ sp ) of the surface free energy of the release agent layer on the side opposite the substrate to a predetermined value or more, it is possible to achieve a balance between the reduction in migration of contaminants to the green sheet and the easy peelability of the green sheet at a high level that exceeds the limits of conventional technology, and have completed the present invention.
That is, the present invention provides:
[1]
A release film for producing a ceramic green sheet, comprising a substrate and a release agent layer provided on at least one side of the substrate,
The present invention relates to the release film for producing a ceramic green sheet, wherein the polar component (γ sp ) of the surface free energy of the release agent layer on the side opposite to the substrate is 0.3 (mN/m) or more.
以下、［２］から［１２］は、いずれも本発明の好ましい一態様又は一実施形態である。
［２］
前記剥離剤層の前記基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が０．３から１．０（ｍＮ／ｍ）である、［１］に記載のセラミックグリーンシート製造用剥離フィルム。
［３］
前記剥離剤層の前記基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が０．３から０．８（ｍＮ／ｍ）である、［１］に記載のセラミックグリーンシート製造用剥離フィルム。
［４］
前記剥離剤層の前記基材とは反対側の面の表面自由エネルギーの分散成分（γｓｄ）が２２（ｍＮ／ｍ）以上である、［１］から［３］のいずれか一項に記載のセラミックグリーンシート製造用剥離フィルム。
［５］
前記剥離剤層が硬化性組成物の硬化物を含有し、該硬化性組成物が少なくとも１種の、（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する反応性化合物（ａ）を含み、且つ該反応性化合物（ａ）の合計量が、質量比率で該剥離剤層の５０％以上であることを特徴とする［１］から［４］のいずれか一項に記載のセラミックグリーンシート製造用剥離フィルム。
［６］
前記硬化性組成物が、前記反応性化合物（ａ）として、（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基、並びにシロキサン骨格を有する反応性シリコーン（ａ１）少なくとも１種と、該反応性シリコーン（ａ１）と同じ反応性官能基を有し、且つ反応性官能基当量が１０００ｇ／ｍｏｌ以下である反応性化合物（ａ２）少なくとも１種と、を含有する、［５］に記載のセラミックグリーンシート製造用剥離フィルム。
［７］
前記硬化性組成物が、更に１分子中に２個以上の（メタ）アクリロイル基を有する膜形成性化合物（ａ３）を含有する、［６］に記載のセラミックグリーンシート製造用剥離フィルム。
［８］
前記基材の前記剥離剤層側の表面の算術平均粗さ（Ｒａ）が１から７０ｎｍである、［１］から［７］のいずれか一項に記載のセラミックグリーンシート製造用剥離フィルム。
［９］
積層セラミックコンデンサ、又は多層セラミック基板の製造に用いる、［１］から［８］のいずれか一項に記載のセラミックグリーンシート製造用剥離フィルム。
［１０］
ａ）［１］から［８］のいずれか一項に記載のセラミックグリーンシート製造用剥離フィルム上にセラミックスラリーを塗布する工程、
ｂ）前記ａ）工程において塗布されたセラミックスラリーからセラミックグリーンシートを形成する工程、及び
ｃ）前記ｂ）工程において形成されたセラミックグリーンシートを前記セラミックグリーンシート製造用剥離フィルムから剥離する工程、
を有する、セラミックグリーンシートの製造方法。
［１１］
［１０］に記載のセラミックグリーンシートの製造方法によりセラミックグリーンシートを製造する工程を有する、セラミック製品の製造方法。
［１２］
前記セラミック製品が積層セラミックコンデンサ、又は多層セラミック基板である、［１１］に記載のセラミック製品の製造方法。 Below, [2] to [12] are each a preferred aspect or embodiment of the present invention.
[2]
The release film for producing a ceramic green sheet according to [1], wherein the polar component (γ sp ) of the surface free energy of the release agent layer on the side opposite to the substrate is 0.3 to 1.0 (mN/m).
[3]
The release film for producing a ceramic green sheet according to [1], wherein the polar component (γ sp ) of the surface free energy of the release agent layer on the side opposite to the substrate is 0.3 to 0.8 (mN/m).
[4]
The release film for producing a ceramic green sheet according to any one of [1] to [3], wherein the dispersion component (γ sd ) of the surface free energy of the release agent layer on the side opposite to the substrate is 22 (mN/m) or more.
[5]
The release film for producing a ceramic green sheet according to any one of [1] to [4], characterized in that the release agent layer contains a cured product of a curable composition, the curable composition contains at least one reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, and the total amount of the reactive compound (a) is 50% or more by mass of the release agent layer.
[6]
The release film for producing a ceramic green sheet according to [5], wherein the curable composition contains, as the reactive compound (a), at least one reactive silicone (a1) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, and a siloxane skeleton, and at least one reactive compound (a2) having the same reactive functional group as the reactive silicone (a1) and having a reactive functional group equivalent of 1000 g/mol or less.
[7]
The release film for producing a ceramic green sheet according to [6], wherein the curable composition further contains a film-forming compound (a3) having two or more (meth)acryloyl groups in one molecule.
[8]
The release film for producing a ceramic green sheet according to any one of [1] to [7], wherein the arithmetic mean roughness (Ra) of the surface of the base material on the release agent layer side is 1 to 70 nm.
[9]
The release film for producing a ceramic green sheet according to any one of [1] to [8], which is used for producing a multilayer ceramic capacitor or a multilayer ceramic substrate.
[10]
a) applying a ceramic slurry onto the release film for producing a ceramic green sheet according to any one of [1] to [8];
b) forming a ceramic green sheet from the ceramic slurry applied in the step a); and c) peeling the ceramic green sheet formed in the step b) from the release film for producing a ceramic green sheet.
The method for producing a ceramic green sheet comprising the steps of:
[11]
A method for producing a ceramic product, comprising the step of producing a ceramic green sheet by the method for producing a ceramic green sheet according to [10].
[12]
The method for producing a ceramic product according to [11], wherein the ceramic product is a multilayer ceramic capacitor or a multilayer ceramic substrate.
［２］
前記剥離剤層の前記基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が０．３から１．０（ｍＮ／ｍ）である、［１］に記載のセラミックグリーンシート製造用剥離フィルム。
［３］
前記剥離剤層の前記基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が０．３から０．８（ｍＮ／ｍ）である、［１］に記載のセラミックグリーンシート製造用剥離フィルム。
［４］
前記剥離剤層の前記基材とは反対側の面の表面自由エネルギーの分散成分（γｓｄ）が２２（ｍＮ／ｍ）以上である、［１］から［３］のいずれか一項に記載のセラミックグリーンシート製造用剥離フィルム。
［５］
前記剥離剤層が硬化性組成物の硬化物を含有し、該硬化性組成物が少なくとも１種の、（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する反応性化合物（ａ）を含み、且つ該反応性化合物（ａ）の合計量が、質量比率で該剥離剤層の５０％以上であることを特徴とする［１］から［４］のいずれか一項に記載のセラミックグリーンシート製造用剥離フィルム。
［６］
前記硬化性組成物が、前記反応性化合物（ａ）として、（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基、並びにシロキサン骨格を有する反応性シリコーン（ａ１）少なくとも１種と、該反応性シリコーン（ａ１）と同じ反応性官能基を有し、且つ反応性官能基当量が１０００ｇ／ｍｏｌ以下である反応性化合物（ａ２）少なくとも１種と、を含有する、［５］に記載のセラミックグリーンシート製造用剥離フィルム。
［７］
前記硬化性組成物が、更に１分子中に２個以上の（メタ）アクリロイル基を有する膜形成性化合物（ａ３）を含有する、［６］に記載のセラミックグリーンシート製造用剥離フィルム。
［８］
前記基材の前記剥離剤層側の表面の算術平均粗さ（Ｒａ）が１から７０ｎｍである、［１］から［７］のいずれか一項に記載のセラミックグリーンシート製造用剥離フィルム。
［９］
積層セラミックコンデンサ、又は多層セラミック基板の製造に用いる、［１］から［８］のいずれか一項に記載のセラミックグリーンシート製造用剥離フィルム。
［１０］
ａ）［１］から［８］のいずれか一項に記載のセラミックグリーンシート製造用剥離フィルム上にセラミックスラリーを塗布する工程、
ｂ）前記ａ）工程において塗布されたセラミックスラリーからセラミックグリーンシートを形成する工程、及び
ｃ）前記ｂ）工程において形成されたセラミックグリーンシートを前記セラミックグリーンシート製造用剥離フィルムから剥離する工程、
を有する、セラミックグリーンシートの製造方法。
［１１］
［１０］に記載のセラミックグリーンシートの製造方法によりセラミックグリーンシートを製造する工程を有する、セラミック製品の製造方法。
［１２］
前記セラミック製品が積層セラミックコンデンサ、又は多層セラミック基板である、［１１］に記載のセラミック製品の製造方法。 Below, [2] to [12] are each a preferred aspect or embodiment of the present invention.
[2]
The release film for producing a ceramic green sheet according to [1], wherein the polar component (γ sp ) of the surface free energy of the release agent layer on the side opposite to the substrate is 0.3 to 1.0 (mN/m).
[3]
The release film for producing a ceramic green sheet according to [1], wherein the polar component (γ sp ) of the surface free energy of the release agent layer on the side opposite to the substrate is 0.3 to 0.8 (mN/m).
[4]
The release film for producing a ceramic green sheet according to any one of [1] to [3], wherein the dispersion component (γ sd ) of the surface free energy of the release agent layer on the side opposite to the substrate is 22 (mN/m) or more.
[5]
The release film for producing a ceramic green sheet according to any one of [1] to [4], characterized in that the release agent layer contains a cured product of a curable composition, the curable composition contains at least one reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, and the total amount of the reactive compound (a) is 50% or more by mass of the release agent layer.
[6]
The release film for producing a ceramic green sheet according to [5], wherein the curable composition contains, as the reactive compound (a), at least one reactive silicone (a1) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, and a siloxane skeleton, and at least one reactive compound (a2) having the same reactive functional group as the reactive silicone (a1) and having a reactive functional group equivalent of 1000 g/mol or less.
[7]
The release film for producing a ceramic green sheet according to [6], wherein the curable composition further contains a film-forming compound (a3) having two or more (meth)acryloyl groups in one molecule.
[8]
The release film for producing a ceramic green sheet according to any one of [1] to [7], wherein the arithmetic mean roughness (Ra) of the surface of the base material on the release agent layer side is 1 to 70 nm.
[9]
The release film for producing a ceramic green sheet according to any one of [1] to [8], which is used for producing a multilayer ceramic capacitor or a multilayer ceramic substrate.
[10]
a) applying a ceramic slurry onto the release film for producing a ceramic green sheet according to any one of [1] to [8];
b) forming a ceramic green sheet from the ceramic slurry applied in the step a); and c) peeling the ceramic green sheet formed in the step b) from the release film for producing a ceramic green sheet.
The method for producing a ceramic green sheet comprising the steps of:
[11]
A method for producing a ceramic product, comprising the step of producing a ceramic green sheet by the method for producing a ceramic green sheet according to [10].
[12]
The method for producing a ceramic product according to [11], wherein the ceramic product is a multilayer ceramic capacitor or a multilayer ceramic substrate.
本発明のセラミックグリーンシート製造用剥離フィルムは、その上の形成したセラミックグリーンシートの剥離が容易であるとともに、セラミックグリーンシートの汚染を効果的に抑制することができる等、高い実用的価値を有する技術的効果を従来技術の限界を超えた高いレベルで同時に実現するものであり、各種セラミック製品の製造に好適に使用することができる。例えば、積層セラミックコンデンサや多層セラミック基板等の、薄膜化したセラミック層で構成され、製造にあたり高い位置精度を要するセラミック製品の製造においては、特に好適に使用される。
The release film for producing ceramic green sheets of the present invention allows easy release of the ceramic green sheets formed thereon, while also effectively suppressing contamination of the ceramic green sheets, simultaneously achieving a high level of technical effects with high practical value that surpass the limits of conventional technology, and can be suitably used in the production of various ceramic products. For example, it is particularly suitable for use in the production of ceramic products such as multilayer ceramic capacitors and multilayer ceramic substrates, which are made up of thin ceramic layers and require high positional precision during production.
本発明は、基材と、前記基材の少なくとも一方に設けられた剥離剤層とを有するセラミックグリーンシート製造用剥離フィルムであって、
前記剥離剤層の前記基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が０．３（ｍＮ／ｍ）以上である、上記セラミックグリーンシート製造用剥離フィルム、である。
すなわち、本発明のセラミックグリーンシート製造用剥離フィルムは、基材と剥離剤層とを有する。本発明のセラミックグリーンシート製造用剥離フィルムは、基材と剥離剤層とを有していればよく、それ以外の層を有していても、有していなくともよい。したがって、本発明のセラミックグリーンシート製造用剥離フィルムは、基材及び剥離剤層のみからなっていてもよく、基材及び剥離剤層に加えて、帯電防止層、等のそれ以外の層を有していてもよい。
以下、上記各層について説明する。 The present invention provides a release film for producing a ceramic green sheet, comprising a substrate and a release agent layer provided on at least one side of the substrate,
In the release film for producing a ceramic green sheet, the polar component (γ sp ) of the surface free energy of the release agent layer on the side opposite to the substrate is 0.3 (mN/m) or more.
That is, the release film for producing a ceramic green sheet of the present invention has a substrate and a release agent layer. The release film for producing a ceramic green sheet of the present invention only needs to have a substrate and a release agent layer, and may or may not have other layers. Therefore, the release film for producing a ceramic green sheet of the present invention may be composed of only a substrate and a release agent layer, or may have other layers such as an antistatic layer in addition to the substrate and the release agent layer.
Each of the above layers will now be described.
前記剥離剤層の前記基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が０．３（ｍＮ／ｍ）以上である、上記セラミックグリーンシート製造用剥離フィルム、である。
すなわち、本発明のセラミックグリーンシート製造用剥離フィルムは、基材と剥離剤層とを有する。本発明のセラミックグリーンシート製造用剥離フィルムは、基材と剥離剤層とを有していればよく、それ以外の層を有していても、有していなくともよい。したがって、本発明のセラミックグリーンシート製造用剥離フィルムは、基材及び剥離剤層のみからなっていてもよく、基材及び剥離剤層に加えて、帯電防止層、等のそれ以外の層を有していてもよい。
以下、上記各層について説明する。 The present invention provides a release film for producing a ceramic green sheet, comprising a substrate and a release agent layer provided on at least one side of the substrate,
In the release film for producing a ceramic green sheet, the polar component (γ sp ) of the surface free energy of the release agent layer on the side opposite to the substrate is 0.3 (mN/m) or more.
