TW201124280A - Release film - Google Patents

Abstract

Provided is a release film, which is consisted of a lamination film having a crystalline polyester (A) layer disposed in a surface layer and a polyester (B) layer. The (A) layer is provided with a heat of crystalline melting from 35 to 50J/g, and a crystalline speed index less than 50 DEG C. The (B) layer is provided with a heat of crystalline melting from 20 to 40J/g, and a crystalline speed index less than 60 DEG C.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a release film which is particularly useful in the production of a printed substrate. More particularly, it relates to a release film which is useful in the case of using a thermosetting adhesive on a printed substrate having a precise pattern and hot stamping a coverlay film. [Prior Art] Release film systems are widely used in the industry. In particular, in the manufacturing steps of a printed wiring board, a flexible printed wiring board, or a multilayer printed wiring board, when a copper clad laminate or a copper box is thermally pressed through a prepreg or a heat resistant film, it is used to prevent the prepreg. Or a heat resistant film followed by a stamped hot plate. Further, in the manufacturing step of the flexible printed circuit board, when the coverable printed circuit board body forming the electronic circuit is thermally punched and then covered with a film using a thermosetting adhesive, the cover film is prevented from coming over with the hot stamping plate. The release film used for such applications may, for example, be a fluorine-based film, a polyoxyethylene-coated polyethylene terephthalate film, a polydecylpentene film or a polypropylene film. However, 'the fluorine-based film which can be used as a release film is excellent in heat resistance, release property, and non-contamination property, but it is difficult to burn in waste incineration after use, and it is toxic. The problem of gas still exists. Further, the polyoxymethylene-coated polyethylene terephthalate film and the polymethylammonium film are contained in the film composition containing polyfluorene oxide or a low molecular weight body, thereby transferring the printed circuit substrate, particularly the substrate. The copper circuit on the 'terrorism and quality. Further, the polypropylene film is inferior in heat resistance and insufficient in release property. 322465 3 201124280 Therefore, it has been disclosed that polybutylene terephthalate, poly(p-propyl phthalate), and poly-pairs are disclosed in terms of softness, heat resistance, release property, non-contamination, and waste incineration. A film of a butyl phthalate and a polyether is used as a film of a release layer (Patent Document 1) or a film as a buffer layer (Patent Document 2). However, in such a technique, the coexistence of release property, heat resistance, and softness is not sufficient. That is, the importance of release property and heat resistance is sacrificial softness, and the embedding property of a printed circuit board having a fine pattern is poor. In addition, when the flexibility is emphasized, 'there is a decrease in the release property or a deterioration in the lubricity of the surface of the film, and the film is wound up, the cutting time is delayed, or wrinkles are caused by the decrease in the elastic modulus. [Patent Document 1] International Publication No. 5/〇〇285 手册 手册 [Patent Document 2] Japanese Patent No. 4,99355 (Draft of the Invention) [Problem to be Solved by the Invention] An object of the present invention is to provide a soft It is excellent in the properties, the release property, the heat resistance, and the non-contamination property, and is particularly excellent in the embedding property of a printed circuit board having a fine pattern, and is excellent in handling workability at the time of winding or cutting of a sheet. [Means for Solving the Problem] The inventors of the present invention have found that the first polyester having specific crystallinity and the substantially amorphous polyester and crystallinity are obtained as a result of intensive research to solve the above problems. The second polyester which is mixed with the polyester and controls the crystallinity is laminated to form a specific crystal state, and the crucible can provide a release property of excellent 322465 4 201124280 * heat resistance, embedding property, and workability at the same time. The superior thin, film 'finishes the present invention. That is, the gist of the present invention is as follows. (1) A release film formed by a laminated film having a crystalline polyester (A) layer disposed on a surface layer and a polyester (B) layer ((A) layer system crystal heat of fusion is 35 Up to 50 J/g, the crystallization rate index is less than 5 (TC, (B) layer crystal heat of fusion is 20 to 40 J/g, and the crystallization speed index is less than 60 ° C. (2) . (1) The release film of the