KR100510336B1 - Method for producing stripping film for producing thin film, method for producing thin film for electronic component, and stripping film for producing thin film - Google Patents

Abstract

In the manufacturing method of the peeling film for thin film manufacture which concerns on this invention, after apply | coating the coating liquid 3a containing a silicone resin to the base film 2, the peeling layer 3 with a silicone resin is dried by drying the coating liquid 3a. ) Is formed on the base film (2), and the base film (2) on which the release layer (3) is formed is rolled into a roll shape to produce a release film (1) for thin film production for electronic components. When the thickness of 2) is 5 micrometers or more and less than 30 micrometers, the base film 2 is wound, applying a tension within the range of 3 newtons or more and 17 newtons per 100 mm of the width of the base film 2 on which the release layer 3 is formed. . Thereby, the flatness of the surface of the peeling layer 3 can be ensured, preventing the unwinding in the wound state and the elongation of the base film 2.

Description

METHODS FOR PRODUCING STRIPPING FILM FOR PRODUCING THIN FILM, METHOD FOR PRODUCING THIN FILM FOR ELECTRONIC COMPONENT, AND STRIPPING FILM FOR PRODUCING THIN FILM}

TECHNICAL FIELD The present invention relates to a method of manufacturing a release film for manufacturing a thin film for manufacturing a thin film for an electronic component, such as a ceramic green sheet or a ferrite green sheet, a method for producing a thin film for an electronic component using the release film, and a release film for manufacturing a thin film. .

For example, when manufacturing a ceramic thin film (ceramic green sheet) used as a dielectric of a ceramic capacitor, first, a ceramic powder and a binder (binder) are placed in a release film for thin film production (hereinafter also referred to as a "peel film"). A slurry coating liquid dispersed in water or the like is applied. Next, the organic solvent, water, etc. are volatilized and removed by heat-processing the peeling film to which the slurry state coating liquid was apply | coated. As a result, the slurry coating liquid is solidified to form a ceramic green sheet. In this case, as a peeling film, the type which formed the peeling layer by silicone resin on the base film so that it may peel easily from a ceramic green sheet is used. At the time of manufacture of this peeling film, the silicone resin for peeling layer formation is apply | coated to the surface of a base film by first sending a base film out from a sending side reel and guiding it to a coating apparatus. Next, the film discharged from the coating device is guided to the dryer to dry the silicone resin. As a result, the silicone resin on a base film hardens | cures and a peeling layer is formed and a peeling film is manufactured by this. In this case, the peeling film after manufacture is very long length about 2000m-3000m in length, for example. For this reason, the peeling film is wound in the shape of a roll about 40 cm in diameter so that conveyance and storage may be easy. In addition, at this time, winding up while applying sufficient tension (for example, 50 Newtons per 100 mm width of a base film) to the peeling film wound on a winding side reel is preventing the unwinding of the roll-shaped peeling film.

1 is a cross-sectional view of a release film 1 according to an embodiment of the present invention;

2 is an external perspective view of a state in which the release film 1 after production is wound in a roll shape;

3 is a configuration diagram showing the configuration of a release film production apparatus 11 for manufacturing the release film 1;

4 is a cross-sectional view of a state in which the slurry ceramic 4a is applied to the release film 1;

5 is a cross-sectional view of the ceramic green sheet 4 in a state in which the release film 1 is peeled off,

6 is an explanatory diagram for explaining the relationship between the thicknesses, the respective tensions, the number of occurrences of the recesses, the roll hardness, the presence of pinholes, and the presence or absence of the base films in Examples 1 to 16 and Comparative Examples 1 to 6;

FIG. 7: is a top view which shows an example of the recessed part H which generate | occur | produced on the surface of a peeling layer.

As a result of examining the above-mentioned conventional manufacturing method of the peeling film for thin film manufacture, the manufacturing method of the thin film (ceramic green sheet) for electronic components, and peeling film, the inventor discovered the following problem. That is, a peeling film is wound in roll shape in order to make carrying and storage of the peeling film after manufacture easy. In this case, in the conventional manufacturing method of a peeling film, in order to prevent winding-up of a roll-shaped peeling film, it winds, applying sufficient tension to the peeling film wound by a winding side reel. For this reason, the surface of the peeling layer in the peeling film wound up, and the back surface of the base film in the peeling film wound around the outer periphery are strongly surface-bonded. Therefore, when the base film coated with the silicone resin is wound on the winding reel, a part of the peeling layer may locally transfer to the back surface of the base film. In this case, as shown in FIG. On the surface, the recessed part H (H, H ...) of 5 micrometers-30 micrometers of width | variety (or diameter) generate | occur | produces countlessly. For this reason, the conventional manufacturing method of the peeling film has a problem that it is difficult to ensure flatness of a peeling layer.

Moreover, in order to improve the antacid property of the thin film for electronic components in recent years, longer lengthening of a peeling film is desired. For this reason, there exists a tendency for a thin base film to employ | adopt a long length peeling film, making it easy to carry and store. Therefore, when excessive tension is applied to the peeling film wound on a winding side reel, a microscopic defect may occur on the surface of the peeling layer due to stretching of the base film. On the other hand, in order to prevent local transition of a peeling layer with respect to the back surface of a base film, and elongation of a base film simultaneously, when the tension applied when winding is made too small, a roll-shaped peeling film will be in the state wound loosely. For this reason, the unwinding generate | occur | produces during conveyance, and when sending a peeling film at the time of manufacture of the ceramic green sheet of a later process mentioned later, the problem that winding | winding arises may arise.

Moreover, when manufacturing a ceramic green sheet using the peeling film in which the flatness of the surface of a peeling layer is not ensured, when apply | coating a slurry state coating liquid to the surface, it is a slurry state by recessed part H, H ... The coating liquid splashes to produce pinholes of about 1 mm in diameter, or the coating thickness may be uneven, resulting in defective products. Moreover, when electronic components, such as a ceramic capacitor, are manufactured using such a defective ceramic green sheet, the problem arises that the electronic component with low breakdown voltage is manufactured. In this case, since the thickness of the recent thin film for electronic components is very thin (5 micrometers or less), it originates in the recessed part H, H ... which exists in the surface of a peeling film at the time of application | coating of a slurry state coating liquid, There is a tendency for defective products to be more likely to occur. For this reason, in the manufacturing method which manufactures the thin film for electronic components using the peeling film manufactured by the conventional manufacturing method of the peeling film, the thin film for electronic components which is suitable for use as a dielectric, and does not have a pinhole is used. There is a problem that it is very difficult to manufacture.

