TW200400879A - Releasing film - Google Patents

Abstract

A releasing film which comprises a polyester base film with a surface exhibiting an appropriate irregularity and a silicone releasing layer, or comprises a polyester base film with a flat and smooth surface and a silicone releasing layer exhibiting an appropriate irregularity. The releasing film has excellent surface characteristics so that it is free from problems wherein concaves and convexes of the surface thereof are transferred to the surface of a formed sheet, is excellent in processability, and also is excellent in releasing characteristics.

Description

200400879 (ii) Description of the invention: [Technical field 3 to which the invention belongs] TECHNICAL FIELD The present invention relates to a release film. More specifically, it relates to a release film which has good surface characteristics such that the unevenness on the surface does not transfer to the formed sheet, and has good processability and mold release. [Prior Art 3 In the past, the release film system is currently used for, for example, resin sheet molding, adhesive 10-part mold release, medical use, and electrical / electronic parts manufacturing. For resins formed from the release film, For a molded product, planarization of the surface of the molded product is an important issue. The quality of the molded body formed from the base film can be said to be related to the accuracy and quality of its surface, that is, the accuracy and quality to the surface of the release film. 15 The release film itself is formed by providing a polyester-based film with a resin layer having a release property such as a silicone resin layer. Generally, particles are blended in a polyester-based film to improve processing suitability such as sliding properties and take-up characteristics. In general, although the addition of particles can improve the workability, the surface of the base film is roughened. If particles are not blended to avoid the above disadvantages and a flat surface is obtained, the sliding and degassing properties of the base film will be sharply deteriorated, and wrinkles will be generated during processing, or it cannot be rolled into a cylindrical shape. . In addition, when a coating layer of silicon is attached to the base film, the silicon layer covers the protrusions on the surface of the polyester base film, which further reduces the processing suitability. In the past, the surface properties of the formed article or formed sheet formed from the release film are not strictly required. Even a rough surface to some extent does not cause quality problems, but in recent years, The requirements for the surface properties of the formed sheet are very strict. For example, the sheets of chlorinated vinyl resin and polyurethane resin are formed by flow-molding such a resin solution on a release film. These sheets are particularly required to have high glossiness on the molding surface. In addition, the release film for an adhesive tape has a concave-convex transfer shape on the surface of the release film on the surface of the adhesive layer of the adhesive tape. Therefore, for example, when an adhesive tape is placed on a glass surface, air enters the transfer shape from the glass surface The rear recessed portion does not make it possible to achieve a good appearance. Therefore, the surface needs to have strict flatness. In addition, the release film used for engineering materials of electronic parts has particularly high requirements for its surface characteristics. For example, in the manufacture of thin layers of ceramic capacitors, a ceramic film and a binder are dispersed in a liquid medium, and a talman slurry is applied to a release film to form a very thin sheet of 3 μm or less. Since the thinner the 15 sheets, the more uneven the surface unevenness of the release film and the increase in the defective rate of the directly formed sheet, the higher the requirements for the surface characteristics of the release film are. In addition, when used as an engineering material for display applications, it is necessary to smooth the surface of the release film due to the thinning of the formed sheet. [Summary of the Invention] The purpose of the invention disclosed in the present invention is to solve the disadvantages of such conventional technologies and provide a surface with large irregularities on the surface of the release film that does not transfer to the good surface characteristics of the formed sheet, and at the same time has excellent processing suitability. , Release film is also good release characteristics. 6 200400879 Other objects and advantages of the present invention will be apparent from the following description. First, according to the present invention, the above-mentioned objects and advantages of the present invention can be achieved through a release film (hereinafter referred to as the first release film of the present invention), which is characterized by including: 5 (a) having a centerline average Poly-based film with a surface having a thickness Ra of 15nrn or less and an average ten-point thickness Rz of 30 to 500 nm; and (b) formed on the aforementioned surfaces of the two polyester-based films and having a thickness equal to Rz of the aforementioned surfaces 〇_8 times the silicon release layer. Secondly, according to the present invention, the above-mentioned objects and advantages of the present invention can be achieved through a release film (hereinafter referred to as the second release film of the present invention), which is characterized by comprising: (a ') a polymer An ester-based film having a surface having a centerline average thickness ^^ below Rugua and a ten-point average thickness Rz below 30nm; and (b ') a silicon release layer formed on the aforementioned surface of the aforementioned polyester-based film And 15 contains 0.3d ^ t ^ 2.5dn of inert particles satisfying the following formula (1), where d is the average particle diameter of the inert particles-the thickness (nm) of the Shi Xi release layer, and the thickness is less than 300nm . [Embodiment] An ideal embodiment of the invention The present invention is described in detail below. First, the first release film will be described. The first release film 'is composed of a polyacetate-based film (a) and a stone wicking film (b) formed on the surface. 