item, wherein the (A) layer has a heat of fusion of 38 to 45 J/g, a crystallization rate of 40 to 46 ° C, and (B) a layer of crystal heat of fusion of 21 to 36 J/g, crystallization The speed index is 47 to 57 ° C. (3) The release film of (1) or (2), wherein the polyester layer is 20 to 50% by mass of the polyester (I) having substantially amorphous The crystalline polyester (II) is contained in an amount of 80 to 50% by mass. (4) The release film of (3), wherein the amorphous polyester (I) of the (B) layer has a glass transition temperature of 30 (5) The release film of any one of (1) to (4) wherein the crystalline polyester (A) is poly-p-acid bismuth vinegar. (6) . The release film of any one of (1), wherein the (β) layer of the crystalline polyester (II) is a polybutylene terephthalate and a polyether [Embodiment] The present invention will be described in detail below. The release film of the present invention has a layered film of a crystalline t 曰 (8) layer disposed on a surface layer and a specific polyester (B) layer. It is composed of a polyester resin, and therefore it is not as problematic as the outgassing of a film using various olefinic resins. 322465 5 201124280 <Polymer (A) layer> Polyester (A) is disposed on a release film The surface layer functions as a release layer. The polyester (A) is preferably a crystalline aromatic polyester, and examples thereof include polyethylene terephthalate (PET), polybutyl phthalate (PBT), and polypyrene. The propylene acrylate is particularly preferably hydrazine from the viewpoint of heat resistance or high crystallinity. In addition to the above-mentioned PET, hydrazine, hydrazine, it can be used from various aromatic dicarboxylic acid components and diol components. The polyester is a crystalline aromatic polyester, and may be a copolymer of such a crystalline aromatic polyester with any of PET, ruthenium and iridium. Ugly acid, ugly acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4,dicarboxylic acid, two a phenoxyethyl acetonate, a ruthenium acid, or an ester-forming derivative thereof. The diol component is preferably a diol having a molecular weight of 300 or less, and examples thereof include ethylene glycol, propylene glycol, and pentane. An aliphatic diol such as an alcohol, hexanediol, neopentyl glycol or decanediol; an alicyclic diol such as hydrazine, 4-cyclohexanedimethanol or tricyclodecane dimethanol; benzenedimethanol; (p-hydroxy)biphenyl, bis(p-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, bis[4-(2-hydroxy)phenyl]propane, M-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 4,4,_monohydroxy-p-terphenyl, 4,4'-dihydroxy-p-tetraphenyl, etc. One of these types of rebel components and monool components can be used in combination. Further, a trifunctional or higher polyfunctional carboxylic acid component, a polyfunctional oxyacid component, a polyfunctional hydroxy component or the like may be copolymerized in a range of 5 mol% or less. Further, a polyester elastomer described later can be used for the polyester (A) layer. 322465

S 6 201124280 The crystallization rate of polyester (A) must be less than 5 °C. When the crystallization rate index is 50 C or more, that is, if the crystallization rate at the time of cooling after melting is later than the predetermined speed, it is difficult to impart heat resistance to the sheet. As a result, peeling failure occurs when the crystallizing treatment is performed by direct heating by a roll, or slack occurs when heat is exchanged by hot air or infrared rays. If the crystallization rate index is less than 50 ° C ', it can be crystallized by cooling after the melt extrusion, and the crystal state of the sheet can be controlled by cooling the temperature or speed of the roller. The lower limit of the crystallization rate index is that if the crystallization rate is too fast, the crystallinity of the sheet is deteriorated immediately before the cooling 轺 is cooled by the melt squeezing, and therefore the planarity of the sheet is deteriorated, so it is preferably 2 ( TC. The crystallization rate index is preferably 25 to 45 ° C, particularly preferably 25 to 40 ° C. The heat of crystallization of the polyester (A) must be 35 to 50 J / g, particularly preferably 40 to 50 J / g. Although the heat of crystal fusion is less than 35 J/g, the heat resistance may be poor, and if it exceeds 50 J/g, the embedding property may be poor. The melting point of the polyester (A) is preferably 200 ° C or more, and if the melting point is lower than 200 ° C, the heat resistance is sometimes poor at the time of hot stamping. The polyester (A) can be produced by a known method, for example, transesterification of a lower alcohol diester of a dicarboxylic acid and an excess amount of a low molecular weight diol in the presence of a solvent a method of performing polycondensation of the obtained reaction product, or a method of esterifying a reaction product obtained by esterifying a diteric acid