KR20190119072A - Release film for green sheet formation - Google Patents

Abstract

The release film for green sheet formation of this invention is a release film 1 for green sheet formation used for formation of a green sheet, The base material 11 and the release agent layer 12 formed in the single side | surface of the said base material 11 are used. The said release agent layer consists of hardened | cured material of the release agent formation material containing (A) energy-beam curable compound, (B) hydrophobized silica sol, and (C) peeling provision component.

Description

Release film for green sheet formation

The present invention relates to a release film for forming a green sheet.

The release film is generally composed of a base material and a release agent layer. A green sheet is manufactured by dispersing ceramic particle and binder resin in the organic solvent on such a peeling film, coating and drying the ceramic slurry which melt | dissolved. Moreover, the manufactured green sheet peels from a peeling film and is used for manufacture of a ceramic capacitor.

Moreover, when manufacturing a green sheet using a peeling film, there existed a problem that pinholes generate | occur | produce on the surface of a green sheet by the unevenness | corrugation of the surface of a peeling film being transferred to a green sheet. Therefore, the smoothness that there is little surface irregularities is calculated | required by the peeling film. On the other hand, with the recent miniaturization and high density of ceramic capacitors, further thinning of the green sheet is required. And further improvement of the smoothness is calculated | required by the peeling film by further thinning of a green sheet.

However, there existed a problem that blocking became easy to occur, so that the smoothness of a peeling film was improved. That is, when a peeling film is generally stored in the state wound by roll shape, is transported, and forms a green sheet, it extracts from a roll shape state and is used. Therefore, when extracting this wound peeling film, there existed a problem that the blocking (sticking) of the peeling agent layer of the surface of a release film and the base material of the back surface of a peeling film becomes easy to generate | occur | produce. Thus, in the peeling film excellent in the smoothness, the performance (anti blocking property) which prevents blocking is calculated | required.

As a technique of improving the anti blocking property of a peeling film, patent document 1 describes the release film which provided the release layer containing inert microparticles | fine-particles on the at least single side | surface of a polyester film, for example. In this release film, the 10-point average roughness (Rz) on the surface of the release layer is 20 to 500 nm.

Japanese Unexamined Patent Publication No. 2004-255704

However, in the peeling film of patent document 1, the peeling film which is compatible with smoothness and anti blocking property was not obtained.

Then, the objective of this invention is providing the peeling film for green sheet formation which is excellent in smoothness and has sufficient anti blocking property.

The release film for green sheet formation which concerns on one aspect of this invention is a release film for green sheet formation used for formation of a green sheet, Comprising: A base material and the release agent layer formed in the single side | surface of the said base material, The said release agent layer, (A) It is comprised from the hardened | cured material of the material for releasing agent formation containing an energy ray curable compound, (B) hydrophobized silica sol, and (C) peeling provision component.

In the peeling film for green sheet formation which concerns on one aspect of this invention, it is preferable that the average particle diameters of the said (B) hydrophobized silica sol are 10 nm or more and 100 nm or less.

In the release film for green sheet formation which concerns on one aspect of this invention, when forming the coating film of said (B) hydrophobized silica sol, it is preferable that the contact angle of water with respect to the said coating film is 100 degrees or more.

In the release film for green sheet formation which concerns on one aspect of this invention, it is preferable that the average thickness of the said release agent layer is 0.2 micrometer or more and 2 micrometers or less.

In the release film for green sheet formation which concerns on one aspect of this invention, the arithmetic mean roughness Ra of the outer surface of the said release agent layer is 8 nm or less, and the maximum protrusion height Rp of the outer surface of the said release agent layer is 50 nm or less. It is preferable.

According to this invention, the peeling film for green sheet formation which is excellent in smoothness and has sufficient anti blocking property can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows the peeling film for green sheet formation which concerns on embodiment of this invention.
It is a schematic diagram for demonstrating notionally the segregation state of hydrophobized silica sol in the peeling film for green sheet formation which concerns on embodiment of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment is described about an example of this invention. This invention is not limited to the content of embodiment.

As shown in FIG. 1, the peeling film 1 for green sheet formation (hereinafter "peel film 1") which concerns on this embodiment is the base material 11 and the 1st surface 11A of the base material 11 The release agent layer 12 formed in the structure is provided.

(materials)

The base material 11 which concerns on this embodiment has 11 A of 1st surfaces, and 11 B of 2nd surfaces.

It does not specifically limit as a material which comprises the base material 11, For example, polyester resin (polybutylene terephthalate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, etc.), polyolefin resin (polypropylene resin, Polymethylpentene resin, etc.), and a film made of plastic such as polycarbonate. The base material 11 may be a single layer film, or may be a multilayer film of two or more layers of the same kind or different kinds. Among these, a polyester film is preferable and a biaxially stretched polyethylene terephthalate film is more preferable from a viewpoint that a particle | grains etc. hardly generate | occur | produce at the time of a process or use. When manufacturing a green sheet using the peeling film 1 manufactured using the polyester film, the coating defect of the ceramic slurry by a dirt etc. can be prevented effectively.

In addition to the above materials, the base material 11 may contain a filler or the like. Examples of the filler include silica, titanium oxide, calcium carbonate, kaolin, aluminum oxide, and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type. By containing such a filler, while providing the mechanical strength of the base material 11, the slipperiness | lubricacy of the front and back surface is improved and blocking can be suppressed.

The surface roughness (arithmetic mean roughness Ra ₁ and Ra ₂ and the maximum protrusion height Rp ₁ and Rp ₂ ) of the first surface 11A and the second surface 11B of the base material 11 are both general grades. The illuminance range of may be sufficient, and both surfaces may be the illuminance range of a high smooth grade. Moreover, one surface among the 1st surface 11A and the 2nd surface 11B may be the roughness range of a high smooth grade, and the other surface may be the roughness range of a general purpose grade. If the 2nd surface 11B of the base material 11 which is not apply | coating the releasing agent layer 12 is a roughness range of a high smooth grade, winding of the peeling film 1 will generate blocking normally, but this implementation Blocking hardly arises in the peeling film 1 of the form.

For high-grade smooth, the arithmetic mean roughness Ra (Ra ₁₎ of the first surface (11A) of the base material 11, and preferably not more than 40 ㎚ ㎚ than 1, more preferably not more than 20 ㎚ least 2 ㎚. Thereby, on the 1st surface 11A of the base material 11, the release agent layer 12 smoothed by filling the unevenness | corrugation of the 1st surface 11A is formed as mentioned later. Accordingly, the arithmetic mean roughness Ra is within the range ₁ is, the smoothing action of the release agent layer outer surface (12A) of this becomes particularly remarkable.

In the case of a high smooth grade, it is preferable that it is 10 nm or more and 500 nm or less, and, as for the largest protrusion height Rp (Rp ₁ ) of the 1st surface 11A of the base material 11, it is more preferable that it is 15 nm or more and 350 nm or less. Thereby, on the 1st surface 11A of the base material 11, the release agent layer 12 smoothed by filling the unevenness | corrugation of the 1st surface 11A is formed as mentioned later. Therefore, when the maximum projection height Rp ₁ is in the above range, the smoothing action of the outer surface 12A of the release agent layer becomes particularly remarkable.

For high-grade smooth, the arithmetic mean roughness Ra (Ra ₂₎ of the second surface (11B) of the base material 11, and preferably not more than 40 ㎚ ㎚ least 1, more preferably not more than 20 ㎚ least 2 ㎚. Further, when a high smoothing grade, the maximum protrusion height Rp (Rp ₂₎ of the second surface (11B) of the base material 11, and more preferably not more than more than 10 ㎚ 500 ㎚ preferable, and not more than 350 ㎚ least 15 ㎚ It is especially preferable that they are 20 nm or more and 300 nm or less.

By using the base material of a high smooth grade in this way, even if the peeling film 1 and the ceramic green sheet formed into a film are wound up, the back surface side (2nd surface 11B side) of the peeling film 1 which contacts a coating surface. Because of this smoothness, there is no damage received by the ceramic green sheet being pressed, and the quality of the ceramic capacitor is improved.

In the case of the general-purpose grade, the arithmetic mean roughness Ra (Ra ₁ ) of the first surface 11A of the substrate 11 is usually 5 nm or more and 80 nm or less, and the first surface 11A of the substrate 11. The maximum protrusion height Rp (Rp ₁ ) of is usually 100 nm or more and 700 nm or less. In the case of a general-purpose grade, and the second surface (11B) of the substrate (11) the second surface (11B), the arithmetic mean roughness Ra (Ra ₂₎ is, usually is not more than 80 ㎚ than 5 ㎚, base 11 of the The maximum protrusion height Rp (Rp ₂ ) of is usually 100 nm or more and 700 nm or less.

In addition, in this specification, the arithmetic mean roughness Ra and the maximum protrusion height Rp of the 1st surface 11A and the 2nd surface 11B of the base material 11 are the surfaces of Mitsutoyo Corp. manufacture based on JISB0601-1994. It is the value measured and calculated | required by the illuminance measuring instrument SV3000S4 (touch type). In addition, in this specification, unless otherwise indicated, "arithmetic mean roughness and maximum protrusion height" points out the value obtained by measuring as mentioned above.

Although the average film thickness of the base material 11 is not specifically limited, It is preferable that they are 10 micrometers or more and 300 micrometers or less, and it is more preferable that they are 15 micrometers or more and 200 micrometers or less. Thereby, while making the moderate flexibility of the release film 1, resistance to tearing or breaking can be made particularly excellent.

(Release layer)

The release agent layer 12 which concerns on this embodiment is formed on 11 A of 1st surfaces of the base material 11. As shown in FIG. The release agent layer 12 consists of hardened | cured material of the material for release agent formation. And in this embodiment, since the (A) energy ray curable compound is used, the release agent layer 12 is formed by irradiating and hardening an active energy ray to the release agent layer formation material. This release agent layer 12 can provide smoothness, peelability, and anti blocking property to the release film 1.

It is preferable that it is 15 nm or less, and, as for the arithmetic mean roughness Ra (Ra ₀ ) of the outer surface 12A of the releasing agent layer 12, it is more preferable that it is 8 nm or less. Further, preferably the maximum protrusion height Rp (Rp ₀₎ is less than or equal to 50 ㎚, the outer surface of the release agent layer 12, and more preferably not more than 45 ㎚. As a result, when the green sheet is molded on the outer surface 12A side of the release agent layer 12, it is possible to more reliably prevent the green sheet from generating a pinhole or a partial thickness variation, thereby making the surface of the green sheet more visible. It can be made highly smooth.

Even if the outer surface 12A of the back surface of the release agent layer 12 according to the present embodiment is high smooth as described above, and the second surface 11B of the base material 11 is also high smooth, blocking does not occur.

In addition, when apply | coating on the 1st surface 11A of the base material 11, the material for releasing agent layer formation mentioned later has moderate fluidity | liquidity. Therefore, when using such a peeling agent layer formation material, the unevenness | corrugation of the 1st surface 11A of the base material 11 can be easily embedded, and the embedded state can be maintained. As a result, it can prevent that the unevenness | corrugation of the base material 11 affects the outer surface 12A side opposite to the base material 11 of the peeling agent layer 12, and it is 12A of the outer surface of the peeling agent layer 12 ) Can be smoothed.

It is preferable that they are 0.2 micrometer or more and 2 micrometers or less, and, as for the average thickness of the release agent layer 12, it is more preferable that they are 0.3 micrometer or more and 1.5 micrometers or less. If the average thickness of the releasing agent layer 12 is more than the said minimum, the smoothness of the outer surface 12A of the releasing agent layer 12 can be improved, and it can reliably generate pinhole or partial thickness deviation to a green sheet more reliably. You can prevent it. On the other hand, if the thickness of the releasing agent layer 12 is below the said upper limit, generation | occurrence | production of the curl of the releasing film 1 by hardening shrinkage of the releasing agent layer 12 can be prevented, and also by winding up the peeling film 1 by It can suppress that blocking generate | occur | produces in the 2nd surface 11B of the base material 11 which contacted, and the outer surface 12A of the peeling agent layer 12.

It is preferable that it is 3.5 GPa or more and 8.0 GPa or less, and, as for the elasticity modulus of the release agent layer 12, it is more preferable that they are 4.0 GPa or more and 8.0 GPa or less. When the average elastic modulus of the releasing agent layer 12 is in the above range, the outer surface 12A of the releasing agent layer 12 is sufficiently hard to suppress the hydrophobized silica segregated on the surface when the release films are in close contact with each other. can do. Therefore, the effect of giving anti blocking property by hydrophobized silica can be heightened more.

In the present specification, the elastic modulus of the release agent layer 12 is a nano indenter (manufactured by MTS Corporation, trade name "Nano Indenter SA4"), and the maximum indentation depth of the indenter is 100 nm, strain rate 0.05 sec ^-1 , and displacement. The nanoindentation test was done on condition of 2 nm of amplitude and 45 Hz of vibration frequencies, and the film elastic modulus of the said peeling film was measured. In addition, in this specification, unless otherwise indicated, an "elastic modulus" refers to the value obtained by measuring as mentioned above.

(Material for forming the release agent)

Here, the material for releasing agent layer formation used in order to form the releasing agent layer 12 which concerns on this embodiment is demonstrated.

The material for release agent layer formation which concerns on this embodiment contains (A) an energy-beam curable compound, (B) hydrophobized silica sol, and (C) peeling provision component.

(Energy ray curable compound)

There is no restriction | limiting in particular as (A) energy ray curable compound which concerns on this embodiment, It can select from conventionally well-known thing. (A) As an energy ray curable compound, an energy ray curable monomer, an oligomer, resin, the composition containing these, etc. are mentioned.

As a specific example, polyfunctional (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, silicone (meth) acrylate, etc. are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.

As a polyfunctional (meth) acrylate, 1, 4- butanediol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) ) Acrylate, propylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylic Elate, dipentaerythritol hexa (meth) acrylate, glycerol tri (meth) acrylate, and triallyl (meth) acrylate etc. are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, it is more preferable to use pentaerythritol tetra (meth) acrylate or dipentaerythritol hexa (meth) acrylate from the point which can provide suitable hardness to the releasing agent layer 12.

Moreover, as polyfunctional (meth) acrylate, the polyfunctional (meth) acrylate containing a functional group may be sufficient. As a functional group to be used, a hydroxyl group is preferable and the dispersibility in the release agent layer formation material of the hydrophobized silica sol of (B) component, and the ubiquitous in the formed release agent layer 12 can be optimized. Specific examples of the hydroxyl group-containing acrylic compound include pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, trimethylolpropanedi (meth) acrylate, pentaerythritoldi (meth) acrylate, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, it is more preferable to use pentaerythritol tri (meth) acrylate from the point which can provide suitable hardness to the releasing agent layer 12. Moreover, when a polyfunctional (meth) acrylate has a functional group, by the bridge | crosslinking by a crosslinking agent, the peeling agent layer 12 can be hardened | cured by the means of two systems of energy rays and heating, and the grade of hardening can be made into a desired level. have.

Moreover, it is also preferable that a polyfunctional (meth) acrylate contains the polyfunctional (meth) acrylate of EO (ethylene oxide) or PO (propylene oxide) addition type.

The polyfunctional (meth) acrylate of EO (ethylene oxide) or PO (propylene oxide) addition type is a compound obtained by esterifying the polyhydric alcohol of EO or PO addition type with acrylic acid. Specifically, EO or PO modified glycerol triacrylate, EO or PO modified trimethylolpropane acrylate, EO or PO modified pentaerythritol tetraacrylate, and EO or PO modified dipentaerythritol hexaacrylate, etc. are mentioned. Can be. These may be used individually by 1 type and may be used in combination of 2 or more type. Among them, EO or PO-modified dipentaerythritol hexaacrylate, EO or PO-modified trimethylolpropane, in that cracking or cracking of the release agent layer 12 can be prevented by imparting proper flexibility to the release agent layer 12. You may use tetraacrylate.

It is preferable that content (content rate in all solid content except a solvent) of solid content conversion of (A) energy-beam curable compound in a peeling agent layer formation material is 50 mass% or more.

(Hydrogenated Silica Sol)

As a kind of (B) hydrophobized silica sol which concerns on this embodiment, the sol of silica microparticles | fine-particles, such as an alkoxysilane compound and a chlorosilane compound, is mentioned. (B) Anti-blocking property can be provided to the releasing agent layer 12 by hydrophobization silica sol.

As an alkoxysilane compound, if it is a silicon compound which has a hydrolyzable alkoxyl group, it will not specifically limit, For example, the compound represented by General formula (1) is mentioned.

R ¹ _n Si (OR ² ) _4-n ... (One)

In the above general formula, R ¹ represents a hydrogen atom or a non-hydrolyzable group. Examples of the non-hydrolyzable group include alkyl groups, substituted alkyl groups (substituents: halogen atoms, epoxy atoms, (meth) acryloyloxy groups, and the like), alkenyl groups, aryl groups, and aralkyl groups. R ² represents a lower alkyl group (alkyl group having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms)). n is an integer of 0-2, and when R <^1> and OR <^2> are ^{two or more} , respectively, some R <^1> may be the same or different, and some OR <^2> may be the same or different.

Here, as the alkoxysilane compound represented by the general formula (1), tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraiso moiety Methoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, trimethoxysilane hydride, triethoxysilane hydride, tripropoxysilane hydride, methyltrimethoxysilane, methyltriethoxy Silane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane , γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, divinyl Methoxy silane, and the like, and divinyl diethoxysilane. These may be used individually by 1 type and may be used in combination of 2 or more type.

In this case, the inorganic silica-based cured product is obtained by completely hydrolyzing a compound having n of 0 or a compound having n of 1 or 2 and R ¹ of a hydrogen atom as the alkoxysilane compound. The hardened | cured material of a organosiloxane system or the hardened | cured system of an inorganic silica system and the polyorganosiloxane system is obtained.

On the other hand, in a compound in which n is 1 or 2 and R ¹ is a non-hydrolyzable group, the polyorganosiloxane-based cured product is obtained by partial or complete hydrolysis.

As a chlorosilane compound, ethyldichlorosilane, ethyl trichlorosilane, dimethyldichlorosilane, trichlorosilane, trimethylchlorosilane, dimethyldichlorosilane, methyl trichlorosilane, etc. are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.

The silica sol is obtained by dispersing silica fine particles in a sol state in water or an organic solvent.

There is no restriction | limiting in particular in such an organic solvent, Methanol, ethanol, isopropanol, ethylene glycol, n-propyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, dimethylacetamide, propylene glycol monomethyl ether, cyclohexane, benzene, and Toluene and the like. These may be used individually by 1 type and may be used in combination of 2 or more type. Among them, methyl isobutyl ketone and propylene glycol monomethyl ether are more preferable from the viewpoint of relatively high boiling point.

The hydrophobized silica sol (B) is characterized in that a part or all of the silanol groups on the surface of the silica particles are hydrophobized silica sols treated with a surface modifier having a hydrophobic group.

Here, as a surface modifier, the silane coupling agent which has a functional group and a hydrophobic group which can react with the silanol group on a silica particle surface is mentioned.

(B) As a commercial item of hydrophobized silica sol, SIRPGM15WT% -E26 by CIK Nano-Tech Co., etc. are mentioned, for example.

(B) Hydrophobicity The degree of hydrophobicity of the silica sol was coated by coating a silica sol on a PET film, removing a solvent to prepare a silica sol coating film, and determining the contact angle of water with respect to the coating film.

More specifically, in the case of forming a coating film of (B) hydrophobized silica sol, the contact angle of water with respect to the coating film is preferably 100 ° or more.

That is, when the contact angle of water with respect to the coating film of a silica sol is a value of 100 degrees or more, it can be judged that the surface of a silica sol is hydrophobic.

Here, the schematic diagram for demonstrating conceptually the segregation state of (B) hydrophobized silica sol in FIG. 2 is shown.

When a coating film is formed using the material for releasing agent layer formation which concerns on this embodiment, as shown in FIG. 2, hydrophobized silica sol (P) is the outer surface of the releasing agent layer 12 in the releasing agent layer 12. It is understood that the ratio present in the large amount in (12A) and in the vicinity of the first surface 11A of the base material 11 and in the release agent layer 12 is low.

Therefore, by adding a small amount of hydrophobized silica sol, appropriate surface roughness can be imparted to the surface of the release agent layer 12. Therefore, even when the peeling film 1 comrades overlap and time passes, the blocking of the 2nd surface 11B of the base material 11 and the peeling agent layer 12 can be prevented.

That is, since it is possible to exhibit the effect of predetermined | prescribed anti blocking property by comparatively small amount addition, it is understood that the release agent layer excellent in the smoothness can be formed.

Moreover, when forming the coating film of (B) hydrophobized silica sol, it is more preferable that the contact angle of water with respect to this coating film is 100 degreeC or more and 130 degrees or less.

On the other hand, when the coating film of a silica sol is formed, when the contact angle of the water with respect to this coating film becomes a value less than 100 degrees, and the hydrophilicity of a silica sol becomes high, the silica sol will be the outer surface 12A of the release agent layer 12. It has been confirmed that it exists in the state disperse | distributed to the whole in the releasing agent layer 12, without segregating in.

Therefore, it is understood that anti blocking property cannot be provided to the releasing agent layer 12.

In addition, when the coating film of a silica sol is formed, the method of measuring the contact angle of the water with respect to this coating film is demonstrated concretely in Example 1. FIG.

(B) It is preferable that the average particle diameter of hydrophobized silica sol is 10 nm or more and 100 nm or less. If the average particle diameter is 10 nm or more, the anti blocking property of the release agent layer 12 can be further improved. On the other hand, if the average particle diameter is 100 nm or less, smoothness of the outer surface 12A of the release agent layer 12 can be ensured.

Therefore, it is more preferable that it is 10 nm or more and 50 nm or less, and, as for the average particle diameter of (B) hydrophobized silica sol, it is still more preferable that it is 15 nm or more and 40 nm or less.

In addition, the average particle diameter of (B) hydrophobized silica sol is the particle diameter (median diameter D50) in 50% of the integrated value in the particle size distribution calculated | required using the laser diffraction scattering type particle size distribution measuring apparatus.

(B) It is preferable that content of hydrophobized silica sol is 0.4 mass part or more and 100 mass parts or less with respect to 100 mass parts of said (A) energy-beam curable compounds, and it is more preferable that they are 0.4 mass part or more and 30 mass parts or less in conversion of solid content. It is preferable that it is more preferable that they are 0.4 mass part or more and 10 mass parts or less, and it is especially preferable that they are 0.4 mass part or more and 3 mass parts or less. Sufficient anti blocking property can be provided to the releasing agent layer 12 as content is more than the said minimum. On the other hand, the adhesiveness of the releasing agent layer 12 and the base material 11 can be ensured that content is below the said upper limit.

(Peeling ingredient)

As (C) peeling provision component which concerns on this embodiment, a silicone compound, a fluorine compound, a long chain alkyl modified compound, etc. are mentioned, for example. These may be used individually by 1 type and may be used in combination of 2 or more type. Especially as (C) peeling provision component, a silicone compound is preferable and the polyorganosiloxane which has a linear or branched molecular chain is mentioned. (C) By the peeling provision component, the peelability of the peeling agent layer 12 can be provided. Moreover, the polyorganosiloxane is reactive which has at least 1 sort (s) chosen from the group which consists of a (meth) acryloyl group, a vinyl group, a hydroxyl group, a thiol group, and a maleimide group in at least any of the terminal and side chain of a molecular chain. It is preferable to have a functional group. Moreover, as for polyorganosiloxane, it is more preferable that the said reactive functional group couple | bonded with the silicon atom in the said molecular chain through the direct or divalent coupling group. What is necessary is just to have the said reactive functional group at least 1 in 1 molecule.

Moreover, as a bivalent coupling group, an alkylene group, an alkyleneoxy group, an oxy group, an imino group, a carbonyl group, the bivalent coupling group which combined them, etc. are mentioned, for example.

It is preferable that it is 1-30, and, as for carbon number of a bivalent coupling group, it is more preferable that it is 1-10.

Moreover, polyorganosiloxane can be used in combination of 2 or more type as needed.

The modified polyorganosiloxane substituted with such a reactive functional group is introduced into and fixed to the crosslinked structure when the (A) energy ray curable compound is cured by irradiation of active energy rays. Thereby, the transfer electrodeposition of the polyorganosiloxane which is a component of the releasing agent layer 12 to the green sheet formed in the outer surface 12A side of the releasing agent layer 12 can be suppressed.

(C) As organic groups other than the reactive functional group which comprises a peeling provision component, the same or different monovalent hydrocarbon group which does not have an aliphatic unsaturated bond, etc. are mentioned.

As a monovalent hydrocarbon group, it is preferable that carbon number is 1-12, and it is more preferable that carbon number is 1-10.

As a monovalent hydrocarbon group, an alkyl group (methyl group, an ethyl group, a propyl group, etc.), an aryl group (phenyl group, a tolyl group, etc.) etc. are mentioned.

Moreover, as a monovalent hydrocarbon group, it is preferable that 80 mol% or more in a monovalent hydrocarbon group is a methyl group. Thereby, the peelability of the releasing agent layer 12 can be made especially excellent.

(C) It is preferable that content of a peeling provision component is 0.01 mass part or more and 20 mass parts or less with respect to 100 mass parts of said (A) energy-beam curable compounds, and it is 0.02 mass part or more and 15 mass parts or less in solid content conversion. It is preferable and it is especially preferable that they are 0.05 mass part or more and 10 mass parts or less. If content is more than the said minimum, the peelability of the releasing agent layer 12 can be improved. On the other hand, when content is below the said upper limit, when apply | coating a ceramic slurry to the surface of the releasing agent layer 12, splashing of a ceramic slurry can be suppressed.

(Photoinitiator)

In order to harden the material for releasing agent layer formation, the material for releasing agent layer formation may contain (D) photoinitiator. By containing (D) a photoinitiator, when an active energy ray is irradiated with respect to the material for releasing agent layer formation, the releasing agent layer 12 can be formed efficiently. Here, a photoinitiator means the compound which generate | occur | produces a radical species by irradiation of active energy rays, such as an ultraviolet-ray.

(D) As a photoinitiator, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino, for example Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydro Hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy Oxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertarybutylanthraquinone , 2-aminoanthraquinone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, benzyl dimethyl ketal , Acetophenone dimethyl ketal, p-dimeth Amine-acid ester, and the oligonucleotide may be mentioned [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane] and so on. These may be used individually by 1 type and may be used in combination of 2 or more type.

(D) When using a photoinitiator, it is preferable that content is 0.5 mass part or more and 20 mass parts or less with respect to 100 mass parts of said (A) energy-ray-curable compounds in solid content conversion, 0.2 mass part or more and 20 mass parts or less It is more preferable that it is parts or less, and it is especially preferable that they are 0.5 mass part or more and 15 mass parts or less. If content is in the said range, even if the thickness of the peeling agent layer 12 is the thickness of the range in which sclerosis | hardenability is hard to be obtained by oxygen inhibition, especially excellent sclerosis | hardenability can be obtained.

The release agent layer forming material according to the present embodiment may contain other components in addition to the component (A), the component (B), the component (C) and the component (D). As another component, a crosslinking agent, antioxidant, a ultraviolet absorber, an antistatic agent, a polymerization promoter, a polymerization inhibitor, an infrared absorber, a plasticizer, etc. are mentioned, for example. As a crosslinking agent, when a hydroxyl group is used for the functional group of the said (A) component, a polyvalent isocyanate compound, a polyvalent epoxy compound, a polyvalent aziridine compound, a polyvalent metal chelate compound, etc. can be used.

When using another component, it is preferable that content is 0.01 mass part or more and 5 mass parts or less with respect to 100 mass parts of said (A) energy-beam curable compounds, and it is 0.02 mass part or more and 3 mass parts or less in conversion of solid content. It is more preferable, and it is especially preferable that they are 0.05 mass part or more and 2 mass parts or less.

The material for release agent layer formation which concerns on this embodiment can be manufactured by mixing and disperse | distributing the said (A1) component, the said (B) component, etc. In addition, when manufacturing the material for releasing agent layer formation, you may mix | blend a solvent as needed.

As a solvent which concerns on this embodiment, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, pentyl alcohol, ethyl cellosolve, benzene, toluene, xyl Ethylene, ethylbenzene, cyclohexane, ethylcyclohexane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, propylene glycol monomethyl ether, and water. These may be used individually by 1 type and may be used in combination of 2 or more type.

(Method for producing peeling film)

Next, the method of manufacturing the peeling film 1 of this embodiment mentioned above is demonstrated.

The peeling film 1 of this embodiment is active energy in the base material preparation process which prepares the base material 11, the coating layer formation process which forms an application layer by apply | coating and drying a material for release agent layer formation, and an application layer. It can manufacture by the method provided with the releasing agent layer formation process which forms the releasing agent layer 12 by irradiating and hardening a line | wire.

In the substrate preparation step, the substrate 11 is prepared.

Surface treatment can be given to 11 A of 1st surfaces of the base material 11. Thereby, adhesiveness of the base material 11 and the releasing agent layer 12 formed in the 1st surface 11A side of the base material 11 can be made especially excellent.

Examples of the surface treatment include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone, and ultraviolet irradiation treatment. Although these surface treatments are suitably selected according to the kind of base material 11, corona discharge treatment is generally used preferably from a viewpoint of an effect and operability.

In a coating layer formation process, the above-mentioned peeling agent layer formation material is apply | coated on 11 A of 1st surfaces of the base material 11, and is dried. This obtains a coating layer.

If the above-mentioned material for forming a release agent layer is used, the unevenness of the first surface 11A of the base material 11 can be filled. As a result, the outer surface 12A of the release agent layer 12 can be smoothed.

As a method of apply | coating the material for releasing agent layer formation, For example, the gravure coating method, the bar coating method, the spray coating method, the spin coating method, the air knife coating method, the roll coating method, the blade coating method, the gate roll coating method, And a die coat method.

Although it does not specifically limit as a method of drying the material for releasing agent layer formation, For example, the method of drying in a hot air drying furnace, etc. are mentioned.

Although it does not specifically limit as dry conditions, It is preferable that drying temperature is 50 degreeC or more and 130 degrees C or less, and it is preferable that a drying time is 5 seconds or more and 1 minute or less. Thereby, unintentional alteration of an application layer can be prevented, and an application layer can be formed especially efficiently. As a result, productivity of the peeling film 1 finally obtained can be improved. Moreover, when a drying temperature is in the said range, when the material for peeling agent layer formation contains a solvent etc., the curvature of a coating layer or generation | occurrence | production of a gold etc. with evaporation of a solvent etc. at the time of drying can be prevented. have.

In a releasing agent layer formation process, the releasing agent layer 12 is formed by irradiating and hardening an active energy ray to the application layer obtained by the said application layer formation process.

In this step, in the coating layer forming step, the coating layer in which the unevenness of the first surface 11A of the base material 11 is accurately embedded is cured while maintaining the smoothness of the outer surface 12A. As a result, the release agent layer 12 in which the outer surface 12A is sufficiently smooth can be obtained. Moreover, the release agent layer 12 which has moderate electroconductivity can be obtained when the material for release agent layer formation contains the structural component mentioned above.

Examples of the active energy rays include electromagnetic waves (infrared rays, visible rays, ultraviolet rays, X-rays, and the like) and particle beams (electron rays, ion beams, neutron rays, α rays, and the like). Among these, it is preferable to use an ultraviolet-ray or visible light, and it is more preferable to use an ultraviolet-ray. Thereby, the release agent layer 12 can be formed more easily and reliably.

When ultraviolet rays are used as the active energy ray, the coating layer can be uniformly cured while sufficiently shortening the curing time for curing the coating layer. Moreover, it does not specifically limit as a means which irradiates an active energy ray, Various general means can be used. For example, as a light source, light source lamps, such as a pressurized silver lamp, a metal halide lamp, and an excimer lamp, can be used.

When irradiating an active energy ray (ultraviolet ray), it is preferable that accumulated light quantity is 30 mJ / cm <2> or more and 400 mJ / cm <2>, and, as for the irradiation amount of an active energy ray, it is more preferable that they are 50 mJ / cm <2> or more and 300 mJ / cm <2> or less. Moreover, it is preferable that the illuminance of an active energy ray is 0.1 W / cm <2> or more and 4.0 W / cm <2> or less. If the irradiation amount and illuminance of an ultraviolet-ray are in the said range, a coating layer can be hardened more uniformly and reliably.

(How to use peeling film)

Next, the method of using the peeling film 1 of this embodiment mentioned above is demonstrated.

The ceramic capacitor can be manufactured using the peeling film 1 of this embodiment. As a manufacturing method of a ceramic capacitor, after apply | coating a ceramic powder dispersion slurry to the surface of the peeling agent layer 12 of the peeling film 1, drying, and forming a green sheet, from the peeling film 1, for example. The method of forming an electrode in the ceramic sheet obtained by laminating | stacking the peeled green sheet and baking is mentioned. Since the peeling film 1 of this embodiment hardly produces blocking, both the outer surface 12A of the peeling agent layer 12 and the 2nd surface 11B of the base material 11 can be made smooth. . Thereby, when a ceramic capacitor is formed by the green sheet formed using the peeling film 1 of this embodiment, the highly reliable ceramic capacitor which prevented generation | occurrence | production of the problem by a short circuit can be obtained.

(Effects of Embodiments)

According to this embodiment, the following effects can be exhibited.

(1) (A) The material for releasing agent layer formation containing an energy-beam curable compound can easily embed the unevenness | corrugation of 11 A of 1st surface of the base material 11, and can maintain the embedded state. As a result, it can prevent that the unevenness | corrugation of the base material 11 affects the outer surface 12A side opposite to the base material 11 of the peeling agent layer 12, and it is 12A of the outer surface of the peeling agent layer 12 ) Can be smoothed.

(2) According to (B) hydrophobized silica sol, even if it is small content, sufficient anti blocking property can be provided to the releasing agent layer 12. And even if (B) hydrophobized silica sol is used, the smoothness of the outer surface 12A of the releasing agent layer 12 can be maintained. Moreover, peelability can also be provided to the peeling agent layer 12 by (C) peeling provision component.

As a more specific example of the peeling film for green sheet formation which concerns on this embodiment, although the following peeling film for green sheet formation is mentioned, for example, this invention is not limited to such an example.

As an example of the peeling film for green sheet formation which concerns on this embodiment, the base material and the peeling agent layer provided in the single side | surface of the said base material are provided, The said peeling agent layer is a hydroxyl-containing acrylic compound as (A) an energy-beam curable compound, ( B) The release film for green sheet formation which consists of a hardened | cured material of the material for peeling agent formation containing a hydrophobized silica sol and (C) silicone compound as a peeling provision component is mentioned.

As an example of the peeling film for green sheet formation which concerns on this embodiment, it has a base material and the peeling agent layer formed in the single side | surface of the said base material, The said peeling agent layer is a hydroxyl-containing acrylic compound as (A) an energy-beam curable compound, ( The release film for green sheet formation which consists of a hardened | cured material of B) hydrophobized silica sol, the silicone compound as (C) peeling provision component, and (D) photoinitiator formation material is mentioned.

Variation of Embodiment

This invention is not limited to embodiment mentioned above, The deformation | transformation, improvement, etc. in the range which can achieve the objective of this invention are included in this invention.

For example, although the base material 11 was demonstrated as having a single layer structure in embodiment mentioned above, it is not limited to this. The base material 11 may form a multilayer structure of two or more layers of the same kind or different kinds. In addition, although the releasing agent layer 12 was demonstrated similarly as having a single layer structure, it is not limited to this. Also about the release agent layer 12, you may comprise the multilayer structure of two or more layers of the same kind or different types.

Moreover, in the above-mentioned embodiment, although the peeling film for green sheet formation which provided the release agent layer 12 in the 1st surface 11A of the base material 11 was demonstrated, it is not limited to this. You may form the release agent layer 12 in the 2nd surface 11B side of the base material 11.

Example

Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by these examples. In addition, the material used by the Example and the comparative example is shown below.

((A) component)

Energy-beam curable compound: Pentaerythritol triacrylate, brand name "NK ester A-TMM-3L", the Shin-Nakamura Chemical Industry Co., Ltd. make, 100 mass% of solid content

((B) component)

Silica sol A: Hydrophobized silica sol, 30 nm of average particle diameters, brand name "SIRPGM15WT% -E26", the CIK nanotech company make.

Silica sol B: Hydrophobized silica sol, 30 nm of average particle diameters, brand name "SIRMIBK15WT% -E83", the CIK nanotech company make.

(Other ingredients)

Silica sol C: Silica sol, 100 nm of average particle diameters, brand name "SIRMIBK15WT% -K18", the CIK nanotech company make.

Silica sol D: Silica sol, 30 nm of average particle diameters, brand name "OSCAL-1632", the Nikki catalyst company make

Silica sol E: Silica sol, 15 nm of average particle diameters, brand name "MIBK-ST", the Nissan Chemical Industries, Ltd. make.

Silica sol F: Silica sol average particle diameter of 100 nm, brand name "SIRMIBK-E65", manufactured by CIK Nano Tech Co., Ltd.

((C) component)

Peeling imparting ingredient: Brand name "SH-28", manufactured by Toray Dow Corning

((D) component)

Photoinitiator: Trade name "Irgacure 184", manufactured by BASF Corporation

Example 1

First, a polyethylene terephthalate film (trade name "Lu mirror U48", manufactured Dore moved, the thickness as a substrate: 38 ㎛, the arithmetic mean roughness of the first surface Ra (Ra _1): the maximum protrusion height of 2 ㎚, the first surface Rp ( Rp _1): 15 ㎚, the arithmetic average roughness Ra (Ra ₂ of the second surface): 2 ㎚, the maximum protrusion height of the second surface Rp (Rp _2): the 15 ㎚) were prepared.

Next, 100 mass parts of an energy-beam curable compound, 0.4 mass part of silica sol A, 5 mass parts of peeling provision components, and 5 mass parts of photoinitiators are mixed, it is diluted with propylene glycol monomethyl ether, and it is 15 mass% of solid content The material for forming a release agent layer was obtained.

Subsequently, the obtained release agent layer-forming material was applied onto the first surface of the Meyer bar substrate, dried at 70 ° C. for 1 minute, and then irradiated with ultraviolet light (accumulated light amount: 300 mJ / cm 2) using a high-pressure mercury lamp. The release agent layer (thickness: 1 micrometer) was formed and the release film for green sheet formation was obtained.

[Examples 2 to 7 and Comparative Examples 1 to 5]

Except having mix | blended each material according to the composition shown in Table 1, it carried out similarly to Example 1, and obtained the material for releasing agent layer formation.

Moreover, the peeling film for green sheet formation was manufactured like Example 1 except having used the obtained material for peeling agent layer formation.

[Evaluation of Silica Sol and Release Film]

Evaluation of the silica sol (contact angle of the silica sol) and evaluation of the release film (anti blocking property, surface roughness of the release agent layer, and elastic modulus of the release agent layer) were performed in the following manner. The obtained results are shown in Table 1.

(1) contact angle of silica sol

The silica sol coating film was formed on the flat glass substrate using the silica sol used by the Example and the comparative example. And when the glass substrate was left still and the inclination of the glass substrate was 0 degree, 2 microliters of water droplets were dripped, and the water contact angle was calculated by Young's formula when the droplet stopped.

(2) anti blocking property

A peeling film is cut out to the magnitude | size of 100 mm x 100 mm, and two or more same peeling films are piled up. The load was applied thereto so that it might become 10 kg / m <2>, and the peeling film which superimposed after 5 days was checked under the fluorescent lamp visually and the presence or absence of blocking. And anti blocking property was evaluated according to the following criteria.

A: Adhesion of film surfaces did not occur.

B: Adhesion between film surfaces occurred.

(3) Surface roughness of the release agent layer

The surface roughness (arithmetic mean roughness Ra ₀ and the maximum protrusion height Rp ₀ , unit: nm) of the release agent layer of the release film was adjusted to the lens in PSI mode using an optical interference surface roughness meter "WYKO-1100" manufactured by Veeco. It measured on the conditions of 50 times the magnification.

(4) modulus of elasticity of the release agent layer

Nano indentation test using a nano indenter (manufactured by MTS, trade name "Nano Indenter SA4") under conditions of a maximum indentation depth of 100 nm, strain rate 0.05 sec ^-1 , displacement amplitude 2 nm, and vibration frequency of 45 Hz Was carried out and the film elastic modulus of the release film was measured.

As is clear from the results shown in Table 1, when the release agent-forming material containing the hydrophobized silica sol was used (Examples 1 to 7), even if both of the release agent layer and the second surface of the substrate were high smooth, sufficient anti blocking It was confirmed that the release film for green sheet formation which has the property was obtained.

Industrial availability

The release film for green sheet formation of this invention can be used suitably as a technique of shape | molding a ceramic green sheet.

1: release film
11: description
12: release agent layer
12A: outer surface of release agent layer

Claims (5)

As a release film for green sheet formation used for formation of a green sheet,
A base material and a release agent layer formed on one side of the base material,
The said release agent layer consists of hardened | cured material of the (A) energy ray curable compound, the (B) hydrophobized silica sol, and the release agent formation material containing (C) peeling provision component, The peeling film for green sheet formation characterized by the above-mentioned. . The method of claim 1,
The average particle diameter of the said (B) hydrophobized silica sol is 10 nm or more and 100 nm or less, The peeling film for green sheet formation characterized by the above-mentioned. The method according to claim 1 or 2,
When the coating film of the said (B) hydrophobized silica sol is formed, the contact angle of the water with respect to the said coating film is 100 degrees or more, The peeling film for green sheet formation characterized by the above-mentioned. The method according to any one of claims 1 to 3,
The average thickness of the said release agent layer is 0.2 micrometer or more and 2 micrometers or less, The peeling film for green sheet formation characterized by the above-mentioned. The method according to any one of claims 1 to 4,
Arithmetic mean roughness Ra of the outer surface of the said release agent layer is 8 nm or less, and the maximum protrusion height Rp of the outer surface of the said release agent layer is 50 nm or less, The peeling film for green sheet formation characterized by the above-mentioned.

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