TW200522807A - Release film - Google Patents

Abstract

Disclosed is a release film which excels in high-temperature flexibility, unevenness follow-up property, thermal stability, mold release capability and non-staining property and after service, can be easily disposed of. The release film is used in the manufacture process of substrates for printed wiring boards, flexible printed wiring boards or multi-layered printed wiring boards. The characteristics of the release film is that it has at least one major surface thereof provided with a layer of resin composition comprising a resin having polar groups on its main chain as a matrix wherein halogen is contained at a ratio of 5 wt.% or less.

Description

200522807 2. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a release film used in the manufacturing process of a printed wiring board, a flexible printed wiring board, or a multilayer printed wiring board. [Prior art] In the manufacturing process of printed wiring boards, flexible printed wiring boards, multilayer printed wiring boards, etc., when hot pressing of copper area laminates or copper foils through prepolymer sheets or heat-resistant films, Use to release film. Furthermore, in the manufacturing process of the flexible printed substrate, a thermosetting adhesive or a thermosetting adhesive sheet is used to heat-bond a laminating film or a reinforcing plate of the flexible printed substrate body on which the electrical circuit is formed. In order to prevent the adhesion between the coating film and the hot press plate, a release film is widely used. For the release film used for the aforementioned application, a fluorine-based film and a silicon-coated polyethylene terephthalate as disclosed in Japanese Patent Laid-Open No. 2-1 75247 or Japanese Patent Laid-Open No. 5-283862 have been used. Ester film, polymethylpentane film, polypropylene film, etc. In recent years, the social requirements for environmental issues and safety have increased, so for these release films, in addition to the heat resistance of hot press forming, the release properties for printed wiring boards or hot dust boards In addition, it is also necessary to improve the performance of the waste treatment. Furthermore, in order to improve the yield of products during hot pressing, the non-contamination of copper circuits has become increasingly important. 200522807 However, the fluorine-based film used as a release film in the past has excellent financial and thermal properties, release, and non-polluting properties, but it is expensive, and it is not easy to burn when it is used for incineration treatment after use. Toxic gases, these are issues. In addition, silicon-coated polyethylene terephthalate films and polymethylpentene films can cause contamination of printed wiring boards, especially copper circuits, due to movement of low molecular weight substances contained in silicon or constituents. Risk of harm to quality. In addition, the polypropylene film has poor heat resistance and insufficient release properties. Also, Japanese Patent Application Laid-Open No. 2003-31 3313 describes a resin having at least one layer containing at least one type of thermoplastic resin and / or thermosetting resin. 〇〇〇parts by weight, layered silicate 0 · 1 10 A release film of a layer composed of 0 parts by weight of a resin composition. This release film does not generate toxic gases like fluorine-based films, nor does it cause pollution due to the movement of low molecular weight, like silicon-coated polyethylene terephthalate films and polymethylpentene films. In addition, it is extremely excellent in heat resistance and release properties. However, the followability of the unevenness is insufficient, and it cannot sufficiently exhibit the printed wiring board, the flexible printed wiring board, the multilayer printed wiring board, and the flexible printed circuit board having unevenness on the surface where the complicated electrical circuit is formed during hot pressing. This is the problem. In addition, in the layered fossilate, the low molecular weight shellfish which is the cause of outgassing is bound to be attached, so even if the low molecular weight substance only causes the generation of some outgassing, the substrate may still be polluted. [Summary of the Invention] The object of the present invention is to provide a release film which is excellent in softness and concavity at high temperatures. The invention is a release film, which is used by a user in the manufacturing process of a printed wiring board, a flexible printed wiring board, or a multilayer printed wiring board; it is characterized in that at least one surface has polarity in the main chain. The base resin is a layer composed of a resin composition having a matrix and a functional composition content of 5% by weight or less. The resin having a polar group in the main chain is preferably a crystalline aromatic polyester, and the crystalline aromatic polyester is more preferably a crystalline component containing at least poly (phenylene terephthalate). At this time, the heat of melting of Kyrgyzstan is preferably 40 J / g or more. The glass transition temperature of the crystalline aromatic polyester is preferably 0 to 100 ° C. In the release film of the present invention, the outgassing amount when heated at 17 ° C for 10 minutes is preferably 200 ppm or less. DETAILED DESCRIPTION OF THE INVENTION The present invention is described in detail below. In addition, the film referred to in this specification is not only a single finger The film also includes a sheet. The release film of the present invention is a release m used in the manufacturing process of a printed wiring board, a flexible printed wiring board, or a multilayer printed wiring board: the release m used, that is, the "release of the present invention" Type film, can be used in printing, for example, flexible printed circuit board, flexible printed wiring board or multilayer printed wiring board. 