That is, the release film for producing a ceramic green sheet of the present invention has a substrate and a release agent layer. The release film for producing a ceramic green sheet of the present invention only needs to have a substrate and a release agent layer, and may or may not have other layers. Therefore, the release film for producing a ceramic green sheet of the present invention may be composed of only a substrate and a release agent layer, or may have other layers such as an antistatic layer in addition to the substrate and the release agent layer.
Each of the above layers will now be described.
基材
本発明のセラミックグリーンシート製造用剥離フィルムを構成する基材には特に制限はなく、従来当該技術分野における基材として公知のものの中から任意のものを適宜選択して用いることができる。このような基材としては、例えば、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステル、ポリプロピレンやポリメチルペンテン等のポリオレフィン、ポリカーボネート、エチレン－酢酸ビニル共重合体などのプラスチックからなるフィルムが挙げられ、単層であってもよいし、同種又は異種の２層以上の多層であってもよい。これらの中でもポリエステルフィルムが好ましく、特にポリエチレンテレフタレートフィルムが好ましく、さらには二軸延伸ポリエチレンテレフタレートフィルムが好ましい。ポリエチレンテレフタレートフィルムは、加工時、使用時等において、埃等が発生しにくいため、例えば、埃等によるセラミックスラリー塗工不良等を効果的に防止することができる。 Substrate There is no particular restriction on the substrate constituting the release film for producing ceramic green sheets of the present invention, and any substrate can be appropriately selected from those conventionally known as substrates in the technical field. Examples of such substrates include films made of plastics such as polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polypropylene and polymethylpentene, polycarbonate, and ethylene-vinyl acetate copolymers, and may be single-layered or multi-layered of two or more layers of the same or different kinds. Among these, polyester films are preferred, and polyethylene terephthalate films are particularly preferred, and biaxially stretched polyethylene terephthalate films are even more preferred. Polyethylene terephthalate films are less likely to generate dust during processing, use, etc., and therefore, for example, ceramic slurry coating defects due to dust, etc. can be effectively prevented.
本発明のセラミックグリーンシート製造用剥離フィルムを構成する基材には特に制限はなく、従来当該技術分野における基材として公知のものの中から任意のものを適宜選択して用いることができる。このような基材としては、例えば、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステル、ポリプロピレンやポリメチルペンテン等のポリオレフィン、ポリカーボネート、エチレン－酢酸ビニル共重合体などのプラスチックからなるフィルムが挙げられ、単層であってもよいし、同種又は異種の２層以上の多層であってもよい。これらの中でもポリエステルフィルムが好ましく、特にポリエチレンテレフタレートフィルムが好ましく、さらには二軸延伸ポリエチレンテレフタレートフィルムが好ましい。ポリエチレンテレフタレートフィルムは、加工時、使用時等において、埃等が発生しにくいため、例えば、埃等によるセラミックスラリー塗工不良等を効果的に防止することができる。 Substrate There is no particular restriction on the substrate constituting the release film for producing ceramic green sheets of the present invention, and any substrate can be appropriately selected from those conventionally known as substrates in the technical field. Examples of such substrates include films made of plastics such as polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polypropylene and polymethylpentene, polycarbonate, and ethylene-vinyl acetate copolymers, and may be single-layered or multi-layered of two or more layers of the same or different kinds. Among these, polyester films are preferred, and polyethylene terephthalate films are particularly preferred, and biaxially stretched polyethylene terephthalate films are even more preferred. Polyethylene terephthalate films are less likely to generate dust during processing, use, etc., and therefore, for example, ceramic slurry coating defects due to dust, etc. can be effectively prevented.
また、この基材においては、その少なくとも一方の面に設けられる剥離剤層との密着性を向上させる目的で、酸化法などによる表面処理、あるいはプライマー処理を施すことができる。上記酸化法としては、例えばコロナ放電処理、プラズマ放電処理、クロム酸化処理（湿式）、火炎処理、熱風処理、オゾン、紫外線照射処理などが挙げられ、これらの表面処理法は、基材フィルムの種類に応じて適宜選ばれるが、一般にコロナ放電処理法が効果および操作性の面から好ましく用いられる。
基材の厚さには特に制限は無く、機械的強度や製造及び使用における取り扱いの容易さ等から適宜厚さを設定すればよいが、通常１０～３００μｍであり、好ましくは１２～２００μｍであり、特に好ましくは１５～１２５μｍである。 In addition, this substrate may be subjected to a surface treatment such as an oxidation method or a primer treatment in order to improve adhesion to a release agent layer provided on at least one surface of the substrate. Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone treatment, and ultraviolet irradiation treatment. These surface treatment methods are appropriately selected depending on the type of substrate film, but generally, corona discharge treatment is preferably used in terms of effectiveness and operability.
There is no particular restriction on the thickness of the substrate, and the thickness may be appropriately set based on the mechanical strength and ease of handling during production and use, but it is usually 10 to 300 μm, preferably 12 to 200 μm, and particularly preferably 15 to 125 μm.
基材の厚さには特に制限は無く、機械的強度や製造及び使用における取り扱いの容易さ等から適宜厚さを設定すればよいが、通常１０～３００μｍであり、好ましくは１２～２００μｍであり、特に好ましくは１５～１２５μｍである。 In addition, this substrate may be subjected to a surface treatment such as an oxidation method or a primer treatment in order to improve adhesion to a release agent layer provided on at least one surface of the substrate. Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone treatment, and ultraviolet irradiation treatment. These surface treatment methods are appropriately selected depending on the type of substrate film, but generally, corona discharge treatment is preferably used in terms of effectiveness and operability.
There is no particular restriction on the thickness of the substrate, and the thickness may be appropriately set based on the mechanical strength and ease of handling during production and use, but it is usually 10 to 300 μm, preferably 12 to 200 μm, and particularly preferably 15 to 125 μm.
基材の剥離剤層側の表面の算術平均粗さ（Ｒａ）は０．１から７０ｎｍであることが好ましく、１～６０ｎｍであることが好ましい。
基材の剥離剤層側の表面の算術平均粗さ（Ｒａ）が０．１から７０ｎｍであると、基材のハンドリング、導通不良抑制等の点で好ましい。また、表面の算術平均粗さ（Ｒａ）が１から７０ｎｍである基材は比較的容易かつ安価に入手可能なので、本発明のセラミックグリーンシート製造用剥離フィルムの入手容易性や製造コストの観点からも好ましい。 The arithmetic mean roughness (Ra) of the surface of the substrate on the release agent layer side is preferably from 0.1 to 70 nm, and more preferably from 1 to 60 nm.
The arithmetic mean roughness (Ra) of the surface on the release agent layer side of the substrate is preferably 0.1 to 70 nm in terms of handling of the substrate, suppression of poor electrical continuity, etc. In addition, substrates having a surface arithmetic mean roughness (Ra) of 1 to 70 nm are relatively easy and inexpensive to obtain, and are therefore also preferable in terms of availability and production costs of the release film for producing the ceramic green sheet of the present invention.
基材の剥離剤層側の表面の算術平均粗さ（Ｒａ）が０．１から７０ｎｍであると、基材のハンドリング、導通不良抑制等の点で好ましい。また、表面の算術平均粗さ（Ｒａ）が１から７０ｎｍである基材は比較的容易かつ安価に入手可能なので、本発明のセラミックグリーンシート製造用剥離フィルムの入手容易性や製造コストの観点からも好ましい。 The arithmetic mean roughness (Ra) of the surface of the substrate on the release agent layer side is preferably from 0.1 to 70 nm, and more preferably from 1 to 60 nm.
The arithmetic mean roughness (Ra) of the surface on the release agent layer side of the substrate is preferably 0.1 to 70 nm in terms of handling of the substrate, suppression of poor electrical continuity, etc. In addition, substrates having a surface arithmetic mean roughness (Ra) of 1 to 70 nm are relatively easy and inexpensive to obtain, and are therefore also preferable in terms of availability and production costs of the release film for producing the ceramic green sheet of the present invention.
基材の剥離剤層側と反対側の表面の算術平均粗さ（Ｒａ）は、５～７０ｎｍであることが好ましく、１０～６０ｎｍであることが特に好ましい。
基材の剥離剤層側と反対側の表面の算術平均粗さ（Ｒａ）が上記下限値以上であることで、本発明のセラミックグリーンシート製造用剥離フィルムの巻き取り時等におけるブロッキングを効果的に抑制することができるともに、上記上限値以下であることで、剥離剤層の表面を平滑にすることが容易になる。 The arithmetic mean roughness (Ra) of the surface of the substrate opposite to the release agent layer side is preferably from 5 to 70 nm, and particularly preferably from 10 to 60 nm.
When the arithmetic mean roughness (Ra) of the surface of the substrate opposite the release agent layer side is not less than the above-mentioned lower limit, blocking during winding of the release film for producing a ceramic green sheet of the present invention can be effectively suppressed, while when it is not more than the above-mentioned upper limit, it becomes easy to smooth the surface of the release agent layer.
基材の剥離剤層側と反対側の表面の算術平均粗さ（Ｒａ）が上記下限値以上であることで、本発明のセラミックグリーンシート製造用剥離フィルムの巻き取り時等におけるブロッキングを効果的に抑制することができるともに、上記上限値以下であることで、剥離剤層の表面を平滑にすることが容易になる。 The arithmetic mean roughness (Ra) of the surface of the substrate opposite to the release agent layer side is preferably from 5 to 70 nm, and particularly preferably from 10 to 60 nm.
When the arithmetic mean roughness (Ra) of the surface of the substrate opposite the release agent layer side is not less than the above-mentioned lower limit, blocking during winding of the release film for producing a ceramic green sheet of the present invention can be effectively suppressed, while when it is not more than the above-mentioned upper limit, it becomes easy to smooth the surface of the release agent layer.
剥離剤層
本発明のセラミックグリーンシート製造用剥離フィルムを構成する剥離剤層の材質には特に制限はなく、基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が０．３（ｍＮ／ｍ）以上であるという条件を満たす限りにおいて、任意の材料を使用することができる。
セラミックグリーンシート製造用剥離フィルムの製造上の容易性や、表面自由エネルギーや表面粗さを適宜制御する観点からは、硬化性組成物を基材上に塗布して硬化させることにより剥離剤層を形成することが好ましく、光硬化性及び／又は熱硬化性の硬化性組成物を塗布して硬化させることにより剥離剤層を形成することが特に好ましい。すなわち、本発明中の剥離剤層は、硬化性組成物の硬化物を含有することが好ましい。 Release Agent Layer There are no particular limitations on the material of the release agent layer constituting the release film for producing a ceramic green sheet of the present invention, and any material can be used as long as it satisfies the condition that the polar component (γ sp ) of the surface free energy on the side opposite the substrate is 0.3 (mN/m) or more.
From the viewpoints of ease of production of the release film for producing a ceramic green sheet and appropriate control of the surface free energy and surface roughness, it is preferable to form the release agent layer by applying a curable composition onto a substrate and curing the composition, and it is particularly preferable to form the release agent layer by applying a photocurable and/or thermosetting curable composition and curing the composition. That is, it is preferable that the release agent layer in the present invention contains a cured product of the curable composition.
本発明のセラミックグリーンシート製造用剥離フィルムを構成する剥離剤層の材質には特に制限はなく、基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が０．３（ｍＮ／ｍ）以上であるという条件を満たす限りにおいて、任意の材料を使用することができる。
セラミックグリーンシート製造用剥離フィルムの製造上の容易性や、表面自由エネルギーや表面粗さを適宜制御する観点からは、硬化性組成物を基材上に塗布して硬化させることにより剥離剤層を形成することが好ましく、光硬化性及び／又は熱硬化性の硬化性組成物を塗布して硬化させることにより剥離剤層を形成することが特に好ましい。すなわち、本発明中の剥離剤層は、硬化性組成物の硬化物を含有することが好ましい。 Release Agent Layer There are no particular limitations on the material of the release agent layer constituting the release film for producing a ceramic green sheet of the present invention, and any material can be used as long as it satisfies the condition that the polar component (γ sp ) of the surface free energy on the side opposite the substrate is 0.3 (mN/m) or more.
From the viewpoints of ease of production of the release film for producing a ceramic green sheet and appropriate control of the surface free energy and surface roughness, it is preferable to form the release agent layer by applying a curable composition onto a substrate and curing the composition, and it is particularly preferable to form the release agent layer by applying a photocurable and/or thermosetting curable composition and curing the composition. That is, it is preferable that the release agent layer in the present invention contains a cured product of the curable composition.
硬化性組成物
本発明において剥離剤層の形成に好ましく用いられる硬化性組成物は、（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する反応性化合物（ａ）を少なくとも１種含有することが好ましい。
（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する反応性化合物（ａ）を少なくとも１種含有する硬化性組成物を用いることで、容易に、かつ表面自由エネルギー等の制御性良く、本実施形態のセラミックグリーンシート製造用剥離フィルムの剥離剤層を形成することができる。 Curable Composition The curable composition preferably used for forming the release agent layer in the present invention preferably contains at least one reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group.
By using a curable composition containing at least one reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, the release agent layer of the release film for producing the ceramic green sheet of this embodiment can be easily formed with good controllability of the surface free energy, etc.
本発明において剥離剤層の形成に好ましく用いられる硬化性組成物は、（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する反応性化合物（ａ）を少なくとも１種含有することが好ましい。
（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する反応性化合物（ａ）を少なくとも１種含有する硬化性組成物を用いることで、容易に、かつ表面自由エネルギー等の制御性良く、本実施形態のセラミックグリーンシート製造用剥離フィルムの剥離剤層を形成することができる。 Curable Composition The curable composition preferably used for forming the release agent layer in the present invention preferably contains at least one reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group.
By using a curable composition containing at least one reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, the release agent layer of the release film for producing the ceramic green sheet of this embodiment can be easily formed with good controllability of the surface free energy, etc.