with an excess amount of a diol in the presence of a catalyst. <Polyester (B) layer> Polyester (B) layer helps on printed boards with precise patterns 7 322465 201 124280 The embedding property of the hot stamping film. Therefore, the polycondensate (B) layer crystal must have a heat of fusion of 20 to 40 J/g, and the crystallization rate index must be less than 60 ° C. If the crystal melting heat is less than 20 J /g may be inferior in heat resistance, and if it exceeds 40 J/g, the embedding property may be inferior. When the crystallization rate index is C or more, it is difficult to impart heat resistance to the sheet. If the crystallization rate index is less than 60 ° C, After melt-squeezing, the crystallized state of the flakes can be controlled by cooling the crystallization of the parent wheel, and the temperature of the roll can be controlled. The lower limit of the crystallization rate index is because the crystallization rate is too fast. The cooling roller after melt extrusion is crystallized before the adhesion, and the flatness of the sheet deteriorates. Therefore, it is preferably 20 ° C. The crystallization speed index is preferably 20 to 58 ° C 'especially 25 to 55 ° C. In order to control the heat of fusion and the crystallization rate of the polyester (B) to be in the above range, it is preferred to form a polyester by a mixture of the substantially amorphous polyester (I) and the crystalline polyester (II). (B) layer. Further, the polyester (I) / polyester (II) is preferably 20 to 50% by mass / 8 to 50 When the ratio of the polyester (I) is less than 20% by mass, the effect of improving the embedding property is small, and if it exceeds 5% by mass, the crystallinity of the mixture tends to decrease. Or the heat of crystal melting is liable to lower, and as a result, the heat resistance of the sheet is lowered, and in severe cases, the resin is oozing out from the end surface of the sheet during hot stamping. Here, the polyester (I) is "substantially amorphous". "When the S-type 1 〇mg is cooled from the smelting state to the glass transition temperature at a speed of 10 °C/min using a differential sweeping type 篁at, the crystal melting peak is not observed when the temperature is raised again to the molten state. . The glass transition temperature of the polyester (I) is preferably from 3 to 1203⁄4, particularly preferably from 50 322465 8 201124280 to 100 °c. If the glass transition temperature is less than 3 (TC, the heat resistance of the sheet may be poor, and if it exceeds 120 ° C, the embedding property is deteriorated when the hot stamping temperature is relatively low. The polyester (II) is only required to be polyester (I). The crystallization property of the mixture is not particularly limited, but it is preferably crystallinity, and the melting point thereof is preferably 200° C. or more. If the melting point is less than 20 (TC, the heat resistance of the sheet is poor, or heat In the case of the press, the (B) layer is oozing from the end of the sheet. The polyester (11) is exemplified by the same crystalline aromatic polyester or copolymer thereof as the polyester (A), and a polyester elastomer. The balance between heat resistance and embedding property is particularly preferably a polyester elastomer. The polyester elastomer system contains a block copolymer of a high melting point crystalline segment and a low melting point segment. A high melting point crystalline segment It is mainly composed of a crystalline aromatic polyacetate unit, and the low melting point segment is composed of an aliphatic polyether unit and/or an aliphatic polyester unit. The high melting point crystalline segment in the polyester elastomer The copolymerization ratio of the low melting point segment is not particularly limited 'but is suitable for low in the polyester elastomer The melting point segment is contained in an amount of 5 to 50% by mass. The crystalline aromatic polyester constituting the high melting point crystalline segment in the polyester elastomer can be used in the same manner as the component which can be used as the polyester (A). Among the polystyrene elastomers, the aliphatic polyether constituting the low melting point segment may, for example, be a poly(oxyethylidene) diol, a poly(oxypropyl) diol, or a poly(oxybutylene butyl). a diol, a poly(oxyhexyl) diol, a copolymer of ethylene oxide and propylene oxide, an ethylene oxide addition polymer of poly(oxypropyl) diol, ethylene oxide and tetrahydrofuran Copolymers, etc. 9 322465 201124280 The aliphatic polyester constituting the low melting point segment may, for example, be poly(ε-caprolactone), polydecene lactone, polyoctanolactone, polybutylene adipate, poly Ethylenediamine adipate, etc. Among these aliphatic polyethers and/or aliphatic polyesters, the elastic properties of the obtained polyester block copolymer are preferably poly(oxybutylene) diols. , an epoxy ethylene oxide adduct of