'Does the copper area laminate or copper fall through the pre-polymer sheet or heat-resistant film? It is used during molding. In addition, the release film of the present invention can be used in the manufacturing process of flexible printed substrates, such as 200522807, by using hot-press molding to make the coating film or reinforcing plate with a thermosetting adhesive or a thermosetting adhesive sheet. The release film of the present invention has a layer (hereinafter also referred to as a release layer) composed of a resin composition having a resin having a polar group in the main chain as a matrix and having a functional element content of 5% by weight or less. Constitutionally The resin composition of the release layer has a halogen content of 5% by weight u. The release film of the present invention having a release layer composed of the resin composition hardly generates a harmful substance containing halogen even when incinerated. It is preferably 3% by weight or less, and more preferably j% by weight or less. As long as the content is less than 1% by weight, a non-vegetable substance recognized in Europe can be obtained. The content of halogen can be measured by a conventional halogen analyzer. 〇The resin composition constituting the release layer is based on a resin having a polar group in the main chain. As long as the resin is used as the substrate, the release film of the present invention can exhibit excellent mechanical properties, especially 4 Excellent mechanical properties can be exhibited in a temperature range of about 1 70 c when hot-pressed. The polar group of the resin having a polar group in the main chain is not particularly limited, and examples thereof include an ester group, amidino group, and amidine. Group, ether group, thiol group, carbonyl group, hydroxy group, amine group, carboxyl group, etc. The resin having a polar group in the main chain is not particularly limited, and examples thereof include polyester compounds, polyphenylene sulfide, and polyetheretherketone. Polyamine compound Materials, polyimide compounds, etc. These 200522807 resins with polar groups in the main chain can be used alone or without heteroatoms in the molecule and can be reduced: 丄 species. Among them, based on the use of reducing the environmental impact of incineration treatment The influence is on the economic level. There are also examples of Qin aromatic polyvinegar. It is suitable for the aromatic dicarboxylic acid or the aromatic dicarboxylic acid. The s-day forming derivative is low. 5. The aliphatic diols are reacted and passed to the low sterilizer. In addition, the above-mentioned, "°" raw aromatic polyester can also be made aromatic : ―End-acid or its ester-forming derivative is obtained by reacting with a low molecular weight diol and $ ίΓίΓ. (The following will also be obtained in this way, crystalline aromatic aromatic records & θ is called the knot with a polyether skeleton in the main chain: sex: aromatic polyvinegar). In addition, the crystalline aromatic polyvinegar may be dissolved in hexamethylene diacetic acid or its intended forming derivative and a low-molecular-weight lipid t. After the early body, 'caprolactone is obtained by ring-opening polymerization (hereinafter, the crystalline aromatic polyester served in this way is also referred to as a crystalline aromatic polyvinegar with a polycaprolactone skeleton in the main chain.) ). Among them, a release film composed of: a crystalline aromatic polyvinegar having an ether skeleton in the chain and / or a crystalline aromatic polyvinegar having a caprolactone skeleton in the main bond; A release film composed of a crystalline aromatic poly ^ obtained by reacting a carboxylic acid or an ester-forming derivative thereof with a low-molecular-weight aliphatic diol not only maintains financial properties, but also has excellent soft blood release properties. Examples of the aromatic dicarboxylic acid or an ester-forming derivative thereof include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid 200522807 acid, terephthalic acid, and terephthalic acid. Dimethyl, isophthalate, dimethyl phthalate, dimethyl naphthalate, dimethyl monocarboxylic acid, etc. These can be used singly or in combination of two: ^ "alcohols, 1, 4 above-mentioned low-molecular-weight aliphatic diols, for example, ethylene glycol, 1,2-propylene glycol, i, 3-propylene glycol, u Monobutylene, monobutylene glycol, neopentyl glycol, 1,5-pentanediol and 50 hexane are used in combination with 1,4-cyclohexanedimethanol. These can be used alone, at least 2 kinds. May-Mobil, T-None-These can be used alone. Examples of the high-molecular-weight diols include polyethylene tetramethylene glycol and polyhexamethylene glycol. A combination of at least two types may be used. Examples of the crystalline mono-aromatic polyacetate formed from the above constituents include polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, and poly (ethylene terephthalate). Ethylene terephthalate, polybutylene terephthalate, polybutylene terephthalate polytetramethylene glycol copolymer, butylene terephthalate-polycaprolactone copolymer, and the like. These can be used alone or in combination of at least two. The crystalline aromatic polyester preferably contains at least butylene terephthalate as a crystalline component. As long as a terephthalic acid terephthalate component is contained, the crystalline aromatic polymer S is intended to be particularly excellent in non-polluting properties and crystallinity. When the component is a crystalline aromatic polyvinegar containing butyl terephthalate as a crystalline component, the crystalline melting heat of the release film of the present invention is preferably 200522807 4 0 J / § or more. ^ "The right is less than 40, and sometimes the heat resistance that can withstand hot-dust molding cannot be developed, and the dimensional change rate in the 17th generation is also large. It may damage the circuit pattern during hot pressing. More preferably, it is 50 J / g or more. In order to improve the crystallinity and increase the heat of crystallization melting, an additive that promotes crystallization such as a crystallization nucleating agent can be added to the resin composition. Further, during the production of the release film of the present invention, the cooling during the melting and forming process is cooled. The temperature is set to the glass transition temperature of the aforementioned aromatic polyacetate

The degree Γ is preferably set to 70 to ⑽. C is better. The crystal melting heat 1 can be measured by differential scanning calorimetry.

