JP3856543B2 - Exfoliation film for green sheet molding - Google Patents

Description

【００３５】
上記の表１の結果から明らかなように、本発明の実施例１，２のグリ―ンシ―ト成形用剥離処理フイルムは、剥離処理面の接着力が５００ｇ／５０mm幅以下と小さく、適度な剥離性を備えており、しかもスラリ―状セラミツク組成物の濡れ性が良好で、はじきなどを生じず、そのうえグリ―ンシ―トの剥離時に剥離処理剤の転着がほとんどみられないものであることがわかる。
【００３６】
【発明の効果】
以上のように、本発明は、長鎖アルキル基を有する化合物をベ―スとして、これにセルロ―スエステル系樹脂および特定の凝集力付与樹脂を特定量配合したことにより、グリ―ンシ―トの剥離性にすぐれてこのシ―トの変形や切れなどの問題を回避でき、かつ剥離後のグリ―ンシ―トの表面にピンホ―ルの発生などの不都合を生じず、また上記シ―ト表面への剥離処理剤の転着がほとんどみられず、上記シ―トの剥離後に繰り返し使用が可能である実用性にすぐれるグリ―ンシ―ト成形用剥離処理フイルムを提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a release treatment film for green sheet molding, in which a long-chain alkyl release agent is provided on a base film.
[0002]
[Prior art]
The green sheet is a sheet-like material containing ceramic powder before it is made into a ceramic by heating and firing. This green sheet is subjected to various processes, and is then subjected to ceramic capacitors, ceramic filters, and resonators. Processed into products such as filter, LC filter, isolator, ceramic package.
[0003]
Such green sheets are usually made of polyethylene terephthalate film, polypropylene film or the like as a molding film, and a slurry containing ceramic powder, plasticizer, binder, solvent, etc. on one or both sides of the molding film. It is manufactured by applying a ceramic composition, drying it by heating, etc., and then peeling it from the molding film.
[0004]
In the production of this green sheet, if the peeling force of the green sheet with respect to the forming film is too great, there is a problem that the green sheet is deformed or cut off. Therefore, usually, a release treatment agent is applied in advance to the surface of the forming film so as to reduce the peeling force.
[0005]
Such release treatment agents include silicone, long-chain alkyl, and fluorine resin. Silicone is a high-temperature heating process for making green sheets into ceramics. Si does not evaporate and remains in the ceramic product, which tends to adversely affect the quality of the ceramic capacitor. For this reason, non-silicone release treatment agents such as long chain alkyl and fluorine resin are more suitable.
[0006]
However, according to such a release treatment agent, although the release force can be appropriately suppressed and problems such as deformation and breakage of the green sheet can be avoided, the wettability of the slurry-like ceramic composition with respect to the release treatment agent. As a result, there were inconveniences such as pinholes formed on the surface of the green sheet after peeling.
[0007]
On the other hand, the inventors of the present invention have excellent peelability of a green sheet when a long-chain alkyl-based release treatment agent is used as a base and a cellulose ester resin is added thereto. -It can avoid problems such as deformation and cutting of the sheet, and can improve the wettability of the slurry-like ceramic composition and avoid inconveniences such as pinholes on the surface of the green sheet after peeling. I knew.
[0008]
[Problems to be solved by the invention]
However, the long-chain alkyl release treatment compounded with the above cellulose ester resin is inferior in cohesion and anchorage to the base film, and the green sheet is peel-molded from the release treatment film provided with this. In this case, there arises a problem that a part of the release treatment agent is transferred to the green sheet side.
[0009]
The release treatment agent transferred in this way is completely decomposed and evaporated when the molded green sheet is finally fired and sintered at a temperature of a few hundreds of hundred degrees. There is no adverse effect. However, due to the above transfer, the peelability of the release treatment film is lowered, so that it is difficult to repeatedly use this release treatment film for forming a green sheet.
[0010]
In light of such circumstances, the present invention has excellent green sheet peelability and can avoid problems such as deformation and breakage of the sheet, and the occurrence of pinholes on the surface of the sheet. In addition, the release treatment film for green sheet molding can be used repeatedly after the above sheet is peeled off. The purpose is to provide.
[0011]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above-mentioned object, the present inventors have further added a specific resin component to a long-chain alkyl-based release treatment compounded with a cellulose ester-based resin. A green sheet that has excellent sheet releasability, can avoid inconveniences such as the occurrence of pinholes on the sheet surface, and is less likely to cause transfer of the release treatment agent to the sheet surface. Knowing that a film-forming release treatment film can be obtained, the present invention has been completed.
[0012]
That is, the present invention provides a cohesive force imparting resin 30 that contributes to the improvement of anchoring properties for 100 parts by weight of a compound having a long-chain alkyl group, 30 to 300 parts by weight of a cellulose ester resin and the base film on the base film. The present invention relates to a release treatment film for forming a green sheet (Claim 1) provided with a release treatment agent containing ˜300 parts by weight, and in particular, the cohesive force imparting resin is the same as the material of the base film. Alternatively, it is possible to provide a green sheet-molding release treatment film (claim 2) made of a similar resin and having the above structure. The present invention also relates to a green sheet molding release treatment film (Claim 3) in which the release treatment agent having the above-described configuration is provided on one side of a base film and an adhesive is provided on the other side. .
[0013]
DETAILED DESCRIPTION OF THE INVENTION
As the compound having a long-chain alkyl group in the present invention, any compound known as a long-chain alkyl-based release treatment agent can be used. Specifically, a higher fatty acid (12 to 12 carbon atoms) of polyvinyl alcohol. 24) Reaction product, higher alkyl (carbon number 12-24) isocyanate reaction product of polyvinyl alcohol, higher alkyl (carbon number 12-24) isocyanate reaction product of polyethyleneimine, higher alkyl (carbon number 12) ~ 24) (meth) acrylate homopolymer, or higher alkyl (12-24 carbon atoms) (meth) acrylate and acrylonitrile, (meth) acrylic acid, (meth) acrylic acid alkyl ester, etc. Mention may be made of copolymers with monomers.
[0014]
The cellulose ester resin in the present invention includes cellulose acetate resin, butyric acid cellulose resin, acetic acid butyric acid cellulose resin, acetic acid propionic acid cellulose resin, and nitric acid cellulose resin. These cellulose ester resins are used in a proportion of 30 to 300 parts by weight, preferably 50 to 200 parts by weight, per 100 parts by weight of the compound having a long-chain alkyl group. When the amount is less than 30 parts by weight, a problem occurs in the wettability of the slurry-like ceramic composition, and pinholes and the like are likely to be generated on the surface of the green sheet after peeling. On the other hand, if the amount exceeds 300 parts by weight, the original effect of the release treatment agent is impaired, and the peeling force becomes large, so that problems such as deformation and breakage of the green sheet are likely to occur during the peeling operation.
[0015]
In the present invention, the cohesive force imparting resin imparts cohesive force to the release treatment agent and contributes to the improvement of anchoring property to the base film, and is usually a resin having excellent affinity for the base film. A resin component that is the same as or similar to the material of the film is selectively used. For example, when the base film is a polyethylene terephthalate film, a polyester resin is preferably used. When the base film is a polyolefin film or a polyvinyl chloride film, a polyolefin resin or a chlorinated polyolefin resin is preferably used.
[0016]
The amount of the cohesive force imparting resin used is 30 to 300 parts by weight, preferably 50 to 200 parts by weight, per 100 parts by weight of the compound having a long-chain alkyl group. If the amount is less than 30 parts by weight, sufficient cohesive force and sufficient anchoring property for the substrate film cannot be obtained. On the other hand, if the amount exceeds 300 parts by weight, the original effect of the release treatment agent is impaired, the release force becomes large, and problems such as deformation and breakage of the green sheet are likely to occur during the release operation.
[0017]
In the present invention, the cellulose ester-based resin and the cohesive strength-imparting resin are blended with the compound having the long-chain alkyl group at the above ratio, and this is diluted with an appropriate solvent such as toluene or ethyl acetate. A release treatment agent is used. Various additives may be added to the release treatment agent as long as the effects of the present invention are not impaired.
[0018]
The release film for green sheet molding of the present invention comprises a general plastic film such as a polyethylene terephthalate film or a polypropylene film, an engineering plastic film, a paper base material, a composite film, a laminate film, etc. A base film having a thickness of about 6 μm to 5 mm is usually used, and the above-mentioned release treatment agent is applied on the base film so that the thickness after drying becomes 0.01 to 5 μm, and dried. It is.
[0019]
Here, the release treatment agent may be provided on one side of the base film or on both sides. Moreover, when providing in one side, the adhesive of thickness 1-100 micrometers can be provided in the other side. The peel-off film provided with an adhesive is applied to the surface of the release-processed surface after the release-processed film is applied to a hard substrate using the adhesive force of the adhesive when forming the green sheet. It is only necessary to apply a ceramic composition, thereby obtaining good results in molding workability.
[0020]
The above adhesives include rubber adhesives based on natural rubber and various synthetic rubbers, acrylic adhesives based on acrylic polymers, and styrene-conjugated diene block copolymer adhesives. In addition, an ultraviolet curable adhesive may be used. Moreover, these adhesives may contain various additives, such as a crosslinking agent, a plasticizer, a filler, anti-aging agent, tackifier, and a pigment.
[0021]
The above acrylic polymers are methyl, ethyl, propyl, butyl, 2-ethylhexyl, isooctyl, isononyl, isodecyl, dodecyl, lauryl, tridecyl, pentadecyl, hexadecyl, heptadecyl. (Meth) acrylic acid alkyl ester having an alkyl group having usually 20 or less carbon atoms such as a group, octadecyl group, nonadecyl group, eicosyl group, etc. as a main monomer, and (meth) acrylic acid, itaconic acid, (meta ) Hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, (meth) acrylonitrile, glycidyl (meth) acrylate, vinyl acetate, styrene, isoprene, butadiene, isobutylene, vinyl ether Etc. monomer added Are those obtained by polymerizing a conventional manner.
[0022]
In the present invention, the green sheet is formed by a conventional method using the green sheet forming release film having the above-described structure. At that time, the slurry-like ceramic composition to be used is obtained by uniformly mixing various ceramic powders with an appropriate plasticizer, binder, solvent, etc., and conventionally known ones can be widely used. . Whichever slurry is used, good peelability can be obtained after heat drying, and there is no risk of pinholes being generated on the surface of the green sheet after peeling. Almost no transfer occurs.
[0023]
For this reason, the green sheet molded using the release film of the present invention is processed into products such as ceramic capacitors, ceramic filters, resonators, LC filters, isolators, ceramic packages, etc. Therefore, it can be widely used as a ceramic intermediate. Further, the peel-treated film after peeling the green sheet can be repeatedly used for forming the green sheet.
[0024]
【Example】
Next, examples of the present invention will be described in more detail. Hereinafter, “parts” means parts by weight.
[0025]
Example 1
A copolymer was obtained by copolymerizing 100 parts of higher alkyl (18 carbon atoms) methacrylate and 75 parts of acrylonitrile. As a compound having a long-chain alkyl group, this copolymer is blended with 100 parts of this compound, 100 parts of cellulose acetate butyrate cellulose resin and 100 parts of polyester resin, diluted with a mixed solvent of toluene and ethyl acetate, A release treatment agent was obtained. A polyethylene terephthalate film having a thickness of 25 μm was used as a base film, and the release agent was applied to one side of the film so that the thickness after drying was 0.1 μm and dried.
[0026]
Next, 5 parts of an isocyanate-based cross-linking agent was blended with 100 parts of a butyl acrylate / acrylic acid / acrylonitrile (weight ratio: 100/3/20) copolymer (weight average molecular weight: 900,000), and toluene was added. Diluted to prepare an adhesive solution. This adhesive solution is applied to the other side of the base film that has been coated with a release treatment agent on one side and dried to a thickness of 30 μm, and dried to form a green sheet. A release film was prepared.
[0027]
Example 2
As a compound having a long-chain alkyl group, a reaction product of polyvinyl alcohol and octadecyl isocyanate having a weight ratio of 1/5 was used. To 100 parts of this compound, 80 parts of cellulose acetate resin and 80% of polyester resin were used. Part was blended and diluted with a mixed solvent of toluene and ethyl acetate to prepare a release treatment agent. A release sheet film for green sheet molding was produced in the same manner as in Example 1 except that this release agent was used.
[0028]
Comparative Example 1
A compound having a long-chain alkyl group was not blended with cellulose acetate resin or polyester resin, and only the above compound was diluted with a mixed solvent of toluene and ethyl acetate to prepare a release treatment agent. A release sheet film for green sheet molding was produced in the same manner as in Example 1 except that this release agent was used.
[0029]
Comparative Example 2
Only 100 parts of cellulose acetate butyrate was blended with 100 parts of the compound having a long-chain alkyl group, and this was diluted with a mixed solvent of toluene and ethyl acetate to obtain a release treatment agent. A release sheet film for green sheet molding was produced in the same manner as in Example 1 except that this release agent was used.
[0030]
For each of the green sheet molding release treatment films of Examples 1 and 2 and Comparative Examples 1 and 2, the adhesive strength of the release treatment surface and the wettability of the slurry-like ceramic composition to the release treatment surface, Furthermore, the non-transferability of the release treatment agent was examined by the following test method. These results were as shown in Table 1 below.
[0031]
<Adhesion test of peeled surface>
Using a polyester adhesive tape [“No. 31B” manufactured by Nitto Denko Corporation], this was bonded to the release treatment surface of the release treatment film for green sheet molding, and in accordance with JIS-C2339. Then, peel adhesion (g / 50 mm width) was measured by a 180 ° peel method.
[0032]
<Wettability test of slurry-like ceramic composition on release surface>
As the slurry-like ceramic composition, a composition prepared to a concentration of 60% by weight using a mixture of barium titanate and methyl cellulose in a weight ratio of 7/3 and butyl cellosolve as a solvent was used. This slurry-like ceramic composition was applied to the release-treated surface of the release-treated film for green sheet molding so that the thickness after drying was 5 μm and dried. At that time, the wet state of the composition was visually observed and evaluated as ○: no repelling and x: repelling.
[0033]
<Non-transferability test of release agent>
In accordance with the wettability test described above, the ceramic composition was applied to the release treated surface and dried, and then peeled off. The peel-treated surface after peeling was subjected to the same adhesion test as described above. When this adhesive strength is increased by 20% or more compared to the original adhesive strength, transfer of the release treatment agent is considerably recognized (x), and when it is less than 20%, the above transfer is almost recognized. No (○).
[0034]

[0035]
As is apparent from the results in Table 1 above, the green sheet-molding release treatment films of Examples 1 and 2 of the present invention have a small adhesive strength of the release treatment surface of 500 g / 50 mm width or less, It has releasability, and the slurry-like ceramic composition has good wettability, does not cause repellency, and the transfer agent is hardly transferred when the green sheet is peeled off. I understand that.
[0036]
【The invention's effect】
As described above, the present invention uses a compound having a long-chain alkyl group as a base, and a cellulose ester-based resin and a specific cohesive force-imparting resin are blended in a specific amount thereof, whereby a green sheet is obtained. This sheet is excellent in peelability and can avoid problems such as deformation and breakage of the sheet, and there is no inconvenience such as pinhole formation on the surface of the green sheet after peeling. Thus, it is possible to provide a release treatment film for forming a green sheet which is excellent in practicality and can be repeatedly used after the release of the sheet.

Claims (3)

Contains 100 parts by weight of a compound having a long-chain alkyl group, 30 to 300 parts by weight of a cellulose ester resin, and 30 to 300 parts by weight of a cohesive force imparting resin that contributes to an improvement in anchoring property to the base film on the base film. A release film for forming a green sheet, which is provided with a release treatment agent. 2. The release film for green sheet molding according to claim 1, wherein the cohesive force imparting resin that contributes to the improvement of anchoring property for the base film is made of the same or similar resin as the material of the base film. 3. The release film for green sheet molding according to claim 1 or 2, wherein a release agent is provided on one side of the substrate film and an adhesive is provided on the other side.