The present invention has been made to solve the above problems, and provides a method for producing a release film for thin film production that can secure the flatness of the surface of the release layer while preventing the unwinding of the wound and the elongation of the base film in the wound state. The main purpose is to. In addition, another object of the present invention is to provide a method for manufacturing a thin film for an electronic component, which can produce a thin film for an electronic component, which is always uniform in thickness and does not have a pinhole. Another object is to provide a thin film for an electronic component that is always uniform in thickness and does not have pinholes, and furthermore, to provide a release film for manufacturing a thin film without unwinding.

In the manufacturing method of the peeling film for thin film manufacture which concerns on this invention, after apply | coating the coating liquid containing silicone resin to a base film, the peeling layer by the said silicone resin is formed on the said base film by drying the said coating liquid, A manufacturing method of manufacturing a release film for manufacturing a thin film for an electronic component by winding a base film on which the release layer is formed, in a roll shape, wherein a width of the base film on which the release layer is formed when the thickness of the base film is 5 μm or more and less than 30 μm. The base film is wound while applying a tension within a range of 3 Newtons to 17 Newtons per 100 mm. In addition, in this invention, although it defines in the tension per 100 mm of the width | variety of the base film in which the peeling layer was formed, when using the base film of a wider width or a narrower width | variety, it is prescribed | regulated to the tension proportional to the width.

In the manufacturing method of the peeling film for thin film manufacture, when a thickness of a base film is 5 micrometers or more and less than 30 micrometers, a base film is applied, applying the tension within the range of 3 newtons or more and 17 newtons per 100 mm of width of the base film in which a peeling layer was formed. By winding up, the force which acts when the back surface of the base film and the surface of a peeling layer in the wound state adhere | attach surface can be suppressed in a predetermined range, As a result, the number of generation | occurrence | production of a recessed part can be reduced. Therefore, peeling property is good, ensuring the flatness of a peeling layer, and the peeling film for thin film manufacture which can prevent unwinding and elongation of a base film in a wound state can be manufactured. Moreover, by using the peeling film for thin film manufacture manufactured by this manufacturing method, a pinhole is hard to produce and the thin film for electronic components of uniform thickness can always be manufactured.

According to another method for producing a release film for thin film production according to the present invention, after applying a coating liquid containing a silicone resin to a base film, the coating liquid is dried to form a release layer with the silicone resin on the base film. A method for manufacturing a release film for manufacturing a thin film for an electronic component by winding a base film on which the release layer is formed in a roll shape, wherein the base film has a release layer formed thereon when the thickness of the base film is 30 μm or more and 100 μm or less. The film is wound while applying a tension within the range of 4 to 28 newtons per 100 mm in width.

In the manufacturing method of the peeling film for thin film manufacture, when a thickness of a base film is 30 micrometers or more and 100 micrometers or less, a base film is applied, applying a tension within the range of 4 newtons or more and 28 newtons per 100 mm of width of the base film in which a peeling layer was formed. By winding up, the force which acts when the back surface of the base film and the surface of a peeling layer in the wound state adhere | attach surface can be suppressed in a predetermined range, As a result, the number of generation | occurrence | production of a recessed part can be reduced. Therefore, peeling property is good, ensuring the flatness of a peeling layer, and the peeling film for thin film manufacture which can prevent unwinding and elongation of a base film in a wound state can be manufactured. Moreover, by using the peeling film for thin film manufacture manufactured by this manufacturing method, a pinhole is hard to produce and the thin film for electronic components of uniform thickness can always be manufactured.

The manufacturing method of the thin film for electronic components which concerns on this invention apply | coats the said slurry state coating liquid, after apply | coating a slurry coating liquid to the peeling film for thin film manufacture for electronic components manufactured by the manufacturing method of the peeling film for thin film manufacture mentioned above. The thin film for electronic components is formed in the said peeling film for thin film manufacture by drying.

In the manufacturing method of the thin film for electronic components, when the thickness of a base film is 5 micrometers or more and less than 30 micrometers, it winds, applying the tension within the range of 3 newtons or more and 17 newtons per 100 mm of width of a base film, and the thickness of a base film By using a release film for thin film production wound while applying a tension within a range of 4 Newtons to 28 Newtons per 100mm width of the base film when the thickness is 30 μm or more and 100 μm or less, the thickness is always uniform for electronic parts without generating pinholes. Thin films can be prepared.

The peeling film for thin film manufacture which concerns on this invention winds the base film in which the peeling layer by silicone resin was formed in at least one surface in roll shape, and is for electronic components whose diameter from the surface of the wound core to a surface layer is 50 mm or more. As a peeling film for thin film manufacture of the above-mentioned, the hardness with respect to the said radial direction toward the said winding core side in the 50 mm radial side layer from the surface of the said winding core exists in the range of 460 or more and 700 or less.

In the peeling film for thin film manufacture, it rolls by forming a base film by roll improvement so that the hardness with respect to the radial direction from the surface of a winding core to the winding core side in the layer of a 50 mm radial direction side may exist in the range of 460 or more and 700 or less. As a result of suppressing the force acting when the back surface of the shape-shaped base film and the surface of the peeling layer adhere to the surface within a predetermined range, the number of occurrences of the recesses can be reduced, and the peelability is ensured while ensuring the flatness of the peeling layer. It is possible to produce a release film for producing a thin film without any unwinding. Moreover, by using this peeling film for thin film manufacture, the thin film for electronic components which does not generate | occur | produce a pinhole and is always uniform can be manufactured.

In addition, the present disclosure relates to the subject matter included in Japanese Patent Application No. 2001-37948, filed February 15, 2001, all of which are expressly incorporated herein by reference.

EMBODIMENT OF THE INVENTION Hereinafter, with reference to an accompanying drawing, suitable embodiment of the manufacturing method of the peeling film for thin film manufacture, the manufacturing method of the thin film for electronic components, and the peeling film for thin film manufacture which concerns on this invention is demonstrated.

First, the manufacturing method of the peeling film 1 corresponded to the peeling film for thin film manufacture in this invention is demonstrated.