200400879 The polyester of the polyester base film (a) is preferably a polyester using an acid component mainly composed of an aromatic dicarboxylic acid and an ethylene glycol component mainly composed of an aliphatic ethylene glycol. These polyesters are substantially linear and have base film formability, especially base film formability by fusion molding. 5 Examples of the aromatic dicarboxylic acid include terephthalic acid, naphthalene dicarboxylic acid, isophthalic acid, diphenoxyethane dicarboxylic acid, diphenyl dicarboxylic acid, and diphenyl ether dicarboxylic acid. , Diphenyl sulfo dicarboxylic acid, benzophenone dicarboxylic acid and onion dicarboxylic acid. Examples of the aliphatic ethylene glycol include ethylene glycol, trimethylene glycol, 10 tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, and decaethylene glycol. The number of carbon atoms is 2 to 10. Polymethylene glycol, and cycloaliphatic diols such as cyclohexanedimethanol. The polyester in the present invention is preferably one which uses an alkylene terephthalate or an alkyl 'qinic acid, and an ester as a main constituent. 15 Such polyesters, such as polyethylene terephthalate or polyethylene-2,6-naphthoate, are preferred. It should be understood that the polyethylene terephthalate contains a total dicarboxylic acid component such as 80% mol or more of terephthalic acid and a full ethylene glycol component such as 80% mol or more of ethylene Copolymer of alcohol. It should also be understood that the polyethylene-2,6-naphthyl ester contains 20% of the dicarboxylic acid component, such as 80% mol or more of 2,6-naphthalenedicarboxylic acid, and the total ethylene glycol component, such as 80% Above Mohr is a copolymer of ethylene glycol. If it is such a copolymer, 20% or less of it may be a dicarboxylic acid component different from p-dicarboxylic acid or 2,6-naphthalenedicarboxylic acid. Other such dicarboxylic acid components may be, for example, the aforementioned aromatic dicarboxylic acids; for example, adipic acid, 8 200400879 sebacic acid-like alicyclic dicarboxylic acids, or, for example, cyclohexane-1,4-dicarboxylic acid Similar to alicyclic dicarboxylic acids and the like. In addition, 20% or less of the total ethylene glycol content may be other ethylene glycol components other than ethylene glycol. Other such ethylene glycol components may be, for example, the above-mentioned ethylene glycols; for example, hydroquinone 'resorcinol, aromatic diols of 2,2-bis (4-hydroxyphenyl) propane; 1,4- Dihydroxydimethylbenzene is an aliphatic diol having an aromatic ring or polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyalkylene glycol (polyoxyalkylene glycol), and the like. In addition, the polyester in the present invention also contains a component derived from an oxygen-containing carboxylic acid, such as an aromatic oxo acid of hydroxybenzoic acid, such as an aliphatic oxyacid of ω-hydroxyhexanoic acid, and the like with respect to dicarboxylic acid. The total amount of the acid component and the oxygen-containing carboxylic acid component is copolymerized or combined at 20% or less. Also in the polyester, the amount in a substantially linear range is, for example, an amount of 2% or less relative to the total acid content, and also contains a polycarboxylic acid with a functional group of 3 or more or a polyacrylic acid compound such as triphenylhexanate. Acid acid, pentaerythritol copolymer. The above-mentioned polyester is known per se, and can be produced by a method known per se. The above-mentioned polyester is preferably a solution in n-chlorophenol and measured at 35 ° C to obtain an inherent viscosity of 0.4 to 0.9. The polyester-based film (a) in the present invention preferably contains inert particles. The average particle diameter of the inert 20 particles is preferably less than 1 μm, more preferably from 0.01 μm to less than 1 μm, and more preferably from 0.03 μm to less than 1 μm. The inert particles may be organic particles, inorganic particles, or mixed particles of organic particles and inorganic particles. The ratio of the major axis to the minor axis of the inert particles (major axis / minor axis) is preferably 1.0 to 1.2. By blending such inert particles, it is possible to form appropriate irregularities on the surface of the base film 9 ZUUUUUO✓7. Specific examples of Λ-producing poles on such inert saccharides include organic particles such as fire-fluoride calcium, amphibious clay, silica, sulfuric acid ^ A_, emulsified titanium, alumina, and the like; cross-linked polybenzene Ethylene, cross-linked ^ Yukiyuki-yuki particles, cross-linked acrylic-yuki-yuki particles, cross-linked polystyrene-yuki-yuki A4, organic resin particles of Hagi-ji Temple, and particles of non-money and organic materials with a shell-core structure . Such inert particles can be used in a mixture of two or more types, such as three or four, in a single word.

The addition amount of such inert particles is read to 0.3% by weight relative to the purpose of polymerization. The base film (a) preferably has a thickness of 0.1 to 30 times the average particle diameter of the inert particles contained. When the thickness of the polyester layer is less than 0.01 times the average particle diameter, the inert particles contained therein are liable to fall off, which is not desirable. When the average particle diameter is more than 30 times, inert particles contained in the polyimide layer are likely to overlap and unevenness is easily formed on the surface of the base film 15, which is also undesirable.

The polyester-based film (a) has a surface having a center line average thickness Ha of 15 m or less and a ten-point average thickness RZ of 30 to 500 nm. When Ra exceeds 15 nm, surface shape transfer of the formed body will occur. Ra is preferably at iwBnm. When Rz is less than 30 nm, the operability of the processing program is deteriorated due to the winding in the form of | Kun or the sliding with the roller, and on the other hand, when it exceeds 500 nm, the shape of the surface of the molded body is transferred.

Rz is preferably 50 to 300 nm. The thickness of the polyester base film (a) is preferably from 10 to 100 μm, and more preferably from 25 to 50 μm. 10 200400879 The first release film of the present invention is formed on the surface of the polyester-based film (a) having the above Ra and Rz, and a silicon release layer (b) described later is formed, but the film may also be formed on the surface On the opposite side surface of the mold layer (b) surface, another polyester layer is provided. The other polyester layer may be laminated with the polyester-based film (a) to form a laminated-based film. The laminated base film may be composed of at least two layers, and is preferably manufactured by co-extrusion. In this case, the polyesters constituting the layer may be the same or different, and the same is preferred. For laminated base film, for example, if B layer and C layer represent other polyester layers, polyester base film (a) layer / B layer, polyester base film (a) layer / B layer / polyester base 10 can be used. The film (a) layer or the polyester-based film (a) layer / B layer / C layer has a similar laminated structure. In the case of a laminated base film, the outermost layer on the opposite side to the polyester base film (a) on which the release layer (b) is formed, such as the B layer and the C layer in the above example, should preferably contain inert particles. At this time, the inert particles preferably have an average particle diameter of 0.1 to 1.0 μm. The laminated base film has a total thickness of 15 layers including the polyester base film (a) as a whole, and preferably has a thickness of 10 to 100 μm, and more preferably has a thickness of 25 to 50 μm. The polyester-based film (a) and the laminated polyester-based film itself can be produced according to a method well-known in the past or a method accumulated in the industry. In order to obtain a biaxially oriented base film, for example, melting and co-extrusion of polyester at a melting point (Tm: ° C) to (Tm + 70) ° C for 20 to produce an intrinsic viscosity of 0.4 to 0.8 dl / g The base film is not stretched. Next, the unstretched wax is 2.5 times or more at a temperature in a uniaxial direction (longitudinal or horizontal direction) (Tg: 10) to (Tg + 70) ° C (where Tg: glass transition temperature of polyester), And the stretching is performed at a better rate of 3 times or more, and then orthogonal to the above-mentioned stretching direction (8 ~ 0 ^ + 70). It is stretched at a temperature of 2.5 times or more and a better rate of 3 11 L or more. Or horizontal extension. After that, if necessary, the extension ratio in the longitudinal direction and / area is 9 times or more, and the full extension ratio of 12 = is made to make it ideal. In addition, the biaxially oriented base film may be better called Γ, especially at 15 to 25 times the temperature (where Tm: poly_ _ g + 7GK ~ (Tm-1 〇) C, the heat treatment of the helmet is performed, for example, 180 ~ 250 ° is preferably 1 to 60 seconds for the thermal fixation time. At this time, the laminated base film of each layer formed by different known base films °° < point and glass transition temperature, π melting point Λ '', Please refer to those who have the same > dish 10 and 0 on the next day. The surface transfer temperature of the poly 1 is for the formation of the secret glass transition temperature surface, as described on the single or double surface of the poly® base film sheet. Surface; the release layer (b) is formed on the polyester base film. The components of osmium or osmium are described in (3) __: Methyl Weisao is made up of the following ⑺ addition and molding stone resin. 20 K-methyl second oxygen polymer has the following D units, Τ unit and ^ early structure & stone eve resin. Blending the stone eve resin with the concentration of methyl groups in the middle layer of polydimethyl silicate fire can increase the surface tension. Also, Blend ratio depends on the solid The serving concentration is preferably 10 to 60% by weight. The resin is blended with Jin Xia, and if it is less than 10% by weight, the thirst is poor when forming a shaped sheet, and the adhesion is not good. When it is 60% by weight Above, the peeling force is large, and the formed body cannot be peeled.

R D —O — One O—difunctional

RRT -O-Ji-O- trifunctional ci- O -Q —〇— 丄 —〇— tetrafunctional, in which R represents an alkyl group, preferably a fluorenyl group, or an aromatic hydrocarbon, and a phenyl group Better. (2) Silica filler. By adding a silica filler to the polydimethylsiloxane polymer, it can be adjusted to increase the concentration of one Si-0H group in the release layer. The average particle diameter of the silica filler is preferably 1 μm or less. When the average particle size exceeds 1 μm, the turbidity (Haze) of the base film increases, and it is difficult to use in applications that require transparency, or the release layer is scratched when the base film slides in the processing step, which is not ideal. . The blending ratio of the silica filler is preferably 0.01 to 1% by weight based on the solid component concentration. When the blending ratio is less than 0.01% by weight, the sliding properties of the surface and the roll deteriorate, and when it exceeds 1% by weight, the oxide oxide filler is scraped off by the release layer and falls off, which is not desirable. (3) Denatured polydioxosiloxane in which a part of the methyl group in the polydimethylsiloxane polymer is substituted with a phenyl group. Due to the steric hindrance of the phenyl group, for example, the rotation motion around a Si—O—Si— bond in the polymer is suppressed, and as a result, the methyl group concentration on the surface of the release layer is reduced, so that its surface tension can be increased. Again, 13

ZUU4UU5 / V The substitution ratio of the phenyl group is less than 10 ～! 0% Mohr forming layer. Is better. This replacement ratio is easy to peel off and may not be applied. When the apricot exceeds 60% Mohr, it may cause poor wetting of the wedge field 5 10 15 20, so it is not ideal. Various adhesives and various sheets (4) Make polydimethylfluorene filaments with relatively high heptyl groups? Oxygen-reactive active lipids (such as alkyd resins, polyisocyanates, and organic tree-type polydimethylsparene oxides with a hydroxyl group in the oxidant. The denaturation is a dilute acid resin). The reaction is changed. 0 / ni ^ Zhongli / 〇 is appropriate. This ratio is less than 10 reset% caused poor mold release 'deprinting, so it is not good. Tian more than 30 weight division occurred Shi Xi's conversion (5) addition reaction type Enemy Xie Xijiu, for example, the Shixueshu type, which is composed of polyethylene dihydrogenation and hydrogenation after the introduction of vinyl, is said to have: polydimethyllithium oxygenation and hydrogenation The ratio of olefinic sintering is relative to that of hydrogenated diene succinate, sigmamor, and polydimethyl sulphur oxysintering in Yixian ~ 2. The ratio of turn ears is suitable. When adjusting the release layer The concentration of the methyl group can increase the surface tension. Therefore, it is also possible to mix the stone resin of the above resin with the stone resin. The blending ratio of the stone resin is from the viewpoint of obtaining an appropriate peeling force, The solid content concentration is preferably 以下 60% by weight or less, and more preferably 0 to 30% by weight. The above-mentioned polydimethyllithium oxide containing a vinyl group In addition to the -Si (CH3) 2- group, it also contains -SiAr2-, -SiAr (R) is not a problem. Among them, aromatic aromatic hydrocarbon group 'phenyl group is more preferred. R group is a carbyl group, and fluorenyl group is Even better. Polydimethyl sulfide with vinyl groups contains a CD3) -based or — 14 200400879