The crystalline aromatic polyacetic acid is obtained by mixing a primary bond with a crystalline aromatic polyacrylic acid obtained by reacting an aromatic dibasic acid or an vinegar-forming derivative thereof with a low-molecular-weight fatty acid glycol. The crystalline aromatic polyacetate of the frame and / or a polycaprolactam skeleton in the main chain, i. :: It is better to make a mixed resin with a fragrant polyester. This mixed resin has a backbone and / or polycaproate in the main chain because the main chain does not contain a polybond skeleton and / or a crystalline aromatic polyacetate with a polycaprolactone skeleton. The crystalline aromatic polyacetate of the internal vinegar skeleton is microdispersed, 'while maintaining heat resistance, it can obtain excellent quality', and its softness and health. The release film of the present invention composed of these resins is excellent in balance between heat resistance and release properties, and followability of uneven shapes on a substrate such as a circuit pattern, a through hole, and the like. The crystalline aromatic polyester preferably has a glass transition temperature of from 0 to loot. If it is ultra-loot, not only the release property required during hot pressing is reduced, but also the flexibility cannot be exhibited. The followability of the concave-convex shape on a substrate such as a circuit pattern or through-hole 12 200522807 will be reduced. The release properties at the time of% hot-press forming are reduced, and the usability of the release film is deteriorated. In addition, the glass transition temperature referred to in the present specification means a temperature exhibited by the micro-Brownian motion among the maximum values of the dielectric loss factor (tan5) obtained by dynamic viscoelasticity measurement. The glass transition temperature can be measured by a conventionally known method using a viscoelasticity spectrometer or the like. A volume of release film, when heated at 170 ° C for 10 minutes, the outgassing volume is preferably below 200Ppm. As long as it has the above-mentioned release layer, the release film of the present invention can not only meet the requirements of the release film / JBL flexibility, but also follow the unevenness, heat resistance, release characteristics, etc., and can release gas. The amount of production is suppressed to a minimum, and a high degree of non-pollution can be achieved. The outgassing amount can be measured by a conventionally known method such as a dynamic headspace gas chromatography analysis. The resin composition constituting the release layer may contain a stabilizer. The female tincture is not particularly limited, and examples thereof include j, 3,5-trimethyl-2'4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3 '9-Bis {2- [3- (3-tertiarybutyl-4-4-methyl-5-methyl-tolyl) -propionyloxy] -Li-dimethylethyl} _2,4,8,1〇 —Tetraoxane = [5,5] Undecane and other blocking phenolic antioxidants; tris (2,4—12—di-King | base) phosphate esters, 1 —.-Bis double j 土 一 α— (One tertiary butyl-4 to hydroxyphenyl) a pair of cumenyl bis (p-nonylphenyl) dish acid vinegar, dimyristyl 3,3, -thiodipropionate vinegar 13 200522807, one hard Thermal stabilizers such as aliphatic 3, 3 'monothiodipropionate, pentaerythritol tetrakis (3 1-lauryl thiopropionate), ditridecyl 3, 3, monothiodipropionate and the like. The resin composition constituting the release layer may contain additives such as fibers, inorganic fillers, flame retardants, ultraviolet absorbers, antistatic agents, inorganic substances, and higher fatty acid salts, as long as the practicality is not impaired. The above-mentioned cut dimensions are not particularly limited, and examples thereof include inorganic fibers such as glass fibers, carbon fibers, boron fibers, silicon carbide fibers, alumina fibers, amorphous fibers, silicon-titanium-carbon fibers, and the like; aromatic amidamine fibers; And other organic fibers. The inorganic filler is not particularly limited, and examples thereof include calcium carbonate, titanium oxide, mica, and talc. The flame retardant is not particularly limited, and examples thereof include hexabromocyclododecane, tri- (2,3-dicyclopropyl) phosphate, and pentaphenylallyl. The ultraviolet absorber is not particularly limited. Examples include tertiary butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-meryl-4-methoxy-2, and 2-benzylbenzophenone. A-trihydroxybutadiene and so on. The above-mentioned antistatic agent is not particularly limited, and examples thereof include fluorenyl ethyl) amine, dilute propyl dicarboxylic acid, and dicarboxylic acid diamine. Examples of the inorganic substance include barium sulfate and oxidation! s, oxide stone eve 14 200522807 and so on. Examples of the noble fatty acid salts include barium and sodium palmitate. It is said that the sodium release layer and stearic acid can be a single-layer structure. In the case of a release film with a layered structure, if you will use fragrant, lysinic acid, or acetic acid or its purpose, and low-molecular-weight aliphatic two yarns ^: 耒 # 取 、 砰 进 仃The reaction product, 、, 日 日 香香 莱 酯 is used as the surface layer, and the softness of Gao, w li & Xi from β bamboo back / dish is excellent