The release film 1 is a film used as a support for applying the raw materials when producing a thin film for electronic parts such as a ceramic green sheet or a ferrite sheet, and as shown in FIG. 1, the base film 2 It is comprised by forming the peeling layer 3 on (PET film). This release film 1 is formed in comparatively long length about 2000m-3000m in length. For this reason, as shown in FIG. 2, the peeling film 1 after manufacture is wound up in the roll shape of about 40 cm in diameter. The base film 2 is a crystalline linear saturated polyester composed of an aromatic dibasic acid component and a diol component (polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene-2, 6-naphtharate, etc.). The unstretched film of is biaxially stretched and is formed. Specifically, for example, an unstretched film of polyester is formed by drying the polyester raw material and then melting it with an extruder, pushing it out from a T die onto a rotary cooling drum and quenching it. Next, the unstretched film is stretched in the biaxial direction by the stretching machine, and thermally fixed as necessary. Thereby, the film-shaped base film 2 of about 5 micrometers-250 micrometers in thickness is manufactured. In this peeling film 1, it is preferable to use the base film with a thickness of 5 micrometers-100 micrometers, and the base film 2 of 38 micrometers thickness is used as an example.

On the other hand, the peeling layer 3 is a layer which gives peeling characteristic to the base film 2, and is formed by apply | coating and drying the coating liquid containing curable silicone resin 3a to one side of the base film 2. . Here, although it does not specifically limit as curable silicone resin 3a, Silicone resins, such as a condensation reaction hardening type, an addition reaction hardening type, an ultraviolet curing type, or an electron beam hardening type, are used. In addition, as a coating liquid containing curable silicone resin 3a, as an example, curable silicone (solid content concentration 30%) is melt | dissolved in the mixed solvent of methyl ethyl ketone and toluene (MEK / toluene = 50/50 solution), and all Solution with a solids concentration of 3% is used.

At the time of manufacture of this peeling film 1, the peeling film manufacturing apparatus 11 shown in FIG. 3 is used, for example. This peeling film manufacturing apparatus 11 apply | coats the sending side rotating shaft 12 which sends out the base film 2, and the silicone resin apply | coating apparatus which apply | coats the coating liquid containing curable silicone resin 3a to the base film 2; (13), the dryer 14 which dries the apply | coated liquid, and the winding side rotating shaft 15 which wind the manufactured peeling film 1 in roll shape are provided. Moreover, the dancer which applies predetermined tension to the peeling film 1 comprised by the guide rolls 16a-16c and wound around the winding side rotating shaft 15 between the dryer 14 and the winding side rotating shaft 15. (16) is provided. In addition, in order to make understanding of this invention easy, the description and illustration of the detailed mechanism of the peeling film manufacturing apparatus 11 are abbreviate | omitted.

At the time of manufacture of the peeling film 1, the base film 2 is sent out and guided to the silicone resin coating device 13 by rotating the sending side rotating shaft 12 to the direction of arrow A1. At this time, in the silicone resin coating device 13, the coating liquid is one side of the base film 2 by a known coating method such as a reverse roll coating method, a gravure roll coating method, or an air knife coating method. It is applied to the cotton. Under the present circumstances, the thickness of the peeling layer 3 in the peeling film 1 after manufacture can be prescribed | regulated in the range of 0.05 micrometer or more and 1 micrometer or less by carrying out coating amount of a coating liquid in the range of 1 g / m <2> or more and 25 g / m <2> or less. have. In this case, when the thickness of the peeling layer 3 is less than 0.05 micrometer, the peeling performance of the peeling film 1 falls. On the contrary, when the thickness of the peeling layer 3 exceeds 1 micrometer, hardening of a coating film will become inadequate and peeling performance will change over time, and recessed parts H and H ... become easy to arise.

On the other hand, when many recesses H generate | occur | produce on the surface of the peeling layer 3, the slurry state ceramic 4a apply | coated to the peeling film 1 will splatter at the time of manufacture of the ceramic green sheet 4 mentioned later. . Specifically, the surface of the peeling layer 3 was observed at a magnification of about 1000 times by using a scanning electron microscope (SEM), and the inventors concave at least 5 μm in diameter per 0.1 mm 2 of the surface of the peeling layer 3. When more than 50 parts (H) exist, it is confirmed that the slurry ceramic 4a is easy to be fried. In addition, it is also confirming that it is hard to produce the recessed part H more than 30 micrometers in general. Therefore, when the number of generation | occurence | production of the recessed part H of 5 micrometers or more and less than 30 micrometers in diameter is 50 or less per 0.1 mm <2>, the crush of the slurry state ceramic 4a at the time of manufacture of the ceramic green sheet 4 can be prevented. . For this reason, it is preferable to define the application amount of a coating liquid in the range of 1.5 g / m <2> or more and 20 g / m <2> or less, and when prescribed | regulated in this range, the thickness of the peeling layer 3 in the peeling film 1 after manufacture. As a result that can be prescribed | regulated in the range of 0.1 micrometer or more and 0.5 micrometer or less, generation | occurrence | production of the recessed parts H and H ... can be suppressed largely, improving the peelability of the peeling film 1.

Next, the base film 2 to which the curable silicone resin 3a of condensation reaction hardening type or addition reaction hardening type was apply | coated is guided to the dryer 14, for example. At this time, the curable silicone resin 3a and the base film 2 are heat-processed by the dryer 14 for 5 second or more in 50-180 degreeC. As a result, the curable silicone resin 3a is dried and cured. At this time, the solvent evaporates and the thickness of the coating film shrinks to a fewths, whereby the release layer 3 is formed on the base film 2. Moreover, it is preferable to define heating temperature in the range of 80 degreeC-160 degreeC, and to continue heating for 10 second or more. As an example, it heats for 40 second at the temperature of 110 degreeC. Thereby, as a result of hardening of the peeling layer 3 almost completely, generation | occurrence | production of the recessed part H, H * at the time of the winding of a post process can be avoided more reliably.