In the case of Si (Ph) 2-groups, the disorder of the molecular structure of the pinch is, from the viewpoint of ensuring a moderate peel force and sufficient hardness, compared to -si (CH3) 2-one group and 1 mole, these groups are in the range of 0.5 Those below Mo'er are preferred. The grandson is phenyl. Addition reaction type grease can also be formed by a three-dimensional cross-linked structure. The three-dimensional cross-linked structure can be obtained by reacting it with a platinum catalyst. 10 15 20 In addition to the above-mentioned heat-curable type of stone evening sclerosis, UV-curable and electron-wire-cured silicon are also used. It is important that the thickness of the release layer of Shi Xi be decomposed into a release layer on the surface of the polymer base film (a) to be ten times the average thickness of 2 × 8 times or less. When the pot of winter life is used, the purpose is to enter the concave part of the base membrane peaks. As a result, the average thickness Ra of the core material of the Wei layer surface mosquito towel Ra and the average thickness Rz of 4 points are reduced, and Tricks &, _ poor workability and mold release mold, even (lunar transfer) disadvantages. ~: The release layer 'contains those particles having inert particles with an average particle size, and the inert particles can be used to improve the internal and adhesion improvement effects. Muzhahe The first release film of the present invention, the stone mold release average thickness Ra is 15 or less and its ten = table: the center line, preferably 500 jobs. Ten "thousand average thickness Rz is rigid,

In the present invention, the release film 1 preferably has a sum of 12 nm or more, and has poor adhesion to the sliding through the roller (back transfer). The average thickness Ra of the centerline of the exposed surfaces of both sides is less than 12_, and the poor operability and release layer 15 of a roll of roll in the form of a roll 15 200400879 The release layer is within a range that does not hinder the object of the present invention. Various well-known additives can be combined. This additive can also be used to order violet absorbers, pigments, defoamers, and antistatic agents as needed. In the present invention, an adhesive layer may be provided between the base film (a) and the release layer ⑻ to improve the adhesion between the polyester base film (a) and the release layer (b). For this adhesive layer, for example, a sintered binder can be appropriately used. The silane coupling agent may be represented by a formula Y-Si-domain. Among them, ¥ represents a functional group represented by an amino group, an epoxy group, a vinyl group, a methacryl group, a mercapto group, and the like, and X represents a hydrolyzable functional group represented by an alkyl group. The ideal thickness of the adhesive layer is about 0.1 to about 0.1, and more preferably about 0.02 to about 0.5 μm. When the thickness of the adhesive layer is within the above range, the adhesion of the polyester-based film (0) and the release layer (b) is good, and the polyester-based film provided with the adhesive layer (b) is difficult to cause trouble when it is difficult to handle due to adhesion. . The release layer in the present invention may be coated on a base film coated with a coating liquid containing 15 parts of the release layer component, and then heat-dried. This coating liquid can be applied by any known coating method. The applicable coating method includes, for example, a roll coating method and a sheet coating method, but is not necessarily limited to such a method. The heat-drying for forming the coating layer is preferably performed at 70 to 170 for 20 to 60 seconds. 20 'Next, the second release film of the present invention will be described. The second release film is composed of a polyester-based film (a ') and a release film (b') formed on the surface. As the polyester of the polyester film (a '), the same polyester as described in the first release sheet can be used. 200400879 8 7 base film (0, either with or without inert particles. When inert particles are contained, the same inert particles as those described for the poly-based base film of the first release film (a >) can be used. . Such inert particles can be used alone or in combination of two or more. Such inert particles can be blended in an amount of 0.2% by weight or less relative to polyacetic acid. Polyimide base film (a,), * with center Line average thickness _5 or less and ten-point average surface roughness ㈣ 3Gnm or less. When the centerline average thickness 5 exceeds 5_, the thin layer forming sheet will damage the surface smoothness, = point average surface roughness (RZ) When the thickness exceeds 30nm, a thick spot will be formed on the formed sheet, and 10 will cause poor electrical characteristics for the use of electronic materials.-~ 0 · 5ηπι is preferred 'Rz is preferably 3 ~ 30nm. The thickness of the film (0 is preferably 10 to 100%, more preferably 15 to 50%). The second release film of the present invention is provided on the surface having the above-mentioned and a base film 15 (a). 'Formation of the below-mentioned ㈣ release layer &,), and a table on the opposite side of the surface forming the release layer (b) It does not matter if there are other polyimide layers. Other such polyimide layers can be combined with the ester-based film (a,) to form a laminated base film. The laminated base film was described in the first film. It should be understood that it is understandable that the polyester-based film (a) is replaced by the polymer-based film 0 ') and is still applicable. 20 Also, the polyester-based film (a') and the above-mentioned laminated base film can be separated from the related The manufacturing method described in the mold film is produced in the same process. As described above, the second release film of the present invention is formed by forming a silicon release layer (b,) on the surface of the polyacetate-based film ⑹. Silicon release The mold layer (b ') is formed on one or both sides of the polyester-based film (a,).

