TW567127B - Release film with ceramic sheet - Google Patents

Abstract

The present invention relates to a method of manufacturing release film with thin ceramic sheet which has a release layer having curing silicone resin as major constituent component on at least one side of the polyester substrate film and formed by laminating a ceramic sheet layer on the surface of the release layer of said release layer film characterized in that the absolute value of the difference between dynamic hardness A of the surface of said ceramic sheet layer and dynamic hardness B of the surface of said release layer is less than 20 gf/mum<2>, and SRz of the surface of the release layer is less than 1/2 of the thickness of the ceramic sheet, as well as the peeling force while separating the release film is small, and free of defects, such as pin hole in the ceramic sheet during the period of manufacturing said thin ceramic sheet.

Description

567127 V. Description of the Invention (Technical Field of the Invention) The present invention relates to a release film with a ceramic sheet and a polyester film as a base material. In particular, it relates to a film having excellent peelability and suitable for manufacturing a film. Release film with ceramic sheet attached to the ceramic sheet. In addition, it is also related to a mold release with a ceramic sheet which is excellent in peelability and smoothness, has a small peeling charge, and is suitable for manufacturing a thin-layer ceramic sheet having a thickness of 3 m or less. [Background of the Invention] A release film based on a polyester film such as polyethylene terephthalate or polyethylene naphthalate, and a release layer provided on the substrate is generally widely used as It is used for label paper, adhesive tape, etc. With the rapid popularity of mobile phones in recent years, the demand for laminated ceramic capacitors is expanding. Laminated ceramic capacitors have the characteristic of temporarily storing electricity. They are an indispensable component in electronic circuits that stabilize current. About 250 laminated ceramic capacitors are used in mobile phones. When manufacturing ceramic sheets for laminated ceramic capacitors, a biaxially stretched polyester film with excellent mechanical strength, dimensional stability, heat resistance, and price is usually used. At least one side of the biaxially stretched polyester film is provided with a silicone resin film. Type film as a carrier film for engineering. Release films having such a silicone-based resin film include JP-A-Sho 60-141 553, JP-A Hei 3-231812, JP-A 4-59207, and JP-A 6-2393. know. In recent years, in order to reduce the size and increase the capacity of laminated ceramic capacitors, it has been required to make the thickness of the ceramic sheet thinner and to laminate multiple layers. The thickness of the ceramic sheet currently used is about 7 to 10 μm. In addition, a ceramic sheet with a thickness of 567127 has been developed. (5) Description of the invention () The ceramic sheet has a thickness of about 3 to 5 μm, and the thickness of about 1 to 2 μm is also under review.

However, as the thickness of the ceramic sheet becomes thinner, the peeling force when the ceramic sheet is peeled from the release layer of the release film becomes larger, and a new problem of poor peeling occurs. Therefore, there is a need for a release film having a smaller peeling force than the previous release film. Although a general-purpose release film used for a conventional label or the like has a small peeling force in terms of use, when a thin-layer ceramic sheet is manufactured, the release property is insufficient, and a release film having a smaller peeling force is desired. However, even when designing a release film with a small peeling force against a ceramic sheet of a specific composition, if the constituents of the ceramic sheet (the type and average particle size of the ceramic, the type of the adhesive, the content ratio of these, etc.) or When the thickness of the ceramic sheet is changed, the peeling force between the ceramic sheet and the release layer of the release film will change. Therefore, it is necessary to design the composition of the release layer of the optimal release film for the ceramic sheet of the specific composition again.