poly(oxypropyl)-alcohol, poly(ε__caprolactone), polybutylene adipate, polyethylene adipate, etc. More preferably, it is a poly(oxybutylene) diol. Further, the number average molecular weight of the low melting point segments is preferably about 300 to 6 Å in the state of copolymerization. A preferred structure of the polyester elastomer is, for example, a block copolymer of polybutylene terephthalate and a polyether. In the copolymer, the copolymerization amount of the polyether is preferably from 10 to 40% by mass, more preferably It is preferably 15 to 3 % by mass. When the amount of the polyether copolymerization is small, the softening effect tends to be small, and if too much, the heat resistance and crystallinity tend to be too low. It is easy to adjust the melting point of the polyester elastomer (glass), the glass transition temperature, the crystallization index, the heat of crystal fusion, etc. The polyester elastomer can be produced by a known method. For example, a lower alcohol diester of direxime A method in which an excess amount of a low molecular weight diol and a low melting point segment component are transesterified in the presence of a catalyst to polycondense the obtained reaction product. Alternatively, a method in which a dicarboxylic acid is esterified with an excess amount of a diol and a low melting point component in the presence of a catalyst to cause polycondensation of the obtained reaction product. Further, for example, a method of preparing a high melting point crystalline segment in advance, adding a low melting point segment component, and randomizing it by a transesterification reaction may be mentioned. Further, the high melting point crystalline segment and the low melting point segment are linked by a chain linking agent 10 322465 201124280, method. Further, a method of adding an ε-caprolactone monomer to a high-melting point crystalline segment when a poly(ε-caprolactone) is used in a low-melting point segment. Can be either method. Polyester (Α) layer and polyester (Β) layer can be added in the range of non-destructive practicality. Organic or inorganic dyes or pigments, matting agents, thermal stabilizers, flame retardants, antistatic agents, defoamers can also be added. , coloring agents, antioxidants, ultraviolet absorbers, crystal nucleating agents, brighteners, lubricants, trapping agents for impurities, tackifiers, surface conditioners, etc. Among them, it is preferred to contain a heat stabilizer or a low molecular weight volatile impurity trapping agent. The heat stabilizer is preferably a 5-valent or/and a trivalent phosphorus compound or a hindered compound. The trapping agent of low molecular weight volatile impurities is preferably a polymer or oligomer of polydecylamine or polyester decylamine, a low molecular weight compound having a guanamine or amine group, and the like. The release film of the present invention is preferably a polyester (ruthenium) layer having a thickness of from i to 50 in a paw. If the thickness of the polyester (A) layer is less than 1 #m, it may be difficult to form a uniform film. If it exceeds 50, the embedding property may be poor. The thickness of the polyester (A) layer is more preferably 2 to 30 / zm. Here, the thickness of the layer (A) is a thickness of one layer when the layer (A) is two or more layers as in the case of two types of three layers. The release film of the present invention should have a total thickness of U 5G () &quot;. When the thickness of the whole is 3 Å or more, the strength of the sheet is high and it is easy to handle. Further, when it exceeds the _ port, the thermal conductivity is increased, and the printed circuit board having an unfavorable pattern is produced. The thickness of the whole eight (four), the most appropriate. For the preferred composition of the release film of the present invention, the layer and the (8) layer of the two types of (A) / (8) / (A) three layers ". I / = = 322465 11 201124280 This, :: (A) layer In the case of being disposed on the surface layer, there may be other differences. The second embodiment describes the method for producing the release film of the present invention. The method of forming a film by the method of co-extrusion τ mold method by pressure T-die method is controlled from the thickness of each layer in the manufacture of the release film of the invention, and imparts a pre-characteristic to the film. Release type, size shirt', and crystallization step. The crystallization method may, for example, heat crystallization: the center must be at a high temperature, and the nucleus is not in the middle of the road. Borrowing - "S. The method of heating and crystallization may be, for example, a method of cooling from a T-die and then simultaneously crystallization, or extruding and post-curing - and then indirectly heating the hot air or the infrared material by a roller directly. method. The method of crystallization by reheating may not only change the