Subsequently, the peeling film 1 is wound in roll shape by the winding side rotating shaft 15 rotated in the direction of arrow A2. Under the present circumstances, the peeling film 1 wound up is tensioned by the dancer 16 in the rotational direction of the winding side rotating shaft 15 and the reverse direction (the direction of arrow B). Specifically, the guide roll (tension roll) 16c is applied downward to the release film 1 (direction of arrow C) between the guide rolls 16a and 16b to the release film 1. Apply tension. In this case, a tension cut device (not shown) is provided between the dryer 14 and the guide roll 16a to prevent the force applied by the guide roll 16c from being applied to the dryer 14 side. . For this reason, by the force applied to the peeling film 1 by the guide roll 16c, the peeling film 1 is wound around the winding side rotating shaft 15 in the state which tension was applied to the direction of arrow B. FIG.

In this case, after winding, the unwinding of the release film 1 and the extension of the base film 2 are avoided, and the number of occurrences of the recesses H of 5 µm or more in diameter per 0.1 mm 2 of the surface of the release layer 3 is avoided. In order to suppress 50 or less, the tension applied to the peeling film 1 in the direction of the arrow B is prescribed | regulated as a tension weaker than the tension applied at the time of the winding process by a conventional method. For example, in the peeling film 1 (corresponding to the base film in which the peeling layer in this invention was formed) about 38 micrometers thick in this embodiment, 4N (Newton) or more and 28N or less per 100 mm in width, Preferably it is prescribed | regulated in the range of 10N or more and 28N or less. In addition, in the manufacture of this kind of release film, in general, the base film 2 whose thickness is 5 micrometers or more and 100 micrometers or less is used, In this invention, whether the thickness of the base film 2 is 30 micrometers or more is used. , The prescribed range of the tension is separately formed depending on whether it is less than 30 μm. This is common when the base film 2 in the range whose thickness is 5 micrometers or more and less than 30 micrometers produces the substantially same number of recessed parts H, respectively, when it winds by arbitrary equal tension in the predetermined range mentioned later. On the other hand, when the base film 2 in the range whose thickness is 30 micrometers or more and 100 micrometers or less is also wound by arbitrary equal tension in the predetermined range mentioned later, the recessed part H of about the same number is the same each, respectively. This is because they have a common property of occurring. Specifically, if the thickness of the base film 2 is in the range of 5 micrometers or more and less than 30 micrometers, it is prescribed | regulated in the range of 3N or more and 17N or less per 100 mm width of the peeling film 1, Preferably it is 7N or more and 17N or less. . On the other hand, if the thickness of the base film 2 exists in the range of 30 micrometers or more and 100 micrometers or less, it is prescribed | regulated in 4N or more and 28N or less per 100 mm width of the peeling film 1, Preferably it is 10N or more and 28N or less. By defining the tension in this manner, the force acting when the back surface of the base film 2 and the surface of the peeling layer 3 in the wound state can be suppressed within a predetermined range, and as a result, the concave portion H The number of occurrences can be greatly reduced. Moreover, even if the thickness of the base film 2 is less than 30 micrometers, it is preferable that 10 micrometers or more and less than 30 micrometers are easy to show the effect of this invention further. Moreover, it is more preferable that it is 15 micrometers or more and less than 30 micrometers from the point which further exhibits the effect of this invention. On the other hand, it is preferable that 30 micrometers or more and 50 micrometers or less are easy to show the effect of this invention further, even if the thickness of the base film 2 is 30 micrometers or more.

Moreover, when the thickness of the base film 2 is 5 micrometers or more and less than 30 micrometers, and the tension | tensile_strength applied to the peeling film 1 is less than 3 N per 100 mm width, and the thickness of the base film 2 is 30 micrometers or more and 100 micrometers. When the tension applied to the release film 1 is below 4N per 100 mm width, the release film 1 wound in a roll shape is loosely wound and unwinding occurs. Moreover, when the thickness of the base film 2 is 5 micrometers or more and less than 30 micrometers, and the tension applied to the peeling film 1 exceeds 17N per 100 mm width, and the thickness of the base film 2 is 30 micrometers or more and 100 micrometers or less When the tension applied to the release film 1 exceeds 28 N per 100 mm width, a large number of recesses H, H ... are likely to occur on the surface of the release layer 3. On the other hand, when the peeling film 1 is wound, it is preferable to prevent the partly strong tension from being applied by winding while always applying a constant tension during the winding start by the winding side rotating shaft 15 to the winding end. Moreover, as long as the amount of attenuation of the peeling film 1 in the winding side rotating shaft 15 becomes large as long as it is in the range of said tension, you may employ | adopt the taper tension damping system which makes the tension with respect to the peeling film 1 small. Also in this system, the unwinding of the peeling film 1 can be prevented, suppressing generation | occurrence | production of the recessed part H, H .... By the above process, as shown in FIG. 2, the peeling film 1 is wound in roll shape.

Thus, according to the manufacturing method of this peeling film 1, when winding up the peeling film 1, when the thickness of the base film 2 is 5 micrometers or more and less than 30 micrometers, the tension which acts on the peeling film 1 When the thickness of the base film 2 is 30 micrometers or more and 100 micrometers or less, and when the thickness of the base film 2 is 30 micrometers or more and 100 micrometers or less, the tension which acts on the peeling film 1 is 4 N or more and 28N or less per 100 mm width. By setting it in the range, the number of generation | occurrence | production of the recessed part H in the peeling layer 3 can be suppressed to 50 or less per 0.1 mm <2>, preventing the unwinding of the peeling film 1 wound by roll shape. Thereby, the thickness can be made uniform, avoiding generation | occurrence | production of the pinhole at the time of manufacture of the ceramic green sheet 4 mentioned later.

Next, the manufacturing method of the thin film for electronic components in this invention is demonstrated, taking the manufacturing method of the ceramic green sheet 4 used as a dielectric of a ceramic capacitor as an example.

First, powders of barium titanate, chromium oxide, yttrium oxide, manganese carbonate, barium carbonate, calcium carbonate and silicon oxide each having a particle diameter of about 0.1 µm to 1.0 µm are calcined. Next, 100 mol% of BaTiO ₃ was 0.3 mol% in terms of Cr ₂ O ₃ , 0.4 mol% in terms of MnO, 2.4 mol% in terms of BaO, 1.6 mol% in terms of CaO, and 1.6 mol% in terms of SiO ₂ . 4 in terms of mol%, Y ₂ O ₃ to be mixed so that a composition of 0.1 mol%. Subsequently, the mixed powder is stirred by a ball mill for about 24 hours, and then dried to prepare a dielectric material. Subsequently, 5 parts by weight of the acrylic resin, 40 parts by weight of methylene chloride, 25 parts by weight of acetone and 6 parts by weight of mineral spirit are added to 100 parts by weight of the dielectric material. Subsequently, a slurry ceramic 4a (dielectric paint) is produced by mixing the zirconia beads of ø10 mm for about 24 hours with a pot hanger.