In addition, the thinner the thickness of the ceramic sheet, not only the rough protrusions on the surface of the release layer of the release film, but also the effect of the unevenness on the surface of the release layer on the thickness of the ceramic sheet. When thinning, the release film used as a support for the ceramic sheet must have higher smoothness. The reason is that if the surface roughness of the polyester base film used as a support for the release film is large, the necessary amount of the release agent cannot be applied to the convex portion, and as a result, the original release of the release agent cannot be exerted. Type. In addition, if there are tall protrusions on the surface of the release film, the convex shape of the release layer of the release film caused by the protrusion is copied into a concave shape on the ceramic sheet, and is copied on the concave portion Shape defect of g ceramic sheet. V. Explanation of the invention () This defect tends to become significant as the thickness of the ceramic sheet becomes thinner, especially in recent years, the progress of extremely thin thickness has been improved. For example, when manufacturing a thin-film ceramic sheet with a thickness of 1 to 3 μm, The concave marks on the ceramic sheet caused by the high protrusions on the surface of the release film become the cause of the poor precision of the thickness of the ceramic sheet. In addition, as the above-mentioned concave copy marks become stronger, they not only stop at depressions but also easily become penetrating holes. In severe cases, the ceramic sheet may be broken when the release film from the support of the ceramic sheet is peeled off. In addition, when a laminated capacitor is made of a ceramic chip having pinholes, a short circuit or poor insulation resistance may cause a fatal defect. In addition, a release layer containing a curable silicone resin as a main constituent is very easy to be charged, and the peeling charge when the ceramic sheet is to be peeled is also large. Therefore, once the peeled ceramic sheet is attached to the release film again to reduce productivity, or problems such as pinholes occur when floating dust is attached to the release film to form a ceramic sheet, people have sought a method that has less peeling and charge than the previous release film. , Or release film with faster charge decay. Therefore, the release layer of the release film of the laminated ceramic sheet should completely avoid the concave copy of the release layer from the release film to the ceramic sheet, and the release layer of the release film should be made flat. However, when a ceramic sheet is laminated on a flat release layer and the ceramic sheet is peeled from a release film, there is a problem that peeling charging becomes extremely large. In addition, in order to flatten the release layer, it is necessary to substantially remove particles in a polyester substrate film generally used for a support, and to remove precipitates caused by a catalyst, and remove them with high radiation. For example, when there is a laminated structure of at least two layers of polyester substrate film, the surface forming the release layer must be laminated. Actually, 567,127. 5. Description of the invention () The absolute hardness difference of the surface of the mold layer is extremely small. The release film of the ceramic sheet shows good peeling and removal properties in the peeling process when the ceramic sheet is manufactured, and the release film with a specific surface unevenness shows ideal uniform coating property in the coating process when the ceramic sheet is manufactured. . That is, the first invention of the present invention is a release film in which a release layer containing a curable silicone resin as a main constituent is provided on at least one side of a polyester substrate film, and further, the release film of the release layer film is further provided. A release film with a ceramic sheet laminated with a ceramic layer on the surface of the mold layer is characterized in that the absolute difference between the dynamic hardness A of the surface of the ceramic sheet layer and the dynamic hardness B of the surface of the release layer satisfies the following formula ( 1), and the relationship between the ten-point average roughness SRzhm of the three-dimensional surface roughness of the surface of the release layer and the thickness of the ceramic sheet (3 (μιη)) satisfies the following formula (2 广 | AB | S 20 (gf / pm2 ) · · · (1) SRz ^ C / 2 · · · (2) With the above structure, the peeling force at the time of peeling can be made small, and in the peeling process when the ceramic sheet is manufactured, there is no defect in peeling. With moderate strength, the release film is removed from the ceramic sheet. In addition, by controlling the surface unevenness of the release surface, especially in the ceramic coating process when manufacturing the thin-film ceramic sheet, a uniform ceramic sheet without pinholes and other shortcomings is produced. The second invention is the release sheet with a ceramic sheet according to the first invention. The polyester substrate film has a single-layer structure, and the film contains particles. The third invention is the release film with a ceramic sheet according to the first invention, wherein the polyester substrate film has at least two layers The above laminated structure, and 567127 V. Description of the invention (6) The polyester film layer containing particles is laminated on the surface opposite to the release layer forming surface. In addition, the fourth invention is by opposing the release layer The surface is provided with a charging prevention layer with a rapid charge decay, and it is found that the peeling charge of the release film and ceramic becomes smaller, and it is found that when the protrusions caused by particles on the release surface of the release film are set to zero, the thickness can be obtained That is, the uniform fine ceramic sheet with good precision. That is, the fourth invention is the release film with a ceramic sheet according to the first or third invention, wherein the release film is provided on one side of a polyester substrate film. The release layer is provided with a particle-containing layer and a charge prevention layer in order on the other side, and the polyester base film does not substantially contain particles, and the charge prevention layer has a ten-point average roughness SRzhm on the three-dimensional surface roughness measurement. ),level Inclined slope SAa, average spatial wavelength SXa (pm) and convex number PC with an area of 0.12 mm2 satisfy the following formulas (3) and (4): 0.05S SRzS 0.5 · · · (3) SAaxPC / SXa ^ 0.2 · · · ( 4) With the above structure, since the peeling charge between the ceramic sheet layer and the release layer is small, it can prevent the trouble of adhesion once it is peeled. In addition, because the release surface has excellent smoothness, it can be extremely The ultra-thin ceramic sheet with a thickness of 3 μm or less is precisely processed, so it is suitable for producing ceramic sheets, especially ultra-thin ceramic sheets. The fifth invention is the release film with a ceramic sheet according to the fourth invention, wherein the above release The film is provided with a polymer resin coating layer containing particles between the polyester base film and the antistatic layer. The sixth invention is the release film with a ceramic sheet according to the fourth invention '567127 V. Description of the invention (7) wherein the particle-containing layer is a polyester film layer containing particles, and the polyester base film has A laminated structure of at least two layers of the polyester film layer. The seventh invention is the release film with a ceramic sheet according to the second, third, fifth, and sixth inventions, wherein the particles are calcium carbonate particles, silica particles, and cross-linked acrylic particles having an average particle size of less than 5 μm. At least one selected from the group consisting of cross-linked propylene particles and ammonium phenanthrene-based particles.

With the above configuration, a release film having excellent surface smoothness while suppressing coarse protrusions can be obtained. The eighth invention is the release film with a ceramic sheet according to the second, third, fifth, sixth, and seventh inventions, wherein the particle size distribution ratio of the particles satisfies the following formula (5), and the average particle size and the particle content The product satisfies the following formula (6). 0.2 ^ D5〇 / D5 ^ 0.6 (5) 150 ^ D50 × E ^ 10000 · · · (6) In the formula, D5G represents the particle size (μιη) when the cumulative weight is 50%,