steps: but also cause poor peeling at the wheel, or when the hot air is heated or the infrared rays are heated, the film quality is poor. Therefore, it is desirable to cool and simultaneously crystallize. When cooling and simultaneously crystallization, the crystallization speed must be considered to set the temperature of the cooling roll. For the reading of the present invention, the temperature of the cooling roller is preferably from 30 to 1003⁄4, more preferably from 5 to 8 (rc. The release film of the present invention is preferably laminated with layers (A) and (B). The crystal heat of fusion of the entire film is 25 to 40 J/g, and particularly preferably 3 to 4 J/g. When the thickness is less than 25 J/g, the heat resistance may be poor, and the film forming workability may be poor. If it exceeds 45 J/g, The embedding property is easily reduced. The crystallization heat of fusion is, for example, in the aforementioned crystallization step 322465

In S 12 201124280, the desired value is appropriately adjusted by setting the temperature of the cooling roller to the aforementioned range. &quot; It is preferred that the release film of the present invention has a heat shrinkage ratio of (10) at 18 °C, more preferably 2%. By setting such a heat shrinkage ratio, it is difficult to wrinkle at the time of pressing, that is, the contact of the lower plate, and the heat resistance at the time of producing a printed substrate is good, and the heat is in the release film of the present invention, the polyester (A) layer. The surface is designed like a bear. It can be smooth, or it can be used for sliding properties for workability. Moreover, it is also intended to be used for air during hot stamping. At least one side of the anti-type film is provided with a moderate embossing pattern. Such embossing can be imparted by surface processing of the cooling roller. The release film of the present invention is excellent in flexibility, heat resistance, release property, and _ property, and can be disposed of safely and easily. Therefore, in a printed circuit board, a flexible printed circuit board, a multilayer printed wiring board, etc., a hot-stamped steel laminate or steel is interposed between a prepreg or a heat-resistant film. A release film attached to a hot plate, a printed circuit board, a self-timer, a line-up printed circuit board, or a multilayer printed wiring board. In the manufacturing process of the flexible printed circuit board, the vermiculite is formed by hot stamping, and when the coating agent is applied to the film, the time may be used as a frost, a hardened stamping plate, or a coating film. _. Both the cover film and the heat: shape may be disposed on the surface layer; [Examples] Hereinafter, the present invention will be described based on examples. The measurement methods of the raw materials of the film, the ', and the characteristics 322465 13 201124280 in the following examples and comparative examples are as follows. Tm means melting point and Tg means glass transition temperature. <Crystalline Polyester (A) and (11)&gt;

.PBT (polybutylene terephthalate): "Novaduran 5010CS" manufactured by Mitsubishi Engineering-Plastics, Tm 223 ° C, Tg 34 ° C

• HTR7277C polyester elastomer): DU P0NT-T0RAY "Hytrel 7277", Tin 221〇C, Tg 12°C

• HTR6377C polyester elastomer): “Hytrel 6377”, manufactured by DU P0NT-T0RAY, Tm 221°C, Tg 3°C

• HTR4777C polyester elastomer): "Hy tre 1 4777" and Tm 20 (TC, Tg -35〇C) manufactured by DU P0NT-T0RAY Co., Ltd. Any of the above two types of polyester elastic systems are polyparaic acid. Block copolymer of butadiene ester and polyether. <Amorphous polyester (I) &gt; • PETG (1,4-cyclohexanedonol copolymerized polyester); "PETG 6763" manufactured by Eastman Chemical Co., Ltd. , Tg 80. 匚 • IP-22 (intermediate acid 22mol copolymerized PET); IV 〇. 65dl / g, Tg 65. (:, containing Sb catalyst lOOppm, Tg 70 ° C. <Others> • TPX (poly "decylpentene": "DX845" manufactured by Mitsui Chemicals Co., Ltd., Tm 233 〇C, Tg 20 ° C. The measurement methods of various characteristics and the evaluation of the measured properties are shown below. (A) Crystallization characteristics 322465 14 201124280 Using a differential scanning calorimeter (Pyrisl • DSC manufactured by Perkin Elmer Co., Ltd.), 10 mg of the sample was heated to 260 ° C at a rate of 20 ° C / min, and the melting point (Tm) and the heat of crystal fusion (ΔHm) were measured. After maintaining at 260 ° C for 3 minutes, the temperature was measured at a rate of 20 ° C / min, and the crystallization peak temperature (Tc) was measured. The peak temperature of the crystallization peak at the melting point and the temperature drop Index difference of the crystallization rate. The properties of the individual layers were measured using a thin film-based sample. Sample-based resin film thicknesses of the layers, extrusion speed, cooling roller temperature becomes the same manner as the manufacturing conditions.