Next, as shown in FIG. 4, on the peeling layer 3 of the peeling film 1 sent out from the roll-shaped peeling film 1, the slurry state ceramic (so that the application | coating thickness after drying may be set to 5 micrometers) 4a) is applied by a doctor blade application method. In this case, since the number of the recessed portions H of 5 micrometers or more in diameter generate | occur | producing in the peeling layer 3 of the peeling film 1 is 50 or less per 0.1 mm <2>, the apply | coated slurry state ceramic 4a does not splash and is uniform Is applied. Thereafter, the ceramic green sheet 4 is formed on the release film 1 by naturally drying the slurry state ceramic 4a at room temperature. Then, the ceramic green sheet 4 shown in FIG. 5 is manufactured by peeling the peeling film 1 from the ceramic green sheet 4. In addition, after the formation of the electrode with respect to the ceramic green sheet 4 is completed, the peeling film 1 is peeled and discarded from the back surface of the ceramic green sheet 4, for example. In this case, since the peeling layer 3 is formed in the surface of the peeling film 1, it can peel easily from the ceramic green sheet 4.

Thus, according to the manufacturing method of this ceramic green sheet 4, the number of generation | occurrence | production of the recessed parts H and H ... of 5 micrometers or more in diameter uses a 50 or less peeling film 1 per 0.1 mm <2> The thickness can be made uniform while preventing generation of pinholes during application of the state ceramic 4a. For this reason, the number of defective items can be reduced, and the manufacturing yield of the ceramic green sheet 4 can be improved by this. In addition, by using this ceramic green sheet 4, a highly reliable ceramic capacitor can be manufactured at high withstand voltage, and the production yield of the ceramic capacitor can also be improved.

Next, the relationship between the hardness of the peeling film wound in roll shape and the thin film (ceramic green sheet) manufactured using this peeling film is demonstrated.

As a result of earnestly examining about the peeling film which generate | occur | produces a problem, such as generation | occurrence | production of the pinhole at the time of manufacture of a thin film, and generation | occurrence | production of winding-up in a wound state, causal relationship between the hardness of a peeling film in a wound state and a problem occurrence Was found to exist. Specifically, when the hardness (hereinafter also referred to as "roll hardness") of the release film wound in a roll shape is set to 700 or more, in the step of applying a slurry state coating liquid (slurry state ceramic 4a) onto the release film. On the surface where the release layer of the release film sent out from the roll-like release film is not formed, the release layer partially transfers, and thus the slurry coating liquid splashes, causing pinholes or roughening in an orange peel. . On the other hand, when roll hardness is less than 460, unwinding arises in roll-shaped peeling film during storage, conveyance, and desorption to a reel for sending out. Therefore, the winding tension at the time of manufacture of a peeling film is adjusted suitably, and the roll hardness is prescribed | regulated to 460 or more and 700 or less, and generation | occurrence | production of the pinhole at the time of thin film manufacture, and generation | occurrence | production of winding-up in a wound state can be prevented.

In this case, about the measurement of roll hardness, in order to remove the influence of a winding core, it is preferable that the winding diameter in the surface of a winding core measures the surface layer of the peeling film of 50 mm or more in the radial direction side as a measurement object. In addition, when winding up in roll shape at the time of manufacture of a peeling film, especially a part of the silicone film (peeling layer 3) by which the peeling film was wound tightly near the winding core transfers to the surface which does not form the peeling layer of a peeling film. The phenomenon that it is easy is confirmed. In this case, the inventor adjusts the roll hardness in the 50 mm radial side layer (hereinafter this layer is also called "L layer") from the surface of the wound core to within the predetermined range as described above, so as to minimize the roll. It has been found that the transition of the peeling layer does not occur in all the peeling films that extend from the outer circumference (surface layer) to the surface of the wound core, so that a thin film for electronic component manufacturing without pinholes can be produced.

In addition, in order to maintain the roll hardness of a peeling film in the range of 460-700, the base film applies the winding tension (tension) which acts on a peeling film when winding to roll shape after apply | coating and drying the coating liquid containing silicone resin. It defines according to the thickness of a base film in the range of 3N or more and 28N or less per 100 mm in width. In this case, you may wind by a constant winding tension until it reaches L layer at least at the time of winding start. In addition, if the tension from the start of winding to the L layer is in the range of 3N or more and 28N or less, taper tension control for appropriately changing the tension from the start of winding to the end of winding (wound as the roll diameter increases). Lower or increase the tension). In addition, as a control method of winding tension, well-known methods, such as draw control, torque control, and dancer control, can be employ | adopted suitably.

Moreover, in order to maintain roll hardness in the range of 460 or more and 700 or less, hardening silicone resin is preferable as a peeling agent used for a peeling layer. The cured silicone resin coating film has a function of imparting peeling characteristics to the base film, and is formed by applying a coating liquid containing a curable silicone resin and then drying and curing. Although it does not specifically limit as curable silicone resin, For example, any of condensation reaction type, an addition reaction type, an ultraviolet curing type, an electron beam curing type, etc. can be used. In this case, as a method of apply | coating curable silicone resin, well-known coating methods, such as a reverse roll coating method, the gravure roll coating method, and the air knife coating method, can be employ | adopted. In addition, about apply | coated curable silicone resin coating material, it heats and hardens by heat processing, for example, and forms a cured film. In this case, as heating temperature, it is preferable to perform heat processing for 5 second or more, Preferably it is 10 second or more within the range of 50 degreeC-180 degreeC, Preferably it is 80 degreeC-160 degreeC. Moreover, as application amount of curable silicone resin, the inside of the range of 1 g / m <2> or more and 25 g / m <2> or less, Furthermore, the range of 1.5 g / m <2> or more and 20 g / m <2> or less is preferable, and the thickness of the silicone resin coating film after hardening by this, It becomes an ideal thickness in the range of 0.05 micrometer or more and 1 micrometer or less, Furthermore, in the range of 0.1 micrometer or more and 0.5 micrometer or less. In this case, peeling performance tends to fall in the state after the heat processing is less than 0.05 micrometer, and curing of a coating film tends to become inadequate in the state exceeding 1 micrometer, and the change of peeling performance with time and the roll hardness change Will result. Therefore, by manufacturing a peeling film according to the manufacturing method of the above-mentioned peeling film 1, the hardness of the L layer in the rolled state is made into the range of 460 or more and 700 or less, generation | occurrence | production of the pinhole at the time of thin film manufacture, The occurrence of unwinding in the wound state can be prevented.