D5 represents the particle size (µιη) when the cumulative weight is 5%, and E represents the particle content (ppm). The ninth invention is the release film with a ceramic sheet according to the first to eighth inventions, in which the release layer of the polyester film is measured after the surface of the release layer is rubbed back and forth ten times with a friction material and bonded to the release film. When the peeling force of the adhesive layer of the ceramic sheet on the surface of the release layer, the ratio (friction ratio (P10 / P0)) of the peeling force (P10) after friction to the peeling force (P0) before friction is less than 10. With the above-mentioned structure, the release layer will never fall off from the polyester film during the ceramic processing process. Therefore, the ceramic coating is uniform and the ceramic sheet is easily peeled off. 9- 567127 V. Description of the invention (9) In the present invention, The stretching temperature of the polyester film during stretching should preferably be higher than the secondary transfer point (Tg) of the polyester and lower than the crystallization temperature. In the case of a biaxially stretched film, a stretching ratio of 1.1 to 8 times in each direction is preferable, 2 to 6 times is preferable, and 3 to 5 times is most preferable. The thickness of the polyester film used in the present invention may be set according to the purpose of use, and is not particularly limited. It is preferably 2 to 300 μιη, and most preferably 10 to 1 25 μηι. The silicone release film constituting the release film of the present invention The silicone resin of the mold layer is not particularly obscured, and hardening silicone resins such as addition reaction systems, condensation reaction systems, ultraviolet or electron beam curing silicone resins can be used. Examples of the addition reaction type silicone include the use of a gold catalyst to cause polydimethylsiloxane introduced at a terminal group to react with a hydrodiene siloxane to form a three-dimensional crosslinked structure. For example, a gold catalyst is used to react a polydimethylsiloxane having a -0Η- group in a terminal group with a hydrodiene siloxane to form a three-dimensional crosslinked structure. For example, the ultraviolet curing type silicone resin has the most basic type, which uses the same radical reaction as ordinary silicone rubber cross-linking, introduces unsaturated groups to make it light hardened, and adds mercaptan to ethylene siloxane. Those who react and crosslink, decompose iron salts with ultraviolet rays to generate strong acids, and crack them to crosslink. The energy of the electron beam is stronger than that of the ultraviolet rays. Therefore, even if the silicone resin of the electron hardening system does not use a cleavage agent like the ultraviolet curing system, a crosslinking reaction due to free radicals occurs.丨 Ben Liming's release film with ceramic deaf film laminated on the release layer Table-11- 567127 V. Description of the invention (1G) The dynamic hardness of the ceramic sheet surface and the dynamics of the release layer above The absolute 値 | Α-Β | of the difference in hardness B must be less than 20gf ~ m2, preferably less than 15gf / pm2, and most preferably less than 10gf / μιη2. As the absolute difference of the above dynamic hardness 値 | A_B | When it exceeds 20gf ~ m2 ', the peelability of the ceramic sheet is reduced when the ceramic sheet layer is peeled from the release film, especially in the case of a thin ceramic sheet. Poor breakage and peeling of ceramic sheets often occur, or problems such as reduction occur. By controlling the absolute 値 | A-B | of the difference in dynamic hardness within the above range, the peeling force when the ceramic sheet layer is peeled from the release film to produce the ceramic sheet is small and easy to peel, so that the damage of the ceramic sheet can be reduced. When the ceramic sheet layer is peeled from a release film to produce a ceramic sheet, the peeling shape changes depending on the hardness of the ceramic sheet, and therefore, it is necessary to change the hardness of the release film layer. That is, when the ceramic sheet is hard or the thickness of the ceramic sheet is thin, when the ceramic sheet layer is to be peeled off, the influence of the viscosity of the ceramic sheet layer is almost invisible. Therefore, it should be used as the release layer structure of the release film. Hardened silicone resin. The peeling action of the interface between the ceramic sheet and the release film is different from that of a normal adhesive film and release interface. That is, when the interface between the adhesive layer of the adhesive film and the release layer of the release film is peeled off, the cohesive energy of the interface becomes the master. On the other hand, when the hard ceramic sheet is peeled from the release thin film interface, if the release layer is hard when the release layer is hardly deformed, the peeling force becomes small. In addition, when the release layer is soft, the release layer is deformed at the time of peeling, and as a result, the peeling force is increased. Therefore, the peeling action of hard ceramic and hard release film is not as sticky as -12-567127 V. Description of the invention () The peeling of the composite film and release film is controlled by the interface peeling force and should be controlled by the interface shear force ( shearing force). To set the absolute 値 | A-B | of the above dynamic hardness to less than 20gf ^ m2, the hardness of the release layer of the release film must be designed in accordance with the hardness of the ceramic sheet layer. For example, the ceramic sheet is composed of ceramic particles (barium titanate, alumina, aluminum nitride, etc.) and a binder (butyral resin, polyvinyl alcohol, etc.), but if the content ratio of the binder to the ceramic particles (weight When the ratio is larger, or when the thickness of the ceramic sheet layer is thicker, the hardness of the ceramic sheet when the ceramic sheet layer is laminated on the release film becomes smaller. In addition, the dispersibility of the ceramic particles in the ceramic slurry also affects the hardness of the ceramic sheet. If the dispersibility of the ceramic particles is insufficient when the ceramic slurry is blended, the hardness of the ceramic sheet becomes small. To peel off the ceramic chips with low hardness, it is necessary to reduce the hardness of the release layer mainly composed of cured silicone resin, for example, 1) increase the limit of the hydrophobic group in the silicone resin as much as possible, 2) reduce the introduction of silicon The content of the cross-linking group in the ketone resin, 3) the use of a silicone resin having a linear molecular structure, and the like are achieved. It is also effective to increase the thickness of the release layer. In addition, when the content ratio (weight ratio) of the binder relative to the ceramic particles is small, or when the thickness of the ceramic sheet layer is thin, the hardness of the ceramic sheet when the ceramic sheet layer is laminated on the release film becomes large. To peel off the high-hardness ceramic sheet as described above, it is necessary to increase the hardness of the release layer containing the hardened silicone resin as the main component. For example, it is necessary to adjust the content of the hydrophobic group introduced into the silicone resin. Methods such as increasing the amount of cross-linking groups introduced into the silicone resin to increase the crosslinking density of the silicone resin can be achieved. -13- 567127 Five 'invention description (μ) Resin uses epoxy group in the cross-linking group, so the durability of close adhesion to polyester film is improved as the cross-linking reaction is promoted. In addition, in order to further improve the adhesion durability of the release layer and the polyester film of the support, before the film is coated with the coating solution for a release layer, a tackifying coating or a corona treatment may be performed on the surface of the polyester film. , Flame treatment and other pretreatment. Examples of the charge preventive agent constituting the charge preventive layer in the release film of the present invention include, for example, an anion-based charge preventive agent having a functional group of an alkyl sulfate type, an alkyl oxalate type, a fourth ammonium salt type, and a fourth ammonium resin type , Imidazoline type cationic charge preventive agent, betaine (betaine) type amphoteric charge preventive agent. Alternatively, a conductive polymer such as polyaniline may be used. By providing the antistatic layer on the side opposite to the release layer, the peeling charge when the ceramic sheet is peeled from the release layer can be reduced. By reducing the peeling and charging of the ceramic sheet layer and the release layer, the problem that the peeled ceramic sheet is reattached to the release film can be prevented. The above-mentioned surface-active agent-type antistatic agent is a polymer type, and a number average molecular weight thereof is preferably greater than 5,000, particularly preferably greater than 50,000. When the number average molecular weight is less than 5000, the bonding force of the release layer to the base film tends to deteriorate. When the release film is rolled into a roll or stacked into a sheet, the components in the charge prevention layer will adhere to On the surface of the release layer of the base film, peeling failure occurs during the secondary processing of the release layer. During the secondary processing, the charging prevents the coating itself from peeling off and contamination occurs during the secondary processing. This is not ideal. In addition, instability of the charging prevention performance due to peeling of the charging prevention layer also occurs, which is not desirable. To prevent such phenomena, waxes, silicone components, etc. may be mixed in the antistatic layer. -16- 567127 V. Description of the invention (15) To reduce the peeling and charging of the ceramic and silicone layer as described above, it can be achieved by providing a charge prevention layer on the opposite side from