TW201725117A - Release film for ceramic green sheet production process - Google Patents

Abstract

A release film 1A for a ceramic green sheet production process equipped with a base material 11 and a release agent layer 12 provided on one side of the base material 11, wherein the release agent layer 12 is obtained by curing a release agent composition containing a melamine resin and a polyorganosiloxane, and the release film 1A for a ceramic green sheet production process has a coating elastic modulus of 3.5-7.0 GPa, measured from the surface of the release agent layer 12 opposite the base material 11 by a nanoindentation test. The migration of the polyorganosiloxane from the release agent layer to the ceramic green sheet is suppressed by the release film 1A for a ceramic green sheet production process.

Description

Release film for ceramic green sheet manufacturing engineering

The present invention relates to a release film used in the manufacture of ceramic green sheets.

Conventionally, in order to produce a laminated ceramic product such as a multilayer ceramic capacitor or a multilayer ceramic substrate, a ceramic green sheet is formed, and a plurality of ceramic green sheets obtained by lamination are laminated and fired.

The ceramic green sheet is formed by applying a ceramic slurry containing a ceramic material such as barium titanate or titanium oxide to a release film. The release film is required to be such that the thin ceramic green sheet formed on the release film does not undergo deformation, breakage, or the like from the release film, and can be peeled off by an appropriate peeling force. Further, when the ceramic slurry is applied and dried, in order to prevent defects such as pinholes and thickness unevenness in the ceramic green sheets, the release film is required to be coated with the surface of the ceramic slurry (with ceramic slurry, ceramics). The smoothness of the surface of the green sheet; the following is the case of the "peeling surface".

Patent Documents 1 and 2 disclose examples of such a release film. The release film disclosed in Patent Document 1 is a layer obtained by disposing a layer composed of an ultraviolet curable resin on a substrate, and a polyoxyxylene resin layer formed by adding an organopolysiloxane to the release agent layer. . The release film disclosed in Patent Document 2 contains a (meth) acrylate component and is (meth) acrylonitrile and/or ethylene. The coating liquid of the modified polyxanthene oil after the base modification is applied onto a substrate to cure the coating film, whereby a layer of a cured product containing a (meth) acrylate component is formed on the base. On the material, a layer containing a polyoxymethylene polymer component is formed thereon as a release agent layer.

Prior technical literature Patent literature

[Patent Document 1] Japanese Patent No. 5675246

[Patent Document 2] Japanese Patent No. 5423975

The polyfluorene oxide component in the release agent composition is in a state where it is easily transferred to the surface of the ceramic green sheet which is in contact with the release agent layer. The surface layer after the polyoxygen transfer has slipperiness, resulting in a decrease in adhesion. When a ceramic green sheet is produced by using such a peeling sheet in which the polyoxygenated component is easily transferred, and when the ceramic green sheet is used to produce a laminated ceramic product, when the laminated ceramic green sheets are pressed against each other, the laminated ceramic product is laminated. There is a case where there is a shift in the plane direction between the layers. When such an offset occurs, the positional accuracy of the electrode or the like in the obtained laminated ceramic article is lowered, and the product properties of the laminated ceramic article cannot be obtained. Therefore, it is required to transfer the polyoxygen component to a release film having less ceramic green sheets.

However, in the release film described in Patent Documents 1 and 2, the transfer of the polyfluorene oxygen component cannot be sufficiently suppressed.

The present invention has been made in view of such actual circumstances, and an object thereof is to provide a pottery capable of suppressing migration of a polyorganosiloxane from a release agent layer to a ceramic green sheet. A peeling film for the production of porcelain green sheets.

In order to achieve the above object, a first aspect of the present invention provides a release film for a ceramic green sheet manufacturing process, which comprises a base material and a release film for a ceramic green sheet manufacturing process provided on a release agent layer on one side of the base material. The release agent layer is obtained by curing a release agent composition containing a melamine resin and a polyorganosiloxane, and is subjected to a nanoindentation test on the substrate from the release agent layer. The film elastic modulus measured for the opposite side surface was 3.5 to 7.0 GPa (Invention 1).

According to the invention (Invention 1), the release agent layer is formed of a release agent composition containing a polyorganosiloxane, the surface free energy is moderately low, and the release film is peeled off from the ceramic green sheet. Excellent. In addition, when the release agent layer is sufficiently cured by the melamine resin, the film elastic modulus is in the above range, and the polyorganosiloxane which is held in the mesh structure is firmly bound, and can be suppressed. The polyorganosiloxane is migrated from the release agent layer to the ceramic green sheet.

Further, the term "melamine resin" as used herein means a mixture of a plurality of melamine compounds and/or a mixture of polynuclear bodies produced by condensation of the melamine compound. In the present specification, the term "melamine resin" means the above mixture or an aggregate of one melamine compound. Further, in the present specification, the melamine resin is cured and referred to as "melamine cured product".

In the above invention (Invention 1), the mass average molecular weight of the polyorganosiloxane is preferably from 500 to 20,000 (Invention 2).

In the above invention (Inventions 1, 2), relative to the melamine resin 100 The content of the polyorganosiloxane in the release agent composition is preferably 0.1 to 30 parts by mass (Invention 3).

In the above invention (Inventions 1 to 3), it is preferred that the melamine resin contained in the release agent composition contains methylated melamine and/or iminomethylol melamine (Invention 4).

In the above invention (Inventions 1 to 4), it is preferable to further provide a resin layer between the substrate and the release agent layer (Invention 5).

In the above invention (Invention 5), it is preferred that the resin layer is cured by a resin composition containing an active energy ray-curable component or a thermosetting component (Invention 6).

In the above invention (Invention 6), the active energy ray-curable component is preferably a polyfunctional acrylate (Invention 7).

In the above invention (Inventions 1 to 7), it is preferable to further include the second resin layer provided on the substrate opposite to the release agent layer (Invention 8).

1A, 1B, 1C‧‧‧Removal film for ceramic green sheet manufacturing engineering

11‧‧‧Substrate

12‧‧‧ Stripper layer

13‧‧‧ resin layer

14‧‧‧2nd resin layer

Fig. 1 is a cross-sectional view showing a release film for a ceramic green sheet manufacturing process according to a first embodiment of the present invention.

Fig. 2 is a cross-sectional view showing a release film for a ceramic green sheet manufacturing process according to a second embodiment of the present invention.

Fig. 3 is a cross-sectional view showing a release film for a ceramic green sheet manufacturing process according to a third embodiment of the present invention.

Form for implementing the invention

Hereinafter, embodiments of the present invention will be described.