17 200400879 Yes. The release layer is composed of polydimethylsiloxane or the main component, and it is preferable to mix the aforementioned (1) or (2) components of the release layer of the first release film. (3) or (4) is made of modified polydimethylsiloxane or the same silicone resin as (5) 5 above. Among these, the addition of silicone resin is ideal. The stone release layer in the second release film is preferably one having a hardness of 100 mgf / μm 2 or more in the measurement of micro hardness. Since the hardness is set to 100 mgf / μηι or more to prevent blocking, the contact area when the base film is rolled into a roll shape can be extremely narrowed, and peeling and charging can be suppressed. The thickness of the release layer of Shi Xi is below 300 nm, preferably 30 to 300 nm, and more preferably 50 to 200 nm. When it exceeds 300nm, it is easy to cause adhesion. When it is less than 30 nm, the peeling characteristics become unstable and peeling becomes difficult, which is not desirable. In this matter, the ε release layer contains inert particles. Inert particles, with many fine unevenness on 15 flat release levels. Since the unevenness is very fine, the shape of the unevenness is such that the defect is not generated even if the release film is transferred to the formed sheet. The addition of the inert particles can improve the transfer (adhesion) to the back surface of the release layer, and can improve processability. For this purpose, the average particle size of the inert particles is preferably from 1 to 100 nm, more preferably from 3 to 20 to 80 nm, and particularly preferably from 3 to 50 nm. The ratio of the major axis to the minor axis of the inert particles (major axis / minor axis) is preferably 1.0 to i.2. Such inert particles may be either organic particles or inorganic particles, and mixed particles of organic particles and inorganic particles may be used. Specific examples of such inert particles include inorganic particles such as calcium carbonate, kaolin, silica, barium sulfate, titanium oxide, 18 200400879 alumina, magnesium oxide, zirconia, crosslinked polystyrene resin particles, and crosslinked silicon. Organic resin particles such as resin particles, cross-linked acrylic resin particles, and cross-linked polystyrene resin particles, and particles having organic and inorganic materials having a shell-core structure. Particularly, in the case of fine particles, inorganic 5 particles are preferable. The blending amount of the inert particles in the release layer of Shi Xi is preferably 0.1 to 25% by weight, and more preferably 0.3 to 5% by weight. When the addition amount is less than 0.1, sliding properties and blocking of the release layer are caused, and the release characteristics of the release layer are unstable, so it is not desirable. When it exceeds 25% by weight, the transparency is lowered, which may cause coarsening of aggregates. 10 Aggregates are not preferable. The silicon release layer must satisfy the following formula (1): 0.3d ^ t ^ 2.5d --- (1) where t (nm) is the thickness of the stone release layer and d (nm) is the thickness of the inert particles. The average particle size. 15 When the degree t (nm) of Shi Xizhi's release layer is less than 0.3d, the inert particles will fall off and cause foreign matter. When it exceeds 2.5d, the fine unevenness on the surface cannot be formed, resulting in poor sliding properties, resulting in handling and coiling. Poor electrical properties and peeling. In the second release film of the present invention, the protrusions on the exposed surface of the release layer are preferably 20 so as to satisfy the relationship of the following formulae (2) and (3). HD52 500 pcs / nm2 --- (2) HD102 100 pcs / nm2 --- (3) HD5 is the number of protrusions above 5nm in height and HD10 is the number of protrusions above 1 Onm in height, 19 to meet the above It is ideal. When HD5 is less than 500, it is not suitable because it causes poor sliding properties, and results in poor handling, rewindability, and peeling charging. When HD10 exceeds 100, its shape is transferred to the surface of the formed sheet, which causes the sheet to have thick spots, which is not ideal. 5 'HD5 and HD10 are more preferable to satisfy the following relationships (2,) and (3,). 10,000 ^ HD5 ^ 1, 〇〇〇… (2,) Hall HD10S70 " · (3,)

In the second release film of the present invention, the center line average roughness Ra of the exposed surface of the silicon release layer (b,) is preferably 5 nm or less, and the ten-point average thickness rz thereof is preferably 300 nm or less. The release layer in the present invention may be added with an additive as long as the object of the present invention is not impaired. Examples of the additive include an ultraviolet absorber, a pigment, an antifoaming agent, and an antistatic agent. Alternatively, the additive may be blended with a resin separately from the release layer, and the resin may be coated on the surface of the polyester-based film (a,) 15.

In the present invention, in order to improve the adhesion between the polyester-based film (a,) and the release film, the polyester-based film (a ') is corona treated or the polyester-based film (a,) and the release layer are corona-treated. It does not matter if there is a bonding layer between them. The next layer is preferably a silane compound. As the silicon-fired bonding agent, the same ones described in the first release film can be used. 20 The ideal thickness of the above-mentioned adhesive layer is about 0.005 to 0. Ιμηι, especially 0.01 to 〇.ΐμπι. When the thickness of the adhesive agent is in the above range, the adhesion between the polyester base film (a,) and the release layer is good. The formation of the release layer can be performed in the same manner as described in the first release film. It should be understood that matters not described in the second release film may be applied in accordance with the matters described in the first release film in 20 sections, or with changes clearly understood by the practitioner. EXAMPLES The present invention will be further illustrated by the following examples. In addition, each characteristic value of the base film was measured by the following method. (1) The average particle diameter (d) of inert particles is measured using a CP-50 centrifugal particle size analyzer (CENTRIFUGAL PARTICLE SIZE ANALYZER) manufactured by Shimadzu Corporation. Based on the obtained telecentric sedimentation curve, a cumulative curve between particles of each particle size and the amount of existence is calculated, and a particle size equivalent to 50% is estimated, and the value 5 is again referred to as the average particle size. (The book "Particle Size Measurement Technology" published by Nikkan Kogyo Shimbun, 1975, pp. 242 ~ 247). (2) The average particle diameter and the major / minor diameter ratio of the inert gardenia in the base film. The base film sample was embedded in epoxy resin, and the section was cut out at a thickness of 50 μm, and then placed in a TEM (transmission electron microscope). ) The particle shape in the cross section is measured. (3) Centerline average thickness (Ra (nm)), HD5 and HD10 contact measurement method Centerline average thickness (Ra) is a value defined in accordance with JIS-B0601, using the stylus of Kosaka Research Institute Surface roughness meter (SURFCORDER SE-30C). The measurement conditions are as follows. (a) Stylus tip radius: 2μηι (b) Measurement pressure: 30mg (c) Die slit ridge: 0.25mm (d) Measurement length: 1.0mm 200400879 (2) Centerline average thickness Ra (nm) Non-contact measurement law