^ One μ ,,, " Interfacial adhesion of Japanese and Japanese aromatic polyesters 樨 s. = For example, butylene terephthalate polytetramethylene glycol copolymer; u-cyclohexylene dimethylene paraben Dicarboxylic acid

Crystal, polyethylene terephthalate, polyamide-polytetramethylene glycol copolymer, or styrene-based thermoplastic elastomer) as the middle layer, not only can maintain the release during press molding In addition, it can provide softness, and it can obtain a release that is excellent in the balance of the release property and the followability of the uneven shape on the substrate such as a circuit pattern or a through hole. 当 When the release layer has a two-layer structure Next, the storage elastic modulus of one layer at 17 ° C is lower than that of the other layer 纟 17 (^). X, when the release layer is a multilayer structure with more than 3 layers, the middle layer The storage elastic modulus of at least one of the layers at 170 ° C is better than that of the surface layer at 17 ° C. If this structure is used, it can not only maintain the release property during press forming, but also Professional softness, a release film that is excellent in the balance between release properties and followability of uneven shapes on a substrate such as a circuit pattern or a through-hole can be obtained. 15 200522807 The surface of the release layer is smooth as Good, can also give the necessary sliding properties, Adhesiveness, etc. Also, for the purpose of degassing during hot pressing, an appropriate embossing pattern can also be set on at least one side. ^ ^ In order to improve financial and thermal properties, release properties, dimensional stability, and release The layer is subjected to heat treatment. The heat treatment temperature is only required to be lower than the temperature of the resin composition constituting the release layer, and the higher the temperature effect is, the better, no. (: The above is better, the 20 (rc or more is better) . Do: Other methods to improve the financial and thermal properties, release properties, and dimensional stability of the release layer include, for example, a method of stretching in the 1-axis or 2-axis direction, and a method of rubbing the surface with a solid. The lower limit of the thickness of the release layer of the present invention is preferably 5 " m, and the upper limit is preferably 200 。. If it is less than 5 有时, the strength may be insufficient, and if it exceeds 200 ^ ', sometimes the thermal conductivity during hot pressing will be The lower limit is more preferably 1 〇 " m, and the upper limit is more than 〇〇 " m. The above-mentioned 3L layer moon b is made by a melting and forming method. The above-mentioned melting and forming method is not particularly limited, and examples include Air-cooled or water-cooled blow molding extrusion methods, T-die extrusion methods, etc. The method and method of the thermoplastic resin film * Although the release film has a multilayer structure, it can be manufactured by, for example, the co-extrusion T-die method. ^ LL ~ M " That is, the release layer is usually not subjected to thermal storage. The storage elastic modulus # 2G side pa, the elongation load is 49.0mN / mm, the tensile elongation at break is 5 or more, and the load is 3MPa at 1 200522807 ° C. The dimensional change rate under 60 minutes of pressure is less than 5%. By exerting such mechanical properties, the release film of the present invention is extremely suitable for use in printed wiring boards, flexible printed wiring boards, or multilayer printed wiring boards. The release film used in the manufacturing process. If the storage elastic modulus at 170C is less than 20 MPa, sometimes it cannot show the heat resistance that can withstand hot pressing, and if it exceeds 200 MPa, it is due to the sheet during hot pressing. The material cannot be sufficiently deformed, so the followability to the uneven shape on the substrate such as a circuit pattern, a through hole, etc. is reduced, and for example, the adhesion of the coating film on a flexible printed circuit board to the uniformity of the circuit pattern may decrease. A more preferable upper limit is 150 MPa, and a particularly preferable upper limit is 100 MPa. The storage elastic modulus can be measured by ordinary dynamic viscoelasticity measurement, and can be measured by a viscoelasticity spectrometer. If the 100% elongation load at 170 ° C is less than 49mN / mm, when it is used as a release film, it may not exhibit the heat resistance that can withstand hot pressing. If it exceeds 490mN / mm, it cannot be used during hot pressing. Since it is sufficiently deformed, the followability to uneven shapes on a substrate such as a circuit pattern or a through hole is reduced. For example, the uniform adhesion of the film layer of a flexible printed circuit board to the circuit pattern is reduced. Here, it is 100 ° /. The elongation load means the load at which deformation is reached in a general tensile test, and can be measured in accordance with the method of JIS K 7127. If the tensile elongation at 170 ° C is less than 500%, it may break when following the uneven shape on the substrate during hot press molding, and the substrate may be contaminated. More preferably, it is 800% or more. The breaking elongation in the present invention can be measured in accordance with the method of JIS K 7127. 