上記硬化性組成物は、（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する反応性化合物（ａ）を１種類のみ含有していてもよく、２種類以上の（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する反応性化合物（ａ）を含有していてもよい。剥離剤層の硬化性、剥離性、表面自由エネルギー等の各種特性を制御する観点からは、２種類以上の反応性化合物（ａ）を組み合わせて使用することが好ましく、特に後述の反応性シリコーン（ａ１）と架橋性化合物（ａ２）とを組み合わせて使用することが好ましく、更に膜形成性化合物（ａ３）を組み合わせることが好ましい。
The curable composition may contain only one type of reactive compound (a) having at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups, or may contain two or more types of reactive compounds (a) having at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups. From the viewpoint of controlling various properties of the release agent layer, such as the curability, releasability, and surface free energy, it is preferable to use two or more types of reactive compounds (a) in combination, and it is particularly preferable to use a combination of the reactive silicone (a1) and the crosslinkable compound (a2) described below, and it is further preferable to combine a film-forming compound (a3).
上記硬化性組成物は、（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する反応性化合物（ａ）のみで構成されていてもよく、溶剤、ラジカル開始剤、カチオン開始剤、レベリング剤、帯電防止剤、染料、顔料等の、それ以外の成分を含有してもよい。
（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する反応性化合物（ａ）の使用量は、合計で、剥離剤層の質量の５０質量％以上であることが好ましく、６０から９６質量％であることが特に好ましい。 The curable composition may be composed only of a reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, or may contain other components such as a solvent, a radical initiator, a cationic initiator, a leveling agent, an antistatic agent, a dye, and a pigment.
The amount of reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group used is preferably 50 mass% or more, and particularly preferably 60 to 96 mass%, of the mass of the release agent layer.
（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する反応性化合物（ａ）の使用量は、合計で、剥離剤層の質量の５０質量％以上であることが好ましく、６０から９６質量％であることが特に好ましい。 The curable composition may be composed only of a reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, or may contain other components such as a solvent, a radical initiator, a cationic initiator, a leveling agent, an antistatic agent, a dye, and a pigment.
The amount of reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group used is preferably 50 mass% or more, and particularly preferably 60 to 96 mass%, of the mass of the release agent layer.
反応性化合物（ａ）
本発明中の剥離剤層の形成に好ましく用いられる反応性化合物（ａ）は、（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する。（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有することで、硬化性組成物に光硬化性及び／又は熱硬化性を付与することができる。 Reactive Compound (a)
The reactive compound (a) preferably used for forming the release agent layer in the present invention has at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group. By having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, it is possible to impart photocurability and/or thermosetting property to the curable composition.
本発明中の剥離剤層の形成に好ましく用いられる反応性化合物（ａ）は、（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する。（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有することで、硬化性組成物に光硬化性及び／又は熱硬化性を付与することができる。 Reactive Compound (a)
The reactive compound (a) preferably used for forming the release agent layer in the present invention has at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group. By having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, it is possible to impart photocurability and/or thermosetting property to the curable composition.
反応性化合物（ａ）は１以上の反応性官能基を有していればよいが、光硬化性及び／又は熱硬化性の観点からは、２以上の反応性官能基を有することが好ましく、２から１５個の反応性官能基を有することがより好ましく、２から１０個の反応性官能基を有することが特に好ましい。反応性化合物（ａ）が２以上の反応性官能基を有する場合、同種の反応性官能基を２以上有していてもよく、異種の反応性官能基の組み合わせを合計で２以上有していてもよい。
反応性化合物（ａ）は、硬化性等の観点からは活性エネルギー線を用いる場合には（メタ）アクリロイル基を有することが好ましく、熱硬化を併用する場合には水酸基あるいはエポキシ基を含有する材料を適宜選択することが出来る。 The reactive compound (a) may have one or more reactive functional groups, but from the viewpoint of photocurability and/or thermosetting property, it preferably has two or more reactive functional groups, more preferably has 2 to 15 reactive functional groups, and particularly preferably has 2 to 10 reactive functional groups. When the reactive compound (a) has two or more reactive functional groups, it may have two or more of the same type of reactive functional groups, or may have a combination of two or more different types of reactive functional groups in total.
From the viewpoint of curability, etc., when active energy rays are used, the reactive compound (a) preferably has a (meth)acryloyl group, and when heat curing is also used, a material containing a hydroxyl group or an epoxy group can be appropriately selected.
反応性化合物（ａ）は、硬化性等の観点からは活性エネルギー線を用いる場合には（メタ）アクリロイル基を有することが好ましく、熱硬化を併用する場合には水酸基あるいはエポキシ基を含有する材料を適宜選択することが出来る。 The reactive compound (a) may have one or more reactive functional groups, but from the viewpoint of photocurability and/or thermosetting property, it preferably has two or more reactive functional groups, more preferably has 2 to 15 reactive functional groups, and particularly preferably has 2 to 10 reactive functional groups. When the reactive compound (a) has two or more reactive functional groups, it may have two or more of the same type of reactive functional groups, or may have a combination of two or more different types of reactive functional groups in total.
From the viewpoint of curability, etc., when active energy rays are used, the reactive compound (a) preferably has a (meth)acryloyl group, and when heat curing is also used, a material containing a hydroxyl group or an epoxy group can be appropriately selected.
反応性化合物（ａ）の好ましい例として、（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基、並びにシロキサン骨格を有する反応性シリコーン（ａ１）、該反応性シリコーン（ａ１）と同じ反応性官能基を有し、且つ反応性官能基当量が１０００ｇ／ｍｏｌ以下である反応性化合物（ａ２）、及び１分子中に２個以上の（メタ）アクリロイル基を有する膜形成性化合物（ａ３）を挙げることができる。
硬化性組成物においては、反応性シリコーン（ａ１）及び反応性化合物（ａ２）を組み合わせて使用することが好ましく、更に膜形成性化合物（ａ３）を組み合わせて使用することが好ましい。 Preferred examples of the reactive compound (a) include a reactive silicone (a1) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, and a siloxane skeleton; a reactive compound (a2) having the same reactive functional group as the reactive silicone (a1) and having a reactive functional group equivalent of 1000 g/mol or less; and a film-forming compound (a3) having two or more (meth)acryloyl groups in one molecule.
In the curable composition, it is preferable to use a combination of the reactive silicone (a1) and the reactive compound (a2), and it is further preferable to use a combination of the film-forming compound (a3).
硬化性組成物においては、反応性シリコーン（ａ１）及び反応性化合物（ａ２）を組み合わせて使用することが好ましく、更に膜形成性化合物（ａ３）を組み合わせて使用することが好ましい。 Preferred examples of the reactive compound (a) include a reactive silicone (a1) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, and a siloxane skeleton; a reactive compound (a2) having the same reactive functional group as the reactive silicone (a1) and having a reactive functional group equivalent of 1000 g/mol or less; and a film-forming compound (a3) having two or more (meth)acryloyl groups in one molecule.
In the curable composition, it is preferable to use a combination of the reactive silicone (a1) and the reactive compound (a2), and it is further preferable to use a combination of the film-forming compound (a3).
反応性シリコーン（ａ１）
上記硬化性組成物は、反応性化合物（ａ）として（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基、並びにシロキサン骨格を有する反応性シリコーン（ａ１）を含有することが好ましい。
反応性シリコーン（ａ１）を使用することで、剥離剤層の表面に所望の剥離性を付与し、セラミックグリーンシートの剥離を一層容易にすることができる。
反応性シリコーン（ａ１）は、（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有し、かつシロキサン骨格を有していればよく、それ以外の制限は課されない。
（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有することで、活性エネルギー線の照射により、または別途の反応工程（例えば加熱工程）により、反応性官能基が反応して、シロキサン骨格が架橋構造に組み込まれ、固定されることとなる。これにより、反応性シリコーン（ａ１）が剥離剤層上に成形されたセラミックグリーンシートを汚染することを一層有効に抑制することができる。
反応性官能基としては、エポキシ基が特に好ましい。 Reactive silicone (a1)
The curable composition preferably contains, as the reactive compound (a), at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, and a reactive silicone (a1) having a siloxane skeleton.
By using the reactive silicone (a1), the surface of the release agent layer can be given the desired releasability, making it easier to peel off the ceramic green sheet.
The reactive silicone (a1) is not limited as long as it has at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, and has a siloxane skeleton.
By having at least one reactive functional group selected from the group consisting of (meth)acryloyl group, hydroxyl group, and epoxy group, the reactive functional group reacts by irradiation with active energy rays or by a separate reaction step (for example, a heating step), and the siloxane skeleton is incorporated into a crosslinked structure and fixed, which makes it possible to more effectively prevent the reactive silicone (a1) from contaminating the ceramic green sheet formed on the release agent layer.
As the reactive functional group, an epoxy group is particularly preferred.
上記硬化性組成物は、反応性化合物（ａ）として（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基、並びにシロキサン骨格を有する反応性シリコーン（ａ１）を含有することが好ましい。
反応性シリコーン（ａ１）を使用することで、剥離剤層の表面に所望の剥離性を付与し、セラミックグリーンシートの剥離を一層容易にすることができる。
反応性シリコーン（ａ１）は、（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有し、かつシロキサン骨格を有していればよく、それ以外の制限は課されない。
（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有することで、活性エネルギー線の照射により、または別途の反応工程（例えば加熱工程）により、反応性官能基が反応して、シロキサン骨格が架橋構造に組み込まれ、固定されることとなる。これにより、反応性シリコーン（ａ１）が剥離剤層上に成形されたセラミックグリーンシートを汚染することを一層有効に抑制することができる。
反応性官能基としては、エポキシ基が特に好ましい。 Reactive silicone (a1)
The curable composition preferably contains, as the reactive compound (a), at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, and a reactive silicone (a1) having a siloxane skeleton.
By using the reactive silicone (a1), the surface of the release agent layer can be given the desired releasability, making it easier to peel off the ceramic green sheet.
The reactive silicone (a1) is not limited as long as it has at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, and has a siloxane skeleton.
By having at least one reactive functional group selected from the group consisting of (meth)acryloyl group, hydroxyl group, and epoxy group, the reactive functional group reacts by irradiation with active energy rays or by a separate reaction step (for example, a heating step), and the siloxane skeleton is incorporated into a crosslinked structure and fixed, which makes it possible to more effectively prevent the reactive silicone (a1) from contaminating the ceramic green sheet formed on the release agent layer.
As the reactive functional group, an epoxy group is particularly preferred.
反応性官能基は、シロキサン骨格の片末端に導入されていてもよいし、両末端に導入されていてもよいし、側鎖に導入されていてもよい。（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基は、反応性シリコーン（ａ１）１分子中に２以上導入されていることが好ましい。２以上の反応性官能基を有する場合には、同種の反応性官能基を２以上有していてもよく、異なる反応性官能基の組み合わせを合計で２以上有していてもよい。
（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる反応性官能基に加えて、ビニル基、マレイミド基、カルボキシル基、イソシアネート基等を更に有していてもよい。 The reactive functional group may be introduced into one end of the siloxane skeleton, may be introduced into both ends, or may be introduced into a side chain.It is preferable that at least one reactive functional group selected from the group consisting of (meth)acryloyl group, hydroxyl group, and epoxy group is introduced into one molecule of the reactive silicone (a1) in an amount of two or more.When having two or more reactive functional groups, it may have two or more of the same type of reactive functional groups, or may have a combination of two or more different reactive functional groups in total.
In addition to the reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, the compound may further have a vinyl group, a maleimide group, a carboxyl group, an isocyanate group, or the like.
（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる反応性官能基に加えて、ビニル基、マレイミド基、カルボキシル基、イソシアネート基等を更に有していてもよい。 The reactive functional group may be introduced into one end of the siloxane skeleton, may be introduced into both ends, or may be introduced into a side chain.It is preferable that at least one reactive functional group selected from the group consisting of (meth)acryloyl group, hydroxyl group, and epoxy group is introduced into one molecule of the reactive silicone (a1) in an amount of two or more.When having two or more reactive functional groups, it may have two or more of the same type of reactive functional groups, or may have a combination of two or more different reactive functional groups in total.
In addition to the reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, the compound may further have a vinyl group, a maleimide group, a carboxyl group, an isocyanate group, or the like.
反応性シリコーン（ａ１）の分子量には特に制限は無いが、適切な剥離性と汚染抑制との観点から、５，０００から１００,０００であることが好ましく、１０，０００から７０，０００であることが特に好ましい。
There are no particular limitations on the molecular weight of the reactive silicone (a1), but from the standpoint of appropriate release properties and contamination prevention, it is preferably 5,000 to 100,000, and particularly preferably 10,000 to 70,000.
上記硬化性組成物において、反応性シリコーン（ａ１）は１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
上記硬化性組成物における反応性シリコーン（ａ１）の含有量には特に制限は無いが、剥離剤層の全質量を基準として、０．１から２０質量％であることが好ましく、０．２から１５質量％であることが特に好ましい。 In the curable composition, the reactive silicone (a1) may be used alone or in combination of two or more kinds.
The content of the reactive silicone (a1) in the curable composition is not particularly limited, but is preferably from 0.1 to 20 mass %, and particularly preferably from 0.2 to 15 mass %, based on the total mass of the release agent layer.
上記硬化性組成物における反応性シリコーン（ａ１）の含有量には特に制限は無いが、剥離剤層の全質量を基準として、０．１から２０質量％であることが好ましく、０．２から１５質量％であることが特に好ましい。 In the curable composition, the reactive silicone (a1) may be used alone or in combination of two or more kinds.
The content of the reactive silicone (a1) in the curable composition is not particularly limited, but is preferably from 0.1 to 20 mass %, and particularly preferably from 0.2 to 15 mass %, based on the total mass of the release agent layer.
反応性化合物（ａ２）（架橋性化合物（ａ２））
上記硬化性組成物は、反応性化合物（ａ）として、上記反応性シリコーン（ａ１）と同じ反応性官能基を有し、且つ反応性官能基当量が１０００ｇ／ｍｏｌ以下である反応性化合物（ａ２）を含有することが好ましい。反応性化合物（ａ２）を反応性シリコーン（ａ１）との組み合わせにおいて使用することが特に好ましい。
反応性化合物（ａ２）は反応性シリコーン（ａ１）等に対する架橋剤として機能し、硬化性組成物の効果を促進し、反応性シリコーン（ａ１）等を架橋構造に組み込み固定することができる。これにより、セラミックグリーンシートの汚染を一層有効に抑制することができる。架橋剤としての機能に鑑み、本明細書では反応性化合物（ａ２）を「架橋性化合物（ａ２）」とも呼ぶ。 Reactive Compound (a2) (Crosslinkable Compound (a2))
The curable composition preferably contains, as the reactive compound (a), a reactive compound (a2) having the same reactive functional group as the reactive silicone (a1) and having a reactive functional group equivalent of 1000 g/mol or less. It is particularly preferable to use the reactive compound (a2) in combination with the reactive silicone (a1).