Centerline average roughness (Ra) is measured using a non-contact surface roughness meter from WYKO CORPORATION NT-2000. The measurement conditions are as described in 5 below. ⑷Measurement range: 0.0462 μηι (b) Measurement magnification: 25 times HDI HD10 according to WYKO measurement data, obtain particle size and protrusion distribution, and set the protrusion number at 5 nm particle size to HD5, 10 face particle size Call of Prominence 10 is set to HD10. (4) Ten-point average roughness (Rz (nrn)) The ten-point average roughness (RZ) of the contact measurement method is a value defined in accordance with JIS-B0601. In the present invention, a stylus type manufactured by Kogyo Co., Ltd. is used. Surface roughness meter 15 (SURFCORDER SE-30C), only the length of the reference length is extracted from the section curve of the obtained data, and the average value of the summit elevation up to No. 5 and the deepest to No. 5 are displayed. The value of the difference between the mean values of the trough bottom elevations. · Non-contact measurement method The ten-point average surface roughness Rz is measured by a non-contact surface roughness meter of WYKO CORPORATION 20 NT-2000. The measurement conditions are as follows. ⑻Measurement range: 0.0462 μηι (b) Measurement magnification: 25 times Even if any kind of measurement method is used, the section curve 22 of the data obtained is obtained from the 200400879 line. Only the length of the reference length is displayed, and No. 5 is displayed. The value of the difference between the average of the peak elevation and the average of the valley bottom elevation from the deepest to the fifth. (5) Film thickness measurement (Tsi (nm)) of Shi Xi The section of the release film was cut with a microtome, and the obtained sample 5 was placed in a TEM and observed to measure the thickness of the silicon layer. (6) Operational dynamic coefficient of friction pS: Put two release films on the glass plate, and then pull the base film under the base film (the base film in contact with the glass plate) after the overlap, and pull it away at a constant speed, and The tester is fixed at one end of the upper base film to test the tensile force (F) between the base film and the base film. In addition, a load (P) of 200 g / 50 cm 2 was placed on the base film. pS = F (g) / P (g) pS = 1 or less Good operability ◎ Operate more than 2 or less is possible.

15 pS = 2 or more can not be X-adhesive: take the release film 1000 rolls, roll at 60 ° C after XI months aging, visually observe the release phenomenon of the release surface of the base film and its back surface according to the following criteria Evaluation. 20 〇: No blocking phenomenon X: There is blocking phenomenon Explosiveness: The surface of the base film was abraded with black paper, and the occurrence of white haze was visually observed and evaluated according to the following criteria. 23 200400879 〇: No white haze phenomenon X: White haze phenomenon (7) Measurement of hardness The hardness is measured by using EKT Co., Ltd. Co., Ltd. 5 Ent-110a 'to directly measure the hardness of the release layer film. The measurement system was placed on a triangular hammer head with a weight of 2 mgf, and the hardness was calculated from the amount of deformation of the release layer. Example 1 Preparations were made of polyethylene terephthalate A and B. Polyethylene terephthalate fe A was used in a layer with a release layer side, and polyethylene terephthalate 10 ethylene glycol was prepared. Alcohol ester B is used in the other layer, and is manufactured as a laminated poly-Si-based film having a two-layer structure. First, dimethyl terephthalate and ethylene glycol, manganese acetate as a vinegar exchange catalyst, trioxide as a polymerization catalyst, and linolenic acid as a stabilizer, and an average particle size of 1 μm of oxidized stone are used. Inert particles with 3% wt I5 as a slip agent were polymerized according to the usual method to obtain polyethylene terephthalate A with inherent viscosity (o-chlorophenol'35 ° C) 0.62. Instead of oxidative breakdown, cross-linked stone particles (major diameter / minor diameter = 1.05) with an average particle diameter of 0 and 0.05% by weight and an average particle diameter of oxidized particles with 0.4% by weight are used as a lubricant. Inert particles, and others were prepared in the same manner as the aforementioned polyethylene terephthalate A polyethylene glycol terephthalate B. The particles of this kind of stupid-ethylene glycol formate were fed to two extruder hoppers after drying for 3 hours in the 17th generation, and were melted at the melting temperature of ~ 3 thieves. Extruded on a surface-processed surface. On the surface of a rotary cooling drum with a surface temperature of 20 ° C and a dish temperature of 20C, an unstretched 2-layer laminated base film was prepared. The non-stretched laminated base film obtained should be obtained. [Preliminarily, an IR heater with a 90 representing surface temperature of 5 is placed above the low-speed and high-speed roller space 15_ to be heated and stretched 36 times, quenched, and then supplied to the tenter, and horizontally at 105 ° C. The direction extends 39 times. Then, the obtained biaxially oriented base film was heat-fixed at a temperature of 205 C for 5 seconds to obtain a thickness% drop (the thickness of the eight-layer polyacetate provided with the release layer side was 36 mm, and the polyacetate on the opposite side was Heat-fixed double-sleeve oriented laminated polyacetate-based film with a thickness of B layer of 2 μm). 1〇 # On this base film, a mixed solution of polydimethylmethane and dimethylhydrodiene stone is added to a platinum catalyst to produce an addition reaction type hardened silicon (manufactured by Koshi Silicone Co., Ltd.) KS-847 (H)) was dissolved in a mixed solvent of methyl ethyl ketone, isobutyl ketone and toluene to make a solution having a solid content concentration of 3% by weight, and by a conventional roll coating method, A release film having a film thickness of 551101 and dried after coating was prepared. Heat and dry, place at 160. (3 for 30 seconds. The characteristics of this release film are shown in Table 1. Example 2 The inert particles blended with polyethylene terephthalate in Example 1 were changed to 0.12% by weight on average. Cross-linked silicon particles with a particle diameter of 0.3 μm; polyethylene terephthalate B is changed to those without inert particles. This polyethylene terephthalate is made The composition of Α / Β / Α was placed in a multi-tube stamper for co-extrusion, and the thickness was adjusted to form A / B / A = 2 μηι / 34 μηι / 2 μηι. The release film was made to 77 nm. Except for this, a release film was prepared in the same manner as in Example 1. 25 200400879 Example 3 Using only polyethylene terephthalate A used in Example 2 to make a 38 μm base film The release layer was made to 77 nm. Except for this, a release film was prepared in the same manner as in Example 2. 5 Comparative Example 1 Dimethyl terephthalate and ethylene glycol were used, and manganese acetate was used as the ester. Exchange catalyst, using antimony trioxide as a polymerization catalyst and phosphorous acid as a stabilizer Viscosity (o-phenol, 35 ° C) of poly (ethylene terephthalate). Polyethylene terephthalate is blended with 10 silicon dioxide with an average particle diameter of 1 · 7 μm 0.05% by weight as a slip The inert fine particles of the agent were used to prepare a single-layered base film and the thickness of the release layer was set to 98 nm. A release film was prepared in the same manner as in Example 1. Comparative Example 2 Comparative Example 1 The inert particles were replaced with particles having an average particle diameter of 0.1 μm, except for 15. In the same manner as in Comparative Example 1, a release film was prepared. Comparative Example 3 A silicon film was coated on the base film prepared in Example 1 A mold release film having a thickness other than 200 nm is prepared in the same manner. 26 200400879 Table 1

\ Polyester-based film release film Ra (one side) (nm) Rz (one side) (nm) Ra (other side) (nm) One side (release side) Other side (nm) Roughness (nm) Tsi (nm) Processing suitability Ra (nm) Rz (nm) Example 1 12 132 12 10 76 12 22 77 〇 Example 2 7 74 9 5 35 9 14 55 〇 Example 3 13 142 14 11 83 13 24 77 〇 Comparison Example 1 29 870 29 27 790 29 56 98 Comparative Example 2 5 58 5 3 12 5 8 55 X Comparative Example 3 7 74 9 2 10 9 11 200 V · J Example 4

First, 'diethyl terephthalate and ethylene glycol are used as a transesterification catalyst, antimony trioxide is used as a polymerization catalyst, and pentanosuccinic acid is used as a stabilizing agent'. Polyethylene terephthalate with inherent viscosity (o-chlorophenol '35 ° C) 0.62. The pellets of polyethylene terephthalate were dried at 170 ° C for 3 hours, and then fed to the extruder hopper. The pellets were melted at a melting temperature of 280 to 3000 ° C, and were extruded on the surface using an extrusion die. At a level of 3s, the surface temperature is reduced on a 10 cooling drum to produce an unstretched base film with a thickness of 540 μm.

The unstretched base film was at 75 ° C. 〇 Preheat and place a 90 ° above 15mm from the low-speed profile and the high-speed profile. 〇The surface temperature of the flood heater is heated on both sides, and the uniaxial extension of the plane in the longitudinal direction is 3.6 times, and then it is quenched, and then the supply expander is extended to 39 times in the transverse direction at 105 ° C to obtain a biaxial orientation base 15 membrane. The biaxially oriented base film is thermally fixed at a temperature of 205t to obtain a heat-fixed cooked oriented base film 4 with a thickness of 38, and the fixing process of the stone eve after uniaxial extension is 3_ An aqueous solution of glycidoxypropyltrimethoxysparite was applied by a kiss coating method. 27 200400879 Take _ on the heat-fixed biaxially oriented base film, add a mixed solution of formazan oxygen and methyl hydrogenated diphenyl below the phenylgomer, from the gold catalyst to produce an addition reaction type of hardening Type Ishiba resin (Shin-Etsu, > Mouth 3 > KS 774, manufactured by the company) 'Cold in a mixed solvent of methyl ethylformamidine, isobutylpyrene and toluene 5, and add 0.5% by weight of Ishiba resin content. Oxide stone eve particles (Nippon Kogyo ':; R972 average particle size manufactured by Kojisha Co., Ltd. was used as inorganic particles to make a solution with a solid content concentration of 1% by weight. The light coating method according to the usual method was used to form the solution after coating The thickness of the dried film was 45-leg mold release film. The heat-drying method in the rough coating method was performed at 15 t for 20 seconds. The characteristics of the release film ^ 10 are shown in Table 2. Dimethyl phthalate and ethylene glycol, using manganese acetate as a vinegar exchange catalyst, using antimony trioxide as a polymerization catalyst, using arsenic acid as a stabilizer, and admixing 0.12% by weight of oxidized stone with an average particle diameter of 0 μm 15 as inert particles of lubricant, according to the usual method Polymerization was carried out to obtain polyethylene terephthalate with an inherent viscosity (orthophenol, 35 ° C) of 0.62. The granules of the polyethylene terephthalate were prepared at i7 (rc for 3 hours). After drying, it is supplied to the extruder hopper and melted at a temperature of 280 ~. C. Into the melt · Use an extruder to extrude on a rotary cooling drum with a surface processing of about 0.3s and a surface temperature of 20 ^ to obtain a thickness of 540μm Extend the base film. Preheat the unstretched base film at 75 ° C, located between the low speed roller and the high speed roller, 15mm away from the high speed roller. The uniaxial stretching was 36 times, and then it was quenched, and then supplied to the tenter, which was extended to 3.9 times in the transverse direction of 105t to obtain a biaxially oriented base film 28 200400879. The heat-fixing was performed at a temperature of 〇5 ° C for 5 seconds to obtain a heat-fixed biaxially oriented base film with a thickness of 38 μm. In addition, after uniaxial stretching, the silicon was fixed with 3-glycidoxypropyltrimethyl The oxysilane solution is applied by a kiss coating method. 5 On the heat-fixed biaxially oriented base film, apply A gold catalyst is added to a mixed solution of polymethylsiloxane and difluorinated hydrogenated diene silane to produce an addition reaction type hardened silicone resin (Shin-Etsu 4: 7 KS-774, manufactured by YI Corporation) and dissolved In the mixed solvent of methyl ethyl ketone, isobutyl ketone and toluene ^ "", plus equivalent; δ resin content 0.2% by weight of oxidized stone particles (manufactured by Nippon Kogyo Co., Ltd. 7 10 R972 average particle diameter 30nm) As inorganic particles, a solution with a solid content concentration of 1% by weight was prepared, and the dry film thickness was M · coated in accordance with the Charm Cloth method of f method to prepare a release film. Roll coating The heating and drying method in the method was performed at 150 t for 20 seconds. The characteristics of this release film are shown in Table 2. 15 Example 6 The polyethylene terephthalate prepared in Example 4 and the polyethylene terephthalate_a prepared in Example 2 were used to prepare polyethylene terephthalate. A release film was prepared in the same manner as in Example 4 except that the base film was composed of diol / polyethylene terephthalate A = 36 ° / 2/2 °. 20 Comparative Example 4 A mold release base film was prepared in the same manner as in Example 4 except that the inorganic particles were not blended with the stone mold release layer of Example 1. The characteristics of this release film are shown in Table 2. Comparative Example 5 29 200400879 A release film was produced in the same manner as in Example 4 except that the thickness of the silicon release layer of Example 4 was set to 100 nm. The characteristics of this release film are shown in Table 2. Comparative Example 6 5 A release film was produced in the same manner as in Example 4 except that the particles added to the silicon release layer of Example 4 were set to 30% by weight. The characteristics of this release film are shown in Table 2. Comparative Example 7 A release film was produced in the same manner as in Example 4 except that diphenylsilane was added to the diphenylsilane content of 10% in the release layer by adding 5% mol. The characteristics of this release film are shown in Table 2. Table 2