17 200522807 If the dimensional change rate at 170 C under a load of 3 MPa for 60 minutes exceeds 1 · 5%, the circuit pattern may be damaged during hot pressing. More preferably, it is 1.0% or less. When the release layer is superposed on polyimide and / or metal foil and pressurized at 170 ° C and 3 MPa for 60 minutes, the release layer has high release properties for polyimide and / or metal foil. Moreover, the so-called release property means that the polyimide and / or metal foil have a low peeling force with respect to the sheet or film after the pressure treatment, and the polyimide and / or Metal foil, sheet or film will not be damaged. The above-mentioned release layer can further exhibit extremely excellent mechanical properties even at a room temperature range around 23 ° C. That is, the above-mentioned release layer is at 23 ° C for normal operation, the storage elastic modulus is 1 000 to 5000 MPa, and the tensile strength is 98 N / mm or more. By utilizing such mechanical properties, the release film of the present invention is extremely excellent in usability, and is used when it is hot-pressed during the manufacturing process of a printed wiring board, a flexible printed wiring board, or a multilayer printed wiring board. A release film or a release film used when a cover film or a reinforcing plate is bonded with a thermosetting adhesive or a thermosetting adhesive sheet by thermocompression molding in the manufacturing process of a flexible printed circuit board is very suitable. If the storage elastic modulus at 23 ° C is less than 1000 MPa, the mechanical strength decreases to> JHL, so the strength is insufficient during the stripping process after pressure forming. The sheet or film at room temperature The usability will also be reduced. If it exceeds 500 OMPa, the followability of the uneven shape during press molding will be adversely affected. 18 200522807 If the tensile strength at 23 ° C is less than 98N / mm, it is used as a release film, and the strength is insufficient during the peeling process after press forming. ’Sometimes resin will adhere to the circuit. This kind of resin adheres to the circuit. The monthly condition ^ seriously affects the conductivity 'The entire printed circuit board becomes a defective product. Also, the above-mentioned tensile strength can be measured in accordance with the method of JIS κ 7128 c method (the right-angle tensile method). The release film of the present invention may be composed of only the above-mentioned release layer, or may further include a resin film layer in addition to the release layer. The release film of the present invention, in which the release layer is laminated on at least one side of the resin film layer, has a cushioning property and strength that can be uniformly applied during hot pressing. The resin constituting the resin film layer is not particularly limited. From the viewpoint of easy disposal after use, for example, polyethylene resin, polypropylene resin, ethylene-methyl methacrylate copolymer, and ethylene-vinyl acetate copolymer are considered. Other olefin-based resins are preferred. These can be used alone or in combination of at least two. In addition, in order to improve the adhesion to the release layer, a modified polyolefin such as an acid-denatured polyolefin, a glycidol-modified polyolefin, or a resin constituting the release layer may be contained. In addition, in order to suppress the exudation of the prepolymer sheet or the thermosetting adhesive to the through-holes, and to obtain a uniform adhesion to the circuit Θ, the melting point of the resin constituting the resin layer is preferably 5130C. In addition, the uniformity and consistency of the circuit pattern are obtained by $, and the re-adhesion coefficient of the resin constituting the resin film layer at 170 ° C is preferably 100 ~ 1000 Pa · s. The softening temperature of the release film of the present invention having the above-mentioned resin film layer is preferably 40 to 120 t. As long as it is within this range, the uniform adhesion of the 19 200522807 prepolymer sheet or the thermosetting adhesive to the circuit pattern can be suppressed. It was performed according to JIS K7196. Penetration of through-holes can be measured relative to the aforementioned softening temperature.

The manufacturing method of the release film of the present invention having the above-mentioned resin film layer is not particularly limited ^, and examples thereof include an air-cooled or water-cooled blow-molded house extrusion method: a co-extrusion T-mold method to produce a film; previously produced On the aforementioned shouting layer, a method for laminating a tree moon t composition constituting a resin film layer by extruding M layers; a method for dry lamination of the aforementioned release layer and tree moon separately; a film layer, etc. . In the middle, the method of forming a film by a co-T-mold method 'can well control the thickness of each layer.