The reactive compound (a2) functions as a crosslinking agent for the reactive silicone (a1) and the like, promotes the effect of the curable composition, and can incorporate and fix the reactive silicone (a1) and the like into a crosslinked structure. This makes it possible to more effectively suppress contamination of the ceramic green sheet. In view of its function as a crosslinking agent, the reactive compound (a2) is also referred to as a "crosslinkable compound (a2)" in this specification.
上記硬化性組成物は、反応性化合物（ａ）として、上記反応性シリコーン（ａ１）と同じ反応性官能基を有し、且つ反応性官能基当量が１０００ｇ／ｍｏｌ以下である反応性化合物（ａ２）を含有することが好ましい。反応性化合物（ａ２）を反応性シリコーン（ａ１）との組み合わせにおいて使用することが特に好ましい。
反応性化合物（ａ２）は反応性シリコーン（ａ１）等に対する架橋剤として機能し、硬化性組成物の効果を促進し、反応性シリコーン（ａ１）等を架橋構造に組み込み固定することができる。これにより、セラミックグリーンシートの汚染を一層有効に抑制することができる。架橋剤としての機能に鑑み、本明細書では反応性化合物（ａ２）を「架橋性化合物（ａ２）」とも呼ぶ。 Reactive Compound (a2) (Crosslinkable Compound (a2))
The curable composition preferably contains, as the reactive compound (a), a reactive compound (a2) having the same reactive functional group as the reactive silicone (a1) and having a reactive functional group equivalent of 1000 g/mol or less. It is particularly preferable to use the reactive compound (a2) in combination with the reactive silicone (a1).
The reactive compound (a2) functions as a crosslinking agent for the reactive silicone (a1) and the like, promotes the effect of the curable composition, and can incorporate and fix the reactive silicone (a1) and the like into a crosslinked structure. This makes it possible to more effectively suppress contamination of the ceramic green sheet. In view of its function as a crosslinking agent, the reactive compound (a2) is also referred to as a "crosslinkable compound (a2)" in this specification.
反応性化合物（ａ２）の反応性官能基当量は１０００ｇ／ｍｏｌ以下であり、５００ｇ／ｍｏｌ以下であることが好ましく、３００ｇ／ｍｏｌ以下であることが特に好ましい。
反応性官能基当量は１０００ｇ／ｍｏｌ以下であることにより、適切な架橋性能を実現するのに十分な数の（メタ）アクリロイル基、水酸基、及び／又はエポキシ基を有することになる。
反応性化合物（ａ２）は、反応性官能基（（メタ）アクリロイル基、水酸基、及び／又はエポキシ基）を合計で１以上有することが好ましく、２から１５個有することが好ましく、２から６個有することが特に好ましい。反応性官能基の数が上記範囲内にあることで、一層適切な架橋性能を実現することができる。 The reactive functional group equivalent of the reactive compound (a2) is 1000 g/mol or less, preferably 500 g/mol or less, particularly preferably 300 g/mol or less.
By having a reactive functional group equivalent of 1000 g/mol or less, the polymer has a sufficient number of (meth)acryloyl groups, hydroxyl groups, and/or epoxy groups to achieve suitable crosslinking performance.
The reactive compound (a2) preferably has a total of 1 or more reactive functional groups ((meth)acryloyl group, hydroxyl group, and/or epoxy group), preferably has 2 to 15 reactive functional groups, and particularly preferably has 2 to 6 reactive functional groups. When the number of reactive functional groups is within the above range, more appropriate crosslinking performance can be achieved.
反応性官能基当量は１０００ｇ／ｍｏｌ以下であることにより、適切な架橋性能を実現するのに十分な数の（メタ）アクリロイル基、水酸基、及び／又はエポキシ基を有することになる。
反応性化合物（ａ２）は、反応性官能基（（メタ）アクリロイル基、水酸基、及び／又はエポキシ基）を合計で１以上有することが好ましく、２から１５個有することが好ましく、２から６個有することが特に好ましい。反応性官能基の数が上記範囲内にあることで、一層適切な架橋性能を実現することができる。 The reactive functional group equivalent of the reactive compound (a2) is 1000 g/mol or less, preferably 500 g/mol or less, particularly preferably 300 g/mol or less.
By having a reactive functional group equivalent of 1000 g/mol or less, the polymer has a sufficient number of (meth)acryloyl groups, hydroxyl groups, and/or epoxy groups to achieve suitable crosslinking performance.
The reactive compound (a2) preferably has a total of 1 or more reactive functional groups ((meth)acryloyl group, hydroxyl group, and/or epoxy group), preferably has 2 to 15 reactive functional groups, and particularly preferably has 2 to 6 reactive functional groups. When the number of reactive functional groups is within the above range, more appropriate crosslinking performance can be achieved.
架橋性化合物（ａ２）の分子量には特に制限は無いが、架橋性能等の観点から、１５０から３５００であることが好ましく、１５０から１５００であることが特に好ましい。
架橋性化合物（ａ２）はシロキサン骨格を有していてもよく、この場合反応性シリコーン（ａ１）のシロキサン骨格とともに、剥離剤層に十分なシロキサン骨格を導入することで、一層好ましい剥離性能を実現することができる。 The molecular weight of the crosslinkable compound (a2) is not particularly limited, but from the viewpoint of crosslinking performance, etc., it is preferably from 150 to 3,500, and particularly preferably from 150 to 1,500.
The crosslinkable compound (a2) may have a siloxane skeleton. In this case, by introducing a sufficient amount of siloxane skeleton into the release agent layer together with the siloxane skeleton of the reactive silicone (a1), more preferable release performance can be achieved.
架橋性化合物（ａ２）はシロキサン骨格を有していてもよく、この場合反応性シリコーン（ａ１）のシロキサン骨格とともに、剥離剤層に十分なシロキサン骨格を導入することで、一層好ましい剥離性能を実現することができる。 The molecular weight of the crosslinkable compound (a2) is not particularly limited, but from the viewpoint of crosslinking performance, etc., it is preferably from 150 to 3,500, and particularly preferably from 150 to 1,500.
The crosslinkable compound (a2) may have a siloxane skeleton. In this case, by introducing a sufficient amount of siloxane skeleton into the release agent layer together with the siloxane skeleton of the reactive silicone (a1), more preferable release performance can be achieved.
上記硬化性組成物において、架橋性化合物（ａ２）は１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
上記硬化性組成物における架橋性化合物（ａ２）の含有量には特に制限は無いが、剥離剤層の全質量を基準として、０．０８から９９質量％であることが好ましく、０．４から５０質量％であることが特に好ましい。また、反応性シリコーン（ａ１）の使用量を基準とした場合、反応性シリコーン（ａ１）１００質量部に対して、８１から９９００質量部使用することが好ましく、８５から１０００質量部使用することが特に好ましい。 In the curable composition, the crosslinkable compound (a2) may be used alone or in combination of two or more kinds.
The content of the crosslinkable compound (a2) in the curable composition is not particularly limited, but is preferably 0.08 to 99 mass%, particularly preferably 0.4 to 50 mass%, based on the total mass of the release agent layer. Also, based on the amount of reactive silicone (a1) used, it is preferably 81 to 9900 mass parts, particularly preferably 85 to 1000 mass parts, based on 100 mass parts of reactive silicone (a1).
上記硬化性組成物における架橋性化合物（ａ２）の含有量には特に制限は無いが、剥離剤層の全質量を基準として、０．０８から９９質量％であることが好ましく、０．４から５０質量％であることが特に好ましい。また、反応性シリコーン（ａ１）の使用量を基準とした場合、反応性シリコーン（ａ１）１００質量部に対して、８１から９９００質量部使用することが好ましく、８５から１０００質量部使用することが特に好ましい。 In the curable composition, the crosslinkable compound (a2) may be used alone or in combination of two or more kinds.
The content of the crosslinkable compound (a2) in the curable composition is not particularly limited, but is preferably 0.08 to 99 mass%, particularly preferably 0.4 to 50 mass%, based on the total mass of the release agent layer. Also, based on the amount of reactive silicone (a1) used, it is preferably 81 to 9900 mass parts, particularly preferably 85 to 1000 mass parts, based on 100 mass parts of reactive silicone (a1).
上記硬化性組成物における反応性化合物（ａ）として、膜形成性能に優れる化合物を使用することも好ましい。膜形成性能に優れる化合物としては、（メタ）アクリロイル基を有する化合物、水酸基を有する化合物のいずれであってもよいが、１分子中に２個以上の（メタ）アクリロイル基を有する膜形成性化合物（ａ３）を使用することが好ましい。
膜形成性化合物（ａ３）
上記硬化性組成物は、反応性化合物（ａ）として、１分子中に２個以上の（メタ）アクリロイル基を有する膜形成性化合物（ａ３）を含有することが好ましい。
１分子中に２個以上の（メタ）アクリロイル基を有する膜形成性化合物（ａ３）を含有することで、硬化性組成物を活性エネルギー線の照射によって硬化させることができる。
膜形成性化合物（ａ３）は、モノマー、オリゴマーまたはポリマーのいずれであってもよいし、それらの混合物であってもよい。膜形成性化合物（ａ３）は、（メタ）アクリル酸エステルであることが好ましい。ここで、（メタ）アクリル酸エステルとは、アクリル酸エステルおよびメタクリル酸エステルの両方を意味する。他の類似用語も同様である。 It is also preferred to use a compound having excellent film-forming properties as the reactive compound (a) in the curable composition.The compound having excellent film-forming properties may be either a compound having a (meth)acryloyl group or a compound having a hydroxyl group, but it is preferred to use a film-forming compound (a3) having two or more (meth)acryloyl groups in one molecule.
Film-forming compound (a3)
The curable composition preferably contains, as the reactive compound (a), a film-forming compound (a3) having two or more (meth)acryloyl groups in one molecule.
By including the film-forming compound (a3) having two or more (meth)acryloyl groups in one molecule, the curable composition can be cured by irradiation with active energy rays.
The film-forming compound (a3) may be any of a monomer, an oligomer, or a polymer, or may be a mixture thereof. The film-forming compound (a3) is preferably a (meth)acrylic acid ester. Here, the (meth)acrylic acid ester means both an acrylic acid ester and a methacrylic acid ester. The same applies to other similar terms.
膜形成性化合物（ａ３）
上記硬化性組成物は、反応性化合物（ａ）として、１分子中に２個以上の（メタ）アクリロイル基を有する膜形成性化合物（ａ３）を含有することが好ましい。
１分子中に２個以上の（メタ）アクリロイル基を有する膜形成性化合物（ａ３）を含有することで、硬化性組成物を活性エネルギー線の照射によって硬化させることができる。
膜形成性化合物（ａ３）は、モノマー、オリゴマーまたはポリマーのいずれであってもよいし、それらの混合物であってもよい。膜形成性化合物（ａ３）は、（メタ）アクリル酸エステルであることが好ましい。ここで、（メタ）アクリル酸エステルとは、アクリル酸エステルおよびメタクリル酸エステルの両方を意味する。他の類似用語も同様である。 It is also preferred to use a compound having excellent film-forming properties as the reactive compound (a) in the curable composition.The compound having excellent film-forming properties may be either a compound having a (meth)acryloyl group or a compound having a hydroxyl group, but it is preferred to use a film-forming compound (a3) having two or more (meth)acryloyl groups in one molecule.
Film-forming compound (a3)
The curable composition preferably contains, as the reactive compound (a), a film-forming compound (a3) having two or more (meth)acryloyl groups in one molecule.
By including the film-forming compound (a3) having two or more (meth)acryloyl groups in one molecule, the curable composition can be cured by irradiation with active energy rays.
The film-forming compound (a3) may be any of a monomer, an oligomer, or a polymer, or may be a mixture thereof. The film-forming compound (a3) is preferably a (meth)acrylic acid ester. Here, the (meth)acrylic acid ester means both an acrylic acid ester and a methacrylic acid ester. The same applies to other similar terms.
（メタ）アクリル酸エステルとしては、多官能の（メタ）アクリレートモノマーおよび（メタ）アクリレートオリゴマーから選ばれる少なくとも１種であることが好ましく、特に、二官能以上の（メタ）アクリレートモノマーおよび（メタ）アクリレートオリゴマーから選ばれる少なくとも１種であることが好ましく、さらには、三官能以上の（メタ）アクリレートモノマーであることが好ましい。二官能以上、更に好ましくは三官能以上であることで、硬化性組成物の硬化性が優れたものとなり、また、得られる剥離剤層の表面の剥離性もより優れたものとなる。
The (meth)acrylic acid ester is preferably at least one selected from polyfunctional (meth)acrylate monomers and (meth)acrylate oligomers, particularly at least one selected from difunctional or higher functional (meth)acrylate monomers and (meth)acrylate oligomers, and more preferably a trifunctional or higher functional (meth)acrylate monomer. Being difunctional or higher, more preferably trifunctional or higher, results in excellent curability of the curable composition, and also in excellent release properties of the surface of the resulting release agent layer.
多官能（メタ）アクリレートモノマーとしては、例えば、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールアジペートジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、カプロラクトン変性ジシクロペンテニルジ（メタ）アクリレート、エチレンオキシド変性リン酸ジ（メタ）アクリレート、アリル化シクロヘキシルジ（メタ）アクリレート、イソシアヌレートジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、プロピオン酸変性ジペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、プロピレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、トリス（（メタ）アクリロキシエチル）イソシアヌレート、プロピオン酸変性ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。
これらは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of polyfunctional (meth)acrylate monomers include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, and isocyanurate di(meth)acrylate. acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, tris((meth)acryloxyethyl)isocyanurate, propionic acid modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, and the like.
These may be used alone or in combination of two or more.
これらは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of polyfunctional (meth)acrylate monomers include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, and isocyanurate di(meth)acrylate. acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, tris((meth)acryloxyethyl)isocyanurate, propionic acid modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, and the like.
These may be used alone or in combination of two or more.
多官能（メタ）アクリレートオリゴマーとしては、例えば、ポリエステルアクリレート系オリゴマー、エポキシアクリレート系オリゴマー、ウレタンアクリレート系オリゴマー、ポリエーテルアクリレート系オリゴマー、ポリブタジエンアクリレート系オリゴマー、シリコーンアクリレート系オリゴマー等が挙げられる。
Examples of polyfunctional (meth)acrylate oligomers include polyester acrylate oligomers, epoxy acrylate oligomers, urethane acrylate oligomers, polyether acrylate oligomers, polybutadiene acrylate oligomers, silicone acrylate oligomers, etc.