Further, in the samples used in the following examples and comparative examples, DSC' was determined to have no heat generation peak when the temperature was raised. That is, the crystallization was not observed at this time. (B) Film-forming workability The coil windability after the end of the film obtained by the cutting was evaluated based on the following criteria, and the state after the wound roller was stored at 40 ° C for 1 day. 〇·There was no problem with the reeling of the parental wheel, and no state change was observed after the preservation. This work 1 was difficult to wind up without wrinkles during the winding of the wheel, and no change was observed in the form of L after storage. (C) Heat shrinkability The longitudinal direction (MD) and the heat shrinkage ratio of the obtained film were measured in the order of the broad side. The test film obtained by cutting the sample film into 1 〇ΙΜΧ 兮 成为 制作 制作 制作 制作 制作 制作 已 已 已 已 已 已 已 已 已 已 已 已 已 已 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 After the oven is cooked, Η八# 77, then take out the test piece and return to room temperature to determine the distance between the marking line 15 322465 201124280. The heat shrinkage ratio was determined according to the following formula, and the average of the five bars was used as the heat shrinkage ratio of each sample film.

Heat shrinkage rate (%ML-L' VAxlOO L: distance between the lines before heat treatment (mm), L': distance between the lines after heat treatment (mm). (D) Performance evaluation of 20ym on double-sided coating A copper foil having a thickness of 25 μm was laminated on both sides of a 25 μm thick polyimide film ("Kapton 100V" manufactured by Du Pont Co., Ltd.) made of an epoxy-based adhesive ("AS-60" manufactured by Toagos Corporation). A copper-clad laminate with a thickness of 25#m polyimide film coated with a 20# m epoxy-based adhesive ("AS-60" manufactured by Toagosei Co., Ltd.) "Kapton 100V" manufactured by Pont Co., Ltd.) is used as a cover film, and further, the test release film is placed on both sides. At this time, the casting surface of the release film is placed inside. Thereafter, the temperature is 140 ° C and After hot pressing at 180 ° C and a pressure of 3 MPa for 5 minutes, after the press was quickly taken out from the hot stamping apparatus and allowed to cool, the release film was peeled off, and heat resistance, embedding property, and release property were evaluated based on the following criteria. At this time, a true round hole having a diameter of 5 mm was opened in the cover film, and the evaluation of the bleeding of the adhesive was used. (D-1) Heat resistance 〇: No wrinkles were observed in the film after the stamping. Δ: Wrinkles were observed in the film after the stamping. (D-2) Buriedness The length of the bleeding of the adhesive covering the pores of the film was observed under a microscope, according to the following criteria. Evaluation.

16 322465 S 201124280 ◎: The exudation length of the adhesive is 50; tzm or less 〇: the exudation length of the adhesive is more than 50/^ni, 70; am or less △: the exudation length of the adhesive is more than 70, 100 &quot; m or less X : The exudation length of the adhesive is more than 1 〇〇 (D-3) Release property ◎: Peeling without resistance 〇: Slightly resistive 'but peeling without affecting the laminate △: Impedance, but without laminate Deformation from X: Strong impedance, deformation with laminate (D-4) at the time of peeling. Use thermal desorption GC-MS, use a non-polar capillary column to heat the film at 180 ° C for 10 minutes. The generated gas was separated, and the amount of hexane in terms of the total area of the detected peak was normalized by the weight of the film, and this was used as the amount of outgas generation. The smaller the outgas production amount, the better, and the 200 ppm or less is judged to be good. [Example 1] A mixture of PE:T (Novaduran 5010CS) (layer A) and dry blend of Hytrel 6377/PETG (B) layer in a ratio of 75/25 (mass) in two separate extruders , melting at 260 ° C, respectively. The respective melts were combined to form a layer of A/B/A before reaching the exit of the T-die, and then extruded from the T-die outlet. Then, the side of the PBT (Novaduran 5010CS) (A) layer was cooled with a cooling roll adjusted to 60 ° C to obtain a layer thickness of A/B/A = 20/60/20 as shown in Table 1. /zm) laminated film. The adhesion time of the cooling roller is 6 seconds. [Examples 2 to 6 and Comparative Examples 1 to 5] 17 322465 201124280 The resin of the layer (A), the layer thickness configuration, and the cooling roll temperature were changed as described in Table 1, as compared with Example 1. In the same manner as in Example 1, two types of three-layered laminated films having a structure of A/B/A were obtained. [Comparative Example 6] The resin (TPX) shown in Table 1 was supplied to an extruder, melted at 280 ° C, and extruded from the T die outlet, and adhered to a temperature of 50 ° C as shown in Table 1. The rolls were cooled and cooled to obtain a single layer film having a thickness of 50 # m as shown in Table 1. The adhesion time for cooling the parent wheel is 6 seconds. [Comparative Example 7] A resin which had been formulated into PBT/IP-22 = 50/50 (mass ratio) was supplied to an extruder, melted at 250 ° C, and extruded from the T die outlet, and the adhesion was adjusted to Cooling roller at 60 ° C for 6 seconds. However, the film was not crystallized, and the peeling property from the cooling roll was poor. Therefore, the film was removed from the cooling roller, and the temperature of the cooling roller was raised to 80 ° C, and the film was again adhered. However, the film was slightly crystallized, but the peeling condition from the cooling roll was remarkably deteriorated. Therefore, the temperature of the cooling roller was further raised to 100 °C. Here, the temperature has been adjusted to 100 ° (the cooling roller is again allowed to adhere to the film, the crystallization proceeds, and the peeling condition is also good, but not complete. Further, the adhesion time is increased to 30 seconds, but the peeling condition is completely Not good, and the resulting film is poor in planarity. 18 322465 201124280.. [Table 1] a &lt; § PBT/IP-22 = 50/50(+) 1 1 ο 7 s Γ5 CM NS CM in SI 1 1 1 神1 « (D ϋ &lt; SK 1 » s CO CO CM s ro esi S i in «〇〇CSJ 〇eo 〇ο ◎ ο 寸 u&gt; a &lt; m S CO 〇CM 甶CL P 〇5 So U 3 & & & & & «V» CM s 〇〇ΙΟ s X ο ζ ir&gt;&lt;&lt; ◎ @ &lt;&lt; S CO * &lt; m to Ο CM will m a. ^ C3 sti ^ so 兮s CO Ol CM s 〇g CM CM f〇Csl CM CO 〇in % c4 &lt; ◎ © ◎ , @ S eg &lt; QQ a δ in u5 Csl CO H ma 1 o Γ- n S eo CM CM o 3 3 〇CSI 〇&gt; ο , ο ο \ &lt;1 ο , 〇ο τ- «&lt;&lt; ms (O CM white 0. s 1 s CO CM Csl o 〇〇CM ra ο CM § 〇, ο &lt;1 &lt; ◎ S (0 &lt; CQ s 1 s H m P ϋ s , ss CO CM ot so r- s 〇o ο ό -◎ @ ◎ ο U) &lt; mo CQ 〇l·—ffl P CD to t 1 ^ oso CO C&gt;4 CM 5 o 5 C*3 CO mas 〇CSi 1 ο , 〇 ◎ , ◎ ◎ @ S inch &lt; m 〇to R- 5 H Csl U IA in s &lt;M C4 CO CO CO CM CM CJ « s 5 〇Csl 〇W ο δ 〇, 〇〇© S CO C0 s &lt;〇δ Csl White a 04 a & s , Ss CO 04 CM so C*&gt; csJ eg CM IA s 00 CO 0 i r-_ 〇ό ◎ , 〇 ◎ ® ο ¥ CQ o σ 00 o White a ^ ϋ aa sssn CM ex so in ol 5 ss Ο o LO ο δ ◎ , 〇 ◎ © S r* 养 s &lt; 〇 s Q. P 〇M a r- § M es CM so IO s 3 0 op 〇, 0 ◎ , @ ◎ ® S « ΪΙ Zhao® M NW * Letter IS 9 PI « /«•n PE »- g to 3 Difficult 5 〇& PEHP 雔DS 3 Shake S 3 δ og 雄 ti m o oblique o Q 2 cargo difficulty 1 § ί I Ρ ο r«· &lt; » ΐ5 § ί5 ο /&quot;Ν 邑α shout ft i\C ite QQ fiQ Μ niw twist: * 19 322465 201124280 From example 1 shown in Table 1 6 results apparent, in particular sheet under this scope of the invention, the system as a release film satisfying all of the performance requirements. In particular, since it is excellent in embedding property, it can also correspond to a printed circuit board having a precise pattern, and has a small amount of outgassing and excellent stain resistance. In Comparative Example 1, since the layer (B) did not contain the amorphous polyester, the heat of fusion of the crystal was too high, so that the embedding property was poor. In Comparative Example 2, since the layer (B) did not contain the amorphous polyester, the heat of fusion of the crystal was too high, so that the embedding property was poor. In comparison with Comparative Example 1, the polyester elastomer (HRT6377) was placed on the surface layer, and the embedding property at 180 °C was improved, but on the other hand, the release property was slightly inferior. In Comparative Example 3, the content of the amorphous polyester in the layer (B) was too large, and as a result, the crystallinity of the layer (B) was remarkably lowered and the crystallization rate index was too high, so that the heat of fusion of the crystal was too low, so the embedding property was good, but Poor heat resistance. In Comparative Example 4, the heat of crystal melting of the layer (A) was too low, so that the film forming workability was poor, and heat resistance and mold release property were also inferior. In Comparative Example 5, the heat of crystal melting of the layer (B) was too low, so that heat resistance was poor. Further, in some cases, the melting point of the layer (B) is low, and the resin is observed to be linearly oozing from the end surface of the sheet at 180 °C. Comparative Example 6 is a film composed of polymethylpentene (TPX) which is widely used as a release film, but the outgas generation amount is remarkably as large as about 10 times that of the film of the examples, which is poor in contamination. In Comparative Example 7, it was attempted to thin the resin composition having a crystallization rate index of more than 50 °C in a single layer, but the film forming property was poor, and performance evaluation could not be performed. Therefore, the stratification is abandoned. 20 322465 201124280 [Simple description of the diagram] None [Key component symbol description]

Claims (1)

201124280 VII. Patent Application Range: 1. A release film consisting of a laminated film having a crystalline polyester (A) layer disposed on the surface layer and a polyester (B) layer, (A) layer system The heat of crystallization heat is 35 to 50 J/g, the crystallization rate is less than 50 ° C, the heat of fusion of (B) layer is 20 to 40 J/g, and the crystallization rate is less than 60 t. 2. The release film according to claim 1, wherein the (A) layer has a heat of fusion of 38 to 45 J/g, a crystallization rate of 40 to 46 ° C, and (B) a layer of crystal melting. The heat is 21 to 36 J/g, and the crystallization rate is 47 to 57 °C. 3. The release film according to claim 1 or 2, wherein the polyester (B) layer is 20 to 50% by mass of the substantially amorphous polyester (1), and contains a crystalline polyester. (11) 80 to 50% by mass. 4. The release film according to claim 3, wherein the non-crystalline polyester (I) of the (B) layer has a glass transition temperature of 30 to 120 °C. 5. The release film according to claim 1 or 2, wherein the crystalline polyester (A) is polybutylene terephthalate. 6. The release film according to claim 1 or 2, wherein the crystalline polyester (II) of the (B) layer is a block copolymer of polybutylene terephthalate and a polyether. 1 322465 201124280 IV. Designated representative map: There is no schema in this case (1) The representative representative map of this case is: (). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: This case does not represent the chemical formula 2 322465