The release film of the present invention is excellent in flexibility, heat resistance, release properties, and non-pollution properties at high temperatures, and is easy to be disposed of after use. Therefore, the release film is extremely suitable for use in printed wiring boards, flexible printed wiring boards, or It is in the manufacturing process of multilayer printed wiring boards. That is, the release film of the present invention can be used for the production of a printed wiring board, a flexible printed wiring board, or a multilayer printed wiring board through a pre-polymer sheet or a heat-resistant film to perform a copper area laminate or copper. It is used when the foil is hot-pressed. In addition, the release film of the present invention can be used at the time of laminating a film or a reinforcing plate with a thermosetting adhesive or a thermosetting adhesive sheet by thermocompression molding during the manufacturing process of a flexible printed substrate. The release film of the present invention can further be used to make a pre-made sheet made of glass cloth carbon fiber or aromatic amine fiber and epoxy resin. Release film for sports goods such as heads, ball stems, and aircraft parts, and release films for polyurethane foam plastics, ceramic sheets, and electrical insulation boards. [Embodiments] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. (Example 1) (1) Production of release film Hetereli 2751 (manufactured by Toray DuPont Co., Ltd.) was used as a resin composition, and was extruded at 250 ° C. (: Melt plasticized, and extruded through a T die to obtain a release film with a thickness of 50 # m. (2) Production of resin film Low density polyethylene resin (manufactured by Polychem Japan: Nobair Tike LDLE425) is heated to 2301 with an extruder to melt plasticize, and extruded through a τ mold to obtain a resin film with a thickness of 100 # claws. (3) Production of copper area laminates with a thickness of 25 / / in polyimide film (manufactured by DuPont; card ordinary) as the base film, on the base film with a thickness of 2Mm epoxy-based adhesive layer followed by a thick 纟 35 ″, 5Mm thick steel to obtain the copper area (4) Laminating film production Polyimide film (manufactured by DuPont; card ordinary) with a thickness of 25 / zm is coated with epoxy adhesive 20 ° C at a starting temperature of 80 ° C to obtain 21 200522807 to cover film. (5) Production of flexible printed circuit board, release film, copper area laminate, cover film, release film, and resin film are laminated as a group in order. 32 sets are placed on a hot press, and hot pressing is performed under the conditions of a pressing temperature not, a pressure of 3 MPa, and a pressing time of 45 minutes. , The pressure was released, the resin film is removed, the release film strip, flexible printed circuit board can be obtained.

The cladding film of the flexible printed circuit board and the main body of the substrate were completed in 4 mouths, and no air remaining part appeared. The release film can be completely peeled from the electrode portion made of the copper foil without the coating film portion, and the copper foil of the electrode portion is completely exposed. X, the electrode part has sufficient conductivity. In addition, the degree of outflow of the adhesive to the surface of the copper foil in the portion without the coating film is 0 ° from the end of the coating film; [_ or less, the effect of preventing the adhesive from flowing out is sufficient. Moreover, no deformation of the circuit was seen at all. (Example 2)

Hetereli 5557 (manufactured by Toray DuPont) was used as the resin composition, and the extruder was used at 25 °. (: Melt plasticizing, extrusion molding using a T-die to obtain a release film with a thickness of 50 mm, and using this release film, the same method as in Example 丨 was used to perform releasable printing. Fabrication of the substrate. (Example 3) Using Perupeline S9001 (manufactured by Toyobo) as the resin composition, melt extrusion plasticizing at 25 ° C with an extruder, and extrusion molding with a τ mold to obtain a thickness of 50 The release film for // m is manufactured using the same method as in Example 丨 except for the release film of 200522807. (Example 4) Use of Peruglian S3001 ( Toyobo Industries Co., Ltd.) was used as the resin composition, melt-plasticized at 25 ° C with an extruder, and extruded by a τ mold to obtain a thickness of 5. 之 m release film: The mold film "other than that" is used to produce flexible printed circuit boards in the same manner as the implementers. (Example 5) Nobatiran 5040ZS (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) was used as a resin composition and extruded. The press is melt-plasticized at 250 ° C with T-die Extrusion molding was performed to obtain a release film having a thickness of 5 Mm, and a flexible printed circuit board was produced in the same manner as in Example 1 except that the release film was used. (Example 6) Nobatiram was used 5040ZS (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) 70 parts by weight and Heitleru 7247 (1 part by Toray DuPont) are used as a resin composition, and melt-plasticized by an extruder at 25.0. Extrusion was performed by a T-die to obtain a release film with a thickness of 50 // m. Except for using this release film, a flexible printed circuit board was produced in the same manner as in Example 1. (Example 7) Using 70 parts by weight of Nobatiran 5040ZS (manufactured by Mitsubishi Engineering Plastics) and Peruline S6001 (manufactured by Toyobo) 30 by weight 23 200522807 parts as a resin composition to extrude 25 Acrylic melted and plasticized 'Extrusion molding through a τ mold to obtain a release m with a thickness of 50 m' using this release film, except that flexible printing was performed in the same manner as in Example 1. Fabrication of the substrate (Example 8) Using Thirap 001 (manufactured by DuPont) as the resin composition to press record 29 (TC (iv) into the plasticized melt, a mold by τ