ポリエステルアクリレート系オリゴマーは、例えば、多価カルボン酸と多価アルコールの縮合によって得られる両末端に水酸基を有するポリエステルオリゴマーの水酸基を（メタ）アクリル酸でエステル化することにより、あるいは、多価カルボン酸にアルキレンオキシドを付加して得られるオリゴマーの末端の水酸基を（メタ）アクリル酸でエステル化することにより得ることができる。
Polyester acrylate oligomers can be obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends, obtained by condensation of a polycarboxylic acid with a polyhydric alcohol, with (meth)acrylic acid, or by esterifying the terminal hydroxyl groups of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid, with (meth)acrylic acid.
エポキシアクリレート系オリゴマーは、例えば、比較的低分子量のビスフェノール型エポキシ樹脂やノボラック型エポキシ樹脂のオキシラン環に、（メタ）アクリル酸を反応しエステル化することにより得ることができる。また、エポキシアクリレート系オリゴマーを部分的に二塩基性カルボン酸無水物で変性したカルボキシル変性型のエポキシアクリレート系オリゴマーを用いることもできる。
Epoxy acrylate oligomers can be obtained, for example, by reacting (meth)acrylic acid with the oxirane ring of a relatively low molecular weight bisphenol epoxy resin or novolac epoxy resin to esterify it. It is also possible to use a carboxyl-modified epoxy acrylate oligomer in which an epoxy acrylate oligomer is partially modified with a dibasic carboxylic acid anhydride.
ウレタンアクリレート系オリゴマーは、例えば、ポリエーテルポリオールやポリエステルポリオールとポリイソシアナートの反応によって得られるポリウレタンオリゴマーを、（メタ）アクリル酸でエステル化することにより得ることができる。
Urethane acrylate oligomers can be obtained, for example, by esterifying polyurethane oligomers obtained by reacting polyether polyol or polyester polyol with polyisocyanate with (meth)acrylic acid.
ポリエーテルアクリレート系オリゴマーは、ポリエーテルポリオールの水酸基を（メタ）アクリル酸でエステル化することにより得ることができる。
Polyether acrylate oligomers can be obtained by esterifying the hydroxyl groups of polyether polyol with (meth)acrylic acid.
上記硬化性組成物において、膜形成性化合物（ａ３）は１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
上記硬化性組成物における膜形成性化合物（ａ３）の含有量には特に制限は無いが、剥離剤層の全質量を基準として、５０から９０質量％であることが好ましく、６０から８５質量％であることが特に好ましい。 In the curable composition, the film-forming compound (a3) may be used alone or in combination of two or more kinds.
The content of the film-forming compound (a3) in the curable composition is not particularly limited, but is preferably from 50 to 90 mass %, and particularly preferably from 60 to 85 mass %, based on the total mass of the release agent layer.
上記硬化性組成物における膜形成性化合物（ａ３）の含有量には特に制限は無いが、剥離剤層の全質量を基準として、５０から９０質量％であることが好ましく、６０から８５質量％であることが特に好ましい。 In the curable composition, the film-forming compound (a3) may be used alone or in combination of two or more kinds.
The content of the film-forming compound (a3) in the curable composition is not particularly limited, but is preferably from 50 to 90 mass %, and particularly preferably from 60 to 85 mass %, based on the total mass of the release agent layer.
剥離剤層は、基材の少なくとも一方の面に剥離剤層の原料、好ましくは上記の硬化性組成物を塗布した後、必要に応じて乾燥し、光等の活性エネルギー線の照射により硬化させることで形成することができる。反応性化合物（ａ）の反応性官能基が熱により反応するものである場合には、このときの乾燥により反応を起こさせ、好ましくはシロキサン骨格を有する反応性化合物（ａ）を架橋構造に組み込むことができる。硬化性組成物の塗布方法には特に制限は無く、例えば、グラビアコート法、バーコート法、スプレーコート法、スピンコート法、ナイフコート法、ロールコート法、ダイコート法等が使用できる。
The release agent layer can be formed by applying a raw material for the release agent layer, preferably the above-mentioned curable composition, to at least one surface of the substrate, followed by drying as necessary and curing by irradiation with active energy rays such as light. If the reactive functional group of the reactive compound (a) is one that reacts with heat, the drying at this time causes a reaction, and the reactive compound (a), preferably having a siloxane skeleton, can be incorporated into a crosslinked structure. There are no particular limitations on the method for applying the curable composition, and for example, gravure coating, bar coating, spray coating, spin coating, knife coating, roll coating, die coating, etc. can be used.
活性エネルギー線としては、通常、紫外線、電子線等が用いられる。活性エネルギー線の照射量は、エネルギー線の種類によって異なるが、例えば紫外線の場合には、光量で１０～１０００ｍＪ／ｃｍ２が好ましく、特に２０～５００ｍＪ／ｃｍ２が好ましい。また、電子線の場合には、０．１～５０ｋＧｙ程度が好ましい。
As the active energy ray, ultraviolet rays, electron beams, etc. are usually used. The irradiation amount of the active energy ray varies depending on the type of energy ray, but for example, in the case of ultraviolet rays, the light amount is preferably 10 to 1000 mJ/ cm2 , and more preferably 20 to 500 mJ/ cm2 . In the case of electron beams, the amount is preferably about 0.1 to 50 kGy.
本発明のセラミックグリーンシート製造用剥離フィルムを構成する剥離剤層の基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）は、０．３（ｍＮ／ｍ）以上である。
剥離剤層の基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が０．３（ｍＮ／ｍ）以上であることで、他の本発明の技術的特徴とも相俟って、本発明のセラミックグリーンシート製造用剥離フィルムは、その上の形成したセラミックグリーンシートの剥離の容易性と、セラミックグリーンシートの汚染の抑制とを高いレベルで両立できる等、実用上高い価値を有する優れた技術的効果を実現することができる。
剥離剤層の基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が０．３（ｍＮ／ｍ）以上であることで、セラミックグリーンシートの剥離の容易性と、セラミックグリーンシートの汚染の抑制とを両立できるメカニズムは必ずしも明らかではないが、剥離剤層の表面自由エネルギーが、剥離性や、セラミックグリーンシート及びその他の被着体への汚染に密接な関係を有し得るところ、剥離性及び耐汚染性を両立し得る表面自由エネルギーの最適値が存在しているものと推定される。 The polar component (γ sp ) of the surface free energy of the surface opposite to the substrate of the release agent layer constituting the release film for producing a ceramic green sheet of the present invention is 0.3 (mN/m) or more.
The polar component (γ sp ) of the surface free energy of the release agent layer on the side opposite the substrate is 0.3 (mN/m) or more, which, in combination with other technical features of the present invention, enables the release film for producing ceramic green sheets of the present invention to achieve excellent technical effects of great practical value, such as a high level of compatibility between ease of peeling of the ceramic green sheet formed thereon and inhibition of contamination of the ceramic green sheet.
The mechanism by which the ease of peeling the ceramic green sheet and the prevention of contamination of the ceramic green sheet can be achieved simultaneously by setting the polar component (γ sp ) of the surface free energy of the release agent layer opposite the substrate to 0.3 (mN/m) or more is not necessarily clear; however, since the surface free energy of the release agent layer may be closely related to the releasability and the contamination of the ceramic green sheet and other adherends, it is presumed that there is an optimal value of the surface free energy that can achieve both releasability and contamination resistance.
剥離剤層の基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が０．３（ｍＮ／ｍ）以上であることで、他の本発明の技術的特徴とも相俟って、本発明のセラミックグリーンシート製造用剥離フィルムは、その上の形成したセラミックグリーンシートの剥離の容易性と、セラミックグリーンシートの汚染の抑制とを高いレベルで両立できる等、実用上高い価値を有する優れた技術的効果を実現することができる。
剥離剤層の基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が０．３（ｍＮ／ｍ）以上であることで、セラミックグリーンシートの剥離の容易性と、セラミックグリーンシートの汚染の抑制とを両立できるメカニズムは必ずしも明らかではないが、剥離剤層の表面自由エネルギーが、剥離性や、セラミックグリーンシート及びその他の被着体への汚染に密接な関係を有し得るところ、剥離性及び耐汚染性を両立し得る表面自由エネルギーの最適値が存在しているものと推定される。 The polar component (γ sp ) of the surface free energy of the surface opposite to the substrate of the release agent layer constituting the release film for producing a ceramic green sheet of the present invention is 0.3 (mN/m) or more.
The polar component (γ sp ) of the surface free energy of the release agent layer on the side opposite the substrate is 0.3 (mN/m) or more, which, in combination with other technical features of the present invention, enables the release film for producing ceramic green sheets of the present invention to achieve excellent technical effects of great practical value, such as a high level of compatibility between ease of peeling of the ceramic green sheet formed thereon and inhibition of contamination of the ceramic green sheet.
The mechanism by which the ease of peeling the ceramic green sheet and the prevention of contamination of the ceramic green sheet can be achieved simultaneously by setting the polar component (γ sp ) of the surface free energy of the release agent layer opposite the substrate to 0.3 (mN/m) or more is not necessarily clear; however, since the surface free energy of the release agent layer may be closely related to the releasability and the contamination of the ceramic green sheet and other adherends, it is presumed that there is an optimal value of the surface free energy that can achieve both releasability and contamination resistance.
剥離剤層の基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）は、当該技術分野において従来公知の方法で測定することができ、例えば接触角法等により測定することができ、例えば複数種類の液体について測定した接触角を北崎―畑、拡張フォークスの式（Ｋｉｔａｚａｋｉ－Ｈａｔａ式）等に当てはめて解析することで、極性成分（γｓｐ）を算出することができる。より具体的には、本願明細書の実施例に記載の方法により測定することができる。
The polar component (γ sp ) of the surface free energy of the surface of the release agent layer opposite to the substrate can be measured by a method conventionally known in the art, for example, a contact angle method, and the polar component (γ sp ) can be calculated by, for example, analyzing contact angles measured for multiple types of liquids by applying them to the Kitazaki-Hata and extended Foulkes equations (Kitazaki-Hata equations), etc. More specifically, it can be measured by the method described in the examples of the present specification.
剥離剤層の基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）は、０．３から１．０（ｍＮ／ｍ）であることが好ましく、０．３から０．８（ｍＮ／ｍ）であることが特に好ましい。
剥離剤層の基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）は、剥離剤層を構成する材料の種類及び使用量や、剥離剤層の塗工量を調整することで、適宜調整することができる。特に（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する反応性化合物（ａ）、中でも反応性シリコーン（ａ１）と同じ反応性官能基を有し、且つ反応性官能基当量が１０００ｇ／ｍｏｌ以下である反応性化合物（ａ２）、の反応性官能基当量及び使用量を調整することで、適宜調整することができる。 The polar component (γ sp ) of the surface free energy of the release agent layer on the side opposite to the substrate is preferably 0.3 to 1.0 (mN/m), and particularly preferably 0.3 to 0.8 (mN/m).
The polar component (γ sp ) of the surface free energy of the surface of the release agent layer opposite to the substrate can be appropriately adjusted by adjusting the type and amount of the material constituting the release agent layer or the coating amount of the release agent layer. In particular, it can be appropriately adjusted by adjusting the reactive functional group equivalent and the amount used of the reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, particularly the reactive compound (a2) having the same reactive functional group as the reactive silicone (a1) and having a reactive functional group equivalent of 1000 g/mol or less.
剥離剤層の基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）は、剥離剤層を構成する材料の種類及び使用量や、剥離剤層の塗工量を調整することで、適宜調整することができる。特に（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する反応性化合物（ａ）、中でも反応性シリコーン（ａ１）と同じ反応性官能基を有し、且つ反応性官能基当量が１０００ｇ／ｍｏｌ以下である反応性化合物（ａ２）、の反応性官能基当量及び使用量を調整することで、適宜調整することができる。 The polar component (γ sp ) of the surface free energy of the release agent layer on the side opposite to the substrate is preferably 0.3 to 1.0 (mN/m), and particularly preferably 0.3 to 0.8 (mN/m).
The polar component (γ sp ) of the surface free energy of the surface of the release agent layer opposite to the substrate can be appropriately adjusted by adjusting the type and amount of the material constituting the release agent layer or the coating amount of the release agent layer. In particular, it can be appropriately adjusted by adjusting the reactive functional group equivalent and the amount used of the reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, particularly the reactive compound (a2) having the same reactive functional group as the reactive silicone (a1) and having a reactive functional group equivalent of 1000 g/mol or less.
本発明のセラミックグリーンシート製造用剥離フィルムは、その剥離剤層の基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が上記条件を満たしていればよく、それ以外の制限は特に課せられないが、剥離剤層の基材とは反対側の面の表面自由エネルギーの分散成分（γｓｄ）が２２（ｍＮ／ｍ）以上であることが好ましい。
剥離剤層の基材とは反対側の面の表面自由エネルギーの分散成分（γｓｄ）が２２（ｍＮ／ｍ）以上であることで、他の本発明の技術的特徴とも相俟って、本実施形態のセラミックグリーンシート製造用剥離フィルムは、その上の形成したセラミックグリーンシートの剥離の容易性と、セラミックグリーンシートの汚染の抑制とを一層高いレベルで両立できる等、実用上一層高い価値を有する優れた技術的効果を実現することができる。
剥離剤層の基材とは反対側の面の表面自由エネルギーの分散成分（γｓｄ）が２２（ｍＮ／ｍ）以上であることで、セラミックグリーンシートの剥離の容易性と、セラミックグリーンシートの汚染の抑制とを一層高いレベルで両立できるメカニズムは必ずしも明らかではないが、剥離剤層の表面自由エネルギーが、剥離性や、セラミックグリーンシート及びその他の被着体への汚染に密接な関係を有し得るところ、剥離性及び耐汚染性を両立し得る表面自由エネルギーの最適値が存在しているものと推定される。 The release film for producing a ceramic green sheet of the present invention is not particularly limited as long as the polar component (γ sp ) of the surface free energy of the release agent layer on the side opposite the substrate satisfies the above-mentioned conditions, but it is preferable that the dispersive component (γ sd ) of the surface free energy of the release agent layer on the side opposite the substrate be 22 (mN/m) or more.
The dispersion component (γ sd ) of the surface free energy of the release agent layer on the side opposite the substrate is 22 (mN/m) or more, which, in combination with other technical features of the present invention, enables the release film for producing ceramic green sheets of this embodiment to achieve excellent technical effects of even greater practical value, such as achieving a higher level of ease in peeling the ceramic green sheet formed thereon while suppressing contamination of the ceramic green sheet.
The mechanism by which a dispersion component (γ sd ) of the surface free energy of the release agent layer on the side opposite the substrate is 22 (mN/m) or more can achieve a higher level of both ease of peeling of the ceramic green sheet and suppression of contamination of the ceramic green sheet is not necessarily clear; however, since the surface free energy of the release agent layer may be closely related to releasability and contamination of the ceramic green sheet and other adherends, it is presumed that there is an optimal value of surface free energy that can achieve both releasability and contamination resistance.
剥離剤層の基材とは反対側の面の表面自由エネルギーの分散成分（γｓｄ）が２２（ｍＮ／ｍ）以上であることで、他の本発明の技術的特徴とも相俟って、本実施形態のセラミックグリーンシート製造用剥離フィルムは、その上の形成したセラミックグリーンシートの剥離の容易性と、セラミックグリーンシートの汚染の抑制とを一層高いレベルで両立できる等、実用上一層高い価値を有する優れた技術的効果を実現することができる。
剥離剤層の基材とは反対側の面の表面自由エネルギーの分散成分（γｓｄ）が２２（ｍＮ／ｍ）以上であることで、セラミックグリーンシートの剥離の容易性と、セラミックグリーンシートの汚染の抑制とを一層高いレベルで両立できるメカニズムは必ずしも明らかではないが、剥離剤層の表面自由エネルギーが、剥離性や、セラミックグリーンシート及びその他の被着体への汚染に密接な関係を有し得るところ、剥離性及び耐汚染性を両立し得る表面自由エネルギーの最適値が存在しているものと推定される。 The release film for producing a ceramic green sheet of the present invention is not particularly limited as long as the polar component (γ sp ) of the surface free energy of the release agent layer on the side opposite the substrate satisfies the above-mentioned conditions, but it is preferable that the dispersive component (γ sd ) of the surface free energy of the release agent layer on the side opposite the substrate be 22 (mN/m) or more.
The dispersion component (γ sd ) of the surface free energy of the release agent layer on the side opposite the substrate is 22 (mN/m) or more, which, in combination with other technical features of the present invention, enables the release film for producing ceramic green sheets of this embodiment to achieve excellent technical effects of even greater practical value, such as achieving a higher level of ease in peeling the ceramic green sheet formed thereon while suppressing contamination of the ceramic green sheet.
The mechanism by which a dispersion component (γ sd ) of the surface free energy of the release agent layer on the side opposite the substrate is 22 (mN/m) or more can achieve a higher level of both ease of peeling of the ceramic green sheet and suppression of contamination of the ceramic green sheet is not necessarily clear; however, since the surface free energy of the release agent layer may be closely related to releasability and contamination of the ceramic green sheet and other adherends, it is presumed that there is an optimal value of surface free energy that can achieve both releasability and contamination resistance.
剥離剤層の基材とは反対側の面の表面自由エネルギーの分散成分（γｓｄ）は、当該技術分野において従来公知の方法で測定することができ、例えば接触角法等により測定することができ、例えば複数種類の液体について測定した接触角を北崎―畑、拡張フォークスの式（Ｋｉｔａｚａｋｉ－Ｈａｔａ式）等に当てはめて解析することで、分散成分（γｓｄ）を算出することができる。より具体的には、本願明細書の実施例に記載の方法により測定することができる。
The dispersion component (γ sd ) of the surface free energy of the surface of the release agent layer opposite to the substrate can be measured by a method conventionally known in the art, for example, a contact angle method, and the dispersion component (γ sd ) can be calculated, for example, by analyzing contact angles measured for multiple types of liquids by applying them to the Kitazaki-Hata and extended Foulkes equations (Kitazaki-Hata equations), etc. More specifically, it can be measured by the method described in the examples of the present specification.
剥離剤層の基材とは反対側の面の表面自由エネルギーの分散成分（γｓｄ）は、２２（ｍＮ／ｍ）以上３０（ｍＮ／ｍ）以下であることが好ましく、２２から２８（ｍＮ／ｍ）であることが特に好ましい。
剥離剤層の基材とは反対側の面の表面自由エネルギーの分散成分（γｓｄ）は、剥離剤層を構成する材料の種類及び使用量や、剥離剤層の塗工量を調整することで、適宜調整することができる。特に（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する反応性化合物（ａ）、中でも反応性シリコーン（ａ１）と同じ反応性官能基を有し、且つ反応性官能基当量が１０００ｇ／ｍｏｌ以下である反応性化合物（ａ２）、の反応性官能基当量及び使用量を調整することで、適宜調整することができる。 The dispersion component (γ sd ) of the surface free energy of the release agent layer on the side opposite to the substrate is preferably 22 (mN/m) to 30 (mN/m), particularly preferably 22 to 28 (mN/m).
The dispersion component (γ sd ) of the surface free energy of the surface of the release agent layer opposite to the substrate can be appropriately adjusted by adjusting the type and amount of the material constituting the release agent layer or the coating amount of the release agent layer. In particular, it can be appropriately adjusted by adjusting the reactive functional group equivalent and the amount used of the reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, particularly the reactive compound (a2) having the same reactive functional group as the reactive silicone (a1) and having a reactive functional group equivalent of 1000 g/mol or less.
剥離剤層の基材とは反対側の面の表面自由エネルギーの分散成分（γｓｄ）は、剥離剤層を構成する材料の種類及び使用量や、剥離剤層の塗工量を調整することで、適宜調整することができる。特に（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する反応性化合物（ａ）、中でも反応性シリコーン（ａ１）と同じ反応性官能基を有し、且つ反応性官能基当量が１０００ｇ／ｍｏｌ以下である反応性化合物（ａ２）、の反応性官能基当量及び使用量を調整することで、適宜調整することができる。 The dispersion component (γ sd ) of the surface free energy of the release agent layer on the side opposite to the substrate is preferably 22 (mN/m) to 30 (mN/m), particularly preferably 22 to 28 (mN/m).
The dispersion component (γ sd ) of the surface free energy of the surface of the release agent layer opposite to the substrate can be appropriately adjusted by adjusting the type and amount of the material constituting the release agent layer or the coating amount of the release agent layer. In particular, it can be appropriately adjusted by adjusting the reactive functional group equivalent and the amount used of the reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, particularly the reactive compound (a2) having the same reactive functional group as the reactive silicone (a1) and having a reactive functional group equivalent of 1000 g/mol or less.
剥離剤層の厚さは、０．０５～２μｍであることが好ましく、特に０．２～１．５μｍであることが好ましい。剥離剤層の厚さが０．０５μｍ以上であることは、剥離剤層表面の平滑性や、セラミックグリーンシートのピンホールや厚みむらの抑制の観点から好ましい。剥離剤層の厚さが２μｍ以下であることは、剥離剤層の硬化収縮によるカールの発生を抑制する観点から好ましい。また、ブロッキングや帯電の抑制の観点からも好ましい。
The thickness of the release agent layer is preferably 0.05 to 2 μm, and particularly preferably 0.2 to 1.5 μm. A thickness of 0.05 μm or more is preferable from the viewpoint of smoothness of the release agent layer surface and suppression of pinholes and uneven thickness of the ceramic green sheet. A thickness of 2 μm or less is preferable from the viewpoint of suppressing curling due to cure shrinkage of the release agent layer. It is also preferable from the viewpoint of suppressing blocking and static electricity.
それ以外の層
本発明のセラミックグリーンシート製造用剥離フィルムは、上述の基材と剥離剤層以外の層を有していてもよく、例えば保護層、接着層、帯電防止層等を有していてもよい。
基材と剥離剤層とは直接積層されていてもよく、接着層等のそれ以外の層を介して積層されていてもよい。 Other Layers The release film for producing a ceramic green sheet of the present invention may have layers other than the above-mentioned substrate and release agent layer, such as a protective layer, an adhesive layer, an antistatic layer, etc.
The substrate and the release agent layer may be laminated directly to each other, or may be laminated via another layer such as an adhesive layer.
本発明のセラミックグリーンシート製造用剥離フィルムは、上述の基材と剥離剤層以外の層を有していてもよく、例えば保護層、接着層、帯電防止層等を有していてもよい。
基材と剥離剤層とは直接積層されていてもよく、接着層等のそれ以外の層を介して積層されていてもよい。 Other Layers The release film for producing a ceramic green sheet of the present invention may have layers other than the above-mentioned substrate and release agent layer, such as a protective layer, an adhesive layer, an antistatic layer, etc.
The substrate and the release agent layer may be laminated directly to each other, or may be laminated via another layer such as an adhesive layer.
セラミックグリーンシート製造用剥離フィルム
本発明のセラミックグリーンシート製造用剥離フィルムは、その上に形成したセラミックグリーンシートの剥離が容易であるとともに、セラミックグリーンシートの汚染を効果的に抑制することができるので、各種セラミック製品に用いるセラミックグリーンシートの製造において好適に使用することができ、例えば積層セラミックコンデンサ、又は多層セラミック基板に用いるセラミックグリーンシートの製造に好適に使用することができる。 Release Film for Producing Ceramic Green Sheets The release film for producing ceramic green sheets of the present invention allows easy release of the ceramic green sheets formed thereon and can effectively suppress contamination of the ceramic green sheets, and therefore can be suitably used in the production of ceramic green sheets for use in various ceramic products, such as multilayer ceramic capacitors or multilayer ceramic substrates.
本発明のセラミックグリーンシート製造用剥離フィルムは、その上に形成したセラミックグリーンシートの剥離が容易であるとともに、セラミックグリーンシートの汚染を効果的に抑制することができるので、各種セラミック製品に用いるセラミックグリーンシートの製造において好適に使用することができ、例えば積層セラミックコンデンサ、又は多層セラミック基板に用いるセラミックグリーンシートの製造に好適に使用することができる。 Release Film for Producing Ceramic Green Sheets The release film for producing ceramic green sheets of the present invention allows easy release of the ceramic green sheets formed thereon and can effectively suppress contamination of the ceramic green sheets, and therefore can be suitably used in the production of ceramic green sheets for use in various ceramic products, such as multilayer ceramic capacitors or multilayer ceramic substrates.
本発明のセラミックグリーンシート製造用剥離フィルムを用いたセラミックグリーンシートの製造方法には特に制限は無いが、例えば以下の工程を有する製造方法において、本発明のセラミックグリーンシート製造用剥離フィルムを好ましく使用することができる。
ａ）本発明のセラミックグリーンシート製造用剥離フィルム上にセラミックスラリーを塗布する工程
ｂ）前記ａ）工程において塗布されたセラミックスラリーからセラミックグリーンシートを形成する工程
ｃ）前記ｂ）工程において形成されたセラミックグリーンシートを前記セラミックグリーンシート製造用剥離フィルムから剥離する工程 There is no particular limitation on the method for producing a ceramic green sheet using the release film for producing a ceramic green sheet of the present invention. For example, the release film for producing a ceramic green sheet of the present invention can be preferably used in a production method having the following steps.
a) applying a ceramic slurry onto the release film for producing a ceramic green sheet of the present invention; b) forming a ceramic green sheet from the ceramic slurry applied in the a) step; and c) peeling the ceramic green sheet formed in the b) step from the release film for producing a ceramic green sheet.
ａ）本発明のセラミックグリーンシート製造用剥離フィルム上にセラミックスラリーを塗布する工程
ｂ）前記ａ）工程において塗布されたセラミックスラリーからセラミックグリーンシートを形成する工程
ｃ）前記ｂ）工程において形成されたセラミックグリーンシートを前記セラミックグリーンシート製造用剥離フィルムから剥離する工程 There is no particular limitation on the method for producing a ceramic green sheet using the release film for producing a ceramic green sheet of the present invention. For example, the release film for producing a ceramic green sheet of the present invention can be preferably used in a production method having the following steps.
a) applying a ceramic slurry onto the release film for producing a ceramic green sheet of the present invention; b) forming a ceramic green sheet from the ceramic slurry applied in the a) step; and c) peeling the ceramic green sheet formed in the b) step from the release film for producing a ceramic green sheet.
上記製造方法により得られたセラミックグリーンシートを焼成することで、各種セラミック製品を製造することができる。
積層セラミックコンデンサの製造にあたっては、上記工程ｂ）と工程ｃ）との間にグリーンシート上に内部電極を印刷する工程を設ける。その後、工程ｃ）（剥離）、積層圧着、切断分離、焼成、外部電極形成工程を経て、積層セラミックコンデンサを製造することができる。 By firing the ceramic green sheet obtained by the above-mentioned production method, various ceramic products can be produced.
In manufacturing a multilayer ceramic capacitor, a step of printing internal electrodes on the green sheet is provided between the above steps b) and c), followed by step c) (peeling), lamination and pressure bonding, cutting and separation, firing, and external electrode formation steps to manufacture the multilayer ceramic capacitor.
積層セラミックコンデンサの製造にあたっては、上記工程ｂ）と工程ｃ）との間にグリーンシート上に内部電極を印刷する工程を設ける。その後、工程ｃ）（剥離）、積層圧着、切断分離、焼成、外部電極形成工程を経て、積層セラミックコンデンサを製造することができる。 By firing the ceramic green sheet obtained by the above-mentioned production method, various ceramic products can be produced.
In manufacturing a multilayer ceramic capacitor, a step of printing internal electrodes on the green sheet is provided between the above steps b) and c), followed by step c) (peeling), lamination and pressure bonding, cutting and separation, firing, and external electrode formation steps to manufacture the multilayer ceramic capacitor.
以下、本発明を実施例により更に詳細に説明するが、本発明は、これにより何ら限定
されるものではない。 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
されるものではない。 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
以下の実施例／比較例において、物性／特性の評価は下記の方法で行った。
（表面自由エネルギー）
以下の条件で、離型剤層表面の水の接触角を測定した。
接触角計：協和界面科学社製 ＤＭ－７０１ 全自動接触角計
接触角計解析ソフト：同社製 ＦＡＭＡＳ
液滴法にて、接触角θを算出した。手順は以下のとおり。
ｉ）短冊上にカットしたサンプルを接触角計にセットした。
ｉｉ）シリンジポンプから、約６．１μＬの水滴を吐出した。
ｉｉｉ）サンプル上に吐出した液滴の状態を画像撮影した。
ｉｖ）サンプルと液滴のなす角を測定し、これを水の接触角（°）とした。
同様にして、ジヨードメタン、及び１－ブロモナフタレンの接触角も測定した。
（ジヨードメタン：２．１μＬ、１－ブロモナフタレン：３．４μＬ）
上記の接触角計解析ソフトを用いて、得られた各接触角から表面自由エネルギーを算出した。算出にあたっては、北崎―畑、拡張フォークスの式（Ｋｉｔａｚａｋｉ－Ｈａｔａ式）を使用し、上記３種の液体について測定した固体（サンプル）との接触角（θ）と、既知である各液体の表面自由エネルギーとを下式に入れ、得られた３元１次方程式を解いて、固体（サンプル）の表面自由エネルギー
を得た。
In the following Examples and Comparative Examples, the physical properties and characteristics were evaluated by the following methods.
(Surface Free Energy)
The contact angle of water on the surface of the release agent layer was measured under the following conditions.
Contact angle meter: DM-701 fully automatic contact angle meter manufactured by Kyowa Interface Science Co., Ltd. Contact angle meter analysis software: FAMAS manufactured by the same company
The contact angle θ was calculated by the sessile drop method according to the following procedure.
i) The sample cut into a rectangular shape was set in a contact angle meter.
ii) A droplet of approximately 6.1 μL of water was dispensed from the syringe pump.
iii) Images of the state of the droplets discharged onto the sample were taken.
iv) The angle between the sample and the droplet was measured and this was taken as the contact angle (°) of water.
In the same manner, the contact angles of diiodomethane and 1-bromonaphthalene were also measured.
(Diiodomethane: 2.1 μL, 1-bromonaphthalene: 3.4 μL)
Using the above contact angle meter analysis software, the surface free energy was calculated from each contact angle obtained. For the calculation, the Kitazaki-Hata and extended Foulkes equation (Kitazaki-Hata equation) was used, and the contact angle (θ) with the solid (sample) measured for the above three types of liquid and the known surface free energy of each liquid were inserted into the following equation, and the resulting three-dimensional linear equation was solved to obtain the surface free energy of the solid (sample).
obtained.
（表面自由エネルギー）
以下の条件で、離型剤層表面の水の接触角を測定した。
接触角計：協和界面科学社製 ＤＭ－７０１ 全自動接触角計
接触角計解析ソフト：同社製 ＦＡＭＡＳ
液滴法にて、接触角θを算出した。手順は以下のとおり。
ｉ）短冊上にカットしたサンプルを接触角計にセットした。
ｉｉ）シリンジポンプから、約６．１μＬの水滴を吐出した。
ｉｉｉ）サンプル上に吐出した液滴の状態を画像撮影した。
ｉｖ）サンプルと液滴のなす角を測定し、これを水の接触角（°）とした。
同様にして、ジヨードメタン、及び１－ブロモナフタレンの接触角も測定した。
（ジヨードメタン：２．１μＬ、１－ブロモナフタレン：３．４μＬ）
上記の接触角計解析ソフトを用いて、得られた各接触角から表面自由エネルギーを算出した。算出にあたっては、北崎―畑、拡張フォークスの式（Ｋｉｔａｚａｋｉ－Ｈａｔａ式）を使用し、上記３種の液体について測定した固体（サンプル）との接触角（θ）と、既知である各液体の表面自由エネルギーとを下式に入れ、得られた３元１次方程式を解いて、固体（サンプル）の表面自由エネルギー
を得た。
(Surface Free Energy)
The contact angle of water on the surface of the release agent layer was measured under the following conditions.
Contact angle meter: DM-701 fully automatic contact angle meter manufactured by Kyowa Interface Science Co., Ltd. Contact angle meter analysis software: FAMAS manufactured by the same company
The contact angle θ was calculated by the sessile drop method according to the following procedure.
i) The sample cut into a rectangular shape was set in a contact angle meter.
ii) A droplet of approximately 6.1 μL of water was dispensed from the syringe pump.
iii) Images of the state of the droplets discharged onto the sample were taken.
iv) The angle between the sample and the droplet was measured and this was taken as the contact angle (°) of water.
In the same manner, the contact angles of diiodomethane and 1-bromonaphthalene were also measured.
(Diiodomethane: 2.1 μL, 1-bromonaphthalene: 3.4 μL)
Using the above contact angle meter analysis software, the surface free energy was calculated from each contact angle obtained. For the calculation, the Kitazaki-Hata and extended Foulkes equation (Kitazaki-Hata equation) was used, and the contact angle (θ) with the solid (sample) measured for the above three types of liquid and the known surface free energy of each liquid were inserted into the following equation, and the resulting three-dimensional linear equation was solved to obtain the surface free energy of the solid (sample).
obtained.
（背面汚染）
寺西化学工業製の油性マジックインキ（大型・赤 筆記線幅：５×８ｍｍ）を用いて、基材の剥離剤層側と反対側に線幅８ｍｍ×長さ７０ｍｍの線を引き、１分後に中心の５０ｍｍ長さ部分を観察した線幅結果に基づき、以下の基準に従い評価した。
５：残存する線幅が９０％以上
４：残存する線幅が７０％以上９０％未満の個所がある
３：残存する線幅が５０％以上７０％未満の個所がある
２：残存する線幅が２０％以上５０％未満の個所がある
１： 残存する線幅が０％以上２０％未満の個所がある
（テープ剥離力）
剥離サンプルを水平台の上に剥離剤層を上にして載置し、その剥離剤層側に粘着テープ「ポリエステル粘着テープＮｏ．３１Ｂ７５ハイ」（銘柄名、日東電工株式会社製）を貼り付けて２００ｍｍ×５０ｍｍの大きさにカットし、さらにその粘着テープの上から２０ｇ／ｃｍ２となるように荷重を載せ、７０℃で２０時間エージングした。
その後、引張試験機にて引張速度３００ｍｍ／分で１８０°剥離を行い、剥離が安定した領域における平均剥離荷重を粘着テープ幅で除した値を剥離力として求めた。 (Backside contamination)
Using an oil-based marker pen manufactured by Teranishi Chemical Industry Co., Ltd. (large, red, writing line width: 5 x 8 mm), a line 8 mm wide x 70 mm long was drawn on the side opposite the release agent layer side of the substrate, and after 1 minute, a central 50 mm long portion was observed for the line width and evaluated according to the following criteria.
5: The remaining line width is 90% or more. 4: There are some areas where the remaining line width is 70% or more and less than 90%. 3: There are some areas where the remaining line width is 50% or more and less than 70%. 2: There are some areas where the remaining line width is 20% or more and less than 50%. 1: There are some areas where the remaining line width is 0% or more and less than 20% (tape peeling force).
The release sample was placed on a horizontal table with the release agent layer facing up, and an adhesive tape "Polyester Adhesive Tape No. 31B75 High" (brand name, manufactured by Nitto Denko Corporation) was attached to the release agent layer side and cut to a size of 200 mm x 50 mm. A load of 20 g/ cm2 was then applied on the adhesive tape, and the sample was aged at 70°C for 20 hours.
Thereafter, 180° peeling was performed at a pulling speed of 300 mm/min using a tensile tester, and the peel force was calculated by dividing the average peel load in the region where peeling became stable by the width of the adhesive tape.
寺西化学工業製の油性マジックインキ（大型・赤 筆記線幅：５×８ｍｍ）を用いて、基材の剥離剤層側と反対側に線幅８ｍｍ×長さ７０ｍｍの線を引き、１分後に中心の５０ｍｍ長さ部分を観察した線幅結果に基づき、以下の基準に従い評価した。
５：残存する線幅が９０％以上
４：残存する線幅が７０％以上９０％未満の個所がある
３：残存する線幅が５０％以上７０％未満の個所がある
２：残存する線幅が２０％以上５０％未満の個所がある
１： 残存する線幅が０％以上２０％未満の個所がある
（テープ剥離力）
剥離サンプルを水平台の上に剥離剤層を上にして載置し、その剥離剤層側に粘着テープ「ポリエステル粘着テープＮｏ．３１Ｂ７５ハイ」（銘柄名、日東電工株式会社製）を貼り付けて２００ｍｍ×５０ｍｍの大きさにカットし、さらにその粘着テープの上から２０ｇ／ｃｍ２となるように荷重を載せ、７０℃で２０時間エージングした。
その後、引張試験機にて引張速度３００ｍｍ／分で１８０°剥離を行い、剥離が安定した領域における平均剥離荷重を粘着テープ幅で除した値を剥離力として求めた。 (Backside contamination)
Using an oil-based marker pen manufactured by Teranishi Chemical Industry Co., Ltd. (large, red, writing line width: 5 x 8 mm), a line 8 mm wide x 70 mm long was drawn on the side opposite the release agent layer side of the substrate, and after 1 minute, a central 50 mm long portion was observed for the line width and evaluated according to the following criteria.
5: The remaining line width is 90% or more. 4: There are some areas where the remaining line width is 70% or more and less than 90%. 3: There are some areas where the remaining line width is 50% or more and less than 70%. 2: There are some areas where the remaining line width is 20% or more and less than 50%. 1: There are some areas where the remaining line width is 0% or more and less than 20% (tape peeling force).
The release sample was placed on a horizontal table with the release agent layer facing up, and an adhesive tape "Polyester Adhesive Tape No. 31B75 High" (brand name, manufactured by Nitto Denko Corporation) was attached to the release agent layer side and cut to a size of 200 mm x 50 mm. A load of 20 g/ cm2 was then applied on the adhesive tape, and the sample was aged at 70°C for 20 hours.
Thereafter, 180° peeling was performed at a pulling speed of 300 mm/min using a tensile tester, and the peel force was calculated by dividing the average peel load in the region where peeling became stable by the width of the adhesive tape.
実施例／比較例で剥離剤層に用いた樹脂等の各構成成分の詳細は、以下のとおりである。
・（ａ３）多官能アクリレート１
新中村化学工業株式会社製、商品名：ＮＫエステル Ａ９３００
３官能イソシアヌルアクリレートモノマー （トリス－（２－アクリロキシエチル）イソシアヌレート）
・（ａ１）エポキシ変性シリコーン１
荒川化学工業株式会社製、商品名：シリコリース ＵＶ ＰＯＬＹ２０１
ジメチルシリコン、脂環エポキシシリコンブロック共重合体
・（ａ２）エポキシ変性シリコーン２
信越化学株式会社製、商品名：信越シリコーン ＫＲ－４７０
脂環式エポキシ基含有環状シロキサン４官能オリゴマー
エポキシ当量：２００ｇ／ｍｏｌ
・（ａ２）エポキシ変性シリコーン３
信越化学株式会社製、商品名：信越シリコーン Ｘ－２２－１６９ＡＳ
両末端型／脂環式エポキシ変性シリコーンオイル
エポキシ当量：５００ｇ／ｍｏｌ
・エポキシ変性シリコーン４
信越化学株式会社製、商品名：信越シリコーン Ｘ－２２－１６９Ｂ
両末端型／脂環式エポキシ変性シリコーンオイル
エポキシ当量：１７００ｇ／ｍｏｌ
・エポキシ変性シリコーン５
信越化学株式会社製、商品名：信越シリコーン ＫＦ－１０２
側鎖型/脂環式エポキシ変性シリコーンオイル
エポキシ当量：３６００ｇ／ｍｏｌ
・カチオン開始剤１
三新化学工業株式会社製 商品名：サンエイド ＳＩ－１００
・ラジカル開始剤１
ＩＧＭ ＲＥＳＩＮＳ製 商品名：Ｅｓａｃｕｒｅ ＯＮＥ
α-ヒドロキシケトンタイプ光重合開始剤
Details of each of the constituent components such as resins used in the release agent layer in the examples and comparative examples are as follows.
(a3) Multifunctional acrylate 1
Product name: NK Ester A9300, manufactured by Shin-Nakamura Chemical Co., Ltd.
Trifunctional isocyanuric acrylate monomer (tris-(2-acryloxyethyl) isocyanurate)
(a1) Epoxy-modified silicone 1
Arakawa Chemical Industries, Ltd., product name: Silicolyse UV POLY201
Dimethyl silicone, alicyclic epoxy silicone block copolymer
(a2) Epoxy-modified silicone 2
Manufactured by Shin-Etsu Chemical Co., Ltd., product name: Shin-Etsu Silicone KR-470
Alicyclic epoxy group-containing cyclic siloxane tetrafunctional oligomer Epoxy equivalent: 200 g/mol
(a2) Epoxy-modified silicone 3
Manufactured by Shin-Etsu Chemical Co., Ltd., product name: Shin-Etsu Silicone X-22-169AS
Both ends/alicyclic epoxy modified silicone oil Epoxy equivalent: 500g/mol
Epoxy modified silicone 4
Manufactured by Shin-Etsu Chemical Co., Ltd., product name: Shin-Etsu Silicone X-22-169B
Both ends/alicyclic epoxy modified silicone oil Epoxy equivalent: 1700g/mol
Epoxy modified silicone 5
Manufactured by Shin-Etsu Chemical Co., Ltd., product name: Shin-Etsu Silicone KF-102
Side chain type/alicyclic epoxy modified silicone oil Epoxy equivalent: 3600g/mol
Cationic initiator 1
Sanshin Chemical Industry Co., Ltd. Product name: San-Aid SI-100
Radical initiator 1
Made by IGM RESINS Product name: Esacure ONE
α-Hydroxyketone type photoinitiator
・（ａ３）多官能アクリレート１
新中村化学工業株式会社製、商品名：ＮＫエステル Ａ９３００
３官能イソシアヌルアクリレートモノマー （トリス－（２－アクリロキシエチル）イソシアヌレート）
・（ａ１）エポキシ変性シリコーン１
荒川化学工業株式会社製、商品名：シリコリース ＵＶ ＰＯＬＹ２０１
ジメチルシリコン、脂環エポキシシリコンブロック共重合体
・（ａ２）エポキシ変性シリコーン２
信越化学株式会社製、商品名：信越シリコーン ＫＲ－４７０
脂環式エポキシ基含有環状シロキサン４官能オリゴマー
エポキシ当量：２００ｇ／ｍｏｌ
・（ａ２）エポキシ変性シリコーン３
信越化学株式会社製、商品名：信越シリコーン Ｘ－２２－１６９ＡＳ
両末端型／脂環式エポキシ変性シリコーンオイル
エポキシ当量：５００ｇ／ｍｏｌ
・エポキシ変性シリコーン４
信越化学株式会社製、商品名：信越シリコーン Ｘ－２２－１６９Ｂ
両末端型／脂環式エポキシ変性シリコーンオイル
エポキシ当量：１７００ｇ／ｍｏｌ
・エポキシ変性シリコーン５
信越化学株式会社製、商品名：信越シリコーン ＫＦ－１０２
側鎖型/脂環式エポキシ変性シリコーンオイル
エポキシ当量：３６００ｇ／ｍｏｌ
・カチオン開始剤１
三新化学工業株式会社製 商品名：サンエイド ＳＩ－１００
・ラジカル開始剤１
ＩＧＭ ＲＥＳＩＮＳ製 商品名：Ｅｓａｃｕｒｅ ＯＮＥ
α-ヒドロキシケトンタイプ光重合開始剤
Details of each of the constituent components such as resins used in the release agent layer in the examples and comparative examples are as follows.
(a3) Multifunctional acrylate 1
Product name: NK Ester A9300, manufactured by Shin-Nakamura Chemical Co., Ltd.
Trifunctional isocyanuric acrylate monomer (tris-(2-acryloxyethyl) isocyanurate)
(a1) Epoxy-modified silicone 1
Arakawa Chemical Industries, Ltd., product name: Silicolyse UV POLY201
Dimethyl silicone, alicyclic epoxy silicone block copolymer
(a2) Epoxy-modified silicone 2
Manufactured by Shin-Etsu Chemical Co., Ltd., product name: Shin-Etsu Silicone KR-470
Alicyclic epoxy group-containing cyclic siloxane tetrafunctional oligomer Epoxy equivalent: 200 g/mol
(a2) Epoxy-modified silicone 3
Manufactured by Shin-Etsu Chemical Co., Ltd., product name: Shin-Etsu Silicone X-22-169AS
Both ends/alicyclic epoxy modified silicone oil Epoxy equivalent: 500g/mol
Epoxy modified silicone 4
Manufactured by Shin-Etsu Chemical Co., Ltd., product name: Shin-Etsu Silicone X-22-169B
Both ends/alicyclic epoxy modified silicone oil Epoxy equivalent: 1700g/mol
Epoxy modified silicone 5
Manufactured by Shin-Etsu Chemical Co., Ltd., product name: Shin-Etsu Silicone KF-102
Side chain type/alicyclic epoxy modified silicone oil Epoxy equivalent: 3600g/mol
Cationic initiator 1
Sanshin Chemical Industry Co., Ltd. Product name: San-Aid SI-100
Radical initiator 1
Made by IGM RESINS Product name: Esacure ONE
α-Hydroxyketone type photoinitiator
［実施例１］
多官能アクリレート１、エポキシ変性シリコーン１、エポキシ変性シリコーン２、カチオン開始剤１、及びラジカル開始剤１を表１に示す質量比で配合して、剥離剤層用の硬化性組成物を調製した。
基材として、厚さ約３０μｍ、表面の算術平均粗さ（Ｒａ）が約２０ｎｍであるポリエチレンテレフタレートフィルムを用い、基材の１面上に上記で調整した硬化性組成物を塗布し、１００℃×１５秒乾燥した後に高圧水銀ランプを用いて紫外線を照射（積算光量：約４０ｍJ／ｃｍ２）して硬化させて剥離剤層を形成し、基材と該基材の一方に設けられた剥離剤層とを有する、剥離フィルムを製造した。
上記で製造された剥離フィルムについて、上記の方法で、表面自由エネルギー、背面汚染、及びテープ剥離力を評価した。結果を表１に示す。 [Example 1]
Polyfunctional acrylate 1, epoxy modified silicone 1, epoxy modified silicone 2, cationic initiator 1, and radical initiator 1 were mixed in the mass ratio shown in Table 1 to prepare a curable composition for the release agent layer.
A polyethylene terephthalate film having a thickness of approximately 30 μm and a surface arithmetic mean roughness (Ra) of approximately 20 nm was used as the substrate. The curable composition prepared above was applied to one side of the substrate, dried at 100°C for 15 seconds, and then cured by irradiating with ultraviolet light using a high-pressure mercury lamp (accumulated light amount: approximately 40 mJ/ cm2 ) to form a release agent layer, thereby producing a release film having a substrate and a release agent layer provided on one side of the substrate.
The release films produced above were evaluated for surface free energy, backside contamination, and tape peel strength by the methods described above. The results are shown in Table 1.
多官能アクリレート１、エポキシ変性シリコーン１、エポキシ変性シリコーン２、カチオン開始剤１、及びラジカル開始剤１を表１に示す質量比で配合して、剥離剤層用の硬化性組成物を調製した。
基材として、厚さ約３０μｍ、表面の算術平均粗さ（Ｒａ）が約２０ｎｍであるポリエチレンテレフタレートフィルムを用い、基材の１面上に上記で調整した硬化性組成物を塗布し、１００℃×１５秒乾燥した後に高圧水銀ランプを用いて紫外線を照射（積算光量：約４０ｍJ／ｃｍ２）して硬化させて剥離剤層を形成し、基材と該基材の一方に設けられた剥離剤層とを有する、剥離フィルムを製造した。
上記で製造された剥離フィルムについて、上記の方法で、表面自由エネルギー、背面汚染、及びテープ剥離力を評価した。結果を表１に示す。 [Example 1]
Polyfunctional acrylate 1, epoxy modified silicone 1, epoxy modified silicone 2, cationic initiator 1, and radical initiator 1 were mixed in the mass ratio shown in Table 1 to prepare a curable composition for the release agent layer.
A polyethylene terephthalate film having a thickness of approximately 30 μm and a surface arithmetic mean roughness (Ra) of approximately 20 nm was used as the substrate. The curable composition prepared above was applied to one side of the substrate, dried at 100°C for 15 seconds, and then cured by irradiating with ultraviolet light using a high-pressure mercury lamp (accumulated light amount: approximately 40 mJ/ cm2 ) to form a release agent layer, thereby producing a release film having a substrate and a release agent layer provided on one side of the substrate.
The release films produced above were evaluated for surface free energy, backside contamination, and tape peel strength by the methods described above. The results are shown in Table 1.
[実施例２から４、及び比較例１から２]
剥離剤層用の硬化剤組成物の配合を表１に示すものに変更したことを除くほか、実施例１と同様にして剥離フィルムを製造し、評価した。
結果を表１に示す。 [Examples 2 to 4 and Comparative Examples 1 to 2]
A release film was produced and evaluated in the same manner as in Example 1, except that the formulation of the curing agent composition for the release agent layer was changed to that shown in Table 1.
The results are shown in Table 1.
剥離剤層用の硬化剤組成物の配合を表１に示すものに変更したことを除くほか、実施例１と同様にして剥離フィルムを製造し、評価した。
結果を表１に示す。 [Examples 2 to 4 and Comparative Examples 1 to 2]
A release film was produced and evaluated in the same manner as in Example 1, except that the formulation of the curing agent composition for the release agent layer was changed to that shown in Table 1.
The results are shown in Table 1.
本発明のセラミックグリーンシート製造用剥離フィルムは、その上に形成したセラミックグリーンシートの剥離が容易であるとともに、セラミックグリーンシートの汚染を効果的に抑制することができる等、高い実用的価値を有する技術的効果を従来技術の限界を超えた高いレベルで同時に実現するものであり、各種セラミック製品の製造に好適に使用することができるので、電気電子産業、電子部品産業、機械産業、自動車産業をはじめとする産業の各分野において高い利用可能性を有する。
The release film for producing ceramic green sheets of the present invention allows easy release of the ceramic green sheets formed thereon, while also effectively suppressing contamination of the ceramic green sheets, simultaneously achieving a high level of technical effects with high practical value that surpass the limits of conventional technology, and can be suitably used in the manufacture of various ceramic products, making it highly applicable in various industrial fields including the electrical and electronics industry, electronic parts industry, machinery industry, and automotive industry.
１１：セラミックグリーンシート製造用剥離フィルム
１２：剥離剤層
１３：基材
11: Release film for producing ceramic green sheet 12: Release agent layer 13: Substrate
１２：剥離剤層
１３：基材
11: Release film for producing ceramic green sheet 12: Release agent layer 13: Substrate
Claims (9)
- 基材と、前記基材の少なくとも一方に設けられた剥離剤層とを有するセラミックグリーンシート製造用剥離フィルムであって、
前記剥離剤層の前記基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が０．３（ｍＮ／ｍ）以上である、上記セラミックグリーンシート製造用剥離フィルム。 A release film for producing a ceramic green sheet, comprising a substrate and a release agent layer provided on at least one side of the substrate,
The release film for producing a ceramic green sheet as described above, wherein the polar component (γ sp ) of the surface free energy of the release agent layer on the side opposite to the substrate is 0.3 (mN/m) or more. - 前記剥離剤層の前記基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が０．３から１．０（ｍＮ／ｍ）である、請求項１に記載のセラミックグリーンシート製造用剥離フィルム。 2. The release film for producing a ceramic green sheet according to claim 1, wherein the polar component (γ sp ) of the surface free energy of the release agent layer on the surface opposite to the substrate is 0.3 to 1.0 (mN/m).
- 前記剥離剤層の前記基材とは反対側の面の表面自由エネルギーの極性成分（γｓｐ）が０．３から０．８（ｍＮ／ｍ）である、請求項１に記載のセラミックグリーンシート製造用剥離フィルム。 2. The release film for producing a ceramic green sheet according to claim 1, wherein the polar component (γ sp ) of the surface free energy of the surface of the release agent layer opposite to the substrate is 0.3 to 0.8 (mN/m).
- 前記剥離剤層の前記基材とは反対側の面の表面自由エネルギーの分散成分（γｓｄ）が２２（ｍＮ／ｍ）以上である、請求項１から３のいずれか一項に記載のセラミックグリーンシート製造用剥離フィルム。 4. The release film for producing a ceramic green sheet according to claim 1, wherein a dispersion component (γ sd ) of the surface free energy of the surface of the release agent layer opposite to the substrate is 22 (mN/m) or more.
- 前記剥離剤層が硬化性組成物の硬化物を含有し、該硬化性組成物が少なくとも１種の、（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基を有する反応性化合物（ａ）を含み、且つ該反応性化合物（ａ）の合計量が、質量比率で該剥離剤層の５０％以上であることを特徴とする請求項１から３のいずれか一項に記載のセラミックグリーンシート製造用剥離フィルム。 The release film for producing ceramic green sheets according to any one of claims 1 to 3, characterized in that the release layer contains a cured product of a curable composition, the curable composition contains at least one reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, and the total amount of the reactive compound (a) is 50% or more of the release layer by mass.
- 前記硬化性組成物が、前記反応性化合物（ａ）として、（メタ）アクリロイル基、水酸基、及びエポキシ基からなる群より選ばれる少なくとも１種の反応性官能基、並びにシロキサン骨格を有する反応性シリコーン（ａ１）少なくとも１種と、該反応性シリコーン（ａ１）と同じ反応性官能基を有し、且つ反応性官能基当量が１０００ｇ／ｍｏｌ以下である反応性化合物（ａ２）少なくとも１種と、を含有する、請求項５に記載のセラミックグリーンシート製造用剥離フィルム。 The release film for producing ceramic green sheets according to claim 5, wherein the curable composition contains, as the reactive compound (a), at least one reactive silicone (a1) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, and a siloxane skeleton, and at least one reactive compound (a2) having the same reactive functional group as the reactive silicone (a1) and having a reactive functional group equivalent of 1000 g/mol or less.
- 前記硬化性組成物が、更に１分子中に２個以上の（メタ）アクリロイル基を有する膜形成性化合物（ａ３）を含有する、請求項６に記載のセラミックグリーンシート製造用剥離フィルム。 The release film for producing ceramic green sheets according to claim 6, wherein the curable composition further contains a film-forming compound (a3) having two or more (meth)acryloyl groups in one molecule.
- 前記基材の前記剥離剤層側の表面の算術平均粗さ（Ｒａ）が１から７０ｎｍである、請求項１から３のいずれか一項に記載のセラミックグリーンシート製造用剥離フィルム。 The release film for producing ceramic green sheets according to any one of claims 1 to 3, wherein the arithmetic mean roughness (Ra) of the surface of the substrate facing the release agent layer is 1 to 70 nm.
- 積層セラミックコンデンサ、又は多層セラミック基板の製造に用いる、請求項１から３のいずれか一項に記載のセラミックグリーンシート製造用剥離フィルム。
The release film for producing a ceramic green sheet according to claim 1 , which is used in producing a multilayer ceramic capacitor or a multilayer ceramic substrate.
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| JP2022191480A JP2024078885A (en) | 2022-11-30 | 2022-11-30 | Release film for ceramic green sheet manufacturing |
| JP2022-191480 | 2022-11-30 |
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| WO2024116437A1 true WO2024116437A1 (en) | 2024-06-06 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002302645A (en) * | 2001-01-31 | 2002-10-18 | Jsr Corp | Coating composition, cured product and laminate, and manufacturing process for cured product |
| WO2013145865A1 (en) * | 2012-03-28 | 2013-10-03 | リンテック株式会社 | Parting film for step for producing ceramic green sheet |
| WO2018079337A1 (en) * | 2016-10-27 | 2018-05-03 | リンテック株式会社 | Release sheet |
| JP2022122830A (en) * | 2021-02-10 | 2022-08-23 | 東レ株式会社 | Laminated polyester film and method for manufacturing polyester film |
-
2022
- 2022-11-30 JP JP2022191480A patent/JP2024078885A/en active Pending
-
2023
- 2023-06-01 WO PCT/JP2023/020428 patent/WO2024116437A1/en unknown
- 2023-09-22 JP JP2023158294A patent/JP2024079568A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002302645A (en) * | 2001-01-31 | 2002-10-18 | Jsr Corp | Coating composition, cured product and laminate, and manufacturing process for cured product |
| WO2013145865A1 (en) * | 2012-03-28 | 2013-10-03 | リンテック株式会社 | Parting film for step for producing ceramic green sheet |
| WO2018079337A1 (en) * | 2016-10-27 | 2018-05-03 | リンテック株式会社 | Release sheet |
| JP2022122830A (en) * | 2021-02-10 | 2022-08-23 | 東レ株式会社 | Laminated polyester film and method for manufacturing polyester film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2024078885A (en) | 2024-06-11 |
| JP2024079568A (en) | 2024-06-11 |
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