JPWO2016158592A1 - Release film for ceramic green sheet manufacturing process - Google Patents

Abstract

A release film 1 for a ceramic green sheet manufacturing process comprising a substrate 11 and a release agent layer 12 provided on one side of the substrate 11, wherein the release agent layer 12 has at least one hydroxyl group in one molecule. And a polyorganosiloxane having at least one organic group selected from a polyester group and a polyether group in one molecule, and a melamine resin capable of undergoing a condensation reaction with the polyorganosiloxane. A release film 1 for a ceramic green sheet manufacturing process formed from a release agent composition. Such a release film 1 for producing a ceramic green sheet is excellent in the coating property of the ceramic slurry and is excellent in the peeling property of the ceramic green sheet even when a highly polar ceramic slurry is used.

Description

  The present invention relates to a release film used in a process for producing a ceramic green sheet.

  Conventionally, 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, and a plurality of obtained ceramic green sheets are stacked and fired.

  The ceramic green sheet is formed by applying a ceramic slurry containing a ceramic material such as barium titanate or titanium oxide on a release film. As the release film, a film base material having a silicone compound such as polysiloxane released is used (Patent Document 1). The release film is required to have a peelability capable of peeling a thin ceramic green sheet formed on the release film without causing cracks or breakage from the release film.

  In recent years, along with miniaturization and high performance of electronic devices, the miniaturization and multilayering of multilayer ceramic capacitors and multilayer ceramic substrates have progressed, and thinning of ceramic green sheets has progressed. When molding such a thin ceramic green sheet on a release film, when the ceramic green sheet is peeled from the release film, cracking due to strength reduction of the ceramic green sheet, breakage such as breakage is likely to occur, The yield of multilayer ceramic capacitors decreases.

  In recent years, the use of highly polar ceramic slurries prepared using a highly polar binder component has increased. When such a ceramic slurry is applied to the release-treated surface of a release film that has been subjected to a release treatment with a silicone compound as described above, repelling occurs during coating, or pinholes are generated after the slurry is dried. Such a problem occurs. In order to solve such a problem, a release film in which generation of repellency and pinholes is suppressed by incorporating a melamine resin in the release agent layer has been developed (Patent Documents 2 and 3).

JP-A-8-267000 JP-A-11-300896 Japanese Patent Laid-Open No. 9-262936

  However, when a ceramic green sheet is formed on the release film described in Patent Documents 2 and 3, there arises a problem that the peel force necessary for peeling the release film from the ceramic green sheet is too strong. In particular, when the thickness of the ceramic green sheet is thin and the strength of the ceramic green sheet is relatively low, due to the peeling force being too strong, the peeling of the ceramic green sheet, such as cracks or breakage, may occur. It is easy to generate and the yield of a multilayer ceramic capacitor falls.

  The present invention has been made in view of such a situation, and even when a highly polar ceramic slurry is used, it is excellent in the coating property of the ceramic slurry, and further excellent in the peelability of the ceramic green sheet. It aims at providing the peeling film for ceramic green sheet manufacturing processes.

  In order to achieve the above object, first, the present invention is a release film for a ceramic green sheet manufacturing process, comprising a base material and a release agent layer provided on one side of the base material, the release agent The layer comprises at least one hydroxyl group in one molecule, and at least one polyorganosiloxane having one or more organic groups selected from polyester groups and polyether groups in one molecule; Provided is a release film for a ceramic green sheet manufacturing process, which is formed from a release agent composition containing siloxane and a melamine resin capable of condensation reaction (Invention 1).

  According to the above invention (Invention 1), the release agent layer is formed from a release agent composition containing a polyorganosiloxane having a hydroxyl group and a specific organic group and a melamine resin. Even if it is a case where it uses, the applicability | paintability of the outstanding ceramic slurry can be achieved, and also the peelability of the outstanding ceramic green sheet can be achieved.

  In the said invention (invention 1), it is preferable that at least 1 of the said hydroxyl group exists in the terminal of the said polyorganosiloxane (invention 2).

  In the said invention (invention 1 and 2), it is preferable that the mass average molecular weights of the said polyorganosiloxane are 500-10000 (invention 3).

（式中、Ｘは、−Ｈ、−ＣＨ_２−ＯＨ、または−ＣＨ_２−Ｏ−Ｒを示し、それぞれ同じであってもよいし、異なっていてもよい。Ｒは、炭素数１〜８個のアルキル基を示し、それぞれ同じであってもよいし、異なっていてもよい。少なくとも１個のＸは、−ＣＨ_２−ＯＨ、または−ＣＨ_２−Ｏ−Ｒである。）
で表される化合物を含有することが好ましい（発明４）。In the said invention (invention 1-3), the said melamine resin is the following general formula (a).

(In the formula, X represents —H, —CH ₂ —OH, or —CH ₂ —O—R, and may be the same or different from each other. R may have 1 to 8 carbon atoms. Each of which may be the same or different, and at least one X is —CH ₂ —OH or —CH ₂ —O—R.)
It is preferable to contain the compound represented by these (invention 4).

  In the said invention (invention 1-4), it is preferable that the said releasing agent composition further contains an acid catalyst (invention 5).

  In the said invention (invention 1-5), it is preferable that the ceramic slurry which uses acrylic resin as a binder component is applied to the surface on the opposite side to the said base material in the said releasing agent layer (invention 6).

2ndly this invention is a peeling film for ceramic green sheet manufacturing processes provided with the base material and the release agent layer provided in the one side of the said base material, Comprising: The said base material in the said release agent layer is opposite The surface free energy of the side surface is 25.0 to 30.0 mJ / m ² , and the storage elastic modulus at 23 ° C. of the release agent layer is 4.0 to 6.0 MPa. A release film for a green sheet manufacturing process is provided (Invention 7).

  In the said invention (invention 7), it is preferable that the peeling force of the surface on the opposite side to the said base material in the said release agent layer is 20.0-50.0mN / 20mm (invention 8).

  The release film for a ceramic green sheet production process according to the present invention is excellent in the coating property of the ceramic slurry even when a highly polar ceramic slurry is used, and is also excellent in the peelability of the ceramic green sheet.

It is sectional drawing of the peeling film for ceramic green sheet manufacturing processes which concerns on one Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described.
[Peeling film for ceramic green sheet manufacturing process]
As shown in FIG. 1, a release film 1 for a ceramic green sheet manufacturing process according to the present embodiment (hereinafter sometimes simply referred to as “release film 1”) includes a base 11 and one surface of the base 11 ( The release agent layer 12 is laminated on the upper surface in FIG.

1. Release Agent Layer The release agent layer 12 of the release film 1 according to this embodiment is selected from at least one hydroxyl group in one molecule and at least one polyester group and polyether group in one molecule. It is formed from a release agent composition containing a polyorganosiloxane having more than one kind of organic group and a melamine resin capable of condensation reaction with the polyorganosiloxane.

  In general, the “melamine resin” means a mixture containing a plurality of types of melamine compounds and / or polynuclear bodies formed by condensation of the melamine compounds. In the present specification, the phrase “melamine resin” means the above mixture or an aggregate of one kind of melamine compounds. Furthermore, in this specification, what the said melamine resin hardened shall be called "melamine hardened | cured material."

  In the release film 1 according to this embodiment, the polyorganosiloxane has the above organic group, so that when the release agent composition is prepared, the polyorganosiloxane and the melamine resin are mixed well. When this release agent composition is applied onto the substrate 11, the polyorganosiloxane and the melamine resin are separated in the thickness direction in the layer of the applied release agent composition. Subsequently, the reaction groups in the melamine resin undergo a condensation reaction, whereby the formation of a melamine cured product proceeds. Further, along with this reaction, the reaction between the reactive group (methylol group or alkoxymethyl group) in the melamine resin and the hydroxyl group of the polyorganosiloxane proceeds. Thereby, the release agent layer 12 having a structure in which the cured melamine and the polyorganosiloxane are integrated is formed. In the release agent layer 12 thus obtained, from the surface on the substrate 11 side, the surface of the release agent layer 12 opposite to the substrate 11 (surface in contact with the ceramic slurry / ceramic green sheet; hereinafter referred to as “release surface” In other words, a gradient structure in which components derived from polyorganosiloxane gradually increase is formed.