the silicone layer. A charge prevention layer having an excellent charge attenuation effect is preferred. Although not particularly limited, among the antistatic agents, cationic antistatic agents and conductive polymers such as polyaniline are preferred. An antistatic agent having nitrogen classified into four levels is preferred. When a charge preventive agent having excellent charge decay properties is used, it is surprising that as long as the charge preventive layer is present on the opposite side of peeling, the effect of reducing the peeling charge on the side of the ceramic sheet to be peeled off is surprising. In the present invention, the thickness of the release layer can be set according to the purpose of use, and is not particularly limited, but it is preferable that the coating amount of the release layer after the chemical conversion is in the range of 0.02 to 0.2.g / m2 ? When the thickness of the release layer is smaller than the above range, the peelability is liable to decrease. In addition, if it is larger than the above range, the hardening time necessary for the adhesiveness of the polyester becomes long, which is uneconomical in production. In addition, it is difficult to control the unevenness on the surface of the release layer, which is not desirable. In the present invention, the thickness of the antistatic layer is not limited as long as it is set according to its purpose of use, but it is preferred that the coating amount of the antistatic layer is within the range of 0.005 to 0.5 g / m2. If the thickness of the release layer is smaller than the above range, the antistatic property is liable to decrease. In addition, if it is larger than the above range, a peeling property (tack) may occur in the electrification preventing layer, and the electrification preventing component may be easily duplicated and peeled off. The method for forming the release layer of the present invention is not particularly limited. For example, a coating liquid in which a hardening silicone resin is dispersed can be spread on the surface of the polyester film of the base material by coating or the like, and the solvent can be removed by drying or the like. Then, the resin is hardened by reacting the resin with heat. -17- 567127 V. Description of the Invention (i6) In addition, the method and method of forming the anti-charge layer of the present invention is not particularly limited. The method of removing the solvent on the surface of the polyester film on the opposite side of the release layer by drying. In addition, the formation of the above-mentioned release layer and charge prevention layer is arbitrary. The method for forming the release layer of the present invention is not particularly limited. For example, a coating solution in which a hardening type silicone resin is dispersed can be applied to the surface of a polyester film on a substrate, and the solvent is dried, and then heated. Method for resin to harden by reaction. 1 The application method of the above-mentioned application liquid may be any conventional application method. For example, a roll coat method such as a gravure coating method or a reverse coating method can be used. Meyer bar (Meyer bar) and other rod coating method, spray method, pneumatic blade coating method and other previously known methods. When a release layer is to be formed in the present invention, a coating liquid containing a hardening type silicone resin without a solvent may be applied to a polyester substrate film and allowed to dry, and then an activation energy hardening reaction or a heat hardening reaction may be performed, or A coating solution in which a silicone-curable resin is dissolved or dispersed in a solvent is applied to a polyester substrate film, and then the energy-hardening reaction or thermal curing is performed after drying and removing the solvent. The activation energy of the resin can be appropriately selected depending on the hardening conditions or thermal hardening conditions, and the drying conditions of the solvent, depending on the type of resin used, the thickness of the release layer, and the size of the release film. For example, when the ultraviolet curing silicone resin layer is irradiated with ultraviolet rays, it should be performed at 100 mJ / cm2 or more, and the solvent should be dried at 100 ° C or less. If the amount of ultraviolet radiation is less than 100mJ / Cm2, the reaction of silicone resin -18- 567127 V. Description of the invention (18) Particles that seriously hinder the transparency of the film are not applicable. Inorganic particles include calcium carbonate particles, silica particles, aluminum silicate composite oxide particles, hydroxyapatite particles, and the like. In addition, the heat-resistant organic particles include cross-linked polypropylene-based particles, cross-linked polystyrene particles, Benzotoluamine-based particles, and the like. These particles are preferably used alone or in combination. Especially in terms of film transparency, silica having a refractive index similar to that of polyester is preferred. The average particle diameter of the particles is not limited as long as it satisfies the above formula (2), but from the viewpoint of suppressing coarse protrusions and surface smoothness, it is preferably less than 5 μm, more preferably less than 2 μm, and particularly preferably less than 0.7 μm. If it exceeds 5 μm, coarse bumps may occur, otherwise the smoothness of the surface will deteriorate. The lower limit of the average particle size 0.01 is preferably 0.01. In addition, the particle size distribution ratio (particle size distribution measuring device: manufactured by Shimadzu Corporation, SA-CP3) and the product of the average particle size and content are preferably located in the following formula (5) from the viewpoint of suppressing the number of coarse protrusions and sliding properties And (6). 0.2 ^ D5〇 / D5 ^ 0.6 ··· (5) 150 ^ D5〇xE ^ 10000 · · · (6) In the formula, D5G represents the particle size when the cumulative weight is 50% (μπ〇 'D5 means tired粒径 The particle size (μηι) when the weight is 5%, Ε means the particle content (ppm) ° This case indicates that the larger the particle size distribution ratio (D50 / D5), the narrower the particle size distribution, and the particle size distribution ratio ( D5G / D5) is ideally in the range of 0.2 to 0.6. It is actually very difficult to make a particle size distribution with a particle size distribution ratio (D5G / D5) exceeding 0.6 in a practical range, and vice versa, such as less than 0.2 , Due to the relationship between the average particle size (D5G), the sliding property is insufficient, or the number of coarse protrusions is 20-567127. V. Description of the invention (21) Ceramic powder such as aluminum nitride is mixed and dispersed in an organic solvent, and then Add polymethyl methyl resin, polyethylene acetal, polyvinyl butyral, polyvinyl alcohol and other polymer binders, plasticizers, dispersants, and mix and disperse using a high-speed agitator or ball mill. , And then filtering treatment (for example, a filter with a pore size of 3 μm), and coating the prepared ceramic slurry The thickness after drying is from 1 to 10 μm after drying on the release layer of the release film. Coating methods include doctor blade method, micro-roll concave roller method, reverse roller method, slit die coating machine or doctor blade coating machine. (Examples) &amp; The present invention will be described in more detail below using examples, but the present invention is not limited by these examples. In addition, the characteristics and physical property evaluations used in the present invention are measured by the following methods. (1) Intrinsic viscosity of polyester Dissolve the polyester in a mixed solvent of 60% by weight of phenol and 40% by weight of 1,1,2,2-tetrachloroethane, and remove the undissolved solid content with a glass filter. Measured at 3 (TC.) (2) Dynamic hardness A dynamic ultra-fine hardness tester (DUH-20 1-202, manufactured by Shimadzu Corporation) is used to push a triangular cone with a load of 2 gf (ceramic sheet or release layer), The dynamic hardness after holding for 2 seconds is determined by the following formula. In addition, the measurement is performed 10 times and the average hardness is used. In addition, the dynamic hardness measurement of the release layer of the release film can be measured before the ceramic sheet layer is installed. Measurement of release film, After the ceramic sheet layer is set, the release film from which the ceramic sheet layer is peeled off can be performed. -23- 567127 V. Description of the invention (23) The release film of the ceramic sheet is cut into a width of 5 cm, and the surface of the ceramic sheet layer is pasted. Polyester tape (manufactured by Nitto Denko Corporation, Nitto 31 B), and the ceramic sheet layer was peeled from the release film by a peeling method (peeling speed: 500 mm / min, T-peel), and evaluated in accordance with the following criteria In addition, the test was performed a total of 5 times, indicating a pass. ○: When the completeness of the peeled ceramic sheet was observed with the naked eye, no pinholes or cracks were found in the ceramic sheet in the five tests. △: When the completeness of the peeled ceramic sheet was observed with the naked eye, one part of the ceramic sheet was broken in one of the five tests. X: When the full surface of the peeled ceramic sheet is observed with the naked eye, the ceramic sheet is cracked and broken once every 5 times. (5) Voltage during peeling of the ceramic sheet The release film with the ceramic sheet laminated with the ceramic sheet layer laminated on the surface of the release layer of the release film prepared in the above (4) was cut into a width of 5 cm. Then, the ceramic sheet layer was peeled from the surface of the release layer of the release film by a peeling method (peeling speed of 500 mm / min, T-peel). Using a digital electrostatic potentiometer (KSD-0103, manufactured by Kasuga Electric Corporation) at 20 ° C and 50% relative humidity, the voltage on the side of the peeled ceramic sheet was measured, and the absolute withstand voltage was evaluated according to the following three criteria: . 〇 means pass.

〇: S lkV

△: More than lkV, less than 5kV X: &gt; 5kV (6) Three-dimensional surface roughness parameters and number of surface protrusions Use a stylus-type three-dimensional surface roughness meter (manufactured by Kosaka Laboratories: SE- -25- 567127 V. Description of the invention (25) The cutting part, SAa can be expressed by the following formula.

Lx Ly SAa = ί ί V &quot; {(6f / (5x) 2+ (5f / c5y) z} dxdy Ο Ο Here 'Z = f (Xy) means the position (X, y ) As a function of the surface height Z of the film, Lx = 500, Ly = 150. In addition, 'SXa is the three-dimensional spatial average wavelength, which means the amplitude of the above surface roughness curve. That is, if the average surface roughness of the center plane is the same, The steeper the bumps, the smaller the SXa. The number of bumps PC is a differential interference microscope (manufactured by Nikon) which photographs the vapor-deposited aluminum film at a final magnification of 160 times, and traces the bumps on the transparent QH film And the image analyzer (Luzex IID) made by Nireco is used to process the area equivalent to 0.12mm2 of the film to calculate the number of protrusions in the above area. (7) The smoothness of the peeled ceramic sheet will be accompanied by ceramics The release film was cut to a width of 5 cm, and a polyester adhesive tape (manufactured by Nitto Denko Corporation, Nitto 31B) was attached to the surface of the ceramic sheet, and the ceramic was peeled (peeling speed: 500 mm / min, T-peeling). The sheet was peeled from the release film, and then observed at 200 times with a differential interference microscope (manufactured by Nikon). On the surface of the separated ceramic sheet, those with no surface unevenness are represented by 0, and those with surface unevenness are represented by X. (8) Pinhole of the ceramic sheet The release film with the ceramic sheet is cut to a width of 100mm and a length of 1 meter. The mold-shaping table (made by Kokuyo Co., Ltd.) is placed on top of the mold-shaping table (-27- 567127). V. Description of the invention (26) The top surface of the film becomes the surface of the ceramic plate, which is illuminated from the bottom, and is calculated by the naked eye. The number of leaked positions is converted to the number per square meter, and the first digit of the decimal point is rounded. 〇: less than 10 / square meter △: 20 to 50 / square meter X: more than 60 Per square meter (Example 1)

A continuous esterification reaction device consisting of a stirring device, a condenser, and a complete mixer provided with a raw material feed inlet and a product take-out outlet is used, and the esterification reaction generated by the first esterification reaction tank is generated. The ethylene glycol slurry is continuously supplied in the plant. The molar ratio of ethylene terephthalate to ethylene glycol is adjusted to 1.7, and each unit of terephthalic acid contains 289 ppm of antimony trioxide as the antimony atom.

At the same time, the ethylene glycol solution of magnesium acetate tetrahydrate is continuously supplied through different supply ports of the ethylene glycol slurry supply port of terephthalic acid, and each polyester unit of each product produced through the reaction in the reaction tank The magnesium atom became 100 ppm, and the average retention time of the reaction was 4.5 hours at normal pressure and 255 ° C. This reaction product was continuously taken out of the apparatus and supplied to the second esterification reaction tank. For the polyester units in the reaction product in the second esterification reaction tank, 0.5 parts by weight of ethylene glycol was continuously supplied from another supply port, and the ethylene glycol solution of trimethyl phosphate made the P (phosphorus) atom into 64PPm, and an ethylene glycol slurry of calcium carbonate having an average particle diameter D5G (manufactured by Shimadzu Corporation, SA-CP3) of 0.9 μm and D5G / D5 of 0.4 was 100 g / liter of sodium tripolyphosphate -28- 567127 V. Description of the invention (27) The aqueous solution of sodium atom becomes 2500 ppm of calcium carbonate in the slurry and the average retention time of the reaction is 5 hours at normal pressure and temperature of 260 ° C. The esterification reaction product was continuously supplied to a two-stage continuous polycondensation reaction device provided with a stirring device, a condenser, a raw material feed inlet and a product inlet to obtain a polyester having an intrinsic viscosity of 0.62 dl / g. . The polymer was melt-extruded at 290 ° C, stretched 3.5 times in the longitudinal direction at 90 ° C, and 3.5 times in the transverse direction at 130 ° C, and then heat-treated at 220 ° C to produce a thickness of 38 μm. The polyester is biaxially stretched and rolled into a tube. Then, the ultraviolet cation hardening type silicone resin (manufactured by Toshiba Silicon Corporation, UV9315) was dispersed in the solvent! In 1 (n-hexane), the solid content of the rhenium resin was 2% by weight, and 1 part by weight of the bis- (alkoxyphenyl) bowl iron hexafluoroantimonate (bis (alkylphenyl) iodoniumhexafluoroantimonate) is used as a hardening catalyst to produce a coating solution containing a silicone resin. The above-mentioned biaxially stretched polyester film with a thickness of 38 μm was spread out, and a coating liquid containing the above-mentioned silicone resin was applied to one side of the film by a wire bar. After drying at 100 ° C for 30 seconds, the device was irradiated with ultraviolet rays. It was irradiated with ultraviolet rays (300 mj / cm2) to form a release film (the application amount of the silicone release layer after drying was 0.10 g / m2) and rolled into a roll. In addition, 100 parts by weight of ceramic particles (the average primary particle diameter of barium laurate (BaTi03), manufactured by Fuji Titanium Corporation) with an average primary particle size of 0.6 μm was mixed with a solvent (toluene / ethanol = 50/50: weight ratio), Oxidized dowels with a diameter of 1.5mm (塡 塡: 200% by weight of the stirrer pulp)-disperse for 24 hours with a ball mill. Then, 10 parts by weight of an adhesive (butyral resin, manufactured by Sekisui Chemical Industry Co., Ltd.) and -29-567127 V. Description of the Invention (29) (Comparative Example 2) In Example 3, except for the thickness of the ceramic sheet layer A release film with a ceramic sheet was prepared in the same manner as in Example 3 except that it was set to 2 μm. The evaluation results of the release film with a ceramic sheet prepared in Examples 1 to 3 and Comparative Examples 1 and 2 are shown in Table 1. Table 1 '' SRz (μηι) on the surface of the release layer Ceramic layer thickness (μηι) Dynamic hardness A (gf / μη2) on the surface of the release layer Dynamic hardness B (gf / μηι2) on the surface of the release layer Difference in dynamic hardness | AB | (gf / μπι2) Pinholes of peelable ceramic sheet of ceramic sheet Example 1 0.47 3 28 30 2 〇〇 Example 2 0.47 3 28 30 2 〇 Example 3 1.11 3 28 30 2 〇Comparative Example 1 0.65 3 28 4 24 X 〇 Comparative Example 2 1.11 2 28 30 2 〇 △ The relationship between the dynamic hardness (A) of the surface of each ceramic sheet in Examples 1, 2, and 3 and the dynamic hardness (B) of the release layer surface is AB | ^ 20, no peeling failure of the ceramic sheet was observed, and the ten-point average thickness SRz of the release layer was less than 1/2 of the thickness of the ceramic sheet, and no pinhole defect occurred. In contrast, the dynamic hardness difference IA-BI of Comparative Example 1 was greater than 20, and the peeling failure of the ceramics appeared. | A-B | S 20 of Comparative Example 2, but the SRz was larger than 1/2 of the thickness of the ceramic sheet, and pinholes occurred in the ceramic sheet. (Example 4) A biaxially stretched polyethylene terephthalate was prepared in the following manner. Ester-31- 567127 V. (31) parts of the coating solution composed of the description of the invention, and dried with hot air at 70 ° C, then, hold the end of the film with a clamp and guide it to the hot air zone heated to 13 (TC) 'After drying, it is stretched to 4 times in the width direction, and then heat-treated at 220 ° C to obtain a biaxially stretched polyester film having a coating layer on one side of 38 μm thick.

0.2 parts by weight of a cationic polymer antistatic agent (trade name Kemisutat 6300Η manufactured by Sanyo Chemical Industry Co., Ltd.), 0.1 part by weight of polyethylene vinegar (trade name High Tek E600: manufactured by Toho Chemical Industry Co., Ltd.), 50 parts by weight of methanol, and 49.7 parts of water Mix parts by weight to adjust the coating solution, and apply it to a biaxially-stretched polyethylene terephthalate film (thickness) with a coating layer on one side prepared by the method described above using a wire bar. The coating amount after coating and drying on the coating of 38 μιη) was 0.08 g / m2, and dried in a hot air dryer at 90 ° C for 30 seconds.

Next, an ultraviolet cation-curable silicone resin (UV93 1 5 manufactured by Toshiba Silicon Corporation) was dispersed in a solvent (n-hexane). The solid content concentration of the resin was 2% by weight, and 1% by weight of 100% by weight of the silicone resin was added. Bis- (alkoxyphenyl) iodoferric hexafluoroantimonate was used as a hardening catalyst to prepare a coating solution containing a silicone resin, dried at 10 ° C for 30 seconds, and then irradiated with an ultraviolet irradiation device. A release film having an anti-charge layer was prepared by ultraviolet (300 mJ / cm2) (the coating amount of the release layer after drying: 0.10 g / m2). Next, in addition to setting the thickness of the ceramic sheet layer to 2 μm, A release film with a ceramic sheet was prepared in the same manner as in Example 1. (Example 5) A thermosetting silicone resin was dispersed on the surface of the opposite side to the charge-preventive layer of the charge-preventive polyester film of Example 4 (Manufactured by Shin-Etsu Chemical Co., Ltd., KS830) -33- 567127 V. Description of the invention (32) In a solvent (toluene), the solid content concentration of the resin is set to 3% by weight, and 1% by weight is added to 1,000 parts by weight of the silicone resin. Parts of platinum catalyst for coating with silicone resin Liquid, coated on one side of the film with a wire bar, and dried at 140 ° C for 30 seconds to prepare a release charge prevention film (dry coating of the silicone release layer 0.05g / m2 Next, except that the thickness of the ceramic sheet layer was set to 2 μm, a release film with a ceramic sheet was prepared in the same manner as in Example 1. (Example 6) Except that the ultraviolet irradiation amount was set to 500 mJ / Except for cm2, a release film having a charge prevention layer was prepared in the same manner as in Example 4. Next, except that the thickness of the ceramic sheet layer was set to 2 μm, an additional film was prepared in the same manner as in Example 1. Release film with ceramic sheet. (Example 7) Calcium carbonate particles (manufactured by Kuroo Calcium Co., Ltd.) having an average particle diameter of 0.6 μm measured by a light transmission type particle size distribution measuring device (manufactured by Shimadzu Corporation, SA-CP3). Put it in ethylene glycol, and filter it with a 95% visor rayon-made filter with a cut diameter of 30 μηι to obtain ethylene carbonate of calcium carbonate particles in the slurry. Then, the temperature of the esterification reaction tank is raised. When reaching 20 (TC, 86,4 parts by weight of terephthalic acid And a slurry consisting of 64.4 parts by weight of ethylene glycol and 0.03 parts by weight of antimony trioxide as a catalyst and 0.088 parts by weight of magnesium acetate tetrahydrate and 0.16 parts by weight of triethylamine while stirring. Pressurize and warm and perform pressure esterification under the conditions of gauge pressure of 3.5 kg / cm2 and 240 ° C. Next, return the esterification reaction tank to -34- 567127 V. Description of the invention (33) to normal pressure Trimethyl phosphate was added at 0.040 wt.%. The temperature was raised to 260 ° C, and 15 minutes after the trimethyl phosphate was added, the ethylene glycol slurry of the calcium carbonate particles was added to make the polyester into l0. 〇〇ppm. After 15 minutes, the produced product of the esterification reaction was transferred to a condensation polymerization reaction tank, and the condensation polymerization reaction was performed under a reduced pressure of 280 ° C. After the polycondensation reaction was completed, a Naslon filter (manufactured by Nippon Seisen Co., Ltd.) with a 95% notch diameter of 28 μm was filtered to obtain polyethylene terephthalate containing calcium carbonate particles with an inherent viscosity of 0.62 dl / g. Diol ester particles (B). The polyethylene terephthalate particles (B) containing the above calcium carbonate particles and the polyethylene terephthalate particles (A) containing the same particles as in Example 4 were reduced at 13 ° C. After 6 hours of pressure drying (3torr), they were supplied to Extruder 1, Extruder 2 and melted at 285 ° C. The two polymers were respectively filtered with a filter material of a stainless steel sintered body (nominal filtering accuracy: 10 μηι particles 95% cut) and laminated with a double-layer converging block having a rectangular laminated portion, and extruded into a sheet shape by a nozzle. The unstretched film was prepared by winding and solidifying on a casting drum with a surface temperature of 30 ° C by a static application casting method. The unstretched film was heated to 100 ° C with a heated roller group and an IR heater and stretched to 3.5 times in the length direction. Then 'hold the end of the uniaxial film with a clamp and guide it to a hot air zone heated to 130 ° C, pull it up to 4.0 times in the width direction, and heat-treat at 21 0 ° C for 5 seconds, and at 130 ° C Delay 3% in the horizontal direction. In this way, a laminated biaxially stretched polyester film containing a polyester layer containing calcium carbonate ion 1000 ppm and a thickness of 5 µm and a particle thickness of 33 µm free was prepared. -35- 567127 V. Description of the invention (34) Then, in the same manner as in Example 4, a release layer is provided on the surface of the polyester layer containing no particles, and a surface of the polyester layer containing carbonate ion is provided with a charging prevention Laminated biaxially stretched polyester film having a charge prevention layer and a release layer on each surface. Next, a release film with a ceramic sheet was prepared in the same manner as in Example 1 except that the thickness of the ceramic sheet layer was set to 2 m. (Comparative Example 3) An addition polymerization reaction type silicone resin (KS830, manufactured by Shin-Etsu Chemical Co., Ltd.) was dispersed in a solvent (toluene) so that the resin solid content concentration was 3% by weight, and 1 part by weight was added to 100 parts by weight of the silicone resin. Platinum catalyst to make a coating solution containing silicone resin. Then, using a wire bar, one side of a biaxially stretched polyester film containing silica particles having an average particle size of 1.0 μm aggregate particles and a thickness of 38 μm was coated with the above-mentioned silicone resin coating solution using a wire bar. Then, the reaction was hardened and dried at 140 ° C for 30 seconds to obtain a release film (the coating amount of the release layer after drying: 0.05 g / m2). Then, a release film with a ceramic sheet was produced in the same manner as in Example 1 except that the thickness of the ceramic sheet layer was set to 2 m. (Comparative Example 4) A release film having a charge prevention layer was prepared in the same manner as in Example 4 except that the ultraviolet irradiation amount was set to 100 mJ / Cm2. Next, a release film with a ceramic sheet was prepared in the same manner as in Example 1 except that the thickness of the ceramic sheet was set to 2 m. (Comparative Example 5) Except that the dry coating amount of the release layer was set to 0.5 g / m2, '-36-567127 V. Description of Invention (35) The same method as in Example 5 was used to obtain Release film. Next, a release film with a ceramic sheet was produced in the same manner as in Example 1 except that the thickness of the ceramic sheet layer was set to 2 m. Table 2 shows the evaluation results of the release film with a ceramic sheet prepared in Example 4-7 and Comparative Examples 3 to 5. Table 2 Test Example Dynamic Hard Friction Peeling Strip SRz SAaxPC Ceramic Sheet Poor Peel Electrical (μηι) -r S Xa Surface IA-BI 値 Smoothness Example 4 2 0.000.19 0.80 〇Example 5 2 〇 〇〇0.19 0.80 〇 Example 6 2 〇〇0.19 0.80 〇 Example 7 2 〇〇0.39 0.64 〇 Comparative Example 3 2 〇 × 0.58 0.35 X Comparative Example 4 22 XX 〇0.19 0.80 〇 Comparative Example 5 24 XX 〇 0.19 0.80 〇 In Examples 4, 5, 6, and 7, the relationship between the dynamic hardness (A) on the surface of the ceramic sheet and the dynamic hardness (B) on the surface of the release layer is | AB | g 20, and the friction peeling 値 is also less than 5, No poor peeling of the ceramic sheet can be seen, and the peeling charge of the ceramic sheet is less than 1 kV, the ceramic sheet and the release film are no longer attached, and can be simply peeled off, and the peeling surface of the ceramic sheet is smooth. In contrast, Comparative Example 3 is | AB | ^ 20, and the friction peeling 値 is also less than 5. Although the peeling failure of the ceramic sheet is not seen, the peeling charge of the ceramic sheet reaches 5 kV, and reattachment of the ceramic sheet and the release film occurs. . In addition, the peeling surface of the ceramic sheet has a convex copy of the silicone release surface, which can be predicted when the ceramic -37-

Claims (1)

567127 Bulletin VI No. 90 1 3 202 0 "Releasing stare with ceramic sheet, fluorescent * 丨 丨 An VI. Patent application scope:-1 · A release film with ceramic sheet, which is based on polyester substrate film A release film with a hardened silicone resin as the main component is provided on at least one side, and a ceramic sheet is laminated on the surface of the release layer of the release layer film to form a release film with a ceramic. , Which is characterized in that the absolute difference between the dynamic hardness A of the surface of the ceramic sheet layer and the dynamic hardness B of the surface of the release layer satisfies the following formula (1), and the tenth-dimensional surface roughness measurement of the surface of the release layer is ten The relationship between the point average thickness SRzUm) and the thickness of the ceramic sheet (: (μπι) satisfies the following formula (2): I A-BI ^ 20 (gf / μίη2) SRz ^ C / 2 In addition, the so-called dynamic hardness refers to the use of dynamic Ultra-fine hardness tester, a triangular cone with a load of 2g f is applied to the sample, and it is measured after 2 seconds. 値 is obtained by the following formula; Dynamic hardness (gf / gm2) = a XP / D2 Here, P is the load (Gf), D is the indentation amount of the indenter to the sample (μιη) 'α is the constant of the indenter shape (115 Triangle cone) and 37.838; SRz is a stylus-type three-dimensional surface roughness meter with a radius of 2μίη at a load of 30mg and a needle speed of 0.1mm / sec in the long axis direction of the film The cut-off length is 0.25 mm, the measured span length is 1.0 mm, and the distance is divided into 500 points at a distance of 2 μm. Each 567127 is measured. 6. The height of the patent application point is input to the three-dimensional analysis device and analyzed. Characteristics 値 2. The release film with a ceramic sheet according to item 1 of the scope of the patent application, wherein the above polyester substrate film has a single-layer structure and the film contains particles. 3. The item 1 of the scope of patent application The release film with a ceramic sheet, wherein the polyester base film has a laminate structure of at least two layers, and a polyester film layer containing particles is laminated on the surface opposite to the release layer forming surface. The release film with a ceramic sheet according to item 1 or 3 of the scope of the patent application, wherein the release film is provided with a release layer on one side of the polyester substrate film, and a particle-containing layer and an electrification prevention layer in order on the other side Layer, the above polyester The substrate film does not substantially contain particles, the ten-point average roughness SRz (pm), the average inclination slope SAa, the average spatial wavelength SAa (pm), and the area of 0.12 mm2 in the three-dimensional surface roughness measurement of the above-mentioned anti-charge layer. The convex number PC satisfies the following formulas (3) and (4): 0.05S SRz '0.5 · · · (3) SA aXPC / S λ 0.2 · · · (4) SA a and S λ a are Needle type three-dimensional surface roughness meter, using a needle with a radius of 2μητι, under the condition of a load of 30mg and a needle speed of 0.1mm / sec, the cut-off in the long axis direction of the film is 0.25mm, and the span is measured. The length is 1.0 mm, and it is divided into 500 points with a distance of 2 μΓΤΐ. The height of each point is measured and input to a three-dimensional analysis device to perform the analysis. The characteristic of the convex number PC is determined by using a differential interference microscope. Magnification 567127 6. Application for a patent coverage of 160 times Photographically vapor-deposited aluminum film, tracking the bumps on a transparent OHP sheet, using an image analyzer to image the film equivalent to an area of 0.12 mm2, and calculating the area within the above area Number of protrusions. 5. The release film with a ceramic sheet according to item 4 of the patent application, wherein the particle-containing layer is a coating layer mainly containing a polymer resin and particles. 6. The release film with a ceramic sheet according to item 4 of the application, wherein the particle-containing layer is a polyester film layer containing particles, and the polyester base film has at least two or more layers containing the polyester film. Laminated structure of layers. 7 · If the release film with a ceramic sheet is applied in item 2 or 3 of the scope of patent application, the above particles are composed of calcium carbonate particles, silica particles, crosslinked propylene particles, and crosslinked polystyrene with an average particle size of less than 5 μm. Particles, at least one selected from phenox ammonium-based particles. 8 · If the release film with a ceramic sheet is applied for item 2 or 3 of the patent application scope, wherein the particle size distribution ratio of the above particles satisfies the following formula (5), and the product of the average particle size and the particle content satisfies the following formula (6 ): 0.2 ^ D5〇 / D5 ~ 0.6 · · · (5) 150 ^ D50XE ^ 10000 ^ · · · (6) In the formula, D5Q represents the particle size (μπι) when the cumulative weight is 50%, and D5 represents the cumulative The particle size (pm) when weight is 5%, and E represents the particle content (ppm). 9 · If the release film with ceramic sheet in any one of the scope of patent application 1, 2, or 3, the release layer of the polyester film and adhered to the release 567127 6. The surface of the layer of the patent scope The peeling force of the adhesive layer of the ceramic sheet was measured by rubbing the surface of the release layer back and forth with a friction material 10 times and before the rubbing. The ratio of the peeling force (P1 0) after rubbing to the peeling force (P0) before rubbing. (Friction Peel (P10 / P0)) is less than 10.