Ra (nm) Rz (nm) Hardness mgf / μηι 2 HD5 pieces / mm2 HD10 pieces / mm2 t / d Adhesive exploitation Example 4 0.9 13 108 1200 70 1.5 〇 Example 5 3.8 28 104 9600 95 2 〇〇 Implementation Example 6 0.9 13 108 1300 72 1.5 〇〇 Comparative Example 4 0.7 10 105 100 40 — X 〇 Comparative Example 5 13 48 104 8 300 180 3, 3 XX Comparative Example 6 26 63 102 13000 230 1.5 〇X Comparative Example 7 0.78 13 93 1100 Ί5 1.5 X 〇t Schematic description 3 (none) 15 [Representative symbol table of main components of the diagram]

Claims (1)

200400879 Scope of patent application: k — A release film, including: (a) a polyester-based film having a surface having a centerline average thickness Ra of 15 nm or less and a ten-point average thickness Rz of 30 to 500 nm; and 5 (b) A silicon release layer formed on the aforementioned surface of the aforementioned polyester-based film and having a thickness of 0.8 times or less the Rz of the aforementioned surface. 2. The release film according to item 丨 of the patent application scope, wherein the average thickness of the center line of the exposed surface of the aforementioned silicon release layer) is ^ is below 15nm and the ten-point average thickness is 1 ^ is 100 ~ 500nm ° 3. The release film according to item 1 of the patent application, wherein the sum of the average thicknesses Ra of the center lines of the two exposed surfaces is above 12 nm. 4. The release film according to item 1 of the patent application, wherein the aforementioned polyester-based resin (a) contains inert particles having an average particle size of less than 1 μm. 15 • The release film according to item 3 or 4 of the patent application, wherein the average particle diameter of the aforementioned inert particles is above 0.01 μηι and less than 1 μηι, and the ratio of the long diameter / short control is 1.0 to 1.2. 6 Female •: The release film of the scope of application for item 丨, in which the aforementioned silicon release layer (b) is composed of polydimethylsiloxane. > OH patent, the release film of item 1 or 6, wherein the front release layer 3) has inert particles having an average particle diameter of 5 to 80 nm. For example, in the release of the patent application No. 丨, there are other polyimide layers on the opposite side of the surface on which the stone release layer (b) of the aforementioned polyester-based film () exists. 9 · —A release mold comprising: 31 200400879 10 (a ') A polyacetate-based film having a surface having a centerline average thickness Ra of 5 nm or less and a ten-point average thickness Rz of 30 nm or less; and (b,) A silicon release layer formed on the aforementioned surface of the aforementioned polyester-based film and containing inert particles 0.3d ^ t ^ 2.5d which satisfy the following formula (1): (1) where d is the average particle diameter of the inert particles (nm), and the thickness (nm) of the t-based silicon release layer is 300 nm or less. 10. The release film according to item 9 of the patent application scope, wherein the center line average roughness Ra of the exposed surface of the foregoing stone release layer (b,) is below 5 nm and the ten-point average thickness Rz is below 30 nm. 15 11. The release film according to item 9 of the scope of application for a patent, wherein the protrusions existing on the exposed surface of the aforementioned Shi Xi release layer (b ') satisfy the following formulae (2) and (3), HD5 2 500 / nm2 ... (2) HDIO ^ 100jgJ / nm2. &Quot; (3) Among them, HD5 is the number of protrusions with a height of 5nm or more, and hd 10 passes the number of protrusions with a height of 10nm or more. 12. The release film according to item 9 of the application, wherein the aforementioned silicon release layer is used as an addition reaction type composed of polydimethylsiloxane containing a vinyl group and hydrogenated diene silane. Made of silicone resin. 13. If the mold release of item 9 or 12 of the scope of the patent application, the micro hardness of the layer (b ') is above 100 mgf / μηι2, among which the aforementioned silicon is released from the mold. 14. The release film of the scope of the patent application, item 12' Which contains vinyl] difluorenylsiloxane, one mole per Si (CH3) 2 ~ 0.5 moles, 32 200400879 of -Si (C6H5) 2. 15. The release film according to item 9 of the application, wherein the inert particles in the aforementioned silicon release layer (b ') are inorganic particles having an average particle diameter of 3 to 80 nm. 16. The release film according to item 9 of the patent application scope, wherein other polyesters are present on the opposite side of the stone release layer of the polyester base film 5 (a ') (the surface to which t0 exists).蠡 勹 Λ 200400879 柒 Designated representative map: (1) The designated representative map in this case is: () Figure. (II) Brief description of the component representative symbols in this representative map: (None) 捌 If there is a chemical formula in this case, Please reveal the chemical formula that best characterizes the invention