  When the release agent layer 12 has the above-described inclined structure, the polyorganosiloxane-derived component is appropriately present on the release surface of the release agent layer 12. Moreover, the storage elastic modulus of the releasing agent layer 12 improves because the releasing agent layer 12 contains the melamine hardened | cured material formed by hardening of a melamine resin. As a result, the peeling force when peeling the release film 1 from the ceramic green sheet is appropriately reduced. Furthermore, when the release agent layer 12 contains a melamine cured product as described above, the surface free energy of the release surface of the release agent layer 12 is increased, and even when a high-polarity ceramic slurry is applied to the release surface, Occurrence of repelling and pinholes is suppressed. Moreover, when the release film 1 is peeled from the ceramic green sheet by forming a structure in which the cured melamine and the polyorganosiloxane are integrated as described above in the release agent layer 12, Migration of polyorganosiloxane is reduced.

The melamine resin preferably contains a compound represented by the following general formula (a).

In formula (a), X represents —H, —CH ₂ —OH, or —CH ₂ —O—R. These groups constitute reactive groups in the condensation reaction between melamine compounds. Specifically, the —NH group formed when X becomes H can undergo a condensation reaction between the —N—CH ₂ —OH group and the —N—CH ₂ —R group. In addition, both —N—CH ₂ —OH group formed by X becoming —CH ₂ —OH and —N—CH ₂ —R group formed by X becoming —CH ₂ —R are both , —NH group, —N—CH ₂ —OH group and —N—CH ₂ —R group can be subjected to a condensation reaction. In addition, the groups represented by —CH ₂ —OH and —CH ₂ —O—R constitute a reactive group that contributes to the condensation reaction between the polyorganosiloxane and the melamine compound. The release agent layer 12 which exhibits the effect mentioned above is formed because a melamine compound has the said reactive group. In the formula (a), it is preferable that all Xs are not —H, and specifically, at least one X is preferably —CH ₂ —OH or —CH ₂ —O—R.

In the group represented by _-CH 2 -O-R, R represents an alkyl group having 1 to 8 carbon atoms. The number of carbon atoms is preferably 1 to 4, and particularly preferably 1 to 2. 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, and a methyl group is particularly preferable.

  Said X may be the same respectively, and may differ. Moreover, said R may be the same respectively, and may differ.

From the viewpoint that the condensation reaction occurs efficiently, in formula (a), the number of X to be -H is preferably 2 or less, particularly preferably 1 or less, and more preferably 0. It is preferable. As an example of a melamine compound in which the number of Xs to be —H is 0, hexamethoxymethylmelamine in which all Xs are —CH ₂ —O—CH ₃ is preferably exemplified.

The polyorganosiloxane is a polymer of a silicon-containing compound represented by the following general formula (b).

In the formula (b), m is an integer of 1 or more. In the formula (b), at least one of R ^{1 to} R ⁸ is one or more organic groups selected from a polyester group and a polyether group. Both polyester groups and polyether groups may be present in one molecule. Since the polyorganosiloxane has the organic group, the polyorganosiloxane and the melamine resin are mixed well in the release agent composition, and further, the separation is good when the release agent composition is coated on the substrate 11. As a result, the release agent layer 12 exhibiting the above-described effects is formed. The organic group may be an epoxy-modified organic group.

In addition, among R ^{1 to} R ⁸ , at least one other than the organic group is a hydroxyl group or an organic group having a hydroxyl group. When the polyorganosiloxane has a hydroxyl group, a condensation reaction occurs between the hydroxyl group and the reactive group of the melamine resin, and as a result, the release agent layer 12 that exhibits the above-described effects is formed. In particular, at least one of R ^{3 to} R ⁸ is preferably a hydroxyl group or an organic group having a hydroxyl group, that is, at least one of the hydroxyl group or the organic group having a hydroxyl group may be present at the end of the polyorganosiloxane. preferable. The presence of the hydroxyl group at the end of the polyorganosiloxane makes it easy for the polyorganosiloxane to undergo a condensation reaction with the melamine resin, thereby effectively forming the release agent layer 12 that exhibits the above-described effects.

In formula (b), among R ^{1 to} R ⁸ , groups other than the groups described above are preferably alkyl groups having 1 to 12 carbon atoms. Examples of the alkyl group having 1 to 12 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, and a methyl group is particularly preferable.

R ^{1 to} R ⁸ may be the same or different. When a plurality of R ¹ and R ² are present, R ¹ and R ² may be the same or different from each other.

  The polyorganosiloxane preferably has a mass average molecular weight of 500 to 10000, particularly preferably 1000 to 8000, and more preferably 1000 to 5000. In addition, the mass mean molecular weight in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.

  The content of the polyorganosiloxane in the release agent composition is preferably 2 to 20 parts by mass, particularly 3 to 15 parts by mass, and more preferably 5 to 5 parts by mass with respect to 100 parts by mass of the melamine resin. It is preferably 10 parts by mass.

  The release agent composition preferably further contains an acid catalyst. As an example of the acid catalyst, hydrochloric acid, p-toluenesulfonic acid and the like are preferable, and p-toluenesulfonic acid is particularly preferable. When the release agent composition contains an acid catalyst, the condensation reaction in the melamine resin proceeds efficiently.

  The content of the acid catalyst in the release agent composition according to the present embodiment is preferably 1 to 20 parts by mass, particularly preferably 2 to 15 parts by mass with respect to 100 parts by mass of the melamine resin. Furthermore, it is preferable that it is 4-10 mass parts.

  The release agent composition according to this embodiment may contain a crosslinking agent, a reaction accelerator, a reaction inhibitor and the like in addition to the above components. As the reaction accelerator, glycol compounds such as ethylene glycol and propanediol may be used.

  The thickness of the release agent layer 12 is preferably 0.01 to 3 μm, particularly preferably 0.03 to 1 μm, and further preferably 0.1 to 0.5 μm. When the thickness of the release agent layer 12 is 0.01 μm or more, the function as the release agent layer 12 can be effectively exhibited. Moreover, when the release agent layer 12 has a thickness of 3 μm or less, it is possible to suppress occurrence of blocking when the release film 1 is wound into a roll.

2. Physical properties of release agent layer In the release film 1 according to this embodiment, the surface free energy of the release surface of the release agent layer 12 is preferably 25.0 to 30.0 mJ / m ² , particularly 25.0 to 28. is preferably .0mJ / ^{m 2,} preferably further is 25.0~26.0mJ / ^{m 2.} When the surface free energy is 25.0 mJ / m ² or more, the occurrence of repelling and pinholes can be effectively suppressed even when a highly polar ceramic slurry is applied to the surface. . Further, when the surface free energy is 30.0 mJ / m ² or less, the peeling force when peeling the release film 1 from the molded ceramic green sheet can be suppressed to an appropriate strength. In addition, the measuring method of surface free energy is as showing in the test example mentioned later. In the release film 1 according to the present embodiment, the release agent layer 12 is formed from a release agent composition containing the above-described polyorganosiloxane and a melamine resin capable of condensation reaction with the polyorganosiloxane. A surface free energy of 25.0-30.0 mJ / m ² can be achieved.

  In the release film 1 according to the present embodiment, the storage elastic modulus at 23 ° C. of the release agent layer 12 is preferably 4.0 to 6.0 MPa, particularly preferably 4.0 to 5.5 MPa. Furthermore, it is preferable that it is 4.5-5.0 MPa. When the storage elastic modulus is 4.0 MPa or more, the peeling force when peeling the release film 1 from the molded ceramic green sheet can be appropriately reduced, and excellent peelability can be achieved. Moreover, it is suppressed that the peeling force at the time of peeling the peeling film 1 from the shape | molded ceramic green sheet is suppressed too much that a storage elastic modulus is 6.0 Mpa or less, and unintentional peeling will generate | occur | produce. Can be prevented. In addition, the measuring method of a storage elastic modulus is as showing in the test example mentioned later. In the release film 1 according to the present embodiment, the release agent layer 12 is formed from a release agent composition containing a melamine resin, whereby a storage elastic modulus of 4.0 to 6.0 MPa can be achieved. .

  In the release film 1 according to the present embodiment, the release force of the release surface of the release agent layer 12 is preferably 20.0 to 50.0 mN / 20 mm, particularly 21.0 to 40.0 mN / 20 mm. It is preferable that it is 22.0-30.0mN / 20mm. When the peeling force is 20.0 mN / 20 mm or more, the release film 1 can be prevented from unintentionally peeling from the ceramic green sheet formed on the release film 1. Moreover, workability | operativity at the time of peeling can be improved because peeling force is 50.0 mN / 20 mm or less, and peeling defects, such as a crack of a ceramic green sheet, and a fracture | rupture, can be suppressed. In addition, the measuring method of peeling force is as showing to the test example mentioned later.

3. Base Material The base material 11 of the release film 1 according to the present embodiment is not particularly limited as long as the release agent layer 12 can be laminated. Examples of the substrate 11 include films made of polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polypropylene and polymethylpentene, plastics such as polycarbonate and polyvinyl acetate, and may be a single layer. However, it may be a multilayer of two or more layers of the same type or different types. Among these, a polyester film is preferable, a polyethylene terephthalate film is particularly preferable, and a biaxially stretched polyethylene terephthalate film is more preferable. Since the polyethylene terephthalate film hardly generates dust or the like during processing or use, for example, it is possible to effectively prevent a ceramic slurry coating failure due to dust or the like. Furthermore, by performing an antistatic treatment on the polyethylene terephthalate film, it is possible to increase the effect of preventing ignition due to static electricity when coating a ceramic slurry using an organic solvent or preventing defective coating.

  Moreover, in this base material 11, for the purpose of improving the adhesiveness with the release agent layer 12 provided on the surface, a surface treatment by an oxidation method or a concavo-convex method or a primer treatment is performed on one or both sides as desired. Can be applied. 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. Examples include a thermal spraying method. These surface treatment methods are appropriately selected depending on the type of the base film, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.

  The thickness of the base material 11 should just be 10-300 micrometers normally, Preferably it is 15-200 micrometers, Especially preferably, it is 20-125 micrometers.

4). Manufacturing method of release film for ceramic green sheet manufacturing process The release film 1 according to the present embodiment is coated on one surface of a substrate 11 with the above-described release agent composition and, optionally, a coating solution containing an organic solvent. Then, it is obtained by drying and curing to form the release agent layer 12. As the coating method, for example, gravure coating method, bar coating method, spray coating method, spin coating method, knife coating method, roll coating method, die coating method and the like can be used.

  There is no restriction | limiting in particular as said organic solvent, A various thing can be used. For example, hydrocarbon compounds such as toluene, hexane, heptane, isopropyl alcohol, isobutyl alcohol, acetone, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof are used. In particular, it is preferable to use a mixed solution (mass ratio 4: 1) of isopropyl alcohol and isobutyl alcohol.

  The release agent composition applied as described above is preferably heat-cured. In this case, the heating temperature is preferably 90 to 140 ° C., and the heating time is preferably about 10 to 120 seconds. In particular, it is preferable to heat at 120 ° C. for 1 minute.

5. Method for Using Release Film for Ceramic Green Sheet Manufacturing Process The release film 1 according to this embodiment can be used for manufacturing a ceramic green sheet. Specifically, after applying a ceramic slurry containing a ceramic material such as barium titanate or titanium oxide to the release surface of the release agent layer 12, a ceramic green sheet is obtained by drying the ceramic slurry. Can do. The coating can be performed using, for example, a slot die coating method or a doctor blade method.

  The ceramic slurry used for the release film 1 according to this embodiment may be a ceramic slurry with high polarity. A ceramic slurry having a high polarity is easy to generate repellency and pinholes when applied to the release surface of a conventional release film, but when used for the release film 1 according to the present embodiment, Generation | occurrence | production is suppressed effectively and favorable coating can be implement | achieved.

  Examples of the ceramic slurry having high polarity include ceramic slurry prepared using an acrylic resin as a binder component. Generally, a ceramic slurry is prepared using a butyral resin or an acrylic resin as a binder component, but a ceramic slurry having a high polarity can be obtained by using an acrylic resin having a higher polarity. . Another example of a ceramic slurry having a high polarity is a ceramic slurry prepared using an aqueous solvent as a solvent.

  According to the peeling film 1 which concerns on this embodiment, even if it is a case where a highly polar ceramic slurry is applied, generation | occurrence | production of a repellency and a pinhole is suppressed. Further, the peeling force when peeling the release film 1 from the ceramic green sheet becomes appropriate. In particular, even when a thin ceramic green sheet having a low strength is formed on the release agent layer, there is no peeling failure such as cracking or breaking. It can peel without generating. Thus, according to the peeling film 1 which concerns on this embodiment, while being excellent in the coating property of a ceramic slurry, it is excellent also in the peeling property of a ceramic green sheet, and the yield in ceramic green sheet manufacture improves.

  The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

  For example, another layer such as an antistatic layer may be provided between the surface of the substrate 11 opposite to the release agent layer 12 or between the substrate 11 and the release agent layer 12.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

[Example 1]
90 parts by mass of melamine resin (main component: hexamethoxymethylmelamine, manufactured by MT Aquapolymer, trade name: Cymel 303, solid content: 100% by mass), and polyester-modified hydroxyl group-containing polydimethylsiloxane (produced by Big Chemie Japan, trade name) : BYK-370, solid content 25 parts by mass) 10 parts by mass and p-toluenesulfonic acid 5 parts by mass as an acid catalyst, a mixed solvent (mass ratio) of isopropyl alcohol and isobutyl alcohol 4: 1) to obtain a coating solution having a solid content of 30% by mass.

  The obtained coating solution was uniformly coated on one side of a biaxially stretched polyethylene terephthalate film (thickness: 38 μm) as a substrate by a bar coater. Subsequently, it heat-dried at 120 degreeC for 1 minute, the release agent composition was hardened, and the peeling film with which the 1.0 micrometer-thick release agent layer was laminated | stacked on the base material was obtained.

[Examples 2 and 3]
A release film was obtained in the same manner as in Example 1 except that the thickness of the release agent layer was changed as shown in Table 1.

Example 4
A release film was obtained in the same manner as in Example 3 except that the content of the polyester-modified hydroxyl group-containing polydimethylsiloxane in the release agent composition was changed as shown in Table 1.

[Comparative Example 1]
A release film was obtained in the same manner as in Example 3 except that the polyester-modified hydroxyl group-containing polydimethylsiloxane was not used.

[Comparative Example 2]
Instead of 10 parts by mass of the polyester-modified hydroxyl group-containing polydimethylsiloxane, the same procedure as in Example 3 was conducted, except that 5 parts by mass of both-end hydroxyl group-modified dimethylsiloxane (trade name: KF-9701, manufactured by Shin-Etsu Chemical Co., Ltd.) was used. A release film was obtained.

[Comparative Example 3]
Exfoliation was carried out in the same manner as in Example 3 except that 5 parts by mass of polydimethylsiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96-50cs) was used instead of 10 parts by mass of the polyester-modified hydroxyl group-containing polydimethylsiloxane. A film was obtained.

[Comparative Example 4]
From 100 parts by mass of a mixture of stearyl-modified alkyd compound and methylated melamine (manufactured by Hitachi Chemical Co., Ltd., trade name: Tesfine 303, solid content 20% by mass) and 3 parts by mass of p-toluenesulfonic acid as an acid catalyst The resulting release agent composition was mixed in a mixed solvent of isopropyl alcohol and isobutyl alcohol (mass ratio 4: 1) to obtain a coating solution having a solid content of 30% by mass.

  The obtained coating solution was uniformly coated on one side of a biaxially stretched polyethylene terephthalate film (thickness: 38 μm) as a substrate by a bar coater. Subsequently, it heat-dried at 120 degreeC for 1 minute (s), the release agent composition was hardened, and the peeling film with which the 0.1 micrometer-thick release agent layer was laminated | stacked on the base material was obtained.

[Comparative Example 5]
100 parts by mass of an addition type organopolysiloxane composed of an organopolysiloxane having a siloxane bond as a main skeleton and a vinyl group and an organohydrogenpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: Silicone KS-847H, solid content: 30% by mass) Is diluted with toluene, and 2 parts by mass of a platinum catalyst (trade name: PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to and mixed with the diluted solution, whereby a release agent composition having a solid content of 1.5% by mass is mixed. A product coating solution was obtained.

  The obtained coating solution was uniformly coated on one side of a biaxially stretched polyethylene terephthalate film (thickness: 38 μm) as a substrate by a bar coater. Subsequently, it heat-dried at 130 degreeC for 1 minute, the release agent composition was hardened, and the peeling film with which the 0.1 micrometer-thick release agent layer was laminated | stacked on the base material was obtained.

[Test Example 1] (Measurement of peel force)
100 parts by mass of barium titanate (BaTiO ₃ ; manufactured by Sakai Chemical Industry Co., Ltd., BT-03), 7 parts by mass of acrylic binder resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dianal BR-106), and dioctyl phthalate (Kanto Chemical) 80 parts by mass of a mixed solution of toluene and ethanol (mass ratio 5: 5) was added to 3 parts by mass of dioctyl phthalate (class 1) manufactured by the company, and mixed and dispersed with a ball mill to prepare a ceramic slurry.

  In the release film that was produced in Examples and Comparative Examples and stored at room temperature for 48 hours, the ceramic slurry was uniformly applied to the release surface of the release agent layer by the doctor blade method, and then 80 ° C. in a dryer. Dry at 1 ° C. for 1 minute. As a result, a ceramic green sheet having a thickness of 3 μm was obtained on the release film. In this way, a release film with a ceramic green sheet was produced.

  An acrylic adhesive tape (manufactured by Nitto Denko Corporation, trade name: 31B tape) was affixed to the surface of the release film with the ceramic green sheet opposite to the release film in the ceramic green sheet. In that state, after standing for 24 hours in an atmosphere of room temperature 23 degrees and humidity 50%, it was cut into a width of 20 mm.

  The adhesive tape side of the cut sample is fixed to a rigid plate, and the force required to peel off the release film from the ceramic green sheet at a peeling angle of 180 ° and a peeling speed of 100 mm / min using a tensile tester. (Peeling force; mN / 20 mm) was measured. The results are shown in Table 1.

[Test Example 2] (Evaluation of slurry coatability)
In the release film that was manufactured in the examples and comparative examples and stored at room temperature for 48 hours, the ceramic slurry manufactured as described above was applied to the release surface of the release agent layer using a die coater with a width of 250 mm and a length of 10 m. Then, a ceramic green sheet having a thickness of 1 μm was formed on the release film by drying at 80 ° C. for 1 minute using a dryer. In this way, a release film with a ceramic green sheet was produced.

About the obtained peeling film with a ceramic green sheet, the whole ceramic green sheet was visually inspected, illuminating the peeling film side with a fluorescent lamp, and the slurry coating property was evaluated based on the following criteria. The results are shown in Table 1.
A: No pinhole was generated in the ceramic green sheet.
B: 1 to 5 pinholes were generated in the ceramic green sheet.
C: Six or more pinholes were generated in the ceramic green sheet.

[Test Example 3] (Measurement of surface free energy)
For the release films obtained in Examples and Comparative Examples, the contact angles of various droplets with respect to the release surface of the release agent layer were measured, and based on the values, surface free energy (mJ / m ²⁾ ) The contact angle was measured according to JIS R3257 by a sessile drop method using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DM-701). For the droplets, diiodomethane was used as the “dispersion component”, 1-bromonaphthalene was used as the “dipole component”, and distilled water was used as the “hydrogen bond component”. The results are shown in Table 1.

[Test Example 4] (Measurement of storage elastic modulus)
The release films obtained in Examples and Comparative Examples were allowed to stand for 24 hours in an atmosphere having a room temperature of 23 degrees and a humidity of 50%, and then cut into a size of 10 mm × 10 mm. Next, the back surface of the base material of the cut release film was fixed with a two-component epoxy adhesive on a glass plate adhered to an aluminum base. Then, using a micro hardness evaluation apparatus (Mano, Nano Indenter SA2), 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 storage elastic modulus (MPa) of the release agent layer of the release film was measured. The results are shown in Table 1.

[Test Example 5] (Evaluation of silicone migration)
Acrylic binder resin (Mitsubishi Rayon Co., Ltd., trade name: Dianal BR-106) is diluted with a mixed solvent of toluene and ethanol (mixing ratio 50:50), and an acrylic resin solution having a solid content concentration of 20% by mass. Got. This acrylic resin solution was uniformly applied to the release surface of the release films obtained in Examples and Comparative Examples using a 35 μm applicator, and then dried at 60 ° C. for 1 minute in a dryer. As a result, a release film on which an acrylic resin sheet having a thickness of 4 μm was laminated was obtained.

The release film is peeled from the acrylic resin sheet, and the silicon atom (Si) and carbon atom (C) measured by X-ray photoelectron spectroscopy (XPS) are measured on the surface of the acrylic resin sheet that is in contact with the release surface. And based on the amount of oxygen atoms (O) (XPS count number), the silicon atom ratio (atomic%) was calculated by the following formula. The results are shown in Table 1. In addition, about the comparative examples 1 and 4 which are not using organopolysiloxane as a material, the said test was not performed.
Silicon atomic ratio (atomic%) = [(Si element amount) / {(C element amount) + (O element amount) + (Si element amount)}] × 100

Furthermore, based on the obtained silicon atom ratio, silicone migration was evaluated according to the following criteria. The results are shown in Table 1.
○: Silicon atom ratio is less than 1.00 atom% × Silicon atom ratio is 1.00 atom% or more Note that when the silicon atom ratio is 1.00 atom% or more, pinholes are generated during slurry coating, or green sheets In the process of laminating the layers, there is a possibility of stacking misalignment, resulting in product defects in the obtained multilayer ceramic product.

Details of abbreviations and the like described in Table 1 are as follows.
Polyester-modified hydroxyl group-containing PDMS: Polyester-modified hydroxyl group-containing polydimethylsiloxane (Bikchemy Japan, trade name: BYK-370, solid content 25 parts by mass)
・ Hydroxyl-containing PDMS: Hydroxyl-modified dimethylsiloxane at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-9701)
PDMS: polydimethylsiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96-50cs)
Tesfine 303: Mixture of stearyl-modified alkyd compound and methylated melamine (manufactured by Hitachi Chemical Polymer Co., Ltd., trade name: Tesfine 303, solid content 20% by mass)
Silicone KS-847H: Addition type organopolysiloxane composed of an organopolysiloxane having a siloxane bond as a main skeleton and a vinyl group and an organohydrogenpolysiloxane (trade name: Silicone KS-847H, solid content 30 manufactured by Shin-Etsu Chemical Co., Ltd.) mass%)

  As is clear from Table 1, the release films obtained in the examples are excellent in coating properties of highly polar slurry, and can be peeled off with an appropriate peeling force when peeling from the ceramic green sheet. It was possible. Moreover, it turns out that the transfer of the silicone to a ceramic green sheet hardly arises.

  On the other hand, the release film obtained in Comparative Example 1 showed a high value of surface free energy, and when peeling from the ceramic green sheet, peeling failure such as cracks and breakage occurred. Further, the release films obtained in Comparative Examples 2 and 3 had a large amount of silicone migration. Further, the release film obtained in Comparative Example 4 showed a relatively high value of surface free energy, and required a relatively strong peeling force when peeling from the ceramic green sheet. In addition, the release film obtained in Comparative Example 5 shows a low value of both surface free energy and storage elastic modulus, and repelling and pinholes are generated, resulting in poor slurry coatability. Required a strong peeling force, and more silicone transferred.

  The release film for manufacturing a ceramic green sheet of the present invention is suitable for forming a ceramic green sheet, and particularly suitable for forming a ceramic green sheet using a ceramic slurry having a high polarity.

DESCRIPTION OF SYMBOLS 1 ... Release film for ceramic green sheet manufacturing process 11 ... Base material 12 ... Release agent layer

Claims (8)

A release film for a ceramic green sheet manufacturing process comprising a substrate and a release agent layer provided on one side of the substrate,
The release agent layer is
A polyorganosiloxane having at least one hydroxyl group in one molecule and at least one organic group selected from a polyester group and a polyether group in one molecule;
A release film for a ceramic green sheet manufacturing process, comprising a release agent composition containing the polyorganosiloxane and a melamine resin capable of condensation reaction.   The release film for a ceramic green sheet production process according to claim 1, wherein at least one of the hydroxyl groups is present at an end of the polyorganosiloxane.   The release film for a ceramic green sheet production process according to claim 1 or 2, wherein the polyorganosiloxane has a mass average molecular weight of 500 to 10,000. The melamine resin has the following general formula (a)

(In the formula, X represents —H, —CH ₂ —OH, or —CH ₂ —O—R, and may be the same or different from each other. R may have 1 to 8 carbon atoms. Each of which may be the same or different, and at least one X is —CH ₂ —OH or —CH ₂ —O—R.)
The release film for a ceramic green sheet manufacturing process according to any one of claims 1 to 3, comprising a compound represented by:   The release film for a ceramic green sheet manufacturing process according to any one of claims 1 to 4, wherein the release agent composition further contains an acid catalyst.   The ceramic slurry which uses acrylic resin as a binder component is applied to the surface on the opposite side to the base material in the release agent layer, according to any one of claims 1 to 5. Release film for ceramic green sheet manufacturing process. A release film for a ceramic green sheet manufacturing process comprising a substrate and a release agent layer provided on one side of the substrate,
The surface free energy of the surface opposite to the substrate in the release agent layer is 25.0 to 30.0 mJ / m ² ,
A release film for producing a ceramic green sheet, wherein the release elastic layer has a storage elastic modulus at 23 ° C. of 4.0 to 6.0 MPa.   The release film for a ceramic green sheet manufacturing process according to claim 7, wherein the release force on the surface of the release agent layer opposite to the substrate is 20.0 to 50.0 mN / 20 mm.

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