(Example)

Next, the peeling film for thin film manufacture and the thin film for electronic components in this invention are demonstrated in detail with an Example, referring drawings.

The characteristics about each release film of Examples 1 to 16 and Comparative Examples 1 to 6 shown in FIG. 6 were measured by the following method.

1. Number of occurrences of recesses H on the surface of the release layer (curable silicone resin)

 Surface observation was carried out using a scanning electron microscope (SEM).

in this case,

Acceleration Voltage: 5.0KV

WD: 16mm

Shooting magnification: 1000 times

TILT: 45 °

The film was photographed at an arbitrary position on the surface of the release layer, and the number of recesses H of 5 µm or more and less than 30 µm in diameter per 0.1 mm 2 was counted.

2. Hardness of release film in roll

The hardness of the peeling film wound in the roll shape is PROCEQ. It measured using the Palotester 2 made from S. A. company. In this case, 5 points | pieces were measured in the width direction of the peeling film in the layer of the 50 mm radial direction from the surface of the winding core, and the average value was calculated | required.

3. The presence of pinhole in thin film (dielectric ceramic, ceramic green sheet)

The dielectric paint produced under the conditions described below is applied to the release layer in the release film by a doctor blade method so that the coating film thickness after drying is 5 μm, and the release film in this state is brought close to a light source such as a fluorescent lamp, It was confirmed visually whether there existed occurrence and whether the application surface was rough like a tangerine peel. The result of this confirmation is shown in FIG. 6 with the thing that is not rough like a pinhole or a tangerine peel as (circle) and a thing rough as a pinhole or a tangerine peel.

4. The presence or absence of stage shift | deviation (unwinding) with respect to the peeling film wound up in roll shape (henceforth "roll").

About the roll wound, the vibration test based on the test method determined by JIS-Z-200 is performed.

in this case,

Direction of vibration: Z axis

Duration of vibration: 20 minutes

Frequency: 5 to 100 Hz (starting at 5 Hz)

Acceleration: 0.75 (GRMS)

Sweep method: logarithmic sweep, one way 10 minutes (0.432 octaves / minute)

This test result indicates that the occurrence of the misalignment is not confirmed, but the occurrence of the misalignment is confirmed. However, if the misalignment amount is within 1 cm and there is no problem in practical use, 6 is shown.

(Example 1)

<Silicone resin solution (coating liquid containing curable silicone resin 3a)>

Methylated curable silicone (KS-847 (H)) manufactured by adding a platinum catalyst to a mixture of a polydimethylsiloxane having a vinyl group and a dimethylhydrogensilane (hydrogensilane-based compound) to be added and reacted. The solution was dissolved in a mixed solvent of ethyl ketone and toluene to prepare a solution having a total solid concentration of 3.0% by weight.

Shin-Sung Chemical Co., Ltd. KS-847H 300g

(30% solids concentration, 90g resin)

Platinum Catalyst CAT-PL-50T (manufactured by Shinko Chemical Co., Ltd.) 3.0g

MEK / toluene = 50/50 (weight ratio) solution 2700 g

<Dielectric ceramic paint (slurry state ceramic 4a)>

After a particle diameter of 0.1㎛ to 1.0㎛ degree of sintering the barium titanate, chromium oxide, yttrium oxide, manganese carbonate, barium carbonate, powder of calcium carbonate, silicon oxide, BaTiO ₃ 100% by mole, a Cr ₂ O ₃ 0.3 mol% in terms of conversion, 0.4 mol% in terms of MnO, 2.4 mol% in terms of BaO, 1.6 mol% in terms of CaO, 4 mol% in terms of SiO ₂ , 0.1 mol% in terms of Y ₂ O ₃ The mixture was mixed to obtain a composition, mixed for 24 hours by a ball mill, and a dielectric material was obtained after drying. 100 parts by weight of this dielectric material, 5 parts by weight of acrylic resin, 40 parts by weight of methylene chloride, 25 parts by weight of acetone, and 6 parts by weight of mineral spirit were mixed and mixed for 24 hours by pot galling using commercially available ø10 mm zirconia beads. To obtain a dielectric ceramic paint.

The silicone resin solution was applied to a biaxially stretched polyethylene terephthalate (PET) film having a width of 100 mm and a thickness of 25 μm with a bar coater so that the coating film thickness after drying was 0.1 μm, and then dried and cured at a heating temperature of 110 ° C. for 40 seconds. The peeling film wound up in roll shape by making it react was produced (length 3000m). At this time, it wound and hold | maintained by the winding tension (tension which acts on a peeling film at the time of winding) of 3N. The dielectric ceramic coating material was apply | coated to this peeling film by the doctor blade application | coating system so that the coating film thickness after drying might be set to 5 micrometers.

(Example 2)

When winding up in roll shape, the winding tension which acts on a peeling film was 7N, and the manufacturing conditions other than that were the same as Example 1, and the peeling film was produced.

(Example 3)

When winding up in roll shape, the winding tension which acts on a peeling film was made into 10N, and the production conditions other than that were made like Example 1, and the peeling film was produced.

(Example 4)

When winding up in roll shape, the winding tension which acts on a peeling film was made into 15N, and the production conditions other than that were made similar to Example 1, and the peeling film was produced.

(Example 5)

When winding up in roll shape, the winding tension which acts on a peeling film was 17N, and the production conditions other than that were the same as Example 1, and the peeling film was produced.

(Comparative Example 1)

The winding tension which acts on a peeling film at the time of winding in roll shape was made into 2.8N, and the production conditions other than that were the same as Example 1, and the peeling film was produced.

(Comparative Example 2)

When winding up in roll shape, the winding tension which acts on a peeling film was made into 18N, and the production conditions other than that were the same as Example 1, and the peeling film was produced.