Extruded, then stretched twice in length, and annealed at 23 ° C to produce a 50 "thickness release film. The release film was used in the same manner as in Example i except that the release film was used. Production of Flexible Printed Board (Example 9)

Using a three-layer co-extrusion machine, a layer of 10 μm thick made of Nobatiran 5040zs (manufactured by Mitsubishi Engineering Plastics Co., Ltd.), and Hetereli 7247 (manufactured by Toray DuPont) A 3-layer structured release film composed of a layer with a thickness of 30 Am and a layer with a thickness of 10 μm formed by Nobatiran 5040ZS (Mitsubishi Engineering Plastics Co., Ltd.) is manufactured using the release film. Except for the mold film, a flexible printed circuit board was produced in the same manner as in Example 2 of Example 2. (Comparative Example 1) Nobatik PP FB3GT (manufactured by Polychem Co., Ltd.) was used as the resin composition, and melt-plasticized at 25 ° C using an extruder, and thickness was obtained by extrusion molding using a τ die. A 50 / zm release film was produced using the same method as in Example 丨 except that the release film was used. (Comparative Example 2) Using a thickness of 50 / zm Opal X88B (manufactured by Mitsui Chemicals) made of polymethylpentane was used as a release film, and a flexible printed circuit board was produced in the same manner as in Example 1 / (Comparative Example 3 10) (10) parts by weight of Hetereli 5557 (manufactured by Toray DuPont) as a thermoplastic resin, a natural montmorillonite (Feng Manufactured by Sun Ocean, Nw S—B⑼D) 7.7 parts by weight was added to the extruder to 23 °. (: Melt plasticized, extrusion molding with τ mold to obtain a film with a thickness of 50 # m, using this film, Except for this, the flexible printed circuit board was produced in the same manner as in Example 1. The release films produced in Examples 1 to 9 and Comparative Examples 丨 to 3 were used to measure the heat of crystal melting, the modulus of storage elasticity, the glass transition temperature, the tensile elongation at break, the dimensional change rate, and the amount of outgassing. ^ In the production of flexible printed substrates using these release films, visual evaluation was performed to evaluate peelability, adhesiveness, electrode contamination of flexible printed substrates after fabrication, circuit deformation, etc. (crystal dissolution) Measurement of heat) Using a differential scanning calorimeter (DSC 2920 manufactured by TA instrument), measurement was performed at a temperature increase rate of 5 ° C / minute. (Measurement of storage elastic modulus) 25 200522807 Using a viscoelasticity spectrometer (Ray Olympiad) Enteflux Affy Company, RSA-11), heating rate 5cc / min, frequency

The measurement was performed at 10 Hz and a deformation of 0.05%, and the storage elastic modulus at 23 ° C and 170 ° C was measured. (Measurement of glass transition temperature) Using a viscoelasticity spectrometer (manufactured by Lei Europe and the United States, Texark, Teflon Affy Company, RSA-11), at a heating rate of 50 ° C / min, a frequency of 10Hz, and a deformation of 0.05% The glass transition temperature was determined using the temperature at which the obtained dielectric loss factor (tan 5) showed a maximum value. (Measurement of tensile elongation at break) The measurement was performed on a No. 2 punching test piece at 170 C and a test speed of 500 mm / min in accordance with JIS K 7127. (Measurement of tensile strength) The rectangular tensile test punched piece was measured at 23 C and a test speed of 500 mm / min in accordance with the JIS K 7128 C method. (Measurement of 100% elongation load) In accordance with JIS K 7127, measurement was performed on a No. 2 punching test piece at 1 70 ° C and a test speed of 500 mm / min. (Measurement of Dimensional Change Rate) For the surface of the release film, it is oriented in the direction of extrusion molding) and at right angles (TD direction) with respect to the direction of extrusion molding. The release film was pressurized at 170 ° C and prepared at 3 MPa for 60 minutes, and then the distance between the marked lines was ^ J 疋. The average value of 32 groups was determined as lmd and LTD. Calculate the dimensional change rate of each direction according to the following formula. Dimensional change in the MD direction Dimensional change in the TD direction (Measurement of the amount of outgassing Chemical conversion rate (% MLMir100) / 10〇〇〇〇〇 Chemical conversion rate (%) = (LTD-1 00) / 1 00 X 1 〇〇

