KR20190119606A - Release film for green sheet formation - Google Patents

Abstract

The release film for green sheet formation of this invention is the release film 1 for green sheet formation used for formation of a green sheet, The release agent layer formed in the base material 11 and the single side | surface 11A of the said base material 11 (12), The said release agent layer 12 is a release agent formation containing the (A) curable compound and the (B) ionic group containing silicone compound which has group containing the zwitterion represented by following General formula (4). It consists of hardened | cured material of the material.

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 disperse | distributing 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 is peeled 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 pinhole generate | occur | produced 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 static electricity generate | occur | produces easily in a peeling film, so that the smoothness of a peeling film is 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 is extracted and used from a roll shape state. Therefore, when taking out this wound peeling film, static electricity generate | occur | produced on the surface of a peeling film, and there existed a problem that foreign substances, such as dust, adhered by the generated static electricity. Moreover, when static electricity generate | occur | produces when peeling a peeling film from the formed green sheet, handling of the green sheet will become difficult, it may become difficult to convey to the next process, or the static electricity may deteriorate the product characteristic as a capacitor | condenser. Thus, in the peeling film excellent in smoothness, antistatic property is calculated | required.

As a technique of improving the antistatic property of a peeling film, patent document 1 describes the release film which provided the base film and the release layer containing inert microparticles | fine-particles on the at least single side | surface of a polyester film, for example. This polymer layer contains the polymer containing a (meth) acrylate polymer component and a silicone polymer component, and electroconductive fine particles.

Japanese Unexamined Patent Publication No. 2011-206996

However, in the peeling film of patent document 1, in order to express sufficient antistatic property, it was necessary to disperse a large amount of electroconductive fine particles in a polymer layer. And when using a large amount of electroconductive fine particles, there existed a problem that sclerosis | hardenability of a polymer layer falls.

Then, the objective of this invention is providing the peeling film for green sheet formation which has sufficient antistatic property, maintaining the curability of a peeling agent layer.

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) Curable compound and (B) Hardened | cured material of the peeling agent formation material containing the ionic group containing silicone compound which has a structural unit represented by following General formula (1), and a structural unit represented by following General formula (2). It is characterized by.

[Formula 1]

[Formula 2]

In said general formula (1), R <^1> and R <^2> may be same or different and shows a C1-C6 alkyl group or phenyl group, respectively.

In said general formula (2), R <^3> represents a C1-C6 alkyl group, a C1-C6 alkoxy group, or a phenyl group, L is a single bond, an alkylene group, a diorganosiloxane group, -O The group or the divalent group represented by the following general formula (3) is represented, and Y represents the group containing the zwitterion represented by the following general formula (4).

[Formula 3]

[Formula 4]

In said general formula (3), l is an integer of 1-4, m is an integer of 1-10.

In said general formula (4), R <^4> and R <^5> may be same or different, C1-C6 alkyl group, a phenyl group, C1-C6 fluorine-substituted alkyl group, or C1-C6 hydroxyl group containing hydroxy An alkyl group is represented, R <^4> and R <^5> may form a ring, and in that case, an alkylene group is represented and n is an integer of 3-6.

In the release film for green sheet formation which concerns on one aspect of this invention, the (A) curable compound may be an (A1) energy ray curable compound.

In the release film for green sheet formation which concerns on one aspect of this invention, the (A) curable compound may be a (A2) thermosetting compound.

In the release film for green sheet formation which concerns on one aspect of this invention, the said (B) ionic group containing silicone compound is chosen from the group which consists of a C2-C6 alkenyl group, acryloyl group, a thiol group, and a hydrosilyl group. It is preferred to have at least one reactive functional group.

In the peeling film for green sheet formation which concerns on one aspect of this invention, it is arithmetic mean roughness Ra of the outer surface of the said peeling agent layer that is 8 nm or less, and that the largest protrusion height Rp of the outer surface of the said peeling agent layer is 80 nm or less. desirable.

According to this invention, the peeling film for green sheet formation which has sufficient antistatic property can be provided, maintaining the hardenability of a releasing agent layer.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows the peeling film for green sheet formation which concerns on 1st Embodiment of this invention.

[First embodiment]

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

In 1st Embodiment, the case where the (A1) energy ray curable compound is used as an (A) curable compound in the material for peeling agent formation is demonstrated as an example.

As shown in FIG. 1, the peeling film 1 for green sheet formation (hereinafter "the peeling 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 dust etc. do not generate | occur | produce well at the time of a process or use. When manufacturing a green sheet using the peeling film 1 manufactured using the polyester film, coating defects, etc. of a ceramic slurry by dust etc. can be prevented effectively.

The base material 11 may contain a filler or the like in addition to the above materials. 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 become easy to generate static electricity by blocking normally, In the release film 1 of this embodiment, blocking hardly occurs.

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 preferably not more than more than 10 ㎚ 500 ㎚, more preferably 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 addition, in the case of general-purpose grade, the arithmetic mean roughness Ra (Ra ₁ ) of the 1st surface 11A of the base material 11 is 5 nm or more and 80 nm or less normally, and is the 1st surface 11A of the base material 11 ), The maximum protrusion height Rp (Rp ₁ ) is usually 100 nm or more and 700 nm or less. In addition, in the case of general-purpose grade, the arithmetic mean roughness Ra (Ra ₂ ) of the 2nd surface 11B of the base material 11 is 5 nm or more and 80 nm or less normally, and the 2nd surface 11B of the base material 11 is carried out. ), The maximum protrusion height Rp (Rp ₂ ) 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" refers to 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 (A1) energy ray curable compound is used as a (A) curable compound, 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 antistatic 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 80 ㎚ the outer surface of the release agent layer 12, and more preferably not more than 60 ㎚. Thereby, when shape | molding a green sheet on the outer surface 12A side of the peeling agent layer 12, it can prevent more reliably that a pinhole or partial thickness deviation arises in a green sheet, and the surface of a green sheet can be prevented more. It can be made highly smooth.

In addition, the material for release agent layer formation mentioned later has moderate fluidity | liquidity in apply | coating on 11 A of 1st surfaces of the base material 11. As shown in FIG. 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 the surface resistivity of the outer surface 12A of the releasing agent layer 12 is 1.0x10 <^12> ohm / square or less, It is more preferable that it is 5.0x10 <^11> ohm / square or less, It is more preferable that it is 1.0x10 <^11> ohm / square or less Particularly preferred. When surface resistivity is in the said range, it can reduce more reliably that the foreign material etc. which originate in generation | occurrence | production of static electricity adhere to the outer surface 12A of the releasing agent layer 12. The unit of surface resistivity uses (ohm / square) in this specification. In addition, the measurement of surface resistivity can be performed based on JISK6911 (1995).

(Material for forming the release agent)

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

The material for releasing agent layer formation which concerns on this embodiment contains (A1) an energy-beam curable compound and (B) ionic group containing silicone compound.

(Energy ray curable compound)

The energy radiation curable compound (A1) according to the present embodiment is a component that contributes to the formation of the release agent layer 12 by curing. Thereby, the mechanical strength of the releasing agent layer 12 can be made more suitable.

There is no restriction | limiting in particular as (A1) energy-beam curable compound which concerns on this embodiment, It can select from a conventionally well-known thing. (A1) As an energy ray curable compound, an energy ray curable monomer, an oligomer, resin, and the composition containing these 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 moderate hardness to the releasing agent layer 12. Do.

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 ionic group containing silicone compound 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, if 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 two systems of an energy beam and heating, and the grade of hardening can be made into a desired level. have.

It is preferable that it is 65 mass% or more, and, as for content (content rate in the total solid except a solvent) of solid content conversion of (A1) energy-beam curable compound in a peeling agent layer forming material, it is more preferable that it is 70 mass% or more. .

(Ionic group-containing silicone compound)

The (B) ionic group containing silicone compound which concerns on this embodiment is a component which can provide antistatic property and peelability to the releasing agent layer 12. FIG.

(B) An ionic group containing silicone compound has a structural unit represented by following General formula (1), and a structural unit represented by following General formula (2). By mix | blending the (B) ionic group containing silicone compound with the release agent layer 12, peelability is provided to the release agent layer 12 mainly by the characteristic of the unit of the structural unit represented by following General formula (1), and mainly Antistatic property is provided to the releasing agent layer 12 by the characteristic of the unit of the structural unit represented by General formula (2).

[Formula 5]

[Formula 6]

In the said General formula (1), R <^1> and R <^2> may be same or different and shows a C1-C6 alkyl group or phenyl group, respectively. Moreover, it is preferable that R <^1> and R <^2> is a methyl group from a viewpoint of providing the outstanding peelability to the releasing agent layer 12.

In the said General formula (2), R <^3> represents a C1-C6 alkyl group, a C1-C6 alkoxy group, or a phenyl group. Moreover, it is more preferable that R <^3> is a C1-C6 alkyl group and a C1-C6 alkoxy group from a viewpoint of providing the outstanding peelability to the releasing agent layer 12, and it is especially preferable that it is a methyl group.

L represents a single bond, an alkylene group, a diorganosiloxane group, an -O- group, or a divalent group represented by the following General Formula (3). Moreover, from a viewpoint of providing sufficient antistatic property to the releasing agent layer 12, it is more preferable that L is bivalent group represented by following General formula (3).

Y represents group containing the zwitterion represented by following General formula (4).

[Formula 7]

[Formula 8]

In the said General formula (3), l is an integer of 1-4. m is an integer of 1-10.

In the said General formula (4), R <^4> and R <^5> may be same or different, C1-C6 alkyl group, phenyl group, C1-C6 fluorine-substituted alkyl group, or C1-C6 hydroxyl group containing hydroxide An oxyalkyl group is shown. R <^4> and R <^5> may form a ring, in that case, represents an alkylene group, n is an integer of 3-6. In addition, when L in the said General formula (2) is a single bond, the tetravalent nitrogen atom which has the static charge in the said General formula (4) couple | bonds with the silicon atom of the diorganosiloxane of a principal chain.

(B) The ionic group-containing silicone compound may further have a structural unit containing a reactive functional group. (B) As a reactive functional group which an ionic group containing silicone compound may have, a C2-C6 alkenyl group, acryloyl group, a thiol group, a hydrosilyl group, etc. are mentioned. Thereby, since (B) ionic group containing silicone compound itself has sclerosis | hardenability, the sclerosis | hardenability of the releasing agent layer 12 can be improved further.

(B) A commercial item can be used as an ionic group containing silicone compound. As this commercial item, "ionic group containing silicone oligomer X-40-2450" by Shin-Etsu Silicone Co., Ltd. is mentioned, for example.

(B) It is preferable that content of an ionic group containing silicone compound is 0.1 mass part or more and 30 mass parts or less with respect to 100 mass parts of said (A1) energy-beam curable compounds, and is 2 mass parts or more and 25 mass parts or less in conversion of solid content. It is more preferable. Sufficient antistatic property can be provided to the releasing agent layer 12 as content is more than the said minimum. On the other hand, when content is below the said upper limit, it can suppress that excess (B) ionic group containing silicone compound is in the release agent layer 12, and the sclerosis | hardenability of the release agent layer 12 can be maintained.

(2nd peeling provision component)

In order to further improve the peelability of the releasing agent layer 12, the material for releasing agent layer formation may contain (C) 2nd peeling provision component.

As (C) 2nd peeling provision component which concerns on this embodiment, the polyorganosiloxane which has a linear or branched molecular chain is mentioned, for example. Moreover, it is preferable that the polyorganosiloxane has a reactive functional group which has at least 1 sort (s) chosen from the group which consists of a (meth) acryloyl group, a vinyl group, and a maleimide group in at least any one of the terminal and side chain of a molecular chain. . 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. The said reactive functional group should just have 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 inserted into and fixed to the crosslinked structure when the (A1) 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 2nd 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) When using 2nd peeling provision component, it is preferable that content is 0.1 mass part or more and 15 mass parts or less with respect to 100 mass parts of said (A1) energy-beam curable compounds in conversion of solid content, and 0.5 mass part As for more than 10 mass parts, it is more preferable. 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, it can suppress that a ceramic slurry rebounds.

(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 the 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, dimethyl, for example Aminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- Hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1-one, 4- (2-hydroxyethoxy) phenyl-2- ( Hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertbutylbutylantra Quinone, 2-aminoanthraquinone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, benzyldimethyl Ketal, acetophenone dimethyl ketal, p-dimeth Tylamine benzoic acid ester, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane], etc. are mentioned. 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 they are 1 mass part or more and 20 mass parts or less with respect to 100 mass parts of said (A1) energy-beam curable compounds in conversion of solid content, 3 mass parts or more and 15 It is more preferable that it is below a mass part. When content is in the said range, even if the thickness of the peeling agent layer 12 is the thickness of the range which hardly obtains sclerosis | hardenability by oxygen inhibition, especially the outstanding sclerosis | hardenability can be obtained.

The release agent layer formation material which concerns on this embodiment may contain other components other than the said (A1) component, the said (B) component, the said (C) component, and the said (D) component. As another component, a crosslinking agent, antioxidant, an ultraviolet absorber, antistatic agents other than the said (B) component, a polymerization promoter, a polymerization inhibitor, an infrared absorber, a plasticizer, etc. are mentioned. As a crosslinking agent, when a hydroxyl group is used for the functional group of (A1) component, a polyvalent isocyanate compound, a polyvalent epoxy compound, a polyvalent aziridine compound, a polyvalent metal chelate compound, etc. can be used.

When using other components, it is preferable that content is 0.1 mass part or more and 10 mass parts or less with respect to 100 mass parts of said (A1) energy-beam curable compounds in conversion of solid content.

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 it is made to dry. 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 drying conditions, It is preferable that drying temperature is 50 degreeC or more and 100 degrees C or less, and it is preferable that a drying time is 5 seconds or more and 1 minute or less. As a result, unintended deterioration of the coating layer can be prevented, and the coating layer can be formed particularly efficiently. As a result, productivity of the peeling film 1 finally obtained can be improved. Moreover, when drying temperature is in the said range, when the material for peeling agent layer formation contains a solvent etc., generation | occurrence | production of the curvature or a crack of an application layer 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 by the material for release agent layer formation containing the structural component as 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 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 to irradiate 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. When a green sheet is manufactured using the peeling film 1 of this embodiment, the trouble which arises by the static electricity at the time of removing a peeling film from a green sheet can be suppressed, and high productivity can be expected. In addition, since the blocking property does not become strong by static electricity, the peeling film 1 of this embodiment makes both the outer surface 12A of the peeling agent layer 12, and both the 2nd surface 11B of the base material 11 open. I can do it smoothly. 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 the First Embodiment)

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

(1) The (B) ionic group-containing silicone compound can impart peelability to the release agent layer 12 and can provide sufficient antistatic property. Moreover, when using this (B) ionic group containing silicone compound, since the hardening component in the material for release agent layer formation does not become small too much, the sclerosis | hardenability of the material for release agent layer formation can be maintained, and the base material (11) The adhesiveness with can also be maintained.

(2) (A1) The material for release agent layer formation containing an energy ray 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.

(3) Since the peeling property of the peeling film 1 of this embodiment does not become strong by static electricity, both the outer surface 12A of the releasing agent layer 12 and the 2nd surface 11B of the base material 11 are removed. I can do it smoothly.

(4) When a green sheet is manufactured using the peeling film 1 of this embodiment, the trouble which arises by the static electricity at the time of removing a peeling film from a green sheet can be suppressed, and high productivity can be expected.

Second Embodiment

Next, a second embodiment of the present invention will be described.

In 2nd Embodiment, the case where a (A2) thermosetting compound is used as an (A) curable compound in the material for peeling agent formation is demonstrated as an example.

In addition, since this embodiment is the same as that of said 1st embodiment except having used the (A2) thermosetting compound as (A) curable compound, the material for peeling agent layer formation containing (A2) thermosetting compound, and its use method Will be described, and other explanations will be omitted or simplified.

(Material for forming a release agent layer)

The material for release agent layer formation which concerns on this embodiment contains a (A2) thermosetting compound and (B) ionic group containing silicone compound.

About the (B) ionic group containing silicone compound which concerns on this embodiment, it is the same as the (B) ionic group containing silicone compound used by said 1st Embodiment.

(Thermosetting compound)

The (A2) thermosetting compound which concerns on this embodiment is a component which contributes to formation of the release agent layer 12 by hardening. Thereby, the mechanical strength of the releasing agent layer 12 can be made more suitable.

As a thermosetting compound (A2), well-known thermosetting compounds, such as an amino resin, such as a melamine resin, a urea resin, a guanamine resin, an epoxy resin, a phenol resin, and an alkyd resin, can be used. Among these thermosetting compounds, melamine resin is particularly preferable.

In addition, generally, a "melamine resin" means the mixture containing at least any one of the melamine compound of several types, and the multinuclear body which condenses and produces a plurality of melamine compounds. In this specification, the phrase "melamine resin" shall mean the mixture of the said mixture or 1 type of melamine compound. In addition, in this specification, what hardened | cured this melamine resin shall be called "melamine hardened | cured material."

It is preferable that melamine resin contains the compound represented by the following general formula (a).

[Formula 9]

In the general formula (a), X is, -H, -CH ₂ represents an -OH group, or -CH ₂ -OR. These groups comprise the reactor in the condensation reaction of melamine compounds. Specifically, it is possible to carry out a condensation reaction between X is the -NH group which is formed by a H, -N-CH ₂ -OH group and a -N-CH ₂ -R group. In addition, the -N-CH ₂ -OH group formed when X is -CH ₂ -OH and the -N-CH ₂ -R group formed when X is -CH ₂ -R group are all -NH group,- among the N-CH ₂ -OH group and a -N-CH ₂ -R group can be carried out the condensation reaction. In addition, the configuration of the reactor which contribute to a condensation reaction between the -CH ₂ -OH group and a -CH ₂ -OR group, a polyorganosiloxane as the melamine compound. When a melamine compound has the said reactor, the release agent layer 12 which exhibits the above-mentioned effect is formed. In the general formula (a), it is preferable that not all X be -H, and specifically, at least one X is preferably a -CH ₂ -OH group or a -CH ₂ -OR group.

In the -CH ₂ -OR group, R represents an alkyl group having 1 to 8 carbon atoms. It is preferable that it is 1-4, and, as for this carbon number, it is more preferable that it is 1 or 2. As a C1-C8 alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, etc. are mentioned, for example, A methyl group is especially preferable.

X may be the same respectively and may differ. In addition, R may be the same respectively and may differ.

From the viewpoint that the condensation reaction takes place efficiently, in the general formula (a), the number of X to be -H is preferably 2 or less, more preferably 1 or less, and particularly preferably 0. Examples of the melamine compound in which the number of X to be -H is 0 are hexamethoxymethylmelamine in which all X are -CH ₂ -O-CH ₃ .

It is preferable that it is 65 mass% or more, and, as for content (content rate in the total solid except a solvent) of solid content conversion of (A2) thermosetting compound in a peeling agent layer formation material, it is more preferable that it is 70 mass% or more.

(remover)

In order to further improve the peelability of the releasing agent layer 12, the material for releasing agent layer formation may contain (C) 2nd peeling provision component.

About (C) 2nd peeling imparting component which concerns on this embodiment, it is the same as (C) 2nd peeling imparting component used by said 1st embodiment.

(Curing agent or catalyst)

In order to harden the material for releasing agent layer formation, the material for releasing agent layer formation may contain the (E) hardening | curing agent or a catalyst. When melamine resin is used as a thermosetting compound, an acid catalyst is used as (E) component.

As such (E) acid catalyst, hydrochloric acid, p-toluenesulfonic acid, etc. are mentioned. Among these, p-toluenesulfonic acid is preferable. When the material for the release agent layer formation contains an acid catalyst, the condensation reaction in the melamine resin can be promoted efficiently.

It is preferable that it is 1 mass part or more and 20 mass parts or less with respect to 100 mass parts of said (A2) thermosetting compounds, and, as for content of the acid catalyst in the peeling agent composition which concerns on this embodiment, it is more preferable that they are 2 mass parts or more and 15 mass parts or less. And it is especially preferable that they are 4 mass parts or more and 10 mass parts or less.

The release agent layer forming material according to the present embodiment may contain other components in addition to the component (A2), the component (B), the component (C) and the component (E). As another component, the component similar to the component described in the said 1st Embodiment is mentioned.

In addition, the material for release agent layer formation which concerns on this embodiment may contain reaction diluents, such as glycol type compounds, such as ethylene glycol and a propanediol.

When using other components, it is preferable that the content is 0.1 mass part or more and 10 mass parts or less with respect to 100 mass parts of said (A2) thermosetting compounds in conversion of solid content.

The material for release agent layer formation which concerns on this embodiment can be manufactured by mixing and disperse | distributing the said (A2) 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.

About the solvent which concerns on this embodiment, it is the same as the solvent used by the said 1st Embodiment.

(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 heat-processes 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 a coating layer. It can manufacture by the method provided with the releasing agent layer formation process which forms the releasing agent layer 12 by performing and hardening.

The substrate preparation step and the coating layer forming step are the same as the substrate preparation step and the coating layer forming step in the first embodiment.

In the release agent layer formation process, the release layer 12 is formed by heat-processing and hardening an application layer to the application layer obtained by the said application layer formation process.

The conditions of the heat treatment differ depending on the kind of the (A2) thermosetting compound and are not particularly limited. When using melamine resin, it is preferable that heating temperature is 90 degreeC or more and 140 degrees C or less. Moreover, it is preferable that heating time is 10 second or more and 120 second or less. If heating temperature and a heat time are in the said range, a coating layer can be hardened more uniformly and reliably.

According to this embodiment, the effect similar to the said 1st Embodiment can be exhibited.

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 formed in the single side | surface of the said base material are provided, The said peeling agent layer is a hydroxyl-containing acrylic compound as (A1) an energy-beam curable compound, ( B) It consists of an ionic group containing silicone compound which has a structural unit represented by the said General formula (1), and a structural unit represented by the said General formula (2), and the hardened | cured material of the release agent formation material containing (D) photoinitiator. And a release film for forming a green sheet.

As an example of the peeling film for green sheet formation which concerns on this embodiment, the base material and the peeling agent layer formed in the single side | surface of the said base material are provided, The said peeling agent layer is a hydroxyl-containing acrylic compound as (A1) an energy-beam curable compound, ( B) Ionic group containing silicone compound which has a structural unit represented by the said General formula (1), and the structural unit represented by the said General formula (2), and (C) linear or branched molecular chain as a 2nd peeling provision component. The peeling film for green sheet formation which consists of a polyorganosiloxane which has the thing and the hardened | cured material of the material for peeling agent formation containing (D) photoinitiator 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 (A2) melamine resin as a thermosetting compound, (B) said general Peeling for green sheet formation which consists of a hardened | cured material of the ionic group containing silicone compound which has a structural unit represented by Formula (1) and the structural unit represented by the said General formula (2), and the (E) acid catalyst-forming material containing an acid catalyst. A film 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 (A2) melamine resin as a thermosetting compound, (B) said general Polyolefin having an ionic group-containing silicone compound having a structural unit represented by the formula (1) and the structural unit represented by the general formula (2) and (C) a linear or branched molecular chain as the second peeling imparting component. The peeling film for green sheet formation which consists of a hardened | cured material of the material of the release agent formation containing an organosiloxane and the (E) acid catalyst 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, in embodiment mentioned above, although the base material 11 demonstrated as having a single layer structure, 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. Moreover, although the peeling 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.

For example, although the above-mentioned embodiment demonstrated the peeling film for green sheet formation which provided the release agent layer 12 in the 1st surface 11A of the base material 11, 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.

For example, in embodiment mentioned above, although (A1) used as a energy ray curable compound, what has reactive functional groups, such as a (meth) acryloyl group, melamine resin was used as (A2) thermosetting compound, It is not limited to these.

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.

((A1) component)

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

((A2) component)

Thermosetting compound: melamine resin (main component: hexamethoxymethylmelamine, solid content 100% by mass, trade name "Nicarac MW-100LM", manufactured by Nippon Carbide Industry Co., Ltd.)

((B) component)

Ionic group containing silicone compound: Brand name "Ionic group containing silicone oligomer X-40-2450", Shin-Etsu Silicone Co., Ltd. product

((C) component)

Release agent: Brand name "SH-28", manufactured by Toray Dow Corning

((D) component)

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

((E) component)

Acid catalyst: p-toluenesulfonic acid

(Other ingredients)

Antistatic agent: Lithium bis (trifluoromethanesulfonyl) imide, a brand name "Estop EF-N", the Mitsubishi Matherial Electrochemical company make

Example 1

First, a polyethylene terephthalate film (trade name "Lu mirror U48", Toray Co., Ltd., thickness as the substrate: 50 ㎛, the arithmetic mean roughness of the first surface Ra (Ra _1): the maximum protrusion height of 2 ㎚, the first surface Rp (Rp ₁ ): 15 nm, arithmetic mean roughness Ra (Ra ₂ ) of the second surface: 2 nm, and the maximum protrusion height Rp (Rp ₂ ) of the second surface: 15 nm.

Next, 100 mass parts of energy ray curable compounds, 5 mass parts of ionic group containing silicone compounds, and 10.5 mass part of photoinitiators were mixed, and it diluted with isopropyl alcohol, and obtained the material for the release agent layer formation of 15 mass% of solid content. .

Subsequently, the obtained release agent layer forming material was applied onto the first surface of the meyer bar, 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. A release agent layer (thickness: 1 micrometer) was formed and the release film for green sheet formation was obtained.

Example 2, Comparative Examples 1 and 2

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 produced like Example 1 except having used the obtained material for peeling agent layer formation.

Example 3

First, a polyethylene terephthalate film (trade name "Lu mirror U48", Toray Co., Ltd., thickness as the substrate: 50 ㎛, the arithmetic mean roughness of the first surface Ra (Ra _1): the maximum protrusion height of 2 ㎚, the first surface Rp (Rp ₁ ): 15 nm, arithmetic mean roughness Ra (Ra ₂ ) of the second surface: 2 nm, and the maximum protrusion height Rp (Rp ₂ ) of the second surface: 15 nm.

Next, 100 parts by mass of the thermosetting compound, 5 parts by mass of the ionic group-containing silicone compound, and 5 parts by mass of the acid catalyst were mixed and diluted with isopropyl alcohol to obtain a release agent layer-forming material having a solid content of 15% by mass.

Subsequently, the obtained release agent layer forming material was applied onto the first surface of the meyer bar, cured by heat treatment at 120 ° C. for 1 minute to form a release agent layer (thickness: 1 μm), and peeling for green sheet formation. A film was obtained.

Comparative Example 3

Except having mix | blended each material according to the composition shown in Table 1, it carried out similarly to Example 3, and obtained the material for releasing agent layer formation.

Moreover, the peeling film for green sheet formation was produced like Example 3 except having used the obtained peeling agent layer formation material.

[Evaluation of peeling film]

Evaluation of the release film (curability, solvent resistance, surface resistivity, charge amount, half-life, surface roughness of the release agent layer, adhesiveness with the base material, and unwinding charge) was performed by the following method. The obtained results are shown in Table 1.

(1) curability

The release agent layer of the release film was rubbed 10 times with a finger, and the cloudiness (smear) and dropping off (love off) of the release agent layer were visually observed under a fluorescent lamp. And cloudy (smear) was evaluated according to the following criteria.

A: There is no change in a releasing agent layer.

B: Cloudiness occurred in the release agent layer.

In addition, dropout (love off) was evaluated according to the following criteria.

A: There is no change in a releasing agent layer.

B: Dropping occurred in the release agent layer.

(2) solvent resistance

With a waste containing an appropriate amount of methyl ethyl ketone, the release agent layer of the release film was rubbed with a 20 reciprocating, 2 kg / cm 2 load, and the clouding and dropping off of the release agent layer was visually observed under a fluorescent lamp. And solvent resistance was evaluated according to the following criteria.

A: There is no change in a releasing agent layer.

B: Cloudiness or dropping occurred in the release agent layer.

(3) surface resistivity

The surface resistivity of the peeling agent layer of a peeling film was measured under the applied voltage 100V and the measurement conditions after 10 second of measurement time using the "Hyrestar UP" by Mitsubishi Chemical Analyzer. In addition, the measurement was performed 5 times and the average value was computed as surface resistivity (unit: ohm / square).

(4) large voltage and half-life

The large voltage (unit: V) and the half-life (second) in a peeling film were measured on the following measurement conditions using the damping measuring instrument "TYPE S-5109 static anneal meter" made by Shishido Electrostatic Co., Ltd. In addition, when more than a measurement limit, it expresses with "∞."

Sample dimension: 40 mm × 40 mm

Applied voltage: 10 ㎸ Measurement time: 60 seconds later

Turntable: 1300 rpm

Distance from sample top surface to electrode and receiver: 20 mm

(5) Surface roughness of the release agent layer

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

(6) Adhesiveness with the base material

The adhesive tape "NITTO31B tape" manufactured by Nitto Electric Co., Ltd. was affixed to the release agent layer of the release film, and immediately after this, the adhesive tape was peeled off at high speed, and the release agent layer was visually observed under a fluorescent lamp. And the adhesiveness with a base material was evaluated according to the following criteria.

A: There is no change in a releasing agent layer.

B: Peeling occurred in the release agent layer.

(7) unwinding war

The peeling film is wound up in roll shape, and after 1 day, the peeling film wound up in roll shape is unwound at a speed | rate of 50 m / min. And the charge quantity of the peeling film immediately after unwinding was measured using the Kaga Electric Digital Potentiometer. Then, the unloading charging was evaluated according to the following criteria.

A: The charge amount is less than 10 mW.

B: The charge amount is 10 kPa or more.

(8) peel force

100 parts by mass of barium titanate (BaTiO ₃ , trade name "BT-02" manufactured by Sakai Chemical Industries, Ltd.), 8 parts by mass of polyvinyl butyral (trade name "Esrek B.KBM-2" manufactured by Sekisui Chemical Industries, Ltd.), and phthalic acid 67 parts by mass of toluene and 67 parts by mass of ethanol were added to 1.4 parts by mass of dioctyl (trade name "Dioctyl Cica Primary, manufactured by Kanto Chemical Co., Ltd.), and the mixture was dispersed and mixed with a ball mill to prepare a ceramic slurry.

In the release film prepared in Examples and Comparative Examples and stored at room temperature for 48 hours, the ceramic slurry was uniformly coated on the release surface of the release agent layer using a 35 μm applicator, and then dried at 60 ° C. in a dryer. It dried for 1 minute. This obtained the ceramic green sheet of thickness 4micrometer on the peeling film. In this way, a release film with a ceramic green sheet was produced.

After leaving this ceramic green sheet affixed for 24 hours in an atmosphere of 23 degrees of room temperature and 50% of humidity, the center part was cut out to the size of 40 mm x 130 mm. Next, the acrylic adhesive tape (brand name "31B tape made by Nitto Electric Works") was affixed along one side of length 40mm as a surface on the opposite side to the peeling film in a ceramic green sheet. This was used as a measurement sample.

The adhesive tape side of this measurement sample was fixed to a flat plate, and it peeled from the ceramic green sheet at 180 degree peeling angle and 300 mm / min peel rate using the tension tester (product name "AG-IS500N" by Shimadzu Corporation). The film was peeled off, and the force (peel force, unit: mN / 40 mm) required for peeling was measured.

As is also apparent from the results shown in Table 1, in the case of using a release agent-forming material containing an ionic group-containing silicone compound (Examples 1 to 3), green having sufficient antistatic properties while maintaining the curability of the release agent layer It was confirmed that the release film for sheet formation is 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 releasing agent layer is a material for releasing agent formation containing the ionic group containing silicone compound which has (A) curable compound, and (B) structural unit represented by following General formula (1), and structural unit represented by following General formula (2). It consists of hardened | cured material of the peeling film for green sheet formation characterized by the above-mentioned.

(In said general formula (1), R <^1> and R <^2> may be same or different and shows a C1-C6 alkyl group or a phenyl group, respectively.)

(In said General Formula (2), R <^3> represents a C1-C6 alkyl group, a C1-C6 alkoxy group, or a phenyl group, and L is a single bond, an alkylene group, a diorganosiloxane group,- O- group or a bivalent group represented by the following general formula (3), and Y represents a group containing a zwitterion represented by the following general formula (4))

(L is an integer of 1-4, and m is an integer of 1-10 in the said General formula (3).)

(In said general formula (4), R <^4> and R <^5> may be same or different, C1-C6 alkyl group, a phenyl group, C1-C6 fluorine-substituted alkyl group, or C1-C6 hydroxyl group containing hydroxide An oxyalkyl group, R ⁴ and R ⁵ may form a ring, in that case, an alkylene group, and n is an integer of 3 to 6; The method of claim 1,
Said (A) curable compound is (A1) energy-beam curable compound, The peeling film for green sheet formation characterized by the above-mentioned. The method of claim 1,
The said (A) curable compound is a (A2) thermosetting compound, The peeling film for green sheet formation characterized by the above-mentioned. The method according to any one of claims 1 to 3,
The said (B) ionic group containing silicone compound has at least 1 reactive functional group chosen from the group which consists of a C2-C6 alkenyl group, acryloyl group, a thiol group, and a hydrosilyl group, The green sheet formation for forming Release film. 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 80 nm or less, The peeling film for green sheet formation characterized by the above-mentioned.

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