[Release film for ceramic green sheet manufacturing engineering]

As shown in Fig. 1, the release film 1A for a ceramic green sheet manufacturing process of the first embodiment (hereinafter referred to simply as "release film 1A") is provided with a substrate 11 and a release agent layer 12.

In addition, as shown in Fig. 2, the release film 1B for ceramic green sheet manufacturing engineering of the second embodiment (hereinafter referred to simply as "release film 1B") is provided with a substrate 11 and laminated on the substrate 11. The resin layer 13 on one surface (upper in FIG. 2) and the release agent layer 12 laminated on the surface of the resin layer 13 opposite to the substrate 11 are formed.

In addition, as shown in FIG. 3, the release film 1C for ceramic green sheet manufacturing engineering of the third embodiment (hereinafter referred to as "peeling film 1C") is provided with a substrate 11 and laminated on the substrate 11. The resin layer 13 on one surface (the upper surface in FIG. 3), the release agent layer 12 laminated on the surface of the resin layer 13 opposite to the substrate 11, and the other layer laminated on the substrate 11 (at the third surface) The figure is the second resin layer 14 of the following).

In the release films 1A, 1B, and 1C, the release agent layer 12 is formed of a release agent composition containing a melamine resin and a polyorganosiloxane. Further, by the nanoindentation test, the film elastic modulus measured on the surface of the release agent layer 12 opposite to the resin layer 13 was 3.5 to 7.0 GPa.

In the release films 1A, 1B, and 1C, since the release agent layer 12 is formed using a release agent composition containing polyorganosiloxane, the free energy of the surface of the release surface of the release agent layer 12 is suitably low. Further, the release films 1A, 1B, and 1C have the above-described film elastic modulus. With these, it will be stripped When the film 1A, 1B, and 1C are peeled off from the ceramic green sheets formed on the release surfaces of the release films 1A, 1B, and 1C, the peeling force is moderately low, and excellent peelability can be exhibited.

Further, in the release films 1A, 1B, and 1C, the polyorganosiloxane is incorporated in a mesh-like structure formed by hardening of a melamine resin. Here, the melamine resin is sufficiently hardened to have the film elastic modulus within the above range, and the polyorganosiloxane which is held in the above-mentioned mesh-like structure is firmly bound, so that the polyorganosiloxane is The free movement in the hardened melamine resin is limited. Therefore, when the ceramic green sheets are formed on the release surfaces of the release films 1A, 1B, and 1C, it is possible to suppress migration of the polyorganosiloxane from the release agent layer 12 to the ceramic green sheets. Thereby, when the ceramic green sheets formed by using the release films 1A, 1B, and 1C are laminated, the adhesion between the ceramic green sheets is improved, and in the production of the laminated ceramic products, it is possible to suppress between the ceramic green sheets or at the electrodes. There is a shift between the printed surface and the face of the ceramic green sheet that is in contact therewith.

Further, in the release films 1A, 1B, and 1C, the release agent layer 12 is formed of a release agent composition containing a melamine resin. Therefore, it is possible to prevent the surface free energy of the release agent layer 12 from becoming too low as compared with the case where the release agent layer is formed only by using the polyorganosiloxane. In addition, unlike the active energy ray-curable resin which is insufficient in the hardening of the surface layer due to the oxygen barrier, the melamine resin is cured by thermal curing, so that not only the entire film elastic modulus of the release agent layer 12 is improved. Moreover, the elastic modulus is also sufficiently improved in each of the layers and the surface layers. Thereby, the polyorganosiloxane which is present in the vicinity of the surface layer of the release agent layer 12 can be sufficiently fixed. Further, the affinity of the melamine resin to the resin contained in the resin layer 13 to be described later is high. Therefore, the peeling of the resin layer 13 is provided The release films 1B and 1C have excellent adhesion between the release agent layer 12 and the resin layer 13, and can prevent peeling of the release agent layer 12 from the resin layer 13.

Stripping agent layer

(1) Melamine resin

The melamine resin contained in the release agent composition contains a melamine compound represented by the following formula (a) or a polynuclear body obtained by condensing two or more of the melamine compounds.

In the formula (a), X represents -H, -CH ₂ -OH, or -CH ₂ -OR. These groups constitute a reactive group in the condensation reaction of the above melamine compounds. Specifically, the -NH group formed by the fact that X is H is capable of undergoing a condensation reaction between the -N-CH ₂ -OH group and the -N-CH ₂ -R group. Further, by X become -CH -N-CH ₂ -OH group formed of ₂ -OH, and -N-CH ₂ -OR group X by -CH ₂ -OR be formed of, based on simultaneously - A condensation reaction is carried out between the NH group, the -N-CH ₂ -OH group and the -N-CH ₂ -OR group.

In the above -CH ₂ -OR group, R represents an alkyl group having 1 to 8 carbon atoms. The number of carbon atoms is preferably from 1 to 6, especially from 1 to 3. The alkyl group having 1 to 8 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or an octyl group, and particularly preferably a methyl group.

The above X systems may be the same or different. Further, the R systems may be the same or different.

The melamine compound usually has the following kinds: all X is a full ether type of -CH ₂ -OR; at least one X is -CH ₂ -OH and at least one X is an imine group of H. a hydroxymethyl group; at least one X is -CH ₂ -OH and H of X is a hydroxymethyl group which is absent; and at least one X is H and -CH ₂ -OH is an imine group which is absent type. As the melamine compound contained in the above melamine resin, methylated melamine (R is a methyl ether monoether type), iminomethylol melamine (imino.hydroxymethyl type), methylol group Melamine (hydroxymethyl type), butylated melamine (R is a butyl full ether type), etc. are preferred. Further, from the viewpoint of being easily dissolved in an organic solvent and being easily cured at a low temperature, it is preferred to use methylated melamine or imidomethylol melamine. In particular, from the viewpoint that the reaction for deprotecting the group is not required to be removed, and the reaction rate is further improved, it is preferred to use an imidomethylol melamine.

The melamine resin may further contain 2 to 50 polynuclear compounds obtained by condensing the compound represented by the above formula (a), or may have 2 to 30 condensed polynuclear bodies, in particular, 2 to 10 The condensed multinuclear body may further contain 2 to 5 condensed polynuclear bodies.

In the release agent composition for forming the release agent layer 12, the mass average molecular weight of the melamine resin is preferably from 120 to 10,000, particularly preferably from 200 to 5,000, more preferably from 1,000 to 4,000. By having a mass average molecular weight of 120 or more, the melamine resin can be stably crosslinked and a smoother peeling surface can be formed. On the other hand, when the mass average molecular weight is 10,000 or less, the viscosity of the release agent composition can be prevented from becoming too high, and when the release agent composition is applied onto the substrate 11, the coatability is improved. Moreover, the mass average molecular weight in the present specification is a standard polyphenylene measured by gel permeation chromatography (GPC). The value in terms of ethylene.

(2) Polyorganooxane

As the polyorganosiloxane which is contained in the release agent composition, a polymer containing a ruthenium compound represented by the following formula (b) can be used.

In the formula (b), m is an integer of 1 or more. In the formula (b), R ¹ to R ⁸ are preferably an alkyl group or an aryl group, and particularly preferably an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an octyl group. Examples of the aryl group having 6 to 8 carbon atoms include aryl groups having 6 to 8 carbon atoms. Phenyl and methylphenyl, among which methyl is particularly preferred.

The R ¹ to R ⁸ systems may be the same or different. Further, when R ¹ and R ² are plural, R ¹ and R ² may be the same or different between the repeating units.

As the polyorganosiloxane which is contained in the release agent composition, it is preferred to have an organic group at the terminal or side chain. That is, at least one of R ¹ to R ⁸ in the formula (b) is preferably an organic group. In the present specification, "organic group" means a group which does not contain the above alkyl group and aryl group. Examples of such an organic group include organic groups having a repeating structure such as a polyether, a polyester, and a polyurethane. In such an organic group, an atomic group at one end of each of a polyether, a polyester, a polyurethane, or the like is bonded to a ruthenium atom at the end or chain of the polyorganosiloxane.

Further, the polyorganosiloxane is preferably a functional group containing a crosslinking reaction. The functional group capable of crosslinking reaction can be directly bonded to the ruthenium atom of the polyorganosiloxane, or can be bonded to the polyorganosiloxane through the aforementioned organic group. That is, at least one of R ¹ to R ⁸ in the formula (b) is preferably a functional group capable of crosslinking or an organic group having a functional group capable of crosslinking. Examples of the functional group capable of crosslinking directly bonded to a ruthenium atom include an alkenyl group, a hydrogen group (hydroalkylene group), a hydroxyl group (hydroxy hydroxyalkyl group), and the like; and a polyorganosiloxane is bonded as an organic group. Examples of the functional group include a hydroxyl group, a carboxyl group, a glycidyl group, and a (meth)acryl fluorenyl group. Among these functional groups, a hydroxyl group (hydroxy hydroxyalkyl group) directly bonded to a ruthenium atom or a hydroxyl group which transmits an organic group is particularly preferred. Moreover, "(meth)acryl fluorenyl" in this specification means both an acryl hydryl group and a methacryl fluorenyl group. The same is true for other similar terms.

When the release agent composition containing the polyorganosiloxane having a hydroxyl group is cured to form the release agent layer 12, the melamine resin and the polyorganosiloxane are chemically bonded through the hydroxyl group, and the polyorganosiloxane is cured by the melamine. fixed. Thereby, the free movement of the polyorganosiloxane in the release agent layer 12 is effectively restricted, and the migration of the polyorganosiloxane from the release agent layer 12 to the ceramic green sheet can be effectively suppressed. As a result, when the ceramic green sheets are laminated, it is possible to effectively suppress the occurrence of the surface direction shift between the ceramic green sheets, or between the electrode printing surfaces and the surfaces of the ceramic green sheets in contact therewith, and to improve the position of the electrodes and the like. degree.

The mass average molecular weight of the polyorganosiloxane is preferably from 500 to 20,000, particularly preferably from 1,000 to 10,000, more preferably from 3,000 to 8,000. When the mass average molecular weight of the polyorganosiloxane is 500 or more, the free energy on the surface of the release surface of the release agent layer 12 is appropriately lowered, and the peeling force when the release films 1A, 1B, and 1C are peeled off from the ceramic green sheet can be removed. Effectively reduced. By gathering The mass average molecular weight of the organic siloxane is 20,000 or less, and it is possible to suppress the viscosity of the release agent composition from becoming too high, and it is easy to apply the release agent composition.

The content of the polyorganosiloxane in the release agent composition is preferably 0.1 to 30 parts by mass, particularly preferably 0.3 to 25 parts by mass, and further preferably 0.5 to 20 parts by mass based on 100 parts by mass of the melamine resin. It is better. When the content of the polyorganosiloxane in the release agent composition is 0.1 part by mass or more, the surface free energy of the release surface of the release agent layer 12 is sufficiently lowered, and an appropriate peeling force can be achieved. On the other hand, when the content of the polyorganosiloxane in the release agent composition is 30 parts by mass or less, the migration of the above polyorganosiloxane can be suppressed. Therefore, it is possible to prevent the surface free energy of the release agent composition from being excessively lowered, and it is possible to suppress the occurrence of rejection when the coating liquid of the release agent composition is applied onto the resin layer 13, and to manufacture the release films 1A, 1B, and 1C favorably.

(3) Other ingredients

The release agent composition is preferably further contained in an acid catalyst. As an example of the acid catalyst, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, p-toluenesulfonic acid or the like is preferred, and p-toluenesulfonic acid is particularly preferred. The condensation reaction of the above melamine resin proceeds efficiently by the release agent composition containing an acid catalyst.

The content of the acid catalyst in the release agent composition is preferably 0.1 to 30 parts by mass, particularly preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the melamine resin. .

The release agent composition may contain a crosslinking agent, a reaction inhibitor or the like in addition to the above components.

(4) Thickness of the release agent layer

The thickness of the release agent layer 12 is preferably from 5 to 2,000 nm. Especially by the substrate In the case of the release sheet 1A composed of the release agent layer 12, the thickness of the release agent layer 12 is preferably 100 to 2000 nm, particularly preferably 150 to 1000 nm, and more preferably 200 to 600 nm. Further, when the release sheet 1B or the release sheet 1C of the resin layer 13 is further provided between the substrate 11 and the release agent layer 12, the thickness of the release agent layer 12 is preferably 5 to 300 nm, particularly preferably 10 to 250 nm. Further, it is preferably 15 to 200 nm. When the thickness of the release agent layer 12 is 5 nm or more, the function as the release agent layer 12 can be effectively exhibited. Further, by the thickness of the release agent layer 12 being 2000 nm or less, curling can be suppressed.

2. Substrate

The base material 11 of the release films 1A, 1B, and 1C is not particularly limited as long as the resin layer 13 can be laminated. Examples of such a substrate 11 include polyesters such as polyethylene terephthalate and polyethylene naphthalate; polyolefins such as polypropylene and polymethylpentene; and polycarbonate. The film made of a plastic such as an ester or a polyvinyl acetate may be a single layer or a multilayer of two or more layers of the same type or different types. Among these, a polyester film is preferred, particularly a polyethylene terephthalate film, and a biaxially oriented polyethylene terephthalate film is preferred. Since the polyethylene terephthalate film is not easily generated by dust or the like during processing or use, it can effectively prevent, for example, coating failure of the ceramic slurry due to dust or the like. Further, by performing an antistatic treatment on the polyethylene terephthalate film, it is possible to prevent the occurrence of ignition due to static electricity when the ceramic slurry using the organic solvent is applied, or to improve the effect of preventing coating failure.

Further, in order to enhance the adhesion to the release agent layer 12 or the resin layer 13 provided on the surface of the substrate 11, the oxidation method or the unevenness method can be applied to one or both surfaces as needed. Surface treatment, or electricity Slurry treatment. Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, and the like. For example, a sand blasting method, a thermal spray treatment method, or the like. These surface treatment methods can be appropriately selected depending on the type of the base film, and in general, the corona discharge treatment can be suitably used in terms of effects and workability.

The thickness of the substrate 11 is usually 10 to 300 μm, preferably 15 to 200 μm, and particularly preferably 20 to 125 μm.

3. Resin layer

In the release film of the present embodiment, the resin layer 13 may be provided between the substrate 11 and the release agent layer 12. The second and third drawings each show the release films 1B and 1C including the resin layer 13. In the release films 1B and 1C, the resin layer 13 provided between the substrate 11 and the release agent layer 12 absorbs the unevenness on the surface of the substrate 11 on the resin layer 13 side. Thereby, the surface of the resin layer 13 on the opposite side to the substrate 11 has high smoothness. Further, by providing the release agent layer 12 on the surface of the resin layer 13, the smoothness of the release surface of the release agent layer 12 is excellent.

The resin which forms the resin layer 13 is not particularly limited as long as smoothness can be imparted to the peeling surface without impairing the effects of the present invention. As the resin for forming the resin layer 13, it is preferable to use a release film 1B or 1C to easily achieve a film elastic modulus of 3.5 to 7.0 GPa. In particular, the resin layer 13 is preferably formed of a resin composition containing a curable component. The curable component may be an active energy ray-curable component or a thermosetting component.

(1) Active energy ray hardening component

As the active energy ray-curable component, as long as it does not hinder the effect of the present invention The component which can be hardened by irradiation with an active energy ray is not particularly limited, and may be any of a monomer, an oligomer or a polymer, or a mixture thereof. In particular, as the active energy ray-curable component, it is preferred to use a component constituting the acrylic resin, particularly preferably a polyfunctional acrylate.

The polyfunctional acrylate may, for example, be 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(methyl) Acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, two Dicyclopentyl (meth)acrylate, caprolactone modified dicyclopentenyl bis(meth)acrylate, ethylene oxide modified di(meth)acrylate, and trimeric isocyanate Bifunctional type of propylene methoxyethyl ester, allylic cyclohexyl (meth) acrylate, etc.; trimethylolpropane tri(meth) acrylate, dipentaerythritol tris (methyl) Acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate a trifunctional type such as isomeric isocyanate (propylene oxyethyl) ester, ε-caprolactone modified isocyanuric acid (2-(methyl) propylene oxyethyl) ester ; diglycerin tetra (meth) acrylate, neopentyl alcohol tetra (methyl) propyl a tetrafunctional type such as an acid ester; a 5-functional type such as propionic acid-modified dipentaerythritol penta (meth) acrylate; dipentaerythritol hexa(meth) acrylate or caprolactone modified bis A 6-functional type such as pentaerythritol hexa(meth)acrylate. These may be used alone or in combination of two or more. From the viewpoint of easily forming a crosslinked structure and easily setting the film elastic modulus of the release films 1B and 1C to a value to be described later, it is preferable that the polyfunctional acrylate has a functional group number of from 3 to 15, particularly It is better to use 3 to 6 people. Among the above polyfunctional acrylates, can be effectively absorbed From the viewpoint of the unevenness of the surface of the substrate and the excellent smoothness of the release surface, it is preferred to use neopentyl alcohol triacrylate or dipentaerythritol hexaacrylate.

When the resin layer 13 is formed of a resin composition containing an active energy ray-curable component, the resin composition preferably further contains a photopolymerization initiator. By containing a photopolymerization initiator, the active energy ray-curable component can be efficiently cured, and the polymerization hardening time and the irradiation amount of the active energy ray can be reduced.

The photopolymerization initiator is not particularly limited, and a conventional one can be used. When a polyfunctional acrylate is used as the active energy ray-curable component, it is preferred to use an α-aminoalkylphenone compound from the viewpoint of promoting the polymerization reaction and improving the curability. The α-aminoalkylphenone-based compound may, for example, be 2-methyl-1[4-(methylthio)phenyl]-2-morpholinan-1-one or 2-benzyl- 2-Dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-dimethylamino-2-[(4-methylphenyl)methyl]-1-[4- (4-morpholinyl)phenyl]-1-butanone and the like. The content of the α-aminoalkylphenone compound in the resin composition is preferably from 1 to 20 parts by mass, particularly preferably from 3 to 15 parts by mass, based on 100 parts by mass of the polyfunctional acrylate. 5 to 10 parts by mass is preferred.

(2) Thermosetting components

The thermosetting component is not particularly limited as long as it does not interfere with the effects of the present invention and can be cured by heating. In particular, as a thermosetting component, a melamine resin, an alkyd resin, an epoxy resin, a phenol resin, a urea resin, a polyester resin, a urethane resin, a polyimide resin, a benzo compound, and the like are used. A benzoxazine resin or an acrylic resin is preferred, and a melamine resin is particularly preferred. By using the melamine resin, the adhesion between the resin layer 13 and the release agent layer 12 is increased, and the release agent layer 12 can be effectively prevented from peeling off from the resin layer 13. Further, by using the melamine resin, the film elastic modulus of the release films 1B and 1C is improved, and the peeling property when the release films 1B and 1C are peeled off from the ceramic green sheets is improved.

Although the melamine resin for forming the resin layer 13 is not particularly limited, it is preferably the same as the melamine resin used to form the release agent layer 12. At this time, the melamine resin between the resin layer 13 and the release agent layer 12 exhibits high affinity with each other, whereby high adhesion can be obtained between the resin layer 13 and the release agent layer 12, and peeling can be further effectively suppressed. The peeling of the agent layer 12.

(3) Other ingredients

In addition to the above components, the resin composition may contain a crosslinking agent, a reaction inhibitor, an antistatic agent, an adhesion promoter, and the like.

(4) Thickness of resin layer

The thickness of the resin layer 13 is preferably from 100 to 3,000 nm, particularly preferably from 300 to 2,000 nm, more preferably from 500 to 1,000 nm. When the thickness of the resin layer 13 is 100 mm or more, the unevenness on the surface of the substrate 11 can be effectively absorbed, and excellent smoothness can be achieved on the peeled surface. Moreover, by the thickness of the resin layer 13 being 3000 nm or less, curling of the peeling films 1B and 1C can be effectively suppressed.

4. Second resin layer

In the release film 1C, the second resin layer 14 is provided on the surface of the substrate 11 opposite to the resin layer 13 (hereinafter, referred to as "substrate back surface"). Since the second resin layer 14 absorbs the unevenness existing on the back surface of the substrate, the smoothness of the surface of the second resin layer 14 opposite to the substrate 11 is higher than that of the back surface of the substrate. . Moreover, the peeling film 1C in which the ceramic green sheet is formed is taken up In the case of a roll shape, the ceramic green sheet is in contact with the surface of the second resin layer 14 having high smoothness, so that a ceramic green sheet having higher smoothness can be provided. In addition, since the curing and shrinkage of the resin layer 13 and/or the release agent layer 12 are offset by the curing shrinkage of the second resin layer 14 by the presence of the second resin layer 14, it is possible to suppress the occurrence of curling in the release film 1C.

The resin for forming the second resin layer 14 is not particularly limited. As the resin for the second resin layer 14, the above-mentioned resin used to form the resin layer 13 can be used. In the release film 1B, the resin layer 13 and the second resin layer 14 may be formed of the same resin or may be formed of a different resin. However, from the viewpoint of suppressing curl, the resin layer 13 and the second resin layer 14 are preferably formed of the same resin.

The thickness of the second resin layer 14 can be set in the same manner as the resin layer 13 . However, from the viewpoint of effectively suppressing the occurrence of curl, the ratio of the thickness of the second resin layer 14 is preferably 0.2 to 2, particularly 0.7 to the total thickness of the resin layer 13 and the release agent layer 12. 1.5 is better, and then 0.8 to 1.2 is preferred.

5. Physical properties of the release film for ceramic green sheet manufacturing engineering

In the release films 1A, 1B, and 1C, the film elastic modulus measured on the surface of the release agent layer 12 opposite to the resin layer 13 by the nanoindentation test was 35 to 7.0 GPa, and 4.0 to 6.5 GPa. Good, especially 4.5~6.3GPa. When the film elastic modulus of the release films 1A, 1B, and 1C is 3.5 GPa or more, good peeling properties when the release films 1A, 1B, and 1C are peeled off from the ceramic green sheets can be effectively achieved. In addition, when the film elastic modulus of the release films 1A, 1B, and 1C is 7.0 GPa or less, the winding of the release films 1A, 1B, and 1C is easy.

Moreover, the measurement of the elastic modulus of the film in the present specification was carried out by a nanoindentation test. Specifically, the release films 1A, 1B, and 1C which were cut to a size of 10 mm × 10 mm were fixed on a glass plate attached to a base made of aluminum using a two-liquid epoxy adhesive. At this time, in the release films 1A and 1B, a two-liquid epoxy adhesive is applied to the surface of the substrate 11 opposite to the release agent layer 12, and the surface is fixed to a glass plate. On the other hand, in the release film 1C, a two-liquid epoxy adhesive is applied to the surface of the second resin layer 14 opposite to the substrate 11, and the surface is fixed to a glass plate. Subsequently, the film hardness modulus was measured from the surface of the release agent layer 12 opposite to the substrate 11 using a micro hardness evaluation device ("Nano Indenter SA2" manufactured by MTS Co., Ltd. in the test example).

The peeling force required for peeling off the peeling films 1A, 1B, and 1C from the ceramic green sheets formed on the peeling surfaces of the release films 1A, 1B, and 1C can be appropriately set, and is 5 to 100 mN/40 mm. Good, especially 7~50mN/40mm is better, and then 10~30mN/40mm is better. In the release films 1A, 1B, and 1C, the release agent layer 12 is formed using a release agent composition containing polyorganosiloxane, and since the release films 1A, 1B, and 1C have appropriate elasticity, they can be appropriately set. It is a peeling force of 5~100mN/40mm.

When the ceramic green sheets are formed by using the release films 1A, 1B, and 1C, it is possible to suppress migration of the polyorganosiloxane from the release agent layer 12 to the ceramic green sheets. After the ceramic green sheets are formed on the release surfaces of the release films 1A, 1B, and 1C, the ceramic green sheets are peeled off from the release films 1A, 1B, and 1C, and the surface of the ceramic green sheets is in contact with the release surface. The migration amount of polyorganosiloxane is lower. Specifically, when the ceramic green sheets are formed by using the release films 1A, 1B, and 1C, the ratio of germanium atoms obtained on the surface of the ceramic green sheets contacting the peeling surface is less than 1.0 atom. % is preferable, particularly preferably less than 0.5 atom%, more preferably 0.3 atom% or less. Further, the atomic ratio of ruthenium, for example, can be measured based on the amount of ruthenium atom (Si), carbon atom (C), and oxygen atom (O) (XPS statistic) measured by X-ray photoelectron spectroscopy (XPS). Calculated by the following formula.

Helium atomic ratio (atomic %) = [(Si element amount) / {(C element amount) + (O element amount) + (Si element amount)}] × 100

Further, in the ceramic green sheet for measurement, it is possible to appropriately select a ceramic green sheet in which ruthenium (i.e., ruthenium-free compound is not contained) by XPS, and to use the ruthenium atom ratio as the polyorganosiloxane of the release agent layer 12. Basis for evaluation of the amount of migration of alkane.

The maximum protrusion height Rp of the release faces of the release films 1A, 1B, and 1C is preferably 5 to 800 nm, particularly preferably 10 to 400 nm, and more preferably 20 to 200 nm. In particular, when the release films 1B and 1C of the resin layer 13 are provided, the maximum protrusion height Rp on the release surface is preferably 5 to 300 nm, particularly preferably 10 to 150 nm, and more preferably 20 to 75 nm. When the maximum projection height Rp of the peeling surface is in the above range, the ceramic green sheet formed using the release films 1A, 1B, and 1C exhibits excellent smoothness, and a laminated ceramic product exhibiting excellent performance can be produced. In particular, in the release films 1B and 1C, by providing the resin layer 13, the maximum protrusion height Rp is set to a very small value as described above, and a ceramic green sheet having more excellent smoothness can be formed. Moreover, the measuring method of the maximum protrusion height Rp on the peeling surface is as shown in the test example mentioned later.

6. Method for producing release film for ceramic green sheet manufacturing engineering

When the release film 1A is produced, a coating liquid containing a release agent composition and an organic solvent as needed is applied to one surface of the substrate 11, and the coating film is dried. The release agent layer 12 is formed by drying and hardening. Thereby, the film 1A was obtained.

When the release film 1B is produced, a coating liquid containing a resin composition and an organic solvent as required is applied to one surface of the substrate 11, and then the resin film 13 is formed by drying and curing the coating film. Further, after the coating liquid containing the release agent composition and the organic solvent as needed is applied to the surface of the resin layer 13 opposite to the substrate 11, the release agent composition is cured by drying and heating. A release agent layer 12 is formed. Thereby, the peeling film 1B was obtained.

In addition, when the release film 1C is produced, a resin composition containing the resin layer 13 and a coating liquid of an organic solvent as required are applied to one surface of the substrate 11, and then the coating film is dried and cured. Resin layer 13. Further, after the resin composition containing the second resin layer 14 and the coating liquid of the organic solvent as needed are applied to the other surface of the substrate 11, the coating film is dried and cured to form a second resin layer. 14. Next, a coating liquid containing a release agent composition and an organic solvent as needed is applied to the surface of the resin layer 13 opposite to the substrate 11, and then the release agent is cured by drying and heating. A release agent layer 12 is formed. Thereby, the peeling film 1C was obtained. Further, the second resin layer 14 may be formed earlier than the resin layer 13, or may be formed after the release agent layer 12.

In the above method, when the resin composition contains the active energy ray-curable component, the coating film composed of the resin composition is cured by irradiating the active energy ray. As the active energy ray, for example, an energy source can be used among electromagnetic waves or charged particle rays, and specifically, ultraviolet rays, electron beams, or the like can be used. In particular, it is preferable to use ultraviolet rays which are easy to handle. The irradiation of ultraviolet rays can be carried out using a high-pressure mercury lamp, a xenon lamp or the like, and the irradiation amount of the ultraviolet rays is preferably about 50 to 1000 mW/cm ² . Further, the amount of light is preferably 50 to 10000 mJ/cm ² , more preferably 80 to 5,000 mJ/cm ^{2 , and particularly} preferably 200 to 2,000 mJ/cm ² . On the other hand, the irradiation of the electron beam can be performed using an electron beam accelerator or the like, and the irradiation amount of the electron beam is preferably about 10 to 1000 krad. Further, the irradiation of the active energy ray of the coating film may be carried out in an atmosphere of an inert gas such as nitrogen.

Further, when the resin composition contains a thermosetting component, it is cured by heating a coating film composed of the resin composition. The heating temperature at this time is preferably from 90 to 140 ° C, particularly preferably from 110 to 130 ° C. Further, the heating time is preferably about 10 to 120 seconds, and particularly preferably about 50 to 70 seconds.

In the above method, as the coating method of the coating liquid, for example, a gravure coating method, a bar coating method, a spray coating method, a spin coating method, a knife coating method, a roll coating method, or a die coating method can be used. Bufa and so on.

The above organic solvent is not particularly limited, and various types can be used. It is possible to use, for example, a hydrocarbon compound such as toluene, hexane, heptane or the like, and isopropanol, isobutanol, acetone, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like. Wait.

7. Method for using release film for ceramic green sheet manufacturing engineering

In order to manufacture a ceramic green sheet, the release films 1A, 1B, and 1C can be used. Specifically, a ceramic slurry containing a ceramic material such as barium titanate or titanium oxide can be applied to the release surface of the release agent layer 12, and then the ceramic slurry can be dried to a ceramic green sheet. The coating system can be used, for example, by a slot die coating method, a doctor blade method, or the like.

Examples of the binder component contained in the ceramic slurry include a butyral resin, an acrylic resin, and the like. Also, as contained in the ceramic slurry Examples of the solvent include organic solvents, aqueous solvents, and the like.

In the release films 1A, 1B, and 1C, the release agent layer 12 is formed by using a release agent composition containing polyorganosiloxane, and the release films 1A, 1B, and 1C have appropriate elasticity, so that excellent release can be exhibited. Sex. Further, in the release agent layer 12, since the polyorganosiloxane is incorporated in a mesh-like structure formed by hardening of the melamine resin, the free movement of the polyorganosiloxane is restricted, and thus the polyorganosiloxane can be suppressed. The migration of the alkane from the stripper layer 12 to the ceramic green sheet. Thereby, when the formed ceramic green sheets are laminated, the adhesion between the ceramic green sheets is improved, and the occurrence of offset between the ceramic green sheets can be suppressed. Further, in the release films 1B and 1C including the resin layer 13, since the unevenness on the surface of the substrate 11 is absorbed by the resin layer 13, excellent smoothness can be achieved on the release surface of the release agent layer 12. Further, the release agent layer 12 is formed of a release agent composition containing a melamine resin, and since the adhesion between the release agent layer 12 and the resin layer 13 is excellent, the release agent layer 12 can be prevented from being generated from the resin layer 13. Peel off.

The embodiments described above are described in order to facilitate the understanding of the present invention and are not intended to limit the present invention. Therefore, the respective elements disclosed in the above embodiments are intended to include all design changes and equivalents belonging to the technical scope of the invention.

For example, between the substrate 11 of the release film 1A and the release agent layer 12, between the substrate 11 of the release film 1B, 1C and the resin layer 13, or between the resin layer 13 and the release agent layer 12, or Other layers such as an antistatic layer may be provided between the substrate 11 of the release film 1C and the second resin layer 14.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples, etc., but The scope of the present invention is not limited by the embodiments and the like.

[Example 1]

(1) Formation of resin layer

100 parts by mass of neopentyl alcohol triacrylate (trade name: A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) as an active energy ray-curable component (in terms of solid content; the same applies hereinafter), and as light 2-methyl-1[4-(methylthio)phenyl]-2-morpholinanpropan-1-one (manufactured by BASF Japan Co., Ltd., trade name: IRGACURE 907, α-aminoalkyl benzophenone) 10 parts by mass of the compound) was mixed with toluene as a solvent to obtain a coating liquid of a resin composition having a solid concentration of 15% by mass.

The coating liquid of the obtained resin composition was uniformly applied to the arithmetic mean roughness Ra of the biaxially-oriented polyethylene terephthalate film (thickness: 31 μm) as a substrate by using a wire bar #6. It is 10 nm and the maximum protrusion height Rp is 80 nm. Next, the coating film was dried at 80 ° C for 60 seconds, and irradiated with ultraviolet light (illuminance: 150 mW/cm ² , light amount: about 350 mJ/cm ² ) in an airless lamp (oxygen concentration: 1% or less) to make the resin. The composition was cured to obtain a laminate in which a resin layer having a thickness of 500 nm was laminated on a substrate.

(2) Formation of release agent layer

Methylated melamine resin (manufactured by Japan CARBIDE INDUSTRIAL CO., LTD., trade name: MX730, mass average molecular weight: 1508), 100 parts by mass, polydimethyl methoxy oxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X -62-1387, mass average molecular weight: 2000) 10 parts by mass, and 8 parts by mass of p-toluenesulfonic acid (manufactured by Hitachi Chemical Co., Ltd., trade name: Drier 900) as an acid catalyst, and mixed in toluene as a solvent. To obtain a solid content concentration of 2% by mass A coating solution of the release agent composition.

The coating liquid of the obtained release agent composition was uniformly applied to the surface of the resin layer of the laminated body opposite to the substrate by using a wire bar #6. Next, the coating film was dried by heating at 120 ° C for 60 seconds to cure the release agent composition, and a release agent layer having a thickness of 100 nm was formed on the laminate. A release film was obtained by the above.

[Embodiment 2]

100 parts by mass of an imido group-type methylated melamine resin (manufactured by JABIDE INDUSTRIAL CO., LTD., trade name: MX730, mass average molecular weight: 1508), polydimethylsiloxane containing a polyester-modified hydroxyl group (BYK-) Manufactured by Chemie Japan Co., Ltd., trade name: BYK-370, mass average molecular weight: 5000) 0.1 parts by mass, and p-toluenesulfonic acid (manufactured by Hitachi Chemical Co., Ltd., trade name: Drier 900) as an acid catalyst, 8 parts by mass, The mixture was mixed with toluene as a solvent to prepare a coating liquid of a release agent composition having a solid concentration of 15% by mass, and dried by heating the coating film at 120 ° C for 60 seconds to form a resin layer. A release film was produced in the same manner as in Example 1 except for the above.

[Example 3]

A release film was obtained in the same manner as in Example 1 except that the content of the polydimethyl siloxane in the release agent composition was changed to 30 parts by mass.

[Example 4]

A release film was obtained in the same manner as in Example 1 except that the content of the polydimethyl siloxane in the release agent composition was changed to 40 parts by mass.

[Example 5]

Change 10 parts by mass of polydimethyl siloxane in the stripper composition 30 parts by mass of a polyester-modified hydroxyl group-containing polydimethyl siloxane (manufactured by BYK-Chemie Japan Co., Ltd., trade name: BYK-370, mass average molecular weight: 5000), and other examples and examples 1 was carried out in the same manner to obtain a release film.

[Comparative Example 1]

100 parts by mass of neopentyl alcohol triacrylate (trade name: A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.), polydimethyl methoxy hydride (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-62-1387 , mass average molecular weight: 2000) 10 parts by mass, and 2-methyl-1[4-(methylthio)phenyl]-2-morpholinepropan-1-one as a photopolymerization initiator (BASF Japan Corporation) 10 parts by mass of the product name: IRGACURE 907, α-aminoalkylphenone compound) was mixed with toluene as a solvent to obtain a coating liquid having a solid content concentration of 15% by mass.

The coating liquid obtained by uniformly applying the wound bar #6 to the biaxially-oriented polyethylene terephthalate film (thickness: 31 μm) as a substrate has an arithmetic mean roughness Ra of 10 nm, and The maximum protrusion height Rp is 80 nm. Next, the coating film was dried at 80 ° C for 60 seconds, and irradiated with ultraviolet light (illuminance: 150 mW/cm ² , light amount: about 350 mJ/cm ² ) in an airless lamp (oxygen concentration: 1% or less) to make the resin. The composition was cured to obtain a laminate in which a resin layer having a thickness of 500 nm was laminated on a substrate.

[Comparative Example 2]

100 parts by mass of a polyfluorene-based stripper (trade name: CF-2172, mass average molecular weight: 300,000), and a platinum-based catalyst (TORAY.DOW CORNING) 2 parts by mass, mixed in toluene as a solvent, and prepared into a solid component A release film was produced in the same manner as in Example 1 except that the coating liquid of the release agent composition having a concentration of 1.5% by mass was used.

[Test Example 1] (Measurement of film elastic modulus)

The release film obtained in the examples and the comparative examples was cut into 10 mm × 10 mm, and then the back surface of the cut release film was fixed to a glass plate attached to an aluminum base using a two-liquid epoxy adhesive. Then, using a microhardness evaluation apparatus (Nano Indenter SA2, manufactured by MTS Co., Ltd.), a nanoindentation test was performed at a maximum indentation depth of 100 nm, a strain rate of 0.05 sec ^-1 , a displacement amplitude of 2 nm, and a vibration frequency of 45 Hz. The film elastic modulus of the release film. The results are shown in Table 1.

[Test Example 2] (Evaluation of mobility of polyorganosiloxane)

An acrylic adhesive tape (manufactured by Nitto Denko Corporation, trade name: 31B TAPE) was attached to the peeling surface of the release agent layer of the release film which was stored at room temperature for 48 hours after the production of the examples and the comparative examples, and stored for 24 hours.

Subsequently, the release film is peeled off from the above adhesive tape, and the germanium atom (Si) and carbon atom (C) are determined based on the surface of the adhesive tape that is in contact with the surface of the release agent layer by X-ray photoelectron spectroscopy (XPS). And the amount of oxygen atom (O) (XPS statistic), and the atomic ratio (atomic %) was calculated according to the following formula.

Helium atomic ratio (atomic %) = [(Si element amount) / {(C element amount) + (O element amount) + (Si element amount)}] × 100

As the measuring device, ESCA 5600 manufactured by Perkinelmer Co., Ltd. was used, and the measurement conditions were as follows.

X-ray source: Mg standard (15kv, 400W)

Take out the angle: 45.

Measurement time: 3 minutes

Determination of elements: germanium atom (Si), carbon atom (C), oxygen atom (O)

Then, the polyorganooxymethane mobility was evaluated based on the following criteria. The atomic ratio and the evaluation results are shown in Table 1.

◎...矽 atomic ratio is less than 0.35 atomic %

○...矽 atomic ratio is 0.35 atom% or more and less than 0.5 atom%

△...矽 atomic ratio is 0.5 atom% or more and less than 1.0 atom%

×...矽 atomic ratio is 1.0 atom% or more

[Test Example 3] (Evaluation of adhesion between layers constituting the release film)

In Examples 1 to 5 and Comparative Example 2, the surface of the resin layer before the formation of the release agent layer on the opposite side to the substrate (hereinafter referred to as "the surface of the resin layer"), and the examples and comparative examples were obtained. The peeling surface of the peeling film was rubbed 10 times with a finger, and it was visually judged by a fluorescent lamp to generate smear and fall off. Then, the adhesion between the layers constituting the release film was evaluated based on the following evaluation criteria. The results are shown in Table 1.

○. . . No turbidity or shedding occurs on either the surface of the rubbing resin layer or the peeling surface, and the adhesion is good.

×. . . When at least one of the surface of the resin layer and the peeling surface is rubbed, at least one of turbidity and peeling occurs, and the adhesion is poor.

[Test Example 4] (Measurement of peeling force)

100 parts by mass of barium titanate (BaTiO ₃ ; 堺 Chemical Industry Co., Ltd., trade name: BT-03), polyvinyl butyral (product name: S-LEC B.KBM-2, manufactured by Sekisui Chemical Co., Ltd.) 1.4 parts by mass of di-octyl phthalate (manufactured by Kanto Chemical Co., Ltd., trade name: Di-octylphthalate deer), adding 69 parts by mass of toluene and 46 parts by mass of ethanol, and mixing and dispersing using a ball mill to prepare Ceramic slurry.

After the production of the examples and the comparative examples, the release film was stored at room temperature for 48 hours, and the ceramic slurry was uniformly applied to the release surface of the release agent layer using an applicator, and then dried at 80 ° C using a dryer. Dry for 1 minute. Thereby, a ceramic green sheet having a thickness of 3 μm was obtained on the release film. In this manner, a release film with a ceramic green sheet was produced.

The release film of the ceramic green sheet was allowed to stand in an environment of 23 ° C and a relative humidity of 50 for 24 hours. Next, an acrylic adhesive tape (manufactured by Nitto Denko Corporation, trade name: 31B TAPE) was attached to the surface of the ceramic green sheet opposite to the release film, and was cut to a width of 20 mm in this state. This was used as a measurement sample.

The adhesive tape side of the measurement sample was fixed to a flat plate, and a peeling film was removed from the peeling angle of 180° and a peeling speed of 100 mm/min using a tensile tester (product name: AG-IS500N, manufactured by Shimadzu Corporation). The ceramic green sheets were peeled off, and the force required for peeling (peeling force; mN/20 mm) was measured. The results are shown in Table 1.

[Test Example 5] (Measurement of surface roughness)

The double-sided tape was attached to the glass plate, and the release film obtained in the examples and the comparative examples was fixed to the glass plate through the double-sided tape so that the surface opposite to the release agent layer became the glass plate side. For the peeling surface of the release film, a light-drying surface shape observation device (manufactured by Bruker AXS Co., Ltd., product name: WYKO-1100) was used, and the maximum protrusion height (Rp; nm) was observed at a magnification of 50 in the PSI mode, based on the obtained Surface shape image of 91.2×119.8μm range The measurement was carried out. The results are shown in Table 1.

As is clear from Table 1, the release film obtained in the examples can be peeled off by using an appropriate peeling force when peeled off from the ceramic green sheets. Further, it was found that the contact area of the acrylic adhesive tape after the release film obtained in the examples was relatively small. That is, it was found that the migration of the polyorganosiloxane to the release agent layer can be effectively suppressed for the ceramic green sheet formed by using the release film of the embodiment. As a result, it is expected that when the laminated ceramic product is produced, it is possible to suppress the shift in the plane direction between the layers of the laminated body of the ceramic green sheet due to the migration of the polyorganosiloxane. Further, it was found that in the release film obtained in the examples, the adhesion of each layer was sufficiently high, and the release agent layer was less likely to peel off from the resin layer. Further, it was confirmed that the release film obtained in the example in which the resin layer was provided as compared with the release film of Comparative Example 1 in which the resin layer was not provided, the maximum protrusion height Rp of the release surface was relatively low, and the smoothness was excellent. .

On the other hand, it was found that after contacting the release film obtained in the comparative example, The contact surface of the acrylic adhesive tape has a relatively large atomic ratio, and does not sufficiently inhibit the migration of the polyorganosiloxane to the ceramic green sheet formed using the release film. Further, with respect to the release film of Comparative Example 2, it was found that the adhesion of each layer was low, and peeling was likely to occur. Further, compared with the release film of the example, the release film of Comparative Example 1 having no resin layer was able to confirm that the maximum protrusion height Rp of the release surface was high and the smoothness was low.

Industrial availability

The release film for ceramic green sheet manufacturing engineering of the present invention is suitable for forming ceramic green sheets having less migration of polyorganosiloxane.

1A‧‧‧Removal film for ceramic green sheet manufacturing engineering

11‧‧‧Substrate

12‧‧‧ Stripper layer

Claims (8)

A release film for a ceramic green sheet manufacturing process, comprising: a base material; and a release film for a ceramic green sheet manufacturing process provided in a release agent layer provided on one side of the base material, wherein the release agent layer is contained The composition of the release agent of the melamine resin and the polyorganosiloxane is hardened, and the film elastic modulus measured from the surface of the release agent layer opposite to the substrate is 3.5 by the nanoindentation test. ~7.0GPa. The release film for ceramic green sheet manufacturing engineering according to claim 1, wherein the polyorganosiloxane has a mass average molecular weight of 500 to 20,000. The release film for a ceramic green sheet manufacturing process according to claim 1, wherein the polyorganosiloxane is contained in the release agent composition in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the melamine resin. . The release film for a ceramic green sheet manufacturing process according to the first aspect of the invention, wherein the melamine resin contained in the release agent composition contains methylated melamine and/or iminomethylol melamine. A release film for a ceramic green sheet manufacturing process according to claim 1, wherein a resin layer is further provided between the substrate and the release agent layer. The release film for a ceramic green sheet manufacturing process according to the fifth aspect of the invention, wherein the resin layer is obtained by curing a resin composition containing an active energy ray-curable component or a thermosetting component. Stripping of ceramic green sheet manufacturing engineering as described in item 6 of the patent application scope a film wherein the aforementioned active energy ray-curable component is a polyfunctional acrylate. The release film for a ceramic green sheet manufacturing process according to the first aspect of the invention, further comprising a second resin layer provided on the substrate opposite to the release agent layer.