(Example 6)

While using the base film of width 100mm and thickness of 38 micrometers, the winding tension acting on a peeling film was 4N when winding to roll shape, and the other production conditions were made the same as Example 1, and the peeling film was produced. .

(Example 7)

While using a base film having a width of 100 mm and a thickness of 38 μm, the winding tension acting on the release film when wound into a roll shape was 10 N, and the other production conditions were the same as those in Example 1, thereby producing a release film. .

(Example 8)

While using a base film having a width of 100 mm and a thickness of 38 µm, the winding tension acting on the release film was 15N when winding in a roll shape, and other production conditions were made in the same manner as in Example 1 to prepare a release film. .

(Example 9)

While using the base film of width 100mm and thickness of 38 micrometers, the winding tension which acts on a peeling film at the time of winding in roll shape was 17N, and the other production conditions were made similar to Example 1, and the peeling film was produced. .

(Example 10)

While using a Jays film having a width of 100 mm and a thickness of 38 µm, the winding tension acting on the release film when the roll was wound was set to 20 N, and the production conditions other than that were the same as in Example 1 to produce a release film. .

(Example 11)

While using the base film of width 100mm and thickness of 38 micrometers, the winding tension acting on a peeling film was 28N when winding to roll shape, and the other production conditions were made the same as Example 1, and the peeling film was produced. .

(Comparative Example 3)

While using a base film having a width of 100 mm and a thickness of 38 µm, the winding tension acting on the release film when winding in a roll shape was 3.8 N, and other production conditions were the same as in Example 1 to produce a release film. did.

(Comparative Example 4)

While using a base film having a width of 100 mm and a thickness of 38 µm, the winding tension acting on the release film was 31N when wound in a roll shape, and the other production conditions were the same as in Example 1 to produce a release film. .

(Example 12)

While using a base film having a width of 100 mm and a thickness of 50 µm, the winding tension acting on the release film was 4N when wound in a roll shape, and the other production conditions were the same as in Example 1 to prepare a release film. .

(Example 13)

While using a base film having a width of 100 mm and a thickness of 50 µm, the winding tension acting on the release film when wound into a roll shape was 10 N, and the production conditions other than that were the same as in Example 1 to produce a release film. .

(Example 14)

While using a base film having a width of 100 mm and a thickness of 50 µm, the winding tension acting on the release film was 14N when wound in a roll shape, and the other production conditions were the same as in Example 1 to prepare a release film. .

(Example 15)

While using a base film having a width of 100 mm and a thickness of 50 µm, the winding tension acting on the release film was 20 N when winding in a roll shape, and other production conditions were made in the same manner as in Example 1 to produce a release film. .

(Example 16)

While using a base film having a width of 100 mm and a thickness of 50 µm, the winding tension acting on the release film was 28N when wound in a roll shape, and other production conditions were made in the same manner as in Example 1 to produce a release film. .

(Comparative Example 5)

While using a base film having a width of 100 mm and a thickness of 50 µm, the winding tension acting on the release film when winding in a roll shape was 3.8 N, and other production conditions were the same as in Example 1 to produce a release film. did.

(Comparative Example 6)

While using a base film having a width of 100 nm and a thickness of 50 µm, the winding tension acting on the release film was 30N when winding in a roll shape, and other production conditions were made in the same manner as in Example 1 to produce a release film. .

In Examples 1 to 5 and Comparative Examples 1 and 2 (the thickness of the base film is 25 μm), as shown in FIG. 6, the winding tension acting on the release film when the roll was wound was set to 17 N or less. In that case, the roll hardness will be in the range of 460 or more and 700 or less, and in this state, a pinhole does not generate | occur | produce in the thin film produced using this peeling film. On the other hand, when the winding tension was 18 N (Comparative Example 2), the roll hardness was 705, and pinholes were generated in the thin film produced using this release film. Moreover, when winding tension was set to 2.8N (comparative example 1), the roll hardness becomes 456, and the stage shift | offset | difference (unwinding) of the peeling film wound to roll shape generate | occur | produces, and when winding tension is made into 3N or more However, the occurrence of misalignment could be prevented. Therefore, when the thickness of a base film is less than 30 micrometers, especially about 25 micrometers, by defining the winding tension which acts on a peeling film in the range of 3N or more and 17N or less, roll hardness may be in the range of 460 or more and 700 or less, While avoiding the occurrence of pinholes, a release film can be produced in which unwinding does not occur.

On the other hand, in Examples 6 to 11 and Comparative Examples 3 and 4 (thickness of the base film is 38 µm), the roll hardness is 460 when the winding tension acting on the release film is 28N or less when wound into a roll shape. It is in the range of 700 or more and in this state, a pinhole does not generate | occur | produce in the thin film produced using this peeling film. On the other hand, when the winding tension was 31 N (Comparative Example 4), the roll hardness was 710, and pinholes were generated in the thin film produced using this release film. Moreover, when winding tension was set to 3.8N (comparative example 3), when the roll hardness becomes 450 and the stage shift | offset | difference (unwinding) of the peeling film wound in roll shape arises, when winding tension is made into 4N or more However, the occurrence of misalignment could be prevented. Therefore, when the thickness of a base film is 30 micrometers or more, especially about 38 micrometers, the winding tension which acts on a peeling film is prescribed | regulated in the range of 4 N or more and 28 N or less, and roll hardness is in the range of 460 or more and 700 or less, and the pin in a thin film While avoiding generation of holes, a release film can be produced in which unwinding does not occur.

In addition, in Examples 12 to 16 and Comparative Examples 5 and 6 (the thickness of the base film is 50 µm), the thickness of the base film is almost the same as those of Examples 6 to 11 and Comparative Examples 3 and 4, which are 38 µm. Result. Specifically, when the winding tension acting on the release film to be 28 N or less when winding in a roll shape, the roll hardness is in the range of 460 or more and 700 or less, and in this state, the thin film produced using this release film Pinholes do not occur. On the other hand, when the winding tension was set to 30N (Comparative Example 6), the roll hardness was 710, and pinholes were generated in the thin film produced using this release film. Moreover, when winding tension was set to 3.8N (comparative example 5), when the roll hardness became 410 and the stage shift | deviation (unwinding) of the peeling film wound to roll shape generate | occur | produced, when winding tension was made into 4N or more However, the occurrence of misalignment can be prevented. Therefore, when the thickness of a base film is about 50 micrometers, it is the same as that when the thickness of a base film is about 38 micrometers, and by defining the winding tension acting on a peeling film in the range of 4N or more and 28N or less, roll hardness is 460 or more and 700. Within the following range, the peeling film which does not produce winding | winding can be manufactured, avoiding generation | occurrence | production of the pinhole in a thin film.