Use ATD-400 manufactured by Parkin Eloma as a thermal desorption device. 'Dynamic head gap method was used to collect the gas generated from the film after heating at 170 C for 10 minutes under a 25 mL / minute inert gas flow. . It was separated by Aut⑽assII-15 manufactured by Japan Electronics Co., Ltd. with a non-polar capillary column connected, and the toluene-converted amount of the total area of the detected peaks was normalized by the weight of the film to be used as the outgassing amount. 0

27 200522807

200522807 < N ^ Remarks 1 1 1 1 1 Blended Resin Blended Resin 1 cd a CL, & s 2 ·· Di PP ^ o — ± i ISt phthalate M $ ro D_ D | n Sh 靼 < + Mic · · 1 1 1 1 Blended with layered silicate Thickness 0 ο Composition 2 1 1 1 1 1 S 1 1 1 1 1 1 1 Species 1 1 1 1 1 Hetereli 7247 Perurup S6001 1 1 1 1 1 1 WQ Jj (D i S Inchina A Λ £ 砩 νζ a? G ^%, 1 sharp ^ H < Ingredient 1 〇Τ— »〇〇Η 〇〇〇〇〇〇 Τ-4 100 ί ο ο 〇100 Kinds of Hetereli 2751 Hetereli 5557 Perurup S9001 Perurup S3001 丨 1 Nobatilan 5040ZS Nobatilan 5040ZS Nobatilan 5040ZS Thira P7001 Nobatiran 5040ZS 1 Haitleru 7247 j Nobatiran 5040ZS Nobatik PPFB3GT Oppland X88B Haitliru 5557 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative example 1 Comparative example 2 Comparative example 3 1 1 200522807 Glass transition temperature CO Bu τ-Η 1 cn νο s 120 v〇1 1 Bu 1 Outgassing amount (ppm) ο r— * 沄 τ-Η τ · Η 250 ο g o H o § 1 600 350 Heat of crystal melting (J / g) ο] On 1 1 1 Evaluation of tensile strength at 23 ° C (N / mm thickness) Ο rH τ-Η ο τ-Η 200 g 490 o τ- Η o τ-Η Storage modulus of elasticity (MPa) ί_ 1 1800 Ο (N 2000 220 2500 1700 1800 4500 1700 1500 2100] 500] 170 ° C Evaluation Dimensional Change Rate (%) MD1.1 / TD1.1 MD1. 3 / TD1.3 MD1.1 / TD1.1 MD1.3 / TD1.4 MD0.7 / TD0.6 MD0.7 / TD0.6 MD0.6 / TD0.6 MD0.1 / TD0.0 MD0.7 /TD0.6! Unable to measure MD1.0 / TD0.8 MD0.5 / TD0.5 100% elongation load (mN / mm width) 450 t 蛘 480 τ-Η 540 500 500 780 TH! Unable to measure § τ-Η 〇 Tensile elongation at break (%) 1 1400 1700 1300 1500 800 o 1000 700 1100 Unable to measure 1150 1 1700 Storage modulus (MPa) S ο g § τ-Η 140 H 420 o (N ο halogen content rate (weight %) 〇ο 〇 ο 〇 o 〇oo 〇〇〇 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative example 1 Comparative example 2 Comparative example 3 oe

200522807 Table 4 Evaluation of Deformable Adhesive Electrode Pollution Circuit Deformation Example 1 Good Good No No Example 2 Slightly difficult to peel but no problem Good No No Example 3 Good Good No No Example 4 Slightly difficult to peel but no problem Good No No Example 5 Good Although several holes were seen but no problem No No No Example 6 Good Good No No Example 7 Good Good No No Example 8 Slightly difficult to peel but no problem Although no holes were seen but no problem No Example 9 Good Good No No Comparative Example 1 Melts and cannot be used for practical Comparative Example 2 Good Good electrode part is unclear, poor conduction occurs No Comparative Example 3 Slightly difficult to peel but no problem Good electrode part is not clear Clear

Industrial Applicability According to the present invention, it is possible to provide a release film which is excellent in high temperature flexibility, followability to unevenness, heat resistance, release property, and non-pollution property, and is easy to be discarded after use.

Claims (1)

200522807 The scope of patent application: 1 · A release film, which is used by users in the manufacturing process of printed wiring boards, flexible printed wiring boards or multilayer printed wiring boards; it is characterized by having at least one surface A resin composition composed of a resin having a polar group in the main chain as a base and having a content of i element of 5% by weight or less. 2. The release film according to item 1 of the patent application scope, wherein the main chain has polarity Based resin is crystalline aromatic polyester. The release film according to the item, wherein the crystal is melted 4. The heat quantity is above 40 J / g as described in the patent application. 5. If the release film of the second crystal 3 or 4 of the scope of the patent application, Pick-up, diagram: 200522807 柒, designated representative map: (1) The designated representative map in this case is: (none) map. (2) Brief description of the representative symbols of the components in this representative diagram: None. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: