JP5485605B2 - Carrier film for green sheet molding - Google Patents

Description

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

In recent years, as electronic devices such as mobile communication devices have been downsized and reduced in power consumption, the use of ceramic capacitors has increased significantly.
A ceramic capacitor is a slurry in which ceramic powder, a solvent, a binder and other additives (plasticizer, dispersant, antistatic agent, etc.) are uniformly dispersed by an appropriate mechanical dispersion method. It is manufactured by coating and drying on a film to form a green sheet, printing an internal electrode on the green sheet, laminating and cutting a predetermined size, and attaching an external electrode.

  As a carrier film used for manufacturing such a ceramic capacitor, a so-called release film in which a release layer made of a silicone resin or the like is provided on a film made of polyester or the like has been conventionally used. Such a release film is required to have excellent surface properties and release properties in order to produce a green sheet having a uniform thickness and free from defects such as pinholes with good productivity.

For example, if the surface of the carrier film is rough, the uneven shape on the surface of the carrier film is transferred as it is to the green sheet formed thereon, which causes defects such as poor thickness and pinholes. Also, if the releasability is insufficient, for example, if the peeling force is too light, the green sheet may be peeled off and floated during the manufacturing process. When peeling from the carrier film, the green sheet breaks or cohesively breaks, resulting in poor productivity.
On the other hand, if the surface of the carrier film is too smooth, the slipping property is lowered and the handling property such as the winding property is deteriorated.

Therefore, by adjusting the lubricant and foreign matter in the carrier film and controlling the surface roughness and coarse protrusions on the surface of the release layer, the technology prevents the transfer to the green sheet, and the surface roughness on the opposite side of the release layer surface. Techniques for adjusting the thickness and imparting appropriate handling properties are disclosed in, for example, Patent Documents 1 to 5.
Further, techniques for controlling the releasability from the green sheet are disclosed in Patent Documents 6 and 7, for example.

Japanese Patent Laid-Open No. 10-16163 Japanese Patent Laid-Open No. 10-229027 JP 2000-30972 A JP 2002-283322 A JP 2004-323766 A JP 2000-49060 A JP 2002-178454 A

  However, in recent years, further miniaturization of ceramic capacitors has been demanded, that is, further thinning of green sheets has been demanded. Specifically, the thickness of the green sheet is required to be about 1 μm, and a carrier film capable of producing such an ultra-thin green sheet is required.

  In the case of a green sheet having a thickness of about 3 μm in the conventional release film as disclosed in the above-mentioned patent documents, the present inventors have no pinholes, no defective thickness, and a good green Sheets can be manufactured, but in the case of ultra-thin green sheets with a thickness of about 1 μm, it is difficult to manufacture ultra-thin green sheets with the required quality due to the occurrence of pinholes and poor thickness. Focused on.

  That is, in the case of an ultra-thin green sheet, the surface property on the surface of the release layer of the carrier film needs to be better than before, and at the same time the surface property of the opposite surface needs to be better. is there. In an ultra-thin green sheet, when the green sheet is formed and wound, the surface irregularities on the surface opposite to the surface of the release layer of the carrier film are transferred to the surface of the green sheet, and a recess is formed in the green sheet. If it becomes defective or the recess is deep, it becomes a pinhole, and defects are more likely to occur than before. Such drawbacks have not been a problem with conventional green sheets having a relatively large thickness.

  In addition, in the case of an ultra-thin green sheet, the green sheet is easily broken, and therefore it is necessary to improve the releasability of the carrier film. Furthermore, as described above, the surface property on the surface of the release layer and the opposite surface is high, but on the other hand, further improvement in handling property is required for further improvement in productivity.

  The first object of the present invention is to solve the above-described problems, even if it is an ultra-thin green sheet having a thickness of about 1 μm, it suppresses defects such as defective thickness and pinholes, and has an appropriate peeling force. An object of the present invention is to provide a carrier film for forming a green sheet having excellent handling properties.

  Furthermore, in recent years, there is a strong demand for cost reduction for electronic devices, and naturally there is a strong demand for cost reduction for electronic components such as capacitors. Therefore, in the process of applying a slurry to a carrier film and drying to produce a green sheet, the coating speed of the slurry is increasing, and accordingly the traveling speed of the carrier film is also increasing. In such a process, the carrier film wound up in a roll is used while being unwound from the roll. However, since the running speed of the carrier film has increased, charging during unwinding tends to occur, causing various problems. . For example, it becomes easy to entrain foreign matter, the surface condition of the release layer changes due to the discharge phenomenon, the slurry coating appearance deteriorates, the release layer is damaged by the discharge phenomenon and loses the release property, and the green sheet is peeled off Defects may occur. Therefore, as a carrier film for forming a green sheet, it is required to suppress the roll charging.

  The second object of the present invention is to solve the above-mentioned problems, even if it is an ultra-thin green sheet having a thickness of about 1 μm, it suppresses defects such as defective thickness and pinholes, and has an appropriate peeling force. Another object of the present invention is to provide a carrier film for forming a green sheet that has excellent handling properties and further suppresses charging during feeding.

  In the production of ultra-thin green sheets, the present inventors are difficult to achieve both defect suppression and handling properties in a green sheet only by adjusting the aspect of the lubricant in the carrier film as in the past. In addition to these, it has been newly found that the above-mentioned problems can be solved by using a base polymer having a specific copolymerization mode as the base polymer in the release layer.

  That is, the present invention provides a base polymer represented by the following formula [Chemical Formula 1], a cross-linking agent represented by the following formula [Chemical Formula 2], and an average particle size of 20 nm or more and 90 nm or less on at least one surface of the base film. A carrier film having a release layer formed by curing a coating film containing as a constituent component of the inert particles, wherein the content of the inert particles in the release layer is 2 masses based on the mass of the release layer. % To 20% by mass, the release layer has a thickness of 5 nm to 40 nm and a 10-point average roughness Rz on at least one surface is 10 nm to 100 nm. .

（式［化１］中、ｍおよびｎはそれぞれ１以上の整数を表し、８≦ｎ／ｍ≦３５の関係を満たす。Ｒ１は炭素数１２以下のアルキレン基を表すか、直接結合を表す。）

(In the formula [Chemical Formula 1], m and n each represent an integer of 1 or more and satisfy the relationship of 8 ≦ n / m ≦ 35. R1 represents an alkylene group having 12 or less carbon atoms or represents a direct bond. )

（式［化２］中、ｐおよびｑはそれぞれ１以上の整数を表す。Ｒ２およびＲ３は炭素数４以下のアルキル基を表す。）

(In the formula [Chemical Formula 2], p and q each represent an integer of 1 or more. R2 and R3 represent an alkyl group having 4 or less carbon atoms.)

  One of the preferred embodiments in the present invention is a carrier film having a release layer on one surface of the substrate film, and the 10-point average roughness Rz on the other surface of the substrate film is 10 nm or more and 100 nm or less. It is the aspect which further comprises being.

  Another preferred embodiment of the present invention is a carrier film having a release layer on both surfaces of a base film, and the 10-point average roughness Rz on at least one surface is 10 nm or more and 100 nm or less. It is the aspect which further comprises.

  Moreover, in this invention, the aspect which has an easily bonding layer which contains an acrylic resin, a polyester resin, and a lubricant particle as a structural component between a base film and a mold release layer is preferable.

  According to the present invention, a green sheet that is used for manufacturing an ultra-thin green sheet having a thickness of about 1 μm, suppresses defects such as defective thickness and pinholes in the green sheet, has an appropriate peeling force, and has excellent handling properties. A carrier film for molding can be provided.

  According to a preferred embodiment of the present invention, in addition to these, a carrier film for forming a green sheet can be provided in which the feeding charge is satisfactorily suppressed. Thereby, the entrainment of foreign matters is reduced and the generation of pinholes in the green sheet can be suppressed. Moreover, the change of the release layer surface state by a discharge phenomenon can be suppressed, and the coating spot of a slurry can be suppressed. Moreover, the ignition by discharge can be suppressed.

The carrier film for forming a green sheet of the present invention has a release layer described later on at least one surface of a substrate film described later.
Here, the 1st aspect in the carrier film for green sheet shaping | molding of this invention has a mold release layer mentioned later on one surface of the base film mentioned later.
Moreover, the 2nd aspect in the carrier film for green sheet shaping | molding of this invention has a release layer mentioned later on both surfaces of the base film mentioned later.
Hereinafter, each component constituting the present invention will be described.

<Base film>
The base film in the present invention is not particularly limited, but a thermoplastic resin film having flexibility and heat resistance is preferably used. Preferred examples of the polymer constituting the thermoplastic resin film include polyesters such as polyethylene terephthalate and polyethylene naphthalate, aliphatic polyamides, aromatic polyamides, polyethylene, and polypropylene. Of these, polyester is preferable.

  The polyester in the present invention comprises a dicarboxylic acid component as the first component and a glycol component as the second component. Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, 4,4'-diphenyldicarboxylic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid and the like. In particular, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable from the viewpoint of excellent mechanical properties of the base film. Examples of the glycol component include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, polyethylene glycol, and the like. . In particular, ethylene glycol is preferable from the viewpoint of excellent rigidity of the base film.

  The polyester may be a copolyester obtained by copolymerizing the dicarboxylic acid component or the glycol component as a third component. As the third component, a copolymer component different from the dicarboxylic acid component selected as the first component or the glycol component selected as the second component can be selected. Further, the third component may include a trifunctional or higher polyvalent carboxylic acid component or a polyol component. In this case, the copolymerization amount is within a range in which the obtained polyester is substantially linear (for example, 5 mol). % Or less, more preferably 3 mol% or less). As the polyester in the present invention as described above, polyethylene terephthalate and polyethylene-2,6-naphthalate are particularly preferable.

  Such a polyester can be produced by a conventional method. When the intrinsic viscosity of the polyester (intrichlorophenol at 35 ° C.) is 0.45 (unit: dl / g) or more, the rigidity of the film is high. It is preferable because of its excellent mechanical properties. In addition, in order to make the above polyester excellent in surface properties, it is preferable that the polyester does not substantially contain particles or contains only a very small amount of particles, but silicon oxide, aluminum oxide, oxidation Contains inorganic fine particles such as magnesium, calcium carbonate, kaolin, talc, titanium oxide, barium sulfate, organic fine particles made of heat-resistant polymers such as crosslinked silicone resin, crosslinked polystyrene resin, crosslinked acrylic resin, urea resin, melamine resin, and slippery It is possible to improve the transparency and adjust the transparency. In addition, other resins such as polyethylene, polypropylene, ethylene / propylene copolymer, olefinic ionomer, stabilizers, antioxidants, ultraviolet absorbers, fluorescent brighteners, and the like can be contained as necessary.

  The base film in the present invention is preferably a biaxially stretched film. Such a biaxially stretched film can be produced by a conventionally known method. For example, in the case of a biaxially stretched film made of polyester, after drying the polyester, it is melted in an extruder at a temperature of Tm to (Tm + 70) ° C. (where Tm represents the melting point (unit: ° C.) of the polyester). , Extruded from a die (for example, T-die, I-die, etc.) onto a rotating cooling drum, rapidly cooled at 20 to 90 ° C. to produce an unstretched film, and then the unstretched film is (Tg-10) to ( Tg + 70) ° C. (where Tg represents the glass transition temperature (unit: ° C.) of the polyester) 2.5 to 8.0 times, preferably 2.9 to 5.0 times in the longitudinal direction, more preferably Is stretched at a magnification of 3.2 to 4.0 times, 2.5 to 8.0 times in the transverse direction, preferably 3.1 to 5.2 times, more preferably 3.4 to 4.2 times. Stretched at a magnification of 1 to 1 at a temperature of 180 to 250 ° C. as necessary. It can be prepared by fixing 0 seconds heat. By setting the draw ratio within the above numerical range, the thickness unevenness of the green sheet can be further reduced.

  The thickness of the substrate film in the present invention is preferably 3 μm or more and 250 μm or less, more preferably 5 μm or more and 100 μm or less, and particularly preferably 10 μm or more, from the viewpoint of excellent mechanical properties and handling properties and the manufacturing cost of the green sheet. 50 μm or less.

  In the present invention, when at least one treatment selected from the group consisting of corona treatment and plasma treatment is applied to the surface of the base film on which the release layer is provided, the adhesion between the base film and the release layer is further improved. It is preferable because it can be used.

<Easily adhesive layer>
In this invention, it is preferable to have an easily bonding layer containing an acrylic resin, a polyester resin, and a lubricant particle as a structural component between a base film and a mold release layer.

  In the 1st aspect of this invention, the adhesiveness of a base film and a mold release layer can be improved by having an easily bonding layer. Moreover, fine unevenness | corrugation can be formed in the mold release layer surface, and handleability (slidability) can be improved more. Such an easy-adhesion layer has the above-described effects if it is on one surface of the base film on the side where the release layer is formed, but it is preferably on both surfaces. By having easy-adhesion layers on both sides of the base film, the handleability can be further improved.

  In the 2nd aspect of this invention, the adhesiveness of a base film and a mold release layer can be improved by having an easily bonding layer. Moreover, fine unevenness | corrugation can be formed in the mold release layer surface, and handleability (slidability) can be improved more. In addition, it is possible to more appropriately suppress the feeding charging. Such an easy-adhesion layer has the above-described effects if it is on at least one surface of the base film, but is preferably on both surfaces. By having an easy-adhesion layer on both sides of the base film, the handleability can be further improved, and the charge trains on both surfaces of the release layer are closer, or the feeding charge is more suitably suppressed. Can do.

(acrylic resin)
Examples of the acrylic resin in the present invention include methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, glycidyl methacrylate, acrylic acid, butyl acrylate, 2-ethylhexyl acrylate, acrylamide, methacrylamide, methacrylic acid, itaconic acid, and sodium acrylate. And a homopolymer or a copolymer of these acrylic monomers, or a copolymer of these monomers with other unsaturated monomers. Examples of other unsaturated monomers include styrene, vinyl acetate, sodium vinyl sulfonate, and acrylonitrile.

  In the present invention, it is preferable that the acrylic resin has a hydroxy group, whereby it is possible to more appropriately suppress the pay-out charge. In order for the acrylic resin to have a hydroxy group, an acrylic monomer having a hydroxy group may be copolymerized. Specifically, it is preferable to contain, for example, 2-ethylhexyl acrylate, acrylamide or methacrylamide having a hydroxy group, and the amount of copolymerization thereof is preferably 1 to 10 mol%, and the feeding charge is further suitably suppressed. be able to.

  Such an acrylic resin can be produced by polymerizing the monomer by a conventional method. In particular, it is preferable to produce it as an aqueous liquid (aqueous solution or aqueous dispersion) from the viewpoints of handleability and environment.

(Polyester resin)
The polyester resin in the present invention can be produced by reacting a polyvalent carboxylic acid or an ester-forming derivative thereof with a polyvalent hydroxy compound by a conventional method. At that time, a compound having a hydrophilic group can be reacted for the purpose of imparting hydrophilicity to the polymer. The polyester resin in the present invention is preferably a water-soluble polyester resin or a water-dispersible polyester resin.

  Examples of the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 5-Na-sulfoisophthalic acid, trimellitic acid ammonium, adipic acid, sebacic acid, trimesic acid and the like. Can do.

  Examples of the polyvalent hydroxy compound include ethylene glycol, 1,4-butanediol, 1,3-propanediol, propylene glycol, neopentyl glycol, 1,6-hexanediol, p-xylylene glycol, 1,4-cyclohexane. Examples include dimethanol, alkylene oxide adducts of bisphenol A, polyalkylene oxide, glycerin, trimethylolpropane, sodium dimethylolpropionate, and the like.

Among the polyvalent carboxylic acid and polyvalent hydroxy compound, an aqueous polyester resin is obtained as if it is water-soluble or water-dispersible by using at least one compound having a hydrophilic group and imparting hydrophilicity to the polymer. be able to. In the present invention, it is preferable to use such an aqueous polyester resin because it is possible to more appropriately suppress the feeding charge. The compound imparting hydrophilicity is preferably 5-Na-sulfoisophthalic acid, and the amount of copolymerization is preferably 1 to 10 mol%, more preferably 1 to 5 with respect to 100 mol% of the total polyvalent carboxylic acid component. It is mol%, and it is possible to more suitably suppress the feeding charge.
The number average molecular weight of the polyester resin is preferably 5,000 to 100,000.

(Lubricant particles)
The lubricant particles in the present invention are preferably lubricant particles having an average particle diameter of 0.01 to 0.1 μm, preferably 0.02 to 0.05 μm. By setting the average particle size within the above numerical range, moderate unevenness can be formed on the surface of the release layer, and the handleability can be further improved. In addition, it is possible to more appropriately suppress the feeding charging. When the average particle size is too small, the slipperiness imparting action tends to be insufficient, and when it is too large, the lubricant particles tend to fall off from the easy-adhesive layer. The lubricant particles may be organic particles or inorganic particles. Examples of the organic particles include lubricant particles made of crosslinked polystyrene, crosslinked acrylic resin, crosslinked polystyrene-acrylic resin, melamine resin, benzoguanamine resin, silicone resin, and the like. Examples of the inorganic particles include lubricant particles made of silica, alumina, titania, zirconia, calcium carbonate, and the like.

  In the present invention, the mixing ratio of the acrylic resin and the polyester resin is preferably 80/20 to 20/80, more preferably 60/40 to 40/60 in terms of mass ratio. When the mixing ratio is in the above numerical range, easy adhesion can be further improved. Further, it is possible to further suppress the extension charging. Further, the content of the lubricant particles is preferably 5 to 30% by mass, more preferably 10 to 20% by mass with respect to the mass of the easy-adhesion layer, and it becomes easy to form an appropriate uneven shape on the surface of the release layer. In addition to being excellent in handleability, it is possible to more suitably suppress the feeding charge.

(Method of forming easy-adhesion layer)
In the present invention, the easy-adhesion layer is formed by applying an aqueous coating liquid containing an acrylic resin, a polyester resin, and lubricant particles to at least one surface of the base film and drying it. The mixing of the acrylic resin, the polyester resin, and the lubricant particles can be performed by any method, but it is simple and preferable to prepare each aqueous liquid and mix the aqueous liquid. Further, an antistatic agent, a surfactant and the like can be added to the aqueous coating liquid as desired. The solid content concentration of the aqueous coating liquid is preferably 1 to 20% by mass, particularly preferably 1.5 to 6% by mass from the viewpoint of coating spots. The coating method can be arbitrarily selected, and for example, a roll coating method, a gravure coating method, a spray coating method, an air knife coating method or the like can be applied. The coating amount can be arbitrarily determined, but the amount that the easy-adhesive layer is 0.001 to 2 μm is preferable, the amount that is 0.01 to 0.05 μm is more preferable, and the thickness of the easy-adhesive layer is in this range. As a result, an appropriate uneven surface shape can be formed, handling properties can be further improved, and pay-out charging can be more suitably suppressed.

  The base film to which the aqueous coating solution is applied may be a biaxially stretched film, but an in-line coating method, that is, a method of further stretching after coating, an unstretched film, a uniaxially stretched film, or the like is preferable. For example, it is preferable to apply a water-based coating solution to a uniaxially stretched film, and then perform drying, stretching, and heat setting treatment to obtain a biaxially stretched film having an easy-adhesion layer.

<Release layer>
The release layer in the present invention is obtained by curing a coating film containing a base polymer, a crosslinking agent, and inert particles, which will be described later, as constituent components.

(Base polymer)
The base polymer in the present invention is represented by the following formula [Chemical Formula 3]: methyl vinyl siloxane (hereinafter sometimes abbreviated as MVS) and dimethyl siloxane (hereinafter sometimes abbreviated as DMS). And a copolymer.

  In the above formula [Chemical Formula 3], m and n each represent an integer of 1 or more, and the base polymer in the present invention is an embodiment in which 8 to 35 moles of DMS units are copolymerized with respect to 1 mole of MVS units. That is, it is necessary that m and n in the above formula [Chemical Formula 3] satisfy 8 ≦ n / m ≦ 35.

  By setting the copolymerization ratio (n / m) between the MVS unit and the DMS unit in the above numerical range, the release layer has an appropriate hardness, so that the handling property and the release property are excellent. Become. In addition, it is possible to more appropriately suppress the feeding charging. Thus, in the present invention, it is important that the release layer has an appropriate hardness. That is, by adopting such an embodiment, it is possible to improve the handling properties, it is not necessary to add excess particles to improve the handling properties, and therefore, excellent handling properties and excellent surface properties Can be achieved at the same time. Further, it is possible to more suitably suppress the feeding charge without adding a component such as an antistatic agent. When the value of n / m is less than 8, since the copolymerization ratio of the MVS unit is too high, the peeling force tends to be too high and the releasability is poor. On the other hand, when the value of n / m exceeds 35, since the copolymerization ratio of the MVS unit is too low, the release layer tends to be soft, blocking tends to occur, and handling properties are poor. Become. In addition, the strength of the release layer tends to be low. From such a viewpoint, the value of n / m is preferably 10 or more and 25 or less, more preferably 12 or more and 20 or less, and particularly preferably 14 or more and 18 or less.

  In the above formula [Chemical Formula 3], m is 50 to 1000, preferably 100 to 800, more preferably 200 to 700, particularly preferably 400 to 600, and n is 400 to 15000, preferably 2000 to 12000, and more preferably. Is preferably in the range of 5000 to 10000, particularly preferably in the range of 7000 to 9000, since the crosslinking reaction suitably proceeds and the strength of the release layer is improved. In addition, the hardness of the release layer tends to be more appropriate, and the release layer and handling properties are more excellent. In addition, it is possible to more appropriately suppress the feeding charging. Furthermore, it is preferable that the value of m + n is 1000 to 15000, preferably 4000 to 12000, more preferably 6000 to 10000, and particularly preferably 7000 to 9000, since the strength of the release layer is further improved. In addition, the hardness of the release layer tends to be more appropriate, and the release properties and handling properties are further improved. Further, it is possible to more suitably suppress the feeding charging. The above formula [Chemical Formula 3] does not mean an embodiment that is a block copolymer, but these merely indicate that the total number of each unit is m and n. Should be understood. Therefore, the polysiloxane in the above formula [Chemical Formula 3] may be a random copolymer or a block copolymer.

  In the above formula [Chemical Formula 3], R1 represents an alkylene group having 12 or less carbon atoms or a direct bond. When R1 represents an alkylene group having 12 or less carbon atoms, if the number of carbon atoms is too large, the release layer tends to be soft, and the strength, releasability, and handling properties tend to be inferior. In addition, it tends to be difficult to suppress the feeding charge. From such a viewpoint, the carbon number is more preferably 8 or less, and particularly preferably 4 or less. The base polymer in the present invention is most preferably an embodiment in which R1 represents a direct bond, that is, an embodiment in which Si and a vinyl group are directly bonded without having an alkylene group.

(Crosslinking agent)
The crosslinking agent in the present invention is a copolymer of methyl hydrogen siloxane (hereinafter sometimes abbreviated as MHS) and dimethyl siloxane as represented by the following formula [Chemical Formula 4].

  In the above formula [Chemical Formula 4], p and q each represent an integer of 1 or more, but p is 5 to 100, preferably 10 to 70, more preferably 15 to 50, particularly preferably 20 to 30, and q is 5 -150, preferably 10-100, more preferably 20-70, particularly preferably 30-40, since the crosslinking reaction proceeds suitably and the strength of the release layer is improved. In addition, the hardness of the release layer tends to be more appropriate, and the release layer and handling properties are more excellent. In addition, it is possible to more appropriately suppress the feeding charging. Furthermore, it is preferable that the value of p + q is 15 to 200, preferably 25 to 150, more preferably 40 to 100, and particularly preferably 50 to 80, since the strength of the release layer is further improved. In addition, the hardness of the release layer tends to be more appropriate, and the release properties and handling properties are further improved. Further, it is possible to more suitably suppress the feeding charging. The above formula [Chemical Formula 4] does not mean an embodiment that is a block copolymer, but these merely indicate that the total number of each unit is p and q. Should be understood. Therefore, the polysiloxane in the above formula [Chemical Formula 4] may be a random copolymer or a block copolymer.

  In the above formula [Chemical Formula 4], R 2 and R 3 represent an alkyl group having 4 or less carbon atoms. When the number of carbon atoms is too large, the release layer tends to be soft, and the strength, releasability, and handling properties tend to be inferior. In addition, it tends to be difficult to suppress the feeding charge. From such a viewpoint, the carbon number is more preferably 2 or less, and particularly preferably 1 or less.

  In the above formula [Chemical Formula 4], the copolymerization ratio (p / q) between the MHS unit and the DMS unit is preferably 0.5 or more. By setting the value of p / q within the above numerical range, the hardness of the release layer tends to be more appropriate, and the release properties and handling properties are more excellent. In addition, it is possible to more appropriately suppress the feeding charging.

  The release layer in the present invention cures a coating film containing the base polymer represented by the above formula [Chemical Formula 3], the cross-linking agent represented by the above Formula [Chemical Formula 4], and inert particles described later as constituent components. In such a coating film, the blending ratio of the base polymer and the crosslinking agent is such that the MHS unit in the crosslinking agent is 1.2 mol or more and 3.0 mol per 1 mol of the MVS unit in the base polymer. A range of less than or equal to a mole is preferred. By setting the blending ratio within the above numerical range, the releasability can be further improved. Moreover, the migration of the silicone component can be suppressed. In addition, it is possible to more appropriately suppress the feeding charging. When the blending ratio is too small, that is, when there are too few MHS units with respect to the MVS unit, there is a tendency that poor curing tends to occur, the strength of the coating film tends to be low, and the silicone component is transferred. It tends to increase. On the other hand, when the content ratio is too large, that is, when there are too many MHS units relative to the MVS units, the residual hydrogen silane that has not been used for the crosslinking reaction tends to increase, and it becomes easy to cause heavy peeling over time. There is a tendency. From such a viewpoint, the content ratio is more preferably in a range where the MHS unit in the crosslinking agent is 1.4 mol or more and 2.5 mol or less with respect to 1 mol of the MVS unit in the base polymer, and 1.5 mol or more. A range of 2.0 mol or less is particularly preferable.

  As the base polymer and the crosslinking agent as described above, those produced by a conventionally known method can be used as long as they satisfy the requirements of the present invention, and ready-made products can be used as they are. Moreover, the silicone mold release agent with which these were mixed beforehand can also be used, for example, Toray Dow Corning Co., Ltd., brand name: SRX345, Shin-Etsu Chemical Co., Ltd., brand name: KS-3601, Momentive Product name: XS56-A5729, XS56-A5731, etc. can be mentioned.

(Inert particles)
The release layer in the present invention contains inert particles.
The average particle diameter of the inert particles is 20 nm or more and 90 nm or less. By setting the average particle size within the above numerical range, it is possible to suppress defects such as defective thickness and pinholes in the green sheet formed on the release layer while maintaining excellent handling properties. When the average particle size is too small, the defects in the green sheet tend to decrease, but the handling properties are inferior. On the other hand, when the average particle size is too large, the handling property tends to be improved, but the defects in the green sheet increase, and the thickness defect and the pinhole are likely to occur. From such a viewpoint, the average particle diameter of the inert particles is preferably 30 nm or more and 80 nm or less, and more preferably 40 nm or more and 60 nm or less.

  The content of the inert particles is 2% by mass or more and 20% by mass or less based on the mass of the release layer. By making content into the said numerical range, it is excellent in balance with handling property and the fault suppression of the above green sheets. When the content is too small, the handling property tends to be inferior. On the other hand, when there is too much content, there exists a tendency for a fault to increase. From such a viewpoint, the content of the inert particles is preferably 3% by mass or more and 18% by mass or less, more preferably 4% by mass or more and 10% by mass or less, and particularly preferably 4%, based on the mass of the release layer. It is not less than 6% by mass and not more than 6% by mass.

  The inert particles in the present invention preferably have a sharp particle size distribution. Specifically, the relative standard deviation representing the steepness of the particle size distribution is preferably 0.5 or less. If the relative standard deviation is small and the particle size distribution is steep, the height of the protrusion on the surface of the release layer becomes uniform. Thereby, the improvement effect of handling property can be made high. Further, coarse particles and coarse protrusions in the release layer tend to be reduced, and defects in the green sheet tend to be further reduced, so that a more preferable green sheet can be obtained. On the other hand, if the relative standard deviation is too large, coarse particles and coarse protrusions tend to increase, and defects in the green sheet tend to increase. From such a viewpoint, the relative standard deviation representing the particle size distribution of the inert particles is more preferably 0.4 or less, still more preferably 0.3 or less, and particularly preferably 0.2 or less.

  In addition, the inert particles in the present invention preferably have an aspect in which the shape is substantially spherical or true spherical. By setting it as such an aspect, the improvement effect of handling property can be made high. Specifically, the particle size ratio representing the degree of sphericalness of the particles is preferably 1.0 or more and 1.3 or less. The particle size ratio is more preferably 1.0 or more and 1.2 or less, and particularly preferably 1.0 or more and 1.1 or less.

The inert particles as described above may be organic particles or inorganic particles. Examples of the inert organic particles include crosslinked polystyrene resin particles, crosslinked silicone resin particles, crosslinked acrylic resin particles, crosslinked styrene-acrylic resin particles, crosslinked divinylbenzene-acrylic resin particles, crosslinked polyester resin particles, polyimide resin particles, and melamine resin particles. Etc. The inert inorganic particles include (1) silicon dioxide (including hydrate, silica sand, quartz, etc.); (2) alumina in various crystal forms; and (3) 30% by mass or more of SiO ₂ component. Silicates (eg amorphous or crystalline clay minerals, aluminosilicates (including calcined and hydrated), warm asbestos, zircon, fly ash, etc.); (4) Mg, Zn, Zr, and Ti (5) Sulfates of Ca and Ba; (6) Phosphate of Li, Ba, and Ca (including monohydrogen and dihydrogen salts); (7) Benzo of Li, Na, and K (8) terephthalate salt of Ca, Ba, Zn and Mn; (9) titanate salt of Mg, Ca, Ba, Zn, Cd, Pb, Sr, Mn, Fe, Co and Ni; 10) Ba and Pb chromate; (11) Carbon (e.g. (12) glass (for example, glass powder, glass beads, etc.); (13) carbonates of Ca and Mg; (14) fluorite; (15) spinel type oxide, etc. . Of these, from the viewpoint of superior slipperiness and abrasion resistance, inert inorganic particles are preferable, among which calcium carbonate particles and silica particles are preferable, and silica particles are particularly preferable. These are preferably spherical as described above, and spherical silica particles are particularly preferred from the viewpoint of further excellent slipperiness and abrasion resistance.

(Platinum catalyst)
In the present invention, the release layer preferably contains a platinum-based catalyst. The platinum-based catalyst is a catalyst for accelerating the addition polymerization of MVS in the base polymer and MHS in the cross-linking agent, and known catalysts can be used for such addition polymerization. Examples of such platinum-based catalysts include chloroplatinic acid, chloroplatinic acid alcohol solutions and aldehyde solutions, chloroplatinic acid complexes with various olefins or vinyl siloxanes, and the like.

  The amount of the platinum-based catalyst added may be a commonly used amount, but the amount of platinum metal is preferably 1 to 1000 ppm, more preferably 10 to 300 ppm with respect to 100 parts by mass of the base polymer. When the amount is added, the strength of the release layer is increased and it is economically excellent.

<Manufacturing method>
In the present invention, a coating film obtained by applying a coating liquid containing as constituent components a base polymer, a crosslinking agent, inert particles, and a platinum-based catalyst which may be optionally added, is obtained. A release layer is formed by curing.

  Such a coating liquid can be produced by uniformly mixing the above base polymer, crosslinking agent, inert particles, and optionally added platinum-based catalyst using a stirring blade or the like. In order to mix each component more uniformly, you may use what was diluted, dissolved, and disperse | distributed using the appropriate organic solvent. Further, as the coating liquid at the time of coating, the coating liquid obtained by mixing may be used as it is, but it is preferable to use a coating liquid that is diluted with an appropriate organic solvent and adjusted to have an appropriate viscosity. It is preferable from the viewpoint that a release layer having a uniform appearance and good appearance can be obtained.

  As a coating method for coating the coating liquid on the base film, any known coating method can be applied. For example, gravure roll coating method, reverse roll coating method, die coating method, kiss coating method, reverse kiss coating method, offset gravure A coating method, a Mayer bar coating method, a roll brush method, a spray coating method, an air knife coating method, an impregnation method, a curtain coating method, a doctor blade method, and the like can be applied alone or in combination. Further, for the purpose of improving the stability of the coating appearance such as repelling, the coating liquid can contain a slight amount of a surfactant.

  The conditions for drying and curing after applying the coating liquid to the base film are preferably heated at a temperature of 100 ° C. or higher and 180 ° C. or lower for a time of 10 seconds or longer and 120 seconds or shorter, and a temperature of 120 ° C. or higher and 160 ° C. or lower. It is more preferable to heat for 20 seconds to 90 seconds, and it is particularly preferable to heat at a temperature of 130 ° C. to 150 ° C. for 30 seconds to 60 seconds. By adopting the drying conditions as described above, the strength of the release layer can be further increased. Moreover, the adhesiveness of a base film and a mold release layer can be made higher. In addition, it is possible to more appropriately suppress the feeding charging.

<Thickness of release layer>
The thickness of the release layer in the present invention is 5 nm or more and 40 nm or less. In the present invention, the average particle diameter of the inert particles contained in the release layer is set to the numerical range specified by the present invention, and at the same time, the thickness is set to the above numerical range, whereby the protrusions due to the inert particles on the surface of the release layer. The height of the sheet is uniform, thereby providing suitable slipperiness, excellent handling, and at the same time suppressing defects such as poor thickness and pinholes in the green sheet formed on the release layer. it can. Furthermore, when the thickness is in the above numerical range, the release property is excellent. In addition, it is possible to more appropriately suppress the feeding charging. When the thickness is too thin, the peeling force tends to increase and the releasability is poor. Furthermore, the inert particles contained in the release layer tend to fall off easily. On the other hand, when the thickness is too thick, protrusions due to inert particles tend not to be formed on the surface of the release layer. Moreover, even if the aspect of a protrusion is equivalent, it exists in the tendency for it to be inferior to sliding property, and exists in the tendency to be inferior to handling property. Further, the peeling force tends to be low, and if the peeling force is too low, there may be a problem that the green sheet is peeled off from the carrier film in the conveying step before peeling the green sheet. From such a viewpoint, the thickness of the silicone release layer is preferably 8 nm to 25 nm, more preferably 10 nm to 20 nm.
The thickness of the release layer can be adjusted by any known method such as appropriately adjusting the concentration of the coating liquid and the wet coating amount when applying the coating liquid.

<Characteristics of carrier film>
(Surface roughness)
The carrier film for forming a green sheet of the present invention is a carrier film having a release layer on at least one surface of the base film, and the 10-point average roughness Rz on at least one surface is 10 nm or more and 100 nm or less. .

(Surface roughness in the first embodiment)
The first embodiment of the carrier film for forming a green sheet of the present invention is a carrier film having a release layer on one side of the base film, but the 10-point average roughness Rz on the other side of the base film is It is 10 nm or more and 100 nm or less. By setting the 10-point average roughness Rz on the other surface of the base film to the above numerical range, the surface shape of the surface is suppressed from being transferred to the green sheet in the step of winding after forming the green sheet. And the defects in the green sheet can be suppressed. At the same time, the handling property can be improved. Further, the floating of the green sheet can be suppressed. When the 10-point average roughness Rz is too small, the handling property tends to be inferior. In addition, the green sheet tends to float. On the other hand, when the 10-point average roughness Rz is too large, defects in the green sheet tend to increase. From such a viewpoint, the 10-point average roughness Rz on the other surface of the base film is preferably 12 nm to 90 nm, more preferably 15 nm to 60 nm, and particularly preferably 20 nm to 30 nm.

  In the first embodiment of the carrier film for forming a green sheet of the present invention, the center line average surface roughness Ra on the other surface of the base film is preferably 2 nm or more and 14 nm or less. By setting the centerline average surface roughness Ra on the other surface of the base film to the above numerical range, transfer to the green sheet can be further suppressed, and defects can be further suppressed. At the same time, the handling property can be improved. When the center line average surface roughness Ra is too small, the improvement in handling properties tends to be low. On the other hand, when the center line average surface roughness Ra is too large, the effect of improving defect suppression in the green sheet tends to be low. From such a viewpoint, the center line average surface roughness Ra on the other surface of the base film is preferably 2 nm or more and 8 nm or less, more preferably 2 nm or more and 6 nm or less, and particularly preferably 2 nm or more and 4 nm or less.

  When the 10-point average roughness Rz and the centerline average surface roughness Ra as described above are appropriately adjusted for the average particle diameter and addition amount of particles contained in the film substrate, or when a coating layer is provided on the film substrate Is achieved by appropriately adjusting the average particle diameter and the amount of particles contained in the coating layer. Particularly preferred embodiments in the present invention contain substantially no particles (5 ppm or less based on the weight of the base film) or only a very small amount (50 ppm or less based on the weight of the base film). In this embodiment, the surface film is roughened by applying a coating containing particles to the uncoated base film.

  As such a coating layer, the same kind of particles as the inert particles contained in the release layer described above are dispersed in a binder component made of an organic polymer resin such as an acrylic resin, a polyester resin, or a urethane resin. Things can be mentioned. The average particle diameter of such particles is preferably 10 nm to 200 nm, more preferably 20 nm to 150 nm, and particularly preferably 30 nm to 50 nm. Moreover, the addition amount of the particles is preferably 5% by mass or more and 30% by mass or less, and more preferably 10% by mass or more and 20% by mass or less, based on the solid content mass of the coating layer. The thickness of the coating layer is preferably 5 nm to 100 nm, more preferably 10 nm to 30 nm. The 10-point average roughness Rz in the present invention can be achieved by providing the above-described coating layer on a substrate film that substantially does not contain particles or contains a very small amount of particles. it can. As the coating layer, the above-mentioned easy adhesion layer is preferable.

  In the present invention, the carrier film having a release layer on one surface of the base film may have the 10-point average roughness Rz as described above on the other surface, and the other surface is You may have functional layers, such as a mold release layer.

  In the first aspect of the green sheet-forming carrier film of the present invention, the 10-point average roughness Rz on the surface of the release layer is preferably 10 nm or more and 100 nm or less. By setting the 10-point average roughness Rz on the surface of the release layer within the above numerical range, it is possible to enhance the handling effect. At the same time, the effect of improving defect suppression in the green sheet can be increased, and the balance between these becomes better. When the 10-point average roughness Rz is too small, the effect of improving the handling property tends to be low. On the other hand, when the 10-point average roughness Rz is too large, the effect of improving defect suppression in the green sheet tends to be low. From such a viewpoint, the 10-point average roughness Rz on the surface of the release layer is preferably 12 nm to 90 nm, more preferably 15 nm to 60 nm, and particularly preferably 20 nm to 30 nm.

  Furthermore, in the first aspect of the carrier film for forming a green sheet of the present invention, the center line average surface roughness Ra on the surface of the release layer is preferably 2 nm or more and 14 nm or less. By setting the center line average surface roughness Ra on the surface of the release layer within the above numerical range, the effect of improving the handling property can be enhanced. At the same time, the effect of improving defect suppression in the green sheet can be increased, and the balance between these becomes better. When the center line average surface roughness Ra is too small, the improvement in handling properties tends to be low. On the other hand, when the center line average surface roughness Ra is too large, the effect of improving defect suppression in the green sheet tends to be low. From such a viewpoint, the center line average surface roughness Ra on the surface of the release layer is preferably 2 nm to 8 nm, more preferably 2 nm to 6 nm, and particularly preferably 2 nm to 4 nm.

  The 10-point average roughness Rz and the centerline average surface roughness Ra on the surface of the release layer as described above can be appropriately adjusted with respect to the average particle diameter and addition amount of the particles contained in the film substrate, In the case of providing a coating layer, the average particle size and addition amount of particles contained in the coating layer are adjusted as appropriate, or the average particle size, addition amount, and release of inert particles contained in the release layer. This is achieved by appropriately adjusting the thickness of the layer. A particularly preferable embodiment for achieving the 10-point average roughness Rz and the centerline average surface roughness Ra on the surface of the release layer substantially contains no particles or contains a very small amount of particles. This is an embodiment in which the non-base film has the release layer in the present invention.

(Surface roughness in the second embodiment)
The second embodiment of the carrier film for forming a green sheet of the present invention is a carrier film having release layers on both sides of the base film, but the 10-point average roughness Rz on at least one side is 10 nm or more and 100 nm or less. It is. Here, at least one surface indicates one surface of the release layer surface on the side where the green sheet is not formed or both release layer surfaces. By setting the 10-point average roughness Rz on the surface to the above numerical range, it is possible to suppress the surface shape of the surface from being transferred to the green sheet in the step of winding after forming the green sheet. It is possible to suppress defects in At the same time, the handling property can be improved. Further, the floating of the green sheet can be suppressed. Further, it is possible to suitably suppress the extension charging. When the 10-point average roughness Rz is too small, the handling property tends to be inferior. In addition, the green sheet tends to float. On the other hand, when the 10-point average roughness Rz is too large, defects in the green sheet tend to increase. From such a viewpoint, the 10-point average roughness Rz on the other surface of the base film is preferably 12 nm to 90 nm, more preferably 15 nm to 60 nm, and particularly preferably 20 nm to 30 nm. In the present invention, if one surface of the surface of the release layer on the side where the green sheet is not formed is the above embodiment, the above-described effects can be obtained, but both release layer surfaces may be the above embodiment. The above-described effects are preferably achieved. Further, it is possible to more suitably suppress the feeding charging.

  In the second embodiment of the green sheet-forming carrier film of the present invention, it is preferable that the center line average surface roughness Ra on at least one surface is 2 nm or more and 14 nm or less. Here, at least one surface indicates one surface of the release layer surface on the side where the green sheet is not formed or both release layer surfaces. By setting the centerline average surface roughness Ra on the other surface of the base film to the above numerical range, transfer to the green sheet can be further suppressed, and defects can be further suppressed. At the same time, the handling property can be improved. In addition, it is possible to more appropriately suppress the feeding charging. When the center line average surface roughness Ra is too small, the improvement in handling properties tends to be low. On the other hand, when the center line average surface roughness Ra is too large, the effect of improving defect suppression in the green sheet tends to be low. From such a viewpoint, the center line average surface roughness Ra on the other surface of the base film is preferably 2 nm or more and 8 nm or less, more preferably 2 nm or more and 6 nm or less, and particularly preferably 2 nm or more and 4 nm or less. In the present invention, if one surface of the surface of the release layer on the side where the green sheet is not formed is the above embodiment, the above-described effects can be obtained, but both release layer surfaces may be the above embodiment. More preferably, the above-described effects are more preferably achieved. Further, it is possible to more suitably suppress the feeding charging.

  In the second embodiment of the green sheet-forming carrier film of the present invention, the 10-point average roughness Rz on the surface of the release layer on the side where the green sheet is formed is preferably 10 nm or more and 100 nm or less. By setting the 10-point average roughness Rz on the surface of the release layer within the above numerical range, it is possible to enhance the handling effect. At the same time, the effect of improving defect suppression in the green sheet can be increased, and the balance between these becomes better. When the 10-point average roughness Rz is too small, the effect of improving the handling property tends to be low. On the other hand, when the 10-point average roughness Rz is too large, the effect of improving defect suppression in the green sheet tends to be low. From such a viewpoint, the 10-point average roughness Rz on the surface of the release layer on the side where the green sheet is formed is preferably 12 nm or more and 90 nm or less, more preferably 15 nm or more and 60 nm or less, and particularly preferably 20 nm or more and 30 nm or less. is there.

  Furthermore, in the second embodiment of the carrier film for forming a green sheet of the present invention, it is preferable that the center line average surface roughness Ra on the surface of the release layer on the side where the green sheet is formed is 2 nm or more and 14 nm or less. By making the center line average surface roughness Ra on the surface of the release layer within the above numerical range, the effect of improving the handling property can be enhanced. At the same time, the effect of improving defect suppression in the green sheet can be increased, and the balance between these becomes better. When the center line average surface roughness Ra is too small, the improvement in handling properties tends to be low. On the other hand, when the center line average surface roughness Ra is too large, the effect of improving defect suppression in the green sheet tends to be low. From such a viewpoint, the center line average surface roughness Ra on the surface of the release layer on the side where the green sheet is formed is preferably 2 nm or more and 8 nm or less, more preferably 2 nm or more and 6 nm or less, and particularly preferably 2 nm or more and 4 nm or less. It is.

  The 10-point average roughness Rz and the centerline average surface roughness Ra on the surface of the release layer as described above can be appropriately adjusted with respect to the average particle diameter and addition amount of the particles contained in the film substrate, In the case of providing a coating layer, the average particle size and addition amount of particles contained in the coating layer are adjusted as appropriate, or the average particle size, addition amount, and release of inert particles contained in the release layer. This is achieved by appropriately adjusting the thickness of the layer. A particularly preferable embodiment for achieving the 10-point average roughness Rz and the centerline average surface roughness Ra on the surface of the release layer substantially contains no particles or contains a very small amount of particles. This is a mode in which a coating layer as described above is provided on a non-base film and the release layer in the present invention is provided thereon. As the coating layer, the above-mentioned easy adhesion layer is preferable.

(Peeling power)
In the green sheet-forming carrier film of the present invention, the green sheet peeling force on the surface of the release layer is preferably 1.0 g / 25 mm or more and 6.0 g / 25 mm or less. When the peeling force is in the above numerical range, it is possible to further suppress the green sheet from peeling or floating from the carrier film in the transporting process or the like. Further, in the step of peeling the green sheet from the carrier film, breakage or cohesive failure of the green sheet can be further suppressed. When the peeling force is too light, the green sheet tends to be peeled off or floated in the conveying step. On the other hand, when the peeling force is too heavy, the green sheet tends to break or cohesively break in the peeling step. In addition, it tends to be difficult to suppress the feeding charge. From such a viewpoint, the peeling force is more preferably 1.5 g / 25 mm or more and 5.0 g / 25 mm or less, and particularly preferably 2.0 g / 25 mm or more and 4.0 g / 25 mm or less.

  The peeling force as described above can be appropriately adjusted in the blending ratio of the base polymer and the crosslinking agent in the release layer, the copolymerization ratio of the MVS unit and the DMS unit in the base polymer can be adjusted appropriately, This is achieved by appropriately adjusting the thickness.

(Coefficient of friction)
In the present invention, the coefficient of friction between one surface of the green sheet-forming carrier film and the other surface is preferably 0.75 or less. When the friction coefficient is low, the effect of improving the handling property is increased. In addition, it is possible to more appropriately suppress the feeding charging. From such a viewpoint, the friction coefficient is more preferably 0.60 or less, and particularly preferably 0.50 or less. The friction coefficient is preferably as low as possible from the viewpoint of handling properties, but the lower limit of the friction coefficient in the present invention is practically about 0.10.

  Hereinafter, the present invention will be further described with reference to examples. Each characteristic value was measured by the following method.

(1) Release Layer Thickness After cutting the carrier film into triangular pieces, a Pt (platinum) layer having a thickness of 2 nm was formed on the release layer surface by coating. The obtained sample was fixed to a multiaxial embedding capsule, embedded using an epoxy resin, sliced in a direction perpendicular to the plane direction of the carrier film using a microtome ULTRACUT-S, and a thickness of 50 nm. An ultra-thin sample was obtained. Next, the obtained ultra-thin sample was placed on a grid and vapor-stained with 2% osmic acid at 60 ° C. for 2 hours. The ultrathin sample after vapor staining was observed with a transmission electron microscope LEM-2000 under the condition of an acceleration voltage of 100 kv, and the thickness of the release layer was measured. The measurement was carried out on any 10 points of the carrier film, and the average value thereof was taken as the thickness (unit: nm) of the release layer.

(2) Average particle diameter The particles are dispersed on the sample stage so that the individual particles do not overlap as much as possible, and a gold thin film deposition layer is formed on the surface with a thickness of 200 to 300 angstroms by a gold sputtering device. , Observed with a scanning electron microscope at a magnification of 10,000 to 3 times, and with a Luzex 500 manufactured by Japan Regulator Co., Ltd., at least 110 particles, a major axis (Dli), minor axis (Dsi), and area circle The equivalent diameter (Di) was determined.

The number n of particles was used, and the value obtained above was used in the following formula, and the number average value of the area equivalent particle diameter (Di) was defined as the average particle diameter (D).

Moreover, the particle size ratio was calculated as Dl / Ds from the average value of the major axis (Dl) and the average value of the minor axis (Ds) obtained from the following formula.

The relative standard deviation was determined from the area equivalent particle diameter (Di) and the average particle diameter (D) by the following formula.

(3) Surface roughness (3-1) Centerline average surface roughness (Ra)
Using a non-contact type three-dimensional roughness meter (manufactured by Kosaka Laboratories, ET30HK) with a semiconductor laser having a wavelength of 780 nm, an optical stylus with a beam diameter of 1.6 μm, a measurement length (Lx) of 1 mm, a sampling pitch of 2 μm, and a cutoff of 0.1. The protrusion profile on the film surface was measured under the conditions of 25 mm, longitudinal magnification of 5000 times, lateral magnification of 200 times, and the number of scanning lines of 100 (thus, the measurement length Ly in the Y direction was 0.2 mm). When the curved surface is represented by Z = f (x, y), the value obtained by the following formula is the center line average surface roughness (Ra, unit: nm).

表面粗さ測定においては、サンプルが片面に離型層を有する場合は、「離型層表面」および「離型層表面と反対面」につき測定を行った。サンプルが両面に離型層を有する場合は、任意の一方の離型層表面を「離型層表面１」（易接着層が片面に設けられている場合は、易接着層を有する側を優先）とし、他方の離型層表面を「離型層表面１と反対面」とし、測定を行った。 (3-2) 10-point average roughness (Rz)
Further, in the projection profile of the film surface obtained as described above, 5 points from the higher peak (Hp) and 5 points from the lower valley (Hv) are taken, and the 10-point average roughness (Rz, Unit: nm).

In the surface roughness measurement, when the sample has a release layer on one side, the measurement was performed on the “release layer surface” and the “opposite side to the release layer surface”. When the sample has a release layer on both sides, the surface of any release layer is designated as “release layer surface 1” (if the easy-adhesion layer is provided on one side, the side having the easy-adhesion layer takes precedence. ), And the other release layer surface was defined as “the surface opposite to the release layer surface 1”.

(4) Coefficient of friction According to ASTM D1894-63, using a slippery measuring instrument manufactured by Toyo Tester, one surface of the carrier film (the surface on the release layer side) and the other surface (the surface on the base film side) ) Was measured. However, the thread plate was a glass plate and the load was 1 kg.

(5) Green sheet molding <Preparation of ceramic powder dispersion slurry>
The following components were mixed and dispersed with a Hegman grind gauge with a ball mill so as to be 7 or more to prepare a ceramic powder dispersion slurry.
(A) Polyvinyl butyral resin (manufactured by Sekisui Chemical Co., Ltd., trade name: ESREC BX-5) (4 parts by mass)
(B) Toluene / ethanol (mass ratio; 1/1) mixed solvent (35 parts by mass)
(C) Ceramic powder (barium titanate) (100 parts by mass)
(D) Dibutyl phthalate (2 parts by mass)

<Creation of a laminate of a carrier film and a green sheet>
The ceramic powder dispersion slurry obtained above was applied to the surface of the release layer of the carrier film using a straight edge applicator having a 1 mil gap, and dried at 100 ° C. for 3 minutes to obtain a green sheet having a thickness of 1 μm. Molding was performed to obtain a laminate of a carrier film and a green sheet.

(6) Green sheet defect inspection (thickness defects and pinholes)
The laminate of the carrier film and the green sheet prepared by the method (5) was cut into a 10 cm × 10 cm square. Ten of the obtained laminate samples were stacked so that the surface of the green sheet and the back surface of the carrier film were in contact with each other, and left at 40 ° C. for 2 weeks under a load of 20 g / cm ² . Next, among the 10 laminate samples, the carrier film was peeled off from the inner 8 laminate samples excluding the top and the bottom to obtain a green sheet having a thickness of 1 μm and enlarged with a backlight. Observation was carried out using a mirror. Here, pinholes and thickness defects due to uneven transfer on the back are observed as bright spots. The occurrence of such bright spots was determined according to the following criteria.
○: Almost no bright spot is seen. (5 or less)
Δ: Some bright spots were observed. (6 to 20)
×: Many bright spots were observed. (21 or more)
Further, in the above, when the 10-layer laminate samples were peeled one by one, the floating state at the interface between the carrier film and the green sheet was visually observed to evaluate the floating of the green sheet.

(7) Green sheet peel test The laminate of the carrier film and the green sheet prepared by the method of (5) above is cut out to a width of 25 mm and a length of 150 mm, and the carrier film side is attached to an aluminum plate with a double-sided tape. The green sheets were peeled off under the conditions of a speed of 300 mm / min and an angle of 180 degrees with a tensile tester, and the peeling force was measured. Measurement was performed on arbitrary five points, and the average value thereof was defined as a peel force (unit: g / 25 mm).

(8) Peeling charge evaluation (feeding charge evaluation)
The roll-shaped carrier film wound up by the coater was rewound into a roll having a length of 1000 m in the slit process, and the roll having a length of 1000 m was unwound from the roll in the process of unwinding and winding at a speed = 80 m / min. Concentrated potential measuring device (trade name: electrostatic potential measuring device SV-, manufactured by Kasuga Electric Co., Ltd.) vertically upward and at a distance of 5 cm from the surface of the carrier film immediately after (in the roll of 1000 m length, the surface inside the winding) 10) was installed, and the peel charge amount was measured in an atmosphere of temperature: 23 ° C. and humidity: 55% RH. While unrolling the entire length of the release film roll of 1000 m, at least 15 points of peeling charge amount were measured every about 50 m, and the average value thereof was defined as the carrier film peeling charge amount (unit: kV).
If the peel charge amount obtained by the above measurement method is 8 kV or less, it means that the feeding charge is sufficiently suppressed. The peel charge amount is more preferably 7 kV or less, further preferably 5 kV or less, and particularly preferably 3 kV or less.

[Example 1]
(Adjustment of coating liquid)
Silicone release agent in which a base polymer having 16 mol of DMS unit and a crosslinking agent are mixed in advance with respect to 1 mol of MVS unit (manufactured by Toray Dow Corning, trade name: SRX345, nonvolatile content 30% by mass) ) 9100 parts by mass of a mixed solvent of methyl ethyl ketone (MEK) and toluene (mixing ratio (volume); MEK: toluene = 70: 30) was added to 100 parts by mass for dilution. To this, 5.3 parts by mass of MEK dispersion (manufactured by Nissan Chemical Industries, trade name: MEK-ST-L, nonvolatile content 30% by mass) of silica particles having an average particle diameter of 50 nm was added as inert particles. Then, 1.5 parts by mass of a product name: NC25 (non-volatile content: 10% by mass) manufactured by Toray Dow Corning Co., Ltd. was added as a platinum-based catalyst to obtain a coating solution having a solid content concentration of 0.32% by mass. . Moreover, the solid content ratio of each component in the release layer 100% by mass obtained from this coating solution is as follows.
Silicone release agent: 94.5% by mass
Inactive particles: 5.0% by mass
Others (component derived from NC25): 0.5% by mass

(Base film 1)
A polyester film having a thickness of 38 μm (manufactured by Teijin DuPont Films, trade name: O3X-38) having an easy-slip coating on one side was used as a base film. In addition, this polyester film had a center line average surface roughness (Ra) of 1 nm and a 10-point average roughness (Rz) of 8 nm on the surface on which the slippery coating was not applied. Further, the center line average surface roughness (Ra) of the surface on which the slippery coating was applied was 3 nm, and the 10-point average roughness (Rz) was 25 nm.

(Creation of carrier film)
Apply the coating solution obtained above to the surface of the base film 1 that is not easily slipped, apply a # 200 gravure roll by reverse rotation and kiss coating, and dry and cure at 140 ° C. for 45 seconds. To obtain a carrier film. Table 1 shows the characteristics of the obtained carrier film and the evaluation results using it.

[Example 2]
Except that the amount of the mixed solvent of MEK and toluene is 29900 parts by mass, the solid content concentration of the coating liquid is 0.11% by mass, and the thickness of the release layer is 5 nm. Thus, a carrier film was obtained. Table 1 shows the characteristics of the obtained carrier film and the evaluation results using it.

[Example 3]
Except that the amount of the mixed solvent of MEK and toluene is 4900 parts by mass, the solid content concentration of the coating liquid is 0.63% by mass, and the thickness of the release layer is 30 nm. Thus, a carrier film was obtained. Table 1 shows the characteristics of the obtained carrier film and the evaluation results using it.

[Example 4]
The coating liquid was applied in the same manner as in Example 1 except that the amount of the mixed solvent of MEK and toluene was 9700 parts by mass, the inert particles were used, and the amount of silica particles added to the MEK dispersion was 3.1 parts by mass. Obtained. The solid content concentration of the obtained coating liquid was 0.32% by mass. Moreover, the solid content ratio of each component in the release layer 100% by mass obtained from this coating solution is as follows.
Silicone release agent: 96.5% by mass
Inactive particles: 3.0% by mass
Others (component derived from NC25): 0.5% by mass
Using the coating solution obtained above, a carrier film was obtained in the same manner as in Example 1. Table 1 shows the characteristics of the obtained carrier film and the evaluation results using it.

[Example 5]
A coating liquid was obtained in the same manner as in Example 1 except that the amount of the mixed solvent of MEK and toluene was 11500 parts by mass, the inert particles were used, and the amount of the MEK dispersion of silica particles was 22 parts by mass. . The solid content concentration of the obtained coating liquid was 0.32% by mass. Moreover, the solid content ratio of each component in the release layer 100% by mass obtained from this coating solution is as follows.
Silicone release agent: 81.6% by mass
Inactive particles: 18.0% by mass
Others (component derived from NC25): 0.4% by mass
Using the coating solution obtained above, a carrier film was obtained in the same manner as in Example 1. Table 1 shows the characteristics of the obtained carrier film and the evaluation results using it.

[Example 6]
As an inert particle, instead of the MEK dispersion of silica particles having an average particle diameter of 50 nm, an MEK dispersion of silica particles having an average particle diameter of 20 nm (trade name: MEK-ST-ML, nonvolatile content 30 manufactured by Nissan Chemical Industries, Ltd.) A carrier film was obtained in the same manner as in Example 1 except that (mass%) was used. Table 1 shows the characteristics of the obtained carrier film and the evaluation results using it.

[Example 7]
As an inert particle, instead of a MEK dispersion of silica particles having an average particle diameter of 50 nm, a MEK dispersion of silica particles having an average particle diameter of 87 nm (trade name: MEK-ST-ZL, nonvolatile content 30 manufactured by Nissan Chemical Industries, Ltd.) A carrier film was obtained in the same manner as in Example 1 except that (mass%) was used. Table 1 shows the characteristics of the obtained carrier film and the evaluation results using it.

[Example 8]
As a silicone release agent, instead of Toray Dow Corning Co., Ltd., product name: SRX345, a silicone in which a base polymer having 12 mols of DMS units and a crosslinking agent are mixed in advance with respect to 1 mol of MVS units A carrier film was obtained in the same manner as in Example 1, except that a release agent (trade name: XS56-A5729, nonvolatile content: 30% by mass, manufactured by Momentive Co., Ltd.) was used. Table 1 shows the characteristics of the obtained carrier film and the evaluation results using it.

[Example 9]
As a silicone release agent, instead of Toray Dow Corning Co., Ltd., product name: SRX345, a silicone in which a base polymer having 30 mol of DMS unit and a crosslinking agent are mixed in advance with respect to 1 mol of MVS unit A carrier film was obtained in the same manner as in Example 1 except that a release agent (trade name: XS56-A5731, manufactured by Momentive Co., Ltd., nonvolatile content: 30% by mass) was used. Table 1 shows the characteristics of the obtained carrier film and the evaluation results using it.

[Comparative Example 1]
A coating solution was obtained in the same manner as in Example 1 except that the amount of the mixed solvent of MEK and toluene was 9400 parts by mass, and no inert particles were added. The solid content concentration of the obtained coating liquid was 0.32% by mass. Moreover, the solid content ratio of each component in the release layer 100% by mass obtained from this coating solution is as follows.
Silicone release agent: 99.5% by mass
Inactive particles: 0.0% by mass
Others (component derived from NC25): 0.5% by mass
Using the coating solution obtained above, a carrier film was obtained in the same manner as in Example 1. Table 1 shows the characteristics of the obtained carrier film and the evaluation results using it.
The carrier film obtained in Comparative Example 1 was poor in slipperiness and could not be wound up by 2000 m or more due to generation of pimples and wrinkles.

[Comparative Example 2]
The coating liquid was prepared in the same manner as in Example 1 except that the amount of the mixed solvent of MEK and toluene was 12500 parts by mass, the inert particles were used, and the amount of silica particles added to the MEK dispersion was 33.5 parts by mass. Obtained. The solid content concentration of the obtained coating liquid was 0.32% by mass. Moreover, the solid content ratio of each component in the release layer 100% by mass obtained from this coating solution is as follows.
Silicone release agent: 74.6% by mass
Inactive particles: 25.0% by mass
Others (component derived from NC25): 0.4% by mass
Using the coating solution obtained above, a carrier film was obtained in the same manner as in Example 1. Table 1 shows the characteristics of the obtained carrier film and the evaluation results using it.

[Comparative Example 3]
As a silicone release agent, instead of Toray Dow Corning Co., Ltd., product name: SRX345, a silicone in which a base polymer having 50 mol of DMS unit and a crosslinking agent are mixed in advance with respect to 1 mol of MVS unit A carrier film was obtained in the same manner as in Example 1 except that a release agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KS847T, nonvolatile content: 30% by mass) was used. Table 1 shows the characteristics of the obtained carrier film and the evaluation results using it.
The carrier film obtained in Comparative Example 3 was poor in slipperiness and could not be wound up by 100 m or more due to generation of pimples and wrinkles.

[Comparative Example 4]
As an inert particle, instead of a MEK dispersion of silica particles having an average particle diameter of 50 nm, a MEK dispersion of silica particles having an average particle diameter of 13 nm (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST, nonvolatile content: 30% by mass) ) Was used in the same manner as in Example 1 except that a carrier film was obtained. Table 1 shows the characteristics of the obtained carrier film and the evaluation results using it.

[Comparative Example 5]
As an inert particle, instead of a MEK dispersion of silica particles having an average particle diameter of 50 nm, a MEK dispersion in which silica particles having an average particle diameter of 100 nm (product name: SG-SO100) are dispersed in MEK ( A carrier film was obtained in the same manner as in Example 1 except that the nonvolatile content was 30% by mass. Table 1 shows the characteristics of the obtained carrier film and the evaluation results using it.

[Comparative Example 6]
As a base film, instead of Teijin DuPont Films Co., Ltd., which has an easy-slip coating on one side, trade name: O3X-38, a polyester film with a thickness of 38 μm without any easy-slip coating (Teijin) The base film 2 was made using DuPont Films Co., Ltd. product name: O3-38. The polyester film had a center line average surface roughness (Ra) of 1 nm and a 10-point average roughness (Rz) of 8 nm.
Using the substrate film 2 described above, a carrier film was obtained in the same manner as in Example 1. Table 1 shows the characteristics of the obtained carrier film and the evaluation results using it.
The carrier film obtained in Comparative Example 6 was poor in slipperiness and could not be wound up by 500 m or more due to generation of pimples and wrinkles.

[Comparative Example 7]
As a base film, instead of Teijin DuPont Films Co., Ltd., which has an easy-slip coating on one side, trade name: O3X-38, a polyester film with a thickness of 38 μm without any easy-slip coating (Teijin) The base film 3 was made using DuPont Films, trade name: X2-38 as it was. The polyester film had a center line average surface roughness (Ra) of 18 nm and a 10-point average roughness (Rz) of 600 nm.
Using the above base film 3, a carrier film was obtained in the same manner as in Example 1. Table 1 shows the characteristics of the obtained carrier film and the evaluation results using it.

[Comparative Example 8]
Except that the amount of the mixed solvent of MEK and toluene is 2900 parts by mass, the solid content concentration of the coating liquid is 1.06% by mass, and the thickness of the release layer is 50 nm. Thus, a carrier film was obtained. Table 1 shows the characteristics of the obtained carrier film and the evaluation results using it.
The carrier film obtained in Comparative Example 8 was poor in slipperiness and could not be wound up by 1000 m or more due to generation of pimples and wrinkles.

[Example 10]
(Adjustment of coating liquid)
Silicone release agent in which a base polymer having 16 mol of DMS unit and a crosslinking agent are mixed in advance with respect to 1 mol of MVS unit (manufactured by Toray Dow Corning, trade name: SRX345, nonvolatile content 30% by mass) ) 9100 parts by mass of a mixed solvent of methyl ethyl ketone (MEK) and toluene (mixing ratio (volume); MEK: toluene = 70: 30) was added to 100 parts by mass for dilution. To this, 5.3 parts by mass of MEK dispersion (manufactured by Nissan Chemical Industries, trade name: MEK-ST-L, nonvolatile content 30% by mass) of silica particles having an average particle diameter of 50 nm was added as inert particles. Then, 1.5 parts by mass of a product name: NC25 (non-volatile content: 10% by mass) manufactured by Toray Dow Corning Co., Ltd. was added as a platinum-based catalyst to obtain a coating solution having a solid content concentration of 0.32% by mass. . Moreover, the solid content ratio of each component in the release layer 100% by mass obtained from this coating solution is as follows.
Silicone release agent: 94.5% by mass
Inactive particles: 5.0% by mass
Others (component derived from NC25): 0.5% by mass

(Base film 4)
A 38 μm thick polyester film (manufactured by Teijin DuPont Films, trade name: O4P3W-38) having an easy adhesion layer on both sides was used as a base film. The polyester film had a center line average surface roughness (Ra) of 4 nm and a 10-point average roughness (Rz) of 36 nm.

(Creation of carrier film)
The coating solution obtained above is applied to both surfaces of the base film 4 (on the easy-adhesion layer) by applying a # 200 gravure roll using the reverse rotation and kiss coating method, and drying and curing at 140 ° C. for 45 seconds. Thus, a carrier film was obtained. Table 2 shows the characteristics of the obtained carrier film and the evaluation results using it.

[Example 11]
Example 10 except that the amount of the mixed solvent of MEK and toluene is 29900 parts by mass, the solid content concentration of the coating liquid is 0.11% by mass, and the thickness of the release layer is 5 nm. Thus, a carrier film was obtained. Table 2 shows the characteristics of the obtained carrier film and the evaluation results using it.

[Example 12]
Example 10 except that the amount of the mixed solvent of MEK and toluene is 4900 parts by mass, the solid content concentration of the coating liquid is 0.63% by mass, and the thickness of the release layer is 30 nm. Thus, a carrier film was obtained. Table 2 shows the characteristics of the obtained carrier film and the evaluation results using it.

[Example 13]
As a silicone release agent, instead of Toray Dow Corning Co., Ltd., product name: SRX345, a silicone in which a base polymer having 30 mol of DMS unit and a crosslinking agent are mixed in advance with respect to 1 mol of MVS unit A carrier film was obtained in the same manner as in Example 10 except that a release agent (trade name: XS56-A5731, manufactured by Momentive Co., Ltd., nonvolatile content: 30% by mass) was used. Table 2 shows the characteristics of the obtained carrier film and the evaluation results using it.

[Example 14]
A carrier film was obtained in the same manner as in Example 10 except that a 38 μm-thick polyester film (manufactured by Teijin DuPont Films, trade name: O3X-38) having an easy-adhesion layer on one side was used as the base film. It was. Table 2 shows the characteristics of the obtained carrier film and the evaluation results using it.
The polyester film had a center line average surface roughness (Ra) of 1 nm and a 10-point average roughness (Rz) of 8 nm. Moreover, the centerline average surface roughness (Ra) of the surface which has an easily bonding layer was 3 nm, and 10 point average roughness (Rz) was 25 nm.

Claims (4)

On at least one surface of the base film, a base polymer represented by the following formula [Chemical Formula 1], a crosslinking agent represented by the following formula [Chemical Formula 2], and inert particles having an average particle size of 20 nm or more and 90 nm or less, A carrier film having a release layer obtained by curing a coating film containing as a constituent component, wherein the content of inert particles in the release layer is 2% by mass or more and 20% by mass based on the mass of the release layer. A green sheet-forming carrier film having a release layer thickness of 5 nm to 40 nm and a 10-point average roughness Rz of 10 nm to 100 nm on at least one surface.

(In the formula [Chemical Formula 1], m and n each represent an integer of 1 or more and satisfy the relationship of 8 ≦ n / m ≦ 35. R1 represents an alkylene group having 12 or less carbon atoms or represents a direct bond. )

(In the formula [Chemical Formula 2], p and q each represent an integer of 1 or more. R2 and R3 represent an alkyl group having 4 or less carbon atoms.)   The carrier film having a release layer on one side of the base film, wherein the 10-point average roughness Rz on the other side of the base film is 10 nm or more and 100 nm or less. Carrier film.   The carrier film for forming a green sheet according to claim 1, wherein the carrier film has a release layer on both sides of the base film, and the 10-point average roughness Rz on at least one side is 10 nm or more and 100 nm or less.   The carrier sheet for forming a green sheet according to any one of claims 1 to 3, further comprising an easy-adhesion layer containing acrylic resin, polyester resin, and lubricant particles as constituent components between the base film and the release layer. .