In addition, this invention is not limited to embodiment of said invention, It can change suitably. For example, in embodiment of this invention, although the example which used as the base film 2 the polyester film which biaxially stretched the crystalline linear saturated polyester which consists of an aromatic dibasic acid component and a diol component was demonstrated, The base film in this invention is not limited to this. In this case, when it is a light-blocking request to the base film (2), it is preferred to use a twin-screw compounding an inorganic pigment such as TiO ₂ or SiO ₂ stretched polyester film. In addition, although embodiment of this invention demonstrated the example which tensions the peeling film 1 by the dancer control system by the dancer 16, this invention is not limited to this, Draw control, torque control, etc. were demonstrated. The tension can be applied by a known control method. In addition, in embodiment of this invention, although the peeling film 1 which provided the peeling layer 3 in one side of the base film 2 was mentioned and demonstrated as an example, this invention is not limited to this, The base film 2 The peeling layer 3 may be formed in the front and back both surfaces. It is also possible to form an adhesive layer between the base film 2 and the release layer 3. In such a case, when the ceramic green sheet 4 and the release film 1 are separated, the peeling of the release layer 3 from the base film 2 can be more reliably avoided.

As mentioned above, according to the manufacturing method of the peeling film for thin film manufacture which concerns on this invention, when the thickness of a base film is 5 micrometers or more and less than 30 micrometers, the range of 3 newtons or more and 17 newtons per 100 mm width of the base film with a peeling layer was formed. By winding the base film while applying the tension inside, the force acting when the back surface of the base film and the surface of the release layer in the wound state adhere to the surface can be suppressed within a predetermined range, and as a result, the number of occurrences of the concave portion can be greatly reduced. have. Therefore, while the flatness of a peeling layer is ensured, peeling property is good and the manufacturing method of the peeling film for thin film manufacture which can prevent unwinding and elongation of a base film in a wound state is implement | achieved. Moreover, by using the release film for thin film manufacture manufactured by this manufacturing method, a pinhole does not arise and the thin film for electronic components of uniform thickness is implement | achieved.

Moreover, according to the manufacturing method of the peeling film for thin film manufacture which concerns on this invention, when the thickness of a base film is 30 micrometers or more and 100 micrometers or less, it is in the range of 4 newtons or more and 28 newtons or less per 100 mm width of the base film with a peeling layer formed. By winding the base film while applying tension, the force acting when the back surface of the base film and the surface of the release layer in the wound state adhere to the surface can be suppressed within a predetermined range, and as a result, the number of occurrences of the recesses can be reduced. . Therefore, while the flatness of a peeling layer is ensured, peeling property is good and the manufacturing method of the peeling film for thin film manufacture which can prevent unwinding and elongation of a base film in a wound state is implement | achieved. Moreover, by using the release film for thin film manufacture manufactured by this manufacturing method, a pinhole does not arise and the thin film for electronic components of uniform thickness is implement | achieved.

Moreover, according to the manufacturing method of the thin film for electronic components which concerns on this invention, when the thickness of a base film is 5 micrometers or more and less than 30 micrometers, it winds, applying the tension in the range of 3 newtons or more and 17 newtons per 100mm width of a base film. When the thickness of a base film is 30 micrometers or more and 100 micrometers or less, by using the peeling film for thin film manufacture wound, applying the tension in the range of 4 newtons or more and 28 newtons per 100 mm of width of a base film, it always makes thickness without generating a pinhole. The manufacturing method of the thin film for electronic components which is uniform is realized.

Moreover, according to the peeling film for thin film manufacture which concerns on this invention, a base film is roll-shaped so that the hardness with respect to the radial direction from the surface of a winding core to the winding core side in the layer of a 50 mm radial direction side may exist in the range of 460 or more and 700 or less. As a result, the force acting when the back surface of the roll-shaped base film and the surface of the peeling layer adhere to the surface can be suppressed within a predetermined range, thereby reducing the number of occurrences of the recesses, and at the same time, the flatness of the peeling layer. The peeling film for thin film manufacture which peels well and does not generate | occur | produce unwinding is implement | achieving, ensuring the is ensured. Moreover, by using this release film for thin film manufacture, the thin film for electronic components which does not generate | occur | produce a pinhole and is always uniform is realized.

Claims (4)

After apply | coating the coating liquid containing a silicone resin to a base film, the said coating liquid is dried, the peeling layer by the said silicone resin is formed on the said base film, and the base film in which the said peeling layer was formed was roll-shaped, and the In the manufacturing method which manufactures the release film for thin film manufacture for components, Preparation of the peeling film for thin film manufacture which winds the said base film, applying the tension in the range of 3 newtons or more and 17 newtons per 100 mm of width of the base film in which the said peeling layer was formed, when the thickness of the said base film is 5 micrometers or more and less than 30 micrometers. Way. After apply | coating the coating liquid containing a silicone resin to a base film, the said coating liquid is dried, the peeling layer by the said silicone resin is formed on the said base film, and the base film in which the said peeling layer was formed was roll-shaped, and the In the manufacturing method which manufactures the release film for thin film manufacture for components, When the thickness of the base film is 30 µm or more and 100 µm or less, production of a release film for thin film production in which the base film is wound while applying a tension within a range of 4 Newtons to 28 Newtons per 100 mm in width of the base film on which the release layer is formed. Way. After apply | coating a slurry coating liquid to the peeling film for thin film manufacture for electronic components manufactured by the manufacturing method of the peeling film for thin film manufacture of Claim 1 or Claim 2, after drying the said slurry state coating liquid, The manufacturing method of the thin film for electronic components which forms a thin film for electronic components on a peeling film. In the peeling film for thin film manufacture for electronic components whose base film in which the peeling layer by a silicone resin was formed in at least one surface was wound in roll shape, and the diameter from the surface of the wound core to a surface layer is 50 mm or more, The peeling film for thin film manufacture whose hardness with respect to the said radial direction toward the said winding core side in the 50 mm radial side layer from the surface of the said winding core exists in the range of 460 or more and 700 or less.